JP2006265040A - Cement admixture, cement composition, and cement mortar using the cement composition - Google Patents

Cement admixture, cement composition, and cement mortar using the cement composition Download PDF

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JP2006265040A
JP2006265040A JP2005085551A JP2005085551A JP2006265040A JP 2006265040 A JP2006265040 A JP 2006265040A JP 2005085551 A JP2005085551 A JP 2005085551A JP 2005085551 A JP2005085551 A JP 2005085551A JP 2006265040 A JP2006265040 A JP 2006265040A
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cement
mortar
admixture
composition
conductive polymer
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JP4937519B2 (en
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Akitoshi Araki
昭俊 荒木
Kazuyuki Mizushima
一行 水島
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Denka Co Ltd
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Denki Kagaku Kogyo KK
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a cement admixture and a cement composition having excellent conductivity by which cement mortar having excellent appearance and workability can be performed and electric corrosion protection work capable of making electric current flow uniform is made possible, and cement mortar using the cement composition. <P>SOLUTION: The admixture contains a conductive polymer, further contains a fiber and contains a non-conductive polymer. The cement composition contains cement and the cement admixture. The cement mortar uses the cement composition. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、セメント混和材、セメント組成物、及びそれを用いたセメントモルタル、特に、コンクリート構造物の電気防食工法で使用するための、導電性に優れたポリマーを含有するセメント混和材、セメント組成物、及びそれを用いたセメントモルタルに関する。   The present invention relates to a cement admixture, a cement composition, and a cement mortar using the cement admixture, and in particular, a cement admixture containing a polymer having excellent conductivity for use in an anticorrosion method for a concrete structure. And a cement mortar using the same.

コンクリート構造物中の鉄筋は、一定量の塩分濃度を超えると鉄筋表面に形成している不導態被膜が破壊されて腐食が進行し、鉄筋に発生する錆びの膨張圧によりコンクリートが破壊され、ひび割れ、浮き、及びコンクリート片のはく落等が発生する。   When the reinforcing bar in the concrete structure exceeds a certain amount of salinity, the non-conductive film formed on the reinforcing bar surface is destroyed and the corrosion progresses, and the concrete is destroyed by the expansion pressure of the rust generated on the reinforcing bar, Cracks, floats, flaking of concrete pieces, etc. occur.

現在、このような鉄筋腐食を防止する手段として電気防食工法がある(非特許文献1参照)。
この工法は、コンクリート表面から内部の鉄筋に防食電流を流す工法であり、コンクリート中の鉄筋を陰極とし、コンクリート表面には鉄筋の対極である陽極を設置する必要がある。
Currently, there is a cathodic protection method as means for preventing such corrosion of reinforcing bars (see Non-Patent Document 1).
This method is a method in which an anticorrosive current is passed from the concrete surface to the internal reinforcing bars, and the reinforcing bars in the concrete must be used as cathodes, and the anode that is the counter electrode of the reinforcing bars must be installed on the concrete surface.

陽極の設置方法としては、チタンメッシュ陽極方式、パネル陽極方式、導電性塗料方式、チタン溶射方式、チタン亜鉛溶射方式、チタンリボンメッシュ陽極方式、チタングリッド方式、チタンロッド方式、亜鉛シート方式、亜鉛−アルミ擬合金溶射方式、及び導電性モルタル方式がある(非特許文献1参照)。
そのうち、他の陽極の設置方法より価格が低く、施工が簡単な面から導電性モルタル方式が採用されている。
As the anode installation method, titanium mesh anode method, panel anode method, conductive paint method, titanium spraying method, titanium zinc spraying method, titanium ribbon mesh anode method, titanium grid method, titanium rod method, zinc sheet method, zinc- There are an aluminum pseudo-alloy spraying method and a conductive mortar method (see Non-Patent Document 1).
Among them, the conductive mortar method is adopted because it is less expensive than other anode installation methods and is easy to install.

従来、導電性モルタル方式で使用される導電性モルタルとしては炭素繊維を含有するモルタルが知られている(特許文献1、特許文献2、及び特許文献3参照)。   Conventionally, mortars containing carbon fibers are known as conductive mortars used in the conductive mortar system (see Patent Document 1, Patent Document 2, and Patent Document 3).

