JP6177658B2 - Quick setting admixture - Google Patents

Quick setting admixture Download PDF

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JP6177658B2
JP6177658B2 JP2013217296A JP2013217296A JP6177658B2 JP 6177658 B2 JP6177658 B2 JP 6177658B2 JP 2013217296 A JP2013217296 A JP 2013217296A JP 2013217296 A JP2013217296 A JP 2013217296A JP 6177658 B2 JP6177658 B2 JP 6177658B2
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信哉 赤江
信哉 赤江
中島 裕
裕 中島
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Taiheiyo Materials Corp
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本発明は、セメントペースト、モルタル又はコンクリート等のセメント系組成物に混和して凝結を早める急結性混和剤に関する。   The present invention relates to a quick-setting admixture that is mixed with a cement-based composition such as cement paste, mortar, or concrete to accelerate setting.

トンネル、地下空間、傾斜面又は法面等の建設工事に対し、地山や壁面補強のためにモルタルやコンクリート等の吹付け施工が行われている。吹付け施工では、セメントペースト或いはモルタル又はコンクリートに急結剤を混和させて急結性を付与し、注水から短時間にセメントの凝結を完了させることで、付着性の担保としている。吹付け施工では、モルタルやコンクリートを吹付けた状態のまま放置して工事を終えることもあるが、吹付けたモルタルやコンクリートの表面を均す作業を行い、仕上げることも多い。この場合、用いる急結剤が強い急結性のものほど早く固まり過ぎるため、均し作業に必要な時間が確保できず、所望の仕上げ面が得られない。さらに、瞬結するほどの急結剤では、吹付けたコンクリートの凝結が吹付ける面の到達前に殆ど完結し、逆に付着性が悪化する虞もあった。このため、急結性の強い急結剤に、例えばアルカリ土類硫酸塩などの急結性抑制成分を添加すると、付着は可能となる。しかし、初期強度も低下するため、コンクリートやモルタルの吹付厚みを厚くすることが困難になる。特に天井面の吹付けでは厚く吹付けると自重を支えるだけの強度が不足し、定着せずに剥落するなどの虞があった。   For construction works such as tunnels, underground spaces, slopes, and slopes, mortar and concrete are sprayed to reinforce grounds and walls. In spraying construction, a quick setting agent is added to cement paste, mortar, or concrete to give quick setting, and cement setting is completed in a short time from pouring water to secure adhesion. In spray construction, the mortar or concrete may be left in the sprayed state to finish the work, but the surface of the sprayed mortar or concrete is often leveled and finished. In this case, the quick setting agent to be used has a quick setting property, so that it quickly hardens, so that the time required for the leveling operation cannot be secured and a desired finished surface cannot be obtained. Furthermore, in the case of the quick-setting agent that causes instantaneous setting, there is a possibility that the condensation of the sprayed concrete is almost completed before reaching the surface to be sprayed, and conversely the adhesiveness is deteriorated. For this reason, adhesion becomes possible when a quick setting inhibitor such as alkaline earth sulfate is added to a quick setting agent having strong setting properties. However, since the initial strength also decreases, it is difficult to increase the spraying thickness of concrete or mortar. In particular, when the ceiling surface is blown thick, the strength is insufficient to support its own weight, and there is a risk of peeling off without fixing.

急結剤の中でもアルミン酸カルシウムは様々な土木・建築工事に多く使用されているが、強い急結性を付与できるため、吹付けモルタルやコンクリートに使用の際は、前記のような問題がつきまとう。吹付けコンクリート中のアルミン酸カルシウムと石膏の比表面積(ブレーン比表面積)を高くすれば、活性が高まることから急結性と初期並びに中長期の強度発現性が共に向上できることが知られている。(例えば、特許文献1参照。)さらに、アルミン酸カルシウムに特定の粒子径の石膏を配合することで、吹付けコンクリートの仕上げ作業時間を確保しつつ、強度が高まることが知られている。(例えば、特許文献2参照。)しかるに、このような吹付けコンクリートでは、付着性と強度発現性を共に適切な値に両立させるバランスまでは考慮されていないため、付着性が十分でなかったり、中長期強度を高くしても短時間強度の発現性は向上しないことがあった。   Among the quick setting agents, calcium aluminate is widely used in various civil engineering and construction work, but it can give strong quick setting properties, so when using it for spraying mortar and concrete, the problems mentioned above are likely to occur. . It is known that if the specific surface area (brane specific surface area) of calcium aluminate and gypsum in the shotcrete is increased, the activity is increased, so that both rapid setting and initial and medium to long-term strength development can be improved. (For example, refer to Patent Document 1) Furthermore, it is known that the strength is increased while ensuring the finishing work time of the shotcrete by blending calcium aluminate with a gypsum having a specific particle diameter. (For example, refer to Patent Document 2) However, in such shotcrete, since the balance that balances both adhesion and strength development to an appropriate value is not considered, the adhesion is not sufficient, Even if the medium- to long-term strength is increased, the short-term strength development may not be improved.

