JP2014152055A - Liquid quick setting agent, cement composition using the same, and spraying method - Google Patents
Liquid quick setting agent, cement composition using the same, and spraying method Download PDFInfo
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- 239000007788 liquid Substances 0.000 title claims abstract description 93
- 239000004568 cement Substances 0.000 title claims abstract description 41
- 239000000203 mixture Substances 0.000 title claims abstract description 15
- 238000005507 spraying Methods 0.000 title claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 55
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 28
- 229920005862 polyol Polymers 0.000 claims abstract description 27
- 150000003077 polyols Chemical class 0.000 claims abstract description 27
- 239000002270 dispersing agent Substances 0.000 claims abstract description 26
- -1 alcohol amines Chemical class 0.000 claims abstract description 12
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 12
- 238000003860 storage Methods 0.000 abstract description 15
- 238000011161 development Methods 0.000 abstract description 14
- 239000000725 suspension Substances 0.000 abstract description 4
- 239000004567 concrete Substances 0.000 description 20
- 239000004570 mortar (masonry) Substances 0.000 description 12
- 238000000926 separation method Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 230000001771 impaired effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- 230000007774 longterm Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 239000011378 shotcrete Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000013065 commercial product Substances 0.000 description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- RUFZJUYWZZUTJE-UHFFFAOYSA-J [F-].[F-].[F-].[F-].F.F.[Na+].[Al+3] Chemical compound [F-].[F-].[F-].[F-].F.F.[Na+].[Al+3] RUFZJUYWZZUTJE-UHFFFAOYSA-J 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 238000009412 basement excavation Methods 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- ASZZHBXPMOVHCU-UHFFFAOYSA-N 3,9-diazaspiro[5.5]undecane-2,4-dione Chemical compound C1C(=O)NC(=O)CC11CCNCC1 ASZZHBXPMOVHCU-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- IBZGBXXTIGCACK-UHFFFAOYSA-N 6,7,9,11-tetrahydroxy-9-(2-hydroxyacetyl)-4-methoxy-8,10-dihydro-7h-tetracene-5,12-dione Chemical compound C1C(O)(C(=O)CO)CC(O)C2=C1C(O)=C1C(=O)C(C=CC=C3OC)=C3C(=O)C1=C2O IBZGBXXTIGCACK-UHFFFAOYSA-N 0.000 description 1
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- NNDGIEARKHXAEO-UHFFFAOYSA-J [F-].[F-].[F-].[F-].F.F.[Al+3].[K+] Chemical compound [F-].[F-].[F-].[F-].F.F.[Al+3].[K+] NNDGIEARKHXAEO-UHFFFAOYSA-J 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012615 aggregate Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- DNEHKUCSURWDGO-UHFFFAOYSA-N aluminum sodium Chemical compound [Na].[Al] DNEHKUCSURWDGO-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229940070337 ammonium silicofluoride Drugs 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Description
本発明は、道路、鉄道、および導水路等のトンネルにおいて、露出した地山面へ吹付けるセメントコンクリートに使用する、液体急結剤、それを用いたセメント組成物および吹付け工法に関する。 The present invention relates to a liquid quick-setting agent, a cement composition using the same, and a spraying method used for cement concrete sprayed to an exposed natural ground surface in tunnels such as roads, railways, and conduits.
従来、トンネル掘削等、露出した地山の崩落を防止するために、急結剤をコンクリートに混合した急結性コンクリートの吹付け工法が用いられている（特許文献１）。
この工法は、通常、掘削工事現場に設置した計量混合プラントで、セメント、骨材、及び水を計量混合して吹付け用のコンクリートを調製し、アジテータ車で運搬し、コンクリートポンプで圧送し、途中に設けた合流管で他方から圧送された急結剤と混合して急結性吹付けコンクリートとし、地山面に所定の厚さになるまで吹付ける工法である。
Conventionally, in order to prevent collapse of exposed ground such as tunnel excavation, a rapid setting concrete spraying method in which a quick setting agent is mixed with concrete is used (Patent Document 1).
This method is usually a metering and mixing plant installed at the excavation site, and cement, aggregate, and water are metered and mixed to prepare concrete for spraying, transported with an agitator car, and pumped with a concrete pump. This is a method of mixing with a quick-setting agent pumped from the other in a confluence pipe provided in the middle to make a quick setting sprayed concrete and spraying it to the ground surface until it reaches a predetermined thickness.
急結剤としては、カルシウムアルミネートにアルカリ金属アルミン酸塩やアルカリ金属炭酸塩等を混合した粉体急結剤が使用される場合が多いが、近年、吹付け時の粉塵量が少なく、アルカリ薬傷がないという点から、アルミニウム塩を主成分とする酸性の液体急結剤の使用が望まれている（特許文献２〜６）。 As the quick setting agent, a powder quick setting agent in which alkali metal aluminate or alkali metal carbonate is mixed with calcium aluminate is often used. From the point that there is no chemical damage, it is desired to use an acidic liquid quick-setting agent mainly composed of an aluminum salt (Patent Documents 2 to 6).
