JP2021038111A - Cement admixture, and cement composition - Google Patents
Cement admixture, and cement composition Download PDFInfo
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- JP2021038111A JP2021038111A JP2019159962A JP2019159962A JP2021038111A JP 2021038111 A JP2021038111 A JP 2021038111A JP 2019159962 A JP2019159962 A JP 2019159962A JP 2019159962 A JP2019159962 A JP 2019159962A JP 2021038111 A JP2021038111 A JP 2021038111A
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Abstract
Description
本発明はセメント混和剤及びセメント組成物に関し、詳しくは、セメント組成物のクラック、色むら、連続性のない多量のクラック模様を抑制できるセメント混和剤、及びこれを含むセメント組成物に関する。 The present invention relates to a cement admixture and a cement composition, and more particularly to a cement admixture capable of suppressing cracks, color unevenness, and a large amount of discontinuous crack patterns in the cement composition, and a cement composition containing the same.
セメント組成物は、広い強度域、様々な形態に製造される設計自由度の高い材料である。また、耐久性の観点のみではなく、非常に厳しく外観性状の均一性が求められる。外観性状はクラック等の潜在的な構造欠陥となる問題のみではなく、所謂見た目としての出来栄えも重要と捉えられている。 Cement compositions are materials with a wide range of strength and a high degree of design freedom that are manufactured in various forms. Moreover, not only from the viewpoint of durability, but also very strict uniformity of appearance and appearance is required. Appearance is considered to be important not only for the problem of potential structural defects such as cracks, but also for the so-called appearance.
セメント組成物の外観性状に包含される要因として、ジャンカ、豆板等のセメント組成物の構成比率または施工上の問題により生じる外観性状を除くと、クラック、色むら、連続性のない多量のクラック模様がある。 Excluding the factors included in the appearance properties of the cement composition, which are caused by the composition ratio of the cement composition such as junkers and bean boards or construction problems, cracks, color unevenness, and a large amount of discontinuous crack patterns There is.
クラックは、内外により生じる拘束条件下でセメント組成物が乾燥に伴い体積変化するために発生する。一般的なクラック緩和対策として、セメント組成物に石灰砕石、膨張材が使用されている。 Cracks occur because the volume of the cement composition changes as it dries under restraint conditions caused by the inside and outside. As a general crack mitigation measure, lime crushed stone and expansion material are used in the cement composition.
色むらに関しては、マット又はシートを使用した養生を行う、養生期間の延長により若干の改善効果を期待する、もしくは、型枠に剥離剤をしっかり散布する、バイブレータを決められた場所に設置し、かつ時間をかけるといった、行われて当然の事項を留意する方法しかない。 For color unevenness, perform curing using a mat or sheet, expect a slight improvement effect by extending the curing period, or spray a release agent firmly on the mold, install a vibrator in a fixed place, and install it in a fixed place. And there is only a way to keep in mind the things that are taken for granted, such as taking time.
連続性のない多量のクラック模様に関しては、セメント組成物のごく表層の乾燥と自己水和に伴う見かけの乾燥を抑制するのが有効と言える。一般的な乾燥抑制対策は、外気に触れさせないこと（例えばビニルシートによる保護）である。 For a large amount of discontinuous crack patterns, it can be said that it is effective to suppress the drying of the very surface layer of the cement composition and the apparent drying due to self-hydration. A general measure to prevent drying is to keep it out of the open air (for example, protection with a vinyl sheet).
セメント組成物の乾燥に伴う体積変化を低減する材料として乾燥体積変化低減剤がある（特許文献１、２、３）。乾燥体積変化低減剤は、セメント組成物に添加すると、無添加と比較して通常１５〜３０％程度体積変化を抑制することができる。また、セメントの水和に伴う体積変化にも効果を発揮するとされている。 As a material for reducing the volume change due to drying of the cement composition, there is a dry volume change reducing agent (Patent Documents 1, 2 and 3). When the dry volume change reducing agent is added to the cement composition, the volume change can be suppressed by about 15 to 30% as compared with the case where the dry volume change reducing agent is not added. It is also said to be effective in changing the volume of cement due to hydration.
しかしながら、特許文献１〜３には、乾燥による体積変化には有効でも、水和に伴う体積変化に特化した材料設計に関し記載されていない。そのため、これらの文献に記載の有効成分を文献に記載の条件でセメントに単に添加しても、色むら、及び、連続性のない多量のクラック模様には効果が認められない可能性がある。水和に伴う体積変化の抑制のためには、乾燥に伴う体積変化とは異なり、セメント組成物中のバルク水の表面張力の低下と飽和蒸気圧の低下による水分逸散の抑制が最も重要であるためである。水和に伴う体積変化の駆動力と、水和物を形成したセメント構造体の乾燥に伴う体積変化の駆動力は、異なる。前者は、セメント粒子間のメニスカスに働く力であり、後者は分離圧である。 However, Patent Documents 1 to 3 do not describe a material design specialized for volume change due to hydration, although it is effective for volume change due to drying. Therefore, even if the active ingredients described in these documents are simply added to cement under the conditions described in the documents, there is a possibility that no effect is observed on color unevenness and a large amount of discontinuous crack patterns. In order to suppress the volume change due to hydration, unlike the volume change due to drying, it is most important to suppress the water dissipation due to the decrease in the surface tension of the bulk water in the cement composition and the decrease in the saturated vapor pressure. Because there is. The driving force for volume change due to hydration and the driving force for volume change due to drying of the cement structure on which hydrate is formed are different. The former is the force acting on the meniscus between the cement particles, and the latter is the separation pressure.
また、特許文献１〜３には、温度、湿度等の外部条件の体積変化抑制効果に対する影響についての言及がない。通常、湿度が高いと体積変化は少なく、低いと大きい。また、セメント構造体に界面活性剤を添加した際の体積変化の抑制効果は、セメント構造体における水和物の生成の程度とその際の湿度等の外部条件により大きく異なる。温度、湿度等の外部条件に応じて界面活性剤の構造、添加方法を最適化する方法について、特許文献１〜３には何ら記載されていない。 Further, Patent Documents 1 to 3 do not mention the influence of external conditions such as temperature and humidity on the effect of suppressing volume change. Generally, when the humidity is high, the volume change is small, and when the humidity is low, the volume change is large. Further, the effect of suppressing the volume change when a surfactant is added to the cement structure greatly differs depending on the degree of hydrate formation in the cement structure and external conditions such as humidity at that time. Patent Documents 1 to 3 do not describe a method of optimizing the structure of the surfactant and the method of adding the surfactant according to external conditions such as temperature and humidity.
色むら、及び連続性のない多量のクラック模様の抑制に関しては、今のところ、先述のような養生、施工による対応が殆どであり、材料による対応が成されていないのが現状である。色むらの抑制には、型枠面へセメントペーストが流動しそこに定位する表面張力を維持することが重要である。若干の乾燥によりセメント粒子間のメニスカスが変化し毛細管引力が発生することがある。例えば、シート等でしっかりと養生を行っても、その後シートを剥いだ瞬間に外気に接する部分はごく少量体積変化し、水和が進んだ内部のセメント構造体に拘束されるため、クラック模様が表面に生じてしまう。連続性のない多量のクラック模様の抑制には、この毛細管引力の発生を防ぐ技術が重要である。しかし、このような連続性のない多量のクラック模様を低減する技術は現存していないといえる。 At present, most of the measures for suppressing color unevenness and a large amount of discontinuous crack patterns are by curing and construction as described above, and the current situation is that no measures are taken by materials. In order to suppress color unevenness, it is important to maintain the surface tension in which the cement paste flows to the mold surface and is localized there. A slight drying may change the meniscus between the cement particles and generate capillary attraction. For example, even if the sheet is firmly cured, the volume of the part that comes into contact with the outside air changes by a very small amount at the moment when the sheet is peeled off, and the crack pattern is formed because it is restrained by the cement structure inside where hydration has progressed. It occurs on the surface. A technique for preventing the generation of this capillary attractive force is important for suppressing a large amount of discontinuous crack patterns. However, it can be said that there is no existing technique for reducing such a large amount of discontinuous crack patterns.
本発明は、セメント組成物のクラック、色むら、連続性のない多量のクラック模様を低減し、外観性状を均一化することのできるセメント混和剤を提供することを目的とする。また、本発明は、定められた使用材料、材料組成比、積算温度、積算湿度の条件で構造物を製造することで、外観性状を損なう現象を抑制することのできるセメント組成物を提供することを目的とする。 An object of the present invention is to provide a cement admixture capable of reducing cracks, color unevenness, and a large amount of discontinuous crack patterns in a cement composition and making the appearance properties uniform. The present invention also provides a cement composition capable of suppressing a phenomenon of impairing appearance properties by producing a structure under the specified materials used, material composition ratio, integrated temperature, and integrated humidity. With the goal.
