JP6192208B2 - Preparation method of non-shrink AE concrete and non-shrink AE concrete - Google Patents
Preparation method of non-shrink AE concrete and non-shrink AE concrete Download PDFInfo
- Publication number
- JP6192208B2 JP6192208B2 JP2013078345A JP2013078345A JP6192208B2 JP 6192208 B2 JP6192208 B2 JP 6192208B2 JP 2013078345 A JP2013078345 A JP 2013078345A JP 2013078345 A JP2013078345 A JP 2013078345A JP 6192208 B2 JP6192208 B2 JP 6192208B2
- Authority
- JP
- Japan
- Prior art keywords
- concrete
- mass
- component
- shrinkable
- structural unit
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000004567 concrete Substances 0.000 title claims description 63
- 238000002360 preparation method Methods 0.000 title claims description 36
- 239000000463 material Substances 0.000 claims description 35
- 239000000126 substance Substances 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- 229920006163 vinyl copolymer Polymers 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000004568 cement Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 17
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 17
- 239000004571 lime Substances 0.000 claims description 17
- -1 polyoxyethylene group Polymers 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 125000006353 oxyethylene group Chemical group 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- 239000004576 sand Substances 0.000 claims description 8
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 claims description 7
- WRKCIHRWQZQBOL-UHFFFAOYSA-N octyl dihydrogen phosphate Chemical group CCCCCCCCOP(O)(O)=O WRKCIHRWQZQBOL-UHFFFAOYSA-N 0.000 claims description 6
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 claims description 6
- 239000004575 stone Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000000047 product Substances 0.000 description 20
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000011398 Portland cement Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 235000019738 Limestone Nutrition 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 239000006028 limestone Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010257 thawing Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 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
- 239000000243 solution Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- BDNDQOCRJGGSJO-UHFFFAOYSA-N 1-amino-2-phenylpropan-2-ol Chemical compound NCC(O)(C)C1=CC=CC=C1 BDNDQOCRJGGSJO-UHFFFAOYSA-N 0.000 description 1
- 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
- DJCYDDALXPHSHR-UHFFFAOYSA-N 2-(2-propoxyethoxy)ethanol Chemical compound CCCOCCOCCO DJCYDDALXPHSHR-UHFFFAOYSA-N 0.000 description 1
- PLLUGRGSPQYBKB-UHFFFAOYSA-N 2-[2-(2-pentoxyethoxy)ethoxy]ethanol Chemical compound CCCCCOCCOCCOCCO PLLUGRGSPQYBKB-UHFFFAOYSA-N 0.000 description 1
- MYCQSOCJLZBPAT-UHFFFAOYSA-N 2-methylprop-2-enoic acid;potassium Chemical compound [K].CC(=C)C(O)=O MYCQSOCJLZBPAT-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 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
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001653 ettringite Inorganic materials 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
- 239000010881 fly ash Substances 0.000 description 1
- 238000006703 hydration reaction Methods 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
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 229910021487 silica fume Inorganic materials 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
- 238000001179 sorption measurement Methods 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
- 230000000007 visual effect Effects 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は無収縮AEコンクリートの調製方法及び無収縮AEコンクリートに関する。近年、建築土木工事におけるコンクリート構造物の長寿命化や高品質化の観点から、乾燥収縮によるひび割れの発生を抑制することが強く要求されている。しかし、建設現場において、乾燥収縮によるひび割れの発生を完全に抑制するためには、特に開口部や部材からの拘束の大きい部位においては、乾燥収縮率を50×10−6以下の実質的に無収縮に抑えることが必要であると指摘されている。本発明は得られる硬化体の乾燥収縮率を50×10−6以下の実質的に無収縮に抑えて、乾燥収縮によるひび割れの発生を完全に抑制することができる無収縮AEコンクリートの調製方法及び無収縮AEコンクリートに関する。 The present invention relates to a method for preparing non-shrinkable AE concrete and non-shrinkable AE concrete. In recent years, there has been a strong demand for suppressing the occurrence of cracks due to drying shrinkage from the viewpoint of extending the life and quality of concrete structures in architectural civil works. However, in order to completely suppress the occurrence of cracks due to drying shrinkage at the construction site, the drying shrinkage rate is substantially less than 50 × 10 −6 or less, particularly in a portion where the restriction from the opening or the member is large. It is pointed out that it is necessary to suppress the contraction. The present invention provides a method for preparing a non-shrinkable AE concrete capable of completely suppressing the occurrence of cracks due to drying shrinkage by suppressing the dry shrinkage rate of the obtained cured product to substantially no shrinkage of 50 × 10 −6 or less, and It relates to non-shrinkable AE concrete.
従来、得られる硬化体の乾燥収縮率を抑えたAEコンクリートの調製方法として、乾燥収縮低減剤(例えば特許文献1参照)を使用して得られる硬化体の乾燥収縮率を200×10−6以下に抑える方法(例えば特許文献2及び3参照)、また乾燥収縮低減剤と膨張材を併用して得られる硬化体の乾燥収縮率を50×10−6以下の実質的に無収縮の領域にまで抑える方法(例えば特許文献4〜6参照)が提案されている。しかし、これらの従来法には、セメント分散剤と乾燥収縮低減剤を別々に加えてAEコンクリートを調製する方法であるため、作業性や経済性の面で問題があり、また調製したAEコンクリートを型枠に流し込み、バイブレータを用いて締め固めながら成型する際に、不安定な空気泡が得られる硬化体(成型体)の上層表面に凝縮して大きなボイドが発生し易く、これに起因して該硬化体の凍結融解抵抗性が弱くなったり、表面に痘痕が発生して平滑で美麗な硬化体が得られないという問題がある。 Conventionally, as a method for preparing AE concrete in which the drying shrinkage rate of the obtained cured body is suppressed, the drying shrinkage rate of the cured body obtained using a drying shrinkage reducing agent (see, for example, Patent Document 1) is 200 × 10 −6 or less. (See, for example, Patent Documents 2 and 3), and the drying shrinkage rate of a cured product obtained by using a drying shrinkage reducing agent and an expansion material in combination is substantially 50 × 10 −6 or less. A method of suppressing (see, for example, Patent Documents 4 to 6) has been proposed. However, since these conventional methods are methods of preparing AE concrete by separately adding a cement dispersant and a drying shrinkage reducing agent, there are problems in terms of workability and economy. When casting into a mold and compacting with a vibrator, it is easy to generate large voids due to condensation on the upper surface of the cured product (molded product) that can produce unstable air bubbles. There is a problem that the freeze-thaw resistance of the cured body is weakened, or scratches are generated on the surface, so that a smooth and beautiful cured body cannot be obtained.
本発明が解決しようとする課題は、セメント分散剤と乾燥収縮低減剤とを一液化した多機能混和剤を使用して作業性及び経済性を向上しつつ、1)調製した無収縮AEコンクリートの流動性及び空気量が経時的に安定した状態で保たれること、2)得られる硬化体の乾燥収縮率が50×10−6以下の実質的に無収縮の領域にあること、3)得られる硬化体の凍結融解に対する抵抗性が強いこと、4)得られる硬化体の表面が平滑であること、以上の1)〜4)の多機能を同時に備えた無収縮AEコンクリートを調製することができる方法及びそのような無収縮AEコンクリートを提供する処にある。 The problem to be solved by the present invention is to improve workability and economy by using a multi-functional admixture in which a cement dispersant and a drying shrinkage reducing agent are made into one component, and 1) of the prepared non-shrinkable AE concrete. The fluidity and the amount of air are kept stable over time, 2) the drying shrinkage of the obtained cured product is in a region of substantially no shrinkage of 50 × 10 −6 or less, and 3) obtained. The hardened body to be obtained has strong resistance to freezing and thawing, 4) the surface of the obtained hardened body is smooth, and the preparation of non-shrinkable AE concrete having the above-mentioned multiple functions 1) to 4) at the same time. There is a method that can be used and such a non-shrinkable AE concrete.
