JPH07187742A - Additive for cement - Google Patents
Additive for cementInfo
- Publication number
- JPH07187742A JPH07187742A JP5347364A JP34736493A JPH07187742A JP H07187742 A JPH07187742 A JP H07187742A JP 5347364 A JP5347364 A JP 5347364A JP 34736493 A JP34736493 A JP 34736493A JP H07187742 A JPH07187742 A JP H07187742A
- Authority
- JP
- Japan
- Prior art keywords
- salt
- additive
- cement
- group
- maleic acid
- 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.)
- Granted
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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- 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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はセメント用添加剤に関す
る。さらに詳しくは、スランプロス防止性に優れ、減水
性が大きく、かつ空気連行性、凝結遅延性が少ないセメ
ント用添加剤に関する。FIELD OF THE INVENTION The present invention relates to an additive for cement. More specifically, the present invention relates to an additive for cement which is excellent in slump loss prevention, has a large water reduction property, and has little air entrainment and delay in setting.
【０００２】[0002]
【従来の技術】コンクリートやモルタル等のセメント配
合物の添加剤として、ナフタレンスルホン酸ホルムアル
デヒド縮合物塩、メラミンスルホン酸ホルムアルデヒド
縮合物塩、リグニンスルホン酸塩、ポリカルボン酸系化
合物等が減水剤として用いられている。近年コンクリー
トには高強度の要求が高まり、コンクリート組成物中の
水の量を少なくする必要性が出てきた。これに伴い、上
記の減水剤中のポリカルボン酸系化合物が使用される場
合が多くなった。しかしながら、ポリカルボン酸系化合
物の減水剤には空気連行性が大きい、凝結遅延性がある
等の問題がある。2. Description of the Related Art As additives for cement compounds such as concrete and mortar, naphthalene sulfonic acid formaldehyde condensate salt, melamine sulfonic acid formaldehyde condensate salt, lignin sulfonate, polycarboxylic acid compounds, etc. are used as water reducing agents. Has been. In recent years, the demand for high strength has increased in concrete, and it has become necessary to reduce the amount of water in concrete compositions. Along with this, the polycarboxylic acid compounds in the water reducing agent are often used. However, the water-reducing agent of the polycarboxylic acid type compound has problems that it has a large air entrainment property and has a setting retardation property.
【０００３】[0003]
【発明が解決しようとする課題】空気連行性が大きいこ
とは、コンクリートの強度低下の原因となる。また凝結
遅延性があることは、作業を非効率的にさせる。本発明
は空気連行性、凝結遅延性が少なく、かつ高い減水性、
低スランプロス性を兼ね備えたセメント用の添加剤の提
供を目的とした。The large air entrainment causes a decrease in the strength of concrete. The delay in setting also makes the work inefficient. INDUSTRIAL APPLICABILITY The present invention has low air entrainment, little delay in setting, and high water reduction,
The purpose is to provide an additive for cement that has low slump loss.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、鋭意研究
を行った結果、特定のポリオキシアルキレン誘導体とマ
レイン酸類との共重合物が、空気連行性、凝結遅延性が
少なく、かつ高い減水性、低スランプロス性を兼ね備え
ていることを見出し、本発明を完成した。すなわち、本
発明は、（イ）下記の一般式［１］ (Ｒ1)2Ｎ(ＡＯ)nＲ2 …［１］ （ただし、Ｒ1は炭素数１〜５の炭化水素基、ＡＯは炭
素数２〜４のオキシアルキレン基、ｎ＝１〜２００、Ｒ
2は炭素数２〜５のアルケニル基を表す。またオキシア
ルキレン基の５０モル％以上はオキシエチレン基であ
る）で示されるポリオキシアルキレン誘導体と（ロ）無
水マレイン酸、マレイン酸及びマレイン酸塩から選ばれ
る１種または２種以上の化合物との共重合物を主成分と
するセメント用添加剤を提供するものである。一般式
［１］のＲ1で示される炭素数１〜５の炭化水素基とし
てはメチル基、エチル基、プロピル基、イソプロピル
基、ブチル基、イソブチル基、第三ブチル基、アミル
基、イソアミル基等がある。一般式［１］のＡＯで示さ
れる炭素数２〜４のオキシアルキレン基としては、オキ
シエチレン基、オキシプロピレン基、オキシブチレン
基、オキシテトラメチレン基などがある。オキシアルキ
レン基の５０モル％以上がオキシエチレン基と限定され
るのは、オキシエチレン基が５０モル％未満の場合は水
