JP6173155B2 - Shrinkage reducing agent for cement composition - Google Patents
Shrinkage reducing agent for cement composition Download PDFInfo
- Publication number
- JP6173155B2 JP6173155B2 JP2013206470A JP2013206470A JP6173155B2 JP 6173155 B2 JP6173155 B2 JP 6173155B2 JP 2013206470 A JP2013206470 A JP 2013206470A JP 2013206470 A JP2013206470 A JP 2013206470A JP 6173155 B2 JP6173155 B2 JP 6173155B2
- Authority
- JP
- Japan
- Prior art keywords
- reducing agent
- shrinkage
- compound
- shrinkage reducing
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003638 chemical reducing agent Substances 0.000 title claims description 118
- 239000004568 cement Substances 0.000 title claims description 58
- 239000000203 mixture Substances 0.000 title claims description 39
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- 150000001875 compounds Chemical class 0.000 claims description 32
- 125000002947 alkylene group Chemical group 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000004567 concrete Substances 0.000 claims description 18
- 229940126062 Compound A Drugs 0.000 claims description 17
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 125000006353 oxyethylene group Chemical group 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
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- 239000000654 additive Substances 0.000 claims description 7
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Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Description
本発明はセメント組成物用の収縮低減剤に関するものであり、詳しくは優れた自己収縮低減性及び乾燥収縮低減性を有し、しかも他のコンクリート添加剤との相溶性に優れ、一液性を向上させてなるセメント組成物用収縮低減剤に関するものである。 The present invention relates to a shrinkage reducing agent for a cement composition. Specifically, it has excellent self-shrinkage reducing properties and dry shrinkage reducing properties, and is excellent in compatibility with other concrete additives, and has a one-component property. The present invention relates to an improved shrinkage reducing agent for cement compositions.
これまでコンクリート用収縮低減剤として、低級又は高級アルコールのアルキレンオキシド付加物などが２０年以上前から使用されている（例えば特許文献１）。これら化合物は、一般にコンクリート又はモルタルが硬化後、数日〜数年後に起こる乾燥収縮の低減を目的として使用されている。 Up to now, alkylene oxide adducts of lower or higher alcohols have been used as concrete shrinkage reducing agents for more than 20 years (for example, Patent Document 1). These compounds are generally used for the purpose of reducing drying shrinkage that occurs several days to several years after concrete or mortar is cured.
近年、設計強度１００Ｎ／ｍｍ２を超える超高強度コンクリートでは、硬化体のひび割れ抑制の観点から、コンクリートの硬化初期に起こる自己収縮、すなわち、セメントの水和反応の進行によってコンクリート、モルタルおよびペーストの体積が減少することによる収縮を如何に低減するかに注目が集まっている。
これまで提案された上記低級アルコールのアルキレンオキシド付加物においても、化合物の構造を最適化することにより、打設直後の極若材齢における自己収縮の低減を図る提案がなされている（例えば特許文献２）。
In recent years, in ultra-high-strength concrete exceeding the design strength of 100 N / mm 2 , from the viewpoint of suppressing cracking of the hardened body, self-shrinkage that occurs at the early stage of hardening of the concrete, that is, the progress of cement hydration reaction, concrete, mortar and paste Attention has been focused on how to reduce shrinkage due to volume reduction.
In the alkylene oxide adducts of the lower alcohols proposed so far, proposals have been made to reduce self-shrinkage at the very young age immediately after placement by optimizing the structure of the compound (for example, Patent Documents). 2).
一方、コンクリートの製造を簡便にする観点より、実用において収縮低減剤は減水剤と一液化して使用されることが好ましい。
例えば特許文献３には、乾燥収縮低減効果と、減水剤との相溶性を考慮した水硬性材料用収縮低減剤として、アルキルアミンのアルキレンオキシド付加物が提案されている。また特許文献４には、減水剤と乾燥収縮低減剤とを配合した水硬性組成物用の一液型添加剤が提案されている。
On the other hand, from the viewpoint of simplifying the production of concrete, it is preferable that the shrinkage reducing agent is practically used as a single component with a water reducing agent.
For example, Patent Document 3 proposes an alkylene oxide adduct of alkylamine as a shrinkage reducing agent for a hydraulic material in consideration of a drying shrinkage reducing effect and compatibility with a water reducing agent. Patent Document 4 proposes a one-component additive for a hydraulic composition containing a water reducing agent and a drying shrinkage reducing agent.
上述したように設計基準強度が１００Ｎ／ｍｍ２を超える超高強度コンクリートでは、硬化に伴う自己収縮が主原因とみられる内部応力やひび割れの発生が大きな問題となっており、従来の乾燥収縮低減効果に加えて自己収縮低減効果のさらなる改良が急務となっている。
また収縮低減剤は、特に自己収縮低減効果を考慮すると、減水剤投入時に同時に投入されることが好ましく、その場合、減水剤との相溶性に優れ、減水剤と一液化できることが望ましく、自己収縮低減性及び減水剤との一液化性の何れをも十分に満足できるような収縮低減剤の提案が求められている。
As described above, in ultra-high-strength concrete with a design standard strength exceeding 100 N / mm 2 , the occurrence of internal stress and cracks, which are mainly caused by self-shrinkage due to hardening, is a major problem, and the conventional drying shrinkage reduction effect In addition, there is an urgent need to further improve the self-shrinkage reduction effect.
In consideration of the self-shrinkage reducing effect, the shrinkage reducing agent is preferably added at the same time as the water reducing agent is added. In that case, the shrinkage reducing agent is preferably compatible with the water reducing agent and can be made into one liquid with the water reducing agent. There is a need for a shrinkage reducing agent that can sufficiently satisfy both the reducing property and the one-component property with a water reducing agent.
本発明は、上述の課題に鑑みなされたものであって、低級アルコールのアルキレンオキシド付加物を変性した化合物により、従来提案された収縮低減剤と比べ、より優れた自己収縮の低減効果を実現できること、更に別成分として高級アミンのアルキレンオキシド付
加物を併用することにより、自己収縮低減効果の向上のみならず、特にポリカルボン酸系減水剤との優れた相溶性を実現でき、技術的に困難とされた一液化を実現できる、セメント組成物用収縮低減剤を提供することを課題とする。
The present invention has been made in view of the above-mentioned problems, and can achieve a superior self-shrinkage reduction effect as compared with conventionally proposed shrinkage reducing agents by a compound obtained by modifying an alkylene oxide adduct of a lower alcohol. In addition, by using an alkylene oxide adduct of a higher amine as a separate component, not only can the self-shrinkage reduction effect be improved, but particularly excellent compatibility with polycarboxylic acid-based water reducing agents can be realized, which is technically difficult. It is an object of the present invention to provide a shrinkage reducing agent for a cement composition that can realize the one-component solution.
本発明者らが検討した結果、低級アルコールのアルキレンオキシド付加物において、アルキレンオキシド付加部分の末端をアルキル化する、すなわち、アルキレンオキシド付加部分の両末端をアルキル化させた化合物を収縮低減剤として採用することにより、収縮低減効果が高まることを見出した。
また、実際の施工現場において為される収縮低減剤と減水剤の一液化しての使用を踏まえ、上記化合物とともに高級アミンのアルキレンオキシド付加物を本発明の収縮低減剤の一成分として採用することにより、常温における両添加剤の相溶性を向上させることができる、すなわち一液性に優れる収縮低減剤となることを見出した。
さらにこれら成分に加え、低級アルコールのアルキレンオキシド付加物を配合することにより、高温（例えば４０℃）における当該収縮低減剤と減水剤との分離性を改善し、一液性をさらに強化できることを見出し、本発明を完成させた。
As a result of the study by the present inventors, in the alkylene oxide adduct of a lower alcohol, a compound in which the end of the alkylene oxide addition moiety is alkylated, that is, a compound in which both ends of the alkylene oxide addition moiety are alkylated is employed as a shrinkage reducing agent. As a result, it was found that the shrinkage reduction effect is enhanced.
In addition, based on the use of a shrinkage reducing agent and water reducing agent that are made in actual construction sites as one component, an alkylene oxide adduct of a higher amine is used as a component of the shrinkage reducing agent of the present invention together with the above compound. Thus, it has been found that the compatibility of both additives at room temperature can be improved, that is, a shrinkage reducing agent having excellent one-component properties.
Furthermore, it has been found that by adding an alkylene oxide adduct of a lower alcohol in addition to these components, the separation property between the shrinkage reducing agent and the water reducing agent at a high temperature (for example, 40 ° C.) can be improved and the one-component property can be further enhanced. The present invention has been completed.
すなわち本発明は、下記式［１］で表される化合物Ａ及び下記式［２］で表される化合物Ｂを含み、化合物Ａと化合物ＢをＡ：Ｂ＝９９：１〜５０：５０の質量比で含むことを特徴とする、セメント組成物用収縮低減剤に関する。
また本発明は、上記収縮低減剤において、上記式［１］で表される化合物Ａ、上記式［Ｂ］で表される化合物Ｂ、さらに低級アルコールのアルキレンオキシド付加物を含み、好ましくは、前記化合物Ａと前記化合物Ｂと該低級アルコールのアルキレンオキシド付加物とを、９８：１：１〜２５：２５：５０の質量比で含むセメント組成物用収縮低減剤も対象とする。 Further, the present invention includes the above shrinkage reducing agent, which includes the compound A represented by the above formula [1], the compound B represented by the above formula [B], and an alkylene oxide adduct of a lower alcohol, A shrinkage reducing agent for cement compositions containing Compound A, Compound B, and an alkylene oxide adduct of the lower alcohol in a mass ratio of 98: 1: 1 to 25:25:50 is also targeted.
本発明のセメント組成物用収縮低減剤は、乾燥収縮のみならずセメントの水和反応による自己収縮の双方の収縮現象を低減することができる。特に本発明のセメント組成物用収縮低減剤は、実際のコンクリート製造現場において減水剤と混合使用される際において、上記収縮低減効果を発揮するだけでなく、減水剤との相溶性に優れ、減水剤と一液化した後の長期間の保管後においても分離せず、減水剤との一液安定性に優れたものとすることができる。
またさらに低級アルコールのアルキレンオキシド付加物を配合した本発明のセメント組成物用収縮低減剤は、常温（例えば２０℃）下だけでなく、高温（例えば４０℃）下における減水剤との一液安定性に優れたものとすることができる。
The shrinkage reducing agent for a cement composition of the present invention can reduce both shrinkage phenomena of not only drying shrinkage but also self-shrinkage due to cement hydration reaction. In particular, the shrinkage reducing agent for cement composition of the present invention not only exhibits the above-mentioned shrinkage reducing effect when mixed with a water reducing agent in an actual concrete production site, but also has excellent compatibility with the water reducing agent, and reduces water reduction. It does not separate even after long-term storage after being made into one liquid with the agent, and can be made excellent in one-liquid stability with the water reducing agent.
Furthermore, the shrinkage reducing agent for a cement composition of the present invention further blended with an alkylene oxide adduct of a lower alcohol is stable with a water reducing agent not only at room temperature (for example, 20 ° C.) but also at high temperature (for example, 40 ° C.). It can be made excellent in properties.
＜セメント組成物用収縮低減剤＞
本発明は、低級アルコールのアルキレンオキシド付加物を変性した化合物（化合物Ａ）、高級アミン、例えば高級アルキルアミン又は高級アルケニルアミンのアルキレンオキシド付加物（化合物Ｂ）とを含みて構成され、さらに低級アルコールのアルキレンオキシド付加物（化合物Ｃ）を含み得る、セメント組成物用収縮低減剤を対象とする。
以下、本発明のセメント組成物用収縮低減剤を構成する各化合物について詳述する。
<Shrinkage reducing agent for cement composition>
The present invention comprises a compound (compound A) obtained by modifying an alkylene oxide adduct of a lower alcohol and a higher amine, for example, an alkylene oxide adduct of a higher alkyl amine or a higher alkenyl amine (compound B), and further comprises a lower alcohol. The shrinkage-reducing agent for cement composition, which can contain an alkylene oxide adduct (compound C) of
Hereafter, each compound which comprises the shrinkage | contraction reducing agent for cement compositions of this invention is explained in full detail.
［化合物Ａ］
本発明のセメント組成物用収縮低減剤を構成する化合物Ａは下記式［１］で表される化合物である。本発明において、従来使用されてきた低級アルコールのアルキレンオキシド付加物（片末端をアルキル化した化合物）に替えて、両末端をアルキル化した化合物を採用することにより、片末端をアルキル化した化合物を用いた場合に比べ、自己収縮低減効果を高めることができる。
Compound A constituting the shrinkage reducing agent for cement composition of the present invention is a compound represented by the following formula [1]. In the present invention, instead of the conventionally used alkylene oxide adducts of lower alcohols (compounds with one end alkylated), by adopting a compound with both ends alkylated, a compound with one end alkylated is obtained. Compared with the case of using, the self-shrinkage reduction effect can be enhanced.
式［１］において、Ｒ１及びＲ２はそれぞれ独立して炭素原子数１乃至４のアルキル基を表す。
上記アルキル基は、直鎖状、分枝鎖状又は環状のアルキル基が挙げられる。従って、Ｒ１及びＲ２の好ましい基としては、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、シクロプロピル基、ｎ−ブチル基、ｉ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、シクロブチル基等が挙げられる。
化合物ＡにおけるＲ１及びＲ２のアルキル基の炭素原子数の合計は、練り混ぜ性向上の観点からは２乃至６であることが好ましく、一液性向上の観点からは、炭素原子数３乃至６が好ましい。さらに自己収縮低減性向上の観点からは３乃至８であることが好ましく、より好ましくは４乃至８である。
中でもＲ１及びＲ２のうち一方がｎ−ブチル基、他方がメチル基を表すことが好ましい。
In the formula [1], R 1 and R 2 each independently represents an alkyl group having 1 to 4 carbon atoms.
Examples of the alkyl group include linear, branched or cyclic alkyl groups. Accordingly, preferred groups for R 1 and R 2 are methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, sec-butyl, tert- A butyl group, a cyclobutyl group, etc. are mentioned.
The total number of carbon atoms of the alkyl groups R 1 and R 2 in Compound A is preferably 2 to 6 from the viewpoint of improving the kneadability, and from the viewpoint of improving the one-component property, the total number of carbon atoms is 3 to 6 is preferred. Further, from the viewpoint of improving self-shrinkage reduction, it is preferably 3 to 8, and more preferably 4 to 8.
Among them, it is preferable that one of R 1 and R 2 represents an n-butyl group and the other represents a methyl group.
式［１］中、ＥＯはオキシエチレン基を表し、ｎはオキシエチレン（ＥＯ）基の平均付加モル数であって２又は３を示す。
なかでもｎを３とすることで、自己収縮低減性向上、練り混ぜ性向上の観点から、状態が更に良好となる。
In the formula [1], EO represents an oxyethylene group, and n is the average number of added moles of the oxyethylene (EO) group and represents 2 or 3.
Among these, by setting n to 3, the state is further improved from the viewpoints of improving self-shrinkage reduction and kneading.
［化合物Ｂ］
本発明のセメント組成物用収縮低減剤を構成する化合物Ｂは下記式［２］で表される化合物である。下記化合物Ｂ（高級アルキルアミン又は高級アルケニルアミンのアルキレンオキシド付加物）を上記化合物Ａと併用することにより、当該収縮低減剤と減水剤等の他の添加剤との常温における相溶性を向上させる（一液化を向上させる）ことができる。
Compound B constituting the shrinkage reducing agent for cement composition of the present invention is a compound represented by the following formula [2]. The following compound B (higher alkylamine or alkylene oxide adduct of higher alkenylamine) is used in combination with the above compound A to improve the compatibility of the shrinkage reducing agent with other additives such as a water reducing agent at room temperature ( (1) can be improved.
式［２］において、Ｒ３は炭素原子数９乃至２４の炭化水素基を表し、一液性向上の観点から炭素原子数は１０乃至２０、流動性向上の観点からは炭素原子数が１２乃至２０であることが好ましく、特に炭素原子数が１２乃至１８の炭化水素基であることが好ましい。
上記炭素原子数９乃至２４の炭化水素基としては、炭素原子数９乃至２４のアルキル基又は炭素原子数９乃至２４のアルケニル基が挙げられ、これらは直鎖状、分枝鎖状又は環状のいずれであってもよい。
Ｒ３の好ましい基としては、デシル基、ドデシル基（ラウリル基）、テトラデシル基（ミリスチル基）、ヘキサデシル基（パルミチル基）、オクタデシル基（ステアリル基）、エイコシル基、ミリストレイル基、パルミトレイル基、オレイル基、リノイル基、リノレイル基、リシノレイル基等が挙げられ、特に好ましくはラウリル基、オレイル基である。
In the formula [2], R 3 represents a hydrocarbon group having 9 to 24 carbon atoms, the number of carbon atoms is 10 to 20 from the viewpoint of improving the one-component property, and the number of carbon atoms is 12 to 12 from the viewpoint of improving the fluidity. 20 is preferable, and a hydrocarbon group having 12 to 18 carbon atoms is particularly preferable.
Examples of the hydrocarbon group having 9 to 24 carbon atoms include an alkyl group having 9 to 24 carbon atoms or an alkenyl group having 9 to 24 carbon atoms, which are linear, branched or cyclic. Either may be sufficient.
Preferred groups for R 3 are decyl, dodecyl (lauryl), tetradecyl (myristyl), hexadecyl (palmityl), octadecyl (stearyl), eicosyl, myristolyl, palmitoleyl, An oleyl group, a linoleyl group, a linoleyl group, a ricinoleyl group and the like can be mentioned, and a lauryl group and an oleyl group are particularly preferable.
式［２］中、ＥＯはオキシエチレン基を表し、ｍ１及びｍ２はそれぞれ独立してオキシエチレン（ＥＯ）基の平均付加モル数であって０乃至３０を表し、但しｍ１とｍ２の合計値は１乃至３０を表す。
中でも、自己収縮低減効果及び一液性向上の観点から、ｍ１とｍ２の合計値は２乃至２０が好ましく、特に２乃至１０がより好ましい。
In the formula [2], EO represents an oxyethylene group, and m 1 and m 2 are each independently an average addition mole number of an oxyethylene (EO) group and represent 0 to 30, provided that m 1 and m 2 The total value of 1 represents 1 to 30.
Among these, from the viewpoint of reducing the self-shrinkage and improving the one-component property, the total value of m 1 and m 2 is preferably 2 to 20, and more preferably 2 to 10.
本発明のセメント組成物用収縮低減剤において、上記式［１］で表される化合物Ａと式［２］で表される化合物Ｂは、Ａ：Ｂ＝９９：１〜５０：５０の質量比で含まれる。これら化合物の配合比を上記範囲とすることにより、当該収縮低減剤は高い自己収縮低減性を得ることができるだけでなく、減水剤との一液性に優れたものとすることができる。
好ましくは、上記化合物Ａ：化合物Ｂの質量比率の数値範囲を、９９：１〜６０：４０とすることにより、水和反応の遅延や阻害といった影響を少なくすることができ、さらに９９：１〜８０：２０とすることで、流動性を向上させ、より一層水和反応への影響を少なくすることができ、早期強度発現性を得ることができる。例えば、これらの配合比（質量比）は８７．５：１２．５〜８０：２０が挙げられる。
In the shrinkage reducing agent for cement composition of the present invention, the compound A represented by the above formula [1] and the compound B represented by the formula [2] have a mass ratio of A: B = 99: 1 to 50:50. Included. By setting the compounding ratio of these compounds in the above range, the shrinkage reducing agent can not only obtain high self-shrinkage reducing properties, but also be excellent in one-part properties with a water reducing agent.
Preferably, by setting the numerical range of the mass ratio of the above compound A: compound B to 99: 1 to 60:40, it is possible to reduce the influence of delay or inhibition of the hydration reaction, and further 99: 1 to By setting it as 80:20, fluidity | liquidity can be improved, the influence on a hydration reaction can be decreased further, and early strength development can be obtained. For example, as for these compounding ratios (mass ratio), 87.5: 12.5-80: 20 is mentioned.
［化合物Ｃ：低級アルコールのアルキレンオキシド付加物］
また本発明のセメント組成物用収縮低減剤は、本発明の効果を損なわない限りにおいて、上記式［１］で表される化合物Ａ、式［２］で表される化合物Ｂに加え、さらに低級アルコールのアルキレンオキシド付加物を配合することができる。このような化合物として、例えば下記式［３］で表される化合物Ｃを挙げることができる。
本発明において、化合物Ｃを適正使用することにより、高温（例えば４０℃）における当該収縮低減剤と分散剤との分離性を改善し、一液性を強化できる。
Further, the shrinkage reducing agent for a cement composition of the present invention is further lower in addition to the compound A represented by the above formula [1] and the compound B represented by the formula [2] as long as the effects of the present invention are not impaired. Alkylene oxide adducts can be blended. An example of such a compound is compound C represented by the following formula [3].
In the present invention, by properly using the compound C, the separation property between the shrinkage reducing agent and the dispersing agent at a high temperature (for example, 40 ° C.) can be improved, and the one-component property can be enhanced.
