JP5975716B2 - Freeze-thaw resistant low shrinkage AE concrete composition and cured body thereof - Google Patents
Freeze-thaw resistant low shrinkage AE concrete composition and cured body thereof Download PDFInfo
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- 238000001035 drying Methods 0.000 claims description 48
- 239000003638 chemical reducing agent Substances 0.000 claims description 36
- 239000004568 cement Substances 0.000 claims description 26
- 239000002270 dispersing agent Substances 0.000 claims description 22
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- 239000000126 substance Substances 0.000 claims description 14
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- 150000001875 compounds Chemical class 0.000 claims description 12
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- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 125000006353 oxyethylene group Chemical group 0.000 claims description 4
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- 150000003839 salts Chemical class 0.000 claims description 4
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 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 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 19
- 239000000047 product Substances 0.000 description 17
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- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000002893 slag Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000007710 freezing Methods 0.000 description 6
- 230000001603 reducing effect Effects 0.000 description 6
- 239000004576 sand Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000008014 freezing Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
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- 238000010257 thawing Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- WRKCIHRWQZQBOL-UHFFFAOYSA-N octyl dihydrogen phosphate Chemical compound CCCCCCCCOP(O)(O)=O WRKCIHRWQZQBOL-UHFFFAOYSA-N 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 239000004571 lime Substances 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
- 239000004373 Pullulan Substances 0.000 description 2
- 229920001218 Pullulan Polymers 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229940077388 benzenesulfonate Drugs 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 235000019423 pullulan Nutrition 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
- 238000003756 stirring Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 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
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
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- 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
- 238000001914 filtration Methods 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 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
- 239000006028 limestone Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000000452 restraining effect Effects 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
- 229910000679 solder Inorganic materials 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は凍結融解抵抗性及び乾燥収縮低減性に優れた硬化体を得ることができる凍結融解抵抗性低収縮ＡＥコンクリート組成物及びその硬化体に関する。近年、コンリート構造物の長寿命化や高品質化の観点から、コンリート構造物には特に乾燥収縮によるひび割れの発生を抑制することが要求されている。例えばコンリート構造物の乾燥収縮によるひび割れを抑制するためには、一般建築物において乾燥収縮率を６００×１０−６（以下、１０−６をマイクロという）以下程度にする必要があるといわれており、なかでも鉄筋の拘束部材断面が大きい場合には乾燥収縮率を４００マイクロ以下程度にする必要があるといわれている。また一方で、寒冷地のコンリート構造物には同時に耐凍害性を確保する必要があることから、特に凍結融解抵抗性に優れていることが要求されている。本発明は、乾燥収縮率を４００マイクロ以下に低減することによって乾燥収縮によるひび割れの発生を抑制し、同時に凍結融解抵抗性に優れた硬化体を得ることができる凍結融解抵抗性低収縮ＡＥコンクリート組成物及びその硬化体に関する。 The present invention relates to a freeze-thaw resistant low-shrinkage AE concrete composition capable of obtaining a cured product excellent in freeze-thaw resistance and drying shrinkage reduction property, and a cured product thereof. In recent years, from the viewpoint of extending the life and quality of a concrete structure, the concrete structure is required to suppress the occurrence of cracks due to drying shrinkage. For example, in order to suppress cracking due to drying shrinkage of a concrete structure, it is said that the drying shrinkage rate in general buildings needs to be about 600 × 10 −6 (hereinafter 10 −6 is referred to as micro) or less. In particular, it is said that when the cross-section of the restraining member of the reinforcing bar is large, it is necessary to make the drying shrinkage rate about 400 micron or less. On the other hand, the concrete structure in a cold region is required to be particularly resistant to freezing and thawing because it is necessary to ensure frost damage resistance at the same time. The present invention suppresses the occurrence of cracks due to drying shrinkage by reducing the drying shrinkage ratio to 400 micron or less, and at the same time, a freeze-thaw resistant low-shrinkage AE concrete composition capable of obtaining a cured body having excellent freeze-thaw resistance. And a cured product thereof.
従来、硬化体の乾燥収縮を低減する手段として、ＡＥコンクリートの調製時に各種の乾燥収縮低減剤を使用することが知られている（例えば特許文献１参照）。一般に、乾燥収縮低減剤はＡＥコンクリート組成物に多く添加すればするほど、その収縮低減効果が上昇する傾向があるため、大きな効果を期待する場合には練り混ぜ水の一部として無視できない程の量（例えばコンクリート１ｍ３当たり５ｋｇ以上）を使用することになる。しかし、得られる硬化体の乾燥収縮を低減することと凍結融解に対する抵抗を強くすることは二律背反現象であるため、乾燥収縮低減剤を多く使用すればするほど、得られる硬化体の凍結融解抵抗性が低下するという問題がある。そのため、かかる問題を改善する提案も報告されている（例えば特許文献２〜６参照）。しかし、乾燥収縮率を４００マイクロ以下に低減し、同時に凍結融解抵抗性にも優れた硬化体を得るという高レベルな段階には至っていないというのが実情である。 Conventionally, as a means for reducing the drying shrinkage of a cured body, it is known to use various drying shrinkage reducing agents during the preparation of AE concrete (for example, see Patent Document 1). Generally, the more the shrinkage reducing agent is added to the AE concrete composition, the more the shrinkage reducing effect tends to increase. Therefore, when a large effect is expected, it cannot be ignored as a part of the kneaded water. It will be used in an amount (such as concrete 1 m 3 per 5kg or more). However, reducing the drying shrinkage of the cured product and increasing the resistance to freezing and thawing is a trade-off phenomenon, so the more the drying shrinkage reducing agent is used, the more the freeze-thaw resistance of the resulting cured product is. There is a problem that decreases. For this reason, proposals for improving such problems have also been reported (see, for example, Patent Documents 2 to 6). However, the actual situation is that it has not yet reached a high-level stage in which a drying shrinkage rate is reduced to 400 μm or less, and at the same time, a cured product having excellent freeze-thaw resistance is obtained.
