JP4761089B2 - Additive composition for cement - Google Patents
Additive composition for cement Download PDFInfo
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- JP4761089B2 JP4761089B2 JP21943499A JP21943499A JP4761089B2 JP 4761089 B2 JP4761089 B2 JP 4761089B2 JP 21943499 A JP21943499 A JP 21943499A JP 21943499 A JP21943499 A JP 21943499A JP 4761089 B2 JP4761089 B2 JP 4761089B2
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- 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
- C04B24/2664—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers
-
- 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
- C04B2103/0046—Polymers chosen for their physico-chemical characteristics added as monomers or as oligomers
- C04B2103/0047—Polymers chosen for their physico-chemical characteristics added as monomers or as oligomers as a mixture of nonomers and prepolymers or oligomers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/308—Slump-loss preventing agents
-
- 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
- C04B2111/34—Non-shrinking or non-cracking materials
Description
【０００１】
【発明の属する技術分野】
本発明はセメント用添加剤組成物に関し、さらに詳しくは、セメントペースト、モルタル、コンクリートなどのセメント組成物に添加することにより、高い減水性と高いスランプロス防止性を十分に発現させると同時に収縮低減性を付与するセメント用添加剤に関する。
【０００２】
【従来の技術】
一般に、コンクリート建造物の耐久性と強度の向上には、セメント組成物中の水量の低減が不可欠である。これまで、従来用いられているナフタレン系、リグニン系、メラミン系等の減水剤に比べて、高い減水性能や経時的に起こる流動性の低下であるスランプロスを防止するために、種々のポリカルボン酸系のセメント分散剤が提案されている。例えば、特開昭５７−１１８０５８号公報ではポリエチレングリコールモノアリルエーテル単量体とマレイン酸系単量体およびこれらの単量体と共重合可能な単量体を特定の比率で用いて導かれた共重合体を主成分とするセメント分散剤、また、特開昭６３−２８５１４０号公報ではポリオキシアルキレンモノアルケニルアルキルエーテルと無水マレイン酸との共重合体を主成分とするセメント分散剤等が提案されている。しかし、これらのポリカルボン酸系セメント分散剤でも、スランプロスを完全に解消することはできず、また打設されたセメント組成物の乾燥収縮の抑制に関しては不十分であるという欠点があった。
【０００３】
【発明が解決しようとする課題】
本発明は、高い減水性と高いスランプロス防止性を十分に発現させると同時に収縮低減性を付与するセメント用添加剤組成物を提供することを目的とするものである。
【０００４】
【課題を解決するための手段】
すなわち、本発明は、（ａ）式［１］で示されるポリオキシアルキレン誘導体の単位と（ｂ）無水マレイン酸、マレイン酸、マレイン酸塩、マレイン酸エステルから選ばれる単位とを必須単量体とし、（ａ）および（ｂ）の組成比がモル比で（ａ）：（ｂ）=３：７〜７：３であり、かつ重量平均分子量が５００〜１００，０００である共重合体（イ）と式［２］で示されるポリオキシアルキレン誘導体（ロ）とを含有し、その配合比が（イ）：（ロ）＝１００：１〜２：１であるセメント用添加剤組成物である。
【０００５】
【化３】
（ただし、式中Ｚ1は２個の水酸基をもつ化合物の残基、Ｒ1は炭素数２〜５のアルケニル基、Ｒ2は水素原子または炭素数１〜２４の炭化水素基、Ａ1Ｏは炭素数２〜３のオキシアルキレン基、ａおよびｂは炭素数２〜３のオキシアルキレン基の平均付加モル数であり、ａ＋ｂ＝１〜１００を満たす。）
【０００７】
【化４】
（ただし、式中Ｚ2は２個の水酸基をもつ化合物の残基、Ｒ3は炭素数２〜５のアルケニル基、Ｒ4は水素原子または炭素数１〜４の炭化水素基、Ａ2Ｏは炭素数２〜３のオキシアルキレン基、ｃおよびｄは炭素数２〜３のオキシアルキレン基の平均付加モル数であり、ｃ＋ｄ＝１〜１００を満たす。）
【０００９】
【発明の実施の形態】
（ａ）式［１］においてＺ1を残基とする２個の水酸基をもつ化合物としては、エチレングリコール、ポリエチレングリコール、プロピレングリコール、ポリプロピレングリコール、ブチレングリコール、ドデシレングリコール、オクタデシレングリコール、ネオペンチルグリコール、スチレングリコール等の２価アルコール；カテコール、レゾルシン、ヒドロキノン等の２価フェノールなどがあり、好ましくは炭素数２〜５の化合物である。