特開2004−323355号公報JP 2004-323355 A 特開2012−121763号公報JP 2012-121863 A

急結性の強い急結剤を用いた吹付けコンクリートやモルタルほど、吹付け後の表面の均し作業等の仕上げのための作業時間が得難く、急結性が強過ぎると付着性そのものを悪化させることがあった。このため強い急結性を抑制すると、自重を安定して支える強度不足から吹付層の厚みを厚くすることが困難になり、吹付けたコンクリートやモルタルの剥落が起き易い。このような問題を鑑み、本発明は、吹付けコンクリートやモルタルの十分な付着性を付与しつつ初期から長期に亘る高い強度発現性を具備させることができ、しかも吹付け後のモルタルやコンクリートに対し、例えば表面を均す等の仕上げ施工のための作業性も確保することが可能な急結性混和剤の提供を課題とする。   Shot concrete and mortar using a quick setting agent with a strong setting property are harder to obtain work time for finishing such as surface leveling after spraying. It sometimes made it worse. For this reason, if strong quick setting property is suppressed, it becomes difficult to increase the thickness of the sprayed layer due to insufficient strength to stably support its own weight, and the sprayed concrete and mortar are likely to peel off. In view of such problems, the present invention can provide high strength development from the beginning to the long term while imparting sufficient adhesion of shotcrete or mortar, and also to mortar and concrete after spraying. On the other hand, it is an object to provide a quick-setting admixture that can ensure workability for finishing work such as leveling the surface.

本発明者は、前記課題解決のため検討した結果、少なくともアルミン酸カルシウムと石膏から構成される急結性混和剤において、両者の含有量を特定のものとし、かつ両者の粒径を詳細に調整することで、吹付性と強度発現性のバランスの制御が可能となった。具体的には、該混和剤を使用した吹付けモルタル又はコンクリートの付着性及び初期並びに中長期の強度発現性を共に向上させることができ、加えて吹付けたモルタル又はコンクリートの表面を、例えば均すなどの仕上げ施工のための適度な作業時間を確保できることも見出し、本発明を完成させた。   As a result of studying to solve the above problems, the present inventor has determined that the contents of both are specific in at least the rapid setting admixture composed of calcium aluminate and gypsum, and the particle diameters of both are adjusted in detail. By doing so, it became possible to control the balance between sprayability and strength development. Specifically, it is possible to improve both the adhesion of sprayed mortar or concrete using the admixture and the initial and medium to long-term strength development. The present inventors have also found that an appropriate working time for finishing construction such as soot can be secured, and completed the present invention.

即ち、本発明は、次の(1)〜(3)で表す急結性混和剤である。(1)アルミン酸カルシウム100質量部と石膏35〜100質量部を含有する急結性混和剤であって、アルミン酸カルシウムが粒径15μm以下の粒子含有率60質量%以上かつ粒径3μm以下の粒子含有率15〜35質量%であり、石膏が粒径10μm以下の粒子含有率75質量%以上かつ粒径1μm以下の粒子含有率5〜20質量%である急結性混和剤。(2)さらに、アルカリ金属アルミン酸塩及び/又はアルカリ金属炭酸塩をアルミン酸カルシウム含有量100質量部に対し、8〜20質量部含有する前記(1)の急結性混和剤。(3)吹付けモルタル又はコンクリートに使用する前記(1)又は(2)の急結性混和剤。   That is, this invention is the quick setting admixture represented by following (1)-(3). (1) A rapid setting admixture containing 100 parts by mass of calcium aluminate and 35-100 parts by mass of gypsum, wherein the calcium aluminate has a particle content of 60 μ% or more and a particle size of 3 μm or less with a particle size of 15 μm or less. A quick-setting admixture having a particle content of 15 to 35% by mass, a gypsum particle content of 75% by mass or more and a particle content of 5 to 20% by mass of 1 μm or less. (2) The quick setting admixture according to (1), further comprising 8 to 20 parts by mass of an alkali metal aluminate and / or an alkali metal carbonate with respect to 100 parts by mass of calcium aluminate. (3) The rapid setting admixture according to (1) or (2), which is used for sprayed mortar or concrete.

本発明によれば、モルタルやコンクリート等のセメント系組成物に強い急結性を付与しつつ、凝結始発時間や凝結速度等の凝結性を適度に調整することができるため、過度の瞬結化や仕上げ作業等に要する可使時間の不足或いは硬化の遅延といったことを容易に改善でき、高い初期強度発現性と長期強度の伸びも良いセメント系組成物を得ることができる。特に、本発明による吹付けモルタルやコンクリートでは強い付着性と長期に亘る高い強度発現性を具備すると共に、吹付後のモルタルやコンクリートを仕上げ調整するため施工作業も可能である。   According to the present invention, it is possible to appropriately adjust the setting properties such as the setting start time and setting speed while imparting strong quick setting property to a cement-based composition such as mortar and concrete, so that excessive instantaneous setting In addition, it is possible to easily improve the shortage of pot life required for finishing work and the like, or delay in curing, and a cement-based composition having high initial strength development and good long-term strength elongation can be obtained. In particular, the sprayed mortar or concrete according to the present invention has strong adhesion and high strength development over a long period of time, and can also perform construction work to finish and adjust the mortar and concrete after spraying.

