JP4626915B2 - Blackening suppression method for hardened concrete - Google Patents

Blackening suppression method for hardened concrete Download PDF

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Publication number
JP4626915B2
JP4626915B2 JP2001029381A JP2001029381A JP4626915B2 JP 4626915 B2 JP4626915 B2 JP 4626915B2 JP 2001029381 A JP2001029381 A JP 2001029381A JP 2001029381 A JP2001029381 A JP 2001029381A JP 4626915 B2 JP4626915 B2 JP 4626915B2
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concrete
concrete admixture
admixture
surfactant
present
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JP2002234763A (en
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孝洋 佐藤
富士桜 倭
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Kao Corp
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Kao Corp
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/40—Surface-active agents, dispersants
    • C04B2103/402—Surface-active agents, dispersants anionic
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/40—Surface-active agents, dispersants
    • C04B2103/406—Surface-active agents, dispersants non-ionic
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Description

【０００１】
【発明の属する技術分野】
本発明は、コンクリート混和剤、好ましくは高炉スラグ、フライアッシュ、シリカヒューム等を含有するコンクリート用の混和剤に関する。
【０００２】
【従来の技術】
コンクリート用混和材は、セメントペーストと反応させてあるいは複合させてコンクリートの性質を改質するために用いられる材であり、無機質の粉末からなるものが多く、セメントの代替やコンクリートに特別の機能を付与するために繁用される。代表的な混和材として、セメント代替を目的とする高炉スラグ、人工ポゾラン（フライアッシュ、シリカヒューム等）等があり、これらを適正に添加することはコンクリート製造において重要である。一般に、高炉スラグや、フライアッシュ、シリカヒュームには黒色微粉等が含まれる。
【０００３】
しかし、近年のシリカヒュームやフライアッシュ、高炉スラグ等の使用の増加、セメントへの焼却灰の混入（産業廃棄物の利用）、不純物の多い骨材、混和材の使用、また、作業性、環境性向上を目的としたコンクリートの高流動化が原因となり、コンクリート硬化後の肌面に黒い斑状が生じる或いは全体的に黒ずむ現象が発生し、有効な改善策が望まれている。
【０００４】
このようなコンクリートの黒ずみを、混練コンクリートに、例えばアルキル硫酸エステル塩などの陰イオン界面活性剤を添加して原因となる黒色微粉を分散させて低減しようとする試みもあるが、黒ずみの解消には効果的でも、コンクリート硬化体の強度低下が著しくなり、実用化は困難である。
【０００５】
【発明が解決しようとする課題】
本発明は、コンクリートの強度低下がなく、コンクリート肌面に発生する黒ずみを改良できるコンクリート混和剤の提供を目的とする。
【０００６】
【課題を解決するための手段】
本発明は、ＨＬＢが１７．５〜１９．５であり１分子あたりのエチレンオキシド基の数が１５〜２００である非イオン性界面活性剤及び１分子あたりのエチレンオキシド基の数が１５〜２００である陰イオン性界面活性剤から選ばれる一種以上の界面活性剤を含有するコンクリート混和剤に関する。この１分子あたりのエチレンオキシド基の数はエチレンオキシドの平均付加モル数（以下、ＥＯ平均付加モル数という）である。
【０００７】
また、本発明は、水硬性化合物と、高炉スラグ、フライアッシュ及びシリカヒュームから選ばれる一種以上と、上記本発明のコンクリート混和剤とを含有する水硬性組成物に関する。該組成物は、コンクリート混和剤を水硬性化合物に対して０．００００１〜０．１重量％（固形分換算）含有することが好ましい。
【０００８】
更に本発明は、水硬性化合物と、高炉スラグ、フライアッシュ及びシリカヒュームから選ばれる一種以上とを含有する水硬性組成物に、上記本発明のコンクリート混和剤を、水硬性化合物に対して０．００００１〜０．１重量％（固形分換算）添加した水硬性組成物を用いる、コンクリート硬化体の製造方法に関する。
【０００９】
【発明の実施の形態】
本発明は、上記特定のＨＬＢ、ＥＯ平均付加モル数を有する非イオン性界面活性剤及び／又は上記特定のＥＯ平均付加モル数を有する陰イオン性界面活性剤を水硬性組成物に添加することに特徴を有する。
【００１０】
一般にコンクリート肌面の黒い斑点や全体の黒ずみは、セメントや骨材、混和材等に含有される強熱減量物質や炭化物質、カーボン等の黒色微粉が、流動性の高い自己充填コンクリート等で、特に振動を加えた場合に表面に移動することで発生すると考えられている。
【００１１】
本発明のコンクリート混和剤が、コンクリートの強度低下を起こさず黒ずみの発生を抑制できる理由は、詳細は不明であるが、コンクリート中の強熱減量物質や炭化物質、カーボン等の黒色微粉の分散が促進されるとともに、空気連行性が低いためと考えられる。
【００１２】
本発明に用いられる界面活性剤は、ＨＬＢが１７．５〜１９．５、好ましくは、１８．０〜１９．３で、且つＥＯ平均付加モル数が１５〜２００、好ましくは１５〜１５０、特に好ましくは１００〜２００である非イオン性界面活性剤、及びＥＯ平均付加モル数が１５〜２００、好ましくは１５〜１００、特に好ましくは１５〜５０である陰イオン性界面活性剤である。ここで、前記非イオン性界面活性剤のＨＬＢは、グリフィン法により算出されるものである。
【００１３】
これら界面活性剤は、いずれも疎水基として炭素数１０〜３０、特には１２〜２０の炭化水素基、中でもアルキル基、アルケニル基、アルキルフェニル基を有するものが好ましい。
【００１４】
界面活性剤としては、ポリオキシエチレンアルキル（炭素数１０〜３０）エーテル又はその硫酸エステル塩もしくはカルボン酸塩及びポリオキシエチレンアルキル（炭素数６〜２０）フェニルエーテル又はその硫酸エステル塩もしくはカルボン酸塩から選ばれる一種以上が好ましい。具体的には、アルコールＥＯ付加物、脂肪酸ＥＯ付加物、アルキルフェノールＥＯ付加物、アルコールＥＯ付加物硫酸エステル塩、アルキルフェノールＥＯ付加物硫酸エステル塩、アルコールＥＯ付加物酢酸塩、アルキルフェノールＥＯ付加物酢酸塩等が一例として挙げられるが、特に、アルコールＥＯ付加物硫酸エステル塩が好ましい。なお、塩としては、Ｎａ、Ｋなどのアルカリ金属塩、アンモニウム塩、モノ、ジ、トリアルカノール（炭素数２〜６）アンモニウム塩、Ｃａ、Ｍｇなどのアルカリ土類金属塩等いずれでもよいが、好ましくはアルカリ金属塩である。
【００１５】
本発明のコンクリート混和剤中の上記界面活性剤の量は限定されないが、本発明のコンクリート混和剤は、水硬性組成物中の水硬性化合物に対して、０．００００１〜０．１重量％（固形分換算）の比率で使用することが好ましく、０．０００１〜０．１重量％（固形分換算）が更に好ましい。
【００１６】
本発明が対象とする水硬性組成物は、水硬性化合物であるセメント類を主成分とするセメントペースト、モルタル、コンクリート等であり、特に限定しないが、特に黒色微紛が多く含まれる、高炉スラグ、フライアッシュやシリカヒュームを含有する水硬性組成物に使用することが好ましい。さらには、これら粉体を含有する流動性の高い自己充填用コンクリートに使用するのが好ましい。水硬性化合物の具体例としては、ポルトランドセメント、高炉セメント、シリカセメント、フライアッシュセメント、アルミナセメント、天然石膏、副成石膏等が挙げられる。
【００１７】
また本発明の水硬性組成物には、各種の材（剤）を使用することができる。例えば、樹脂石鹸、飽和もしくは不飽和脂肪酸、ラウリルサルフェート、アルキルベンゼンスルホン酸（塩）、アルカンスルホネート等のＡＥ剤；グルコン酸、クエン酸等のオキシカルボン酸系、デキストリン、糖アルコール系等の遅延剤；起泡剤；増粘剤；珪砂；ＡＥ減水剤；早強剤又は促進剤；発泡剤；防水剤；流動化剤；ジメチルポリシロキサン系、ポリアルキレングリコール脂肪酸エステル系、鉱油系、油脂系、オキシアルキレン系、アルコール系、アミド系等の消泡剤；防泡剤；メラミンスルホン酸ホルマリン縮合物系、アミノスルホン酸系、ポリカルボン酸系、ポリマレイン酸系等の高性能減水剤；防錆剤；メチルセルロース、ヒドロキシエチルセルロース等の水溶性高分子；（メタ）アクリル酸アルキル等の高分子エマルジョンが挙げられる。これらのうち、非イオン性界面活性剤、陰イオン性界面活性剤からなるものは、ＨＬＢやＥＯ平均付加モル数が本発明の界面活性剤の範囲外のものが使用される。また、上記成分は本発明のコンクリート混和剤中に配合してもよい。
【００１８】
【実施例】
シリカヒュームセメント５５０ｇ、砂８００ｇ、水１７５ｇ、消泡剤〔フォームレックス７９７（日華化学（株）製）〕０．０１１ｇ、表１の界面活性剤０．００７１５ｇ（有効分）を、モルタルミキサーにて混練する。その際、モルタルフローが２６０〜３００ｍｍになるように減水剤〔マイテイ２１ＨＦ（ポリカルボン酸系分散剤、花王（株）製）〕を添加して調整した。
【００１９】
混練後、モルタルを型枠（モルタル供試体用型枠）に充填し、更に振動〔２５回タッピング（１回／１秒）〕を加え、その後２４時間標準養生し、外観を目視観察し下記基準で黒ずみを評価した。また、養生２８日後の硬化体の圧縮破壊強度を測定し、界面活性剤無添加の場合の強度に対する百分率を算出し、下記基準で評価した。表１に試験結果を示す。
黒ずみ判断基準：◎黒ずみなし ○僅かに有り ×発生
強度判断基準：◎９６％以上 △８６％以上９６％未満 ×８６％未満
【００２０】
【表１】

Figure 0004626915
【００２１】
【発明の効果】
本発明の混和剤により、コンクリート硬化体の強度を低下させることなく、表面の黒ずみを解消できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a concrete admixture, preferably an admixture for concrete containing blast furnace slag, fly ash, silica fume and the like.
[0002]
[Prior art]
Concrete admixtures are materials used to modify the properties of concrete by reacting with or mixing with cement paste, and are often made of inorganic powders, which have a special function for cement substitutes and concrete. Used frequently to grant. Typical admixtures include blast furnace slag and artificial pozzolanes (fly ash, silica fume, etc.) for the purpose of cement replacement, and it is important in concrete production to add these appropriately. Generally, blast furnace slag, fly ash, and silica fume contain black fine powder.
[0003]
However, recent use of silica fume, fly ash, blast furnace slag, etc., incineration ash in cement (use of industrial waste), use of aggregates with high impurities, admixtures, workability, environment Due to the high fluidity of the concrete for the purpose of improving the properties, a black spot is generated on the skin surface after hardening of the concrete or a phenomenon in which the entire surface is darkened occurs, and an effective improvement measure is desired.
[0004]
There is also an attempt to reduce the darkness of concrete by adding anionic surfactant such as alkyl sulfate ester salt to the kneaded concrete to disperse the black fine powder causing the darkness. Is effective, but the strength of the hardened concrete is markedly lowered, and practical application is difficult.
[0005]
[Problems to be solved by the invention]
An object of this invention is to provide the concrete admixture which can improve the darkening which generate | occur | produces on the concrete skin surface, without the strength fall of concrete.
[0006]
[Means for Solving the Problems]
The present invention is a nonionic surfactant having an HLB of 17.5 to 19.5 and an ethylene oxide group number of 15 to 200 per molecule, and an ethylene oxide group number of 15 to 200 per molecule. The present invention relates to a concrete admixture containing one or more surfactants selected from anionic surfactants. The number of ethylene oxide groups per molecule is the average added mole number of ethylene oxide (hereinafter referred to as EO average added mole number).
[0007]
The present invention also relates to a hydraulic composition containing a hydraulic compound, one or more selected from blast furnace slag, fly ash and silica fume, and the concrete admixture of the present invention. The composition preferably contains a concrete admixture in an amount of 0.00001 to 0.1% by weight (in terms of solid content) based on the hydraulic compound.
[0008]
Furthermore, the present invention provides a hydraulic composition containing a hydraulic compound and one or more selected from blast furnace slag, fly ash, and silica fume, and the concrete admixture of the present invention is added to the hydraulic compound in an amount of 0.1%. The present invention relates to a method for producing a hardened concrete using a hydraulic composition to which 00001 to 0.1% by weight (in terms of solid content) is added.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the nonionic surfactant having the specific HLB, the EO average addition mole number and / or the anionic surfactant having the specific EO average addition mole number are added to the hydraulic composition. It has the characteristics.
[0010]
In general, the black spots on the concrete surface and the entire darkening are made of self-filling concrete with high flowability of black powder such as ignition loss substance, carbonized substance, carbon, etc. contained in cement, aggregate, admixture, etc. In particular, it is thought to occur by moving to the surface when vibration is applied.
[0011]
The reason why the concrete admixture of the present invention can suppress the occurrence of darkening without causing a decrease in the strength of the concrete is not known in detail, but the dispersion of black fine powders such as ignition loss substances, carbonized substances, and carbon in the concrete is not possible. This is thought to be because it is promoted and air entrainment is low.
[0012]
The surfactant used in the present invention has an HLB of 17.5 to 19.5, preferably 18.0 to 19.3, and an EO average added mole number of 15 to 200, preferably 15 to 150, particularly A nonionic surfactant that is preferably 100 to 200 and an anionic surfactant that has an EO average addition mole number of 15 to 200, preferably 15 to 100, and particularly preferably 15 to 50. Here, the HLB of the nonionic surfactant is calculated by the Griffin method.
[0013]
These surfactants are preferably those having a hydrocarbon group having 10 to 30 carbon atoms, particularly 12 to 20 carbon atoms, especially an alkyl group, an alkenyl group, or an alkylphenyl group as a hydrophobic group.
[0014]
Surfactants include polyoxyethylene alkyl (carbon number 10 to 30) ether or sulfate ester salt or carboxylate thereof and polyoxyethylene alkyl (carbon number 6 to 20) phenyl ether or sulfate ester salt or carboxylate thereof One or more selected from are preferred. Specifically, alcohol EO adduct, fatty acid EO adduct, alkylphenol EO adduct, alcohol EO adduct sulfate, alkylphenol EO adduct sulfate, alcohol EO adduct acetate, alkylphenol EO adduct acetate, etc. Is an example, and an alcohol EO adduct sulfate ester salt is particularly preferable. The salt may be any of alkali metal salts such as Na and K, ammonium salts, mono-, di- and trialkanol (carbon number 2 to 6) ammonium salts, alkaline-earth metal salts such as Ca and Mg, etc. Alkali metal salts are preferred.
[0015]
The amount of the surfactant in the concrete admixture of the present invention is not limited, but the concrete admixture of the present invention is 0.00001 to 0.1% by weight based on the hydraulic compound in the hydraulic composition ( It is preferably used at a ratio of (solid content conversion), more preferably 0.0001 to 0.1% by weight (solid content conversion).
[0016]
The hydraulic composition targeted by the present invention is cement paste, mortar, concrete or the like mainly composed of cement, which is a hydraulic compound, and is not particularly limited, but particularly contains a lot of black fine powder. It is preferably used for a hydraulic composition containing fly ash or silica fume. Further, it is preferably used for self-filling concrete containing these powders and having high fluidity. Specific examples of the hydraulic compound include Portland cement, blast furnace cement, silica cement, fly ash cement, alumina cement, natural gypsum and by-product gypsum.
[0017]
Various materials (agents) can be used for the hydraulic composition of the present invention. For example, resin soap, saturated or unsaturated fatty acid, lauryl sulfate, alkylbenzene sulfonic acid (salt), alkane sulfonate and other AE agents; gluconic acid, citric acid and other oxycarboxylic acids, dextrin, sugar alcohols and other retarders; Foaming agent; thickener; silica sand; AE water reducing agent; early strengthening agent or accelerator; foaming agent; waterproofing agent; fluidizing agent; dimethylpolysiloxane, polyalkylene glycol fatty acid ester, mineral oil, fat and oil, oxy Anti-foaming agents such as alkylene-based, alcohol-based, and amide-based; antifoaming agents; high-performance water reducing agents such as melamine sulfonic acid formalin condensate-based, aminosulfonic acid-based, polycarboxylic acid-based, polymaleic acid-based; Water-soluble polymers such as methylcellulose and hydroxyethylcellulose; Polymer emulsions such as alkyl (meth) acrylate And the like. Among these, those composed of a nonionic surfactant and an anionic surfactant are those having an HLB or EO average addition mole number outside the range of the surfactant of the present invention. Moreover, you may mix | blend the said component in the concrete admixture of this invention.
[0018]
【Example】
Silica fume cement 550 g, sand 800 g, water 175 g, defoaming agent [foam Rex 797 (manufactured by Nikka Chemical Co., Ltd.)] 0.011 g, and surfactant 0.00715 g (effective amount) in Table 1 in a mortar mixer Knead. At that time, a water reducing agent [Mighty 21HF (polycarboxylic acid-based dispersant, manufactured by Kao Corporation)] was added to adjust the mortar flow to 260 to 300 mm.
[0019]
After kneading, the mortar is filled into a mold (form for mortar specimen), further subjected to vibration [25 times tapping (1 time / 1 second)], then subjected to standard curing for 24 hours, and the appearance is visually observed, and the following standards And evaluated darkening. Moreover, the compression fracture strength of the cured body after 28 days of curing was measured, and the percentage with respect to the strength when no surfactant was added was calculated and evaluated according to the following criteria. Table 1 shows the test results.
Blackening judgment criteria: ◎ No blackening ○ Slightly present × Generation strength judgment criteria: ◎ 96% or more △ 86% or more and less than 96% × less than 86% [0020]
[Table 1]
Figure 0004626915
[0021]
【The invention's effect】
The admixture of the present invention can eliminate surface darkening without lowering the strength of the hardened concrete.

Claims (1)

水硬性化合物と、高炉スラグ、フライアッシュ及びシリカヒュームから選ばれる一種以上とを含有する水硬性組成物からコンクリート硬化体を製造するにあたり、下記のコンクリート混和剤を、水硬性化合物に対して０．００００１〜０．１重量％（固形分換算）添加する、コンクリート硬化体の黒ずみ抑制方法。In producing a hardened concrete from a hydraulic composition containing a hydraulic compound and at least one selected from blast furnace slag, fly ash and silica fume, the following concrete admixture is added to the hydraulic compound in an amount of 0. A method for suppressing darkening of a hardened concrete, which is added at 00001 to 0.1% by weight (in terms of solid content).
＜コンクリート混和剤＞<Concrete admixture>
ＨＬＢが１７．５〜１９．５であり１分子あたりのエチレンオキシド基の数が１００〜２００である非イオン性界面活性剤及び１分子あたりのエチレンオキシド基の数が１５〜２００である陰イオン性界面活性剤から選ばれる一種以上の界面活性剤を含有するコンクリート混和剤であって、Nonionic surfactant having an HLB of 17.5 to 19.5 and an ethylene oxide group number of 100 to 200 per molecule, and an anionic interface having an ethylene oxide group number of 15 to 200 per molecule A concrete admixture containing one or more surfactants selected from activators,
界面活性剤が、ポリオキシエチレンアルキル（炭素数１０〜３０）エーテル又はその硫酸エステル塩もしくはカルボン酸塩及びポリオキシエチレンアルキル（炭素数６〜２０）フェニルエーテル又はその硫酸エステル塩もしくはカルボン酸塩から選ばれる一種以上であるコンクリート混和剤。The surfactant is a polyoxyethylene alkyl (carbon number 10 to 30) ether or a sulfate ester salt or carboxylate thereof and a polyoxyethylene alkyl (carbon number 6 to 20) phenyl ether or a sulfate ester salt or carboxylate thereof. A concrete admixture that is one or more selected.
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JP2004284884A (en) * 2003-03-24 2004-10-14 Grace Chemicals Kk Method of preventing concrete from blackening
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