JP3443454B2 - Cement additive for grouting method - Google Patents
Cement additive for grouting methodInfo
- Publication number
- JP3443454B2 JP3443454B2 JP15483894A JP15483894A JP3443454B2 JP 3443454 B2 JP3443454 B2 JP 3443454B2 JP 15483894 A JP15483894 A JP 15483894A JP 15483894 A JP15483894 A JP 15483894A JP 3443454 B2 JP3443454 B2 JP 3443454B2
- Authority
- JP
- Japan
- Prior art keywords
- mol
- acid
- copolymer
- monomer
- cement additive
- 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
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2641—Polyacrylates; Polymethacrylates
-
- 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
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00732—Uses not provided for elsewhere in C04B2111/00 for soil stabilisation
-
- 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】[0001]
【産業上の利用分野】本発明は軟弱地盤改良の地下工法
におけるグラウト工法用セメント添加剤に関する。更に
詳しくは、軟弱地盤を超高圧噴流液 (ジェット) によっ
て切削しながら、セメント系硬化剤を注入、硬化体とす
る工法に使用するセメント添加剤に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cement additive for a grout method in an underground method for improving soft ground. More specifically, the present invention relates to a cement additive used in a method of injecting a cement-based hardening agent to form a hardening body while cutting soft ground with an ultra-high pressure jet liquid (jet).
【０００２】[0002]
【従来の技術】グラウト工法とは、地上から地中深くま
で15cm程度の穴を開け、その中に管を通してセメント系
硬化材を高圧 (50〜700kg/cm2)でジェット噴流体として
送り、回りの土砂を削り取り、土砂を地上に排出しなが
ら、硬化材との置換によって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。 2. Description of the Related Art The grout method is a method in which a cement-based hardening material is sent as a jet fluid at high pressure (50 to 700 kg / cm 2 ) through a pipe through which a hole of about 15 cm is drilled from above ground to deep underground. This is an improvement method for soft ground where the pillars and walls are constructed by excavating the earth and sand and discharging it to the ground while replacing it with a hardening material.
【０００３】この工法には高流動性のセメント硬化材
(以下、硬化材と称す) が要求されることから、従来、
この目的の剤として、水・セメント比による強度 (28日
後の強度＝30kg/cm2以上) を満足し、流動効果のあるナ
フタレンスルホン酸塩ホルムアルデヒド縮合物 (以下、
ナフタレン系と称す) が添加剤として使用されている。[0003] The cement hardening material with high fluidity is used in this method.
(Hereinafter, referred to as a curing material) is required,
As an agent for this purpose, a naphthalene sulfonate formaldehyde condensate (hereinafter referred to as "condensation product" that satisfies the strength by water / cement ratio (strength after 28 days = 30 kg / cm 2 or more) and has a fluidizing effect
Naphthalene type) is used as an additive.
【０００４】[0004]
【発明が解決しようとする課題】さらに、この工法では
ジェット噴流体として注入する硬化材の一部は、切削し
た土砂を混合して管を通し、地上へ排出する必要があ
り、硬化材の特性としては排泥液の粘性を下げる作用が
要求される。Further, in this method, a part of the hardening material to be injected as a jet jet fluid needs to be mixed with the cut earth and sand and passed through a pipe to be discharged to the ground. As a result, the action of lowering the viscosity of the sludge is required.
【０００５】しかしながら、従来のナフタレン系の添加
剤では注入時の硬化材の粘性低下能は大きいものの、粘
土質に対する減粘硬化は小さいことから排泥液の粘性が
下がらずに排出が困難な状況である。その結果、硬化材
の注入効率が低下するばかりではなく、硬化材が土中に
おいて設計外への拡散や、それに伴う表層部への突起な
どの現象が生じ、問題となっている。However, although the conventional naphthalene-based additive has a large ability to reduce the viscosity of the hardening material at the time of injection, the viscosity of the clay mud is small, so that the viscosity of the sludge is not lowered and the discharge is difficult. Is. As a result, not only the efficiency of injecting the curing material decreases, but also the curing material causes problems such as diffusion outside the design in the soil and accompanying protrusions to the surface layer.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記の問
題点を鑑み、硬化材の高流動性と粘土質に対する減粘性
の両性能を併せもち、基準強度 (28日後の強度＝30kg/c
m2以上) を満足する添加剤を目標に鋭意検討の結果、セ
メント及び粘土質の分散に保水能の大きいアルキレンオ
キシドを有する分散剤骨格が有効であることを捉え、ア
ルキレンオキシド鎖に注力して研究したところ、アルキ
レンオキシド鎖長が 110〜300 モル範囲の高付加モル数
において極めて有効であることを見出し、本発明を完成
した。[Means for Solving the Problems] In view of the above problems, the present inventors have both the high fluidity of a hardened material and the ability to reduce the viscosity of clay, and have a standard strength (strength after 28 days = 30 kg). / c
As a result of earnest studies aiming at an additive satisfying (m 2 or more), it was found that a dispersant skeleton having an alkylene oxide having a large water retention capacity is effective for dispersion of cement and clay, and focusing on the alkylene oxide chain. As a result of research, they have found that the alkylene oxide chain length is extremely effective at high addition mole numbers in the range of 110 to 300 moles, and completed the present invention.
【０００７】即ち、本発明は、下記の一般式(A) で表さ
れる単量体(a) と下記の一般式(B)及び(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(b) とを重合
して得られる共重合体 (イ) を必須成分とするグラウト
工法用セメント添加剤に関する。That is, the present invention is one kind selected from a monomer (a) represented by the following general formula (A) and a compound represented by the following general formulas (B) and (C). The present invention relates to a cement additive for a grout method, which contains a copolymer (a) obtained by polymerizing the above monomer (b) as an essential component.
【０００８】[0008]
【化３】 [Chemical 3]
【０００９】(式中、R1, R2：水素、メチル基 m1 ：０〜２の整数 AO ：炭素数２〜３のオキシアルキレン基 n ： 110〜300 の整数 X ：水素または炭素数１〜３のアルキル基 を表す。)(Wherein R 1 and R 2 are hydrogen and a methyl group m 1 is an integer of 0 to 2 AO is an oxyalkylene group having 2 to 3 carbon atoms n is an integer of 110 to 300 and X is hydrogen or 1 carbon atom. ~ Represents an alkyl group of 3.)
【００１０】[0010]
【化４】 [Chemical 4]
【００１１】(式中、R3〜R5 ：水素、メチル基、(CH2)
m2COOM2
R6 ：水素、メチル基
M1,M2,Y ：水素、アルカリ金属、アルカリ土類金属、ア
ンモニウム、アルキルアンモニウムまたは置換アルキル
アンモニウム
m2 ：０〜２の整数
を表す。)
また、本発明は、上記の一般式(A) で表される単量体
(a) と上記の一般式(B)及び(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(b) とを重合して得られ
る共重合体 (イ) 及びオキシカルボン酸もしくはその
塩、糖及び糖アルコールからなる群から選ばれる１種以
上の化合物 (ロ) を必須成分とするグラウト工法用セメ
ント添加剤に関する。(In the formula, R 3 to R 5 : hydrogen, methyl group, (CH 2 )
m 2 COOM 2 R 6 : hydrogen, methyl group M 1 , M 2 , Y: hydrogen, alkali metal, alkaline earth metal, ammonium, alkylammonium or substituted alkylammonium m 2 : represents an integer of 0 to 2. ) Further, the present invention is a monomer represented by the above general formula (A)
a copolymer (a) obtained by polymerizing (a) with at least one monomer (b) selected from the compounds represented by the above general formulas (B) and (C); The present invention relates to a cement additive for a grout method, which contains, as an essential component, at least one compound (b) selected from the group consisting of carboxylic acid or a salt thereof, sugar and sugar alcohol.