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、セメント、水、細骨材、粗骨材、膨張材、多機能混和剤及び空気量調節剤を用いて無収縮AEコンクリートを調製するに際して、多機能混和剤としてセメント分散剤と乾燥収縮低減剤とを含有する一液型の特定のものを特定割合で用い、また粗骨材として特定の石灰砕石を特定割合で用い、更に膨張材を特定割合で用いて、且つ水/結合材比及び連行空気量を特定範囲となるように調製する方法及びかかる調製方法によって得られる無収縮AEコンクリートが正しく好適であることを見出した。 As a result, the present inventors have studied to solve the above-mentioned problems, and as a result, non-shrinkable AE concrete using cement, water, fine aggregate, coarse aggregate, expansion material, multifunctional admixture and air amount adjusting agent. In preparing a specific one-component type containing a cement dispersant and a drying shrinkage reducing agent as a multifunctional admixture in a specific ratio, and using a specific limestone as a coarse aggregate in a specific ratio, Furthermore, it has been found that a method for preparing an expansion material in a specific ratio and adjusting a water / binder ratio and entrained air amount to a specific range, and a non-shrinkable AE concrete obtained by such a preparation method are suitable. .
すなわち本発明は、セメント、水、細骨材、粗骨材、膨張材、多機能混和剤及び空気量調節剤を用いて無収縮AEコンクリートを調製する方法であって、粗骨材として下記の石灰砕石を単位量850〜1200kg/m3及び膨張材を単位量15〜40kg/m3で用い、且つ下記の多機能混和剤の20〜70質量%水溶液をセメント100質量部当たり多機能混和剤として0.3〜2.5質量部の割合となるよう用いて、水/結合材比を35〜65%及び連行空気量を3〜7容量%に調製することを特徴とする無収縮AE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無収縮AEコンクリートに係る。 That is, the present invention is a method for preparing non-shrinkable AE concrete using cement, water, fine aggregate, coarse aggregate, expanded material, multifunctional admixture, and air amount adjusting agent. Multifunctional admixture using lime crushed stone in unit amount of 850 to 1200 kg / m 3 and expansive material in unit amount of 15 to 40 kg / m 3 and 20 to 70 mass% aqueous solution of the following multifunctional admixture per 100 parts by mass of cement Non-shrinkable AE concrete characterized in that the ratio of water / binder is adjusted to 35 to 65% and the amount of entrained air is adjusted to 3 to 7% by volume. This relates to the preparation method. The present invention also relates to non-shrinkable AE concrete obtained by such a preparation method.
石灰砕石:化学成分としてCaO≧70質量%及びMgO≦1質量%の割合で含有するもの。 Lime crushed stone: Chemical component containing CaO ≧ 70 mass% and MgO ≦ 1 mass%.
多機能混和剤:下記のA成分を10〜25質量%、下記のB成分を10〜45質量%及び下記のC成分を30〜65質量%(合計100質量%)の割合で含有するもの。 Multifunctional admixture: A composition containing 10 to 25 mass% of the following A component, 10 to 45 mass% of the following B component, and 30 to 65 mass% (100 mass% in total) of the following C component.
A成分:分子中に下記の構成単位Lを35〜85モル%、下記の構成単位Mを15〜65モル%及び下記の構成単位Nを0〜5モル%(合計100モル%)の割合で有する質量平均分子量3000〜80000の水溶性ビニル共重合体。 Component A: 35 to 85 mol% of the following structural unit L in the molecule, 15 to 65 mol% of the following structural unit M, and 0 to 5 mol% (100 mol% in total) of the following structural unit N A water-soluble vinyl copolymer having a mass average molecular weight of 3000 to 80000.
構成単位L: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M:分子中に5〜80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から選ばれる一つ又は二つ以上
構成単位N:メタ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 L: One or more selected from structural units formed from methacrylic acid and structural units formed from methacrylic acid salt Structural unit M: Consists of 5 to 80 oxyethylene units in the molecule One or two or more structural units selected from structural units formed from methoxypolyethylene glycol methacrylate having a polyoxyethylene group. Structural unit N: From structural units formed from methallyl sulfonate and structural units formed from methyl acrylate. One or more selected
B成分:下記の化1で示される化合物 Component B: Compound represented by the following chemical formula 1
化1において、
A1,A2,A3:分子中に1〜10個のオキシプロピレン単位で構成された(ポリ)オキシプロピレン基を有する(ポリ)プロピレングリコールから全ての水酸基を除いた残基であって、且つA1、A2及びA3中のオキシプロピレン単位の個数の合計が7〜20個を満足するもの。
In chemical formula 1,
A 1 , A 2 , A 3 : Residues obtained by removing all hydroxyl groups from (poly) propylene glycol having (poly) oxypropylene groups composed of 1 to 10 oxypropylene units in the molecule, In addition, the total number of oxypropylene units in A 1 , A 2 and A 3 satisfies 7 to 20.
C成分:下記の化2で示される化合物 Component C: Compound represented by the following chemical formula 2
化2において、
R:炭素数3〜5のアルキル基
A4:分子中に1〜4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(ポリ)エチレングリコールから全ての水酸基を除いた残基。
In chemical formula 2,
R: an alkyl group having 3 to 5 carbon atoms A 4 : a residue obtained by removing all hydroxyl groups from (poly) ethylene glycol having a (poly) oxyethylene group composed of 1 to 4 oxyethylene units in the molecule .
本発明に係る無収縮AEコンクリートの調製方法(以下、本発明の調製方法という)は、セメント、水、細骨材、粗骨材、膨張材、多機能混和剤及び空気量調節剤を用いて無収縮AEコンクリートを調整する方法である。 The preparation method of non-shrinkable AE concrete according to the present invention (hereinafter referred to as the preparation method of the present invention) uses cement, water, fine aggregate, coarse aggregate, expansion material, multifunctional admixture, and air amount adjusting agent. This is a method of adjusting non-shrinkable AE concrete.
本発明の調製方法に供するセメントとしては、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、低熱ポルトランドセメント等の各種ポルトランドセメントの他に、高炉セメント、フライアッシュセメント、シリカフュームセメント等の各種混合セメントが挙げられる。 As the cement used in the preparation method of the present invention, various portland cements such as ordinary portland cement, early-strength portland cement, medium-heated portland cement, low heat portland cement, and various blends such as blast furnace cement, fly ash cement, silica fume cement, etc. Cement is mentioned.
本発明の調製方法に供する多機能混和剤は、前記のA成分、B成分及びC成分から成るものである。A成分は、前記の構成単位Lと構成単位Mとで構成された水溶性ビニル共重合体又は前記の構成単位Lと構成単位Mと構成単位Nとで構成された水溶性ビニル共重合体である。 The multifunctional admixture used for the preparation method of the present invention is composed of the aforementioned A component, B component and C component. Component A is a water-soluble vinyl copolymer composed of the structural unit L and the structural unit M, or a water-soluble vinyl copolymer composed of the structural unit L, the structural unit M, and the structural unit N. is there.
構成単位Lは、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である。メタクリル酸塩としては、メタクリル酸のリチウム、ナトリウム、カリウム等のアルカリ金属塩、ジエタノールアミン、トリエタノールアミン等の有機アミン塩が挙げられるが、なかでもナトリウム塩が好ましい。 The structural unit L is one or two or more selected from a structural unit formed from methacrylic acid and a structural unit formed from methacrylate. Examples of the methacrylic acid salt include alkali metal salts such as lithium, sodium and potassium methacrylic acid, and organic amine salts such as diethanolamine and triethanolamine. Among them, sodium salt is preferable.
構成単位Mは、分子中に5〜80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から選ばれる一つ又は二つ以上である。
The structural unit M is one or two or more selected from structural units formed from methoxypolyethylene glycol methacrylate having a polyoxyethylene group composed of 5 to 80 oxyethylene units in the molecule.
構成単位Nは、メタ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である。メタリルスルホン酸の塩としては、メタリルスルホン酸のリチウム、ナトリウム、カリウム等のアルカリ金属塩が挙げられるが、なかでもナトリウム塩が好ましい。 The structural unit N is one or more selected from a structural unit formed from methallyl sulfonate and a structural unit formed from methyl acrylate. Examples of the salt of methallyl sulfonic acid include alkali metal salts of methallyl sulfonic acid such as lithium, sodium, and potassium. Among them, sodium salt is preferable.
本発明の調製方法において、多機能混和剤の一成分として用いるA成分は、以上説明したような構成単位Lと構成単位Mとで構成された水溶性ビニル共重合体又は構成単位Lと構成単位Mと構成単位Nとで構成された水溶性ビニル共重合体であって、分子中に構成単位Lを35〜85モル%、構成単位Mを15〜65モル%及び構成単位Nを0〜5モル%(合計100モル%)の割合で有する水溶性ビニル共重合体である。各構成単位の割合がこれらの範囲から外れると、そのような水溶性ビニル共重合体は流動性能が著しく低下する。なかでもA成分としては、それが構成単位Lと構成単位Mとで構成された水溶性ビニル共重合体である場合、構成単位Lを45〜85モル%及び構成単位Mを15〜55モル%(合計100モル%)の割合で有するものが好ましく、またそれが構成単位Lと構成単位Mと構成単位Nとで構成された水溶性ビニル共重合体である場合、構成単位Lを45〜85モル%、構成単位Mを15〜55モル%及び構成単位Nを5モル%以下(合計100モル%)の割合で有するものが好ましい。 In the preparation method of the present invention, the component A used as one component of the multifunctional admixture is a water-soluble vinyl copolymer composed of the structural unit L and the structural unit M as described above, or the structural unit L and the structural unit. A water-soluble vinyl copolymer composed of M and a structural unit N, wherein the structural unit L is 35 to 85 mol%, the structural unit M is 15 to 65 mol%, and the structural unit N is 0 to 5 in the molecule. It is a water-soluble vinyl copolymer having a mol% (total of 100 mol%) ratio. When the proportion of each structural unit is out of these ranges, the flow performance of such a water-soluble vinyl copolymer is significantly reduced. Among them, as the component A, when it is a water-soluble vinyl copolymer composed of the structural unit L and the structural unit M, the structural unit L is 45 to 85 mol% and the structural unit M is 15 to 55 mol%. What has a ratio of (total 100 mol%) is preferable, and when it is a water-soluble vinyl copolymer comprised by the structural unit L, the structural unit M, and the structural unit N, the structural unit L is 45-85. Those having a mole percentage of 15 to 55 mole% of structural unit M and 5 mole% or less of structural unit N (total of 100 mole%) are preferred.
A成分としての水溶性ビニル共重合体は公知の方法で合成できる。これには例えば、特開昭58−74552号公報や特開平1−226757号公報に記載されているような水系ラジカル共重合による方法が適用できる。いずれにしても、これらの方法で合成される水溶性ビニル共重合体の質量平均分子量(GPC法によるポリスチレン換算の質量平均分子量、以下同じ)は、3000〜80000の範囲内のものとする。質量平均分子量がかかる範囲から外れると、そのような水溶性ビニル共重合体は流動性能が低下する。水溶性ビニル共重合体の好ましい質量平均分子量の範囲は5000〜60000である。 The water-soluble vinyl copolymer as the component A can be synthesized by a known method. For example, a method based on aqueous radical copolymerization as described in JP-A-58-74552 and JP-A-1-226757 can be applied. In any case, the water-soluble vinyl copolymer synthesized by these methods has a mass average molecular weight (polystyrene equivalent weight average molecular weight by GPC, the same shall apply hereinafter) in the range of 3000 to 80000. When the mass average molecular weight is out of such a range, the flow performance of such a water-soluble vinyl copolymer is lowered. The range of the preferable mass average molecular weight of a water-soluble vinyl copolymer is 5000-60000.
本発明の調製方法において、多機能混和剤の一成分として用いるB成分は、前記の化1で示される化合物、すなわちグリセリンのプロピレンオキサイド付加物である。化1中のA1、A2及びA3は分子中に1〜10個のオキシプロピレン単位で構成された(ポリ)オキシプロピレン基を有する(ポリ)プロピレングリコールから全ての水酸基を除いた残基であって、且つA1、A2、及びA3中のオキシプロピレン単位の個数の合計が7〜20個を満足するものである。なかでもB成分の化1で示される化合物としては、グリセリン1分子が有する3個の各水酸基に対してオキシプロピレン単位を1〜10モルの範囲としたものであって、且つそれらのオキシプロピレン単位の個数の合計が7〜20個の範囲となるように付加したものが好ましい。オキシプロピレン単位の個数の合計が前記の7個よりも少ないと、得られる硬化体の乾燥収縮率が大きくなり、逆にオキシプロピレン単位の個数の合計が前記の20個よりも多いと、水に不溶化して連行空気量の調製が困難になる。以上説明したB成分の化1で示される化合物はグリセリンにプロピレンオキサイドを付加重合する公知の方法で合成できる。 In the preparation method of the present invention, the component B used as one component of the multifunctional admixture is a compound represented by the above chemical formula 1, that is, a propylene oxide adduct of glycerin. A 1 , A 2 and A 3 in Chemical Formula 1 are residues obtained by removing all hydroxyl groups from (poly) propylene glycol having a (poly) oxypropylene group composed of 1 to 10 oxypropylene units in the molecule In addition, the total number of oxypropylene units in A 1 , A 2 , and A 3 satisfies 7 to 20. Among them, the compound represented by chemical formula 1 of the B component is one in which the oxypropylene unit is in the range of 1 to 10 moles with respect to each of the three hydroxyl groups of one molecule of glycerin, and those oxypropylene units. Those added in such a way that the total number of these is in the range of 7 to 20 are preferred. If the total number of oxypropylene units is less than the above 7, the resulting cured product has a high drying shrinkage rate. Conversely, if the total number of oxypropylene units is more than the above 20, the water Insolubilization makes it difficult to adjust the amount of entrained air. The compound represented by the chemical formula 1 of the B component described above can be synthesized by a known method of addition polymerization of propylene oxide to glycerin.
本発明の調製方法において、多機能混和剤の一成分として用いるC成分は、前記の化2で示される化合物、すなわち(ポリ)エチレングリコールモノアルキルエーテルである。化2中のRは炭素数3〜5のアルキル基であるが、炭素数4のブチル基が好ましい。ブチル基には、ノルマルブチル基、セカンダリーブチル基、ターシャリーブチル基等の異性体が含まれるが、なかでもR1としてはノルマルブチル基が好ましい。また化2中のA4は、分子中に1〜4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(ポリ)エチレングリコールから全ての水酸基を除いた残基である。なかでも、C成分の化2で示される化合物としては、ジエチレングリコールモノブチルエーテルが好ましい。以上説明したC成分の化2で示される化合物は、炭素数3〜5の脂肪族アルコールにエチレンオキサイドを付加重合する公知の方法で合成できる。 In the preparation method of the present invention, the component C used as one component of the multifunctional admixture is the compound represented by the chemical formula 2, that is, (poly) ethylene glycol monoalkyl ether. R in Chemical Formula 2 is an alkyl group having 3 to 5 carbon atoms, preferably a butyl group having 4 carbon atoms. The butyl group includes isomers such as a normal butyl group, a secondary butyl group, and a tertiary butyl group. Among them, R 1 is preferably a normal butyl group. A 4 in Chemical Formula 2 is a residue obtained by removing all hydroxyl groups from (poly) ethylene glycol having a (poly) oxyethylene group composed of 1 to 4 oxyethylene units in the molecule. Of these, diethylene glycol monobutyl ether is preferable as the compound represented by Chemical Formula 2 of the C component. The compound represented by the chemical formula 2 of component C described above can be synthesized by a known method of addition polymerization of ethylene oxide to an aliphatic alcohol having 3 to 5 carbon atoms.
本発明の調製方法に供する多機能混和剤は、以上説明したようなA成分、B成分及びC成分から成り、該A成分を10〜25質量%、該B成分を10〜45質量%及び該C成分を30〜65質量%(合計100質量%)の割合で含有して成るものである。各成分の含有割合がこれらの範囲から外れると、そのような多機能混和剤を用いて調製したAEコンクリートは前記した所期の多機能を同時に備えるのが難しくなる。 The multifunctional admixture used for the preparation method of the present invention comprises the A component, the B component and the C component as described above, the A component being 10 to 25% by mass, the B component being 10 to 45% by mass and the The component C is contained in a proportion of 30 to 65% by mass (total of 100% by mass). When the content ratio of each component deviates from these ranges, it becomes difficult for the AE concrete prepared using such a multifunctional admixture to have the desired multifunctional functions as described above.
本発明の調製方法では、空気量調節剤を用いる。かかる空気量調節剤としては、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アルキルリン酸エステル塩等が挙げられるが、なかでもアルキルリン酸エステル塩が好ましく、オクチルリン酸モノエステル塩が特に好ましい。 In the preparation method of the present invention, an air amount adjusting agent is used. Examples of the air amount regulator include polyoxyalkylene alkyl ether sulfate, alkylbenzene sulfonate, polyoxyethylene alkylbenzene sulfonate, rosin soap, higher fatty acid soap, alkyl phosphate ester salt, polyoxyalkylene alkyl ether alkyl phosphate Examples include ester salts, among which alkyl phosphate ester salts are preferable, and octyl phosphate monoester salts are particularly preferable.
本発明の調製方法では、粗骨材として特定の石灰砕石を用いる。かかる石灰砕石は、その化学成分としてCaOを70質量%以上及びMgOを1質量%以下の割合で含有するものである。粗骨材としてのかかる石灰砕石は、調製する無収縮AEコンクリート中においてその単位量が850〜1200kg/m3となる範囲で用いるが、好ましくは900〜1150kg/m3となる範囲で用いる。用いる石灰砕石の化学成分が前記の数値範囲から外れたり、またその使用量が前記の単位量の数値範囲から外れると、得られる硬化体の収縮率を50×10−6以下に抑えることができない。 In the preparation method of the present invention, specific crushed stone is used as the coarse aggregate. Such crushed limestone contains, as its chemical components, CaO in a proportion of 70% by mass or more and MgO in a proportion of 1% by mass or less. The crushed limestone as a coarse aggregate is used in a range in which the unit amount is 850 to 1200 kg / m 3 in the non-shrinkable AE concrete to be prepared, and is preferably used in a range of 900 to 1150 kg / m 3 . If the chemical composition of the limestone used is out of the numerical range, or the amount used is out of the numerical range of the unit amount, the shrinkage of the resulting cured product cannot be suppressed to 50 × 10 −6 or less. .
本発明の調製方法に供する細骨材としては、公知の川砂、山砂、海砂、砕砂、石灰砕砂等が挙げられる。なかでも、その化学成分としてCaOを50質量%以上及びMgOを2質量%以下の割合で含有する石灰砕砂が、得られる硬化体の乾燥収縮率をより一層低く抑える上で好ましい。 Examples of the fine aggregate used in the preparation method of the present invention include known river sand, mountain sand, sea sand, crushed sand, lime crushed sand and the like. Among them, crushed lime containing 50 mass% or more of CaO and 2 mass% or less of MgO as the chemical components is preferable for further reducing the drying shrinkage of the obtained cured product.
本発明の調製方法では、膨張材を用いる。膨張材の種類は特に制限されず、石灰系膨張材や、カルシウムスルホアルミネート(以下、CSAと略す)/石灰複合系膨張材等の市販のもの、例えば3CaO・3Al2O3・CaSO4、CaO及びCaSO4の3成分を含有するもの等が挙げられる。これらの石灰系膨張材やCSA/石灰複合系膨張材を用いると、得られる硬化体が膨張するのは、かかる膨張材がセメントとの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、これらの水和物が硬化体中で膨張するためとされている。本発明の調製方法では、用いる他の材料との組み合わせによる相乗効果の観点から、膨張材としては石灰系膨張材が好ましい。以上説明した膨張材は、単位量が15〜40kg/m3となる割合で用いるが、単位量が18〜35kg/m3となる割合で用いるのが好ましい。本発明の調製方法においてかかる膨張材は、結合材の一部として用いる。 In the preparation method of the present invention, an expanding material is used. The type of the expansion material is not particularly limited, and is commercially available such as lime-based expansion material, calcium sulfoaluminate (hereinafter abbreviated as CSA) / lime composite expansion material, such as 3CaO.3Al 2 O 3 .CaSO 4 , Examples include those containing three components of CaO and CaSO 4 . When these lime-based expansion materials and CSA / lime composite expansion materials are used, the resulting cured body expands because such expansion materials generate ettringite and calcium hydroxide by hydration reaction with cement. This is because the hydrate expands in the cured body. In the preparation method of the present invention, a lime-based expansion material is preferable as the expansion material from the viewpoint of a synergistic effect due to the combination with other materials used. Above-described expandable material is used in a proportion that the amount of the unit is 15~40kg / m 3, the amount of units preferably used in a proportion to be 18~35kg / m 3. In the preparation method of the present invention, the expansion material is used as a part of the binder.
本発明の調製方法では、以上説明したように、セメント、水、細骨材、粗骨材、膨張材、多機能混和剤及び空気量調節剤を練り混ぜ、無収縮AEコンクリートを調製する。この際、多機能混和剤は、その20〜70質量%水溶液をセメント100質量部当たり多機能混和剤として0.3〜2.5質量部となる割合で用いる。多機能混和剤は、練り混ぜ水の一部と混合した混合水溶液として用いるが、濃度20〜70質量%の混合水溶液として用いるのである。多機能混和剤の使用量が前記の範囲より少ないと、調製した無収縮AEコンクリートの流動性が悪く、そもそも前記した所期の多機能を同時に備えることが難しくなる。逆に多機能混和剤の使用量を前記の範囲より多くしても、それに見合うだけの効果が得られない。また空気量調節剤の使用量は通常、セメント100質量部当たり0.001〜0.01質量部の割合とする。 In the preparation method of the present invention, as described above, cement, water, fine aggregate, coarse aggregate, expansion material, multifunctional admixture, and air amount adjusting agent are kneaded to prepare non-shrinkable AE concrete. In this case, the multifunctional admixture is used in an amount of 0.3 to 2.5 parts by mass of the 20 to 70% by mass aqueous solution as a multifunctional admixture per 100 parts by mass of cement. The multifunctional admixture is used as a mixed aqueous solution mixed with a part of the kneaded water, but is used as a mixed aqueous solution having a concentration of 20 to 70% by mass. If the amount of the multifunctional admixture used is less than the above range, the prepared non-shrinkable AE concrete has poor fluidity, and it becomes difficult to simultaneously provide the desired multifunctional functions. Conversely, even if the amount of the multi-functional admixture is increased beyond the above range, an effect commensurate with it cannot be obtained. Moreover, the usage-amount of an air quantity regulator is normally set as the ratio of 0.001-0.01 mass part per 100 mass parts of cement.
本発明の調製方法では、調製する無収縮AEコンクリートの連行空気量を3〜7容量%、好ましくは4〜6容量%に調製する。連行空気量が3容量%より少ないと、そのような無収縮AEコンクリートから得られる硬化体の凍結融解に対する抵抗性が弱くなり、逆に連行空気量が7容量%より多いと、そのような無収縮AEコンクリートから得られる硬化体の強度が低くなる。 In the preparation method of the present invention, the entrained air amount of the non-shrinkable AE concrete to be prepared is adjusted to 3 to 7% by volume, preferably 4 to 6% by volume. If the amount of entrained air is less than 3% by volume, the resistance to freezing and thawing of the hardened body obtained from such non-shrinkable AE concrete is weakened. Conversely, if the amount of entrained air is more than 7% by volume, The strength of the hardened body obtained from the contracted AE concrete is lowered.
本発明の調製方法では、前記したように、セメント、水、細骨材、粗骨材、膨張材、多機能混和剤及び空気量調節剤を練り混ぜ、無収縮AEコンクリートを調製する。この際、一般に期待される圧縮強度が20〜55N/mm2の硬化体を得るためには、水/結合材比を35〜65%とするが、好ましくは40〜60%とする。なお前記したように、本発明の調製方法では、膨張材はセメントと同様に結合材の一部とみなしている。 In the preparation method of the present invention, as described above, cement, water, fine aggregate, coarse aggregate, expansion material, multifunctional admixture and air amount adjusting agent are kneaded to prepare non-shrinkable AE concrete. At this time, in order to obtain a cured product having a compression strength generally expected to be 20 to 55 N / mm 2 , the water / binding material ratio is set to 35 to 65%, preferably 40 to 60%. As described above, in the preparation method of the present invention, the expansion material is regarded as a part of the binding material in the same manner as the cement.
本発明の調製方法では、前記したような方法で各材料を練り混ぜて、無収縮AEコンクリートを調製するが、この際、本発明の効果を損なわない範囲内で、必要に応じて消泡剤、凝結促進剤、凝結遅延剤、防水剤、防腐剤、防錆剤等の添加剤を併用することができる。 In the preparation method of the present invention, each material is kneaded by the method as described above to prepare a non-shrinkable AE concrete. At this time, an antifoaming agent is used as necessary within the range not impairing the effect of the present invention. Additives such as setting accelerators, setting retarders, waterproofing agents, preservatives, and rust inhibitors can be used in combination.
以上説明した本発明の調製方法によると、乾燥収縮率が50×10−6以下の実質的に無収縮で、外観の優れた硬化体を得ることができる。その理由は、以下の1)〜4)の性質が相互的に累積して相乗効果をもたらすためと推察される。1)減水性能と乾燥収縮低減性能を併せもつ多機能混和剤を使用することにより、単位水量を減らすことができ、優れた流動性を確保できると同時に、得られる硬化体の乾燥収縮を低減することができる。2)特定の高品質な石灰砕石を粗骨材として使用することにより、得られる硬化体の乾燥収縮を低減することができる。3)膨張材の膨張効果により得られる硬化体が一定量膨張することによって、得られる硬化体の乾燥収縮を減らすことができる。4)得られる硬化体の表面に粗大気泡の少ない安定した微細気泡を導入できるので、凍結融解抵抗性に優れると同時に表面美観に優れた硬化体を得ることができる。 According to the preparation method of the present invention described above, it is possible to obtain a cured product having a dry shrinkage rate of 50 × 10 −6 or less and substantially no shrinkage and having an excellent appearance. The reason is presumed that the following properties 1) to 4) are cumulatively accumulated to bring about a synergistic effect. 1) By using a multifunctional admixture that has both water reduction performance and drying shrinkage reduction performance, the unit water volume can be reduced, and excellent fluidity can be secured, while at the same time reducing the drying shrinkage of the resulting cured product. be able to. 2) By using specific high-quality crushed limestone as coarse aggregate, drying shrinkage of the obtained cured product can be reduced. 3) When the cured body obtained by the expansion effect of the expansion material expands by a certain amount, drying shrinkage of the obtained cured body can be reduced. 4) Since stable fine bubbles with few coarse bubbles can be introduced into the surface of the obtained cured product, a cured product having excellent freeze-thaw resistance and excellent surface aesthetics can be obtained.
次に本発明に係る無収縮AEコンクリート(以下、本発明の無収縮AEコンクリートという)について説明する。本発明の無収縮AEコンクリートは、以上説明したような本発明の調製方法によって得られるもので、その乾燥収縮率が50×10−6以下の実質的に無収縮なものとなる。更に加えて、得られる硬化体はその表面に気泡径3mm以上の粗大気泡が少なく、表面平滑性の優れたものとなる。本発明の無収縮AEコンクリートは、一般の水漏れを嫌う床スラブのひび割れ防止対策や壁面の開口部でのひび割れ防止対策等に有用であり、また美観の優れた硬化体を得る場合にも有用である。 Next, the non-shrinkable AE concrete according to the present invention (hereinafter referred to as the non-shrinkable AE concrete of the present invention) will be described. The non-shrinkable AE concrete of the present invention is obtained by the preparation method of the present invention as described above, and is substantially non-shrinkable with a dry shrinkage rate of 50 × 10 −6 or less. In addition, the obtained cured product has few coarse bubbles with a bubble diameter of 3 mm or more on the surface, and has excellent surface smoothness. The non-shrinkable AE concrete of the present invention is useful for preventing cracks in floor slabs that dislike general water leaks, preventing cracks at the opening of the wall surface, etc., and also useful for obtaining hardened bodies with excellent aesthetics. It is.
本発明によると、セメント分散剤と乾燥収縮低減剤とを一液化した多機能混和剤を使用して作業性及び経済性を向上しつつ、1)調製した無収縮AEコンクリートの流動性及び空気量が経時的に安定した状態で保たれること、2)得られる硬化体の乾燥収縮率が50×10−6以下の実質的に無収縮の領域にあること、3)得られる硬化体の凍結融解に対する抵抗性が強いこと、4)得られる硬化体の表面が平滑であること、以上の1)〜4)の多機能を同時に備えた無収縮AEコンクリートを調製することができる。 According to the present invention, while using a multifunctional admixture in which a cement dispersant and a drying shrinkage reducing agent are made into one component, workability and economy are improved, and 1) fluidity and air amount of the prepared non-shrinkable AE concrete. Is kept stable over time, 2) the drying shrinkage of the resulting cured body is in a substantially non-shrinkable region of 50 × 10 −6 or less, and 3) the resulting cured body is frozen. It is possible to prepare non-shrinkable AE concrete having strong resistance to melting, 4) the surface of the resulting cured body being smooth, and the above-mentioned multiple functions 1) to 4).
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、B成分及びC成分の合成)
・A成分としての水溶性ビニル共重合体(a−1)の合成
メタクリル酸60g、メトキシポリ(オキシエチレン単位の個数が23個、以下n=23という)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、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、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34000の水溶性ビニル共重合体であった。
Test category 1 (synthesis of A, B and C components)
Synthesis of water-soluble vinyl copolymer (a-1) as component A: 60 g of methacrylic acid, methoxypoly (23 units of oxyethylene units, hereinafter referred to as n = 23) 300 g of ethylene glycol methacrylate, 5 g of sodium methallylsulfonate After charging 4 g of 3-mercaptopropionic 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% aqueous sodium hydroxide solution was added to completely neutralize the reaction product, thereby obtaining a 40% aqueous solution of the water-soluble vinyl copolymer (a-1). When the water-soluble vinyl copolymer (a-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. The structural unit was a water-soluble vinyl copolymer having a mass average molecular weight of 34,000 having a ratio of 70/27/3 (mol%).
・A成分の水溶性ビニル共重合体(a−2)〜(a−4)及び(ar−1)〜(ar−3)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)〜(a−4)及び(ar−1)〜(ar−3)を合成した。以上で合成したA成分の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 (a-2) to (a-4) and (ar-1) to (ar-3) of component A Same as the synthesis of water-soluble vinyl copolymer (a-1) Thus, water-soluble vinyl copolymers (a-2) to (a-4) and (ar-1) to (ar-3) were synthesized. The contents of each water-soluble vinyl copolymer of component A synthesized above are summarized in Table 1.
表1において、
L−1:メタクリル酸ナトリウムから形成された構成単位
L−2:メタクリル酸から形成された構成単位
M−1:メトキシポリ(n=23)エチレングリコールメクリレートから形成された構成単位
M−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から形成された構成単位
M−3:メトキシポリ(n=45)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
N−1: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
N−2:メチルアクリレートから形成された構成単位
*1:GPC法によるポリスチレン換算の質量平均分子量
In Table 1,
L-1: Structural unit formed from sodium methacrylate L-2: Structural unit formed from methacrylic acid M-1: Structural unit formed from methoxypoly (n = 23) ethylene glycol methacrylate M-2: Methoxypoly (N = 68) Structural unit formed from ethylene glycol methacrylate M-3: Structural unit formed from methoxypoly (n = 45) ethylene glycol methacrylate N-1: Structural unit formed from sodium methallylsulfonate N- 2: Constituent unit formed from methyl acrylate * 1: Mass average molecular weight in terms of polystyrene by GPC method
・B成分としての化1で示される化合物(b−1)の合成
グリセリン184g(2.0モル)をオートクレーブに仕込み、触媒として水酸化カリウムを1.8g加えた後、オートクレーブ内を窒素置換した。攪拌しながら、反応温度を125〜140℃に保ち、プロピレンオキサイド1160g(20モル)を圧入して付加反応を行なった。圧入終了後、同温度で2時間熟成して反応を終了し、生成物を得た。この生成物の残存触媒を吸着材を用いて吸着処理した後、濾別精製した。この精製処理物は常温で液状の化合物であり、水酸基価等の分析結果により、B成分としてのグリセリンのプロピレンオキサイド10モル付加物(b−1)であった。
-Synthesis | combination of the compound (b-1) shown by Chemical formula 1 as B component Glycerin 184g (2.0 mol) was prepared to the autoclave, and after adding 1.8g of potassium hydroxide as a catalyst, the inside of the autoclave was substituted with nitrogen. . While stirring, the reaction temperature was kept at 125 to 140 ° C., and 1160 g (20 mol) of propylene oxide was injected to carry out an addition reaction. After completion of the press-fitting, the reaction was terminated by aging at the same temperature for 2 hours to obtain a product. The residual catalyst of this product was subjected to adsorption treatment using an adsorbent, and then purified by filtration. This purified product was a liquid compound at room temperature, and was a propylene oxide 10 mol adduct (b-1) of glycerin as component B according to the analysis results such as hydroxyl value.
B成分としての化1で示される化合物等(b−2)、(b−3)及び(br−1)〜(br−3)の合成
化1で示される化合物(b−1)と同様にして、化1で示される化合物等(b−2)、(b−3)及び(br−1)〜(br−3)を合成した。合成したB成分としての化1で示される化合物等の内容を表2にまとめて示した。
Compound (b-2), (b-3) and (br-1) to (br-3) represented by the chemical formula 1 as the B component In the same manner as the compound (b-1) represented by the chemical formula 1 Thus, compounds (b-2), (b-3) and (br-1) to (br-3) represented by Chemical Formula 1 were synthesized. Table 2 summarizes the contents of the compounds represented by Chemical Formula 1 as the synthesized B component.
・C成分としての化2で示される化合物(c−1)の合成
n−ブタノール740g(10モル)をオートクレーブに仕込み、触媒として水酸化カリウムを1.8g加えた後、オートクレーブ内を窒素置換した。攪拌しながら、反応温度を120〜135℃に保ち、エチレンオキサイド900g(20モル)を圧入して付加反応を行なった。圧入終了後、同温度で2時間熟成して反応を終了した。残存触媒を吸着材を用いて吸着処理した後、濾別精製した。精製物は水酸基価等の分析結果により、C成分としてのジエチレングリコールモノブチルエーテル(c−1)であった。
Synthesis of compound (c-1) represented by chemical formula 2 as component C: 740 g (10 mol) of n-butanol was charged into an autoclave, and 1.8 g of potassium hydroxide was added as a catalyst, and then the inside of the autoclave was purged with nitrogen. . While stirring, the reaction temperature was kept at 120 to 135 ° C., and 900 g (20 mol) of ethylene oxide was injected to carry out the addition reaction. After completion of the press-fitting, the reaction was terminated by aging for 2 hours at the same temperature. The residual catalyst was adsorbed using an adsorbent and then purified by filtration. The purified product was diethylene glycol monobutyl ether (c-1) as the C component according to the analysis results such as the hydroxyl value.
C成分としての化2で示される化合物等(c−2)、(c−3)、(cr−1)及び(cr−2)の合成
化2で示される化合物(c−1)と同様にして、化2で示される化合物等(c−2)、(c−3)、(cr−1)及び(cr−2)を合成した。合成したC成分としての化2で示される化合物等の内容を表3の脚注にまとめて示した。
Compound (C-2), (c-3), (cr-1), and (cr-2) represented by Chemical Formula 2 as Component C In the same manner as Compound (c-1) represented by Chemical Formula 2 Thus, compounds (c-2), (c-3), (cr-1) and (cr-2) represented by the chemical formula 2 were synthesized. The contents of the compound represented by Chemical Formula 2 as the synthesized C component are summarized in the footnotes of Table 3.
試験区分2(多機能混和剤の調製)
・多機能混和剤(f−1)の調製
ガラス容器に表1記載のA成分(a−1)を20部(固形濃度40%の水溶液として50部)、表2記載のB成分(b−1)30部、C成分(c−1)50部及び水70部を投入して混合し、多機能混和剤(f−1)の50%濃度水溶液200部を調製した。
Test Category 2 (Preparation of multifunctional admixture)
-Preparation of multifunctional admixture (f-1)
20 parts of A component (a-1) described in Table 1 (50 parts as an aqueous solution having a solid concentration of 40%), 30 parts of B component (b-1) described in Table 2, C component (c-1) 50 parts and 70 parts of water were added and mixed to prepare 200 parts of a 50% strength aqueous solution of the multifunctional admixture (f-1).
・多機能混和剤(f−2)〜(f−12)及び(fr−1)〜(fr−12)の調製
多機能混和剤(f−1)の調製と同様にして、(f−2)〜(f−12)及び(fr−1)〜(fr−12)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 multifunctional admixtures (f-2) to (f-12) and (fr-1) to (fr-12) In the same manner as the preparation of the multifunctional admixture (f-1), (f-2 ) To (f-12) and (fr-1) to (fr-12) were prepared. The contents of each prepared multifunctional admixture are summarized in Table 3.
表3において、
a−1〜a−4及びar−1〜ar−3:表1記載の水溶性ビニル共重合体
b−1〜b−3及びbr−1〜br−3:表2記載の化合物
c−1:ジエチレングリコールモノブチルエーテル
c−2:ジエチレングリコールモノプロピルエーテル
c−3:トリエチレングリコールモノペンチルエーテル
cr−1:ジエチレングリコールモノエチルエーテル
cr−2:テトラエチレングリコールモノオクチルエーテル
In Table 3,
a-1 to a-4 and ar-1 to ar-3: water-soluble vinyl copolymers described in Table 1 b-1 to b-3 and br-1 to br-3: compounds described in Table 2 c-1 : Diethylene glycol monobutyl ether c-2: Diethylene glycol monopropyl ether c-3: Triethylene glycol monopentyl ether cr-1: Diethylene glycol monoethyl ether cr-2: Tetraethylene glycol monooctyl ether
試験区分3(無収縮AEコンクリート等の調製及び物性測定結果等)
実施例1〜17及び比較例1〜16、18
表4に記載した配合条件で、50リットルのパン型強制練りミキサーに普通ポルトランドセメント、膨張材、細骨材及び粗骨材を順次投入して15秒間空練りした。次いで、目標スランプが18±1cm、目標空気量が4.5〜5.5%の範囲となるよう、試験区分2で調製した表3記載の多機能混和剤及び空気量調節剤のそれぞれ所定量を練り混ぜ水で希釈した後に投入して練り混ぜ、各例の無収縮AEコンクリート等を調製した。各例の無収縮AEコンクリート等について、多機能混和剤の添加量、空気量調節剤の添加量及び調製した無収縮AEコンクリート等の物性測定結果等を表6に、また各例の無収縮AEコンクリート等を硬化して得た硬化体の物性測定結果等を表7にまとめて示した。
Test category 3 (preparation of non-shrinkable AE concrete, physical property measurement results, etc.)
Examples 1-17 and Comparative Examples 1-16, 18
Under the blending conditions shown in Table 4, ordinary Portland cement, expanded material, fine aggregate and coarse aggregate were sequentially added to a 50-liter pan-type forced kneader and kneaded for 15 seconds. Next, predetermined amounts of the multifunctional admixture and air amount adjusting agent described in Table 3 prepared in Test Category 2 so that the target slump is 18 ± 1 cm and the target air amount is in the range of 4.5 to 5.5%. After mixing with water and diluting with water, it was added and kneaded to prepare non-shrinkable AE concrete of each example. Regarding the non-shrinkable AE concrete of each example, the addition amount of the multifunctional admixture, the addition amount of the air amount adjusting agent and the physical property measurement results of the prepared non-shrinkage AE concrete are shown in Table 6, and the non-shrinkage AE of each example. Table 7 summarizes the physical property measurement results and the like of the cured bodies obtained by curing concrete and the like.