本発明の急結性混和剤に含有するアルミン酸カルシウムは、化学成分としてCaOとAl23からなる結晶質又はガラス化が進んだ構造の水和活性物質であれば何れのものでも良い。また、CaOとAl23に加えて他の化学成分が加わった化合物、固溶体若しくはガラス質物質又はこれらの混合物等であっても、本発明の効果を実質喪失させない限り何れのものでも良い。前者は、例えば12CaO・7Al23、CaO・Al23、3CaO・Al23、CaO・2Al23、CaO・6Al23等が挙げられ、後者は、例えば4CaO・3Al23・SO3、11CaO・7Al23・CaF2、Na2O・8CaO・3Al23等を挙げることができるが、記載例に限定されるものではない。好ましくは、水和活性が高く、急結性に優れていることから、CaOとAl23の含有モル比がCaO/Al23=1.8以上でガラス化率90%以上のアルミン酸カルシウムが良い。より好ましくは、含有モル比CaO/Al23=2.0〜2.3でガラス化率90%以上のアルミン酸カルシウムとする。ガラス化率90%以上のアルミン酸カルシウムを得る方法は特に限定されない。一例を示すと、所定のCaOとAl23の含有モル比となるようにCaO又はCaO源となる原料とAl23又はAl23源となる原料を配合した混合物を、これが溶融するまで加熱し、次いで水中や散水による急冷以外の任意の方法で急冷することで得られる。 The calcium aluminate contained in the rapid setting admixture of the present invention may be any hydrated active substance having a crystal structure or advanced vitrification composed of CaO and Al 2 O 3 as chemical components. Further, a compound, a solid solution, a glassy substance, a mixture thereof, or the like in which other chemical components are added in addition to CaO and Al 2 O 3 may be used as long as the effect of the present invention is not substantially lost. The former, for example, 12CaO · 7Al 2 O 3, CaO · Al 2 O 3, 3CaO · Al 2 O 3, CaO · 2Al 2 O 3, CaO · 6Al 2 O 3 and the like, the latter, for example, 4CaO · 3Al 2 O 3 .SO 3 , 11CaO.7Al 2 O 3 .CaF 2 , Na 2 O.8CaO.3Al 2 O 3 and the like can be mentioned, but are not limited to the description examples. Preferably, since the hydration activity is high and the quick setting property is excellent, the content molar ratio of CaO and Al 2 O 3 is CaO / Al 2 O 3 = 1.8 or more and the vitrification rate is 90% or more. Calcium acid is good. More preferably, calcium aluminate having a molar ratio of CaO / Al 2 O 3 = 2.0 to 2.3 and a vitrification rate of 90% or more is used. A method for obtaining calcium aluminate having a vitrification ratio of 90% or more is not particularly limited. As an example, this is a mixture of a raw material that becomes a CaO or CaO source and a raw material that becomes an Al 2 O 3 or Al 2 O 3 source so as to have a predetermined molar ratio of CaO and Al 2 O 3. Until it is heated, and then quenched by any method other than quenching by water or sprinkling.

また、本発明で含有使用するアルミン酸カルシウムは、粒径15μm以下の粒子含有率60質量%以上かつ粒径3μm以下の粒子含有率15〜35質量%のアルミン酸カルシウムであることも必須とする。好ましくは、粒径15μm以下の粒子含有率70質量%以上かつ粒径3μm以下の粒子含有率22〜28質量%のアルミン酸カルシウムとする。より好ましくは、さらに最大粒径が50μm以下のものとする。粒径15μm以下の粒子含有率60質量%未満であると反応活性が低下し、初期強度発現性が低下し過ぎるため好ましくない。また、粒径3μm以下の粒子含有率35質量%を超える場合は瞬結性が強過ぎて、付着性が低下するので好ましくなく、また粒径3μm以下の粒子含有率15質量%未満では初期強度発現性が低下するので好ましくない。   In addition, it is essential that the calcium aluminate used in the present invention is calcium aluminate having a particle content of 60% by mass or more with a particle size of 15 μm or less and a particle content of 15 to 35% by mass with a particle size of 3 μm or less. . Preferably, the calcium aluminate has a particle content of 70% by mass or more with a particle size of 15 μm or less and a particle content of 22 to 28% by mass with a particle size of 3 μm or less. More preferably, the maximum particle size is 50 μm or less. When the particle content is less than 60% by mass with a particle size of 15 μm or less, the reaction activity is lowered, and the initial strength development property is excessively lowered. Further, if the particle content exceeds 35% by mass with a particle size of 3 μm or less, the instantaneous setting property is too strong and the adhesion decreases, which is not preferable, and if the particle content with a particle size of 3 μm or less is less than 15% by mass, the initial strength Since expression is reduced, it is not preferable.

