JP6707228B2 - Concrete composition and hardened concrete - Google Patents
Concrete composition and hardened concrete Download PDFInfo
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- JP6707228B2 JP6707228B2 JP2016122766A JP2016122766A JP6707228B2 JP 6707228 B2 JP6707228 B2 JP 6707228B2 JP 2016122766 A JP2016122766 A JP 2016122766A JP 2016122766 A JP2016122766 A JP 2016122766A JP 6707228 B2 JP6707228 B2 JP 6707228B2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000002463 lignoceryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000002819 montanyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- 125000001196 nonadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001402 nonanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000016 octadecenoyl group Chemical group O=C([*])C([H])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002801 octanoyl group Chemical group C(CCCCCCC)(=O)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001312 palmitoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002460 pentacosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 125000001325 propanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229940001607 sodium bisulfite Drugs 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000003696 stearoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 125000002469 tricosyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
- C04B18/08—Flue dust, i.e. fly ash
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/04—Waste materials; Refuse
- C04B18/14—Waste materials; Refuse from metallurgical processes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/02—Acids; Metal salts or ammonium salts thereof, e.g. maleic acid or itaconic acid
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Civil Engineering (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明はコンクリート組成物及びコンクリート硬化体に関し、更に詳しくは流動性の高いコンクリート組成物であってその材料分離抵抗性を改善したコンクリート組成物及びかかるコンクリート組成物から得られる表面美観を改善したコンクリート硬化体に関する。 The present invention relates to a concrete composition and a hardened concrete, more specifically, a concrete composition having a high fluidity and having improved material separation resistance, and a concrete having an improved surface aesthetics obtained from the concrete composition. Regarding cured products.
近年、作業性向上や省力化を図るため、中流動コンクリート組成物（スランプフロー値が３５〜５０ｃｍ）や高流動コンクリート組成物（スランプフロー値が５０ｃｍ超）のような流動性の高いコンクリート組成物の使用事例が増加している。一例としてトンネルの覆工工事が挙げられ、作業性の悪い狭小空間での打設において、流動性の高いコンクリート組成物を用いることにより、その高い充填性から作業性の向上や締固めの省力化が図られている。 In recent years, in order to improve workability and save labor, highly fluid concrete compositions such as medium fluidity concrete composition (slump flow value is 35 to 50 cm) and high fluidity concrete composition (slump flow value is more than 50 cm). The use cases of are increasing. One example is lining work for tunnels.When pouring in a narrow space where workability is poor, a highly fluid concrete composition is used to improve workability and save labor in compaction due to its high filling property. Is being pursued.
しかし、このような流動性の高いコンクリート組成物は、骨材等の材料の分離が生じやすくなる。材料の分離はそのようなコンクリート組成物のポンプ圧送性の低下や品質低下の原因となり、更には材料中に含まれる黒色微粉の浮揚により、得られるコンクリート硬化体の表面美観を損なう原因となる。 However, such a highly fluid concrete composition is likely to cause separation of materials such as aggregate. Separation of materials causes deterioration in pumpability and quality of such concrete composition, and further causes levitating black fine powder contained in the material to impair the surface aesthetics of the hardened concrete obtained.
従来、前記のような材料分離を改善するため、コンクリート組成物に石灰石微粉末のような微粉末を加えたり（例えば、特許文献１参照）、粉末状のセルロースや多糖類のような増粘剤を加えたりすることが提案されている（例えば、特許文献２及び３参照）。 Conventionally, in order to improve the above-mentioned material separation, fine powder such as limestone fine powder is added to a concrete composition (for example, refer to Patent Document 1), and thickeners such as powdery cellulose and polysaccharides. Has been proposed (see, for example, Patent Documents 2 and 3).
しかし、特許文献１のような従来手段には、貯蔵サイロ等が別に必要となり、またそれらには黒色微粉が多量に存在することが多いという問題がある。また特許文献２や３のような従来手段には、計量等が別に必要になるという問題がある。増粘剤を減水剤等と一液化して加えることも提案されているが（例えば、特許文献４参照）、特許文献４のような減水剤との組み合わせでは黒色微粉の浮揚による黒ずみの発生を抑制することができないという問題がある。 However, the conventional means as in Patent Document 1 has a problem that a storage silo or the like is additionally required and that black fine powder is often present in a large amount in them. Further, the conventional means as disclosed in Patent Documents 2 and 3 has a problem in that weighing or the like is required separately. It has also been proposed to add a thickener with a water-reducing agent and the like in a liquefied manner (see, for example, Patent Document 4), but in combination with a water-reducing agent as in Patent Document 4, generation of darkening due to floating of fine black powder There is a problem that it cannot be suppressed.
近年、産業副産物の有効利用を図りつつ、単位水量の低減、マスコンクリートにおける水和熱の抑制や水密性の向上、硫酸塩や海水に対する化学抵抗性の向上等、コンクリート組成物の性能向上を図るため、フライアッシュや高炉スラグ微粉末等の使用事例が増加してきている。しかし、とりわけ石炭を燃焼させる際の副産物であるフライアッシュには多量の未燃カーボンが残存しており、コンクリート用フライアッシュのＪＩＳ規格（ＪＩＳ Ａ６０２１）では、未燃カーボン量の目安となる強熱減量は８．０％以下で管理されている。未燃カーボンは比較的流動性の高いコンクリート組成物においてその表面に浮揚し、得られるコンクリート硬化体に黒ずみを生じ易い。 In recent years, while making effective use of industrial by-products, we aim to improve the performance of concrete compositions by reducing the amount of unit water, suppressing the heat of hydration in mass concrete and improving watertightness, and improving chemical resistance to sulfates and seawater. Therefore, the use cases of fly ash and blast furnace slag fine powder are increasing. However, a large amount of unburned carbon remains in fly ash, which is a by-product of burning coal. In particular, the JIS standard for fly ash for concrete (JIS A6021) indicates that the amount of unburned carbon is a strong heat. The weight loss is controlled to be 8.0% or less. Unburned carbon easily floats on the surface of a concrete composition having a relatively high fluidity, resulting in darkening of the obtained concrete hardened body.
従来、得られるコンクリート硬化体の黒ずみを防止するため、コンクリート組成物にアミン化合物やオレフィン−マレイン酸共重合体のような黒ずみ抑制剤を加えることが提案されている（例えば、特許文献５及び６参照）。 Conventionally, it has been proposed to add a darkening inhibitor such as an amine compound or an olefin-maleic acid copolymer to a concrete composition in order to prevent darkening of the obtained hardened concrete (for example, Patent Documents 5 and 6). reference).
しかし、特許文献５や６のように黒ずみ抑制剤のみを用いたのでは、流動性の高いコンクリート組成物の場合、得られるコンクリート硬化体に黒ずみが発生するのを充分に防止できないだけでなく、コンクリート組成物が分離するという問題がある。 However, when only the blackening inhibitor is used as in Patent Documents 5 and 6, in the case of a concrete composition having high fluidity, it is not possible to sufficiently prevent blackening from occurring in the hardened concrete obtained, There is a problem that the concrete composition separates.
本発明が解決しようとする課題は、流動性の高いコンクリート組成物において、骨材等の材料の分離や黒色微粉の分離を抑制する材料分離抵抗性の高いコンクリート組成物及びかかるコンクリート組成物を硬化させたコンクリート硬化体を提供する処にある。 The problem to be solved by the present invention is, in a concrete composition having high fluidity, a concrete composition having high material separation resistance that suppresses separation of materials such as aggregate and separation of black fine powder, and hardening of such concrete composition. There is a place to provide the hardened concrete.
本発明者らは、前記の課題を解決するべく鋭意研究した結果、流動性の高いコンクリート組成物においては、混和剤として特定のＡ成分、特定のＢ成分及び特定のＣ成分を組み合わせたものを用いたコンクリート組成物が正しく好適であることを見出した。 As a result of intensive studies to solve the above problems, the present inventors have found that a concrete composition having a high fluidity is obtained by combining a specific A component, a specific B component and a specific C component as an admixture. It has been found that the concrete composition used is correct and suitable.
すなわち本発明は、結合材、水、細骨材、粗骨材及び混和剤からなるコンクリート組成物であって、水／結合材比が３０〜７０質量％、またスランプフロー値が３５〜８０ｃｍであり、結合材中にポルトランドセメントを２０質量％以上の割合で含有し、且つ下記の混和剤を結合材１００質量部に対して０．０５〜０．５質量部の割合で含有することを特徴とするコンクリート組成物に係る。また本発明は、かかるコンクリート組成物を硬化させて得られるコンクリート硬化体に係る。 That is, the present invention is a concrete composition comprising a binder, water, a fine aggregate, a coarse aggregate and an admixture, wherein the water/binder ratio is 30 to 70% by mass, and the slump flow value is 35 to 80 cm. Yes, the binder contains Portland cement in a proportion of 20% by mass or more, and the following admixture in a proportion of 0.05 to 0.5 parts by mass relative to 100 parts by mass of the binder. Related to the concrete composition. The present invention also relates to a hardened concrete product obtained by hardening the concrete composition.
混和剤：下記のＡ成分、下記のＢ成分及び下記のＣ成分を含有して成るもの。 Admixture: A compound containing the following A component, the following B component and the following C component.
Ａ成分：分子中に下記の化１で示される単量体から形成された構成単位Ｌと、（メタ）アクリル酸、クロトン酸、（無水）マレイン酸、（無水）イタコン酸、フマル酸及びそれらの塩から選ばれる少なくとも一つから形成された構成単位Ｍとを有し、且つ全構成単位中に構成単位Ｌを５０〜９９質量％及び構成単位Ｍを１〜３０質量％の割合で有する質量平均分子量２０００〜５０００００の水溶性ビニル共重合体。 Component A: a structural unit L formed from a monomer represented by the following chemical formula 1 in the molecule, (meth)acrylic acid, crotonic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, fumaric acid, and them And a structural unit M formed from at least one selected from the salts of 50 to 99% by mass of the structural unit L and 1 to 30% by mass of the structural unit M in all structural units. Water-soluble vinyl copolymer having an average molecular weight of 2000 to 500000.
