JP5545616B2 - Concrete composition using blast furnace cement composition - Google Patents
Concrete composition using blast furnace cement composition Download PDFInfo
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- JP5545616B2 JP5545616B2 JP2009137968A JP2009137968A JP5545616B2 JP 5545616 B2 JP5545616 B2 JP 5545616B2 JP 2009137968 A JP2009137968 A JP 2009137968A JP 2009137968 A JP2009137968 A JP 2009137968A JP 5545616 B2 JP5545616 B2 JP 5545616B2
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- 239000000203 mixture Substances 0.000 title claims description 101
- 239000004567 concrete Substances 0.000 title claims description 90
- 239000011400 blast furnace cement Substances 0.000 title claims description 54
- 239000000843 powder Substances 0.000 claims description 45
- 238000001035 drying Methods 0.000 claims description 23
- 239000002893 slag Substances 0.000 claims description 22
- 229920006163 vinyl copolymer Polymers 0.000 claims description 20
- 239000011398 Portland cement Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 17
- -1 polyoxyethylene group Polymers 0.000 claims description 14
- 239000004568 cement Substances 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 12
- 239000000920 calcium hydroxide Substances 0.000 claims description 12
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 12
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical group [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 9
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 8
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- 229910052602 gypsum Inorganic materials 0.000 claims description 7
- 239000010440 gypsum Substances 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- JWHXUTHLAWCPLP-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol;2-(2-hydroxypropoxy)propan-1-ol Chemical compound CC(O)COC(C)CO.CCCCOCCOCCO JWHXUTHLAWCPLP-UHFFFAOYSA-N 0.000 claims description 4
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 4
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 4
- 125000006353 oxyethylene group Chemical group 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 26
- 238000000034 method Methods 0.000 description 16
- 239000001569 carbon dioxide Substances 0.000 description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000002518 antifoaming agent Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 2
- 239000004575 stone Substances 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 1
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 241000287462 Phalacrocorax carbo Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 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
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical class OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 229910001653 ettringite Inorganic materials 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/34—Non-shrinking or non-cracking materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Description
本発明は高炉セメント組成物を用いたコンクリート組成物に関する。近年、二酸化炭素の排出量の削減やエネルギー消費効率の改善についての要求が益々強くなっている。かかる事情に鑑み、コンクリート組成物の分野においても、製鉄所から副産する高炉水砕スラグが、高炉スラグ微粉末の形で高炉セメントの原料として有効利用されている。一般にコンクリート組成物に使用されている高炉セメントは、普通ポルトランドセメントに高炉スラグ微粉末を混合して造られ、ＪＩＳ−Ｒ５２１１の規格では、高炉スラグ微粉末の分量によって、Ａ種（５％超〜３０％）、Ｂ種（３０％超〜６０％）及びＣ種（６０％超〜７０％）の３種類に分けられている。かかる高炉セメントは、水和熱が低い、長期強度の伸びが大きい、水密性が大きい、硫酸塩に対する化学的侵食に対して抵抗性が大きい、アルカリ骨材反応の抑制効果がある等の有利な点を有しているが、乾燥収縮がポルトランドセメントに比べて大きく、高炉セメントを用いたコンクリート組成物から得られる硬化体は収縮ひび割れが発生し易いという問題や、ポルトランドセメントに比べて中性化による劣化が速いという不利な点も有している。このような理由から、高炉セメントとしては、性能バランスの良い高炉セメントＢ種に限られて使用されているのが実情であるが、高炉セメントＢ種はコンクリート１ｍ３中に２５０〜４５０ｋｇの割合で混入するのが一般的であり、高炉セメントＢ種１トンを工場で製造するために約４００ｋｇの二酸化炭素を排出しているので、高炉セメントＢ種を用いてコンクリート組成物１ｍ３を調製するためには、施工機械の運転や材料の運搬等により発生する二酸化炭素の排出を除き、１００〜１８０ｋｇの二酸化炭素を排出していることになる。そのため、コンクリート工事においては、施工性を確保しつつ、得られる硬化体が必要な強度を有することを前提として、高炉スラグ微粉末をもっと高い割合で使用することにより二酸化炭素の発生を抑制する技術の出現が要求されている。本発明はかかる要求に応える高炉セメント組成物を用いたコンクリート組成物に関する。 The present invention relates to a concrete composition using a blast furnace cement composition. In recent years, demands for reducing carbon dioxide emissions and improving energy consumption efficiency have been increasing. In view of such circumstances, blast furnace granulated slag produced as a by-product from an ironworks is also effectively used as a raw material for blast furnace cement in the form of blast furnace slag fine powder. The blast furnace cement generally used in concrete compositions is made by mixing ordinary Portland cement with blast furnace slag fine powder. According to the standard of JIS-R5211, type A (over 5% to 30%), B type (over 30% to 60%) and C type (over 60% to 70%). Such blast furnace cement has advantages such as low heat of hydration, large long-term strength elongation, high water tightness, high resistance to chemical erosion to sulfate, and suppression effect of alkali aggregate reaction. However, the drying shrinkage is larger than that of Portland cement, and the hardened body obtained from the concrete composition using blast furnace cement is prone to shrinkage cracking and is neutralized compared to Portland cement. There is also a disadvantage that deterioration due to is fast. For this reason, as blast furnace cement, the fact is that it is limited to blast furnace cement type B with a good performance balance, but blast furnace cement type B is in a ratio of 250 to 450 kg in 1 m 3 of concrete. In order to prepare 1 m 3 of concrete composition using Blast Furnace Cement B, it is common to mix, and about 400 kg of carbon dioxide is discharged to produce 1 ton of Blast Furnace Cement B at the factory. In this case, 100 to 180 kg of carbon dioxide is discharged except for the discharge of carbon dioxide generated by the operation of the construction machine and the transportation of materials. Therefore, in concrete construction, technology that suppresses the generation of carbon dioxide by using finer blast furnace slag powder at a higher rate, assuming that the obtained hardened body has the required strength while ensuring workability. The appearance of is required. The present invention relates to a concrete composition using a blast furnace cement composition that meets such requirements.
従来、用いる高炉スラグ微粉末の粉末度や置換率がコンクリート組成物に及ぼす影響について報告されている（例えば、非特許文献１参照）。ここでは、普通ポルトランドセメントに対する高炉スラグ微粉末の使用量が多くなると、普通ポルトランドセメント単独使用に比べて、初期強度が低下し、中性化が早くなり、乾燥収縮が大きくなる等、コンクリート物性のマイナス傾向が顕著になることが報告されている。別に、かかる高炉スラグ微粉末等に加えて各種の混和材を用いたいくつかの提案も報告されている（例えば、特許文献１〜９参照）。しかし、これらの従来提案には実際のところ、高炉スラグ微粉末の使用量を多くすると、１）良好な施工性を確保できない、２）硬化体の乾燥収縮率を抑えることが難しい、３）硬化体の圧縮強度の低下が大きい等、何らかの点で重大な支障をきたすという問題がある。 Conventionally, the influence which fineness and substitution rate of the blast furnace slag fine powder to use have on a concrete composition has been reported (for example, refer nonpatent literature 1). Here, when the amount of blast furnace slag fine powder used for ordinary Portland cement increases, the initial strength decreases, neutralization becomes faster, and drying shrinkage increases compared to ordinary Portland cement alone. It has been reported that the negative trend becomes prominent. Separately, some proposals using various admixtures in addition to such blast furnace slag fine powder have been reported (for example, see Patent Documents 1 to 9). However, these conventional proposals, in fact, increase the amount of blast furnace slag fine powder used, 1) cannot ensure good workability, 2) it is difficult to suppress the drying shrinkage of the cured product, and 3) curing. There is a problem that it causes serious problems in some respects, such as a large decrease in the compressive strength of the body.
本発明が解決しようとする課題は、高炉スラグ微粉末の使用割合を高くすることにより二酸化炭素の排出量を抑制しつつ、１）調製したコンクリート組成物の経時的な流動性の低下や空気量の低下を抑えて良好な施工性を確保すること、２）得られる硬化体の乾燥収縮率が高炉セメントＢ種を用いた場合に比べて大きくならないようにすること、３）得られる硬化体が必要な強度を発現すること、以上の１）〜３）の基本的な諸性能を同時に発現できるコンクリート組成物を提供する処にある。 The problem to be solved by the present invention is to suppress the discharge amount of carbon dioxide by increasing the use ratio of blast furnace slag fine powder, while 1) lowering the fluidity of the prepared concrete composition over time and the amount of air 2) Ensure that good workability is ensured by suppressing the decrease in 2) The drying shrinkage rate of the resulting cured body is not increased compared to the case of using blast furnace cement type B, 3) The resulting cured body is The present invention is to provide a concrete composition capable of expressing necessary strength and simultaneously exhibiting the basic performances 1) to 3) above.
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、結合材として、高炉スラグ微粉末を高い割合で含有する特定の高炉セメント組成物を特定の混和材と共に特定割合で用いたコンクリート組成物が正しく好適であることを見出した。 Therefore, as a result of researches to solve the above problems, the present inventors have used a specific blast furnace cement composition containing a high proportion of blast furnace slag fine powder as a binder together with a specific admixture. It has been found that the concrete composition is correct and suitable.
すなわち本発明は、少なくとも、結合材、水、細骨材、粗骨材及び混和材を含有して成るコンクリート組成物であって、結合材として下記の高炉セメント組成物を用いて、水／該高炉セメント組成物の質量比を３０〜６０％に調製し、また混和材の少なくとも一部として、下記のポリカルボン酸系の水溶性ビニル共重合体からなるセメント分散剤を、高炉セメント組成物１００質量部当たり０．１〜１．５質量部の割合で含有し、更に混和材の少なくとも一部として、下記の乾燥収縮低減剤及び／又は膨張材を、乾燥収縮低減剤は高炉セメント組成物１００質量部当たり０．２〜４．０質量部の割合で含有し、また膨張材はコンクリート組成物１ｍ３当たり１０〜２５ｋｇの割合で含有して成ることを特徴とする高炉セメント組成物を用いたコンクリート組成物に係る。 That is, the present invention is a concrete composition comprising at least a binder, water, fine aggregate, coarse aggregate, and admixture, wherein the following blast furnace cement composition is used as a binder, The mass ratio of the blast furnace cement composition is adjusted to 30 to 60%, and a cement dispersant made of the following polycarboxylic acid-based water-soluble vinyl copolymer is used as at least a part of the admixture. It is contained at a ratio of 0.1 to 1.5 parts by mass per part by mass, and further, as at least a part of the admixture, the following drying shrinkage reducing agent and / or expansion material is used, and the drying shrinkage reducing agent is a blast furnace cement composition 100. A blast furnace cement composition characterized in that it is contained at a rate of 0.2 to 4.0 parts by mass per part by mass, and the expansion material is contained at a rate of 10 to 25 kg per 1 m 3 of the concrete composition. It relates to a concrete composition.
高炉セメント組成物：粉末度が３０００〜１３０００ｃｍ２／ｇの高炉スラグ微粉末を６０〜９０質量％、石膏を５〜２０質量％及びポルトランドセメントを５〜３５質量％（合計１００質量％）の割合で含有する混合物１００質量部当たり、解体コンクリートから分離した水酸化カルシウム含有率が３〜１５質量％の再生コンクリート微粉末を１０〜３０質量部の割合で添加した高炉セメント組成物。 Blast furnace cement composition: 60 to 90% by mass of fine powder of blast furnace slag having a fineness of 3000 to 13000 cm 2 / g, 5 to 20% by mass of gypsum, and 5 to 35% by mass of Portland cement (total 100% by mass) A blast furnace cement composition in which a reclaimed concrete fine powder having a calcium hydroxide content of 3 to 15% by mass separated from demolition concrete is added at a rate of 10 to 30 parts by mass per 100 parts by mass of the mixture.
ポリカルボン酸系の水溶性ビニル共重合体：分子中に下記の構成単位Ａを４５〜８５モル％、下記の構成単位Ｂを１５〜５５モル％及び下記の構成単位Ｃを０〜１０モル％（合計１００モル％）の割合で有する質量平均分子量が２０００〜８００００水溶性ビニル共重合体。
構成単位Ａ：メタクリル酸から形成された構成単位及びメタクリル酸塩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Ｂ：分子中に５〜１５０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メトキシポリエチレングリコールメタクリレートから形成された構成単位
構成単位Ｃ：（メタ）アリルスルホン酸塩から形成された構成単位及びメチルアクリレート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
Polycarboxylic acid-based water-soluble vinyl copolymer: 45 to 85 mol% of the following structural unit A, 15 to 55 mol% of the following structural unit B, and 0 to 10 mol% of the following structural unit C in the molecule. A water-soluble vinyl copolymer having a mass average molecular weight of 2000 to 80000 in a ratio of (total 100 mol%).
Structural unit A: One or more selected from structural units formed from methacrylic acid and structural units formed from methacrylates Structural unit B: Consists of 5 to 150 oxyethylene units in the molecule Structural unit formed from methoxypolyethylene glycol methacrylate having a polyoxyethylene group Structural unit C: one or two selected from a structural unit formed from (meth) allyl sulfonate and a structural unit formed from methyl acrylate that's all
乾燥収縮低減剤：ジエチレングリコールモノブチルエーテル及びジプロピレングリコールジエチレングリコールモノブチルエーテルから選ばれる一つ又は二つ以上。 Dry shrinkage reducing agent: one or more selected from diethylene glycol monobutyl ether and dipropylene glycol diethylene glycol monobutyl ether.
本発明に係る高炉スラグ組成物を用いたコンクリート組成物（以下、本発明のコンクリート組成物という）は、少なくとも、結合材、水、細骨材、粗骨材及び混和材を含有して成るものである。本発明のコンクリート組成物は結合材として特定の高炉セメント組成物を用いたものであり、かかる高炉セメント組成物は、粉末度が３０００〜１３０００ｃｍ２／ｇの高炉スラグ微粉末を６０〜９０質量％、石膏を５〜２０質量％及びポルトランドセメントを５〜３５質量％（合計１００質量％）の割合で含有する混合物１００質量部当たり、解体コンクリートから分離した水酸化カルシウム含有率が３〜１５質量％の再生コンクリート微粉末を１０〜３０質量部の割合で添加したものである。 A concrete composition using the blast furnace slag composition according to the present invention (hereinafter referred to as the concrete composition of the present invention) contains at least a binder, water, fine aggregate, coarse aggregate and admixture. It is. The concrete composition of the present invention uses a specific blast furnace cement composition as a binder, and the blast furnace cement composition contains 60 to 90% by mass of blast furnace slag fine powder having a fineness of 3000 to 13000 cm 2 / g. The content of calcium hydroxide separated from the demolished concrete is 3 to 15% by mass per 100 parts by mass of the mixture containing 5 to 20% by mass of gypsum and 5 to 35% by mass (total 100% by mass) of Portland cement. The recycled concrete fine powder is added at a ratio of 10 to 30 parts by mass.
前記の高炉スラグ微粉末は、粉末度が３０００〜１３０００ｃｍ２／ｇのものを使用するが、好ましくは３０００〜８０００ｃｍ２／ｇのものを使用し、より好ましくは３５００〜６５００ｃｍ２／ｇのものを使用する。粉末度が３０００〜１３０００ｃｍ２／ｇの範囲を外れたものを使用すると、調製したコンクリート組成物の流動性が悪くなったり、得られる硬化体の強度発現が低下したりする。尚、本発明において粉末度はブレーン法による比表面積で表したものである。 The blast furnace slag fine powder has a fineness of 3000 to 13000 cm 2 / g, preferably 3000 to 8000 cm 2 / g, more preferably 3500 to 6500 cm 2 / g. use. When the powder having a fineness outside the range of 3000 to 13000 cm 2 / g is used, the fluidity of the prepared concrete composition is deteriorated, or the strength expression of the obtained cured product is lowered. In the present invention, the fineness is expressed by the specific surface area by the Blaine method.
また石膏としては、無水石膏、二水石膏、半水石膏が挙げられるが、無水石膏が好ましい。無水石膏としては、それを９０質量％以上の純度で含有するものであれば使用でき、天然無水石膏や副産無水石膏等を使用できる。粉末度は、３０００〜８０００ｃｍ２／ｇのものが好ましく、３５００〜６５００ｃｍ２／ｇのものがより好ましい。 Examples of the gypsum include anhydrous gypsum, dihydrate gypsum, and hemihydrate gypsum, and anhydrous gypsum is preferable. Any anhydrous gypsum can be used as long as it contains 90% by mass or more, and natural anhydrous gypsum, by-product anhydrous gypsum, and the like can be used. Fineness is preferably a 3000~8000cm 2 / g, more preferably from 3500~6500cm 2 / g.
更に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。 Furthermore, 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.
そして再生コンクリート微粉末としては、好ましくは粉末度が２０００〜７０００ｃｍ２／ｇのものを使用する。また水酸化カルシウム含有率が３〜１５質量％のものを使用するが、好ましくは６〜１２質量％のものを使用する。解体コンクリートから分離する方法は特に限定されず、これには例えば、破砕機を用いて破砕する方法や破砕物どうしを機械で擦りもむ方法が挙げられる。解体コンクリートから分離された再生コンクリート微粉末は、例えば、解体コンクリートから粗骨材や細骨材を取り除くことにより得ることができる。このとき解体コンクリートから分離された粗骨材や細骨材も再生品として使用することができる。解体コンクリートから分離した再生コンクリート微粉末であって、水酸化カルシウムを上記の含有率で含む再生コンクリート微粉末を得る手段としては、機械擦りもみ方式が好ましく、機械擦りもみ方式のなかでは偏心ロータ方式がより好ましい。以下、このような再生コンクリート微粉末の製造方法について説明する。本発明における好ましい再生コンクリート微粉末は、加熱を行わない機械擦りもみ方式により製造されることが、製造時の二酸化炭素の削減及び得られる微粉末の品質にばらつきがないという観点から好適である。特に、偏心ロータ方式や遊星ミル等の機械擦りもみ装置で製造する際に、機械擦りもみプロセスを密閉された空間内で行い、空間内の空気中のＣＯ２を除去する方法、或いは、チッソガスなどの不活性ガスを封入する方法をとることで、処理中の炭酸化による水酸化カルシウム含有率の減少を抑制した再生コンクリート微粉末は本発明における如き、アルカリ刺激材として使用するのに最適な水酸化カルシウム含有率の微粉末を得ることができる。他方、解体コンクリート魂をジョークラッシャーやインペラーブレーカー等の破砕機を用いて破砕する方法においては、骨材とモルタル・ペーストが同時に破砕されるため、再生コンクリート微粉末中に骨材粉が多くなり易く、また、微粉中の骨材粉とモルタル・ペースト粉の比率もコンクリートの配（調）合によっては相当変化することとなり、高炉スラグ微粉末のアルカリ刺激材として用いるには、品質のコントロールが極めて困難であり、また、加熱と機械擦りもみによって骨材を取り出す加熱擦りもみ方式で製造した微粉末は骨材粉が少なく、アルカリ刺激材として適しているものの、加熱によって解体コンクリート中の水和物が変化する懸念があり、また、製造エネルギーが大きくなり、セメント製造時の二酸化炭素を削減するという観点からも好適とは言い難い。 As the recycled concrete fine powder, one having a fineness of 2000 to 7000 cm 2 / g is preferably used. Moreover, although calcium hydroxide content rate uses 3-15 mass%, Preferably a 6-12 mass% thing is used. The method of separating from demolition concrete is not particularly limited, and examples thereof include a method of crushing using a crusher and a method of rubbing crushed materials with a machine. The recycled concrete fine powder separated from the demolished concrete can be obtained, for example, by removing coarse aggregate or fine aggregate from the demolished concrete. At this time, coarse aggregates and fine aggregates separated from the demolished concrete can also be used as recycled products. As a means for obtaining reclaimed concrete fine powder separated from demolition concrete and containing calcium hydroxide at the above-mentioned content rate, a mechanical rubbing method is preferred, and an eccentric rotor method among mechanical rubbing methods Is more preferable. Hereinafter, a method for producing such recycled concrete fine powder will be described. The preferred recycled concrete fine powder in the present invention is preferably produced by a mechanical rubbing method without heating from the viewpoint of reducing carbon dioxide during production and ensuring that the quality of the fine powder obtained does not vary. In particular, when manufacturing with a mechanical rubbing apparatus such as an eccentric rotor type or planetary mill, a mechanical rubbing process is performed in a sealed space to remove CO 2 in the air in the space, or nitrogen gas By using the method of enclosing the inert gas, regenerated concrete fine powder that suppresses the decrease in the content of calcium hydroxide due to carbonation during the treatment is water that is optimal for use as an alkali stimulant as in the present invention. A fine powder having a calcium oxide content can be obtained. On the other hand, in the method of crushing the demolished concrete soul using a crusher such as a jaw crusher or impeller breaker, aggregate and mortar paste are crushed at the same time, so aggregate powder tends to increase in recycled concrete fine powder. In addition, the ratio of aggregate powder to mortar paste powder in the fine powder will change considerably depending on the arrangement (condition) of the concrete, and quality control is extremely difficult to use as an alkali stimulant for blast furnace slag fine powder. It is difficult, and the fine powder produced by the heat-scrubbing method, which takes out the aggregate by heating and mechanical rubbing, is low in aggregate powder and suitable as an alkali stimulating material, but hydrated in demolition concrete by heating There is a concern that the manufacturing energy will increase, and if the production energy increases and carbon dioxide is reduced during cement production, It is hard to say that preferably also from cormorant point of view.
本発明のコンクリート組成物において、細骨材としては、公知の川砂、砕砂、山砂等を使用でき、粗骨材としては、公知の川砂利、砕石、軽量骨材等を使用できる。 In the concrete composition of the present invention, known river sand, crushed sand, mountain sand or the like can be used as the fine aggregate, and known river gravel, crushed stone, lightweight aggregate or the like can be used as the coarse aggregate.
本発明のコンクリート組成物では、水／高炉セメント組成物の質量比を３０〜６０％に調製するが、好ましくは３５〜５５％に調製する。かかる質量比が６０％より大きいと、得られる硬化体の乾燥収縮が大きくなり過ぎたり、強度の低下が著しくなる。逆に、かかる質量比が３０％より小さいと、調製したコンクリート組成物の流動性や空気量の経時的な低下が大きくなり、施工性が低下する。尚、本発明において水／高炉セメント組成物の質量比は、（用いた水の質量／用いた高炉セメント組成物の質量）×１００で求められるものである。 In the concrete composition of the present invention, the mass ratio of the water / blast furnace cement composition is adjusted to 30 to 60%, preferably 35 to 55%. When this mass ratio is larger than 60%, the resulting cured product has too much drying shrinkage, and the strength is remarkably reduced. On the other hand, when the mass ratio is less than 30%, the fluidity of the prepared concrete composition and the amount of air over time decrease greatly, and the workability deteriorates. In the present invention, the mass ratio of the water / blast furnace cement composition is obtained by (mass of water used / mass of blast furnace cement composition used) × 100.
本発明のコンクリート組成物では、混和材として、特定のセメント分散剤と特定の乾燥収縮低減剤を組み合せて、また特定のセメント分散剤と膨張材を組み合わせて、更には特定のセメント分散剤と特定の乾燥収縮低減剤と膨張材を組み合せて使用する。 In the concrete composition of the present invention, as the admixture, a specific cement dispersant and a specific drying shrinkage reducing agent are combined, a specific cement dispersant and an expansion material are combined, and a specific cement dispersant is specified. A combination of a drying shrinkage reducing agent and an expansion material is used.
セメント分散剤としては、ポリカルボン酸系の水溶性ビニル共重合体を用い、なかでも分子中に下記の構成単位Ａを４５〜８５モル％、下記の構成単位Ｂを１５〜５５モル％及び下記の構成単位Ｃを０〜１０モル％（合計１００モル％）の割合で有する質量平均分子量２０００〜８００００（ＧＰＣ法、プルラン換算、以下同じ）の水溶性ビニル共重合体を用いる。 As the cement dispersant, a polycarboxylic acid-based water-soluble vinyl copolymer is used, and among them, the following structural unit A is 45 to 85 mol%, the following structural unit B is 15 to 55 mol%, and A water-soluble vinyl copolymer having a mass average molecular weight of 2000 to 80000 (GPC method, pullullan conversion, the same shall apply hereinafter) having a structural unit C of 0 to 10 mol% (100 mol% in total) is used.
構成単位Ａ：メタクリル酸から形成された構成単位及びメタクリル酸塩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Ｂ：分子中に５〜１５０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メトキシポリエチレングリコールメタクリレートから形成された構成単位
構成単位Ｃ：（メタ）アリルスルホン酸塩から形成された構成単位及びメチルアクリレート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 A: One or more selected from structural units formed from methacrylic acid and structural units formed from methacrylates Structural unit B: Consists of 5 to 150 oxyethylene units in the molecule Structural unit formed from methoxypolyethylene glycol methacrylate having a polyoxyethylene group Structural unit C: one or two selected from a structural unit formed from (meth) allyl sulfonate and a structural unit formed from methyl acrylate that's all
以上説明したポリカルボン酸系の水溶性ビニル共重合体からなるセメント分散剤それ自体は公知の方法で合成でき、例えば特開昭５８−７４５５２号公報、特開平１−２２６７５７号公報等に記載されている方法で合成できる。これらのポリカルボン酸系の水溶性ビニル共重合体からなるセメント分散剤の使用量は、高炉セメント組成物１００質量部当たり、０．１〜１．５質量部の割合とする。 The cement dispersant comprising the polycarboxylic acid-based water-soluble vinyl copolymer described above can be synthesized by a known method, and is described in, for example, JP-A-58-74552 and JP-A-1-226757. Can be synthesized. The amount of the cement dispersant made of these polycarboxylic acid-based water-soluble vinyl copolymers is 0.1 to 1.5 parts by mass per 100 parts by mass of the blast furnace cement composition.
乾燥収縮低減剤としては、ジエチレングリコールモノブチルエーテル及びジプロピレングリコールジエチレングリコールモノブチルエーテルから選ばれるものを用いる。かかる乾燥収縮低減剤の使用量は、高炉セメント組成物１００質量部当たり、０．２〜４．０質量部の割合とする。 As the drying shrinkage reducing agent, one selected from diethylene glycol monobutyl ether and dipropylene glycol diethylene glycol monobutyl ether is used. The amount of the drying shrinkage reducing agent used is 0.2 to 4.0 parts by mass per 100 parts by mass of the blast furnace cement composition.
膨張材としては、公知のものを使用でき、大別してカルシウムスルホアルミネート系のものと石灰系のものとの２種類が挙げられる。いずれも水和反応によりエトリンガイト及び水酸化カルシウムを生成して膨張する無機系の混和材であり、コンクリート用膨張材として、ＪＩＳ−Ａ６２０２の規格を満足するものが好ましい。かかる膨張材の使用量は、コンクリート組成物１ｍ３当たり、１０〜２５ｋｇの割合とする。 A well-known thing can be used as an expanding material, and it divides roughly and two types, a calcium sulfo aluminate type thing and a lime type thing, are mentioned. Any of these is an inorganic admixture that expands by producing ettringite and calcium hydroxide by a hydration reaction, and a concrete expansion material that satisfies the standard of JIS-A6202 is preferred. The amount of the expansion material used is 10 to 25 kg per 1 m 3 of the concrete composition.
本発明のコンクリート組成物を、通常３〜６容量％の空気を連行させたＡＥコンクリートとする場合、空気連行（ＡＥ）剤を補助剤として使用できる。かかるＡＥ剤としては、公知のものを使用でき、特に限定されないが、ポリオキシアルキレンアルキルエーテル硫酸塩、アルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルベンゼンスルホン酸塩、ロジン石けん、高級脂肪酸石けん、アルキルリン酸エステル塩、ポリオキシアルキレンアルキルエーテルリン酸エステル塩等の公知のＡＥ剤を使用できる。逆に、本発明のコンクリート組成物を調製する際に空気量過多になる場合には、消泡剤を単独使用したり、又は前記の空気連行剤と併用することができる。かかる消泡剤としては、公知のものを使用でき、特に限定されないが、ポリオキシアルキレングリコールエーテル誘導体、変性ポリジメチルシロキサン、リン酸トリアルキル等の消泡剤を使用できる。これらの空気量調節剤の使用量は、高炉セメント組成物１００質量部当たり、０．００１〜０．０１質量部の割合とするのが好ましい。 When the concrete composition of the present invention is usually AE concrete entrained with 3 to 6% by volume of air, an air entrainment (AE) agent can be used as an auxiliary agent. As such AE agents, known ones can be used and are not particularly limited, but polyoxyalkylene alkyl ether sulfates, alkylbenzene sulfonates, polyoxyethylene alkylbenzene sulfonates, rosin soaps, higher fatty acid soaps, alkyl phosphate esters. Known AE agents such as salts and polyoxyalkylene alkyl ether phosphates can be used. On the contrary, when the amount of air is excessive when preparing the concrete composition of the present invention, the antifoaming agent can be used alone or in combination with the air entraining agent. As such an antifoaming agent, a known one can be used, and is not particularly limited, but an antifoaming agent such as a polyoxyalkylene glycol ether derivative, a modified polydimethylsiloxane, or a trialkyl phosphate can be used. The amount of these air amount regulators used is preferably 0.001 to 0.01 parts by mass per 100 parts by mass of the blast furnace cement composition.
本発明のコンクリート組成物は公知の方法で調製できるが、高炉セメント組成物、水、細骨材及び粗骨材をミキサーで空練りする一方で、前記したセメント分散剤、乾燥収縮低減剤、膨張材、空気量調節剤等を適宜に練り混ぜ水で希釈し、しかる後に双方を練り混ぜる方法が好ましい。本発明のコンクリート組成物の調製に際しては、本発明の効果を損なわない範囲内で、必要に応じて、硬化促進剤、凝結遅延剤、防錆剤、防水剤、防腐剤等の添加剤を併用することもできる。 The concrete composition of the present invention can be prepared by a known method. However, while the blast furnace cement composition, water, fine aggregate and coarse aggregate are kneaded with a mixer, the above-mentioned cement dispersant, drying shrinkage reducing agent, expansion It is preferable to mix a material, an air amount adjusting agent and the like appropriately and dilute with water, and then knead both. In preparing the concrete composition of the present invention, additives such as a curing accelerator, a setting retarder, a rust inhibitor, a waterproofing agent, and an antiseptic agent are used in combination as long as the effects of the present invention are not impaired. You can also
以上説明した本発明のコンクリート組成物によると、得られる硬化体は乾燥収縮率が８００×１０−６以下のものとなる。また本発明のコンクリート組成物は建設現場で打設されるコンクリート組成物としてだけでなく、コンクリート製品工場で加工される二次製品用のコンクリート組成物としても適用できる。 According to the concrete composition of the present invention described above, the obtained cured product has a drying shrinkage of 800 × 10 −6 or less. The concrete composition of the present invention can be applied not only as a concrete composition placed at a construction site, but also as a concrete composition for a secondary product processed in a concrete product factory.
本発明によると、コンクリート組成物を調製するに当たり二酸化炭素の排出量を抑制しつつ、調製したコンクリート組成物の経時的な流動性の低下や空気量の低下を抑えて良好な施工性を確保することができ、また得られる硬化体の乾燥収縮を抑制することができ、更に得られる硬化体に必要な強度を発現させることができるという効果がある。 According to the present invention, while suppressing the amount of carbon dioxide emission in preparing a concrete composition, the deterioration of fluidity and the amount of air over time of the prepared concrete composition is suppressed to ensure good workability. Further, there is an effect that drying shrinkage of the obtained cured product can be suppressed, and further, the strength necessary for the obtained cured product can be expressed.
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（水溶性ビニル共重合体の合成）
・水溶性ビニル共重合体（ｐ−１）の合成
メタクリル酸６０ｇ、メトキシポリ（オキシエチレン単位数が２３個、以下ｎ＝２３とする）エチレングリコールメタクリレート３００ｇ、メタリルスルホン酸ナトリウム５ｇ、３−メルカプトプロピオン酸４ｇ及び水４９０ｇを反応容器に仕込んだ後、４８％水酸化ナトリウム水溶液５８ｇを加え、攪拌しながら部分中和して均一に溶解した。反応容器内の雰囲気を窒素置換した後、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２５ｇを加えてラジカル重合反応を開始し、５時間反応を継続して反応を終了した。その後、４８％水酸化ナトリウム水溶液２３ｇを加えて反応物を完全中和し、メタクリル酸塩から形成された単位を構成単位にもつポリカルボン酸系の水溶性ビニル共重合体（ｐ−１）の４０％水溶液を得た。水溶性ビニル共重合体（ｐ−１）を分析したところ、メタクリル酸ナトリウムから形成された構成単位／メトキシポリ（ｎ＝２３）エチレングリコールメタクリレートから形成された構成単位／メタリルスルホン酸ナトリウムから形成された構成単位＝７０／２７／３（モル％）の割合で有する質量平均分子量が３３８００の水溶性ビニル共重合体であった。
Test Category 1 (Synthesis of water-soluble vinyl copolymer)
Synthesis of water-soluble vinyl copolymer (p-1) 60 g of methacrylic acid, methoxypoly (23 oxyethylene units, hereinafter n = 23) ethylene glycol methacrylate 300 g, sodium methallylsulfonate 5 g, 3-mercapto After charging 4 g of propionic acid and 490 g of water into the reaction vessel, 58 g of a 48% aqueous sodium hydroxide solution was added, and the mixture was partially neutralized with stirring and dissolved uniformly. After the atmosphere in the reaction vessel was replaced with nitrogen, the temperature of the reaction system was maintained at 60 ° C. in a warm water bath, 25 g of a 20% aqueous solution of sodium persulfate was added to start radical polymerization reaction, and the reaction was continued for 5 hours. The reaction was terminated. Thereafter, 23 g of a 48% sodium hydroxide aqueous solution was added to completely neutralize the reaction product, and a polycarboxylic acid-based water-soluble vinyl copolymer (p-1) having units formed from methacrylate as structural units. A 40% aqueous solution was obtained. When the water-soluble vinyl copolymer (p-1) was analyzed, it was formed from a structural unit formed from sodium methacrylate / a structural unit formed from methoxypoly (n = 23) ethylene glycol methacrylate / sodium methallylsulfonate. It was a water-soluble vinyl copolymer having a mass average molecular weight of 33,800 in the proportion of structural unit = 70/27/3 (mol%).
・水溶性ビニル共重合体（ｐ−２）〜（ｐ−４）及び（ｐｒ−１）〜（ｐｒ−４）の合成
水溶性ビニル共重合体（ｐ−１）の合成と同様にして、水溶性ビニル共重合体（ｐ−２）〜（ｐ−４）及び（ｐｒ−１）〜（ｐｒ−４）を合成した。以上で合成した各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 (p-2) to (p-4) and (pr-1) to (pr-4) In the same manner as the synthesis of water-soluble vinyl copolymer (p-1), Water-soluble vinyl copolymers (p-2) to (p-4) and (pr-1) to (pr-4) were synthesized. The contents of each water-soluble vinyl copolymer synthesized above are summarized in Table 1.
表１において、
構成単位Ａ〜Ｃ：各構成単位を形成することとなる単量体で表示した。
Ａ−１：メタクリル酸ナトリウム
Ａ−２：メタクリル酸
Ｂ−１：メトキシポリ（ｎ＝２３）エチレングリコールメタクリレート
Ｂ−２：メトキシポリ（ｎ＝６８）エチレングリコールメタクリレート
Ｂ−３：メトキシポリ（ｎ＝９）エチレングリコールメタクリレート
Ｃ−１：メタリルスルホン酸ナトリウム
Ｃ−２：アリルスルホン酸ナトリウム
Ｃ−３：メチルアクリレート
In Table 1,
Structural units A to C: Indicated by monomers that form each structural unit.
A-1: Sodium methacrylate A-2: Methacrylic acid B-1: Methoxypoly (n = 23) ethylene glycol methacrylate B-2: Methoxypoly (n = 68) ethylene glycol methacrylate B-3: Methoxypoly (n = 9) ethylene Glycol methacrylate C-1: Sodium methallyl sulfonate C-2: Sodium allyl sulfonate C-3: Methyl acrylate
試験区分２（高炉セメント組成物の調製）
表２に記載の調合条件で、高炉スラグ微粉末、無水石膏、ポルトランドセメント及び再生コンクリート微粉末を混合して高炉セメント組成物を調製し、高炉セメント組成物（Ｓ−１）〜（Ｓ−５）及び（Ｒ−１）〜（Ｒ−６）を得た。
Test Category 2 (Preparation of blast furnace cement composition)
A blast furnace cement composition (S-1) to (S-5) was prepared by mixing blast furnace slag fine powder, anhydrous gypsum, Portland cement and recycled concrete fine powder under the blending conditions shown in Table 2. ) And (R-1) to (R-6).
表２において、
ｓｇ−１：粉末度が４１００ｃｍ２／ｇの高炉スラグ微粉末
ｓｇ−２：粉末度が５９００ｃｍ２／ｇの高炉スラグ微粉末
ｓｇ−３：粉末度が１０２０ｃｍ２／ｇの高炉スラグ微粉末
ｇｐ−１：粉末度が４１５０ｃｍ２／ｇの無水石膏
ｇｐ−２：粉末度が５８００ｃｍ２／ｇの無水石膏
ｐｃ−１：普通ポルトランドセメント
ｐｃ−２：早強ポルトランドセメント
ｒｃ−１：粉末度が５８６０ｃｍ２／ｇ且つ水酸化カルシウム含有率が９．２％の再生コンクリート微粉末
ｒｃ−２：粉末度が４６２０ｃｍ２／ｇ且つ水酸化カルシウム含有率が６．５％の再生コンクリート微粉末
ｒｃ−３：粉末度が４３５０ｃｍ２／ｇ且つ水酸化カルシウム含有率が１．５％の再生コンクリート微粉末
ｒｃ−４：、粉末度が１２００ｃｍ２／ｇ且つ水酸化カルシウム含有率が６．１％の再生コンクリート微粉末
In Table 2,
sg-1: Ground granulated blast furnace slag having a fineness of 4100 cm 2 / g sg-2: Fine powder of blast furnace slag having a fineness of 5900 cm 2 / g sg-3: Fine powder of blast furnace slag having a fineness of 1020 cm 2 / g gp- 1: Anhydrous gypsum with a fineness of 4150 cm 2 / g gp-2: Anhydrous gypsum with a fineness of 5800 cm 2 / g pc-1: Ordinary Portland cement pc-2: Early strength Portland cement rc-1: Fineness of 5860 cm 2 / G and regenerated concrete fine powder with a calcium hydroxide content of 9.2% rc-2: Recycled concrete fine powder with a fineness of 4620 cm 2 / g and a calcium hydroxide content of 6.5% rc-3: Powder Recycled concrete fine powder rc-4 having a degree of 4350 cm 2 / g and a calcium hydroxide content of 1.5%, a fineness of 1200 cm 2 / g Recycled concrete fine powder with a calcium hydroxide content of 6.1%
試験区分３（コンクリート組成物の調製）
実施例１〜１３
表３に記載の配合条件で、５０リットルのパン型強制練りミキサーに、練り混ぜ水（水道水）、高炉セメント組成物、細骨材（大井川水系産川砂、密度＝２．５８ｇ／ｃｍ３）の各所定量を投入し、またセメント分散剤、乾燥収縮低減剤、膨張材等の混和材の各所定量を投入して、更に空気量調節剤（竹本油脂社製のＡＥ剤、商品名ＡＥ−３００）を投入し、４５秒間練り混ぜた。最後に、粗骨材（岡崎産砕石、密度＝２．６８ｇ／ｃｍ３）の所定量を投入し、６０秒間練り混ぜて、目標スランプが１８±１cm、目標空気量が４．５±１％とした水／高炉セメント組成物比が４５％又は４０％のコンクリート組成物を調製した。
Test category 3 (Preparation of concrete composition)
Examples 1-13
Under the blending conditions shown in Table 3, in a 50 liter pan-type forced kneading mixer, kneading water (tap water), blast furnace cement composition, fine aggregate (Oikawa water system river sand, density = 2.58 g / cm 3 ) And a predetermined amount of admixtures such as a cement dispersant, a drying shrinkage reducing agent, and an expansion material, and an air amount adjusting agent (AE agent manufactured by Takemoto Yushi Co., Ltd., trade name AE-300). ) And kneaded for 45 seconds. Finally, a predetermined amount of coarse aggregate (Okazaki crushed stone, density = 2.68 g / cm 3 ) is added and kneaded for 60 seconds. The target slump is 18 ± 1 cm and the target air amount is 4.5 ± 1%. A concrete composition having a water / blast furnace cement composition ratio of 45% or 40% was prepared.
比較例１〜１３
表３に記載の配合条件で、実施例と同様な練り混ぜ方法により、水／高炉セメント組成物比が４５％のコンクリート組成物を調製した。
Comparative Examples 1-13
A concrete composition having a water / blast furnace cement composition ratio of 45% was prepared by the same kneading method as in the example under the blending conditions shown in Table 3.
比較例１４及び１５
表３に記載の配合条件で、実施例と同様な練り混ぜ方法により、高炉セメントＢ種を用いた水／高炉セメント組成物比が４５％又は５０％のコンクリート組成物を調製した。
Comparative Examples 14 and 15
A concrete composition having a water / blast furnace cement composition ratio of 45% or 50% using a blast furnace cement type B was prepared by the same mixing method as in the examples under the blending conditions shown in Table 3.
表３において、
二酸化炭素排出量：コンクリート組成物１ｍ３を製造する場合の二酸化炭素の排出量（kg）。但し、石膏及び再生コンクリート微粉末の製造に必要なエネルギーに由来する二酸化炭素の排出量を除いてポルトランドセメントの使用量から計算した値
セメント分散剤の種類：表１に記載した水溶性ビニル共重合体
使用量：高炉セメント組成物１００質量部当たりの、セメント分散剤、乾燥収縮低減剤又は膨張材の固形分としての質量部
高炉セメント組成物の種類：表２に記載したもの
＊１：ジエチレングリコールモノブチルエーテル
＊２：ジプロピレングリコールジエチレングリコールモノブチルエーテル
＊３：太平洋マテリアル社製の商品名が太平洋ハイパーエクスパン（石灰系膨張材）
＊４：高炉セメントＢ種（密度＝３．０４ｇ／ｃｍ３、ブレーン値３８５０ｃｍ２／ｇ）
In Table 3,
Carbon dioxide emissions: Carbon dioxide emissions (kg) when producing 1 m 3 of concrete composition. However, the value calculated from the amount of Portland cement used, excluding the amount of carbon dioxide emissions derived from the energy required for the production of gypsum and recycled concrete fine powder. Type of cement dispersant: water-soluble vinyl co-polymer described in Table 1 Combined Amount used: parts by mass as solid content of cement dispersant, drying shrinkage reducing agent or expansion material per 100 parts by mass of blast furnace cement composition Type of blast furnace cement composition: those listed in Table 2 * 1: Diethylene glycol mono Butyl ether * 2: Dipropylene glycol diethylene glycol monobutyl ether * 3: Taiheiyo Materials Co., Ltd. product name is Taiheiyo Hyperexpan
* 4: Blast furnace cement type B (density = 3.04 g / cm 3 , brain value 3850 cm 2 / g)
試験区分４（調製したコンクリート組成物の評価）
調製した各例のコンクリート組成物について、空気量、スランプ、スランプ残存率を下記のように求めた。また各コンクリート組成物から得た硬化体について、乾燥収縮率及び圧縮強度を下記のように求めた。
Test category 4 (Evaluation of prepared concrete composition)
About the prepared concrete composition of each example, the air content, slump, and slump residual rate were calculated | required as follows. Moreover, about the hardening body obtained from each concrete composition, the drying shrinkage rate and the compressive strength were calculated | required as follows.
・空気量（容量％）：練り混ぜ直後のコンクリート組成物及び更に６０分間静置後のコンクリート組成物について、ＪＩＳ−Ａ１１２８に準拠して測定した。
・スランプ（ｃｍ）：空気量の測定と同時に、ＪＩＳ−Ａ１１０１に準拠して測定した。
・スランプ残存率（％）：（６０分間静置後のスランプ／練り混ぜ直後のスランプ）×１００で求めた。
・乾燥収縮率：ＪＩＳ−Ａ１１２９に準拠し、各例のコンクリート組成物を２０℃×６０％ＲＨの条件下で保存した材齢２６週の供試体についてコンパレータ法により乾燥収縮ひずみを測定し、乾燥収縮率を求めた。この数値は小さいほど、乾燥収縮が小さいことを示す。
・圧縮強度（Ｎ／ｍｍ２）：各例のコンクリート組成物について、ＪＩＳ−Ａ１１０８に準拠し、材齢７日及び材齢２８日で測定した。
Air content (volume%): The concrete composition immediately after kneading and the concrete composition after still standing for 60 minutes were measured according to JIS-A1128.
-Slump (cm): Measured according to JIS-A1101 simultaneously with the measurement of the air amount.
-Slump residual rate (%): (slump after standing for 60 minutes / slump immediately after kneading) x 100.
-Drying shrinkage: In accordance with JIS-A1129, dry shrinkage strain was measured by a comparator method on a 26-week-old specimen in which the concrete composition of each example was stored under the conditions of 20 ° C x 60% RH and dried. Shrinkage was determined. The smaller this value, the smaller the drying shrinkage.
-Compressive strength (N / mm < 2 >): About the concrete composition of each example, based on JIS-A1108, it measured by material age 7 days and material age 28 days.
結果を表４にまとめて示した。各実施例で調製した本発明のコンクリート組成物は、高炉セメントＢ種を用いた場合に比べて、コンクリート１ｍ３を製造するための二酸化炭素の排出量が少なく、またコンクリート組成物の経時的な流動性に優れ、得られる硬化体の乾燥収縮率が８００×１０−６よりも小さく、必要とされる充分な圧縮強度が得られている。
The results are summarized in Table 4. The concrete composition of the present invention prepared in each example has less carbon dioxide emission to produce 1 m 3 of concrete than when blast furnace cement type B is used, and the concrete composition has changed over time. It has excellent fluidity, and the resulting cured product has a drying shrinkage ratio of less than 800 × 10 −6 , and the required sufficient compressive strength is obtained.
表４において、
比較例２、３及び１１〜１３：目標とする流動性（スランプ値）が得られなかったので測定しなかった。
In Table 4,
Comparative Examples 2, 3 and 11-13: The target fluidity (slump value) was not obtained, so measurement was not performed.
Claims (7)
高炉セメント組成物：粉末度が３０００〜１３０００ｃｍ２／ｇの高炉スラグ微粉末を６０〜９０質量％、石膏を５〜２０質量％及びポルトランドセメントを５〜３５質量％（合計１００質量％）の割合で含有する混合物１００質量部当たり、解体コンクリートから分離した水酸化カルシウム含有率が３〜１５質量％の再生コンクリート微粉末を１０〜３０質量部の割合で添加した高炉セメント組成物。
ポリカルボン酸系の水溶性ビニル共重合体：分子中に下記の構成単位Ａを４５〜８５モル％、下記の構成単位Ｂを１５〜５５モル％及び下記の構成単位Ｃを０〜１０モル％（合計１００モル％）の割合で有する質量平均分子量が２０００〜８００００水溶性ビニル共重合体。
構成単位Ａ：メタクリル酸から形成された構成単位及びメタクリル酸塩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Ｂ：分子中に５〜１５０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メトキシポリエチレングリコールメタクリレートから形成された構成単位
構成単位Ｃ：（メタ）アリルスルホン酸塩から形成された構成単位及びメチルアクリレート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
乾燥収縮低減剤：ジエチレングリコールモノブチルエーテル及びジプロピレングリコールジエチレングリコールモノブチルエーテルから選ばれる一つ又は二つ以上。 A concrete composition comprising at least a binder, water, fine aggregate, coarse aggregate and admixture, wherein the following blast furnace cement composition is used as a binder , and water / the blast furnace cement composition: the mass ratio papermaking adjusted to 30% to 60%, and as at least a portion of the admixture, the cement dispersant comprising a water-soluble vinyl copolymer of polycarboxylic acid described below, blast furnace cement composition per 100 parts 0 0.1 to 1.5 parts by mass, and further, as at least a part of the admixture, the following drying shrinkage reducing agent and / or expansion material is used, and the drying shrinkage reducing agent is 0 per 100 parts by mass of the blast furnace cement composition. in a proportion of .2～4.0 parts by weight, also the concrete composition expanded material using the blast furnace cement composition characterized by containing a proportion of the concrete composition 1 m 3 per 10~25kg .
Blast furnace cement composition: 60 to 90% by mass of fine powder of blast furnace slag having a fineness of 3000 to 13000 cm 2 / g, 5 to 20% by mass of gypsum, and 5 to 35% by mass of Portland cement (total 100% by mass) A blast furnace cement composition in which a reclaimed concrete fine powder having a calcium hydroxide content of 3 to 15% by mass separated from demolition concrete is added at a rate of 10 to 30 parts by mass per 100 parts by mass of the mixture.
Polycarboxylic acid-based water-soluble vinyl copolymer: 45 to 85 mol% of the following structural unit A, 15 to 55 mol% of the following structural unit B, and 0 to 10 mol% of the following structural unit C in the molecule. A water-soluble vinyl copolymer having a mass average molecular weight of 2000 to 80000 in a ratio of (total 100 mol%).
Structural unit A: one or two or more selected from structural units formed from methacrylic acid and structural units formed from methacrylate
Structural unit B: a structural unit formed from methoxypolyethylene glycol methacrylate having a polyoxyethylene group composed of 5 to 150 oxyethylene units in the molecule
Structural unit C: one or two or more selected from structural units formed from (meth) allyl sulfonate and structural units formed from methyl acrylate
Dry shrinkage reducing agent: one or more selected from diethylene glycol monobutyl ether and dipropylene glycol diethylene glycol monobutyl ether.
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| JP5818254B2 (en) * | 2011-11-29 | 2015-11-18 | 竹本油脂株式会社 | Admixture for blast furnace slag concrete and method for preparing blast furnace slag concrete |
| JP2013155049A (en) * | 2012-01-26 | 2013-08-15 | Ohbayashi Corp | Cement composition and premix material |
| JP5892696B2 (en) * | 2012-03-29 | 2016-03-23 | 株式会社竹中工務店 | Concrete composition and concrete hardened body using blast furnace cement |
| JP6021260B2 (en) * | 2012-12-26 | 2016-11-09 | 株式会社竹中工務店 | Hydraulic blast furnace slag composition and hardened concrete |
| JP5728545B2 (en) * | 2013-09-24 | 2015-06-03 | ゼニス羽田株式会社 | Hardened salt-resistant cement |
| JP6618743B2 (en) * | 2015-09-17 | 2019-12-11 | 株式会社竹中工務店 | Concrete composition and hardened concrete |
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