式［１］においてＲ1で示される炭素数２〜５のアルケニル基としては、ビニル基、アリル基、メタリル基、１，１−ジメチル−２−プロペニル基、３−メチル−３−ブテニル基等があり、これらは１種または２種以上を混合して用いてもよく、好ましくはアリル基またはメタリル基である。
【００１０】
式［１］においてＲ2で示される炭素数１〜２４の炭化水素基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、第二ブチル基、第三ブチル基、ペンチル基、イソペンチル基、ネオペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、イソトリデシル基、テトラデシル基、ヘキサデシル基、イソヘキサデシル基、オクタデシル基、イソオクタデシル基、オクチルドデシル基、ドコシル基、デシルテトラデシル基等の脂肪族飽和炭化水素基；シクロヘキシル基、メチルシクロヘキシル基等の脂環式飽和炭化水素基；シクロペンテニル基、シクロヘキセニル基等の脂環式不飽和炭化水素基；フェニル基、ベンジル基、クレジル基、ブチルフェニル基、ジブチルフェニル基、オクチルフェニル基、ノニルフェニル基、ドデシルフェニル基、ジオクチルフェニル基、ジノニルフェニル基、α−メチルベンジルフェニル基等の芳香族炭化水素基または置換芳香族炭化水素基があり、これらは１種または２種以上を混合して用いてもよく、好ましくはメチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、第二ブチル基、第三ブチル基であり、より好ましくはメチル基である。炭素数が２４を超えると、本発明における、分散性が低下するため好ましくない。
【００１１】
式［１］において、Ａ1Ｏで示される炭素数２〜３のオキシアルキレン基としては、オキシエチレン基およびオキシプロピレン基等であり、好ましくはオキシエチレン基がモル比で５０モル％以上であり、さらに好ましくはオキシエチレン基がモル比で９０モル％以上である。また、オキシアルキレン基が２種のときはブロック状またはランダム状のどのように結合していてもよい。
また、ａおよびｂは炭素数２〜３のオキシアルキレン基の平均付加モル数を表し、ａ＋ｂ＝１〜１００を満たし、好ましくはａ＋ｂ＝２０〜７０である。ａ＋ｂが１００より大きくなると式［１］で示されるポリオキシアルキレン化合物の製造が困難となるため好ましくない。
【００１２】
（ｂ）のマレイン酸系化合物としては、無水マレイン酸、マレイン酸、マレイン酸塩およびマレイン酸エステルなどがあり、好ましくは無水マレイン酸である。マレイン酸塩としては、リチウム、ナトリウム、カリウム等のアルカリ金属塩、アンモニウム塩、メチルアミン、ジメチルアミン、エチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、メチルエタノールアミン等のアミン塩が挙げられる。
【００１３】
また、共重合体（イ）は、ベンゾイルペルオキシド、ジ第三ブチルペルオキシド、クメンヒドロペルオキシド、ジクミルペルオキシド等の過酸化物系開始剤、あるいはアゾビスイソブチロニトリル、アゾビスメチルブチロニトリルなどのアゾ系開始剤を用いて共重合させることによって容易に得ることができる。その際、ベンゼン、トルエン、キシレン等の溶剤を用いることができる。また、水溶液中でも過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩等の開始剤を用いて共重合させることによっても容易に得ることができる。（ａ）と（ｂ）の組成比はモル比で３：７〜７：３であり、特に１：１が好ましい。
【００１４】
共重合体（イ）の重量平均分子量は、５００〜１００，０００であり、好ましくは１０，０００〜３０，０００である。重量平均分子量が５００より小さいかまたは１００，０００より大きいと分散性が低下するため好ましくない。
【００１５】
また、共重合体（イ）には、本発明の効果に影響を与えない程度で、他の共重合可能な単量体を共重合することができる。このような単量体としては、例えば、スチレン、酢酸ビニル、ビニルスルホン酸、アリルスルホン酸、メタリルスルホン酸、アクリル酸、メタクリル酸、およびそれらの塩、アクリルニトリル、メタクリルニトリル、アクリルアミド、メタクリルアミド、オレフィン等がある。
【００１６】
式［２］においてＺ2を残基とする２個の水酸基をもつ化合物としては、エチレングリコール、ポリエチレングリコール、プロピレングリコール、ポリプロピレングリコール、ブチレングリコール、ドデシレングリコール、オクタデシレングリコール、ネオペンチルグリコール、スチレングリコール等の２価アルコール；カテコール、レゾルシン、ヒドロキノン等の２価フェノールなどがあり、好ましくは炭素数２〜５の化合物である。
式［２］においてＲ3で示される炭素数２〜５のアルケニル基としては、ビニル基、アリル基、メタリル基、１，１−ジメチル−２−プロペニル基、３−メチル−３−ブテニル基等があり、これらは１種または２種以上を混合して用いてもよく、好ましくはアリル基またはメタリル基である。
【００１７】
式［２］においてＲ4で示される炭素数１〜４の炭化水素基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、第二ブチル基、第三ブチル基等の脂肪族飽和炭化水素基があり、これらは１種または２種以上を混合して用いてもよく、好ましくはメチル基である。炭素数が４を超えると、収縮低減効果が低下するため好ましくない。
【００１８】