【００１２】本発明に使用する共重合体 (イ) と類似構
造の不飽和結合を有する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及び／又は不飽和ジカ
ルボン酸系単量体との共重合物類としては、公知特許
(特公昭59-18338、特公平2-78978 、特公平2-7898、特
公平2-7901、特公平2-11542 、特開平3-75252 、特開昭
59-162163)がある。しかし、これらアルキレン鎖を持つ
ポリカルボン酸塩をグラウト工法用セメント添加剤とし
て用いても、粘土質の粘性低下が充分ではない。The copolymer (a) used in the present invention is a copolymer of a polyalkylene glycol monoester monomer having an unsaturated bond with a similar structure and an acrylic acid-based and / or unsaturated dicarboxylic acid-based monomer. Known patents for polymers
(Japanese Patent Publication No. 59-18338, Japanese Patent Publication No. 2-78978, Japanese Patent Publication No. 2-7898, Japanese Patent Publication No. 2-7901, Japanese Patent Publication No. 211542, Japanese Patent Laid-Open No. 3-75252, Japanese Patent Publication No.
59-162163). However, even if the polycarboxylic acid salt having these alkylene chains is used as a cement additive for the grout method, the viscosity of the clay is not sufficiently reduced.
【００１３】本発明者等はオキシアルキレン基の鎖長に
ついて種々検討した結果、ある特定領域の高鎖長 (付加
モル数＝ 110〜300)範囲において、セメントと粘土質の
減粘性が極めて高いことを見出したものである。即ち、
公知特許 (前述の共重合物に関する特許) のようなエチ
レンオキシド及び／又はプロピレンオキシドのモル数が
２〜100 モルの範囲では充分な効果が発現されない。As a result of various studies on the chain length of the oxyalkylene group, the present inventors have found that the cement and clay have extremely high viscosity reducing in a high chain length (additional mole number = 110 to 300) range of a specific region. Is found. That is,
When the number of moles of ethylene oxide and / or propylene oxide is in the range of 2 to 100 moles as in the known patents (the patents relating to the above-mentioned copolymers), a sufficient effect cannot be exhibited.
【００１４】本発明の共重合体 (イ) において、一般式
(A) で表される単量体(a) としては、メトキシポリエチ
レングリコール、メトキシポリエチレンポリプロピレン
グリコール、エトキシポリエチレングリコール、エトキ
シポリエチレンポリプロピレングリコール、プロポキシ
ポリエチレングリコール、プロポ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封鎖ポリアル
キレングリコールとアクリル酸、メタクリル酸又は脂肪
酸の脱水素 (酸化) 反応物とのエステル化物やアクリル
酸、メタクリル酸又は脂肪酸の脱水素 (酸化) 反応物へ
のエチレンオキシド、プロピレンオキシド付加物が用い
られる。ポリアルキレングリコールの付加モル数は 110
〜300 であり、エチレンオキシド、プロピレンオキシド
の両付加物についてはランダム付加、ブロック付加、交
互付加等のいずれでも用いることができる。ポリアルキ
レングリコールの付加モル数が 110未満の場合は粘土質
の粘性低下が充分でなく、 300を超えるとセメントの流
動性が低下する。In the copolymer (a) of the present invention, the general formula
Examples of the monomer (a) represented by (A) include methoxy polyethylene glycol, methoxy polyethylene polypropylene glycol, ethoxy polyethylene glycol, ethoxy polyethylene polypropylene glycol, propoxy polyethylene glycol, propoxy polyethylene polypropylene glycol, and the like. An esterification product of glycol with a dehydrogenation (oxidation) reaction product of acrylic acid, methacrylic acid or a fatty acid, or an ethylene oxide or propylene oxide adduct to a dehydrogenation (oxidation) reaction product of acrylic acid, methacrylic acid or a fatty acid is used. The number of moles of polyalkylene glycol added is 110
It is up to 300, and both additions of ethylene oxide and propylene oxide can be carried out by random addition, block addition, alternating addition and the like. When the number of added moles of polyalkylene glycol is less than 110, the viscosity of the clay is not sufficiently lowered, and when it exceeds 300, the fluidity of the cement is lowered.
【００１５】また、一般式(B) で表される化合物として
は、アクリル酸、メタクリル酸、クロトン酸及びこれら
の金属塩が挙げられる。また、不飽和ジカルボン酸系単
量体として、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、又はこれのアルカリ金属塩、アルカリ土類金
属塩、アンモニウム塩、アミン塩、置換アミン塩が使用
される。Examples of the compound represented by the general formula (B) include acrylic acid, methacrylic acid, crotonic acid and their metal salts. Further, as the unsaturated dicarboxylic acid-based monomer, maleic anhydride, maleic acid, itaconic anhydride, itaconic acid, citraconic anhydride, citraconic acid,
Fumaric acid or an alkali metal salt, alkaline earth metal salt, ammonium salt, amine salt or substituted amine salt thereof is used.
【００１６】また、一般式(C) で表される化合物として
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、アミン塩、置換アミン塩が使用される。Examples of the compound represented by the general formula (C) include allylsulfonic acid, methallylsulfonic acid, or their alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts and substituted amine salts. used.
【００１７】本発明の共重合体 (イ) を構成する単量体
(a) と単量体(b) の反応単位は、単量体(a) ／単量体
(b) ＝ 0.1／100 〜 100／100(モル比) の範囲が特に、
粘土質の粘性低下とセメントの流動性に優れる。上記の
モル比が 0.1／100 よりも小さい場合は粘土質の減粘性
が低下傾向になり、 100／100 よりも大きい場合はセメ
ントの流動性が低下傾向となる。Monomers constituting the copolymer (a) of the present invention
The reaction unit of (a) and monomer (b) is monomer (a) / monomer
In particular, the range of (b) = 0.1 / 100 to 100/100 (molar ratio) is
Excellent clay viscosity reduction and cement fluidity. When the above molar ratio is less than 0.1 / 100, the clay viscosity tends to decrease, and when it exceeds 100/100, the fluidity of the cement tends to decrease.
【００１８】本発明の共重合体 (イ) の製造法は公知の
方法で製造することができる。例えば、特開昭59-16216
3 、特公平2-11542 、特公平2-7901、特公平2-7897等の
溶媒重合法が挙げられる。The copolymer (A) of the present invention can be produced by a known method. For example, JP-A-59-16216
3, the Japanese Patent Publication No. 211542, the Japanese Patent Publication No. 2-7901, the Japanese Patent Publication No. 2-7897, etc. solvent polymerization methods.
【００１９】溶媒重合法において用いる溶剤としては、
水、メチルアルコール、エチルアルコール、イソプロピ
ルアルコール、ベンゼン、トルエン、キシレン、シクロ
ヘキサン、ｎ−ヘキサン、脂肪族炭化水素、酢酸エチ
ル、アセトン、メチルエチルケトン等が挙げられる。取
扱と反応設備から考慮すると水および１〜４級アルコー
ルが好ましい。The solvent used in the solvent polymerization method is
Examples thereof include water, methyl alcohol, ethyl alcohol, isopropyl alcohol, benzene, toluene, xylene, cyclohexane, n-hexane, aliphatic hydrocarbons, ethyl acetate, acetone and methyl ethyl ketone. Water and primary to quaternary alcohols are preferable in consideration of handling and reaction equipment.