外観性状の均一性を向上させる方法として、様々な温湿度条件下でも、構造体内部のバルク水の飽和蒸気圧を低下させることのできるセメント混和剤を見出した。
すなわち、本発明は以下を提供する。
〔１〕Ａ成分：平均分子量２００〜６００のポリプロピレングリコール、及び／又は
Ｂ成分：一般式（Ｉ） Ｒ−Ｏ−（ＡＯ）n−Ｈ
（一般式（Ｉ）中、Ｒは水素原子または炭素原子数２〜４の炭化水素基であり、ＡＯは炭素原子数２〜３のオキシアルキレン基であり、ｎは１〜１０の整数である。）
で表される化合物を有効成分とするセメント混和剤。
〔２〕Ａ成分は、平均分子量が３００〜４００であるポリプロピレングリコールを少なくとも含む、〔１〕に記載のセメント混和剤。
〔３〕Ｂ成分は、一般式（Ｉ）中のＲが炭素原子数２〜４の炭化水素基である化合物を少なくとも含む、〔１〕又は〔２〕に記載のセメント混和剤。
〔４〕有効成分のセメント組成物への添加量が、以下の工程（１）〜（４）を含む添加量確認方法により確認されるａ質量％（対セメント質量）である、〔１〕〜〔３〕のいずれか１項に記載のセメント混和剤：
工程（１）：有効成分、セメント及び水からなる、有効成分の含有量がａ質量％（対セメント質量）であるサンプルを得ること；
工程（２）：サンプルを脱水し分離水を得ること；
工程（３）：分離水の表面張力をＷｉｌｈｅｌｍｙ法により測定すること；及び
工程（４）：測定された表面張力が６０ｄｙｎ／ｃｍ以下であることを確認する工程。
〔５〕添加量確認方法がさらに、工程（５）及び（６）を含む、〔４〕記載のセメント混和剤：
工程（５）：分離水中の炭素量と、工程（１）においてセメント混和剤無添加の他はサンプルと同様の組成のブランク組成物を工程（２）と同様に処理して得たブランク分離水中の炭素量を測定し、以下の式にて未吸着率を算出する工程
式：
未吸着率＝〔分離水中の炭素量／ブランク分離水中の炭素量〕×１００；及び
工程（６）：算出された未吸着率が３０％以上であることを確認する工程。
〔６〕分離水中の炭素量及びブランク分離水中の炭素量の測定時期は、工程（１）におけるサンプル調整時から１時間経過後である、〔５〕に記載のセメント混和剤。
〔７〕工程（１）におけるサンプルの水セメント質量比（Ｗ／Ｃ）は、１００％である、〔５〕又は〔６〕に記載のセメント混和剤。
〔８〕ａ質量％は、０．１〜１５．０質量％である〔４〕〜〔７〕のいずれか１項に記載のセメント混和剤。
〔９〕〔１〕〜〔８〕のいずれか１項に記載のセメント混和剤、セメント及び水を含むセメント組成物。
〔１０〕〔１〕〜〔８〕のいずれか１項に記載のセメント混和剤の含有量が、以下の工程（１）〜（４）を含む添加量確認方法により確認されるａ質量％（対セメント質量）である、〔９〕に記載のセメント組成物。
工程（１）：有効成分、セメント及び水からなる、有効成分の含有量がａ質量％（対セメント質量）であるサンプルを得ること；
工程（２）：サンプルを脱水し分離水を得ること；
工程（３）：分離水の表面張力をＷｉｌｈｅｌｍｙ法により測定すること；及び
工程（４）：測定された表面張力が６０ｄｙｎ／ｃｍ以下であることを確認する工程。
〔１１〕添加量確認方法がさらに、工程（５）及び（６）を含む、〔１０〕記載のセメント組成物。
工程（５）：分離水中の炭素量と、工程（１）においてセメント混和剤無添加の他はサンプルと同様の組成のブランク組成物を工程（２）と同様に処理して得たブランク分離水中の炭素量を測定し、以下の式にて未吸着率を算出する工程
式：
未吸着率＝〔分離水中の炭素量／ブランク分離水中の炭素量〕×１００；及び
工程（６）：算出された未吸着率が３０％以上であることを確認する工程。
〔１２〕ａ質量％は、０．１〜１５．０質量％である〔１０〕又は〔１１〕に記載のセメント組成物。
〔１３〕水分含有量がセメント組成物に対し３〜１５質量％であること、及び
セメント含有量がセメント組成物に対し５〜９５質量％であること、
の少なくともいずれかを満たす〔９〕〜〔１２〕のいずれか１項に記載のセメント組成物。
〔１４〕結合材、細骨材、及び粗骨材からなる群より選ばれる少なくとも１つの成分を更に含む〔９〕〜〔１３〕のいずれか１項に記載のセメント組成物。
〔１５〕結合材の含有量が５〜９５質量％であること、
細骨材の含有量が３〜９０質量％であること、及び
粗骨材の含有量が８５質量％以下であること、
からなる群より選ばれるいずれかを満たす、〔１４〕に記載のセメント組成物。
〔１６〕〔１〕〜〔８〕に記載のセメント混和剤、セメント及び水を含む原料を配合する工程を含む、〔９〕〜〔１５〕のいずれか１項に記載のセメント組成物の製造方法。
〔１７〕以下の工程（１）〜（４）を含む、〔１〕〜〔８〕のいずれか１項に記載のセメント混和剤の、セメント組成物における含有量の確認、決定または評価方法。
工程（１）：有効成分、セメント及び水からなる、有効成分の含有量がａ質量％（対セメント質量）であるサンプルを得ること；
工程（２）：サンプルを脱水し分離水を得ること；
工程（３）：分離水の表面張力をＷｉｌｈｅｌｍｙ法により測定すること；及び
工程（４）：測定された表面張力が６０ｄｙｎ／ｃｍ以下である場合にことを確認し、セメント組成物におけるセメント混和剤の含有量をａ質量％と決定する工程。
〔１８〕少なくとも以下のいずれかを満たす、〔９〕〜〔１５〕のいずれか１項に記載のセメント組成物由来の構造物。
探傷減少率が５０％以上であること、
含水率比が１００．１〜１１０．０％であること、
自己体積変化低減率が１０％以上であること、
乾燥体積変化低減率が１０％以上であること、
積算温度が２００，２６８〜１，３７８，９５５Ｋ・時間であること、及び
積算湿度が３６，０００〜４３２，０００％Ｒ．Ｈ．・時間であること
〔１９〕〔９〕〜〔１５〕のいずれか１項に記載のセメント組成物を、
積算温度が２００，２６８〜１，３７８，９５５Ｋ・時間であること、及び、養生期間中の積算湿度が３６，０００〜４３２，０００％Ｒ．Ｈ．・時間であること、の少なくともいずれかを満たすよう養生する工程を含む、構造物の製造方法。
As a method for improving the uniformity of appearance properties, we have found a cement admixture that can reduce the saturated vapor pressure of bulk water inside a structure even under various temperature and humidity conditions.
That is, the present invention provides the following.
[1] Component A: Polypropylene glycol having an average molecular weight of 200 to 600 and / or Component B: General formula (I) RO- (AO) n- H
(In the general formula (I), R is a hydrogen atom or a hydrocarbon group having 2 to 4 carbon atoms, AO is an oxyalkylene group having 2 to 3 carbon atoms, and n is an integer of 1 to 10. .)
A cement admixture containing the compound represented by.
[2] The cement admixture according to [1], wherein the component A contains at least polypropylene glycol having an average molecular weight of 300 to 400.
[3] The cement admixture according to [1] or [2], wherein the component B contains at least a compound in which R in the general formula (I) is a hydrocarbon group having 2 to 4 carbon atoms.
[4] The amount of the active ingredient added to the cement composition is a mass% (% of cement mass) confirmed by the addition amount confirmation method including the following steps (1) to (4), [1] to The cement admixture according to any one of [3]:
Step (1): Obtaining a sample consisting of the active ingredient, cement and water and having an active ingredient content of a mass% (% by mass of cement);
Step (2): Dehydrate the sample to obtain separated water;
Step (3): Measure the surface tension of the separated water by the Wilhelmy method; and Step (4): Confirm that the measured surface tension is 60 dyn / cm or less.
[5] The cement admixture according to [4], wherein the method for confirming the amount of addition further includes steps (5) and (6):
Step (5): The amount of carbon in the separated water and the blank composition obtained by treating the blank composition having the same composition as the sample except that the cement admixture was not added in the step (1) in the same manner as in the step (2). Process formula to measure the carbon content of and calculate the non-adsorption rate by the following formula:
Unadsorbed rate = [Carbon amount in separated water / Carbon amount in blank separated water] × 100; and step (6): Step of confirming that the calculated unadsorbed rate is 30% or more.
[6] The cement admixture according to [5], wherein the carbon content in the separated water and the carbon content in the blank separated water are measured one hour after the sample preparation in the step (1).
[7] The cement admixture according to [5] or [6], wherein the water-cement mass ratio (W / C) of the sample in the step (1) is 100%.
[8] The cement admixture according to any one of [4] to [7], wherein a mass% is 0.1 to 15.0 mass%.
[9] A cement composition containing the cement admixture, cement and water according to any one of [1] to [8].
[10] The content of the cement admixture according to any one of [1] to [8] is a mass% (a mass%) confirmed by an addition amount confirmation method including the following steps (1) to (4). The cement composition according to [9], which is (mass with respect to cement).
Step (1): Obtaining a sample consisting of the active ingredient, cement and water and having an active ingredient content of a mass% (% by mass of cement);
Step (2): Dehydrate the sample to obtain separated water;
Step (3): Measure the surface tension of the separated water by the Wilhelmy method; and Step (4): Confirm that the measured surface tension is 60 dyn / cm or less.
[11] The cement composition according to [10], wherein the method for confirming the amount of addition further comprises steps (5) and (6).
Step (5): The amount of carbon in the separated water and the blank composition obtained by treating the blank composition having the same composition as the sample except that the cement admixture was not added in the step (1) in the same manner as in the step (2). Process formula to measure the carbon content of and calculate the non-adsorption rate by the following formula:
Unadsorbed rate = [Carbon amount in separated water / Carbon amount in blank separated water] × 100; and step (6): Step of confirming that the calculated unadsorbed rate is 30% or more.
[12] The cement composition according to [10] or [11], wherein a mass% is 0.1 to 15.0 mass%.
[13] The water content is 3 to 15% by mass with respect to the cement composition, and the cement content is 5 to 95% by mass with respect to the cement composition.
The cement composition according to any one of [9] to [12], which satisfies at least one of the above.
[14] The cement composition according to any one of [9] to [13], further comprising at least one component selected from the group consisting of a binder, a fine aggregate, and a coarse aggregate.
[15] The content of the binder is 5 to 95% by mass.
The content of fine aggregate is 3 to 90% by mass, and the content of coarse aggregate is 85% by mass or less.
The cement composition according to [14], which satisfies any of those selected from the group consisting of.
[16] Production of the cement composition according to any one of [9] to [15], which comprises a step of blending the cement admixture, cement and a raw material containing water according to [1] to [8]. Method.
[17] A method for confirming, determining or evaluating the content of the cement admixture according to any one of [1] to [8], which comprises the following steps (1) to (4), in a cement composition.
Step (1): Obtaining a sample consisting of the active ingredient, cement and water and having an active ingredient content of a mass% (% by mass of cement);
Step (2): Dehydrate the sample to obtain separated water;
Step (3): Measure the surface tension of the separated water by the Wilhelmy method; and Step (4): Confirm that the measured surface tension is 60 dyn / cm or less, and the cement admixture in the cement composition. Step of determining the content of a mass%.
[18] The structure derived from the cement composition according to any one of [9] to [15], which satisfies at least one of the following.
The flaw detection reduction rate is 50% or more,
The moisture content ratio is 10.1 to 110.0%,
The self-volume change reduction rate is 10% or more,
The dry volume change reduction rate is 10% or more,
The integrated temperature is 200,268 to 1,378,955 K · hours, and the integrated humidity is 36,000 to 432,000% R.I. H. -The time is the cement composition according to any one of [19] [9] to [15].
The integrated temperature is 200,268 to 1,378,955 K · hours, and the integrated humidity during the curing period is 36,000 to 432,000% R.I. H. A method of manufacturing a structure, including a step of curing to satisfy at least one of being time.
本発明によれば、セメント組成物に添加した際に、その構造物の外観性状を均一化し、乾燥及び水和反応に伴う収縮を低減することができ、クラック、色むら、連続性のない多量のクラック模様を抑制することのできるセメント混和剤が提供される。 According to the present invention, when added to a cement composition, the appearance properties of the structure can be made uniform, shrinkage due to drying and hydration reactions can be reduced, and a large amount without cracks, color unevenness, and continuity. A cement admixture capable of suppressing the crack pattern of the above is provided.
［セメント混和剤］
セメント混和剤は、以下のＡ及びＢ成分から選ばれる少なくともいずれかを有効成分とする。すなわち、セメント混和剤はＡ成分か、Ｂ成分か、又は、Ａ成分及びＢ成分の組みあわせを含む。
[Cement admixture]
The cement admixture contains at least one of the following A and B components as an active ingredient. That is, the cement admixture contains either the A component, the B component, or a combination of the A component and the B component.
（Ａ成分）
Ａ成分は、ポリプロピレングリコールである。ポリプロピレングリコールの製造方法としては例えば、プロピレングリコール等を出発原料とし、水酸化ナトリウム等のアルカリ触媒存在下、高温条件（例えば、１００〜２００℃）でプロピレンオキサイドを付加する方法が挙げられ、特に限定されない。ポリプロピレングリコールの平均分子量は、通常は２００以上、好ましくは３００以上である。これにより、所望の未吸着率と含水率が得られやすくなる。一方、上限は、通常６００以下、好ましくは４００以下である。これにより、水に添加して安定な水溶液を得ることができる。ポリプロピレングリコールの平均分子量は、通常２００〜６００、好ましくは３００〜４００である。３００〜４００である場合、溶液の安定性が良好となり得る。
(Component A)
Component A is polypropylene glycol. Examples of the method for producing polypropylene glycol include a method in which propylene glycol or the like is used as a starting material and propylene oxide is added under high temperature conditions (for example, 100 to 200 ° C.) in the presence of an alkaline catalyst such as sodium hydroxide, and is particularly limited. Not done. The average molecular weight of polypropylene glycol is usually 200 or more, preferably 300 or more. This makes it easier to obtain the desired non-adsorption rate and water content. On the other hand, the upper limit is usually 600 or less, preferably 400 or less. This makes it possible to obtain a stable aqueous solution by adding it to water. The average molecular weight of polypropylene glycol is usually 200-600, preferably 300-400. When it is 300 to 400, the stability of the solution can be good.
