JPH0679974B2 - Water reducing agent for cement - Google Patents
Water reducing agent for cementInfo
- Publication number
- JPH0679974B2 JPH0679974B2 JP13044691A JP13044691A JPH0679974B2 JP H0679974 B2 JPH0679974 B2 JP H0679974B2 JP 13044691 A JP13044691 A JP 13044691A JP 13044691 A JP13044691 A JP 13044691A JP H0679974 B2 JPH0679974 B2 JP H0679974B2
- Authority
- JP
- Japan
- Prior art keywords
- cement
- parts
- reducing agent
- water reducing
- water
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/30—Condensation polymers of aldehydes or ketones
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/40—Surface-active agents, dispersants
- C04B2103/408—Dispersants
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明はセメントペースト、モル
タル、コンクリートなどセメント組成物に関するもので
あり、特に流動性の経時的低下が少なく、また減水性が
高く、施工性、作業性の改善されたセメント用減水剤に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cement composition such as cement paste, mortar, concrete, etc., in particular, its fluidity is less likely to decrease with time, and its water reducing property is high. Water reducing agent for cement.
【０００２】[0002]
【従来の技術と発明が解決しようとする課題】セメント
ペースト、モルタル、コンクリート等は、土木、建築等
に大量に使用されている。そして、その作業性の改善、
強度や耐久性の向上、ひび割れ性の減少等諸物性の向上
を目的として、ナフタレンスルホン酸ホルマリン縮合物
を主成分とする減水剤が従来より主として用いられてき
た。2. Description of the Related Art Cement paste, mortar, concrete, etc. are used in large quantities in civil engineering, construction, etc. And improving its workability,
A water reducing agent containing a naphthalenesulfonic acid formalin condensate as a main component has been mainly used conventionally for the purpose of improving various properties such as improvement of strength and durability and reduction of cracking property.
【０００３】一方近年の都市部等での交通事情の悪化
は、セメント組成物の運搬に長時間を必要としてきてお
り、流動性の経時的低下が極めて少ないセメント用減水
剤への要求が特に高まってきた。しかしながらこの要求
に対し、現今までナフタレンスルホン酸ホルマリン縮合
物の他、種々のセメント用減水剤が公知ではあるが、こ
の流動性の経時的低下が極めて少なく、しかも減水性が
高く、また強度や耐久性に重大な影響を与えるセメント
組成物中の空気量の経時的安定性がよいという点におい
ては不十分であった。On the other hand, the recent deterioration of traffic conditions in urban areas has required a long time to carry the cement composition, and there is a particular demand for a water-reducing agent for cement, which has a very small decrease in fluidity over time. It's getting higher. In response to this requirement, however, various water reducing agents for cement other than naphthalene sulfonic acid formalin condensate have been known up to now, but this fluidity has very little decrease with time, and the water reducing ability is high, and strength and durability are high. It was insufficient in that the stability of the amount of air in the cement composition, which has a significant effect on the property, is good over time.
【０００４】[0004]
【課題を解決するための手段】そこで本発明者等は、特
に流動性の経時的低下が少なく、また減水効果が大き
く、またセメント組成物中の空気量の経時的安定性のよ
いセメント用減水剤を目標に研究を重ねた結果、本発明
に到達したものである。Therefore, the present inventors have found that the decrease in fluidity with time is small, the water-reducing effect is large, and the amount of air in the cement composition is stable with time and the water-reducing agent for cement. The present invention has been achieved as a result of repeated research aimed at agents.
【０００５】即ち一般式（Ｉ） ［式中Ｘは のいずれかを示す（但し、ｎは１から５の整数、Ｒ１、
Ｒ３は夫々独立して水素、またはアルキル基、Ｒ２はア
ルキル基、Ｒ４はアルケニル基を示す）］で示される化
合物またはその塩と、アルデヒド類、及びアミノ酸また
はその塩とを水性条件下、任意の順序で反応させて得ら
れる縮合生成物を分散剤として含有することを特徴とす
るセメント用減水剤を提供するものである。That is, the general formula (I) [Where X is (Where n is an integer of 1 to 5, R 1 ,
R 3 independently represents hydrogen, or an alkyl group, R 2 represents an alkyl group, R 4 represents an alkenyl group)] or a salt thereof, an aldehyde, and an amino acid or a salt thereof under an aqueous condition. A water reducing agent for cement, comprising a condensation product obtained by reacting in any order as a dispersant.
【０００６】本発明に用いる一般式（Ｉ）で示される化
合物としては２，２−ビス（４−ヒドロキシフェニル）
プロパン、４，４´−ジヒドロキシジフェニルメタン、
４，４´−ジヒドロキシジフェニルスルホン、４，４´
−ジヒドロキシビフェニル、４，４´−ジヒドロキシジ
フェニルエーテル、４，４´−エチリデン−ビスフェノ
ール、４，４−ビス（４−ヒドロキシフェニル）吉草
酸、４，４−ビス（４−ヒドロキシフェニル）酪酸、及
びそれらの異性体が好んで用いられ、またこれらを組み
合わせて用いることもできる。The compound represented by the general formula (I) used in the present invention is 2,2-bis (4-hydroxyphenyl)
Propane, 4,4'-dihydroxydiphenylmethane,
4,4'-dihydroxydiphenyl sulfone, 4,4 '
-Dihydroxybiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-ethylidene-bisphenol, 4,4-bis (4-hydroxyphenyl) valeric acid, 4,4-bis (4-hydroxyphenyl) butyric acid, and them The isomer of is preferably used, and these can also be used in combination.
【０００７】またアミノ酸としては、グルタミン酸、グ
リシン、イミノ二酢酸、アラニン、アスパラギン酸、セ
リン、アミノ酪酸、グルタチオン、アミノカプロン酸、
バリン、フェニルアラニン、メチオニン、ロイシン等が
あげられる。The amino acids include glutamic acid, glycine, iminodiacetic acid, alanine, aspartic acid, serine, aminobutyric acid, glutathione, aminocaproic acid,
Examples include valine, phenylalanine, methionine, leucine and the like.
【０００８】アルデヒド類としては、ホルムアルデヒ
ド、パラホルムアルデヒド、ヘキサメチレンテトラミン
等のホルムアルデヒド重合及び縮合物、アセトアルデヒ
ド等が有用であり、特に好ましくは、ホルムアルデヒド
及びその誘導体である。As aldehydes, formaldehyde polymerization and condensation products of formaldehyde, paraformaldehyde, hexamethylenetetramine and the like, acetaldehyde and the like are useful, and formaldehyde and its derivatives are particularly preferable.
【０００９】本発明の縮合物は、一般式（Ｉ）の化合物
またはその塩30ないし70重量部、アミノ酸またはその塩
10ないし60重量部、及びアルデヒド類10ないし50重量部
を水性条件下、常圧ないし加圧下に、反応することによ
り得ることができる。また通常反応温度は30ないし 130
℃、反応時間は１ないし50時間で行う。The condensate of the present invention is a compound of formula (I) or a salt thereof in an amount of 30 to 70 parts by weight, an amino acid or a salt thereof.
It can be obtained by reacting 10 to 60 parts by weight and 10 to 50 parts by weight of an aldehyde under aqueous conditions under atmospheric pressure or pressure. The reaction temperature is usually 30 to 130.
The reaction time is 1 to 50 hours at ℃.
【００１０】本発明のセメント用減水剤は以下の効果を
有する。 ・流動性の経時的低下が極めて少ない。 ・空気量の経時的安定性がよい。 ・減水効果が大きい。The water reducing agent for cement of the present invention has the following effects.・ Little deterioration in fluidity over time.・ Good stability of air volume over time.・ Great water reduction effect.
【００１１】なお、本発明のセメント用減水剤は、セメ
ント重量の0.01％ないし 2.0％、好ましくは 0.1％ない
し 0.6％の割合で使用される。配合量が少なすぎると期
待した効果は得られず、多すぎるとセメントが過度に分
散し、分離現象を起こし好ましくない。The water reducing agent for cement of the present invention is used in an amount of 0.01% to 2.0%, preferably 0.1% to 0.6% of the weight of cement. If the blending amount is too small, the expected effect cannot be obtained, and if the blending amount is too large, the cement is excessively dispersed and a separation phenomenon occurs, which is not preferable.
【００１２】セメントは、普通ポルトランドセメント、
早強セメント、超早強セメント、高炉セメント、中庸熱
セメント、フライアッシュセメント、耐硫酸塩セメント
などが用いられる。また他のセメント用添加剤、例えば
減水剤、空気連行剤、凝結遅延剤、防水剤、膨脹剤、シ
リカヒューム、石粉等と併用することもできる。The cement is ordinary Portland cement,
Early strength cement, super early strength cement, blast furnace cement, moderate heat cement, fly ash cement, sulfate resistant cement and the like are used. Further, it can be used in combination with other cement additives such as water reducing agents, air entraining agents, setting retarders, waterproofing agents, expanding agents, silica fume, stone powder and the like.
【００１３】[0013]
【実施例】以下、実施例によって本発明を詳細に説明す
るが、実施例中の部は重量部を示している。 合成例（１） ４，４´−ジヒドロキシジフェニルメタン40.0部とＬ−
グルタミン酸ナトリウム37.4部、及び47％水酸化ナトリ
ウム水溶液17.0部を水 182.6部に加える。この固液に温
度90℃にて37％ホルマリン40.5部を 0.5時間で滴下す
る。その後、温度80℃で３時間反応させて縮合物の水溶
液を得た。EXAMPLES The present invention will be described in detail below with reference to examples, but parts in the examples indicate parts by weight. Synthesis example (1) 4,4'-dihydroxydiphenylmethane 40.0 parts and L-
Add 37.4 parts of sodium glutamate and 17.0 parts of 47% aqueous sodium hydroxide solution to 182.6 parts of water. To this solid liquid, 40.5 parts of 37% formalin is added dropwise at a temperature of 90 ° C over 0.5 hour. Then, the reaction was carried out at a temperature of 80 ° C. for 3 hours to obtain an aqueous solution of a condensate.
【００１４】合成例（２） ２，２−ビス（４−ヒドロキシフェニル）プロパン38.1
部とＬ−グルタミン酸ナトリウム31.2部、及び47％水酸
化ナトリウム水溶液14.2部を水 180.2部に加える。この
固液に温度90℃にて37％ホルマリン33.8部を 0.5時間で
滴下する。その後、温度80℃で４時間反応させて縮合物
の水溶液を得た。Synthesis Example (2) 2,2-bis (4-hydroxyphenyl) propane 38.1
Parts, 31.2 parts of sodium L-glutamate, and 14.2 parts of 47% aqueous sodium hydroxide solution are added to 180.2 parts of water. To this solid liquid, 33.8 parts of 37% formalin is added dropwise at a temperature of 90 ° C over 0.5 hour. Then, the reaction was carried out at a temperature of 80 ° C. for 4 hours to obtain an aqueous solution of a condensate.
【００１５】合成例（３） ４，４´−ジヒドロキシジフェニルスルホン50.1部とＬ
−グルタミン酸ナトリウム37.4部、及び47％水酸化ナト
リウム水溶液22.1部を水 207.8部に加える。この固液に
温度90℃にて37％ホルマリン40.5部を 0.5時間で滴下す
る。その後、温度 100℃で12時間反応させて縮合物の水
溶液を得た。Synthesis example (3) 4,4'-dihydroxydiphenyl sulfone 50.1 parts and L
-Add 37.4 parts of sodium glutamate and 22.1 parts of 47% aqueous sodium hydroxide solution to 207.8 parts of water. To this solid liquid, 40.5 parts of 37% formalin is added dropwise at a temperature of 90 ° C over 0.5 hour. Then, the reaction was carried out at a temperature of 100 ° C. for 12 hours to obtain an aqueous solution of a condensate.
【００１６】合成例（４） ２，２−ビス（４−ヒドロキシフェニル）プロパン45.6
部とＬ−グリシン15.0部、及び47％水酸化ナトリウム水
溶液17.1部を水 188.4部に加える。この固液に温度90℃
にて37％ホルマリン40.5部を 0.5時間で滴下する。その
後、温度70℃で３時間反応させて縮合物の水溶液を得
た。Synthesis Example (4) 2,2-bis (4-hydroxyphenyl) propane 45.6
Parts and 15.0 parts of L-glycine, and 17.1 parts of 47% aqueous sodium hydroxide solution are added to 188.4 parts of water. The temperature of this solid-liquid is 90 ° C.
Add 40.5 parts of 37% formalin over 0.5 hour. Then, the reaction was carried out at a temperature of 70 ° C. for 3 hours to obtain an aqueous solution of a condensate.
【００１７】合成例（５） ２，２−ビス（４−ヒドロキシフェニル）プロパン45.6
部とイミノ二酢酸26.6部、及び47％水酸化ナトリウム水
溶液34.2部を水 205.1部に加える。この固液に温度90℃
にて37％ホルマリン40.5部を 0.5時間で滴下する。その
後、温度80℃で４時間反応させて縮合物の水溶液を得
た。Synthesis Example (5) 2,2-bis (4-hydroxyphenyl) propane 45.6
And 26.6 parts of iminodiacetic acid and 34.2 parts of 47% aqueous sodium hydroxide solution are added to 205.1 parts of water. The temperature of this solid-liquid is 90 ° C.
Add 40.5 parts of 37% formalin over 0.5 hour. Then, the reaction was carried out at a temperature of 80 ° C. for 4 hours to obtain an aqueous solution of a condensate.
【００１８】（コンクリート試験）上記本発明の各減水
剤を添加したコンクリートのコンシステンシーを、比較
例としてナフタレンスルホン酸ホルマリン縮合物（花王
（株）製 マイティー１５０）のコンシステンシーと比
較し、コンクリートのスランプロス（流動性の経時変
化）を比較した。なおコンクリートの配合を表１に示
す。そして、コンクリートは、セメント、骨材、及び減
水剤を含む水を 100リットル可搬傾胴式ミキサーにて90
秒混練し、直後、60、 120分後にスランプを測定した。
コンクリートのスランプ、及び空気量はＪＩＳに準拠し
て行った。(Concrete Test) The consistency of the concrete to which each water reducing agent of the present invention was added was compared with that of naphthalenesulfonic acid formalin condensate (Mighty 150 manufactured by Kao Co., Ltd.) as a comparative example. The slump loss (fluidity change with time) was compared. Table 1 shows the mix of concrete. The concrete is mixed with cement, aggregate, and water containing a water reducing agent in a 100-liter portable tilt-type mixer.
Immediately after 60 seconds and 120 minutes after kneading for seconds, slump was measured.
The slump of concrete and the amount of air were measured according to JIS.
【００１９】[0019]
【表１】 [Table 1]
【００２０】測定結果を表２に示す。The measurement results are shown in Table 2.
【００２１】[0021]
【表２】 [Table 2]
【００２２】本発明の減水剤は、比較例の減水剤より少
ない添加率で目標スランプを得ることができ、これは分
散性（減水性）に優れていることを示している。またス
ランプの経時変化から、本発明の減水剤は、流動性の経
時的低下が極めて少ないことを示している。さらに空気
量の経時変化もほとんどなく、安定性がよいことを示し
ている。これらの結果より本発明の減水剤が優れた効果
を有するのは明らかである。The water reducing agent of the present invention can obtain the target slump with a smaller addition rate than the water reducing agent of the comparative example, which shows that it has excellent dispersibility (water reducing property). Also, from the change with time of the slump, it is shown that the water reducing agent of the present invention has a very small decrease in fluidity with time. Furthermore, there is almost no change over time in the amount of air, indicating that the stability is good. From these results, it is clear that the water reducing agent of the present invention has excellent effects.
Claims (2)
Ｒ３は夫々独立して水素、またはアルキル基、Ｒ２はア
ルキル基、Ｒ４はアルケニル基を示す）］で示される化
合物またはその塩と、アルデヒド類、及びアミノ酸また
はその塩とを水性条件下、任意の順序で反応させて得ら
れる縮合生成物を分散剤として含有することを特徴とす
るセメント用減水剤。1. A general formula (I) [Where X is (Where n is an integer of 1 to 5, R 1 ,
R 3 independently represents hydrogen, or an alkyl group, R 2 represents an alkyl group, R 4 represents an alkenyl group)] or a salt thereof, an aldehyde, and an amino acid or a salt thereof under an aqueous condition. A water reducing agent for cement, which contains a condensation product obtained by reacting in any order as a dispersant.
−ビス（４−ヒドロキシフェニル）プロパンであり、ア
ミノ酸またはその塩がグルタミン酸ナトリウムである請
求項１記載のセメント用減水剤。2. The compound represented by the general formula (I) is 2,2.
The water reducing agent for cement according to claim 1, which is -bis (4-hydroxyphenyl) propane and the amino acid or salt thereof is sodium glutamate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13044691A JPH0679974B2 (en) | 1991-05-02 | 1991-05-02 | Water reducing agent for cement |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13044691A JPH0679974B2 (en) | 1991-05-02 | 1991-05-02 | Water reducing agent for cement |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04331751A JPH04331751A (en) | 1992-11-19 |
| JPH0679974B2 true JPH0679974B2 (en) | 1994-10-12 |
Family
ID=15034437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13044691A Expired - Fee Related JPH0679974B2 (en) | 1991-05-02 | 1991-05-02 | Water reducing agent for cement |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0679974B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100400479B1 (en) * | 2002-10-08 | 2003-10-04 | Envitech Inc | Concrete admixture using liquor generated from monosodium glutamate fermentation process as by-product |
| CN117659302A (en) * | 2023-12-20 | 2024-03-08 | 科之杰新材料集团有限公司 | Slump-retaining water reducer and preparation method thereof |
-
1991
- 1991-05-02 JP JP13044691A patent/JPH0679974B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04331751A (en) | 1992-11-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |