JPH06100346A - Admixture for concrete - Google Patents

Admixture for concrete

Info

Publication number
JPH06100346A
JPH06100346A JP24923892A JP24923892A JPH06100346A JP H06100346 A JPH06100346 A JP H06100346A JP 24923892 A JP24923892 A JP 24923892A JP 24923892 A JP24923892 A JP 24923892A JP H06100346 A JPH06100346 A JP H06100346A
Authority
JP
Japan
Prior art keywords
concrete
formula
copolymer
group
hydrogen
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
Application number
JP24923892A
Other languages
Japanese (ja)
Other versions
JP3206982B2 (en
Inventor
Fujio Yamato
富士桜 倭
Ryoichi Tamaoki
良市 玉置
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kao Corp
Original Assignee
Kao Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kao Corp filed Critical Kao Corp
Priority to JP24923892A priority Critical patent/JP3206982B2/en
Publication of JPH06100346A publication Critical patent/JPH06100346A/en
Application granted granted Critical
Publication of JP3206982B2 publication Critical patent/JP3206982B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24Macromolecular compounds
    • C04B24/26Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/0068Ingredients with a function or property not provided for elsewhere in C04B2103/00
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/56Compositions suited for fabrication of pipes, e.g. by centrifugal casting, or for coating concrete pipes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PURPOSE:To reduce air bubbles by mixing a copolymer synthesized through polymerization of plural monomers each represented by a specified formula and/or its metal salt and a compound of a specified formula as the essential components. CONSTITUTION:A copolymer having 1000 to 1000000 weight-average molecular weight and/or its metal salt is obtained by polymerizing 10 to 99wt.% unsaturated bond-containing polyalkylene glycol monoester-based monomer represented by formula I [R3 to R4 are each H, methyl, (CH2)m2CO2M, formula II, etc.] and 90 to 1wt.% acrylic acid-and/or unsaturated dicarboxylic acid-based monomer represented by formula III or IV (AO is a 2 to 3C oxyalkylene; R5 and R8 are each H or methyl; R6 to R7 and R9 to R10 are each H, methyl, (CH2)m7 CO2M5; (m1 to m7) is each 0 to 2; (n1 to n5) is each 3 to 500; M3 and M5 are each H, a univalent metal, etc.; M4 and M6 are a divalent metal; X1 to X5 is H or a 1 to 3C alkyl]. As admixtures for concrete, the resultant copolymer and a compound represented by formula V (R1 to R2 are each H or a 8 to 18C alkyl; M1 to M2 are each an alkaline metal) are blended with cement respectively in an amount of 0,10 to 1.0wt.% and 0.0025 to 0.1wt.%.

Description

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

【0001】[0001]

【産業上の利用分野】本発明はコンクリート用混和剤、
さらに詳しくは遠心力によるコンクリート成型法におい
て、コンクリートの締め固め性を向上させ、締め固め時
間の短縮を可能にする混和剤に関するものである。
The present invention relates to a concrete admixture,
More specifically, the present invention relates to an admixture that improves the compaction property of concrete in a concrete molding method using centrifugal force and enables shortening of compaction time.

【0002】[0002]

【従来の技術】従来、パイル、ポール、ヒューム管等の
コンクリート製品は遠心力による締め固めを行い製造し
ている。これらの製品に使用されるコンクリートは強度
を確保するために、高性能減水剤、例えばナフタレン
系、メラミン系等の混和剤の添加が必須となっている。
2. Description of the Related Art Conventionally, concrete products such as piles, poles and fume pipes are manufactured by compaction by centrifugal force. In order to secure the strength of the concrete used in these products, it is essential to add a high-performance water reducing agent, for example, an admixture of naphthalene type, melamine type or the like.

【0003】[0003]

【発明が解決しようとする課題】しかし、高性能減水剤
を添加したコンクリートは一定の流動性(スランプ値)
の発現は可能であるが、コンクリートの粘性が高まり、
遠心力による締め固め性が低下する傾向にある。従っ
て、この問題を改善する混和剤、即ち、遠心成型に用い
られるコンクリートの流動性の向上と粘性の低下による
締め固め時間の短縮の両方が可能な混和剤が望まれてい
る。
However, the concrete to which the high-performance water reducing agent is added has a certain fluidity (slump value).
Is possible, but the viscosity of concrete increases,
The compaction property due to centrifugal force tends to decrease. Therefore, an admixture capable of improving this problem, that is, an admixture capable of both improving the fluidity of concrete used for centrifugal molding and shortening the compaction time by decreasing the viscosity is desired.