本明細書において、平均分子量は、ヒドロキシル価（基準油脂分析試験法２．３．６．２＿１９９６）の測定値を数式（１）：平均分子量＝（５６１０８／ヒドロキシル価）×２に代入して求めることができる。実施例の平均分子量は、斯かる方法で算出された数値である。 In the present specification, the average molecular weight is obtained by substituting the measured value of the hydroxyl value (reference oil and fat analysis test method 2.3.6.2_1996) into the mathematical formula (1): average molecular weight = (56108 / hydroxyl value) × 2. be able to. The average molecular weight of the examples is a numerical value calculated by such a method.
Ａ成分は、ポリプロピレングリコール１種でもよいし、分子量の異なる２種以上の組み合わせでもよい。 The component A may be one type of polypropylene glycol or a combination of two or more types having different molecular weights.
（Ｂ成分）
Ｂ成分は、以下の一般式（Ｉ）で表される化合物である。
Ｒ−Ｏ−（ＡＯ）n−Ｈ （Ｉ）
(B component)
The B component is a compound represented by the following general formula (I).
RO- (AO) n- H (I)
Ｒは、水素または炭素原子数２〜４の炭化水素基である。炭素原子数２〜４の炭化水素基は、不飽和結合を有していてもよいが、アルキル基（直鎖、分岐鎖）が好ましい。炭素原子数２〜４の炭化水素基としては、例えば、エチル基、プロピル基、イソプロピル基及びブチル基（ｎ−ブチル基、イソブチル基、ｔ−ブチル基）が挙げられる。Ｒは、炭素原子数２〜４の炭化水素基が好ましく、炭素原子数３〜４の炭化水素基（例えば、プロピル基、イソプロピル基、ブチル基、中でも、プロピル基、ブチル基）がより好ましく、炭素原子数４の炭化水素基（ブチル基）がさらに好ましい。 R is hydrogen or a hydrocarbon group having 2 to 4 carbon atoms. The hydrocarbon group having 2 to 4 carbon atoms may have an unsaturated bond, but an alkyl group (straight chain, branched chain) is preferable. Examples of the hydrocarbon group having 2 to 4 carbon atoms include an ethyl group, a propyl group, an isopropyl group and a butyl group (n-butyl group, isobutyl group, t-butyl group). R is preferably a hydrocarbon group having 2 to 4 carbon atoms, more preferably a hydrocarbon group having 3 to 4 carbon atoms (for example, a propyl group, an isopropyl group, a butyl group, particularly a propyl group or a butyl group). A hydrocarbon group (butyl group) having 4 carbon atoms is more preferable.
ＡＯは、オキシアルキレン基である。オキシアルキレン基の炭素原子数は、通常２〜３である。３以下であることにより、ａ質量％水への溶解性が良好となり、様々な温湿度環境下で本発明の効果を発現し得る。ＡＯは、１種のオキシアルキレン基のみで構成されてもよく、２種のオキシアルキレン基の組み合わせで構成されてもよい。ＡＯは、炭素原子数が炭素原子数２のオキシアルキレン基、又は、炭素原子数２のオキシアルキレン基と炭素原子数３のオキシアルキレン基の組み合わせがより好ましい。 AO is an oxyalkylene group. The number of carbon atoms of the oxyalkylene group is usually 2 to 3. When it is 3 or less, the solubility in a mass% water becomes good, and the effect of the present invention can be exhibited under various temperature and humidity environments. The AO may be composed of only one kind of oxyalkylene group or may be composed of a combination of two kinds of oxyalkylene groups. The AO is more preferably an oxyalkylene group having 2 carbon atoms or a combination of an oxyalkylene group having 2 carbon atoms and an oxyalkylene group having 3 carbon atoms.
ｎはオキシアルキレン基の付加モル数であり、オキシアルキレン基が２種の場合にはそれらの合計付加モル数である。ｎは１〜１０の整数であり、２〜５が好ましい。炭素原子数が２のオキシアルキレン基の付加モル数は２〜３が好ましい。炭素原子数が３のオキシアルキレン基の付加モル数は２以下が好ましい。 n is the number of moles of oxyalkylene groups added, and when there are two types of oxyalkylene groups, it is the total number of moles of oxyalkylene groups added. n is an integer of 1 to 10, preferably 2 to 5. The number of moles of the oxyalkylene group having 2 carbon atoms is preferably 2 to 3. The number of moles of the oxyalkylene group having 3 carbon atoms is preferably 2 or less.
一般式（Ｉ）で表される化合物の平均分子量は、Ｒが水素原子の場合、２００〜６００が好ましく、３００〜４００がより好ましい。一方、例えば、Ｒが炭素原子数２〜４の炭化水素基の場合、化合物の平均分子量は１００〜２５００又は１５０〜２５００が好ましく、１００〜６００又は１５０〜６００がより好ましい。 When R is a hydrogen atom, the average molecular weight of the compound represented by the general formula (I) is preferably 200 to 600, more preferably 300 to 400. On the other hand, for example, when R is a hydrocarbon group having 2 to 4 carbon atoms, the average molecular weight of the compound is preferably 100 to 2500 or 150 to 2500, more preferably 100 to 600 or 150 to 600.
Ｂ成分は、一般式（Ｉ）で表される化合物１種でもよいし、構造の異なる２種以上の組み合わせでもよい。 The B component may be one kind of the compound represented by the general formula (I), or may be a combination of two or more kinds having different structures.
（任意成分）
セメント混和剤は、任意成分を含んでもよい。任意成分としては、例えば、安定剤、賦形剤、保存剤、防腐剤、香料、着色料、他のセメント混和剤が挙げられる。他のセメント混和剤についてはセメント組成物の欄で説明する。任意成分の種類及び含有量は本発明の効果を阻害しない程度で適宜選択すればよい。
(Arbitrary ingredient)
The cement admixture may contain any component. Optional ingredients include, for example, stabilizers, excipients, preservatives, preservatives, fragrances, colorants and other cement admixtures. Other cement admixtures will be described in the section on cement compositions. The type and content of the optional component may be appropriately selected to the extent that the effect of the present invention is not impaired.
（セメント混和剤の添加量）
セメント混和剤は、セメント組成物の一成分として使用できる。セメント混和剤の、セメント組成物への添加量は、以下の工程（１）〜（４）を含む添加量確認方法により確認できる。
工程（１）：有効成分、セメント及び水からなる、有効成分のセメント質量に対する質量比がａ質量％であるサンプルを得ること；
工程（２）：サンプルを脱水し分離水を得ること；
工程（３）：分離水の表面張力をＷｉｌｈｅｌｍｙ法により測定すること；及び
工程（４）：測定された表面張力が６０ｄｙｎ／ｃｍ以下であることを確認する工程。
(Amount of cement admixture added)
The cement admixture can be used as a component of the cement composition. The amount of the cement admixture added to the cement composition can be confirmed by an addition amount confirmation method including the following steps (1) to (4).
Step (1): Obtaining a sample consisting of the active ingredient, cement and water, in which the mass ratio of the active ingredient to the cement mass is a mass%;
Step (2): Dehydrate the sample to obtain separated water;
Step (3): Measure the surface tension of the separated water by the Wilhelmy method; and Step (4): Confirm that the measured surface tension is 60 dyn / cm or less.
添加量確認工程は、さらに以下の工程（５）と（６）を含んでもよい。
工程（５）：分離水中の炭素量と、工程（１）においてセメント混和剤を添加しない他は同様に調製したブランク組成物を工程（２）と同様に処理して得たブランク分離水中の炭素量を測定し、以下の式にて未吸着率を算出する工程
式：
未吸着率＝〔分離水中の炭素量／ブランク分離水中の炭素量〕×１００；及び
工程（６）：算出された未吸着率が３０％以上であることを確認する工程。
The addition amount confirmation step may further include the following steps (5) and (6).
Step (5): Carbon in the blank separation water obtained by treating the amount of carbon in the separation water and the blank composition prepared in the same manner as in the step (2) except that the cement admixture was not added in the step (1). Process formula to measure the amount and calculate the non-adsorption rate by the following formula:
Unadsorbed rate = [Carbon amount in separated water / Carbon amount in blank separated water] × 100; and step (6): Step of confirming that the calculated unadsorbed rate is 30% or more.
工程（１）では、セメント混和剤の有効成分、セメント及び水からなる、有効成分のセメント質量に対する質量比がａ質量％であるサンプルを得る。セメント混和剤の有効成分は、使用されるセメント混和剤の有効成分であり、Ａ成分及びＢ成分からなる群より選ばれる少なくとも１種である。セメントは、セメント混和剤が添加されるセメント組成物に用いるセメントと同じでも別でもよいが、普通ポルトランドセメントが好ましい。サンプルにおける水セメント質量比（Ｗ／Ｃ）は特に限定されないが、通常は１００％である。サンプルの調製は、通常のセメントペーストの調製方法によればよく、ハンドミキサ等の撹拌装置を用いてもよい。サンプルは、通常、ペースト状を呈する。 In the step (1), a sample consisting of the active ingredient of the cement admixture, cement and water, in which the mass ratio of the active ingredient to the mass of the cement is a mass% is obtained. The active ingredient of the cement admixture is the active ingredient of the cement admixture used, and is at least one selected from the group consisting of the A component and the B component. The cement may be the same as or different from the cement used in the cement composition to which the cement admixture is added, but usually Portland cement is preferable. The water-cement mass ratio (W / C) in the sample is not particularly limited, but is usually 100%. The sample may be prepared according to a usual cement paste preparation method, and a stirring device such as a hand mixer may be used. The sample is usually in the form of a paste.
工程（２）では、サンプルを脱水し分離水を得る。脱水方法は、遠心分離、ろ過等の常法でよい。遠心分離の条件は特に限定されないが、例えば、遠心分離の時間は１〜４分の範囲で定めることができ、回転数は２，０００〜３，０００ｒｐｍの範囲で定めることができる。ろ過は、ガラス繊維ろ紙を用いることができる。 In step (2), the sample is dehydrated to obtain separated water. The dehydration method may be a conventional method such as centrifugation or filtration. The conditions for centrifugation are not particularly limited, but for example, the time for centrifugation can be set in the range of 1 to 4 minutes, and the rotation speed can be set in the range of 2,000 to 3,000 rpm. For filtration, glass fiber filter paper can be used.
工程（３）では、分離水の表面張力をＷｉｌｈｅｌｍｙ法により測定する。Ｗｉｌｈｅｌｍｙ法は、測定子（固体平板）の先端を液体表面に接触させ引き上げた時に測定子と界面の接触角θと、測定子に働く力Ｆ（ｄｙｎ）を測定し、濡れ長さＬ（ｃｍ）より、以下の式で表面張力σ（ｄｙｎ／ｃｍ）を算出する方法である。
式：σ＝Ｆ／（Ｌｃｏｓθ）
In step (3), the surface tension of the separated water is measured by the Wilhelmy method. In the Wilhelmy method, when the tip of a stylus (solid flat plate) is brought into contact with the liquid surface and pulled up, the contact angle θ between the stylus and the interface and the force F (dyn) acting on the stylus are measured, and the wet length L (cm) is measured. ) To calculate the surface tension σ (dyn / cm) by the following formula.
Equation: σ = F / (Lcosθ)
表面張力の測定時期は、分離水を調整直後でもよいし、３０分以内の時間経過後でもよい。表面張力測定時の温度は、１５〜２５℃が好ましく、１９〜２１℃がより好ましい。表面張力の測定には機器（例えば、高精度表面張力計、高機能表面張力計、児童表面張力計、動的接触角測定器）を用いてもよい。 The surface tension may be measured immediately after the separated water is adjusted, or after a lapse of time within 30 minutes. The temperature at the time of measuring the surface tension is preferably 15 to 25 ° C, more preferably 19 to 21 ° C. An instrument (for example, a high-precision surface tension meter, a high-performance surface tension meter, a child surface tension meter, a dynamic contact angle measuring device) may be used for measuring the surface tension.
工程（４）では、測定された表面張力が６０ｄｙｎ／ｃｍ以下であることを確認する。これにより、セメント混和剤を含むセメント組成物において、型枠面へ流動させるための表面張力を確保することができ、セメント粒子間に形成されるメニスカスに働く毛細管張力を低減することができる。そのため、確認が取れたａ質量％をサンプルにおける有効成分の量（セメント質量に対する質量比）をそのまま採用することで、様々な温湿度条件下で本発明の効果を得ることができる。 In step (4), it is confirmed that the measured surface tension is 60 dyn / cm or less. Thereby, in the cement composition containing the cement admixture, the surface tension for flowing to the mold surface can be secured, and the capillary tension acting on the meniscus formed between the cement particles can be reduced. Therefore, the effect of the present invention can be obtained under various temperature and humidity conditions by directly adopting the confirmed a mass% as the amount of the active ingredient (mass ratio with respect to the cement mass) in the sample.
工程（５）では、分離水中の炭素量と、工程（１）においてセメント混和剤を添加しない他は同様に調製したブランク組成物を工程（２）と同様に処理して得たブランク分離水中の炭素量を測定し、以下の式にて未吸着率を算出する。
式：
未吸着率＝〔分離水中の炭素量／ブランク分離水中の炭素量〕×１００
In step (5), the amount of carbon in the separated water and the blank composition prepared in the same manner except that the cement admixture was not added in step (1) were treated in the same manner as in step (2) in the blank separated water. The amount of carbon is measured, and the non-adsorption rate is calculated by the following formula.
formula:
Unadsorbed rate = [Carbon content in separated water / Carbon content in blank separated water] x 100
未吸着率とは、有効成分（Ａ又はＢ成分）の全量に対するセメントへ吸着していない量の比率である。炭素量の測定時期は、分離水を調整直後でもよいが、工程（１）におけるサンプルの調製時（すなわち、セメントと水分が接触した時）から１時間後が好ましい。炭素量測定時の温度は、１５〜２５℃が好ましく、１９〜２１℃がより好ましい。炭素量の測定には機器（例えば、全有機炭素測定装置）を用いてもよい。 The non-adsorption rate is the ratio of the amount of the active ingredient (A or B component) not adsorbed to the cement to the total amount. The carbon content may be measured immediately after the separated water is adjusted, but is preferably one hour after the sample is prepared in step (1) (that is, when the cement and water come into contact with each other). The temperature at the time of carbon content measurement is preferably 15 to 25 ° C, more preferably 19 to 21 ° C. An instrument (for example, a total organic carbon measuring device) may be used for measuring the amount of carbon.
工程（６）では、工程（５）で算出された未吸着率が３０％以上であることを確認する。未吸着率が３０％以上であることにより、水和反応後もバルク水に残存するＡ成分及び／又はＢ成分を確保することで，セメントや結合材粒子の近接を抑制し、セメント組成物を打設した際、セメントペーストの型枠面への移動を促し，バルク水の飽和蒸気圧の低下によりセメント組成物内の内部相対湿度を高く保つ効果により，硬化過程の体積変化を低減し、水分逸散による体積変化を低減させることができる。そのため本工程において確認が取れれば、ａ質量％をそのまま採用することで、本発明の効果を得ることができる。 In the step (6), it is confirmed that the non-adsorption rate calculated in the step (5) is 30% or more. When the non-adsorption rate is 30% or more, the A component and / or the B component remaining in the bulk water even after the hydration reaction is secured, so that the proximity of cement and binder particles is suppressed, and the cement composition is formed. When placed, it promotes the movement of cement paste to the mold surface, reduces the volume change in the hardening process by the effect of keeping the internal relative humidity in the cement composition high by lowering the saturated vapor pressure of bulk water, and reduces the moisture content. The volume change due to dissipation can be reduced. Therefore, if confirmation can be obtained in this step, the effect of the present invention can be obtained by adopting a mass% as it is.
セメント混和剤の添加量は、上記の添加量確認方法により確認される有効成分の量（ａ質量％：対セメント質量）が好ましいが、通常０．１質量％以上、好ましくは０．２７質量％以上である。上限は、通常１５．０質量％以下、１０．０質量％以下、７．０質量％以下、６．０質量％以下、５．０質量％以下、３．０質量％以下、又は２．０質量％以下、好ましくは０．９質量％以下、より好ましくは０．８２質量％以下である。従って、セメント混和剤の使用量は、セメント組成物質量に対し通常０．１〜１５．０質量％又は０．１〜１０．０質量％、０．１〜７．０質量％、０．１〜６．０質量％、０．１〜５．０質量％、０．１〜３．０質量％、又は０．１〜２．０質量％、好ましくは０．１〜０．９質量％、より好ましくは０．２７〜０．８２質量％である。 The amount of the cement admixture added is preferably the amount of the active ingredient (a mass%: mass relative to cement) confirmed by the above-mentioned addition amount confirmation method, but is usually 0.1% by mass or more, preferably 0.27% by mass. That is all. The upper limit is usually 15.0% by mass or less, 10.0% by mass or less, 7.0% by mass or less, 6.0% by mass or less, 5.0% by mass or less, 3.0% by mass or less, or 2.0. It is mass% or less, preferably 0.9 mass% or less, and more preferably 0.82 mass% or less. Therefore, the amount of the cement admixture used is usually 0.1 to 15.0% by mass or 0.1 to 10.0% by mass, 0.1 to 7.0% by mass, 0.1 with respect to the amount of the cement composition substance. ~ 6.0% by mass, 0.1 to 5.0% by mass, 0.1 to 3.0% by mass, or 0.1 to 2.0% by mass, preferably 0.1 to 0.9% by mass, More preferably, it is 0.27 to 0.82% by mass.
［セメント組成物］
セメント組成物は、上述のセメント混和剤、セメント及び水を含む。セメント混和剤の含有量は、上述のセメント混和剤における添加量確認方法にて確認した添加量を採用することが好ましい。
[Cement composition]
The cement composition comprises the above-mentioned cement admixtures, cement and water. As the content of the cement admixture, it is preferable to adopt the addition amount confirmed by the above-mentioned addition amount confirmation method in the cement admixture.
（水、セメントの構成比率）
セメント組成物は、セメント混和剤以外にセメントと水を少なくとも含めばよく、それらの構成比率（セメント組成物に対する質量比）は、特に限定されない。一例をあげると以下のとおりである。水分の構成比率は、下限は通常３質量％以上である。上限は通常１５質量％以下、好ましくは１２質量％以下である。従って、水分の構成比率は好ましくは３〜１５質量％、好ましくは５〜１２質量％である。セメントの構成比率は、下限は通常５質量％以上又は１０質量％以上である。上限は通常９５質量％以下、好ましくは６５質量％以下である。従って、セメントの構成比率は好ましくは５〜９５質量％、好ましくは１０〜６５質量％である。セメント組成物の水セメント質量比は、通常は０．６以下、好ましくは０．４５以下である。
(Composition ratio of water and cement)
The cement composition may contain at least cement and water in addition to the cement admixture, and their composition ratio (mass ratio to cement composition) is not particularly limited. An example is as follows. The lower limit of the composition ratio of water is usually 3% by mass or more. The upper limit is usually 15% by mass or less, preferably 12% by mass or less. Therefore, the composition ratio of water is preferably 3 to 15% by mass, preferably 5 to 12% by mass. The lower limit of the composition ratio of cement is usually 5% by mass or more or 10% by mass or more. The upper limit is usually 95% by mass or less, preferably 65% by mass or less. Therefore, the composition ratio of cement is preferably 5 to 95% by mass, preferably 10 to 65% by mass. The water-cement mass ratio of the cement composition is usually 0.6 or less, preferably 0.45 or less.
（セメント）
本明細書においてセメントは、セメント自体のほか、石膏（半水石膏、二水石膏など）、ドロマイト等の水硬性材料一般を包含する。
(cement)
In the present specification, cement includes not only cement itself but also general hydraulic materials such as gypsum (hemihydrate gypsum, dihydric gypsum, etc.) and dolomite.
セメントは、水硬性セメントであれば特に限定されない。例えば、ポルトランドセメント（普通、早強、超早強、中庸熱、耐硫酸塩およびそれぞれの低アルカリ形）、高炉セメント（Ａ種、Ｂ種、Ｃ種）、シリカセメント（Ａ種、Ｂ種、Ｃ種）、フライアッシュセメント（Ａ種、Ｂ種、Ｃ種）、エコセメント（普通、速硬）、シリカフュームセメント、白色ポルトランドセメント、アルミナセメント、超速硬セメント（１クリンカー速硬性セメント、２クリンカー速硬性セメント、リン酸マグネシウムセメント）、グラウト用セメント、油井セメント、低発熱セメント（低発熱型高炉セメント、フライアッシュ混合低発熱型高炉セメント、ビーライト高含有セメント）、超高強度セメント、セメント系固化材、エコセメント（都市ごみ焼却灰、下水汚泥焼却灰の１種以上を原料として製造されたセメント）が挙げられる。セメントは、結合材を含んでいてもよい。 The cement is not particularly limited as long as it is a hydraulic cement. For example, Portoland cement (normal, fast-strength, super-fast-strength, moderate heat, sulfate-resistant and each low-alkali form), blast furnace cement (A, B, C), silica cement (A, B, etc.) Type C), Fly Ash Cement (Type A, Type B, Type C), Eco Cement (Normal, Fast Hard), Silica Fume Cement, White Portoland Cement, Alumina Cement, Ultra Fast Hard Cement (1 Clinker Fast Hard Cement, 2 Clinker Fast) Hard cement, magnesium phosphate cement), grout cement, oil well cement, low heat generation cement (low heat generation type blast furnace cement, fly ash mixed low heat generation type blast furnace cement, belite high content cement), ultra-high strength cement, cement-based solidification Materials and eco-cement (cement manufactured from one or more of municipal waste incineration ash and sewage sludge incineration ash) can be mentioned. The cement may contain a binder.
（水）
水としては、例えば、ＪＩＳ Ａ ５３０８（２０１９）付属書Ｃに示される上水道水、上水道水以外の水（河川水、湖沼水、井戸水等）、回収水が挙げられる。
(water)
Examples of the water include tap water shown in Annex C of JIS A 5308 (2019), water other than tap water (river water, lake water, well water, etc.), and recovered water.
（任意成分）
セメント組成物は、セメント混和剤、水及びセメント以外の任意成分を含んでもよい。任意成分としては、例えば、骨材（例えば、細骨材、粗骨材）、結合材、他のセメント混和剤が挙げられる。
(Arbitrary ingredient)
The cement composition may contain any component other than cement admixture, water and cement. Optional components include, for example, aggregates (eg, fine aggregates, coarse aggregates), binders, and other cement admixtures.
骨材は、細骨材及び粗骨材のいずれであってもよい。細骨材としては例えば、砂（例、川砂、山砂、海砂、砕砂）、砕石、重量骨材、軽量骨材、スラグ骨材（例、水砕スラグ）、再生骨材、石灰石骨材、回収骨材、人工軽量骨材、耐火骨材が挙げられる。粗骨材としては、例えば、砂利（例、川砂利）、砕石、重量骨材、軽量骨材、スラグ骨材（例、水砕スラグ）、再生骨材、耐火骨材が挙げられる。骨材の成分としては、例えば、珪石質、粘土質、ジルコン質、ハイアルミナ質、炭化珪素質、黒鉛質、クロム質、クロマグ質、マグネシア質が挙げられる。 The aggregate may be either a fine aggregate or a coarse aggregate. Examples of fine aggregates include sand (eg, river sand, mountain sand, sea sand, crushed sand), crushed stone, heavy aggregate, lightweight aggregate, slag aggregate (eg, granulated slag), recycled aggregate, limestone aggregate. , Recovered aggregate, artificial lightweight aggregate, fireproof aggregate. Examples of the coarse aggregate include gravel (eg, river gravel), crushed stone, heavy aggregate, lightweight aggregate, slag aggregate (eg, granulated slag), recycled aggregate, and fireproof aggregate. Examples of the components of the aggregate include silica stone, clay, zircon, high alumina, silicon carbide, graphite, chromium, chromag, and magnesia.
結合材としては例えば、高炉スラグ微粉末、フライアッシュ、シンダーアッシュ、クリンカーアッシュ、ハスクアッシュ、シリカフューム、シリカ粉末、石灰石微粉末等の微粉体が挙げられる。 Examples of the binder include fine powders such as blast furnace slag fine powder, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, and limestone fine powder.
他のセメント混和剤としては例えば、硬化促進剤、消泡剤、凝結遅延剤、防錆剤、防水剤、セメント分散剤、水溶性高分子、高分子エマルジョン、セメント湿潤剤、膨張剤、防水剤、遅延剤、増粘剤、凝集剤、乾燥収縮低減剤、強度増進剤、消泡剤、ＡＥ剤、界面活性剤、減水剤、高性能減水剤、ＡＥ減水剤、高性能ＡＥ減水剤、流動化剤、圧送助剤、低チキソトロピー性助剤等が挙げられ、これらのうち１種又は２種以上の組み合わせを用い得る。各剤の含有量は特に限定されない。 Other cement admixtures include, for example, hardening accelerators, defoamers, setting retarders, rust preventives, waterproofing agents, cement dispersants, water-soluble polymers, polymer emulsions, cement wetting agents, swelling agents, waterproofing agents. , Delaying agent, thickener, flocculant, drying shrinkage reducing agent, strength enhancing agent, defoaming agent, AE agent, surfactant, water reducing agent, high performance water reducing agent, AE water reducing agent, high performance AE water reducing agent, flow Agents, pumping aids, low thixotropic aids and the like can be mentioned, and one or a combination of two or more of these can be used. The content of each agent is not particularly limited.
硬化促進剤としては、例えば、塩化カルシウム、亜硝酸カルシウム、硝酸カルシウム等の可溶性カルシウム塩類；塩化鉄、塩化マグネシウム等の塩化物類；チオ硫酸塩；ギ酸及びギ酸カルシウム等のギ酸塩類が挙げられる。消泡剤としては、例えば、フローリック社製「ＤＦ−７５３」が挙げられる。セメント分散剤としては、例えば、ナフタレンスルホン酸ホルムアルデヒド縮合物、メラミンスルホン酸ホルムアルデヒド縮合物等の分散剤が挙げられる。水溶性高分子としては、例えば、ポリアルキレングリコールが挙げられる。より詳細には、ポリエチレングリコール、ポリプロピレングリコール、ポリエチレンポリプロピレングリコール、ポリエチレンポリブチレングリコール等が挙げられる。遅延剤としては、例えば、グルコン酸（塩）、クエン酸（塩）等のオキシカルボン酸類；グルコース等の糖類；ソルビトール等の糖アルコール類が挙げられる。増粘剤としては、例えば、メチルセルロース、ヒドロキシプロピルメチルセルロース、カルボキシメチルセルロース、セルロースナノファイバー、セルロースナノクリスタルが挙げられる。高性能ＡＥ減水剤としては、例えば、フローリック社製「フローリックＳＦ５００Ｓ」「フローリックＳＦ５００Ｈ」「フローリックＳＦ５００Ｕ」が挙げられる。低チキソトロピー性助剤としては、例えば、フローリック社製「フローリックＦＢＬ−２００」が挙げられる。 Examples of the curing accelerator include soluble calcium salts such as calcium chloride, calcium nitrite and calcium nitrate; chlorides such as iron chloride and magnesium chloride; thiosulfates; and formates such as formic acid and calcium formate. Examples of the defoaming agent include "DF-753" manufactured by Floric. Examples of the cement dispersant include dispersants such as naphthalene sulfonic acid formaldehyde condensate and melamine sulfonic acid formaldehyde condensate. Examples of the water-soluble polymer include polyalkylene glycol. More specifically, polyethylene glycol, polypropylene glycol, polyethylene polypropylene glycol, polyethylene polybutylene glycol and the like can be mentioned. Examples of the delaying agent include oxycarboxylic acids such as gluconic acid (salt) and citric acid (salt); sugars such as glucose; and sugar alcohols such as sorbitol. Examples of the thickener include methyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, cellulose nanofibers, and cellulose nanocrystals. Examples of the high-performance AE water reducing agent include "Floric SF500S", "Floric SF500H" and "Floric SF500U" manufactured by Floric. Examples of the low thixotropy aid include "Floric FBL-200" manufactured by Floric.
（任意成分の構成比率）
任意成分の構成比率は特に限定されない。一例をあげると次のとおりである。結合材の構成比率は、下限は通常５質量％以上、好ましくは１０質量％以上である。上限は通常９５質量％以下、好ましくは４７．５質量％以下である。結合材が高炉スラグである場合、高炉スラグの含有量の上限は、１５質量％以下が好ましい。従って、結合材の構成比率は、好ましくは５〜９５質量％、より好ましくは５〜６０質量％である。細骨材の構成比率の下限は、通常３質量％以上である。上限は通常９０質量％以下、より好ましくは７０質量％以下である。従って、細骨材の構成比率は、好ましくは３〜９０質量％又は１０〜７０質量％である。粗骨材の構成比率は、８５質量％以下が好ましい。
(Composition ratio of arbitrary components)
The composition ratio of the optional component is not particularly limited. An example is as follows. The lower limit of the composition ratio of the binder is usually 5% by mass or more, preferably 10% by mass or more. The upper limit is usually 95% by mass or less, preferably 47.5% by mass or less. When the binder is blast furnace slag, the upper limit of the content of blast furnace slag is preferably 15% by mass or less. Therefore, the composition ratio of the binder is preferably 5 to 95% by mass, more preferably 5 to 60% by mass. The lower limit of the composition ratio of the fine aggregate is usually 3% by mass or more. The upper limit is usually 90% by mass or less, more preferably 70% by mass or less. Therefore, the composition ratio of the fine aggregate is preferably 3 to 90% by mass or 10 to 70% by mass. The composition ratio of the coarse aggregate is preferably 85% by mass or less.
（結合材を含む場合の水とセメント及び結合材の合計量との質量比）
例えば、セメント組成物が結合材を含まない場合、水セメント質量比は上述のとおり０．４５以下が好ましい。結合材が高炉スラグ微粉末である場合、（好ましくはセメント質量に対して１５％以下使用）は、水とセメントおよび結合材合計量との質量比（水／（セメント＋結合材））は０．４５以下が好ましい。高炉スラグ微粉末の添加量がセメント質量に対して６０％以下、８０％の場合、前記質量比はそれぞれ０．４３以下、０．３５以下が好ましい。結合材が高炉スラグ微粉末以外（例えばフライアッシュ）である場合、前記質量比は、水セメント質量比０．４５の場合と同等の強度発現性を発揮し得る質量比とすることが好ましい。
(Mass ratio of water to total amount of cement and binder when binder is included)
For example, when the cement composition does not contain a binder, the water-cement mass ratio is preferably 0.45 or less as described above. When the binder is blast furnace slag fine powder (preferably 15% or less of the cement mass is used), the mass ratio of water to the total amount of cement and cement (water / (cement + cement)) is 0. .45 or less is preferable. When the amount of the blast furnace slag fine powder added is 60% or less and 80% with respect to the cement mass, the mass ratio is preferably 0.43 or less and 0.35 or less, respectively. When the binder is other than blast furnace slag fine powder (for example, fly ash), the mass ratio is preferably a mass ratio capable of exhibiting strength equivalent to that in the case of a water cement mass ratio of 0.45.
セメント組成物の性状は特に限定されず、例えば、セメント及び水から成るセメントペースト、セメントペーストと細骨材から成るモルタル、又は、モルタルと粗骨材から成るコンクリートに、上記セメント混和剤と任意の他のセメント混和剤が添加されて成る組成物が挙げられる。セメント組成物の製造方法は特に限定されず、例えば、各成分を配合し混練する方法が挙げられる。 The properties of the cement composition are not particularly limited, and for example, a cement paste composed of cement and water, a mortar composed of cement paste and fine aggregate, or concrete composed of mortar and coarse aggregate can be mixed with the above cement admixture and any of the above cement admixtures. Examples thereof include compositions in which other cement admixtures are added. The method for producing the cement composition is not particularly limited, and examples thereof include a method of blending and kneading each component.
［セメント組成物の構造体］
セメント組成物を必要に応じて運搬し、打設、養生することにより、セメント組成物の構造体が得られる。構造体を得る方法は特に限定されないが、一例をあげると以下のとおりである。セメント組成物を必要に応じて運搬し、打設後、常温（例えば２０℃）で乾燥しないように２４時間静置し、注水２４時間後に脱形、２０℃の水槽で２８日水中養生した際の強度（材齢２８日）が３６ＭＰａ以上であることが好ましい。これにより、収縮の原因となる体積変化が改善でき、かつ、セメント組成物の外観性状も改善できる。また、セメント組成物の養生条件は、養生期間中の積算温度が２００，２６８〜１，３７８，９５５Ｋ・時間、及び積算湿度が３６，０００〜４３２，０００％Ｒ．Ｈ．・時間であること、の少なくともいずれかを満たすよう養生することが好ましい。積算温度及び積算湿度は、養生期間中に受ける温度及び湿度の積算値である。養生期間とは、組成物の調製時（全材料の混練完了時）から養生完了時までの期間であり、通常、７２０〜４３９２時間である。養生期間中の温度は、通常９０℃以下、好ましくは６０℃以下である。下限は、通常−５℃以上、好ましくは５℃以上である。従って、養生期間中の温度は、通常−５〜９０℃、より好ましくは５〜９０℃、更に好ましくは５〜６０℃である。養生期間中の湿度は、通常５０％Ｒ．Ｈ．以上であり、好ましくは５０〜１００％Ｒ．Ｈ．である。
[Structure of cement composition]
The structure of the cement composition is obtained by transporting, placing and curing the cement composition as needed. The method for obtaining the structure is not particularly limited, but an example is as follows. When the cement composition is transported as needed, after casting, it is allowed to stand for 24 hours so as not to dry at room temperature (for example, 20 ° C), deformed 24 hours after water injection, and cured in water at 20 ° C for 28 days. The strength (material age 28 days) is preferably 36 MPa or more. As a result, the volume change that causes shrinkage can be improved, and the appearance properties of the cement composition can also be improved. The curing conditions of the cement composition were as follows: the integrated temperature during the curing period was 200,268 to 1,378,955 K · hours, and the integrated humidity was 36,000 to 432,000% R.I. H. -It is preferable to cure so as to satisfy at least one of the time. The integrated temperature and integrated humidity are integrated values of the temperature and humidity received during the curing period. The curing period is a period from the time when the composition is prepared (when the kneading of all the materials is completed) to the time when the curing is completed, and is usually 720 to 4392 hours. The temperature during the curing period is usually 90 ° C. or lower, preferably 60 ° C. or lower. The lower limit is usually −5 ° C. or higher, preferably 5 ° C. or higher. Therefore, the temperature during the curing period is usually −5 to 90 ° C., more preferably 5 to 90 ° C., still more preferably 5 to 60 ° C. Humidity during the curing period is usually 50% R.M. H. The above is preferable, and 50 to 100% R.I. H. Is.
セメント組成物の構造体は、探傷減少率が５０％以上（好ましくは、５５％以上、より好ましくは，６５％以上）であること、含水率比が１００．１〜１１０％（好ましくは、１００．１〜１０８％、より好ましくは１００．１〜１０５％）であること、自己体積変化低減率が１０％以上（好ましくは、１５％以上、より好ましくは３０％以上）であること、乾燥体積変化低減率が１０％以上（好ましくは、１５％以上、より好ましくは３０％以上）であること、積算温度が２００，２６８〜１，３７８，９５５Ｋ・時間（好ましくは、７８９，６０７〜１，３７８，９５５Ｋ・時間、より好ましくは１，０８４，２８３〜１，３７８，９５５Ｋ・時間）、及び積算湿度が３６，０００〜４３２，０００％Ｒ．Ｈ．・時間（好ましくは、２１６，０００〜４３２，０００％Ｒ．Ｈ．・時間、より好ましくは３３３，０００〜４３２，０００％Ｒ．Ｈ．・時間）であること、からなる群より選ばれるいずれかを満たすことが好ましく、少なくとも２つを満たすことがより好ましく、全てを満たすことがさらに好ましい。これにより、構造体がクラック、色むら、連続性のない多量のクラック模様が抑制されていることを確認できる。
探傷減少率とは、構造体の探傷面積の、本発明のセメント混和剤が無添加であるほかは同配合の比較構造体の探傷面積に対する減少率（％）である。探傷面積は、探傷検査により行うことができる。探傷検査は、例えば、以下の手順で進めることができる。蛍光振盪探傷剤をサンプルに塗布し、塗布面にブラックライトを照射して撮影し、撮影した画像の発色部分の面積を測定し、探傷面積の測定値を得る。
含水率比とは、構造体の含水率の、本発明のセメント混和剤が無添加であるほかは同配合の比較構造体の含水率に対する比率（％）である。含水率は、例えば、以下の手順で算出できる。温水にサンプルを浸漬した後質量を測定し、その後乾燥して乾燥質量を測定し、逸散した水分質量を乾燥質量で除して含水率（％）を算出する。
自己体積変化低減率とは、構造体の自己体積変化量の、本発明のセメント混和剤が無添加であるほかは同配合の比較構造体の自己体積変化量に対する比率（％）である。自己体積変化量の測定は、ＪＣＩ自己体積変化に関する研究委員会の試験方法（ＪＣＩ−ＳＡＳ２−２）に基づき実施すればよい。
乾燥体積変化低減率とは、構造体の乾燥体積変化量の、本発明のセメント混和剤が無添加であるほかは同配合の比較構造体の乾燥体積変化量に対する比率（％）である。乾燥体積変化量の測定は、ＪＩＳ Ａ １１２９（２０１０）に準拠して実施すればよい。
積算温度とは、ケルビン温度と時間を乗じたものである。積算温度の算出は、例えば、セルシウス温度２０度で１時間の積算温度は、２９３．１５２５１９Ｋ×１Ｈｏｕｒ＝２９３．１５２５１９Ｋ・Ｈとなる。
積算湿度とは、相対湿度と時間を乗じたものである。積算湿度の算出は、例えば、８０％Ｒ．Ｈ．で１時間の積算湿度は、８０％Ｒ．Ｈ．×１Ｈｏｕｒ＝８０％Ｒ．Ｈ．・Ｈとなる。
The structure of the cement composition has a scratch detection reduction rate of 50% or more (preferably 55% or more, more preferably 65% or more) and a water content ratio of 10.1 to 110% (preferably 100). 1 to 108%, more preferably 10.1 to 105%), self-volume change reduction rate of 10% or more (preferably 15% or more, more preferably 30% or more), dry volume The change reduction rate is 10% or more (preferably 15% or more, more preferably 30% or more), and the integrated temperature is 200,268 to 1,378,955 K · hours (preferably 789,607 to 1,). 378,955 K. hours, more preferably 1,084,283 to 1,378,955 K. hours), and an integrated humidity of 36,000 to 432,000% R. et al. H. -Any selected from the group consisting of hours (preferably 216,000 to 432,000% RH-hours, more preferably 333,000 to 432,000% RH-hours). It is preferable to satisfy the above, it is more preferable to satisfy at least two, and it is further preferable to satisfy all of them. As a result, it can be confirmed that cracks, color unevenness, and a large amount of discontinuous crack patterns are suppressed in the structure.
The flaw detection reduction rate is the reduction rate (%) of the flaw detection area of the structure with respect to the flaw detection area of the comparative structure having the same composition except that the cement admixture of the present invention is not added. The flaw detection area can be determined by flaw detection inspection. The flaw detection inspection can be carried out by the following procedure, for example. A fluorescent shaking flaw detector is applied to the sample, the coated surface is irradiated with black light and photographed, and the area of the colored portion of the photographed image is measured to obtain a measured value of the flaw detection area.
The water content ratio is the ratio (%) of the water content of the structure to the water content of the comparative structure having the same composition except that the cement admixture of the present invention is not added. The water content can be calculated, for example, by the following procedure. After immersing the sample in warm water, the mass is measured, then dried to measure the dry mass, and the dispersed water mass is divided by the dry mass to calculate the water content (%).
The self-volume change reduction rate is the ratio (%) of the self-volume change amount of the structure to the self-volume change amount of the comparative structure having the same composition except that the cement admixture of the present invention is not added. The measurement of the amount of self-volume change may be carried out based on the test method (JCI-SAS2-2) of the Research Committee on JCI self-volume change.
The dry volume change reduction rate is the ratio (%) of the dry volume change amount of the structure to the dry volume change amount of the comparative structure having the same composition except that the cement admixture of the present invention is not added. The amount of change in dry volume may be measured in accordance with JIS A 1129 (2010).
The integrated temperature is the product of the Kelvin temperature and the time. For the calculation of the integrated temperature, for example, the integrated temperature for 1 hour at a Celsius temperature of 20 degrees is 293.152519K × 1Hour = 293.152519K · H.
The integrated humidity is the product of the relative humidity and the time. The cumulative humidity is calculated, for example, by 80% R.I. H. The cumulative humidity for 1 hour is 80% R. H. × 1Hour = 80% R. H.・ It becomes H.
以下に実施例及び比較例を挙げ、本発明の有効性を説明するが、実施例のみに本発明は限定されるものではない。 The effectiveness of the present invention will be described below with reference to Examples and Comparative Examples, but the present invention is not limited to the Examples.
［試験の概要］
試験区分１では、表面張力と未吸着率を確認した。表面張力は、セメントペーストが型枠面へ移動するために必要な項目である。骨材が型枠面に近接した場合、セメント組成物中のセメント成分と骨材の線膨張係数差及び収縮差，急激な乾燥により連続性のない多量のクラック模様の一要因である。また、クラックや連続性のない多量のクラック模様に影響を及ぼす水和に伴う体積変化に関しても、表面張力の低下によりメニスカスに働く毛細管張力を低減することで抑制が可能となる。さらに、表面張力の低下機能、乾燥及び水和に伴う体積変化を抑制するためには、界面活性剤が固相に吸着、捕捉されては効果を発揮しない。そのため、セメントペーストの分離水において表面張力及び未吸着率を測定することで、界面活性剤がバルク水に存在することを検証した。
[Outline of test]
In test category 1, surface tension and non-adsorption rate were confirmed. Surface tension is an item required for the cement paste to move to the formwork surface. When the aggregate is close to the formwork surface, it is one of the causes of a large amount of discontinuous crack patterns due to the difference in linear expansion coefficient and contraction between the cement component in the cement composition and the aggregate, and rapid drying. Further, the volume change due to hydration, which affects cracks and a large amount of discontinuous crack patterns, can be suppressed by reducing the capillary tension acting on the meniscus by reducing the surface tension. Further, in order to suppress the function of lowering the surface tension and the volume change due to drying and hydration, the surfactant is not effective if it is adsorbed and trapped in the solid phase. Therefore, it was verified that the surfactant was present in the bulk water by measuring the surface tension and the non-adsorption rate in the separated water of the cement paste.
試験区分２では、セメント組成物の構造物の圧縮強度、乾燥体積変化低減率、自己体積変化低減率、及び含水率の測定、探傷検査を実施した。乾燥及び自己体積変化率は、セメント組成物が内外の拘束条件下でのクラック発生に影響を及ぼす要因である。含水率比は、界面活性剤の保水性を評価する項目である。含水率比が高いと、急激な乾燥に対する耐性を付与できるとともに、セメントの水和に必要な水分の確保、体積変化の抑制効果が認められる。ただし、含水率が高くなると（例えば１０％以上）、強度の低下等の問題が生じる懸念がある。探傷検査は、クラック、色むら、連続性のない多量のクラック模様を包含して評価ができる試験である。これらの試験で性能を照査しその効果を実証した。 In Test Category 2, the compressive strength, dry volume change reduction rate, self-volume change reduction rate, and water content of the structure of the cement composition were measured and flaw detection inspection was carried out. Drying and self-volume change are factors that affect the formation of cracks in the cement composition under internal and external restraint conditions. The water content ratio is an item for evaluating the water retention of the surfactant. When the water content ratio is high, resistance to rapid drying can be imparted, water required for hydration of cement can be secured, and volume change can be suppressed. However, if the water content becomes high (for example, 10% or more), there is a concern that problems such as a decrease in strength may occur. The flaw detection inspection is a test that can include and evaluate a large number of crack patterns that are not continuous, such as cracks, color unevenness, and discontinuity. These tests verified the performance and demonstrated its effectiveness.
［界面活性剤］
試験区分１及び２のいずれにおいても、表１に示す界面活性剤Ｉ〜ＶＩを用いた。
[Surfactant]
In both test categories 1 and 2, the surfactants I to VI shown in Table 1 were used.
［試験区分１：表面張力と未吸着率］
環境温度２０℃の室内で、普通ポルトランドセメント（太平洋セメント社製、密度＝３．１６ｇ／ｃｍ3）、上水道水、界面活性剤Ｉ〜ＶＩを所定量計量し、ハンドミキサを用いてＷ／Ｃ＝１００％のセメントペーストを製作した。完全に練り上がった直後に３分間４，０００ｒｐｍで遠心分離にかけ、採取した分離水を５０マイクロのガラス繊維ろ紙でろ過し、試料を採取した。一方、界面活性剤Ｉ〜ＶＩを添加しない他は上記と同様の処理を実施し、ブランク試料を調製した。
[Test category 1: Surface tension and non-adsorption rate]
Weigh a predetermined amount of ordinary Portland cement (manufactured by Taiheiyo Cement, density = 3.16 g / cm 3 ), tap water, and surfactants I to VI in a room with an environmental temperature of 20 ° C, and use a hand mixer to perform W / C. = 100% cement paste was produced. Immediately after it was completely kneaded, it was centrifuged at 4,000 rpm for 3 minutes, and the collected separated water was filtered through a 50-micro glass fiber filter paper to collect a sample. On the other hand, a blank sample was prepared by carrying out the same treatment as above except that the surfactants I to VI were not added.
（表面張力）
各試料の表面張力をＷｉｌｈｅｌｍｙ法にて測定した。すなわち、測定機器（メーカー名：協和界面科学株式会社、商品名：ＤＹ−５００）を用いて、ろ過終了から５〜２０分後の２０℃における表面張力を測定した。
(surface tension)
The surface tension of each sample was measured by the Wilhelmy method. That is, the surface tension at 20 ° C. 5 to 20 minutes after the end of filtration was measured using a measuring device (manufacturer name: Kyowa Interface Science Co., Ltd., trade name: DY-500).
（未吸着率）
セメントペーストの調製（セメントと水分の接触）から１時間後に、各試料及びブランク試料の、ろ過終了から５〜２０分後の２０℃における炭素量を測定し、前者を後者で除した値を百分率して未吸着率を算出した。炭素量の測定には、全有機炭素測定装置を用いた。
(Unadsorbed rate)
One hour after the preparation of the cement paste (contact between cement and moisture), the carbon content of each sample and blank sample at 20 ° C. 5 to 20 minutes after the end of filtration was measured, and the value obtained by dividing the former by the latter was used as a percentage. The non-adsorption rate was calculated. A total organic carbon measuring device was used for measuring the amount of carbon.
［試験区分２：セメント組成物の試験］
原料（セメント、水、表１の化合物Ｉ〜ＶＩのいずれか、細骨材、粗骨材、減水剤）を混練し、セメント組成物を調製した。表３に、各実施例におけるセメント組成物の配合を示す。表３中、Ｗ／Ｃ、ｓ／ａ、Ｗ、Ｃはそれぞれ、水セメント質量比（％）、全骨材中の細骨材の占める容積比率（％）、水の単位量、セメントの単位量（Ｃ）を示した。また、表４〜６に、各実施例及び比較例におけるセメント組成物に配合した化合物の種類及び量を示した。
[Test Category 2: Cement Composition Test]
The raw materials (cement, water, any of the compounds I to VI in Table 1, fine aggregate, coarse aggregate, water reducing agent) were kneaded to prepare a cement composition. Table 3 shows the formulation of the cement composition in each example. In Table 3, W / C, s / a, W, and C are water cement mass ratio (%), volume ratio of fine aggregate in total aggregate (%), water unit amount, and cement unit, respectively. The quantity (C) is shown. In addition, Tables 4 to 6 show the types and amounts of the compounds blended in the cement compositions in each Example and Comparative Example.
（セメント）
普通ポルトランドセメント３種等量混合（密度＝３．１６ｇ／ｃｍ3、比表面積＝３３００ｃｍ2／ｇ）：Ｗ／Ｃ３０％以上のセメント組成物に使用
シリカフュームプレミクスセメント（密度＝３．０８ｇ／ｃｍ3、比表面積＝６２７０ｃｍ2／ｇ）：Ｗ／Ｃ３０％未満のセメント組成物に使用
(cement)
Ordinary Portland cement 3 types equal amount mixture (density = 3.16 g / cm 3 , specific surface area = 3300 cm 2 / g): Used for cement compositions with W / C of 30% or more Silica fume premix cement (density = 3.08 g / cm) 3 , Specific surface area = 6270 cm 2 / g): Used for cement compositions with W / C less than 30%
（細骨材）
掛川産山砂、密度＝２．５８ｇ／ｃｍ3
(Fine aggregate)
Kakegawa mountain sand, density = 2.58 g / cm 3
（粗骨材）
青梅産硬質砂岩砕石、密度＝２．６５ｇ／ｃｍ3
(Coarse aggregate)
Hard sandstone crushed stone from Ome, density = 2.65 g / cm 3
（減水剤）
（株）フローリック社製高性能ＡＥ減水剤ＳＦ５００Ｓ：Ｗ／Ｃ４０％以上のセメント組成物において、セメント質量に対し０．７質量％使用
（株）フローリック社製高性能ＡＥ減水剤ＳＦ５００Ｈ：Ｗ／Ｃ３０％以上４０％未満のセメント組成物において、セメント質量に対し１．２質量％使用
（株）フローリック製高性能減水剤ＳＦ５００Ｕ：Ｗ／Ｃ３０％未満のセメント組成物において、セメント質量に対し１．５質量％使用
(Water reducing agent)
High-performance AE water reducing agent SF500S manufactured by Floric Co., Ltd .: 0.7% by mass is used with respect to the cement mass in a cement composition having W / C of 40% or more. High-performance AE water reducing agent SF500H: W manufactured by Floric Co., Ltd. 1.2% by mass with respect to cement mass is used in cement compositions with / C of 30% or more and less than 40%. High-performance water reducing agent SF500U manufactured by Floric Co., Ltd .: With respect to cement mass in cement compositions with W / C of less than 30%. Use 1.5% by mass
調製されたセメント組成物について、以下の測定を実施した。測定結果を表４〜６に示す。 The following measurements were carried out on the prepared cement composition. The measurement results are shown in Tables 4 to 6.
（空気量）
目標空気量を１．５±０．５％に設定し、目標空気量となるよう消泡剤（（株）フローリック社製、ＤＦ−７５３）を使用し調整した。空気量の測定は、ＪＩＳ Ａ １１２８（２０１４）に準拠して実施し、全ての試験で目標空気量を満足した。なお、目標スランプ及び目標スランプフローは定めなかった。
(Amount of air)
The target air volume was set to 1.5 ± 0.5%, and the target air volume was adjusted using an antifoaming agent (DF-753, manufactured by Floric Co., Ltd.). The measurement of the air volume was carried out in accordance with JIS A 1128 (2014), and the target air volume was satisfied in all the tests. The target slump and target slump flow were not set.
（圧縮強度）
Ｗ／Ｃ＝５０％未満では３６ＭＰａ以上強度が発現するため、圧縮強度は、Ｗ／Ｃ＝５０％以上のみを確認した。２０℃水中養生で２８日間養生した後、圧縮強度を測定した。試験は、ＪＩＳ Ａ １１０８（２０１８）に準拠した。
(Compression strength)
Since the strength of 36 MPa or more is exhibited when W / C is less than 50%, only W / C = 50% or more is confirmed as the compression strength. After curing in water at 20 ° C. for 28 days, the compressive strength was measured. The test was in accordance with JIS A 1108 (2018).
（自己体積変化低減率）
自己体積変化の測定は、Ｗ／Ｃ＝３０％以下のみ、ＪＣＩ自己体積変化に関する研究委員会の試験方法（ＪＣＩ−ＳＡＳ２−２）を参考に実施した。自己体積変化の起点は注水後１０時間とし、所定の積算温度（湿度）時の自己体積変化量を測定した。自己体積変化低減率は、界面活性剤無添加の同配合の自己体積変化からの低減率であり、１０％以上を合格とした。
(Self-volume change reduction rate)
The self-volume change was measured only when W / C = 30% or less with reference to the test method (JCI-SAS2-2) of the Research Committee on JCI self-volume change. The starting point of the self-volume change was 10 hours after water injection, and the amount of self-volume change at a predetermined integrated temperature (humidity) was measured. The self-volume change reduction rate is a reduction rate from the self-volume change of the same formulation without the addition of a surfactant, and 10% or more was accepted.
（乾燥体積変化低減率）
Ｗ／Ｃ＝３１％以上のみ乾燥体積変化率を測定した。乾燥体積変化率の測定は、ＪＩＳ Ａ １１２９（２０１０）に準拠して実施した。すなわち、打設後直ちに１０×１０×４０ｃｍの供試体を作製し、２４時間後に脱形を行い、刻線を引いた後、２０℃の水中で１日から１週間養生を行い、その後、２０℃、Ｒ．Ｈ．６０％の恒温恒湿室で保存し、所定の積算温度（湿度）時の乾燥体積変化率を測定した。乾燥体積変化低減率は、界面活性剤無添加の同配合の乾燥体積変化率からの低減率であり、１０％以上を合格とした。
(Dry volume change reduction rate)
The dry volume change rate was measured only when W / C = 31% or more. The measurement of the dry volume change rate was carried out in accordance with JIS A 1129 (2010). That is, a specimen of 10 × 10 × 40 cm was prepared immediately after placing, demolded 24 hours later, engraved, and cured in water at 20 ° C. for 1 day to 1 week, and then 20 ° C., R. H. It was stored in a constant temperature and humidity chamber of 60%, and the rate of change in dry volume at a predetermined integrated temperature (humidity) was measured. The dry volume change reduction rate is a reduction rate from the dry volume change rate of the same formulation without the addition of a surfactant, and 10% or more was accepted.
（含水率比）
含水率の測定は、以下の手順にて実施した。直径１０ｃｍ、高さ２０ｃｍの円柱供試体を用い、所定の積算温度（積算湿度）経過後に２４時間２０℃の水中に浸漬した。表面を乾いた布で拭った後に質量を測定し、４０℃の恒温槽に４８時間入れた。続いて乾燥質量を測定、逸散した水分質量を乾燥質量で除した百分率により含水率を測定した。含水率比は、測定された含水率を、界面活性剤無添加の同配合の含水率で除し百分率で示して算出した値であり、１００．１以上１１０以下を合格とした。
(Moisture content ratio)
The water content was measured according to the following procedure. Using a cylindrical specimen having a diameter of 10 cm and a height of 20 cm, the sample was immersed in water at 20 ° C. for 24 hours after a predetermined integrated temperature (integrated humidity) had elapsed. After wiping the surface with a dry cloth, the mass was measured and placed in a constant temperature bath at 40 ° C. for 48 hours. Subsequently, the dry mass was measured, and the water content was measured by the percentage obtained by dividing the diffused water mass by the dry mass. The water content ratio is a value calculated by dividing the measured water content by the water content of the same composition without the addition of a surfactant and indicating it as a percentage, and a value of 100.1 or more and 110 or less was regarded as acceptable.
