JP4267100B2 - Additive for cement composition for grout method - Google Patents
Additive for cement composition for grout method Download PDFInfo
- Publication number
- JP4267100B2 JP4267100B2 JP25241598A JP25241598A JP4267100B2 JP 4267100 B2 JP4267100 B2 JP 4267100B2 JP 25241598 A JP25241598 A JP 25241598A JP 25241598 A JP25241598 A JP 25241598A JP 4267100 B2 JP4267100 B2 JP 4267100B2
- Authority
- JP
- Japan
- Prior art keywords
- cement
- copolymer
- polymer
- clay
- weight
- 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
- 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
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0059—Graft (co-)polymers
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/70—Grouts, e.g. injection mixtures for cables for prestressed concrete
Description
【0001】
【発明の属する技術分野】
本発明は、特にグラウト工法に適した水硬性組成物用添加剤に関する。グラウト工法とは、地中に水硬性組成物を50〜700kg/cm2程度の高圧でジェット噴流体として送り、周囲の土砂を削り取り、排泥液として地上に排出しながら、地中に柱体や壁体を構築する軟弱地盤の改良工法である。
【0002】
【従来の技術】
従来この工法に用いる水硬性組成物には、基準強度(28日後の強度=30kg/cm2)を満足し、流動効果のあるナフタレンスルホン酸ホルムアルデヒド縮合物(ナフタレン系添加剤)が使用され、またポリアルキレングリコールモノエステル系単量体とアクリル酸系単量体等の共重合体を必須成分とするポリエーテル系添加剤が使用されている(特開平8−12398号公報)。
【0003】
しかし従来のナフタレン系添加剤では、粘土質に対する減粘効果が小さく、排泥液の粘性が下がらずに排出が困難になる問題がある。またポリエーテル系添加剤では、ナフタレン系添加剤に比べ粘土質の減粘効果は向上するものの、例えばベントナイト成分の多い粘土質など土質によっては十分な減粘効果が発現しない場合がある。
【0004】
【発明が解決しようとする課題】
水硬性組成物に対する高い流動性付与性と粘土質に対する向上した減粘性の両性能を併せ持ち、基準強度を満足する水硬性組成物用添加剤を提供することである。
【0005】
【課題を解決するための手段】
本発明は、下記共重合体(イ)と重合体(ロ)を重量比で(イ)/(ロ)=5/95〜95/5の割合で含有する水硬性組成物用添加剤である。
【0006】
(イ)分子内に炭素数2〜3のポリオキシアルキレン基(平均付加モル数2〜300)を含有する重量平均分子量5000〜500000のビニル系共重合体
(ロ)下記一般式(A)で表される単量体(a)の1種以上を重合した分子量1000〜20000の重合体
【0007】
【化5】
【0008】
[式中、R1 :水素原子又はメチル基
R2、R3:水素原子、メチル基又はM2O(CO)(CH2)m1
M1、M2:水素原子、アルカリ金属、アルカリ土類金属、アンモニウム、
水酸基が置換されていてもよいモノ、ジ、トリアルキルアン モニウム
m1 :0〜2の整数]
ポリアクリル酸系添加剤は、水硬性組成物の流動性が従来のナフタレン系添加剤に比べて劣り、凝結時間が遅く強度発現に劣るため、従来はグラウト工法用水硬性組成物の添加剤として顧みられることはなかった。しかしポリアクリル酸系添加剤は粘土質の分散性に優れ、ポリエーテル系添加剤に配合することで、水硬性組成物の高流動性と粘土質に対する減粘性を同時に高い水準で改善することに成功した。
【0009】
【発明の実施の形態】
本発明の共重合体(イ)は、高いセメント分散性を得る観点から下記一般式(B)で表される単量体(b)の1種以上と下記一般式(C)及び(D)で表される化合物の中から選ばれる1種以上の単量体(c)とを重合して得られる共重合体を必須成分とすることが好ましい。
【0010】
【化6】
【0011】
[式中、R4、R5:水素原子又はメチル基
m2:0〜2の整数
AO:炭素数2〜3のオキシアルキレン基
n :2〜300の数
X :水素原子又は炭素数1〜3のアルキル基
を示す。]
【0012】
【化7】
【0013】
[式中、R6 :水素原子又はメチル基
R7、R8:水素原子、メチル基又はM4O(CO)(CH2)m3
M3、M4:水素、アルカリ金属、アルカリ土類金属、アンモニウム、
水酸基が置換されていてもよいモノ、ジ、トリアルキルアン モニウム
m3 :0〜2の整数
を示す。]
【0014】
【化8】
【0015】
[式中、R9 :水素原子又はメチル基
Y :水素原子、アルカリ金属、アルカリ土類金属、アンモニウム、
水酸基が置換されていてもよいモノ、ジ、トリアルキルアン モニウム
を示す。]
一般式(B)で表される単量体(b)としては、メトキシポリエチレングリコール、メトキシポリプロピレングリコール、エトキシポリエチレンポリプロピレングリコール等の片末端アルキル基封鎖ポリアルキレングリコールと(メタ)アクリル酸とのエスエル化物や、(メタ)アクリル酸へのエチレンオキシド、プロピレンオキシド付加物が好ましく用いられる。付加形態は単独、ランダム、ブロック又は交互のいずれでもよい。より好ましくはメトキシポリエチレングリコールと(メタ)アクリル酸とのエステル化物である。ポリアルキレングリコールの平均付加モル数は2〜300の範囲が流動性に優れるため好ましく、100〜200がより好ましい。また平均付加モル数の異なる2種以上の単量体を用いてもよく、平均付加モル数がn1=60〜300とn2=2〜40の範囲で異なる単量体を用いると流動性と粘土質に対する減粘性に優れる。これらの範囲はn1=100〜200とn2=2〜23がより好ましい。両単量体のモル比はn1/n2=10/90〜90/10が好ましい。
【0016】
一般式(C)で示される単量体(c)としては、(メタ)アクリル酸、クロトン酸等の不飽和モノカルボン酸系単量体、無水マレイン酸、マレイン酸、無水イタコン酸、イタコン酸、フマル酸等の不飽和ジカルボン酸系単量体、又はこれらのアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、水酸基が置換されていてもよいモノ、ジ、トリアルキルアンモニウム塩が好ましく、より好ましくは(メタ)アクリル酸又はこれらのアルカリ金属塩である。
【0017】
一般式(D)で示される単量体(c)としては、アリルスルホン酸、メタリルスルホン酸、又はこれらのアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、水酸基が置換されていてもよいモノ、ジ、トリアルキルアンモニウム塩が使用される。
【0018】
共重合体を構成する単量体(b)、単量体(c)の反応単位は、(b)/(c)=0.1/99.9〜70/30(モル比)が流動性に優れ、好ましい。より好ましくは(b)/(c)=1/99〜50/50(モル比)であり、特に好ましくは(b)/(c)=5/95〜40/60(モル比)である。
【0019】
共重合体(イ)の重量平均分子量は、流動性の点より5000〜500000の範囲が良く、20000〜100000の範囲が流動性に特に優れる。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法(標準物質ポリスチレンスルホン酸ナトリウム換算/水系)による。
【0020】
共重合体(イ)は公知の方法で製造できる。例えば、特開平7−223852号公報、特開昭58−74552号公報、特開平4−209737号公報の溶液重合法が挙げられ、水や炭素数1〜4の低級アルコール中、過硫酸アンモニウム、過酸化水素等の重合開始剤存在下、要すれば、亜硫酸水素ナトリウムやメルカプトエタノール等を添加し、50〜100℃で0.5〜10時間反応させればよい。
【0021】
なお、本発明の効果を損なわない範囲で、他の共重合可能な単量体を反応させてもよい。こうした単量体としては、アクリロニトリル、アクリル酸エステル、(メタ)アクリルアミド、スチレン、スチレンスルホン酸等が挙げられる。
【0022】
本発明の重合体(ロ)は上記一般式(A)で表される単量体(a)の1種以上を重合した分子量1000〜20000の重合体である。単量体(a)は例えばカルボン酸系やジカルボン酸系の化合物であり、無水物であってもよい。具体的には例えば(メタ)アクリル酸、クロトン酸等の不飽和モノカルボン酸系単量体、無水マレイン酸、マレイン酸、無水イタコン酸、イタコン酸、無水シトラコン酸、シトラコン酸、フマル酸等の不飽和ジカルボン酸系単量体、又はこれらのアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、水酸基が置換されていてもよいモノ、ジ、トリアルキルアンモニウム塩が好ましい。重合体(ロ)がモノカルボン酸とジカルボン酸をモル比で30/70〜100/0の割合で重合してなるものは、粘土質の減粘効果に優れ好ましく、特に好ましくは重合体(ロ)は(メタ)アクリル酸又はこれらのアルカリ金属塩を重合してなる。
【0023】
重合体(ロ)の重量平均分子量は、1000〜20000の範囲が粘土質の減粘効果に優れ、5000〜10000の範囲が特に優れる。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法(標準物質ポリスチレンスルホン酸ナトリウム換算/水系)による。
【0024】
重合体(ロ)も公知の方法で製造可能であり、一部は市販され一般に入手可能である。重合体(ロ)も本発明の効果を損なわない範囲で、アクリロニトリル、アクリル酸エステル、(メタ)アクリルアミド、スチレン、スチレンスルホン酸等他の共重合可能な単量体を共重合してもよい。
【0025】
化合物(イ)と化合物(ロ)の重量比は、水硬性組成物の流動性を確保すると同時に特にベントナイト成分の多い特定粘土質の減粘性を向上させる点から(イ)/(ロ)=5/95〜95/5が良く、好ましくは10/90〜90/10、特に好ましくは20/80〜80/20である。
【0026】
本発明の添加剤は、一般に化合物(イ)と化合物(ロ)の合計がセメントに対して固形分で0.02〜1.0重量%、好ましくは0.1〜0.5重量%となるように添加される。
【0027】
本発明の添加剤はセメント系の水硬性材料に添加するのが好ましく、セメントとしては普通ポルトランドセメントの他、高炉セメント、フライアッシュセメント、早強セメント等がある。本発明の共重合体(イ)と重合体(ロ)は水硬性材料に対し、予め両者を配合してから添加しても、別々に添加してもよい。また先に混練水で希釈してから用いてもよい。
【0028】
尚、本発明の水硬性組成物用添加剤は、更に公知の添加剤(材)と併用することができる。例えば、AE剤、AE減水剤、流動化剤、遅延剤、早強剤、促進剤、起泡剤、発泡剤、消泡剤、防水剤、防泡剤、珪砂、高炉スラグ、フライアッシュ、シリカフューム等が挙げられる。
【0029】
【実施例】
例示的に、表1の共重合体イ−4の合成例を下記により示す。
反応容器に水15モルを仕込み、窒素雰囲気中75℃でイ−4の単量体(b)0.20モル、メタクリル酸0.80モル、水15モルを混合溶解したもの、20%過硫酸アンモニウム水溶液0.01モル、及び2-メルカプトエタノール4gを同時に2時間かけて滴下する。次いで20%過硫酸アンモニウム水溶液0.03モルを30分で滴下し、1時間同温度で、更に90℃に昇温して35%過酸化水素水12gを加え2時間熟成する。熟成終了後、48%水酸化ナトリウム水溶液を加えて中和、分子量55000の共重合体を得た。
【0030】
表1に示す共重合体(イ)と表2に示す重合体(ロ)を表3に示す重量比で混合してなる添加剤を以下により評価した。
【0031】
[セメント流動性]
普通ポルトランドセメント800gと有効分で対セメント0.1%の添加剤を含む混練水320g(W/C=40%)をモルタルミキサーで低速(63r/m)で1.5分間攪拌混合後、速やかに排出し、B型粘度計で粘度を測定した。
【0032】
[粘土質減粘性]
ベントナイト5%(対粘土重量)を練り込んだ木節粘土800gと有効分で対木節粘土0.1%の添加剤を含む混練水480g(W/C=60%)をモルタルミキサーで低速(63r/m)で1.5分間攪拌混合後、速やかに排出し、B型粘度計で粘度を測定した。
【0033】
以上の結果を表3に合わせて示す。なおグラウト工法に使用する標準的なポンプでは、これらの評価条件下で、セメント流動性は2000mPa・s以下、粘土質減粘性は100mPa・s以下の粘度が必要である。また実施例のものの28日後の強度はいずれも50〜70kg/cm2であり、基準強度を満足していた。
【0034】
【表1】
【0035】
【表2】
【0036】
【表3】
【0037】
【発明の効果】
本発明の水硬性組成物用添加剤を用いることで、高い流動性付与性と粘土質に対する向上した減粘性の両性能を併せ持ち基準強度を満足する、特にグラウト工法用セメント組成物として有用な水硬性組成物を提供できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an additive for a hydraulic composition particularly suitable for the grout method. The grout method is a method of sending a hydraulic composition into the ground as a jet jet fluid at a high pressure of about 50 to 700 kg / cm 2 , scraping the surrounding earth and sand, and discharging it to the ground as mud drainage, It is an improved method for soft ground that builds walls and walls.
[0002]
[Prior art]
Conventionally, the hydraulic composition used in this construction method uses a naphthalenesulfonic acid formaldehyde condensate (naphthalene-based additive) that satisfies the standard strength (strength after 28 days = 30 kg / cm 2 ) and has a fluid effect, and A polyether-based additive having a copolymer such as a polyalkylene glycol monoester monomer and an acrylic acid monomer as essential components is used (Japanese Patent Laid-Open No. 8-12398).
[0003]
However, the conventional naphthalene-based additive has a problem that the effect of reducing the viscosity of clay is small, and it is difficult to discharge without lowering the viscosity of the mud. In addition, although the polyether additive improves the clay thinning effect as compared with the naphthalene additive, it may not exhibit a sufficient thinning effect depending on the soil, for example, a clay having a large amount of bentonite components.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide an additive for a hydraulic composition that has both high fluidity imparting properties for a hydraulic composition and improved viscosity reduction properties for a clay and satisfies the standard strength.
[0005]
[Means for Solving the Problems]
The present invention is an additive for a hydraulic composition containing the following copolymer (I) and polymer (B) in a weight ratio of (A) / (B) = 5/95 to 95/5. .
[0006]
(A) A vinyl copolymer having a weight average molecular weight of 5,000 to 500,000 containing a polyoxyalkylene group having 2 to 3 carbon atoms (average added mole number of 2 to 300) in the molecule (b) in the following general formula (A) Polymer having a molecular weight of 1000 to 20000 obtained by polymerizing one or more of the monomers (a) represented
[Chemical formula 5]
[0008]
[Wherein R 1 is a hydrogen atom or a methyl group
R 2 , R 3 : hydrogen atom, methyl group or M 2 O (CO) (CH 2 ) m 1
M 1 and M 2 : hydrogen atom, alkali metal, alkaline earth metal, ammonium,
Mono-, di-, and trialkylammonium, optionally substituted with a hydroxyl group
m 1 : integer from 0 to 2]
Polyacrylic acid additives are poor in fluidity of hydraulic compositions compared to conventional naphthalene additives, and have a slow setting time and inferior strength, so they are conventionally considered as additives for hydraulic compositions for grout methods. It was never done. However, polyacrylic acid-based additives are excellent in clay dispersibility, and by adding them to polyether-based additives, it is possible to improve the high fluidity of the hydraulic composition and the viscosity reduction to the clay at the same time. Successful.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
From the viewpoint of obtaining high cement dispersibility, the copolymer (I) of the present invention includes at least one monomer (b) represented by the following general formula (B) and the following general formulas (C) and (D). It is preferable to use a copolymer obtained by polymerizing at least one monomer (c) selected from the compounds represented by
[0010]
[Chemical 6]
[0011]
[Wherein, R 4 , R 5 : hydrogen atom or methyl group
m 2 : integer from 0 to 2
AO: C2-C3 oxyalkylene group
n: Number from 2 to 300
X: A hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]
[0012]
[Chemical 7]
[0013]
[Wherein R 6 is a hydrogen atom or a methyl group.
