JP7012313B1 - Defoaming agent for hydraulic composition, aqueous liquid containing it and hydraulic composition - Google Patents

Defoaming agent for hydraulic composition, aqueous liquid containing it and hydraulic composition Download PDF

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JP7012313B1
JP7012313B1 JP2020162335A JP2020162335A JP7012313B1 JP 7012313 B1 JP7012313 B1 JP 7012313B1 JP 2020162335 A JP2020162335 A JP 2020162335A JP 2020162335 A JP2020162335 A JP 2020162335A JP 7012313 B1 JP7012313 B1 JP 7012313B1
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hydraulic composition
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defoaming agent
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JP2022055003A (en
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郁香 村松
裕樹 内藤
章宏 古田
伸二 玉木
陽 澤田
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Takemoto Oil and Fat Co Ltd
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    • 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
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • 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
    • C04B22/00—Use of inorganic materials as active ingredients for mortars, concrete or artificial stone, e.g. accelerators, shrinkage compensating agents
    • C04B22/08—Acids or salts thereof
    • C04B22/16—Acids or salts thereof containing phosphorus in the anion, e.g. phosphates
    • 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
    • C04B24/02—Alcohols; Phenols; Ethers
    • 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
    • C04B24/04—Carboxylic acids; Salts, anhydrides or esters thereof
    • 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
    • C04B24/04—Carboxylic acids; Salts, anhydrides or esters thereof
    • C04B24/06—Carboxylic acids; Salts, anhydrides or esters thereof containing hydroxy groups
    • 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
    • C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

Abstract

【課題】分離安定性に優れ、水で希釈したときの乳化安定性にも優れ、他の水硬性組成物用添加剤との相溶性にも優れ、更には、少量で優れた消泡性を有する水硬性組成物用消泡剤を提供する。【解決手段】一般式（１）で示され、式（２）で示されるＨＬＢが０．１～６の範囲内であるポリアルキレンオキシド付加物と、分子量が５００以下の酸と、を含有することを特徴とする水硬性組成物用消泡剤。【選択図】なしPROBLEM TO BE SOLVED: To have excellent separation stability, excellent emulsion stability when diluted with water, excellent compatibility with other additives for hydraulic composition, and further excellent defoaming property with a small amount. Provided is an antifoaming agent for a hydraulic composition having. SOLUTION: The polyalkylene oxide adduct represented by the general formula (1) and having an HLB in the range of 0.1 to 6 represented by the formula (2) and an acid having a molecular weight of 500 or less are contained. A defoaming agent for hydraulic compositions. [Selection diagram] None

Description

本発明は、水硬性組成物用消泡剤、これを含有する水性液及び水硬性組成物に関する。更に詳しくは、分離安定性、乳化安定性及び他の水硬性組成物用添加剤との相溶性に優れ、更に、少量でも優れた消泡性を発揮する水硬性組成物用消泡剤、水硬性組成物用消泡剤の水性液及び水硬性組成物に関する。 The present invention relates to a defoaming agent for a hydraulic composition, an aqueous liquid containing the defoaming agent, and a hydraulic composition. More specifically, a defoaming agent for a water-hard composition, which has excellent separation stability, emulsification stability and compatibility with other additives for a water-hard composition, and further exhibits excellent defoaming property even in a small amount, water. The present invention relates to an aqueous solution of an antifoaming agent for a rigid composition and a hydraulic composition.

従来、コンクリートに代表される水硬性組成物には、水硬性組成物の硬化前のワーカビリティを改善するために減水剤が添加されている。 Conventionally, a water reducing agent has been added to a hydraulic composition typified by concrete in order to improve the workability of the hydraulic composition before curing.

一方で、水硬性組成物に減水剤（特にポリカルボン酸系減水剤）を添加すると、コンクリート等の水硬性組成物中に気泡を巻き込みやすくなり、気泡の巻き込みにより粗大な空気が発生する傾向がある。そこで、水硬性組成物中の粗大な空気を減少させたり、空気量を適切な範囲に調整したりするために消泡剤が配合されることが多い。 On the other hand, when a water reducing agent (particularly a polycarboxylic acid-based water reducing agent) is added to the hydraulic composition, air bubbles tend to be easily entrained in the hydraulic composition such as concrete, and coarse air tends to be generated due to the entrainment of air bubbles. be. Therefore, an antifoaming agent is often added to reduce the coarse air in the hydraulic composition or to adjust the amount of air to an appropriate range.

なお、このような消泡剤として、例えば、オキシアルキレン系、シリコーン系、アルコール系、鉱油系、脂肪酸系、脂肪酸エステル系等の消泡剤が知られている。 As such defoaming agents, for example, oxyalkylene-based, silicone-based, alcohol-based, mineral oil-based, fatty acid-based, fatty acid ester-based defoaming agents and the like are known.

また、ポリカルボン酸系化合物と、特定の含窒素ポリオキシアルキレン化合物との混合物からなる添加剤（例えば、特許文献１参照）や、特定のポリオキシアルキレン系化合物が提案されている（例えば、特許文献２～６参照）。 Further, an additive composed of a mixture of a polycarboxylic acid-based compound and a specific nitrogen-containing polyoxyalkylene compound (see, for example, Patent Document 1) and a specific polyoxyalkylene-based compound have been proposed (for example, patent). Refer to Documents 2 to 6).

更には、水不溶性脱泡剤及びアミン可溶化剤等を含む混和剤組成物や、水溶性アルカノールアミン塩を含み脱泡剤となることができる水溶性試薬が報告されている（例えば、特許文献７，８参照）。 Further, an admixture composition containing a water-insoluble defoaming agent, an amine solubilizer and the like, and a water-soluble reagent containing a water-soluble alkanolamine salt and capable of serving as a defoaming agent have been reported (for example, Patent Documents). See 7 and 8).

特開平７－２３２９４５号公報Japanese Unexamined Patent Publication No. 7-232945 特開平１０－２２６５５０号公報Japanese Unexamined Patent Publication No. 10-226550 特開２００３－２２６５６５号公報Japanese Patent Application Laid-Open No. 2003-226565 特開２００３－２２６５６６号公報Japanese Patent Application Laid-Open No. 2003-226566 特開２００３－２２６５６７号公報Japanese Patent Application Laid-Open No. 2003-226567 特開２００３－３００７６６号公報Japanese Patent Application Laid-Open No. 2003-300766 特表２００６－５１１４１８号公報Japanese Patent Publication No. 2006-511418 特開平７－１７２８８７号公報Japanese Unexamined Patent Publication No. 7-172887

ここで、一般的に、疎水性の高い（ＨＬＢの低い）消泡剤は、消泡性に優れるが、水に馴染みにくく、他の水硬性組成物用添加剤とも相溶性が低く分離してしまう。この点、特許文献１～６では、他の水硬性組成物用添加剤との相溶性に改善は見られる。しかしながら、上記特許文献１～８などでは、優れた消泡性及び安定性を同時に発揮し難いなどの問題がある。 Here, in general, a defoaming agent having high hydrophobicity (low HLB) has excellent defoaming property, but is difficult to be compatible with water and has low compatibility with other additives for water-hard composition and is separated. It ends up. In this respect, in Patent Documents 1 to 6, improvement in compatibility with other additives for hydraulic composition can be seen. However, the above-mentioned Patent Documents 1 to 8 have problems such as difficulty in exhibiting excellent defoaming property and stability at the same time.

そこで、本発明は、上記実情に鑑み、分離安定性に優れ、水で希釈したときの乳化安定性にも優れ、他の水硬性組成物用添加剤との相溶性にも優れ、更には、少量で優れた消泡性を有する水硬性組成物用消泡剤、水硬性組成物用消泡剤の水性液、及び水硬性組成物の提供を課題とするものである。 Therefore, in view of the above circumstances, the present invention has excellent separation stability, excellent emulsion stability when diluted with water, excellent compatibility with other additives for water-hard composition, and further. An object of the present invention is to provide a defoaming agent for a water-hardening composition having excellent defoaming property in a small amount, an aqueous solution of a defoaming agent for a water-hardening composition, and a water-hardening composition.

本発明者らは、前記の課題を解決すべく鋭意研究した結果、消泡性能を発揮する特定の化合物に対して所定の酸を配合することによって、上記課題を解決できることを見出した。本発明によれば、以下の水硬性組成物用消泡剤、水硬性組成物用消泡剤の水性液、及び水硬性組成物が提供される。 As a result of diligent research to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by blending a predetermined acid with a specific compound exhibiting defoaming performance. According to the present invention, the following defoaming agents for water-hardening compositions, aqueous liquids for defoaming agents for water-hardening compositions, and water-hardening compositions are provided.

［１］ 下記一般式（１）で示され、下記式（２）で示されるＨＬＢが０．１～６の範囲内であるポリアルキレンオキシド付加物と、
分子量が５００以下の酸と、を含有し、
下記式（３）で示されるＥＱが、０．３～３．５の範囲内であることを特徴とする、水硬性組成物用消泡剤。 [1] A polyalkylene oxide adduct represented by the following general formula (1) and having an HLB in the range of 0.1 to 6 represented by the following formula (2).
Contains an acid having a molecular weight of 500 or less ,
An antifoaming agent for a hydraulic composition, wherein the EQ represented by the following formula (3) is in the range of 0.3 to 3.5 .

Figure 0007012313000001
（但し、一般式（１）中、Ｒ１は、炭素数１～３０の炭化水素基である。Ｒ２，Ｒ３は、それぞれ独立に、水素原子、炭素数１～２２の炭化水素基である。Ａ１Ｏ，Ａ２Ｏは、それぞれ独立に、炭素数２～４のオキシアルキレン基である。ｍ，ｎは、それぞれ独立に０～２００の整数であり、ｍ＋ｎは３～２００を満たす整数である。）
Figure 0007012313000001
 (However, in the general formula (1), R 1 is a hydrocarbon group having 1 to 30 carbon atoms. R 2 and R 3 are independently hydrogen atoms and hydrocarbon groups having 1 to 22 carbon atoms, respectively. A 1 O and A 2 O are independently oxyalkylene groups having 2 to 4 carbon atoms. M and n are independently integers of 0 to 200, and m + n satisfies 3 to 200. It is an integer.)

Figure 0007012313000002
（但し、式（２）中、Ｙは、一般式（１）で示されるポリアルキレンオキシド付加物の分子中に含まれる（ポリ）オキシエチレン基の含有割合（質量％）である。）
Figure 0007012313000003
 （但し、前記式（３）中、Ｗは、前記酸から求められる酸価である。ｂは、前記一般式（１）で示されるポリアルキレンオキシド付加物と前記酸の含有割合の合計を１００質量％とした場合における前記酸の含有割合（質量％）である。Ｖは、前記一般式（１）で示されるポリアルキレンオキシド付加物から求められるアミン価である。ａは、前記一般式（１）で示されるポリアルキレンオキシド付加物と前記酸の含有割合の合計を１００質量％とした場合における前記一般式（１）で示されるポリアルキレンオキシド付加物の含有割合（質量％）である。）
Figure 0007012313000002
 (However, in the formula (2), Y is the content ratio (mass%) of the (poly) oxyethylene group contained in the molecule of the polyalkylene oxide adduct represented by the general formula (1).)
Figure 0007012313000003
 (However, in the formula (3), W is the acid value obtained from the acid. B is the total content ratio of the polyalkylene oxide adduct represented by the general formula (1) and the acid to 100. It is the content ratio (mass%) of the acid in the case of mass%. V is the amine value obtained from the polyalkylene oxide adduct represented by the general formula (1). A is the general formula (1). It is the content ratio (mass%) of the polyalkylene oxide adduct represented by the general formula (1) when the sum of the content ratios of the polyalkylene oxide adduct represented by 1) and the acid is 100% by mass. )

［２］ 前記一般式（１）におけるＲ２，Ｒ３が、いずれも水素原子である、前記［１］に記載の水硬性組成物用消泡剤。 [2] The defoaming agent for a hydraulic composition according to the above [1], wherein both R 2 and R 3 in the general formula (1) are hydrogen atoms.

［３］ 前記一般式（１）におけるＲ１が、炭素数１０～２０の炭化水素基である、前記［１］または［２］に記載の水硬性組成物用消泡剤。 [3] The defoaming agent for a hydraulic composition according to the above [1] or [2], wherein R 1 in the general formula (1) is a hydrocarbon group having 10 to 20 carbon atoms.

［４］ 前記一般式（１）における－（Ａ１Ｏ）ｍ－，－（Ａ２Ｏ）ｎ－は、その炭素数２～４のオキシアルキレン基の構成割合の合計を１００モル％とすると、炭素数３～４のオキシアルキレン基を７５モル％以上の割合で有する、前記［１］～［３］のいずれかに記載の水硬性組成物用消泡剤。 [4] In the general formula (1),-(A 1 O) m -,-(A 2 O) n- is assumed to be 100 mol% in total of the composition ratios of the oxyalkylene groups having 2 to 4 carbon atoms. The defoaming agent for a water-hard composition according to any one of the above [1] to [3], which has an oxyalkylene group having 3 to 4 carbon atoms in a proportion of 75 mol% or more.

［５］ 前記一般式（１）における－（Ａ１Ｏ）ｍ－，－（Ａ２Ｏ）ｎ－が、炭素数２～４のオキシアルキレン基をブロック重合させたものである、前記［１］～［４］のいずれかに記載の水硬性組成物用消泡剤。 [5] -(A 1 O) m -,-(A 2 O) n -in the general formula (1) is a block-polymerized oxyalkylene group having 2 to 4 carbon atoms. ] To [4]. The defoaming agent for a hydraulic composition according to any one of.

［６］ 前記一般式（１）におけるｍ，ｎは、これらの和であるｍ＋ｎが、２０～８０の整数である、前記［１］～［５］のいずれかに記載の水硬性組成物用消泡剤。 [6] The hydraulic composition according to any one of the above [1] to [5], wherein m and n in the general formula (1) are m + n, which is the sum of these, is an integer of 20 to 80. Defoamer.

［７］ 前記一般式（１）で示されるポリアルキレンオキシド付加物は、前記式（２）におけるＨＬＢが０．１～３．５の範囲内である、前記［１］～［６］のいずれかに記載の水硬性組成物用消泡剤。 [7] The polyalkylene oxide adduct represented by the general formula (1) has an HLB in the range of 0.1 to 3.5 in the formula (2), any of the above [1] to [6]. Defoaming agent for hydraulic composition described in Crab.

［８］ 前記式（３）で示されるＥＱが、０．７～３．５の範囲内である、前記［１］～［７］のいずれかに記載の水硬性組成物用消泡剤。 [8] The defoaming agent for a hydraulic composition according to any one of the above [1] to [7], wherein the EQ represented by the formula (3) is in the range of 0.7 to 3.5.

削除delete

［９］ 前記［１］～［８］のいずれかに記載の水硬性組成物用消泡剤、及び水を含有することを特徴とする、水硬性組成物用消泡剤の水性液。 [9] An aqueous liquid of the defoaming agent for a hydraulic composition, which comprises the defoaming agent for a hydraulic composition according to any one of [1] to [8] above, and water.

［１０］ 前記一般式（１）で示されるポリアルキレンオキシド付加物、前記酸、及び前記水の含有割合の合計を１００質量％とすると、前記水を０．０１～２５質量％の割合で含有する、前記［９］に記載の水硬性組成物用消泡剤の水性液。 [10] Assuming that the total content of the polyalkylene oxide adduct represented by the general formula (1), the acid, and the water is 100% by mass, the water is contained in a ratio of 0.01 to 25% by mass. The aqueous liquid of the defoaming agent for the water-hardening composition according to the above [9].

［１１］ 前記［１］～［８］のいずれかに記載の水硬性組成物用消泡剤を含有することを特徴とする、水硬性組成物。 [11] A hydraulic composition comprising the defoaming agent for a hydraulic composition according to any one of the above [1] to [8].

本発明の水硬性組成物用消泡剤及び本発明の水硬性組成物用消泡剤の水性液は、分離安定性に優れ、水で希釈したときの乳化安定性にも優れ、他の水硬性組成物用添加剤との相溶性にも優れ、少量で優れた消泡性を有するという効果を奏するものである。 The aqueous liquid of the defoaming agent for a water-hardening composition of the present invention and the defoaming agent for a water-hardening composition of the present invention has excellent separation stability, excellent emulsification stability when diluted with water, and other water. It has excellent compatibility with additives for rigid compositions, and has the effect of having excellent defoaming properties even in a small amount.

本発明の水硬性組成物は、本発明の水硬性組成物用消泡剤を含有しており、当該水硬性組成物用消泡剤と減水剤等の水硬性組成物用添加剤との相溶性が良好である。そのため、本発明の水硬性組成物は、タンク等で消泡剤と減水剤等を混合した混合液を攪拌せず静置しても、混合液が均一に保たれ、空気量のばらつきが少ないという効果を奏するものである。 The hydraulic composition of the present invention contains the defoaming agent for the hydraulic composition of the present invention, and the phase between the defoaming agent for the hydraulic composition and the additive for the hydraulic composition such as a water reducing agent. Good solubility. Therefore, in the water-hardening composition of the present invention, even if the mixed solution of the defoaming agent and the water reducing agent is allowed to stand in a tank or the like without stirring, the mixed solution is kept uniform and the amount of air does not vary much. It has the effect of.

以下、本発明の実施形態について説明する。しかし、本発明は以下の実施形態に限定されるものではない。したがって、本発明の趣旨を逸脱しない範囲で、当業者の通常の知識に基づいて、以下の実施形態に対し適宜変更、改良等が加えられ得ることが理解されるべきである。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, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments. Therefore, it should be understood that the following embodiments can be appropriately modified, improved, or the like based on the ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. In the following examples and the like, unless otherwise specified,% means mass% and parts mean parts by mass.

（１）水硬性組成物用消泡剤：
本発明の水硬性組成物用消泡剤は、下記一般式（１）で示され、下記式（２）で示されるＨＬＢが０．１～６の範囲内であるポリアルキレンオキシド付加物と、分子量が５００以下の酸と、を含有するものである。 (1) Defoaming agent for hydraulic composition:
The defoaming agent for a water-hardening composition of the present invention comprises a polyalkylene oxide adduct represented by the following general formula (1) and having an HLB in the range of 0.1 to 6 represented by the following formula (2). It contains an acid having a molecular weight of 500 or less.

このような水硬性組成物用消泡剤は、分離安定性に優れ、水で希釈したときの乳化安定性にも優れ、他の水硬性組成物用添加剤との相溶性にも優れ、少量で優れた消泡性を有する。 Such a defoaming agent for a water-hard composition has excellent separation stability, excellent emulsification stability when diluted with water, excellent compatibility with other additives for a water-hard composition, and a small amount. Has excellent defoaming properties.

Figure 0007012313000004
（但し、一般式（１）中、Ｒ１は、炭素数１～３０の炭化水素基である。Ｒ２，Ｒ３は、それぞれ独立に、水素原子、炭素数１～２２の炭化水素基である。Ａ１Ｏ，Ａ２Ｏは、それぞれ独立に、炭素数２～４のオキシアルキレン基である。ｍ，ｎは、それぞれ独立に０～２００の整数であり、ｍ＋ｎは３～２００を満たす整数である。）
Figure 0007012313000004
 (However, in the general formula (1), R 1 is a hydrocarbon group having 1 to 30 carbon atoms. R 2 and R 3 are independently hydrogen atoms and hydrocarbon groups having 1 to 22 carbon atoms, respectively. A 1 O and A 2 O are independently oxyalkylene groups having 2 to 4 carbon atoms. M and n are independently integers of 0 to 200, and m + n satisfies 3 to 200. It is an integer.)

Figure 0007012313000005
（但し、式（２）中、Ｙは、一般式（１）で示されるポリアルキレンオキシド付加物の分子中に含まれる（ポリ）オキシエチレン基（炭素数２のオキシアルキレン基）の含有割合（質量％）である。）
Figure 0007012313000005
 (However, in the formula (2), Y is the content ratio of the (poly) oxyethylene group (oxyalkylene group having 2 carbon atoms) contained in the molecule of the polyalkylene oxide adduct represented by the general formula (1). Mass%).)

例えば、一般式（１）で示されるポリアルキレンオキシド付加物の分子中に含まれる（ポリ）オキシエチレン基の含有割合が２５質量％である場合、ＨＬＢは、式：２５／５で計算され、５となる。 For example, when the content ratio of the (poly) oxyethylene group contained in the molecule of the polyalkylene oxide adduct represented by the general formula (1) is 25% by mass, the HLB is calculated by the formula: 25/5. It becomes 5.

式（２）で示されるＨＬＢは、下記式（２ａ）で示されるＨＬＢと記すこともできる。 The HLB represented by the formula (2) can also be described as the HLB represented by the following formula (2a).

Figure 0007012313000006
（但し、式（２ａ）中、Ｚ１は、一般式（１）で示されるポリアルキレンオキシド付加物の分子量である。Ｚ２は、一般式（１）で示されるポリアルキレンオキシド付加物の分子中に含まれる炭素数２のオキシアルキレン基の式量である。）
Figure 0007012313000006
 (However, in the formula (2a), Z1 is the molecular weight of the polyalkylene oxide adduct represented by the general formula (1). Z2 is the molecular weight of the polyalkylene oxide adduct represented by the general formula (1). It is the formula amount of the oxyalkylene group having 2 carbon atoms contained.)

（１－１）一般式（１）で示されるポリアルキレンオキシド付加物：
一般式（１）で示されるポリアルキレンオキシド付加物は、消泡性能を発揮するアミン系の化合物である。 (1-1) Polyalkylene oxide adduct represented by the general formula (1):
The polyalkylene oxide adduct represented by the general formula (1) is an amine-based compound exhibiting defoaming performance.

一般式（１）中、Ｒ１は、炭素数１～３０の炭化水素基であり、炭素数１０～２０の炭化水素基であることが好ましい。このような炭化水素基であると、分離安定性、乳化安定性、及び、他の水硬性組成物用添加剤との相溶性に優れ、少量で優れた消泡性を有する水硬性組成物用消泡剤とすることができる。 In the general formula (1), R 1 is a hydrocarbon group having 1 to 30 carbon atoms, and preferably a hydrocarbon group having 10 to 20 carbon atoms. Such a hydrocarbon group is excellent in separation stability, emulsion stability, compatibility with other additives for water-hard composition, and for water-hard composition having excellent defoaming property even in a small amount. It can be used as an antifoaming agent.

Ｒ１の炭素数１～３０の炭化水素基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ペンチル基、へキシル基、ヘプチル基、オクチル基、イソオクチル基、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、イコシル基、ヘンイコシル基、ドコシル基、テトラコシル基、ヘキサコシル基、オクタコシル基、トリアコンチル基、エチニル基、プロペニル基、ブテニル基、ヘキセニル基、オクテニル基、ノネニル基、デセニル基、ドデセニル基、テトラデセニル基、ヘキサデセニル基、オクタデセニル基などを挙げることができる。なお、これらは、１種類または２種以上であってもよい。 Examples of the hydrocarbon group having 1 to 30 carbon atoms of R 1 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group and a nonyl group. , Decyl group, undecyl group, dodecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henicosyl group, docosyl group, tetracosyl group, hexacosyl group, octacosyl group, triacontyl group, ethynyl Examples thereof include a group, a propenyl group, a butenyl group, a hexenyl group, an octenyl group, a nonenyl group, a decenyl group, a dodecenyl group, a tetradecenyl group, a hexadecenyl group, an octadecenyl group and the like. In addition, these may be 1 type or 2 or more types.

一般式（１）中、Ｒ２，Ｒ３は、それぞれ独立に、水素原子、炭素数１～２２の炭化水素基であるが、これらの中でも、Ｒ２，Ｒ３が、いずれも水素原子または炭素数１～３の炭化水素基であることが好ましく、いずれも水素原子であることが更に好ましい。 In the general formula (1), R 2 and R 3 are independently hydrogen atoms and hydrocarbon groups having 1 to 22 carbon atoms. Among these, R 2 and R 3 are all hydrogen atoms or hydrogen atoms. It is preferably a hydrocarbon group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

一般式（１）中、のＲ２，Ｒ３における炭素数１～２２の炭化水素基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ペンチル基、へキシル基、ヘプチル基、オクチル基、イソオクチル基、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、イコシル基、ヘンイコシル基、ドコシル基、エチニル基、プロペニル基、ブテニル基、ヘキセニル基、オクテニル基、ノネニル基、デセニル基、ドデセニル基、テトラデセニル基、ヘキサデセニル基、オクタデセニル基などを挙げることができる。 Examples of the hydrocarbon group having 1 to 22 carbon atoms in R2 and R3 in the general formula (1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group and a hexyl group. Heptyl group, octyl group, isooctyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henicosyl group, docosyl group, ethynyl group. , Propenyl group, butenyl group, hexenyl group, octenyl group, nonenyl group, decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group and the like.

一般式（１）中、Ａ１Ｏ，Ａ２Ｏは、それぞれ独立に、炭素数２～４のオキシアルキレン基であり、炭素数２または３のオキシアルキレン基であることが好ましい。上記炭素数２～４のオキシアルキレン基としては、具体的には、オキシエチレン基、オキシプロピレン基、オキシブチレン基を挙げることができる。但し、Ａ１Ｏ，Ａ２Ｏのいずれか一方または両方には、炭素数２のオキシアルキレン基（即ち、オキシエチレン基）を含む。 In the general formula (1), A 1 O and A 2 O are independently oxyalkylene groups having 2 to 4 carbon atoms, and preferably oxyalkylene groups having 2 or 3 carbon atoms. Specific examples of the oxyalkylene group having 2 to 4 carbon atoms include an oxyethylene group, an oxypropylene group and an oxybutylene group. However, either one or both of A 1 O and A 2 O contains an oxyalkylene group having 2 carbon atoms (that is, an oxyethylene group).

オキシプロピレン基としては、１，２－オキシプロピレン基、１，３－オキシプロピレン基が挙げられる。 Examples of the oxypropylene group include a 1,2-oxypropylene group and a 1,3-oxypropylene group.

オキシブチレン基としては、１，２－オキシブチレン基、１，３－オキシブチレン基、１，４－オキシブチレン基、２，３－オキシブチレン基、オキシイソブチレン基が挙げられる。 Examples of the oxybutylene group include a 1,2-oxybutylene group, a 1,3-oxybutylene group, a 1,4-oxybutylene group, a 2,3-oxybutylene group and an oxyisobutylene group.

一般式（１）において、ｍはＡ１Ｏの付加モル数を表し、ｎは、Ａ２Ｏの付加モル数を表す。 In the general formula (1), m represents the number of added moles of A 1 O, and n represents the number of added moles of A 2 O.

一般式（１）中、ｍ，ｎは、それぞれ独立に０～２００の整数であり、好ましくは０～８０の整数である。 In the general formula (1), m and n are independently integers of 0 to 200, preferably 0 to 80.

また同時に、ｍ＋ｎは、３～２００を満たす整数である。即ち、ｍ及びｎは、３≦ｍ＋ｎ≦２００の条件を満たす整数である。そして、ｍ＋ｎは、２０～８０を満たす整数であることが好ましい。このような範囲とすることにより、分離安定性、乳化安定性、相溶性、及び、消泡性が更に向上する。一方、下限値未満であると、消泡性が不十分であり、安定性も低下する。上限値超であると、高粘度のため製造が困難となり、また、水硬性組成物用添加剤との相溶性も不十分となる。 At the same time, m + n is an integer satisfying 3 to 200. That is, m and n are integers satisfying the condition of 3 ≦ m + n ≦ 200. And m + n is preferably an integer satisfying 20 to 80. Within such a range, separation stability, emulsion stability, compatibility, and defoaming property are further improved. On the other hand, if it is less than the lower limit, the defoaming property is insufficient and the stability is also lowered. If it exceeds the upper limit, the production becomes difficult due to the high viscosity, and the compatibility with the additive for the hydraulic composition becomes insufficient.

一般式（１）における－（Ａ１Ｏ）ｍ－，－（Ａ２Ｏ）ｎ－は、その炭素数２～４のオキシアルキレン基の構成割合の合計を１００モル％とすると、炭素数３～４のオキシアルキレン基を７５モル％以上の割合で有することが好ましく、７８モル％以上の割合で有することが更に好ましく、８０モル％以上の割合で有することが特に好ましい。このような範囲とすることによって、水硬性組成物用消泡剤の消泡性が更に向上する。 In the general formula (1),-(A 1 O) m -,-(A 2 O) n- has 3 carbon atoms, assuming that the total composition ratio of the oxyalkylene groups having 2 to 4 carbon atoms is 100 mol%. It is preferable to have the oxyalkylene group of 4 to 4 in a proportion of 75 mol% or more, further preferably in a proportion of 78 mol% or more, and particularly preferably in a proportion of 80 mol% or more. Within such a range, the defoaming property of the defoaming agent for hydraulic composition is further improved.

一般式（１）における－（Ａ１Ｏ）ｍ－，－（Ａ２Ｏ）ｎ－は、Ａ１Ｏ及びＡ２Ｏのそれぞれが２種類以上の場合は、ランダム付加体、ブロック付加体、交互付加体のいずれの形態であってもよいが、好ましくは炭素数２～４のオキシアルキレン基をブロック重合させたものである。即ち、－（Ａ１Ｏ）ｍ－，－（Ａ２Ｏ）ｎ－は、それぞれ、炭素数２～４のオキシアルキレン基のうちの少なくとも１種（例えば、炭素数２のオキシアルキレン基）が連続する領域を有しているものである。 In the general formula (1),-(A 1 O) m -,-(A 2 O) n -is a random adduct, a block adduct, when there are two or more types of A 1 O and A 2 O, respectively. It may be in any form of an alternating adduct, but it is preferably a block-polymerized oxyalkylene group having 2 to 4 carbon atoms. That is, each of − (A 1 O) m − and − (A 2 O) n − has at least one of the oxyalkylene groups having 2 to 4 carbon atoms (for example, the oxyalkylene group having 2 carbon atoms). It has a continuous area.

なお、このような－（Ａ１Ｏ）ｍ－，－（Ａ２Ｏ）ｎ－としては、炭素数２～４のオキシアルキレン基をランダム重合、ブロック重合、交互重合させて得ることができる。 It should be noted that such − (A 1 O) m −, − (A 2 O) n − can be obtained by random polymerization, block polymerization, or copolymerization of an oxyalkylene group having 2 to 4 carbon atoms.

一般式（１）で示されるポリアルキレンオキシド付加物は、上記式（２）におけるＨＬＢ（Ｈｙｄｒｏｐｈｉｌｅ－Ｌｉｐｏｐｈｉｌｅ Ｂａｌａｎｃｅ）が０．１～６の範囲内であることが必要であり、このような範囲であると、泡膜に対して難溶性を示し、優れた消泡性を発揮することができる。更に、上記ＨＬＢは、０．１～３．５の範囲内であることが好ましく、１～３．０の範囲内であることが更に好ましく、１～２．５の範囲内であることが特に好ましい。このような範囲であると、消泡性が更に向上することになる。上記ＨＬＢが下限値未満であると、乳化安定性が低下するという不具合がある。上記ＨＬＢが上限値超であると、消泡効果が低下するという不具合がある。 The polyalkylene oxide adduct represented by the general formula (1) needs to have an HLB (Hydrophile-Lipophile Balance) in the range of 0.1 to 6 in the above formula (2), and in such a range. If there is, it exhibits poor solubility in the foam film and can exhibit excellent defoaming property. Further, the HLB is preferably in the range of 0.1 to 3.5, more preferably in the range of 1 to 3.0, and particularly preferably in the range of 1 to 2.5. preferable. Within such a range, the defoaming property is further improved. If the HLB is less than the lower limit, there is a problem that the emulsification stability is lowered. If the above HLB exceeds the upper limit value, there is a problem that the defoaming effect is lowered.

一般式（１）で示されるポリアルキレンオキシド付加物としては、具体的には、デシルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、ウンデシルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、ドデシルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、トリデシルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、テトラデシルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、ペンタデシルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、ヘキサデシルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、２－ヘキシルデシルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、ヘプタデシルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、オクタデシルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、ノナデシルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、イコシルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、ヘンイコシルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、ドコシルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、トリコシルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、テトラコシルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、デセニルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、ウンデセニルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、ドデセニルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、トリデセニルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、テトラデセニルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、ペンタデセニルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、ヘキサデセニルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、ヘプタデセニルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、オクタデセニルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、ノナデセニルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、イコセニルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、ヘンイコセニルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、ドコセニルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、トリコセニルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、テトラコセニルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、牛脂アミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、硬化牛脂アミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、テトラデシルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン・（ポリ）オキシブチレン付加物、ペンタデシルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン・（ポリ）オキシブチレン付加物、ヘキサデシルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン・（ポリ）オキシブチレン付加物、２－ヘキシルデシルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン・（ポリ）オキシブチレン付加物、ヘプタデシルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン・（ポリ）オキシブチレン付加物、オクタデシルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン・（ポリ）オキシブチレン付加物、テトラデセニルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン・（ポリ）オキシブチレン付加物、ペンタデセニルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン・（ポリ）オキシブチレン付加物、ヘキサデセニルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン・（ポリ）オキシブチレン付加物、ヘプタデセニルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン・（ポリ）オキシブチレン付加物、オクタデセニルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン・（ポリ）オキシブチレン付加物、牛脂アミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン・（ポリ）オキシブチレン付加物、硬化牛脂アミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン・（ポリ）オキシブチレン付加物、硬化牛脂アミン－（ポリ）オキシエチレン・（ポリ）オキシブチレン付加物等が挙げられる。 Specific examples of the polyalkylene oxide adduct represented by the general formula (1) include decylamine- (poly) oxyethylene / (poly) oxypropylene adduct and undecylamine- (poly) oxyethylene / (poly). Oxypropylene adduct, dodecylamine- (poly) oxyethylene / (poly) oxypropylene adduct, tridecylamine- (poly) oxyethylene / (poly) oxypropylene adduct, tetradecylamine- (poly) oxyethylene (Poly) oxypropylene adduct, pentadecylamine- (poly) oxyethylene / (poly) oxypropylene adduct, hexadecylamine- (poly) oxyethylene / (poly) oxypropylene adduct, 2-hexyldecylamine- (Poly) oxyethylene / (poly) oxypropylene adduct, heptadecylamine- (poly) oxyethylene / (poly) oxypropylene adduct, octadecylamine- (poly) oxyethylene / (poly) oxypropylene adduct, nonadesylamine -(Poly) oxyethylene / (poly) oxypropylene adduct, icosylamine- (poly) oxyethylene / (poly) oxypropylene adduct, henicosylamine- (poly) oxyethylene / (poly) oxypropylene adduct, Docosylamine- (poly) oxyethylene / (poly) oxypropylene adduct, tricosylamine- (poly) oxyethylene / (poly) oxypropylene adduct, tetracosylamine- (poly) oxyethylene / (poly) oxypropylene adduct , Decenylamine- (poly) oxyethylene / (poly) oxypropylene adduct, undecenylamine- (poly) oxyethylene / (poly) oxypropylene adduct, dodecenylamine- (poly) oxyethylene / (poly) oxypropylene adduct , Tridecenylamine- (poly) oxyethylene- (poly) oxypropylene adduct, tetradecenylamine- (poly) oxyethylene- (poly) oxypropylene adduct, pentadecenylamine- (poly) oxyethylene-( Poly) oxypropylene adduct, hexadecenylamine- (poly) oxyethylene / (poly) oxypropylene adduct, heptadecenylamine- (poly) oxyethylene / (poly) oxypropylene adduct, octadecenylamine- (Poly) Oxyethylene ・ (Poly) Oxypropylene Additive, Nonadesenylamine- (Poly) Oxyethylene ・(Poly) oxypropylene adduct, icosenylamine- (poly) oxyethylene / (poly) oxypropylene adduct, henicosenylamine- (poly) oxyethylene / (poly) oxypropylene adduct, docosenylamine- (poly) oxyethylene -(Poly) oxypropylene adduct, tricosenylamine- (poly) oxyethylene- (poly) oxypropylene adduct, tetracosenylamine- (poly) oxyethylene- (poly) oxypropylene adduct, beef aminium- ( Poly) Oxyethylene / (Poly) Oxypropylene Additive, Hardened Beef Aminium- (Poly) Oxyethylene / (Poly) Oxypropylene Additive, Tetradecylamine- (Poly) Oxyethylene / (Poly) Oxypropylene / (Poly) Oxybutylene adduct, pentadecylamine- (poly) oxyethylene, (poly) oxypropylene, (poly) oxybutylene adduct, hexadecylamine- (poly) oxyethylene, (poly) oxypropylene, (poly) oxybutylene Additives, 2-hexyldecylamine- (poly) oxyethylene, (poly) oxypropylene, (poly) oxybutylene adduct, heptadecylamine- (poly) oxyethylene, (poly) oxypropylene, (poly) oxybutylene Additives, octadecylamine- (poly) oxyethylene, (poly) oxypropylene, (poly) oxybutylene adducts, tetradecenylamine- (poly) oxyethylene, (poly) oxypropylene, (poly) oxybutylene adducts , Pentadecenylamine- (poly) oxyethylene, (poly) oxypropylene, (poly) oxybutylene adduct, hexadecenylamine- (poly) oxyethylene, (poly) oxypropylene, (poly) oxybutylene adduct , Heptadecenylamine- (poly) oxyethylene, (poly) oxypropylene, (poly) oxybutylene adduct, octadecenylamine- (poly) oxyethylene, (poly) oxypropylene, (poly) oxybutylene adduct , Beef Amin- (Poly) Oxyethylene / (Poly) Oxypropylene / (Poly) Oxybutylene Additives, Hardened Beef Amin- (Poly) Oxyethylene / (Poly) Oxypropylene / (Poly) Oxybutylene Additives, Hardened Beef Fat Examples thereof include amine- (poly) oxyethylene and (poly) oxybutylene adduct.

これらの中でも、テトラデシルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、ペンタデシルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、ヘキサデシルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、２－ヘキシルデシルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、ヘプタデシルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、オクタデシルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、テトラデセニルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、ペンタデセニルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、ヘキサデセニルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、ヘプタデセニルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、オクタデセニルアミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、牛脂アミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物、硬化牛脂アミン－（ポリ）オキシエチレン・（ポリ）オキシプロピレン付加物等を挙げることができる。 Among these, tetradecylamine- (poly) oxyethylene- (poly) oxypropylene adduct, pentadecylamine- (poly) oxyethylene- (poly) oxypropylene adduct, hexadecylamine- (poly) oxyethylene- (Poly) oxypropylene adduct, 2-hexyldecylamine- (poly) oxyethylene / (poly) oxypropylene adduct, heptadecylamine- (poly) oxyethylene / (poly) oxypropylene adduct, octadecylamine-( Poly) oxyethylene / (poly) oxypropylene adduct, tetradecenylamine- (poly) oxyethylene / (poly) oxypropylene adduct, pentadecenylamine- (poly) oxyethylene / (poly) oxypropylene adduct , Hexadecenylamine- (poly) oxyethylene- (poly) oxypropylene adduct, heptadecenylamine- (poly) oxyethylene- (poly) oxypropylene adduct, octadecenylamine- (poly) oxyethylene- Examples thereof include (poly) oxypropylene adduct, beef aminium- (poly) oxyethylene / (poly) oxypropylene adduct, and cured beef aminium- (poly) oxyethylene / (poly) oxypropylene adduct.

（１－１ａ）ポリアルキレンオキシド付加物の製造方法：
一般式（１）で示されるポリアルキレンオキシド付加物の製造方法は、特に制限はないが、例えば、触媒の存在下で、特定のアルキルアミンに特定のオキシアルキレンを付加させることにより一般式（１）で表されるポリアルキレンオキシド付加物を製造する方法などを挙げることができる。 (1-1a) Method for producing polyalkylene oxide adduct:
The method for producing the polyalkylene oxide adduct represented by the general formula (1) is not particularly limited, but for example, by adding a specific oxyalkylene to a specific alkylamine in the presence of a catalyst, the general formula (1) is used. ), And the like, a method for producing the polyalkylene oxide adduct represented by).

ここで、触媒としては、アルカリ金属、アルカリ土類金属やそれらの水酸化物、アルカリ金属水素化物、アルコラート等のアルカリ触媒やルイス酸触媒、複合金属触媒などを挙げることができる。これらの中でも、アルカリ触媒が好ましい。 Here, examples of the catalyst include alkali catalysts such as alkali metals, alkaline earth metals and their hydroxides, alkali metal hydrides, and alcoholates, Lewis acid catalysts, and composite metal catalysts. Among these, an alkaline catalyst is preferable.

アルカリ触媒としては、具体的には、水酸化ナトリウム、水酸化カリウム、ナトリウムメトキシド、カリウムメトキシド、カリウムブトキシドなどを挙げることができる。 Specific examples of the alkaline catalyst include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, potassium butoxide and the like.

触媒は、付加反応後に中和し、除去することも可能であるが、付加反応液中に含有したままでもよい。 The catalyst can be neutralized and removed after the addition reaction, but it may remain contained in the addition reaction solution.

（１－２）酸：
酸は、分子量が５００以下のものであり、このような酸を含有することによって、分離安定性、乳化安定性、及び他の水硬性組成物用添加剤との相溶性に優れた水硬性組成物用消泡剤とすることができる。より具体的には、一般式（１）で示されるポリアルキレンオキシド付加物は、優れた消泡性能を発揮するため泡膜に対して難溶性を示すものであるが、難溶性であると、減水剤との分離を引き起こし、コンクリート等の水硬性組成物中において空気量のばらつきが発生する傾向がある。そこで、水硬性組成物用消泡剤には、泡膜に対する難溶性以外に、減水剤との分離を防止するという観点から、減水剤に対する相溶性の性能も要求される。このような２つの性能を備えるという観点において、消泡性能を有する上記特定のポリアルキレンオキシド付加物に、上記酸を配合することが重要となる。 (1-2) Acid:
The acid has a molecular weight of 500 or less, and by containing such an acid, it has an excellent water-hardness composition with excellent separation stability, emulsion stability, and compatibility with other additives for water-hard composition. It can be used as a defoaming agent for physical objects. More specifically, the polyalkylene oxide adduct represented by the general formula (1) exhibits poor solubility in a foam film in order to exhibit excellent defoaming performance, but it is said that the polyalkylene oxide adduct is poorly soluble. It causes separation from the water reducing agent and tends to cause variation in the amount of air in the hydraulic composition such as concrete. Therefore, the defoaming agent for hydraulic composition is required to have compatibility with the water reducing agent from the viewpoint of preventing separation from the water reducing agent, in addition to being poorly soluble in the foam film. From the viewpoint of having such two performances, it is important to add the acid to the specific polyalkylene oxide adduct having defoaming performance.

酸としては、分子量が５００以下のものである限り特に制限はないが、例えば、クエン酸、硫酸、メタンスルホン酸、リンゴ酸、乳酸、マレイン酸、酒石酸、リン酸、フマル酸、オレイン酸、ドデシルベンゼンスルホン酸、シュウ酸、グルコン酸、コハク酸、酢酸、フタル酸、塩酸、硝酸、イタコン酸、メタクリル酸、アクリル酸、安息香酸などを挙げることができる。なお、これらの酸は、１種類だけであってもよいし、２種以上であってもよい。 The acid is not particularly limited as long as it has a molecular weight of 500 or less, but for example, citric acid, sulfuric acid, methanesulfonic acid, malic acid, lactic acid, maleic acid, tartrate acid, phosphoric acid, fumaric acid, oleic acid and dodecyl. Examples thereof include benzenesulfonic acid, oxalic acid, gluconic acid, succinic acid, acetic acid, phthalic acid, hydrochloric acid, nitrate, itaconic acid, methacrylic acid, acrylic acid and benzoic acid. In addition, these acids may be only one kind, or may be two or more kinds.

（１－３）当量（ＥＱ）：
本発明の水硬性組成物用消泡剤は、式（３）で示される当量（ＥＱ）が所定の範囲であることが好ましい。即ち、式（３）で示される当量（ＥＱ）を満たすことで、一般式（１）で示されるポリアルキレンオキシド付加物と酸とが特に良好な含有割合となる。 (1-3) Equivalent (EQ):
The defoaming agent for a hydraulic composition of the present invention preferably has an equivalent (EQ) represented by the formula (3) in a predetermined range. That is, by satisfying the equivalent (EQ) represented by the formula (3), the content ratio of the polyalkylene oxide adduct represented by the general formula (1) and the acid becomes particularly good.

具体的には、式（３）で示される当量（ＥＱ）が０．７～３．５の範囲内であることが好ましく、０．７～３．２の範囲内であることが更に好ましく、０．８～３．０の範囲内であることが更に好ましい。このような範囲とすることによって、分離安定性及び乳化安定性が更に向上することになる。上記当量（ＥＱ）が下限値未満であったり、上限値超であったりすると、分離安定性または乳化安定性が十分に発揮されないおそれがある。 Specifically, the equivalent (EQ) represented by the formula (3) is preferably in the range of 0.7 to 3.5, more preferably in the range of 0.7 to 3.2. It is more preferably in the range of 0.8 to 3.0. By setting it in such a range, the separation stability and the emulsification stability will be further improved. If the equivalent (EQ) is less than the lower limit value or exceeds the upper limit value, separation stability or emulsification stability may not be sufficiently exhibited.

Figure 0007012313000007
（但し、式（３）中、Ｗは、酸から求められる酸価である。ｂは、一般式（１）で示されるポリアルキレンオキシド付加物と酸の含有割合の合計を１００質量％とした場合における酸の含有割合（質量％）である。Ｖは、一般式（１）で示されるポリアルキレンオキシド付加物から求められるアミン価である。ａは、一般式（１）で示されるポリアルキレンオキシド付加物と酸の含有割合の合計を１００質量％とした場合における一般式（１）で示されるポリアルキレンオキシド付加物の含有割合（質量％）である。）
Figure 0007012313000007
 (However, in the formula (3), W is the acid value obtained from the acid. B is the total content ratio of the polyalkylene oxide adduct represented by the general formula (1) and the acid to be 100% by mass. The acid content ratio (% by mass) in the case. V is the amine value obtained from the polyalkylene oxide adduct represented by the general formula (1). A is the polyalkylene represented by the general formula (1). It is the content ratio (mass%) of the polyalkylene oxide adduct represented by the general formula (1) when the total content ratio of the oxide adduct and the acid is 100% by mass.

酸や、一般式（１）で示されるポリアルキレンオキシド付加物は、２種類以上を併用することができる。このように２種類以上を併用する場合、酸の酸価（Ｗ）及び一般式（１）で示されるポリアルキレンオキシド付加物のアミン価（Ｖ）は、以下のように算出できる。即ち、２種類以上の酸を混合し併用する場合、混合した酸の酸価（Ｗ）を測定すればよく、また、２種類以上の一般式（１）で示されるポリアルキレンオキシド付加物を併用する場合、一般式（１）で示されるポリアルキレンオキシド付加物の混合物のアミン価（Ｖ）を測定すればよい。それぞれ混合した酸と一般式（１）で示されるポリアルキレンオキシド付加物の混合物の合計を１００質量％とし、混合した酸の含有割合（ｂ）と一般式（１）で示されるポリアルキレンオキシド付加物の混合物の含有割合（ａ）を用いて上記式（３）により当量（ＥＱ）を求めることができる。 Two or more kinds of acids and polyalkylene oxide adducts represented by the general formula (1) can be used in combination. When two or more kinds are used in combination as described above, the acid value (W) of the acid and the amine value (V) of the polyalkylene oxide adduct represented by the general formula (1) can be calculated as follows. That is, when two or more kinds of acids are mixed and used in combination, the acid value (W) of the mixed acids may be measured, and two or more kinds of polyalkylene oxide adducts represented by the general formula (1) may be used in combination. In this case, the amine value (V) of the mixture of the polyalkylene oxide adduct represented by the general formula (1) may be measured. The total of the mixture of the mixed acid and the polyalkylene oxide adduct represented by the general formula (1) is 100% by mass, and the content ratio (b) of the mixed acid and the polyalkylene oxide adduct represented by the general formula (1) are added. The equivalent (EQ) can be determined by the above formula (3) using the content ratio (a) of the mixture of the substances.

（１－４）その他の成分：
本発明の水硬性組成物用消泡剤は、一般式（１）で示されるポリアルキレンオキシド付加物及び酸以外に、その他の成分を更に含有していてもよい。このような他の成分としては、例えば、アルキルアミンや低級アルコール等の溶媒や、ポリアルキレンオキシド等の副生物などを挙げることができる。 (1-4) Other ingredients:
The defoaming agent for a hydraulic composition of the present invention may further contain other components in addition to the polyalkylene oxide adduct and the acid represented by the general formula (1). Examples of such other components include solvents such as alkylamines and lower alcohols, and by-products such as polyalkylene oxides.

その他の成分の含有割合としては、例えば、水硬性組成物用消泡剤全体の０～１０質量％とすることができ、更に、０～５質量％とすることができる。 The content ratio of the other components may be, for example, 0 to 10% by mass of the entire defoaming agent for the hydraulic composition, and further may be 0 to 5% by mass.

本発明の水硬性組成物用消泡剤は、土木、建築、二次製品等の水硬性結合材を含有する水硬性組成物に用いる添加剤として使用することができる。この水硬性組成物としては、具体的には、ペースト、モルタル、コンクリート等が挙げられる。 The defoaming agent for a hydraulic composition of the present invention can be used as an additive used in a hydraulic composition containing a hydraulic binder for civil engineering, construction, secondary products and the like. Specific examples of this hydraulic composition include pastes, mortars, concrete and the like.

本発明の水硬性組成物用消泡剤は、既存の混和剤と併用することができる。混和剤としては、例えば、ＡＥ減水剤、高性能ＡＥ減水剤、ＡＥ剤、消泡剤、収縮低減剤、増粘剤、硬化促進剤等を挙げることができる。 The defoaming agent for a hydraulic composition of the present invention can be used in combination with an existing admixture. Examples of the admixture include an AE water reducing agent, a high-performance AE water reducing agent, an AE agent, a defoaming agent, a shrinkage reducing agent, a thickener, a curing accelerator and the like.

本発明の水硬性組成物用消泡剤と併用する混和剤は、水硬性組成物用消泡剤との優れた相溶性を得るという観点から、そのｐＨが８以下であることが好ましく、７以下であることがより好ましく、６以下であることが特に好ましい。 The pH of the admixture used in combination with the defoaming agent for a water-hard composition of the present invention is preferably 8 or less, preferably 7 or less, from the viewpoint of obtaining excellent compatibility with the defoaming agent for a water-hard composition. It is more preferably less than or equal to, and particularly preferably 6 or less.

（２）水硬性組成物用消泡剤の水性液：
本発明の水硬性組成物用消泡剤の水性液は、上述した本発明の水硬性組成物用消泡剤、及び水を含有するものである。このような水硬性組成物用消泡剤の水性液は、本発明の水硬性組成物用消泡剤を含有するので、分離安定性に優れ、水で希釈したときの乳化安定性にも優れ、他の水硬性組成物用添加剤との相溶性にも優れ、少量で優れた消泡性を有する。 (2) Aqueous solution of antifoaming agent for hydraulic composition:
The aqueous solution of the defoaming agent for a water-hardening composition of the present invention contains the above-mentioned defoaming agent for a water-hardening composition of the present invention and water. Since the aqueous solution of such a defoaming agent for a water-hard composition contains the defoaming agent for a water-hard composition of the present invention, it is excellent in separation stability and emulsification stability when diluted with water. It also has excellent compatibility with other additives for water-hardening compositions, and has excellent defoaming properties even in a small amount.

水硬性組成物用消泡剤の水性液は、水の含有量について特に制限はないが、ポリアルキレンオキシド付加物、酸、及び水の含有割合の合計を１００質量％とすると、水を０．０１～２５質量％の割合で含有することが好ましく、０．０５～１５質量％の割合で含有することが更に好ましい。このようにすると、分離安定性が更に優れるようになる。 The aqueous solution of the defoaming agent for a water-hard composition is not particularly limited in terms of water content, but when the total content of the polyalkylene oxide adduct, acid, and water is 100% by mass, water is 0. It is preferably contained in a proportion of 01 to 25% by mass, and more preferably in a proportion of 0.05 to 15% by mass. By doing so, the separation stability becomes further excellent.

（３）水硬性組成物：
本発明の水硬性組成物は、本発明の水硬性組成物用消泡剤を含有するものであり、より具体的には、水硬性結合材、水、細骨材、及び、粗骨材を更に含有する。このような水硬性組成物は、本発明の水硬性組成物用消泡剤を含有しているので、当該水硬性組成物用消泡剤と減水剤等の他の水硬性組成物用添加剤との相溶性が良好である。そのため、本発明の水硬性組成物は、タンク等で消泡剤と他の水硬性組成物用添加剤等を混合した混合液を攪拌せず静置しても、混合液が均一に保たれ、空気量のばらつきが少ないというものである。 (3) Hydraulic composition:
The hydraulic composition of the present invention contains the antifoaming agent for the hydraulic composition of the present invention, and more specifically, the hydraulic binder, water, fine aggregate, and coarse aggregate are used. Further contained. Since such a hydraulic composition contains the defoaming agent for the hydraulic composition of the present invention, the defoaming agent for the hydraulic composition and other additives for the hydraulic composition such as a water reducing agent are contained. Good compatibility with. Therefore, in the hydraulic composition of the present invention, the mixed solution of the defoaming agent and other additives for the hydraulic composition is kept uniform even if the mixed solution is allowed to stand without stirring in a tank or the like. , There is little variation in the amount of air.

水硬性結合材としては、例えば、普通ポルトランドセメント、早強ポルトランドセメント、中庸熱ポルトランドセメント、低熱ポルトランドセメント等の各種ポルトランドセメントの他に、高炉セメント、フライアッシュセメント、シリカフュームセメント等の各種混合セメントが挙げられる。 Examples of the water-hardening binder include various Portland cements such as ordinary Portland cement, early-strength Portland cement, moderate heat Portland cement, and low heat Portland cement, as well as various mixed cements such as blast furnace cement, fly ash cement, and silica fume cement. Can be mentioned.

水硬性結合材は、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、膨張剤などの各種混和材を上記各種セメントと併用してもよい。 As the hydraulic binder, various admixtures such as fly ash, blast furnace slag fine powder, limestone fine powder, stone powder, silica fume, and leavening agent may be used in combination with the above-mentioned various cements.

細骨材としては、例えば、川砂、山砂、陸砂、海砂、珪砂、砕砂、各種スラグ細骨材などが挙げられる。 Examples of the fine aggregate include river sand, mountain sand, land sand, sea sand, silica sand, crushed sand, and various slag fine aggregates.

粗骨材としては、例えば、川砂利、山砂利、陸砂利、砕石、各種スラグ粗骨材、軽量骨材などが挙げられる。 Examples of the coarse aggregate include river gravel, mountain gravel, land gravel, crushed stone, various slag coarse aggregates, and lightweight aggregates.

本発明の水硬性組成物は、水硬性結合材１００質量部に対して、本発明の水硬性組成物用消泡剤を０．０００１～０．１質量部の割合で含有することができる。このような割合で本発明の水硬性組成物用消泡剤を含有すると、更に高い消泡性や気泡安定性、併用する混和剤への更に高い相溶性が発揮される。 The water-hardening composition of the present invention can contain the defoaming agent for the water-hardening composition of the present invention in a proportion of 0.0001 to 0.1 parts by mass with respect to 100 parts by mass of the water-hardening binder. When the defoaming agent for a water-hardening composition of the present invention is contained in such a ratio, higher defoaming property, bubble stability, and higher compatibility with the admixture used in combination are exhibited.

本発明の水硬性組成物は、その水／結合材比（Ｗ／Ｃ）は、特に限定されず適宜設定することができ、一般的に採用される水／結合材比において、高い効果を発現する。 The water / binder ratio (W / C) of the hydraulic composition of the present invention is not particularly limited and can be appropriately set, and a high effect is exhibited at a generally adopted water / binder ratio. do.

なお、本発明の水硬性組成物は、上述した、水硬性結合材、細骨材、粗骨材、及び、本発明の水硬性組成物用消泡剤以外に、その他の成分を更に含有していてもよい。このような他の成分としては、例えば、ＡＥ調整剤、ＡＥ減水剤、高性能ＡＥ減水剤、流動化剤、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、防錆剤等を挙げることができる。 The hydraulic composition of the present invention further contains other components in addition to the above-mentioned hydraulic binder, fine aggregate, coarse aggregate, and defoaming agent for the hydraulic composition of the present invention. May be. Examples of such other components include AE adjusters, AE water reducing agents, high-performance AE water reducing agents, fluidizing agents, defoaming agents, condensation retarders, curing accelerators, drying shrinkage reducing agents, preservatives, and waterproofing agents. Agents, rust preventives and the like can be mentioned.

以下、本発明を実施例に基づいて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.

（合成例１）水硬性組成物用消泡剤（Ｎ－１）の合成：
オートクレーブにオクタデシルアミン４９０．４ｇを仕込んだ。その後、オートクレーブ内を十分に窒素で置換し、攪拌しながら１５０℃に維持してエチレンオキサイド１６５ｇを圧力０．５ＭＰａを維持するように圧入した。そして、当該温度で０．５時間熟成し、６０℃まで冷却した後、触媒として水酸化カリウム粉末を５．０ｇ投入した。その後、オートクレーブ内を十分に窒素で置換し、攪拌しながら１５０℃に維持して１，２－プロピレンオキサイド４３３９ｇを圧力０．５ＭＰａを維持するように圧入した。そして、当該温度で１時間熟成し、反応を完結させた。その後、キョーワード６００（協和化学工業社製）で処理し触媒を吸着、濾過し、オクタデシルアミン－ポリオキシエチレン（２モル）・ポリオキシプロピレン（４０モル）付加物（Ｎ－１）を得た。 (Synthesis Example 1) Synthesis of antifoaming agent (N-1) for hydraulic composition:
490.4 g of octadecylamine was charged in the autoclave. Then, the inside of the autoclave was sufficiently replaced with nitrogen, and 165 g of ethylene oxide was press-fitted so as to maintain a pressure of 0.5 MPa while maintaining the temperature at 150 ° C. with stirring. Then, after aging at the temperature for 0.5 hour and cooling to 60 ° C., 5.0 g of potassium hydroxide powder was added as a catalyst. Then, the inside of the autoclave was sufficiently replaced with nitrogen, and the temperature was maintained at 150 ° C. with stirring, and 4339 g of 1,2-propylene oxide was press-fitted so as to maintain a pressure of 0.5 MPa. Then, it was aged at the temperature for 1 hour to complete the reaction. Then, it was treated with Kyoward 600 (manufactured by Kyowa Chemical Industry Co., Ltd.) to adsorb and filter the catalyst to obtain an octadecylamine-polyoxyethylene (2 mol) / polyoxypropylene (40 mol) adduct (N-1). ..

（合成例２～５）水硬性組成物用消泡剤（Ｎ－２）～（Ｎ－５）の合成：
原料のアミン及び仕込み比率を変更したこと以外は、水硬性組成物用消泡剤（Ｎ－１）と同様にして、水硬性組成物用消泡剤（Ｎ－２）～（Ｎ－５）を合成した。なお、牛脂アミンは、ニッサンアミンＡＢＴ－２（日油社製、アミン価２１４．０ｍｇ／ｇ）を使用した。 (Synthesis Examples 2 to 5) Synthesis of antifoaming agents (N-2) to (N-5) for hydraulic compositions:
Defoaming agents for hydraulic composition (N-2) to (N-5) in the same manner as the defoaming agent for hydraulic composition (N-1) except that the amine of the raw material and the charging ratio were changed. Was synthesized. As the beef tallow amine, Nissan Amine ABT-2 (manufactured by NOF CORPORATION, amine value 214.0 mg / g) was used.

（合成例６）水硬性組成物用消泡剤（Ｎ－６）の合成：
オートクレーブに硬化牛脂アミン（ＦＥＴＡＮＡＭＩＮＥ ＡＨＴ、ＳＯＬＶＡＹ社製、アミン価２１３．７ｍｇ／ｇ）を４３２．９ｇ仕込んだ。その後、オートクレーブ内を十分に窒素で置換し、攪拌しながら１５０℃に維持してエチレンオキサイド２１８ｇを圧力０．５ＭＰａを維持しながら圧入した。そして、当該温度で０．５時間熟成し、６０℃まで冷却した後、触媒として水酸化カリウム粉末を１０．０ｇ投入した。その後、オートクレーブ内を十分に窒素で置換し、攪拌しながら１２０℃に維持してエチレンオキサイド５０８ｇを圧力０．５ＭＰａを維持しながら圧入した。そして、当該温度で１時間熟成し、その後、温度を１５０℃まで昇温し、１，２－プロピレンオキサイド３８３０ｇを圧力０．５ＭＰａを維持しながら圧入した。その後、当該温度で１時間熟成し、反応を完結させた。その後、キョーワード６００（協和化学工業社製）で処理し触媒を吸着、濾過し、硬化牛脂アミン－ポリオキシエチレン（１０モル）・ポリオキシプロピレン（４０モル）付加物（Ｎ－６）を得た。 (Synthesis Example 6) Synthesis of antifoaming agent (N-6) for hydraulic composition:
432.9 g of cured beef tallow amine (FETANAMINE AHT, manufactured by SOLVAY, amine value 213.7 mg / g) was charged into the autoclave. Then, the inside of the autoclave was sufficiently replaced with nitrogen, and 218 g of ethylene oxide was press-fitted while maintaining a pressure of 0.5 MPa while maintaining the temperature at 150 ° C. with stirring. Then, after aging at the temperature for 0.5 hour and cooling to 60 ° C., 10.0 g of potassium hydroxide powder was added as a catalyst. Then, the inside of the autoclave was sufficiently replaced with nitrogen, and 508 g of ethylene oxide was press-fitted while maintaining the pressure at 120 ° C. with stirring. Then, the mixture was aged at the temperature for 1 hour, then the temperature was raised to 150 ° C., and 3830 g of 1,2-propylene oxide was press-fitted while maintaining a pressure of 0.5 MPa. Then, it was aged at the said temperature for 1 hour, and the reaction was completed. After that, it was treated with Kyoward 600 (manufactured by Kyowa Chemical Industry Co., Ltd.) to adsorb and filter the catalyst to obtain a cured beef tallow amine-polyoxyethylene (10 mol) / polyoxypropylene (40 mol) adduct (N-6). rice field.

（合成例７～１６）水硬性組成物用消泡剤（Ｎ－７）～（Ｎ－１１）、（Ｎ－１３）、（Ｎ－１５）～（Ｎ－１７）及び（ｒＮ－１）の合成：
原料のアミン及び仕込み比率を変更したこと以外は、水硬性組成物用消泡剤（Ｎ－６）と同様にして、水硬性組成物用消泡剤（Ｎ－７）～（Ｎ－１１）、（Ｎ－１３）、（Ｎ－１５）～（Ｎ－１７）及び（ｒＮ－１）を合成した。 (Synthetic Examples 7 to 16) Antifoaming agents for hydraulic compositions (N-7) to (N-11), (N-13), (N-15) to (N-17) and (rN-1) Synthesis:
Defoaming agents for hydraulic composition (N-7) to (N-11) in the same manner as the defoaming agent for hydraulic composition (N-6) except that the amine of the raw material and the charging ratio were changed. , (N-13), (N-15) to (N-17) and (rN-1) were synthesized.

（合成例１７）水硬性組成物用消泡剤（Ｎ－１２）の合成：
ガラス製の反応容器に、メトキシポリオキシプロピレン（２０モル）・ポリオキシエチレン（７モル）ブロック付加物を２９７０ｇ投入し、更に、トリエチルアミンを２０２４ｇ投入した後、０℃に冷却した。その後、反応容器内を十分に窒素で置換し、攪拌しながらメシルクロライド２５２ｇを滴下した後、２５℃まで昇温し、２時間攪拌した。その後、反応系を０℃まで冷却し、ｎ－ブチルアミン７３ｇをエタノール６３０ｇに溶解した溶液を、徐々に滴下した。滴下終了後、４０℃まで昇温し、４時間熟成し、精製し、ｎ－ブチルアミン－メトキシポリオキシエチレン（７モル）・ポリオキシプロピレン（２０モル）付加物（Ｎ－１２）を得た。 (Synthesis Example 17) Synthesis of antifoaming agent (N-12) for hydraulic composition:
In a glass reaction vessel, 2970 g of a methoxypolyoxypropylene (20 mol) / polyoxyethylene (7 mol) block adduct was added, and 2024 g of triethylamine was further added, and then the mixture was cooled to 0 ° C. Then, the inside of the reaction vessel was sufficiently replaced with nitrogen, 252 g of mesylate chloride was added dropwise while stirring, the temperature was raised to 25 ° C., and the mixture was stirred for 2 hours. Then, the reaction system was cooled to 0 ° C., and a solution prepared by dissolving 73 g of n-butylamine in 630 g of ethanol was gradually added dropwise. After completion of the dropping, the temperature was raised to 40 ° C., and the mixture was aged for 4 hours and purified to obtain an adduct (N-12) of n-butylamine-methoxypolyoxyethylene (7 mol) and polyoxypropylene (20 mol).

（合成例１８）水硬性組成物用消泡剤（Ｎ－１４）の合成：
オートクレーブに牛脂アミン（ニッサンアミンＡＢＴ－２、日油社製、アミン価２１４．０ｍｇ／ｇ）を４３２．９ｇ仕込んだ。その後、オートクレーブ内を十分に窒素で置換し、攪拌しながら１５０℃に維持してエチレンオキサイド１４５ｇを圧力０．５ＭＰａを維持しながら圧入した。そして、当該温度で０．５時間熟成し、６０℃まで冷却した後、触媒として水酸化カリウム粉末を１０．０ｇ投入した。その後、オートクレーブ内を十分に窒素で置換し、攪拌しながら１５０℃まで昇温し、１，２－プロピレンオキサイド３８３０ｇ及び１，２－ブチレンオキシド２３６５ｇを圧力０．５ＭＰａを維持しながら圧入した。その後、当該温度で１時間熟成し、反応を完結させた。その後、キョーワード６００（協和化学工業社製）で処理し触媒を吸着、濾過し、牛脂アミン－ポリオキシエチレン（２モル）・ポリオキシプロピレン（４０モル）・ポリオキシブチレン（２０モル）付加物（Ｎ－１４）を得た。 (Synthesis Example 18) Synthesis of antifoaming agent (N-14) for hydraulic composition:
432.9 g of beef tallow amine (Nissan Amine ABT-2, manufactured by NOF CORPORATION, amine value 214.0 mg / g) was charged into the autoclave. Then, the inside of the autoclave was sufficiently replaced with nitrogen, and 145 g of ethylene oxide was press-fitted while maintaining a pressure of 0.5 MPa while maintaining the temperature at 150 ° C. with stirring. Then, after aging at the temperature for 0.5 hour and cooling to 60 ° C., 10.0 g of potassium hydroxide powder was added as a catalyst. Then, the inside of the autoclave was sufficiently replaced with nitrogen, the temperature was raised to 150 ° C. with stirring, and 3830 g of 1,2-propylene oxide and 2365 g of 1,2-butylene oxide were press-fitted while maintaining a pressure of 0.5 MPa. Then, it was aged at the said temperature for 1 hour, and the reaction was completed. After that, it is treated with Kyoward 600 (manufactured by Kyowa Kagaku Kogyo Co., Ltd.) to adsorb and filter the catalyst, and beef tallow amine-polyoxyethylene (2 mol), polyoxypropylene (40 mol), polyoxybutylene (20 mol) adduct. (N-14) was obtained.

（合成例１９）水硬性組成物用消泡剤（ｒＮ－２）の合成：
オートクレーブにステアリルアルコール４６０．１ｇと触媒として水酸化カリウム粉末５．０ｇを仕込んだ。そして、オートクレーブ内を十分に窒素で置換し、攪拌しながら１５０℃に維持してエチレンオキサイド４６３．１２ｇを圧力０．５ＭＰａを維持しながら圧入した。当該温度で１時間熟成し、攪拌しながら１５０℃に維持して１，２－プロピレンオキサイド４０７１ｇを圧力０．５ＭＰａを維持しながら圧入した。そして、当該温度で１時間熟成し、反応を完結させた。その後、触媒を除去し、ステアリルアルコール－ポリオキシエチレン（６モル）・ポリオキシプロピレン（４０モル）付加物（ｒＮ－２）を得た。 (Synthesis Example 19) Synthesis of antifoaming agent (rN-2) for hydraulic composition:
460.1 g of stearyl alcohol and 5.0 g of potassium hydroxide powder as a catalyst were charged into the autoclave. Then, the inside of the autoclave was sufficiently replaced with nitrogen, and the pressure was maintained at 150 ° C. with stirring, and 463.12 g of ethylene oxide was press-fitted while maintaining the pressure of 0.5 MPa. The mixture was aged at the same temperature for 1 hour, maintained at 150 ° C. with stirring, and 4071 g of 1,2-propylene oxide was press-fitted while maintaining a pressure of 0.5 MPa. Then, it was aged at the temperature for 1 hour to complete the reaction. Then, the catalyst was removed to obtain a stearyl alcohol-polyoxyethylene (6 mol) / polyoxypropylene (40 mol) adduct (rN-2).

（合成例２０）水硬性組成物用消泡剤（ｒＮ－３）の合成：
原料のアルコールをドデシルアルコールとし、仕込み比を変更したこと以外は、水硬性組成物用消泡剤（ｒＮ－２）と同様にして、水硬性組成物用消泡剤（ｒＮ－３）を合成した。 (Synthesis Example 20) Synthesis of antifoaming agent (rN-3) for hydraulic composition:
A defoaming agent for hydraulic composition (rN-3) was synthesized in the same manner as the defoaming agent for hydraulic composition (rN-2) except that the raw material alcohol was dodecyl alcohol and the charging ratio was changed. did.

（合成例２１）水硬性組成物用消泡剤（ｒＮ－４）の合成：
オートクレーブにトリエチレングリコール７５０．９ｇを仕込んだ。その後、触媒として水酸化カリウム粉末４．７ｇを仕込んだ。そして、オートクレーブ内を十分に窒素で置換し、攪拌しながら１５０℃に維持して１，２－プロピレンオキサイド８７１５ｇを圧入（０．４ＭＰａ）した。そして、当該温度で１時間熟成し、反応を完結させた。その後、触媒を除去し、ポリオキシエチレン（３モル）・ポリオキシプロピレン（３０モル）縮合物（ｒＮ－４）を得た。 (Synthesis Example 21) Synthesis of antifoaming agent (rN-4) for hydraulic composition:
750.9 g of triethylene glycol was charged in the autoclave. Then, 4.7 g of potassium hydroxide powder was charged as a catalyst. Then, the inside of the autoclave was sufficiently replaced with nitrogen, and the temperature was maintained at 150 ° C. with stirring, and 8715 g of 1,2-propylene oxide was press-fitted (0.4 MPa). Then, it was aged at the temperature for 1 hour to complete the reaction. Then, the catalyst was removed to obtain a polyoxyethylene (3 mol) -polyoxypropylene (30 mol) condensate (rN-4).

以上で合成した水硬性組成物用消泡剤（Ｎ－１）～（Ｎ－１７）、（ｒＮ－１）～（ｒＮ－４）の内容を表１に示す。 Table 1 shows the contents of the defoaming agents (N-1) to (N-17) and (rN-1) to (rN-4) for the hydraulic composition synthesized as described above.

Figure 0007012313000008
Figure 0007012313000008

表１中、「牛脂由来の炭化水素基」は、炭素数１４～１８の飽和・不飽和炭化水素基の混合物であり、「硬化牛脂由来の炭化水素基」は、炭素数１４～１８のアルキル基の混合物である。 In Table 1, the "hydrocarbon group derived from beef fat" is a mixture of saturated / unsaturated hydrocarbon groups having 14 to 18 carbon atoms, and the "hydrocarbon group derived from hardened beef fat" is an alkyl having 14 to 18 carbon atoms. A mixture of groups.

表１中、アミン価は、ＪＩＳ Ｋ １５５７－７に準拠して測定した。 In Table 1, the amine value was measured according to JIS K 1557-7.

次に、水硬性組成物用消泡剤に使用した酸について、以下の表２に示す。 Next, the acids used in the defoaming agent for the hydraulic composition are shown in Table 2 below.

Figure 0007012313000009
Figure 0007012313000009

酸価は、ＪＩＳ Ｋ ００７０に準拠して電位差滴定法により測定した。 The acid value was measured by the potentiometric titration method according to JIS K 0070.

次に、水硬性組成物に使用したポリカルボン酸系減水剤の合成について以下に説明する。 Next, the synthesis of the polycarboxylic acid-based water reducing agent used in the hydraulic composition will be described below.

（合成例２２）減水剤（ＰＣ－１）の合成：
まず、水道水１５０．５ｇを反応容器に仕込み、雰囲気を窒素置換し、攪拌しながら６５℃に昇温した。その後、上記反応容器に、水２４４．９ｇ、メトキシポリ（２３モル）オキシエチレンメタクリレート３３５．３ｇ、メタクリル酸４４．６ｇ及びβーメルカプトプロピオン酸３．４ｇの混合物を２時間かけて滴下し、同時に、１０％過硫酸ソーダ水溶液５５．１ｇを３時間かけて滴下して、さらに１時間、６５℃を保持し、重合反応を行った。共重合体に、３０％水酸化ナトリウム水溶液を加えてｐＨを６に調整し、水道水で希釈することで固形分の濃度２０％である減水剤（ＰＣ－１）を得た。得られた減水剤（ＰＣ－１）を分析したところ、質量平均分子量が１８，２００であった。なお、質量平均分子量は、後述するゲルパーミエーションクロマトグラフィーにて測定した。 (Synthesis Example 22) Synthesis of water reducing agent (PC-1):
First, 150.5 g of tap water was charged into a reaction vessel, the atmosphere was replaced with nitrogen, and the temperature was raised to 65 ° C. with stirring. Then, a mixture of 244.9 g of water, 335.3 g of methoxypoly (23 mol) oxyethylene methacrylate, 44.6 g of methacrylic acid and 3.4 g of β-mercaptopropionic acid was added dropwise to the reaction vessel over 2 hours, and at the same time, simultaneously. 55.1 g of a 10% aqueous solution of sodium persulfate was added dropwise over 3 hours, and the temperature was maintained at 65 ° C. for another 1 hour to carry out a polymerization reaction. A 30% aqueous sodium hydroxide solution was added to the copolymer to adjust the pH to 6, and the mixture was diluted with tap water to obtain a water reducing agent (PC-1) having a solid content concentration of 20%. When the obtained water reducing agent (PC-1) was analyzed, the mass average molecular weight was 18,200. The mass average molecular weight was measured by gel permeation chromatography described later.

（合成例２３）減水剤（ＰＣ－２）の合成：
まず、イオン交換水７６．６ｇ及びα－（３－メチル－３－ブテニル）－ω－ヒドロキシ－ポリ（５３モル）オキシエチレン１５０．７ｇを反応容器に仕込み、攪拌しながら均一に溶解した。その後、雰囲気を窒素置換し、反応系の温度を温水浴にて６５℃に保持した。次に、１％過酸化水素水８．８ｇを３時間かけて滴下するとともに、イオン交換水３９．１ｇにアクリル酸９．６ｇを均一に溶解させた水溶液を３時間かけて滴下した。更にそれと同時に、イオン交換水７．０ｇにＬ－アスコルビン酸０．８ｇと連鎖移動剤としてチオグリコール酸０．６ｇを均一に溶解させた水溶液を４時間かけて滴下した。その後、６５℃で２時間保持し、重合反応を終了した。重合反応終了後、３０％水酸化ナトリウム水溶液を加えて反応系のｐＨを５に調整し、イオン交換水にて２０％に調整して、ビニル共重合体の２０％水溶液である減水剤（ＰＣ－２）を得た。得られた減水剤（ＰＣ－２）を分析したところ、質量平均分子量が４４０００であった。なお、質量平均分子量は、後述するゲルパーミエーションクロマトグラフィーにて測定した。 (Synthesis Example 23) Synthesis of water reducing agent (PC-2):
First, 76.6 g of ion-exchanged water and 150.7 g of α- (3-methyl-3-butenyl) -ω-hydroxy-poly (53 mol) oxyethylene were charged into a reaction vessel and uniformly dissolved with stirring. Then, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was maintained at 65 ° C. in a warm water bath. Next, 8.8 g of 1% hydrogen peroxide solution was added dropwise over 3 hours, and an aqueous solution in which 9.6 g of acrylic acid was uniformly dissolved in 39.1 g of ion-exchanged water was added dropwise over 3 hours. At the same time, an aqueous solution in which 0.8 g of L-ascorbic acid and 0.6 g of thioglycolic acid as a chain transfer agent were uniformly dissolved in 7.0 g of ion-exchanged water was added dropwise over 4 hours. Then, it was held at 65 ° C. for 2 hours to complete the polymerization reaction. After completion of the polymerization reaction, the pH of the reaction system is adjusted to 5 by adding a 30% aqueous sodium hydroxide solution, adjusted to 20% with ion-exchanged water, and a water reducing agent (PC) which is a 20% aqueous solution of the vinyl copolymer. -2) was obtained. When the obtained water reducing agent (PC-2) was analyzed, the mass average molecular weight was 44000. The mass average molecular weight was measured by gel permeation chromatography described later.

（合成例２４）減水剤（ＰＣ－３）の合成：
まず、イオン交換水７６．６ｇ及びα－メタリル－ω－ヒドロキシ－ポリ（６８モル）オキシエチレン１５８．３ｇを反応容器に仕込み、攪拌しながら均一に溶解した。その後、雰囲気を窒素置換し、反応系の温度を温水浴にて６５℃に保持した。次に、１％過酸化水素水８．８ｇを３時間かけて滴下するとともに、イオン交換水３９．１ｇにアクリル酸７．０ｇとアクリル酸ヒドロキシエチル１０．６ｇを均一に溶解させた水溶液を３時間かけて滴下した。更にそれと同時に、イオン交換水７．０ｇにＬ－アスコルビン酸０．８ｇと連鎖移動剤として３－メルカプトプロピオン酸１．１ｇを均一に溶解させた水溶液を４時間かけて滴下した。その後、６５℃で２時間保持し、重合反応を終了した。重合反応終了後、３０％水酸化ナトリウム水溶液を加えて反応系のｐＨを６に調整し、イオン交換水にて２０％に調整して、ビニル共重合体の２０％水溶液である減水剤（ＰＣ－３）を得た。得られた減水剤（ＰＣ－３）を分析したところ、質量平均分子量が３４０００であった。なお、質量平均分子量は、後述するゲルパーミエーションクロマトグラフィーにて測定した。 (Synthesis Example 24) Synthesis of water reducing agent (PC-3):
First, 76.6 g of ion-exchanged water and 158.3 g of α-metharyl-ω-hydroxy-poly (68 mol) oxyethylene were charged into a reaction vessel and uniformly dissolved with stirring. Then, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was maintained at 65 ° C. in a warm water bath. Next, 8.8 g of 1% hydrogen peroxide solution was added dropwise over 3 hours, and an aqueous solution prepared by uniformly dissolving 7.0 g of acrylic acid and 10.6 g of hydroxyethyl acrylate in 39.1 g of ion-exchanged water was added. Dropped over time. At the same time, an aqueous solution in which 0.8 g of L-ascorbic acid and 1.1 g of 3-mercaptopropionic acid as a chain transfer agent were uniformly dissolved in 7.0 g of ion-exchanged water was added dropwise over 4 hours. Then, it was held at 65 ° C. for 2 hours to complete the polymerization reaction. After completion of the polymerization reaction, the pH of the reaction system is adjusted to 6 by adding a 30% aqueous sodium hydroxide solution, adjusted to 20% with ion-exchanged water, and a water reducing agent (PC) which is a 20% aqueous solution of the vinyl copolymer. -3) was obtained. When the obtained water reducing agent (PC-3) was analyzed, the mass average molecular weight was 34000. The mass average molecular weight was measured by gel permeation chromatography described later.

［質量平均分子量の測定条件］
合成した減水剤の質量平均分子量の測定条件を以下に示す。
［ＧＰＣ法］
装置：昭和電工株式会社製 Ｓｈｏｄｅｘ ＧＰＣ－１０１
カラム：昭和電工株式会社 ＯＨＰａｋ ＳＢ－Ｇ＋ＳＢ－８０６Ｍ ＨＱ＋ＳＢ－８０６Ｍ ＨＱ
検出器：示差屈折計（ＲＩ）
溶離液：５０ｍＭ硝酸ナトリウム水溶液
流速：０．７ｍＬ／分
カラム温度：４０℃
標準物質：ＰＥＧ／ＰＥＯ（アジレント社製） [Measurement conditions for mass average molecular weight]
The measurement conditions for the mass average molecular weight of the synthesized water reducing agent are shown below.
[GPC method]
Equipment: Showa Denko Corporation Shodex GPC-101
Column: Showa Denko OHPak SB-G + SB-806M HQ + SB-806M HQ
Detector: Differential Refractometer (RI)
Eluent: 50 mM sodium nitrate aqueous solution Flow rate: 0.7 mL / min Column temperature: 40 ° C
Standard material: PEG / PEO (manufactured by Agilent)

（実施例１～１６、比較例１～５）
表３に示すように、各成分を混合して水硬性組成物用消泡剤及び水硬性組成物用消泡剤の水性液を作製した。 (Examples 1 to 16, Comparative Examples 1 to 5)
As shown in Table 3, each component was mixed to prepare an aqueous solution of a defoaming agent for a hydraulic composition and a defoaming agent for a hydraulic composition.

作製した各水硬性組成物用消泡剤の水性液（各水硬性組成物用消泡剤）について製剤安定性及び乳化安定性の評価を以下のようにして行った。結果を表３に示す。 The pharmaceutical product stability and emulsion stability of the prepared aqueous solution of the defoaming agent for the hydraulic composition (the defoaming agent for each hydraulic composition) were evaluated as follows. The results are shown in Table 3.

［製剤安定性（分離安定性）］
表３に示す割合で合計質量が１００ｇとなるように、一般式（１）で示されるポリアルキレンオキシド付加物、酸、及び水を配合し、振とう攪拌した。その後、２０℃で静置し、目視確認を行い、以下の評価基準で評価を行った。 [Pharmaceutical stability (separation stability)]
The polyalkylene oxide adduct represented by the general formula (1), an acid, and water were mixed and shaken and stirred so that the total mass was 100 g at the ratio shown in Table 3. Then, it was allowed to stand at 20 ° C., visually confirmed, and evaluated according to the following evaluation criteria.

Ｓ：非常に良好（振とう後４週間経過後の段階でも分離せず安定であった）
Ａ：良好（振とう後２週間以上４週間未満の間で分離が確認された）
Ｂ：可（振とう後１週間以上２週間未満の間で分離が確認された）
Ｃ：悪い（振とう後１週間未満の間で分離が確認された） S: Very good (stable without separation even at the stage 4 weeks after shaking)
A: Good (separation was confirmed between 2 weeks and less than 4 weeks after shaking)
B: Possible (separation was confirmed within 1 week or more and less than 2 weeks after shaking)
C: Bad (separation was confirmed within less than 1 week after shaking)

［乳化安定性］
表３に示す割合で各成分が配合された水硬性組成物用消泡剤における０．１％水溶液（水硬性組成物用消泡剤の水性液）を１００ｇ作製し、これを２０℃で静置し、その後、目視確認を行い、以下の評価基準で評価を行った。 [Emulsification stability]
100 g of a 0.1% aqueous solution (an aqueous solution of a defoaming agent for a water-hard composition) in a defoaming agent for a water-hard composition containing each component in the ratio shown in Table 3 was prepared, and this was allowed to stand at 20 ° C. After that, it was visually confirmed and evaluated according to the following evaluation criteria.

Ｓ：非常に良好（振とう後２４時間経過後の段階でも分離せず安定であった）
Ａ：良好（振とう後１２時間以上２４時間未満の間で分離が確認された）
Ｂ：可（振とう後１時間以上１２時間未満の間で分離が確認された）
Ｃ：悪い（振とう後１時間以内の間で分離が確認された） S: Very good (stable without separation even at the stage 24 hours after shaking)
A: Good (separation was confirmed between 12 hours and more and less than 24 hours after shaking)
B: Possible (separation was confirmed within 1 hour or more and less than 12 hours after shaking)
C: Bad (separation was confirmed within 1 hour after shaking)

Figure 0007012313000010
Figure 0007012313000010

表３中、「式３における当量（ＥＱ）」は、具体的には、下記式（３）により算出した。 In Table 3, the "equivalent (EQ) in the formula 3" was specifically calculated by the following formula (3).

Figure 0007012313000011
Figure 0007012313000011

なお、式（３）中、Ｗは、酸から求められる酸価である。ｂは、一般式（１）で示されるポリアルキレンオキシド付加物と酸の含有割合の合計を１００質量％とした場合における酸の含有割合（質量％）である。Ｖは、一般式（１）で示されるポリアルキレンオキシド付加物から求められるアミン価である。ａは、一般式（１）で示されるポリアルキレンオキシド付加物と酸の含有割合の合計を１００質量％とした場合における一般式（１）で示されるポリアルキレンオキシド付加物の含有割合（質量％）である。 In the formula (3), W is an acid value obtained from the acid. b is an acid content ratio (mass%) when the total content ratio of the polyalkylene oxide adduct represented by the general formula (1) and the acid is 100% by mass. V is an amine value obtained from the polyalkylene oxide adduct represented by the general formula (1). a is the content ratio (mass%) of the polyalkylene oxide adduct represented by the general formula (1) when the total content ratio of the polyalkylene oxide adduct represented by the general formula (1) and the acid is 100% by mass. ).

（実施例１７～３２、比較例６～１０）
（水硬性組成物（コンクリート組成物）の調製）
まず、表５に示すように、合成した各水硬性組成物用減水剤ＰＣ－１、ＰＣ－２、ＰＣ－３の２０００ｇに対して、水硬性組成物用消泡剤ＡＦ－１～１６、ＲＡＦ－１～５を２．０ｇ添加した混合液を調整し、よく撹拌をした。この減水剤と水硬性組成物用消泡剤との混合液を「混合液Ｘ」とした。 (Examples 17 to 32, Comparative Examples 6 to 10)
(Preparation of hydraulic composition (concrete composition))
First, as shown in Table 5, with respect to 2000 g of the synthesized water reducing agents PC-1, PC-2 and PC-3 for each hydraulic composition, the defoaming agents AF-1 to 16 for hydraulic compositions, A mixed solution containing 2.0 g of RAF-1 to 5 was prepared and stirred well. The mixed solution of this water reducing agent and the defoaming agent for a hydraulic composition was designated as "mixed solution X".

次に、表４に示す配合にて、コンクリートの練り混ぜ容積３０Ｌとし、コンクリート試験を行った。 Next, a concrete test was conducted with a concrete mixing volume of 30 L with the formulations shown in Table 4.

具体的には、２０℃の試験室内で５０Ｌのパン型強制練りミキサーに普通ポルトランドセメントからなる水硬性結合材と、骨材として陸砂及び砕石を投入した。更に、上述の混合液Ｘをセメント質量に対して０．５０％と、ＡＥ剤「ＡＥ－３００（竹本油脂社製）」をセメント質量に対して０．００４％と、を練り混ぜ水（蒲郡市上水道水）の一部として計量し、ミキサーに投入して９０秒間練り混ぜた。このようにして、コンクリート組成物（水硬性組成物）を調製し、スランプが１９±２．５ｃｍとなった。このように「混合液Ｘ」を使用して水硬性組成物を調製する試験を「試験１」とする。 Specifically, a hydraulic binder made of ordinary Portland cement and land sand and crushed stone as aggregates were put into a 50 L bread-type forced kneading mixer in a test room at 20 ° C. Further, the above-mentioned mixed liquid X is mixed with 0.50% with respect to the cement mass, and the AE agent "AE-300 (manufactured by Takemoto Oil & Fat Co., Ltd.)" is mixed with 0.004% with respect to the cement mass. Weighed as part of the city tap water), put into a mixer and kneaded for 90 seconds. In this way, a concrete composition (hydraulic composition) was prepared, and the slump became 19 ± 2.5 cm. The test for preparing the hydraulic composition using the "mixture X" in this way is referred to as "test 1".

水硬性組成物の調製に使用した材料は、具体的には以下の通りである。
水：蒲郡市上水道水
セメント：普通ポルトランドセメント（太平洋セメント社製、宇部三菱セメント社製、及び住友大阪セメント社製等量混合、密度＝３．１６ｇ／ｃｍ３）
細骨材：陸砂（大井川水系産、密度＝２．５８ｇ／ｃｍ３）
粗骨材：砕石（岡崎産砕石、密度＝２．６６ｇ／ｃｍ３） Specifically, the materials used for preparing the hydraulic composition are as follows.
Water: Gamagori City Waterworks Cement: Ordinary Portland cement (Mixed in equal amounts by Taiheiyo Cement, Ube-Mitsubishi Cement, and Sumitomo Osaka Cement, density = 3.16 g / cm 3 )
Fine aggregate: Land sand (Oigawa river system, density = 2.58 g / cm 3 )
Coarse aggregate: Crushed stone (crushed stone from Okazaki, density = 2.66 g / cm 3 )

Figure 0007012313000012
Figure 0007012313000012

表４中、「Ｗ／Ｃ」は、水／結合材比を示している。 In Table 4, "W / C" indicates the water / binder ratio.

（水硬性組成物（コンクリート）の評価）
作製した各水硬性組成物について、以下の方法で、スランプ（ｃｍ）及び空気量（容量％）の各評価を行った。更に、各水硬性組成物に基づいて、減水剤との相溶性、及び消泡性の評価を行った。 (Evaluation of hydraulic composition (concrete))
For each of the prepared hydraulic composition, each evaluation of slump (cm) and air content (volume%) was performed by the following method. Further, the compatibility with the water reducing agent and the defoaming property were evaluated based on each hydraulic composition.

［スランプ（ｃｍ）］
練り混ぜ直後の水硬性組成物について、ＪＩＳ Ａ １１０１に準拠して測定した。測定結果を表５に示す。なお、表５中、「試験１」の欄は、上述した混合液Ｘを使用して作製した水硬性組成物の結果を示し、「試験２」の欄は、混合液Ｙを使用して作製した水硬性組成物の結果を示す。 [Slump (cm)]
The hydraulic composition immediately after kneading was measured according to JIS A 1101. The measurement results are shown in Table 5. In Table 5, the column of "Test 1" shows the result of the hydraulic composition prepared by using the above-mentioned mixed solution X, and the column of "Test 2" is prepared by using the mixed solution Y. The results of the hydraulic composition are shown.

試験２で使用した混合液Ｙは、以下のようにして作製したものを用いた。具体的には、まず、作製直後の混合液Ｘのうち、１０００ｇ分を別のポリビン（ポリ瓶）に移し、４０℃で１週間静置し、その状態における上層部をスポイトで２００ｇ採取、廃棄した。その後、長尺スポイトで下層部（残部）から１５０ｇ採取し、これを「混合液Ｙ」とした。この混合液Ｙは、保存後の混合液（即ち、所定の方法で保存後の、減水剤と水硬性組成物用消泡剤との混合液）であり、保存により水硬性組成物用消泡剤に分離が生じると、水硬性組成物の空気量等に差異が生じることになる。 The mixed solution Y used in Test 2 was prepared as follows. Specifically, first, 1000 g of the mixed solution X immediately after preparation is transferred to another polybin (poly bottle), allowed to stand at 40 ° C. for 1 week, and 200 g of the upper layer in that state is collected with a dropper and discarded. did. Then, 150 g was collected from the lower layer (remaining portion) with a long dropper, and this was designated as “mixed liquid Y”. This mixed solution Y is a mixed solution after storage (that is, a mixed solution of a water reducing agent and a defoaming agent for a hydraulic composition after storage by a predetermined method), and defoaming for a hydraulic composition by storage. If the agent is separated, the amount of air in the hydraulic composition will be different.

［空気量（容量％）］
空気量（容量％）は、上記スランプの測定と同時に、ＪＩＳ Ａ １１２８に準拠して測定した。測定結果を表５に示す。なお、スランプ（ｃｍ）と同様、表５中、「試験１」の欄は、上述した混合液Ｘを使用して作製した水硬性組成物の結果を示し、「試験２」の欄は、混合液Ｙを使用して作製した水硬性組成物の結果を示す。 [Amount of air (capacity%)]
The amount of air (% by volume) was measured in accordance with JIS A 1128 at the same time as the measurement of the slump. The measurement results are shown in Table 5. As with the slump (cm), in Table 5, the column of "Test 1" shows the result of the hydraulic composition prepared by using the above-mentioned mixed solution X, and the column of "Test 2" is the mixture. The result of the hydraulic composition prepared using liquid Y is shown.

［減水剤との相溶性］
混合液Ｙを用いたこと以外は、上述した「試験１」と同様にして、水硬性組成物を調製した。これを「試験２」とした。 [Compatibility with water reducing agent]
A hydraulic composition was prepared in the same manner as in "Test 1" described above, except that the mixed solution Y was used. This was designated as "test 2".

試験１における空気量Ａと、試験２における空気量Ｂとの差（空気量Ｂ－空気量Ａ）を算出し、以下の基準で減水剤との相溶性を評価した。なお、試験１と試験２とで空気量の差が小さいことは、消泡剤の相溶性が高く分離が少ないことを意味する。 The difference between the air amount A in the test 1 and the air amount B in the test 2 (air amount B-air amount A) was calculated, and the compatibility with the water reducing agent was evaluated according to the following criteria. The small difference in the amount of air between Test 1 and Test 2 means that the defoaming agent has high compatibility and less separation.

Ｓ：非常に良好（空気量Ｂから空気量Ａを減じた値が±０．５％以下である）
Ａ：良好（空気量Ｂから空気量Ａを減じた値が０．５％超１．０％以下である）
Ｂ：可（空気量Ｂから空気量Ａを減じた値が１．０％超２．０％以下である）
Ｃ：悪い（空気量Ｂから空気量Ａを減じた値が２．０％超である） S: Very good (the value obtained by subtracting the air amount A from the air amount B is ± 0.5% or less)
A: Good (the value obtained by subtracting the air amount A from the air amount B is more than 0.5% and 1.0% or less)
B: Possible (the value obtained by subtracting the air amount A from the air amount B is more than 1.0% and 2.0% or less)
C: Bad (the value obtained by subtracting the air amount A from the air amount B is more than 2.0%)

［消泡性］
上記「試験１」と同様にして空気量Ａを測定した。更に、基準１～３における空気量を測定し、これを基準空気量とした。各基準１～３における基準空気量から空気量Ａを減じた値を算出し、以下の評価基準で評価を行った。基準１～３は、各減水剤ＰＣ－１～ＰＣ－３のみを使用し、水硬性組成物用消泡剤を使用しないで作製した水硬性組成物の結果であり、基準１～３のうち同じ減水剤を採用しているものを基準として採用した。つまり、例えば実施例１７のように減水剤ＰＣ－１を配合した水硬性組成物については、減水剤ＰＣ－１のみを用いた基準１を採用し、その空気量を基準空気量とした。 [Defoaming property]
The air amount A was measured in the same manner as in the above "test 1". Further, the amount of air in the standards 1 to 3 was measured, and this was used as the reference air amount. A value obtained by subtracting the air amount A from the reference air amount in each of the criteria 1 to 3 was calculated and evaluated according to the following evaluation criteria. Criteria 1 to 3 are the results of the hydraulic composition prepared by using only the respective water reducing agents PC-1 to PC-3 and not using the defoaming agent for the hydraulic composition, and among the criteria 1 to 3. It was adopted based on the one that uses the same water reducing agent. That is, for example, for the hydraulic composition containing the water reducing agent PC-1 as in Example 17, the standard 1 using only the water reducing agent PC-1 was adopted, and the air amount thereof was used as the reference air amount.

Ｓ：非常に良好（基準空気量から空気量Ａを減じた値が３．０％以上である）
Ａ：良好（基準空気量から空気量Ａを減じた値が２．０％以上３．０％未満である）
Ｂ：可（基準空気量から空気量Ａを減じた値が１．０％以上２．０％未満である）
Ｃ：悪い（基準空気量から空気量Ａを減じた値が１．０％未満である） S: Very good (the value obtained by subtracting the air amount A from the standard air amount is 3.0% or more)
A: Good (the value obtained by subtracting the air amount A from the standard air amount is 2.0% or more and less than 3.0%)
B: Possible (the value obtained by subtracting the air amount A from the standard air amount is 1.0% or more and less than 2.0%)
C: Bad (the value obtained by subtracting the air amount A from the standard air amount is less than 1.0%)

Figure 0007012313000013
Figure 0007012313000013

なお、表５中、「水硬性組成物」には、減水剤と、水硬性組成物用消泡剤の水性液を特に示しており、実施例１７～３２、比較例６～１０の水硬性組成物は、上述の通り、減水剤と、水硬性組成物用消泡剤の水性液以外に、上述したように水硬性結合材等を含有するものである。 In Table 5, the "hydraulic composition" particularly indicates an aqueous solution of a water reducing agent and a defoaming agent for a hydraulic composition, and the hydraulic properties of Examples 17 to 32 and Comparative Examples 6 to 10 are shown. As described above, the composition contains a hydraulic binder and the like as described above, in addition to the aqueous solution of the water reducing agent and the defoaming agent for the hydraulic composition.

表５中、水硬性組成物の欄の「使用量」は、減水剤２０％の水溶液に本発明の水硬性組成物用消泡剤を０．１％加えた混合液の使用量を示す。 In Table 5, "amount used" in the column of the water-hardening composition indicates the amount of a mixed solution obtained by adding 0.1% of the defoaming agent for the water-hardening composition of the present invention to an aqueous solution of a water-reducing agent of 20%.

（結果）
表３、表５に示される結果から明らかなように、本発明の水硬性組成物用消泡剤及び水硬性組成物用消泡剤の水性液は、分離安定性（製剤安定性）に優れ、水で希釈したときの乳化安定性にも優れ、他の水硬性組成物用添加剤（特に、減水剤）との相溶性にも優れ、更には、少量で優れた消泡性を有することが確認された。 (result)
As is clear from the results shown in Tables 3 and 5, the aqueous solution of the defoaming agent for a water-hard composition and the defoaming agent for a water-hard composition of the present invention is excellent in separation stability (formulation stability). It has excellent emulsion stability when diluted with water, has excellent compatibility with other additives for water-hard composition (particularly, water reducing agent), and has excellent defoaming property even in a small amount. Was confirmed.

また、例えば比較例６で示す水硬性組成物用消泡剤の水性液（即ち、水硬性組成物用消泡剤）は、静置の有無によってコンクリートの評価における空気量（空気量Ｂと空気量Ａ）に差が生じた。この結果より、混合液Ｙの消泡剤の濃度は、混合液Ｘよりも低いことが分かる。つまり、例えば比較例６で示すようなＨＬＢが小さく減水剤への相溶性が低い消泡剤は、浮上して分離しやすく、静置することで混合液中に消泡剤の濃度分布（消泡剤の濃度に偏り）が生じてしまったことがうかがえる。一方で、実施例に示すように、本発明の水硬性組成物用消泡剤の水性液は、静置の有無によるコンクリートの評価における空気量（空気量Ｂと空気量Ａ）の差がわずかであった。つまり、混合液Ｘ中の消泡剤の濃度と混合液Ｙ中の消泡剤の濃度とは、ほとんど同一であったと言える。従って、本発明の水硬性組成物用消泡剤の水性液（即ち、水硬性組成物用消泡剤）によれば、ＨＬＢが小さく減水剤への相溶性が低い消泡剤であっても、静置した際にも混合液中の分離が認められず、消泡剤の濃度が均一に保たれていることが分かる。このようなことから、本発明の水硬性組成物としては空気量がばらつかず、均一な、目標とした空気量とすることができる。 Further, for example, the aqueous liquid of the defoaming agent for hydraulic composition shown in Comparative Example 6 (that is, the defoaming agent for hydraulic composition) has an air amount (air amount B and air) in the evaluation of concrete depending on whether or not it is left to stand. There was a difference in the amount A). From this result, it can be seen that the concentration of the defoaming agent in the mixed solution Y is lower than that in the mixed solution X. That is, for example, a defoaming agent having a small HLB and low compatibility with a water reducing agent as shown in Comparative Example 6 floats and is easily separated, and by standing still, the concentration distribution of the defoaming agent (disappearing) in the mixed solution. It can be seen that the concentration of the foaming agent is biased). On the other hand, as shown in Examples, the aqueous solution of the defoaming agent for hydraulic composition of the present invention has a slight difference in the amount of air (air amount B and air amount A) in the evaluation of concrete depending on whether or not it is left standing. Met. That is, it can be said that the concentration of the defoaming agent in the mixed liquid X and the concentration of the defoaming agent in the mixed liquid Y were almost the same. Therefore, according to the aqueous liquid of the defoaming agent for a water-hard composition of the present invention (that is, the defoaming agent for a water-hard composition), even a defoaming agent having a small HLB and low compatibility with a water reducing agent. It can be seen that separation in the mixed solution was not observed even when the mixture was allowed to stand, and the concentration of the defoaming agent was kept uniform. Therefore, in the hydraulic composition of the present invention, the amount of air does not vary, and a uniform and targeted amount of air can be obtained.

また、本発明の水硬性組成物は、本発明の水硬性組成物用消泡剤を含有しており、当該水硬性組成物用消泡剤と、減水剤等の混和剤との相溶性が良好である。この結果からすると、本発明の水硬性組成物は、空気量のばらつきが少なくなることが分かる。 Further, the hydraulic composition of the present invention contains the defoaming agent for the hydraulic composition of the present invention, and the compatibility between the defoaming agent for the hydraulic composition and the admixture such as a water reducing agent is high. It is good. From this result, it can be seen that the hydraulic composition of the present invention has less variation in the amount of air.

本発明の水硬性組成物用消泡剤及び水硬性組成物用消泡剤の水性液は、水硬性組成物用の消泡剤として利用することができる。また、本発明の水硬性組成物は、コンクリート等として利用することができる。 The aqueous solution of the defoaming agent for a hydraulic composition and the defoaming agent for a hydraulic composition of the present invention can be used as a defoaming agent for a hydraulic composition. Further, the hydraulic composition of the present invention can be used as concrete or the like.

Claims (11)

下記一般式（１）で示され、下記式（２）で示されるＨＬＢが０．１～６の範囲内であるポリアルキレンオキシド付加物と、
分子量が５００以下の酸と、を含有し、
下記式（３）で示されるＥＱが、０．３～３．５の範囲内であることを特徴とする、水硬性組成物用消泡剤。
Figure 0007012313000014
 （但し、一般式（１）中、Ｒ１は、炭素数１～３０の炭化水素基である。Ｒ２，Ｒ３は、それぞれ独立に、水素原子、炭素数１～２２の炭化水素基である。Ａ１Ｏ，Ａ２Ｏは、それぞれ独立に、炭素数２～４のオキシアルキレン基である。ｍ，ｎは、それぞれ独立に０～２００の整数であり、ｍ＋ｎは３～２００を満たす整数である。）
Figure 0007012313000015
 （但し、式（２）中、Ｙは、一般式（１）で示されるポリアルキレンオキシド付加物の分子中に含まれる（ポリ）オキシエチレン基の含有割合（質量％）である。）
Figure 0007012313000016
 （但し、前記式（３）中、Ｗは、前記酸から求められる酸価である。ｂは、前記一般式（１）で示されるポリアルキレンオキシド付加物と前記酸の含有割合の合計を１００質量％とした場合における前記酸の含有割合（質量％）である。Ｖは、前記一般式（１）で示されるポリアルキレンオキシド付加物から求められるアミン価である。ａは、前記一般式（１）で示されるポリアルキレンオキシド付加物と前記酸の含有割合の合計を１００質量％とした場合における前記一般式（１）で示されるポリアルキレンオキシド付加物の含有割合（質量％）である。） A polyalkylene oxide adduct represented by the following general formula (1) and having an HLB in the range of 0.1 to 6 represented by the following formula (2).
Contains an acid having a molecular weight of 500 or less ,
An antifoaming agent for a hydraulic composition, wherein the EQ represented by the following formula (3) is in the range of 0.3 to 3.5 .
Figure 0007012313000014
 (However, in the general formula (1), R 1 is a hydrocarbon group having 1 to 30 carbon atoms. R 2 and R 3 are independently hydrogen atoms and hydrocarbon groups having 1 to 22 carbon atoms, respectively. A 1 O and A 2 O are independently oxyalkylene groups having 2 to 4 carbon atoms. M and n are independently integers of 0 to 200, and m + n satisfies 3 to 200. It is an integer.)
Figure 0007012313000015
 (However, in the formula (2), Y is the content ratio (mass%) of the (poly) oxyethylene group contained in the molecule of the polyalkylene oxide adduct represented by the general formula (1).)
Figure 0007012313000016
 (However, in the formula (3), W is the acid value obtained from the acid. B is the total content ratio of the polyalkylene oxide adduct represented by the general formula (1) and the acid to 100. It is the content ratio (mass%) of the acid in the case of mass%. V is the amine value obtained from the polyalkylene oxide adduct represented by the general formula (1). A is the general formula (1). It is the content ratio (mass%) of the polyalkylene oxide adduct represented by the general formula (1) when the sum of the content ratios of the polyalkylene oxide adduct represented by 1) and the acid is 100% by mass. ) 前記一般式（１）におけるＲ２，Ｒ３が、いずれも水素原子である、請求項１に記載の水硬性組成物用消泡剤。 The defoaming agent for a hydraulic composition according to claim 1, wherein both R 2 and R 3 in the general formula (1) are hydrogen atoms. 前記一般式（１）におけるＲ１が、炭素数１０～２０の炭化水素基である、請求項１または２に記載の水硬性組成物用消泡剤。 The defoaming agent for a hydraulic composition according to claim 1 or 2, wherein R 1 in the general formula (1) is a hydrocarbon group having 10 to 20 carbon atoms. 前記一般式（１）における－（Ａ１Ｏ）ｍ－，－（Ａ２Ｏ）ｎ－は、その炭素数２～４のオキシアルキレン基の構成割合の合計を１００モル％とすると、炭素数３～４のオキシアルキレン基を７５モル％以上の割合で有する、請求項１～３のいずれか一項に記載の水硬性組成物用消泡剤。 In the general formula (1),-(A 1 O) m -,-(A 2 O) n -has carbon atoms, assuming that the total composition ratio of the oxyalkylene groups having 2 to 4 carbon atoms is 100 mol%. The defoaming agent for a water-hard composition according to any one of claims 1 to 3, which has 3 to 4 oxyalkylene groups in a proportion of 75 mol% or more. 前記一般式（１）における－（Ａ１Ｏ）ｍ－，－（Ａ２Ｏ）ｎ－が、炭素数２～４のオキシアルキレン基をブロック重合させたものである、請求項１～４のいずれか一項に記載の水硬性組成物用消泡剤。 Claims 1 to 4, wherein − (A 1 O) m −, − (A 2 O) n − in the general formula (1) is a block-polymerized oxyalkylene group having 2 to 4 carbon atoms. The defoaming agent for a hydraulic composition according to any one of the following items. 前記一般式（１）におけるｍ，ｎは、これらの和であるｍ＋ｎが、２０～８０の整数である、請求項１～５のいずれか一項に記載の水硬性組成物用消泡剤。 The defoaming agent for a hydraulic composition according to any one of claims 1 to 5, wherein m and n in the general formula (1) are the sum of these, m + n is an integer of 20 to 80. 前記一般式（１）で示されるポリアルキレンオキシド付加物は、前記式（２）におけるＨＬＢが０．１～３．５の範囲内である、請求項１～６のいずれか一項に記載の水硬性組成物用消泡剤。 The polyalkylene oxide adduct represented by the general formula (1) is according to any one of claims 1 to 6, wherein the HLB in the formula (2) is in the range of 0.1 to 3.5. Defoaming agent for hydraulic compositions. 前記式（３）で示されるＥＱが、０．７～３．５の範囲内である、請求項１～７のいずれか一項に記載の水硬性組成物用消泡剤。 The defoaming agent for a hydraulic composition according to any one of claims 1 to 7, wherein the EQ represented by the formula (3) is in the range of 0.7 to 3.5 . 請求項１～８のいずれか一項に記載の水硬性組成物用消泡剤、及び水を含有することを特徴とする、水硬性組成物用消泡剤の水性液。 An aqueous liquid of a defoaming agent for a hydraulic composition, which comprises the defoaming agent for a hydraulic composition according to any one of claims 1 to 8. 前記一般式（１）で示されるポリアルキレンオキシド付加物、前記酸、及び前記水の含有割合の合計を１００質量％とすると、前記水を０．０１～２５質量％の割合で含有する、請求項９に記載の水硬性組成物用消泡剤の水性液。 Assuming that the total content of the polyalkylene oxide adduct represented by the general formula (1), the acid, and the water is 100% by mass, the water is contained in a ratio of 0.01 to 25% by mass. Item 9. An aqueous solution of the defoaming agent for a water-hardening composition according to Item 9. 請求項１～８のいずれか一項に記載の水硬性組成物用消泡剤を含有することを特徴とする、水硬性組成物。
A hydraulic composition comprising the defoaming agent for a hydraulic composition according to any one of claims 1 to 8.
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Citations (8)

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Publication number Priority date Publication date Assignee Title
JPS6311557A (en) * 1986-07-01 1988-01-19 株式会社日本触媒 Control for entraining air volume of cement mortar or concrete
JPH07232945A (en) * 1994-02-22 1995-09-05 Nippon Oil & Fats Co Ltd Additive composition for cement
JPH08295545A (en) * 1995-04-25 1996-11-12 Shikoku Electric Power Co Inc Air entraining agent for fly ash-containing cement composition
JP2000247704A (en) * 1999-03-03 2000-09-12 Lion Corp Antifoaming agent for cement composition
JP2005500232A (en) * 2001-05-01 2005-01-06 ダブリュー・アール・グレイス・アンド・カンパニー−コネチカット Antifoaming agent for water reducing agent admixture
JP2006199953A (en) * 2004-12-24 2006-08-03 Takenaka Komuten Co Ltd Admixture for fly ash containing high concentration of unburned carbon and concrete
WO2019244386A1 (en) * 2018-06-21 2019-12-26 竹本油脂株式会社 Additive for hydraulic composition
WO2020202435A1 (en) * 2019-04-01 2020-10-08 竹本油脂株式会社 Defoaming agent for hydraulic composition, and hydraulic composition

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6311557A (en) * 1986-07-01 1988-01-19 株式会社日本触媒 Control for entraining air volume of cement mortar or concrete
JPH07232945A (en) * 1994-02-22 1995-09-05 Nippon Oil & Fats Co Ltd Additive composition for cement
JPH08295545A (en) * 1995-04-25 1996-11-12 Shikoku Electric Power Co Inc Air entraining agent for fly ash-containing cement composition
JP2000247704A (en) * 1999-03-03 2000-09-12 Lion Corp Antifoaming agent for cement composition
JP2005500232A (en) * 2001-05-01 2005-01-06 ダブリュー・アール・グレイス・アンド・カンパニー−コネチカット Antifoaming agent for water reducing agent admixture
JP2006199953A (en) * 2004-12-24 2006-08-03 Takenaka Komuten Co Ltd Admixture for fly ash containing high concentration of unburned carbon and concrete
WO2019244386A1 (en) * 2018-06-21 2019-12-26 竹本油脂株式会社 Additive for hydraulic composition
WO2020202435A1 (en) * 2019-04-01 2020-10-08 竹本油脂株式会社 Defoaming agent for hydraulic composition, and hydraulic composition

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