JP4709359B2 - Hydraulic composition - Google Patents
Hydraulic composition Download PDFInfo
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- JP4709359B2 JP4709359B2 JP2000273750A JP2000273750A JP4709359B2 JP 4709359 B2 JP4709359 B2 JP 4709359B2 JP 2000273750 A JP2000273750 A JP 2000273750A JP 2000273750 A JP2000273750 A JP 2000273750A JP 4709359 B2 JP4709359 B2 JP 4709359B2
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- polycarboxylic acid
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/06—Aluminous cements
Description
【０００１】
【発明の属する技術分野】
本発明は、Ｃ３Ａを主成分とするセメント系水硬性組成物に関する。
【０００２】
【従来技術とその問題点】
Ｃ３Ａ、即ちＣａＯ・３Ａｌ2Ｏ3の如く水和活性の極めて高い化合物を大量に含有するセメントは、初期強度発現性はかなり優れるものの、反面水添加混練時に急激な流動性の低下が生じ易く、混練後の作業が著しく制約を受け易い。このような流動性低下の防止策として、クエン酸などの公知の有機系遅延剤を使用して初期水和反応を抑制する方法や、ナフタレンスルホン酸ホルマリン縮合物又はメラミンスルホン酸ホルマリン縮合物等の公知の分散剤を使用する方法、更には前者と後者の方法を同時に併用する方策も挙げられる。前者即ちクエン酸などの有機系遅延剤の使用は、初期水和反応が過度に抑制され易く、初期強度発現性までが低下することがある。また、後者の分散剤を使用する方法は、高流動性を確保する上で添加量を増大させたり、水セメント比を高くせねばならず、この結果凝結が遅延したり、強度発現性が低下することがある。更に、両者を併用する場合には互いの影響で作用効果が低減され易いため、有機系遅延剤の配合量を単独使用する場合よりもかなり多くしないと安定した流動状態が一定時間維持できない。このことは水和反応の過度の抑制からもたらされるため、強度発現性の低下、とりわけ初期強度の発現性を損なう。
【０００３】
【発明が解決する課題】
本発明は、前記問題点の解決、即ち、水和活性が極めて高く、初期強度発現性に優れた影響を及ぼすＣ３Ａを主成分に含む水硬性組成物に対し、水添加後の混練物に一定時間流動性を付与でき、かつ凝結遅延や初期強度発現性低下が殆ど生じないようにした水硬性組成物を提供することを目的とする。
【０００４】
【課題を解決する手段】
本発明者らは、前記課題に対し検討を重ねた結果、水和活性が極めて高く、早期強度発現性の優れたＣ３Ａを主成分とし、これに初期から中長期に渡って安定した強度発現作用を付与させるためのＣ３Ｓ、Ｃ２ＳおよびＣ４ＡＦに、凝結・水和調整作用を有する石膏を加えてセメント系組成物とし、該組成物の水添加時に高い流動性を付与させるための特定の高分子化合物を配合することで混練時や混練後の作業性を高めることができ、凝結遅延や初期強度発現性低下を殆ど生じない水硬性組成物が得られたことから本発明を完成するに至った。
【０００５】
即ち、本発明は、下記の（Ａ）、（Ｂ）、（Ｃ）および（Ｄ）を含む水硬性組成物（但し、高強度湿式吹き付け用水硬性組成物を除く）である。
（Ａ）Ｃ３Ａを５〜５０重量％と、Ｃ３Ｓ、Ｃ２ＳおよびＣ４ＡＦを含むセメント形成成分。
（Ｂ）含有量がクリンカー焼成物１００重量部に対し１〜３０重量％である石膏類。
（Ｃ）含有量がセメント形成成分の固形分総量１００重量部に対し、固形分換算で０．０１〜５重量部である、下記の（i）、（ii）および（iii）の物性を有するポリカルボン酸系高分子化合物。
（i）ポリカルボン酸系高分子化合物が分子内に下記の（Ｉ）式と（ＩＩ）式で表される構成単位を有する。
【０００８】
〔式中、Ｒ1〜Ｒ4は、同一又は異なって、水素原子又はメチル基又はエチル基を表し、Ｘ1 は（ＣＨ2）ｍＣＯＯＭ1を表し、Ｘ2はＣＯＯＭ1を表す。Ｍ1は、水素原子、アルカリ金属、アンモニウム又は有機アミンの何れかを表し、ｍは０〜２の整数を表す。Ｒ5は炭素数１〜３のアルキル基、Ｙは−ＣＨ2Ｏ−又は−ＣＯＯ−を表し、ｎは２０〜３００の整数を表す。〕
（ii）ポリカルボン酸系高分子化合物を構成する構成単位の含有量が単量体モル比換算で（Ｉ）式／（ＩＩ）式＝１００／０．１〜１００／１００である。
（iii）ポリカルボン酸系高分子化合物の重量平均分子量がポリエチレングリコール換算で２０００〜２０００００である。
（Ｄ）含有量がポリカルボン酸系高分子化合物の固形分１００重量部に対し、１〜４０重量部である遅延剤。
【０００９】
【発明の実施の形態】
本発明の水硬性組成物は、セメント形成成分、石膏類、遅延剤、およびポリカルボン酸系高分子化合物からなる。前者に関わる成分として、本発明ではＣ３ＡことＣａＯ・３Ａｌ2Ｏ3を必須成分とし、且つＣ３ＳことＣａＯ・３ＳｉＯ2、Ｃ２ＳことＣａＯ・２ＳｉＯ2、およびＣ４ＡＦことＣａＯ・４Ａｌ2Ｏ3・Ｆｅ2Ｏ 3 を構成物質として含むものであって、Ｃ３Ａが５〜５０重量％含まれるものである。尚、Ｃ３Ａの含有量が５重量％未満では初期強度発現性が乏しくなるため好ましくなく、また５０重量％を超えると流動性が著しく低下するため好ましくない。更にセメント形成成分には石膏類が必須成分として加わる。
【００１０】
また、Ｃ３Ａ、Ｃ３Ｓ、Ｃ２Ｓ、Ｃ４ＡＦの各成分を供するための原料は、特に限定されるものではなく、例えば石灰石、粘土鉱物、石炭灰、高炉スラグを始めとする各種スラグ類、炭酸カルシウム、珪石粉、鉄粉、廃棄物や汚泥等の各種焼却灰、石灰処理した下水汚泥乾粉、その他セメント製造で使用されている原料などを用いることができる。
【００１１】
かかる原料を例えばロータリーキルンなどで１２００〜１５００℃で焼成してクリンカーを作製し、これを粉砕したクリンカー粉砕物に、石膏類を加え、水硬性組成物を作製する。クリンカー粉砕方法や粉砕粒度は特に限定されず、一般のセメント製造で行われているのと概ね同様で良く、例えばクリンカー粉砕物の粒度は２０００〜１００００ｃｍ2／ｇとすることができる。このクリンカー粉砕物に石膏類を添加するが、本発明で使用する石膏類は特に限定されず、例えば無水石膏、半水石膏、二水石膏を挙げることができる。その配合量は概ねクリンカー焼成物１００重量部に対し１〜３０重量部が好ましい。配合量が１重量部未満では水和反応調整効果が乏しいため好ましくなく、また配合量が３０重量部を超えると膨張するため好ましくない。
【００１２】
更に、本発明の水硬性組成物は、ポリカルボン酸系高分子化合物を含むものである。該ポリカルボン酸系高分子化合物は、分子内に次の（Ｉ）式と（ＩＩ）式で表される構成単位を有するものが好ましい。また、ポリカルボン酸系高分子化合物の含有量は水硬性組成物を構成するＣ３Ａ等のセメント形成成分に対し、固形分換算で０．０１〜５重量％とする。
【００１３】
【化５】
【化６】
〔式中、Ｒ1〜Ｒ4は、同一又は異なって、水素原子又はメチル基又はエチル基を表し、Ｘ1は水素原子又はメチル基又は（ＣＨ2）ｍＣＯＯＭ1を表し、Ｘ2はＣＯＯＭ1を表す。Ｍ1は、水素原子、アルカリ金属、アンモニウム又は有機アミンの何れかを表し、ｍは０〜２の整数を表す。Ｒ5は炭素数１〜３のアルキル基、Ｙは−ＣＨ2Ｏ−又は−ＣＯＯ−を表し、ｎは２０〜３００の整数を表す。〕該ポリカルボン酸系高分子化合物は、水硬性組成物中のＣ３Ａ等のセメント形成成分の固形分総量１００重量部に対し、固形分換算で好ましくは０．０１〜５重量部、より好ましくは０．０５〜３重量部を含むのが良く、０．０１重量部未満の配合では配合効果が殆ど得られないので好ましくなく、また５重量部を超える配合では凝結遅延や硬化後の強度発現性が不良となることがあるので好ましくない。また、ポリカルボン酸系高分子化合物を構成する構成単位の含有量が単量体モル比換算で（Ｉ）式／（ＩＩ）式＝１００／０．１〜１００／１００であることが好ましい。これは、（Ｉ）式／（ＩＩ）式の値が１００／０．１より大であると流動性の低下が大きくなり、１００／１００未満であると泡沫安定性や分散性が低下するため何れも好ましくないことによる。
【００１６】
また、該ポリカルボン酸系高分子化合物の重量平均分子量はポリエチレングリコール換算で２０００〜２０００００であることが好ましい。重量平均分子量が２０００未満や、２０００００を超えると何れも分散性が低下するため好ましくない。
【００１７】
また、本発明の水硬性組成物は、前記ポリカルボン酸系高分子化合物に加えて、セメント用やコンクリート用の公知混和剤（混和材）を適宜含むことができる。
【００１８】
本発明の水硬性組成物は、遅延剤を含む。遅延剤は公知のものであれば何れのものでも良く、例えばオキシカルボン酸やその塩、ケト酸又はその塩、アミノカルボン酸又はその塩、糖類、糖アルコール類等の公知の有機系遅延剤、ケイフッ化物、硼酸類、燐酸類、亜鉛化合物、鉛化合物、銅化合物等の公知無機系遅延剤が挙げられる。このうち、オキシカルボン酸若しくはその塩、糖類、糖アルコール類がより好ましい。遅延剤の添加量は、ポリカルボン酸系高分子化合物の配合量の固形分換算１００重量部に対し、１〜４０重量部であり、１重量部未満では流動性保持の改善効果が殆ど認められないため好ましくなく、４０重量部を超えると過度の凝結遅延を起こすことがあるため好ましくない。その配合添加の際は、ポリカルボン酸系高分子化合物に予め混合してポリカルボン酸系高分子化合物と共に配合添加しても良い。
【００１９】
また、本発明の水硬性組成物は、骨材として、通常のコンクリートやモルタル等で使用されている公知骨材であれば何れのものでも含むことができる。このような公知骨材としては、例えば川砂、陸砂、砕石、珪砂等の天然骨材が特に好ましいが、他にフライアッシュ、スラグ、水洗を施した海砂、炭酸カルシウム等を用いることができる。骨材配合量は水硬性成分１００重量部に対し、３０〜１０００重量部、コンクリートを製造する場合では好ましくは１００〜７００重量部とする。３０重量部未満では組成物の収縮量が増大するので好ましくなく、１０００重量部を超えると水添加時の流動性と硬化体強度の低下を来すので好ましくない。
【００２０】
本発明の水硬性組成物に水を配合する際の配合量は、該組成物中のセメント形成成分１００重量部に対し、２０〜１００重量部とする。水の配合中や配合直後は混練を行うのが望ましいが、本水硬性組成物は混練停止後も直ぐには硬化せず、暫くの間は良好な流動状態を維持することができるので、その間に施工作業等を特段の制約なく行うことができる。
【００２１】
【実施例】
以下、本発明を実施例を用いて具体的に説明する。
石灰石粉、アルミ灰、粘土並びに鉄粉の混合物を約１４００℃で焼成した後、粉砕しブレーン比表面積を４０００ｃｍ2／ｇにした表１の鉱物成分を含むクリンカー粉砕物に、ＳＯ3換算で２．２重量％の半水石膏を添加し、これを再粉砕してブレーン比表面積４７００ｃｍ2／ｇの表２に記した化学組成（重量％）の２種類のセメント組成物（Ａ、Ｂ）を作製した。このセメント組成物に、細骨材として最大粒径５ｍｍの小笠産陸砂、更に表３に記したモル組成比（配合割合をモル％で表す）の単量体を公知手法で共重合させて得た高分子化合物（１〜５）の固形分濃度約２５％溶液又はナフタレンスルホン酸ホルマリン縮合物を主成分とする市販分散剤（Ｎ）、遅延剤並びに水を表４に記した配合割合でホバートミキサーで３分間混練し、水硬性組成物（実施例１〜１３、比較例１〜３）を作製した。作製した水硬性組成物の混練終了直後から一定時間経たモルタルフロー値、該混練物を用いたモルタル供試体によるモルタル圧縮強さを、何れもＪＩＳ Ｒ５２０１に準拠した方法で調整・測定した。結果を表４に記す。
【００２２】
【表１】
【表２】
【表３】
【表４】
また、前記セメント組成物に、前記小笠産陸砂と粗骨材として最大粒径約２０ｍｍの砕石を混合した骨材（重量比で小笠産陸砂：粗骨材＝１：１．５）、表３に記したモル組成比（配合割合をモル％で表す）の単量体を公知手法で共重合させてなる高分子化合物（１〜６）の固形分濃度約２５％の溶液又はナフタレンスルホン酸ホルマリン縮合物を主成分とする市販分散剤（Ｎ）、遅延剤並びに水を表５記載の配合量となるように強制２軸型ミキサーにて混合・混練したもの（実施例１４〜２８、比較例４〜６）を、ＪＩＳ Ａ１１０１に準じた方法にて混練直後と混練後６０分経過した時点でのスランプを測定した。更にこの混練物を直径１０ｃｍ、高さ２０ｃｍの円柱型枠に充填し、２４時間経過後脱型して得た成形物の圧縮強度を測定した。スランプ値並びに圧縮強度の測定結果等を表５に併せて記す。
【００２７】
【表５】
【発明の効果】
本発明の水硬性組成物は、水添加後も適度な流動性を一定時間維持することができる。それ故、施工や型枠成形などの作業時間を十分確保できると共に、凝結遅延を起こすこともなく、硬化後は極めて優れた初期強度発現性を示し、中長期に渡っても安定した強度発現性を示す。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a cement-based hydraulic composition containing C3A as a main component.
[0002]
[Prior art and its problems]
C3A, that is, a cement containing a large amount of a compound having a very high hydration activity such as CaO.3Al 2 O 3 has a considerably excellent initial strength, but on the other hand, a sudden drop in fluidity is likely to occur during water addition and kneading. The work after kneading is extremely restricted. As a preventive measure for such a decrease in fluidity, a method of suppressing an initial hydration reaction using a known organic retarder such as citric acid, a naphthalene sulfonic acid formalin condensate or a melamine sulfonic acid formalin condensate, etc. A method of using a known dispersant, and a method of simultaneously using the former method and the latter method can also be mentioned. The former, ie, the use of an organic retarder such as citric acid, tends to excessively suppress the initial hydration reaction, and may reduce the initial strength development. In addition, the method using the latter dispersant has to increase the amount added to ensure high fluidity or increase the water-cement ratio. As a result, setting is delayed or strength development is reduced. There are things to do. Furthermore, when both are used in combination, the action and effect are likely to be reduced due to mutual influences. Therefore, a stable fluid state cannot be maintained for a certain period of time unless the amount of the organic retarder blended is significantly increased compared to the case where the organic retarder is used alone. Since this results from excessive suppression of the hydration reaction, it deteriorates strength development, particularly initial strength development.
[0003]
[Problems to be solved by the invention]
The present invention solves the above problems, that is, the kneaded product after addition of water is constant for a hydraulic composition containing C3A as a main component, which has a very high hydration activity and has an excellent effect on initial strength development. It is an object of the present invention to provide a hydraulic composition which can impart temporal fluidity and hardly causes a setting delay or a decrease in initial strength development.
[0004]
[Means for solving the problems]
As a result of repeated investigations on the above problems, the present inventors have C3A as a main component, which has extremely high hydration activity and excellent early strength development, and has a stable strength development action from the beginning to the middle to long term. C3S for imparting a, C2S and C4A F, the addition of gypsum having a condensation-hydration modulating effects and cementitious compositions, specific polymer for imparting high fluidity upon addition of water of the composition compounds can improve the workability after kneading time and kneading by compounding, leading to completion of the present invention since the hydraulic compositions that do not produce a setting retardation and early strength development decreases mostly obtained It was.
[0005]
That is, the present invention is a hydraulic composition containing the following (A), (B), (C) and (D) (excluding a hydraulic composition for high strength wet spraying) .
(A) A cement-forming component containing 5 to 50% by weight of C3A and C3S, C2S and C4AF.
(B) Gypsum whose content is 1 to 30% by weight with respect to 100 parts by weight of the clinker fired product.
(C) The content of the following (i), (ii) and (iii) is 0.01 to 5 parts by weight in terms of solid content with respect to 100 parts by weight of the total solid content of the cement-forming component. Polycarboxylic acid polymer compound.
(I) The polycarboxylic acid polymer compound has structural units represented by the following formulas (I) and (II) in the molecule.
[0008]
Wherein, R 1 to R 4 are the same or different, represent a hydrogen atom or a methyl or ethyl group, X 1 represents a (CH 2) mCOOM 1, X 2 represents COOM 1. M 1 represents any of a hydrogen atom, an alkali metal, ammonium, or an organic amine, and m represents an integer of 0 to 2. R 5 represents an alkyl group having 1 to 3 carbon atoms, Y represents —CH 2 O— or —COO—, and n represents an integer of 20 to 300. ]
(Ii) The content of the structural unit constituting the polycarboxylic acid polymer compound is (I) formula / (II) formula = 100 / 0.1 to 100/100 in terms of monomer molar ratio.
(Iii) The weight average molecular weight of the polycarboxylic acid polymer compound is 2000 to 200000 in terms of polyethylene glycol.
(D) A retarder whose content is 1 to 40 parts by weight with respect to 100 parts by weight of the solid content of the polycarboxylic acid polymer compound.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The hydraulic composition of the present invention comprises a cement forming component , gypsum, a retarder, and a polycarboxylic acid polymer compound. As a component related to the former, in the present invention, C3A, CaO.3Al 2 O 3 is an essential component, and C3S, CaO.3SiO 2 , C2S, CaO.2SiO 2 , and C4AF, CaO.4Al 2 O 3 .Fe 2 O. 3 be those containing, as a constituent, in which C3A is contained 5 to 50 wt%. If the content of C3A is less than 5% by weight, the initial strength developability becomes poor, and if it exceeds 50% by weight, the fluidity is remarkably lowered. Furthermore, gypsum is added as an essential component to the cement-forming component.
[0010]
Moreover, the raw material for providing each component of C3A, C3S, C2S, C4AF is not specifically limited, For example, various slags including limestone, clay mineral, coal ash, blast furnace slag, calcium carbonate, silica stone Various incineration ash such as powder, iron powder, waste and sludge, lime-treated sewage sludge dry powder, and other raw materials used in cement production can be used.
[0011]
The raw material is fired at, for example, a rotary kiln at 1200 to 1500 ° C. to produce a clinker, and gypsum is added to the pulverized clinker to produce a hydraulic composition. The clinker pulverization method and the pulverized particle size are not particularly limited, and may be substantially the same as those performed in general cement production. For example, the particle size of the clinker pulverized product can be 2000 to 10000 cm 2 / g. Gypsum is added to the pulverized clinker, and the gypsum used in the present invention is not particularly limited, and examples thereof include anhydrous gypsum, hemihydrate gypsum, and dihydrate gypsum. The blending amount is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the clinker fired product. If the blending amount is less than 1 part by weight, the effect of adjusting the hydration reaction is poor, which is not preferable.
[0012]
Furthermore, the hydraulic composition of the present invention contains a polycarboxylic acid polymer compound. The polycarboxylic acid polymer compound preferably has structural units represented by the following formulas (I) and (II) in the molecule. In addition, the content of the polycarboxylic acid polymer compound is 0.01 to 5% by weight in terms of solid content with respect to a cement-forming component such as C3A constituting the hydraulic composition.
[0013]
[Chemical formula 5]
[Chemical 6]
[Wherein, R 1 to R 4 are the same or different and each represents a hydrogen atom, a methyl group, or an ethyl group, X 1 represents a hydrogen atom, a methyl group, or (CH 2 ) mCOOM 1 , and X 2 represents COOM 1 Represents. M 1 represents any of a hydrogen atom, an alkali metal, ammonium, or an organic amine, and m represents an integer of 0 to 2. R 5 represents an alkyl group having 1 to 3 carbon atoms, Y represents —CH 2 O— or —COO—, and n represents an integer of 20 to 300. The polycarboxylic acid-based polymer compound is preferably 0.01 to 5 parts by weight, more preferably in terms of solids, based on 100 parts by weight of the total solids of cement-forming components such as C3A in the hydraulic composition. It is preferable to contain 0.05 to 3 parts by weight, and blending less than 0.01 part by weight is not preferable because almost no blending effect can be obtained. Is not preferable because it may become defective. Moreover, it is preferable that content of the structural unit which comprises a polycarboxylic acid type high molecular compound is (I) type | formula / (II) type | formula = 100 / 0.1-100 / 100 in conversion of monomer molar ratio. This is because when the value of the formula (I) / (II) is larger than 100 / 0.1, the decrease in fluidity is large, and when it is less than 100/100, the foam stability and dispersibility are decreased. Both are not preferable.
[0016]
Moreover, it is preferable that the weight average molecular weight of this polycarboxylic acid-type high molecular compound is 2000-200000 in conversion of polyethyleneglycol. If the weight average molecular weight is less than 2,000 or exceeds 200,000, any of them is not preferable because the dispersibility is lowered.
[0017]
Moreover, the hydraulic composition of the present invention can appropriately contain a known admixture (admixture) for cement or concrete in addition to the polycarboxylic acid polymer compound.
[0018]
The hydraulic composition of the present invention, including a retarder. The retarder may be any known one, for example, oxycarboxylic acids and salts thereof, keto acids or salts thereof, aminocarboxylic acids or salts thereof, known organic retarders such as saccharides, sugar alcohols, Known inorganic retarders such as silicofluorides, boric acids, phosphoric acids, zinc compounds, lead compounds, copper compounds and the like can be mentioned. Of these, oxycarboxylic acids or salts thereof, saccharides, and sugar alcohols are more preferable. The addition amount of the retarder is 1 to 40 parts by weight with respect to 100 parts by weight in terms of solid content of the blended amount of the polycarboxylic acid polymer compound , and if it is less than 1 part by weight, the improvement effect of fluidity retention is almost recognized. It is not preferable because it is not present, and an amount exceeding 40 parts by weight is not preferable because excessive setting delay may occur. At the time of compounding addition, it may be mixed in advance with the polycarboxylic acid polymer compound and added together with the polycarboxylic acid polymer compound.
[0019]
In addition, the hydraulic composition of the present invention can include any known aggregate that is used in ordinary concrete, mortar, or the like as the aggregate. As such a known aggregate, natural aggregates such as river sand, land sand, crushed stone, and quartz sand are particularly preferable, but fly ash, slag, washed sea sand, calcium carbonate, and the like can also be used. . The aggregate content is 30 to 1000 parts by weight with respect to 100 parts by weight of the hydraulic component, and preferably 100 to 700 parts by weight when producing concrete. If the amount is less than 30 parts by weight, the amount of shrinkage of the composition increases, which is not preferable.
[0020]
The amount of water added to the hydraulic composition of the present invention is 20 to 100 parts by weight with respect to 100 parts by weight of the cement-forming component in the composition. While it is desirable to knead during or immediately after the mixing of water, the hydraulic composition does not harden immediately after the kneading is stopped, and can maintain a good fluid state for a while. Construction work and the like can be performed without any particular restrictions.
[0021]
【Example】
Hereinafter, the present invention will be specifically described with reference to examples.
Limestone powder, after firing the aluminum ash, a mixture of clay and iron at about 1400 ° C., the clinker grinding comprising ground mineral ingredients in Table 1 in which the Blaine specific surface area 4000 cm 2 / g, 2 converted to SO 3 2 wt% hemihydrate gypsum was added and reground to obtain two types of cement compositions (A, B) of the chemical composition (wt%) listed in Table 2 having a Blaine specific surface area of 4700 cm 2 / g. Produced. This cement composition was copolymerized with fine sand aggregate of Ogasa land sand having a maximum particle size of 5 mm and a monomer having a molar composition ratio (mixing ratio expressed in mol%) shown in Table 3 by a known method. The obtained polymer compound (1-5) solid content concentration of about 25% solution or commercially available dispersant (N) mainly composed of naphthalene sulfonic acid formalin condensate, retarder and water in the blending ratios shown in Table 4 It knead | mixed for 3 minutes with the Hobart mixer, and produced the hydraulic composition (Examples 1-13, Comparative Examples 1-3). The mortar flow value after a certain period of time immediately after the kneading of the prepared hydraulic composition and the mortar compressive strength by the mortar specimen using the kneaded material were both adjusted and measured by a method based on JIS R5201. The results are shown in Table 4.
[0022]
[Table 1]
[Table 2]
[Table 3]
[Table 4]
Moreover, the aggregate (the Ogasa land sand: coarse aggregate = 1: 1.5 by weight ratio) which mixed the crushed stone with a maximum particle size of about 20 mm as the coarse sand aggregate with the Ogasa land sand in the cement composition, A solution having a solid composition concentration of about 25% or naphthalene sulfone obtained by copolymerizing monomers having a molar composition ratio (mixing ratio expressed in mol%) shown in Table 3 by a known method. What knead | mixed and kneaded the commercially available dispersing agent (N) which has an acid formalin condensate as a main component, a retarder, and water with the forced biaxial mixer so that it might become the compounding quantity of Table 5 (Examples 14-28, In Comparative Examples 4 to 6, slumps were measured immediately after kneading and 60 minutes after kneading by a method according to JIS A1101. Further, this kneaded product was filled into a cylindrical mold having a diameter of 10 cm and a height of 20 cm, and the compression strength of the molded product obtained by demolding after 24 hours was measured. Table 5 also shows the slump value and the measurement result of the compressive strength.
[0027]
[Table 5]
【The invention's effect】
The hydraulic composition of the present invention can maintain appropriate fluidity for a certain period of time even after the addition of water. Therefore, it is possible to secure sufficient work time for construction and mold forming, etc., without causing a delay in setting, and exhibiting excellent initial strength development after curing, and stable strength development over the medium to long term Indicates.
Claims (1)
（Ａ）Ｃ３Ａを５〜５０重量％と、Ｃ３Ｓ、Ｃ２ＳおよびＣ４ＡＦを含むセメント形成成分。
（Ｂ）含有量がクリンカー焼成物１００重量部に対し、１〜３０重量％である石膏類。
（Ｃ）含有量がセメント形成成分の固形分総量１００重量部に対し、固形分換算で０．０１〜５重量部である、下記の（i）、（ii）および（iii）の物性を有するポリカルボン酸系高分子化合物。
（i）ポリカルボン酸系高分子化合物が分子内に下記の（Ｉ）式と（ＩＩ）式で表される構成単位を有する。
（ii）ポリカルボン酸系高分子化合物を構成する構成単位の含有量が単量体モル比換算で（Ｉ）式／（ＩＩ）式＝１００／０．１〜１００／１００である。
（iii）ポリカルボン酸系高分子化合物の重量平均分子量がポリエチレングリコール換算で２０００〜２０００００である。
（Ｄ）含有量がポリカルボン酸系高分子化合物の固形分１００重量部に対し、１〜４０重量部である遅延剤。 A hydraulic composition comprising the following (A), (B), (C) and (D) (excluding a hydraulic composition for high-strength wet spraying):
(A) A cement-forming component containing 5 to 50% by weight of C3A and C3S, C2S and C4AF.
(B) Gypsum whose content is 1 to 30% by weight with respect to 100 parts by weight of the clinker fired product.
(C) The content of the following (i), (ii) and (iii) is 0.01 to 5 parts by weight in terms of solid content with respect to 100 parts by weight of the total solid content of the cement-forming component. Polycarboxylic acid polymer compound.
(I) The polycarboxylic acid polymer compound has structural units represented by the following formulas (I) and (II) in the molecule.
(Ii) The content of the structural unit constituting the polycarboxylic acid polymer compound is (I) formula / (II) formula = 100 / 0.1 to 100/100 in terms of monomer molar ratio.
(Iii) The weight average molecular weight of the polycarboxylic acid polymer compound is 2000 to 200000 in terms of polyethylene glycol.
(D) A retarder whose content is 1 to 40 parts by weight with respect to 100 parts by weight of the solid content of the polycarboxylic acid polymer compound.
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| JP2000273750A JP4709359B2 (en) | 1999-09-27 | 2000-09-08 | Hydraulic composition |
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| JP11-271683 | 1999-09-27 | ||
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| JP2000273750A JP4709359B2 (en) | 1999-09-27 | 2000-09-08 | Hydraulic composition |
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| JP4448274B2 (en) * | 2002-01-23 | 2010-04-07 | 株式会社日本触媒 | Method of constructing cement admixture and cement composition |
| JP4344111B2 (en) * | 2002-01-25 | 2009-10-14 | 株式会社日本触媒 | Cement admixture and cement composition |
| JP7303525B2 (en) * | 2020-01-09 | 2023-07-05 | 株式会社大林組 | ADDITIVE FOR HYDRAULIC COMPOSITION, AND HYDRAULIC COMPOSITION |
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| JPH0717749A (en) * | 1993-06-30 | 1995-01-20 | Chichibu Onoda Cement Corp | Production of highly flowable rapid-hardening cement mix material |
| JPH08217508A (en) * | 1995-02-08 | 1996-08-27 | Denki Kagaku Kogyo Kk | Cement admixture and cement composition |
| JPH10279341A (en) * | 1997-04-02 | 1998-10-20 | Denki Kagaku Kogyo Kk | Cement composition |
| JPH11199301A (en) * | 1998-01-13 | 1999-07-27 | Taiheiyo Cement Corp | Hydraulic cement composition |
| JPH11217250A (en) * | 1998-01-27 | 1999-08-10 | Taiheiyo Cement Corp | Cement composition |
| JP3665804B2 (en) * | 1998-06-03 | 2005-06-29 | 竹本油脂株式会社 | Ready-mixed concrete for high-strength wet spraying, method for forming a high-strength hardened body to be sprayed, and high-strength hardened body to be obtained by spraying the same |
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