【００２０】水系の重合開始剤としては、アンモニウム
又はアルカリ金属の過硫酸塩あるいは過酸化水素等の水
溶性の開始剤が使用される。水系以外の溶剤を用いる溶
媒重合にはベンゾイルパーオキシド、ラウロイルパーオ
キシド等が重合開始剤として使用される。As the water-based polymerization initiator, a water-soluble initiator such as ammonium or alkali metal persulfate or hydrogen peroxide is used. Benzoyl peroxide, lauroyl peroxide and the like are used as a polymerization initiator for solvent polymerization using a solvent other than an aqueous solvent.
【００２１】また、重合開始剤と併用して、促進剤とし
て亜硫酸水素ナトリウムやメルカプトエタノールやアミ
ン化合物を使用することも可能であり、これら重合開始
剤あるいは促進剤を適宜選択して用いることができる。It is also possible to use sodium bisulfite, mercaptoethanol or an amine compound as an accelerator in combination with the polymerization initiator, and these polymerization initiators or accelerators can be appropriately selected and used. .
【００２２】本発明の共重合体 (イ) の重量平均分子量
(ゲルパーミエーションクロマトグラフィー法／ポリス
チレンスルホン酸ナトリウム換算) は 3,000〜1,000,00
0 の範囲が良く、 5,000〜100,000 がより好ましい。分
子量が大きすぎるとセメントの流動性が低下し、また分
子量が小さすぎると粘土質の減粘性が低下傾向を示す。Weight average molecular weight of the copolymer (a) of the present invention
(Gel permeation chromatography method / sodium polystyrene sulfonate conversion) is 3,000 to 1,000,00
A range of 0 is preferable, and 5,000 to 100,000 is more preferable. If the molecular weight is too high, the fluidity of the cement will decrease, and if the molecular weight is too low, the viscosity reduction of the clay will tend to decrease.
【００２３】また、本発明における共重合体 (イ) は、
本発明の効果を損なわない範囲内で他の共重合可能な単
量体と反応させてもよい。例えば、アクリロニトリル、
アクリル酸エステル、アクリルアミド、メタクリルアミ
ド、スチレン、スチレンスルホン酸等が挙げられる。Further, the copolymer (a) in the present invention is
You may react with another copolymerizable monomer within the range which does not impair the effect of this invention. For example, acrylonitrile,
Examples thereof include acrylic acid ester, acrylamide, methacrylamide, styrene, styrene sulfonic acid and the like.
【００２４】更に、本発明における共重合体 (イ) とオ
キシカルボン酸もしくはその塩、糖及び糖アルコールか
らなる群から選ばれる１種以上の化合物 (ロ) の２成分
を必須として添加することで、粘土質の減粘性がさらに
高まることを見出した。Furthermore, by essentially adding two components of the copolymer (a) in the present invention and one or more compounds (b) selected from the group consisting of oxycarboxylic acid or a salt thereof, sugar and sugar alcohol. , And found that the viscosity of clay is further increased.
【００２５】オキシカルボン酸としては、グルコン酸、
グルコヘプトン酸、アラボン酸、リンゴ酸またはクエン
酸が挙げられる。これらの塩としては、例えば、ナトリ
ウム、カリウム、カルシウム、マグネシウム、アンモニ
ウム、トリエタノールアミン等の無機塩または有機塩が
挙げられる。また、糖としては、グルコース、フラクト
ース、ガラクトース、マンノース、キシロース、アラビ
トース、リポーズ、異性化糖などの単糖類や、二糖、三
糖などのオリゴ糖、またはデキストリンなどの多糖類な
どが挙げられる。また、これらを含む糖蜜類も含まれ
る。更に、糖アルコールとしてはソルビトールなどが挙
げられる。As the oxycarboxylic acid, gluconic acid,
Examples include glucoheptonic acid, arabonic acid, malic acid or citric acid. Examples of these salts include inorganic or organic salts such as sodium, potassium, calcium, magnesium, ammonium and triethanolamine. Examples of sugars include monosaccharides such as glucose, fructose, galactose, mannose, xylose, arabitolose, repose and isomerized sugar, oligosaccharides such as disaccharide and trisaccharide, and polysaccharides such as dextrin. Moreover, molasses containing these is also included. Furthermore, examples of the sugar alcohol include sorbitol.
【００２６】本発明の共重合体 (イ) の添加量は、セメ
ントに対して固形分で 0.1〜3.0 重量％程度が使用範囲
であり、 0.2〜0.5 重量％が好ましく使用される。The addition amount of the copolymer (a) of the present invention is about 0.1 to 3.0% by weight based on the solid content of the cement, and 0.2 to 0.5% by weight is preferably used.
【００２７】オキシカルボン酸もしくはその塩、糖及び
糖アルコールからなる群から選ばれる１種以上の化合物
(ロ) を併用する場合において、共重合体 (イ) と化合
物 (ロ) の配合比は、 (イ) ／ (ロ) ＝ 100／0.01〜5.
0(固形分重量比) 程度であり、 100／0.1〜1.0が好まし
く使用される。 100／0.01未満では粘土質の減粘性が低
下傾向となり、 100／5.0 を超えると硬化時間が遅延さ
れる傾向となり、好ましくない。One or more compounds selected from the group consisting of oxycarboxylic acids or salts thereof, sugars and sugar alcohols
When (B) is used in combination, the compounding ratio of the copolymer (A) and the compound (B) is (A) / (B) = 100 / 0.01 to 5.
It is about 0 (weight ratio of solid content), and 100 / 0.1 to 1.0 is preferably used. If it is less than 100 / 0.01, the viscosity reduction of the clay tends to decrease, and if it exceeds 100 / 5.0, the curing time tends to be delayed, which is not preferable.
【００２８】また、共重合体 (イ) と化合物 (ロ) を併
用して添加する場合、予め共重合体(イ) と化合物 (ロ)
を配合したものを添加しても、あるいは別々に添加し
てもよく、限定されるものではない。When the copolymer (a) and the compound (b) are added together, the copolymer (a) and the compound (b) are previously added.
It is possible to add a mixture of the above compounds or to add them separately, without any limitation.
【００２９】本発明の添加剤は、セメント系硬化材に添
加するものであり、セメント類としては、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、早強セメント等のセメント類が対象となる。ま
た、セメントの他に各種の混和材、例えば、フライアッ
シュ、高炉スラグ、シリカヒューム、膨張材を含む硬化
材も使用することができ、限定されるものでない。The additive of the present invention is to be added to a cement-based hardening material, and as the cements, in addition to ordinary Portland cement, cements such as blast furnace cement, fly ash cement and early strength cement are targeted. . In addition to cement, various admixtures such as fly ash, blast furnace slag, silica fume, and hardeners including expansive materials can also be used and are not limited.
【００３０】更に本発明の添加剤は、他の公知の添加
剤、例えば、ＡＥ剤、ＡＥ減水剤、高性能減水剤、遅延
剤、早強剤、促進剤、起泡剤、発泡剤、消泡剤、増粘
剤、防水剤、防泡剤等が挙げられる。Further, the additives of the present invention include other known additives such as an AE agent, an AE water reducing agent, a high performance water reducing agent, a retarder, an early strengthening agent, an accelerator, a foaming agent, a foaming agent and a defoaming agent. Foaming agents, thickening agents, waterproofing agents, antifoaming agents and the like can be mentioned.
【００３１】[0031]
【実施例】以下、本発明を具体的に説明するが、本発明
はこれらの実施例に限定されるものではない。尚、以下
の例における「％」は、特にことわりのない限り、「重
量％」である。EXAMPLES The present invention will be specifically described below, but the present invention is not limited to these examples. In addition, "%" in the following examples is "% by weight" unless otherwise specified.
【００３２】また、実施例中で示す共重合体 (イ) の平
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
／ポリスチレンスルホン酸ナトリウム換算による分子量
から求めたものである。Further, the average molecular weight of the copolymer (a) shown in the examples is obtained from the gel permeation chromatography method / molecular weight in terms of sodium polystyrene sulfonate.
【００３３】本発明の重合に使用した単量体(a) の内容
と記号を以下に示す。但し、EOはエチレンオキシド、PO
はプロピレンオキシドを表す。The contents and symbols of the monomer (a) used in the polymerization of the present invention are shown below. However, EO is ethylene oxide, PO
Represents propylene oxide.
【００３４】Ａ−１：メタノールEO・メタクリル酸モノ
エステル (EO付加モル数＝115)
Ａ−２：メタノールEO・アクリル酸モノエステル (EO付
加モル数＝220)
Ａ−３：メタノールEO・メタクリル酸モノエステル (EO
付加モル数＝280)
Ａ−４：アクリル酸EO付加物 (EO付加モル数＝130)
Ａ−５：アクリル酸PO・EOブロック付加物(PO付加モル
数＝10・EO付加モル数＝135)
Ａ−６：アクリル酸EO・POブロック付加物(EO付加モル
数＝135・PO付加モル数＝５)
Ａ−７：メタノールEO・メタクリル酸モノエステル (EO
付加モル数＝23)(比較)
Ａ−８：メタノールEO・メタクリル酸モノエステル (EO
付加モル数＝102)(比較)
A-9:メタノールEO・メタクリル酸モノエステル (EO付加モル
数＝350)(比較) 。A-1: Methanol EO / methacrylic acid monoester (EO addition mole number = 115) A-2: Methanol EO / acrylic acid monoester (EO addition mole number = 220) A-3: Methanol EO / methacrylic acid Monoester (EO
Addition mol number = 280) A-4: Acrylic acid EO adduct (EO addition mol number = 130) A-5: Acrylic acid PO / EO block adduct (PO addition mol number = 10 / EO addition mol number = 135) A-6: Acrylic acid EO / PO block addition product (EO addition mole number = 135 / PO addition mole number = 5) A-7: Methanol EO / methacrylic acid monoester (EO
Addition mol number = 23) (Comparison) A-8: Methanol EO / methacrylic acid monoester (EO
Addition mol number = 102) (Comparison) A-9: Methanol EO / methacrylic acid monoester (EO addition mol number = 350) (Comparison).
【００３５】以下に共重合体 (イ) の製造例を示す。製造例１ (混和剤の記号Ｃ−１)
攪拌機付き反応容器に水10モルを仕込み、攪拌しながら
窒素置換し、窒素雰囲気中で75℃まで昇温した。Ａ−１
0.09 モルとアクリル酸１モル (モル比＝9/100)、水
7.5モルを混合溶解したものと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の
３者をそれぞれ同時に反応系に２時間かけて滴下する。
次に20％過硫酸アンモニウム水溶液0.03モルを30分かけ
て滴下し、１時間同温度 (75℃) で熟成する。熟成後95
℃に昇温して、35％過酸化水素12ｇを１時間かけて滴下
し、２時間同温度 (95℃) で熟成する。熟成終了後、48
％水酸化ナトリウム 0.7モルを加えて中和、分子量22,0
00の共重合体を得た。The production examples of the copolymer (a) are shown below. Production Example 1 (Symbol C-1 for admixture) 10 mol of water was charged into a reaction vessel equipped with a stirrer, the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 75 ° C in a nitrogen atmosphere. A-1
0.09 mol and acrylic acid 1 mol (molar ratio = 9/100), water
A mixture of 7.5 mol, 0.01 mol of a 20% aqueous solution of ammonium persulfate, and 4 g of 2-mercaptoethanol were added dropwise to the reaction system simultaneously over 2 hours.
Next, 0.03 mol of 20% ammonium persulfate aqueous solution is added dropwise over 30 minutes, and the mixture is aged at the same temperature (75 ° C) for 1 hour. After aging 95
The temperature is raised to ℃, 12g of 35% hydrogen peroxide is added dropwise over 1 hour, and the mixture is aged at the same temperature (95 ℃) for 2 hours. After aging, 48
Add 0.7 mol% sodium hydroxide to neutralize, molecular weight 22,0
A copolymer of 00 was obtained.
【００３６】製造例２ (混和剤の記号Ｃ−２)
攪拌機付き反応容器に水８モルを仕込み、攪拌しながら
窒素置換し、窒素雰囲気中で75℃まで昇温した。Ａ−２
0.05 モルとメタクリル酸１モル (モル比＝5/100)、水
8.5モルを混合溶解したものと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３ｇの
３者をそれぞれ同時に反応系に２時間かけて滴下する。
次に20％過硫酸アンモニウム水溶液0.03モルを30分かけ
て滴下し、１時間同温度 (75℃) で熟成する。熟成後95
℃に昇温して、35％過酸化水素９ｇを１時間かけて滴下
し、２時間同温度 (95℃) で熟成する。熟成終了後、48
％水酸化ナトリウム 0.7モルを加えて中和、分子量85,0
00の共重合体を得た。 Production Example 2 (Symbol C-2 for admixture) 8 mol of water was charged into a reaction vessel equipped with a stirrer, the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 75 ° C. in a nitrogen atmosphere. A-2
0.05 mol and 1 mol of methacrylic acid (molar ratio = 5/100), water
A mixture of 8.5 mol, 0.01 mol of a 20% ammonium persulfate aqueous solution, and 3 g of 2-mercaptoethanol were simultaneously added dropwise to the reaction system over 2 hours.
Next, 0.03 mol of 20% ammonium persulfate aqueous solution is added dropwise over 30 minutes, and the mixture is aged at the same temperature (75 ° C) for 1 hour. After aging 95
The temperature is raised to 0 ° C., 9 g of 35% hydrogen peroxide is added dropwise over 1 hour, and the mixture is aged at the same temperature (95 ° C.) for 2 hours. After aging, 48
Add 0.7 mol% sodium hydroxide to neutralize, molecular weight 85,0
A copolymer of 00 was obtained.
【００３７】製造例３ (混和剤の記号Ｃ−３)
攪拌機付き反応容器に水５モルを仕込み、攪拌しながら
窒素置換し、窒素雰囲気中で95℃まで昇温した。Ａ−３
0.002モルとマレイン酸モノナトリウム塩１モル (モル
比＝0.2/100)、90℃温水15モルを混合溶解したものと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３ｇの３者をそれぞれ同時に反応系に２
時間かけて滴下する。次に20％過硫酸アンモニウム水溶
液0.03モルを30分かけて滴下し、１時間同温度 (95℃)
で熟成する。熟成後95℃で35％過酸化水素９ｇを１時間
かけて滴下し、２時間同温度 (95℃) で熟成する。熟成
終了後、48％水酸化ナトリウム 0.7モルを加えて中和、
分子量12,000の共重合体を得た。 Production Example 3 (Symbol C-3 for admixture) 5 mol of water was charged into a reaction vessel equipped with a stirrer, the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 95 ° C in a nitrogen atmosphere. A-3
20 with a mixture of 0.002 mol, 1 mol of maleic acid monosodium salt (molar ratio = 0.2 / 100), and 15 mol of 90 ° C warm water
% Mol ammonium persulfate aqueous solution 0.01 mol, and 2-mercaptoethanol 3 g simultaneously into the reaction system
Drop over time. Next, 0.03 mol of 20% ammonium persulfate aqueous solution was added dropwise over 30 minutes, and the temperature was kept at the same temperature (95 ° C) for 1 hour.
Mature in. After aging, 9% of 35% hydrogen peroxide was added dropwise at 95 ° C over 1 hour, and the mixture was aged at the same temperature (95 ° C) for 2 hours. After aging, add 0.7 mol of 48% sodium hydroxide to neutralize,
A copolymer having a molecular weight of 12,000 was obtained.
【００３８】製造例４ (混和剤の記号Ｃ−４)
攪拌機付き反応容器に水10モルを仕込み、攪拌しながら
窒素置換し、窒素雰囲気中で75℃まで昇温した。Ａ−４
0.01 モルとアクリル酸 0.9モルとメタリルスルホン酸
ナトリウム 0.1モル (モル比＝1/90/10)、水 7.5モルを
混合溶解したものと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の３者をそれ
ぞれ同時に反応系に２時間かけて滴下する。次に20％過
硫酸アンモニウム水溶液0.03モルを30分かけて滴下し、
１時間同温度 (75℃) で熟成する。熟成後95℃に昇温し
て、35％過酸化水素12ｇを１時間かけて滴下し、２時間
同温度 (95℃) で熟成する。熟成終了後、48％水酸化ナ
トリウム 0.6モルを加えて中和、分子量 7,200の共重合
体を得た。 Production Example 4 (Symbol C-4 of admixture) 10 mol of water was charged into a reaction vessel equipped with a stirrer, the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 75 ° C in a nitrogen atmosphere. A-4
A mixture of 0.01 mol, 0.9 mol of acrylic acid, 0.1 mol of sodium methallyl sulfonate (molar ratio = 1/90/10) and 7.5 mol of water and dissolved, and a 20% ammonium persulfate aqueous solution 0.01
Mol and 2-mercaptoethanol (4 g) are simultaneously added dropwise to the reaction system over 2 hours. Next, 0.03 mol of 20% ammonium persulfate aqueous solution was added dropwise over 30 minutes,
Aging at the same temperature (75 ℃) for 1 hour. After aging, the temperature is raised to 95 ° C., 12 g of 35% hydrogen peroxide is added dropwise over 1 hour, and aging is performed at the same temperature (95 ° C.) for 2 hours. After completion of aging, 0.6 mol of 48% sodium hydroxide was added for neutralization to obtain a copolymer having a molecular weight of 7,200.
【００３９】製造例５ (混和剤の記号Ｃ−５)
攪拌機付き反応容器に水10モルを仕込み、攪拌しながら
窒素置換し、窒素雰囲気中で75℃まで昇温した。Ａ−５
0.01 モルとメタクリル酸１モル (モル比＝1/100)、水
7.5モルを混合溶解したものと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１ｇの
３者をそれぞれ同時に反応系に２時間かけて滴下する。
次に20％過硫酸アンモニウム水溶液0.03モルを30分かけ
て滴下し、１時間同温度 (75℃) で熟成する。熟成後95
℃に昇温して、35％過酸化水素５ｇを１時間かけて滴下
し、２時間同温度 (95℃) で熟成する。熟成終了後、48
％水酸化ナトリウム 0.7モルを加えて中和、分子量105,
000 の共重合体を得た。 Production Example 5 (Symbol C-5 for admixture) 10 mol of water was charged into a reaction vessel equipped with a stirrer, the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 75 ° C in a nitrogen atmosphere. A-5
0.01 mol and 1 mol of methacrylic acid (molar ratio = 1/100), water
A mixture of 7.5 mol, 0.01 mol of a 20% aqueous solution of ammonium persulfate, and 1 g of 2-mercaptoethanol are simultaneously added dropwise to the reaction system over 2 hours.
Next, 0.03 mol of 20% ammonium persulfate aqueous solution is added dropwise over 30 minutes, and the mixture is aged at the same temperature (75 ° C) for 1 hour. After aging 95
The temperature is raised to 0 ° C., 5 g of 35% hydrogen peroxide is added dropwise over 1 hour, and the mixture is aged at the same temperature (95 ° C.) for 2 hours. After aging, 48
Add 0.7 mol% sodium hydroxide to neutralize, molecular weight 105,
000 copolymers were obtained.
【００４０】製造例６ (混和剤の記号Ｃ−６)
攪拌機付き反応容器に水10モルを仕込み、攪拌しながら
窒素置換し、窒素雰囲気中で75℃まで昇温した。Ａ−６
0.01 モルとアクリル酸ナトリウム１モル (モル比＝1/
100)、水 7.5モルを混合溶解したものと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２ｇの３者をそれぞれ同時に反応系に２時間かけて滴
下する。次に20％過硫酸アンモニウム水溶液0.03モルを
30分かけて滴下し、１時間同温度 (75℃) で熟成する。
熟成後95℃に昇温して、35％過酸化水素９ｇを１時間か
けて滴下し、２時間同温度 (95℃) で熟成する。熟成終
了後、48％水酸化ナトリウム 0.7モルを加えて中和、分
子量77,000の共重合体を得た。 Production Example 6 (Symbol C-6 for admixture) 10 mol of water was charged into a reaction vessel equipped with a stirrer, and the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 75 ° C in a nitrogen atmosphere. A-6
0.01 mol and 1 mol of sodium acrylate (molar ratio = 1 /
100), 7.5 mol of water mixed and dissolved, 0.01 mol of 20% ammonium persulfate aqueous solution, and 2 g of 2-mercaptoethanol are simultaneously added dropwise to the reaction system over 2 hours. Next, 0.03 mol of 20% ammonium persulfate aqueous solution
Drop over 30 minutes and age for 1 hour at the same temperature (75 ° C).
After aging, the temperature is raised to 95 ° C., 9 g of 35% hydrogen peroxide is added dropwise over 1 hour, and aging is performed at the same temperature (95 ° C.) for 2 hours. After the aging was completed, 48 mol of sodium hydroxide (0.7 mol) was added for neutralization to obtain a copolymer having a molecular weight of 77,000.
【００４１】製造例７ (混和剤の記号Ｃ−７)
攪拌機付き反応容器に水23モルを仕込み、攪拌しながら
窒素置換し、窒素雰囲気中で75℃まで昇温した。Ａ−２
0.045モルとアクリル酸 0.3モル (モル比＝15/100) 、
水10モルを混合溶解したものと20％過硫酸アンモニウム
水溶液 0.003モル、及び２−メルカプトエタノール 1.2
ｇの３者をそれぞれ同時に反応系に２時間かけて滴下す
る。次に20％過硫酸アンモニウム水溶液 0.009モルを30
分かけて滴下し、１時間同温度 (75℃) で熟成する。熟
成後95℃に昇温して、35％過酸化水素４ｇを１時間かけ
て滴下し、２時間同温度 (95℃) で熟成する。熟成終了
後、48％水酸化ナトリウム0.21モルを加えて中和、分子
量51,000の共重合体を得た。 Production Example 7 (Symbol C-7 as an admixture) 23 mol of water was charged into a reaction vessel equipped with a stirrer, the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 75 ° C in a nitrogen atmosphere. A-2
0.045 mol and acrylic acid 0.3 mol (molar ratio = 15/100),
A mixture of 10 mol of water and 0.003 mol of 20% ammonium persulfate aqueous solution, and 2-mercaptoethanol 1.2.
g of each of the three is simultaneously added dropwise to the reaction system over 2 hours. Next, 0.009 mol of a 20% ammonium persulfate aqueous solution is added to 30%.
Drop over a period of minutes and age for 1 hour at the same temperature (75 ° C). After aging, the temperature is raised to 95 ° C., 4 g of 35% hydrogen peroxide is added dropwise over 1 hour, and aging is performed at the same temperature (95 ° C.) for 2 hours. After the completion of aging, 0.21 mol of 48% sodium hydroxide was added for neutralization to obtain a copolymer having a molecular weight of 51,000.
【００４２】製造例８ (混和剤の記号Ｃ−８)
攪拌機付き反応容器に水23モルを仕込み、攪拌しながら
窒素置換し、窒素雰囲気中で75℃まで昇温した。Ａ−１
0.08 モルとアクリル酸 0.2モル (モル比＝40/100) 、
水12モルを混合溶解したものと20％過硫酸アンモニウム
水溶液 0.002モル、及び２−メルカプトエタノール 0.6
ｇの３者をそれぞれ同時に反応系に２時間かけて滴下す
る。次に20％過硫酸アンモニウム水溶液 0.006モルを30
分かけて滴下し、１時間同温度 (75℃) で熟成する。熟
成後95℃に昇温して、35％過酸化水素３ｇを１時間かけ
て滴下し、２時間同温度 (95℃) で熟成する。熟成終了
後、48％水酸化ナトリウム0.14モルを加えて中和、分子
量56,000の共重合体を得た。 Production Example 8 (Symbol C-8 for admixture) 23 mol of water was charged into a reaction vessel equipped with a stirrer, the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 75 ° C. in a nitrogen atmosphere. A-1
0.08 mol and acrylic acid 0.2 mol (molar ratio = 40/100),
A mixture of 12 mol of water, 0.002 mol of 20% ammonium persulfate aqueous solution, and 2-mercaptoethanol 0.6
g of each of the three is simultaneously added dropwise to the reaction system over 2 hours. Next, 0.006 mol of 20% ammonium persulfate aqueous solution is added to 30%.
Drop over a period of minutes and age for 1 hour at the same temperature (75 ° C). After aging, the temperature is raised to 95 ° C., 3 g of 35% hydrogen peroxide is added dropwise over 1 hour, and aging is performed at the same temperature (95 ° C.) for 2 hours. After the aging was completed, 0.14 mol of 48% sodium hydroxide was added to neutralize and obtain a copolymer having a molecular weight of 56,000.
【００４３】製造例９ (混和剤の記号Ｃ−９)
攪拌機付き反応容器に水18モルを仕込み、攪拌しながら
窒素置換し、窒素雰囲気中で75℃まで昇温した。Ａ−１
0.06 モルとアクリル酸 0.1モル (モル比＝60/100) 、
水８モルを混合溶解したものと20％過硫酸アンモニウム
水溶液 0.001モル、及び２−メルカプトエタノール 0.3
ｇの３者をそれぞれ同時に反応系に２時間かけて滴下す
る。次に20％過硫酸アンモニウム水溶液 0.003モルを30
分かけて滴下し、１時間同温度 (75℃) で熟成する。熟
成後95℃に昇温して、35％過酸化水素２ｇを１時間かけ
て滴下し、２時間同温度 (95℃) で熟成する。熟成終了
後、48％水酸化ナトリウム0.07モルを加えて中和、分子
量45,000の共重合体を得た。 Production Example 9 (symbol C-9 as an admixture) 18 mol of water was charged into a reaction vessel equipped with a stirrer, the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 75 ° C in a nitrogen atmosphere. A-1
0.06 mol and acrylic acid 0.1 mol (molar ratio = 60/100),
A mixture of 8 moles of water, 0.001 mole of 20% aqueous ammonium persulfate solution, and 2-mercaptoethanol 0.3
g of each of the three is simultaneously added dropwise to the reaction system over 2 hours. Next, 0.003 mol of 20% ammonium persulfate aqueous solution is added to 30%.
Drop over a period of minutes and age for 1 hour at the same temperature (75 ° C). After aging, the temperature is raised to 95 ° C., 2 g of 35% hydrogen peroxide is added dropwise over 1 hour, and aging is performed at the same temperature (95 ° C.) for 2 hours. After completion of the aging, 0.07 mol of 48% sodium hydroxide was added for neutralization to obtain a copolymer having a molecular weight of 45,000.
【００４４】製造例10 (混和剤の記号Ｃ−10)
攪拌機付き反応容器に水30モルを仕込み、攪拌しながら
窒素置換し、窒素雰囲気中で75℃まで昇温した。Ａ−１
0.1モルとアクリル酸 0.1モル (モル比＝100/100)、水
13モルを混合溶解したものと20％過硫酸アンモニウム水
溶液 0.001モル、及び２−メルカプトエタノール 0.3ｇ
の３者をそれぞれ同時に反応系に２時間かけて滴下す
る。次に20％過硫酸アンモニウム水溶液 0.003モルを30
分かけて滴下し、１時間同温度 (75℃) で熟成する。熟
成後95℃に昇温して、35％過酸化水素２ｇを１時間かけ
て滴下し、２時間同温度 (95℃) で熟成する。熟成終了
後、48％水酸化ナトリウム0.07モルを加えて中和、分子
量72,000の共重合体を得た。 Production Example 10 (Symbol C-10 of admixture) 30 mol of water was charged into a reaction vessel equipped with a stirrer, and the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 75 ° C in a nitrogen atmosphere. A-1
0.1 mol and acrylic acid 0.1 mol (molar ratio = 100/100), water
A mixture of 13 mol and dissolved, 0.001 mol of 20% ammonium persulfate aqueous solution, and 0.3 g of 2-mercaptoethanol
Each of the three is simultaneously added dropwise to the reaction system over 2 hours. Next, 0.003 mol of 20% ammonium persulfate aqueous solution is added to 30%.
Drop over a period of minutes and age for 1 hour at the same temperature (75 ° C). After aging, the temperature is raised to 95 ° C., 2 g of 35% hydrogen peroxide is added dropwise over 1 hour, and aging is performed at the same temperature (95 ° C.) for 2 hours. After completion of the aging, 0.07 mol of 48% sodium hydroxide was added for neutralization to obtain a copolymer having a molecular weight of 72,000.
【００４５】製造例11 (混和剤の記号Ｃ−11)
攪拌機付き反応容器に水10モルを仕込み、攪拌しながら
窒素置換し、窒素雰囲気中で75℃まで昇温した。Ａ−７
0.1モルとアクリル酸１モル (モル比＝10/100) 、水
7.5モルを混合溶解したものと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の
３者をそれぞれ同時に反応系に２時間かけて滴下する。
次に20％過硫酸アンモニウム水溶液0.03モルを30分かけ
て滴下し、１時間同温度 (75℃) で熟成する。熟成後95
℃に昇温して、35％過酸化水素12ｇを１時間かけて滴下
し、２時間同温度 (95℃) で熟成する。熟成終了後、48
％水酸化ナトリウム 0.7モルを加えて中和、分子量11,0
00の共重合体を得た。 Production Example 11 (Symbol C-11 as an admixture) 10 mol of water was charged into a reaction vessel equipped with a stirrer, the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 75 ° C in a nitrogen atmosphere. A-7
0.1 mol and acrylic acid 1 mol (molar ratio = 10/100), water
A mixture of 7.5 mol, 0.01 mol of a 20% aqueous solution of ammonium persulfate, and 4 g of 2-mercaptoethanol were added dropwise to the reaction system simultaneously over 2 hours.
Next, 0.03 mol of 20% ammonium persulfate aqueous solution is added dropwise over 30 minutes, and the mixture is aged at the same temperature (75 ° C) for 1 hour. After aging 95
The temperature is raised to ℃, 12g of 35% hydrogen peroxide is added dropwise over 1 hour, and the mixture is aged at the same temperature (95 ℃) for 2 hours. After aging, 48
Add 0.7 mol% sodium hydroxide to neutralize, molecular weight 11,0
A copolymer of 00 was obtained.
【００４６】製造例12 (混和剤の記号Ｃ−12)
攪拌機付き反応容器に水10モルを仕込み、攪拌しながら
窒素置換し、窒素雰囲気中で75℃まで昇温した。Ａ−８
0.05 モルとアクリル酸１モル (モル比＝5/100)、水
7.5モルを混合溶解したものと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３ｇの
３者をそれぞれ同時に反応系に２時間かけて滴下する。
次に20％過硫酸アンモニウム水溶液0.03モルを30分かけ
て滴下し、１時間同温度 (75℃) で熟成する。熟成後95
℃に昇温して、35％過酸化水素10ｇを１時間かけて滴下
し、２時間同温度 (95℃) で熟成する。熟成終了後、48
％水酸化ナトリウム 0.7モルを加えて中和、分子量31,0
00の共重合体を得た。 Production Example 12 (symbol C-12 as an admixture) 10 mol of water was charged into a reaction vessel equipped with a stirrer, the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 75 ° C in a nitrogen atmosphere. A-8
0.05 mol and acrylic acid 1 mol (molar ratio = 5/100), water
A mixture of 7.5 mol, 0.01 mol of a 20% ammonium persulfate aqueous solution, and 3 g of 2-mercaptoethanol are simultaneously added dropwise to the reaction system over 2 hours.
Next, 0.03 mol of 20% ammonium persulfate aqueous solution is added dropwise over 30 minutes, and the mixture is aged at the same temperature (75 ° C) for 1 hour. After aging 95
The temperature is raised to 10 ° C., 10 g of 35% hydrogen peroxide is added dropwise over 1 hour, and the mixture is aged at the same temperature (95 ° C.) for 2 hours. After aging, 48
Add 0.7 mol% sodium hydroxide to neutralize, molecular weight 31,0
A copolymer of 00 was obtained.
【００４７】製造例13 (混和剤の記号Ｃ−13)
攪拌機付き反応容器に水５モルを仕込み、攪拌しながら
窒素置換し、窒素雰囲気中で95℃まで昇温した。Ａ−９
0.005モルとアクリル酸１モル (モル比＝0.5/100)、75
℃温水15モルを混合溶解したものと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３
ｇの３者をそれぞれ同時に反応系に２時間かけて滴下す
る。次に20％過硫酸アンモニウム水溶液0.03モルを30分
かけて滴下し、１時間同温度 (95℃) で熟成する。熟成
後95℃で35％過酸化水素９ｇを１時間かけて滴下し、２
時間同温度 (95℃) で熟成する。熟成終了後、48％水酸
化ナトリウム 0.7モルを加えて中和、分子量25,000の共
重合体を得た。 Production Example 13 (symbol C-13 as an admixture) 5 mol of water was charged into a reaction vessel equipped with a stirrer, the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 95 ° C in a nitrogen atmosphere. A-9
0.005 mol and acrylic acid 1 mol (molar ratio = 0.5 / 100), 75
Mixture of 15 mol of warm water, 0.01 mol of 20% ammonium persulfate aqueous solution, and 2-mercaptoethanol 3
g of each of the three is simultaneously added dropwise to the reaction system over 2 hours. Next, 0.03 mol of a 20% ammonium persulfate aqueous solution is added dropwise over 30 minutes, followed by aging at the same temperature (95 ° C) for 1 hour. After aging, add 9 g of 35% hydrogen peroxide at 95 ° C over 1 hour, and add 2
Aging at the same temperature (95 ℃) for a certain period of time. After completion of the aging, 0.7 mol of 48% sodium hydroxide was added to neutralize and obtain a copolymer having a molecular weight of 25,000.
【００４８】共重合体の比較重合物の他に、実施例に使
用した比較混和剤の内容と記号を以下に示す。
混和剤の記号ＮＳ：ナフタレン系混和剤 (マイテイ150
; 花王（株）製）
実施例に使用した化合物 (ロ) の内容と記号を表１に示
す。The contents and symbols of the comparative admixtures used in the examples are shown below in addition to the comparative polymer of the copolymer. Symbol for admixture NS: Naphthalene admixture (Mighty 150
Manufactured by Kao Co., Ltd. Table 1 shows the contents and symbols of the compounds (b) used in the examples.
【００４９】[0049]
【表１】 [Table 1]
【００５０】コンクリート試験の評価方法
表２に示す配合組成で硬化材と粘土物質を調整し、本発
明の添加剤および比較添加剤を加えて流動性を測定し
た。さらに、添加剤を含む硬化材を粘土物質に加えて粘
度と強度を測定した。強度は粘土物質と硬化材の混合さ
れた土中状態での強度を想定し、本実施例では硬化材と
粘土物質を１対２ (重量比) に想定して実施した。 Evaluation Method of Concrete Test A hardening material and a clay material were prepared with the composition shown in Table 2, and the fluidity was measured by adding the additive of the present invention and the comparative additive. Further, a hardening material containing additives was added to the clay substance to measure viscosity and strength. The strength is assumed to be the strength in a soil state in which a clay material and a hardening material are mixed, and in this example, the hardening material and the clay material were assumed to be 1 to 2 (weight ratio).
【００５１】[0051]
【表２】 [Table 2]
【００５２】測定は下記に示す方法で実施した。
・硬化材の流動性；土木学会制定試験法「プレパックド
コンクリートの注入モルタル流動性試験」に基づき、Ｊ
ロートから流下するのに要した時間 (秒) で表した。
・硬化材と粘土物質を混合した粘度；Ｂ型粘度計を用い
「cps」で表した。
・圧縮強度；直径10cm、高さ20cmの円筒上供試体を作成
し、28日後の強度をJISA 1108法にて測定した。The measurement was carried out by the method shown below.・ Fluidity of hardened material; J
It was expressed as the time (seconds) required to flow down from the funnel. -Viscosity obtained by mixing a hardener and a clay substance; expressed in "cps" using a B-type viscometer. -Compressive strength: A cylindrical specimen having a diameter of 10 cm and a height of 20 cm was prepared, and the strength after 28 days was measured by the JIS A 1108 method.
【００５３】目標の要求性能を以下に示す。 ・硬化材の流動性；18秒以下 ・硬化材＋粘土の粘度；5000cps 以下 ・圧縮強度；30kg/cm2以上。The target performance requirements are shown below.・ Flowability of hardened material: 18 seconds or less ・ Viscosity of hardened material + clay; 5000 cps or less ・ Compressive strength: 30 kg / cm 2 or more.
【００５４】試験結果を表３に示す。The test results are shown in Table 3.
【００５５】[0055]
【表３】 [Table 3]
【００５６】評価結果
表３に示すように、本発明の添加剤を用いることによ
り、高流動性と粘土質に対する減粘性の両性能を併せ持
ち、基準強度 (28日後の強度＝30kg/cm2以上) を満足す
る硬化材を得ることが可能となる。また、注入作業の向
上が可能となったことから、今後高圧注入工法による地
盤改良工法の発展に寄与できる。 Evaluation results As shown in Table 3, by using the additive of the present invention, both the high fluidity and the viscosity reducing property for clay are obtained, and the standard strength (strength after 28 days = 30 kg / cm 2 or more) is obtained. It is possible to obtain a hardened material that satisfies Further, since the injection work can be improved, it can contribute to the development of the ground improvement method by the high pressure injection method in the future.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ０４Ｂ 24/10 Ｃ０４Ｂ 24/10 24/38 24/38 Ｚ 28/02 28/02 Ｃ０９Ｋ 17/10 Ｃ０９Ｋ 17/10 Ｈ 17/44 17/44 Ｈ // Ｃ０７Ｃ 309/04 Ｃ０７Ｃ 309/04 Ｃ０８Ｆ 290/06 Ｃ０８Ｆ 290/06 Ｃ０４Ｂ 103:40 Ｃ０４Ｂ 103:40 111:70 111:70 ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI C04B 24/10 C04B 24/10 24/38 24/38 Z 28/02 28/02 C09K 17/10 C09K 17/10 H 17 / 44 17/44 H // C07C 309/04 C07C 309/04 C08F 290/06 C08F 290/06 C04B 103: 40 C04B 103: 40 111: 70 111: 70
Claims (8)
と下記の一般式(B)及び(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(b) とを重合して得られる共
重合体 (イ) を必須成分とするグラウト工法用セメント
添加剤。 【化１】 (式中、R1, R2：水素、メチル基 m1 ：０〜２の整数 AO ：炭素数２〜３のオキシアルキレン基 n ： 110〜300 の整数 X ：水素または炭素数１〜３のアルキル基 を表す。) 【化２】 (式中、R3〜R5 ：水素、メチル基、(CH2)m2COOM2 R6 ：水素、メチル基 M1,M2,Y ：水素、アルカリ金属、アルカリ土類金属、ア
ンモニウム、アルキルアンモニウムまたは置換アルキル
アンモニウム m2 ：０〜２の整数 を表す。)1. A monomer (a) represented by the following general formula (A):
And a copolymer (a) obtained by polymerizing a monomer (b) selected from the compounds represented by the following general formulas (B) and (C) as an essential component Cement additive for grout method. [Chemical 1] (In the formula, R 1 and R 2 : hydrogen, a methyl group m 1 : an integer of 0 to 2 AO: an oxyalkylene group having 2 to 3 carbon atoms n: an integer of 110 to 300 X: hydrogen or a carbon number of 1 to 3 Represents an alkyl group.) (In the formula, R 3 to R 5 : hydrogen, methyl group, (CH 2 ) m 2 COOM 2 R 6 : hydrogen, methyl group M 1 , M 2 , Y: hydrogen, alkali metal, alkaline earth metal, ammonium, (Alkyl ammonium or substituted alkyl ammonium m 2 : represents an integer of 0 to 2. )
塩、糖及び糖アルコールからなる群から選ばれる１種以
上の化合物 (ロ) を必須成分とする請求項１記載のグラ
ウト工法用セメント添加剤。2. The cement additive for the grout method according to claim 1, which further comprises at least one compound (b) selected from the group consisting of oxycarboxylic acid or a salt thereof, sugar and sugar alcohol.
単量体(b) の反応単位が、単量体(a) ／単量体(b) ＝
0.1／100 〜 100／100(モル比) である請求項１または
２記載のグラウト工法用セメント添加剤。3. A monomer (a) constituting the copolymer (a),
The reaction unit of monomer (b) is monomer (a) / monomer (b) =
The cement additive for the grout method according to claim 1 or 2, which is 0.1 / 100 to 100/100 (molar ratio).
パーミエーションクロマトグラフィー法／ポリスチレン
スルホン酸ナトリウム換算) が 3,000〜1,000,000 であ
る請求項１〜３の何れか１項に記載のグラウト工法用セ
メント添加剤。4. The grout method according to claim 1, wherein the copolymer (a) has a weight average molecular weight (gel permeation chromatography method / sodium polystyrene sulfonate conversion) of 3,000 to 1,000,000. Cement additive.
が、 (イ) ／ (ロ)＝ 100／0.01〜5.0(固形分重量比)
である請求項２〜４の何れか１項に記載のグラウト工法
用セメント添加剤。5. The compounding ratio of the copolymer (a) and the compound (b) is (a) / (b) = 100 / 0.01 to 5.0 (solid content weight ratio).
The cement additive for the grout method according to any one of claims 2 to 4.
ヘプトン酸、アラボン酸、リンゴ酸またはクエン酸であ
る請求項２〜５の何れか１項に記載のグラウト工法用セ
メント添加剤。6. The cement additive for the grout method according to claim 2, wherein the oxycarboxylic acid is gluconic acid, glucoheptonic acid, arabonic acid, malic acid or citric acid.
ある請求項２〜６の何れか１項に記載のグラウト工法用
セメント添加剤。7. The grout method according to any one of claims 2 to 6, wherein the sugar is a monosaccharide, an oligosaccharide or a polysaccharide .
Cement additive .
項２〜７の何れか１項に記載のグラウト工法用セメント
添加剤。8. The cement for grouting method according to claim 2, wherein the sugar alcohol is sorbitol.
Additives .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15483894A JP3443454B2 (en) | 1994-07-06 | 1994-07-06 | Cement additive for grouting method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15483894A JP3443454B2 (en) | 1994-07-06 | 1994-07-06 | Cement additive for grouting method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0812398A JPH0812398A (en) | 1996-01-16 |
| JP3443454B2 true JP3443454B2 (en) | 2003-09-02 |
Family
ID=15592995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15483894A Expired - Fee Related JP3443454B2 (en) | 1994-07-06 | 1994-07-06 | Cement additive for grouting method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3443454B2 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6310143B1 (en) | 1998-12-16 | 2001-10-30 | Mbt Holding Ag | Derivatized polycarboxylate dispersants |
| US6673885B1 (en) * | 1999-08-23 | 2004-01-06 | Kao Corporation | Process for the production of (meth)acrylic polymers |
| JP2002114550A (en) * | 2000-10-06 | 2002-04-16 | Terunaito:Kk | Admixing agent for soil cement fluid and method for controlling the fluid |
| JP4562954B2 (en) * | 2001-06-20 | 2010-10-13 | 花王株式会社 | Additive for grout |
| JP4899007B2 (en) * | 2005-02-24 | 2012-03-21 | サンノプコ株式会社 | Fluidizer for soil cement |
| JP2010006701A (en) * | 2009-10-06 | 2010-01-14 | Nippon Shokubai Co Ltd | Method for producing cement admixture |
| JP5467859B2 (en) * | 2009-12-25 | 2014-04-09 | 花王株式会社 | Method for producing cement dispersant |
| CN105924592B (en) * | 2016-06-04 | 2020-09-01 | 石家庄市长安育才建材有限公司 | Viscosity-reducing polycarboxylic acid water reducer and preparation method thereof |
| JP7144304B2 (en) * | 2018-12-14 | 2022-09-29 | 株式会社日本触媒 | Composition for hydraulic material |
| JP7285737B2 (en) * | 2019-08-23 | 2023-06-02 | 株式会社日本触媒 | Dispersant for ground improvement cement composition, ground improvement cement composition, ground improvement body and ground improvement method |
| KR102487454B1 (en) * | 2020-06-05 | 2023-01-11 | 주식회사 맥테크놀로지 | Stabilizer for the cement solution for backfilling, cement composition for backfilling containing the same, and method for manufacturing thereof |
-
1994
- 1994-07-06 JP JP15483894A patent/JP3443454B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0812398A (en) | 1996-01-16 |
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