本発明が解決しようとする課題は、乾燥収縮率を４００マイクロ以下に低減し、同時に凍結融解抵抗性にも優れた硬化体を得ることができる凍結融解抵抗性低収縮ＡＥコンクリート組成物及びこれを硬化して得られる硬化体を提供する処にある。 The problem to be solved by the present invention is to provide a freeze-thaw resistant low-shrinkage AE concrete composition capable of reducing the drying shrinkage rate to 400 micron or less and at the same time obtaining a cured product excellent in freeze-thaw resistance, and It exists in the place which provides the hardening body obtained by hardening.
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、早強ポルトランドセメント、水、細骨材、粗骨材、乾燥収縮低減剤、セメント分散剤及び空気量調節剤を含有して成るＡＥコンクリート組成物であって、乾燥収縮低減剤として特定のものを特定の割合で用い、またセメント分散剤として特定のものを用いて、且つ単位量率及び空気量を特定範囲となるようにしたＡＥ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。 As a result, the present inventors have studied to solve the above-mentioned problems, and as a result, contain the early strong Portland cement, water, fine aggregate, coarse aggregate, dry shrinkage reducing agent, cement dispersant and air amount adjusting agent. A specific composition as a drying shrinkage reducing agent is used at a specific ratio, a specific composition is used as a cement dispersant, and the unit amount ratio and the air amount are within a specific range. It was found that the AE concrete composition made was correctly suitable.
すなわち本発明は、早強ポルトランドセメント、水、細骨材、粗骨材、乾燥収縮低減剤、セメント分散剤及び空気量調節剤を含有して成るＡＥコンクリート組成物であって、乾燥収縮低減剤として下記の乾燥収縮低減剤を単位量７〜３０ｋｇ／ｍ３の割合で用い、またセメント分散剤として下記のセメント分散剤を用いて、且つ下記の数１から求められる単位量率を３０〜４３％となるようにし、また空気量を３〜７容量％となるようにしたことを特徴とする凍結融解抵抗性低収縮ＡＥコンクリート組成物に係る。また本発明は、かかる凍結融解抵抗性低収縮ＡＥコンクリート組成物を硬化して得られる硬化体に係る。 That is, the present invention is an AE concrete composition comprising an early-strength Portland cement, water, fine aggregate, coarse aggregate, a drying shrinkage reducing agent, a cement dispersant, and an air amount adjusting agent, and the drying shrinkage reducing agent. The following dry shrinkage reducing agent is used at a ratio of unit amount of 7 to 30 kg / m 3 , the following cement dispersant is used as the cement dispersant, and the unit amount ratio obtained from the following Equation 1 is 30 to 43 The freeze-thaw resistant low-shrinkage AE concrete composition is characterized in that the air content is 3 to 7% by volume. The present invention also relates to a cured product obtained by curing the freeze-thaw resistant low-shrinkage AE concrete composition.
乾燥収縮低減剤：下記の化１で示される化合物又はジエチレングリコールモノブチルエーテルと下記の化１で示される化合物との混合物
Drying shrinkage reducing agent: a compound represented by the following chemical formula 1 or a mixture of diethylene glycol monobutyl ether and a compound represented by the following chemical formula 1
化１において、
ｐ，ｑ，ｒ：０又は正の整数であって、かつｐ＋ｑ＋ｒ＝５〜２５を満足する整数
In chemical formula 1,
p, q, r: 0 or a positive integer that satisfies p + q + r = 5 to 25
セメント分散剤：分子中に下記の構成単位Ａを３５〜８５モル％、下記の構成単位Ｂを１５〜６５モル％及び下記の構成単位Ｃを０〜６モル％（合計１００モル％）有する質量平均分子量５０００〜１０００００の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７〜１５０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
Cement dispersant: Mass having 35 to 85 mol% of the following structural unit A, 15 to 65 mol% of the following structural unit B, and 0 to 6 mol% of the following structural unit C (total of 100 mol%) in the molecule. Water-soluble vinyl copolymer having an average molecular weight of 5,000 to 100,000 Structural unit A: One or more selected from structural units formed from methacrylic acid and structural units formed from methacrylic acid salt Structural unit B: in the molecule Structural unit formed from methoxypolyethylene glycol methacrylate having a polyoxyethylene group composed of 7 to 150 oxyethylene units Structural unit C: Structural unit formed from (meth) allyl sulfonate
本発明に係る凍結融解抵抗性低収縮ＡＥコンクリート組成物（以下、本発明のＡＥコンクリート組成物という）は、早強ポルトランドセメント、水、細骨材、粗骨材、乾燥収縮低減剤、セメント分散剤及び空気量調節剤を含有して成るものである。 The freeze-thaw resistant low-shrinkage AE concrete composition according to the present invention (hereinafter referred to as the AE concrete composition of the present invention) is an early-strength Portland cement, water, fine aggregate, coarse aggregate, dry shrinkage reducing agent, cement dispersion And an air amount adjusting agent.