Ｂ成分：全構成単位中にカルボキシル基を有するビニル単量体から形成された構成単位を３０質量％超〜８０質量％有する数平均分子量２００００〜２００００００のビニル共重合体。 Component B: A vinyl copolymer having a number average molecular weight of 20,000 to 2,000,000 and having 30% by mass to 80% by mass of structural units formed from vinyl monomers having a carboxyl group in all structural units.
Ｃ成分：黒ずみ抑制剤。 Component C: Blackening inhibitor.
化１において、
Ｒ１：炭素数２〜５のアルケニル基又は炭素数３又は４の不飽和アシル基
Ｒ２：水素原子、炭素数１〜２２のアルキル基又は炭素数１〜２２の脂肪族アシル基
Ａ１：１〜３００個の炭素数２〜４のオキシアルキレン単位で構成された（ポリ）オキシアルキレン基）
In chemical formula 1,
R 1 : an alkenyl group having 2 to 5 carbon atoms or an unsaturated acyl group having 3 or 4 carbon atoms R 2 : a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an aliphatic acyl group having 1 to 22 carbon atoms A 1 : (Poly)oxyalkylene group composed of 1 to 300 oxyalkylene units having 2 to 4 carbon atoms)
本発明に係るコンクリート組成物は、結合材、水、細骨材、粗骨材及び混和剤からなるものであり、水／結合材比が３０〜７０質量％、スランプフロー値が３５〜８０ｃｍであるものである。 The concrete composition according to the present invention comprises a binder, water, a fine aggregate, a coarse aggregate and an admixture, and has a water/binder ratio of 30 to 70% by mass and a slump flow value of 35 to 80 cm. There is something.
水／結合材比が３０質量％より小さい場合やスランプフロー値が３５ｃｍより小さい場合は、そのようなコンクリート組成物に過剰の粘性を付与し、施工性の悪化を招くこととなるので好ましくない。逆に水／結合材比が７０質量％より大きい場合やスランプフロー値が８０ｃｍより大きい場合は、そのようなコンクリート組成物に充分な材料分離抵抗性を付与することができず、所望のコンクリート組成物を得ることができない。 If the water/binder ratio is less than 30% by mass or if the slump flow value is less than 35 cm, excessive viscosity will be imparted to such a concrete composition, resulting in deterioration of workability, which is not preferable. On the contrary, when the water/binder ratio is larger than 70% by mass or the slump flow value is larger than 80 cm, it is not possible to impart sufficient material separation resistance to such a concrete composition, resulting in a desired concrete composition. I can't get things.
所望通りのコンクリート組成物を調製し、コンクリート硬化体を得るためには、水／結合材比を３０〜７０質量％とし、またスランプフロー値を３５〜８０ｃｍとするが、好ましくは水／結合材比を４０〜６５質量％とし、またスランプフロー値を４５〜７５ｃｍとする。 In order to prepare a concrete composition as desired and obtain a hardened concrete, the water/binder ratio is 30 to 70% by mass, and the slump flow value is 35 to 80 cm, preferably water/binder. The ratio is 40 to 65% by mass, and the slump flow value is 45 to 75 cm.
本発明に係るコンクリート組成物に用いる結合材は、結合材中にポルトランドセメントを２０質量％以上の割合で含有するものである。ポルトランドセメントの含有割合が２０質量％を下回ると、初期強度の発現性が低下し、型枠の設置期間が長くなる。結合材の構成成分としては、ポルトランドセメントの他に、フライアッシュ、高炉スラグ微粉末、石灰石微粉末、石粉、シリカフューム、膨張剤等が挙げられるが、なかでも結合材としては、ポルトランドセメントを２０〜９０質量％、フライアッシュを５〜３５質量％及び高炉スラグ微粉末を５〜４５質量％の割合で含有し、且つポルトランドセメント、フライアッシュ及び高炉スラグ微粉末を合計で７０質量％以上となる割合で含有するものが好ましい。フライアッシュや高炉スラグ微粉末の使用により、得られるコンクリート硬化体の強度調整が可能になり、低強度領域のコンクリート硬化体を得る場合に経済性を高めることができる。本発明によると、より低強度のコンクリート硬化体を得るためのコンクリート組成物をも高流動化できるのである。またフライアッシュや高炉スラグ微粉末を使用すると、コンクリート組成物の流動性や材料分離抵抗性が向上し、マスコンクリートにおける水和熱の抑制効果などその性能を向上する。コンクリート硬化体においては水密性の向上、硫酸塩や海水に対する化学抵抗性の向上などの効果がある。ポルトランドセメントとしては、普通ポルトランドセメント、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、早強ポルトランドセメント、超早強ポルトランドセメント、耐硫酸塩ポルトランドセメントなどの各種ポルトランドセメントを使用することができる。 The binder used in the concrete composition according to the present invention contains Portland cement in a proportion of 20% by mass or more in the binder. When the content ratio of Portland cement is less than 20% by mass, the initial strength is deteriorated and the period for installing the form becomes longer. As the constituent components of the binder, in addition to Portland cement, fly ash, fine powder of blast furnace slag, fine powder of limestone, stone powder, silica fume, expander and the like can be mentioned. Among them, as the binder, Portland cement 20 to 90% by mass, fly ash 5 to 35% by mass, and blast furnace slag fine powder at a ratio of 5 to 45% by mass, and a ratio of Portland cement, fly ash and blast furnace slag fine powder at 70% by mass or more in total. Those contained in are preferable. By using fly ash or blast furnace slag fine powder, the strength of the hardened concrete obtained can be adjusted, and the economical efficiency can be improved when obtaining a hardened concrete in the low strength region. According to the present invention, it is possible to fluidize a concrete composition for obtaining a hardened concrete having a lower strength. When fly ash or blast furnace slag fine powder is used, the fluidity and material separation resistance of the concrete composition are improved, and its performance such as the effect of suppressing heat of hydration in mass concrete is improved. In the case of hardened concrete, it is effective in improving water tightness and chemical resistance to sulfate and seawater. As the Portland cement, various Portland cements such as ordinary Portland cement, moderate heat Portland cement, low heat Portland cement, early strength Portland cement, ultra-early early strength Portland cement and sulfate resistant Portland cement can be used.
本発明に係るコンクリート組成物において、結合材の調製方法は、特に限定されるものではない。結合材の調製方法としては、セメント工場での調製や生コンクリート工場での調製が挙げられる。 In the concrete composition according to the present invention, the method for preparing the binder is not particularly limited. Examples of the method for preparing the binder include preparation in a cement factory and preparation in a ready-mixed concrete factory.
本発明に係るコンクリート組成物に供する混和剤は、特定のＡ成分、特定のＢ成分及び特定のＣ成分を含有して成るものである。 The admixture for use in the concrete composition according to the present invention comprises a specific A component, a specific B component and a specific C component.
Ａ成分は前記の水溶性ビニル共重合体であり、主にコンクリートの流動性を高める減水剤としての性能を有する。この水溶性ビニル共重合体は、前記した通り、分子中に化１で示される単量体から形成された構成単位Ｌと、（メタ）アクリル酸、クロトン酸、（無水）マレイン酸、（無水）イタコン酸、フマル酸及びそれらの塩から選ばれる少なくとも一つから形成された構成単位Ｍとを有し、且つ全構成単位中に構成単位Ｌを５０〜９９質量％、好ましくは６０〜９８質量％、より好ましくは７０〜９７質量％及び構成単位Ｍを１〜３０質量％、好ましくは２〜３０質量％、より好ましくは３〜３０質量％の割合で有する質量平均分子量２０００〜５０００００の水溶性ビニル共重合体であり、好ましくは質量平均分子量１００００〜１０００００の水溶性ビニル共重合体である。 The component A is the above-mentioned water-soluble vinyl copolymer, and mainly has a performance as a water reducing agent that enhances the fluidity of concrete. As described above, this water-soluble vinyl copolymer comprises the structural unit L formed from the monomer represented by Chemical formula 1 in the molecule, (meth)acrylic acid, crotonic acid, (anhydrous) maleic acid, (anhydrous) ) It has a structural unit M formed from at least one selected from itaconic acid, fumaric acid and salts thereof, and the structural unit L in all structural units is 50 to 99% by mass, preferably 60 to 98% by mass. %, more preferably 70 to 97% by mass and the structural unit M in a proportion of 1 to 30% by mass, preferably 2 to 30% by mass, more preferably 3 to 30% by mass, and having a mass average molecular weight of 2,000 to 500,000 and water solubility. It is a vinyl copolymer, preferably a water-soluble vinyl copolymer having a mass average molecular weight of 10,000 to 100,000.
構成単位Ｌを形成することとなる化１で示される単量体において、化１中のＲ１としては、１）ビニル基、アリル基、メタリル基、３−ブテニル基、２−メチル−１−ブテニル基、３−メチル−１−ブテニル基、２−メチル−３−ブテニル基、３−メチル−３−ブテニル基等の炭素数２〜５のアルケニル基、２）アクリロイル基、メタクリロイル基等の炭素数３又は４の不飽和アシル基が挙げられる。なかでも化１中のＲ１としては、アリル基、メタリル基、３−メチル−１−ブテニル基、アクリロイル基、メタクリロイル基が好ましい。 In the monomer represented by Chemical formula 1 which forms the structural unit L, R 1 in Chemical formula 1 is 1) vinyl group, allyl group, methallyl group, 3-butenyl group, 2-methyl-1- Carbon 2-5 alkenyl groups such as butenyl group, 3-methyl-1-butenyl group, 2-methyl-3-butenyl group, 3-methyl-3-butenyl group, and 2) carbons such as acryloyl group and methacryloyl group. The unsaturated acyl group of the number 3 or 4 is mentioned. Among them, R 1 in Chemical formula 1 is preferably an allyl group, a methallyl group, a 3-methyl-1-butenyl group, an acryloyl group or a methacryloyl group.
化１中のＲ２としては、１）水素原子、２）メチル基、エチル基、ブチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、ノナデシル基、エイコシル基、ヘンエイコシル基、ドコシル基、トリコシル基、テトラコシル基、ペンタコシル基、ヘキサコシル基、ヘプタコシル基、オクタコシル基、２−メチル−ペンチル基、２−エチル−ヘキシル基、２−プロピル−ヘプチル基、２−ブチル−オクチル基、２−ペンチル−ノニル基、２−ヘキシル−デシル基、２−ヘプチル−ウンデシル基、２−オクチル−ドデシル基、２−ノニル−トリデシル基、２−デシル−テトラデシル基、２−ウンデシル−ペンタデシル基、２−ドデシル−ヘキサデシル基等の炭素数１〜２２のアルキル基、３）ホルミル基、アセチル基、プロパノイル基、ブタノイル基、ヘキサノイル基、ヘプタノイル基、オクタノイル基、ノナノイル基、デカノイル基、ヘキサデカノイル基、オクタデカノイル基、ヘキサデセノイル基、エイコセノイル基、オクタデセノイル基等の炭素数１〜２２の脂肪族アシル基が挙げられる。なかでも化１中のＲ２としては、水素原子、炭素数１〜４のアルキル基、炭素数１〜４の脂肪族アシル基が好ましい。 R 2 in Chemical Formula 1 is 1) hydrogen atom, 2) methyl group, ethyl group, butyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, pentadecyl group. Group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group, heneicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacosyl group, octacosyl group, 2-methyl-pentyl group, 2- Ethyl-hexyl group, 2-propyl-heptyl group, 2-butyl-octyl group, 2-pentyl-nonyl group, 2-hexyl-decyl group, 2-heptyl-undecyl group, 2-octyl-dodecyl group, 2-nonyl -Alkyl group having 1 to 22 carbon atoms such as tridecyl group, 2-decyl-tetradecyl group, 2-undecyl-pentadecyl group, 2-dodecyl-hexadecyl group, 3) formyl group, acetyl group, propanoyl group, butanoyl group, hexanoyl Examples thereof include aliphatic acyl groups having 1 to 22 carbon atoms such as a group, a heptanoyl group, an octanoyl group, a nonanoyl group, a decanoyl group, a hexadecanoyl group, an octadecanoyl group, a hexadecenoyl group, an eicosenoyl group and an octadecenoyl group. Among them, R 2 in Chemical formula 1 is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aliphatic acyl group having 1 to 4 carbon atoms.
化１中のＡ１としては、１）炭素数２〜４のオキシアルキレン基、２）合計２〜３００個の炭素数２〜４のオキシアルキレン単位で構成されたポリオキシアルキレン基が挙げられる。なかでも化１中のＡ１としては、合計１〜１６０個のオキシエチレン単位及び／又はオキシプロピレン単位で構成された（ポリ）オキシアルキレン基が好ましい。尚、ポリオキシアルキレン基はブロック結合でもランダム結合でもよい。 Examples of A 1 in Chemical Formula 1 include 1) an oxyalkylene group having 2 to 4 carbon atoms, and 2) a polyoxyalkylene group composed of a total of 2 to 300 oxyalkylene units having 2 to 4 carbon atoms. Among them, as A 1 in Chemical formula 1 , a (poly)oxyalkylene group composed of a total of 1 to 160 oxyethylene units and/or oxypropylene units is preferable. The polyoxyalkylene group may be a block bond or a random bond.
以上説明した化１で示される単量体の具体例としては、α−アリル−ω−アセチル−（ポリ）オキシエチレン、α−アリル−ω−アセチル−（ポリ）オキシエチレン（ポリ）オキシプロピレン、α−アリル−ω−ヒドロキシ−（ポリ）オキシエチレン、α−アリル−ω−ヒドロキシ−（ポリ）オキシエチレン（ポリ）オキシプロピレン、α−アリル−ω−メトキシ−（ポリ）オキシエチレン、α−アリル−ω−メトキシ−（ポリ）オキシエチレン（ポリ）オキシプロピレン、α−メタリル−ω−アセチル−（ポリ）オキシエチレン、α−メタリル−ω−アセチル−（ポリ）オキシエチレン（ポリ）オキシプロピレン、α−メタリル−ω−ヒドロキシ−（ポリ）オキシエチレン、α−メタリル−ω−ヒドロキシ−（ポリ）オキシエチレン（ポリ）オキシプロピレン、α−メタリル−ω−メトキシ−（ポリ）オキシエチレン、α−メタリル−ω−メトキシ−（ポリ）オキシエチレン（ポリ）オキシプロピレン、α−メタリル−ω−ブトキシ−（ポリ）オキシエチレン、α−メタリル−ω−ブトキシ−（ポリ）オキシエチレン（ポリ）オキシプロピレン、α−（３−メチル−３−ブテニル）−ω−ヒドロキシ−（ポリ）オキシエチレン、α−（３−メチル−３−ブテニル）−ω−ヒドロキシ−（ポリ）オキシエチレン（ポリ）オキシプロピレン、α−（３−メチル−３−ブテニル）−ω−メトキシ−（ポリ）オキシエチレン、α−（３−メチル−３−ブテニル）−ω−メトキシ−（ポリ）オキシエチレン（ポリ）オキシプロピレン、ヒドロキシエチルアクリレート、ヒドロキシプロピルアクリレート、α−アクリロイル−ω−ヒドロキシ−（ポリ）オキシエチレン、α−アクリロイル−ω−ヒドロキシ−（ポリ）オキシエチレン（ポリ）オキシプロピレン、α−アクリロイル−ω−メトキシ−（ポリ）オキシエチレン、α−アクリロイル−ω−メトキシ−（ポリ）オキシエチレン（ポリ）オキシプロピレン、α−アクリロイル−ω−ブトキシ−（ポリ）オキシエチレン、α−アクリロイル−ω−ブトキシ−（ポリ）オキシエチレン（ポリ）オキシプロピレン、α−メタクリロイル−ω−アセチル−（ポリ）オキシエチレン、α−メタクリロイル−ω−アセチル−（ポリ）オキシエチレン（ポリ）オキシプロピレン、α−メタクリロイル−ω−ヒドロキシ−（ポリ）オキシエチレン、α−メタクリロイル−ω−ヒドロキシ−（ポリ）オキシエチレン（ポリ）オキシプロピレン、α−メタクリロイル−ω−メトキシ−（ポリ）オキシエチレン、α−メタクリロイル−ω−メトキシ−（ポリ）オキシエチレン（ポリ）オキシプロピレン、α−メタクリロイル−ω−ブトキシ−（ポリ）オキシエチレン、α−メタクリロイル−ω−ブトキシ−（ポリ）オキシエチレン（ポリ）オキシプロピレン、α−ビニル−ω−ヒドロキシ−（ポリ）オキシエチレン、α−ビニル−ω−ヒドロキシ−（ポリ）オキシエチレン（ポリ）オキシプロピレン、α−ビニル−ω−メトキシ−（ポリ）オキシエチレン、α−ビニル−ω−メトキシ−（ポリ）オキシエチレン（ポリ）オキシプロピレン等が挙げられる。 Specific examples of the monomer represented by Chemical Formula 1 described above include α-allyl-ω-acetyl-(poly)oxyethylene, α-allyl-ω-acetyl-(poly)oxyethylene (poly)oxypropylene, α-allyl-ω-hydroxy-(poly)oxyethylene, α-allyl-ω-hydroxy-(poly)oxyethylene (poly)oxypropylene, α-allyl-ω-methoxy-(poly)oxyethylene, α-allyl -Ω-methoxy-(poly)oxyethylene (poly)oxypropylene, α-methallyl-ω-acetyl-(poly)oxyethylene, α-methallyl-ω-acetyl-(poly)oxyethylene (poly)oxypropylene, α -Methallyl-ω-hydroxy-(poly)oxyethylene, α-methallyl-ω-hydroxy-(poly)oxyethylene (poly)oxypropylene, α-methallyl-ω-methoxy-(poly)oxyethylene, α-methallyl- ω-methoxy-(poly)oxyethylene(poly)oxypropylene, α-methallyl-ω-butoxy-(poly)oxyethylene, α-methallyl-ω-butoxy-(poly)oxyethylene(poly)oxypropylene, α- (3-Methyl-3-butenyl)-ω-hydroxy-(poly)oxyethylene, α-(3-methyl-3-butenyl)-ω-hydroxy-(poly)oxyethylene (poly)oxypropylene, α-( 3-methyl-3-butenyl)-ω-methoxy-(poly)oxyethylene, α-(3-methyl-3-butenyl)-ω-methoxy-(poly)oxyethylene(poly)oxypropylene, hydroxyethyl acrylate, Hydroxypropyl acrylate, α-acryloyl-ω-hydroxy-(poly)oxyethylene, α-acryloyl-ω-hydroxy-(poly)oxyethylene (poly)oxypropylene, α-acryloyl-ω-methoxy-(poly)oxyethylene , Α-acryloyl-ω-methoxy-(poly)oxyethylene(poly)oxypropylene, α-acryloyl-ω-butoxy-(poly)oxyethylene, α-acryloyl-ω-butoxy-(poly)oxyethylene(poly) Oxypropylene, α-methacryloyl-ω-acetyl-(poly)oxyethylene, α-methacryloyl-ω-acetyl-(poly)oxyethylene (poly)oxypropylene, α-methacryloyl-ω-hydroxy-(poly)oxyethylene, α-methacryloyl-ω-hydroxy-(poly) Oxyethylene (poly)oxypropylene, α-methacryloyl-ω-methoxy-(poly)oxyethylene, α-methacryloyl-ω-methoxy-(poly)oxyethylene (poly)oxypropylene, α-methacryloyl-ω-butoxy-( Poly)oxyethylene, α-methacryloyl-ω-butoxy-(poly)oxyethylene (poly)oxypropylene, α-vinyl-ω-hydroxy-(poly)oxyethylene, α-vinyl-ω-hydroxy-(poly)oxy Examples thereof include ethylene (poly)oxypropylene, α-vinyl-ω-methoxy-(poly)oxyethylene, α-vinyl-ω-methoxy-(poly)oxyethylene (poly)oxypropylene and the like.
構成単位Ｍを形成することとなる単量体は、（メタ）アクリル酸、クロトン酸、（無水）マレイン酸、（無水）イタコン酸、フマル酸及びそれらの塩から選ばれるものである。 The monomer forming the structural unit M is selected from (meth)acrylic acid, crotonic acid, maleic acid (anhydrous), itaconic acid (anhydrous), fumaric acid, and salts thereof.
構成単位Ｍを形成する単量体の塩としては、特に制限するものではないが、例えばナトリウム塩やカリウム塩等のアルカリ金属塩、カルシウム塩やマグネシウム塩等のアルカリ土類金属塩、アンモニウム塩、ジエタノールアミン塩やトリエタノールアミン塩等のアミン塩等が挙げられる。 The salt of the monomer forming the structural unit M is not particularly limited, but examples thereof include alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium salt and magnesium salt, ammonium salt, Examples thereof include amine salts such as diethanolamine salt and triethanolamine salt.
本発明に係る水溶性ビニル共重合体は、公知の方法で合成することができる。これには、溶媒に水を用いたラジカル重合、溶媒に有機溶媒を用いたラジカル重合、無溶媒のラジカル重合等が挙げられる。ラジカル重合に用いるラジカル重合開始剤は、過酸化水素、過硫酸アンモニウム、過硫酸ナトリウム、過硫酸カリウム等の過酸化物、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス（２−メチルブチロニトリル）等のアゾ系化合物のように、重合反応温度下において分解し、ラジカル発生するものであればその種類は特に制限されない。また、促進剤として亜硫酸水素ナトリウム、重亜硫酸ナトリウム、アスコルビン酸等の還元剤や、エチレンジアミン、グリシン等のアミン化合物等も併用することもできる。得られる水溶性ビニル重合体の質量平均分子量を所望の範囲とするため、連鎖移動剤を使用することもできる。 The water-soluble vinyl copolymer according to the present invention can be synthesized by a known method. These include radical polymerization using water as a solvent, radical polymerization using an organic solvent as a solvent, and radical polymerization without a solvent. Radical polymerization initiators used in radical polymerization include peroxides such as hydrogen peroxide, ammonium persulfate, sodium persulfate and potassium persulfate, 2,2′-azobisisobutyronitrile, 2,2′-azobis(2 The type of azo compound such as (methylbutyronitrile) is not particularly limited as long as it decomposes at the polymerization reaction temperature and generates a radical. Further, a reducing agent such as sodium hydrogen sulfite, sodium bisulfite, and ascorbic acid, or an amine compound such as ethylenediamine and glycine can also be used in combination as an accelerator. A chain transfer agent may be used in order to adjust the mass average molecular weight of the resulting water-soluble vinyl polymer to a desired range.
かかる水溶性ビニル共重合体は、本発明の効果を損なわない範囲内で、上記のもの以外の共重合可能な単量体を共重合させたものとすることができるが、その共重合割合は２０質量％以下とするのが好ましく、１０質量％以下とするのがより好ましい。 Such a water-soluble vinyl copolymer can be obtained by copolymerizing a copolymerizable monomer other than the above-mentioned ones, within a range that does not impair the effects of the present invention. It is preferably 20% by mass or less, and more preferably 10% by mass or less.
Ｂ成分は前記のビニル共重合体であり、主にコンクリートの粘性を高める増粘剤としての性能を有する。このビニル共重合体は、前記した通り、全構成単位中にカルボキシル基を有するビニル単量体から形成された構成単位を３０質量％超〜８０質量％有する数平均分子量２００００〜２００００００のビニル共重合体であり、好ましくは数平均分子量５００００〜１００００００のビニル共重合体である。 The component B is the above-mentioned vinyl copolymer, and mainly has a performance as a thickener for increasing the viscosity of concrete. As described above, the vinyl copolymer has a number average molecular weight of 20,000 to 2,000,000 and a structural unit formed of a vinyl monomer having a carboxyl group in all the structural units in an amount of more than 30% by mass to 80% by mass. It is a united body, preferably a vinyl copolymer having a number average molecular weight of 50,000 to 1,000,000.
カルボキシル基を有するビニル単量体としては、エチレン性不飽和モノカルボン酸、エチレン性不飽和ジカルボン酸及びそれらの塩等が挙げられる。エチレン性不飽和モノカルボン酸の具体例としては、アクリル酸、メタクリル酸、クロトン酸及びそれらの塩等が挙げられ、またエチレン性不飽和ジカルボン酸としては、マレイン酸、イタコン酸、フマル酸及びそれらの塩等が挙げられる。なかでもカルボキシル基を有するビニル単量体としては、アクリル酸、メタクリル酸が好ましい。 Examples of the vinyl monomer having a carboxyl group include ethylenically unsaturated monocarboxylic acid, ethylenically unsaturated dicarboxylic acid and salts thereof. Specific examples of the ethylenically unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid and salts thereof, and as the ethylenically unsaturated dicarboxylic acid, maleic acid, itaconic acid, fumaric acid and them. And the like. Of these, acrylic acid and methacrylic acid are preferable as the vinyl monomer having a carboxyl group.
カルボキシル基を有するビニル単量体の塩としては、特に制限するものではないが、例えばナトリウム塩やカリウム塩等のアルカリ金属塩、カルシウム塩やマグネシウム塩等のアルカリ土類金属塩、アンモニウム塩、ジエタノールアミン塩やトリエタノールアミン塩等のアミン塩等が挙げられる。 The salt of a vinyl monomer having a carboxyl group is not particularly limited, but examples thereof include alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium salt and magnesium salt, ammonium salt, diethanolamine. Examples thereof include salts and amine salts such as triethanolamine salts.
Ｃ成分は、黒ずみ抑制剤である。黒ずみ抑制剤としては、炭素数が９〜１５のアルキルベンゼンスルホン酸ナトリウムやポリアオキシエチレンアルキルエーテル硫酸ナトリウムのような分子中に長鎖のアルキル基を有するアニオン界面活性剤、特開平５−１３２３４７号公報に例示されるようなアミン化合物等が挙げられるが、炭素数６〜１０のオレフィンから形成された構成単位と、（無水）マレイン酸及びその塩から選ばれるものから形成された構成単位とを有する質量平均分子量１０００〜２００００の水溶性ビニル共重合体が好ましい。 Component C is a darkening inhibitor. As the darkening inhibitor, an anionic surfactant having a long-chain alkyl group in the molecule, such as sodium alkylbenzenesulfonate having 9 to 15 carbon atoms or sodium polyaoxyethylene alkyl ether sulfate, is disclosed in JP-A-5-132347. Examples of the amine compound include a structural unit formed from an olefin having 6 to 10 carbon atoms and a structural unit formed from (anhydrous) maleic acid and a salt thereof. A water-soluble vinyl copolymer having a mass average molecular weight of 1,000 to 20,000 is preferable.
炭素数６〜１０のオレフィンの具体例としては、ヘキセン、ヘプテン、オクテン、ジイソブチレン、メチルペンテン等が挙げられる。 Specific examples of the olefin having 6 to 10 carbon atoms include hexene, heptene, octene, diisobutylene, methylpentene and the like.
（無水）マレイン酸の塩としては、特に制限するものではないが、例えばナトリウム塩やカリウム塩等のアルカリ金属塩、カルシウム塩やマグネシウム塩等のアルカリ土類金属塩、アンモニウム塩、ジエタノールアミン塩やトリエタノールアミン塩等のアミン塩等が挙げられる。 The (anhydrous) maleic acid salt is not particularly limited, but examples thereof include alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as calcium salts and magnesium salts, ammonium salts, diethanolamine salts and triethanolamine salts. Examples thereof include amine salts such as ethanolamine salts.
本発明に係るコンクリート組成物は、以上説明した混和剤を、結合材１００質量部に対し０．０５〜０．５質量％の割合で含有するものである。混和剤を構成する各成分の好ましい含有割合は、調製するコンクリート組成物に求められる条件により異なるが、Ａ成分を６０〜９６質量％、Ｂ成分を２〜２０質量％及びＣ成分を２〜２０質量％（合計１００質量％）の割合で含有するものが好ましい。 The concrete composition according to the present invention contains the admixture described above in a proportion of 0.05 to 0.5 mass% with respect to 100 mass parts of the binder. The preferred content ratio of each component constituting the admixture varies depending on the conditions required for the concrete composition to be prepared, but the component A is 60 to 96 mass %, the component B is 2 to 20 mass %, and the component C is 2 to 20 mass %. It is preferable that the content is 100% by mass (total 100% by mass).
混和剤としては、前記のＡ成分、Ｂ成分及びＣ成分に加えて、更に下記のＤ成分を０．０２〜５質量％の割合で含有するものが好ましい。Ｄ成分はアルキレンオキサイド付加物であり、主にコンクリート中の巻き込み空気を消す消泡剤としての性能を有する。 As the admixture, it is preferable that the admixture further contains the following D component in a proportion of 0.02 to 5 mass% in addition to the above A component, B component and C component. The component D is an alkylene oxide adduct, and has a performance as a defoaming agent that mainly eliminates entrapped air in concrete.
Ｄ成分：下記の化２で示されるアルキレンオキサイド付加物。 Component D: an alkylene oxide adduct represented by the following chemical formula 2.
化２において、
Ｒ３：水素原子又は炭素数１〜２０の脂肪族炭化水素基
Ａ２：１０〜１００個の炭素数２〜４のオキシアルキレン単位で構成されたポリオキシアルキレン基であり、且つ全オキシアルキレン単位中に炭素数３のオキシプロピレン単位を７０モル％以上有するポリオキシアルキレン基である。この場合、オキシアルキレン単位の結合状態は、ブロック結合でもランダム結合でもよいが、ブロック結合が好ましい。
In chemical formula 2,
R 3 : a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms A 2 : a polyoxyalkylene group composed of 10 to 100 oxyalkylene units having 2 to 4 carbon atoms, and all oxyalkylene units It is a polyoxyalkylene group having 70 mol% or more of oxypropylene units having 3 carbon atoms. In this case, the bond state of the oxyalkylene units may be a block bond or a random bond, but a block bond is preferable.
本発明に係るコンクリート組成物に供する混和剤は、その水溶液のｐＨが５〜１０となるものが好ましく、ｐＨが６〜９となるものがより好ましい。より良い状態のコンクリート組成物を調製し、コンクリート硬化体を得るためである。 The admixture used in the concrete composition according to the present invention preferably has an aqueous solution with a pH of 5 to 10, more preferably a pH of 6 to 9. This is for preparing a concrete composition in a better condition and obtaining a concrete hardened body.
本発明に係るコンクリート組成物の調製方法は特に制限されない。調製方法それ自体には公知の方法を適用することができるが、Ａ成分、Ｂ成分及びＣ成分を含有して成る混和剤、更にはＤ成分を含有して成る混和剤は、水性液の状態、例えばＡ成分、Ｃ成分及びＤ成分は水溶液の状態、またＢ成分は水性エマルションの状態で用意してこれらを混合した後、コンクリート組成物の調製に用いるのが好ましい。 The method for preparing the concrete composition according to the present invention is not particularly limited. Although a known method can be applied to the preparation method itself, the admixture containing the components A, B and C, and further the admixture containing the component D is in an aqueous liquid state. For example, it is preferable that the components A, C and D are prepared in the form of an aqueous solution, and the component B is prepared in the form of an aqueous emulsion, and these are mixed and then used for the preparation of the concrete composition.
本発明に係る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ＡＥ調整剤、消泡剤、凝結遅延剤、硬化促進剤、乾燥収縮低減剤、防腐剤、防水剤、防錆剤等を併用することができる。 The concrete composition according to the present invention is an AE modifier, a defoaming agent, a setting retarder, a curing accelerator, a drying shrinkage reducing agent, an antiseptic agent, and a waterproofing agent, if necessary, within a range not impairing the effects of the present invention. , A rust preventive and the like can be used together.
本発明に係るコンクリート硬化体は、以上説明したような本発明に係るコンクリート組成物を硬化させて得られるものである。硬化の方法は特に制限されず、公知の方法が適用できる。 The hardened concrete according to the present invention is obtained by hardening the concrete composition according to the present invention as described above. The curing method is not particularly limited, and a known method can be applied.
本発明によると、流動性の高いコンクリート組成物を調製することを前提として、骨材など材料の分離や黒色微粉の分離を抑制する材料分離抵抗性の高いコンクリート組成物を調製することができ、同時に肌面への黒い斑点や全体的な黒ずみの発生を抑制した表面美観に優れたコンクリート硬化体を得ることができるという効果がある。 According to the present invention, on the premise of preparing a concrete composition having high fluidity, it is possible to prepare a concrete composition having high material separation resistance that suppresses separation of materials such as aggregate and separation of black fine powder, At the same time, there is an effect that it is possible to obtain a concrete hardened body which is excellent in surface aesthetics and which suppresses the generation of black spots on the skin surface and the overall darkening.
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、本発明がこれらの実施例に限定されるというものではない。尚、以下の実施例等において、別に記載しない限り、％は質量％を意味する。 Examples will be given below to make the constitution and effects of the present invention more specific, but the present invention is not limited to these examples. In the following examples and the like,% means mass% unless otherwise specified.
試験区分１（結合材の調製）
表１に記載の内容で、ポルトランドセメント、フライアッシュ及び高炉スラグ微粉末を混合して、表１に記載の結合材（Ｃ−１）〜（Ｃ−５）及び（Ｃｒ−１）を調製した。尚、結合材（Ｃ−３）は普通ポルトランドセメントをそのまま使用した。
Test category 1 (preparation of binder)
The binders (C-1) to (C-5) and (Cr-1) shown in Table 1 were prepared by mixing Portland cement, fly ash and blast furnace slag fine powder with the contents shown in Table 1. .. As the binder (C-3), ordinary Portland cement was used as it was.
表１において、
ｐｃ−１：早強ポルトランドセメント
ｐｃ−２：普通ポルトランドセメント
ｆａ−１：粉末度３３００ｃｍ２／ｇ、強熱減量３．２％のフライアッシュ
ｆａ−２：粉末度３６２０ｃｍ２／ｇ、強熱減量５．４％のフライアッシュ
ｓｇ−１：比表面積が４１００ｃｍ２／ｇの高炉スラグ微粉末
ｓｇ−２：比表面積が６１５０ｃｍ２／ｇの高炉スラグ微粉末
ｌｐ−１：比表面積が４３００ｃｍ２／ｇの石灰石微粉末
ｓｆ−１：比表面積が１４８０００ｃｍ２／ｇのシリカフューム
In Table 1,
pc-1: early strong Portland cement pc-2: ordinary Portland cement fa-1: fineness 3300 cm 2 /g, ignition loss 3.2% fly ash fa-2: fineness 3620 cm 2 /g, ignition loss 5.4% of the fly ash sg-1: ground granulated blast furnace slag having a specific surface area of 4100cm 2 / g sg-2: ground granulated blast furnace slag having a specific surface area of 6150cm 2 / g lp-1: a specific surface area of 4300cm 2 / g Limestone fine powder sf-1: Silica fume with a specific surface area of 148000 cm 2 /g
試験区分２（Ａ成分の水溶性ビニル共重合体の合成）
・水溶性ビニル共重合体（ｄ−１）の合成
α−アリル−ω−メトキシ−ポリ（３３モル）エチレングリコール１５００ｇ及び無水マレイン酸１４６ｇを反応容器に仕込み、反応容器内の雰囲気を窒素置換した後、徐々に加温して撹拌しながら均一に溶解した。反応系の温度を温水浴にて８０℃に保ち、アゾビスイソブチロニトリル１０ｇを投入してラジカル重合反応を開始した。２時間経過後、更にアゾビスイソブチロニトリル５ｇを投入し、ラジカル重合反応を２時間継続して反応させた。得られた共重合体に水を加えて、水溶性ビニル共重合体（ｄ−１）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、質量平均分子量４００００（ＧＰＣ法、プルラン換算）の水溶性ビニル共重合体であった。
Test Category 2 (Synthesis of water-soluble vinyl copolymer of component A)
-Synthesis of water-soluble vinyl copolymer (d-1) 1500 g of α-allyl-ω-methoxy-poly(33 mol) ethylene glycol and 146 g of maleic anhydride were charged in a reaction vessel, and the atmosphere in the reaction vessel was replaced with nitrogen. After that, it was gradually heated and uniformly dissolved with stirring. The temperature of the reaction system was kept at 80° C. in a warm water bath, and 10 g of azobisisobutyronitrile was added to initiate a radical polymerization reaction. After 2 hours, 5 g of azobisisobutyronitrile was further added, and the radical polymerization reaction was continued for 2 hours for reaction. Water was added to the obtained copolymer to obtain a 40% aqueous solution of the water-soluble vinyl copolymer (d-1). When this water-soluble vinyl copolymer was analyzed, it was a water-soluble vinyl copolymer having a mass average molecular weight of 40,000 (GPC method, pullulan conversion).
・水溶性ビニル共重合体（ｄ−２）の合成
水１５００ｇ、３−メチル−３−ブテン−１オール・ポリ（８０モル）エチレングリコール付加物１５００ｇを反応容器に仕込み、反応容器内の雰囲気を窒素置換した後、撹拌しながら徐々に加温した。反応系の温度を温水浴にて７０℃に保ち、温度を安定させた。その後、アクリル酸３７５ｇを３時間かけて滴下した。同時に、チオグリコール酸１２ｇ、Ｌ−アスコルビン酸８ｇを水５００ｇに溶解させた水溶液及び５％過酸化水素水１７０ｇをそれぞれ３時間かけて滴下し、ラジカル重合反応を開始した。滴下終了から１時間経過後、得られた共重合体に水を加え、水溶性ビニル共重合体（ｄ−２）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、質量平均分子量７１０００（ＧＰＣ法、プルラン換算）の水溶性ビニル共重合体であった。
-Synthesis of water-soluble vinyl copolymer (d-2) 1500 g of water and 1500 g of 3-methyl-3-buten-1ol poly(80 mol) ethylene glycol adduct were charged in a reaction vessel, and the atmosphere in the reaction vessel was changed. After purging with nitrogen, the mixture was gradually heated with stirring. The temperature of the reaction system was kept at 70° C. in a warm water bath to stabilize the temperature. Then, 375 g of acrylic acid was added dropwise over 3 hours. At the same time, 12 g of thioglycolic acid and 8 g of L-ascorbic acid were dissolved in 500 g of water, and 170 g of 5% hydrogen peroxide was added dropwise over 3 hours to initiate a radical polymerization reaction. One hour after the completion of dropping, water was added to the obtained copolymer to obtain a 40% aqueous solution of the water-soluble vinyl copolymer (d-2). When this water-soluble vinyl copolymer was analyzed, it was a water-soluble vinyl copolymer having a mass average molecular weight of 71,000 (GPC method, pullulan conversion).
・水溶性ビニル共重合体（ｄ−３）の合成
水１４００ｇ、メトキシポリ（４５モル）エチレングリコールモノメタクリレート１０３４ｇ、メタクリル酸１４１ｇ、３０％水酸化ナトリウム水溶液４６ｇ及び３−メルカプトプロピオン酸２２ｇを反応容器に仕込み、反応容器内の雰囲気を窒素置換した後、撹拌しながら徐々に加温した。反応系の温度を温水浴にて６０℃に保ち、過硫酸ナトリウムの２０％水溶液５５ｇを投入してラジカル重合反応を開始した。２時間経過後、更に過硫酸ナトリウムの２０％水溶液３０ｇを投入し、ラジカル重合反応を６時間継続して反応させた。得られた共重合体に水を加え、水溶性ビニル共重合体（ｄ−３）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、質量平均分子量４３０００（ＧＰＣ法、プルラン換算）の水溶性ビニル共重合体であった。同様にして、水溶性ビニル共重合体（ｄ−４）及び（ｄ−５）を合成した。
-Synthesis of water-soluble vinyl copolymer (d-3) 1400 g of water, 1034 g of methoxypoly (45 mol) ethylene glycol monomethacrylate, 141 g of methacrylic acid, 46 g of 30% sodium hydroxide aqueous solution and 22 g of 3-mercaptopropionic acid were placed in a reaction vessel. After charging, the atmosphere in the reaction vessel was replaced with nitrogen, and then gradually heated while stirring. The temperature of the reaction system was kept at 60° C. in a warm water bath, and 55 g of a 20% aqueous solution of sodium persulfate was added to initiate a radical polymerization reaction. After 2 hours, 30 g of a 20% aqueous solution of sodium persulfate was further added, and the radical polymerization reaction was continued for 6 hours to carry out the reaction. Water was added to the obtained copolymer to obtain a 40% aqueous solution of the water-soluble vinyl copolymer (d-3). When this water-soluble vinyl copolymer was analyzed, it was found to be a water-soluble vinyl copolymer having a mass average molecular weight of 43000 (GPC method, pullulan conversion). Similarly, water-soluble vinyl copolymers (d-4) and (d-5) were synthesized.
・水溶性ビニル共重合体（ｄｒ−１）及び（ｄｒ−２）の合成
水溶性ビニル共重合体（ｄ−１）や（ｄ−３）と同様にして、水溶性ビニル共重合体（ｄｒ−１）及び（ｄｒ−２）を合成した。
-Synthesis of water-soluble vinyl copolymers (dr-1) and (dr-2) In the same manner as the water-soluble vinyl copolymers (d-1) and (d-3), the water-soluble vinyl copolymer (dr) -1) and (dr-2) were synthesized.
以上で合成した水溶性ビニル共重合体（ｄ−１）〜（ｄ−５）及び（ｄｒ−１）、（ｄｒ−２）の内容を表２にまとめて示した。
Table 2 shows the contents of the water-soluble vinyl copolymers (d-1) to (d-5) and (dr-1) and (dr-2) synthesized above.
表２において、
質量平均分子量：ＧＰＣ法、プルラン換算
Ｌ―１：α−アリル−ω−メトキシポリ（３３モル）エチレングリコールから形成された構成単位
Ｌ―２：３−メチル−３−ブテン−１−オール・ポリ（８０モル）エチレングリコール付加物から形成された構成単位
Ｌ―３：メトキシポリ（４５モル）エチレングリコールモノメタクリレートから形成された構成単位
Ｍ―１：無水マレイン酸から形成された構成単位
Ｍ―２：アクリル酸から形成された構成単位
Ｍ―３：メタクリル酸から形成された構成単位
Ｓ−１：アクリル酸メチルから形成された構成単位
In Table 2,
Mass average molecular weight: GPC method, pullulan conversion L-1: α-allyl-ω-methoxy poly (33 mol) A structural unit formed from ethylene glycol L-2: 3-methyl-3-buten-1-ol poly( 80 mol) a structural unit formed from an ethylene glycol adduct L-3: a structural unit formed from methoxypoly(45 mol) ethylene glycol monomethacrylate M-1: a structural unit formed from maleic anhydride
M-2: Structural unit formed of acrylic acid M-3: Structural unit formed of methacrylic acid S-1: Structural unit formed of methyl acrylate
試験区分３（Ｂ成分のビニル共重合体の合成）
・ビニル共重合体（ｆ−１）の合成
水２３００ｇ、アクリル酸４９０ｇ、アクリル酸エチル４７０ｇ、乳化剤としてポリオキシエチレンアルキルフェノール硫酸ナトリウム４０ｇを反応容器に仕込み、３０℃で撹拌しながら乳化した。反応容器内の雰囲気を窒素置換した後、徐々に加温して反応系の温度を５０℃に保ち、過硫酸ナトリウムの２％水溶液及び亜硫酸ナトリウムの２％水溶液をそれぞれ８０ｇ滴下して重合を開始した。重合を開始してから２時間後、過硫酸ナトリウムの２％水溶液及び亜硫酸ナトリウムの２％水溶液をそれぞれ４０ｇ滴下し、２時間反応を継続して重合反応を完結した。得られた共重合体に水を加え、ビニル共重合体（ｆ−１）の２０％水性エマルションを得た。このビニル共重合体を分析したところ、アクリル酸から形成された構成単位の割合は５１％、数平均分子量は２１００００（ＧＰＣ法、ポリスチレン換算）であった。
Test Category 3 (Synthesis of B component vinyl copolymer)
-Synthesis of vinyl copolymer (f-1) 2300 g of water, 490 g of acrylic acid, 470 g of ethyl acrylate, and 40 g of sodium polyoxyethylene alkylphenol sulfate as an emulsifier were placed in a reaction vessel and emulsified while stirring at 30°C. After the atmosphere in the reaction vessel was replaced with nitrogen, the temperature of the reaction system was gradually heated to 50° C., and 80 g each of a 2% aqueous solution of sodium persulfate and a 2% aqueous solution of sodium sulfite were added dropwise to start polymerization. did. Two hours after the polymerization was started, 40 g of a 2% aqueous solution of sodium persulfate and 40% of a 2% aqueous solution of sodium sulfite were added dropwise, and the reaction was continued for 2 hours to complete the polymerization reaction. Water was added to the obtained copolymer to obtain a 20% aqueous emulsion of vinyl copolymer (f-1). When this vinyl copolymer was analyzed, the proportion of the constituent units formed from acrylic acid was 51%, and the number average molecular weight was 210000 (GPC method, polystyrene conversion).
・ビニル共重合体（ｆ−２）、（ｆｒ−１）及び（ｆｒ−２）の合成
ビニル共重合体（ｆ−１）と同様にして、ビニル共重合体（ｆ−２）、（ｆｒ−１）及び（ｆｒ−２）を合成した。
-Synthesis of vinyl copolymers (f-2), (fr-1) and (fr-2) In the same manner as the vinyl copolymer (f-1), vinyl copolymers (f-2) and (fr -1) and (fr-2) were synthesized.
以上で合成したビニル共重合体（ｆ−１）、（ｆ−２）、（ｆｒ−１）及び（ｆｒ−２）の内容を表３にまとめて示した。
The contents of the vinyl copolymers (f-1), (f-2), (fr-1) and (fr-2) synthesized above are summarized in Table 3.
表３において、
数平均分子量：ＧＰＣ法、ポリスチレン換算
In Table 3,
Number average molecular weight: GPC method, polystyrene conversion
試験区分４（Ｃ成分の黒ずみ抑制剤としての水溶性ビニル共重合体の合成）
・水溶性ビニル共重合体（ｇ−１）の合成
トルエン４００ｇ、１−ヘキセン８４ｇ、無水マレイン酸９８ｇを反応容器に仕込み、反応容器内の雰囲気を窒素置換した後、徐々に加温して反応系の温度を７５℃に保ち、ベンゾイルパーオキサイド４ｇを加え、８時間重合した。重合反応終了後、析出した重合体を濾別収集して減圧乾燥し、白色粉末状の共重合体を得た。得られた共重合体に水及び水酸化ナトリウムを加え、８０℃で加熱撹拌して溶解し、水溶性ビニル共重合体（ｇ−１）の２０％水溶液を得た。これを分析したところ、質量平均分子量１４３００（ＧＰＣ法、ポリスチレンスルホン酸換算）であった。
Test Category 4 (Synthesis of water-soluble vinyl copolymer as C component darkening inhibitor)
-Synthesis of water-soluble vinyl copolymer (g-1) 400 g of toluene, 84 g of 1-hexene, and 98 g of maleic anhydride were charged in a reaction vessel, the atmosphere in the reaction vessel was replaced with nitrogen, and then gradually heated to react. The temperature of the system was kept at 75° C., 4 g of benzoyl peroxide was added, and polymerization was carried out for 8 hours. After the completion of the polymerization reaction, the precipitated polymer was collected by filtration and dried under reduced pressure to obtain a white powdery copolymer. Water and sodium hydroxide were added to the obtained copolymer, and the mixture was heated with stirring at 80° C. and dissolved to obtain a 20% aqueous solution of the water-soluble vinyl copolymer (g-1). When this was analyzed, the mass average molecular weight was 14300 (GPC method, polystyrene sulfonic acid conversion).
・水溶性ビニル共重合体（ｇ−２）、（ｇｒ−１）及び（ｇｒ−２）の合成
水溶性ビニル共重合体（ｇ−１）と同様にして、水溶性ビニル共重合体（ｇ−２）、（ｇｒ−１）及び（ｇｒ−２）を合成した。
-Synthesis of water-soluble vinyl copolymer (g-2), (gr-1) and (gr-2) In the same manner as the water-soluble vinyl copolymer (g-1), the water-soluble vinyl copolymer (g -2), (gr-1) and (gr-2) were synthesized.
以上で合成した水溶性ビニル共重合体（ｇ−１）、（ｇ−２）、（ｇｒ−１）及び（ｇｒ−２）の内容を表４にまとめて示した。 The contents of the water-soluble vinyl copolymers (g-1), (g-2), (gr-1) and (gr-2) synthesized above are summarized in Table 4.
表４において、
数平均分子量：ＧＰＣ法、ポリスチレンスルホン酸換算
In Table 4,
Number average molecular weight: GPC method, polystyrene sulfonic acid conversion
試験区分５（Ｄ成分のアルキレンオキサイド付加物の合成）
・アルキレンオキサイド付加物（ｅ−１）の合成
ラウリルアルコール５５９ｇをオートクレーブに仕込み、触媒として水酸化カリウム５．４ｇを加えた後、オートクレーブ内を窒素置換した。撹拌しながら、反応温度を１２５〜１４０℃に保ち、エチレンオキサイド６６０ｇ、プロピレンオキサイド４２０８ｇを圧入して付加反応を行った。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、吸着剤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、水酸基価の分析結果より、化２で示される化合物に相当する、ラウリルアルコール１モルにエチレンオキサイド５モル及びプロピレンオキサイド２５モルを付加したアルキレンオキサイド付加物（ｅ−１）であった。
Test Category 5 (synthesis of alkylene oxide adduct of component D)
-Synthesis of alkylene oxide adduct (e-1) After adding 559 g of lauryl alcohol to an autoclave and adding 5.4 g of potassium hydroxide as a catalyst, the inside of the autoclave was replaced with nitrogen. While stirring, the reaction temperature was kept at 125 to 140° C., and 660 g of ethylene oxide and 4208 g of propylene oxide were press-fitted to carry out the 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 filtered and purified. This purified product is an alkylene oxide adduct (e-1) obtained by adding 5 mol of ethylene oxide and 25 mol of propylene oxide to 1 mol of lauryl alcohol, which corresponds to the compound represented by Chemical formula 2, from the analysis result of the hydroxyl value. there were.
・アルキレンオキサイド付加物（ｅ−２）、（ｅ−３）、（ｅｒ−１）及び（ｅｒ−２）の合成
表５に示すように出発物質とアルキレンオキサイドの種類及び量を変更した以外はアルキレンオキサイド付加物（ｅ−１）と同様にして、アルキレンオキサイド付加物（ｅ−２）、（ｅ―３）、（ｅｒ−１）及び（ｅｒ−２）を合成した。
-Synthesis of alkylene oxide adducts (e-2), (e-3), (er-1) and (er-2), except that the types and amounts of the starting material and the alkylene oxide were changed as shown in Table 5. Alkylene oxide adducts (e-2), (e-3), (er-1) and (er-2) were synthesized in the same manner as the alkylene oxide adduct (e-1).
以上で合成したアルキレンオキサイド付加物（ｅ−１）〜（ｅ―３）、（ｅｒ−１）及び（ｅｒ−２）の内容を表５にまとめて示した。 The contents of the alkylene oxide adducts (e-1) to (e-3), (er-1) and (er-2) synthesized above are summarized in Table 5.
表５において、
ｅ−１：ラウリルアルコールにエチレンオキサイドとプロピレンオキサイドとをランダムに付加反応させた共重合体
ｅ−２：オレイルアルコールにエチレンオキサイドを付加した後、プロピレンオキサイドを付加反応させた共重合体
ｅ−３：ポリプロプレンオキサイドにエチレンオキサイドを付加反応させた共重合体
ｅｒ−１：ブチルアルコールにエチレンオキサイドとプロピレンオキサイドをランダムに付加反応させた共重合体
ｅｒ−２：オレイルアルコールにエチレンオキサイドを付加反応させた後、プロピレンオキサイドを付加反応させた共重合体
In Table 5,
e-1: Copolymer obtained by randomly adding ethylene oxide and propylene oxide to lauryl alcohol e-2: Copolymer obtained by adding ethylene oxide to oleyl alcohol and then addition reaction of propylene oxide e-3 : Copolymer of addition reaction of ethylene oxide to polypropylene oxide er-1: Copolymer of addition reaction of butyl alcohol with ethylene oxide and propylene oxide at random er-2: Addition reaction of oleyl alcohol with ethylene oxide And then propylene oxide addition reaction
試験区分６（混和剤の調製）
・混和剤（ｈ−１）の調製
表２に記載の水溶性ビニル共重合体（ｄ−３）の４０％水溶液８６．５ｇ、表３に記載のビニル共重合体（ｆ−１）の２０％水性エマルション１６ｇ、表４に記載の水溶性ビニル共重合体（ｇ−２）の２０％水溶液６ｇ、表５に記載のアルキレンオキサイド付加物（ｅ−２）１ｇ及び水９０．５ｇをガラス容器に投入して撹拌混合し、水溶性ビニル共重合体（ｄ−３）を８６．５質量％、ビニル共重合体の水性エマルション（ｆ−１）を８質量％、水溶性ビニル共重合体（ｇ−２）を３質量％及びアルキレンオキサイド付加物（ｅ−２）を２．５質量％の割合で含有する混和剤（ｈ−１）の２０％水溶液を調製した。
Test Category 6 (Preparation of admixture)
-Preparation of admixture (h-1) 86.5 g of a 40% aqueous solution of the water-soluble vinyl copolymer (d-3) shown in Table 2 and 20 of the vinyl copolymer (f-1) shown in Table 3 % Aqueous emulsion 16 g, 6% of 20% aqueous solution of water-soluble vinyl copolymer (g-2) shown in Table 4, 1 g of alkylene oxide adduct (e-2) shown in Table 5 and 90.5 g of water in a glass container. , And the mixture is stirred and mixed, the water-soluble vinyl copolymer (d-3) is 86.5% by mass, the vinyl copolymer aqueous emulsion (f-1) is 8% by mass, and the water-soluble vinyl copolymer ( A 20% aqueous solution of the admixture (h-1) containing 3% by mass of g-2) and 2.5% by mass of the alkylene oxide adduct (e-2) was prepared.
・混和剤（ｈ−２）〜（ｈ−１７）及び（ｈｒ−１）〜（ｈｒ−１０）の調製
混和剤（ｈ−１）の調製と同様にして、混和剤（ｈ−２）〜（ｈ−１７）及び（ｈｒ−１）〜（ｈｒ−１０）を調製した。
-Preparation of admixtures (h-2) to (h-17) and (hr-1) to (hr-10) In the same manner as in preparation of the admixture (h-1), the admixture (h-2) to (h-2). (H-17) and (hr-1) to (hr-10) were prepared.
以上で調製した混和剤の内容を表６にまとめて示した。
Table 6 shows the contents of the admixtures prepared above.
表６において、
ｇ−３：アルキルベンゼンスルホン酸ナトリウム（テイカ社製の商品名テイカパワーＢＮ２０６０）
ｇ−４：ポリオキシエチレンアルキルエーテル硫酸ナトリウム（テイカ社製の商品名テイカポールＮＥ７０３０）
＊１：ナフタレンスルホン酸ホルマリン高縮合物塩（竹本油脂社製のコンクリート用高性能減水剤、商品名ポールファイン５１０ＡＮ）
＊２：メラミンスルホン酸ホルマリン高縮合物塩（竹本油脂社製のコンクリート用高性能減水剤、商品名ポールファインＭＦ）
In Table 6,
g-3: sodium alkylbenzene sulfonate (trade name Teika Power BN2060 manufactured by Teika Co.)
g-4: sodium polyoxyethylene alkyl ether sulfate (trade name: Teikapol NE7030 manufactured by Teika)
*1: Naphthalene sulfonic acid formalin high-condensation salt (high-performance water reducing agent for concrete made by Takemoto Yushi Co., Ltd., trade name PALLFINE 510AN)
*2: Highly condensed melamine sulfonate formalin salt (high-performance water reducing agent for concrete manufactured by Takemoto Yushi Co., Ltd., product name Pole Fine MF)
試験区分７（コンクリート組成物の調製）
・実施例１〜２８及び比較例１〜１３
容量６０リットルの傾動二軸ミキサーを用い、表７、表８及び表９に記載の条件で、９０秒間練混ぜを行い、表８及び表９に記載した各例のコンクリート組成物を調製した。尚、各例のコンクリート組成物について、ＡＥ剤（竹本油脂社製の商品名ＡＥ−３００）を用い、目標空気量を４．５±１．０％とし、また目標スランプフロー値を６０±５ｃｍとした。
Test Category 7 (Preparation of concrete composition)
-Examples 1-28 and Comparative Examples 1-13
Using a tilting twin-screw mixer having a capacity of 60 liters, the mixture was kneaded for 90 seconds under the conditions shown in Tables 7, 8 and 9 to prepare concrete compositions for each example shown in Tables 8 and 9. In addition, about the concrete composition of each example, AE agent (Takemoto Yushi Co., Ltd. brand name AE-300) was used, the target air amount was set to 4.5±1.0%, and the target slump flow value was 60±5 cm. And
表７において、
細骨材：陸砂（表乾密度２．５０ｇ／ｃｍ３）
粗骨材：陸石（表乾密度２．５７ｇ／ｃｍ３）
In Table 7,
Fine aggregate: Land sand (surface dry density 2.50 g/cm 3 )
Coarse aggregate: land stone (Table dry density of 2.57g / cm 3)
試験区分８（調製したコンクリート組成物の物性評価）
調製した各例のコンクリート組成物について、練混ぜ直後のスランプフロー値、空気量を下記のように測定し、結果を表８及び表９にまとめて示した。
Test Category 8 (Evaluation of physical properties of prepared concrete composition)
For the prepared concrete compositions of each example, the slump flow value and air content immediately after mixing were measured as described below, and the results are summarized in Tables 8 and 9.
・スランプフロー（ｃｍ）：練混ぜ直後のコンクリート組成物について、ＪＩＳ−Ａ１１５０に準拠して測定した。
・空気量（容積％）：練混ぜ直後のコンクリート組成物について、ＪＩＳ−Ａ１１２８に準拠して測定した。
-Slump flow (cm): The concrete composition immediately after mixing was measured according to JIS-A1150.
Amount of air (% by volume): The concrete composition immediately after mixing was measured according to JIS-A1128.
表８及び表９において、
配合Ｎｏ．：表７に記載の配合Ｎｏ．
結合材の種類：表１に記載の結合材の種類
混和剤の種類：表６に記載の混和剤の種類
添加量：結合材１００質量部に対する混和剤の割合（質量部）
In Table 8 and Table 9,
Formulation No. : Compound No. shown in Table 7.
Binder type: Binder type listed in Table 1 Admixture type: Admixture type listed in Table 6 Addition amount: Ratio of admixture to 100 parts by weight of binder (parts by mass)
試験区分９
調製した各例のコンクリート組成物及びこれらを硬化させて得られたコンクリート硬化体（２４時間後）を次のように評価した。結果を表１０及び表１１にまとめて示した。
Test category 9
The prepared concrete composition of each example and the concrete hardened|cured material (after 24 hours) obtained by hardening these were evaluated as follows. The results are summarized in Table 10 and Table 11.
・流動性の評価：練混ぜ直後のコンクリート組成物について、目標スランプスランプフロー値を得るための混和剤添加割合により次の基準で評価した。
◎：結合材１００質量部に対して混和剤の添加割合が０．２８質量部未満
○：結合材１００質量部に対して混和剤の添加割合が０．２８質量部〜０．５０質量部
×：結合材１００質量部に対して混和剤の添加割合が０．５０質量部超
-Evaluation of fluidity: The concrete composition immediately after mixing was evaluated according to the following criteria based on the proportion of the admixture added to obtain the target slump slump flow value.
⊚: Addition ratio of the admixture is less than 0.28 parts by mass relative to 100 parts by mass of the binder ○: Addition ratio of the admixture is 0.28 parts by mass to 0.50 parts by mass relative to 100 parts by mass of the binder : Addition ratio of the admixture is more than 0.50 parts by mass with respect to 100 parts by mass of the binder.
・黒ずみの程度の評価：コンクリート組成物及びコンクリート硬化体について、目視により、黒ずみの程度を次の基準で評価した。
◎：黒ずみは確認されなかった
○：ごく少量の黒ずみが確認された
×：黒ずみが確認された
Evaluation of degree of darkening: The degree of darkening was visually evaluated for the concrete composition and the hardened concrete according to the following criteria.
◎: No darkening was confirmed ○: A very small amount of darkening was confirmed ×: Darkening was confirmed
・コンクリート組成物の状態：コンクリート組成物について、目視により、材料の一体感を次の基準で評価した。
◎：非常に良好（骨材とモルタル・ペーストの分離なし）
○：良好（わずかに骨材とモルタル・ペーストが分離）
×：悪い（骨材とモルタル・ペーストが分離）
××：非常に悪い（骨材とモルタル・ペーストの分離が顕著）
State of concrete composition: The concrete composition was visually evaluated for unity of the materials according to the following criteria.
◎: Very good (no separation of aggregate and mortar paste)
○: Good (slightly separate aggregate and mortar paste)
×: Poor (aggregate and mortar paste separated)
XX: Very bad (separation of aggregate and mortar paste is remarkable)
・コンクリート表面の気泡の評価：コンクリート硬化体の表面気泡（あばた）の状態を評価した。
◎：あばたがほとんどなく美麗
○：わずかにあばたが目立つ
×：あばたが目立つ
-Evaluation of bubbles on the surface of concrete: The state of bubbles on the surface of the hardened concrete was evaluated.
◎: Beautiful with almost no pockmark ○: Slightly noticeable patter ×: Conspicuous pockmark
比較例１、比較例５及び比較例１０の場合には、コンクリート硬化体の初期強度発現性が著しく悪く、翌日に脱型することができなかった。 In the case of Comparative Examples 1, 5 and 10, the initial concrete strength development of the hardened concrete was remarkably poor, and the mold could not be removed the next day.
表８及び表９、とりわけ表１０及び表１１の結果から明らかなように、本発明によると、流動性の高いコンクリート組成物を調製することを前提として、骨材など材料の分離や黒色微粉の分離を抑制する材料分離抵抗性の高いコンクリート組成物を得ることができ、同時に肌面への黒い斑点や全体的な黒ずみの発生を抑制した表面美観に優れたコンクリート硬化体を得ることができる。 As is clear from the results of Table 8 and Table 9, especially Table 10 and Table 11, according to the present invention, it is assumed that a concrete composition having high fluidity is prepared, and separation of materials such as aggregates and black fine powder It is possible to obtain a concrete composition having high resistance to material separation, and at the same time, it is possible to obtain a concrete hardened body excellent in surface aesthetics in which black spots on the skin surface and overall darkening are suppressed.
Claims (7)
混和剤：下記のＡ成分、下記のＢ成分及び下記のＣ成分を含有して成るもの。
Ａ成分：分子中に下記の化１で示される単量体から形成された構成単位Ｌと、（メタ）アクリル酸、クロトン酸、（無水）マレイン酸、（無水）イタコン酸、フマル酸及びそれらの塩から選ばれる少なくとも一つから形成された構成単位Ｍとを有し、且つ全構成単位中に構成単位Ｌを５０〜９９質量％及び構成単位Ｍを１〜３０質量％の割合で有する質量平均分子量２０００〜５０００００の水溶性ビニル共重合体。
Ｂ成分：全構成単位中にカルボキシル基を有するビニル単量体から形成された構成単位を３０質量％超〜８０質量％有する数平均分子量２００００〜２００００００のビニル共重合体。
Ｃ成分：黒ずみ抑制剤。
Ｒ１：炭素数２〜５のアルケニル基又は炭素数３又は４の不飽和アシル基
Ｒ２：水素原子、炭素数１〜２２のアルキル基又は炭素数１〜２２の脂肪族アシル基
Ａ１：１〜３００個の炭素数２〜４のオキシアルキレン単位で構成された（ポリ）オキシアルキレン基） A concrete composition comprising a binder, water, a fine aggregate, a coarse aggregate and an admixture having a water/binder ratio of 30 to 70% by mass and a slump flow value of 35 to 80 cm. To 20% by mass or more of Portland cement, and 0.05 to 0.5 parts by mass of the following admixture with respect to 100 parts by mass of the binder. ..
Admixture: A compound containing the following A component, the following B component and the following C component.
Component A: a structural unit L formed from a monomer represented by the following chemical formula 1 in the molecule, (meth)acrylic acid, crotonic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, fumaric acid, and them And a structural unit M formed from at least one selected from the salts of 50 to 99% by mass of the structural unit L and 1 to 30% by mass of the structural unit M in all structural units. Water-soluble vinyl copolymer having an average molecular weight of 2000 to 500000.
Component B: A vinyl copolymer having a number average molecular weight of 20,000 to 2,000,000 and having 30% by mass to 80% by mass of structural units formed from vinyl monomers having a carboxyl group in all structural units.
Component C: Blackening inhibitor.
R 1 : an alkenyl group having 2 to 5 carbon atoms or an unsaturated acyl group having 3 or 4 carbon atoms R 2 : a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an aliphatic acyl group having 1 to 22 carbon atoms A 1 : (Poly)oxyalkylene group composed of 1 to 300 oxyalkylene units having 2 to 4 carbon atoms)
Ｄ成分：下記の化２で示されるアルキレンオキサイド付加物。
Ｒ３：水素原子又は炭素数１〜２０の脂肪族炭化水素基
Ａ２：１０〜１００個の炭素数２〜４のオキシアルキレン単位で構成されたポリオキシアルキレン基であり、且つ全オキシアルキレン単位中に炭素数３のオキシプロピレン単位を７０モル％以上有するポリオキシアルキレン基） The concrete composition according to any one of claims 1 to 4, wherein the admixture further contains the following D component in a proportion of 0.02 to 5 mass%.
Component D: an alkylene oxide adduct represented by the following chemical formula 2.
R 3 : a hydrogen atom or an aliphatic hydrocarbon group having 1 to 20 carbon atoms A 2 : a polyoxyalkylene group composed of 10 to 100 oxyalkylene units having 2 to 4 carbon atoms, and all oxyalkylene units (A polyoxyalkylene group having 70 mol% or more of oxypropylene units having 3 carbon atoms)
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