式［３］において、Ｒ４は炭素原子数１乃至８のアルキル基を表し、化合物Ａとの相溶性の観点から、炭素原子数１乃至４のアルキル基であることが好ましい。
上記アルキル基は直鎖状、分枝鎖状又は環状のいずれであってもよい。
Ｒ４の好ましい基としては、メチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、シクロプロピル基、ｎ−ブチル基、ｉ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、シクロブチル基等が挙げられ、中でも好ましいものとして、メチル基及びｎ−ブチル基を挙げることができる。
In the formula [3], R 4 represents an alkyl group having 1 to 8 carbon atoms, and is preferably an alkyl group having 1 to 4 carbon atoms from the viewpoint of compatibility with the compound A.
The alkyl group may be linear, branched or cyclic.
Preferred groups for R 4 are methyl, ethyl, n-propyl, i-propyl, cyclopropyl, n-butyl, i-butyl, sec-butyl, tert-butyl, cyclobutyl. Among them, preferred are methyl group and n-butyl group.
式［３］中、ＡＯは炭素原子数２乃至４のオキシアルキレン基を表す。好ましくはオキシエチレン基又はオキシプロピレン基であり、特にオキシエチレン基であることが好ましい。
また、ｑはオキシアルキレン基ＡＯの平均付加モル数であって２乃至１０を表し、好ましくは２乃至８、より好ましくは３乃至４である。
なお、付加するオキシアルキレン基は同一のオキシアルキレン基であっても、２種以上の異なるオキシアルキレン基であってもよく、異なるオキシアルキレン基が付加する場合
にはランダム付加又はブロック付加の何れであってもよい。
In the formula [3], AO represents an oxyalkylene group having 2 to 4 carbon atoms. An oxyethylene group or an oxypropylene group is preferable, and an oxyethylene group is particularly preferable.
Further, q is an average addition mole number of the oxyalkylene group AO and represents 2 to 10, preferably 2 to 8, and more preferably 3 to 4.
The oxyalkylene groups to be added may be the same oxyalkylene group or two or more different oxyalkylene groups, and when different oxyalkylene groups are added, either random addition or block addition may be used. There may be.
上記低級アルコールのアルキレンオキシド付加物（化合物Ｃ）を配合する場合、化合物Ａ：化合物Ｂ：化合物Ｃを９８：１：１〜２５：２５：５０の質量比で配合することが好ましい。特にＡ：Ｂ：Ｃの質量比率の数値範囲を７８：１：２０〜３０：２０：５０とすることにより、本発明の収縮低減剤と減水剤との一液性の高温下（例えば４０℃）における安定性がより確保されやすくなる（分離し難くなる）ため好ましい。例えば、これらの配合比（質量比）は７０：１０：２０〜４０：１０：５０が挙げられる。 When blending the alkylene oxide adduct (compound C) of the lower alcohol, compound A: compound B: compound C is preferably blended in a mass ratio of 98: 1: 1 to 25:25:50. In particular, by setting the numerical range of the mass ratio of A: B: C to 78: 1: 20 to 30:20:50, the one-part high temperature (for example, 40 ° C.) of the shrinkage reducing agent and the water reducing agent of the present invention. ) Is more easily secured (it is difficult to separate). For example, 70: 10: 20-40: 10: 50 is mentioned as these compounding ratios (mass ratio).
本発明のセメント組成物用収縮低減剤は、コンクリートの材料を含めた配合条件によりその添加量は変わるが、セメント質量に対し固形分換算で通常０．１〜５．０質量％程度添加される。収縮低減性を得るためには添加量が多いほどよいが、多過ぎると凝結遅延を起こし、場合によっては硬化不良となる。
本発明のセメント組成物用収縮低減剤は、コンクリート又はモルタルを練り混ぜた後（打設直前）に添加し再度均一に混練してもよいが、優れた自己収縮低減効果を得るには、コンクリート混練時に減水剤とともに原液添加するか、又は予め混練水に希釈して添加することにより使用する。
The amount of addition of the shrinkage reducing agent for cement composition of the present invention varies depending on the blending conditions including the concrete material, but is usually about 0.1 to 5.0% by mass in terms of solid content with respect to the cement mass. . In order to obtain shrinkage-reducing properties, a larger amount is better. However, if the amount is too large, a setting delay occurs, and in some cases, a curing failure occurs.
The shrinkage reducing agent for cement composition of the present invention may be added after kneading concrete or mortar (immediately before placing) and kneaded uniformly again. To obtain an excellent self-shrinkage reducing effect, concrete may be used. It is used by adding the undiluted solution together with the water reducing agent during kneading or by diluting and adding to the kneading water beforehand.
本発明の収縮低減剤が適用されるセメント組成物を構成する成分は、従来慣用のコンクリート用成分であり、セメント、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、超早強ポルトランドセメント、低熱・中庸熱ポルトランドセメント又は高炉セメント等、骨材、すなわち細骨材及び粗骨材、混和材、例えばシリカフューム、炭酸カルシウム粉末、高炉スラグ微粉末、フライアッシュ、膨張材及び水を挙げることができる。
本発明のセメント組成物用収縮低減剤は、優れた収縮低減性とともに、水及び減水剤との優れた相溶性を有するため、これらに任意の割合で溶解させることが可能である。このため、水／セメント比の適用範囲が広く、水／セメント比（質量％）で６０〜１５％の種々の強度を有するコンクリートに適用可能である。なかでも、水／セメント比が２０％以下となるような超高強度コンクリートにおいて好適に適用可能であり、優れた自己収縮低減効果を発揮できる。
The component constituting the cement composition to which the shrinkage reducing agent of the present invention is applied is a conventional concrete component, such as ordinary portland cement, early strong portland cement, very early strong portland cement, low heat / moderate heat. Mention may be made of aggregates, i.e. fine and coarse aggregates, admixtures such as silica fume, calcium carbonate powder, blast furnace slag fine powder, fly ash, expansion material and water, such as Portland cement or blast furnace cement.
Since the shrinkage reducing agent for cement composition of the present invention has excellent shrinkage-reducing properties and excellent compatibility with water and a water reducing agent, it can be dissolved in them at an arbitrary ratio. For this reason, the application range of water / cement ratio is wide, and it can be applied to concrete having various strengths of 60 to 15% in water / cement ratio (mass%). In particular, it can be suitably applied to ultra-high strength concrete having a water / cement ratio of 20% or less, and can exhibit an excellent self-shrinkage reducing effect.
＜セメント混和剤＞
本発明のセメント組成物用収縮低減剤は、公知公用の化学混和剤等を適宜採用して組合せ、セメント混和剤とすることができ、該セメント混和剤も本発明の対象である。具体的には、該セメント混和剤には、高性能ＡＥ減水剤、高性能減水剤、ＡＥ減水剤、減水剤、空気連行剤（ＡＥ剤）、起泡剤、消泡剤、養生剤、撥水剤、凝結促進剤及び凝結遅延剤からなる群から選択される少なくとも一種の他のコンクリート添加剤を配合することができる。
本発明のセメント混和剤とは、本発明のセメント組成物用収縮低減剤以外に公知の混和剤を配合しセメント混和剤とした形態、又はコンクリート製造時に本発明のセメント組成物用収縮低減剤と公知公用の混和剤が別々に添加され最終的にはコンクリート中で混合される形態の何れをも含む。
<Cement admixture>
The shrinkage reducing agent for cement composition of the present invention can be combined by appropriately adopting known and publicly used chemical admixtures and the like, and the cement admixture is also an object of the present invention. Specifically, the cement admixture includes high performance AE water reducing agent, high performance water reducing agent, AE water reducing agent, water reducing agent, air entraining agent (AE agent), foaming agent, antifoaming agent, curing agent, repellent. At least one other concrete additive selected from the group consisting of a liquid agent, a setting accelerator and a setting retarder can be blended.
