JPH05270875A - Cement admixture - Google Patents

Cement admixture

Info

Publication number
JPH05270875A
JPH05270875A JP6565892A JP6565892A JPH05270875A JP H05270875 A JPH05270875 A JP H05270875A JP 6565892 A JP6565892 A JP 6565892A JP 6565892 A JP6565892 A JP 6565892A JP H05270875 A JPH05270875 A JP H05270875A
Authority
JP
Japan
Prior art keywords
cement
polyparahydroxystyrene
admixture
cement admixture
present
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
JP6565892A
Other languages
Japanese (ja)
Inventor
Fujio Yamato
富士桜 倭
Ryoichi Tamaoki
良市 玉置
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 JP6565892A priority Critical patent/JPH05270875A/en
Publication of JPH05270875A publication Critical patent/JPH05270875A/en
Pending legal-status Critical Current

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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
    • C04B24/16—Sulfur-containing compounds
    • C04B24/20—Sulfonated aromatic compounds
    • 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
    • C04B2103/308—Slump-loss preventing agents

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

PURPOSE:To improve fluidity of a cement compsn. even in a region of small water amt. and to reduce slump loss by compounding a sulfonate of polyparahydroxystyrene to a cement admixture. CONSTITUTION:This cement admixture contains a sulfonate of polyparahydroxystyrene. The sulfonate of polyparahydroxystyrene has preferably 1000-50000 weight average mol.wt. and 0.3-1.0 sulfonation degree.

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【産業上の利用分野】本発明はセメント混和剤、さらに
詳しくは建築材料及び二次製品材料として使用するセメ
ントペースト、モルタル、コンクリート等のセメント組
成物の流動性を高め、減水性並びにスランプロス等に優
れた性状を与えるセメント混和剤に関するものである。FIELD OF THE INVENTION The present invention relates to a cement admixture, and more specifically to improve the fluidity of cement compositions such as cement paste, mortar and concrete, which are used as building materials and secondary product materials, to reduce the water content, slump loss, etc. The present invention relates to a cement admixture that gives excellent properties to cement.

【０００２】[0002]

【従来の技術及び発明が解決しようとする課題】従来か
らセメント混和剤として高度な流動性を示す代表的なも
のとして、ナフタレンスルホン酸ナトリウム・ホルマリ
ン縮合物（以下ナフタレン系混和剤と称す）が知られて
いる。ナフタレン系混和剤は、セメント組成物の流動性
の向上による作業性の改善と減水効果により、高強度コ
ンクリートの製造に古くから使用されている。2. Description of the Related Art Sodium naphthalenesulfonate / formalin condensate (hereinafter referred to as naphthalene-based admixture) has been known as a typical cement admixture showing high fluidity. Has been. Naphthalene-based admixtures have been used for a long time in the production of high-strength concrete because of their improved workability due to the improved fluidity of cement compositions and their water-reducing effects.

【０００３】近年、建築物の高層化に伴いセメントに対
する水の比率（Ｗ／Ｃ）を25％以下にする超高強度コン
クリートの製造法に検討が進められている。しかしなが
ら、従来のナフタレン系混和剤を代表とする既存の混和
剤ではＷ／Ｃ＝25％以下になるとセメント組成物の流動
性が発現しないのが現状であり、これらに対応した混和
剤の開発が望まれている。[0003] In recent years, along with the increase in the thickness of buildings, studies have been conducted on a method for producing ultrahigh strength concrete in which the ratio of water to cement (W / C) is 25% or less. However, with the existing admixtures represented by conventional naphthalene-based admixtures, the fluidity of the cement composition is not expressed when W / C = 25% or less, and the development of admixtures corresponding to these is currently underway. Is desired.

【０００４】本発明はセメント組成物の流動性を改良
し、水量の低い領域においてもセメント組成物の流動性
が大きく、時間経過による流動性の低下（以下、スラン
プロスと称す）が少ないセメント混和剤を提供すること
を目的とするものである。The present invention improves the fluidity of a cement composition, the fluidity of the cement composition is large even in a low water amount region, and the fluidity of the cement composition is less deteriorated with time (hereinafter referred to as slump loss). The purpose is to provide an agent.

【０００５】[0005]

【課題を解決するための手段】一般に分散系の粘性低下
は粒子の媒体への分散作用によるもので、そのメカニズ
ムは粒子表面に吸着した混和剤の電気的反発や吸着層の
外在による凝集の抑制であると考えられている〔材料，
34，No. 378 ，347 (1985)〕。本発明者らは、セメント
粒子に対して水量の少ない領域において凝集を防ぐこ
と、即ち分散させることに関して鋭意検討した結果、ポ
リパラヒドロキシスチレンのスルホン化物が極めて優れ
た流動性とスランプ保持に効果のあることを見出し、本
発明を完成するに至った。Generally, the decrease in the viscosity of a dispersion system is due to the dispersion action of particles in a medium, and the mechanism thereof is the electrical repulsion of the admixture adsorbed on the particle surface and the aggregation due to the external presence of the adsorption layer. Is considered to be a suppression [materials,
34, No. 378, 347 (1985)]. The present inventors have made extensive studies on preventing aggregation in a region having a small amount of water with respect to cement particles, that is, as a result of dispersion, and a sulfonated product of polyparahydroxystyrene is extremely effective for fluidity and slump retention. It was found that there is something, and the present invention has been completed.

【０００６】即ち、本発明はポリパラヒドロキシスチレ
ンのスルホン化物を含有することを特徴とするセメント
混和剤を提供するものであり、ポリパラヒドロキシスチ
レンのスルホン化物は官能基として水酸基とスルホン酸
基の２個を有し、セメントへの吸着力を強くし、しかも
吸着層に厚み（ポリマー化）を持たせる構造にしている
のが特徴である。That is, the present invention provides a cement admixture characterized by containing a sulfonated product of polyparahydroxystyrene, wherein the sulfonated product of polyparahydroxystyrene contains a hydroxyl group and a sulfonic acid group as functional groups. The structure is characterized in that it has two pieces and the adsorption force to cement is strengthened and the adsorption layer has a thickness (polymerization).

【０００７】本発明に用いる出発原料のポリパラヒドロ
キシスチレンは公知の方法から得られるもの、例えば特
公昭55−2444号開示の方法等のものが使用される。ポリ
パラヒドロキシスチレンのスルホン化はクロルスルホン
酸や発煙硫酸等の強酸類を反応させることで得られる。
又、ポリパラヒドロキシスチレンのスルホン化物は、酸
のままで使用可能であるが、一般的には塩の形で使用す
るのが好ましい。形成する塩としてはNa、K 、Ca、Mg、
NH4 、アルカノールアミン、 N−アルキル置換ポリアミ
ン、エチレンジアミン、ポリエチレンポリアミン、ポリ
エチレンイミン又はこれらのアルキレンオキシド付加物
等が挙げられる。The starting material polyparahydroxystyrene used in the present invention is obtained by a known method, for example, the method disclosed in Japanese Examined Patent Publication No. 55-2444. The sulfonation of polyparahydroxystyrene can be obtained by reacting strong acids such as chlorosulfonic acid and fuming sulfuric acid.
Further, the sulfonated product of polyparahydroxystyrene can be used as an acid, but it is generally preferable to use it in the form of a salt. The salts formed are Na, K, Ca, Mg,
Examples thereof include NH 4 , alkanolamine, N-alkyl-substituted polyamine, ethylenediamine, polyethylene polyamine, polyethyleneimine, and their alkylene oxide adducts.

【０００８】さらに本発明のポリパラヒドロキシスチレ
ンのスルホン化物は重量平均分子量で1000〜50000 の範
囲のものが分散性とスランプ保持性の面から好ましく使
用できる。1000未満の重量平均分子量又は50000 以上の
重量平均分子量では前述の分子量域に比較して分散性と
スランプ保持性が劣る。Further, the sulfonated product of polyparahydroxystyrene of the present invention preferably has a weight average molecular weight in the range of 1,000 to 50,000 in view of dispersibility and slump retention. When the weight average molecular weight is less than 1000 or the weight average molecular weight is 50,000 or more, the dispersibility and the slump retention are inferior as compared with the above-mentioned molecular weight range.

【０００９】又、本発明のポリパラヒドロキシスチレン
のスルホン化物におけるフェノール骨格１個あたりのス
ルホン酸基数（スルホン化度）は 0.3〜1.0 の範囲が特
に優れた分散性のスランプ保持性を示す。スルホン化度
が 0.3未満では官能基量が少なく、前述のスルホン化度
に比較して分散性とスランプ保持性に劣る。又、スルホ
ン化度が 1.0を越える化合物を得ることは通常の反応で
は困難である。Further, the number of sulfonic acid groups (degree of sulfonation) per phenol skeleton in the sulfonated product of polyparahydroxystyrene of the present invention is in the range of 0.3 to 1.0, which shows particularly excellent dispersibility slump retention. If the degree of sulfonation is less than 0.3, the amount of functional groups is small, and the dispersibility and slump retention are inferior to the degree of sulfonation described above. Further, it is difficult to obtain a compound having a sulfonation degree of more than 1.0 by an ordinary reaction.

【００１０】本発明のセメント混和剤は、従来のナフタ
レン系混和剤と同様にセメントペースト、モルタル、コ
ンクリート等のセメント組成物の分散剤として用いられ
る。The cement admixture of the present invention is used as a dispersant for cement compositions such as cement paste, mortar and concrete, as in the conventional naphthalene admixture.

【００１１】分散剤のセメント組成物に対する添加時期
は注水と同時から注水直後あるいは混練終了までの間で
あり、限定するものではない。The dispersant is added to the cement composition at the same time as water injection, immediately after water injection, or until the end of kneading, and is not limited.

【００１２】また、本発明のセメント混和剤は、他の公
知の添加剤、例えば、ＡＥ剤、高性能減水剤、ＡＥ減水
剤、減水剤、徐放分散剤、徐放性起泡剤、水溶性高分
子、硬化遅延剤、硬化促進剤等と併用することができ
る。Further, the cement admixture of the present invention includes other known additives such as AE agents, high-performance water reducing agents, AE water reducing agents, water reducing agents, sustained-release dispersants, sustained-release foaming agents, and water-soluble agents. It can be used in combination with a functional polymer, a curing retarder, a curing accelerator and the like.

【００１３】更に、本発明を実施するに当たり使用し得
る水硬性セメントの一例としてはポルトランドセメン
ト、高炉セメント、シリカセメント、アルミナセメント
等が挙げられる。また、各種の混和材料、例えば、フラ
イアッシュ、高炉スラグ、シリカヒューム、膨張材等を
加えた水硬性セメント組成物への使用も可能である。Further, examples of hydraulic cement that can be used in the practice of the present invention include Portland cement, blast furnace cement, silica cement, alumina cement and the like. Further, it can be used for a hydraulic cement composition to which various admixtures such as fly ash, blast furnace slag, silica fume and expansive material are added.

【００１４】[0014]

【実施例】以下、実施例と参考例により本発明を説明す
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。EXAMPLES The present invention will be described below with reference to examples and reference examples, but the present invention is not limited to these examples.

【００１５】(1) ポリパラヒドロキシスチレンのスルホ
ン化物の製造例 重量平均分子量 50000のポリパラヒドロキシスチレンを
ρ−ジオキサンに溶解後、所定量のクロルスルホン酸を
滴下し、80℃で３時間反応した。その後水酸化ナトリウ
ムを加え、中和後、水溶液層を回収した。その後副生物
の塩化ナトリウム等を除去する精製処理を行い本発明品
を得る。同様の方法でポリパラヒドロキシスチレンのス
ルホン化物の分子量、スルホン化度を変えて得られた本
発明品の一覧（混和剤 No.１〜９）を表１に示す。(1) Production Example of Sulfonated Polyparahydroxystyrene After dissolving polyparahydroxystyrene having a weight average molecular weight of 50,000 in ρ-dioxane, a predetermined amount of chlorosulfonic acid was added dropwise and reacted at 80 ° C. for 3 hours. . After that, sodium hydroxide was added to neutralize and the aqueous layer was recovered. After that, a purification treatment for removing by-product sodium chloride etc. is performed to obtain the product of the present invention. Table 1 shows a list (compounding agents Nos. 1 to 9) of the products of the present invention obtained by changing the molecular weight and the sulfonation degree of the sulfonated product of polyparahydroxystyrene by the same method.

【００１６】[0016]

【表１】 [Table 1]

【００１７】注）＊１：重量平均分子量はゲルパーミエ
ーションクロマトグラフィー法により測定した値である
（ポリスチレンスルホン酸ナトリウム基準）。Note) * 1: The weight average molecular weight is a value measured by gel permeation chromatography (based on sodium polystyrene sulfonate).

【００１８】(2) セメント混和剤としての評価 以下に上記で製造されたセメント混和剤 No.１〜９のセ
メント混和剤としての評価方法を示す。コンクリート配合 水／セメント比；55％ 細骨材量；49％ 単位セメント量； 320kg／m3 使用材料 セメント；中央ポルトランドセメント 比重＝3.17 細骨材；紀の川産川砂 比重＝2.60 粗骨材；宝塚産砕石 比重＝2.62測定項目 スランプ値；JIS A 1101法による セメント混和剤は目標スランプ20±１cmを得るための添
加量とする。使用したミキサーは傾胴式で、３分間練
後、１分間に４回転させて60分間攪拌した。評価結果を
表２に示す。(2) Evaluation as Cement Admixture The cement admixture Nos. 1 to 9 produced above will be evaluated as a cement admixture. Concrete mixed water / cement ratio: 55% Fine aggregate amount: 49% Unit cement amount: 320kg / m 3 Materials used Cement: Central Portland cement Specific gravity = 3.17 Fine aggregates; Crushed stone Specific gravity = 2.62 Measurement item Slump value; JIS A 1101 method Admixture of cement admixture to obtain target slump of 20 ± 1 cm. The mixer used was a tilting type and kneaded for 3 minutes, then rotated 4 times for 1 minute and stirred for 60 minutes. The evaluation results are shown in Table 2.

【００１９】[0019]

【表２】 [Table 2]

【００２０】注） *1：セメントに対する混和剤の固形分重量％ *2：ナフタレン系混和剤（マイテイ150 ：花王（株）
製） :3：メラミン系混和剤（マイテイ150V−２：花王（株）
製） 〔評価結果〕表２に示すように、本発明による混和剤は
比較品に比べて少ない添加量で流動性が得られ、しかも
スランプ値の直後と60分後の差が小さい。即ち、優れた
減水効果とスランプロス防止に顕著な効果を示すもので
ある。Note) * 1: Solid content% by weight of the admixture with respect to cement * 2: Naphthalene admixture (Mighty 150: Kao Corporation)
: Melamine admixture (Mighty 150V-2: Kao Corporation)
Manufacture) [Evaluation Results] As shown in Table 2, the admixture according to the present invention exhibits fluidity with a smaller addition amount than the comparative product, and the difference between the slump value immediately after and after 60 minutes is small. That is, it shows an excellent water reducing effect and a remarkable effect in preventing slump loss.

【００２１】[0021]

【発明の効果】本発明によるセメント混和剤をセメント
組成物に添加すれば、長時間にわたりスランプロスがな
いため、ポンプ圧送による輸送トラブルが解消される。
さらに本発明によるセメント混和剤はセメント組成物の
流動性を向上させることから、型枠への充填作業を容易
にし、また本発明によるセメント混和剤は減水効果も大
きいことから、高強度コンクリートへの応用も期待され
る。When the cement admixture according to the present invention is added to the cement composition, there is no slump loss for a long period of time, so that transport troubles due to pumping are eliminated.
Furthermore, since the cement admixture according to the present invention improves the fluidity of the cement composition, it facilitates the work of filling the formwork, and the cement admixture according to the present invention also has a large water-reducing effect. Applications are also expected.

Claims (3)

【特許請求の範囲】[Claims] 【請求項１】 ポリパラヒドロキシスチレンのスルホン
化物を含有することを特徴とするセメント混和剤。1. A cement admixture containing a sulfonated product of polyparahydroxystyrene. 【請求項２】 ポリパラヒドロキシスチレンのスルホン
化物の重量平均分子量が1000〜50000 であることを特徴
とする請求項１記載のセメント混和剤。2. The cement admixture according to claim 1, wherein the sulfonated product of polyparahydroxystyrene has a weight average molecular weight of 1,000 to 50,000. 【請求項３】 ポリパラヒドロキシスチレンのスルホン
化物のスルホン化度が 0.3〜1.0 であることを特徴とす
る請求項１又は２記載のセメント混和剤。3. The cement admixture according to claim 1 or 2, wherein the sulfonation degree of the sulfonated product of polyparahydroxystyrene is 0.3 to 1.0.
JP6565892A 1992-03-24 1992-03-24 Cement admixture Pending JPH05270875A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP6565892A JPH05270875A (en) 1992-03-24 1992-03-24 Cement admixture

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP6565892A JPH05270875A (en) 1992-03-24 1992-03-24 Cement admixture

Publications (1)

Publication Number Publication Date
JPH05270875A true JPH05270875A (en) 1993-10-19

Family

ID=13293321

Family Applications (1)

Application Number Title Priority Date Filing Date
JP6565892A Pending JPH05270875A (en) 1992-03-24 1992-03-24 Cement admixture

Country Status (1)

Country Link
JP (1) JPH05270875A (en)

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