JP6871570B2 - Repair materials and repair methods - Google Patents
Repair materials and repair methods Download PDFInfo
- Publication number
- JP6871570B2 JP6871570B2 JP2017071416A JP2017071416A JP6871570B2 JP 6871570 B2 JP6871570 B2 JP 6871570B2 JP 2017071416 A JP2017071416 A JP 2017071416A JP 2017071416 A JP2017071416 A JP 2017071416A JP 6871570 B2 JP6871570 B2 JP 6871570B2
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- Prior art keywords
- repair material
- repair
- water
- cement
- calcium
- Prior art date
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- MZYRDLHIWXQJCQ-YZOKENDUSA-L potassium alginate Chemical compound [K+].[K+].O1[C@@H](C([O-])=O)[C@@H](OC)[C@H](O)[C@H](O)[C@@H]1O[C@@H]1[C@@H](C([O-])=O)O[C@@H](O)[C@@H](O)[C@H]1O MZYRDLHIWXQJCQ-YZOKENDUSA-L 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
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- 239000000770 propane-1,2-diol alginate Substances 0.000 description 1
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- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
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- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 230000002623 sporogenic effect Effects 0.000 description 1
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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Description
本発明は、コンクリートやモルタルなどのセメント系構造物の補修に用いる補修材料と、それを用いた補修方法に関する。 The present invention relates to a repair material used for repairing a cement-based structure such as concrete or mortar, and a repair method using the same.
コンクリートやモルタル等のセメントの硬化物は建築構造物などに広く使用されている。このようなセメント系の構造物は、経年劣化によりひび割れなどの劣化が起こり、補修が必要となることがある。 Hardened cement products such as concrete and mortar are widely used in building structures. Such cement-based structures may deteriorate due to aging, such as cracks, and may need to be repaired.
補修材料としては、アルギン酸、アルギン酸プロピレングリコールエステル又はこれらの塩を含むものが公知である（特許文献１）。この補修材料は幅０．２ｍｍ以下の微細ひび割れにも浸透して硬化するという利点はあるものの、硬化速度が遅い上、幅広のひび割れに対しては補修効果が低い欠点があった。しかも、この補修材料は、特に繊維を混入した構造物に適したものであって（請求項１）、その用途は限られている。 As a repair material, a material containing alginic acid, propylene glycol alginate, or a salt thereof is known (Patent Document 1). Although this repair material has an advantage that it penetrates into fine cracks having a width of 0.2 mm or less and cures, it has a drawback that the curing speed is slow and the repair effect is low for wide cracks. Moreover, this repair material is particularly suitable for structures mixed with fibers (claim 1), and its use is limited.
特許文献２は、少なくともケイ酸ナトリウムを含む第１の液体と、細菌材料、カルシウム源、栄養源などを含む第２の液体とを反応させてゲル化する方法を開示している。しかし、この方法では、カルシウム源とケイ酸ナトリウムとの反応を防ぐため２液とする必要があり、取り扱いが煩雑である上、第１の液体と第２の液体の混合開始直後に上記のような反応が進行するため、補修材料がひび割れ深部に浸透する前にゲル化が起こり、深部が十分な補修されない問題もある。
また、非特許文献１には、微生物の活動によりセメント系構造物に含まれるカルシウムイオンを析出させ、ひび割れを補修する方法が開示されている。この方法では比較的ひび割れ深部にまで補修材料が到達しやすいという利点はあるものの、補修に時間が要するという問題があった。
Further, Non-Patent
本発明は上記課題を解決するためになされたものであって、その目的は、セメント系構造物を迅速かつ簡易な方法で補修可能な補修材料及び補修方法を提供することである。 The present invention has been made to solve the above problems, and an object of the present invention is to provide a repair material and a repair method capable of repairing a cement-based structure by a quick and simple method.
特許文献２は、プラノコッカス等の通性好気性細菌を好適としており、これら細菌も炭酸カルシウムの析出に寄与すると考えられるが、通性好気性細菌は好気代謝が優勢であるため、セメント系構造物が地上構造物であっても炭酸カルシウムを析出する速度が数週間と極めて遅い問題がある（特許文献２の請求項１０、段落００２８、００７５等）。
これに対し、本発明者等は嫌気性微生物の嫌気代謝に着目した。例えば、栄養源または栄養源の代謝生成物がグルコースである場合、酸素不存在下で下記式（１）によりエタノールと二酸化炭素が発生する。 On the other hand, the present inventors focused on the anaerobic metabolism of anaerobic microorganisms. For example, when the nutrient source or the metabolic product of the nutrient source is glucose, ethanol and carbon dioxide are generated by the following formula (1) in the absence of oxygen.
Ｃ６Ｈ１２Ｏ６ → ２Ｃ２Ｈ５ＯＨ ＋ ２ＣＯ２ … 式（１） C 6 H 12 O 6 → 2C 2 H 5 OH + 2CO 2 … Equation (1)
式（１）で発生した二酸化炭素が水と反応すると、下記式（２）のように炭酸イオンが発生する。 When the carbon dioxide generated by the formula (1) reacts with water, carbonate ions are generated as shown in the following formula (2).
ＣＯ２ ＋ Ｈ２Ｏ → ＣＯ３ ２− ＋ ２Ｈ＋ … 式（２） CO 2 + H 2 O → CO 3 2- + 2H + … Equation (2)
セメント系構造物からは水酸化カルシウム（Ｃａ（ＯＨ２））由来のカルシウムイオンが遊離するが、このカルシウムイオンは式（２）で生じた炭酸イオンと反応し、下記式（３）のように炭酸カルシウムが析出する。 Calcium hydroxide derived from calcium hydroxide (Ca (OH 2 )) is liberated from the cement-based structure, and this calcium ion reacts with the carbonate ion generated by the formula (2), as shown in the following formula (3). Calcium carbonate precipitates.
Ｃａ２＋ ＋ ＣＯ３ ２− → ＣａＣＯ３ … 式（３） Ca 2+ + CO 3 2- → CaCO 3 … Equation (3)
ところで、水溶性ポリマーかカルボキシル基などの反応基を有する場合、多価陽イオンであるカルシウムイオンが存在すると、下記式（４）のような架橋が生じ、水溶性ポリマーの親水性が急激に低下してゲル化が起こる。 By the way, when a water-soluble polymer or a reactive group such as a carboxyl group is present, the presence of calcium ion, which is a polyvalent cation, causes cross-linking as shown in the following formula (4), and the hydrophilicity of the water-soluble polymer sharply decreases. Then gelation occurs.
２Ｒ−ＣＯＯ− ＋ Ｃａ２＋ ＋ ＲＣＯＯ−Ｃａ−ＯＯＣＲ … 式（４） 2R- COO- + Ca 2+ + RCOO-Ca-OOCR ... Equation (4)
本発明者等は、嫌気代謝による反応（１）〜（３）と、ゲル化反応（４）との相乗効果に着目して本発明を完成するに至った。 The present inventors have completed the present invention by paying attention to the synergistic effect of the reactions (1) to (3) by anaerobic metabolism and the gelation reaction (4).
従って、本発明は下記の構成を有する。 Therefore, the present invention has the following configuration.