本発明のＡＥコンクリート組成物で使用するセメントは、早強ポルトランドセメントである。それ以外の普通ポルトランドセメント、中庸熱ポルトランドセメント及び低熱ポルトランドセメント等の他のポルトランドセメントを使用すると、前記したように乾燥収縮低減剤を多量に含有するＡＥコンクリート組成物において、目的とする優れた凍結融解抵抗性が得られない。 The cement used in the AE concrete composition of the present invention is an early strength Portland cement. When other Portland cements such as ordinary Portland cement, medium-heated Portland cement, and low heat Portland cement are used, in the AE concrete composition containing a large amount of the drying shrinkage reducing agent as described above, excellent excellent freezing can be achieved. Melting resistance is not obtained.
本発明のＡＥ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、海砂、山砂、砕砂等を使用できる。本発明のＡＥコンクリート組成物では、これらの細骨材の一部として高炉スラグ細骨材を用いるのが好ましい。かかる高炉スラグ細骨材は、ＪＩＳ−Ａ５０１１−１に記載されたものであって、高炉スラグ細骨材の粒度による区分に含まれるものが好ましい。なかでも、高炉スラグ細骨材としては、粒度による区分が５ｍｍ高炉スラグ細骨材及び／又は２．５ｍｍ高炉スラグ細骨材が好ましく、更に粗粒率を２．０〜３．１の範囲に調製したものがより好ましい。本発明のＡＥコンクリート組成物では、細骨材の一部としてかかる高炉スラグ細骨材を単位量が５０〜２４９ｋｇ／ｍ３の範囲で用いるのが得られる硬化体の乾燥収縮率を更に低減する上で好ましい。 In the AE concrete composition of the present invention, known river sand, sea sand, mountain sand, crushed sand and the like can be used as the fine aggregate. In the AE concrete composition of the present invention, it is preferable to use blast furnace slag fine aggregate as a part of these fine aggregates. Such blast furnace slag fine aggregate is described in JIS-A5011-1 and is preferably included in the classification according to the particle size of the blast furnace slag fine aggregate. Among them, as the blast furnace slag fine aggregate, the classification by particle size is preferably 5 mm blast furnace slag fine aggregate and / or 2.5 mm blast furnace slag fine aggregate, and the coarse particle ratio is in the range of 2.0 to 3.1. What was prepared is more preferable. In the AE concrete composition of the present invention, the drying shrinkage rate of a cured body obtained by using the blast furnace slag fine aggregate as a part of the fine aggregate in a unit amount of 50 to 249 kg / m 3 is further reduced. Preferred above.
本発明のＡＥコンクリート組成物において、粗骨材としては、公知の川砂利、砕石、石灰砕石、軽量骨材等を使用できる。なかでも石灰砕石が好ましい。また水としては水道水を使用できる。 In the AE concrete composition of the present invention, as the coarse aggregate, known river gravel, crushed stone, lime crushed stone, lightweight aggregate and the like can be used. Among these, crushed limestone is preferable. Moreover, tap water can be used as water.
本発明のＡＥコンクリート組成物において、乾燥収縮低減剤としては、化１で示される化合物又はジエチレングリコールモノブチルエーテルと化１で示される化合物との混合物を使用する。混合物を使用する場合、それらの混合比率は特に制限されない。なかでも、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と化１で示される化合物との混合物を使用するのが好ましい。 In the AE concrete composition of the present invention, as the drying shrinkage reducing agent, a compound represented by Chemical Formula 1 or a mixture of diethylene glycol monobutyl ether and a compound represented by Chemical Formula 1 is used. When a mixture is used, the mixing ratio thereof is not particularly limited. Among these, as the drying shrinkage reducing agent, it is preferable to use a mixture of diethylene glycol monobutyl ether and a compound represented by Chemical Formula 1.
化１で示される化合物は、グリセリンのプロピレンオキサイド付加物であり、また化１で示される化合物において、ｐ、ｑ及びｒはいずれも０又は正の整数であって、かつｐ＋ｑ＋ｒ＝５〜２５を満足する整数である。なかでも、ｐ、ｑ及びｒがいずれも１〜１０の整数であって、且つｐ＋ｑ＋ｒ＝７〜２０を満足するものが好ましい。ｐ＋ｑ＋ｒが小さすぎる場合、また逆にｐ＋ｑ＋ｒが大きすぎる場合には、目標とする乾燥収縮低減効果が得られない。また本発明では、かかる乾燥収縮低減剤を、単位量７〜３０ｋｇ／ｍ３の割合で用いるが、好ましくは単位量９〜２７ｋｇ／ｍ３の割合で用いる。化１で示される化合物はいずれも公知の方法で合成できる。 The compound represented by Chemical formula 1 is a propylene oxide adduct of glycerin. In the compound represented by Chemical formula 1, p, q and r are all 0 or a positive integer, and p + q + r = 5 to 25. A satisfying integer. Especially, p, q, and r are all the integers of 1-10, and what satisfies p + q + r = 7-20 is preferable. When p + q + r is too small, and conversely, when p + q + r is too large, the target drying shrinkage reduction effect cannot be obtained. In the present invention, the drying shrinkage reducing agent is used in a unit amount of 7 to 30 kg / m 3 , and preferably used in a unit amount of 9 to 27 kg / m 3 . Any of the compounds represented by Chemical Formula 1 can be synthesized by a known method.
また本発明のＡＥコンクリート組成物において、セメント分散剤としては分子中に下記の構成単位Ａを３５〜８５モル％、下記の構成単位Ｂを１５〜６５モル％及び下記の構成単位Ｃを０〜６モル％（合計１００モル％）有する質量平均分子量５０００〜１０００００の水溶性ビニル共重合体を使用する。かかるセメント分散剤の使用量は通常、早強ポルトランドセメント１００質量部当たり、０．０５〜２質量部の割合とする。 Moreover, in the AE concrete composition of the present invention, the cement dispersing agent includes 35 to 85 mol% of the following structural unit A, 15 to 65 mol% of the following structural unit B and 0 to 0 of the following structural unit C in the molecule. A water-soluble vinyl copolymer having a mass average molecular weight of 5000 to 100,000 having 6 mol% (total of 100 mol%) is used. The amount of the cement dispersant used is usually 0.05 to 2 parts by mass per 100 parts by mass of early strong Portland cement.
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７〜１５０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
Structural unit A: One or more selected from a structural unit formed from methacrylic acid and a structural unit formed from methacrylate salt. Structural unit B: composed of 7 to 150 oxyethylene units in the molecule. Structural unit formed from methoxypolyethylene glycol methacrylate having a polyoxyethylene group Structural unit C: Structural unit formed from (meth) allyl sulfonate
更に本発明のＡＥコンクリート組成物において、空気量調節剤としては公知のものを使用できる。これには例えば、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、アルキルリン酸モノエステル塩、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が挙げられるが、なかでも得られる硬化体の凍結融解抵抗性に優れる点で、アルキルリン酸モノエステル塩が好ましい。かかる空気量調節剤の使用量は通常、早強ポルトランドセメント１００質量部当たり、０．００１〜０．０１質量部の割合とする。 Furthermore, in the AE concrete composition of the present invention, known air amount adjusting agents can be used. For example, polyoxyalkylene alkyl ether sulfate, alkyl benzene sulfonate, polyoxyethylene alkyl benzene sulfonate, rosin soap, higher fatty acid soap, alkyl phosphate monoester salt, polyoxyalkylene alkyl ether phosphate salt, etc. Among them, an alkyl phosphate monoester salt is preferable in that the cured product obtained has excellent freeze-thaw resistance. The amount of the air amount regulator used is usually 0.001 to 0.01 parts by mass per 100 parts by mass of early strong Portland cement.
本発明のＡＥコンクリート組成物において、得られる硬化体の凍結融解抵抗性を確保するうえで空気量の調節が不可欠である。空気量は３〜７容量％とするが、好ましくは４〜６容量％とする。空気量が少ない場合は得られる硬化体の凍結融解抵抗性が弱くなり、逆に空気量が多い場合は得られる硬化体の強度が低下する。 In the AE concrete composition of the present invention, it is indispensable to adjust the air amount in order to secure the freeze-thaw resistance of the obtained cured product. The amount of air is 3 to 7% by volume, preferably 4 to 6% by volume. When the amount of air is small, the freeze-thaw resistance of the resulting cured body is weakened. Conversely, when the amount of air is large, the strength of the obtained cured body is reduced.
更にまた本発明のＡＥコンクリート組成物において、前記した数１から求められる単位量率を３０〜４３％となるようにし、好ましくは３４〜４１％となるようにすることが重要である。単位量率が４３％を超えると、得られる硬化体の凍結融解抵抗性が低くなり、逆に単位量率が３０％未満になると、得られる硬化体の自己収縮が大きくなって、いずれにしても単位量率が前記数値の範囲から外れると、本発明の所期の効果が充分に得られない。 Furthermore, in the AE concrete composition of the present invention, it is important that the unit amount ratio obtained from the above-mentioned formula 1 is 30 to 43%, preferably 34 to 41%. When the unit amount ratio exceeds 43%, the freeze-thaw resistance of the resulting cured body is lowered. Conversely, when the unit amount ratio is less than 30%, self-shrinkage of the obtained cured body is increased. However, if the unit amount ratio is out of the above numerical range, the desired effect of the present invention cannot be obtained sufficiently.