溶性が不十分となり、減水性が劣るからである。一般式
［１］のｎは１〜２００であり、２００より大きくなる
と粘度が高くなり、製造が困難となる。一般式［１］の
Ｒ2で示される炭素数２〜５のアルケニル基としてはビ
ニル基、アリル基、メタリル基、３−ブテニル基、４−
ペンテニル基、３−メチル−３−ブテニル基等がある。
マレイン酸塩としては、リチウム塩、ナトリウム塩、カ
リウム塩等のアルカリ金属塩：マグネシウム塩、カルシ
ウム塩等のアルカリ土類金属塩：アンモニウム塩や有機
アミン塩類がある。有機アミン塩としては、メチルアミ
ン塩、エチルアミン塩、プロピルアミン塩、ブチルアミ
ン塩、ジメチルアミン塩、ジエチルアミン塩、アニリン
塩、エチレンジアミン塩、プロピレンジアミン塩、ジエ
チレントリアミン塩、モノエタノールアミン塩、ジエタ
ノールアミン塩、トリエタノールアミン塩、モノイソプ
ロパノールアミン塩、ジイソプロパノールアミン塩、ト
リイソプロパノールアミン塩等のアミン塩がある。好ま
しくは、アルカリ金属塩、アンモニウム塩、アルカノー
ルアミン塩である。一般式［１］のポリオキシアルキレ
ン誘導体とマレイン酸類との共重合物は、一般式［１］
のポリオキシアルキレン誘導体と無水マレイン酸、マレ
イン酸及びマレイン酸塩から選ばれる１種又は２種以上
の化合物とを、過酸化物系開始剤あるいはアゾ系開始剤
を用いて共重合させることにより、容易に得ることがで
きる。その際、ベンゼン、トルエン、キシレン等の溶剤
を用いることができる。また、水溶液中で一般式［１］
のポリオキシアルキレン誘導体と無水マレイン酸、マレ
イン酸及びマレイン酸塩から選ばれる１種または２種以
上の化合物とを、過硫酸塩等の開始剤を用いて共重合さ
せることによっても容易に得ることができる。またさら
に、共重合の際、スチレン、酢酸ビニル等の他の共重合
可能な成分を混合することができる。一般式［１］のポ
リオキシアルキレン誘導体とマレイン酸類との共重合の
際のモル比は、３：７〜７：３であり、好ましくは４：
６〜６：４であり、特に約１：１が好ましい。本発明に
おいては、一般式［１］のポリオキシアルキレン誘導体
と無水マレイン酸を共重合すること、得られた共重合物
を加水分解すること、さらに得られた加水分解物を塩に
することによっても本発明の共重合物を得ることができ
る。さらに一般式［１］のポリオキシアルキレン誘導体
とマレイン酸を共重合すること、及び得られた共重合物
を塩とすることによっても本発明の共重合物を得ること
ができる。本発明の添加剤の添加濃度はセメントに対し
て０.０１〜３重量％、好ましくは０.０４〜１重量％で
ある。本発明の添加剤は、ナフタレンスルホン酸ホルム
アルデヒド縮合物塩、メラミンスルホン酸ホルムアルデ
ヒド縮合物塩、ポリカルボン酸系化合物等の他の添加
剤、あるいは消泡剤、空気連行剤、防錆剤、凝結促進
剤、凝結遅延剤等と併用することができる。As a result of earnest studies, the inventors of the present invention have found that a copolymer of a specific polyoxyalkylene derivative and a maleic acid has a high air entrainment property and a low setting retardation property and is high. The present invention has been completed by finding that it has both water reducing property and low slump loss property. That is, the present invention provides (a) the following general formula [1] (R 1 ) 2 N (AO) n R 2 ... [1] (wherein R 1 is a hydrocarbon group having 1 to 5 carbon atoms, AO is An oxyalkylene group having 2 to 4 carbon atoms, n = 1 to 200, R
2 represents an alkenyl group having 2 to 5 carbon atoms. Further, 50 mol% or more of the oxyalkylene group is an oxyethylene group) and (b) one or more compounds selected from maleic anhydride, maleic acid and maleic acid salts. It is intended to provide an additive for cement containing a copolymer as a main component. The hydrocarbon group having 1 to 5 carbon atoms represented by R 1 of the general formula [1] is methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, amyl group, isoamyl group. Etc. Examples of the C2-C4 oxyalkylene group represented by AO of the general formula [1] include an oxyethylene group, an oxypropylene group, an oxybutylene group, and an oxytetramethylene group. The reason that 50 mol% or more of the oxyalkylene group is limited to the oxyethylene group is that when the oxyethylene group is less than 50 mol%, the water solubility becomes insufficient and the water reducing property is poor. In the general formula [1], n is 1 to 200, and when it is larger than 200, the viscosity becomes high and the production becomes difficult. Examples of the alkenyl group having 2 to 5 carbon atoms represented by R 2 of the general formula [1] are vinyl group, allyl group, methallyl group, 3-butenyl group, 4-
Examples include a pentenyl group and a 3-methyl-3-butenyl group.
Examples of the maleate salt include alkali metal salts such as lithium salt, sodium salt and potassium salt: alkaline earth metal salts such as magnesium salt and calcium salt: ammonium salt and organic amine salts. As the organic amine salt, methylamine salt, ethylamine salt, propylamine salt, butylamine salt, dimethylamine salt, diethylamine salt, aniline salt, ethylenediamine salt, propylenediamine salt, diethylenetriamine salt, monoethanolamine salt, diethanolamine salt, triethanol. There are amine salts such as amine salt, monoisopropanolamine salt, diisopropanolamine salt and triisopropanolamine salt. Preferred are alkali metal salts, ammonium salts and alkanolamine salts. The copolymer of the polyoxyalkylene derivative of the general formula [1] and the maleic acid has the general formula [1]
By copolymerizing the polyoxyalkylene derivative of 1) with one or more compounds selected from maleic anhydride, maleic acid and maleic acid salts using a peroxide-based initiator or an azo-based initiator, Can be easily obtained. At that time, a solvent such as benzene, toluene, or xylene can be used. In addition, the general formula [1] in an aqueous solution
Easily obtainable by copolymerizing the polyoxyalkylene derivative of 1) with one or more compounds selected from maleic anhydride, maleic acid and maleate using an initiator such as persulfate. You can Furthermore, during copolymerization, other copolymerizable components such as styrene and vinyl acetate can be mixed. The molar ratio at the time of copolymerization of the polyoxyalkylene derivative of the general formula [1] and maleic acid is 3: 7 to 7: 3, preferably 4:
It is 6 to 6: 4, and particularly preferably about 1: 1. In the present invention, by copolymerizing the polyoxyalkylene derivative of the general formula [1] with maleic anhydride, hydrolyzing the obtained copolymer, and further converting the obtained hydrolyzate into a salt. Also, the copolymer of the present invention can be obtained. Furthermore, the copolymer of the present invention can be obtained by copolymerizing the polyoxyalkylene derivative of the general formula [1] with maleic acid and converting the obtained copolymer into a salt. The additive concentration of the additive of the present invention is 0.01 to 3% by weight, preferably 0.04 to 1% by weight, based on cement. The additives of the present invention include other additives such as naphthalene sulfonic acid formaldehyde condensate salt, melamine sulfonic acid formaldehyde condensate salt, polycarboxylic acid compound, etc., or antifoaming agents, air entraining agents, rust preventives, and coagulation accelerators. It can be used in combination with agents, setting retarders and the like.
【０００５】[0005]
【実施例】次に、実施例により本発明をさらに詳細に説
明するが、本発明はこれらの例によってなんら限定され
るものではない。 製造例１ 撹拌装置、温度計、窒素吹き込み管、冷却管のついた１
リットル四つ口フラスコにジメチルアミンのエチレンオ
キシド１１モル付加物のアリルエーテル化物３００ｇ、
無水マレイン酸５２ｇ、過硫酸アンモニウム１０ｇ、水
２４１ｇを仕込み、窒素気流下、８０℃、６時間反応を
行い、共重合物の水溶液を得た。 製造例２〜１０ 第１表に示した一般式［１］の化合物とマレイン酸類と
を第１表に示した比率で用いたほかは製造例１に準じて
反応を行い、共重合物の水溶液を得た。 実施例１〜１０ 第１表に示した一般式［１］のポリオキシアルキレン誘
導体とマレイン酸類との共重合物を用いてモルタルによ
る試験を実施した。配合組成、試験条件を次に示す。 配合組成 水 １８０ｇ セメント ３６０ｇ 砂 １０８０ｇ 添加剤 第２表に示す量 水／セメント比 ５０.０％ 上記の各成分をモルタルミキサーにとり、３分間練り混
ぜたのち取り出し、フロー値（ＪＩＳ Ｒ−５２０１に
よる）および空気量（単位容積重量法による）、凝結時
間（ＪＩＳ Ａ−６２０４による）を測定した。さらに
３０分後、６０分後のフロー値および空気量を測定し
た。これらの結果を第２表に示した。The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. Production Example 1 1 equipped with a stirrer, thermometer, nitrogen blowing tube, cooling tube
300 g of allyl ether compound of 11 mol of ethylene oxide of dimethylamine was added to a 4-liter four-necked flask.
52 g of maleic anhydride, 10 g of ammonium persulfate and 241 g of water were charged, and the reaction was carried out at 80 ° C. for 6 hours under a nitrogen stream to obtain an aqueous solution of a copolymer. Production Examples 2 to 10 Aqueous solutions of copolymers were obtained by reacting according to Production Example 1 except that the compound of the general formula [1] shown in Table 1 and maleic acid were used in the ratios shown in Table 1. Got Examples 1 to 10 Mortar tests were carried out using copolymers of the polyoxyalkylene derivative of the general formula [1] shown in Table 1 and maleic acids. The composition and test conditions are shown below. Mixture composition Water 180g Cement 360g Sand 1080g Additive Amount shown in Table 2 Water / cement ratio 50.0% Mix the components above in a mortar mixer and mix for 3 minutes, then remove. Flow value (according to JIS R-5201) The amount of air (according to the unit volume weight method) and the setting time (according to JIS A-6204) were measured. After 30 minutes and 60 minutes, the flow value and the air amount were measured. The results are shown in Table 2.
【０００６】[0006]
【表１】 [Table 1]
【０００７】[0007]
【表２】 [Table 2]
【０００８】比較例１〜５ 次に示す化合物を比較例として、実施例１〜１０と同様
の試験を行った。その結果を第２表に示す。 比較例１ ナフタレンスルホン酸ホルムアルデヒド縮合
物ナトリウム塩 比較例２ ジイソブチレンと無水マレイン酸との共重合
物のナトリウム塩 比較例３ ポリオキシエチレン（１０モル）モノアリル
エーテルとマレイン酸ナトリウム塩との共重合物 比較例４ ポリオキシエチレン（１１モル）モノアリル
モノメチルエーテルと無水マレイン酸との共重合物 比較例５ 添加剤なし 比較例５のみ配合組成は次のとおりである。 配合組成 水 ２２５ｇ セメント ３６０ｇ 砂 １０８０ｇ 水／セメント比 ６２.５％ 本発明品は比較例１よりフロー値の経時変化（スランプ
ロス）が小さい。本発明品は比較例２〜４はより空気量
が少なく、凝結時間が短い。本発明品は比較例５よりは
配合組成中の水の量が少ないため、強度が高い。Comparative Examples 1 to 5 Using the compounds shown below as comparative examples, the same tests as in Examples 1 to 10 were conducted. The results are shown in Table 2. Comparative Example 1 Sodium salt of naphthalenesulfonic acid formaldehyde condensate Comparative Example 2 Sodium salt of copolymer of diisobutylene and maleic anhydride Comparative Example 3 Copolymerization of polyoxyethylene (10 mol) monoallyl ether and sodium salt of maleic acid Product Comparative Example 4 Copolymer of polyoxyethylene (11 mol) monoallyl monomethyl ether and maleic anhydride Comparative Example 5 No additive Additives Only Comparative Example 5 has the following composition. Blend composition Water 225 g Cement 360 g Sand 1080 g Water / cement ratio 62.5% The product of the present invention has a smaller change in flow value over time (slump loss) than Comparative Example 1. The products of the present invention have a smaller amount of air in Comparative Examples 2 to 4 and a shorter setting time. The product of the present invention has a smaller amount of water in the composition than Comparative Example 5, and therefore has higher strength.
【０００９】[0009]
【発明の効果】本発明の添加剤は特定のポリオキシアル
キレン誘導体とマレイン酸類との共重合物を主成分とす
ることにより、モルタル、コンクリート等に使用した場
合、空気連行性、凝結遅延性が少なく、かつ減水性、ス
ランプロス防止性の高いものである。EFFECTS OF THE INVENTION The additive of the present invention contains a copolymer of a specific polyoxyalkylene derivative and maleic acid as a main component, so that when used in mortar, concrete, etc., air entrainment and setting retardation are exhibited. It is low in water content and highly resistant to slump loss.
Claims (1)
素数２〜４のオキシアルキレン基、ｎ＝１〜２００、Ｒ
2は炭素数２〜５のアルケニル基を表す。またオキシア
ルキレン基の５０モル％以上はオキシエチレン基であ
る）で示されるポリオキシアルキレン誘導体と（ロ）無
水マレイン酸、マレイン酸及びマレイン酸塩から選ばれ
る１種または２種以上の化合物との共重合物を主成分と
するセメント用添加剤。(A) The following general formula [1] (R 1 ) 2 N (AO) n R 2 ... [1] (wherein R 1 is a hydrocarbon group having 1 to 5 carbon atoms, AO is carbon An oxyalkylene group of the number 2 to 4, n = 1 to 200, R
2 represents an alkenyl group having 2 to 5 carbon atoms. Further, 50 mol% or more of the oxyalkylene group is an oxyethylene group) and (b) one or more compounds selected from maleic anhydride, maleic acid and maleic acid salts. Cement additive whose main component is a copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34736493A JP3265784B2 (en) | 1993-12-24 | 1993-12-24 | Additive for cement |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34736493A JP3265784B2 (en) | 1993-12-24 | 1993-12-24 | Additive for cement |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07187742A true JPH07187742A (en) | 1995-07-25 |
| JP3265784B2 JP3265784B2 (en) | 2002-03-18 |
Family
ID=18389734
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34736493A Expired - Lifetime JP3265784B2 (en) | 1993-12-24 | 1993-12-24 | Additive for cement |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3265784B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516475A (en) * | 2011-12-31 | 2012-06-27 | 上海多纶化工有限公司 | Polycarboxylic concrete water reducer |
| CN102516474A (en) * | 2011-12-31 | 2012-06-27 | 上海多纶化工有限公司 | Method for preparing copolymer of polycarboxylic concrete water reducer |
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|---|---|---|---|---|
| US9422964B2 (en) | 2009-04-10 | 2016-08-23 | 3M Innovative Properties Company | Blind fasteners |
| KR101634415B1 (en) | 2009-04-10 | 2016-06-28 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | Blind Fasteners |
| JP5907878B2 (en) | 2009-11-16 | 2016-04-26 | スリーエム イノベイティブ プロパティズ カンパニー | Joining pipe joints |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5118732A (en) * | 1974-08-06 | 1976-02-14 | Katetsukusu Kk | SEMENTOHAIGOYORATETSUKUSUSOSEIBUTSU |
| JPS6027638A (en) * | 1983-07-19 | 1985-02-12 | 花王株式会社 | Cement dispersant |
| JPS6311557A (en) * | 1986-07-01 | 1988-01-19 | 株式会社日本触媒 | Control for entraining air volume of cement mortar or concrete |
| JPS63285142A (en) * | 1987-05-18 | 1988-11-22 | Nippon Shokubai Kagaku Kogyo Co Ltd | Cement dispersing agent |
| JPH04175254A (en) * | 1990-11-06 | 1992-06-23 | N M B:Kk | Cement dispersing agent preventing lowering of fluidity |
| JPH05132347A (en) * | 1991-11-06 | 1993-05-28 | Takemoto Oil & Fat Co Ltd | Method for preventing placed skin surface of concrete from blackening |
| JPH06279083A (en) * | 1992-09-01 | 1994-10-04 | Wr Grace & Co Connecticut | Admixture for decreasing bug hole of hydraulic cement and method for use thereof |
| JPH06298556A (en) * | 1993-04-12 | 1994-10-25 | Nippon Oil & Fats Co Ltd | Admixture for cement |
-
1993
- 1993-12-24 JP JP34736493A patent/JP3265784B2/en not_active Expired - Lifetime
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5118732A (en) * | 1974-08-06 | 1976-02-14 | Katetsukusu Kk | SEMENTOHAIGOYORATETSUKUSUSOSEIBUTSU |
| JPS6027638A (en) * | 1983-07-19 | 1985-02-12 | 花王株式会社 | Cement dispersant |
| JPS6311557A (en) * | 1986-07-01 | 1988-01-19 | 株式会社日本触媒 | Control for entraining air volume of cement mortar or concrete |
| JPS63285142A (en) * | 1987-05-18 | 1988-11-22 | Nippon Shokubai Kagaku Kogyo Co Ltd | Cement dispersing agent |
| JPH04175254A (en) * | 1990-11-06 | 1992-06-23 | N M B:Kk | Cement dispersing agent preventing lowering of fluidity |
| JPH05132347A (en) * | 1991-11-06 | 1993-05-28 | Takemoto Oil & Fat Co Ltd | Method for preventing placed skin surface of concrete from blackening |
| JPH06279083A (en) * | 1992-09-01 | 1994-10-04 | Wr Grace & Co Connecticut | Admixture for decreasing bug hole of hydraulic cement and method for use thereof |
| JPH06298556A (en) * | 1993-04-12 | 1994-10-25 | Nippon Oil & Fats Co Ltd | Admixture for cement |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516475A (en) * | 2011-12-31 | 2012-06-27 | 上海多纶化工有限公司 | Polycarboxylic concrete water reducer |
| CN102516474A (en) * | 2011-12-31 | 2012-06-27 | 上海多纶化工有限公司 | Method for preparing copolymer of polycarboxylic concrete water reducer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3265784B2 (en) | 2002-03-18 |
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