本発明の急結性混和剤に含有する石膏は、無水石膏、半水石膏、二水石膏又は硫酸カルシウムの何れでも良く、また2種以上の併用も可能である。好ましくは、強度発現性に優れることから、無水石膏を使用する。含有使用する石膏は、粒径10μm以下の粒子含有率75質量%以上かつ粒径1μm以下の粒子含有率5〜20質量%の石膏であることを必須とする。好ましくは粒径10μm以下の粒子含有率85質量%以上かつ粒径1μm以下の粒子含有率10〜15質量%の石膏とする。粒径10μm以下の粒子含有率75質量%未満の石膏では高い初期強度発現性が得られないので好ましくない。より好ましくは、さらに最大粒径が25μm以下のものとする。また粒径1μm以下の粒子含有率5質量%未満でも初期強度発現性や付着性が向上し難くなるため好ましくない。また粒径1μm以下の粒子含有率が20質量%以上では急結性の抑制作用が低下し、吹付け後の吹付物表面の仕上げ作業が行い難いので好ましくない。石膏の含有は、アルミン酸カルシウムによる強い急結性を抑制し、吹付後のモルタル・コンクリートの表面を仕上げ施工するための作業時間を確保し易くなる他、中長期の強度発現性を大きく向上させる作用がある。急結性混和剤中の石膏含有量はアルミン酸カルシウムの含有量100質量部に対し、35〜100質量部とする。好ましくは、60〜75質量部とする。石膏含有量35質量部未満では長期強度発現性が向上し難くなるので好ましくなく、石膏含有量100質量部を超えると急結性が不足し、付着性が低下することがあるので好ましくない。   The gypsum contained in the rapid setting admixture of the present invention may be any of anhydrous gypsum, hemihydrate gypsum, dihydrate gypsum, or calcium sulfate, and two or more types may be used in combination. Preferably, anhydrous gypsum is used because of excellent strength development. It is essential that the gypsum to be used is a gypsum having a particle content of 75% by mass or more with a particle size of 10 μm or less and a particle content of 5 to 20% by mass with a particle size of 1 μm or less. Preferably, the gypsum has a particle content of 85% by mass or more with a particle size of 10 μm or less and a particle content of 10 to 15% by mass with a particle size of 1 μm or less. A gypsum having a particle size of less than 75% by mass with a particle size of 10 μm or less is not preferable because high initial strength cannot be obtained. More preferably, the maximum particle size is 25 μm or less. Further, if the particle content is less than 5% by mass with a particle size of 1 μm or less, the initial strength development and adhesion are difficult to improve, such being undesirable. On the other hand, when the content of particles having a particle size of 1 μm or less is 20% by mass or more, the action of suppressing rapid setting is reduced, and it is difficult to finish the surface of the sprayed product after spraying. The inclusion of gypsum suppresses strong rapid setting due to calcium aluminate, makes it easy to secure work time for finishing the surface of mortar / concrete after spraying, and greatly improves medium- and long-term strength development. There is an effect. The gypsum content in the quick setting admixture is 35 to 100 parts by mass with respect to 100 parts by mass of the calcium aluminate content. Preferably, it is 60-75 mass parts. If the gypsum content is less than 35 parts by mass, the long-term strength development is difficult to improve, and if the gypsum content exceeds 100 parts by mass, the quick setting property is insufficient and the adhesion may be lowered.

本発明の急結性混和剤は、好ましくはアルカリ金属アルミン酸塩及び/又はアルカリ金属炭酸塩をカルシウムアルミネート含有量100質量部に対し、8〜20質量部含有するものである。8質量部未満では含有効果が実質的に得られず、また20質量部を超える量を含有させても含有効果は殆ど向上せず不経済である。アルカリ金属アルミン酸塩及び/又はアルカリ金属炭酸塩の含有により初期凝結が促進され、凝結始発時間を早くすることができる。アルカリ金属アルミン酸塩の具体例としては、アルミン酸リチウム、アルミン酸カリウム、アルミン酸ナトリウム等が挙げられる。好ましくは、アルミン酸ナトリウムを使用するが、限定されるものではない。また、アルカリ金属炭酸塩の具体例として、炭酸リチウム、炭酸カリウム、炭酸ナトリウム等を挙げることができる。アルカリ金属アルミン酸塩を単独使用する場合の好ましい含有量はカルシウムアルミネート含有量100質量部に対し、10〜20質量部であり、より好ましい含有量は12〜16質量部である。また、アルカリ金属炭酸塩を単独使用する場合の好ましい含有量はカルシウムアルミネート含有量100質量部に対し、8〜20質量部であり、より好ましい含有量は12〜16質量部である。両者を併用する場合のそれぞれの含有比は特に制限されない。好ましくは概ね均等質量とする。   The quick setting admixture of the present invention preferably contains 8 to 20 parts by mass of alkali metal aluminate and / or alkali metal carbonate with respect to 100 parts by mass of calcium aluminate. If the amount is less than 8 parts by mass, the content effect is not substantially obtained, and even if the content exceeds 20 parts by mass, the content effect is hardly improved, which is uneconomical. By containing the alkali metal aluminate and / or alkali metal carbonate, the initial setting is promoted, and the initial setting time can be shortened. Specific examples of the alkali metal aluminate include lithium aluminate, potassium aluminate, sodium aluminate and the like. Preferably, sodium aluminate is used, but it is not limited. Specific examples of alkali metal carbonates include lithium carbonate, potassium carbonate, sodium carbonate and the like. When alkali metal aluminate is used alone, the preferable content is 10 to 20 parts by mass with respect to 100 parts by mass of calcium aluminate, and the more preferable content is 12 to 16 parts by mass. Moreover, preferable content in the case of using an alkali metal carbonate alone is 8-20 mass parts with respect to 100 mass parts of calcium aluminate contents, and more preferable content is 12-16 mass parts. Each content ratio in the case of using both together is not particularly limited. Preferably, the mass is approximately equal.

本発明の急結性混和剤は前記成分に加えて、本発明の効果を喪失させない範囲で他の成分を含有するものであっても良い。含有可能な成分として、モルタルやコンクリートに使用できる減水剤類(高性能減水剤、高性能AE減水剤又は分散剤或いは流動化剤と称されているものも含む。)、粉塵低減剤、収縮低減剤、膨張材等を挙げることができる。好ましくは、付着性と強度発現性が共に向上し易くなるため高性能減水剤を含むものが良い。使用可能な減水剤の有効成分は限定されず、例えば、アルカリアリルスルホン酸系、ナフタレンスルホン酸系、メラミンスルホン酸系又はポリカルボン酸系等の高性能減水剤が挙げられる。   In addition to the above components, the quick setting admixture of the present invention may contain other components as long as the effects of the present invention are not lost. Containable components include water reducing agents that can be used in mortar and concrete (including those called high performance water reducing agents, high performance AE water reducing agents, dispersants or fluidizing agents), dust reducing agents, shrinkage reduction. An agent, an expansion material, etc. can be mentioned. Preferably, those containing a high-performance water reducing agent are preferred because both adhesion and strength development are easily improved. The active ingredient of the water reducing agent that can be used is not limited, and examples thereof include high performance water reducing agents such as alkali allyl sulfonic acid, naphthalene sulfonic acid, melamine sulfonic acid, and polycarboxylic acid.

また、本発明の急結性混和剤の粉末度は特に制限されないが、好ましくは適度な反応活性を備える上で、粉末度は4000〜8000cm2/gのブレーン比表面積とする。この粉末度から外れるものでも幾分弱くはなるが本発明による効果を奏することは可能である。ブレーン比表面積4000cm2/g未満では反応活性が緩慢化し、急結性や早期強度発現性が低下することがあり、ブレーン比表面積8000cm2/gを超えると付着性の低下や吹付後のモルタルやコンクリートの表面を仕上げ調整するための作業時間が確保できないことがある。 Further, the fineness of the quick setting admixture of the present invention is not particularly limited, but preferably the fineness is set to 4000 to 8000 cm 2 / g of Blaine specific surface area for providing appropriate reaction activity. Even if it falls outside this fineness, the effect of the present invention can be obtained although it is somewhat weakened. When the Blaine specific surface area is less than 4000 cm 2 / g, the reaction activity is slowed down, and the rapid setting property and early strength development may be reduced. When the Blaine specific surface area exceeds 8000 cm 2 / g, the adhesiveness is lowered, the mortar after spraying, The working time for finishing and adjusting the concrete surface may not be secured.

本発明の急結性混和剤は、吹付け用のモルタル(セメントペーストを含む。)やコンクリートに好適に使用できる。その使用方法は特に限定されないが、一例を示すと、セメント又はセメントと骨材に、必要に応じて他の混和剤・材も添加し、混練水を加えて混練して得たベースモルタルやベースコンクリートに、好ましくは吹付施工直前に、本発明の急結性混和剤を添加する。急結性混和剤の添加量は、吹付けモルタルやコンクリート中のセメント含有量100質量部に対し、6〜15質量部が推奨される。6質量部未満では急結性や初期強度発現性が十分得られないことがあるため適当ではない。また、15質量部を超える含有量では十分付着しないことがあったり、吹付け後のモルタルやコンクリートの表面を仕上げ調整する施工作業が行えないことがあるので適当ではない。また、本発明の急結性混和剤は、吹付け用以外のモルタル、コンクリート、セメントペースト又は水硬性組成物スラリー等に使用することは特に制限されない。   The rapid setting admixture of the present invention can be suitably used for spraying mortar (including cement paste) and concrete. The method of use is not particularly limited. For example, base mortar or base obtained by adding other admixtures / materials to cement or cement and aggregate as necessary, and kneading with kneaded water. The rapid setting admixture of the present invention is added to concrete, preferably immediately before spraying. The addition amount of the quick setting admixture is recommended to be 6 to 15 parts by mass with respect to 100 parts by mass of the cement content in sprayed mortar or concrete. If the amount is less than 6 parts by mass, the quick setting property and the initial strength development property may not be sufficiently obtained. In addition, if the content exceeds 15 parts by mass, it may not adhere sufficiently, or it may not be possible to perform construction work for finishing and adjusting the surface of mortar or concrete after spraying. In addition, the rapid setting admixture of the present invention is not particularly limited for use in mortar, concrete, cement paste or hydraulic composition slurry other than spraying.

以下、本発明を実施例によって具体的に説明するが、本発明は記載した実施例に限定されるものではない。   EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the described examples.