（探傷減少率）
探傷減少率の測定は、以下の手順で、試験体を作製後蛍光浸透探傷剤を用いる探傷検査により実施した。縦４０ｃｍ×横４０ｃｍ×高さ５ｃｍの平板を作成し、高さ２．５ｃｍの位置に４ｃｍピッチでＤ１０の異形鉄筋を格子状に埋設し、探傷検査用の試験体とした。探傷検査は、以下の手順で行った。試験体に所定の積算温度及び積算湿度（表４〜６）を与えた後、２４時間２０℃、６０％Ｒ．Ｈ．の恒温恒湿室で乾燥させた。続いて、平板の打設面に蛍光浸透探傷剤を塗布し、軽く液だまりを乾いた布で拭った後、ブラックライトを照射して撮影を実施した。撮影した画像を画像解析ソフトに取り込み、発色部分の面積を算出した。探傷減少率は、界面活性剤無添加の同配合の探傷面積からの低減率であり、５０％以上を合格とした。
(Reduction rate of flaw detection)
The flaw detection reduction rate was measured by a flaw detection inspection using a fluorescent penetrant after preparing the test piece according to the following procedure. A flat plate having a length of 40 cm, a width of 40 cm, and a height of 5 cm was prepared, and D10 deformed reinforcing bars were embedded in a grid pattern at a position of 2.5 cm in height at a pitch of 4 cm to prepare a test piece for flaw detection inspection. The flaw detection inspection was carried out according to the following procedure. After applying the predetermined integrated temperature and integrated humidity (Tables 4 to 6) to the test piece, 24 hours at 20 ° C., 60% R. H. It was dried in a constant temperature and humidity chamber. Subsequently, a fluorescent penetrant was applied to the casting surface of the flat plate, the puddle was lightly wiped with a dry cloth, and then black light was irradiated to take a picture. The captured image was imported into image analysis software, and the area of the colored portion was calculated. The flaw detection reduction rate is the reduction rate from the flaw detection area of the same formulation without the addition of a surfactant, and 50% or more was accepted.
（目視検査）
目視検査は、上記探傷検査にて作製した蛍光探傷剤散布前の試験体を複数人（１０人）で確認し、人の目でクラック、色むら、連続性のない多量のクラック模様を客観的に判断し、美観に優れる（○）、可も不可もない（△）、あまり綺麗ではない（×）の３段階で評価した。
(Visual examination)
In the visual inspection, the test specimens prepared by the above flaw detection inspection before spraying the fluorescent flaw detector are confirmed by a plurality of people (10 people), and cracks, color unevenness, and a large amount of discontinuous crack patterns are objectively observed by human eyes. The evaluation was made on a three-point scale: excellent in aesthetics (○), neither good nor bad (△), and not very beautiful (×).
（合否）
合格基準からはずれる項目が１つもないものを○、１つでもあるもの（△も含む）を×と評価した。
(Pass / Fail)
Items that did not deviate from the acceptance criteria were evaluated as ○, and items that did not deviate from the acceptance criteria (including Δ) were evaluated as ×.
Claims (19)
Ｂ成分：一般式（Ｉ） Ｒ−Ｏ−（ＡＯ）n−Ｈ
（一般式（Ｉ）中、Ｒは水素原子または炭素原子数２〜４の炭化水素基であり、ＡＯは炭素原子数２〜３のオキシアルキレン基であり、ｎは１〜１０の整数である。）
で表される化合物を有効成分とするセメント混和剤。 Component A: Polypropylene glycol with an average molecular weight of 200 to 600 and / or Component B: General formula (I) RO- (AO) n- H
(In the general formula (I), R is a hydrogen atom or a hydrocarbon group having 2 to 4 carbon atoms, AO is an oxyalkylene group having 2 to 3 carbon atoms, and n is an integer of 1 to 10. .)
A cement admixture containing the compound represented by.
工程（１）：有効成分、セメント及び水からなる、有効成分の含有量がａ質量％（対セメント質量）であるサンプルを得ること；
工程（２）：サンプルを脱水し分離水を得ること；
工程（３）：分離水の表面張力をＷｉｌｈｅｌｍｙ法により測定すること；及び
工程（４）：測定された表面張力が６０ｄｙｎ／ｃｍ以下であることを確認する工程。 Any of claims 1 to 3, wherein the amount of the active ingredient added to the cement composition is a mass% (mass with respect to cement) confirmed by the method for confirming the amount of addition including the following steps (1) to (4). Cement admixture according to item 1:
Step (1): Obtaining a sample consisting of the active ingredient, cement and water and having an active ingredient content of a mass% (% by mass of cement);
Step (2): Dehydrate the sample to obtain separated water;
Step (3): Measure the surface tension of the separated water by the Wilhelmy method; and Step (4): Confirm that the measured surface tension is 60 dyn / cm or less.
工程（５）：分離水中の炭素量と、工程（１）においてセメント混和剤無添加の他はサンプルと同様の組成のブランク組成物を工程（２）と同様に処理して得たブランク分離水中の炭素量を測定し、以下の式にて未吸着率を算出する工程
式：
未吸着率＝〔分離水中の炭素量／ブランク分離水中の炭素量〕×１００；及び
工程（６）：算出された未吸着率が３０％以上であることを確認する工程。 The cement admixture according to claim 4, wherein the method for confirming the amount of addition further comprises steps (5) and (6).
Step (5): The amount of carbon in the separated water and the blank composition obtained by treating the blank composition having the same composition as the sample except that the cement admixture was not added in the step (1) in the same manner as in the step (2). Process formula to measure the carbon content of and calculate the non-adsorption rate by the following formula:
Unadsorbed rate = [Carbon amount in separated water / Carbon amount in blank separated water] × 100; and step (6): Step of confirming that the calculated unadsorbed rate is 30% or more.
工程（１）：有効成分、セメント及び水からなる、有効成分の含有量がａ質量％（対セメント質量）であるサンプルを得ること；
工程（２）：サンプルを脱水し分離水を得ること；
工程（３）：分離水の表面張力をＷｉｌｈｅｌｍｙ法により測定すること；及び
工程（４）：測定された表面張力が６０ｄｙｎ／ｃｍ以下であることを確認する工程。 The content of the cement admixture according to any one of claims 1 to 8 is a mass% (based on cement mass) confirmed by the addition amount confirmation method including the following steps (1) to (4). The cement composition according to claim 9.
Step (1): Obtaining a sample consisting of the active ingredient, cement and water and having an active ingredient content of a mass% (% by mass of cement);
Step (2): Dehydrate the sample to obtain separated water;
Step (3): Measure the surface tension of the separated water by the Wilhelmy method; and Step (4): Confirm that the measured surface tension is 60 dyn / cm or less.
工程（５）：分離水中の炭素量と、工程（１）においてセメント混和剤無添加の他はサンプルと同様の組成のブランク組成物を工程（２）と同様に処理して得たブランク分離水中の炭素量を測定し、以下の式にて未吸着率を算出する工程
式：
未吸着率＝〔分離水中の炭素量／ブランク分離水中の炭素量〕×１００；及び
工程（６）：算出された未吸着率が３０％以上であることを確認する工程。 The cement composition according to claim 10, wherein the method for confirming the amount of addition further comprises steps (5) and (6).
Step (5): The amount of carbon in the separated water and the blank composition obtained by treating the blank composition having the same composition as the sample except that the cement admixture was not added in the step (1) in the same manner as in the step (2). Process formula to measure the carbon content of and calculate the non-adsorption rate by the following formula:
Unadsorbed rate = [Carbon amount in separated water / Carbon amount in blank separated water] × 100; and step (6): Step of confirming that the calculated unadsorbed rate is 30% or more.
セメント含有量がセメント組成物に対し５〜９５質量％であること、
の少なくともいずれかを満たす請求項９〜１２のいずれか１項に記載のセメント組成物。 The water content is 3 to 15% by mass with respect to the cement composition, and the cement content is 5 to 95% by mass with respect to the cement composition.
The cement composition according to any one of claims 9 to 12, which satisfies at least one of the above.
細骨材の含有量が３〜９０質量％であること、及び
粗骨材の含有量が８５質量％以下であること、
からなる群より選ばれるいずれかを満たす、請求項１４に記載のセメント組成物。 The content of the binder is 5 to 95% by mass,
The content of fine aggregate is 3 to 90% by mass, and the content of coarse aggregate is 85% by mass or less.
The cement composition according to claim 14, which satisfies any of those selected from the group consisting of.
工程（１）：有効成分、セメント及び水からなる、有効成分の含有量がａ質量％（対セメント質量）であるサンプルを得ること；
工程（２）：サンプルを脱水し分離水を得ること；
工程（３）：分離水の表面張力をＷｉｌｈｅｌｍｙ法により測定すること；及び
工程（４）：測定された表面張力が６０ｄｙｎ／ｃｍ以下である場合にことを確認し、セメント組成物におけるセメント混和剤の含有量をａ質量％と決定する工程。 A method for confirming, determining or evaluating the content of the cement admixture according to any one of claims 1 to 8, which comprises the following steps (1) to (4), in a cement composition.
Step (1): Obtaining a sample consisting of the active ingredient, cement and water and having an active ingredient content of a mass% (% by mass of cement);
Step (2): Dehydrate the sample to obtain separated water;
Step (3): Measure the surface tension of the separated water by the Wilhelmy method; and Step (4): Confirm that the measured surface tension is 60 dyn / cm or less, and the cement admixture in the cement composition. Step of determining the content of a mass%.
探傷減少率が５０％以上であること、
含水率比が１００．１〜１１０．０％であること、
自己体積変化低減率が１０％以上であること、
乾燥体積変化低減率が１０％以上であること、
積算温度が２００，２６８〜１，３７８，９５５Ｋ・時間であること、及び
積算湿度が３６，０００〜４３２，０００％Ｒ．Ｈ．・時間であること The structure derived from the cement composition according to any one of claims 9 to 15, which satisfies at least one of the following.
The flaw detection reduction rate is 50% or more,
The moisture content ratio is 10.1 to 110.0%,
The self-volume change reduction rate is 10% or more,
The dry volume change reduction rate is 10% or more,
The integrated temperature is 200,268 to 1,378,955 K · hours, and the integrated humidity is 36,000 to 432,000% R.I. H.・ Being time
積算温度が２００，２６８〜１，３７８，９５５Ｋ・時間であること、及び、養生期間中の積算湿度が３６，０００〜４３２，０００％Ｒ．Ｈ．・時間であること、の少なくともいずれかを満たすよう養生する工程を含む、構造物の製造方法。 The cement composition according to any one of claims 9 to 15.
The integrated temperature is 200,268 to 1,378,955 K · hours, and the integrated humidity during the curing period is 36,000 to 432,000% R.I. H. -A method of manufacturing a structure, which comprises a step of curing to satisfy at least one of being time.
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| JPS5637259A (en) * | 1979-08-30 | 1981-04-10 | Sanyo Chemical Ind Ltd | Cement contraction reducing agent |
| JPS59152253A (en) * | 1983-02-15 | 1984-08-30 | 竹本油脂株式会社 | Dry shrinkage reducing agent for hydraulic cement |
| JP2001163653A (en) * | 1999-12-06 | 2001-06-19 | Asahi Denka Kogyo Kk | Shrinkage reducing agent for cement or the like |
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| JPS5637259A (en) * | 1979-08-30 | 1981-04-10 | Sanyo Chemical Ind Ltd | Cement contraction reducing agent |
| JPS59152253A (en) * | 1983-02-15 | 1984-08-30 | 竹本油脂株式会社 | Dry shrinkage reducing agent for hydraulic cement |
| JP2001163653A (en) * | 1999-12-06 | 2001-06-19 | Asahi Denka Kogyo Kk | Shrinkage reducing agent for cement or the like |
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| CN114460281A (en) * | 2022-01-09 | 2022-05-10 | 三峡大学 | Experimental device and method for repairing concrete cracks of film bag by adopting vacuum grouting |
| CN114460281B (en) * | 2022-01-09 | 2023-09-29 | 温州市文景市政园林有限公司 | Experimental device and method for repairing concrete cracks of membrane bags by adopting vacuum grouting |
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