【0004】[0004]

【課題を解決するための手段】本発明者等は混和剤、界
面活性剤等によるコンクリートの流動性と粘性の関係を
鋭意研究の結果、特定の分散剤と低泡性で浸透力の強い
特定の界面活性剤を併用することにより、コンクリート
の流動性が高まり、しかもコンクリートの粘性を著しく
低下させ、遠心力による締め固め時間が短縮されること
を見出し、本発明を完成するに至った。
Means for Solving the Problems As a result of intensive studies on the relationship between the fluidity and the viscosity of concrete by admixtures, surfactants, etc., the present inventors have found that a specific dispersant and a low foaming agent having a strong penetrating power are specified. The inventors have found that the combined use of the above-mentioned surfactants enhances the fluidity of concrete, significantly reduces the viscosity of concrete, and shortens the compaction time by centrifugal force, and has completed the present invention.

【0005】即ち、本発明は(1) 下記(A) 、(B) に示さ
れた単量体を重合して得られる共重合体及び/又はその
共重合体の金属塩と、(2) 下記一般式(C) で表される化
合物を必須成分とするコンクリート用混和剤を提供する
ものである。 (A) 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。 (B) アクリル酸系単量体及び/又は不飽和ジカルボン酸
系単量体。
That is, the present invention comprises (1) a copolymer obtained by polymerizing the monomers shown in the following (A) and (B) and / or a metal salt of the copolymer, and (2) The present invention provides an admixture for concrete, which contains a compound represented by the following general formula (C) as an essential component. (A) Polyalkylene glycol monoester monomer having an unsaturated bond. (B) Acrylic acid-based monomer and / or unsaturated dicarboxylic acid-based monomer.

【0006】[0006]

【化5】 [Chemical 5]

【0007】本発明は、上記(A) 、(B) に示された単量
体を重合して得られる共重合体及び/又はその共重合体
の金属塩と前記一般式(C) で表される化合物を併用する
ことで、前述の如く、遠心コンクリートの流動性と粘性
を改善するものである。この効果は各々の成分の単独使
用では得られず、本発明のように両者を併用することに
より、初めて得られる。
The present invention provides a copolymer obtained by polymerizing the monomers shown in (A) and (B) above and / or a metal salt of the copolymer and the above-mentioned general formula (C). As described above, the combined use of the compound described above improves the fluidity and viscosity of the centrifugal concrete. This effect cannot be obtained by using each component alone, but can be obtained only by using both components together as in the present invention.

【0008】本発明において前記共重合体(1) を構成す
る単量体としては、単量体(A) が下記の一般式(I) 、単
量体(B) が下記の一般式(II)、(III) で表される単量体
群から選ばれる1種以上の単量体を使用するのが好まし
い。
In the present invention, as the monomer constituting the copolymer (1), the monomer (A) is the following general formula (I) and the monomer (B) is the following general formula (II). ) And (III), it is preferable to use at least one monomer selected from the group of monomers.

【0009】[0009]

【化6】 [Chemical 6]

【0010】〔式中、R3、R4:水素、メチル基、(CH2)
m2COOM3 、〔(CH2)m3COO〕2M4 、(CH2)m4CONH(AO)
n2X2
[In the formula, R 3 and R 4 are hydrogen, methyl group, and (CH 2 ).
m2 COOM 3 , ((CH 2 ) m3 COO) 2 M 4 , (CH 2 ) m4 CONH (AO)
n2 x 2 ,

【0011】[0011]

【化7】 [Chemical 7]

【0012】(CH2)m6COO(AO)n5X5 AO:炭素数2〜3のオキシアルキレン基 m1〜m6:0〜2の整数 n1〜n5:3〜500 の整数 M3:水素、1価金属、アンモニウム基、アミノ基又は置
換アミノ基 M4:2価金属 X1〜X5:水素、炭素数1〜3のアルキル基〕
(CH 2 ) m6 COO (AO) n5 X 5 AO: an oxyalkylene group having 2 to 3 carbon atoms m 1 to m 6 : an integer of 0 to 2 n 1 to n 5 : an integer of 3 to 500 M 3 : hydrogen, a monovalent metal, an ammonium group, an amino group or a substituted amino group M 4: 2-valent metal X 1 to X 5: hydrogen, an alkyl group having 1 to 3 carbon atoms]

【0013】[0013]

【化8】 [Chemical 8]

【0014】〔式中、R5、R8:水素、メチル基 R6、R7、R9、R10 :水素、メチル基、又は(CH2)m7COOM5 M5:水素、1価金属、アンモニウム基、アミノ基又は置
換アミノ基 M6:2価金属 m7:0〜2の整数〕。
[In the formula, R 5 , R 8 : hydrogen, methyl group R 6 , R 7 , R 9 , R 10 : hydrogen, methyl group, or (CH 2 ) m7 COOM 5 M 5 : hydrogen, monovalent metal , An ammonium group, an amino group or a substituted amino group M 6 : a divalent metal m 7 : an integer of 0 to 2].

【0015】本発明に用いられる単量体(A) のポリアル
キレングリコールモノエステルとしては、例えば、 トリエチレングリコールモノアクリレート(以下3E-Aと
称す) ポリエチレングリコール(分子量200)モノアクリレート
(以下4E-Aと称す) ポリエチレングリコール(分子量400)モノアクリレート
(以下9E-Aと称す) ポリエチレングリコール(分子量600)モノアクリレート
(以下14E-A と称す) ポリエチレングリコール(分子量1000)モノアクリレー
ト(以下23E-A と称す) ポリエチレングリコール(分子量2000)モノアクリレー
ト(以下46E-A と称す) ポリエチレングリコール(分子量4000)モノアクリレー
ト(以下92E-A と称す) ポリエチレングリコール(分子量6000)モノアクリレー
ト(以下138E-Aと称す) トリエチレングリコールモノメタクリレート(以下3E-M
A と称す) ポリエチレングリコール(分子量200)モノメタクリレー
ト(以下4E-MA と称す) ポリエチレングリコール(分子量400)モノメタクリレー
ト(以下9E-MA と称す) ポリエチレングリコール(分子量600)モノメタクリレー
ト(以下14E-MAと称す) ポリエチレングリコール(分子量1000)モノメタクリレー
ト(以下23E-MAと称す) ポリエチレングリコール(分子量2000)モノメタクリレー
ト(以下46E-MAと称す) ポリエチレングリコール(分子量4000)モノメタクリレー
ト(以下92E-MAと称す) ポリエチレングリコール(分子量6000) モノメタクリレ
ート(以下138E-MAと称す) 等のポリエチレングリコールモノエステル類、ポリプロ
ピレンオキサイドモノエステル類、ポリエチレングリコ
ール/ポリプロピレンオキサイド共重合物のモノエステ
ル類及びこれらのグリコール末端の水素をエーテル化し
た誘導体等が挙げられるが、アルキレングリコールの付
加モル数の増大に伴い反応性が低下するため、付加モル
数 500以下のポリアルキレングリコールモノエステル
類、及びこれらのグリコール末端の水素をエーテル化し
た誘導体が好ましい。
Examples of the polyalkylene glycol monoester of the monomer (A) used in the present invention include triethylene glycol monoacrylate (hereinafter referred to as 3E-A) polyethylene glycol (molecular weight 200) monoacrylate (hereinafter referred to as 4E-A). Polyethylene glycol (molecular weight 400) monoacrylate (hereinafter referred to as 9E-A) Polyethylene glycol (molecular weight 600) monoacrylate (hereinafter referred to as 14E-A) Polyethylene glycol (molecular weight 1000) monoacrylate (hereinafter referred to as 23E-A) Polyethylene glycol (molecular weight 2000) monoacrylate (hereinafter referred to as 46E-A) Polyethylene glycol (molecular weight 4000) monoacrylate (hereinafter referred to as 92E-A) Polyethylene glycol (molecular weight 6000) monoacrylate (hereinafter referred to as 138E-A) Triethylene glycol monomethacrylate (Following 3E-M
Polyethylene glycol (molecular weight 200) monomethacrylate (hereinafter referred to as 4E-MA) Polyethylene glycol (molecular weight 400) monomethacrylate (hereinafter referred to as 9E-MA) Polyethylene glycol (molecular weight 600) monomethacrylate (hereinafter referred to as 14E-MA) Polyethylene glycol (molecular weight 1000) monomethacrylate (hereinafter referred to as 23E-MA) Polyethylene glycol (molecular weight 2000) monomethacrylate (hereinafter referred to as 46E-MA) Polyethylene glycol (molecular weight 4000) monomethacrylate (hereinafter referred to as 92E-MA) Polyethylene glycol (molecular weight 6000) Monomethacrylate (hereinafter referred to as 138E-MA) and other polyethylene glycol monoesters, polypropylene oxide monoesters, polyethylene glycol / polypropylene oxide copolymer monoesters and glycos thereof Examples include etherified derivatives of hydrogen at the terminal end, but since the reactivity decreases as the number of moles of alkylene glycol added increases, polyalkylene glycol monoesters with a number of moles of addition of 500 or less, and those glycol terminals The etherified derivative of hydrogen is preferred.

【0016】ポリアルキレングリコールモノエステルを
合成する際の不飽和結合を有する酸としては、アクリル
酸、メタクリル酸、及びクロトン酸等のカルボン酸系、
マレイン酸、フマル酸、イタコン酸、シトラコン酸等の
ジカルボン酸及び誘導体(不飽和アミド類)系、ビニル
スルホン酸、アリルスルホン酸、スルホエチル(メタ)
アクリル酸及びスチレンスルホン酸等のスルホン酸系が
挙げられ、これらの群から選ばれた1種又は2種以上を
用いることができるが、モノカルボン酸系、ジカルボン
酸及びその誘導体系がより好ましい。
As the acid having an unsaturated bond at the time of synthesizing the polyalkylene glycol monoester, carboxylic acids such as acrylic acid, methacrylic acid and crotonic acid,
Maleic acid, fumaric acid, itaconic acid, citraconic acid and other dicarboxylic acids and derivatives (unsaturated amides), vinyl sulfonic acid, allyl sulfonic acid, sulfoethyl (meth)
Examples thereof include sulfonic acid type such as acrylic acid and styrene sulfonic acid, and one or more selected from these groups can be used, but monocarboxylic acid type, dicarboxylic acid and its derivative type are more preferable.

【0017】本発明に用いられる単量体(B) のアクリル
酸系単量体としては、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。又、不飽和ジ
カルボン酸系単量体としては、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、又はこれらの金属塩、ア
ンモニウム塩、アミン塩、あるいはこれらの酸と炭素数
2〜3のポリアルキレングリコール(グリコール付加モ
ル数2〜500)とのモノエステルあるいはジエステルが挙
げられる。
Examples of the acrylic acid type monomer of the monomer (B) used in the present invention include acrylic acid, methacrylic acid, crotonic acid and metal salts thereof. Further, as the unsaturated dicarboxylic acid-based monomer, maleic anhydride, maleic acid, itaconic anhydride, itaconic acid, citraconic anhydride, citraconic acid, fumaric acid, or their metal salts, ammonium salts, amine salts, or, Examples thereof include monoesters or diesters of these acids and polyalkylene glycols having 2 to 3 carbon atoms (glycol addition mole number 2 to 500).

【0018】本発明の共重合体中の単量体 (A)、(B) の
割合(重量%)は、 (A):(B) =10〜99:90〜1の範囲
が適しており、より好ましくは、 (A):(B) =40〜99:
60〜1の範囲がよい。(A) の単量体割合が10%以下にな
ると、一般式(C) で表される化合物と併用しても充分な
気泡低減効果は得られない。
The proportion (% by weight) of the monomers (A) and (B) in the copolymer of the present invention is preferably in the range of (A) :( B) = 10 to 99:90 to 1. , And more preferably (A) :( B) = 40 to 99:
A range of 60 to 1 is good. When the monomer ratio of (A) is 10% or less, a sufficient effect of reducing bubbles cannot be obtained even when used in combination with the compound represented by the general formula (C).

【0019】本発明の共重合体(1) 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、1000〜1000000
の範囲が良く、5000〜500000がより好ましい。重量平均
分子量が、1000未満では分散性が充分でない。また、10
00000 を超えると凝集性が顕著になるため好ましくな
い。
The weight average molecular weight (gel permeation chromatography / sodium polystyrene sulfonate conversion) of the copolymer (1) of the present invention is from 1000 to 100000.
The range is good, and 5000 to 500000 is more preferable. When the weight average molecular weight is less than 1000, the dispersibility is insufficient. Also, 10
If it exceeds 00000, cohesiveness becomes remarkable, which is not preferable.

【0020】本発明の共重合体(1) 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59−162163
号公報、特公平2− 11542号公報、特公平2−7901号公
報、特公平2−7897号公報等に記載の方法が挙げられ
る。
The copolymer (1) of the present invention can be produced by a known method. For example, JP-A-59-162163
The methods described in Japanese Patent Publication No. 2-11542, Japanese Patent Publication No. 27901 and Japanese Patent Publication No. 27897 are cited.

【0021】これらの製造法により得られた共重合体の
単独の使用では、本発明の目的とする粘性の低下効果を
示さない。本発明では更に一般式(C) で表される化合物
の1種又は2種以上が使用される。一般式(C) で表され
る化合物は、式中のR 、R'がH 又は炭素数8〜18の飽和
アルキル基であり、アルキルジフェニルエーテルスルホ
ン酸塩である。
The use of the copolymers obtained by these production methods alone does not show the effect of decreasing the viscosity which is the object of the present invention. In the present invention, one or more compounds represented by the general formula (C) are used. The compound represented by the general formula (C) is an alkyldiphenyl ether sulfonate in which R and R'in the formula are H or a saturated alkyl group having 8 to 18 carbon atoms.

【0022】本発明のコンクリート用混和剤を用いたコ
ンクリートの遠心成型時の重力加速度は3G〜60Gの範
囲が好ましく、5G〜30Gの範囲がより最適である。
The gravity acceleration during centrifugal molding of concrete using the admixture for concrete of the present invention is preferably in the range of 3G to 60G, more preferably in the range of 5G to 30G.

【0023】本発明の混和剤のコンクリートへの添加量
はセメント重量に対して、(1) の共重合体及び/又はそ
の塩が0.10〜1.0 %、一般式(C) で表される化合物が0.
0025〜0.1 %の範囲が好まして、この範囲において特に
粘性低下による締め固め時間が短縮される。
The amount of the admixture of the present invention added to concrete is 0.10 to 1.0% of the copolymer of (1) and / or a salt thereof, and the compound represented by the general formula (C) is based on the weight of cement. 0.
A range of 0.1 to 0.1% is preferred, in which range compaction time due to reduced viscosity is particularly shortened.

【0024】本発明の混和剤は、遠心力による締め固め
を行うコンクリートに使用するもので、成型されるコン
クリート製品は、土木、建築、二次製品等、用途を特に
限定するものではない。
The admixture of the present invention is used for concrete which is compacted by centrifugal force, and the concrete product to be molded is not particularly limited in its use such as civil engineering, construction, secondary products and the like.

【0025】本発明の混和剤には公知の消泡剤や添加剤
(材)を併用することができる。例えば、AE剤、AE
減水剤、流動化剤、高性能減水剤、遅延剤、早強剤、促
進剤、起泡剤、発泡剤、保水剤、増粘剤、防水剤、防泡
剤、水溶性高分子、界面活性剤等や、セメントペース
ト、モルタル、コンクリートを構成するセメント類、高
炉スラグ、フライアッシュ、シリカヒューム等を使用す
る水硬性組成物が挙げられる。
Known antifoaming agents and additives (materials) can be used in combination with the admixture of the present invention. For example, AE agent, AE
Water-reducing agent, superplasticizer, high-performance water-reducing agent, retarder, early-strengthening agent, accelerator, foaming agent, foaming agent, water retention agent, thickener, waterproofing agent, antifoaming agent, water-soluble polymer, surfactant Examples thereof include agents and the like, cement paste, mortar, cements constituting concrete, blast furnace slag, fly ash, and hydraulic composition using silica fume.

【0026】[0026]

【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、例
中、「%」及び「部」は特記しない限り重量基準であ
る。
EXAMPLES The present invention will be specifically described below, but the present invention is not limited to these examples. In the examples, “%” and “part” are based on weight unless otherwise specified.

【0027】本発明に使用する混和剤成分のうち、単量
体(A) 、(B) からの共重合体(1) の製造法を以下に示
す。
Among the admixture components used in the present invention, a method for producing the copolymer (1) from the monomers (A) and (B) is shown below.

【0028】製造例1(共重合体AB−1の製造) 攪拌機付き反応容器に水 265部を仕込み、攪拌しながら
窒素置換し、窒素雰囲気中で60℃迄昇温した。ポリエチ
レングリコールモノメタクリレート(9E−ME)50部、メ
タクリル酸ナトリウム50部を仕込み、30%水酸化ナトリ
ウム水溶液2部でpH9に調整した。窒素置換後、25%過
硫酸アンモニウム水溶液10部を添加し重合を開始する。
3時間反応させ重合完了後、30%水酸化ナトリウム水溶
液3部で完全中和させ、分子量7500の共重合体(AB−
1)を得た。
Production Example 1 (Production of Copolymer AB-1) 265 parts of water was charged into a reaction vessel equipped with a stirrer, nitrogen substitution was carried out with stirring, and the temperature was raised to 60 ° C. in a nitrogen atmosphere. 50 parts of polyethylene glycol monomethacrylate (9E-ME) and 50 parts of sodium methacrylate were charged, and the pH was adjusted to 9 with 2 parts of 30% sodium hydroxide aqueous solution. After purging with nitrogen, 10 parts of 25% ammonium persulfate aqueous solution is added to start polymerization.
After reaction for 3 hours and completion of polymerization, the mixture was completely neutralized with 3 parts of a 30% aqueous sodium hydroxide solution to give a copolymer having a molecular weight of 7500 (AB-
1) was obtained.

【0029】製造例2(共重合体AB−2の製造) 攪拌機付き反応容器に水 150部を仕込み、攪拌しながら
窒素置換し、窒素雰囲気中で60℃迄昇温した。ポリエチ
レングリコールモノアクリレート(92E −A)60部、メタ
クリル酸ナトリウム40部を仕込み、30%水酸化ナトリウ
ム水溶液2部でpH9に調整した。窒素置換後、15%過硫
酸アンモニウム水溶液20部を添加し重合を開始する。3
時間反応させ重合完了後、30%水酸化ナトリウム水溶液
3部で完全中和させ、分子量32500 の共重合体(AB−
2)を得た。
Production Example 2 (Production of Copolymer AB-2) A reaction vessel equipped with a stirrer was charged with 150 parts of water, the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to 60 ° C. in a nitrogen atmosphere. 60 parts of polyethylene glycol monoacrylate (92E-A) and 40 parts of sodium methacrylate were charged, and the pH was adjusted to 9 with 2 parts of 30% sodium hydroxide aqueous solution. After purging with nitrogen, 20 parts of 15% ammonium persulfate aqueous solution is added to start polymerization. Three
After reaction for a period of time and completion of polymerization, the mixture was completely neutralized with 3 parts of a 30% aqueous sodium hydroxide solution to give a copolymer having a molecular weight of 32500 (AB-
2) was obtained.

【0030】製造例3(共重合体AB−3の製造) 攪拌機付き反応容器にイソプロピルアルコール 265部を
仕込み、攪拌しながら窒素置換し、窒素雰囲気中で沸点
迄昇温した。ポリエチレングリコールモノメタクリレー
ト(92E−MA)80部、アクリル酸ナトリウム20部を仕込
み、30%水酸化ナトリウム水溶液2部でpH8に調整し
た。窒素置換後、ベンゾイルパーオキサイドの10%イソ
プロピルアルコール溶液30部を添加し重合を開始する。
5時間反応させ重合を完了後、30%水酸化ナトリウム水
溶液3部で完全中和させ、分子量460000の共重合体(AB
−3)を得た。
Production Example 3 (Production of Copolymer AB-3) A reaction vessel equipped with a stirrer was charged with 265 parts of isopropyl alcohol, the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to the boiling point in a nitrogen atmosphere. 80 parts of polyethylene glycol monomethacrylate (92E-MA) and 20 parts of sodium acrylate were charged, and the pH was adjusted to 8 with 2 parts of 30% sodium hydroxide aqueous solution. After purging with nitrogen, 30 parts of a 10% isopropyl alcohol solution of benzoyl peroxide is added to start polymerization.
After reacting for 5 hours to complete the polymerization, the mixture was completely neutralized with 3 parts of 30% sodium hydroxide aqueous solution to give a copolymer having a molecular weight of 460000 (AB
-3) was obtained.

【0031】製造例4(共重合体AB−4の製造) 攪拌機付き反応容器に水 100部及びイソプロピルアルコ
ール70部を仕込み、攪拌しながら窒素置換し、窒素雰囲
気中で沸点迄昇温した。ポリエチレングリコールモノア
クリレート(14E −A )50部、ポリエチレングリコール
モノメタクリレート(14E−MA) 20部、アクリル酸ナトリ
ウム15部、メタクリル酸ナトリウム15部を仕込み、25%
水酸化ナトリウム水溶液1部でpH 7.5に調整した。窒素
置換後、20%過硫酸アンモニウム水溶液10部を添加し重
合を開始する。6時間反応させ重合を完了後、30%水酸
化ナトリウム水溶液3部で完全中和させ、分子量69000
の共重合体(AB−4)を得た。
Production Example 4 (Production of Copolymer AB-4) 100 parts of water and 70 parts of isopropyl alcohol were charged into a reaction vessel equipped with a stirrer, and the atmosphere was replaced with nitrogen while stirring, and the temperature was raised to the boiling point in a nitrogen atmosphere. Charge 50 parts of polyethylene glycol monoacrylate (14E-A), 20 parts of polyethylene glycol monomethacrylate (14E-MA), 15 parts of sodium acrylate, 15 parts of sodium methacrylate, 25%
The pH was adjusted to 7.5 with 1 part of an aqueous sodium hydroxide solution. After purging with nitrogen, 10 parts of 20% ammonium persulfate aqueous solution is added to start polymerization. After reacting for 6 hours to complete the polymerization, completely neutralize with 3 parts of 30% aqueous sodium hydroxide solution to give a molecular weight of 69000.
A copolymer (AB-4) of was obtained.

【0032】また、実施例に使用した一般式(C) のアル
キルジフェニルエーテルスルホン酸塩を以下に示す。
The alkyl diphenyl ether sulfonate of the general formula (C) used in the examples is shown below.

【0033】[0033]

【化9】 [Chemical 9]

【0034】コンクリート配合の使用材料Materials used for concrete mixing

【0035】[0035]

【表1】 [Table 1]

【0036】使用材料 W :水道水 C :中央普通ポルトランドセメント 比重=3.16 S :紀の川産川砂 比重=2.56 G :宝塚産砕石 比重=2.62 s/a :砂/砂+砂利(容積率) コンクリート物性の試験方法 表1に示すコンクリートの配合で本発明の混和剤と比較
の混和剤を添加してスランプ3±1cmに調整した。その
後、φ20cm、高さ30cmの型枠にコンクリートを13kg投入
して、遠心締め固めを行なった。締め固め時間による硬
化コンクリートの強度測定とコンクリート締り程度を肉
眼で観察した。 ・遠心条件 重力加速度5Gで1分、次いで15Gで2分、次いで30G
で2分後、4分後、6分後の性能を確認した。 ・コンクリート締り程度 ×:砂利の露出、内面、外面の平滑性が著しく悪い △:内面、外面の平滑性がやや悪い ○:平滑に締まっている 試験結果を表2に示す。
Materials used W: Tap water C: Central ordinary Portland cement Specific gravity = 3.16 S: Kinoko's river sand Specific gravity = 2.56 G: Takarazuka crushed stone Specific gravity = 2.62 s / a: Sand / sand + gravel (volume ratio) Concrete physical properties Test method In the concrete composition shown in Table 1, the admixture of the present invention and a comparative admixture were added to adjust the slump to 3 ± 1 cm. After that, 13 kg of concrete was put into a mold having a diameter of 20 cm and a height of 30 cm, and centrifugal compaction was performed. The strength of the hardened concrete was measured by the compaction time and the degree of compaction of the concrete was visually observed.・ Centrifugal condition Gravity acceleration 5G for 1 minute, then 15G for 2 minutes, then 30G
The performance was confirmed after 2 minutes, 4 minutes, and 6 minutes.・ Concrete tightness x: Exposed gravel, remarkably poor smoothness on inner and outer surfaces △: Slightly poor smoothness on inner and outer surfaces ○: Smoothly tightened Test results are shown in Table 2.

【0037】[0037]

【表2】 [Table 2]

【0038】注) *1:前記遠心条件の30Gの遠心時間4分の試験体の28
日後の強度 *2:ナフタレンスルホン酸ホルマリン縮合物ナトリウ
ム塩(マイティ150 、花王 (株) 製) *3:コンクリート流動効果がなく、所定のスランプが
得られない。
Note) * 1: 28 of the test body under the above-mentioned centrifugation conditions of 30 G for 4 minutes.
Strength after day * 2: Naphthalenesulfonic acid formalin condensate sodium salt (Mighty 150, manufactured by Kao Co., Ltd.) * 3: There is no concrete flow effect and the prescribed slump cannot be obtained.

【0039】[0039]

【発明の効果】本発明の混和剤は、遠心力によるコンク
リート成型法により製造されたコンクリート製品の表面
気泡の低減が顕著であり、表面美観性が著しく改善され
ることから、コンクリート構造物の表面補修作業の合理
化が可能となる。
EFFECTS OF THE INVENTION The admixture of the present invention is remarkably reduced in surface bubbles of a concrete product produced by a concrete molding method by centrifugal force, and the surface aesthetic appearance is remarkably improved. It enables rationalization of repair work.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 FI 技術表示箇所 C08L 33/02 LHR 7921−4J 35/00 LHR 7921−4J 71/02 LQC 9167−4J ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical display location C08L 33/02 LHR 7921-4J 35/00 LHR 7921-4J 71/02 LQC 9167-4J

Claims (4)

【特許請求の範囲】[Claims] 【請求項1】 (1) 下記(A) 、(B) に示された単量体を
重合して得られる共重合体及び/又はその共重合体の金
属塩と、(2) 下記一般式(C) で表される化合物を必須成
分とするコンクリート用混和剤。 (A) 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。 (B) アクリル酸系単量体及び/又は不飽和ジカルボン酸
系単量体。 【化1】
1. A copolymer obtained by polymerizing the monomers shown in the following (A) and (B) and / or a metal salt of the copolymer, and (2) the following general formula: An admixture for concrete, which contains the compound represented by (C) as an essential component. (A) Polyalkylene glycol monoester monomer having an unsaturated bond. (B) Acrylic acid-based monomer and / or unsaturated dicarboxylic acid-based monomer. [Chemical 1]
【請求項2】 重力加速度3G〜60Gの遠心力を加えて
成型するコンクリートに用いることを特徴とする請求項
1記載のコンクリート用混和剤。
2. The admixture for concrete according to claim 1, which is used for concrete which is molded by applying a centrifugal force of gravity acceleration of 3 G to 60 G.
【請求項3】 単量体(A) が下記の一般式(I) 、単量体
(B) が下記の一般式(II)、(III) で表される単量体群か
ら選ばれる1種以上の単量体である請求項1又は2記載
のコンクリート用混和剤。 【化2】 〔式中、R3、R4:水素、メチル基、(CH2)m2COOM3
〔(CH2)m3COO〕2M4 、(CH2)m4CONH(AO)n2X2、 【化3】 (CH2)m6COO(AO)n5X5 AO:炭素数2〜3のオキシアルキレン基 m1〜m6:0〜2の整数 n1〜n5:3〜500 の整数 M3:水素、1価金属、アンモニウム基、アミノ基又は置
換アミノ基 M4:2価金属 X1〜X5:水素、炭素数1〜3のアルキル基〕 【化4】 〔式中、R5、R8:水素、メチル基 R6、R7、R9、R10 :水素、メチル基、又は(CH2)m7COOM5 M5:水素、1価金属、アンモニウム基、アミノ基又は置
換アミノ基 M6:2価金属 m7:0〜2の整数〕
3. The monomer (A) is represented by the following general formula (I):
The admixture for concrete according to claim 1 or 2, wherein (B) is at least one monomer selected from the group of monomers represented by the following general formulas (II) and (III). [Chemical 2] (In the formula, R 3 and R 4 : hydrogen, methyl group, (CH 2 ) m 2 COOM 3 ,
[(CH 2 ) m3 COO] 2 M 4 , (CH 2 ) m4 CONH (AO) n2 X 2 , [Chemical Formula 3] (CH 2 ) m6 COO (AO) n5 X 5 AO: an oxyalkylene group having 2 to 3 carbon atoms m 1 to m 6 : an integer of 0 to 2 n 1 to n 5 : an integer of 3 to 500 M 3 : hydrogen, Monovalent metal, ammonium group, amino group or substituted amino group M 4 : divalent metal X 1 to X 5 : hydrogen, alkyl group having 1 to 3 carbon atoms] [In the formula, R 5 , R 8 : hydrogen, methyl group R 6 , R 7 , R 9 , R 10 : hydrogen, methyl group, or (CH 2 ) m7 COOM 5 M 5 : hydrogen, monovalent metal, ammonium group , Amino group or substituted amino group M 6 : divalent metal m 7 : integer of 0 to 2]
【請求項4】 請求項1記載の(1) の共重合体及び/又
はその共重合体の塩のセメントへの添加量が固形分量と
して0.10〜1.0 重量%、前記一般式(C) で表される化合
物のセメントへの添加量が固形分量として0.0025〜0.1
重量%であることを特徴とする請求項1〜3の何れか1
項記載のコンクリート用混和剤。
4. The amount of the copolymer of (1) and / or the salt of the copolymer according to claim 1 added to cement is 0.10 to 1.0% by weight as a solid content, which is represented by the general formula (C). The amount of compound added to cement is 0.0025-0.1 as solid content.
It is weight%, Any one of Claims 1-3 characterized by the above-mentioned.
Admixture for concrete according to the item.
JP24923892A 1992-09-18 1992-09-18 Admixture for concrete Expired - Lifetime JP3206982B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP24923892A JP3206982B2 (en) 1992-09-18 1992-09-18 Admixture for concrete

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP24923892A JP3206982B2 (en) 1992-09-18 1992-09-18 Admixture for concrete

Publications (2)

Publication Number Publication Date
JPH06100346A true JPH06100346A (en) 1994-04-12
JP3206982B2 JP3206982B2 (en) 2001-09-10

Family

ID=17189985

Family Applications (1)

Application Number Title Priority Date Filing Date
JP24923892A Expired - Lifetime JP3206982B2 (en) 1992-09-18 1992-09-18 Admixture for concrete

Country Status (1)

Country Link
JP (1) JP3206982B2 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001253750A (en) * 2000-03-08 2001-09-18 Kao Corp Concrete composition for centrifugal forming
JP2008007351A (en) * 2006-06-28 2008-01-17 Kao Corp Hydraulic composition for centrifugally molded hardened body

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001253750A (en) * 2000-03-08 2001-09-18 Kao Corp Concrete composition for centrifugal forming
JP4554023B2 (en) * 2000-03-08 2010-09-29 花王株式会社 Concrete composition for centrifugal molding
JP2008007351A (en) * 2006-06-28 2008-01-17 Kao Corp Hydraulic composition for centrifugally molded hardened body

Also Published As

Publication number Publication date
JP3206982B2 (en) 2001-09-10

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