一方、導電性ポリマーは、電池、コンデンサー、塗料、帯電防止材、有機EL発光材料、電磁波シールド、及び印刷基盤等の電気・電子分野の用途で使用されているが、セメントコンクリート分野では使用されていない。   On the other hand, conductive polymers are used in electric and electronic fields such as batteries, capacitors, paints, antistatic materials, organic EL light-emitting materials, electromagnetic wave shields, and printed boards, but are not used in cement concrete. Absent.

土木学会コンクリート委員会電気化学的補修工法研究小委員会編集、電気化学的防食工法設計指針(案)、電気防食工法設計施工マニュアル、pp55〜116、平成13年Edited by the Japan Society of Civil Engineers' Concrete Committee Electrochemical Repair Method Research Subcommittee, Electrochemical Protection Method Design Guidelines (Draft), Electrocorrosion Method Design and Construction Manual, pp55-116, 2001 特開平07−206502号公報Japanese Patent Application Laid-Open No. 07-206502 特許第2550093号公報Japanese Patent No. 2550093 特許第2624269号公報Japanese Patent No. 2624269

導電性モルタルにおいて、充分な導電性を付与するためには、炭素繊維を比較的多く混合する必要があり、混合するときの混合性に課題があった。
炭素繊維の添加量を多くすると、ファイバーボールができたり、モルタルのフレッシュ性状に支障をきたしたり、施工性が悪くなる場合があった。
さらに、繊維が混入したモルタルは表面が毛羽立ち、仕上がりが悪るくなる場合もあった。そのため、できるだけ繊維を混入しないか、少ない添加量で導電性モルタルを調製した方が美観や施工性の面で好ましいものであった。
また、炭素繊維は、モルタル内では均一分散しづらく、電流が均一に流れないという課題もあった。
In order to give sufficient conductivity in the conductive mortar, it is necessary to mix a relatively large amount of carbon fibers, and there is a problem in the mixing property when mixing.
If the amount of carbon fiber added is increased, fiber balls may be formed, the fresh properties of the mortar may be hindered, and workability may be deteriorated.
Furthermore, the surface of the mortar mixed with fibers may become fuzzy and the finish may be poor. For this reason, it is preferable in terms of aesthetics and workability to mix the fibers as little as possible or to prepare the conductive mortar with a small addition amount.
In addition, the carbon fiber is difficult to uniformly disperse in the mortar, and there is a problem that the current does not flow uniformly.

本発明者は、前記の課題を解決するために鋭意検討を重ねた結果、導電性ポリマーを含有するセメント組成物とすることによって、電気防食工法に適するセメントモルタルが得られるという知見を得て、本発明を完成するに至った。   As a result of intensive studies to solve the above-mentioned problems, the present inventor obtained the knowledge that a cement mortar suitable for an anticorrosion method can be obtained by using a cement composition containing a conductive polymer. The present invention has been completed.

本発明は、導電性ポリマーを含有してなるセメント混和材であり、繊維を含有してなる該セメント混和材であり、非導電性ポリマーを含有してなる該セメント混和材であり、セメントと該セメント混和材とを含有してなるセメント組成物であり、該セメント組成物を使用したセメントモルタルである。   The present invention is a cement admixture containing a conductive polymer, the cement admixture containing fibers, the cement admixture containing a non-conductive polymer, cement and the cement A cement composition comprising a cement admixture, and a cement mortar using the cement composition.

本発明のセメント組成物は、優れた導電性を示し、それを使用することによって、美観や施工性にも優れたセメントモルタルの施工が可能となり、均一に電流を流すことができる電気防食工法が可能となる。   The cement composition of the present invention exhibits excellent electrical conductivity, and by using it, it is possible to construct cement mortar with excellent aesthetics and workability, and an anti-corrosion method that allows a current to flow uniformly. It becomes possible.

以下、本発明を詳細に説明する。
本発明における部や%は、特に規定しない限り質量基準で示す。
なお、本発明のセメントモルタルとは、セメントペースト、モルタル、及びコンクリートを総称するものである。
Hereinafter, the present invention will be described in detail.
Unless otherwise specified, parts and% in the present invention are shown on a mass basis.
The cement mortar of the present invention is a general term for cement paste, mortar, and concrete.

本発明で使用する導電性ポリマーとは、ポリピロール類、ポリアニリン類、ポリチオフェン類、及びポリチエニレンビニレン類等のヘテロ原子含有導電性ポリマーや、ポリアセチレン類、ポリアズレン類、ポリフェニレン類、ポリフェニレンビニレン類、ポリアセン類、ポリフェニルアセチレン類、及びポリジアセチレン類等の炭化水素系導電性ポリマーが挙げられる。これらの導電性ポリマーは、粉末状や水を分散させたディスパージョンのいずれでも使用可能である。これらのうち、比較的高い導電性を示すポリチオフェン類の使用が好ましい。
導電性ポリマーの使用量は、セメント100部に対して、0.1〜20部が好ましく、0.5〜10部がより好ましい。0.1部未満ではセメントモルタルに導電性を付与することが難しい場合があり、20部を超えるとセメントモルタルの強度が低下する場合がある。
The conductive polymer used in the present invention is a heteroatom-containing conductive polymer such as polypyrroles, polyanilines, polythiophenes, and polythienylene vinylenes, polyacetylenes, polyazulenes, polyphenylenes, polyphenylene vinylenes, polyacene. , Hydrocarbon-based conductive polymers such as polyphenylacetylenes and polydiacetylenes. These conductive polymers can be used in either a powder form or a dispersion in which water is dispersed. Of these, use of polythiophenes exhibiting relatively high conductivity is preferable.
The amount of the conductive polymer used is preferably 0.1 to 20 parts, more preferably 0.5 to 10 parts, relative to 100 parts of cement. If it is less than 0.1 part, it may be difficult to impart conductivity to the cement mortar, and if it exceeds 20 parts, the strength of the cement mortar may be lowered.

本発明で使用するセメントとしては特に限定されるものではないが、JIS R 5210に規定されている各種ポルトランドセメント、JIS R 5211、JIS R 5212、及びJIS R 5213に規定されている各種混合セメント、並びに、JISに規定された以上の混和材混入率で製造した高炉セメント、フライアッシュセメント、又はシリカセメント、石灰石粉末等を混合したフィラーセメントからなる群より選ばれる一種又は二種以上が挙げられる。   The cement used in the present invention is not particularly limited, but various portland cements defined in JIS R 5210, various mixed cements defined in JIS R 5211, JIS R 5212, and JIS R 5213, In addition, one or two or more types selected from the group consisting of blast furnace cement, fly ash cement, silica cement, limestone powder mixed with blast furnace cement, fly ash cement manufactured at the above admixture ratio specified in JIS may be mentioned.

本発明で使用する繊維は、接着剤で束状にした収束タイプや、繊維が1本毎分離している非収束タイプがあり、セメントモルタルのダレやひび割れを低減したり、導電性を補ったりすることを目的に使用するものである。
繊維の種類としては、ビニロン繊維やプロピレン繊維に代表される高分子繊維、鋼繊維、ガラス繊維、及び炭素繊維に代表される無機繊維が挙げられ、特に限定されるものではない。
また、繊維の長さは、収束タイプや非収束タイプ共に、混合性を考慮して0.2〜20mmが好ましい。0.2mm未満ではダレやひび割れを低減する効果が小さい場合があり、20mmを超えると練り混ぜ時に均一に分散しずらく、コテ仕上げする場合に毛羽立ちが目立つ場合がある。
繊維の使用量は、非収束タイプの場合は、セメントモルタル1m3に対して、0.1〜1容量部が好ましく、0.2〜0.5容量部がより好ましい。0.1容量部未満ではダレやひび割れ抵抗性を向上させる効果が小さい場合があり、1容量部を超えるとセメントモルタルの流動性に悪影響を与える場合がある。また、収束タイプの場合は、0.03〜0.5容量部が好ましく、0.05〜0.3容量部がより好ましい。0.03容量部未満ではダレやひび割れ抵抗性を向上させる効果が小さい場合があり、0.5容量部を超えると流動性を悪くする場合がある。
The fibers used in the present invention include a convergence type bundled with an adhesive and a non-convergence type in which the fibers are separated one by one, reducing dripping and cracking of cement mortar, and supplementing conductivity. It is used for the purpose of doing.
Examples of the fiber include, but are not particularly limited to, polymer fibers represented by vinylon fibers and propylene fibers, steel fibers, glass fibers, and inorganic fibers represented by carbon fibers.
The length of the fiber is preferably 0.2 to 20 mm in consideration of the mixing property for both the convergence type and the non-convergence type. If it is less than 0.2 mm, the effect of reducing sagging and cracking may be small. If it exceeds 20 mm, it is difficult to disperse uniformly during kneading, and fluffing may be noticeable when finishing the iron.
In the case of a non-converging type, the amount of fiber used is preferably 0.1 to 1 part by volume, more preferably 0.2 to 0.5 part by volume with respect to 1 m 3 of cement mortar. If the amount is less than 0.1 part by volume, the effect of improving sagging and cracking resistance may be small. If the amount exceeds 1 part by volume, the fluidity of cement mortar may be adversely affected. Moreover, in the case of a convergence type, 0.03-0.5 volume part is preferable and 0.05-0.3 volume part is more preferable. If the amount is less than 0.03 part by volume, the effect of improving sagging and cracking resistance may be small, and if it exceeds 0.5 part by volume, the fluidity may be deteriorated.

本発明で使用する非導電性ポリマーとは、JIS A 6203で規定されているセメント混和用のポリマーであり、従来よりセメント混和用として、一般的に使用されてきたポリマーであり、中性化、塩害、及び凍害等の耐久性を向上させる目的で使用するものである。例えば、アクリロニトリル−ブタジエンゴム、スチレン−ブタジエンゴム、クロロプレンゴム、及び天然ゴムなどのゴムラテックス、エチレン−酢酸ビニル共重合体、ポリアクリル酸エステル共重合体、酢酸ビニルビニルバーサテート系共重合体、スチレン−アクリル酸エステル共重合体等の合成樹脂エマルジョン、並びに、エポキシ樹脂や不飽和ポリエステル樹脂に代表される液状ポリマーなどが挙げられ、これらのうちの一種又は二種以上の混合物も使用可能である。
非導電性ポリマーの使用量は、セメント100部に対して、0.5〜20部が好ましく、2〜10部がより好ましい。0.5部より少ないと耐久性を向上させることが難しい場合があり、20部を超えると導電性ポリマーと併用しても導電効果が無くなる場合がある。
The non-conductive polymer used in the present invention is a polymer for cement admixture specified in JIS A 6203, and is a polymer that has been generally used as an admixture for cement from the past. It is used for the purpose of improving durability such as salt damage and frost damage. For example, rubber latex such as acrylonitrile-butadiene rubber, styrene-butadiene rubber, chloroprene rubber, and natural rubber, ethylene-vinyl acetate copolymer, polyacrylate copolymer, vinyl acetate vinyl versatate copolymer, styrene -Synthetic resin emulsions such as acrylic acid ester copolymers, and liquid polymers typified by epoxy resins and unsaturated polyester resins can be used, and one or a mixture of two or more of these can also be used.
The amount of the non-conductive polymer used is preferably 0.5 to 20 parts, more preferably 2 to 10 parts with respect to 100 parts of cement. If the amount is less than 0.5 part, it may be difficult to improve the durability. If the amount exceeds 20 parts, the conductive effect may be lost even when used in combination with a conductive polymer.

本発明において、導電性ポリマーを含有したセメントモルタルに電子供与剤を併用することは、さらに導電性を向上させることができるので好ましい。
電子供与剤としては、塩素、臭素、ヨウ素、及びこれらの化合物等のハロゲン類、五フッ化リン、五フッ化ヒ素、及び五フッ化アンチモンなどのルイス酸が挙げられる。
In the present invention, it is preferable to use an electron donor in combination with cement mortar containing a conductive polymer because the conductivity can be further improved.
Examples of the electron donor include halogens such as chlorine, bromine, iodine, and compounds thereof, and Lewis acids such as phosphorus pentafluoride, arsenic pentafluoride, and antimony pentafluoride.

本発明のセメントモルタルには、品質に悪影響を与えない範囲で、AE剤、減水剤、AE減水剤、流動化剤、高性能AE減水剤、分離低減剤、発泡剤、凝結促進剤、凝結遅延剤、防錆剤、防凍剤、収縮低減剤、防水剤、及び抗菌剤等の各種添加剤を併用することが可能である。   The cement mortar of the present invention has an AE agent, a water reducing agent, an AE water reducing agent, a fluidizing agent, a high performance AE water reducing agent, a separation reducing agent, a foaming agent, a setting accelerator, and a setting delay as long as the quality is not adversely affected. It is possible to use various additives such as an agent, an antirust agent, an antifreeze agent, a shrinkage reducing agent, a waterproofing agent, and an antibacterial agent.

本発明のセメント組成物は、水と混合し、骨材を含まないペーストとして使用することもでき、骨材を含むモルタルやコンクリートとして使用することも可能である。   The cement composition of the present invention can be mixed with water and used as a paste containing no aggregate, and can also be used as mortar or concrete containing aggregate.

本発明のセメント組成物の施工方法は、ミキサーで練り混ぜたセメントモルタルをコテで塗ってもよく、型枠を作りその内部に充填してもよく、圧縮空気を用いてセメントモルタルを吹き飛ばす吹付けで施工することも可能である。   The method of constructing the cement composition of the present invention may be applied with a mortar that has been kneaded with a mixer with a trowel, may be filled into a mold, and may be blown off using compressed air. It is also possible to construct with.

実験例1
セメント100部に対して、細骨材200部、表1に示す導電性ポリマー、及び水50部を配合し、モルタルを調製し、導電性試験を行った。結果を表1に併記する。
Experimental example 1
To 100 parts of cement, 200 parts of fine aggregate, a conductive polymer shown in Table 1, and 50 parts of water were blended to prepare a mortar, and a conductivity test was conducted. The results are also shown in Table 1.

<使用材料>
セメント :普通ポルトランドセメント、市販品
細骨材 :新潟県青海町産石灰砂乾燥品、最大粒径1.2mm
導電性ポリマーA:ポリエチレンオキシジオキシチオフェン水分散液、固形分1.2%、市販品
導電性ポリマーB:ポリピロール、市販品
<Materials used>
Cement: Ordinary Portland cement, commercially available fine aggregate: Dry lime sand from Aomi-cho, Niigata Prefecture, maximum particle size 1.2mm
Conductive polymer A: Polyethyleneoxydioxythiophene aqueous dispersion, solid content 1.2%, commercially available conductive polymer B: polypyrrole, commercially available

<測定方法>
抵抗率 :導電性試験、練り混ぜたモルタルを4×4×16cmに成形し、その中にアルミニウム製の電極を埋め込んだ後、28日間、温度20℃、湿度60%で養生して試験体とし、インピーダンス測定装置を用いて材齢28日の試験体の抵抗率を、抵抗率(Ω・cm)=(抵抗×電極面積)/電極間距離の式から算出
<Measurement method>
Resistivity: Conductivity test, kneaded mortar is molded into 4x4x16cm, embedded with aluminum electrodes, and then cured for 28 days at 20 ° C and 60% humidity. Using the impedance measurement device, calculate the resistivity of the specimen 28 days of age from the equation: resistivity (Ω · cm) = (resistance × electrode area) / distance between electrodes

実験例2
導電性ポリマーAをセメント100部に対して0.5部使用したモルタル1m3に対して、表2に示す繊維を配合し、ダレ性試験と導電性試験とを行ったこと以外は実験例1と同様に行った。結果を表2に併記する。
Experimental example 2
Similar to Experimental Example 1 except that the fiber shown in Table 2 was blended with 1 m 3 of mortar using 0.5 part of conductive polymer A per 100 parts of cement, and the sag test and conductivity test were conducted. Went to. The results are also shown in Table 2.

<使用材料>
繊維a :炭素繊維、繊維長6mm、繊維径0.2mm、非収束タイプ、市販品
繊維b :ビニロン繊維、繊維長6mm、繊維径0.026mm、収束タイプ、市販品
<Materials used>
Fiber a: Carbon fiber, fiber length 6 mm, fiber diameter 0.2 mm, non-convergent type, commercially available fiber b: Vinylon fiber, fiber length 6 mm, fiber diameter 0.026 mm, convergent type, commercially available product

<測定方法>
ダレ性 :ダレ性試験、ダレの有無、下地をコンクリート製平板とし、厚さ10mm×縦150mm×横250mmの型枠内にモルタルを塗り付け、コテ仕上げを行った後に、その枠を取りはずし、垂直に平板を立ててズレ落ちなければ可、ずり落ちれば不可とした。
<Measurement method>
Sagging property: Sagging property test, presence of sagging, base plate is made of concrete, mortar is applied in a 10mm thickness x 150mm x 250mm width mold, and after finishing the trowel, the frame is removed and vertical A flat plate was placed on the plate, and it was acceptable if it did not fall off.

実験例3
導電性ポリマーAをセメント100部に対して0.5部使用したモルタル中のセメント100部に対して、表3に示す非導電性ポリマーと水50部を配合し、遮塩性試験と導電性試験とを行った。結果を表3に併記する。
Experimental example 3
The non-conductive polymer shown in Table 3 and 50 parts of water are blended with 100 parts of cement in mortar using 0.5 parts of conductive polymer A for 100 parts of cement. Went. The results are also shown in Table 3.

<使用材料>
非導電性ポリマー:アクリル−酢酸ビニル−バーサチック酸ビニル系粉末ポリマー
<Materials used>
Non-conductive polymer: Acrylic-vinyl acetate-vinyl versatate powder polymer

塩分浸透深さ:遮塩性試験、JIS A 1171に準拠 Salt penetration depth: Salt barrier test, compliant with JIS A 1171

Claims (7)

導電性ポリマーを含有してなるセメント混和材。   A cement admixture containing a conductive polymer. 繊維を含有してなる請求項1に記載のセメント混和材。   The cement admixture according to claim 1, comprising a fiber. 非導電性ポリマーを含有してなる請求項1又は請求項2に記載のセメント混和材。   The cement admixture according to claim 1 or 2, comprising a non-conductive polymer. セメントと、請求項1〜請求項3のうちのいずれか1項に記載のセメント混和材とを含有してなるセメント組成物。   A cement composition comprising cement and the cement admixture according to any one of claims 1 to 3. セメントと導電性ポリマーとを含有してなるセメント組成物。   A cement composition comprising cement and a conductive polymer. セメント、導電性ポリマー、繊維、及び非導電性ポリマーを含有してなるセメント組成物。   A cement composition comprising cement, conductive polymer, fiber, and non-conductive polymer. 請求項4〜請求項6のうちのいずれか1項に記載のセメント組成物を用いてなるセメントモルタル。   Cement mortar using the cement composition according to any one of claims 4 to 6.
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JP2006273605A (en) * 2005-03-28 2006-10-12 Denki Kagaku Kogyo Kk Cement admixture, cement composition, and cement mortar obtained by using the same
JP2006273604A (en) * 2005-03-28 2006-10-12 Denki Kagaku Kogyo Kk Rust-preventive agent composition and rust preventive treatment method using the same
JP2006273603A (en) * 2005-03-28 2006-10-12 Denki Kagaku Kogyo Kk Cement admixture, cement composition, and cement mortar obtained by using the same
KR101738336B1 (en) * 2015-05-19 2017-05-22 유한회사 한스 Concrete composite for foundation of street lamp with functionality and foundation of street lamp using the composite

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* Cited by examiner, † Cited by third party
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JP2006273604A (en) * 2005-03-28 2006-10-12 Denki Kagaku Kogyo Kk Rust-preventive agent composition and rust preventive treatment method using the same
JP2006273603A (en) * 2005-03-28 2006-10-12 Denki Kagaku Kogyo Kk Cement admixture, cement composition, and cement mortar obtained by using the same
KR101738336B1 (en) * 2015-05-19 2017-05-22 유한회사 한스 Concrete composite for foundation of street lamp with functionality and foundation of street lamp using the composite

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