（１）カルシウムイオンと架橋可能な官能基を有する水溶性ポリマーと、嫌気性微生物の両方をセメント系構造物の補修材料に含有させる。この補修材料をカルシウムイオンが存在する塗布対象、すなわち、セメント系構造物に供給すると、水溶性ポリマーがカルシウムイオンによりゲル化する。また、ゲル化前の補修材料（液状）とゲル化後の補修材料は、大気が侵入し難い嫌気環境となるので、嫌気性微生物が栄養源を嫌気代謝して最終的に炭酸カルシウムを析出させる。従って、水溶性ポリマーのゲル化と、炭酸カルシウムの析出の両方が発生し、より機械的強度が高いゲル膜が形成されることになる。
（２）嫌気性微生物として酵母のような胞子形成微生物を用いれば、補修材料の保存性が向上する。
（３）水溶性ポリマーはＣａイオンのような陽イオンと反応して架橋する官能基（カルボキシル基、硫酸基など）を有するものであれば特に限定されないが、例えば、アルギン酸、アルギン酸エステル、ペクチン、ジェランガム、ポリ（メタ）アクリル酸、カルボキシメチルセルロース、カラギーナン及びこれらの塩からなる群より１種以上を選択することができる。
（４）補修材料中のカルシウム化合物の含有量を５質量％未満にすれば、使用前の補修材料のゲル化が防止されるので、一液化など取扱いが容易な上、微細なひび割れの深部にまで補修材料を供給することができる。
(1) Both a water-soluble polymer having a functional group crosslinkable with calcium ions and an anaerobic microorganism are contained in the repair material of the cement-based structure. When this repair material is supplied to a coating target in which calcium ions are present, that is, a cement-based structure, the water-soluble polymer is gelled by the calcium ions. In addition, since the repair material before gelation (liquid) and the repair material after gelation create an anaerobic environment in which the air does not easily invade, anaerobic microorganisms anaerobically metabolize the nutrient source and finally precipitate calcium carbonate. .. Therefore, both gelation of the water-soluble polymer and precipitation of calcium carbonate occur, and a gel film having higher mechanical strength is formed.
(2) If a sporulation microorganism such as yeast is used as an anaerobic microorganism, the storage stability of the repair material is improved.
(3) The water-soluble polymer is not particularly limited as long as it has a functional group (carboxyl group, sulfate group, etc.) that reacts with a cation such as Ca ion to crosslink, but for example, alginic acid, alginic acid ester, pectin, and the like. One or more can be selected from the group consisting of gellan gum, poly (meth) alginic acid, carboxymethyl cellulose, carrageenan and salts thereof.
(4) If the content of the calcium compound in the repair material is less than 5% by mass, gelation of the repair material before use is prevented, so that it is easy to handle such as liquefaction, and it is deep in fine cracks. Can supply repair materials up to.
本発明は補修材料に限定されず、下記の方法をも提供する。 The present invention is not limited to repair materials, and also provides the following methods.
（５）上記いずれかの補修材料を用いてセメント系構造物の欠陥（表面、内部、ひび割れ）を補修することができる。 (5) Defects (surface, inside, cracks) in the cement-based structure can be repaired using any of the above repair materials.
本発明の補修材料は補修箇所に供給開始直後は粘度が低いので、微細なひび割れであってもその深部にまで到達し、補修可能となる。補修箇所への供給後は硬化速度が速い上、硬化後のゲル膜は緻密で機械的強度が高いので、幅広のひび割れであっても強固に補修可能である。 Since the repair material of the present invention has a low viscosity immediately after the start of supply to the repaired portion, even a fine crack reaches the deep part thereof and can be repaired. After being supplied to the repaired part, the curing speed is fast, and the cured gel film is dense and has high mechanical strength, so even wide cracks can be repaired firmly.
本発明は、コンクリート、モルタル、ノロ等のセメント系硬化物を用いたセメント系構造物の補修に用いられる補修材料と、その補修方法に関する。先ず、本発明の補修材料をより具体的に説明するが、本発明はいかなる具体例に限定されることもない。 The present invention relates to a repair material used for repairing a cement-based structure using a cement-based hardened material such as concrete, mortar, and slag, and a repair method thereof. First, the repair material of the present invention will be described in more detail, but the present invention is not limited to any specific example.
［補修材料］
本発明の補修材料は、嫌気性微生物と水溶性ポリマーとを含むものであれば、その配合割合や他の添加剤など特に限定されない。
[Repair material]
As long as the repair material of the present invention contains an anaerobic microorganism and a water-soluble polymer, the blending ratio thereof and other additives are not particularly limited.
‐嫌気性微生物
嫌気性微生物は、栄養源を直接又は間接的に代謝し、酸素不存在下で二酸化炭素を生成するものであれば特に限定されず、偏性（絶対）嫌気性微生物、通性嫌気性微生物、通性好気性微生物から１種以上を選択して用いることができるが、嫌気代謝効率を考慮すると偏性嫌気性微生物、通性嫌気性微生物が好ましく、取り扱いの簡易さからは通性嫌気性微生物が好ましい。
-Anaerobic microorganisms Anaerobic microorganisms are not particularly limited as long as they directly or indirectly metabolize nutrient sources and produce carbon dioxide in the absence of oxygen, and are obligate (absolute) anaerobic microorganisms and facultative. One or more of anaerobic microorganisms and facultative anaerobic microorganisms can be selected and used, but obligate anaerobic microorganisms and facultative anaerobic microorganisms are preferable in consideration of anaerobic metabolism efficiency, and they are easy to handle. Sexually anaerobic microorganisms are preferred.
なお、微生物とは、細菌類、酵母、真菌、原生生物、原生動物等広く使用することが可能である。これらの中でも、補修対象であるセメント系構造物がアルカリ環境であることを考慮すると、胞子（子嚢胞子、芽胞、分正子）形成能がある胞子形成微生物が好ましい。 In addition, the microorganism can be widely used such as bacteria, yeast, fungi, protists, and protozoa. Among these, considering that the cement-based structure to be repaired is in an alkaline environment, sporulation microorganisms capable of forming spores (spores, spores, spores) are preferable.
胞子形成微生物としては、例えば、枯草菌（Bacillus属、主に好気性）、放線菌（Streptomyces属等）、真菌類（不完全菌門、子嚢菌門、接合菌門、担子菌門、ツボカビ門）などを１種以上使用することが可能である。これらの中でも、真菌類が特に好ましく、取扱いと、嫌気代謝効率の点で特に酵母が好ましい。 Examples of sporogenic microorganisms include Bacillus (Bacillus genus, mainly aerobic), actinomycetes (Streptomyces genus, etc.), fungi (Fungi imperfecti, Ascomycota, Zygomycota, Basidiomycete, Chytrids). ) Etc. can be used in one or more types. Among these, fungi are particularly preferable, and yeast is particularly preferable in terms of handling and anaerobic metabolism efficiency.
酵母は、Ｓａｃｃｈａｒｏｍｙｃｅｓ属、Ｃａｎｄｉｄａ属、Ｚｙｇｏｓａｃｃｈａｒｏｍｙｃｅｓ属、Ｓｃｈｉｚｏｓａｃｃｈａｒｏｍｙｃｅｓ属、Ｋｌｕｙｖｅｒｏｍｙｃｅｓ属、Ｐａｓｔｏｒｉｓ属、Ｓａｃｃｈａｒｏｍｙｃｏｐｓｉ属、Ｐａｓｔｏｒｉｓ属、Ｐａｃｈｙｓｏｌｅｎ属など多様な属種から１種以上を選択できるが、特にＳａｃｃｈａｒｏｍｙｃｅｓ属のものが好ましい。 Yeasts include the genus Saccharomyces, the genus Candida, the genus Zygosaccharomyces, the genus Schizoccharomyces, the genus Kluyveromyces, the genus Pastoris, the genus Saccharomycopsi, the genus Saccharomycopsi, the genus Pastoris ..
Ｓａｃｃｈａｒｏｍｙｃｅｓ属としては、具体的には、Ｓａｃｃｈａｒｏｍｙｃｅｓ ｃｅｒｅｖｉｓｉａｅ、Ｓａｃｃｈａｒｏｍｙｃｅｓ Ｐａｓｔｏｒｉａｎｕｓ、Ｓａｃｃｈａｒｏｍｙｃｅｓ ｉｎｔｅｒｍｅｄｉｕｓ、Ｓａｃｃｈａｒｏｍｙｃｅｓ ｖａｌｉｄｕｓ、ｓａｃｃｈａｒｏｍｙｃｅｓ ｅｌｌｉｐｓｏｉｄｅｒｓ、Ｓａｃｃｈａｒｏｍｙｃｅｓ ｍａｌｉ ｒｉｓｌｅｒ、Ｓａｃｃｈａｒｏｍｙｃｅｓ ｍａｎｄｓｃｈｕｒｉｃｕｓ、Ｓａｃｃｈａｒｏｍｙｃｅｓ Ｖｏｒｄｅｒｍａｎｎｉｉ、Ｓａｃｃｈａｒｏｍｙｃｅｓ Ｐｅｋａ、Ｓａｃｃｈａｒｏｍｙｃｅｓ ｓｈａｓｓｈｉｎｇ、Ｓａｃｃｈａｒｏｍｙｃｅｓ ｐｉｒｉｆｏｒｍｉｓ、Ｓａｃｃｈａｒｏｍｙｃｅｓ ａｎａｍｅｎｓｉｓ、ｓａｃｃｈａｒｏｍｙｃｅｓ ｃａｒｔｉｌａｇｉｎｏｓｕｓ、Ｓａｃｃｈａｒｏｍｙｃｅｓ Ａｗａｍｏｒｉ、Ｓａｃｃｈａｒｏｍｙｃｅｓ Ｂａｔａｔａｅ、Ｓａｃｃｈａｒｏｍｙｃｅｓ Ｃｏｒｅａｎｕｓ、Ｓａｃｃｈａｒｏｍｙｃｅｓ ｒｏｂｕｓｔｕｓ、Ｓａｃｃｈａｒｏｍｙｃｅｓ Ｃａｒｌｓｂｅｒｇｅｎｓｉｓ、Ｓａｃｃｈａｒｏｍｙｃｅｓ Ｍｏｎａｃｅｎｓｉｓ、Ｓａｃｃｈａｒｏｍｙｃｅｓ Ｍａｒｘｉａｎｕｓ、Ｓａｃｃｈａｒｏｍｙｃｅｓ ｌａｃｔｅｓ、Ｓａｃｃｈａｒｏｍｙｃｅｓ Ｒｏｕｘｉｉなどから選択される１種以上を用いることができるが、特に好ましくはＳａｃｃｈａｒｏｍｙｃｅｓ ｃｅｒｅｖｉｓｉａｅ（通性嫌気性）である。 The genus Saccharomyces, specifically, Saccharomyces cerevisiae, Saccharomyces Pastorianus, Saccharomyces intermedius, Saccharomyces validus, saccharomyces ellipsoiders, Saccharomyces mali risler, Saccharomyces mandschuricus, Saccharomyces Vordermannii, Saccharomyces Peka, Saccharomyces shasshing, Saccharomyces piriformis, Saccharomyces anamensis, saccharomyces cartilaginosus, Saccharomyces awamori, Saccharomyces Batatae, Saccharomyces Coreanus, Saccharomyces robustus, Saccharomyces carlsbergensis, Saccharomyces Monacensis, Saccharomyces marxianus, Saccharomyces lactes, can be used one or more selected from such Saccharomyces rouxii, particularly preferably Saccharomyces cerevisiae (facultative anaerobic Gender).
なお、Ｓａｃｃｈａｒｏｍｙｃｅｓ ｃｅｒｅｖｉｓｉａｅのような嫌気性微生物と、他の微生物と組み合わせて使用することも可能である。この場合は、多様な環境に対応できるように異なる性質の微生物（例えば通性好気性微生物）と組み合わせることが好ましく、特に、Ｂａｃｉｌｌｕｓ ｓｕｂｔｉｌｉｓのような胞子（芽胞）形成能がある通性好気性微生物との組み合わせが好ましい。 It is also possible to use an anaerobic microorganism such as Saccharomyces cerevisiae in combination with another microorganism. In this case, it is preferable to combine it with a microorganism having different properties (for example, a spore-forming microorganism) so as to be able to cope with various environments, and in particular, a spore-forming microorganism such as Bacillus subtilis. The combination with is preferable.
嫌気性微生物としては乳酸菌を用いることも可能であり、例えば、Ｌａｃｔｏｂａｃｉｌｌｕｓ属、Ｂｉｆｉｄｏｂａｃｔｅｒｉｕｍ属、Ｌｅｕｃｏｎｏｓｔｏｃ属などの乳酸菌はヘテロ乳酸発酵によりグルコースから乳酸と二酸化炭素を生成し、二酸化炭素が炭酸カルシウムを析出させるだけではなく、乳酸が過剰なアルカリ環境を緩和する。しかしながら、乳酸のような有機酸が過剰に発生すると、セメント系構造物の腐食の原因にもなるので、上記のような乳酸菌は単独で使用することは不適切であり、使用する場合は他の嫌気性微生物（酵母など）よりも少ない量での使用とし、より好ましくは乳酸菌を使用しない。 Lactic acid bacteria can also be used as the anaerobic microorganisms. For example, lactic acid bacteria such as Lactobacillus, Bifidobacterium, and Leuconostoc produce lactic acid and carbon dioxide from glucose by heterolactic fermentation, and carbon dioxide precipitates calcium carbonate. Not only does lactic acid alleviate the excess alkaline environment. However, excessive generation of organic acids such as lactic acid can cause corrosion of cement-based structures, so it is inappropriate to use lactic acid bacteria as described above alone, and when used, other lactic acid bacteria are used. Use in a smaller amount than anaerobic microorganisms (yeast, etc.), and more preferably do not use lactic acid bacteria.
上記のような微生物は、自家培養品、市販品のいずれか一方又は両方を用いてもよい。例えば、Saccharomyces cerevisiaeの場合は、多様な市販品が公知である（オリエンタル酵母工業（株）製、ルサッフル社製、秋田十条化成株式会社など）。 As the above-mentioned microorganism, either one or both of the self-cultured product and the commercially available product may be used. For example, in the case of Saccharomyces cerevisiae, various commercially available products are known (manufactured by Oriental Yeast Co., Ltd., manufactured by Rusaffle, Akita Jujo Kasei Co., Ltd., etc.).
微生物は生菌（栄養細胞）、乾燥品、冷凍品、真空凍結乾燥品など多様な態様で用いることができるが、酵母のような胞子形成微生物を用いる場合は、その微生物にストレスを与えて胞子数を増加させると同時に、他の微生物数を減少（滅菌）させてから使用することもできる。ここで、ストレス環境とは、貧栄養、乾燥、高温、低温、高圧、化学処理のいずれか１種以上のストレスを胞子形成微生物に付与する状態を意味する。 Microorganisms can be used in various forms such as live bacteria (nutrient cells), dried products, frozen products, and vacuum freeze-dried products. However, when spore-forming microorganisms such as yeast are used, the microorganisms are stressed to spores. At the same time as increasing the number, the number of other microorganisms can be reduced (sterilized) before use. Here, the stress environment means a state in which one or more kinds of stress of oligotrophic, dry, high temperature, low temperature, high pressure, and chemical treatment are applied to sporulation microorganisms.
上記のような嫌気性微生物の使用量は特に限定されず、微生物の種類や補修対象物により適宜変更することもできるが、一例を述べると、液状補修材料（使用時）１リットル当たりの微生物合計量を５．０ｇ〜３０．０ｇ（乾燥品）とし、好ましくは１５．０ｇ〜３０．０ｇとする The amount of anaerobic microorganisms used as described above is not particularly limited and can be appropriately changed depending on the type of microorganism and the object to be repaired. However, for example, the total amount of microorganisms per liter of the liquid repair material (when used) The amount is 5.0 g to 30.0 g (dried product), preferably 15.0 g to 30.0 g.
‐水溶性ポリマー
水溶性ポリマーは、カルシウムイオンとの反応によりゲル化する官能基（カルボキシル基、硫酸基など）を有する物質であれば特に限定されないが、具体的には、アルギン酸（アルギン酸塩、アルギン酸エステルも含む）、ポリ（メタ）アクリル酸、ペクチン、ジェランガム、カルボキシメチルセルロース、カラギーナン及びこれらの塩からなる群より選択される１種以上の水溶性ポリマーを用いることができる。ここで、塩とは、ナトリウムやカリウム等のアルカリ金属塩の他、アンモニウム塩をも含む概念ではあるが、より好ましくはナトリウムとカリウムから選択し、最も好ましくはナトリウム塩である。
-Water-soluble polymer The water-soluble polymer is not particularly limited as long as it is a substance having a functional group (carboxyl group, sulfate group, etc.) that gels by reaction with calcium ions, but specifically, alginic acid (alginate, alginic acid, etc.) One or more water-soluble polymers selected from the group consisting of (including esters), poly (meth) alginic acid, pectin, gellan gum, carboxymethyl cellulose, carrageenan and salts thereof can be used. Here, the salt is a concept that includes an ammonium salt in addition to an alkali metal salt such as sodium and potassium, but is more preferably selected from sodium and potassium, and most preferably a sodium salt.
ペクチンは特に限定されないが、ゲル化性を考慮すると、エステル化度（ガラクチュロン酸メチルエステルの割合）が５０％未満のＬＭペクチン（Ｌｏｗ Ｍｅｔｈｙｌｅｓｔｅｒ ｐｅｃｔｉｎ）が好ましい。ジェランガムやカラギーナンは、二価陽イオンと結合してゲル化するもの、例えばＬＡジェランガム（脱アシル化ジェランガム）、イオタカラギーナン、カッパカラギーナン（特にイオタカラギーナン）などが好ましい。 The pectin is not particularly limited, but in consideration of gelling property, LM pectin (Low Fatty acid pectin) having a degree of esterification (ratio of galacturonic acid methyl ester) of less than 50% is preferable. As the gellan gum and carrageenan, those that bind to divalent cations and gel, for example, LA gellan gum (deacylated gellan gum), iota carrageenan, kappa carrageenan (particularly iota carrageenan) and the like are preferable.
ただし、ＬＭペクチンやＬＡジェランガムは溶解やゲル化に加熱が必要なものが多く、取り扱い性、ゲル化速度などを考慮すると、上記水溶性ポリマーの中でもアルギン酸とポリ（メタ）アクリル酸が好ましく、特に好ましくはアルギン酸である。 However, many of LM pectin and LA gellan gum require heating for dissolution and gelation, and alginic acid and poly (meth) acrylic acid are preferable among the above water-soluble polymers in consideration of handleability and gelation rate. Alginic acid is preferred.
ただし、アルギン酸の中でも、アルギン酸のプロピレングリコールエステルは、プロピレングリコールでカルボキシル基がマスクされているためカルシウムイオンで架橋し難く、しかも、水に溶解したときに溶液を酸性に傾ける上に、アルカリ条件ではエステル結合が加水分解されるため、セメント系構造物のようなアルカリ環境維持が特に要求される場合には不適切である。従って、アルギン酸エステル以外のアルギン酸、すなわち、アルギン酸またはその塩が好ましく、水溶性の点ではアルギン酸塩が好ましく、より好ましくはアルギン酸ナトリウムとアルギン酸カリウムであり、最も好ましくはアルギン酸ナトリウムである。 However, among the alginic acids, the propylene glycol ester of alginic acid is difficult to crosslink with calcium ions because the carboxyl group is masked with propylene glycol, and the solution is tilted acidic when dissolved in water, and under alkaline conditions. Since the ester bond is hydrolyzed, it is not suitable when maintaining an alkaline environment such as a cement-based structure is particularly required. Therefore, alginic acid other than alginic acid ester, that is, alginic acid or a salt thereof is preferable, alginate is preferable in terms of water solubility, sodium alginate and potassium alginate are more preferable, and sodium alginate is most preferable.
‐その他添加剤
本発明の補修材料は、上記嫌気性微生物と水溶性ポリマーに限定されず、他のポリマー（バインダー）、微生物栄養源（有機、無機）、着色剤、フィラー、ｐＨ緩衝剤、ｐＨ調整剤、老化防止剤、分散剤、界面活性剤など１種以上の添加剤を添加することができる。これらの中でも、最も好ましい添加剤は微生物栄養源である。
-Other additives The repair material of the present invention is not limited to the above-mentioned anaerobic microorganisms and water-soluble polymers, but other polymers (binders), microbial nutrient sources (organic and inorganic), colorants, fillers, pH buffers, pH. One or more additives such as a regulator, an antioxidant, a dispersant, and a surfactant can be added. Of these, the most preferred additive is a microbial nutrient source.
微生物栄養源は特に限定されず、有機炭素源（糖類、デンプン、脂質等）、無機炭素源（炭酸ナトリウム等）、有機窒素源（アミノ酸、ペプトン、タンパク質等）、無機窒素源（アンモニウム塩、硝酸塩等）、無機栄養源（Ｐ、Ｓ、Ｋ、Ｍｇ、Ｆｅ、Ｎａ等）を１種以上用いることができる。 The microbial nutrient source is not particularly limited, and is an organic carbon source (sugar, starch, lipid, etc.), an inorganic carbon source (sodium carbonate, etc.), an organic nitrogen source (amino acid, peptone, protein, etc.), an inorganic nitrogen source (ammonium salt, nitrate, etc.). Etc.), and one or more inorganic nutrient sources (P, S, K, Mg, Fe, Na, etc.) can be used.
これらの中でも、嫌気代謝のためには有機炭素源を栄養源に含めることが好ましく、有機炭素源としては糖類が好ましく、特に、単糖類（グルコース、フルクトース、ガラクトース、マンノースなど）とニ糖類（マルトース、ラクトース、スクロースなど）から選択されるいずれか１種以上が好ましい。無機栄養源は特に限定されないが、無機栄養源のうち、カルシウム等のセメント系構造物に含まれる無機栄養源は、別途添加する必要はない。 Among these, it is preferable to include an organic carbon source as a nutrient source for anaerobic metabolism, and saccharides are preferable as the organic carbon source, and in particular, monosaccharides (glucose, fructose, galactose, mannose, etc.) and disaccharides (maltose) are preferable. , Lactose, sucrose, etc.), and any one or more thereof is preferable. The inorganic nutrient source is not particularly limited, but among the inorganic nutrient sources, the inorganic nutrient source contained in the cement-based structure such as calcium does not need to be added separately.
栄養源は、代謝により腐食性物質を排出しないものが好ましい。栄養源としての炭素源（糖類等）が有機酸（酢酸、乳酸、ピルビン酸）のような腐食性物質の原因となる場合は、栄養源に窒素源を添加し、微生物が産出するアンモニアにより有機酸をマスクしてもよい。嫌気性微生物が胞子形成微生物の場合には、栄養源として発芽誘導物質を添加することもできる。 The nutrient source is preferably one that does not excrete corrosive substances by metabolism. If a carbon source (sugar, etc.) as a nutrient source causes corrosive substances such as organic acids (acetic acid, lactic acid, pyruvic acid), add a nitrogen source to the nutrient source and use ammonia produced by microorganisms to make it organic. The acid may be masked. When the anaerobic microorganism is a sporulation microorganism, a germination inducer can be added as a nutrient source.
このように、添加剤は特に限定されないが、補修材料がカルシウム源を多量に含むと、補修材料のゲル化が急激に進行し、セメント系構造物への塗布、供給が困難になるので、硝酸カルシウム、炭酸カルシウム、リン酸カルシウム、乳酸カルシウム、ケイ酸カルシウム水和物、ギ酸カルシウム、酢酸カルシウム、グルコン酸カルシウムなどから選択されるカルシウム化合物の合計含有量が液状補修材料（使用時）全体の５質量％未満とすることが好ましく、より好ましくはカルシウム化合物の含有量が３質量％未満、更に好ましくは１質量％未満、特に好ましくはカルシウム源を実質的に添加しない。 As described above, the additive is not particularly limited, but if the repair material contains a large amount of calcium source, gelation of the repair material progresses rapidly, and it becomes difficult to apply and supply the repair material to the cement-based structure. The total content of calcium compounds selected from calcium, calcium carbonate, calcium phosphate, calcium lactate, calcium silicate hydrate, calcium formate, calcium acetate, calcium gluconate, etc. is 5% by mass of the total liquid repair material (when used). The content of the calcium compound is preferably less than 3% by mass, more preferably less than 1% by mass, and particularly preferably no calcium source is substantially added.
本発明は、ケイ酸塩のような析出剤を用いてもよいが、例えばケイ酸ナトリウムを水に溶解すると一般にｐＨがアルカリ側に傾くため、酵母のように酸性〜弱アルカリ性（例：ｐＨ３〜８、好ましくはｐＨ３．５〜７）での生育に適した嫌気微生物を用いる場合は不適切である。従って、ケイ酸塩の含有量は好ましくは液状補修材料（使用時）全体の１０質量％未満、より好ましくは１質量％未満、更に好ましくは０．５質量％未満とし、特に好ましくは０．１質量％未満とし、また、ケイ酸塩を実質的に補修材料に含めないこともできる。
In the present invention, a precipitate such as silicate may be used, but for example, when sodium silicate is dissolved in water, the pH generally tends to be alkaline, so that it is acidic to weakly alkaline (eg,
［補修材料の製造方法］
本発明の補修材料は、液状、固体（乾燥品）のいずれの形態でもよく、液状の場合は上記嫌気性微生物、水溶性ポリマー、栄養源などの添加剤を、媒質に溶解又は分散させて液状とする。媒質は水と有機溶媒のいずれも用いることができるが、好ましくは水を含有し、より好ましくは水を主成分（５０質量％以上）とし、より好ましくは水で構成される。
[Manufacturing method of repair materials]
The repair material of the present invention may be in any form of liquid or solid (dried product), and in the case of liquid, the above additives such as anaerobic microorganisms, water-soluble polymers and nutrient sources are dissolved or dispersed in a medium to be liquid. And. As the medium, either water or an organic solvent can be used, but it preferably contains water, more preferably water as a main component (50% by mass or more), and more preferably composed of water.
液状補修材料が水を含む場合、嫌気性微生物と栄養源（発芽誘導物質、補酵素含む）の両方を添加すると、保存の間に栄養源の代謝が進行し、補修材料の棚時間が短くなるおそれがある。従って、栄養源を嫌気性微生物とは別剤とし、使用直前に混合するいわゆる２成分型にすれば、補修材料の棚時間が長くなる。２成分型は、補修材料を水溶液又は水分散液として保存する場合に特に効果的である。 When the liquid repair material contains water, the addition of both anaerobic microorganisms and nutrient sources (including germination inducers and coenzymes) promotes metabolism of the nutrient source during storage and shortens the shelf time of the repair material. There is a risk. Therefore, if the nutrient source is a separate agent from the anaerobic microorganisms and the so-called two-component type is mixed immediately before use, the shelf time of the repair material becomes long. The two-component type is particularly effective when the repair material is stored as an aqueous solution or an aqueous dispersion.
ただし、水溶性ポリマーのゲル化と嫌気性微生物による炭酸カルシウムの析出は、カルシウムの不存在下では進行しないので、水溶性ポリマーと嫌気性微生物を１成分型（１液型）としても補修材料のゲル化はおこらず、液状補修材料を長時間保存することができる。 However, since gelation of the water-soluble polymer and precipitation of calcium carbonate by anaerobic microorganisms do not proceed in the absence of calcium, the water-soluble polymer and anaerobic microorganisms can be used as a one-component type (one-component type) as a repair material. No gelation occurs, and the liquid repair material can be stored for a long time.
補修材料が乾燥品であって、水分活性値が低い場合は、水溶性ポリマーと嫌気性微生物と添加剤（栄養源など）を１成分型としても、補修材料の棚時間を長くすることができる。乾燥品の形状は特に限定されず、紛状、粒状、タブレット状等多様な形状にすることが可能であり、必要であれば結着剤を使用して、この結着剤に好気性微生物及び／又は水溶性ポリマーを付着させて成形することも可能である。 When the repair material is a dry product and has a low water activity value, the shelf time of the repair material can be lengthened even if the water-soluble polymer, the anaerobic microorganism, and the additive (nutrient source, etc.) are used as one component type. .. The shape of the dried product is not particularly limited, and various shapes such as powder, granules, and tablets can be used. If necessary, a binder is used to use the binder to aerobic microorganisms and aerobic microorganisms. / Or it is also possible to attach and mold a water-soluble polymer.
結着剤は特に限定されず、樹脂等多様なものを使用可能であるが、嫌気性微生物を使用する場合は、デンプン、糖類（多糖を含む）、セルロース、タンパク質、及びこれらの誘導体（変性物質）からなる群より選択されるいずれか１以上を用いれば、水と接触したときにこれら結着剤が嫌気性微生物の栄養源にもなりうる。 The binder is not particularly limited, and various substances such as resins can be used. However, when anaerobic microorganisms are used, starch, sugars (including polysaccharides), celluloses, proteins, and derivatives thereof (modifying substances) can be used. If any one or more selected from the group consisting of) is used, these binders can also be a nutrient source for anaerobic microorganisms when in contact with water.
［補修対象物］
本発明の補修材料は、コンクリート、モルタル等の多様なセメント系硬化物を利用したセメント系構造物の補修に使用することができる。以下に具体的に説明する。
[Repair target]
The repair material of the present invention can be used for repairing cement-based structures using various cement-based hardened materials such as concrete and mortar. This will be described in detail below.
本発明の補修材料は多様なセメントを利用した構造物に使用可能であり、その原料となるセメントとしては、例えば、ポルトランドセメント（ＪＩＳ Ｒ５２１０）、混合セメント（ＪＩＳ Ｒ５２１１、Ｒ５２１２、Ｒ５２１３）、エコセメント（ＪＩＳ Ｒ５２０４）等を１種以上がある。これらセメント材料には、セメント系プレミックスには、必要に応じて、化学混和剤、減水剤、流動化剤等の１種以上の混和剤を添加することも可能である。 The repair material of the present invention can be used for structures using various cements, and the cements used as raw materials thereof include, for example, Portland cement (JIS R5210), mixed cement (JIS R5211, R5212, R5213), and eco-cement. There is one or more types such as (JIS R5204). To these cement materials, one or more admixtures such as a chemical admixture, a water reducing agent, and a fluidizing agent can be added to the cement-based premix, if necessary.
上記のようなセメント系硬化物は多様な建築構造物に利用されるが、乾燥収縮、熱膨張、熱収縮、機械的ストレス、化学的ストレス、製法上の問題（例：コールドジョイント）などの様々な理由で表面や内部に欠陥部分（ひび割れ、凹部）が生ずることがある。次に、このような欠陥部分の補修方法について説明する。 Cement-based hardened materials such as those mentioned above are used in various building structures, but there are various types such as drying shrinkage, thermal expansion, thermal shrinkage, mechanical stress, chemical stress, and manufacturing problems (eg cold joints). For some reason, defective parts (cracks, recesses) may occur on the surface or inside. Next, a method of repairing such a defective portion will be described.
［補修方法］
先ず、補修材料が紛体の場合は媒質に溶解又は分散させて液状とする。補修材料が液状の場合はそのまま使用することもできるが、必要に応じて媒質（水）で希釈して粘度調整をしてから使用することもできる。希釈の有無に関わらず、本発明の補修材料は、水溶性ポリマーと嫌気性微生物とその他成分（特に栄養源）が同じ媒質に溶解又は分散した１液型（１成分型）としてから使用する。
[Repair method]
First, when the repair material is a powder, it is dissolved or dispersed in a medium to make it liquid. When the repair material is liquid, it can be used as it is, but if necessary, it can be used after diluting it with a medium (water) to adjust its viscosity. Regardless of the presence or absence of dilution, the repair material of the present invention is used as a one-component type (one-component type) in which a water-soluble polymer, an anaerobic microorganism, and other components (particularly nutrient sources) are dissolved or dispersed in the same medium.
液状の補修材料を欠陥部分に塗布、散布又は注入して適量を供給する。本発明の補修材料は、供給直後ではゲル化が急激に進行しないので、欠陥部分（ひび割れ）の幅が狭い場合や、その深さが深い場合であっても、欠陥深部にまで補修材料が入り込む。 A liquid repair material is applied to the defective part, sprayed or injected to supply an appropriate amount. Since the repair material of the present invention does not rapidly gel immediately after being supplied, the repair material penetrates into the deep part of the defect even if the width of the defective portion (crack) is narrow or the depth is deep. ..
欠陥部分はセメント系硬化物が露出しているため、セメント系硬化物と補修材料とが接触すると、補修材料の水溶性ポリマーがセメント系硬化物由来のカルシウムイオンと反応してゲル化し、このゲル化により補修材料の表面部分が欠陥部分の表面に接着した状態となる。 Since the cement-based cured product is exposed in the defective part, when the cement-based cured product comes into contact with the repair material, the water-soluble polymer of the repair material reacts with the calcium ions derived from the cement-based cured product and gels, and this gel As a result, the surface portion of the repair material is in a state of being adhered to the surface of the defective portion.
欠陥表面に接着した状態では、補修材料の移動（落下）による攪拌が起こらず、その内部に空気が侵入し難い嫌気状態になる。他方、上記ゲルは水を透過、吸収するので、補修材料の内部には外部（セメント系構造物側）から、水と、水に溶解した物質（カルシウムイオン）が侵入する。 In the state of being adhered to the defect surface, agitation does not occur due to the movement (dropping) of the repair material, and the air does not easily enter the inside thereof, resulting in an anaerobic state. On the other hand, since the gel permeates and absorbs water, water and a substance dissolved in water (calcium ions) invade the inside of the repair material from the outside (cement-based structure side).
本発明の補修材料は嫌気性微生物を有しているので、空気が侵入し難い嫌気状態であっても嫌気代謝により二酸化炭素を生成し、この二酸化炭素が、補修材料の内部でカルシウムイオンと反応するか、補修材料の表面又は外部に移動してカルシウムイオンと反応し、その結果、補修材料の内部、表面及び／又は外部で炭酸カルシウムが析出する。 Since the repair material of the present invention has anaerobic microorganisms, carbon dioxide is generated by anaerobic metabolism even in an anaerobic state where air does not easily enter, and this carbon dioxide reacts with calcium ions inside the repair material. Or move to the surface or outside of the repair material and react with calcium ions, resulting in the precipitation of calcium carbonate inside, surface and / or outside the repair material.
補修材料の内部では、炭酸カルシウムの析出のみならず、水溶性ポリマーがカルシウムイオンで架橋され、水を吸収した状態でゲル化する。すなわち、補修材料が吸水膨潤して欠陥部に隙間なく密着すると共に、補修材料の内部と外部では炭酸カルシウムが析出するので、欠陥部分は炭酸カルシウムが析出した機械的強度の高いゲルに充填されて凝集破壊が抑制され、また、ゲルの表面は水溶性ポリマーの接着力と析出した炭酸カルシウムで欠陥部表面に強固に固定されて接着破壊（界面剥離）も抑制される。 Inside the repair material, not only the precipitation of calcium carbonate but also the water-soluble polymer is crosslinked with calcium ions and gels in a state of absorbing water. That is, the repair material absorbs water and swells and adheres tightly to the defective portion, and calcium carbonate is precipitated inside and outside the repair material. Therefore, the defective portion is filled with a gel having high mechanical strength in which calcium carbonate is precipitated. Aggregate fracture is suppressed, and the surface of the gel is firmly fixed to the surface of the defective portion by the adhesive strength of the water-soluble polymer and the precipitated calcium carbonate, and adhesive fracture (interfacial peeling) is also suppressed.
このように、本発明の補修方法は、幅狭の欠陥部分や、深さが深い欠陥部分においても、その深部まで補修材料で隙間なく充填することが可能であり、しかも、機械的強度の高い補修材料のゲルで強固に固定されるので、欠陥部分が１ｍｍ程度の幅広であっても補修材料が破損し難く、極めて優れた補修効果が得られる。なお、幅狭の欠陥部分に対しては、補修材料の粘度調整により対応できるので、本発明では、幅１ｍｍ以下の欠陥部分に広く対応できる。 As described above, in the repair method of the present invention, even in a narrow defect portion or a deep defect portion, it is possible to fill the deep portion with the repair material without a gap, and the mechanical strength is high. Since it is firmly fixed by the gel of the repair material, the repair material is not easily damaged even if the defective portion is as wide as about 1 mm, and an extremely excellent repair effect can be obtained. Since the narrow defect portion can be dealt with by adjusting the viscosity of the repair material, the present invention can widely deal with the defect portion having a width of 1 mm or less.
しかも、本発明の補修材料は、補修対象に多価陽イオン（カルシウムイオン）が存在するだけで高い補修効果が得られるので、硬化補助剤などが不要な上、セメント系構造物の組成も限定されない。例えば、セメント系構造物の補修箇所に、繊維などの補強材が含まれない（又は補強材の含有量が低い）場合も、本発明の補修材料で容易に補修することができる。 Moreover, since the repair material of the present invention can obtain a high repair effect only by the presence of multivalent cations (calcium ions) in the repair target, a hardening aid or the like is not required, and the composition of the cement-based structure is also limited. Not done. For example, even when the repaired portion of the cement-based structure does not contain a reinforcing material such as fiber (or the content of the reinforcing material is low), the repair material of the present invention can be easily repaired.
［その他］
以上は、補修材料に嫌気性微生物を直接添加する場合について説明したが本発明はこれに限定されるものではない。例えば、嫌気性微生物をマイクロカプセルに封入してから補修材料に添加することもできる。
[Other]
The above has described the case where an anaerobic microorganism is directly added to the repair material, but the present invention is not limited thereto. For example, anaerobic microorganisms can be encapsulated in microcapsules and then added to the repair material.
マイクロカプセルの製造方法は特に限定されないが、例えば、水溶性ポリマーと嫌気性微生物と任意の添加剤（栄養源等）を含む原料液に、ゲル化剤（カルシウム化合物等）を添加してゲル化する。マイクロカプセル用の水溶性ポリマーの種類は特に限定されないが、補修材料に使用する水溶性ポリマーと同種のものを用いると、マイクロカプセルとゲル化した補修材料とが一体化し、ゲル化後の補修材料の機械的強度が向上する。 The method for producing microcapsules is not particularly limited, but for example, a gelling agent (calcium compound, etc.) is added to a raw material solution containing a water-soluble polymer, an anaerobic microorganism, and an arbitrary additive (nutrient source, etc.) to gel. To do. The type of water-soluble polymer for microcapsules is not particularly limited, but if the same type of water-soluble polymer is used as the repair material, the microcapsules and the gelled repair material are integrated, and the gelled repair material is used. The mechanical strength of the gel is improved.
本発明は上記補修材料を用いるのであれば、その使用方法や用途は特に限定されない。二価以上の陽イオン、特にカルシウムイオンが外部から補修材料に浸透するのであれば、岩壁などの自然物の補修にも用いることができるし、他の補修材料と併用することもできる。 If the above-mentioned repair material is used in the present invention, the method of use and use thereof are not particularly limited. If divalent or higher cations, especially calcium ions, permeate the repair material from the outside, it can be used for repairing natural objects such as rock walls, and can also be used in combination with other repair materials.
次に、実施例により本発明をより具体的に説明する。 Next, the present invention will be described in more detail with reference to Examples.
＜実施例１＞
アルギン酸ナトリウム（関東化学株式会社製、鹿１級、カタログＮｏ．３７０９４−０１）を蒸留水に添加し、スターラーを用いて３０分間撹拌して溶解させ、アルギン酸ナトリウムを１．０質量％含む水溶液を得た。この水溶液１Ｌに、嫌気性微生物である乾燥酵母（秋田十条化成株式会社製の商品名「白新こだま酵母ドライ」）２７．０ｇ／Ｌと、栄養源であるグルコース０．３ｍｏｌ／Ｌとを添加して更に３０分間攪拌して、実施例１の補修材料とした。
<Example 1>
Sodium alginate (manufactured by Kanto Chemical Co., Inc., first grade deer, Catalog No. 37094-01) is added to distilled water, and the mixture is dissolved by stirring for 30 minutes using a stirrer to prepare an aqueous solution containing 1.0% by mass of sodium alginate. Obtained. To 1 L of this aqueous solution, 27.0 g / L of dried yeast (trade name "Shiroshin Kodama Yeast Dry" manufactured by Akita Jujo Kasei Co., Ltd.), which is an anaerobic microorganism, and 0.3 mol / L of glucose, which is a nutrient source, are added. The mixture was further stirred for 30 minutes to obtain the repair material of Example 1.
＜比較例１＞
嫌気性微生物と栄養源を添加しない以外は、上記実施例１と同じ条件で比較例１の補修材料とした。これら実施例１、比較例１の補修材料を用いて下記試験を行った。
<Comparative example 1>
The repair material of Comparative Example 1 was used under the same conditions as in Example 1 above, except that anaerobic microorganisms and nutrient sources were not added. The following tests were conducted using the repair materials of Example 1 and Comparative Example 1.
‐透水試験
ＣＥＭ ＩＩＩ ４２．５Ｎ（ＥＮ１９７−１：２０００に基づき分類される高炉セメント）を用い、直径３０ｍｍ、長さ５０ｍｍ円柱状であって、その円柱外周側面の円柱中心軸を挟んで対向する位置にひび割れ誘導用ノッチが２本形成されたモルタル硬化物を製造し、円柱供試体とした。
-Water permeability test Using CEM III 42.5N (blast furnace cement classified based on EN197-1: 2000), it is a cylinder with a diameter of 30 mm and a length of 50 mm, and faces each other across the central axis of the cylinder on the outer peripheral side surface of the cylinder. A cured mortar having two notches for inducing cracks formed at the position was produced and used as a cylindrical specimen.
この円柱供試体を材齢２８日間まで封緘養生した後、ポリエチレンフィルムで外周を包み、ノッチと対面する位置にそれぞれスペーサー（スチールロッド）を挟んだ状態で、スペーサーを介して円柱供試体を圧縮試験機で載荷し、幅０．６ｍｍのひび割れを形成した。ノッチに迄達したひび割れの両端部のみに、メタクリル酸メチルを用いた接着剤でシールを施した。 After sealing and curing this columnar specimen for up to 28 days of age, the columnar specimen is subjected to a compression test by wrapping the outer circumference with a polyethylene film and sandwiching spacers (steel rods) at positions facing the notches. It was loaded by the machine and formed cracks with a width of 0.6 mm. Only both ends of the crack that reached the notch were sealed with an adhesive using methyl methacrylate.
実施例１の補修材料と比較例１の補修材料を、それぞれ円柱供試体のひび割れが形成された表面に塗布した。塗布から２４時間経過後には、実施例１の補修材料は、炭酸カルシウムの析出に由来すると思われる硬いゲル膜となっていた。補修材料を塗布してから２日後に、円柱供試体を塩化ビニル製管の内部に設置し、定水位による透水試験に供した。 The repair material of Example 1 and the repair material of Comparative Example 1 were applied to the cracked surfaces of the cylindrical specimen, respectively. After 24 hours from the application, the repair material of Example 1 was a hard gel film which was considered to be derived from the precipitation of calcium carbonate. Two days after the repair material was applied, the cylindrical specimen was placed inside a vinyl chloride pipe and subjected to a hydraulic conductivity test at a constant water level.
透水試験は、底面に管が接続された容器（リザーバー）を用意し、この管の内部に、塩化ビニル製管に設置した円柱供試体を隙間なくはめ込み、容器に海水を収容して、円柱供試体から容器の海水面までの高さを１．０５ｍの定水位に維持して円柱供試体に一定水圧を１０分間付与した。 For the water permeation test, prepare a container (reservoir) with a pipe connected to the bottom, fit a cylindrical specimen installed in a vinyl chloride pipe without a gap inside this pipe, store seawater in the container, and supply the cylinder. The height from the specimen to the sea surface of the container was maintained at a constant water level of 1.05 m, and a constant water pressure was applied to the cylindrical specimen for 10 minutes.
比較例１の補修材料を用いた円柱供試体では、上記透水試験中に、円柱供試体のひび割れを通過したと思われる水分が検出された。これに対し、実施例１の補修材料を用いた円柱供試体では、ひび割れを通過したと思われる水分は確認されず、閉塞効果が確認された。 In the cylindrical specimen using the repair material of Comparative Example 1, moisture that seems to have passed through the cracks of the cylindrical specimen was detected during the water permeability test. On the other hand, in the columnar specimen using the repair material of Example 1, the water content which seems to have passed through the crack was not confirmed, and the blocking effect was confirmed.
図１（ａ）、（ｂ）は実施例１の補修材料で補修した円柱供試体の、透水試験前（図１（ａ））と透水試験後（図１（ｂ））を撮影した光学顕微鏡写真であり、図２（ａ）、（ｂ）は比較例１の補修材料で補修した円柱供試体の、透水試験前（図２（ａ））と透水試験後（図２（ｂ））を撮影した光学顕微鏡写真である。 1 (a) and 1 (b) are optical microscopes taken before the hydraulic conductivity test (FIG. 1 (a)) and after the hydraulic conductivity test (FIG. 1 (b)) of the columnar specimen repaired with the repair material of Example 1. 2 (a) and 2 (b) are photographs of the columnar specimen repaired with the repair material of Comparative Example 1 before the hydraulic conductivity test (FIG. 2 (a)) and after the hydraulic conductivity test (FIG. 2 (b)). It is an optical microscope photograph taken.
図１（ａ）、（ｂ）、図２（ａ）、（ｂ）を比較すると明らかなように、比較例１では補修材料のゲル自体が破損しており（図２（ｂ））、ゲル化した補修材料の強度が足りず、閉塞効果が低いことが確認された。 As is clear from comparing FIGS. 1 (a), 1 (b), 2 (a), and (b), in Comparative Example 1, the gel itself of the repair material was damaged (FIG. 2 (b)), and the gel itself was damaged. It was confirmed that the strength of the repair material was insufficient and the blocking effect was low.
これに対し、実施例１の補修材料を用いた場合は透水試験前（図１（ａ））と透水試験後（図１（ｂ））のいずれも補修材料のゲルに破損が見られず、補修材料のゲルがひび割れを隙間なく充填している態様が確認できた。 On the other hand, when the repair material of Example 1 was used, no damage was observed in the gel of the repair material both before the water permeability test (FIG. 1 (a)) and after the water permeability test (FIG. 1 (b)). It was confirmed that the gel of the repair material filled the cracks without any gaps.
‐Ｅ−ＳＥＭ（環境制御型電子顕微鏡）
実施例１の補修材料で補修した円柱供試体を透水試験の後、温度５０℃の乾燥炉で２４時間乾燥させた。乾燥後の円柱供試体にエポキシ樹脂を直接含浸させ、ひび割れ内に形成された補修材料のゲル被膜の変形、変質を防ぐための前処理を施した。更に、円柱供試体を、円柱軸線に沿って、ひび割れと直交する方向に乾式で切断した。
-E-SEM (Environmentally Controlled Electron Microscope)
The columnar specimen repaired with the repair material of Example 1 was subjected to a water permeability test and then dried in a drying oven at a temperature of 50 ° C. for 24 hours. The dried columnar specimen was directly impregnated with epoxy resin and pretreated to prevent deformation and deterioration of the gel film of the repair material formed in the cracks. Further, the cylindrical specimen was dry-cut along the cylindrical axis in a direction orthogonal to the crack.
切断面を湿式で研磨して徐々にエポキシ樹脂を除去し、ひび割れ表面にゲル被膜の露出が確認できた時点で、Ｅ−ＳＥＭでＳＥＭ画像を撮影した。撮影倍率を変えた撮影結果を図３（ａ）〜（ｃ）に示す。 The cut surface was wet-polished to gradually remove the epoxy resin, and when the gel film was confirmed to be exposed on the cracked surface, an SEM image was taken by E-SEM. The shooting results with different shooting magnifications are shown in FIGS. 3 (a) to 3 (c).
図３（ｂ）から明らかなように、実施例１の補修材料はそのゲル被膜内に均質な多孔体を形成していた。また、図３（ｃ）から実施例１の補修材料では炭酸カルシウムと思われる結晶が確認された。 As is clear from FIG. 3B, the repair material of Example 1 formed a homogeneous porous body in the gel film. Further, from FIG. 3C, crystals thought to be calcium carbonate were confirmed in the repair material of Example 1.
‐ＥＤＸ（エネルギー分散型Ｘ線分光法）
上記Ｅ−ＳＥＭに用いた円柱供試体からゲル被膜中の析出物を採取し、ＥＤＸ分析にかけた結果を図４に示す。図４のチャートからＣａとＣとＯの位置にピークが出願しており、微生物の代謝により、ゲル被膜内に炭酸カルシウムが析出することが確認できた。
-EDX (Energy Dispersive X-ray Spectroscopy)
FIG. 4 shows the results of collecting the precipitates in the gel film from the cylindrical specimen used for the E-SEM and subjecting them to EDX analysis. From the chart of FIG. 4, peaks were filed at the positions of Ca, C, and O, and it was confirmed that calcium carbonate was precipitated in the gel film due to the metabolism of microorganisms.
Claims (5)
嫌気性微生物と、
カルシウムイオンと架橋する官能基を有する水溶性ポリマーと、
を含有し、
カルシウム源を実質的に添加しないことを特徴とする補修材料。 It is a repair material for cement-based structures.
With anaerobic microorganisms
A water-soluble polymer having a functional group that crosslinks with calcium ions,
Contains ,
A repair material characterized by substantially no addition of a calcium source.
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