R 7 , R 8 : hydrogen atom, methyl group or M 4 O (CO) (CH 2 ) m 3
M 3 , M 4 : hydrogen, alkali metal, alkaline earth metal, ammonium,
Mono-, di-, and trialkylammonium, optionally substituted with a hydroxyl group
m 3 : represents an integer of 0-2. ]
[0014]
[Chemical 8]
[0015]
[Wherein R 9 is a hydrogen atom or a methyl group.
Y: hydrogen atom, alkali metal, alkaline earth metal, ammonium,
Mono, di, and trialkylammonium, which may be substituted with a hydroxyl group. ]
As the monomer (b) represented by the general formula (B), a sulylated product of one-end alkyl group-blocked polyalkylene glycol such as methoxypolyethylene glycol, methoxypolypropylene glycol, ethoxypolyethylenepolypropyleneglycol and (meth) acrylic acid Also, an ethylene oxide or propylene oxide adduct to (meth) acrylic acid is preferably used. The additional form may be single, random, block, or alternating. More preferred is an esterified product of methoxypolyethylene glycol and (meth) acrylic acid. The average number of added moles of polyalkylene glycol is preferably in the range of 2 to 300 because of excellent fluidity, and more preferably 100 to 200. Two or more types of monomers having different average added mole numbers may be used, and if different monomers are used in the range where the average added mole number is n 1 = 60 to 300 and n 2 = 2 to 40, fluidity is obtained. Excellent viscosity reduction for clay. These ranges are more preferably n 1 = 100 to 200 and n 2 = 2 to 23. The molar ratio of both monomers is preferably n 1 / n 2 = 10/90 to 90/10.
[0016]
The monomer (c) represented by the general formula (C) includes unsaturated monocarboxylic acid monomers such as (meth) acrylic acid and crotonic acid, maleic anhydride, maleic acid, itaconic anhydride, itaconic acid , Unsaturated dicarboxylic acid monomers such as fumaric acid, or alkali metal salts, alkaline earth metal salts, ammonium salts, mono-, di-, and trialkylammonium salts in which a hydroxyl group may be substituted are more preferable. Preferred is (meth) acrylic acid or an alkali metal salt thereof.
[0017]
As the monomer (c) represented by the general formula (D), allyl sulfonic acid, methallyl sulfonic acid, or an alkali metal salt, alkaline earth metal salt, ammonium salt, or a hydroxyl group thereof may be substituted. Mono, di and trialkylammonium salts are used.
[0018]
The reaction unit of monomer (b) and monomer (c) constituting the copolymer is preferably (b) / (c) = 0.1 / 99.9 to 70/30 (molar ratio) because of excellent fluidity. . More preferably, (b) / (c) = 1/99 to 50/50 (molar ratio), and particularly preferably (b) / (c) = 5/95 to 40/60 (molar ratio).
[0019]
The weight average molecular weight of the copolymer (I) is preferably in the range of 5000 to 500,000 from the viewpoint of fluidity, and the range of 2000 to 100,000 is particularly excellent in fluidity. The weight average molecular weight is determined by gel permeation chromatography (standard polystyrene sodium sulfonate equivalent / water system).
[0020]
Copolymer (I) can be produced by a known method. Examples thereof include solution polymerization methods disclosed in JP-A-7-223852, JP-A-58-74552, and JP-A-4-209737. In water and lower alcohols having 1 to 4 carbon atoms, ammonium persulfate, In the presence of a polymerization initiator such as hydrogen oxide, sodium bisulfite or mercaptoethanol may be added, if necessary, and reacted at 50 to 100 ° C. for 0.5 to 10 hours.
[0021]
In addition, you may make it react with the other copolymerizable monomer in the range which does not impair the effect of this invention. Examples of such a monomer include acrylonitrile, acrylic acid ester, (meth) acrylamide, styrene, styrene sulfonic acid, and the like.
[0022]
The polymer (b) of the present invention is a polymer having a molecular weight of 1,000 to 20,000 obtained by polymerizing one or more monomers (a) represented by the general formula (A). The monomer (a) is, for example, a carboxylic acid or dicarboxylic acid compound, and may be an anhydride. Specifically, for example, unsaturated monocarboxylic acid monomers such as (meth) acrylic acid and crotonic acid, maleic anhydride, maleic acid, itaconic anhydride, itaconic acid, citraconic anhydride, citraconic acid, fumaric acid, etc. Unsaturated dicarboxylic acid monomers or their alkali metal salts, alkaline earth metal salts, ammonium salts, and mono-, di-, or trialkylammonium salts optionally substituted with a hydroxyl group are preferred. A polymer (b) obtained by polymerizing a monocarboxylic acid and a dicarboxylic acid in a molar ratio of 30/70 to 100/0 is preferably excellent in the clay thinning effect, and particularly preferably a polymer (b). ) Is obtained by polymerizing (meth) acrylic acid or an alkali metal salt thereof.
[0023]
As for the weight average molecular weight of the polymer (b), a range of 1000 to 20000 is excellent in the clay thinning effect, and a range of 5000 to 10,000 is particularly excellent. The weight average molecular weight is determined by gel permeation chromatography (standard polystyrene sodium sulfonate equivalent / water system).
[0024]
The polymer (b) can also be produced by a known method, and a part thereof is commercially available and generally available. The polymer (b) may also be copolymerized with other copolymerizable monomers such as acrylonitrile, acrylic acid ester, (meth) acrylamide, styrene, styrenesulfonic acid, and the like within the range not impairing the effects of the present invention.
[0025]
The weight ratio of the compound (a) to the compound (b) is (i) / (b) = 5 from the viewpoint of improving fluidity of the hydraulic composition and at the same time improving the viscosity reduction of a specific clay having a lot of bentonite components. / 95 to 95/5 is preferable, preferably 10/90 to 90/10, and particularly preferably 20/80 to 80/20.
[0026]
The additive of the present invention is generally added so that the total of the compound (a) and the compound (b) is 0.02 to 1.0% by weight, preferably 0.1 to 0.5% by weight in terms of solid content with respect to the cement.
[0027]
The additive of the present invention is preferably added to a cement-based hydraulic material. Examples of the cement include ordinary Portland cement, blast furnace cement, fly ash cement, and early strength cement. The copolymer (I) and polymer (B) of the present invention may be added to the hydraulic material after blending both in advance or separately. Alternatively, it may be used after first diluted with kneaded water.
[0028]
In addition, the additive for hydraulic compositions of the present invention can be used in combination with a known additive (material). For example, AE agent, AE water reducing agent, fluidizing agent, retarder, early strengthening agent, accelerator, foaming agent, foaming agent, antifoaming agent, waterproofing agent, antifoaming agent, quartz sand, blast furnace slag, fly ash, silica fume Etc.
[0029]
【Example】
Illustratively, a synthesis example of copolymer A-4 in Table 1 is shown below.
A reaction vessel was charged with 15 mol of water, and 0.20 mol of the monomer (b) (b) at 75 ° C. in a nitrogen atmosphere, 0.80 mol of methacrylic acid, and 15 mol of water mixed and dissolved, 0.01 mol of 20% aqueous ammonium persulfate solution, And 4 g of 2-mercaptoethanol are added dropwise simultaneously over 2 hours. Next, 0.03 mol of 20% ammonium persulfate aqueous solution is dropped in 30 minutes, and the temperature is further raised to 90 ° C. at the same temperature for 1 hour, followed by adding 12 g of 35% hydrogen peroxide solution and aging for 2 hours. After completion of the aging, a 48% sodium hydroxide aqueous solution was added to neutralize and obtain a copolymer having a molecular weight of 55,000.
[0030]
Additives prepared by mixing the copolymer (A) shown in Table 1 and the polymer (B) shown in Table 2 at a weight ratio shown in Table 3 were evaluated as follows.
[0031]
[Cement fluidity]
800 g of ordinary Portland cement and 320 g of kneaded water (W / C = 40%) containing 0.1% of the additive for the effective amount are stirred and mixed with a mortar mixer at a low speed (63 r / m) for 1.5 minutes, and then quickly discharged. The viscosity was measured with a B-type viscometer.
[0032]
[Clay thinning]
800 g of Kibushi clay kneaded with 5% bentonite (vs. clay weight) and 480 g of kneaded water (W / C = 60%) containing 0.1% of Kibushi clay in an effective amount with a mortar mixer at low speed (63r / After stirring and mixing at 1.5) for 1.5 minutes, the mixture was immediately discharged and the viscosity was measured with a B-type viscometer.
[0033]
The above results are shown in Table 3. Note The standard pump used to grout method, in these evaluation conditions, the cement fluidity 2000 mPa · s or less, clay quality thinning is required following a viscosity 100 mPa · s. The strength after 28 days of the examples was 50 to 70 kg / cm 2 , which satisfied the standard strength.
[0034]
[Table 1]
[0035]
[Table 2]
[0036]
[Table 3]
[0037]
【The invention's effect】
By using the additive for a hydraulic composition of the present invention, water that has both high fluidity imparting properties and improved viscosity reduction properties for clay and satisfies the standard strength, is particularly useful as a cement composition for a grout method. A rigid composition can be provided.
Claims (5)
(イ)分子内にポリオキシエチレン基(平均付加モル数2〜180)を含有する重量平均分子量5000〜500000のビニル系共重合体であって、下記一般式(B)で表される単量体(b)の1種以上と下記一般式(C)で表される化合物の中から選ばれる1種以上の単量体(c)とを、モル比で(b)/(c)=10/90〜25/75の割合で重合して得られる共重合体
m2:0の整数
AO:炭素数2のオキシアルキレン基
n :2〜180の数
X :炭素数1のアルキル基
を示す。]
R7、R8:水素原子又はメチル基
M3、M4:水素、アルカリ金属、又はアルカリ土類金属
を示す。]
(ロ)アクリル酸又はそのアルカリ金属塩もしくはアルカリ土類金属塩(ロ−I)、マレイン酸又はそのアルカリ金属塩もしくはアルカリ土類金属塩(ロ−II)、及び無水マレイン酸(ロ−III)から選ばれる単量体(a)の1種以上を重合した分子量1000〜20000の重合体であって、モノカルボン酸である(ロ−I)とジカルボン酸である(ロ−II)又は(ロ−III)とをモル比で70/30〜100/0の割合で重合してなる重合体
[セメント流動性]
普通ポルトランドセメント800gと有効分で対セメント0.1%の添加剤を含む混練水320g(W/C=40%)をモルタルミキサーで低速(63r/m)で1.5分間攪拌混合後、速やかに排出し、B型粘度計で粘度を測定する。
[粘土質減粘性]
ベントナイト5%(対粘土重量)を練り込んだ木節粘土800gと有効分で対木節粘土0.1%の添加剤を含む混練水480g(W/C=60%)をモルタルミキサーで低速(63r/m)で1.5分間攪拌混合後、速やかに排出し、B型粘度計で粘度を測定する。The following copolymer (I) and polymer (B) are contained in a weight ratio of (A) / (B) = 10/90 to 50/50, and the cement fluidity by the following method is 1900 mPa · s or less. An additive for a cement composition for a grout method, having a clay thinning viscosity of 70 mPa · s or less by the following method.
(A) A vinyl copolymer having a weight average molecular weight of 5000 to 500,000 containing a polyoxyethylene group (average added mole number of 2 to 180) in the molecule, and represented by the following general formula (B) (B) / (c) = 10 in terms of a molar ratio of one or more of the body (b) and one or more monomers (c) selected from the compounds represented by the following general formula (C) Copolymer obtained by polymerization at a ratio of / 90 to 25/75
m2: integer of 0
AO: C2 oxyalkylene group
n: Number from 2 to 180
X: An alkyl group having 1 carbon atom. ]
R 7 , R 8 : hydrogen atom or methyl group
M 3 , M 4 : represents hydrogen, alkali metal, or alkaline earth metal. ]
(B) Acrylic acid or its alkali metal salt or alkaline earth metal salt (b), maleic acid or its alkali metal salt or alkaline earth metal salt (b), and maleic anhydride (b) A polymer having a molecular weight of 1000 to 20000 obtained by polymerizing one or more monomers (a) selected from (1) and (ii) or (ii) which is a monocarboxylic acid and (ii) a dicarboxylic acid. -III) and a polymer obtained by polymerizing at a molar ratio of 70/30 to 100/0 [cement fluidity]
800 g of ordinary Portland cement and 320 g of kneaded water (W / C = 40%) containing 0.1% of the additive in an effective amount are stirred and mixed with a mortar mixer at a low speed (63 r / m) for 1.5 minutes, and then quickly discharged. Viscosity is measured with a B-type viscometer.