液体急結剤に用いられるアルミニウム塩は硫酸塩である場合が多く、濃度が高いほど、急結性が高くなり、吹付け時の添加率を減らすこともできる。しかし、高濃度の液体急結剤は、長期間貯蔵すると、液中に析出物が生成したり、液がゲル化したり、懸濁粒子が沈降したりする場合があった。
硫酸アルミニウムの水に対する溶解度は、２０℃で２７％であり、共存する溶質や液温によって変動するが、溶解度以上の硫酸アルミニウムを含有する液体急結剤は、貯蔵安定性が悪く、製造直後の性状を保持することが難しい。液中に析出物が生成したり、液がゲル化したり、懸濁粒子が沈降したりした状態の液体急結剤を使用すると、ポンプが閉塞したり、コンクリートとの混合性が悪くなり、優れた性状が得られなかったりする場合があった。また、溶解度は液温によって変動するため、この貯蔵性の問題は、貯蔵する温度に依存し、高温または低温で貯蔵すると、より顕著に現れる場合があった。
In many cases, the aluminum salt used in the liquid quick-setting agent is a sulfate, and the higher the concentration, the higher the quick setting property, and the addition rate during spraying can be reduced. However, when the high-concentration liquid accelerator is stored for a long period of time, precipitates may be generated in the liquid, the liquid may gel, or suspended particles may settle.
The solubility of aluminum sulfate in water is 27% at 20 ° C. and varies depending on the coexisting solute and liquid temperature. However, the liquid accelerator containing aluminum sulfate having a solubility higher than the solubility is poor in storage stability and is immediately after production. It is difficult to maintain the properties. Use of a liquid quick-setting agent in which precipitates are formed in the liquid, the liquid is gelled, or suspended particles are settled, the pump is clogged, the mixing with concrete is poor, and it is excellent In some cases, the properties could not be obtained. In addition, since the solubility varies depending on the liquid temperature, this storage problem depends on the temperature to be stored, and may be more prominent when stored at high or low temperatures.
ポリオール系分散剤は、コンクリートやモルタルの減水剤として一般的に使用されており、コンクリートやモルタルに添加して、流動性を高めるために用いられる。ポリオール系分散剤は、セメント粒子の表面に付着することで、コンクリートやモルタルに分散性を付与する材料であり、特に、水／セメント比が低く、流動性が低いセメント組成物に対して有効である。
急結剤をセメント組成物に添加すると、流動性が急速に低下するため、急結剤とセメント組成物が十分に混合しない場合があるが、分散剤を併用することで、流動性が高まり、急結剤とセメント組成物の混合性が良好になる（特許文献７）。
また、硫酸アルミニウム、亜硫酸塩類、分散剤を含有してなるセメント混和材は知られているが、ここで言う分散剤とはポリカルボン酸系であり、本発明とは異なる（特許文献８）。また、既存の報告の硫酸アルミニウムの形態は、粉状あるいは水溶液状であるため、懸濁液のような高濃度の硫酸アルミニウムの液体に関する検討はなされていない。
A polyol-based dispersant is generally used as a water reducing agent for concrete or mortar, and is added to concrete or mortar to increase fluidity. A polyol-based dispersant is a material that imparts dispersibility to concrete or mortar by adhering to the surface of cement particles, and is particularly effective for cement compositions having a low water / cement ratio and low fluidity. is there.
When the quick setting agent is added to the cement composition, the fluidity decreases rapidly, so the quick setting agent and the cement composition may not be mixed well. Mixability of the quick setting agent and the cement composition is improved (Patent Document 7).
A cement admixture containing aluminum sulfate, sulfites, and a dispersant is known, but the dispersant referred to here is a polycarboxylic acid type and is different from the present invention (Patent Document 8). Moreover, since the form of the aluminum sulfate of the existing report is a powder form or aqueous solution form, examination about the liquid of high concentration aluminum sulfate like a suspension is not made | formed.
本発明は、前記課題を種々検討した結果、硫酸アルミニウムにポリオール系分散剤を含有させることで、液のゲル化や懸濁粒子の沈降を抑え、前述の課題を解決する知見を得て本発明を完成するに至った。 As a result of various studies on the above-mentioned problems, the present invention has obtained knowledge that the solution of the above-mentioned problems can be obtained by suppressing the gelation of liquid and sedimentation of suspended particles by containing a polyol-based dispersant in aluminum sulfate. It came to complete.
すなわち、本発明は、（１）硫酸アルミニウム、ポリオール系分散剤を含有し、−１０〜４０℃において体積割合で液の９０%以上が懸濁している液体急結剤、（２）液体急結剤の硫酸アルミニウム濃度が３０〜５０質量％、ポリオール系分散剤濃度が０．０１〜５質量％である（１）の液体急結剤、（３）さらに、フッ素化合物を含有する（１）または（２）のうちのいずれかの液体急結剤、（４）さらに、アルコールアミン類を含有する（１）〜（３）のうちのいずれかの液体急結剤、（５）（１）〜（４）のうちのいずれかの液体急結剤をセメント１００質量部に対し３〜２０質量部含有するセメント組成物、（６）（５）のセメント組成物を用いた吹付け工法、である。 That is, the present invention includes (1) a liquid quick-setting agent containing aluminum sulfate and a polyol-based dispersant and suspending 90% or more of the liquid in a volume ratio at −10 to 40 ° C., (2) liquid quick-setting (1) liquid quick-setting agent having an aluminum sulfate concentration of 30-50% by mass and a polyol-based dispersant concentration of 0.01-5% by mass, and (3) further containing a fluorine compound (1) or (2) The liquid quick setting agent in any one of (4), Furthermore, the liquid quick setting agent in any one of (1)-(3) containing alcohol amines, (5) (1)- (4) A cement composition containing 3 to 20 parts by mass of the liquid quick-setting agent with respect to 100 parts by mass of cement, and (6) a spraying method using the cement composition of (5). .
本発明の液体急結剤は、従来の硫酸アルミニウムを使用した液体急結剤に比べ、貯蔵安定性に優れる。さらに、この液体急結剤を使用することで、従来の液体急結剤に比べ、急結性吹付けコンクリートの急結性、強度発現性が向上するなどの効果を奏する。 The liquid quick setting agent of this invention is excellent in storage stability compared with the liquid quick setting agent which used the conventional aluminum sulfate. Furthermore, by using this liquid quick setting agent, the quick setting property of the quick setting sprayed concrete and the strength development property are exhibited as compared with the conventional liquid quick setting agent.
以下、本発明を詳細に説明する。
なお、本発明でいうコンクリートとは、セメントペースト、モルタル、およびセメントコンクリートの総称である。
なお、本発明で言う部や％は、特に規定のない限り質量基準である。
Hereinafter, the present invention will be described in detail.
In addition, the concrete as used in the field of this invention is a general term for cement paste, mortar, and cement concrete.
In the present invention, “parts” and “%” are based on mass unless otherwise specified.
本発明で使用する硫酸アルミニウムは、無水物、水和物、さらに水溶液のいずれの形態でも使用することができ、これらのうち１種または２種以上を使用することができる。この中では、液体中での分散性が優れるという点で、水和物が好ましく、１４水和物がより好ましい。
液体急結剤の硫酸アルミニウムの濃度は、３０〜５０％が好ましく、３３〜４０％がより好ましい。３０％未満ではコンクリートと混合した際に、優れた急結性が得られない場合があり、５０％を超えると液の貯蔵安定性が損なわれたり、長期強度発現性を阻害したりする場合がある。
The aluminum sulfate used in the present invention can be used in any form of an anhydride, a hydrate, and an aqueous solution, and one or more of these can be used. Among these, hydrates are preferable and 14 hydrates are more preferable in that the dispersibility in a liquid is excellent.
The concentration of aluminum sulfate in the liquid accelerator is preferably 30 to 50%, more preferably 33 to 40%. If it is less than 30%, excellent rapid setting properties may not be obtained when mixed with concrete, and if it exceeds 50%, the storage stability of the liquid may be impaired, or long-term strength development may be impaired. is there.
本発明で使用するポリオール系分散剤は、セメント系減水剤として一般に市販されているものが使用でき、変性したものであっても使用できる。また、ポリカルボン酸系化合物、リグニンスルホン酸化合物、グリシトール誘導体等とポリオールとの複合物であっても使用できる。
ポリオール系分散剤は、液体急結剤が懸濁状である場合に、不溶性粒子の凝集や沈降を抑え、分散性を向上させる。液体急結剤のポリオール系分散剤の濃度は、０．０１〜５％が好ましく、０．１〜３％がより好ましい。０．０１％未満では液の貯蔵安定性が損なわれる場合があり、５％以上ではコンクリートと混合した際に、強度発現性を阻害する場合がある。
As the polyol dispersant used in the present invention, commercially available cement-based water reducing agents can be used, and even modified ones can be used. Moreover, it can be used even if it is a composite of a polycarboxylic acid compound, a lignin sulfonic acid compound, a glycitol derivative or the like and a polyol.
The polyol-based dispersant suppresses aggregation and sedimentation of insoluble particles and improves dispersibility when the liquid quick-setting agent is in a suspended state. The concentration of the polyol-based dispersant in the liquid accelerator is preferably 0.01 to 5%, more preferably 0.1 to 3%. If it is less than 0.01%, the storage stability of the liquid may be impaired. If it is 5% or more, strength development may be impaired when mixed with concrete.
貯蔵安定性は、吹付け施工時にタンクから液体急結剤を圧送する際に重要となる性状である。液がゲル化したり、懸濁粒子が沈降したりすると、タンクからの排出が困難になる場合がある。また、排出できたとしても、懸濁粒子が沈降していると、液体急結剤の濃度が不均一であるため、吹付けたコンクリートの凝結性状や強度発現性にむらができる場合がある。
本発明の液体急結剤の貯蔵安定性を、分離度で評価すると、１０％以下が好ましく、５％以下がより好ましい。なお、ここで言う分離度とは、懸濁粒子が沈降して生じる上澄み液の、液全体に対する体積割合のことであり、分離度が極めて少ないことを、液が均一であると言う。
本発明の液体急結剤は、−１０〜４０℃において体積割合で液の９０%以上が懸濁しているものであり、この温度範囲で分離度が極めて少なく液が均一である。−１０℃未満では液が凝固する場合があり、４０℃を超えると分離度が大きくなる場合がある。
Storage stability is an important property when pumping a liquid quick-set agent from a tank during spraying. If the liquid gels or the suspended particles settle, it may be difficult to discharge from the tank. Even if the particles can be discharged, if the suspended particles are settled, the concentration of the liquid quick-setting agent is not uniform, so that there may be unevenness in the setting properties and strength development properties of the sprayed concrete.
When the storage stability of the liquid setting agent of the present invention is evaluated by the degree of separation, it is preferably 10% or less, more preferably 5% or less. The degree of separation referred to here is the volume ratio of the supernatant liquid produced by sedimentation of suspended particles to the whole liquid, and the fact that the degree of separation is extremely small means that the liquid is uniform.
In the liquid accelerator of the present invention, 90% or more of the liquid is suspended in a volume ratio at −10 to 40 ° C., and the liquid is uniform with a very low degree of separation in this temperature range. If it is less than −10 ° C., the liquid may solidify, and if it exceeds 40 ° C., the degree of separation may increase.
本発明の液体急結剤は、フッ素化合物を含有してもよい。フッ素化合物は、凝結性状や初期強度発現性を向上する目的で使用する。フッ素化合物は、水または酸性水溶液に溶解するものであれば、特に限定されるものではない。
フッ素化合物としては、フッ化水素、フッ化リチウム、フッ化ナトリウム、フッ化マグネシウム、フッ化カリウム、フッ化アルミニウム、フッ化亜鉛、フッ化アンモニウム、フッ化水素カリウム、三フッ化ホウ素、六フッ化アルミニウムナトリウム、六フッ化アルミニウムカリウム、ケイフッ化水素、ケイフッ化ナトリウム、ケイフッ化マグネシウム、ケイフッ化カリウム、ケイフッ化亜鉛、ケイフッ化アンモニウム等が挙げられ、これらのうち1種または2種以上が使用可能である。この中では、凝結性状が優れるという点で、六フッ化アルミニウムナトリウムが好ましい。
液体急結剤のフッ素化合物の濃度は、０．１〜１０％が好ましく、０．３〜８％がより好ましい。０．１％未満では凝結性状や初期強度発現性の向上が小さい場合があり、１０％を超えると貯蔵安定性が低下したり、長期強度発現性を阻害したりする場合がある。
The liquid quick setting agent of the present invention may contain a fluorine compound. The fluorine compound is used for the purpose of improving the setting property and initial strength development. The fluorine compound is not particularly limited as long as it is soluble in water or an acidic aqueous solution.
Fluorine compounds include hydrogen fluoride, lithium fluoride, sodium fluoride, magnesium fluoride, potassium fluoride, aluminum fluoride, zinc fluoride, ammonium fluoride, potassium hydrogen fluoride, boron trifluoride, hexafluoride Examples include aluminum sodium, potassium aluminum hexafluoride, hydrogen silicofluoride, sodium silicofluoride, magnesium silicofluoride, potassium silicofluoride, zinc silicofluoride, ammonium silicofluoride, and one or more of these can be used. is there. Among these, sodium aluminum hexafluoride is preferable in terms of excellent setting properties.
The concentration of the fluorine compound in the liquid accelerator is preferably 0.1 to 10%, and more preferably 0.3 to 8%. If it is less than 0.1%, the improvement of the setting property and initial strength development may be small, and if it exceeds 10%, the storage stability may be lowered or the long-term strength development may be inhibited.
本発明の液体急結剤は、アルコールアミン類を含有してもよい。アルコールアミン類は、凝結性状や初期強度発現性を向上する目的で使用する。アルコールアミン類は、水または酸性水溶液に溶解するものであれば、特に限定されるものではない。
アルコールアミン類とは、アミノ基とヒドロキシル基の両方を有する有機化合物の総称である。アルコールアミン類としては、エタノールアミン、ジエタノールアミン、トリエタノールアミン、Ｎ−メチルエタノールアミン等が挙げられ、これらのうち１種または２種以上が使用可能である。この中では、凝結性状が優れるという点で、ジエタノールアミンが好ましい。
液体急結剤のアルコールアミン類の濃度は０．１〜５％が好ましく、０．５〜３％がより好ましい。０．１％未満では凝結性状や初期強度発現性の向上が小さい場合があり、５％を超えると貯蔵安定性が損なわれたり、長期強度発現性を阻害したりする場合がある。
The liquid accelerating agent of the present invention may contain alcohol amines. Alcohol amines are used for the purpose of improving the setting properties and initial strength development. The alcohol amine is not particularly limited as long as it is soluble in water or an acidic aqueous solution.
Alcoholamines are a general term for organic compounds having both an amino group and a hydroxyl group. Examples of alcohol amines include ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, and the like, and one or more of these can be used. Among these, diethanolamine is preferable in that the setting property is excellent.
The concentration of alcohol amines in the liquid accelerator is preferably from 0.1 to 5%, more preferably from 0.5 to 3%. If it is less than 0.1%, the improvement of the setting properties and initial strength development may be small, and if it exceeds 5%, storage stability may be impaired or long-term strength development may be inhibited.
本発明のセメント組成物において、液体急結剤の使用量は、セメント１００部に対して、３〜２０部が好ましく、５〜１５部がより好ましく、７〜１０部が最も好ましい。３部未満では急結性吹付けコンクリートの急結性を促進しにくい場合があり、２０部を超えると長期強度発現性が損なわれる場合がある。 In the cement composition of the present invention, the amount of the liquid quick-setting agent is preferably 3 to 20 parts, more preferably 5 to 15 parts, and most preferably 7 to 10 parts with respect to 100 parts of cement. If it is less than 3 parts, it may be difficult to promote the quick setting property of the quick setting shot concrete, and if it exceeds 20 parts, long-term strength development may be impaired.
ここでセメントとは、特に限定されるものものではないが、市販されている普通、早強、中庸熱、および超早強などの各種ポルトランドセメントや、これら各種ポルトランドセメントにフライアッシュや高炉スラグなどを混合した各種混合セメントなどが挙げられ、これらを微粉末化して使用することも可能である。 Here, the cement is not particularly limited, but various commercially available portland cements such as normal strength, early strength, moderate heat, and ultra-early strength, fly ash, blast furnace slag, etc. Various mixed cements and the like mixed together can be mentioned, and these can be used after being pulverized.
本発明で使用するセメントコンクリートはセメントと骨材とを含有するものである。ここで骨材としては、吸水率が低く、骨材強度が高いものが好ましい。骨材の最大寸法は吹付けできれば特に限定されるものではない。
細骨材としては、川砂、山砂、石灰砂、及び珪砂などが使用可能であり、粗骨材としては、川砂利、山砂利、及び石灰砂利などが使用可能である。
The cement concrete used in the present invention contains cement and aggregate. Here, as the aggregate, those having low water absorption and high aggregate strength are preferable. The maximum dimension of the aggregate is not particularly limited as long as it can be sprayed.
River sand, mountain sand, lime sand, and quartz sand can be used as the fine aggregate, and river gravel, mountain gravel, lime gravel, and the like can be used as the coarse aggregate.
セメントコンクリートに使用する水の量は、強度発現性の面から水／セメント比で３５％以上が好ましく、４０〜５５％がより好ましい。３５％未満ではセメントコンクリートを十分に混合できない場合がある。 The amount of water used for the cement concrete is preferably 35% or more, more preferably 40 to 55% in terms of water / cement ratio in terms of strength development. If it is less than 35%, cement concrete may not be sufficiently mixed.
本発明の吹付け工法は、特に限定されるものではないが、湿式吹付け工法では、例えば、セメント、細骨剤、粗骨材、及び水を加えて練り混ぜ、空気圧送し、途中にＹ字管を設け、その一方から液体急結剤供給装置により圧送した液体急結剤を合流混合して急結性湿式吹付けコンクリートとしたものを吹付ける方法が挙げられる。 The spraying method of the present invention is not particularly limited, but in the wet spraying method, for example, cement, fine bone, coarse aggregate, and water are added and mixed, pneumatically fed, and Y in the middle. There is a method in which a tube is provided and a liquid quick setting agent pumped from one side by a liquid quick setting agent supply apparatus is mixed and mixed to form a quick setting wet spray concrete.
また、液体急結剤を圧送する圧送空気の圧力は、コンクリートが液体急結剤の圧送管内に混入した際に圧送管内が閉塞しないように、コンクリートの圧送圧力より０．０１〜０．３ＭＰａ高いことが好ましい。 Moreover, the pressure of the pumping air for pumping the liquid quick-setting agent is 0.01 to 0.3 MPa higher than the pumping pressure of the concrete so that the inside of the pumping pipe is not blocked when the concrete is mixed in the pumping pipe of the liquid quick-setting agent. It is preferable.
以下、実施例に基づき本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail based on examples.
「実験例１」
硫酸アルミニウムとポリオール系分散剤を、表１に示す濃度になるように添加し、１時間攪拌することで、種々の液体急結剤を調製した。また、攪拌後、液を静置し、液の分離度を評価した。結果を表１に併記する。なお、比較例として、ポリオール系分散剤を添加しない硫酸アルミニウム２５％水溶液と３０％懸濁液も評価した。
"Experiment 1"
Aluminum sulfate and a polyol-based dispersant were added so as to have the concentrations shown in Table 1, and stirred for 1 hour to prepare various liquid quick setting agents. Further, after stirring, the liquid was allowed to stand and the degree of separation of the liquid was evaluated. The results are also shown in Table 1. In addition, as a comparative example, a 25% aluminum sulfate aqueous solution and a 30% suspension without adding a polyol-based dispersant were also evaluated.
＜使用材料＞
硫酸アルミニウム：硫酸アルミニウム１４水和物、粉末、市販品
ポリオール系分散剤Ａ：ＢＡＳＦジャパン社製、商品名「ポゾリスＮｏ．７０Ｌ」、高変性ポリオール複合体
ポリオール系分散剤Ｂ：日本シーカ社製、商品名「プラストクリート３０Ｎ」、変性ポリオールとポリカルボン酸系化合物
<Materials used>
Aluminum sulfate: Aluminum sulfate 14 hydrate, powder, commercially available polyol-based dispersant A: manufactured by BASF Japan, trade name “Pozoris No. 70L”, highly modified polyol complex polyol-based dispersant B: manufactured by Nippon Seika Co., Ltd. Product name "Plastocrete 30N", modified polyol and polycarboxylic acid compound
＜測定条件＞
試験環境温度：２０℃に設定。
分離度：液全体に対する懸濁相の体積割合をメスシリンダーで評価。分離度とは、懸濁粒子が沈降して生じる上澄み液の、液全体に対する体積割合。
<Measurement conditions>
Test environment temperature: set to 20 ° C.
Separation degree: The volume ratio of the suspension phase to the whole liquid was evaluated with a graduated cylinder. The degree of separation is the volume ratio of the supernatant produced by sedimentation of suspended particles to the total liquid.
表１より、硫酸アルミニウム濃度が３０〜５０％、ポリオール系分散剤濃度が０．０１〜５％の配合の液体は分離度が低く、液体急結剤の貯蔵安定性として望ましい。 From Table 1, the liquid of the mixing | blending whose aluminum sulfate density | concentration is 30 to 50% and polyol type dispersing agent density | concentration is 0.01 to 5% has a low separation degree, and is desirable as the storage stability of a liquid quick setting agent.
「実験例２」
実験例１と同様の方法で、促進剤の濃度が表２に示す通り、硫酸アルミニウム濃度が３５％、ポリオール系分散剤濃度が１％となるような液体急結剤を調製した。また、実験例１と同様に、分離度を評価した。結果を表２に併記する。
"Experimental example 2"
In the same manner as in Experimental Example 1, a liquid accelerator was prepared such that the accelerator concentration was 35% and the polyol-based dispersant concentration was 1% as shown in Table 2. Further, as in Experimental Example 1, the degree of separation was evaluated. The results are also shown in Table 2.
＜使用材料＞
促進剤ア：六フッ化アルミニウムナトリウム（ア）、市販品
促進剤イ：ジエタノールアミン（イ）、市販品
<Materials used>
Accelerator A: Sodium aluminum hexafluoride (A), commercial product accelerator A: Diethanolamine (I), commercial product
表２より、液体急結剤のフッ素化合物の濃度が１０％まで、アルコールアミン類の濃度が５％までであれば、分離度が著しく大きくはならず、貯蔵安定性が大きく低下することはない。 From Table 2, if the concentration of the fluorine compound in the liquid accelerator is up to 10% and the concentration of alcoholamines is up to 5%, the degree of separation does not increase significantly, and the storage stability does not decrease significantly. .
「実験例３」
表３に示すように、実験例１、実験例２で示した配合の液体急結剤を調製した。また、調製後の液を、−１０、２０、４０℃の温度で、実験例１と同様の手順で、３か月後の分離度を評価した。結果を表３に併記する。
"Experiment 3"
As shown in Table 3, liquid quick setting agents having the formulations shown in Experimental Examples 1 and 2 were prepared. Moreover, the resolution after 3 months was evaluated for the liquid after preparation at the temperature of -10, 20, and 40 degreeC by the procedure similar to Experimental example 1. FIG. The results are also shown in Table 3.
表３より、液体急結剤１００の硫酸アルミニウムの濃度が３０〜５０％、ポリオール系分散剤の濃度が０．０１〜５％の液体急結剤は、−１０〜４０℃において、調製後少なくとも３か月間、分離度が小さく、液の９０％以上が均一であり、貯蔵安定性に優れる。
さらに、硫酸アルミニウムの濃度が３５％、ポリオール系分散剤の濃度が１％、一定の濃度の促進剤（フッ素化合物の濃度が０．１〜１０％、あるいはアルコールアミン類の濃度が０．１〜５％）を含有する液体急結剤も、同様の条件で、貯蔵安定性に優れる。
From Table 3, the liquid quick-setting agent 100 having a concentration of 30-50% aluminum sulfate and a concentration of polyol-based dispersing agent of 0.01-5% is at least after preparation at −10 to 40 ° C. For 3 months, the degree of separation is small, 90% or more of the liquid is uniform, and the storage stability is excellent.
Furthermore, the concentration of aluminum sulfate is 35%, the concentration of the polyol-based dispersant is 1%, and a certain concentration of accelerator (the concentration of fluorine compound is 0.1 to 10%, or the concentration of alcohol amines is 0.1 to 0.1%). 5%) is also excellent in storage stability under the same conditions.
「実験例４」
実験例１と同様の方法で、硫酸アルミニウム、ポリオール系分散剤の濃度が、表４に示す値になるように、液体急結剤を調製した。また、細骨材／セメント比＝３、水／セメント比＝５０％のモルタルを調製し、そのセメント１００部に対して、液体急結剤を７部添加し、急結性モルタルとし、その凝結時間、さらに圧縮強度を測定した。液体急結剤は、製造１週間後のものを使用した。結果を表４に併記する。
"Experimental example 4"
In the same manner as in Experimental Example 1, a liquid accelerating agent was prepared so that the concentrations of aluminum sulfate and polyol dispersant became values shown in Table 4. Also, a mortar with a fine aggregate / cement ratio = 3 and a water / cement ratio = 50% was prepared, and 7 parts of a liquid setting agent was added to 100 parts of the cement to form a quick setting mortar. Time and further compressive strength were measured. The liquid accelerator was used one week after production. The results are also shown in Table 4.
＜使用材料＞
セメント：普通ポルトランドセメント、市販品、ブレーン比表面積３，４００ｃｍ２／ｇ、比重３．１６
細骨材：新潟県糸魚川市姫川産川砂、表乾状態、比重２．６２、５ｍｍ下品
<Materials used>
Cement: Ordinary Portland cement, commercial product, Blaine specific surface area 3,400 cm 2 / g, specific gravity 3.16
Fine aggregate: Niigata prefecture Itoigawa city Himekawa production river sand, surface dry state, specific gravity 2.62, 5mm vulgar
＜測定方法＞
凝結試験：急結性モルタルを土木学会基準「吹付けコンクリート用急結剤品質規格（ＪＳＣＥＤ−１０２）」に準じて測定
圧縮強度：急結性モルタルをＪＩＳ Ｒ ５２０１に準じて測定
試験環境温度：２０℃に設定
<Measurement method>
Setting test: Quick setting mortar measured in accordance with Japan Society of Civil Engineers standard "Quality standards for quick setting for sprayed concrete (JSCED-102)" Compressive strength: Quick setting mortar measured in accordance with JIS R 5201 Environmental test temperature: Set to 20 ° C
表４より、硫酸アルミニウム濃度３０〜５０％、ポリオール系分散剤濃度０．０１〜５％の配合であることが、液体急結剤の性状として望ましい。 From Table 4, it is desirable as the properties of the liquid quick-setting agent that the aluminum sulfate concentration is 30 to 50% and the polyol dispersant concentration is 0.01 to 5%.
「実験例５」
実験例１と同様の方法で、液体急結剤の濃度が、硫酸アルミニウム３５％、ポリオール系分散剤１％の液体急結剤を調製した。また、実験例４と同様のモルタルを調製し、そのセメント１００部に対して、液体急結剤を表５に示す量添加し、急結性モルタルとし、その凝結時間を、さらに、圧縮強度を測定した。液体急結剤は、製造１週間後のものを使用した。結果を表５に併記する。
“Experimental Example 5”
In the same manner as in Experimental Example 1, a liquid quick-setting agent having a liquid quick-setting agent concentration of 35% aluminum sulfate and 1% polyol-based dispersant was prepared. Also, a mortar similar to that of Experimental Example 4 was prepared, and with respect to 100 parts of the cement, a liquid quick-setting agent was added in an amount shown in Table 5 to form a quick-setting mortar, and the setting time was further increased in compression strength. It was measured. The liquid accelerator was used one week after production. The results are also shown in Table 5.
表５より、液体急結剤の添加量は、セメント１００部に対し、３〜２０部であることが、吹付け材料の性状として望ましい。 From Table 5, it is desirable as the property of the spray material that the addition amount of the liquid quick-setting agent is 3 to 20 parts with respect to 100 parts of cement.
「実験例６」
実験例１、２と同様の方法で、表６に示す種類および濃度の促進剤を含有し、硫酸アルミニウム濃度３５％、ポリオール系分散剤濃度１％の液体急結剤を調製した。また、実験例４と同様のモルタルを調製し、そのセメント１００部に対して、急結剤を７部添加し、急結性モルタルとし、その凝結時間、さらに圧縮強度を測定した。液体急結剤は、製造１週間後のものを使用した。結果を表６に併記する。
"Experimental example 6"
In the same manner as in Experimental Examples 1 and 2, liquid accelerators containing the promoters of the types and concentrations shown in Table 6 and having an aluminum sulfate concentration of 35% and a polyol dispersant concentration of 1% were prepared. Further, a mortar similar to Experimental Example 4 was prepared, and 7 parts of a quick setting agent was added to 100 parts of the cement to obtain a quick setting mortar. The setting time and further compressive strength were measured. The liquid accelerator was used one week after production. The results are also shown in Table 6.
表６より、液体急結剤のフッ素化合物の濃度が０．１〜１０％、アルコールアミン類の濃度が０．１〜５％であれば、凝結性状が向上し、強度発現性が大きく損なわることがないため、液体急結剤の性状として望ましい。 From Table 6, if the concentration of the fluorine compound in the liquid accelerator is 0.1 to 10% and the concentration of alcohol amines is 0.1 to 5%, the setting property is improved and the strength development is greatly impaired. Therefore, it is desirable as a property of the liquid setting agent.
本発明の液体急結剤は、硫酸アルミニウム系液体急結剤で課題だった液のゲル化や懸濁粒子の沈降を抑え、貯蔵安定性が優れるので、凝結性状や強度発現性が高い吹付け材料とすることが可能となり、土木、建築の分野等に好適である。 The liquid accelerating agent of the present invention suppresses gelation of liquids and sedimentation of suspended particles, which are problems with aluminum sulfate liquid accelerating agents, and has excellent storage stability. It can be used as a material and is suitable for the civil engineering and construction fields.
Claims (6)
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109265064A (en) * | 2018-09-28 | 2019-01-25 | 镇江苏博特新材料有限公司 | A kind of preparation method of high-strength alkali-free chlorine-free accelerator |
| CN111333357A (en) * | 2020-03-11 | 2020-06-26 | 四川津宏康泰新材料有限公司 | Accelerating agent and preparation method thereof |
| JP2021143090A (en) * | 2020-03-12 | 2021-09-24 | デンカ株式会社 | Liquid rapid-hardening agent and rapid-hardening cement concrete |
| CN113480221A (en) * | 2021-08-02 | 2021-10-08 | 江西立晶新材料科技有限公司 | Liquid alkali-free accelerator and preparation method and application thereof |
| WO2022092081A1 (en) * | 2020-10-30 | 2022-05-05 | デンカ株式会社 | Two material-type ready-mix shipped rapid-hardening concrete material and ready-mix shipped rapid-hardening concrete composition |
| CN115353317A (en) * | 2022-10-21 | 2022-11-18 | 石家庄市长安育才建材有限公司 | High-aluminum-content accelerator and preparation method thereof |
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| JP2010517923A (en) * | 2007-02-13 | 2010-05-27 | シーカ・テクノロジー・アーゲー | Coagulation / curing accelerator for hydraulic binder and preparation method thereof |
| JP2011169498A (en) * | 2010-02-17 | 2011-09-01 | Kurosaki Harima Corp | Wet-spraying method |
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| JP2001270768A (en) * | 2000-03-28 | 2001-10-02 | Denki Kagaku Kogyo Kk | Spraying material and method of spraying method using the same |
| JP2010517923A (en) * | 2007-02-13 | 2010-05-27 | シーカ・テクノロジー・アーゲー | Coagulation / curing accelerator for hydraulic binder and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109265064A (en) * | 2018-09-28 | 2019-01-25 | 镇江苏博特新材料有限公司 | A kind of preparation method of high-strength alkali-free chlorine-free accelerator |
| CN109265064B (en) * | 2018-09-28 | 2021-04-20 | 镇江苏博特新材料有限公司 | Preparation method of high-strength alkali-free chlorine-free accelerator |
| CN111333357A (en) * | 2020-03-11 | 2020-06-26 | 四川津宏康泰新材料有限公司 | Accelerating agent and preparation method thereof |
| JP2021143090A (en) * | 2020-03-12 | 2021-09-24 | デンカ株式会社 | Liquid rapid-hardening agent and rapid-hardening cement concrete |
| WO2022092081A1 (en) * | 2020-10-30 | 2022-05-05 | デンカ株式会社 | Two material-type ready-mix shipped rapid-hardening concrete material and ready-mix shipped rapid-hardening concrete composition |
| CN113480221A (en) * | 2021-08-02 | 2021-10-08 | 江西立晶新材料科技有限公司 | Liquid alkali-free accelerator and preparation method and application thereof |
| CN115353317A (en) * | 2022-10-21 | 2022-11-18 | 石家庄市长安育才建材有限公司 | High-aluminum-content accelerator and preparation method thereof |
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