The cement admixture of the present invention is a form in which a known admixture is blended in addition to the shrinkage reducing agent for cement composition of the present invention to form a cement admixture, or the shrinkage reducing agent for cement composition of the present invention at the time of concrete production. Any known and commonly used admixture is added separately and finally mixed in concrete.
例えば公知の減水剤（セメント分散剤）としては特公昭５８−３８３３８０号公報、特公昭５９−１８３３８号公報、特許２６２８４８６号公報、特許第２７７４４４５号公報、特許第３２３５００２号公報、特許第３３３６４５６号公報、特許第３７８０４５６号公報などのポリカルボン酸系共重合体の塩があり、またナフタレンスルホン酸ホルマリン縮合物の塩、メラミンスルホン酸ホルマリン縮合物の塩、リグニンスルホン酸塩、グルコン酸ソーダ、糖アルコールなどが挙げられる。 For example, as known water reducing agents (cement dispersants), Japanese Patent Publication No. 58-383380, Japanese Patent Publication No. 59-18338, Japanese Patent No. 2628486, Japanese Patent No. 2774445, Japanese Patent No. 323002, Japanese Patent No. 3336456 are disclosed. Patent No. 3780456, etc., and salts of polycarboxylic acid copolymers, naphthalene sulfonic acid formalin condensate salt, melamine sulfonic acid formalin condensate salt, lignin sulfonic acid salt, gluconic acid soda, sugar alcohol Etc.
空気連行剤（ＡＥ剤）を具体的に例示すると＜１＞アニオン系空気連行剤、＜２＞ノニ
オン系空気連行剤、＜３＞両性系空気連行剤が挙げられる。＜１＞アニオン系空気連行剤としては高級アルコール（又はそのアルキレンオキシド付加物）の硫酸エステル塩、アルキルベンゼンスルホン酸塩、ロジン石鹸、マレイン化ロジン石鹸などの樹脂石鹸塩、高級アルコール（又はそのアルキレンオキシド付加物）のリン酸エステル塩など、＜２＞ノニオン系空気連行剤としてはアルキレングリコール、高級アルコールのアルキレンオキシド付加物、脂肪酸とアルキレングルコールとのエステル、糖アルコールのアルキレングルコール付加物など、＜３＞アニオン、カチオンからなる両性系空気連行剤としてはアルキルベタイン型、アルキルアミドベタイン型、アミノ酸系両性活性剤型などが挙げられる。
Specific examples of the air entraining agent (AE agent) include <1> anionic air entraining agent, <2> nonionic air entraining agent, and <3> amphoteric air entraining agent. <1> As anionic air entraining agents, sulfate salts of higher alcohols (or adducts thereof), alkylbenzene sulfonates, rosin soaps, maleated rosin soaps and other resin soap salts, higher alcohols (or alkylene oxides thereof) (2) nonionic air entraining agents such as alkylene glycol, higher alcohol alkylene oxide adduct, fatty acid and alkylene glycol ester, sugar alcohol alkylene glycol adduct, etc. <3> Examples of amphoteric air entraining agents composed of anions and cations include alkylbetaine type, alkylamide betaine type, and amino acid type amphoteric activator type.
消泡剤を例示すると脂肪族アルコールアルキレンオキシド付加物、脂肪酸アルキレンオキシド付加物、アルキレンオキシドジ脂肪酸エステル、多価アルコールアルキレンオキシド付加物、ポリアルキレンポリアミンアルキレンオキシド付加物等の非イオン系消泡剤類、シリコーンオイルをエマルションとしたシリコーン系消泡剤類、高級アルコールをエマルションとした高級アルコール類、これらを主成分とした混合物などが挙げられる。 Examples of antifoaming agents include nonionic defoaming agents such as aliphatic alcohol alkylene oxide adducts, fatty acid alkylene oxide adducts, alkylene oxide difatty acid esters, polyhydric alcohol alkylene oxide adducts, polyalkylene polyamine alkylene oxide adducts, etc. And silicone-based antifoaming agents using silicone oil as an emulsion, higher alcohols using higher alcohol as an emulsion, and mixtures containing these as main components.
凝結促進剤を例示すると塩化カルシウム、亜硝酸カルシウムなどで代表される無機系促進剤、アルカノールアミンなどで代表される有機系促進剤が挙げられる。 Examples of the setting accelerator include inorganic accelerators represented by calcium chloride, calcium nitrite and the like, and organic accelerators represented by alkanolamine and the like.
凝結遅延剤を例示すると、＜１＞無機質系凝結遅延剤：リン酸塩、珪フッ化物、酸化亜鉛、炭酸化亜鉛、塩化亜鉛、一酸化亜鉛、水酸化銅、マグネシア塩、ホウ砂、酸化ホウ素、＜２＞有機質系凝結遅延剤：ホスホン誘導体、糖類やその誘導体、オキシカルボン酸塩、リグニンスルホン酸塩が挙げられ、さらに詳しく例示するとホスホン誘導体：アミノトリ（メチレンホスホン酸）、アミノトリ（メチレンホスホン酸）５ナトリウム塩、１−ヒドロキシエチリデン−１、１−ジホスホン酸、ジエチレントリアミンペンタ（メチレンホスホン酸）及びアルカリ金属塩、アルカリ土類金属塩のホスホン酸及びその誘導体、糖類：サッカロース、マルトース、ラフィノース、ラクトース、グルコース、フラクトース、マンノース、アラビノース、キシロース、アビトース、リポーズ、オキシカルボン酸塩：グルコン酸、クエン酸、グルコヘプトン酸、リンゴ酸、酒石酸、これらのアルカリ金属塩、アルカリ土類金属塩が挙げられる。 Examples of setting retarders include: <1> inorganic setting retarders: phosphates, silicofluorides, zinc oxide, zinc carbonate, zinc chloride, zinc monoxide, copper hydroxide, magnesia salts, borax, boron oxide <2> Organic coagulation retarders: phosphonic derivatives, saccharides and derivatives thereof, oxycarboxylates, lignin sulfonates, and more specific examples include phosphonic derivatives: aminotri (methylenephosphonic acid), aminotri (methylenephosphonic acid) ) Pentasodium salt, 1-hydroxyethylidene-1, 1-diphosphonic acid, diethylenetriaminepenta (methylenephosphonic acid) and alkali metal salts, phosphonic acids of alkaline earth metal salts and derivatives thereof, saccharides: saccharose, maltose, raffinose, lactose Glucose, fructose, mannose, arabinose, key Loin, Abitosu, Repose, oxycarboxylate: gluconic acid, citric acid, glucoheptonic acid, malic acid, tartaric acid, their alkali metal salts, alkaline earth metal salts.