本発明のＡＥコンクリート組成物は、以上説明したように、少なくとも早強ポルトランドセメント、水、細骨材、粗骨材、乾燥収縮低減剤、セメント分散剤及び空気量調節剤を用い、これらを練り混ぜて調製されるが、練り混ぜ手順は特に制限されない。 As described above, the AE concrete composition of the present invention uses at least early-strength Portland cement, water, fine aggregate, coarse aggregate, dry shrinkage reducing agent, cement dispersant and air amount adjusting agent, and kneads them. Although it is prepared by mixing, the mixing procedure is not particularly limited.
また本発明のＡＥコンクリート組成物は、本発明の効果を損なわない範囲内で、必要に応じて適宜、消泡剤、防錆剤、急結剤、凝結促進剤、凝結遅延剤、防水剤等の添加剤を併用することができる。 In addition, the AE concrete composition of the present invention is within the range that does not impair the effects of the present invention, and if necessary, an antifoaming agent, a rust inhibitor, a quick setting agent, a setting accelerator, a setting retarder, a waterproofing agent, and the like. These additives can be used in combination.
本発明のＡＥコンクリート組成物によると、乾燥収縮率を１５０〜４００マイクロ程度に大きく低減し、同時に凍結融解抵抗性に優れた硬化体を得ることができる。メカニズムが複雑であるため、その理由を説明することは難しいが、主に以下の１）と２）が協力して作用するためと推察される。すなわち、１）乾燥収縮低減剤の添加量を制限せずに所定量を混入できることによって、得られる硬化体の乾燥収縮率を大幅に低減する。同時に、２）早強ポルトランドセメント、水及び乾燥収縮低減剤を、単位量率が所定の範囲となるように配合することによって得られる硬化体の組織を緻密化し、水和反応の速い早強ポルトランドセメントの硬化体中に残存する未反応の自由水の絶対量を少なくして、低温凍結した際に自由水が氷に変化する体積膨張圧の破壊力を抑え、凍結融解抵抗性を高める。 According to the AE concrete composition of the present invention, it is possible to greatly reduce the drying shrinkage rate to about 150 to 400 micrometers, and at the same time, it is possible to obtain a cured body having excellent freeze-thaw resistance. Because the mechanism is complex, it is difficult to explain the reason, but it is presumed that the following 1) and 2) act mainly in cooperation. That is, 1) A predetermined amount can be mixed without limiting the addition amount of the drying shrinkage reducing agent, thereby greatly reducing the drying shrinkage rate of the obtained cured product. At the same time, 2) early strength Portland cement with a fast hydration reaction by densifying the structure of the hardened body obtained by blending early strength Portland cement, water and a drying shrinkage reducing agent so that the unit amount ratio falls within a predetermined range. The absolute amount of unreacted free water remaining in the hardened body of the solder is reduced, the destructive force of the volume expansion pressure at which the free water changes to ice when frozen at low temperature is suppressed, and the freeze-thaw resistance is increased.
本発明に係る硬化体は、以上説明した本発明のＡＥコンクリート組成物を硬化して得られるものである。かかる硬化体のなかでも、乾燥収縮率が１５０〜４００マイクロ（１５０×１０−６〜４００×１０−６）となるものが好ましい。 The cured body according to the present invention is obtained by curing the AE concrete composition of the present invention described above. Among these hardened bodies, those having a drying shrinkage of 150 to 400 micro (150 × 10 −6 to 400 × 10 −6 ) are preferable.
本発明のＡＥコンクリート組成物は、建設現場で打設されるＡＥ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ＡＥコンクリート組成物としても適用できる。 The AE concrete composition of the present invention can be applied not only as an AE concrete composition placed at a construction site, but also as an AE concrete composition for a secondary product processed in a concrete product factory.
本発明によると、得られる硬化体が優れた圧縮強度を発現するだけでなく、同時に乾燥収縮率が大幅に小さく、しかも凍結融解に対する抵抗性が強いという効果がある。 According to the present invention, the obtained cured product not only exhibits excellent compressive strength, but also has an effect that the drying shrinkage rate is significantly small and resistance to freezing and thawing is strong.
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（乾燥収縮低減剤としての化１で示される化合物の合成）
・乾燥収縮低減剤（ｇ−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除くため、吸着材を用いて吸着処理した後、濾別精製した。精製物は、その水酸基価等の分析結果により、化１で示される化合物であるグリセリンのプロピレンオキサイド１０モル付加物であった。これを乾燥収縮低減剤（ｇ−１）とした。
Test Category 1 (Synthesis of compounds represented by Chemical Formula 1 as a drying shrinkage reducing agent)
-Synthesis | combination of drying shrinkage reducing agent (g-1) 184g (2.0 mol) of glycerol was prepared to the autoclave, and after adding 1.8g of potassium hydroxide as a catalyst, the inside of an autoclave was nitrogen-substituted. 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. In order to remove the residual catalyst of this product, it was subjected to adsorption treatment using an adsorbent and then purified by filtration. The purified product was a propylene oxide 10 mol adduct of glycerin, which is a compound represented by Chemical Formula 1, according to the analysis result of the hydroxyl value and the like. This was designated as a drying shrinkage reducing agent (g-1).
