JP2011132039A - Fluidizing agent for anti-washout underwater hydraulic composition - Google Patents
Fluidizing agent for anti-washout underwater hydraulic composition Download PDFInfo
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- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
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Abstract
Description
本発明は、水中不分離性水硬性組成物用流動化剤に関し、より詳しくは、添加量が少なくとも、水硬性組成物の流動性保持時間を長くし、且つ優れた初期強度が得られる水中不分離性水硬性組成物用流動化剤及びこれを含有する水中不分離性水硬性組成物に関する。 The present invention relates to a fluidizing agent for a non-separable hydraulic composition in water, and more specifically, the amount of addition is at least an increase in the fluidity retention time of the hydraulic composition and an excellent initial strength. The present invention relates to a fluidizing agent for a separable hydraulic composition and an underwater non-separable hydraulic composition containing the fluidizing agent.
従来、海洋中又は河川中の橋脚基礎など、コンクリートを水中に打設する場合には、構造体としての満足なコンクリートの品質を確保するため、プレパックドコンクリート工法，トレミー管や底開き容器を用いる水中コンクリートが用いられてきた。一方、これらの工法は、施工段取りが特に重要であり、海洋工事の大型化に伴う打設水深、流動距離、水質汚濁、コンクリート品質等の施工条件を満足することが厳しく、制約を受ける場合が増えてきた。 Conventionally, when concrete is placed in the water, such as in a pier foundation in the ocean or river, a pre-packed concrete method, tremy pipe or bottom opening container is used to ensure satisfactory concrete quality as a structure. Underwater concrete has been used. On the other hand, the construction setup is particularly important for these construction methods, and it is difficult to satisfy the construction conditions such as the water depth, flow distance, water pollution, concrete quality, etc. accompanying the increase in the size of offshore construction. It has increased.
このような状況を受け、ヨーロッパの技術である水中不分離性コンクリートが導入されるようになった。これはコンクリート自身の性質を未硬化な状態で水の洗い作用を受けても材料分離を生じ難いように改良したコンクリートである。このコンクリートは、流動性・充填性を高めた設計のため、薄くて広い面積の水中コンクリートの施工、鉄筋コンクリート部材など高品質を要求される構造物の施工、水質汚濁防止が要求される施工、災害復旧の応急工事など、従来の水中コンクリートでは施工が難しい用途にも用いられるようになっている。 Under these circumstances, underwater non-separable concrete, a European technology, has been introduced. This is a concrete in which the properties of the concrete itself are improved so that material separation does not easily occur even when subjected to a water washing action in an uncured state. Because this concrete is designed to improve fluidity and filling properties, it is necessary to construct thin and wide-area underwater concrete, construct reinforced concrete members and other structures that require high quality, construct water structures that require water pollution prevention, and disasters. It is also used in applications where construction is difficult with conventional underwater concrete, such as emergency repair work.
水中不分離性コンクリートは、通常の未硬化のコンクリートに、水中不分離性混和剤という特殊な増粘剤及び流動化剤を加えることにより製造される。水中不分離性混和剤としては主にセルロース系、あるいはアクリル系の水溶性高分子が用いられるが、これらは凝結・強度発現の遅延が著しいのが欠点である。この水中不分離性混和剤の欠点を克服するために硬化促進剤を添加すると、経時での流動性の低下が著しく、施工可能時間が大幅に制約されてしまう。
そこで、カルシウムアルミネートやアルミノケイ酸カルシウムガラス（以下合わせて「カルシウムアルミネート類」という。）等を水中不分離性コンクリートに添加することが提案されている（例えば特許文献１及び特許文献２参照）。
しかし、カルシウムアルミネート類を水中不分離性コンクリートに添加する場合、その添加量は水中不分離性コンクリート中のセメント１００質量部に対し５質量部以上必要である。このため、コンクリート打設現場において、充分な効果を得る量のカルシウムアルミネート類及び水中不分離性混和剤を添加することは困難であり、所謂「生コン工場」と呼ばれているコンクリート製造工場におけるコンクリート製造時に、カルシウムアルミネート類及び水中不分離性混和剤を添加しなければならない。また、カルシウムアルミネート類を多く含有する水中不分離性コンクリートを海中の施工に用いると、海中の硫酸イオンとの反応で、異常膨張が起こる虞がある。
また、最近、アニオン系・カチオン系の界面活性剤の相互作用により増粘し、凝結及び強度発現への影響の少ない水中不分離混和剤が開発されたが、双方の界面活性剤のバランスが敏感で、コンクリート中のその他の原料の影響や温度の影響を受け易く、しばしば意図した水中不分離性が得られないという問題があった（例えば特許文献３参照）。
Underwater non-separable concrete is produced by adding a special thickener and a fluidizing agent called an underwater inseparable admixture to ordinary uncured concrete. Cellulose or acrylic water-soluble polymers are mainly used as the inseparable admixture in water, but these are disadvantageous in that the delay in setting and strength development is remarkable. If a curing accelerator is added to overcome the disadvantages of this non-separable admixture in water, the fluidity will deteriorate significantly over time, and the workable time will be greatly restricted.
Therefore, it has been proposed to add calcium aluminate, calcium aluminosilicate glass (hereinafter referred to as “calcium aluminates”) and the like to the underwater non-separable concrete (see, for example, Patent Document 1 and Patent Document 2). .
However, when calcium aluminates are added to the underwater inseparable concrete, the added amount is required to be 5 parts by mass or more with respect to 100 parts by mass of the cement in the underwater inseparable concrete. For this reason, it is difficult to add a sufficient amount of calcium aluminate and an underwater non-separable admixture at a concrete placement site. In a concrete manufacturing factory called a “raw concrete factory” Calcium aluminates and non-separable admixtures in water must be added during concrete production. Moreover, when underwater non-separable concrete containing a large amount of calcium aluminates is used for underwater construction, abnormal expansion may occur due to reaction with sulfate ions in the sea.
Recently, an underwater non-separable admixture has been developed that thickens due to the interaction of anionic and cationic surfactants and has little effect on condensation and strength development, but the balance of both surfactants is sensitive. Therefore, there is a problem that it is easily affected by the influence of other raw materials in concrete and the temperature, and often the intended inseparability cannot be obtained (see, for example, Patent Document 3).
本発明は、配合計算時に体積を無視できる程少ない添加量であっても、添加した水硬性組成物の流動性保持時間が長く、且つ優れた初期強度が得られる水中不分離性水硬性組成物用流動化剤及びこれを含有する水中不分離性水硬性組成物を提供することを目的とする。 The present invention is a non-separable hydraulic composition in water that has a long fluidity retention time of the added hydraulic composition and an excellent initial strength, even if the addition amount is so small that the volume can be ignored at the time of blending calculation. An object of the present invention is to provide a fluidizing agent for water and a non-separable hydraulic composition containing water.
本発明者等は、前記課題解決のため鋭意検討した結果、特定のセメント分散剤と硫酸リチウムを配合することにより、上記課題を解決できることを見出し、本発明を完成させた。
即ち、本発明は、（Ａ）ポリカルボン酸系セメント分散剤及び（Ｂ）硫酸リチウムを含有する水中不分離性水硬性組成物用流動化剤を提供するものである。
また、本発明は、水硬性物質、水中不分離性混和剤及びこの水中不分離性水硬性組成物用流動化剤を含有する水中不分離性水硬性組成物を提供するものである。
As a result of intensive investigations for solving the above problems, the present inventors have found that the above problems can be solved by blending a specific cement dispersant and lithium sulfate, and have completed the present invention.
That is, the present invention provides a fluidizing agent for an underwater non-separable hydraulic composition containing (A) a polycarboxylic acid cement dispersant and (B) lithium sulfate.
The present invention also provides an underwater inseparable hydraulic composition containing a hydraulic substance, an underwater inseparable admixture and a fluidizing agent for the underwater inseparable hydraulic composition.
本発明の水中不分離性水硬性組成物用流動化剤によれば、配合計算時に体積を無視できる程少ない添加量であっても、添加した水硬性組成物は流動性保持時間が長く、且つ優れた初期強度を発現する。また、本発明の水中不分離性水硬性組成物用流動化剤はコンクリート打設現場においても添加可能である。また、本発明の水中不分離性水硬性組成物は海中の施工に用いた場合においても、海中の硫酸イオンとの反応で異常膨張が起こる虞がない。 According to the fluidizing agent for an underwater non-separable hydraulic composition of the present invention, the added hydraulic composition has a long fluidity retention time, even if the addition amount is so small that the volume can be ignored at the time of blending calculation, and Expresses excellent initial strength. Moreover, the fluidizing agent for an underwater non-separable hydraulic composition of the present invention can also be added at the concrete placement site. Moreover, even when the underwater inseparable hydraulic composition of the present invention is used for underwater construction, there is no possibility of abnormal expansion due to reaction with sulfate ions in the sea.
本発明において、水中不分離性水硬性組成物とは、ポルトランドセメント、アルミナセメント、コロイドセメント、フライアッシュセメント、高炉セメント、エコセメント、半水石膏等の広義の水硬性セメント或いは高炉スラグ等の潜在水硬性物質等の水硬性物質と、水中不分離性混和剤と、必要により更に添加される他の混和材料或いは骨材を含有する水硬性の組成物をいう。 In the present invention, the underwater inseparable hydraulic composition is a latent hydraulic cement such as Portland cement, alumina cement, colloidal cement, fly ash cement, blast furnace cement, eco cement, hemihydrate gypsum, or the like. A hydraulic composition containing a hydraulic substance such as a hydraulic substance, an inseparable admixture in water, and other admixtures or aggregates that are further added as necessary.
本発明の流動化剤に用いる（Ａ）ポリカルボン酸系セメント分散剤は、ポリカルボン酸系水溶性高分子を含有しセメント粒子を水中に分散させる効果を有するものであればよく、例えば、ポリカルボン酸系減水剤，ポリカルボン酸系ＡＥ減水剤，ポリカルボン酸系高性能減水剤，ポリカルボン酸系高性能ＡＥ減水剤が挙げられるが、ポリカルボン酸系高性能減水剤又はポリカルボン酸系高性能ＡＥ減水剤が好ましい。これらは液体状のもの、粉末状のもの何れも使用可能である。用いるポリカルボン酸系セメント分散剤が粉末状のものであれば、水分が含まれないのでより添加量を少なくできることから好ましい。また、グラフト共重合体のポリカルボン酸系水溶性高分子を含有するセメント分散剤も、セメント分散剤の添加量を少なくできることから好ましい。更に、分子内に下式（１）及び（２）で表される構成単位を有するポリカルボン酸系水溶性高分子を含有するものがより好ましい。 The (A) polycarboxylic acid-based cement dispersant used in the fluidizing agent of the present invention may be any one that contains a polycarboxylic acid-based water-soluble polymer and has an effect of dispersing cement particles in water. Carboxylic acid-based water reducing agent, polycarboxylic acid-based AE water reducing agent, polycarboxylic acid-based high-performance water reducing agent, polycarboxylic acid-based high-performance water reducing agent, and the like. High performance AE water reducing agents are preferred. These can be used either in liquid form or in powder form. If the polycarboxylic acid type cement dispersant to be used is in a powder form, it is preferable because the amount of addition can be reduced because it does not contain moisture. A cement dispersant containing a polycarboxylic acid-based water-soluble polymer of a graft copolymer is also preferable because the amount of cement dispersant added can be reduced. Furthermore, what contains the polycarboxylic acid type water-soluble polymer which has a structural unit represented by the following Formula (1) and (2) in a molecule | numerator is more preferable.
（式中、Ｒ1、Ｒ2及びＲ3は同一又は異なって水素原子又はメチル基を示し、Ｒ4は炭素数１〜３のアルキル基を示し、Ｍは水素原子、アルカリ金属、アルカリ土類金属、アンモニウム又は有機アミンを示し、Ｙは−ＣＨ2Ｏ−又は−ＣＯＯ−を示し、ｎは２０〜１０９の数を示す。）
式（１）及び（２）で表される構成単位を有するポリカルボン酸系水溶性高分子を含有するポリカルボン酸系セメント分散剤は、太平洋マテリアル社製ポリカルボン酸系高性能減水剤（商品名「コアフロー２００Ｌ」）等の市販されているものを使用することができる。
(In the formula, R 1 , R 2 and R 3 are the same or different and each represents a hydrogen atom or a methyl group; R 4 represents an alkyl group having 1 to 3 carbon atoms; M represents a hydrogen atom, an alkali metal or an alkaline earth; metal, shows the ammonium or organic amine, Y is -CH 2 O-or -COO- are shown, n is a number of from 20 to 109.)
The polycarboxylic acid-based cement dispersant containing the polycarboxylic acid-based water-soluble polymer having the structural units represented by the formulas (1) and (2) is a polycarboxylic acid-based high-performance water reducing agent (product of Pacific Materials) A commercially available product such as “Core Flow 200L”) can be used.
本発明に用いる（Ｂ）硫酸リチウムは、無水物でも水和物でもよく、他のイオンを含有していてもよい。また、水溶液でも粉末状でもよい。粉末状のものであれば、水分が含まれないのでより添加量を少なくできることから好ましい。より好ましくは、硫酸リチウムの無水物（Ｌｉ2ＳＯ4）又は一水和物（Ｌｉ2ＳＯ4・Ｈ2Ｏ）である。 The lithium sulfate (B) used in the present invention may be an anhydride or a hydrate, and may contain other ions. Further, it may be an aqueous solution or powder. If it is in a powder form, it is preferable because the amount of addition can be reduced because it does not contain moisture. More preferred is lithium sulfate anhydride (Li 2 SO 4 ) or monohydrate (Li 2 SO 4 .H 2 O).
本発明に含まれる硫酸リチウムとポリカルボン酸系セメント分散剤との割合は、少ない添加量で本発明の効果を得る観点から、（Ａ）ポリカルボン酸系セメント分散剤中の不揮発成分（本発明において１０５℃における不揮発成分を意味する）に対する（Ｂ）硫酸リチウムのＬｉ2ＳＯ4換算の質量比（Ｂ／Ａ）を０．１〜１０とすることが好ましく、更に０．３〜８とすることが好ましく、特に０．５〜７とすることが好ましい。 From the viewpoint of obtaining the effects of the present invention with a small addition amount, the ratio of lithium sulfate and polycarboxylic acid-based cement dispersant contained in the present invention is (A) a non-volatile component in the polycarboxylic acid-based cement dispersant (the present invention). The mass ratio (B / A) in terms of Li 2 SO 4 of lithium sulfate to (B) is preferably 0.1 to 10, more preferably 0.3 to 8. It is particularly preferable to set it to 0.5-7.
本発明の水中不分離性水硬性組成物用流動化剤に、更に、（Ｃ）硫酸リチウム以外のアルカリ金属硫酸塩及び／または石膏を配合すると、本発明の効果をあまり損なうことなく高価な硫酸リチウムの使用量を抑制し得ることが可能となることから好ましい。すなわち、硫酸リチウム以外のアルカリ金属硫酸塩及び石膏は、硫酸リチウムの一部代用となる。硫酸リチウム以外のアルカリ金属硫酸塩としては、例えば、硫酸カリウム、硫酸ナトリウム、硫酸水素カリウム又は硫酸水素ナトリウム、或いはこれらの水和物が挙げられ、これらの一種又は二種以上を用いることができる。また、石膏としては、ニ水石膏、半水石膏、無水石膏が挙げられ、これらの一種又は二種以上を用いることができる。
硫酸リチウム以外のアルカリ金属硫酸塩及び／または石膏を含有させる場合は、硫酸リチウムのＬｉ2ＳＯ4に対するアルカリ金属硫酸塩及び石膏の合計の質量比を、０．０１〜１．０とすることが好ましく、０．０１〜０．５とすることがより好ましい。
When the fluidizing agent for an underwater inseparable hydraulic composition of the present invention is further blended with (C) an alkali metal sulfate other than lithium sulfate and / or gypsum, an expensive sulfuric acid is obtained without significantly impairing the effects of the present invention. It is preferable because the amount of lithium used can be suppressed. That is, alkali metal sulfates and gypsum other than lithium sulfate serve as a partial substitute for lithium sulfate. Examples of the alkali metal sulfate other than lithium sulfate include potassium sulfate, sodium sulfate, potassium hydrogen sulfate, sodium hydrogen sulfate, and hydrates thereof, and one or more of these can be used. Examples of gypsum include dihydrate gypsum, hemihydrate gypsum, and anhydrous gypsum, and one or more of these can be used.
When an alkali metal sulfate other than lithium sulfate and / or gypsum is included, the total mass ratio of the alkali metal sulfate and gypsum to Li 2 SO 4 of lithium sulfate may be 0.01 to 1.0. Preferably, it is more preferable to set it as 0.01-0.5.
本発明の水中不分離性水硬性組成物用流動化剤には、上記（Ａ）、（Ｂ）及び（Ｃ）以外の混和材料の一種又は二種以上を本発明の効果を損なわない範囲で使用することができる。このような混和材料としては、例えばセメント用ポリマー、発泡剤、起泡剤、防水材、防錆剤、収縮低減剤、保水剤、顔料、繊維、撥水剤、白華防止剤、膨張材(剤)、急結剤(材)、急硬剤(材)、消泡剤、高炉スラグ微粉末、フライアッシュ、石粉、シリカフューム、表面硬化剤、ナフタレン系セメント分散剤、メラミン系セメント分散剤、リグニン系セメント分散剤及びポリオール系セメント分散剤等が挙げられる。 In the fluidizing agent for an underwater non-separable hydraulic composition of the present invention, one or more admixtures other than the above (A), (B) and (C) may be used as long as the effects of the present invention are not impaired. Can be used. Examples of such admixture materials include cement polymers, foaming agents, foaming agents, waterproofing materials, rust preventives, shrinkage reducing agents, water retention agents, pigments, fibers, water repellents, whitening prevention agents, expansion materials ( Agent), quick setting agent (material), rapid hardening agent (material), antifoaming agent, fine powder of blast furnace slag, fly ash, stone powder, silica fume, surface hardening agent, naphthalene cement dispersant, melamine cement dispersant, lignin Based cement dispersants and polyol cement dispersants.
本発明の水中不分離性水硬性組成物用流動化剤を製造する方法は、特に限定されず、例えば、Ｖ型混合機や可傾式コンクリートミキサ等の重力式ミキサ、ヘンシェル式ミキサ、リボンミキサ等のミキサにより、上記（Ａ）、（Ｂ）及びその他の任意成分を混合することで製造することができる。このとき用いるミキサは、連続式ミキサでもバッチ式ミキサでも良い。各材料のミキサ内への投入順序は特に限定されず、一種ずつ投入してもよく、一部又は全部を同時に投入してもよい。また、袋やポリエチレン製容器等の容器に各材料を計り取り投入する方法により、本発明の水中不分離性水硬性組成物用流動化剤を製造することもできる。 The method for producing the fluidizing agent for an underwater inseparable hydraulic composition of the present invention is not particularly limited. For example, a gravity mixer such as a V-type mixer or a tiltable concrete mixer, a Henschel mixer, a ribbon mixer It can manufacture by mixing said (A), (B) and other arbitrary components with mixers. The mixer used at this time may be a continuous mixer or a batch mixer. The order in which each material is charged into the mixer is not particularly limited, and one material may be charged at a time, or part or all may be charged simultaneously. Moreover, the fluidizing agent for an underwater non-separable hydraulic composition of the present invention can also be produced by a method of measuring and introducing each material into a container such as a bag or a polyethylene container.
本発明の水中不分離性水硬性組成物は、上記の水中不分離性水硬性組成物用流動化剤、水硬性物質及び水中不分離性混和剤を含有するものである。 The underwater inseparable hydraulic composition of the present invention contains the fluidizing agent for an underwater inseparable hydraulic composition, a hydraulic substance, and an underwater inseparable admixture.
本発明に用いる水硬性物質としては、特に限定されず、例えば、ポルトランドセメント、アルミナセメント、コロイドセメント、フライアッシュセメントや高炉セメント等の混合セメント、太平洋セメント社製「ジェットセメント」（商品名）や住友大阪セメント社製「ジェットセメント」（商品名）等の超速硬セメント、エコセメント、半水石膏等の広義の水硬性セメント或いは高炉スラグ等の潜在水硬性物質から選ばれる一種又は二種以上を挙げることができる。 The hydraulic substance used in the present invention is not particularly limited, and examples thereof include Portland cement, alumina cement, colloidal cement, mixed cement such as fly ash cement and blast furnace cement, “Jet Cement” (trade name) manufactured by Taiheiyo Cement Co., Ltd. Sumitomo Osaka Cement Co., Ltd. “Jet Cement” (trade name), such as super fast-hardening cement, eco-cement, hydraulic cement in a broad sense such as hemihydrate gypsum, or one or more types selected from latent hydraulic materials such as blast furnace slag Can be mentioned.
また、本発明に用いる水中不分離性混和剤としては、例えばヒドロキシメチルセルロースやヒドロキシプロピルセルロース等の水溶性セルロースからなるセルロース系水中不分離性混和剤、アクリル樹脂やメタクリル樹脂等のアクリル系水中不分離性混和剤、アルギン酸、β-１，３グルカン、プルラン、ウェランガム等の多糖類からなる中不分離性混和剤等が挙げられ、これらの一種又は二種以上の使用が可能であるが、少量で水中不分離性が高いセルロース系水中不分離性混和剤が好ましい。
水中不分離性混和剤の添加量は施工目的に必要とされる水中不分離性の程度によって適宜決定すればよいが、水中不分離性水硬性組成物の混練物１ｍ3当り０．５〜１０ ｋｇが好ましく、１〜５ ｋｇが更に好ましい。０．５ｋｇ未満では水中不分離性が得られず、１０ｋｇを超えると硬化遅延が著しく、もはや本流動化剤の使用を以ってしても回復は難しい、或いは粘性が高過ぎ施工に支障をきたす虞がある。
The water-insoluble separable admixture used in the present invention is, for example, a cellulose-based water-insoluble separable admixture made of water-soluble cellulose such as hydroxymethylcellulose or hydroxypropylcellulose, or an acrylic water-insoluble separable admixture such as acrylic resin or methacrylic resin. Non-separable admixtures composed of polysaccharides such as alcoholic admixture, alginic acid, β-1,3 glucan, pullulan, welan gum, etc., and these can be used alone or in combination of two or more. Cellulose-based water-inseparable admixtures with high water-inseparability are preferred.
The addition amount of the water inseparable admixture may be appropriately determined depending on the degree of water inseparability required for the construction purpose, but is 0.5 to 10 per 1 m 3 of the kneaded product of the water inseparable hydraulic composition. kg is preferable, and 1 to 5 kg is more preferable. If it is less than 0.5 kg, inseparability in water will not be obtained, and if it exceeds 10 kg, the curing delay will be significant, and recovery will no longer be possible even with the use of this fluidizing agent, or the viscosity will be too high and will hinder construction. There is a risk of coming.
水中不分離性水硬性組成物に含まれる（Ａ）ポリカルボン酸系セメント分散剤の量は、水中不分離性水硬性組成物中の水硬性物質の量に対し、不揮発成分換算で０．０５〜１．０質量％となる量が好ましく、０．２〜０．６質量％となる量が更に好ましい。０．０５質量％となる量未満では流動性が不足し、１．０質量％となる量を超えると凝結遅延が著しくなることがある。 The amount of the (A) polycarboxylic acid-based cement dispersant contained in the underwater inseparable hydraulic composition is 0.05 in terms of non-volatile components with respect to the amount of the hydraulic material in the underwater inseparable hydraulic composition. The amount of -1.0% by mass is preferred, and the amount of 0.2-0.6% by mass is more preferred. If the amount is less than 0.05% by mass, the fluidity is insufficient, and if it exceeds 1.0% by mass, the setting delay may be remarkable.
また、本発明の水中不分離性水硬性組成物に含まれる（Ｂ）硫酸リチウムの量は、水中不分離性水硬性組成物中の水硬性物質の量に対し、硫酸リチウム一水和物固形分換算で，０．０５〜３質量％となる量が好ましく、０．３〜２質量％となる量が更に好ましい。０．０５質量％となる量未満では凝結遅延を防ぐ効果が充分ではなく、また流動性の保持時間も充分ではない。３質量％となる量を超えると高価な硫酸リチウムを多量に使用すること、またポリカルボン酸系セメント分散剤が多量に必要となることから経済的に得策でない。 In addition, the amount of (B) lithium sulfate contained in the underwater inseparable hydraulic composition of the present invention is such that lithium sulfate monohydrate solids with respect to the amount of hydraulic material in the underwater inseparable hydraulic composition. An amount of 0.05 to 3% by mass in terms of minutes is preferred, and an amount of 0.3 to 2% by mass is more preferred. If the amount is less than 0.05% by mass, the effect of preventing the setting delay is not sufficient, and the holding time for fluidity is not sufficient. If the amount exceeds 3% by mass, a large amount of expensive lithium sulfate is used, and a large amount of polycarboxylic acid-based cement dispersant is required, which is not economically advantageous.
本発明の水中不分離性水硬性組成物に、（Ｃ）石膏を用いる場合の該石膏の量は、水中不分離性水硬性組成物中の水硬性物質の量に対し、０．１〜１．５質量％となる量とすることが好ましい。１．５質量％となる量を超えると、ポリカルボン酸系セメント分散剤が多量に必要となることから経済的に得策でない。 The amount of gypsum when (C) gypsum is used for the underwater inseparable hydraulic composition of the present invention is 0.1 to 1 with respect to the amount of hydraulic substance in the underwater inseparable hydraulic composition. The amount is preferably 5% by mass. If the amount exceeds 1.5% by mass, a large amount of polycarboxylic acid-based cement dispersant is required, which is not economical.
本発明の水中不分離性水硬性組成物には、水硬性物質、水中不分離性混和剤及び本発明の流動化剤以外の他の成分を本発明の効果を損なわない範囲で併用することができる。このような成分としては、例えば、骨材、セメント用ポリマー、発泡剤、起泡剤、防水材、防錆剤、収縮低減剤、保水剤、顔料、繊維、撥水剤、白華防止剤、膨張材(剤)、急結剤(材)、急硬剤(材)、消泡剤、高炉スラグ微粉末、フライアッシュ、石粉、シリカフューム、表面硬化剤、ナフタレン系セメント分散剤、メラミン系セメント分散剤、リグニン系セメント分散剤、ポリオール系セメント分散剤等が挙げられる。また、骨材としては、例えば川砂、海砂、山砂、砕砂、人工細骨材、スラグ細骨材、再生細骨材、スラグ細骨材、珪砂、石粉、川砂利、陸砂利、砕石、人工粗骨材、スラグ粗骨材、再生粗骨材、スラグ粗骨材等が挙げられる。 In the water-inseparable hydraulic composition of the present invention, other components other than the hydraulic substance, the water-inseparable admixture and the fluidizing agent of the present invention may be used in combination as long as the effects of the present invention are not impaired. it can. Such components include, for example, aggregates, polymers for cement, foaming agents, foaming agents, waterproofing materials, rust preventives, shrinkage reducing agents, water retention agents, pigments, fibers, water repellents, white flower prevention agents, Expanding material (agent), quick setting agent (material), hardener (material), antifoaming agent, fine powder of blast furnace slag, fly ash, stone powder, silica fume, surface hardener, naphthalene cement dispersant, melamine cement dispersion Agents, lignin-based cement dispersants, polyol-based cement dispersants and the like. In addition, as aggregates, for example, river sand, sea sand, mountain sand, crushed sand, artificial fine aggregate, slag fine aggregate, recycled fine aggregate, slag fine aggregate, quartz sand, stone powder, river gravel, land gravel, crushed stone, Artificial coarse aggregate, slag coarse aggregate, recycled coarse aggregate, slag coarse aggregate and the like can be mentioned.
本発明の水中不分離性水硬性組成物を製造する方法としては、Ｖ型混合機や可傾式コンクリートミキサ等の重力式ミキサ、ヘンシェル式ミキサ、リボンミキサ等のミキサにより、流動化剤以外の所定量の本発明の水中不分離性水硬性組成物の各材料を混合した後、流動化剤を添加し更に混練する方法が好ましい。このとき用いるミキサは、連続式ミキサでもバッチ式ミキサでも良い。流動化剤以外の各材料のミキサ内への投入順序は特に限定されない。一種ずつ添加してもよく、一部又は全部を同時に添加してもよい。また、袋やポリエチレン製容器等の容器に各材料を計り取り投入する方法により、本発明の水中不分離性水硬性組成物を製造することもできる。 As a method for producing the underwater non-separable hydraulic composition of the present invention, a gravity mixer such as a V-type mixer or a tiltable concrete mixer, a Henschel mixer, a ribbon mixer or the like can be used. A method is preferable in which a predetermined amount of each material of the underwater inseparable hydraulic composition of the present invention is mixed, and then a fluidizing agent is added and further kneaded. The mixer used at this time may be a continuous mixer or a batch mixer. The order in which each material other than the fluidizing agent is charged into the mixer is not particularly limited. One by one may be added, or part or all may be added simultaneously. Moreover, the underwater non-separable hydraulic composition of the present invention can also be produced by a method of measuring and introducing each material into a container such as a bag or a polyethylene container.
本発明の水中不分離性水硬性組成物は、流動化剤添加前に水と混練して用いる。このときの水／結合材比は特に限定されるものではないが、２０〜７０％が好ましく、２５〜６５％が更に好ましい。単位水量も特に限定されるものではないが、コンクリートにおいては１ｍ3当たり１４０〜３００ｋｇが好ましく、１５０〜２５０ｋｇがさらに好ましい。モルタルにおいては１ｍ3当たり１６０〜５８０ｋｇ好ましく、１８０〜５００ｋｇが更に好ましい。 The underwater non-separable hydraulic composition of the present invention is used by kneading with water before adding the fluidizing agent. The water / binder ratio at this time is not particularly limited, but is preferably 20 to 70%, and more preferably 25 to 65%. The unit water amount is not particularly limited, but in concrete, 140 to 300 kg is preferable per 1 m 3, and 150 to 250 kg is more preferable. In mortar, 160 to 580 kg is preferable per 1 m 3 , and 180 to 500 kg is more preferable.
流動化剤添加前に水中不分離性水硬性組成物と水とを混練する方法は特に限定されず、例えば水に水中不分離性水硬性組成物を全量加え混練する方法、水に水中不分離性水硬性組成物を混練しながら加え更に混練する方法、水中不分離性水硬性組成物に水を全量加え混練する方法、水中不分離性水硬性組成物に水を混練しながら加え更に混練する方法、水及び水中不分離性水硬性組成物のそれぞれ一部ずつを２以上に分けて混練し、混練したものを合わせて更に混練する方法等がある。また、混練に用いる器具や混練装置も特に限定されないが、ミキサを用いることが量を多く混練できるので好ましい。用いることのできるミキサとしては連続式ミキサでもバッチ式ミキサでも良く、例えばパン型コンクリートミキサ、パグミル型コンクリートミキサ、重力式コンクリートミキサ、グラウトミキサ、ハンドミキサ、左官ミキサ等が挙げられる。 There is no particular limitation on the method of kneading the water-inseparable hydraulic composition and water before adding the fluidizing agent, for example, the method of adding the whole amount of the water-inseparable hydraulic composition to water and kneading, the water being inseparable in water A method of adding and kneading the water-soluble hydraulic composition while kneading, a method of adding and kneading all of the water to the water-insoluble separable hydraulic composition, and kneading the water-inseparable hydraulic composition while kneading water. There are a method, a method of kneading a part of water and an inseparable hydraulic composition in water into two or more, kneading them together, and further kneading them. Moreover, although the apparatus and kneading apparatus used for kneading are not particularly limited, it is preferable to use a mixer because a large amount can be kneaded. The mixer that can be used may be a continuous mixer or a batch mixer, and examples thereof include a pan type concrete mixer, a pug mill type concrete mixer, a gravity type concrete mixer, a grout mixer, a hand mixer, and a plastering mixer.
本発明の水中不分離性水硬性組成物用流動化剤は、コンクリート製造工場等における水中不分離性水硬性組成物の混練物の製造後、当該混練物の打設現場おけるトラックアジテータ又はミキサに投入しても良い。 The fluidizing agent for an underwater inseparable hydraulic composition of the present invention is used in a track agitator or a mixer at the installation site of the underwater inseparable hydraulic composition in a concrete manufacturing plant or the like after the kneaded material is produced. It may be thrown in.
以下、実施例を挙げて本発明を更に詳細に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to these.
実施例に用いた材料は次の通りである。
セメント： 太平洋セメント社製 普通ポルトランドセメント，比重３．１６
太平洋セメント社製 早強ポルトランドセメント，比重３．１２
AE減水剤： BASFポゾリス社製 （商品名「ポゾリスＮｏ．７０」）
（リグニンスルホン酸化合物とポリオールの複合体）
粗骨材： 茨城県桜川市産 砕石2005及び1305，比重２．６４
細骨材： 静岡県菊川市産 山砂，比重２．６０，Ｆ．Ｍ．２．７８
消泡剤： サンノプコ社製 （商品名「ＳＮデフォーマーＡＨＰ」）
水中不分離性混和剤： 太平洋マテリアル社製 （商品名「太平洋エルコン」）
メラミン系流動化剤： 太平洋マテリアル社製 （商品名「ＬＣ−１０００」）
ポリカルボン酸系分散剤： 太平洋マテリアル社製ポリカルボン酸系高性能減水剤
（商品名「コアフローＮＦ−２００Ｌ」）
硫酸リチウム一水和物： 関東化学社製 一級試薬
無水硫酸ナトリウム： 関東化学社製 一級試薬
II型無水石こう： セントラル硝子社製 ブレーン比表面積 ８０００ｃｍ2／ｇに調整
The materials used in the examples are as follows.
Cement: Taiheiyo Cement, ordinary Portland cement, specific gravity 3.16
Hayashi Portland Cement made by Taiheiyo Cement Co., specific gravity 3.12
AE water reducing agent: BASF Pozzolith (trade name “Pozoris No. 70”)
(Lignin sulfonic acid compound and polyol complex)
Coarse aggregate: Crushed stone 2005 and 1305, Sakuragawa, Ibaraki, 2.64 specific gravity
Fine aggregate: mountain sand from Kikugawa city, Shizuoka prefecture, specific gravity 2.60, F.R. M.M. 2.78
Antifoaming agent: San Nopco (trade name “SN Deformer AHP”)
Non-separable admixture in water: Taiheiyo Materials (trade name "Pacific Elcon")
Melamine based fluidizer: Taiheiyo Materials Co., Ltd. (trade name “LC-1000”)
Polycarboxylic acid-based dispersant: Taiheiyo Materials' polycarboxylic acid-based high-performance water reducing agent
(Product name "Core Flow NF-200L")
Lithium sulfate monohydrate: First grade reagent manufactured by Kanto Chemical Co., Ltd. Anhydrous sodium sulfate: First grade reagent manufactured by Kanto Chemical Co., Ltd.
Type II anhydrous gypsum: manufactured by Central Glass Co., Ltd. Adjusted to a specific brain surface area of 8000 cm 2 / g
実施例１〜６／比較例１〜３ （モルタル、ＡＥ減水剤あり、流動化剤後添加）
表１に示す配合割合（表１中の各材料欄の単位は質量部）で、水及びAE減水剤をペール缶（内容量２０リットル）に計りとり、更にセメント、砂、水中不分離性混和剤及び消泡剤を投入し、ハンドミキサ（撹拌羽根の直径１５ｃｍ，１１００Ｒ．Ｐ．Ｍ．）で90秒間混練した。
１５分間静置の後、メラミン系流動化剤又は本発明の流動化剤（ポリカルボン酸系分散剤、硫酸リチウム一水和物）を添加して90秒間混練した。このようにして得られた水硬性組成物ついて下記の方法により評価した。結果を表１に示す。
Examples 1 to 6 / Comparative Examples 1 to 3 (with mortar and AE water reducing agent, added after fluidizing agent)
Measure water and AE water reducing agent in a pail can (with a content of 20 liters) at the blending ratio shown in Table 1 (units for each material in Table 1 are parts by mass), and further mix in cement, sand and water inseparablely. The agent and the antifoaming agent were added and kneaded for 90 seconds with a hand mixer (diameter of stirring blade 15 cm, 1100 RPM).
After standing for 15 minutes, the melamine fluidizer or the fluidizer of the present invention (polycarboxylic acid dispersant, lithium sulfate monohydrate) was added and kneaded for 90 seconds. The hydraulic composition thus obtained was evaluated by the following method. The results are shown in Table 1.
テーブルフロー：アクリル板上でJIS R 5201に規定されるフローコーンにモルタルを詰め、静かに上方に引抜き、モルタルの動きが止まった後、その拡がりの長径と短径を測り、その平均を以ってテーブルフロー値とした。流動化剤添加・混練直後及び２，４時間後に計測し、経時での計測の折には計測前に上記ハンドミキサで30秒間練り返してから行った。
（流動性の指標。流動化剤添加・混練直後の目標225±10 mmとし、４時間後の保持率80%以上を合格とした）。
密度：JIS A 1171に規定する単位容積質量試験に従って計測した。
pH：JSCE-D 104の附属書２「水中不分離性コンクリートの水中分離度試験」に準じて実施した。但し、水中落下させるモルタル試料は300 gとした。
（水中不分離性の指標。ここではpH12以下を合格とした）。
圧縮強度：JIS A 1108に従って実施した。
（ここでは２４時間強度≧3 N/mm2を目標とした）。
Table flow: A flow cone specified in JIS R 5201 on an acrylic plate is filled with mortar, gently pulled upward, and after the mortar stops moving, the major and minor diameters of the spread are measured and the average is taken. Table flow values. The measurement was performed immediately after addition of the fluidizing agent and after kneading and after 2 to 4 hours, and when the measurement was performed over time, the mixture was kneaded with the hand mixer for 30 seconds before measurement.
(Indicator of fluidity. The target is 225 ± 10 mm immediately after the addition of the fluidizing agent and kneading, and a retention rate of 80% or more after 4 hours is accepted).
Density: Measured according to a unit volume mass test specified in JIS A 1171.
pH: Measured according to JSCE-D 104, Annex 2, “Underwater separability test for non-separable concrete in water”. However, the mortar sample dropped in water was 300 g.
(Indicator of inseparability in water. Here, pH 12 or less was accepted).
Compressive strength: Measured according to JIS A 1108.
(Here, the target is 24 hour strength ≧ 3 N / mm 2 ).
実施例７〜１１／比較例４〜６（コンクリート、AE減水剤あり、流動化剤後添加）
２軸強制練り（パグミル型）コンクリートミキサ（公称容量６０リットル）に、表２に示す配合割合（表２中の各材料欄の単位は質量部）で４０リットルとなる量の、セメント、砂、粗骨材、水中不分離混和剤及び消泡剤を投入、水及びAE減水剤を加えた後、90秒間混練した。３０分間静置の後、メラミン系流動化剤又は本発明の流動化剤（ポリカルボン酸系分散剤、硫酸リチウム一水和物）を添加して60秒間混練した。このようにして得られた水硬性組成物ついて下記の方法により評価した。結果を表２に示す。
Examples 7-11 / Comparative Examples 4-6 (Concrete, with AE water reducing agent, added after fluidizing agent)
In a biaxial forced kneading (pug mill type) concrete mixer (nominal capacity 60 liters), cement, sand, and an amount of 40 liters in a blending ratio shown in Table 2 (units in each material column in Table 2 are parts by mass) Coarse aggregate, an underwater non-separable admixture and an antifoaming agent were added, water and an AE water reducing agent were added, and then kneaded for 90 seconds. After standing for 30 minutes, a melamine fluidizer or a fluidizer of the present invention (polycarboxylic acid dispersant, lithium sulfate monohydrate) was added and kneaded for 60 seconds. The hydraulic composition thus obtained was evaluated by the following method. The results are shown in Table 2.
スランプフロー： JIS A 1150に従って実施。
流動化剤添加・混練直後及び２，４時間後に計測し、経時の間は可傾式（重力式）コンクリートミキサ（公称容量５０リットル）で低速で攪拌した。
（流動性の指標。流動化剤添加・混練直後の目標60.0±5 cmとし、４時間後の保持率80%以上を合格とした）。
空気量：JIS A 1118に従って実施した。
pH：JSCE-D 104の附属書２「水中不分離性コンクリートの水中分離度試験」に準じて実施した。規定通り、水中落下させるコンクリート試料は500 gとした。
（水中不分離性の指標。ここではpH12以下を合格とした）。
圧縮強度：JIS A 1108に従って実施。
（ここでは２４時間強度≧3 N/mm2を目標とした）。
Slump flow: Implemented according to JIS A 1150.
Immediately after addition of the fluidizing agent and after kneading and after 2 to 4 hours, the mixture was stirred at a low speed with a tiltable (gravity) concrete mixer (nominal capacity 50 liters) during the time.
(Indicator of fluidity. Target immediately after addition of fluidizing agent and kneading was set to 60.0 ± 5 cm, and a retention rate of 80% or more after 4 hours was accepted).
Air volume: Measured according to JIS A 1118.
pH: Measured according to JSCE-D 104, Annex 2, “Underwater separability test for non-separable concrete in water”. As specified, the concrete sample dropped in water was 500 g.
(Indicator of inseparability in water. Here, pH 12 or less was accepted).
Compressive strength: Implemented according to JIS A 1108.
(Here, the target is 24 hour strength ≧ 3 N / mm 2 ).
以上の実施例の結果から、本発明品は、流動性保持時間が長く、且優れた初期強度が得られることが判る。 From the results of the above examples, it can be seen that the product of the present invention has a long fluidity retention time and an excellent initial strength.
Claims (4)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2013133266A (en) * | 2011-12-27 | 2013-07-08 | Sumitomo Osaka Cement Co Ltd | Cement composition and method for producing cement hardened product |
| JP2014034826A (en) * | 2012-08-09 | 2014-02-24 | Nishimuragumi:Kk | Construction method of structure using recycled aggregate, and recycled aggregate |
| JP2017171562A (en) * | 2016-03-25 | 2017-09-28 | 住友大阪セメント株式会社 | Cement composition, and cement mixture |
| KR102177687B1 (en) * | 2020-02-11 | 2020-11-11 | 신누리산업개발 주식회사 | Method for manufacturing high-durable polymer mortar including natural coir fiber, metacaulin, and water spray separator, and methods for surface repair and cross section recovery that can be dredged under water using the same |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013133266A (en) * | 2011-12-27 | 2013-07-08 | Sumitomo Osaka Cement Co Ltd | Cement composition and method for producing cement hardened product |
| JP2014034826A (en) * | 2012-08-09 | 2014-02-24 | Nishimuragumi:Kk | Construction method of structure using recycled aggregate, and recycled aggregate |
| JP2017171562A (en) * | 2016-03-25 | 2017-09-28 | 住友大阪セメント株式会社 | Cement composition, and cement mixture |
| KR102177687B1 (en) * | 2020-02-11 | 2020-11-11 | 신누리산업개발 주식회사 | Method for manufacturing high-durable polymer mortar including natural coir fiber, metacaulin, and water spray separator, and methods for surface repair and cross section recovery that can be dredged under water using the same |
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