[アルミン酸カルシウムの作製]
何れも市販粉末試薬の、CaCO3及びAl23を用い、ヘンシェル型混合機を使用し、CaO及びAl23の含有モル比(CaO/Al23)の値が2.2となるように、また、一部は値が2.4となるように調合した。調合物は電気炉で約1600℃(±50℃)に加熱し、当該温度で60分間保持した後、直ちに炉外に取出した。取出した加熱物表面に冷却用の窒素ガスを流速約30ml/秒で吹付けて急冷し、アルミン酸カルシウムを得た。得られた急冷物は、全鋼製のボールミルで粉砕し、市販の分級装置にかけ、表1の粒度構成になるよう調整せしめたアルミン酸カルシウムを作製した。また、このアルミン酸カルシウムのガラス化率を、粉末エックス線回折装置を用い、質量がM1のアルミン酸カルシウムに含まれる各鉱物の質量を内部標準法等で定量し、定量できた含有鉱物相の総和質量(M2)を算出し、残部が純ガラス相と見なし、次式でガラス化率を算出した結果、何れもそのガラス化率は99%超であった。
ガラス化率(%)=(1−M2/M1)×100
[Production of calcium aluminate]
Both use commercially available powder reagents, CaCO 3 and Al 2 O 3 , use a Henschel type mixer, and the content molar ratio of CaO and Al 2 O 3 (CaO / Al 2 O 3 ) is 2.2. In addition, a part was prepared so that the value was 2.4. The formulation was heated to about 1600 ° C. (± 50 ° C.) in an electric furnace, held at that temperature for 60 minutes, and immediately taken out of the furnace. Nitrogen for cooling was blown onto the surface of the heated product taken out at a flow rate of about 30 ml / second to rapidly cool to obtain calcium aluminate. The obtained rapidly cooled product was pulverized with a ball mill made of all steel, and applied to a commercially available classifier to produce calcium aluminate adjusted to have the particle size constitution shown in Table 1. In addition, the vitrification rate of this calcium aluminate is determined by using an X-ray powder diffraction apparatus, and the mass of each mineral contained in calcium aluminate having a mass of M1 is quantified by an internal standard method or the like. The mass (M2) was calculated, the remainder was regarded as a pure glass phase, and the vitrification rate was calculated by the following formula. As a result, in all cases, the vitrification rate was over 99%.
Vitrification rate (%) = (1-M2 / M1) × 100

[混和剤の作製]
前記作製のアルミン酸カルシウム粉末と、粉砕・分級処理により表2の粒度構成に調整した市販のII型無水石膏、アルミン酸ナトリウム(市販粉末試薬)、炭酸ナトリウム(市販粉末試薬)、クエン酸(市販試薬)、ポリカルボン酸系高性能減水剤(市販品)から選定される材料を表3の配合量となるようヘンシェルミキサで180秒間乾式混合し、混和剤を作製した。
[Preparation of admixture]
Calcium aluminate powder prepared as described above, commercially available type II anhydrous gypsum adjusted to the particle size constitution of Table 2 by pulverization and classification, sodium aluminate (commercial powder reagent), sodium carbonate (commercial powder reagent), citric acid (commercially available) Reagent) and a polycarboxylic acid-based high-performance water reducing agent (commercially available) were dry-mixed for 180 seconds with a Henschel mixer so as to have the blending amounts shown in Table 3 to prepare an admixture.

[急結性の評価]
市販の普通ポルトランドセメント400g及び水200gを内容量500ccの底付円筒容器に入れ、ハンドミキサで1分間混合した後、温度20℃の屋内で30分静置した。この静置後、ハンドミキサで1分間再混合し、前記作製の混和剤を48g添加し、さらに5秒間攪拌してペーストを作製した。混和剤添加30秒後のペーストに対し、20℃でのプロクター貫入抵抗値を測定することで初期の急結性の評価を行った。同様に混和剤添加1分及び6分経過後のペーストのプロクター貫入抵抗値も測定した。測定方法は、土木学会コンクリート標準指方書「吹付けコンクリート用急結剤品質規格」付属書「貫入抵抗によるモルタルの瞬結時間測定方法」に準拠し、断面積0.125cm2のプロクター針を使用して行った。この測定結果を表4に表す。また、一部のペーストは、その作製からプロクター貫入抵抗値の測定に至るまでの温度を全て10℃で行った以外は前記と同じ条件とし、そのプロクター貫入抵抗値を測定した。この10℃の測定結果は表5に表す。
[Evaluation of quick setting]
400 g of commercially available ordinary Portland cement and 200 g of water were placed in a bottomed cylindrical container having an internal capacity of 500 cc, mixed with a hand mixer for 1 minute, and then allowed to stand indoors at a temperature of 20 ° C. for 30 minutes. After this standing, the mixture was remixed for 1 minute with a hand mixer, 48 g of the admixture prepared above was added, and the mixture was further stirred for 5 seconds to prepare a paste. The initial setting property was evaluated by measuring the Procter penetration resistance value at 20 ° C. for the paste 30 seconds after the admixture was added. Similarly, the Procter penetration resistance value of the paste after the addition of the admixture 1 minute and 6 minutes was also measured. The measurement method conforms to the Japan Society of Civil Engineers Concrete Standard Specification "Quality Standards for Spray Concrete" Appendix "Method for Measuring Instantaneous Mortation Time of Mortar Using Penetration Resistance" and a Proctor Needle with a Cross Section of 0.125cm 2 Done using. The measurement results are shown in Table 4. Further, some of the pastes were measured under the same conditions as described above except that the temperature from the production to the measurement of the proctor penetration resistance value was all 10 ° C., and the proctor penetration resistance value was measured. The measurement results at 10 ° C. are shown in Table 5.

