JP4611331B2 - Pop-out prevention expansion material composition and hardened cement body using the same - Google Patents

Pop-out prevention expansion material composition and hardened cement body using the same Download PDF

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JP4611331B2
JP4611331B2 JP2007075743A JP2007075743A JP4611331B2 JP 4611331 B2 JP4611331 B2 JP 4611331B2 JP 2007075743 A JP2007075743 A JP 2007075743A JP 2007075743 A JP2007075743 A JP 2007075743A JP 4611331 B2 JP4611331 B2 JP 4611331B2
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勉 木田
健太郎 栖原
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Denka Co Ltd
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Denki Kagaku Kogyo KK
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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
    • 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
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/008—Cement and like inorganic materials added as expanding or shrinkage compensating ingredients in mortar or concrete compositions, the expansion being the result of a recrystallisation
    • 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
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Description

本発明は、膨張材とポップアウト防止材とを含有してなるポップアウト防止用膨張材組成物およびそれを用いたセメント硬化体に関する。   The present invention relates to an expansion material composition for preventing pop-out comprising an expansion material and a pop-out prevention material, and a cement hardened body using the same.

従来、骨材性状の悪化やポンプ圧送の確保等から、コンクリート硬化体は、その製造時、コンクリートの所定のワーカビリティーを確保するために、必要以上の水とセメントが使用され、乾燥収縮量が大きくなっている。
そのため、ひび割れを生じ、コンクリート構造物の美観や耐久性を損なう場合があった。
この課題を解決するために、膨張材を使用する方法が提案されている。 Conventionally, due to the deterioration of aggregate properties and ensuring pumping, etc., hardened concrete is used with more water and cement than necessary to ensure the specified workability of the concrete, and the drying shrinkage is large. It has become.
For this reason, cracks may occur and the aesthetics and durability of the concrete structure may be impaired.
In order to solve this problem, a method using an expanding material has been proposed.

膨張材を使用した膨張コンクリートは、レデイーミクストコンクリートとして供給されることが多く、膨張材を生コンプラントで練り混ぜて調製されている。そして、よく分散された膨張コンクリートを得るために、混ぜ時間を延ばしたり、最適な膨張材の投入方法を選択したりしている。
しかしながら、膨張材の塊が少量でもコンクリート中に存在すると、数日〜数年を経てコンクリートの表面付近でポップアウト現象を生じ、美観のみならず耐久性を損なうという課題があった。
これら課題解決のために、種々、膨張材の改良が試みられているが、条件によりポップアウト現象を生じる場合があるのが現状である（特許文献１、特許文献２、及び特許文献３参照）。 Expanded concrete using an expanded material is often supplied as ready-mixed concrete, and is prepared by kneading the expanded material in a green plant. Then, in order to obtain well-dispersed expanded concrete, the mixing time is extended, or an optimal expansion material charging method is selected.
However, if a small amount of the expansion material is present in the concrete, a pop-out phenomenon occurs near the surface of the concrete after several days to several years, and there is a problem that not only the beauty but also the durability is impaired.
In order to solve these problems, various attempts have been made to improve the expansion material, but the present situation is that pop-out phenomenon may occur depending on conditions (see Patent Document 1, Patent Document 2, and Patent Document 3). .

一方、膨潤性粘土は、層間に水が入って膨張する粘土鉱物であり、ハロイサイト、モンモリロナイト、バイデライト、バーミキュライト、及びスメクタイトなどの層状珪酸塩の粘土が挙げられ、なかでも、膨潤度が高いモンモリロナイトを主成分とするベントナイトがセメント分野で多量に使用されている。
例えば、ベントナイト、ポリビニルアルコール、及び膨張材を併用するヒューム管の遠心成形におけるノロ低減又は防止材が提案されているが、ベントナイトは、ノロ低減又は防止材として使用され、本発明のポップアウトを防止することを目的とするものではない（特許文献４参照）。
さらに、ベントナイト、ベントナイトの膨潤性を高める添加剤、及び膨張材からなるセメント組成物が提案されているが、ベントナイトは、ブリーディング防止や粘性の増加のために使用され、本発明のポップアウトを防止することを目的とするものではない（特許文献５参照） On the other hand, swellable clay is a clay mineral that expands when water enters between layers, and examples include lamellar silicate clays such as halloysite, montmorillonite, beidellite, vermiculite, and smectite. Bentonite, the main component, is used in large quantities in the cement field.
For example, noro reduction or prevention material has been proposed for centrifugal molding of fume pipes using bentonite, polyvinyl alcohol, and an expansion material, but bentonite is used as a reduction or prevention material to prevent pop-out of the present invention. It is not intended to do (see Patent Document 4).
Furthermore, a cement composition comprising bentonite, an additive that increases the swelling property of bentonite, and an expansion material has been proposed, but bentonite is used for preventing bleeding and increasing viscosity, thereby preventing pop-out of the present invention. It is not intended to do (see Patent Document 5)

また、リグニンスルホン酸塩は、サルファイトパルプ廃液の塩置換、その他の化学処理、スラッジ分離、及び噴霧乾燥して得られる粉体であり、一般に、セメント、粘土、顔料、染料、石膏、及び掘削泥水等の分散剤、練炭やレンガなどの粘結剤又は粘結助剤、並びに、ボイラのスケール除去剤等に使用されている。
本発明者は、流動性の改善や単位水量を低減するために、膨張材とリグニンスルホン酸カルシウムなどの減水剤を併用して、フローダウンやスランプロスの少ない、ワーカビリティーの良好な膨張材含有セメント組成物を提案したが、特定割合で、膨張材とリグニンスルホン酸カルシウムを併用することによって、ポップアウトを防止することを目的とするものではない（特許文献６参照）。 Lignin sulfonate is a powder obtained by salt substitution of sulfite pulp waste liquor, other chemical treatment, sludge separation, and spray drying. Generally, cement, clay, pigment, dye, gypsum, and drilling It is used for dispersants such as muddy water, binders or binders such as briquettes and bricks, and boiler scale removers.
In order to improve fluidity and reduce unit water volume, the present inventor uses an expansion material and a water reducing agent such as calcium lignin sulfonate in combination with an expandable material-containing cement that has low flow down and slump loss and good workability. Although the composition was proposed, it is not intended to prevent pop-out by using the expansion material and calcium lignin sulfonate together at a specific ratio (see Patent Document 6).

さらに、高吸水性樹脂は、自重の数百倍の水を吸水できる高分子で、水に膨潤してヒドロゲルを形成するもので、水を、形あるものとして保持し、吸水や保水に関する用途開発が進められている。具体的には、紙オムツ、化粧品、湿布剤、土壌改良剤、及びコンクリート養生マットなどに使用されているが、膨張材のポップアウトを防止することを目的として使用されるものではない。   In addition, a highly water-absorbent resin is a polymer that can absorb water several hundred times its own weight, and swells in water to form a hydrogel. It retains water as a form, and develops applications for water absorption and water retention. Is underway. Specifically, it is used for paper diapers, cosmetics, poultices, soil conditioners, concrete curing mats, etc., but is not used for the purpose of preventing the expansion material from popping out.

特開２００２−２２６２４３号公報JP 2002-226243 A 特開２００２−０６８８０８号公報JP 2002-068808 A 特開平１１−３０２０４７号公報JP 11-302047 A 特開２００６−２１９３２０号公報JP 2006-219320 A 特開２００６−２４８８８７号公報JP 2006-248887 A 特開平１０−２２６５４９号公報Japanese Patent Laid-Open No. 10-226549

数日〜数年を経てから、コンクリートの表面付近でポップアウト現象が生じる課題に対して、本発明者は、特定のポップアウト防止材を含有してなるポップアウト防止用膨張材組成物を使用することによって、前記課題が解消できるという知見を得て、本発明を完成するに至った。   After several days to several years, the present inventor uses an expansion material composition for preventing pop-out, which contains a specific pop-out prevention material, for the problem that a pop-out phenomenon occurs near the surface of concrete. As a result, the inventors have obtained the knowledge that the above problems can be solved, and have completed the present invention.

即ち、本発明は、膨張材と、膨潤性粘土からなるポップアウト防止材とを含有してなり、膨張材とポップアウト防止材との合計100部中、膨張材が99.9〜98.0部であり、ポップアウト防止材が0.1〜２部であるポップアウト防止用膨張材組成物であり、ポップアウト防止材が、さらに、リグニンスルホン酸カルシウム及び／又は高吸水性樹脂を含有してなる該ポップアウト防止用膨張材組成物であり、セメントと該ポップアウト防止用膨張材組成物とを含有してなるセメント組成物であり、該ポップアウト防止用膨張材組成物が、セメントと該ポップアウト防止用膨張材組成物とからなる結合材100部中、３〜20部である該セメント組成物であり、セメント、膨張材、及び膨潤性粘土からなるポップアウト防止材を含有してなり、膨張材とポップアウト防止材との合計100部中、膨張材が99.9〜98.0部、ポップアウト防止材が0.1〜２部であるセメント組成物であり、該セメント組成物を用いたセメント硬化体である。 That is, the present invention, the expansion member and, and also contains a pop-out preventing member made of swellable clay, in total 100 parts of the expandable member and the pop-out preventing member, the expansion member is 99.9-9 8.0 parts of And an anti-pop-out expansion material composition having a pop-out prevention material of 0.1 to 2 parts, and the pop-out prevention material further contains calcium lignin sulfonate and / or a superabsorbent resin. An expansion material composition for preventing pop-out, comprising a cement and the expansion material composition for preventing pop-out, wherein the expansion composition for preventing pop-out comprises cement and the pop-out The cement composition is 3 to 20 parts in 100 parts of a binder composed of an expansion material composition for prevention, and contains a pop-out prevention material composed of cement, an expansion material, and a swelling clay, and expands. Wood and pop-out During a total of 100 parts of the bets prevention material, 99.9-9 8.0 parts of the expansion member, the pop-out preventing member is a cement composition is from 0.1 to 2 parts, is hardened cement body using the cement composition .

本発明のポップアウト防止用膨張材組成物を使用したセメント硬化体は、ポップアウトの生じないものとなり、耐久性があり、美観のあるものとなる。   The hardened cement body using the expansion material composition for preventing pop-out according to the present invention does not cause pop-out, has durability, and has a beautiful appearance.

以下、本発明を詳細に説明する。
本発明のコンクリートはセメントモルタルも含む場合がある。 Hereinafter, the present invention will be described in detail.
The concrete of the present invention may also contain cement mortar.

本発明のポップアウト防止用膨張材組成物（以下、単に膨張材組成物という）は、膨張材とポップアウト防止材とを含有するものである。   The expansion material composition for preventing pop-out of the present invention (hereinafter simply referred to as expansion material composition) contains an expansion material and a pop-out prevention material.

本発明で使用する膨張材としては、カルシウムサルホアルミネート系膨張材や石灰系膨張材等がある。
膨張材の粒度は特に限定されるものではないが、通常、ブレーン比表面積値(以下、ブレーン値という)2,000〜7,000cm2/gが好ましい。2,000cm2/g未満では未反応物が長期間残存して耐久性が低下するおそれがあり、7,000cm2/gを超えると水和反応が早く、所定の膨張が得られなくなるおそれがある。 Examples of the expansion material used in the present invention include calcium sulfoaluminate-based expansion materials and lime-based expansion materials.
The particle size of the intumescent material is not particularly limited, but usually a Blaine specific surface area value (hereinafter referred to as a Blaine value) of 2,000 to 7,000 cm 2 / g is preferable. If it is less than 2,000 cm 2 / g, unreacted substances may remain for a long period of time and durability may be reduced. If it exceeds 7,000 cm 2 / g, the hydration reaction may be fast and a predetermined expansion may not be obtained.

本発明で使用するポップアウト防止材は、膨潤性粘土を、また、膨潤性粘土と、リグニンスルホン酸カルシウム及び／又は高級水性樹脂とを含有するものである。   The pop-out preventing material used in the present invention contains swellable clay, swellable clay, and calcium lignin sulfonate and / or a higher aqueous resin.

本発明で使用する膨潤性粘土は、層間に水が入って膨張する粘土鉱物であり、ハロイサイト、モンモリロナイト、バイデライト、バーミキュライト、及びスメクタイトなどの層状珪酸塩の粘土が挙げられる。
これらのうち、膨潤度が高いモンモリロナイトを主成分とするベントナイト、特に、ベントナイトナトリウム塩が好ましく、水分含有量が少ないのもがより好ましい。
ベントナイトは、粉鉄鉱石等を団粒化し、落下強度の向上、耐圧強度の向上、及び粉化防止に効果があり利用されている。
膨潤性粘土の使用量は、膨張材と、膨潤性粘土からなるポップアウト防止材との合計100部中、0.1〜１部が好ましく、0.2〜0.8部がより好ましい。0.1部未満ではポップアウト防止効果が得にくくなるおそれがあり、１部を超えてもポップアウト防止効果はかわらず、流動性の低下が大きくなるおそれがある。 The swellable clay used in the present invention is a clay mineral that expands when water enters between layers, and examples thereof include lamellar silicate clays such as halloysite, montmorillonite, beidellite, vermiculite, and smectite.
Among these, bentonite mainly composed of montmorillonite having a high degree of swelling, in particular, bentonite sodium salt is preferable, and it is more preferable that the water content is small.
Bentonite agglomerates fine iron ore and the like, and is effective in improving the drop strength, the pressure resistance, and preventing pulverization.
The amount of the swellable clay used is preferably 0.1 to 1 part, more preferably 0.2 to 0.8 part, out of a total of 100 parts of the expansion material and the popout prevention material made of the swellable clay. If it is less than 0.1 part, it may be difficult to obtain the effect of preventing pop-out, and if it exceeds 1 part, the effect of preventing pop-out will not be achieved, and the fluidity may decrease significantly.

本発明では、膨潤性粘土に、リグニンスルホン酸カルシウム及び／又は高級水性樹脂を併用することは、流動性や強度の低下を防ぐ面から好ましい。   In the present invention, it is preferable to use calcium lignin sulfonate and / or a higher aqueous resin in combination with the swellable clay from the viewpoint of preventing fluidity and strength from being lowered.

通常、リグニンスルホン酸塩には、ナトリウム塩とカルシウム塩があるが、本発明では、カルシウム塩でないと所用の性能が得られないため、リグニンスルホン酸カルシウムを使用する。   Usually, lignin sulfonate has a sodium salt and a calcium salt. However, in the present invention, a calcium lignin sulfonate is used because a desired performance cannot be obtained unless it is a calcium salt.

本発明で使用するリグニンスルホン酸カルシウム（以下、リグニンCaという）は、低分子量のものから高分子量のものまで使用可能であり、水分含有量が７％以下のものが好ましく、３％以下のものがより好ましい。
ポップアウト防止材が、膨潤性粘土とリグニンCaからなる場合、膨潤性粘土とリグニンCaの配合割合は、膨潤性粘土100部に対して、10〜100部が好ましい。10部未満では併用効果が認められなくなるおそれがあり、100部を超えてもポップアウト効果は向上しない。 The calcium lignin sulfonate (hereinafter referred to as lignin Ca) used in the present invention can be used from a low molecular weight to a high molecular weight, and preferably has a water content of 7% or less, and 3% or less. Is more preferable.
When the pop-out preventing material is composed of swelling clay and lignin Ca, the blending ratio of the swelling clay and lignin Ca is preferably 10 to 100 parts with respect to 100 parts of the swelling clay. If it is less than 10 parts, the combined effect may not be recognized, and if it exceeds 100 parts, the pop-out effect is not improved.

本発明で使用する高吸水性樹脂は、自重の数百倍の水を吸水できる高分子で、水に膨潤してヒドロゲルを形成する。
高吸水性樹脂は、製造方法により、デンプン・アクリロニトリル系高吸水性樹脂、デンプン・アクリル酸系高吸水性樹脂、カルボキシルメチルセルロース系高吸水性樹脂、ポリアクリル酸系高吸水性樹脂、及びビニルアルコール・アクリル酸系高吸水性樹脂があり、これらのいずれの高吸水性樹脂も使用可能であり、カルシウム飽和水溶液中での吸水量が大きいものが好ましい。
高吸水性樹脂の粒度は、平均粒径20〜300μｍが好ましい。
高吸水性樹脂と膨潤性粘土の配合割合は、膨潤性粘土100部に対して、10〜100部が好ましい。10部未満では併用効果が認められなくなるおそれがあり、100部を超えてもポップアウト効果は向上しない。 The superabsorbent resin used in the present invention is a polymer that can absorb water several hundred times its own weight, and swells in water to form a hydrogel.
Depending on the production method, the superabsorbent resin may be starch / acrylonitrile superabsorbent resin, starch / acrylic acid superabsorbent resin, carboxylmethylcellulose superabsorbent resin, polyacrylic superabsorbent resin, vinyl alcohol There is an acrylic acid-based superabsorbent resin, and any of these superabsorbent resins can be used, and those having a large water absorption in a saturated calcium aqueous solution are preferable.
The average particle size of the superabsorbent resin is preferably 20 to 300 μm.
The blending ratio of the superabsorbent resin and the swellable clay is preferably 10 to 100 parts with respect to 100 parts of the swellable clay. If it is less than 10 parts, the combined effect may not be recognized, and if it exceeds 100 parts, the pop-out effect is not improved.

本発明の膨張材組成物は、膨張材と、膨潤性粘土、又は膨潤性粘土とリグニンCa及び／又は高吸水性樹脂とを含有するポップアウト防止材とを含有する。
ポップアウト防止材は、水分含有ができるだけ少ないことが、膨張材の性能を保持させることから好ましい。
また、ポップアウト防止材は、膨張材によく分散していることが、ポップアウト防止上必要である。
ポップアウト防止材の使用量は、ポップアウト防止材が、膨潤性粘土からなる場合、膨潤性粘土とリグニンCaからなる場合、膨潤性粘土と高吸水性樹脂からなる場合、膨潤性粘土とリグニンCaと高吸水性樹脂からなる場合のいずれも、膨張材とポップアウト防止材との合計100部中、0.1〜２部が好ましい。0.1部未満ではポップアウト防止効果が得られないおそれがあり、２部を超えると、強度の低下や流動性の低下が大きくなるおそれがあり、ポップアウト防止効果が変わらず経済的に無駄になるおそれがある。 The expansion material composition of the present invention contains an expansion material and a swellable clay, or a popout prevention material containing the swellable clay and lignin Ca and / or a superabsorbent resin.
It is preferable that the pop-out prevention material has as little water content as possible because the performance of the expansion material is maintained.
Moreover, it is necessary for pop-out prevention material that the pop-out prevention material is well dispersed in the expansion material.
The amount of the pop-out prevention material used is that when the pop-out prevention material is made of swellable clay, when it is made of swellable clay and lignin Ca, when it is made of swellable clay and highly absorbent resin, swellable clay and lignin Ca In the case of the high water-absorbent resin, 0.1 to 2 parts are preferable in 100 parts in total of the expansion material and the pop-out prevention material. If the amount is less than 0.1 part, the pop-out prevention effect may not be obtained. If the amount exceeds 2 parts, the strength and fluidity may decrease significantly, and the pop-out prevention effect remains unchanged and is economically wasteful. There is a fear.

膨張材組成物の使用量は、セメントと膨張材組成物からなる結合材100部中、３〜20部が好ましく、５〜15部がより好ましい。３部未満では収縮低減効果が少なくなるおそれがあり、20部を超えると膨張量が大きすぎて強度が低下するおそれがある。   The amount of the expansion material composition used is preferably 3 to 20 parts, more preferably 5 to 15 parts, in 100 parts of the binder composed of cement and the expansion material composition. If it is less than 3 parts, the shrinkage reduction effect may be reduced, and if it exceeds 20 parts, the amount of expansion is too large and the strength may be reduced.

ここで、セメントとしては、低熱、普通、早強、及び超早強等の各種ポルトランドセメント、これらのポルトランドセメントに、高炉スラグやフライアッシュなどを混合した各種混合セメントなどが使用可能である。
セメントの使用量は、モルタル又はコンクリートの配合等により異なるが、セメント単位量で270〜1,000kg/m3が好ましい。270kg/m3未満では構造上の耐久性や強度が得られなくなるおそれがあり、1,000kg/m3を超えると作業性が得られなくなるおそれがあり、水和発熱や乾燥収縮によるひび割れを生じるおそれがある。 Here, as the cement, various portland cements such as low heat, normal, early strength, and ultra early strength, and various mixed cements obtained by mixing blast furnace slag, fly ash, and the like with these portland cements can be used.
The amount of cement used is preferably 270 to 1,000 kg / m 3 in terms of the unit of cement, although it varies depending on the blending of mortar or concrete. If it is less than 270 kg / m 3 , structural durability and strength may not be obtained, and if it exceeds 1,000 kg / m 3 , workability may not be obtained, and hydration heat generation and cracking due to drying shrinkage may occur. There is.

水の使用量は、モルタル又はコンクリートの配合等によってかわり特に限定されるものではないが、単位量で120〜600kg/m3が好ましい。120kg/m3未満では骨材の表面水管理を厳しくしなければならない場合や、特殊な減水剤を併用しなければならない場合などがあり、施工性が悪化するおそれがある。また、600kg/m3を超えると長期の耐久性が得にくくなるおそれがあり、所定のコンクリート構造物としての強度が得にくくなるおそれがある。 The amount of water used is not particularly limited and varies depending on the blending of mortar or concrete, but the unit amount is preferably 120 to 600 kg / m 3 . If it is less than 120 kg / m 3, there are cases where it is necessary to strictly control the surface water of the aggregate and there are cases where a special water reducing agent must be used in combination, which may deteriorate the workability. Further, if it exceeds 600 kg / m 3 , long-term durability may be difficult to obtain, and strength as a predetermined concrete structure may be difficult to obtain.

本発明のセメント組成物、特に、膨張材組成物の混合方法は、膨張材とポップアウト防止材とがよく分散できれば特に限定されるものではなく、通常のミキサやブレンダーの使用が可能である。   The mixing method of the cement composition of the present invention, particularly the expansion material composition is not particularly limited as long as the expansion material and the pop-out prevention material can be well dispersed, and a normal mixer or blender can be used.

以下、本発明を実験例に基づいてさらに説明するが、本発明はこれらに限定されるものではない。   Hereinafter, although this invention is further demonstrated based on an experiment example, this invention is not limited to these.

実験例１
ポップアウト現象は、膨張材の塊が、モルタルやコンクリート中で吸水し、固まり、分散せずに、長時間の膨張により生じる。そのため、プレスした成形体が、水中で崩壊しやすいものは、分散して塊が生じず、ポップアウトが生じないことから、本発明のポップアウト防止材の効果を迅速に確認する方法として下記の試験方法を行った。
表１に示す膨張材αと、膨張材とポップアウト防止材との合計100部中、表１に示すポップアウト防止材を混合した粉体を、φ19mmの円柱型に入れ、２分間、プレス圧15.9N/mm2でプレスして成形体を作製した。
作製した成形体の崩壊までの時間と金網中に残り吸水した成形体の残存量を測定した。結果を表１に併記する。 Experimental example 1
The pop-out phenomenon is caused by long-time expansion of the expansion material lump, which absorbs water in mortar or concrete and does not solidify or disperse. Therefore, the pressed molded body, which is easily disintegrated in water, is dispersed and does not form a lump and does not cause pop-out, so the method for quickly confirming the effect of the pop-out prevention material of the present invention is as follows. The test method was performed.
In a total of 100 parts of the expansion material α shown in Table 1 and the expansion material and the pop-out prevention material, the powder mixed with the pop-out prevention material shown in Table 1 is put into a φ19 mm cylindrical mold and pressed for 2 minutes. A compact was produced by pressing at 15.9 N / mm 2 .
The time until collapse of the produced molded body and the remaining amount of the molded body remaining in the wire net and absorbing water were measured. The results are also shown in Table 1.

＜使用材料＞
膨張材α ：カルシウムサルホアルミネート系膨脹材、市販品
ポップアウト防止材ａ：膨潤性粘土、ベントナイトナトリウム塩、粉体、市販品
ポップアウト防止材ｂ：膨潤性粘土、ベントナイトカルシウム塩、粉体、市販品
ポップアウト防止材ｃ：非膨潤性粘土、カオリン
ポップアウト防止材ｄ：非膨潤性粘土、タルク <Materials used>
Expansion material α: Calcium sulfoaluminate-based expansion material, commercially available pop-out prevention material a: swelling clay, bentonite sodium salt, powder, commercial product pop-out prevention material b: swelling clay, bentonite calcium salt, powder, Commercially available pop-out prevention material c: non-swelling clay, kaolin pop-out prevention material d: non-swelling clay, talc

＜測定方法＞
崩壊までの時間：２リットルのポリ容器に水1.2リットルを入れ、水を撹拌しながら、作製した成形体を入れた金網を、２分間浸漬し、接水から、成形体が崩れ、金網内に残らなくなる時間
残存量 ：金網中に残った成形体の質量／金網中に入れた成形体全体の質量 <Measurement method>
Time to collapse: Put 1.2 liters of water in a 2 liter plastic container, stir the water and immerse the wire mesh containing the prepared compact for 2 minutes. Remaining amount of time that does not remain: mass of the molded body remaining in the wire mesh / mass of the entire molded body placed in the wire mesh

Figure 0004611331
Figure 0004611331

実験例２
膨張材βを使用し、膨張材とポップアウト防止材との合計100部中、表２に示すポップアウト防止材を用い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
The experiment was performed in the same manner as in Experimental Example 1 except that the expansion material β was used, and the popout prevention material shown in Table 2 was used in 100 parts in total of the expansion material and the popout prevention material. The results are also shown in Table 2.

＜使用材料＞
膨張材β ：石灰系膨張材、市販品
ポップアウト防止材ｅ：リグニンCa、粉体、市販品、平均分子量51,000
ポップアウト防止材ｆ：リグニンCa、粉体、市販品、平均分子量11,000
ポップアウト防止材ｇ：リグニンCa、粉体、市販品、平均分子量 5,100 <Materials used>
Expansion material β: Lime-based expansion material, commercially available pop-out prevention material e: Lignin Ca, powder, commercial product, average molecular weight 51,000
Pop-out prevention material f: Lignin Ca, powder, commercial product, average molecular weight 11,000
Pop-out prevention material g: Lignin Ca, powder, commercial product, average molecular weight 5,100

Figure 0004611331
Figure 0004611331

実験例３
膨張材βを使用し、膨張材とポップアウト防止材との合計100部中、表３に示すポップアウト防止材を用いたこと以外は実験例１と同様に行った。結果を表３に併記する。 Experimental example 3
The experiment was performed in the same manner as in Experimental Example 1 except that the expansion material β was used, and the popout prevention material shown in Table 3 was used in 100 parts in total of the expansion material and the popout prevention material. The results are also shown in Table 3.

＜使用材料＞
ポップアウト防止材ｈ：デンプン・アクリロニトリル系高吸水性樹脂、市販品、粒度20〜50μｍ
ポップアウト防止材ｉ：デンプン・アクリル酸系高吸水性樹脂、市販品、粒度50〜150μｍ
ポップアウト防止材ｊ：ポリアクリル酸系高吸水性樹脂、市販品、粒度150〜300μｍ <Materials used>
Pop-out prevention material h: starch / acrylonitrile-based superabsorbent resin, commercially available, particle size 20-50 μm
Pop-out prevention material i: starch / acrylic acid-based superabsorbent resin, commercially available product, particle size of 50 to 150 μm
Pop-out prevention material j: polyacrylic acid-based superabsorbent resin, commercially available product, particle size of 150 to 300 μm

Figure 0004611331
Figure 0004611331

実験例４
膨張材βと、膨張材とポップアウト防止材からなる膨張材組成物100部中、表４に示すポップアウト防止材とからなる膨張材組成物を使用して、実験例１と同様に成形体を作製した。
セメント93.4部、水54部、減水剤0.25部、細骨材260部、及び粗骨材337部のコンクリート配合でコンクリートを練り混ぜた中に、セメントと膨張材組成物からなる結合材100部に対して、セメント組成物中の膨張材に換算して6.6部となるように作製した成形品を、壊れないようにバラバラに分散して押し込み、２分後に、30秒練り混ぜた。
練り混ぜたコンクリートを用いて、40×40×10cmの型枠に打設した。
翌日脱枠し、20℃水中養生を行い、ポップアウトの発生時期を測定した、結果を成形体の崩壊までの時間とともに表４に併記する。 Experimental Example 4
A molded body in the same manner as in Experimental Example 1 using an expansion material composition comprising the expansion material β and 100 parts of the expansion material composition including the expansion material and the pop-out prevention material. Was made.
While mixing concrete with 93.4 parts of cement, 54 parts of water, 0.25 parts of water reducing agent, 260 parts of fine aggregate, and 337 parts of coarse aggregate, 100 parts of binder consisting of cement and expansion material composition On the other hand, the molded product produced to be 6.6 parts in terms of the expansion material in the cement composition was dispersed and pushed in so as not to break, and kneaded for 30 seconds after 2 minutes.
Using the mixed concrete, it was placed in a 40 × 40 × 10 cm formwork.
The next day, the frame was removed, the water curing at 20 ° C. was performed, and the pop-out occurrence time was measured. The results are shown in Table 4 together with the time until the compact collapses.

＜使用材料＞
セメント ：普通ポルトランドセメント
細骨材 ：川砂、密度2.57g/cm3、粗粒率2.80
粗骨材 ：川砂利、５〜25mm、密度2.67g/cm3、粗粒率6.82
減水剤 ：ポリオール系ＡＥ減水剤、市販品 <Materials used>
Cement: Ordinary Portland cement fine aggregate: River sand, density 2.57g / cm 3 , coarse grain ratio 2.80
Coarse aggregate: River gravel, 5-25mm, density 2.67g / cm 3 , coarse grain rate 6.82
Water reducing agent: Polyol AE water reducing agent, commercial product

＜測定方法＞
ポップアウト発生時期：平滑なコンクリート表面が盛り上がり、ポップアウトが生じるまでの時間 <Measurement method>
Pop-out occurrence time: Time until the smooth concrete surface rises and pop-out occurs

Figure 0004611331
Figure 0004611331

実験例５
膨張材と、膨張材組成物100部中、表５に示すポップアウト防止材とからなる膨張材組成物を調製した。
セメントと、セメントと膨張材組成物からなる結合材100部中、表５に示す膨張材組成物を使用して成形体を作製したこと以外は実験例４と同様に行った。結果を表５に併記する。 Experimental Example 5
An expansion material composition comprising an expansion material and a pop-out prevention material shown in Table 5 in 100 parts of the expansion material composition was prepared.
It was carried out in the same manner as in Experimental Example 4 except that a molded body was produced using cement and an expanding material composition shown in Table 5 in 100 parts of a binder composed of the cement and the expanding material composition. The results are also shown in Table 5.

Figure 0004611331
Figure 0004611331

Claims (7)

膨張材と、膨潤性粘土からなるポップアウト防止材とを含有してなり、膨張材とポップアウト防止材との合計100部中、膨張材が99.9〜98.0部であり、ポップアウト防止材が0.1〜２部であるポップアウト防止用膨張材組成物。 And expanding material, and also contains a pop-out preventing member made of swellable clay, in total 100 parts of the expandable member and the pop-out preventing member, the expansion member is 99.9-9 8.0 parts of anti-pop-out An expansion material composition for preventing pop-out, wherein the material is 0.1 to 2 parts. ポップアウト防止材が、リグニンスルホン酸カルシウムを含有してなる請求項１に記載のポップアウト防止用膨張材組成物。   The expansion material composition for popout prevention according to claim 1, wherein the popout prevention material contains calcium lignin sulfonate. ポップアウト防止材が、高吸水性樹脂を含有してなる請求項１又は請求項２に記載のポップアウト防止用膨張材組成物。   The expansion material composition for preventing pop-out according to claim 1 or 2, wherein the pop-out preventing material contains a highly water-absorbent resin. セメントと、請求項１〜請求項３のうちのいずれか１項に記載のポップアウト防止用膨張材組成物とを含有してなるセメント組成物。   The cement composition containing a cement and the expansion material composition for popout prevention of any one of Claims 1-3. ポップアウト防止用膨張材組成物が、セメントとポップアウト防止用膨張材組成物とからなる結合材100部中、３〜20部である請求項４に記載のセメント組成物。   The cement composition according to claim 4, wherein the expansion material composition for preventing pop-out is 3 to 20 parts in 100 parts of a binder composed of cement and the expansion material composition for preventing pop-out. セメント、膨張材、及び膨潤性粘土からなるポップアウト防止材を含有してなり、膨張材とポップアウト防止材との合計100部中、膨張材が99.9〜98.0部、ポップアウト防止材が0.1〜２部であるセメント組成物。 Cement, expansive, and it contains a pop-out preventing member made of swellable clay, in total 100 parts of the expandable member and the pop-out preventing member, the expansion member is 99.9-9 8.0 parts of pop-out preventing member A cement composition having a content of 0.1 to 2 parts. 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硬化体。   A hardened cement body using the cement composition according to any one of claims 4 to 6.
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