・乾燥収縮低減剤（ｇ−２）及び（ｇ−３）の合成
乾燥収縮低減剤（ｇ−１）の場合と同様にして、グリセリンのプロピレンオキサイド付加物を合成し、これらを乾燥収縮低減剤（ｇ−２）及び（ｇ−３）とした。
-Synthesis of drying shrinkage reducing agents (g-2) and (g-3) In the same manner as in the case of the drying shrinkage reducing agent (g-1), a propylene oxide adduct of glycerin was synthesized, and these were dried shrinkage reducing agents. It was set as (g-2) and (g-3).
・乾燥収縮低減剤（ｇｒ−２）及び（ｇｒ−３）の合成
乾燥収縮低減剤（ｇ−１）の場合と同様にして、グリセリンのプロピレンオキサイド付加物を合成し、これらを乾燥収縮低減剤（ｇｒ−２）及び（ｇｒ−３）とした。以上で合成した乾燥収縮低減剤の内容等を表１に示した。尚、乾燥収縮低減剤（ｇｒ−１）はグリセリンである。
Synthesis of drying shrinkage reducing agents (gr-2) and (gr-3) In the same manner as in the case of the drying shrinkage reducing agent (g-1), a propylene oxide adduct of glycerin was synthesized, and these were dried shrinkage reducing agents. It was set as (gr-2) and (gr-3). Table 1 shows the contents of the drying shrinkage reducing agent synthesized above. The drying shrinkage reducing agent (gr-1) is glycerin.
試験区分２（セメント分散剤としての水溶性ビニル共重合体の合成）
・セメント分散剤（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及び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３ｇ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の４０％水溶液を得た。この水溶性ビニル共重合体を分析したところ、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３５５００（ＧＰＣ法、プルラン換算）の水溶性ビニル共重合体であった。これをセメント分散剤（ａ−１）とした。
Test Category 2 (Synthesis of water-soluble vinyl copolymer as cement dispersant)
Synthesis of cement dispersant (a-1) 60 g of methacrylic acid, methoxypoly (23 oxyethylene units, hereinafter referred to as n = 23) 300 g of ethylene glycol methacrylate, 5 g of sodium methallylsulfonate, 3 g of 3-mercaptopropionic acid and After 490 g of water was charged 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 a water-soluble vinyl copolymer. When this water-soluble vinyl copolymer was analyzed, structural units formed from sodium methacrylate / structural units formed from methoxypoly (n = 23) ethylene glycol methacrylate / structural units formed from sodium methallylsulfonate = It was a water-soluble vinyl copolymer having a mass average molecular weight of 35500 (GPC method, converted to pullulan) having a ratio of 70/27/3 (mol%). This was designated as cement dispersant (a-1).
セメント分散剤（ａ−２）、（ａ−３）及び（ａｒ−１）〜（ａｒ−３）の合成
セメント分散剤（ａ−１）の場合と同様にして、水溶性ビニル共重合体を合成し、これらをセメント分散剤（ａ−２）、（ａ−３）及び（ａｒ−１）〜（ａｒ−３）とした。以上で合成したセメント分散剤の内容を表２にまとめて示した。
Synthesis of cement dispersants (a-2), (a-3) and (ar-1) to (ar-3) In the same manner as in the case of the cement dispersant (a-1), a water-soluble vinyl copolymer was prepared. These were synthesized and used as cement dispersants (a-2), (a-3) and (ar-1) to (ar-3). Table 2 summarizes the contents of the cement dispersant synthesized above.
表２において、
＊１：ＧＰＣ法、プルラン換算
Ｘ−１：メタクリル酸ナトリウムから形成された構成単位
Ｘ−２：メタクリル酸から形成された構成単位
Ｙ−１：メトキシポリ（２３モル）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
Ｙ−２：メトキシポリ（６８モル）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
Ｚ−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
Ｚ−２：アリルスルホン酸ナトリウムから形成された構成単位
In Table 2,
* 1: GPC method, pullulan conversion X-1: constitutional unit formed from sodium methacrylate X-2: constitutional unit formed from methacrylic acid Y-1: constitution formed from methoxypoly (23 mol) ethylene glycol methacrylate Unit Y-2: Structural unit formed from methoxypoly (68 mol) ethylene glycol methacrylate Z-1: Structural unit formed from sodium methallyl sulfonate Z-2: Structural unit formed from sodium allyl sulfonate
試験区分３（ＡＥコンクリート組成物の調製）
実施例１
表３の実施例１に記載した配合条件で、５０Ｌのパン型強制練りミキサーに早強ポルトランドセメント（太平洋セメント社製の早強ポルトランドセメント、密度＝３．１４ｇ／ｃｍ３、ブレーン値４５２０）、山砂（君津産山砂、密度＝２．６０ｇ／ｃｍ３）、セメント分散剤（表２のセメント分散剤（ａ−１））、空気量調節剤（オクチルリン酸モノエステルカリウム塩）及び乾燥収縮低減剤（ジエチレングリコールモノブチルエーテル（ｂ−１）／グリセリンのプロピレンオキサイド付加物（ｇ−１）＝７５／２５（質量比）の混合物）のそれぞれ所定量を練り混ぜ水（水道水）と共に投入して４５秒間練り混ぜた。次に、粗骨材（秩父産石灰砕石、密度＝２．７０ｇ／ｃｍ３）の所定量を投入して６０秒間練り混ぜ、目標スランプが１８±１cm、目標空気量が４．５±０．５％の範囲とした実施例１のＡＥコンクリート組成物を調製した。調製したＡＥコンクリート組成物の内容を表３に示した。
Test Category 3 (Preparation of AE concrete composition)
Example 1
Under the compounding conditions described in Example 1 of Table 3, a 50 L pan-type forced kneading mixer was subjected to early strong Portland cement (early strong Portland cement manufactured by Taiheiyo Cement, density = 3.14 g / cm 3 , brain value 4520), Mountain sand (Kimitsu mountain sand, density = 2.60 g / cm 3 ), cement dispersant (cement dispersant (a-1) in Table 2), air amount regulator (octyl phosphate monoester potassium salt) and drying shrinkage Each predetermined amount of a reducing agent (diethylene glycol monobutyl ether (b-1) / propylene oxide adduct of glycerin (g-1) = 75/25 (mass ratio)) is mixed with water (tap water). Kneaded for 45 seconds. Next, a predetermined amount of coarse aggregate (Chichibu lime crushed stone, density = 2.70 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 ± 0. An AE concrete composition of Example 1 having a range of 5% was prepared. The contents of the prepared AE concrete composition are shown in Table 3.
実施例２〜１１及び比較例１〜１７
実施例１の場合と同様にして、それぞれ表３に記載した配合条件でＡＥコンクリート組成物を調製した。調製したＡＥコンクリート組成物の内容を表３に示した。
Examples 2-11 and Comparative Examples 1-17
In the same manner as in Example 1, AE concrete compositions were prepared under the blending conditions described in Table 3, respectively. The contents of the prepared AE concrete composition are shown in Table 3.
表３において、
単位量：調製したＡＥコンクリート組成物１ｍ３当たりのｋｇ
細骨材：君津産山砂、密度＝２．６０ｇ／ｃｍ３
粗骨材：秩父産石灰砕石、密度＝２．７０ｇ／ｃｍ３
添加量：セメント１００質量部当たりの質量部（固形分としての質量部）
ｃ−１：早強ポルトランドセメント、密度＝３．１４ｇ／cｍ３
ｃ−２：普通ポルトランドセメント、密度＝３．１６ｇ／cｍ３
ｂ−１：ジエチレングリコールモノブチルエーテル
ｇ−１〜ｇ−３，ｇｒ−１〜ｇｒ−３：表１に記載した乾燥収縮低減剤
ａ−１〜ａ−３，ａｒ−１〜ａｒ−３：表２に記載したセメント分散剤
ｍ−１：ジエチレングリコールモノブチルエーテル（ｂ−１）／グリセリンのプロピレンオキサイド付加物（ｇ−１）＝７５／２５（質量比）の混合物
ｍ−２：ジエチレングリコールモノブチルエーテル（ｂ−１）／グリセリンのプロピレンオキサイド付加物（ｇ−１）＝５０／５０（質量比）の混合物
ｄ−１：オクチルリン酸モノエステルカリウム塩
ｄ−２：ロジン石鹸
In Table 3,
Unit weight: kg of AE concrete composition 1 m 3 per prepared
Fine aggregate: Kimitsu mountain sand, density = 2.60 g / cm 3
Coarse aggregate: lime crushed stone from Chichibu, density = 2.70 g / cm 3
Addition amount: parts by mass per 100 parts by mass of cement (parts by mass as solid content)
c-1: Early strong Portland cement, density = 3.14 g / cm 3
c-2: Ordinary Portland cement, density = 3.16 g / cm 3
b-1: Diethylene glycol monobutyl ether g-1 to g-3, gr-1 to gr-3: dry shrinkage reducing agents described in Table 1 a-1 to a-3, ar-1 to ar-3: Table 2 M-1: Mixture of diethylene glycol monobutyl ether (b-1) / propylene oxide adduct of glycerin (g-1) = 75/25 (mass ratio) m-2: diethylene glycol monobutyl ether (b- 1) / Propylene oxide adduct of glycerin (g-1) = 50/50 (mass ratio) mixture d-1: Octyl phosphate monoester potassium salt d-2: Rosin soap
試験区分４（ＡＥコンクリート組成物の評価）
試験区分１で調製した各例のＡＥコンクリート組成物について、空気量及びスランプを下記のように求め、結果を表４にまとめて示した。また各例のＡＥコンクリート組成物を硬化させた硬化体について、乾燥収縮率、凍結融解抵抗性の指標としての凍結融解耐久性指数（３００サイクル）及び圧縮強度を下記のように求め、結果を表４にまとめて示した。
Test Category 4 (Evaluation of AE concrete composition)
About the AE concrete composition of each example prepared in Test Category 1, the air amount and slump were determined as follows, and the results are summarized in Table 4. Moreover, about the hardening body which hardened the AE concrete composition of each example, the freeze shrinkage durability index (300 cycles) and compressive strength as an index of dry shrinkage rate, freeze-thaw resistance were calculated | required as follows, and a result was represented. The results are summarized in FIG.
・空気量（容量％）：練り混ぜ直後のＡＥ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。
Air content (volume%): AE concrete composition immediately after kneading was measured according to JIS-A1128.
-Slump (cm): Measured according to JIS-A1101 simultaneously with the measurement of the air amount.
・乾燥収縮率：ＪＩＳ−Ａ１１２９に準拠し、各例のＡＥ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。 -Drying shrinkage ratio: Based on JIS-A1129, the dry shrinkage strain was measured by a comparator method for a 26-week-old specimen in which the AE concrete composition 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.
・凍結融解耐久性指数（３００サイクル）：各例のＡＥコンクリート組成物の硬化体について、ＪＩＳＡ１１４８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値を示した。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ＡＥコンクリート組成物の硬化体について、ＪＩＳ−Ａ１１０８に準拠し、材齢７日と材齢２８日で測定した。
-Freezing and thawing durability index (300 cycles): About the hardened | cured material of the AE concrete composition of each example, the value calculated by the durability index of ASTM-C666-75 was shown using the value measured based on JISA1148. . 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 hardened | cured material of the AE concrete composition of each example, based on JIS-A1108, it measured by material age 7 days and material age 28 days.
表４において、
＊１：所望の流動性が得られなかったので測定しなかった。
○，×：乾燥収縮率の場合は４００×１０−６以下、また凍結融解耐久性指数の場合は８０％以上をクリアしたときを○、これらをクリアできなかったときを×とした。
In Table 4,
* 1: Since the desired fluidity was not obtained, it was not measured.
○, ×: 400 × 10 −6 or less in the case of drying shrinkage, and 80% or more in the case of the freeze-thaw durability index, and × when these could not be cleared.
表４の結果からも明らかなように、各実施例のＡＥコンクリート組成物は、流動性が確保されると同時に、得られる硬化体の乾燥収縮率が４００×１０−６よりも小さく、同時に凍結融解耐久性指数が高く、また必要とされる圧縮強度が得られている。一方、比較例のＡＥコンクリート組成物では、乾燥収縮低減剤の単位量が所定の割合から外れた場合、また単位量率が所定の範囲から外れた場合、更に早強ポルトランドセメント以外の普通ポルトランドセメントを使用した場合等、本発明の構成要件を満たさない場合には、本発明が目的とする凍結融解抵抗性に優れた低収縮ＡＥコンクリート組成物は得られていない。 As is clear from the results in Table 4, the AE concrete composition of each example has fluidity, and at the same time, the resulting cured product has a drying shrinkage of less than 400 × 10 −6 and is frozen at the same time. The melt durability index is high, and the required compressive strength is obtained. On the other hand, in the AE concrete composition of the comparative example, when the unit amount of the drying shrinkage reducing agent deviates from the predetermined ratio, or when the unit amount ratio deviates from the predetermined range, the ordinary Portland cement other than the early strong Portland cement is used. In the case where the constituent requirements of the present invention are not satisfied, such as the case of using a low-shrinkage AE concrete composition excellent in freeze-thaw resistance, which is the object of the present invention, has not been obtained.
Claims (7)
ｐ，ｑ，ｒ：０又は正の整数であって、且つｐ＋ｑ＋ｒ＝５〜２５を満足する整数）
セメント分散剤：分子中に下記の構成単位Ａを３５〜８５モル％、下記の構成単位Ｂを１５〜６５モル％及び下記の構成単位Ｃを０〜６モル％（合計１００モル％）有する質量平均分子量５０００〜１０００００の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７〜１５０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 AE concrete composition containing early strength Portland cement, water, fine aggregate, coarse aggregate, dry shrinkage reducing agent, cement dispersant and air amount adjusting agent, and the following dry shrinkage as a dry shrinkage reducing agent using reducing agent in a proportion of unit quantity 7~30kg / m 3, and using the cement dispersant of the following as a cement dispersing agent, so that the unit dose rates obtained from 且 one number below 1 becomes 30 to 43% And a freeze-thaw resistant low-shrinkage AE concrete composition characterized in that the amount of air is 3-7% by volume .
p, q, r: 0 or a positive integer and an integer satisfying p + q + r = 5 to 25)
Cement dispersant: Mass having 35 to 85 mol% of the following structural unit A, 15 to 65 mol% of the following structural unit B, and 0 to 6 mol% of the following structural unit C (total of 100 mol%) in the molecule. Water-soluble vinyl copolymer having an average molecular weight of 5,000 to 100,000
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 7 to 150 oxyethylene units in the molecule
Structural unit C: a structural unit formed from (meth) allylsulfonate
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