表4において、
*2:普通ポルトランドセメント(密度=3.16g/cm3、ブレーン値3300)
*3:石灰系膨張材(太平洋マテリアル社製、商品名ハイパーエクスパン、密度=3.16g/cm3)
*4:石灰砕石(密度=2.61g/cm3、F.M.6.70)
*6:岩瀬産砕石(密度=2.63g/cm3、F.M.6.74)
*7:石灰砕砂(密度=2.58g/cm3、F.M.2.67)
*8:岩瀬産砕砂(密度=2.61g/cm3、F.M.2.83)
尚、表4で用いた石灰砕石の化学成分を表5に示した。
In Table 4,
* 2: Normal Portland cement (Density = 3.16 g / cm 3 , Blaine value 3300)
* 3: Lime-based expansion material (trade name Hyper Expan, manufactured by Taiheiyo Materials Co., Ltd., density = 3.16 g / cm 3 )
* 4: Limestone (density = 2.61 g / cm 3 , FM 6.70)
* 6: Crushed stone from Iwase (density = 2.63 g / cm 3 , FM 6.74)
* 7: Crushed lime sand (density = 2.58 g / cm 3 , FM 2.67)
* 8: Crushed sand from Iwase (density = 2.61 g / cm 3 , FM 2.83)
In addition, Table 5 shows chemical components of the limestone used in Table 4.
・無収縮AEコンクリート等の物性測定等
調製した各例の無収縮AEコンクリート等について、空気量、スランプ、スランプ残存率を下記のように求め、結果を表6にまとめて示した。また各例の無収縮AEコンクリート等を硬化して得た硬化体について、乾燥収縮率、気泡間隔係数、凍結融解耐久性指数及び圧縮強度を下記のように求め、結果を表7にまとめて示した。
-Physical property measurement etc. of non-shrinkable AE concrete etc. About the non-shrinkage AE concrete etc. of each prepared example, air quantity, slump, and slump residual rate were calculated | required as follows, and the result was put together in Table 6 and shown. Moreover, about the hardened | cured material obtained by hardening | curing the non-shrinkable AE concrete etc. of each example, a drying shrinkage rate, a bubble space | interval coefficient, a freeze-thaw durability index, and compressive strength were calculated | required as follows, and a result is shown in Table 7 collectively. It was.
・連行空気量(容量%):練り混ぜ直後(調製直後)の無収縮AEコンクリート等及び60分間静置後の無収縮AEコンクリート等について、JIS−A1128に準拠して測定した。
・スランプ(cm):連行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、各例の無収縮AEコンクリート等を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。
・気泡間隔係数(μm):各例の無収縮AEコンクリート等を、20℃×60%RHの条件下で26週間保存し、得られた硬化体の表面を研磨仕上げした供試体について、気泡組織をASTM−C457のリニアトラバース法に準拠して顕微鏡で測定した。
・凍結融解耐久性指数(300サイクル):各例の無収縮AEコンクリート等について、JIS−A1148に準拠して測定した値を用い、ASTM−C666−75の耐久性指数で計算した数値を求めた。この数値は、最大値が100で、100に近いほど、凍結融解に対する抵抗性が優れていることを示す。
・圧縮強度(N/mm2):各例の無収縮AEコンクリート等について、JIS−A1108に準拠し、材齢7日と材齢28日で測定した。
Entrained air volume (volume%): measured for non-shrinkable AE concrete immediately after mixing (immediately after preparation) and non-shrinkable AE concrete after standing for 60 minutes in accordance with JIS-A1128.
-Slump (cm): Simultaneously with the measurement of the amount of entrained air, the slump was measured according to JIS-A1101.
-Slump residual rate (%): (slump after standing for 60 minutes / slump immediately after kneading) x 100.
-Drying shrinkage: Based on JIS-A1129, dry shrinkage strain was measured by the comparator method for a 26-week-old specimen in which the non-shrinkable AE concrete of each example was stored at 20 ° C x 60% RH. Then, the drying shrinkage was determined. The smaller this value, the smaller the drying shrinkage.
・ Bubble spacing coefficient (μm): For each specimen in which the non-shrinkable AE concrete of each example was stored for 26 weeks under the condition of 20 ° C. × 60% RH and the surface of the obtained cured body was polished, Was measured with a microscope in accordance with the linear traverse method of ASTM-C457.
-Freeze-thaw durability index (300 cycles): Using the values measured in accordance with JIS-A1148 for the non-shrinkable AE concrete of each example, the numerical value calculated by the durability index of ASTM-C666-75 was obtained. . This numerical value indicates that the maximum value is 100, and the closer to 100, the better the resistance to freezing and thawing.
-Compressive strength (N / mm < 2 >): About the non-shrinkable AE concrete of each example, based on JIS-A1108, it measured by material age 7 days and material age 28 days.
更に複数の無収縮AEコンクリート等については、それらを硬化して得た硬化体の表面仕上り状態を、下記のように求めた気泡数で評価すると共に、目視観察でも評価した。
結果を表8にまとめて示した。
Furthermore, about several non-shrinkable AE concrete etc., while evaluating the surface finishing state of the hardening body obtained by hardening | curing them, it evaluated also by visual observation while calculating | requiring by the number of bubbles calculated | required as follows.
The results are summarized in Table 8.
・気泡数の測定(個/0.09m2):練り混ぜ直後の無収縮AEコンクリート等を、縦×横×高さが0.15m×1m×1mの木製化粧型枠に流し込み、棒状バイブレータを用いて締め固め、材齢3日後に脱枠し、得られた硬化体の型枠剥離面(合計2面で2m2)に存在する気泡径が3mm以上の気泡数を数え、これを0.3m×0.3m=0.09m2中に存在する気泡数に換算した。
・ Measurement of the number of bubbles (pieces / 0.09 m 2 ): Non-shrinkable AE concrete immediately after kneading is poured into a wooden decorative mold of length × width × height 0.15 m × 1 m × 1 m, and a rod-like vibrator is used. The number of bubbles with a bubble diameter of 3 mm or more present on the mold release surface (2 m 2 in total) of the obtained cured product was counted. The number of bubbles present in 3 m × 0.3 m = 0.09 m 2 was converted.
表6及び表7において、
添加量:普通ポルトランドセメント100質量部に対する質量部
*9: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。
*10:測定対象となるような供試体が得られなかったので測定しなかった。
f−1〜f−12及びfr−1〜fr−12:表3に記載の多機能混和剤
s−1:オクチルリン酸モノエステルカリウム塩
s−2:樹脂酸石けん系AE剤(竹本油脂社製の商品名チューポールAE−300)
In Table 6 and Table 7,
Addition amount: part by mass with respect to 100 parts by mass of ordinary Portland cement * 9: Since the target fluidity (slump value) was not obtained, measurement was not performed.
* 10: Measurement was not performed because a specimen to be measured was not obtained.
f-1 to f-12 and fr-1 to fr-12: Multifunctional admixture described in Table 3 s-1: Octyl phosphate monoester potassium salt s-2: Resin acid soap-based AE agent (Takemoto Yushi Co., Ltd.) Product name Tupole AE-300)
表6〜表8の結果からも明らかなように、本発明によると、セメント分散剤と乾燥収縮低減剤とを一液化した多機能混和剤を使用して作業性及び経済性を向上しつつ、1)調製した無収縮AEコンクリートの流動性及び空気量が経時的に安定した状態で保たれること、2)得られる硬化体の乾燥収縮率が50×10−6以下の実質的に無収縮の領域にあること、3)得られる硬化体の凍結融解に対する抵抗性が強いこと、4)得られる硬化体の表面が平滑であること、以上の1)〜4)の多機能を同時に備えた無収縮AEコンクリートを調製することができる。 As is apparent from the results of Tables 6 to 8, according to the present invention, while using a multi-functional admixture in which a cement dispersant and a drying shrinkage reducing agent are made into one component, improving workability and economy, 1) Fluidity and air volume of the prepared non-shrinkable AE concrete must be kept stable over time. 2) The resulting cured product has a dry shrinkage rate of 50 × 10 −6 or less. 3) Strong resistance to freezing and thawing of the resulting cured body, 4) The surface of the obtained cured body is smooth, and the above functions 1) to 4) were simultaneously provided. Non-shrinkable AE concrete can be prepared.
Claims (9)
石灰砕石:化学成分としてCaO≧70質量%及びMgO≦1質量%の割合で含有するもの。
多機能混和剤:下記のA成分を10〜25質量%、下記のB成分を10〜45質量%及び下記のC成分を30〜65質量%(合計100質量%)の割合で含有するもの。
A成分:分子中に下記の構成単位Lを35〜85モル%、下記の構成単位Mを15〜65モル%及び下記の構成単位Nを0〜5モル%(合計100モル%)の割合で有する質量平均分子量3000〜80000の水溶性ビニル共重合体。
構成単位L: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M:分子中に5〜80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から選ばれる一つ又は二つ以上
構成単位N:メタ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
B成分:下記の化1で示される化合物
A1,A2,A3:分子中に1〜10個のオキシプロピレン単位で構成された(ポリ)オキシプロピレン基を有する(ポリ)プロピレングリコールから全ての水酸基を除いた残基であって、且つA1、A2及びA3中のオキシプロピレン単位の個数の合計が7〜20個を満足するもの。)
C成分:下記の化2で示される化合物
R:炭素数3〜5のアルキル基
A4:分子中に1〜4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(ポリ)エチレングリコールから全ての水酸基を除いた残基。) A method for preparing non-shrinkable AE concrete using cement, water, fine aggregate, coarse aggregate, expanded material, multifunctional admixture and air amount adjusting agent, and the following lime crushed stone as a coarse aggregate Using 850 to 1200 kg / m 3 and an expanding material in a unit amount of 15 to 40 kg / m 3 , a 20 to 70% by mass aqueous solution of the following multifunctional admixture is used as a multifunctional admixture per 100 parts by mass of cement. 2.5 using so that the ratio of the mass portion, a process for the preparation of non-shrink AE concrete, which comprises preparing a water / binder ratio to 35% to 65% and the amount of air entrained 3-7 volume%.
Lime crushed stone: Chemical component containing CaO ≧ 70 mass% and MgO ≦ 1 mass%.
Multifunctional admixture: A composition containing 10 to 25 mass% of the following A component, 10 to 45 mass% of the following B component, and 30 to 65 mass% (100 mass% in total) of the following C component.
Component A: 35 to 85 mol% of the following structural unit L in the molecule, 15 to 65 mol% of the following structural unit M, and 0 to 5 mol% (100 mol% in total) of the following structural unit N A water-soluble vinyl copolymer having a mass average molecular weight of 3000 to 80000.
Structural unit L: One or more selected from structural units formed from methacrylic acid and structural units formed from methacrylic acid salt Structural unit M: Consists of 5 to 80 oxyethylene units in the molecule One or two or more structural units selected from structural units formed from methoxypolyethylene glycol methacrylate having a polyoxyethylene group. Structural unit N: From structural units formed from methallyl sulfonate and structural units formed from methyl acrylate. One or more selected B component: Compound represented by the following chemical formula 1
A 1 , A 2 , A 3 : Residues obtained by removing all hydroxyl groups from (poly) propylene glycol having (poly) oxypropylene groups composed of 1 to 10 oxypropylene units in the molecule, In addition, the total number of oxypropylene units in A 1 , A 2 and A 3 satisfies 7 to 20 . )
Component C: Compound represented by the following chemical formula 2
R: an alkyl group having 3 to 5 carbon atoms A 4 : a residue obtained by removing all hydroxyl groups from (poly) ethylene glycol having a (poly) oxyethylene group composed of 1 to 4 oxyethylene units in the molecule . )
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013078345A JP6192208B2 (en) | 2013-04-04 | 2013-04-04 | Preparation method of non-shrink AE concrete and non-shrink AE concrete |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013078345A JP6192208B2 (en) | 2013-04-04 | 2013-04-04 | Preparation method of non-shrink AE concrete and non-shrink AE concrete |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2014201478A JP2014201478A (en) | 2014-10-27 |
JP6192208B2 true JP6192208B2 (en) | 2017-09-06 |
Family
ID=52352254
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2013078345A Active JP6192208B2 (en) | 2013-04-04 | 2013-04-04 | Preparation method of non-shrink AE concrete and non-shrink AE concrete |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP6192208B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102536071B1 (en) * | 2022-04-07 | 2023-05-30 | 주식회사 삼표산업 | Methods for Preparing Shrinkage Reduced Concrete Compositions |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102191877B1 (en) | 2017-06-29 | 2020-12-16 | 미쓰이스미토모겐세쓰 가부시키가이샤 | Concrete composition and its manufacturing method |
JP6887739B2 (en) * | 2017-12-14 | 2021-06-16 | 花王株式会社 | Surface aesthetic improver composition for hydraulic composition |
JP7012354B2 (en) * | 2018-03-01 | 2022-02-14 | 竹本油脂株式会社 | Cement admixture and cement composition |
JP7291346B2 (en) * | 2019-03-12 | 2023-06-15 | 株式会社竹中工務店 | Admixture for hydraulic composition and hydraulic composition |
JP7274145B2 (en) * | 2019-07-03 | 2023-05-16 | 株式会社竹中工務店 | Non-shrinkage concrete composition |
CN115335346A (en) * | 2020-03-17 | 2022-11-11 | 陶氏东丽株式会社 | Precast concrete molding |
US20230131818A1 (en) * | 2020-03-17 | 2023-04-27 | Dow Toray Co., Ltd. | Cement composition and cured product thereof |
JP6813225B1 (en) * | 2020-07-13 | 2021-01-13 | 竹本油脂株式会社 | Additives for hydraulic compositions and hydraulic compositions |
CN115974449B (en) * | 2022-12-29 | 2024-02-23 | 中铁上海工程局集团有限公司 | Regulator for sandstone concrete by iron tailing machine and preparation method and using method thereof |
CN117088652B (en) * | 2023-10-19 | 2024-01-05 | 长沙凯瑞重工机械有限公司 | Active excitation copper slag concrete and preparation method thereof |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11180747A (en) * | 1997-12-22 | 1999-07-06 | Nof Corp | Contraction reducing agent for cement |
JP4999188B2 (en) * | 2008-04-07 | 2012-08-15 | 株式会社竹中工務店 | Ultra-low shrinkage AE concrete composition |
JP5660724B2 (en) * | 2011-03-31 | 2015-01-28 | 株式会社竹中工務店 | Preparation method of non-shrink AE concrete and non-shrink AE concrete |
-
2013
- 2013-04-04 JP JP2013078345A patent/JP6192208B2/en active Active
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102536071B1 (en) * | 2022-04-07 | 2023-05-30 | 주식회사 삼표산업 | Methods for Preparing Shrinkage Reduced Concrete Compositions |
Also Published As
Publication number | Publication date |
---|---|
JP2014201478A (en) | 2014-10-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6192208B2 (en) | Preparation method of non-shrink AE concrete and non-shrink AE concrete | |
JP5443338B2 (en) | Concrete or mortar admixture composition | |
WO1995011204A1 (en) | Self-leveling water-base composition | |
JP6077156B2 (en) | Dispersant composition for hydraulic composition | |
JP4999188B2 (en) | Ultra-low shrinkage AE concrete composition | |
JP4798806B2 (en) | Low shrinkage AE concrete composition using blast furnace cement | |
JP2007153652A (en) | Method of producing ae concrete and ae concrete | |
JP4459912B2 (en) | Drying shrinkage reducing agent and hardened cement using the same | |
MX2008007269A (en) | Composition and its use for improving the processibility of hydraulically setting compositions | |
JP5748271B2 (en) | Non-shrink AE concrete composition | |
JP5058098B2 (en) | Method for preparing low shrinkage AE concrete for civil engineering and low shrinkage AE concrete for civil engineering | |
JPH07118047A (en) | Self-leveling water-based composition | |
JP5046472B2 (en) | Cement admixture and cement composition | |
JP6029233B2 (en) | AE concrete preparation method and AE concrete | |
JP5863296B2 (en) | Method for producing ultra-high-strength cement-based hardened body | |
JP3135781B2 (en) | Self-leveling aqueous composition | |
JP4994289B2 (en) | Ultra-low shrinkage AE concrete composition | |
JP5344692B2 (en) | Preparation method of AE concrete using blast furnace cement and AE concrete | |
JP2004284873A (en) | Hydraulic complex material | |
JP5975716B2 (en) | Freeze-thaw resistant low shrinkage AE concrete composition and cured body thereof | |
JP2014025323A (en) | Pavement concrete and manufacturing method for the same | |
JP5595068B2 (en) | Cement composition and cured body thereof | |
JP5120651B2 (en) | Shrinkage reducing agent for cement composition | |
JP7158825B2 (en) | cement composition | |
JP6887739B2 (en) | Surface aesthetic improver composition for hydraulic composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20160301 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20170119 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20170130 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170309 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20170807 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20170807 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6192208 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |