JP6263405B2 - Preparation method of concrete containing blast furnace slag - Google Patents
Preparation method of concrete containing blast furnace slag Download PDFInfo
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- JP6263405B2 JP6263405B2 JP2014019897A JP2014019897A JP6263405B2 JP 6263405 B2 JP6263405 B2 JP 6263405B2 JP 2014019897 A JP2014019897 A JP 2014019897A JP 2014019897 A JP2014019897 A JP 2014019897A JP 6263405 B2 JP6263405 B2 JP 6263405B2
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- 239000002893 slag Substances 0.000 title claims description 80
- 239000004567 concrete Substances 0.000 title claims description 76
- 238000002360 preparation method Methods 0.000 title claims description 30
- 238000000034 method Methods 0.000 claims description 38
- 239000011230 binding agent Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 229920006163 vinyl copolymer Polymers 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 19
- 229920001353 Dextrin Polymers 0.000 claims description 16
- 239000004375 Dextrin Substances 0.000 claims description 16
- 239000011400 blast furnace cement Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 16
- 235000019425 dextrin Nutrition 0.000 claims description 16
- 125000006353 oxyethylene group Chemical group 0.000 claims description 16
- 239000011398 Portland cement Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 13
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 12
- -1 polyoxyethylene group Polymers 0.000 claims description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 10
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052602 gypsum Inorganic materials 0.000 claims description 8
- 239000010440 gypsum Substances 0.000 claims description 8
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 239000011976 maleic acid Substances 0.000 claims description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 2
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 claims 1
- 238000004898 kneading Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001723 curing Methods 0.000 description 9
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000006703 hydration reaction Methods 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 239000004576 sand Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 230000020169 heat generation Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 238000010526 radical polymerization reaction Methods 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 239000001263 FEMA 3042 Substances 0.000 description 2
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- MSJMDZAOKORVFC-UAIGNFCESA-L disodium maleate Chemical compound [Na+].[Na+].[O-]C(=O)\C=C/C([O-])=O MSJMDZAOKORVFC-UAIGNFCESA-L 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 235000013373 food additive Nutrition 0.000 description 2
- 239000002778 food additive Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 2
- 229940033123 tannic acid Drugs 0.000 description 2
- 235000015523 tannic acid Nutrition 0.000 description 2
- 229920002258 tannic acid Polymers 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は高炉スラグ含有コンクリートの調製方法、高炉スラグ含有コンクリート及びその硬化体に関する。近年、副産物の有効利用、省資源・省エネルギー、地球温暖化対策のための炭酸ガス削減等の観点から、製鉄所から副産する高炉水砕スラグの微粉末をポルトランドセメントと混合した結合材の利用が、コンクリートを調製する上において益々重要になっている。本発明はかかる結合材を用いたコンクリート（以下、高炉スラグ含有コンクリートという）の性能を大きく向上することができる高炉スラグ含有コンクリートの調製方法、該調製方法によって得られる高炉スラグ含有コンクリート及びその硬化体に関する。 The present invention relates to a method for preparing blast furnace slag-containing concrete, blast furnace slag-containing concrete, and a cured body thereof. In recent years, from the viewpoint of effective use of by-products, resource saving and energy saving, carbon dioxide reduction for global warming countermeasures, etc., use of binders mixed with fine powder of granulated blast furnace slag by-produced from steelworks with Portland cement However, it has become increasingly important in preparing concrete. The present invention provides a method for preparing blast furnace slag-containing concrete capable of greatly improving the performance of concrete (hereinafter referred to as blast furnace slag-containing concrete) using such a binder, blast furnace slag-containing concrete obtained by the preparation method, and a cured body thereof. About.
従来から、高炉スラグ含有コンクリートを調製すると、下記の１）〜３）のような問題があることが指摘されている。すなわち、１）高炉スラグ含有コンクリートは、調製後の経時的な流動性の保持性（スランプ保持性）が低い。２）高炉スラグ含有コンクリートは、高炉スラグ微粉末の分量が多いものほど、ポルトランドセメントを用いて調製したコンクリートに比べて、得られる硬化体の圧縮強度が低い（標準水中養生供試体の強度が低い）。３）高炉スラグ含有コンクリートは、水和反応により硬化する過程で発熱により温度上昇する熱履歴を受けると、得られる硬化体の圧縮強度が低下する（高温履歴供試体の強度が低い）。かかる問題は、高炉スラグ含有コンクリートの調製時の温度が高いほど、また高炉スラグ微粉末の分量が多い高炉スラグ含有コンクリートほど著しい。その一方で、高炉スラグ微粉末を含有する高炉セメント、或いは高炉スラグ微粉末を多く含有する結合材を用いてＣＯ２の発生を抑制した環境性能の高いコンクリートの調製方法が知られており（例えば特許文献１参照）、またコンクリートの水和反応による発熱を抑える添加剤、例えばデキストリンやタンニン酸等を用いるコンクリートの調製方法も知られている（例えば特許文献２〜６参照）。しかし、これらの従来技術では、前記の１）〜３）の問題を同時に且つ充分に解決することができないという問題があり、実情はかかる問題を低コストでしかも簡便な方法で解決することが望まれているのである。 Conventionally, it has been pointed out that when blast furnace slag-containing concrete is prepared, there are the following problems 1) to 3). That is, 1) Blast furnace slag-containing concrete has low fluidity retention (slump retention) over time after preparation. 2) In concrete containing blast furnace slag, the higher the amount of blast furnace slag fine powder, the lower the compressive strength of the resulting cured body compared to the concrete prepared using Portland cement (the strength of the standard underwater curing specimen is lower) ). 3) When the blast furnace slag-containing concrete is subjected to a heat history that rises due to heat generation in the process of hardening by a hydration reaction, the compressive strength of the resulting cured body decreases (the strength of the high-temperature history specimen is low). Such a problem is more remarkable as the temperature at the time of preparing the blast furnace slag-containing concrete is higher and the blast furnace slag-containing concrete having a larger amount of fine blast furnace slag powder. On the other hand, there is known a method for preparing concrete with high environmental performance that suppresses the generation of CO2 using a blast furnace cement containing blast furnace slag fine powder or a binder containing a large amount of blast furnace slag fine powder (for example, patents). There is also known a method for preparing concrete using an additive that suppresses heat generation due to the hydration reaction of concrete, such as dextrin and tannic acid (see, for example, Patent Documents 2 to 6). However, these conventional techniques have the problem that the above problems 1) to 3) cannot be solved simultaneously and sufficiently, and the actual situation is desired to solve these problems at a low cost and with a simple method. It is rare.
本発明が解決しようとする課題は、１）高炉スラグ含有コンクリートは、調製後の経時的な流動性の保持性（スランプ保持性）が低い、２）高炉スラグ含有コンクリートは、得られる硬化体の圧縮強度が低い、３）高炉スラグ含有コンクリートは、水和反応により硬化する過程での発熱により温度上昇する熱履歴を受けると、得られる硬化体の圧縮強度が低下する、という以上の１）〜３）の問題を同時に且つ充分に解決できる高炉スラグ含有コンクリートの調製方法、該調製方法によって得られる高炉スラグ含有コンクリート及びその硬化体を提供する処にある。 The problems to be solved by the present invention are as follows: 1) Blast furnace slag-containing concrete has low fluidity retention (slump retention) over time after preparation; 2) Blast furnace slag-containing concrete is a hardened body obtained. Low compressive strength 3) When the blast furnace slag-containing concrete is subjected to a heat history that rises due to heat generation in the process of hardening by a hydration reaction, the compressive strength of the resulting hardened body decreases. The present invention is to provide a method for preparing blast furnace slag-containing concrete that can simultaneously and sufficiently solve the problem 3), a blast furnace slag-containing concrete obtained by the preparation method, and a hardened body thereof.
しかして本発明者らは、前記の課題を解決するべく研究した結果、特定の結合材に、特定の３成分を特定割合で含有して成る特定の多機能混和剤を特定割合で用いる方法が正しく好適であることを見出した。 Thus, as a result of researches to solve the above-mentioned problems, the present inventors have found a method of using a specific multifunctional admixture containing a specific three component in a specific ratio in a specific ratio in a specific binder. It was found to be correct and suitable.
すなわち本発明は、下記の結合材、水、細骨材、粗骨材及び下記の多機能混和剤を用いる高炉スラグ含有コンクリートの調製方法であって、下記の結合材１００質量部当たり下記の多機能混和剤を０．１〜１．５質量部の割合となるよう用いることを特徴とする高炉スラグ含有コンクリートの調製方法に係る。また本発明は、かかる調製方法によって得られる高炉スラグ含有コンクリートに係る。更に本発明は、かかる高炉スラグ含有コンクリートを硬化して得られる硬化体に係る。 That is, the present invention is a method for preparing blast furnace slag-containing concrete using the following binder, water, fine aggregate, coarse aggregate and the following multifunctional admixture, wherein The present invention relates to a method for preparing blast furnace slag-containing concrete, wherein the functional admixture is used at a ratio of 0.1 to 1.5 parts by mass. Moreover, this invention relates to the blast furnace slag containing concrete obtained by this preparation method. Furthermore, this invention relates to the hardening body obtained by hardening | curing this blast furnace slag containing concrete.
結合材：高炉スラグ微粉末を４０〜７５質量％、ポルトランドセメントを２３〜５３質量％及び石膏を２〜７質量％（合計１００質量％）の割合で含有してなるもの。 Binder: What contains 40-75 mass% of blast furnace slag fine powder, 23-53 mass% of Portland cement, and 2-7 mass% (total 100 mass%) of gypsum.
多機能混和剤：下記のＡ成分を２０〜８０質量％、下記のＢ成分を１９．９９〜７９質量％及び下記のＣ成分を０．０１〜１質量％（合計１００％）の割合で含有してなるもの。 Multifunctional admixture: 20-80% by mass of the following A component, 19.99-79% by mass of the following B component, and 0.01-1% by mass (100% in total) of the following C component What you do.
Ａ成分：分子中に下記の構成単位Ｄを４０〜６０モル％及び下記の構成単位Ｅを６０〜４０モル％（合計１００モル％）の割合で有する質量平均分子量２０００〜８００００の水溶性ビニル共重合体。 Component A: A water-soluble vinyl copolymer having a mass average molecular weight of 2000 to 80000 having the following constitutional unit D in the molecule in a proportion of 40 to 60 mol% and the following constitutional unit E in a proportion of 60 to 40 mol% (total 100 mol%) Polymer.
構成単位Ｄ：マレイン酸から形成された構成単位及びマレイン酸塩からから形成された構成単位から選ばれる一つ又は二つ以上 Structural unit D: one or more selected from a structural unit formed from maleic acid and a structural unit formed from maleate
構成単位Ｅ：分子中に１５〜８０個のオキシエチレン単位で構成されたポリオキシエチレン基を有するα−アリル−ω−メチル−ポリオキシエチレンから形成された構成単位及び分子中に１５〜８０個のオキシエチレン単位で構成されたポリオキシエチレン基を有するα−アリル−ω−ヒドロキシ−ポリオキシエチレンから形成された構成単位から選ばれる一つ又は二つ以上。 Structural unit E: Structural unit formed from α-allyl-ω-methyl-polyoxyethylene having a polyoxyethylene group composed of 15 to 80 oxyethylene units in the molecule and 15 to 80 in the molecule One or two or more selected from structural units formed from α-allyl-ω-hydroxy-polyoxyethylene having a polyoxyethylene group composed of oxyethylene units.
Ｂ成分：質量平均分子量が１０００〜２００００であり、且つ分散度が１．２〜６．０の水溶性デキストリン化合物。 Component B: A water-soluble dextrin compound having a mass average molecular weight of 1,000 to 20,000 and a dispersity of 1.2 to 6.0.
Ｃ成分：ハイドロキノン、ハイドロキノンモノメチルエーテル、モノメチルハイドロキノン及びｐ−ベンゾキノンから選ばれる一つ又は二つ以上。 Component C: One or two or more selected from hydroquinone, hydroquinone monomethyl ether, monomethyl hydroquinone and p-benzoquinone.
本発明に係る高炉スラグ含有コンクリートの調製方法（以下、本発明の調製方法という）に供する結合材は、高炉スラグ微粉末を４０〜７５質量％、ポルトランドセメントを２３〜５３質量％及び石膏を２〜７質量％（合計１００質量％）の割合で含有してなるものである。高炉スラグ微粉末としては、粉末度が３０００〜８０００ｃｍ２／ｇのものが挙げられるが、粉末度が３５００〜６５００ｃｍ２／ｇのものが好ましい。ポルトランドセメントとしては、普通ポルトランドセメント、早強ポルトランドセメント、中庸熱ポルトランドセメント等が挙げられるが、汎用の普通ポルトランドセメントが好ましい。石膏としては、二水石膏、半水石膏、無水石膏等が挙げられるが、無水石膏が好ましい。一般に、普通ポルトランドセメント、高炉スラグ微粉末及び石膏を含有する混合セメントとして、ＪＩＳ規格を満足する高炉セメントがある。かかる高炉セメントは、高炉スラグ微粉末の分量によって、高炉セメントＡ種（５質量％超〜３０質量％）、高炉セメントＢ種（３０質量％超〜６０質量％）、及び高炉セメントＣ種（６０質量％超〜７０質量％）の３種類に分類されている。本発明の調製方法に供する結合材としては、前記したものであればよいが、なかでも高炉スラグ微粉末の分量がより多い高炉セメントＢ種又は高炉セメントＣ種を使用することが環境性能の優れた高炉スラグ含有コンクリートを調製する上で好ましい。 The binder used in the method for preparing blast furnace slag-containing concrete according to the present invention (hereinafter referred to as the preparation method of the present invention) is 40-75 mass% blast furnace slag fine powder, 23-53 mass% Portland cement, and 2 gypsum. It is contained at a ratio of ˜7 mass% (total 100 mass%). The blast furnace slag, but powder degree include the 3000~8000cm 2 / g, fineness is preferably from 3500~6500cm 2 / g. Examples of Portland cement include ordinary Portland cement, early-strength Portland cement, moderately hot Portland cement, and the like, and general-purpose ordinary Portland cement is preferable. Examples of the gypsum include dihydrate gypsum, hemihydrate gypsum, and anhydrous gypsum, and anhydrous gypsum is preferable. Generally, as a mixed cement containing ordinary Portland cement, blast furnace slag fine powder and gypsum, there is a blast furnace cement that satisfies the JIS standard. Such blast furnace cement is classified into blast furnace cement type A (over 5 mass% to 30 mass%), blast furnace cement type B (over 30 mass% to over 60 mass%), and blast furnace cement type C (60% depending on the amount of blast furnace slag fine powder. (Over mass% to 70 mass%). The binder used in the preparation method of the present invention may be any of those described above, and in particular, it is excellent in environmental performance to use Blast Furnace Cement B or Blast Furnace Cement C which has a larger amount of fine blast furnace slag powder. It is preferable for preparing blast furnace slag-containing concrete.
本発明の調製方法に供する多機能混和剤は、Ａ成分、Ｂ成分及びＣ成分の３成分からなる混合物である。Ａ成分は主に分散成分としての役割を担い、分子中に前記の構成単位Ｄを４０〜６０モル％及び前記の構成単位Ｅを６０〜４０モル％（合計１００モル％）の割合で有する質量平均分子量２０００〜８００００の水溶性ビニル共重合体であるが、好ましくは構成単位Ｄを４５〜５５モル％及び構成単位Ｅを５５〜４５モル％（合計１００モル％）の割合で有する質量平均分子量３０００〜６００００の水溶性ビニル共重合体である。本発明の調製方法において、Ａ成分の水溶性ビニル共重合体の質量平均分子量はＧＰＣ法（ゲル浸透クロマトグラフ法、以下同じ）で測定したポリエチレングリコール換算の質量平均分子量である。 The multifunctional admixture used for the preparation method of the present invention is a mixture composed of three components of A component, B component and C component. A component mainly plays a role as a dispersing component, and has a mass of 40 to 60 mol% of the structural unit D and 60 to 40 mol% of the structural unit E (100 mol% in total) in the molecule. A water-soluble vinyl copolymer having an average molecular weight of 2000 to 80000, preferably having a constitutional unit D in a proportion of 45 to 55 mol% and a constitutional unit E in a proportion of 55 to 45 mol% (total 100 mol%). It is a 3000 to 60000 water-soluble vinyl copolymer. In the preparation method of the present invention, the weight average molecular weight of the water-soluble vinyl copolymer of component A is a weight average molecular weight in terms of polyethylene glycol measured by GPC method (gel permeation chromatography, the same applies hereinafter).
構成単位Ｄはマレイン酸から形成された構成単位及びマレイン酸塩から形成された構成単位から選ばれるものである。また構成単位Ｅは分子中に１５〜８０個のオキシエチレン単位で構成されたポリオキシエチレン基を有するα−アリル−ω−メチル−ポリオキシエチレンから形成された構成単位及び分子中に１５〜８０個のオキシエチレン単位で構成されたポリオキシエチレン基を有するα−アリル−ω−ヒドロキシ−ポリオキシエチレンから形成された構成単位の中から選ばれるものであるが、好ましくは分子中に２０〜５０個のオキシエチレン単位で構成されたポリオキシエチレン基を有するα−アリル−ω−メチル−ポリオキシエチレンから形成された構成単位及び分子中に２０〜５０個のオキシエチレン単位で構成されたポリオキシエチレン基を有するα−アリル−ω−ヒドロキシ−ポリオキシエチレンから形成された構成単位から選ばれる一つ又は二つ以上である。 The structural unit D is selected from a structural unit formed from maleic acid and a structural unit formed from maleate. The structural unit E is a structural unit formed from α-allyl-ω-methyl-polyoxyethylene having a polyoxyethylene group composed of 15 to 80 oxyethylene units in the molecule and 15 to 80 in the molecule. It is selected from structural units formed from α-allyl-ω-hydroxy-polyoxyethylene having a polyoxyethylene group composed of individual oxyethylene units, and preferably 20 to 50 in the molecule. A structural unit formed from α-allyl-ω-methyl-polyoxyethylene having a polyoxyethylene group composed of one oxyethylene unit and a polyoxy composed of 20 to 50 oxyethylene units in the molecule One or two selected from structural units formed from α-allyl-ω-hydroxy-polyoxyethylene having an ethylene group That's it.
以上説明したＡ成分の水溶性ビニル共重合体自体は公知の方法で合成できる。これには例えば、特開昭５８−３８３８０号公報や特開２０１２−５１７３７号公報等に記載されている方法が挙げられる。 The water-soluble vinyl copolymer of component A described above can be synthesized by a known method. This includes, for example, methods described in JP-A-58-38380 and JP-A-2012-51737.
Ｂ成分は主に強度増進成分及び流動性保持成分としての役割を担い、質量平均分子量が１０００〜２００００、好ましくは１５００〜１５０００、より好ましくは２０００〜１００００の水溶性デキストリン化合物である。本発明の調製方法において、水溶性デキストリン化合物の質量平均分子量は水系のＧＰＣ法で測定したポリエチレングリコール換算の質量平均分子量である。またＢ成分としての水溶性デキストリン化合物は、水系のＧＰＣ法で測定した分子量分布曲線における分散度（質量平均分子量Ｍｗ／数平均分子量Ｍｎの比）が１．２〜６．０、好ましくは３．０〜５．５のものである。分散度が６．０よりも大きいと、前記した本発明の目的とする効果が発揮されない。Ｂ成分のような分散度の小さい水溶性デキストリン化合物は公知の合成方法（例えば特開２００８−２２２８２２号公報に記載の方法）で得ることができるが、食品添加物などの用途で通常は粉末品として市販されているものを使用することもできる。 The B component is a water-soluble dextrin compound mainly serving as a strength enhancing component and a fluidity-holding component and having a mass average molecular weight of 1000 to 20000, preferably 1500 to 15000, more preferably 2000 to 10,000. In the preparation method of the present invention, the mass average molecular weight of the water-soluble dextrin compound is a polyethylene glycol equivalent mass average molecular weight measured by an aqueous GPC method. The water-soluble dextrin compound as the component B has a dispersity (ratio of mass average molecular weight Mw / number average molecular weight Mn) in a molecular weight distribution curve measured by an aqueous GPC method of 1.2 to 6.0, preferably 3. 0 to 5.5. When the degree of dispersion is greater than 6.0, the above-described effect of the present invention is not exhibited. A water-soluble dextrin compound having a low degree of dispersion such as component B can be obtained by a known synthesis method (for example, the method described in JP-A-2008-222822), but is usually a powder product for use as a food additive. What is marketed as can also be used.
本発明の調製方法における特徴の一つは、前記したような結合材に対し、多機能混和剤の主に強度増進成分及び流動性保持成分として前記したような特定の水溶性デキストリン化合物を用いた所にある。前記したような特定の水溶性デキストリン化合物は、高炉スラグ含有コンクリートを調製する際に高炉スラグ微粉末に吸着して適度の分散性を付与する働きをし、また高炉スラグ微粉末が水和する過程での初期に水和反応の速度をコントロールして中長期の反応率を高め、結果として高い圧縮強度の硬化体を与えるものと推察される。 One of the features in the preparation method of the present invention is that the specific water-soluble dextrin compound as described above is mainly used as the strength-enhancing component and the fluidity-holding component of the multifunctional admixture for the binder as described above. In place. The specific water-soluble dextrin compound as described above functions to adsorb to the blast furnace slag fine powder and impart appropriate dispersibility when preparing the blast furnace slag-containing concrete, and the process of hydrating the blast furnace slag fine powder. It is presumed that the rate of hydration reaction is controlled at the initial stage to increase the reaction rate over the medium to long term, resulting in a cured product with high compressive strength.
Ｃ成分は主に保存性安定成分としての役割を担い、ハイドロキノン、ハイドロキノンモノメチルエーテル、モノメチルハイドロキノン及びｐ−ベンゾキノンから選ばれるものである。これらは、水に中性〜アルカリ性の領域で溶解する重合禁止剤或いは酸化劣化防止剤として知られる化合物である。本発明の調製方法において、多機能混和剤を、Ａ成分、Ｂ成分及びＣ成分の３成分を混合した一液型混和剤として使用するためには、それが長期間経過しても化学的に安定な品質を保つことが重要である。なかでも前記したＢ成分は、溶液の状態で共存すると、加熱、ｐＨの変化、雑菌等の影響を受けて変質したり、腐敗したりするという問題があり、かかる問題を解消するためにＣ成分を使用する。Ｃ成分としては、なかでもハイドロキノン及び／又はｐ−ベンゾキノンが好ましく、これらを用いると、調製した多機能混和剤を一液型混和剤として長期間保存しても、化学的に安定な品質を保つことができる。 The component C mainly plays a role as a preservative stabilizing component and is selected from hydroquinone, hydroquinone monomethyl ether, monomethyl hydroquinone and p-benzoquinone. These are compounds known as polymerization inhibitors or antioxidants that dissolve in water in a neutral to alkaline region. In the preparation method of the present invention, in order to use the multifunctional admixture as a one-component admixture obtained by mixing the three components of the A component, the B component and the C component, It is important to maintain stable quality. Above all, when the above-mentioned B component coexists in the state of a solution, there is a problem that it deteriorates or decays due to the influence of heating, pH change, bacteria, etc. In order to solve such a problem, the C component Is used. As the component C, hydroquinone and / or p-benzoquinone are preferable, and when these are used, a chemically stable quality is maintained even when the prepared multifunctional admixture is stored as a one-component admixture for a long period of time. be able to.
本発明の調製方法に供する多機能混和剤は、以上説明したＡ成分、Ｂ成分及びＣ成分の３成分からなり、且つＡ成分を２０〜８０質量％、Ｂ成分を１９．９９〜７９質量％及びＣ成分を０．０１〜１質量％（合計１００％）の割合で含有してなるものであるが、好ましくはＡ成分を２０．５〜７９．９質量％、Ｂ成分を２０．０５〜７９質量％及びＣ成分を０．０５〜０．５質量％（合計１００％）の割合で含有してなるものである。Ａ成分、Ｂ成分及びＣ成分の割合がかかる特定の範囲から外れると、これらを混合した一液型混和剤としての品質保存性が低下するのみならず、調製した高炉スラグ含有コンクリートのスランプロスが大きくなって作業性が低下したり、或いは凝結時間が長くなり過ぎたり、更には得られる硬化体の圧縮強度が低くなったり、また硬化する過程での発熱により温度上昇する熱履歴を受けたときに得られる硬化体の圧縮強度が低下したりする。温度上昇する熱履歴により得られる硬化体の圧縮強度が低下するという問題は、高炉スラグ含有コンクリートを調製する際の練り混ぜ温度が１５〜４５℃で、なかでも夏期における２０〜４５℃の温度で顕著となる。 The multifunctional admixture used for the preparation method of the present invention comprises the above-described three components of the A component, the B component and the C component, and the A component is 20 to 80% by mass and the B component is 19.99 to 79% by mass. And C component in a proportion of 0.01 to 1% by mass (total 100%), preferably 20.5 to 79.9% by mass of A component and 20.05 to B component. 79 mass% and C component are contained in the ratio of 0.05-0.5 mass% (total 100%). When the ratio of the A component, the B component and the C component deviates from such a specific range, not only the quality preservation as a one-component admixture in which these components are mixed, but also the slump loss of the prepared blast furnace slag-containing concrete When it becomes large and workability deteriorates, or the setting time becomes too long, and further, the compression strength of the obtained cured product becomes low, or when it receives a heat history that rises in temperature due to heat generation during the curing process The compressive strength of the cured product obtained in this manner is reduced. The problem that the compressive strength of the hardened body obtained due to the heat history that rises in temperature is reduced is that the kneading temperature at the time of preparing the blast furnace slag-containing concrete is 15 to 45 ° C., especially at the temperature of 20 to 45 ° C. in summer. Become prominent.
本発明の調製方法に供する以上説明した多機能混和剤は、結合材１００質量部当たり、水溶液として用いる場合には固形分換算で、０．１〜１．５質量部の割合となるように用いるが、０．１５〜０．８質量部の割合となるように用いるのが好ましい。 The multifunctional admixture described above provided for the preparation method of the present invention is used in a ratio of 0.1 to 1.5 parts by mass in terms of solid content when used as an aqueous solution per 100 parts by mass of the binder. However, it is preferable to use it so that it may become a ratio of 0.15-0.8 mass part.
本発明の調製方法に供する細骨材としては、それ自体は公知の川砂、砕砂、山砂等が挙げられ、また粗骨材としては、これもそれ自体は公知の川砂利、砕石、軽量骨材等が挙げられる。 Examples of the fine aggregate used in the preparation method of the present invention include known river sand, crushed sand, mountain sand and the like, and as coarse aggregate, this is also known per se known river gravel, crushed stone, lightweight bone. Materials and the like.
本発明の調製方法において、水／結合材比は特に制限されないが、水／結合材比は１５〜６０％に調製するのが好ましく、１７〜５５％に調製するのがより好ましい。水／結合材比が大きくなり過ぎると、得られる硬化体の中性化速度が速くなり、圧縮強度が低下する傾向を示し、逆に水／結合材比が小さくなり過ぎると、調製した高炉スラグ含有コンクリートの流動性が低下し易くなり、施工性が低下する傾向を示す。 In the preparation method of the present invention, the water / binder ratio is not particularly limited, but the water / binder ratio is preferably adjusted to 15 to 60%, more preferably 17 to 55%. If the water / binder ratio becomes too large, the neutralization rate of the resulting cured product increases and the compressive strength tends to decrease. Conversely, if the water / binder ratio becomes too small, the prepared blast furnace slag The fluidity of the contained concrete tends to decrease, and the workability tends to decrease.
本発明の調製方法では、本発明の効果を損なわない範囲内で、ＡＥ（空気連行）剤、消泡剤、防水剤、防腐剤、防錆剤等の他の添加剤を併用することができる。 In the preparation method of the present invention, other additives such as an AE (air entrainment) agent, an antifoaming agent, a waterproofing agent, a preservative, and a rustproofing agent can be used in combination as long as the effects of the present invention are not impaired. .
本発明の調製方法では、以上説明した結合材、水、細骨材、粗骨材及び多機能混和剤を公知の方法で練り混ぜる。具体的には、結合材、水の一部、細骨材及び粗骨材をミキサーで混練する一方で、前記した多機能混和剤と必要に応じてＡＥ調節剤を水の残部で希釈して、しかる後に双方を練り混ぜる方法で調製することができる。この場合、多機能混和剤は予め、固形分濃度が１０〜５０質量％の水溶液に調整した一液型混和剤として用いるのが、取扱い上の簡便性及び練り混ぜの均一性を図る上で好ましく、特に生コンクリートプラントにおいて混和剤の貯蔵及び計量を効率的に行える利点がある。 In the preparation method of the present invention, the binder, water, fine aggregate, coarse aggregate and multifunctional admixture described above are kneaded by a known method. Specifically, the binder, a portion of water, fine aggregate and coarse aggregate are kneaded with a mixer, while the above-mentioned multifunctional admixture and, if necessary, the AE modifier are diluted with the remainder of the water. Then, it can be prepared by a method in which both are kneaded. In this case, the multifunctional admixture is preferably used in advance as a one-component admixture adjusted to an aqueous solution having a solid content concentration of 10 to 50% by mass for ease of handling and uniformity of mixing. In particular, there is an advantage that the admixture can be efficiently stored and metered in a ready-mixed concrete plant.
本発明に係る高炉スラグ含有コンクリートは、以上説明した本発明の調製方法によって得られるものである。また本発明に係る硬化体は、本発明に係る高炉スラグ含有コンクリートを硬化させて得られるものである。硬化の方法は特に限定されず、これには公知の方法が適用できる。本発明に係る硬化体の具体的な形態としては、小型或いは薄型のコンクリート硬化体はもちろんのこと、特に水和熱による温度上昇により高温履歴を受ける建築用途の大型ＲＣ柱や大型鋼管コンクリート柱、更には土木用マスコンクリート等の大型コンクリート硬化体等が挙げられる。 The blast furnace slag-containing concrete according to the present invention is obtained by the preparation method of the present invention described above. The cured body according to the present invention is obtained by curing the blast furnace slag-containing concrete according to the present invention. The curing method is not particularly limited, and a known method can be applied to this. As a concrete form of the hardened body according to the present invention, not only a small or thin hardened concrete body, but particularly a large RC column or a large steel pipe concrete column for architectural use that receives a high temperature history due to a temperature rise due to heat of hydration, Furthermore, large concrete hardened bodies, such as mass concrete for civil engineering, etc. are mentioned.
以上説明した本発明には、１）高炉スラグ含有コンクリートは、調製後の経時的な流動性の保持性（スランプ保持性）が低い、２）高炉スラグ含有コンクリートは、得られる硬化体の圧縮強度が低い、３）高炉スラグ含有コンクリートは、水和反応により硬化する過程での発熱により温度上昇する熱履歴を受けると、得られる硬化体の圧縮強度が低下する、という以上の１）〜３）の問題を同時に且つ充分に解決できるという効果がある。 In the present invention described above, 1) the blast furnace slag-containing concrete has low fluidity retention (slump retention) over time after preparation, and 2) the blast furnace slag-containing concrete has a compressive strength of the obtained cured body 3) Blast furnace slag-containing concrete is subjected to a heat history that rises due to heat generation in the process of hardening by a hydration reaction, and the compressive strength of the resulting hardened body is reduced 1) to 3) above There is an effect that the problem can be solved simultaneously and sufficiently.
以下、本発明の構成及び効果をより具体的にするため、実施例等を挙げるが、本発明が該実施例に限定されるというものではない。なお、以下の実施例等において、別に記載しない限り、％は質量％を、また部は質量部を意味する。 Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to the examples. In the following examples and the like, unless otherwise indicated,% means mass%, and part means mass part.
試験区分１（Ａ成分としての水溶性ビニル共重合体の合成）
・Ａ成分としての水溶性ビニル共重合体（ａ−１）の合成
無水マレイン酸９８ｇ（１．０モル）及びα−アリル−ω−メチル−ポリ（ｎ＝３３）オキシエチレン１５２０ｇ（１．０モル）を反応容器に仕込み、徐々に加温して攪拌しながら均一に溶解した後、反応容器内の雰囲気を窒素置換した。反応系の温度を温水中にて８３℃に保ち、過酸化ベンゾイル２ｇを投入してラジカル重合反応を開始した。更に過酸化ベンゾイル３ｇを分割投入し、ラジカル重合反応を４時間継続して行なった。得られた共重合体に水を加えて加水分解し、水溶性ビニル共重合体（ａ−１）の４０％水溶液を得た。水溶性ビニル共重合体（ａ−１）を分析したところ、マレイン酸から形成された構成単位／α−アリル−ω−メチル−ポリ（ｎ＝３３）オキシエチレンから形成された構成単位＝５０／５０（モル比）の割合で有する質量平均分子量４２０００（ＧＰＣ法、ポリエチレングリコール換算）の水溶性ビニル共重合体であった。
Test Category 1 (Synthesis of water-soluble vinyl copolymer as component A)
Synthesis of water-soluble vinyl copolymer (a-1) as component A Maleic anhydride 98 g (1.0 mol) and α-allyl-ω-methyl-poly (n = 33) oxyethylene 1520 g (1.0 Mol) was charged into a reaction vessel and gradually heated and stirred to dissolve uniformly, and then the atmosphere in the reaction vessel was replaced with nitrogen. The temperature of the reaction system was maintained at 83 ° C. in warm water, and 2 g of benzoyl peroxide was added to initiate radical polymerization reaction. Further, 3 g of benzoyl peroxide was added in portions, and the radical polymerization reaction was continued for 4 hours. The obtained copolymer was hydrolyzed by adding water to obtain a 40% aqueous solution of the water-soluble vinyl copolymer (a-1). When the water-soluble vinyl copolymer (a-1) was analyzed, structural unit formed from maleic acid / structural unit formed from α-allyl-ω-methyl-poly (n = 33) oxyethylene = 50 / It was a water-soluble vinyl copolymer having a mass average molecular weight of 42000 (GPC method, converted to polyethylene glycol) having a ratio of 50 (molar ratio).
水溶性ビニル共重合体（ａ−２）、（ａｒ−１）及び（ａｒ−２）の合成
水溶性ビニル共重合体（ａ−１）の合成と同様にして、水溶性ビニル共重合体（ａ−２）、（ａｒ−１）及び（ａｒ−２）を合成した。
Synthesis of water-soluble vinyl copolymer (a-2), (ar-1) and (ar-2) In the same manner as the synthesis of water-soluble vinyl copolymer (a-1), a water-soluble vinyl copolymer ( a-2), (ar-1) and (ar-2) were synthesized.
・Ａ成分としての水溶性ビニル共重合体（ａ−３）の合成
α−アリル−ω−ヒドロキシ−ポリ（ｎ＝３０）オキシエチレン１３７０ｇ（１．０モル）、マレイン酸１１６ｇ（１．０モル）及び水１７６０ｇを反応容器に仕込み、撹拌しながら均一に溶解した後、雰囲気を窒素置換した。反応系の温度を温水浴にて６０℃に保ち、過硫酸ナトリウムの２０％水溶液８ｇを加えてラジカル重合反応を開始した。更に過硫酸ナトリウムの２０％水溶液５ｇを加え、ラジカル重合反応を５時間継続して行なった。その後、４８％水酸化ナトリウム水溶液１６７ｇ（２．０モル）を加えて反応物を中和し、更に水を３９０ｇ加えて、水溶性ビニル共重合体（ａ−３）の４０％水溶液を得た。水溶性ビニル共重合体（ａ−３）を分析したところ、マレイン酸ナトリウムから形成された構成単位／α−アリル−ω−ヒドロキシ−ポリ（ｎ＝３０）オキシエチレンから形成された構成単位＝５０／５０（モル比）の割合で有する質量平均分子量５１６００（ＧＰＣ法、ポリエチレングリコール換算）の水溶性ビニル共重合体であった。
Synthesis of water-soluble vinyl copolymer (a-3) as component A α-allyl-ω-hydroxy-poly (n = 30) oxyethylene 1370 g (1.0 mol), maleic acid 116 g (1.0 mol) ) And 1760 g of water were charged into a reaction vessel and dissolved uniformly with stirring, and the atmosphere was replaced with nitrogen. The temperature of the reaction system was kept at 60 ° C. in a warm water bath, and 8 g of a 20% aqueous solution of sodium persulfate was added to initiate radical polymerization reaction. Further, 5 g of a 20% aqueous solution of sodium persulfate was added, and the radical polymerization reaction was continued for 5 hours. Thereafter, 167 g (2.0 mol) of a 48% aqueous sodium hydroxide solution was added to neutralize the reaction product, and 390 g of water was further added to obtain a 40% aqueous solution of the water-soluble vinyl copolymer (a-3). . When the water-soluble vinyl copolymer (a-3) was analyzed, structural unit formed from sodium maleate / structural unit formed from α-allyl-ω-hydroxy-poly (n = 30) oxyethylene = 50. It was a water-soluble vinyl copolymer having a mass average molecular weight of 51600 (GPC method, in terms of polyethylene glycol) having a ratio of / 50 (molar ratio).
水溶性ビニル共重合体（ａｒ−３）〜（ａｒ−５）の合成
水溶性ビニル共重合体（ａ−３）の合成と同様にして、水溶性ビニル共重合体（ａｒ−３）〜（ａｒ−５）を合成した。以上で合成した水溶性ビニル共重合体の内容を表１にまとめて示した。
Synthesis of water-soluble vinyl copolymers (ar-3) to (ar-5) In the same manner as the synthesis of water-soluble vinyl copolymers (a-3), water-soluble vinyl copolymers (ar-3) to (ar-3) to ( ar-5) was synthesized. The contents of the water-soluble vinyl copolymer synthesized above are summarized in Table 1.
表１において、
質量平均分子量：ＧＰＣ法、ポリエチレングリコール換算
Ｄ−１：マレイン酸
Ｄ−２：マレイン酸ナトリウム
Ｅ−１：α−アリル−ω−メチル−ポリ（ｎ＝３３）オキシエチレン
Ｅ−２：α−アリル−ω−メチル−ポリ（ｎ＝４８）オキシエチレン
Ｅ−３：α−アリル−ω−ヒドロキシ−ポリ（ｎ＝３０）オキシエチレン
Ｅ−４：α−アリル−ω−ヒドロキシ−ポリ（ｎ＝１０５）オキシエチレン
Ｅ−５：α−アリル−ω−ヒドロキシ−ポリ（ｎ＝９）オキシエチレン
In Table 1,
Mass average molecular weight: GPC method, converted into polyethylene glycol D-1: maleic acid D-2: sodium maleate E-1: α-allyl-ω-methyl-poly (n = 33) oxyethylene E-2: α-allyl -Ω-methyl-poly (n = 48) oxyethylene E-3: α-allyl-ω-hydroxy-poly (n = 30) oxyethylene E-4: α-allyl-ω-hydroxy-poly (n = 105 ) Oxyethylene E-5: α-allyl-ω-hydroxy-poly (n = 9) oxyethylene
試験区分２（Ｂ成分としての水溶性デキストリン化合物の水溶液の調製）
食品添加物として市販されている多くの水溶性デキストリン化合物について、ＧＰＣ法による分子量及び分散度の測定分析を行い、それらのなかから分子量及び分散度が異なる複数の水溶性デキストリン化合物を用意し、それらの固形分濃度４０％水溶液（室温で完全溶解）を調製した。用意した複数の水溶性デキストリン化合物（ｂ−１）〜（ｂ−４）及び（ｂｒ−１）〜（ｂｒ−３）の内容を表２にまとめて示した。
Test category 2 (Preparation of aqueous solution of water-soluble dextrin compound as component B)
For many water-soluble dextrin compounds marketed as food additives, the molecular weight and dispersity are measured and analyzed by the GPC method. Among them, a plurality of water-soluble dextrin compounds having different molecular weights and dispersities are prepared. A 40% solid concentration aqueous solution (completely dissolved at room temperature) was prepared. The contents of the prepared water-soluble dextrin compounds (b-1) to (b-4) and (br-1) to (br-3) are shown together in Table 2.
表２において、
分子量：ＧＰＣ法によるポリエチレングリコール換算の質量平均分子量（Ｍｗ）又は数平均分子量（Ｍｎ）
分散度：質量平均分子量（Ｍｗ）を数平均分子量（Ｍｎ）で除した数値（Ｍｗ／Ｍｎ）
In Table 2,
Molecular weight: Mass average molecular weight (Mw) or number average molecular weight (Mn) in terms of polyethylene glycol by GPC method
Dispersity: Numerical value (Mw / Mn) obtained by dividing mass average molecular weight (Mw) by number average molecular weight (Mn)
試験区分３（多機能混和剤の３０％水溶液の調製及び評価）
・多機能混和剤（Ｐ−１）の３０％水溶液の調製
Ａ成分として前記の水溶性ビニル共重合体（ａ−１）の水溶液（固形分濃度４０％）６００部、Ｂ成分として前記のデキストリン化合物（ｂ−１）の水溶液（固形分濃度４０％）４９０部、Ｃ成分としてハイドロキノン０．５部及び水３６４部を２リットルのフラスコ容器に投入して混合し、Ａ成分とＢ成分とＣ成分の３成分からなる多機能混和剤の３０％水溶液を調製した。
Test Category 3 (Preparation and evaluation of 30% aqueous solution of multifunctional admixture)
Preparation of 30% aqueous solution of multifunctional admixture (P-1) 600 parts of aqueous solution (solid content concentration 40%) of water-soluble vinyl copolymer (a-1) as component A, dextrin as component B 490 parts of an aqueous solution of compound (b-1) (solid content concentration: 40%), 0.5 part of hydroquinone and 364 parts of water as C component are put into a 2 liter flask and mixed, and A component, B component and C are mixed. A 30% aqueous solution of a multifunctional admixture composed of three components was prepared.
・多機能混和剤（Ｐ−２）〜（Ｐ−１２）及び（Ｒ−１）〜（Ｒ−１５）の３０％水溶液の調製
多機能混和剤（Ｐ−１）の３０％水溶液の調製と同様にして、多機能混和剤（Ｐ−２）〜（Ｐ−１２）及び（Ｒ−１）〜（Ｒ−１５）の３０％水溶液を調製した。調製した各多機能混和剤の内容を表３にまとめて示した。
Preparation of 30% aqueous solution of multifunctional admixtures (P-2) to (P-12) and (R-1) to (R-15) Preparation of 30% aqueous solution of multifunctional admixture (P-1) Similarly, 30% aqueous solutions of multifunctional admixtures (P-2) to (P-12) and (R-1) to (R-15) were prepared. The contents of each prepared multifunctional admixture are summarized in Table 3.
・多機能混和剤の安定性の評価
調製した各多機能混和剤（Ｐ−１）〜（Ｐ−１２）及び（Ｒ−１）〜（Ｒ−１５）の３０％水溶液を、１００ｍｌ容量のメスシリンダーに入れ、室温で２ヶ月間放置した後に目視判定し、下記の基準で評価した。結果を表３にまとめて示した。
評価基準
○：均一透明
×：分離又は濁りが認められる。
Evaluation of stability of multifunctional admixture A 30 ml aqueous solution of each of the prepared multifunctional admixtures (P-1) to (P-12) and (R-1) to (R-15) was added to a 100 ml volume female. The sample was placed in a cylinder and allowed to stand at room temperature for 2 months, then visually judged and evaluated according to the following criteria. The results are summarized in Table 3.
Evaluation criteria ○: Uniform transparency ×: Separation or turbidity is observed.
表３において、
ａ−１〜ａ−３，ａｒ−１〜ａｒ−５：表１に記載の水溶性ビニル共重合体
ｂ−１〜ｂ−４，ｂｒ−１〜ｂｒ−３：表２に記載の水溶性デキストリン化合物
＊１：タンニン酸
＊２：デンプン
＊３：ブドウ糖
＊４：グルコン酸
ｃ−１：ハイドロキノン
ｃ−２：ハイドロキノンモノメチルエーテル
ｃ−３：モノメチルハイドロキノン
ｃ−４：ｐ−ベンゾキノン
In Table 3,
a-1 to a-3, ar-1 to ar-5: water-soluble vinyl copolymers described in Table 1 b-1 to b-4, br-1 to br-3: water-soluble properties described in Table 2 Dextrin compound * 1: Tannic acid * 2: Starch * 3: Glucose
* 4: Gluconic acid c-1: Hydroquinone c-2: Hydroquinone monomethyl ether c-3: Monomethyl hydroquinone c-4: p-benzoquinone
試験区分４（高炉スラグ含有コンクリートの調製及び評価）
実施例１〜１２
試験区分３で調製した表３に記載の多機能混和剤の３０％水溶液を用いて、表４に記載の配合条件１で、５０リットルのパン型強制練りミキサーに、結合材｛高炉セメントＢ種相当：高炉スラグ微粉末４４質量％、普通ポルトランドセメント５１質量％及び石膏５質量％（合計１００質量％）、密度＝３．０４ｇ／ｃｍ３）、細骨材（大井川水系砂、密度＝２．５８ｇ／ｃｍ３）、練り混ぜ水（水道水）、多機能混和剤（Ｐ−１）の３０％水溶液及び空気量調整剤（竹本油脂社製のＡＥ剤、商品名ＡＥ３００）の各所定量を順次投入してスラリーが均一となるまで練り混ぜた。多機能混和剤の使用量（固形分としての使用量）は表５に記載した。次に、粗骨材（岡崎産砕石、密度＝２．６８ｇ／ｃｍ３）を投入し、３０秒間練り混ぜ、目標スランプが１８±１ｃｍ、目標空気量が４．５±０．５％の実施例１の高炉スラグ含有コンクリートを調製した。同様にして、実施例２〜１２の高炉スラグ含有コンクリートを調製した。練り混ぜ時の温度はいずれも３０℃で行なった。
Test category 4 (Preparation and evaluation of concrete containing blast furnace slag)
Examples 1-12
Using a 30% aqueous solution of the multifunctional admixture described in Table 3 prepared in Test Category 3 and a compounding condition 1 described in Table 4 to a 50-liter pan-type forced kneader mixer, a binder {Blast furnace cement type B Equivalent: 44% by mass of blast furnace slag fine powder, 51% by mass of ordinary Portland cement and 5% by mass of gypsum (total 100% by mass), density = 3.04 g / cm 3 ), fine aggregate (Oikawa water sand, density = 2. 58 g / cm 3 ), kneaded water (tap water), 30% aqueous solution of multifunctional admixture (P-1) and air amount adjusting agent (AE agent manufactured by Takemoto Yushi Co., Ltd., trade name AE300) in order. It was added and kneaded until the slurry was uniform. The amount of multifunctional admixture used (the amount used as a solid content) is shown in Table 5. Next, coarse aggregate (Okazaki crushed stone, density = 2.68 g / cm 3 ) is added and mixed for 30 seconds. The target slump is 18 ± 1 cm and the target air volume is 4.5 ± 0.5%. The blast furnace slag-containing concrete of Example 1 was prepared. Similarly, concrete containing blast furnace slag of Examples 2 to 12 was prepared. The kneading temperature was 30 ° C. for all.
実施例１３〜２４
実施例１〜１２と同様にして、但し表４に記載の配合条件２で、実施例１３〜２４の高炉スラグ含有コンクリートを調製した。練り混ぜ時の温度はいずれも３０℃で行なった。
Examples 13-24
The blast furnace slag-containing concretes of Examples 13 to 24 were prepared in the same manner as in Examples 1 to 12 except that the mixing conditions 2 described in Table 4 were used. The kneading temperature was 30 ° C. for all.
実施例２５〜２８
試験区分３で調製した表３に記載の多機能混和剤の３０％水溶液を用いて、表４に記載の配合条件３で、５０リットルのパン型強制練りミキサーに、結合材｛高炉セメントＣ種相当：高炉スラグ微粉末６５質量％、普通ポルトランドセメント３０質量％及び石膏５質量％（合計１００質量％）、密度＝３．０１ｇ／ｃｍ３｝、細骨材（大井川水系砂、密度＝２．５８ｇ／ｃｍ３）、練り混ぜ水（水道水）、多機能混和剤（ｐ−１）及び空気量調整剤（前記のＡＥ３００）の各所定量を順次投入してスラリーが均一となるまで練り混ぜた。多機能混和剤の使用量（固形分としての使用量）は表５に記載した。次に、粗骨材（岡崎産砕石、密度＝２．６８ｇ／ｃｍ３）を投入し３０秒間練り混ぜ、目標スランプフローが５５±５ｃｍ、目標空気量が３．０±０．５％の実施例２５の高炉スラグ含有コンクリートを調製した。同様にして、実施例２６〜２８の高炉スラグ含有コンクリートを調製した。練り混ぜ時の温度はいずれも２０℃で行なった。
Examples 25-28
Using a 30% aqueous solution of the multifunctional admixture described in Table 3 prepared in Test Category 3 and a compounding condition 3 described in Table 4 to a 50-liter pan-type forced kneader mixer, a binder {classified blast furnace cement C Equivalent: 65% by mass of blast furnace slag fine powder, 30% by mass of ordinary Portland cement and 5% by mass of gypsum (total of 100% by mass), density = 3.01 g / cm 3 }, fine aggregate (Oikawa water sand, density = 2. 58 g / cm 3 ), kneaded water (tap water), multifunctional admixture (p-1) and air amount adjuster (AE300) were sequentially added and kneaded until the slurry was uniform. . The amount of multifunctional admixture used (the amount used as a solid content) is shown in Table 5. Next, coarse aggregate (Okazaki crushed stone, density = 2.68 g / cm 3 ) is added and mixed for 30 seconds, with a target slump flow of 55 ± 5 cm and a target air volume of 3.0 ± 0.5%. The blast furnace slag-containing concrete of Example 25 was prepared. Similarly, concrete containing blast furnace slag of Examples 26 to 28 was prepared. The kneading temperature was 20 ° C.
実施例２９〜３２
実施例２５〜２８と同様にして、但し表４に記載の配合条件４で、実施例２９〜３２の高炉スラグ含有コンクリートを調製した。練り混ぜ時の温度はいずれも２０℃で行なった。
Examples 29-32
The blast furnace slag-containing concrete of Examples 29 to 32 was prepared in the same manner as in Examples 25 to 28 except that the blending condition 4 described in Table 4 was used. The kneading temperature was 20 ° C.
実施例３３〜３６
実施例２５〜２８と同様にして、但し表４に記載の配合条件５で、実施例３３〜３６の高炉スラグ含有コンクリートを調製した。練り混ぜ時の温度はいずれも２０℃で行なった。以上の各実施例で調製した高炉スラグ含有コンクリートの内容を表５にまとめて示した。
Examples 33-36
Blast furnace slag-containing concretes of Examples 33 to 36 were prepared in the same manner as in Examples 25 to 28 except that the blending condition 5 shown in Table 4 was used. The kneading temperature was 20 ° C. Table 5 summarizes the contents of the blast furnace slag-containing concrete prepared in each of the above examples.
比較例１〜４０
表４に記載の配合条件で、比較例１〜１５は実施例１〜１２と同様にして、比較例１６〜３０は実施例１３〜２４と同様にして、比較例３１〜３４は実施例２５〜２８と同様にして、比較例３５〜３７は実施例２９〜３２と同様にして、比較例３８〜４０は実施例３３〜３６と同様にして、高炉スラグ含有コンクリートを調製した。以上の各比較例で調製した高炉スラグ含有コンクリートの内容を表７にまとめて示した。
Comparative Examples 1-40
In the blending conditions shown in Table 4, Comparative Examples 1 to 15 are the same as Examples 1 to 12, Comparative Examples 16 to 30 are the same as Examples 13 to 24, and Comparative Examples 31 to 34 are Example 25. In the same manner as in Examples 28 to 28, Comparative Examples 35 to 37 were made in the same manner as Examples 29 to 32, and Comparative Examples 38 to 40 were made in the same manner as in Examples 33 to 36 to prepare blast furnace slag-containing concrete. Table 7 summarizes the contents of the blast furnace slag-containing concrete prepared in the above comparative examples.
表４において、
＊５：高炉スラグ微粉末６５％、普通ポルトランドセメント３０％及び無水石膏５％（合計１００％）からなる高炉セメントＣ種相当（密度＝３．０１ｇ/ｃｍ３、ブレーン値４１８０cm２/ｇ）の結合材
＊６：高炉スラグ微粉末４４％、普通ポルトランドセメント５１％及び無水石膏５％（合計１００％）からなる高炉セメントＢ種相当（密度＝３．０４ｇ/ｃｍ３、ブレーン値３８５０cm２/ｇ）の結合材
細骨材：大井川水系砂（密度＝２．５８ｇ/ｃｍ３）
粗骨材：岡崎産砕石（密度＝２．６８ｇ/ｃｍ３）
In Table 4,
* 5: Blast furnace cement C type consisting of 65% fine powder of blast furnace slag, 30% ordinary Portland cement and 5% anhydrous gypsum (total 100%) (density = 3.01 g / cm 3 , brane value 4180 cm 2 / g) Binder * 6: Blast furnace cement B type consisting of 44% blast furnace slag fine powder, ordinary Portland cement 51% and anhydrous gypsum 5% (total 100%) (density = 3.04 g / cm 3 , brane value 3850 cm 2 / g) ) Bonding material Fine aggregate: Oikawa water sand (density = 2.58 g / cm 3 )
Coarse aggregate: Crushed stone from Okazaki (density = 2.68 g / cm 3 )
・高炉スラグ含有コンクリートの物性評価
調製した各例の高炉スラグ含有コンクリートについて、練り混ぜ直後のスランプ又はスランプフローと空気量、練り混ぜ直後から６０分静置後のスランプ又はスランプフローと空気量、スランプ残存率又はスランプフロー残存率、標準水中養生供試体の圧縮強度及び高温履歴供試体の圧縮強度を下記のように求め、結果を表５〜表８にまとめて示した。
・ Evaluation of physical properties of blast furnace slag-containing concrete About the prepared blast furnace slag-containing concrete, slump or slump flow and air amount immediately after mixing, slump or slump flow and air amount after standing for 60 minutes immediately after mixing, slump The residual rate or the slump flow residual rate, the compressive strength of the standard water curing specimen and the compressive strength of the high temperature history specimen were determined as follows, and the results are shown in Tables 5 to 8.
・スランプ（ｃｍ）：練り混ぜ直後及びそれから６０分静置後の高炉スラグ含有コンクリートについて、ＪＩＳ−Ａ１１０１に準拠して測定した。
・スランプフロー（ｃｍ）：練り混ぜ直後及びそれから６０分静置後の高炉スラグ含有コンクリートについて、ＪＩＳ−Ａ１１５０に準拠して測定した。
・空気量（容量％）：練り混ぜ直後及びそれから６０分静置後の高炉スラグ含有コンクリートについて、ＪＩＳ−Ａ１１２８に準拠して測定した。
・スランプ残存率（％）：（６０分静置後のスランプ値／練り混ぜ直後のスランプ値）×１００で求めた。
・スランプフロー残存率（％）：（６０分静置後のスランプフロー値／練り混ぜ直後のスランプフロー値）×１００で求めた。
・標準水中養生供試体の圧縮強度（Ｎ／ｍｍ２）：練り混ぜて調製した各例の高炉スラグ含有コンクリートを直径１０ｃｍ×高さ２０ｃｍの円柱モールドに充填し、２０℃水中で所定の材齢まで水中養生した供試体について、ＪＩＳ−Ａ１１０８に準拠し、材齢７日と２８日で測定した。
・高温履歴供試体の圧縮強度（Ｎ／ｍｍ２）：練り混ぜて調製した各例の高炉スラグ含有コンクリートを直径１０ｃｍ×高さ２０ｃｍの円柱モールドに充填し、内寸が５００ｍｍ×５００ｍｍ×４００ｍｍの周囲６面を断熱材（厚さ約３０ｃｍの発砲スチレン）で覆った簡易断熱箱に前記の円柱モールド９本を静置した。中心位置の円柱モールドに熱電対を設置して内部の温度上昇履歴を測定しつつ、所定の材齢まで高温履歴（最高温度は４０〜６０℃）の負荷を継続した高温履歴供試体について、ＪＩＳ−Ａ１１０８に準拠し、材齢２８日で測定した。
-Slump (cm): It measured based on JIS-A1101 about the blast furnace slag containing concrete immediately after kneading | mixing and after leaving still for 60 minutes.
-Slump flow (cm): It measured based on JIS-A1150 about the blast furnace slag containing concrete immediately after kneading | mixing and after leaving still for 60 minutes.
-Air amount (volume%): It measured based on JIS-A1128 about the blast furnace slag containing concrete immediately after mixing and after leaving still for 60 minutes.
Slump residual ratio (%): (slump value after standing for 60 minutes / slump value immediately after kneading) × 100.
Slump flow residual ratio (%): (slump flow value after standing for 60 minutes / slump flow value immediately after kneading) × 100.
Compressive strength (N / mm 2 ) of standard water curing specimen: Each blast furnace slag-containing concrete prepared by kneading was filled into a cylindrical mold having a diameter of 10 cm and a height of 20 cm, and a predetermined age in water at 20 ° C. The specimens cured underwater were measured at 7 and 28 days of age according to JIS-A1108.
Compressive strength (N / mm 2 ) of high-temperature history specimen: Each blast furnace slag-containing concrete prepared by kneading was filled into a cylindrical mold having a diameter of 10 cm and a height of 20 cm, and the inner dimensions were 500 mm × 500 mm × 400 mm. Nine of the above-mentioned cylindrical molds were allowed to stand in a simple heat insulation box whose six surrounding surfaces were covered with a heat insulating material (foamed styrene having a thickness of about 30 cm). A high temperature history specimen that has been loaded with a high temperature history (maximum temperature is 40-60 ° C) until a predetermined age while a thermocouple is installed in a cylindrical mold at the center position and the temperature rise history inside is measured. -Based on -A1108, measured at a material age of 28 days.
表５〜表８において、
配合条件：表４に記載した配合条件
多機能混和剤の種類：表３に記載した多機能混和剤の種類
多機能混和剤の使用量：結合材１００質量部に対する多機能混和剤の添加質量部（固形分としての添加質量部）
＊７：各実施例の標準水中養生供試体の圧縮強度（材齢７日又は２８日）から相当する配合条件の混和剤を用いなかった比較例（表３の混和剤Ｒ−１を用いた比較例１、１６、３１、３５又は３８）の標準水中養生供試体の圧縮強度（材齢７日又は２８日）を差し引いた値。
＊８：各実施例の高温履歴供試体の圧縮強度（材齢２８日）から相当する配合条件の混和剤を用いなかった比較例（表３の混和剤Ｒ−１を用いた比較例１、１６、３１、３５又は３８）の高温履歴供試体の圧縮強度（材齢２８日）を差し引いた値。
＊９：目標とする流動性のコンクリートが得られなかったので測定しなかった。
＊１０：多機能混和剤の水溶液に沈殿又は濁りが生じていたので使用せず、測定しなかった。
In Tables 5 to 8,
Compounding conditions: Compounding conditions described in Table 4 Types of multifunctional admixture: Types of multifunctional admixture described in Table 3 Use amount of multifunctional admixture: Addition parts by mass of multifunctional admixture with respect to 100 parts by mass of binder (Additional mass part as solid content)
* 7: Comparative example (admixture R-1 in Table 3 was used) in which the admixture with the corresponding blending conditions was not used from the compressive strength (age 7 or 28 days) of the standard water curing specimen of each example A value obtained by subtracting the compressive strength (age 7 days or 28 days) of the standard underwater curing specimen of Comparative Example 1, 16, 31, 35 or 38).
* 8: Comparative Example (Comparative Example 1 using Admixture R-1 in Table 3) that did not use the admixture with the corresponding blending conditions from the compressive strength (age 28 days) of the high temperature history specimen of each Example The value obtained by subtracting the compressive strength (age 28 days) of the high temperature history specimen of 16, 31, 35 or 38).
* 9: Measurement was not performed because the target fluid concrete was not obtained.
* 10: Precipitation or turbidity occurred in the aqueous solution of the multifunctional admixture, so it was not used and was not measured.
表５〜表８の結果からも明らかなように、本発明の各実施例によると、調製した高炉スラグ含有コンクリートに良好な流動性を与え、しかも調製後の経時的な流動性の低下が少なく、同時に得られる硬化体の圧縮強度が高く、強度増進効果が顕著に得られていて、かかる高い圧縮強度及びその強度増進効果は高温履歴の硬化体にも顕著に得られている。そしてこれらの効果は、結合材として、高炉スラグ微粉末の含有量がより多い高炉セメントＢ種相当の結合材や高炉セメントＣ種相当の結合材を用いた場合に大きくなっている。 As is apparent from the results of Tables 5 to 8, according to each example of the present invention, the prepared blast furnace slag-containing concrete was given good fluidity, and the decrease in fluidity with time after preparation was small. At the same time, the cured product obtained has a high compressive strength, and the effect of enhancing the strength is remarkably obtained. The high compressive strength and the effect of enhancing the strength are also remarkably obtained for the cured product having a high temperature history. These effects are increased when a binder equivalent to the type B blast furnace cement B or a binder equivalent to the type C blast furnace cement is used as the binder.
Claims (10)
結合材：高炉スラグ微粉末を４０〜７５質量％、ポルトランドセメントを２３〜５３質量％及び石膏を２〜７質量％（合計１００質量％）の割合で含有してなるもの。
多機能混和剤：下記のＡ成分を２０〜８０質量％、下記のＢ成分を１９．９９〜７９質量％及び下記のＣ成分を０．０１〜１質量％（合計１００質量％）の割合で含有してなるもの。
Ａ成分：分子中に下記の構成単位Ｄを４０〜６０モル％及び下記の構成単位Ｅを６０〜４０モル％（合計１００モル％）の割合で有する質量平均分子量２０００〜８００００の水溶性ビニル共重合体。
構成単位Ｄ：マレイン酸から形成された構成単位及びマレイン酸塩からから形成された構成単位から選ばれる一つ又は二つ以上
構成単位Ｅ：分子中に１５〜８０個のオキシエチレン単位で構成されたポリオキシエチレン基を有するα−アリル−ω−メチル−ポリオキシエチレンから形成された構成単位及び分子中に１５〜８０個のオキシエチレン単位で構成されたポリオキシエチレン基を有するα−アリル−ω−ヒドロキシ−ポリオキシエチレンから形成された構成単位から選ばれる一つ又は二つ以上。
Ｂ成分：質量平均分子量が１０００〜２００００であり、且つ分散度が１．２〜６．０の水溶性デキストリン化合物。
Ｃ成分：ハイドロキノン、ハイドロキノンモノメチルエーテル、モノメチルハイドロキノン及びｐ−ベンゾキノンから選ばれる一つ又は二つ以上。 A method for preparing blast furnace slag-containing concrete using the following binder, water, fine aggregate, coarse aggregate and the following multifunctional admixture, wherein the following multifunctional admixture is 0 per 100 parts by mass of the following binder: A method for preparing concrete containing blast furnace slag, which is used in a proportion of 1 to 1.5 parts by mass.
Binder: What contains 40-75 mass% of blast furnace slag fine powder, 23-53 mass% of Portland cement, and 2-7 mass% (total 100 mass%) of gypsum.
Multifunctional admixture: 20 to 80% by mass of the following A component, 19.99 to 79% by mass of the following B component, and 0.01 to 1% by mass (100% by mass in total) of the following C component Contains.
Component A: A water-soluble vinyl copolymer having a mass average molecular weight of 2000 to 80000 having the following constitutional unit D in the molecule in a proportion of 40 to 60 mol% and the following constitutional unit E in a proportion of 60 to 40 mol% (total 100 mol%). Polymer.
Structural unit D: One or more selected from a structural unit formed from maleic acid and a structural unit formed from maleate Structural unit E: Consists of 15 to 80 oxyethylene units in the molecule Α-Allyl-ω-methyl-polyoxyethylene having a polyoxyethylene group and α-allyl having a polyoxyethylene group composed of 15 to 80 oxyethylene units in the molecule One or more selected from structural units formed from ω-hydroxy-polyoxyethylene.
Component B: A water-soluble dextrin compound having a mass average molecular weight of 1,000 to 20,000 and a dispersity of 1.2 to 6.0.
Component C: One or two or more selected from hydroquinone, hydroquinone monomethyl ether, monomethyl hydroquinone and p-benzoquinone.
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