[Clay thinning]
800 g of Kibushi clay kneaded with 5% bentonite (vs. clay weight) and 480 g of kneaded water (W / C = 60%) containing 0.1% of Kibushi clay in an effective amount with a mortar mixer at low speed (63r / After stirring for 1.5 minutes in m), the mixture is immediately discharged and the viscosity is measured with a B-type viscometer.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP25241598A JP4267100B2 (en) | 1998-09-07 | 1998-09-07 | Additive for cement composition for grout method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP25241598A JP4267100B2 (en) | 1998-09-07 | 1998-09-07 | Additive for cement composition for grout method |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2000086315A JP2000086315A (en) | 2000-03-28 |
JP4267100B2 true JP4267100B2 (en) | 2009-05-27 |
Family
ID=17237044
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP25241598A Expired - Fee Related JP4267100B2 (en) | 1998-09-07 | 1998-09-07 | Additive for cement composition for grout method |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4267100B2 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1471042B1 (en) | 2000-11-28 | 2008-01-09 | Kao Corporation | Powder dispersant for hydraulic compositions |
JP4562954B2 (en) * | 2001-06-20 | 2010-10-13 | 花王株式会社 | Additive for grout |
JP6603476B2 (en) * | 2015-04-24 | 2019-11-06 | 東邦化学工業株式会社 | Polycarboxylic acid copolymer and dispersant comprising the same |
WO2020115788A1 (en) * | 2018-12-03 | 2020-06-11 | 竹本油脂株式会社 | Additive for hydraulic compositions, and hydraulic composition |
JP7202915B2 (en) * | 2019-02-08 | 2023-01-12 | オリエンタル白石株式会社 | PC grout composition and PC grout material |
-
1998
- 1998-09-07 JP JP25241598A patent/JP4267100B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JP2000086315A (en) | 2000-03-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP3600100B2 (en) | Concrete admixture | |
JP3683176B2 (en) | Cement admixture and cement composition | |
JP2774445B2 (en) | Concrete admixture | |
JP4410438B2 (en) | Cement dispersant and cement composition using the same | |
US20060004149A1 (en) | Admixture composition for hydraulic material | |
JP2001002734A (en) | Production of polymer | |
JP5909359B2 (en) | Copolymer for cement admixture, method for producing the same, and cement admixture containing the copolymer | |
JP3443454B2 (en) | Cement additive for grouting method | |
JP4267100B2 (en) | Additive for cement composition for grout method | |
JP3964096B2 (en) | Concrete admixture | |
JPH0812397A (en) | Self-packing concrete admixture | |
JP4311348B2 (en) | Additive for cement | |
JP2003073157A (en) | Cement admixture and method of execution of cement composition | |
JP6955967B2 (en) | Blast furnace slag-containing cement slurry composition and method for preparing soil cement slurry using the same | |
JP4650972B2 (en) | Method for adjusting the fluidity of concrete | |
JPH09142905A (en) | Concrete admixture | |
JPH06256054A (en) | Cement dispersant | |
JP3436920B2 (en) | Admixture for hydraulic compositions | |
JPH09241056A (en) | Admixture for concrete | |
JP2011116587A (en) | Early strengthening agent for hydraulic composition | |
JPH06279082A (en) | Concrete admixture | |
JP2004323347A (en) | Concrete composition | |
JP2003183338A (en) | New copolymer and its use | |
JP4004671B2 (en) | Centrifugal concrete production | |
JP3514998B2 (en) | Cement dispersants and cement blends |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040917 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20040917 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20070418 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20070424 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20070625 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20071023 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20071221 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080311 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080509 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20090217 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20090218 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120227 Year of fee payment: 3 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120227 Year of fee payment: 3 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130227 Year of fee payment: 4 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140227 Year of fee payment: 5 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
LAPS | Cancellation because of no payment of annual fees |