式［２］において、Ａ2Ｏで示される炭素数２〜３のオキシアルキレン基としては、オキシエチレン基、オキシプロピレン基等があり、好ましくはオキシエチレン基がモル比で５０モル％以上であり、さらに好ましくはオキシエチレン基がモル比で９０モル％以上である。また、オキシアルキレン基が２種のときはブロック状またはランダム状のどのように結合していてもよい。
また、ｃおよびｄはオキシアルキレン基の平均付加モル数を表し、ｃ＋ｄ＝１〜１００、好ましくは２０〜７０である。ｃ＋ｄが１００より大きくなると式［２］で示されるポリオキシアルキレン化合物の製造が困難となるため好ましくない。
【００１９】
共重合体（イ）とポリオキシアルキレン誘導体（ロ）の配合比は（イ）：（ロ）＝１００：１〜２：１であり、（イ）：（ロ）＝１０：１〜３：１であることがより好ましい。（イ）：（ロ）が１００：１よりも（イ）の比率が大きくなると、本発明の効果は得られず、（イ）：（ロ）が２：１よりも（ロ）の比率が大きくなるとセメント用添加剤組成物としての減水性が低下してしまうため好ましくない。
【００２０】
本発明のセメント用添加剤組成物の使用量は、通常セメントに対して０．０１〜１．５重量％である。
本発明の添加剤は、セメント用の他の減水剤、ＡＥ減水剤、高性能減水剤、高性能ＡＥ減水剤のほか、消泡剤、空気連行剤、防錆剤、凝結促進剤、凝結遅延剤、分離低減剤、撥水剤、防凍剤等と併用することができる。
本発明のセメント用添加剤組成物をセメントに添加した際には、通常はセメント配合物１ｍ3あたりのセメント使用量、単位水量にはとりたてて制限はないが、単位水量１２０〜１８５ｋｇ／ｍ3、水／セメント重量比＝０．１５〜０．７、好ましくは単位水量１２０〜１７５ｋｇ／ｍ3、水／セメント重量比＝０．２〜０．６が推奨される。
【００２１】
【発明の効果】
本発明のセメント用添加剤は、セメントペースト、モルタル、コンクリートなどのセメント組成物に添加することにより、高い減水性と高いスランプロス防止性を十分に発現させると同時に収縮低減性を付与することができる。
【００２２】
【実施例】
実施例１
表１に示した配合で、普通ポルトランドセメント（太平洋セメント(株)製、比重３．１５）、神奈川県厚木産山砂（比重２．６５）および大分県津久見産砕石（比重２．６５）、表２に示した本発明のセメント添加剤組成物Ａ、およびコンクリート中の空気量が４．５±０．５％になるように消泡剤および空気連行剤を適宣調製して配合し、ＪＩＳ Ａ １１３８に準じてコンクリートを調製した。なお、練り混ぜ量は容量５０Ｌのパン型強制練りミキサを使用し、１バッチあたりのコンクリート量は３０Ｌとした。得られたコンクリートの試験項目および試験方法は以下の通りで、スランプ、圧縮強度および乾燥収縮の試験結果を表３に示す。
【００２３】
［スランプ］：ＪＩＳ Ａ １１０１「コンクリートのスランプ試験方法」に準拠し、練り混ぜ直後と６０分に測定した。
［圧縮強度］：ＪＩＳ Ａ １１０８「コンクリートの圧縮強度試験方法」に準拠し、打設翌日にキャッピング、翌々日に脱型、その後２８日まで２０℃水中養生とした。
［乾燥収縮］：ＪＩＳ Ａ １１２９「モルタルおよびコンクリートの長さ変化試験方法（コンタクトゲージ法）」に準拠し、材齢２４時間で脱型後、材齢７日まで２０℃水中養生を行い、基長を測定した。その後所定材齢まで２０℃、相対湿度６０％の気乾条件とした。
【００２４】
【表１】
【表２】
注．[ ／ ]は、ランダム状付加を示す。
【００２７】
実施例２〜６
セメント添加剤組成物を表２に示すように、Ｂ〜Ｆに変えた以外は実施例１と同様にしてコンクリートを作成し、同様の試験を行った。試験結果を表３に示す。
【００２８】
【表３】
＊セメントに対する重量比
【００３０】
比較例１
セメント用添加剤組成物を表２のＧに示すようにセメント用分散剤である共重合体（イ）のみを使用した以外は実施例１と同様にしてコンクリートを作成し、同様の試験を行った。試験結果を表３に示す。
【００３１】
比較例２
セメント用添加剤組成物を表２のＨに変えた以外は比較例１と同様にしてコンクリートを作成し、同様の試験を行った。試験結果を表３に示す。
表３の結果より、実施例１〜６のセメント添加剤組成物は比較例１〜２のセメント添加剤組成物に比べて、初期流動性が良好であり、かつスランプロス防止性に優れ、さらに乾燥初期から長期材齢にかけて乾燥収縮量が小さく、優れた収縮低減効果を示していることがわかる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an additive composition for cement, and more specifically, by adding it to a cement composition such as cement paste, mortar, concrete, etc., the present invention sufficiently exhibits high water reduction and high slump loss prevention and at the same time reduces shrinkage. The present invention relates to an additive for cement that imparts properties.
[0002]
[Prior art]
In general, it is indispensable to reduce the amount of water in a cement composition in order to improve the durability and strength of a concrete structure. In order to prevent slump loss, which is a high water-reducing performance and fluidity deterioration with time, compared to conventionally used water-reducing agents such as naphthalene-based, lignin-based, and melamine-based materials, various polycarboxylic acids are used. Acid-based cement dispersants have been proposed. For example, in Japanese Patent Application Laid-Open No. 57-118058, a polyethylene glycol monoallyl ether monomer, a maleic acid monomer, and a monomer copolymerizable with these monomers are used at a specific ratio. A cement dispersant mainly comprising a copolymer, and JP-A 63-285140 proposes a cement dispersant mainly comprising a copolymer of polyoxyalkylene monoalkenyl alkyl ether and maleic anhydride. Has been. However, even with these polycarboxylic acid type cement dispersants, the slump loss cannot be completely eliminated, and there is a drawback that it is insufficient for suppressing the drying shrinkage of the cast cement composition.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide an additive composition for cement that sufficiently exhibits high water reduction and high anti-slump loss and at the same time imparts shrinkage reduction.
[0004]
[Means for Solving the Problems]
That is, the present invention provides an essential monomer comprising (a) a unit of a polyoxyalkylene derivative represented by the formula [1] and (b) a unit selected from maleic anhydride, maleic acid, maleate and maleate. And a copolymer (a) and (b) having a molar ratio of (a) :( b) = 3: 7 to 7: 3 and a weight average molecular weight of 500 to 100,000 ( A cement additive composition comprising a) and a polyoxyalkylene derivative (B) represented by the formula [2], wherein the blending ratio is (A) :( B) = 100: 1 to 2: 1 is there.
[0005]
[Chemical 3]
(Wherein, Z 1 is a residue of a compound having two hydroxyl groups, R 1 is an alkenyl group having 2 to 5 carbon atoms, R 2 is a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms, A 1 O Is an oxyalkylene group having 2 to 3 carbon atoms, a and b are the average number of moles added of the oxyalkylene group having 2 to 3 carbon atoms, and a + b = 1 to 100 is satisfied.
[0007]
[Formula 4]
Wherein Z 2 is a residue of a compound having two hydroxyl groups, R 3 is an alkenyl group having 2 to 5 carbon atoms, R 4 is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, A 2 O Is an oxyalkylene group having 2 to 3 carbon atoms, c and d are the average number of added moles of the oxyalkylene group having 2 to 3 carbon atoms, and satisfies c + d = 1 to 100.)
[0009]
DETAILED DESCRIPTION OF THE INVENTION
(A) As a compound having two hydroxyl groups having Z 1 as a residue in the formula [1], ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, butylene glycol, dodecylene glycol, octadecylene glycol, Examples include dihydric alcohols such as neopentyl glycol and styrene glycol; dihydric phenols such as catechol, resorcin, and hydroquinone, and compounds having 2 to 5 carbon atoms are preferred.
Examples of the alkenyl group having 2 to 5 carbon atoms represented by R 1 in the formula [1] include a vinyl group, an allyl group, a methallyl group, a 1,1-dimethyl-2-propenyl group, and a 3-methyl-3-butenyl group. These may be used alone or in combination of two or more, and are preferably an allyl group or a methallyl group.
[0010]
Examples of the hydrocarbon group having 1 to 24 carbon atoms represented by R 2 in the formula [1] include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, Pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, isotridecyl group, tetradecyl group, hexadecyl group, isohexadecyl group, octadecyl group, isooctadecyl group Aliphatic saturated hydrocarbon groups such as octyldodecyl group, docosyl group and decyltetradecyl group; alicyclic saturated hydrocarbon groups such as cyclohexyl group and methylcyclohexyl group; alicyclic groups such as cyclopentenyl group and cyclohexenyl group Saturated hydrocarbon group: phenyl group, benzyl group, cresyl group, butylphenyl group, dibu There are aromatic hydrocarbon groups or substituted aromatic hydrocarbon groups such as ruphenyl group, octylphenyl group, nonylphenyl group, dodecylphenyl group, dioctylphenyl group, dinonylphenyl group, α-methylbenzylphenyl group, etc. Species or a mixture of two or more may be used, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, more preferably methyl It is a group. When the number of carbon atoms exceeds 24, dispersibility in the present invention is lowered, which is not preferable.
[0011]
In the formula [1], the oxyalkylene group having 2 to 3 carbon atoms represented by A 1 O includes an oxyethylene group and an oxypropylene group, and preferably the oxyethylene group is 50 mol% or more in a molar ratio. More preferably, the molar ratio of oxyethylene groups is 90 mol% or more. Further, when there are two kinds of oxyalkylene groups, they may be bonded in any form of block or random.
Moreover, a and b represent the average addition mole number of a C2-C3 oxyalkylene group, satisfy | fill a + b = 1-100, Preferably it is a + b = 20-70. When a + b is larger than 100, it is not preferable because it is difficult to produce the polyoxyalkylene compound represented by the formula [1].
[0012]
Examples of the maleic acid type compound (b) include maleic anhydride, maleic acid, maleate and maleate, and maleic anhydride is preferred. Examples of maleate include alkali metal salts such as lithium, sodium and potassium, ammonium salts, amine salts such as methylamine, dimethylamine, ethylamine, monoethanolamine, diethanolamine, triethanolamine and methylethanolamine.
[0013]
Copolymer (I) is a peroxide initiator such as benzoyl peroxide, di-tert-butyl peroxide, cumene hydroperoxide, dicumyl peroxide, azobisisobutyronitrile, azobismethylbutyronitrile, etc. It can be easily obtained by copolymerization using an azo initiator. At that time, a solvent such as benzene, toluene, xylene or the like can be used. It can also be easily obtained in an aqueous solution by copolymerization using an initiator such as persulfate such as sodium persulfate, potassium persulfate, and ammonium persulfate. The composition ratio of (a) and (b) is 3: 7 to 7: 3 in terms of molar ratio, and 1: 1 is particularly preferable.
[0014]
The weight average molecular weight of the copolymer (I) is 500 to 100,000, preferably 10,000 to 30,000. If the weight average molecular weight is less than 500 or more than 100,000, the dispersibility is lowered, which is not preferable.
[0015]
In addition, the copolymer (a) can be copolymerized with other copolymerizable monomers to such an extent that the effects of the present invention are not affected. Examples of such monomers include styrene, vinyl acetate, vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, acrylic acid, methacrylic acid, and salts thereof, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide. And olefins.
[0016]
In the formula [2], as the compound having two hydroxyl groups having Z 2 as a residue, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, butylene glycol, dodecylene glycol, octadecylene glycol, neopentyl glycol And dihydric alcohols such as styrene glycol; dihydric phenols such as catechol, resorcin, and hydroquinone, etc., preferably a compound having 2 to 5 carbon atoms.
Examples of the alkenyl group having 2 to 5 carbon atoms represented by R 3 in the formula [2] include a vinyl group, an allyl group, a methallyl group, a 1,1-dimethyl-2-propenyl group, and a 3-methyl-3-butenyl group. These may be used alone or in combination of two or more, and are preferably an allyl group or a methallyl group.
[0017]
Examples of the hydrocarbon group having 1 to 4 carbon atoms represented by R 4 in the formula [2] include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group, and a tertiary butyl group. These aliphatic saturated hydrocarbon groups may be used, and these may be used alone or in combination of two or more, preferably a methyl group. When the number of carbon atoms exceeds 4, the shrinkage reduction effect is lowered, which is not preferable.
[0018]
In the formula [2], the oxyalkylene group having 2 to 3 carbon atoms represented by A 2 O includes an oxyethylene group, an oxypropylene group and the like, and preferably the oxyethylene group is 50 mol% or more in molar ratio. More preferably, the molar ratio of oxyethylene groups is 90 mol% or more. Further, when there are two kinds of oxyalkylene groups, they may be bonded in any form of block or random.
C and d represent the average number of moles added of the oxyalkylene group, and c + d = 1 to 100, preferably 20 to 70. When c + d is larger than 100, it is not preferable because it is difficult to produce the polyoxyalkylene compound represented by the formula [2].
[0019]
The blending ratio of the copolymer (I) and the polyoxyalkylene derivative (B) is (A) :( B) = 100: 1 to 2: 1, and (A) :( B) = 10: 1 to 3: 1 is more preferable. When the ratio of (A) :( B) is greater than 100: 1, the effect of the present invention cannot be obtained, and the ratio of (B) is higher than (B) :( B) is 2: 1. When it becomes large, the water-reducing property as an additive composition for cement is lowered, which is not preferable.
[0020]
The usage-amount of the additive composition for cements of this invention is 0.01 to 1.5 weight% normally with respect to cement.
Additives of the present invention include other water reducing agents for cement, AE water reducing agents, high performance water reducing agents, high performance AE water reducing agents, antifoaming agents, air entraining agents, rust preventives, setting accelerators, setting delays It can be used in combination with an agent, a separation reducing agent, a water repellent, an antifreeze and the like.
When the additive composition for cement according to the present invention is added to cement, there is usually no limitation on the amount of cement used and the amount of unit water per 1 m 3 of the cement compound, but the unit water amount is 120 to 185 kg / m 3. Water / cement weight ratio = 0.15 to 0.7, preferably unit water amount 120 to 175 kg / m 3 , water / cement weight ratio = 0.2 to 0.6 is recommended.
[0021]
【The invention's effect】
The additive for cement of the present invention, when added to a cement composition such as cement paste, mortar, concrete, etc., can sufficiently exhibit high water reduction and high slump loss prevention and at the same time impart shrinkage reduction. it can.
[0022]
【Example】
Example 1
In the formulation shown in Table 1, ordinary Portland cement (manufactured by Taiheiyo Cement Co., Ltd., specific gravity 3.15), mountain sand from Atsugi, Kanagawa (specific gravity 2.65), and crushed stone from Tsukumi, Oita (specific gravity 2.65), table The cement additive composition A of the present invention shown in FIG. 2 and an antifoaming agent and an air entraining agent were appropriately prepared and blended so that the amount of air in the concrete was 4.5 ± 0.5%. Concrete was prepared according to A1138. In addition, the mixing amount used the bread type forced kneading mixer of a capacity | capacitance 50L, and the concrete amount per batch was 30L. The test items and test methods of the obtained concrete are as follows, and the test results of slump, compressive strength, and drying shrinkage are shown in Table 3.
[0023]
[Slump]: Measured according to JIS A 1101 “Concrete slump test method” immediately after kneading and 60 minutes.
[Compressive strength]: In accordance with JIS A 1108 “Concrete compressive strength test method”, capping was carried out on the next day after placing, demolding on the next day, and then curing at 20 ° C. until 28 days.
[Drying shrinkage]: In accordance with JIS A 1129 “Testing method for changing the length of mortar and concrete (contact gauge method)”, after demolding at a material age of 24 hours, water curing at 20 ° C. until the material age is 7 days. The length was measured. Thereafter, air-drying conditions of 20 ° C. and a relative humidity of 60% were set until a predetermined age.
[0024]
[Table 1]
[Table 2]
note. [/] Indicates random addition.
[0027]
Examples 2-6
As shown in Table 2, concrete was prepared in the same manner as in Example 1 except that the cement additive composition was changed to B to F, and the same test was performed. The test results are shown in Table 3.
[0028]
[Table 3]
* Weight ratio to cement [0030]
Comparative Example 1
Concrete was prepared in the same manner as in Example 1 except that only the copolymer (I), which is a cement dispersant, was used as the cement additive composition indicated by G in Table 2, and the same test was performed. It was. The test results are shown in Table 3.
[0031]
Comparative Example 2
Concrete was prepared in the same manner as in Comparative Example 1 except that the cement additive composition was changed to H in Table 2, and the same test was performed. The test results are shown in Table 3.
From the results in Table 3, the cement additive compositions of Examples 1 to 6 have better initial fluidity and superior slump loss prevention properties than the cement additive compositions of Comparative Examples 1 and 2, and It can be seen that the amount of drying shrinkage is small from the initial stage of drying to the long-term age, indicating an excellent shrinkage reducing effect.
Claims (1)
Ｈ２Ｃ＝ＣＨＣＨ２Ｏ(ＣＨ２ＣＨ２Ｏ)３４ＣＨ３ ［３］
Ｈ２Ｃ＝ＣＨＣＨ２Ｏ(ＣＨ２ＣＨ２Ｏ)６８ＣＨ３ ［４］
Ｈ２Ｃ＝ＣＨＣＨ２Ｏ[(ＣＨ２ＣＨ２Ｏ)４/(ＣＨ(ＣＨ３)ＣＨ２Ｏ)６ＣＨ３ ［５］(A) The polyoxyalkylene derivative unit represented by the formula [3] and the (b) maleic anhydride unit are essential monomers, and the composition ratio of (a) and (b) is a molar ratio of (a): (B) = 1: 1 and the copolymer (A) having a weight average molecular weight of 22,200 and the polyoxyalkylene derivative (B) represented by the formula [3], the blending ratio of (A): (ro) = 77: 23, or (a) a polyoxyalkylene derivative unit represented by formula [4] and (b) a maleic anhydride unit as essential monomers, (A) and (b) have a molar ratio of (a) :( b) = 1: 1 and a weight average molecular weight of 25,400 (i) and formula [5] The polyoxyalkylene derivative (B) shown in FIG. 1 is used, and the blending ratio is (A) :( B) = 72: 28 That consists of composition, cement additive composition.
H 2 C═CHCH 2 O (CH 2 CH 2 O) 34 CH 3 [3]
H 2 C═CHCH 2 O (CH 2 CH 2 O) 68 CH 3 [4]
H 2 C═CHCH 2 O [(CH 2 CH 2 O) 4 / (CH (CH 3 ) CH 2 O) 6 CH 3 [5]
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| US6911494B2 (en) | 2001-09-28 | 2005-06-28 | Nippon Shokubai Co., Ltd. | Cement admixture and cement composition |
| JP4056809B2 (en) * | 2002-07-09 | 2008-03-05 | 花王株式会社 | Powder shrinkage reducing agent |
| CN100542989C (en) | 2003-03-05 | 2009-09-23 | 株式会社日本触媒 | The method of cement additive, cement composition and laying method thereof and production hardening of cement product |
| JP2006522734A (en) | 2003-04-08 | 2006-10-05 | 株式会社日本触媒 | Cement admixture and cement composition |
| JP2006168997A (en) * | 2003-11-20 | 2006-06-29 | Mitani Sekisan Co Ltd | High-strength concrete-molded body and material to be charged in mold |
| JP4979135B2 (en) * | 2008-04-28 | 2012-07-18 | 竹本油脂株式会社 | Cement dispersant and cement composition |
| JP7291346B2 (en) * | 2019-03-12 | 2023-06-15 | 株式会社竹中工務店 | Admixture for hydraulic composition and hydraulic composition |
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| JP3342525B2 (en) * | 1992-02-14 | 2002-11-11 | ダブリュー・アール・グレース・アンド・カンパニー−コーン | Cement dispersant composition |
| JP2695087B2 (en) * | 1992-03-11 | 1997-12-24 | ダブリュー・アール・グレース・アンド・カンパニー−コーン | High fluidity concrete composition |
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| JP3306983B2 (en) * | 1993-03-16 | 2002-07-24 | 日本油脂株式会社 | Additive for cement |
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