[付着性の評価]
市販の普通ポルトランドセメント400g及び水200gを内容量500ccの底付円筒容器に入れ、ハンドミキサで1分間混合した後、温度20℃の屋内で30分静置した。この静置後、ハンドミキサで1分間再混合し、前記作製の混和剤を48g添加し、さらに5秒間攪拌してペーストを作製した。作製後のペーストを直ちに吹付機(市販のモルタルガン)に移し、20℃の環境下で150cm離れた場所の地面に垂直に設置した2m四方のコンクリート製平滑壁面に向かって吹付けた。目視観察で、壁面に吹付けたペーストが垂れや剥落・剥離が見られずに付着し続けたものを付着性が「良好」と判定し、それ以外の状態になったものは全て付着性が「不良」と判定することで付着性を評価した。この結果を表4に表す。また、一部のペーストは、その作製から壁面への吹付けによる付着状態の目視観察までの温度を全て10℃で行った以外は前記と同じ条件とし、その付着性を評価した。この結果は表5に表す。
[Evaluation of adhesion]
400 g of commercially available ordinary Portland cement and 200 g of water were placed in a bottomed cylindrical container having an internal capacity of 500 cc, mixed with a hand mixer for 1 minute, and then allowed to stand indoors at a temperature of 20 ° C. for 30 minutes. After this standing, the mixture was remixed for 1 minute with a hand mixer, 48 g of the admixture prepared above was added, and the mixture was further stirred for 5 seconds to prepare a paste. The prepared paste was immediately transferred to a spraying machine (commercially available mortar gun), and sprayed toward a 2 m square concrete smooth wall surface installed vertically on the ground at a distance of 150 cm in an environment of 20 ° C. By visual observation, if the paste sprayed on the wall surface continues to adhere without dripping, peeling or peeling, it is judged that the adhesiveness is “good”, and all the other conditions are adhesive. Adhesiveness was evaluated by determining “bad”. The results are shown in Table 4. In addition, the adhesiveness of some pastes was evaluated under the same conditions as described above except that the temperature from the preparation to the visual observation of the adhesion state by spraying on the wall surface was all 10 ° C. The results are shown in Table 5.

[強度発現性の評価]
市販の普通ポルトランドセメント450g、JIS標準砂1350g及び水225gをホバートミキサに一括投入し、1分間混合した後、20℃の屋内に30分間静置した。静置後1分間再混合した後、前記作製の混和剤を40.5g添加し、さらに10秒間混合することでモルタルを作製した。作製したモルタルは直ちに、内寸40×40×160mmの成形用型枠に充填し、これを20℃の屋内で所定時間静置し、静置後に脱型して材齢1日、7日及び28日のモルタル硬化成形体を得た。この成形体の20℃での一軸圧縮強度をアムスラー式圧縮強度試験機を用いて測定した。この結果を表4に表す。また、一部のモルタルについてはその作製からモルタル硬化成形体に対する一軸圧縮強度の測定に至るまでの温度を全て10℃で行った以外は前記と同じ条件とし、その材齢1日及び28日の一軸圧縮強度を測定した。この10℃の一軸圧縮強度の測定結果を表5に表す。
[Evaluation of strength development]
Commercially available ordinary Portland cement (450 g), JIS standard sand (1350 g), and water (225 g) were put together into a Hobart mixer, mixed for 1 minute, and then allowed to stand indoors at 20 ° C. for 30 minutes. After standing for 1 minute and remixing, 40.5 g of the admixture prepared above was added and mixed for 10 seconds to prepare a mortar. The produced mortar is immediately filled into a molding mold with an inner size of 40 × 40 × 160 mm, left standing in a room at 20 ° C. for a predetermined time, removed from the mold after standing, and ages 1 day, 7 days and A 28-day mortar-cured molded body was obtained. The uniaxial compressive strength at 20 ° C. of this molded body was measured using an Amsler type compressive strength tester. The results are shown in Table 4. In addition, for some mortars, the same conditions as described above except that the temperature from the preparation to the measurement of the uniaxial compressive strength for the mortar-cured molded body was all performed at 10 ° C. Uniaxial compressive strength was measured. The measurement results of the uniaxial compressive strength at 10 ° C. are shown in Table 5.

[混和剤の混和量に関する諸試験]
市販の普通ポルトランドセメント400g及び水200gを内容量500ccの底付円筒容器に入れ、ハンドミキサで1分間混合した後、温度20℃の屋内で30分静置した。静置後、ハンドミキサで1分間再混合し、前記作製の混和剤をセメント100質量部に対し表6に表す量となるよう添加した。添加後、さらに5秒間攪拌してペーストを作製した。混和剤添加30秒後のペーストに対し、20℃でのプロクター貫入抵抗値を測定することで初期の急結性の評価を行った。同様に混和剤添加1分及び6分経過後のペーストのプロクター貫入抵抗値を測定した。測定方法は、前記の「急結性の評価」と同じ方法で行った。また、同様に作製したペーストを直ちに吹付機(市販のモルタルガン)に移し、20℃の環境下で150cm離れた場所の地面に垂直に設置した2m四方のコンクリート製平滑壁面に向かって吹付けた。目視観察で、壁面に吹付けたセメントペーストが垂れや剥落・剥離が見られずに付着し続たものを吹付性が「良好」と判定し、それ以外の状態になったものは全て付着性が「不良」と判定することで付着性を評価した。以上の評価結果は表6に表す。
[Various tests on admixture of admixture]
400 g of commercially available ordinary Portland cement and 200 g of water were placed in a bottomed cylindrical container having an internal capacity of 500 cc, mixed with a hand mixer for 1 minute, and then allowed to stand indoors at a temperature of 20 ° C. for 30 minutes. After standing, the mixture was remixed for 1 minute with a hand mixer, and the admixture prepared above was added to the amount shown in Table 6 with respect to 100 parts by mass of cement. After the addition, the mixture was further stirred for 5 seconds to prepare a paste. The initial setting property was evaluated by measuring the Procter penetration resistance value at 20 ° C. for the paste 30 seconds after the admixture was added. Similarly, the Procter penetration resistance value of the paste after the addition of the admixture 1 minute and 6 minutes was measured. The measurement method was the same as the above-mentioned “Evaluation of quick setting”. Also, the paste prepared in the same manner was immediately transferred to a spraying machine (commercially available mortar gun), and sprayed toward a 2 m square concrete smooth wall surface installed vertically on the ground at a distance of 150 cm in an environment of 20 ° C. . By visual observation, the cement paste sprayed on the wall surface was judged to be “good” if the cement paste adhered without any sag, peeling or peeling, and all the other conditions were adherent. Was judged as “bad” to evaluate adhesion. The above evaluation results are shown in Table 6.

表4の結果から、本発明の混和剤を用いたペーストは、何れも、混和剤添加から少なくとも1分経過時まではプロクター貫入抵抗値が十分低く、しかも経時上昇傾向が見られることから、吹付後も概ね1分余は表面仕上げ施工が可能なことがわかる。これに対し、本発明から外れるペーストは、アルミン酸カルシウムに石膏を配合し、さらに他の凝結促進や早強成分を配合したものでも、混和剤添加1分経過で既にプロクター貫入抵抗値が上限近傍に達し、瞬結化が見られ、吹付後の仕上げ作業には適さない(例えば、No.10−20)か、過剰瞬結によってかえって付着性が失われる(例えば、No.19−20)ことがわかる。さらに、表5の結果から本発明の混和剤を用いたペーストは、10℃の比較的低温でも20℃と同様に、混和剤添加から少なくとも1分経過時まではプロクター貫入抵抗値が十分低いことから、吹付後に仕上げ施工を行うための作業性は確保可能なことがわかり、また、付着性や強度発現性とも20℃と殆ど遜色ない性状を発現できることがわかる。   From the results of Table 4, all pastes using the admixture of the present invention have a sufficiently low Procter penetration resistance value until at least 1 minute has elapsed since the addition of the admixture, and a tendency to increase with time is observed. After that, it can be seen that the surface finish can be applied for about 1 minute. On the other hand, the paste that is not included in the present invention is a mixture of calcium aluminate and gypsum, and further blended with other accelerating or early strength components, but the Procter penetration resistance value is already close to the upper limit after 1 minute of admixture addition. In this case, it is not suitable for finishing work after spraying (for example, No. 10-20), or the adhesiveness is lost due to excessive instantaneous setting (for example, No. 19-20). I understand. Furthermore, from the results of Table 5, the paste using the admixture of the present invention has a sufficiently low Proctor penetration resistance value at least 1 minute after the admixture addition, even at a relatively low temperature of 10 ° C., as at 20 ° C. From this, it can be seen that the workability for performing the finishing work after spraying can be ensured, and it can be seen that the adhesion and strength development properties can be expressed at 20 ° C., which is almost inferior.

Claims (3)

アルミン酸カルシウム100質量部と石膏35〜100質量部を含有する急結性混和剤であって、アルミン酸カルシウムが粒径15μm以下の粒子含有率60質量%以上かつ粒径3μm以下の粒子含有率15〜35質量%であり、石膏が粒径10μm以下の粒子含有率75質量%以上かつ粒径1μm以下の粒子含有率5〜20質量%である急結性混和剤。 A quick-setting admixture containing 100 parts by mass of calcium aluminate and 35 to 100 parts by mass of gypsum, wherein the calcium aluminate has a particle content of 60 μ% or more and a particle size of 3 μm or less with a particle size of 15 μm or less. A quick-setting admixture having a particle content of 15 to 35% by mass, a gypsum particle content of 75% by mass or more and a particle size of 5 to 20% by mass of 1 μm or less. さらに、アルカリ金属アルミン酸塩及び/又はアルカリ金属炭酸塩をアルミン酸カルシウム含有量100質量部に対し、8〜20質量部含有する請求項1記載の急結性混和剤。 Furthermore, the rapid setting admixture of Claim 1 which contains alkali metal aluminate and / or alkali metal carbonate 8-20 mass parts with respect to 100 mass parts of calcium aluminate content. 吹付けモルタル又はコンクリートに使用する請求項1又は2記載の急結性混和剤。 The quick setting admixture according to claim 1 or 2 used for spraying mortar or concrete.
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