これら添加剤の中でも減水剤との併用が好ましく、具体例を挙げるとすれば、特に日本シーカ（株）製のポリカルボン酸系高性能ＡＥ減水剤であるシーカメント１１００ＮＴ、シーカメント１２００Ｎとの配合が好ましい。その配合割合（質量比）としては、減水剤：本発明の収縮低減剤＝１：９９〜９９：１、好ましくは７０：３０〜９９：１である。この収縮低減剤と減水剤が配合されたセメント混和剤は、セメントに対して通常０．１〜１０質量％の範囲で用いられるが、０．１〜５質量％の範囲で用いることが好ましい。 Among these additives, combined use with a water reducing agent is preferable, and as a specific example, blending with Seakament 1100NT and Seakament 1200N which are polycarboxylic acid-based high performance AE water reducing agents manufactured by Nippon Seika Co., Ltd. is particularly preferable. . The blending ratio (mass ratio) is water reducing agent: shrinkage reducing agent of the present invention = 1: 99 to 99: 1, preferably 70:30 to 99: 1. The cement admixture in which the shrinkage reducing agent and the water reducing agent are blended is usually used in the range of 0.1 to 10% by mass with respect to the cement, but is preferably used in the range of 0.1 to 5% by mass.
本発明の収縮低減剤が有する優れた収縮低減効果が如何にして得られるのかについて、明確な理由の解明には至っていない。その仮定の一つとして、セメント組成物の水和反応過程において、セメント組成物の内部温度の上昇に伴い、本発明の収縮低減剤が系内の疎水化を効果的に促進することにより、優れた収縮低減効果ならびに強度発現性を有しているとみている。 A clear reason has not yet been clarified as to how the excellent shrinkage reducing effect of the shrinkage reducing agent of the present invention can be obtained. As one of the assumptions, in the hydration reaction process of the cement composition, the shrinkage reducing agent of the present invention effectively promotes the hydrophobization in the system as the internal temperature of the cement composition increases. It is considered to have a shrinkage reducing effect and strength development.
以下実施例により本発明を説明する。ただし本発明は、これらの実施例及び比較例によって何ら制限されるものではない。 The following examples illustrate the invention. However, the present invention is not limited to these examples and comparative examples.
［収縮低減剤の調製］
表１に示す化合物Ａ〜Ｃ、及びその混合比率（質量比）にて、収縮低減剤Ｘ１〜Ｘ１１及び比較収縮低減剤Ｙ１〜Ｙ４を調製した。
Shrinkage reducing agents X1 to X11 and comparative shrinkage reducing agents Y1 to Y4 were prepared using the compounds A to C shown in Table 1 and the mixing ratio (mass ratio) thereof.
さらに比較収縮低減剤Ｙ５として、特開２０１０−２２９０１４号公報の自己収縮低減
剤（ａ−１）（２−エチルヘキサノール３モルＥＯ付加物）を採用し、製造例１（段落［００３３］に記載の手順に従い、調製した。
Further, as the comparative shrinkage reducing agent Y5, the self-shrinkage reducing agent (a-1) (2-ethylhexanol 3 mol EO adduct) of JP 2010-229014 A is employed, and described in Production Example 1 (paragraph [0033]). It was prepared according to the procedure.
調製した収縮低減剤Ｘ３及びＸ１０、並びに比較収縮低減剤Ｙ１、Ｙ２及びＹ５について、曇点（℃）、粒度分布及び一液性安定性について、以下の手順及び評価に従い測定・評価した。得られた結果を表２に示す。 For the prepared shrinkage reducing agents X3 and X10 and comparative shrinkage reducing agents Y1, Y2 and Y5, the cloud point (° C.), the particle size distribution and the one-component stability were measured and evaluated according to the following procedure and evaluation. The obtained results are shown in Table 2.
《曇点の測定方法》
各収縮低減剤を水で希釈し、５及び１６質量％水溶液を調製し、曇点を測定した。
《粒度分布の測定方法》
各収縮低減剤を水で希釈して１６質量％水溶液を調製し、各水溶液の曇点における粒度分布をレーザ回折式粒子径分布測定装置 ＳＡＬＤ−２３００（（株）島津製作所製）を用いて測定した。
《減水剤への一液性確認試験》
市販の減水剤（シーカメント１１００ＮＴ（日本シーカ（株）製）８５部と、各収縮低減剤１５部とを混合した。混合後、２０℃及び４０℃で３ヶ月間静置保存し、目視にて外観の比較を行った。以下の評価指標に従い、収縮低減剤の一液性安定性を評価した。
＜一液性安定性の評価指標＞
◎：減水剤の外観が、透明均一を保っている状態
○：減水剤の外観は霞んでいるが、均一に分散している状態
×：減水剤と収縮低減剤が２層に分離している状態
<Method of measuring cloud point>
Each shrinkage reducing agent was diluted with water to prepare 5 and 16 mass% aqueous solutions, and the cloud point was measured.
<Measurement method of particle size distribution>
Each shrinkage reducing agent is diluted with water to prepare a 16% by mass aqueous solution, and the particle size distribution at the cloud point of each aqueous solution is measured using a laser diffraction particle size distribution analyzer SALD-2300 (manufactured by Shimadzu Corporation). did.
《One-component confirmation test for water reducing agent》
85 parts of a commercially available water reducing agent (Seacament 1100NT (manufactured by Nippon Seika Co., Ltd.)) and 15 parts of each shrinkage reducing agent were mixed, and after standing, stored at 20 ° C. and 40 ° C. for 3 months, and visually The appearance of the shrinkage reducing agent was evaluated according to the following evaluation index.
<One-component stability evaluation index>
A: Appearance of the water reducing agent is kept transparent and uniform ○: Appearance of the water reducing agent is stagnant but uniformly dispersed ×: Water reducing agent and shrinkage reducing agent are separated into two layers State
表２に示す通り、本発明のセメント組成物用収縮低減剤は、曇点における１μｍ未満の粒度分布が１００％となった。また、２０℃及び４０℃における一液安定性に優れるものであった。特に化合物Ｃ（低級アルコールアルキレンオキシド付加物）を配合した収縮低減剤Ｘ１０においては、４０℃で３ヶ月保管後においても透明均一を保っており、卓越した一液安定性を示す結果が得られた。
なお、収縮低減剤の粒子径が収縮低減性や強度発現性に及ぼし得る影響は未だ解明されていない。ただ、本発明のセメント組成物用収縮低減剤において化合物Ａ及びＢを最適な比率で組み合わせることにより、水中で温度刺激により粒子径が調節される機能を有する会合体を形成しているものと考えられる。粒子径が調節された収縮低減剤は、セメント組成物の微細構造中に最適な大きさでとどまるとみられ、これにより、水和反応の進行に伴う収縮を低減しているものと推察される。
As shown in Table 2, the shrinkage reducing agent for cement composition of the present invention had a particle size distribution of less than 1 μm at the cloud point of 100%. Moreover, it was excellent in the one liquid stability in 20 degreeC and 40 degreeC. In particular, in the shrinkage reducing agent X10 containing Compound C (lower alcohol alkylene oxide adduct), a transparent and uniform state was maintained even after storage at 40 ° C. for 3 months, and a result showing excellent one-component stability was obtained. .
The influence that the particle size of the shrinkage reducing agent may have on shrinkage reduction and strength development has not yet been elucidated. However, in the shrinkage reducing agent for cement composition of the present invention, it is considered that an aggregate having the function of adjusting the particle size by temperature stimulation in water is formed by combining compounds A and B in an optimal ratio. It is done. The shrinkage-reducing agent having a controlled particle size is considered to remain at an optimum size in the microstructure of the cement composition, and it is thus presumed that the shrinkage accompanying the progress of the hydration reaction is reduced.
［試験１：フレッシュモルタル試験］
セメント及び細骨材に、減水剤（シーカメント１２００Ｎ（日本シーカ（株）製））、セメントに対して２．０質量％）のみ（比較例１）、又は減水剤（同上、セメントに対して２．０質量％）と上記各収縮低減剤（セメントに対する添加量は表４参照）を予め加えて調製した練り混ぜ水を加え、ハイパワーミキサー（（株）丸東製作所製）を用い、低速で練り混ぜた。低速での練り混ぜは、目視で材料が一体化するまで継続し、一体化した時間を練り混ぜ時間として記録した。次いで高速で１２０秒間練り混ぜ、試験モルタルを作製した。なお試験に供したモルタルの各材料の単位量を表３に示す。
これら練り上がり直後のモルタルについて、ＪＩＳ Ａ １１７１「ポリマーセメントモルタルの試験方法」に準拠したミニスランプコーン（上端内径５０ｍｍ、下端内径１００ｍｍ、高さ１５０ｍｍ）を用い、モルタルの広がり（ミニフロー）を測定した。ミニフロー測定後、モルタルの状態を目視にて確認した。また、練り上がり直後及び６０分後の空気量を測定した。空気量の測定には全質量方式を採用し、メスシリンダーを用いて測定した結果より、下記式により空気量を算出した。
空気量（％）＝[１−（モルタル質量）／（配合から求める空気量０％でのモルタル質量
）]×１００
尚、試験に用いたモルタルには適宜消泡剤（ポリオキシアルキレンアルキルエーテル脂肪酸エステル系消泡剤）を併用し、この使用量を調節することで、練り上がり直後のモルタル空気量が２．０％以下となるように調整した。収縮低減剤を含めたこれらの薬剤は、すべて水の一部として計量して試験に供した。
得られた結果を表４に示す。
[Test 1: Fresh mortar test]
For cement and fine aggregate, water reducing agent (SEICAMENT 1200N (manufactured by Nippon Sika Co., Ltd.)), 2.0% by mass relative to cement) (Comparative Example 1) or water reducing agent (same as above, 2 for cement) 0.0% by mass) and the above-mentioned shrinkage reducing agents (see Table 4 for the amount added to the cement), kneaded water prepared in advance was added, and a high power mixer (manufactured by Maruto Seisakusho Co., Ltd.) was used. Kneaded. The mixing at low speed was continued until the materials were integrated visually, and the integration time was recorded as the mixing time. Subsequently, it knead | mixed for 120 second at high speed, and produced the test mortar. Table 3 shows the unit amount of each material of the mortar subjected to the test.
For these mortars just after kneading, the spread of the mortar (miniflow) is measured using a mini slump cone (top inner diameter 50 mm, lower end inner diameter 100 mm, height 150 mm) according to JIS A 1171 “Test method for polymer cement mortar”. did. After the miniflow measurement, the state of the mortar was visually confirmed. Further, the amount of air immediately after kneading and after 60 minutes was measured. The total mass method was adopted for the measurement of the air amount, and the air amount was calculated by the following formula from the result of measurement using a graduated cylinder.
Air amount (%) = [1- (Mortar mass) / (Mortar mass at 0% of air amount determined from formulation)] × 100
In addition, an antifoaming agent (polyoxyalkylene alkyl ether fatty acid ester-based antifoaming agent) is appropriately used in combination with the mortar used in the test, and by adjusting the amount of use, the mortar air amount immediately after kneading is 2.0. It adjusted so that it might become below%. All of these drugs, including shrinkage reducing agents, were weighed as part of the water for testing.
Table 4 shows the obtained results.
［試験２．硬化性状確認試験］
試験１の手順にて作製したモルタルを、φ１０ｃｍ、高さ１２ｃｍのプラスチック製容器に充填し、これをウレタンフォーム製の簡易断熱箱の中心部に入れ、（株）共和電業製コンクリート埋込型ひずみゲージ：ＫＭＣ−７０−１２０−Ｈ４、データロガー：ＮＴＢ−１００Ａ−１２０及びＮＴＢ−２０１Ａを用いて、モルタルの内部温度及び水和反応過程における収縮ひずみを測定した。
そしてモルタルの内部温度の履歴から、最高温度及び最高温度への到達時間（発熱ピーク）を確認した。本試験は、凝結時間や初期強度に影響を与える初期の水和反応の活性状態をはかる試験であり、最高温度はセメントの水和反応に伴う反応熱を反映し、収縮低減剤を配合していない例における最高温度及び発熱ピークを大きく逸脱する結果は、初期の水和反応に与える影響が大きいことを示す。
また、試験１の手順にて作製したモルタルを、φ５ｃｍ、高さ１０ｃｍのプラスチック製モールドに充填し、２４時間後に脱型した。脱型した供試体を２０℃にて水中養生し、材齢７日及び２８日における圧縮強度をＪＩＳ Ａ １１０８の手順に従って測定した。
得られた結果を表４に示す。
[Test 2. Curing property confirmation test]
Fill the mortar produced in the procedure of Test 1 into a plastic container with a diameter of 10 cm and a height of 12 cm, put it in the center of a simple insulated box made of urethane foam, and embedded concrete with Kyowa Denki Co., Ltd. Using a strain gauge: KMC-70-120-H4 and a data logger: NTB-100A-120 and NTB-201A, the internal temperature of the mortar and the shrinkage strain in the hydration reaction process were measured.
The maximum temperature and the time to reach the maximum temperature (exothermic peak) were confirmed from the history of the internal temperature of the mortar. In this test, the active state of the initial hydration reaction that affects the setting time and initial strength is measured.The maximum temperature reflects the heat of reaction accompanying the hydration reaction of the cement, and a shrinkage reducing agent is blended. Results that deviate significantly from the maximum temperature and exothermic peak in the absence of examples indicate a significant impact on the initial hydration reaction.
Moreover, the mortar produced in the procedure of Test 1 was filled into a plastic mold having a diameter of 5 cm and a height of 10 cm, and demolded after 24 hours. The removed specimen was cured in water at 20 ° C., and the compressive strength at the age of 7 and 28 days was measured according to the procedure of JIS A 1108.
Table 4 shows the obtained results.
［試験３．乾燥収縮試験］
ＪＩＳ Ｒ ５２０１の規定に従い、下記表５に示すモルタル配合にてモルタルを調製し、モルタル試験に供した。
詳細には、モルタルの練り混ぜにはホバートミキサーを使用し、はじめに水とセメントを低速で３０秒間練り混ぜたのち、砂を投入し低速で３０秒練り混ぜた。なお本試験において、収縮低減剤Ｘ３及びＸ１０を使用する場合、セメント質量に対して一律２質量％の添加量で、練り水と共に加えた。その後高速で３０秒練り混ぜたのちに撹拌を停止し、９０秒間静置した。静置開始から１５秒間で容器の壁に付着したモルタルを掻き落とし、静
置後、高速で６０秒練り混ぜを行った。ここでモルタルの空気量は７〜９％となるように、適宜ＡＥ剤と消泡剤にて調整した。
モルタルフローの測定はＪＩＳフローコーンを使用して試験１と同様に実施し、また空気量の測定についても試験１と同様に行った。
収縮低減率の測定は、ＪＩＳ Ｒ ５２０１に従い、４×４×１６ｃｍの型枠に充填して作製したモルタルの供試体を用いて行なった。硬化後の供試体を２４時間後に脱型し、その後１週間の水中養生（２０℃）を行った。水中養生終了後、ＪＩＳ Ａ １１２９−２記載のコンタクトゲージ方法にて供試体の寸法を測定し、これを乾燥材齢１日の基準値とした。その後、供試体を温度２０℃、湿度６０％の条件にて保存し、乾燥材齢５６日で再度供試体の寸法を測定し、乾燥材齢１〜５６日での長さ変化率を算出した。収縮低減率の値は、前述のモルタル供試体の長さ変化率と、ブランクとして収縮低減剤を使用していないモルタル供試体の長さ変化率とを用いて、下記式により算出した。尚、収縮低減率の値が大きい供試体（すなわち、供試体の長さ変化率がブランクに比べて少ない）ほど、収縮を抑制できていることを意味する。
収縮低減率（％）＝[１−（実施例の供試体の長さ変化率）／（収縮低減剤を使用してい
ないブランクの長さ変化率）]×１００
以上、得られた結果を表６に示す。
[Test 3. Drying shrinkage test]
In accordance with the provisions of JIS R 5201, mortar was prepared with the mortar formulation shown in Table 5 below, and was subjected to a mortar test.
Specifically, a Hobart mixer was used for kneading the mortar. First, water and cement were kneaded at low speed for 30 seconds, then sand was added and kneaded at low speed for 30 seconds. In this test, when shrinkage reducing agents X3 and X10 were used, they were added together with the kneading water at an addition amount of 2% by mass uniformly with respect to the cement mass. Then, after kneading at high speed for 30 seconds, stirring was stopped and the mixture was allowed to stand for 90 seconds. The mortar adhering to the wall of the container was scraped off in 15 seconds from the start of standing, and after standing, kneading was performed at high speed for 60 seconds. Here, the amount of air in the mortar was appropriately adjusted with an AE agent and an antifoaming agent so as to be 7 to 9%.
The mortar flow was measured in the same manner as in Test 1 using a JIS flow cone, and the air amount was also measured in the same manner as in Test 1.
The shrinkage reduction rate was measured using a mortar specimen prepared by filling a 4 × 4 × 16 cm mold in accordance with JIS R 5201. The cured specimen was demolded after 24 hours, and then subjected to water curing (20 ° C.) for 1 week. After the underwater curing, the dimensions of the specimen were measured by the contact gauge method described in JIS A 1129-2, and this was used as the reference value for the dry material age of 1 day. Thereafter, the specimen was stored under conditions of a temperature of 20 ° C. and a humidity of 60%, the dimensions of the specimen were measured again at a dry material age of 56 days, and the length change rate at a dry material age of 1 to 56 days was calculated. . The value of the shrinkage reduction rate was calculated by the following formula using the above-mentioned rate of change of the mortar specimen and the rate of change of the mortar specimen that did not use the shrinkage reducing agent as a blank. In addition, it means that shrinkage | contraction can be suppressed, so that the specimen with a large value of shrinkage | contraction reduction rate (namely, the length change rate of a specimen is small compared with a blank).
Shrinkage reduction rate (%) = [1− (length change rate of specimen of example) / (blank length change rate without using shrinkage reducing agent)] × 100
The results thus obtained are shown in Table 6.
表４に示すように、水／セメント比が１５％である超高強度コンクリートを想定したフレッシュモルタル試験及び硬化性状確認試験において、本発明のセメント組成物用収縮低減剤Ｘ１〜Ｘ１１を使用した実施例１〜１１は、比較収縮低減剤Ｙ１〜Ｙ５を用いた比較例２〜７と比べ、モルタル状態において各材料が一体となって表面が瑞々しいという結果が得られた。
また実施例１〜１１は、比較例２〜７と比べ発熱ピークが早く且つ最高温度が高く、収縮低減剤無添加の比較例１の結果と同程度の結果が得られていることから、初期の水和反応への影響が小さい（水和反応の遅延や阻害が少ない）と推察される。また圧縮強度に関しても収縮低減剤無添加の比較例１に匹敵する強度を得られるという結果が得られており
、この結果も水和反応の進行を阻害しないという効果を反映した結果と推察される。
さらに、本発明のセメント組成物用収縮低減剤Ｘ１〜Ｘ１１を使用した実施例１〜１１は、収縮低減剤無添加の比較例１と比べて水和反応過程における収縮ひずみがおよそ２３％〜３３％程度も低減され、比較収縮低減剤Ｙ１〜Ｙ５を用いた比較例２〜６と比べても１割以上も収縮低減されるという結果を得た。なお比較例７は収縮低減剤を２倍量使用することにより、実施例と同程度の収縮低減効果を発揮しているが、発熱ピークや最高温度の結果にみられるように初期の水和反応への影響が非常に大きく、圧縮強度に劣るとする結果となった。
As shown in Table 4, in the fresh mortar test and the curing property confirmation test assuming ultra high strength concrete having a water / cement ratio of 15%, the shrinkage reducing agents X1 to X11 for cement composition of the present invention were used. In Examples 1 to 11, as compared with Comparative Examples 2 to 7 using the comparative shrinkage reducing agents Y1 to Y5, the results were obtained that the surfaces of each material were united in a mortar state and the surface was fresh.
In addition, Examples 1 to 11 had a faster exothermic peak and higher maximum temperature than Comparative Examples 2 to 7, and the same results as those of Comparative Example 1 with no addition of a shrinkage reducing agent were obtained. It is presumed that the influence of hydration on the hydration reaction is small (the delay or inhibition of the hydration reaction is small). Further, with respect to the compressive strength, a result that the strength comparable to that of Comparative Example 1 with no addition of the shrinkage reducing agent was obtained was obtained, and this result is also presumed to reflect the effect of not inhibiting the progress of the hydration reaction. .
Furthermore, Examples 1 to 11 using the shrinkage reducing agents X1 to X11 for the cement composition of the present invention have a shrinkage strain of about 23% to 33 in the hydration reaction process as compared with Comparative Example 1 in which no shrinkage reducing agent was added. As a result, the shrinkage was reduced by 10% or more as compared with Comparative Examples 2 to 6 using the comparative shrinkage reducing agents Y1 to Y5. In Comparative Example 7, the same amount of shrinkage reducing effect as that of the Example was exhibited by using twice the amount of shrinkage reducing agent, but the initial hydration reaction was observed as seen in the exothermic peak and maximum temperature results. As a result, the impact on the water was very large and the compression strength was poor.
また表６に示すように、水／セメント比が５０％である一般のコンクリートを想定した乾燥収縮試験では、収縮剤無添加の比較例８と比べ、乾燥による収縮が低減されている結果が得られた。 Further, as shown in Table 6, in the drying shrinkage test assuming general concrete having a water / cement ratio of 50%, the shrinkage due to drying was reduced as compared with Comparative Example 8 in which no shrinkage agent was added. It was.
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| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |