JPH03137045A - Cement dispersant - Google Patents

Cement dispersant

Info

Publication number
JPH03137045A
JPH03137045A JP27324989A JP27324989A JPH03137045A JP H03137045 A JPH03137045 A JP H03137045A JP 27324989 A JP27324989 A JP 27324989A JP 27324989 A JP27324989 A JP 27324989A JP H03137045 A JPH03137045 A JP H03137045A
Authority
JP
Japan
Prior art keywords
cement
dispersant
phenol
present
concrete
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.)
Pending
Application number
JP27324989A
Other languages
Japanese (ja)
Inventor
Fujio Yamato
富士桜 倭
Shuichi Fujita
修一 藤田
Tatsuo Izumi
達男 泉
Yoshiaki Yadokoro
美明 谷所
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kao Corp
Original Assignee
Kao Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kao Corp filed Critical Kao Corp
Priority to JP27324989A priority Critical patent/JPH03137045A/en
Publication of JPH03137045A publication Critical patent/JPH03137045A/en
Pending legal-status Critical Current

Links

Abstract

PURPOSE:To provide the cement dispersant having high dispersibility by forming the dispersant of a copolycondensation product formed by cocondensation of phenol sulfonate and formaldehyde at alkaline side. CONSTITUTION:The cement dispersant is formed by using the copolycondensation product formed by cocondensating 4 to 30mol, more particularly 8 to 15mol formaldehyde per 1mol phenol sulfonate (sodium salt, potassium salt is suitable) for 5 to 15 hours at pH 7 to 9 as its essential component. The amt. of this dispersant to be added is 0.1 to 1.5W% of the solid content of the hydraulic cement compsn..

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明はセメント配合物、例えばコンクリート、モルタ
ル、セメントペースト等の分散剤に関する。
DETAILED DESCRIPTION OF THE INVENTION [Industrial Field] The present invention relates to dispersants for cement formulations, such as concrete, mortar, cement paste, etc.

〔従来の技術及びその課題〕[Conventional technology and its problems]

窯業製品用分散剤としてフェノールのスルホン化物とホ
ルムアルデヒドとの重縮合物が提案されている(特開昭
49−104919号公報等)。
A polycondensate of a sulfonated phenol and formaldehyde has been proposed as a dispersant for ceramic products (Japanese Unexamined Patent Publication No. 104919/1984, etc.).

しかしながら、フェノールスルホン酸をホルマリン縮合
する従来の技術では、重縮合物中に分散性向上に効果の
ある分子量領域の部分が少なく、高分子量部分及び/又
は低分子量部分が多くなる。
However, in the conventional technique of condensing phenolsulfonic acid with formalin, the polycondensate contains a small portion in the molecular weight range that is effective in improving dispersibility, and a large amount of high molecular weight portions and/or low molecular weight portions.

即ち、フェノールスルホン酸を中性以下の酸性領域でホ
ルマリン縮合すると反応速度が速く、生成物が樹脂化す
る。逆に中性以上のアルカリ領域でホルマリン縮合する
と反応が進まず生成物は低分子締金物となる。従ってセ
メント配合物の分散に寄与するに充分な分子量領域を有
する分子量分布の重縮金物が得られないという欠点があ
る。
That is, when phenolsulfonic acid is subjected to formalin condensation in an acidic region below neutrality, the reaction rate is fast and the product becomes a resin. Conversely, when formalin is condensed in an alkaline region above neutrality, the reaction does not proceed and the product becomes a low-molecular clamp. Therefore, there is a drawback that a polycondensed metal material having a molecular weight distribution having a sufficient molecular weight range to contribute to the dispersion of cement mixtures cannot be obtained.

〔課題を解決するための手段〕[Means to solve the problem]

本発明者らは上記問題点を解消すべく鋭意研究した結果
、フェノールスルホン酸塩と該フェノールスルホン酸塩
に対して特定割合のフェノールとを中性以上のアルカリ
領域でホルムアルデヒドと共縮合させることにより、セ
メント配合物の分散性の向上に有効な分子量分布を有す
る重縮合物が得られることを見出し、本発明を完成する
に至った。
As a result of intensive research to solve the above problems, the present inventors found that by co-condensing phenol sulfonate and phenol in a specific proportion to the phenol sulfonate with formaldehyde in an alkaline region above neutrality. It was discovered that a polycondensate having a molecular weight distribution effective for improving the dispersibility of cement mixtures can be obtained, and the present invention was completed.

すなわち本発明は、フェノールスルホン酸塩と該フェノ
ールスルホン酸塩に対し4〜30モル%のフェノールと
をアルカリ性でホルムアルデヒドと共縮合させた共重縮
合物を主成分とするセメント分散剤を提供するものであ
る。
That is, the present invention provides a cement dispersant whose main component is a copolycondensate obtained by cocondensing a phenol sulfonate and 4 to 30 mol% of phenol with formaldehyde in an alkaline environment. It is.

本発明ではフェノールスルホン酸塩とフェノールをp)
17以上のアルカリ性領域でホルマリン縮合することに
より、介在するフェノールにより立体的な分子構造を持
つ重縮合物となり、セメント配合物の分散性の向上に有
効な分子量分布を有する重縮合物となるものと推察され
、−般のフェノールスルホン酸単独の直線状低縮合物と
は異なる。
In the present invention, phenol sulfonate and phenol p)
By formalin condensation in an alkaline region of 17 or more, the intervening phenol results in a polycondensate with a three-dimensional molecular structure, and a polycondensate with a molecular weight distribution effective for improving the dispersibility of cement compounds. This is expected to be different from the general linear low condensate of phenolsulfonic acid alone.

本発明に使用するフェノールスルホン酸塩としては、フ
ェノールスルホン酸の水酸化ナトリウム、水酸化カリウ
ム、炭酸ナトリウム、炭酸カルシウム、アンモニア水、
トリエタノールアミン塩等のアルカリとの有機あるいは
無機の中和塩が挙げられるが、特に溶解度の大きい水酸
化ナトリウム、水酸化カリウムによる塩が好ましい、ま
た、フェノールスルホン酸塩の他にスルホメチル基を導
入したフェノールの使用も可能である。
The phenolsulfonic acid salts used in the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, calcium carbonate, aqueous ammonia,
Examples include organic or inorganic neutralized salts with alkalis such as triethanolamine salts, but salts with sodium hydroxide and potassium hydroxide, which have particularly high solubility, are preferred.In addition to phenolsulfonates, sulfomethyl groups are introduced. It is also possible to use purified phenol.

本発明において、共縮合反応に用いるフェノールスルホ
ン酸塩とフェノールのモル比は、フェノールスルホン酸
塩1モルに対してフェノールが4〜30モル%であり、
8〜15モル%が特に好ましい。フェノールのモル比が
4モル%未満では縮合が進まず、分散性に有効な縮合度
の重縮金物が得られない。また、フェノールのモル比が
30モル%を超えると高分子量部分の多い、分子量分布
幅の広い重縮合物となり、有効な分散性が得られない。
In the present invention, the molar ratio of phenol sulfonate and phenol used in the cocondensation reaction is 4 to 30 mol% of phenol to 1 mol of phenol sulfonate,
Particularly preferred is 8 to 15 mol%. If the molar ratio of phenol is less than 4 mol %, condensation will not proceed and a polycondensed metal product with a degree of condensation effective for dispersibility cannot be obtained. On the other hand, if the molar ratio of phenol exceeds 30 mol %, a polycondensate containing many high molecular weight portions and a wide molecular weight distribution will result, making it impossible to obtain effective dispersibility.

また、本発明にはフェノールをスルホン化するに際して
、未反応フェノールが残存している反応生成物をそのま
ま原料としても良い。
Further, in the present invention, when sulfonating phenol, a reaction product in which unreacted phenol remains may be used as a raw material as it is.

本発明による重縮合物の製造に使用するホルムアルデヒ
ドは、濃度が30〜39重量%の水溶液であるホルマリ
ンが好ましい。
The formaldehyde used in the production of the polycondensate according to the present invention is preferably formalin, which is an aqueous solution having a concentration of 30 to 39% by weight.

以下に本発明のセメント分散剤の標準的製造法を示すが
、これによって本発明は何ら限定されるものではない。
A standard manufacturing method for the cement dispersant of the present invention is shown below, but the present invention is not limited thereby.

反応容器中にフェノールスルホン酸ナトリウム塩、フェ
ノール、ホルマリンを所定量仕込み、p)Iを7〜9に
調整し、還流下において5〜15時間攪拌する(第一工
程)0次いで30″Cに冷却し、pHを10〜11に調
整する。更に還流下で2〜3時間撹拌して冷却し、本発
明の分散剤を得る(第二工程)。
Pour predetermined amounts of phenolsulfonic acid sodium salt, phenol, and formalin into a reaction vessel, adjust p)I to 7 to 9, and stir under reflux for 5 to 15 hours (first step) 0 and then cool to 30"C. and adjust the pH to 10 to 11. The mixture is further stirred under reflux for 2 to 3 hours and cooled to obtain the dispersant of the present invention (second step).

得られたセメント分散剤の添加量は、水硬性セメント組
成物に対して0.1〜1.5固形分重量%が良い0分散
剤の添加量が0.1固形分重量%未満ではセメントに対
して充分な分散効果を与えられない。また、分散剤の添
加量が1.5固形分重量%を超えるとセメント粒子の分
散が過度となり、ペースト分離やブリージングが多くな
る。
The amount of the obtained cement dispersant to be added is preferably 0.1 to 1.5% by weight of solids based on the hydraulic cement composition. If the amount of the dispersant added is less than 0.1% by weight of solids, it may not be suitable for the cement. cannot provide a sufficient dispersion effect. Further, if the amount of the dispersant added exceeds 1.5% by weight of solid content, the dispersion of cement particles becomes excessive, resulting in increased paste separation and bleeding.

本発明によるセメント分散剤のセメント配合物への添加
方法は、水溶液、粉末又は粒状のいずれの形態によって
も可能であり、その添加時期は混練水への溶解又はセメ
ント配合物の混練開始時、即ちセメントへの注水と同時
もしくは注水直後からセメント配合物の混練終了までの
間に添加することも可能であり、−旦練り上がったセメ
ント配合物への添加も可能である。また、本発明のセメ
ント分散剤は一時に全量を添加する方法あるいは数回に
分割して添加する方法のいずれも可能である。
The cement dispersant according to the present invention can be added to a cement mixture in the form of an aqueous solution, powder, or granules, and the addition time can be either by dissolving it in mixing water or at the start of mixing the cement mixture, i.e. It is possible to add it at the same time as water is poured into cement, or immediately after water is poured into the cement until the end of kneading of the cement mixture, and it is also possible to add it to the cement mixture that has already been kneaded. Furthermore, the cement dispersant of the present invention can be added in its entirety at once or in several divided doses.

本発明のセメント分散剤は、他のセメント添加剤(材)
、例えばAE減水剤、流動化剤、高性能減水剤、高性能
AE減水剤、AE剤、(超)遅延剤、早強剤、起泡剤、
保水剤、増粘剤、防水剤、防錆剤、ひびわれ低減剤、高
分子エマルジッン、界面活性剤、膨張材、フライアッシ
ュ、高炉スラグ、シリカヒエーム、シリカ粉末等との併
用も可能である。
The cement dispersant of the present invention can be used with other cement additives (materials).
, such as AE water reducer, superplasticizer, high performance water reducer, high performance AE water reducer, AE agent, (super) retarder, early strength agent, foaming agent,
It can also be used in combination with water retention agents, thickeners, waterproofing agents, rust preventive agents, crack reducing agents, polymer emulsions, surfactants, expansion materials, fly ash, blast furnace slag, silica hieme, silica powder, etc.

(実 施 例) 以下、実施例により本発明を詳述するが、本発明はこれ
らの実施例に限定されるものではない 〈コンクリートの調製〉 以下の材料を用いて第1表に示す調合にてコンクリート
を調製した。
(Example) The present invention will be described in detail with reference to Examples below, but the present invention is not limited to these Examples. <Preparation of Concrete> Using the following materials, the formulation shown in Table 1 was prepared. concrete was prepared.

細骨材(S)・・・紀の用度川砂(比重2.57)粗骨
材(G)・・・宝塚産砕石(比重2.59)水(W) 
  ・・・水 道 水 第 表 実施例1〜4 フェノールスルホン酸ナトリウム196.2 g、水2
00g、37%ホルマリン85.2g及びフェノール4
.7gの混合物をpH8,5に調整し、還流下において
12時間攪拌する(第一工程)。
Fine aggregate (S)...Yodo river sand (specific gravity 2.57) Coarse aggregate (G)...crushed stone from Takarazuka (specific gravity 2.59) Water (W)
...Water Water Table Examples 1 to 4 Sodium phenolsulfonate 196.2 g, water 2
00g, 37% formalin 85.2g and phenol 4
.. 7 g of the mixture is adjusted to pH 8.5 and stirred under reflux for 12 hours (first step).

反応物を室温に冷却し、pHを10.5に調整し、還流
下において3時間攪拌して(第二工程)、本発明のセメ
ント分散剤を得た。
The reactant was cooled to room temperature, the pH was adjusted to 10.5, and the mixture was stirred under reflux for 3 hours (second step) to obtain the cement dispersant of the present invention.

また、第2表に示すようにフェノールスルホン酸ナトリ
ウム、フェノール及び37%ホルマリンのモル比と、反
応時間を変えて各種セメント分散剤を得た。
Further, as shown in Table 2, various cement dispersants were obtained by changing the molar ratios of sodium phenolsulfonate, phenol and 37% formalin and the reaction time.

これらの分散剤を以下の方法によって前述のコンクリー
トと練り混ぜる。
These dispersants are mixed with the concrete described above in the following manner.

コンク1−トの   せ 上記の実施例によって得られたセメント分散剤を対セメ
ント固形分重量%が第3表に示す量となるように予め練
り混ぜ水に溶解し、これを前述のコンクリート材料に一
度に投入して100iの強制ミキサーで50fのコンク
リートを2分間コンクリート混練した。
The cement dispersant obtained in the above example was mixed in advance and dissolved in water so that the solid content weight % based on the cement was as shown in Table 3, and this was added to the concrete material described above. The concrete was added at once and 50f of concrete was mixed for 2 minutes using a 100i forced mixer.

涯璽方抜 分散剤を添加して混練した上記のコンクリートを用い−
て分散性をJIS−A−1101コンクリートのスラン
プ試験法により評価し、空気量をJIS−A−1128
の空気圧力法により測定した。
Using the above concrete mixed with the addition of a dispersant,
The dispersibility was evaluated using the JIS-A-1101 concrete slump test method, and the air content was evaluated using the JIS-A-1128 concrete slump test method.
Measured by air pressure method.

その結果を第3表に示す。The results are shown in Table 3.

実施例5〜7 フェノールスルホン酸ナトリウム196.2g。Examples 5-7 Sodium phenolsulfonate 196.2g.

水206g、37%ホルマリン81.2 gの混合物を
pH8,5に調整し、還流下において10時間攪拌する
A mixture of 206 g of water and 81.2 g of 37% formalin is adjusted to pH 8.5 and stirred under reflux for 10 hours.

次に室温に冷却し、フェノール9.4gを加えpHを8
.5に調整し、還流下において5時間攪拌する(第一工
程)。
Next, cool to room temperature, add 9.4 g of phenol, and adjust the pH to 8.
.. 5 and stirred under reflux for 5 hours (first step).

反応物を室温に冷却し、pHを10.5に調整し、還流
下において3時間攪拌して(第二工程)、本発明のセメ
ント分散剤を得た。
The reactant was cooled to room temperature, the pH was adjusted to 10.5, and the mixture was stirred under reflux for 3 hours (second step) to obtain the cement dispersant of the present invention.

また、第2表に示すようにフェノールスルホン酸ナトリ
ウム、フェノール及び37%ホルマリンのモル比と反応
時間を種々変えて各種セメント分散剤を得た。
Further, as shown in Table 2, various cement dispersants were obtained by varying the molar ratios and reaction times of sodium phenolsulfonate, phenol, and 37% formalin.

それらの分散剤を用いて実施例1〜4と同様に分散性と
空気量を測定した。
Using these dispersants, the dispersibility and air content were measured in the same manner as in Examples 1 to 4.

その結果を第3表に示す。The results are shown in Table 3.

比較例1 フェノールスルホン酸ナトリウム、フェノール及び37
%ホルマリンのモル比及び反応時間を第2表に示すよう
に変えて比較のためのセメント分散剤を得た。
Comparative Example 1 Sodium phenolsulfonate, phenol and 37
Comparative cement dispersants were obtained by varying the molar ratio of % formalin and reaction time as shown in Table 2.

その分散剤を用いて上記と同様に分散性と空気量を測定
した。
Using the dispersant, the dispersibility and air content were measured in the same manner as above.

その結果を第3表に示す。The results are shown in Table 3.

比較例2 特開昭49−104919号公報に記載の合成例(サン
プルN[1−6)に準じて分散剤を製造し、上記と同様
にして分散性と空気量を測定した。
Comparative Example 2 A dispersant was produced according to the synthesis example (sample N[1-6) described in JP-A-49-104919, and the dispersibility and air content were measured in the same manner as above.

その結果を第3表に示す。The results are shown in Table 3.

第 2 表 尚、表中 FN−Na・・・フェノールスルホン酸ナトリウムFN
・・・フェノール を意味する。
Table 2 In addition, in the table, FN-Na...sodium phenolsulfonate FN
...means phenol.

詰二、1 第2表、第3表の結果から、本発明の分散剤がセメント
に対し極めて優れた分散効果を与えていることは明白で
ある。
2.1 From the results in Tables 2 and 3, it is clear that the dispersant of the present invention has an extremely excellent dispersion effect on cement.

〔発明の効果〕〔Effect of the invention〕

本発明によれば、従来のフェノールスルホン酸ホルマリ
ン縮金物(その塩)より極めて高い分散性を有するセメ
ント分散剤が得られる。
According to the present invention, a cement dispersant having extremely higher dispersibility than conventional phenolsulfonic acid formalin condensates (salts thereof) can be obtained.

従って本発明のセメント分散剤は種々の用途に用いて顕
著な効果を発揮する。例えば、生コンクリートや二次製
品の中、低強度領域のコンクリート分野から高強度コン
クリート分野まで、高減水が可能であり、添加量の節約
、セメント量の節約等の経済的メリットを有し、また乾
燥収縮等に起因するコンクリートのひび割れ等を著しく
減少することを可能とする。
Therefore, the cement dispersant of the present invention exhibits remarkable effects when used in various applications. For example, in ready-mixed concrete and secondary products, from low-strength concrete to high-strength concrete, high water reduction is possible, and it has economic benefits such as saving on the amount of additive and cement. It is possible to significantly reduce cracks in concrete caused by drying shrinkage, etc.

Claims (1)

【特許請求の範囲】[Claims] 1 フェノールスルホン酸塩と該フェノールスルホン酸
塩に対し4〜30モル%のフェノールとをアルカリ性で
ホルムアルデヒドと共縮合させた共重縮合物を主成分と
するセメント分散剤。
1. A cement dispersant whose main component is a copolycondensate obtained by cocondensing a phenol sulfonate and 4 to 30 mol% of phenol with formaldehyde in an alkaline environment.
JP27324989A 1989-10-20 1989-10-20 Cement dispersant Pending JPH03137045A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP27324989A JPH03137045A (en) 1989-10-20 1989-10-20 Cement dispersant

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP27324989A JPH03137045A (en) 1989-10-20 1989-10-20 Cement dispersant

Publications (1)

Publication Number Publication Date
JPH03137045A true JPH03137045A (en) 1991-06-11

Family

ID=17525203

Family Applications (1)

Application Number Title Priority Date Filing Date
JP27324989A Pending JPH03137045A (en) 1989-10-20 1989-10-20 Cement dispersant

Country Status (1)

Country Link
JP (1) JPH03137045A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0984031A1 (en) * 1998-02-20 2000-03-08 Nagoya Oilchemical Co., Ltd. Molding material, inner material using the same, and method for producing the same
CN108047404A (en) * 2017-12-11 2018-05-18 山东非金属材料研究所 A kind of water base self-dispersion type thermosetting phenolic resin and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0984031A1 (en) * 1998-02-20 2000-03-08 Nagoya Oilchemical Co., Ltd. Molding material, inner material using the same, and method for producing the same
EP0984031A4 (en) * 1998-02-20 2000-12-13 Nagoya Oilchemical Molding material, inner material using the same, and method for producing the same
CN108047404A (en) * 2017-12-11 2018-05-18 山东非金属材料研究所 A kind of water base self-dispersion type thermosetting phenolic resin and preparation method thereof

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