JP4425581B2 - Additive for poor blended concrete - Google Patents

Description

【００２４】
〔式中、Ｒ¹は炭素数８〜２２のアルキル基もしくはアルケニル基、又は２以上のベンゼン環を有する炭化水素基、ＡＯは炭素数２〜４のオキシアルキレン基、ｎは平均付加モル数であり１〜５０の数を示す。ｋは１又は２、Ｍは水素原子、アルカリ金属、アルカリ土類金属、アンモニウム基、アルキルアンモニウム基又は水酸基置換アルキルアンモニウム基を示す。〕
【００２５】
一般式（１−１）において、ｋが１のときの２個のＭ、ｋが２のときの２個のＲ¹とｎは、ぞれぞれ異なっていてもよい。
【００２６】
（Ａ）成分は、リン原子に結合する一般式（１）で表される基を有するリン酸のモノエステルもしくはジエステル又はこれらの塩である。そして、本発明の添加剤を水溶液にした場合の製品安定性の観点から、モノエステル体とジエステル体（ジエステル体にはピロリン酸のジエステル体を含む）の重量比は、モノエステル体／（モノエステル体＋ジエステル体）で０．４〜０．９５であり、貧配合コンクリートの流動性および添加剤水溶液のポンプ輸送性の観点から、好ましくは０．５〜０．９５、より好ましくは０．６５〜０．９５、さらに好ましくは０．７〜０．９５であり、さらに工業的な製造容易性の観点から、特に好ましくは０．７〜０．８５である。
【００２７】
また、本発明の貧配合コンクリート用添加剤は、（Ａ）成分（モノエステル体とジエステル体）以外に、一般式（１）で表される基を有するリン酸のトリエステル（以下、トリエステル体という）を含有していてもよい。（Ａ）成分が上記のモノエステル体とジエステル体の比率と後述の本発明の貧配合コンクリート用添加剤中の含有量を満たせば、トリエステル体の比率や量は特に限定されないが、（モノエステル体＋ジエステル体）／（モノエステル体＋ジエステル体＋トリエステル体）の重量比は、好ましくは０．７以上、更に好ましくは０．８以上である。
【００２８】
なお、（Ａ）成分は、上記重量比を満たすことが重要であり、モノエステル体とジエステル体、更にトリエステル体のＲ¹、ＡＯ、ｎは同一でも異なっていてもよい。
【００２９】
（Ａ）成分は、例えばアルコールにアルキレンオキサイドを付加した後、リン酸エステル化することによって得ることができる。あるいは、市販されているアルコールのアルキレンオキサイド付加物を原料として、リン酸エステル化反応によって得ることもできる。アルコールとして、天然アルコールや合成アルコールを使用できる。アルキレンオキサイドは炭素数２〜４のものであり、エチレンオキサイド（以下、ＥＯと表記する）、プロピレンオキサイド（以下、ＰＯと表記する）、ブチレンオキサイド（以下、ＢＯと表記する）が挙げられ、好ましくはＥＯ、又はＥＯとＰＯの併用が好ましく、特に好ましくはＥＯである。また、２種以上のアルキレンオキサイド基の付加形態は、ブロック結合、ランダム結合、それらが混在したものの何れでも良い。
【００３０】
リン酸エステル化反応の方法としては、一般的な方法を用いることができる。例えば、無水リン酸を用いる方法の他にも、無水リン酸とリン酸水溶液、無水リン酸と水、オキシ塩化リン、ポリリン酸を用いる方法などによっても（Ａ）成分を製造することができる。本発明において、（Ａ）成分中のモノエステル体の比率を調整するには、上記のような製造方法において、ポリオキシアルキレンアルキルエーテルとリン酸化剤の比率と反応時間を調整したり、加水分解反応をしたりする他、晶析、蒸留等の精製や、別添等により調整すればよい。特に、加水分解反応は（Ａ）成分中のモノエステル体比率を増加させるのに有効である。また、分子量分布範囲の狭いポリオキシアルキレンアルキルエーテル（ナロー化エトキシレート）を使用することは、貧配合コンクリートの流動性の観点から、好ましい。
【００３１】
＜実施態様II＞
本発明の貧配合コンクリート用添加剤は、（Ａ）成分単独で用いる場合よりも、流動性を向上させる点で、（Ｂ１）炭素数８〜２６のアルキル基もしくはアルケニル基又は１以上のベンゼン環を有する炭素数６〜３５の炭化水素基と、炭素数２〜４のオキシアルキレン基から構成され、平均付加モル数が３〜４００であるポリオキシアルキレン基とを有する非イオン性化合物〔以下、（Ｂ１）成分という〕、及び（Ｂ２）炭素数８〜２６のアルキル基もしくはアルケニル基又は１以上のベンゼン環を有する炭素数６〜３５の炭化水素基と、炭素数２〜４のオキシアルキレン基から構成され、平均付加モル数が５〜４００であるポリオキシアルキレン基とを有するイオン性化合物（前記一般式（１）で表される基を有するリン酸エステル又はその塩を除く）〔以下、（Ｂ２）成分という〕より選ばれる１種類以上の化合物（Ｂ）〔以下、（Ｂ）成分という〕を含有することが好ましい。（Ｂ）成分は、前記ポリオキシアルキレン基を１〜２個有することが好ましい。以下、本発明の貧配合コンクリート用添加剤において（Ａ）成分と（Ｂ）成分とを併用する場合（実質的な有効成分が（Ａ）成分と（Ｂ）成分である場合）を実施態様IIとして説明する。
【００３２】
（Ｂ）成分に付加するアルキレンオキサイド中、好ましくはＥＯを５０モル％以上、より好ましくは７０モル％以上、特に好ましくは１００モル％用いる。
【００２６．５】
一般式（２）の非イオン性化合物は、Ｒ²の基を有するアルコールに、ＥＯ、ＰＯ及びＢＯから選ばれるアルキレンオキサイド、好ましくはＥＯ、又はＥＯとＰＯ、更に好ましくはＥＯを付加することにより得られる。同様に、一般式（３）、（４）の非イオン性化合物は、Ｒ³又はＲ⁵の基を有する化合物に、ＥＯ、ＰＯ及びＢＯから選ばれるアルキレンオキサイド、好ましくはＥＯ、又はＥＯとＰＯを付加することにより得られる。水溶液性状の観点から、付加するアルキレンオキサイド中、好ましくはＥＯを５０モル％以上、より好ましくは７０モル％以上、特に好ましくは１００モル％用いる。（Ｂ１）成分としては、特に一般式（２）の非イオン性化合物が好ましい。また、フレッシュコンクリートの気泡安定性の観点からは、さらにオキシプロピレン基が含まれることが好ましく、ポリオキシアルキレン基中のオキシエチレン基の比率は、好ましくは１０モル％以上、より好ましくは２５モル％以上である。水溶性と気泡安定性の総合的な観点からは、オキシエチレン基とオキシプロピレン基のモル比は、好ましくは９０／１０〜３０／７０、より好ましくは８０／２０〜４０／６０である。また、２種以上のアルキレンオキサイド基の付加形態は、ブロック結合、ランダム結合、それらが混在したものの何れでも良い。
【００３３】
（Ｂ）成分としては、一般式（２）で表される化合物、一般式（３）で表される化合物及び一般式（４）で表される化合物から選ばれる一種以上の化合物、及び 、その他にポリオキシアルキレンソルビタンアルキルエステル、ポリオキシアルキレングリセリンアルキルエステル、ポリオキシアルキレン硬化ヒマシ油等が挙げられ、実施態様IIでの水溶液粘性の観点から、一般式（２）で表される化合物、一般式（３）で表される化合物及び一般式（４）で表される化合物から選ばれる一種以上の化合物が好ましい。
Ｒ²−Ｏ−(ＡＯ)_p−Ｒ （２）
Ｒ³−ＣＯＯ−(ＡＯ)_q−Ｒ⁴ （３）
Ｒ⁵−ＮＨ_(2-t)〔(ＡＯ)_s−Ｈ〕_t （４）
〔式中、Ｒ²、Ｒ³及びＲ⁵は、それぞれ炭素数８〜２６のアルキル基もしくはアルケニル基又は１以上のベンゼン環を有する炭素数６〜３５の炭化水素基、Ｒ及びＲ⁴は、それぞれ水素原子、炭素数１〜２６のアルキル基もしくはアルケニル基又は１以上のベンゼン環を有する炭素数６〜３５の炭化水素基、好ましくは水素原子、ＡＯは炭素数２〜４のオキシアルキレン基、ｐ、ｑ及びｓは、それぞれ平均付加モル数であり３〜４００、好ましくは５〜２００、より好ましくは８〜１５０の数、ｔは１又は２を示す。ｔが２のときの２個の(ＡＯ)_sは異なっていてもよい。〕
【００３４】
一般式（２）〜（４）において、Ｒ²、Ｒ³及びＲ⁵は、それぞれ炭素数１０〜２２、更に１４〜２０、特に１４〜１８の直鎖のアルキル基又はアルケニル基が好ましく、特にオレイル基が好ましい。１以上のベンゼン環を有する炭素数６〜３５の炭化水素基の場合、２以上のベンゼン環を有する炭化水素基（特に１以上のベンゼン環を含む基を置換基として有するアリール基）が好ましく、３又は４のベンゼン環を有する炭化水素基（特に２又は３のベンゼン環を含む基を置換基として有するアリール基）が更に好ましく、総炭素数としては２０〜３０が好ましい。Ｒ及びＲ⁴は、それぞれ水素原子、炭素数１〜２６のアルキル基もしくはアルケニル基又は１以上のベンゼン環を有する炭素数６〜３５の炭化水素基であり、水素原子、炭素数１〜８のアルキル基、炭素数２〜８のアルケニル基が好ましく、水素原子、炭素数１〜４のアルキル基、炭素数２〜４のアルケニル基が更に好ましく、特に水素原子、炭素数１〜２のアルキル基、炭素数２のアルケニル基が好ましい。
【００３５】
（Ｂ１）成分のうち、一般式（２）の非イオン性化合物としては、ポリオキシアルキレンアルキルエーテル、ポリオキシアルキレンアルキルフェニルエーテル、ポリオキシアルキレンポリスチレン化フェニルエーテル、ポリオキシアルキレンポリベンジル化フェニルエーテルが好ましく、ポリオキシアルキレン（ジ又はトリ）スチレン化フェニルエーテル、ポリオキシアルキレン（ジ又はトリ）ベンジル化フェニルエーテルが、フレッシュコンクリートの気泡安定性の観点から、より好ましく、一般式（３）の非イオン性化合物としては、ポリオキシアルキレンアルキルエステル、アルコキシポリオキシアルキレンアルキルエステルが、一般式（４）の非イオン性化合物としては、ポリオキシアルキレンアルキルアミン等が挙げられる。また、（Ｂ１）成分の特定のアルキル基、アルケニル基、１以上のベンゼン環を有する炭素数６〜３５の炭化水素基の代わりに、オルガノシロキサン等の疎水基を有する化合物、例えばシリコーン系界面活性剤等を用いることもできる。（Ｂ１）成分としては、製品安定性の観点から、より好ましくは、一般式（２）の非イオン性化合物としてはポリオキシアルキレンアルキルエーテル、一般式（３）の非イオン性化合物としてはポリオキシアルキレンアルキルエステル、一般式（４）の非イオン性化合物としてはポリオキシアルキレンアルキルアミンであり、これらの中でも特に好ましくは、ポリオキシアルキレンアルキルエーテルである。
【００３６】
（Ｂ１）成分としては、特に一般式（２）の非イオン性化合物が好ましい。
【００３７】
また、（Ｂ２）成分としては、ポリオキシアルキレンアルキルエーテル硫酸塩やポリオキシアルキレンアルキルエーテルカルボン酸塩が好ましい。これらのポリオキシアルキレン部分の構造（炭素数、平均付加モル数等）やアルキル基の炭素数等については、（Ｂ１）成分と同様である。
【００３８】
水溶液性状の観点から、（Ｂ１）の方が、（Ｂ２）よりも好ましい。
【００３９】
（Ａ）成分と（Ｂ）成分とを併用する実施態様IIにおいて、モノエステル体／（モノエステル体＋ジエステル体）の重量比は、製品安定性と貧配合コンクリートの流動性の観点から、好ましくは０．５〜０．９５、より好ましくは０．６５〜０．９５、より好ましくは０．７〜０．９５、さらに工業的な製造容易性の観点から、特に好ましくは０．７〜０．８５である。モノエステル体／（モノエステル体＋ジエステル体）の重量比が０．４未満では、添加剤水溶液のポンプ輸送性の観点から好ましくない。
【００４０】
また、（Ａ）成分と（Ｂ）成分とを併用する実施態様IIにおいて（Ａ）成分の与える貧配合コンクリートの流動性がより向上するため、ｎは３〜３５が好ましく、５〜３０がさらに好ましく、８〜２５が特に好ましい。
【００２６．３】
さらに、貧配合コンクリートの流動性の観点から、（Ａ）／（Ｂ）の重量比は、９９／１〜１０／９０が好ましく、更に９０／１０〜３０／７０が好ましく、特に８０／２０〜４５／５５が好ましい。
【００４１】
＜実施態様III＞
本発明の貧配合コンクリート用添加剤は、（Ａ）成分、（Ｂ）成分に加えて、貧配合コンクリートの流動性の保持性を向上しさらにブリージングを抑制する観点から、一般式（５）で表される単量体由来の構成単位と、一般式（６）で表される単量体由来の構成単位及び一般式（７）で表される単量体由来の構成単位から選ばれる一種以上の構成単位とを有する共重合体（Ｃ）〔以下、（Ｃ）成分という〕を含有することが好ましい。以下、本発明の貧配合コンクリート用添加剤において（Ａ）成分と（Ｂ）成分と（Ｃ）成分とを併用する場合（実質的な有効成分が（Ａ）成分と（Ｂ）成分と（Ｃ）成分である場合）を実施態様IIIとして説明する。
【００４２】
（Ｃ）成分は、一般式（５）で表される単量体と、一般式（６）で表される単量体及び一般式（７）で表される単量体から選ばれる一種以上とを重合して得られる共重合体が挙げられる。一般式（５）で表される単量体としては、平均付加モル数１〜３００のオキシアルキレン基もしくはポリオキシアルキレン基を有するエチレン系不飽和カルボン酸エステルが好ましい。ここで、オキシアルキレン基はオキシスチレン基でもよく、ポリオキシアルキレン基はオキシスチレン基を含んでもよく、ポリオキシスチレン基でもよい。一般式（５）で表される単量体、一般式（６）で表される単量体及び一般式（７）で表される単量体は、それぞれ２種以上を併用してもよい。
【００４３】
【化５】

【００４４】
〔式中、
Ｒ⁶、Ｒ⁷：それぞれ水素原子又はメチル基
ｍ：０〜２の数
Ｒ⁸：水素原子又は−ＣＯＯ(ＡＯ)_n1Ｙ
ｐ：０又は１の数
ＡＯ：炭素数２〜４のオキシアルキレン基又はオキシスチレン基
ｎ１：平均付加モル数であり１〜３００の数
Ｙ：水素原子又は炭素数１〜１８のアルキル基もしくはアルケニル基
を表す。〕
【００４５】
【化６】

【００４６】
〔式中、
Ｒ⁹〜Ｒ¹¹：それぞれ、水素原子、メチル基又は(ＣＨ₂)_m1ＣＯＯＭ²であり、(ＣＨ₂)_m1ＣＯＯＭ²はＣＯＯＭ¹又は他の(ＣＨ₂)_m1ＣＯＯＭ²と無水物を形成していてもよく、その場合、それらの基のＭ¹、Ｍ²は存在しない。
Ｍ¹、Ｍ²：それぞれ、水素原子、アルカリ金属、アルカリ土類金属、アンモニウム基、アルキルアンモニウム基又は水酸基置換アルキルアンモニウム基
ｍ１：０〜２の数
【００４７】
【化７】

【００４８】
Ｚ：水素原子、アルカリ金属、アルカリ土類金属、アンモニウム基、アルキルアンモニウム基又は水酸基置換アルキルアンモニウム基
を表す。〕
【００４９】
一般式（５）で表される単量体としては、メトキシポリエチレングリコール、メトキシポリプロピレングリコール、メトキシポリブチレングリコール、メトキシポリスチレングリコール、エトキシポリエチレンポリプロピレングリコール等の片末端アルキル封鎖ポリアルキレングリコールと（メタ）アクリル酸、マレイン酸との（ハーフ）エステル化物や、（メタ）アリルアルコールとのエーテル化物、及び（メタ）アクリル酸、マレイン酸、（メタ）アリルアルコールへのＥＯ、ＰＯ付加物が好ましく用いられ、Ｒ⁸は水素原子が好ましく、ｍは０が好ましく、ｐは１が好ましい。より好ましくはアルコキシ、特にはメトキシポリエチレングリコールと（メタ）アクリル酸とのエステル化物、さらに特に好ましくはメトキシポリエチレングリコールとメタクリル酸とのエステル化物である。エステル化は単量体に行ってもよいし、上述の一般式（６）の単量体及び／又は一般式（７）の単量体との共重合の後に行ってもよい。アルキレンオキサイドの平均付加モル数ｎ１は流動性及び流動保持性に優れることから１〜３００の範囲であるが、更に８〜２００、特に２０〜１５０の範囲が好ましい。Ｙは炭素数１〜４のアルキル基又はアルケニル基がより好ましく、特にメチル基が好ましい。アルキレンオキサイドはＥＯ又はＥＯとＰＯが好ましく、特にＥＯが好ましい。
【００５０】
また、一般式（６）で表される単量体として、（メタ）アクリル酸、クロトン酸等の不飽和モノカルボン酸系単量体、マレイン酸、イタコン酸、フマル酸等の不飽和ジカルボン酸系単量体、又はこれらの塩、例えばアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、アミン塩等が挙げられ、好ましくは、（メタ）アクリル酸又はこれらのアルカリ金属塩であり、さらに好ましくは、メタクリル酸又はこれらのアルカリ金属塩であり、特に好ましくは、メタクリル酸又はこれらのナトリウム塩である。また、一般式（７）で表される単量体として、（メタ）アリルスルホン酸又はこれらの塩、例えばアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、アミン塩等が挙げられ、特に好ましくは、メタリルスルホン酸又はそのナトリウム塩である。
【００５１】
（Ｃ）成分の共重合体の重量平均分子量〔ゲルパーミエーションクロマトグラフィー法、ポリエチレングリコール換算、カラム：G4000PWXL ＋ G2500PWXL（東ソー（株）製）、溶離液：0.2Mリン酸緩衝液／アセトニトリル＝７／３（体積比）〕は、水硬性粉体に対する充分な流動性及び流動保持性を得るため、１０００〜２０万が好ましく、１．５万〜１０万が特に好ましい。
【００５２】
（Ｃ）成分は、一般式（５）で表される単量体（５）と、一般式（６）で表される単量体（６）及び一般式（７）で表される単量体（７）とを、（５）／〔（６）＋（７）〕のモル比が９９／１〜１／９９、更には６０／４０〜１／９９、特に４０／６０〜５／９５で用いて製造されることが好ましい。また、一般式（６）で表される単量体と一般式（７）で表される単量体のモル比（６）／（７）は１００／０〜８０／２０が好ましく、１００／０〜９０／１０が好ましい。
【００５３】
なお、（Ｃ）成分は、アクリロニトリル、（メタ）アクリルアミド、スチレン、（メタ）アクリル酸アルキル（水酸基を有していてもよい炭素数１〜１２のもの）エステル、スチレンスルホン酸等の共重合可能な単量体を併用してもよい。これらは全単量体中好ましくは５０重量％以下、更に好ましくは３０重量％以下の比率で使用できるが、０重量％が特に好ましい。
【００５４】
（Ｃ）成分の共重合体は、公知の方法で製造することができる。例えば、特開平１１−１５７８９７号公報の溶液重合法が挙げられ、水や炭素数１〜４の低級アルコール中、過硫酸アンモニウム、過酸化水素等の重合開始剤存在下、必要ならば、亜硫酸ナトリウムやメルカプトエタノール等を添加し、５０〜１００℃で０．５〜１０時間反応させればよい。
【００５５】
水硬性粉体の種類等を考慮して、（Ｃ）成分の共重合体を２種以上併用することも好ましい。
【００５６】
なお、実施態様IIIにおける（Ａ）成分、（Ｂ）成分それぞれの具体的な化合物、モノエステル体／（モノエステル体＋ジエステル体）重量比の範囲、（Ａ）／（Ｂ）重量比の範囲等は、実施態様Ｉ又は実施態様IIから適宜選択できる。
【００５７】
また、（Ａ）成分と（Ｃ）成分の重量比は、（Ａ）／（Ｃ）＝９９／１〜１０／９０、更に９０／１０〜３０／７０、特に８０／２０〜４５／５５であることが、流動保持効果の点で好ましい。
【００５８】
＜貧配合コンクリート用添加剤＞
本発明が対象とする貧配合コンクリートは、セメント等の水硬性粉体、細骨材、粗骨材を主成分とし、本発明の添加剤を添加して製造されるものであり、水硬性粉体の重量、好ましくはセメントの重量が１９０〜３５０ｋｇ／ｍ³、特に２７０〜３３０ｋｇ／ｍ³のセメントペースト、モルタル、コンクリート等の水硬性組成物である。さらに、前記水硬性粉体の重量を満たして、かつ、水／水硬性粉体比が、５０〜７０％、更に５０〜６５％、特に５５〜６５％であるコンクリートが挙げられる。
【００５９】
本発明の貧配合コンクリート用添加剤は、実施態様Ｉ〜IIIの何れも、水量を低減できるので分散剤や流動化剤として、また粘性低減効果を有するので粘性低減剤等として用いることができる。
【００６０】
本発明の貧配合コンクリート用添加剤は、実施態様Ｉ〜IIIの何れも、水硬性粉末１００重量部に対して、（Ａ）成分が０．０１〜７．５重量部、更に０．０１〜５重量部、更に０．０２〜３重量部、特に０．０２〜１重量部となるように用いられることが、貧配合コンクリートの分散性、流動性、あるいは粘性低減効果の点で好ましい。
【００６１】
また、（Ｂ）成分は、水硬性粉末１００重量部に対して、０．０１〜５重量部、更に０．０２〜３重量部、特に０．０２〜１重量部となるように用いられることが、貧配合コンクリートの流動性の点で好ましい。
【００６２】
また、（Ｃ）成分は、水硬性粉末１００重量部に対して、０．０１〜５重量部、更に０．０５〜２重量部、特に０．０５〜１重量部となるように用いられることが、貧配合コンクリートの流動保持効果の点で好ましい。
【００６３】
また、（Ａ）成分と（Ｂ）成分の重量比は、（Ａ）／（Ｂ）＝９９／１〜１０／９０、更に９０／１０〜３０／７０、特に８０／２０〜４５／５５であることが、貧配合コンクリートの流動性の点で好ましい。
【００６４】
また、本発明の貧配合コンクリート用添加剤において、（Ａ）成分と（Ｂ）成分と（Ｃ）成分との合計量〔（Ｂ）成分と（Ｃ）成分はそれぞれ０重量％でもよい〕の占める比率は、添加剤中に５〜１００重量％、更に１０〜１００重量％、特に２０〜１００重量％が好ましい。また、この合計量の比率は、添加剤の（Ａ）成分と（Ｂ）成分と（Ｃ）成分とこれら以外の成分の合計中に５０〜１００重量％、更に７０〜１００重量％、特に８０〜１００重量％が好ましい。
【００６５】
本発明の貧配合コンクリート用添加剤は、溶液として用いることが作業性の点で好ましい。溶媒として水や有機溶剤を用いることができ、水を溶媒とする水溶液として用いることが安全性の点で好ましく、（Ａ）成分と（Ｂ）成分と（Ｃ）成分の合計（以下、有効分ともいう）の濃度を２０重量％以上とした水溶液が、２０℃で均一な外観を呈することが好ましい。また、当該水溶液の２０℃における粘度が５００ｍＰａ・ｓ以下であることが好ましく、更に３００ｍＰａ・ｓ以下、更に１〜３００ｍＰａ・ｓ、更に１５０ｍＰａ・ｓ以下、更に１〜１５０ｍＰａ・ｓとなることが、作業性の点で好ましい。
【００６６】
本発明の貧配合コンクリート用添加剤には、他の成分、例えば（Ａ）成分、（Ｂ）成分、（Ｃ）成分以外の構造を有する分散剤を併用してもよい。該分散剤とは一般にコンクリート用混和剤として使用されているものであればよいが、グルコン酸ナトリウム等のオキシカルボン酸もしくはその塩、ナフタレンスルホン酸塩ホルムアルデヒド縮合物、メラミンスルホン酸塩ホルムアルデヒド縮合物、ポリカルボン酸もしくはそのエステルもしくはその塩、精製リグニンスルホン酸もしくはその塩、ポリスチレンスルホン酸塩、フェノール骨格を有するセメント分散剤（例えば、フェノールスルホン酸と共重合可能な他の単量体とのホルムアルデヒド共縮合物）、アニリンスルホン酸を主成分とするセメント分散剤（例えば、アニリンスルホン酸と共縮合可能な他の単量体とのホルムアルデヒド共縮合物）など、従来減水剤と称されるものが好ましく使用され、フレッシュコンクリートの気泡安定性の観点から、ナフタレンスルホン酸塩ホルムアルデヒド縮合物、メラミンスルホン酸塩ホルムアルデヒド縮合物がより好ましい。
【００６７】
また、（Ｃ）成分の共重合体の代わりに、特開平１１−１３９８５５号公報の特許請求の範囲に記載されているような、エチレン性不飽和単量体をポリエーテル化合物にグラフト重合してなる重合体を用いることもできる。
【００６８】
以上の実施態様に係る本発明の添加剤は、水溶液にした場合の製品安定性が良好で、貧配合コンクリートに使用すると、貧配合コンクリートに良好な流動性を付与した上で、その粘性を低減でき、さらに、かかる貧配合コンクリートのフレッシュ性状を安定に発現できるため、ポンプ圧送、打ち込み、型枠への充填等の貧配合コンクリートを使用する際の作業性、施工性が大幅に改善される。
【００６９】
また、本発明の貧配合コンクリート用添加剤は公知の添加剤（材）と併用することができる。一例を挙げれば、ＡＥ剤、流動化剤、遅延剤、早強剤、促進剤、起泡剤、保水剤、増粘剤、防水剤、消泡剤、収縮低減剤、水溶性高分子、界面活性剤各種等や珪石粉末、高炉スラグ、フライアッシュ、シリカフューム等が挙げられる。
【００７０】
なかでも、消泡剤を含有することが好ましい。消泡剤〔（Ｂ）成分を除く〕としては、（１）メタノール、エタノール等の低級アルコール系、（２）ジメチルシリコーンオイル、フルオロシリコーンオイル等のシリコーン系、（３）鉱物油と界面活性剤の配合品等の鉱物油系、（４）リン酸トリブチル等のトリアルキルリン酸エステル系、（５）オレイン酸、ソルビタンオレイン酸モノエステル、ポリエチレングリコール脂肪酸エステル、ポリエチレングリコール／ポリプロピレングリコール脂肪酸エステル等の脂肪酸又は脂肪酸エステル系、（６）ポリプロピレングリコール、ポリエチレングリコール／ポリプロピレングリコールアルキルエーテル等のポリオキシアルキレン系が挙げられる。好ましくは、脂肪酸又は脂肪酸エステル系消泡剤、シリコーン系消泡剤、ポリオキシアルキレン系消泡剤及びトリアルキルリン酸エステル系消泡剤から選ばれる１種以上の消泡剤であり、本発明の貧配合コンクリート用添加剤との混合安定性の観点から、より好ましくは脂肪酸又は脂肪酸エステル系消泡剤、シリコーン系消泡剤、ポリオキシアルキレン系消泡剤から選ばれる１種以上の消泡剤であり、さらに好ましくは脂肪酸又は脂肪酸エステル系消泡剤、シリコーン系消泡剤から選ばれる１種以上の消泡剤であり、特に好ましくはシリコーン系消泡剤である。消泡剤の添加量は、貧配合コンクリートにより要求される空気量の範囲が異なるが、貧配合コンクリートの強度や凍結融解抵抗性の観点から、本発明の添加剤中の（Ａ）成分と（Ｂ）成分と（Ｃ）成分の合計量１００重量部に対し０．０１〜１０重量部が好ましく、０．０５〜５重量部が更に好ましく、０．１〜３重量部が特に好ましい。
【００７１】
＜貧配合コンクリート＞
本発明は、上記本発明の貧配合コンクリート用添加剤と、水硬性粉体と、水とを含有する貧配合コンクリートに関する。該貧配合コンクリートは、上記の通り、水硬性粉体の重量が１９０〜３５０ｋｇ／ｍ³、更に２２０〜３３０ｋｇ／ｍ³、特に２７０〜３３０ｋｇ／ｍ³であり、Ｗ／Ｐが５０〜７０％、更に５０〜６５％、特に５５〜６５％であり、特に、水硬性粉体の重量が２７０〜３３０ｋｇ／ｍ³かつＷ／Ｐが５５〜６５％であることが好ましい。
【００７２】
本発明の貧配合コンクリートにおいては、水硬性粉体１００重量部に対して、（Ａ）成分を０．０１〜７．５重量部、更に０．０５〜５重量部、更に０．０２〜３重量部、特に０．０２〜１重量部含有することが好ましい。また、本発明の貧配合コンクリートにおいては、水硬性粉体１００重量部に対して、（Ａ）成分と（Ｂ）成分と（Ｃ）成分の合計量を０．０１〜１０重量部、更に０．０１〜７．５重量部、特に０．０５〜３重量部含有することが好ましい。
【００７３】
セメントとして、普通ポルトランドセメント、早強ポルトランドセメント、超早強ポルトランドセメント、エコセメント（例えばＪＩＳ Ｒ５２１４等）が挙げられる。本発明の貧配合コンクリートには、セメント以外の水硬性粉体として、高炉スラグ、フライアッシュ、シリカヒューム等が含まれてよく、また、非水硬性の石灰石微粉末等が含まれていてよい。セメントと混合されたシリカヒュームセメントや高炉セメントを用いてもよい。
【００７４】
また、本発明の貧配合コンクリートは骨材を含有してもよい。骨材として細骨材や粗骨材等が挙げられ、細骨材は山砂、陸砂、川砂、砕砂が好ましく、粗骨材は山砂利、陸砂利、川砂利、砕石が好ましい。用途によっては、軽量骨材を使用してもよい。なお、骨材の用語は、「コンクリート総覧」（１９９８年６月１０日、技術書院発行）による。
【００７５】
【発明の効果】
本発明によれば、添加作業性が良好で、貧配合コンクリートのフレッシュ状態（混練直後より打設終了まで）における連行空気量、流動性及び流動保持性が安定する貧配合コンクリート用添加剤が得られる。
【実施例】
以下において、各成分の製造例で単に％と記載するものは重量％を意味する。
【００７６】
＜（Ａ）成分＞
実施例及び比較例に用いた（Ａ）成分は表１の通りであり、それらは以下の製造例Ａ−１〜Ａ−２に準じて製造した。
【００７７】
（１）製造例Ａ−１
撹拌機付き反応容器に、オレイルアルコールのＥＯ付加物（平均付加モル数２０、水酸基価４９．９）５００ｇ（０．４４モル）を仕込み、撹拌しながら窒素置換し、窒素雰囲気とした。約８０℃まで加熱し、減圧下で含有水分を除去した。常圧、約４０℃に戻した後、市販無水リン酸（純度９８％）を２１．５ｇ（０．１５モル）添加した。無水リン酸の添加は３回に分けて行った。添加後、液温度を６５〜７５℃に調整し、約６時間熟成を行った。反応生成物の酸価１を測定し、酸価１に対して中和度が０．５から１．０であって、且つ濃度が２０重量％となるように、水道水と４８％−水酸化カリウム水溶液で調整し、表１中の（Ａ）成分ａ−１を得た。また、ａ−２をこの方法に準じて製造したが、無水リン酸の添加後の熟成を行った後、２６．１ｇの水道水を添加し、液温度を約８０℃に調整し、更に約４時間加水分解反応させた。
【００７８】
（２）製造例Ａ−２
撹拌機付き反応容器に、オレイルアルコールのＥＯ付加物（平均付加モル数２０、水酸基価４９．９）５００ｇ（０．４４モル）を仕込み、撹拌しながら窒素置換し、窒素雰囲気とした。約８０℃まで加熱し、減圧下で含有水分を除去した。常圧、約６０℃にした後、リン酸（純度８５％）を９．４０ｇ（０．０８モル）滴下する。完全に均一状態になった後、市販無水リン酸（純度９８％）を２６．２ｇ（０．１８モル）添加した。無水リン酸の添加は３回に分けて行った。添加後、液温度を６５〜７５℃に調整し、約６時間熟成を行った。２６．８ｇの水道水を添加し、液温度を約８０℃に調整し、更に約４時間反応させた。
【００７９】
反応生成物の酸価１を測定し、酸価１に対して中和度が０．５から１．０であって、且つ濃度が２０重量％となるように、水道水と４８％−水酸化カリウム水溶液で調整し、表１中の（Ａ）成分ａ−３を得た。同様の方法によって（Ａ）成分ａ−４、５、６、７、８を得た。
【００８０】
ここで、反応生成物の酸価は、以下のように求めた。
反応生成物をエタノール／水（７０体積％／３０体積％）に溶解して、０．５ｍｏｌ／ｌ水酸化カリウム水溶液（試薬）を滴定標準液として、電位差自動滴定装置ＡＴ−５００（京都電子工業）を使用し、多段階滴定によって測定した。反応生成物の酸価１と酸価２は続けて測定を行う。酸価３については、酸価１と酸価２とは別のサンプルで測定する。酸価１の測定と同様に測定を始め、酸価１の滴定終了後にすばやく、測定液に１Ｍ塩化カルシウム水溶液を約２０ｍｌ加える。いくつか滴定終点が出る場合があるが、最後の終点を酸価３の滴定終点とする。
【００８１】
（モノエステル体比率の計算方法）
【００８２】
³¹Ｐ−ＮＭＲ測定により（Ａ）成分中に含まれるリン酸モノエステル、リン酸ジエステル、ピロリン酸モノエステル、ピロリン酸ジエステル、リン酸トリエステル、ピロリン酸、リン酸を定量して算出した（内部標準試料としてトリメチルフォスフェートを使用）。ここで、測定装置は、ＵＮＩＴＹ ＩＮＯＶＡ ３００（ＶＡＲＩＡＮ社）を用い、測定条件は、パルス幅９０°パルス（１７．２μｓ）、待ち時間３０ｓ（ｔ１の５倍以上）とした。スペクトル分解能向上のために、前処理として、２０重量％水溶液のサンプル１体積に対して、２体積の重メタノールを加え、更に上記で測定したサンプルの酸価３に対して中和度１．０に相当する水酸化カリウムを２０重量％水酸化カリウム水溶液で添加した。ポリオキシアルキレンアルキルエーテルの分子量は、それぞれの水酸基価より求めた。
【００８３】
＜（Ｂ）成分＞
実施例及び比較例に用いた（Ｂ）成分は表２の通りであり、非イオン性界面活性剤等、一般的な非イオン性化合物の製造方法によって得ることができる。製造例Ｂ−１に、ポリオキシアルキレンアルキルエーテルｂ−１の製造方法を示す。
【００８４】
製造例Ｂ−１
オレイルアルコール（水酸基価２０９ｍｇＫＯＨ／ｇ）２６８ｇと水酸化カリウム０．５６ｇを圧力容器（３リットル）に仕込み、撹拌し、減圧した後、窒素置換をした。１１０℃まで昇温した後、２．７ｋＰａで３０分間脱水した。１５５℃まで昇温し、０．０２〜０．４ＭＰａの圧力でＥＯを８８１．０ｇ反応させたのち、３０分間熟成を行った。８０℃まで冷却し、１．３ｋＰａで１５分間減圧処理した後、同温（８０℃）で酢酸０．６０ｇを添加し、中和を行い、ｂ−１を得た。
【００８５】
＜（Ｃ）成分＞
実施例及び比較例に用いた（Ｃ）成分は表３の通りであり、それらは以下の製造例Ｃ−１〜Ｃ−３に準じて製造した。
【００８６】
（１）製造例Ｃ−１
温度計、撹拌機、滴下ロート、窒素導入管及び環流冷却器を備えたガラス製反応容器に、水３６６重量部を仕込み、窒素置換を行った。続いて窒素雰囲気下で８０℃まで昇温した後、メタノールＥＯ（平均付加モル数１２０）付加物・メタクリル酸モノエステルの６０％水溶液８９８重量部及びメタクリル酸３４．４重量部を混合した液と、５％−２−メルカプトエタノール水溶液６２．３重量部と、５％−過硫酸アンモニウム水溶液６８．４重量部の３液を同時に滴下し、３液とも９０分かけて滴下を終了させた。次に同温で１時間熟成した後、５％−過硫酸アンモニウム水溶液２２．８重量部を３０分かけて滴下し、滴下後同温で２時間熟成させた。更に、４８％−水酸化ナトリウム水溶液２３．３重量部を加えて中和した後、３５％−過酸化水素水８．０重量部を添加し、９０℃まで昇温し、同温にて１時間保持した後、冷却し重量平均分子量５３，０００の共重合体（ナトリウム塩、中和度７０％）ｃ−１を得た。また、メタノールＥＯ（平均付加モル数１８）付加物・メタクリル酸モノエステルを表３のモル比で使用した以外はｃ−１と同様にして、ｃ−４を製造した。
【００８７】
（２）製造例Ｃ−２
温度計、撹拌機、滴下ロート、窒素導入管及び環流冷却器を備えたガラス製反応容器に、水７０モルを仕込み、撹拌しながら窒素置換し、窒素雰囲気下で７５℃まで昇温した、メタノールＥＯ（平均付加モル数１２０）付加物・メタクリル酸モノエステル０．１モルとアクリル酸メチル０．７モルとメタクリル酸０．２モルとを混合溶解したものと、２０％−過硫酸アンモニウム水溶液０．０５モル（有効分換算、以下、本製造例の水溶液について同様）と、２０％−２−メルカプトエタノール水溶液０．１モルとの３者を一緒に２時間かけて滴下した。次に２０％−過硫酸アンモニウム水溶液０．０２モルを３０分かけて滴下し、１時間同温度（７５℃）で熟成した。熟成後９５℃に昇温して３５％−過酸化水素水０．２モルを３０分かけて滴下し、２時間同温（９５℃）で熟成後、４８％−水酸化ナトリウム水溶液０．０７モルを添加し、重量平均分子量４０，０００の共重合体ｃ−２を得た。
【００８８】
（３）製造例Ｃ−３
特開２００１−１８０９９８号公報の実施例８に準じて共重合体ｃ−３を得た。但し、該公報における単量体（Ａ−IV）に代えて、メタノールＥＯ（平均付加モル数１２０）付加物・メタクリル酸モノエステルを使用した。
【００８９】
実施例１
表１の（Ａ）成分と、表２の（Ｂ）成分及び表３の（Ｃ）成分を、表４のコンクリート配合に対して表５〜７のように用いて貧配合コンクリートを調製し以下の評価を行った。結果を表５〜７に示す。
【００９０】
（１）水溶液の状態
添加剤水溶液〔（Ａ）成分、（Ｂ）成分、（Ｃ）成分の合計の濃度が２０重量％となる水溶液〕の状態を水溶液調製後２０℃で２４時間静置後、目視で観察した。水溶液が均一である場合は、２０℃における粘度を、Ｐｒｏｇｒａｍｍａｂｌｅ ｖｉｓｃｏｍｅｔｅｒ ＤＶII＋（Ｂｒｏｏｋｆｉｅｌｄ社製）を使用して測定し、以下の基準で水溶液の状態を評価した。この評価が△、○又は◎であれば、ポンプ輸送性等において問題のない水溶液性状を有する添加剤が提供できる。
◎：粘度が１５０ｍＰａ．ｓ未満
○：粘度が１５０ｍＰａ．ｓ以上３００ｍＰａ．ｓ未満
△：粘度が３００ｍＰａ・ｓ以上５００ｍＰａ．ｓ未満
×：粘度が５００ｍＰａ．ｓ以上、又は水溶液が不均一
【００９１】
（２）コンクリート試験
（２−１）コンクリート配合（調合）
Ｗ：水道水
Ｃ：普通ポルトランドセメント（太平洋セメント（株））、密度＝３．１６ｇ／ｃｍ³
Ｓ１：瀬戸内産海砂、表乾比重＝２．５６ｇ／ｃｍ³
Ｓ２：城陽産山砂、表乾比重＝２．５６ｇ／ｃｍ³
Ｇ：茨木産砕石、表乾比重＝２．６４ｇ／ｃｍ³
上記材料を表４のコンクリート配合Ｉ〜IIIの調製に用いた。
【００９２】
（２−２）評価方法
表４のコンクリート配合における水道水（練り混ぜ水）に添加剤水溶液〔（Ａ）成分、（Ｂ）成分、（Ｃ）成分の合計の濃度が２０重量％となる水溶液〕を添加した。このとき必要に応じて消泡剤として、脂肪酸エステル系消泡剤フォームレックス７９７（日華化学社製）とシリコーン系消泡剤アンチフォーム０１３Ｂ（ダウ・コーニング・アジア社製；ポリオルガノシロキサン系）を添加した。
【００９３】
次いで、二軸強制ミキサー（ＩＨＩ社製）に砂利、約半量の砂、セメント、残部の砂の順に投入した。空練りを１０秒間行った後、すばやく上記練り混ぜ水を撹拌して均一にして添加し、9０秒間練り混ぜた。得られたコンクリートについて、スランプフローを測定した。その際、コンクリート配合Ｉはスランプ１５ｃｍ±１．５ｃｍ、コンクリート配合IIはスランプ２１ｃｍ±１．５ｃｍ、コンクリート配合IIIはスランプ１８ｃｍ±１．５ｃｍとなるように添加剤の添加量を調整した。
【００９４】
（３）コンクリート流動性の経時安定性
上記（２）において、製造されたコンクリートを角型コンテナー（通称練り板）に静置保管しコンクリート混練直後より３０分後、６０分後、９０分後のコンクリートのスランプ（ＪＩＳ Ａ １１０１に基づいて）をそれぞれ測定した。ただし、測定前にスコップを用いて練り返しを行った。
【００９５】
（４）空気量の測定
空気量測定方法は、フレッシュコンクリートの空気量の容積による試験方法（ＪＩＳ−Ａ１１１８法）にて測定した。その際、混練直後の空気量（初期空気量）はコンクリート配合３種類ともに、４．５±１．５体積％になるように気泡連行剤マイテイＡＥ−０３：花王（株）製）と消泡剤（アンチフォームＥ−２０：花王（株）製）で調整した。空気安定性は、混練直後から３０分後、６０分後、９０分後まで測定した。初期空気量に対する差が小さいほど空気安定性が良好である。
【００９６】
（５）ブリージング率
ＪＩＳ−Ａ１１２３法に準じてブリージング率を測定した。
【００９７】
【表１】

【００９８】
【表２】

【００９９】
【表３】

【０１００】
【表４】

【０１０１】
【表５】

【０１０２】
【表６】

【０１０３】
【表７】

【０１０４】
表５〜７中の添加量は、（Ａ）成分と（Ｂ）成分と（Ｃ）成分とその他の成分の合計量の対セメント重量％である。また、比較例１−１〜１−３で用いた成分は以下のものである。
＊リグニンスルホン酸Ｎａ塩（１）：ウルトラジンＮＡＳ、ボレガード社製、脱糖（１％以下）
＊リグニンスルホン酸Ｎａ塩（２）パールレックスＣＰ、日本製紙（株）製
＊ポリカルボン酸塩系分散剤：マイテイ３０００Ｓ、花王（株）製[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an additive for poor blended concrete having a small cement blend amount.
[0002]
[Prior art]
From the aspect of preventing cracking due to heat of hydration and not requiring high strength in design, concrete 1m^ThreeThe weight of hydraulic powder per unit (hereinafter also simply referred to as weight) is 190 to 350 kg / m^ThreeAnd water / hydraulic powder ratio [weight percentage (% by weight) of water and hydraulic powder in the composition, hereinafter referred to as W / P. ] Of 50 to 70%, so-called poor blended concrete is widely used for dam concrete, mass concrete such as concrete using AE water reducing agent (JIS 6204), and the like.
[0003]
Conventionally, lignin sulfonic acid and oxycarboxylic acid admixtures have been used as dispersants for poor blended concrete, but they have caused water separation (breathing) and gravel separation, resulting in workability and properties of hardened concrete. In some cases, it was damaged.
[0004]
Patent Document 1 discloses a surfactant composition containing a polycarboxylic acid polymer to which alkylene oxide is added in order to improve these.
[0005]
On the other hand, a technique using a phosphate ester-based additive as an additive for a hydraulic composition is disclosed. For example, Patent Document 2 contains a specific polycarboxylic acid-based cement dispersant, a specific nonionic compound, and a polyoxyalkylene alkyl ether phosphate ester as one selected from compounds used for the AE agent. Techniques using additive compositions are disclosed.
[0006]
[Patent Document 1]
JP 2000-351992 A
[Patent Document 2]
Japanese Patent Publication No.53-37251
[0007]
[Problems to be solved by the invention]
An object of the present invention is to provide an additive for poor blending concrete that has good additive workability, has stable entrained air amount, fluidity and fluidity retention in a fresh state of poor blended concrete, and suppresses breathing. .
[0008]
[Means for Solving the Problems]
In poorly blended concrete, particularly, a large amount of breathing water is likely to be generated. Therefore, adhesion of the mortar portion and the coarse aggregate is prevented, and the coarse aggregate is discharged onto the concrete surface, resulting in a rough concrete surface. Further, such a concrete having a high amount of breathing water is adversely affected by a decrease in the concrete strength itself, a decrease in the adhesion strength with the reinforcing bars, or an increase in the water permeability and air permeability of the hardened concrete.
[0009]
A lignin-based cement dispersant widely used as an additive for poor blended concrete can give good fluidity to the fresh state of poor blended concrete, but the material separation resistance is insufficient and breathing occurs. Or the amount of entrained air in the concrete that plays an important role in the frost resistance of the concrete is unstable.
[0010]
Although the occurrence of breathing can be suppressed by using a polycarboxylic acid-based cement dispersant that has become popular in recent years, it cannot be said that the stability of the entrained air amount has been sufficiently improved.
[0011]
In addition, phosphate ester additives that have been used as conventional AE agents (admixtures that are used to improve the workability and durability against freezing and thawing by entraining countless fine air bubbles in concrete) The amount of addition at the time of concrete kneading is extremely small, especially in a poorly blended concrete system in which the amount of water is large together with the amount of cement, the amount of addition is even smaller, and the stability of the entrained air amount has not been improved.
[0012]
The inventors of the present invention have studied various additives for stabilizing the amount of entrained air without reducing the freshness fluidity and fluidity retention and breathing suppressing power of poor blended concrete. It has been found that such a problem can be solved by an additive containing an ester.
[0013]
The present invention includes a phosphoric acid monoester having a group represented by the following general formula (1) or a salt thereof (hereinafter referred to as a monoester form) and a phosphoric acid diester having a group represented by the following general formula (1). (The diester includes a diester of pyrophosphate) or a salt thereof (hereinafter referred to as a diester body), an additive for poor blended concrete, wherein the weight ratio of the monoester body to the diester body is a monoester body / It relates to an additive for poor blended concrete (monoester body + diester body) of 0.4 to 0.95 (hereinafter referred to as component (A) together with the monoester body and the diester body).
R¹-O (AO)_n-(1)
[In the formula, R¹Is an alkyl group or alkenyl group having 8 to 22 carbon atoms, or a hydrocarbon group having two or more benzene rings, AO is an oxyalkylene group having 2 to 4 carbon atoms, n is an average number of moles added, and is a number from 1 to 50 Indicates. ]
[0014]
Moreover, this invention relates to the poor mixing | blending concrete containing the additive for poor mixing | blending concretes of the said invention, hydraulic powder, and water.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
<Embodiment I>
By using the component (A) in the additive for poor blended concrete of the present invention, an additive having good fresh properties of the poor blended concrete and excellent product stability can be obtained. Hereinafter, the case where the component (A) is used alone in the additive for poor blended concrete of the present invention (when the only effective component is the component (A)) will be described as Embodiment I.
[0016]
The component (A) needs to have a group represented by the general formula (1) from the viewpoint of fluidity and breathing. Where R¹Is an alkyl or alkenyl group having 8 to 22 carbon atoms, preferably 10 to 20 carbon atoms, or a hydrocarbon group having two or more benzene rings. As the component (A), an alkyl ether phosphate monoester having an alkyl ether group or a salt thereof, an alkenyl ether phosphate monoester having an alkenyl ether group or a salt thereof, an aryl having an aryl ether group having two or more benzene rings Examples include ether phosphate monoesters or salts thereof. From the viewpoint of the pumpability of the aqueous additive solution of the present invention (viscosity of aqueous solution and uniformity of aqueous solution), fluidity of poor blended concrete, and bubble stability, the alkyl group has 12 to 16 carbon atoms and the alkenyl group has carbon atoms. 16 to 20, and the hydrocarbon group having two or more benzene rings preferably has a total carbon number of 13 to 38. Further, from the viewpoint of air content stability of poor blended concrete, the alkyl group or alkenyl group is particularly preferably a myristyl group and an oleyl group, and the hydrocarbon group having two or more benzene rings has a total carbon number of 20. ~ 30. The hydrocarbon group having two or more benzene rings is preferably an aryl group having a group containing one or more benzene rings as a substituent, and particularly an aryl group having a group containing two or three benzene rings as a substituent. Further preferred. AO is an oxyalkylene group having 2 to 4 carbon atoms, such as oxyethylene group, oxypropylene group, and oxybutylene group, preferably oxyethylene group and oxypropylene group. The ratio of the ethylene group is preferably 50 mol% or more, more preferably 70 mol% or more, and particularly preferably 100 mol%. n is the average number of added moles and represents a number of 1 to 50. From the viewpoint of the fluidity of poor blended concrete, n is preferably 3 to 35, more preferably 5 to 30, and particularly preferably 10 to 25. . The structure of general formula (1) is important and R¹When the carbon number, type, and n in the above range are within the above ranges, excellent air volume stability and appropriate fluidity imparting effect for poor blended concrete can be obtained.
[0017]
The phosphate ester having such a structure not only exhibits the fluidity of the hydraulic composition well, but also stably maintains the amount of entrained air in the hydraulic composition (hereinafter, also simply referred to as bubbles) for a long time. , Excellent in suppressing the breathing.
[0018]
When the cross section of the cured body of the hydraulic composition using the phosphate ester of the present invention is observed, extremely fine bubbles are found in the mortar (mixture of water, hydraulic powder and fine aggregate in the hydraulic composition). You can see that it has occurred.
[0019]
Thus, in the fresh state of the hydraulic composition using the phosphate ester of the present invention, it is considered that a large amount of fine bubbles are generated, hardly coalesced, and hardly broken.
[0020]
Due to the generation of such stable bubbles, even a hydraulic composition with low mortar content such as poor blended concrete, the entrained air volume is stable for a long time, the material separation resistance of the mortar itself is strong, and the affinity with coarse aggregate It is presumed that it is possible to secure properties that are good in properties and hardly cause breathing.
[0021]
Examples of the salt of component (A) include alkali metal salts, alkaline earth metal salts, ammonium salts, and amine salts, preferably alkali metal salts and hydroxyl group-substituted alkylamine salts, particularly preferably potassium salts and sodium salts. , Triethanolamine salt, and particularly preferably sodium salt, potassium salt, most preferably potassium salt from the viewpoint of product stability.
[0022]
The monoester body and diester body of the component (A) preferably have a structure represented by the general formula (1-1).
[0023]
[Formula 4]

[0024]
[In the formula, R¹Is an alkyl group or alkenyl group having 8 to 22 carbon atoms, or a hydrocarbon group having two or more benzene rings, AO is an oxyalkylene group having 2 to 4 carbon atoms, n is an average number of moles added, and is a number from 1 to 50 Indicates. k represents 1 or 2, and M represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkylammonium group, or a hydroxyl group-substituted alkylammonium group. ]
[0025]
In general formula (1-1), two M when k is 1, and two R when k is 2.¹And n may be different from each other.
[0026]
The component (A) is a monoester or diester of phosphoric acid having a group represented by the general formula (1) bonded to a phosphorus atom, or a salt thereof. From the viewpoint of product stability when the additive of the present invention is an aqueous solution, the weight ratio of the monoester body and the diester body (the diester body includes a diester body of pyrophosphoric acid) is monoester body / (mono Ester body + diester body) is 0.4 to 0.95, and preferably 0.5 to 0.95, more preferably 0.8 from the viewpoint of the fluidity of poor blended concrete and the pumpability of the aqueous additive solution. It is 65 to 0.95, more preferably 0.7 to 0.95, and more preferably 0.7 to 0.85 from the viewpoint of industrial ease of production.
[0027]
Further, the additive for poor blended concrete of the present invention is a triester of phosphoric acid having a group represented by the general formula (1) in addition to the component (A) (monoester and diester) (hereinafter referred to as triester). May be included). If the component (A) satisfies the above-mentioned ratio of the monoester body and the diester body and the content in the additive for poor blended concrete of the present invention described later, the ratio and amount of the triester body are not particularly limited. The weight ratio of ester body + diester body / (monoester body + diester body + triester body) is preferably 0.7 or more, more preferably 0.8 or more.
[0028]
In addition, it is important that the component (A) satisfies the above weight ratio, and the monoester body and the diester body, and further the R of the triester body.¹, AO, n may be the same or different.
[0029]
The component (A) can be obtained, for example, by adding an alkylene oxide to an alcohol, followed by phosphoric esterification. Alternatively, it can also be obtained by a phosphoric esterification reaction using a commercially available alkylene oxide adduct of alcohol as a raw material. Natural alcohol or synthetic alcohol can be used as the alcohol. The alkylene oxide has 2 to 4 carbon atoms, and examples thereof include ethylene oxide (hereinafter referred to as EO), propylene oxide (hereinafter referred to as PO), and butylene oxide (hereinafter referred to as BO). Is preferably EO or a combination of EO and PO, particularly preferably EO. Moreover, the addition form of 2 or more types of alkylene oxide groups may be any of block bonds, random bonds, or a mixture of them.
[0030]
As a method for the phosphoric acid esterification reaction, a general method can be used. For example, in addition to the method using phosphoric anhydride, component (A) can also be produced by a method using phosphoric anhydride and phosphoric acid aqueous solution, phosphoric anhydride and water, phosphorus oxychloride, polyphosphoric acid, and the like. In the present invention, in order to adjust the ratio of the monoester compound in the component (A), in the above production method, the ratio and reaction time of the polyoxyalkylene alkyl ether and the phosphorylating agent are adjusted, or hydrolysis is performed. In addition to reaction, adjustment may be performed by purification such as crystallization and distillation, attachment, or the like. In particular, the hydrolysis reaction is effective for increasing the proportion of the monoester in the component (A). In addition, it is preferable to use a polyoxyalkylene alkyl ether (narrowed ethoxylate) having a narrow molecular weight distribution range from the viewpoint of fluidity of poor blended concrete.
[0031]
<Embodiment II>
The additive for poor blended concrete of the present invention is (B1) an alkyl group or alkenyl group having 8 to 26 carbon atoms or one or more benzene rings in terms of improving fluidity as compared with the case where the component (A) is used alone. A nonionic compound having a hydrocarbon group having 6 to 35 carbon atoms and a polyoxyalkylene group having an average addition mole number of 3 to 400, which is composed of an oxyalkylene group having 2 to 4 carbon atoms. (Referred to as component (B1)], and (B2) an alkyl group or alkenyl group having 8 to 26 carbon atoms or a hydrocarbon group having 6 to 35 carbon atoms having one or more benzene rings and an oxyalkylene group having 2 to 4 carbon atoms. An ionic compound having a polyoxyalkylene group having an average addition mole number of 5 to 400 (a phosphate ester having a group represented by the general formula (1) or Excluding salt) [hereinafter, (B2) of Component] one or more compounds selected from (B) [hereinafter referred to as component (B)] is preferably contained. The component (B) preferably has 1 to 2 polyoxyalkylene groups. Hereinafter, the case where the component (A) and the component (B) are used in combination in the additive for poor blended concrete of the present invention (when the substantial active component is the component (A) and the component (B)) is embodiment II Will be described.
[0032]
In the alkylene oxide added to the component (B), EO is preferably used in an amount of 50 mol% or more, more preferably 70 mol% or more, and particularly preferably 100 mol%.
[0026]
The nonionic compound of general formula (2) is R²It is obtained by adding an alkylene oxide selected from EO, PO, and BO, preferably EO, or EO and PO, more preferably EO, to an alcohol having the following group. Similarly, the nonionic compounds of general formulas (3) and (4) are R^ThreeOr R^FiveIt can be obtained by adding an alkylene oxide selected from EO, PO and BO, preferably EO, or EO and PO, to a compound having the above group. From the viewpoint of aqueous solution properties, EO is preferably used in an amount of 50 mol% or more, more preferably 70 mol% or more, and particularly preferably 100 mol% in the alkylene oxide to be added. As the component (B1), a nonionic compound represented by the general formula (2) is particularly preferable. Further, from the viewpoint of foam stability of fresh concrete, it is preferable that an oxypropylene group is further contained, and the ratio of the oxyethylene group in the polyoxyalkylene group is preferably 10 mol% or more, more preferably 25 mol%. That's it. From the comprehensive viewpoint of water solubility and bubble stability, the molar ratio of oxyethylene group to oxypropylene group is preferably 90/10 to 30/70, more preferably 80/20 to 40/60. Moreover, the addition form of 2 or more types of alkylene oxide groups may be any of block bonds, random bonds, or a mixture of them.
[0033]
As the component (B), one or more compounds selected from the compound represented by the general formula (2), the compound represented by the general formula (3) and the compound represented by the general formula (4), and others And polyoxyalkylene sorbitan alkyl ester, polyoxyalkylene glycerin alkyl ester, polyoxyalkylene hydrogenated castor oil and the like. From the viewpoint of aqueous solution viscosity in embodiment II, the compound represented by general formula (2), general formula One or more compounds selected from the compound represented by (3) and the compound represented by formula (4) are preferred.
R²-O- (AO)_p-R (2)
R^Three-COO- (AO)_q-R^Four          (3)
R^Five-NH_(2-t)[(AO)_s-H]_t        (4)
[In the formula, R², R^ThreeAnd R^FiveAre each an alkyl group or alkenyl group having 8 to 26 carbon atoms or a hydrocarbon group having 6 to 35 carbon atoms having one or more benzene rings, R and R^FourAre each a hydrogen atom, an alkyl or alkenyl group having 1 to 26 carbon atoms, or a hydrocarbon group having 6 to 35 carbon atoms having one or more benzene rings, preferably a hydrogen atom, and AO is an oxyalkylene having 2 to 4 carbon atoms. Group, p, q, and s are average addition mole numbers, respectively, 3-400, Preferably it is 5-200, More preferably, it is the number of 8-150, t shows 1 or 2. 2 (AO) when t is 2_sMay be different. ]
[0034]
In the general formulas (2) to (4), R², R^ThreeAnd R^FiveAre each preferably a linear alkyl group or alkenyl group having 10 to 22 carbon atoms, more preferably 14 to 20 carbon atoms, especially 14 to 18 carbon atoms, and particularly preferably an oleyl group. In the case of a C6-C35 hydrocarbon group having one or more benzene rings, a hydrocarbon group having two or more benzene rings (particularly an aryl group having a group containing one or more benzene rings as a substituent) is preferable. A hydrocarbon group having 3 or 4 benzene rings (particularly an aryl group having a group containing 2 or 3 benzene rings as a substituent) is more preferable, and the total carbon number is preferably 20 to 30. R and R^FourAre a hydrogen atom, a C1-C26 alkyl group or alkenyl group or a C6-C35 hydrocarbon group having one or more benzene rings, a hydrogen atom, a C1-C8 alkyl group, carbon An alkenyl group having 2 to 8 carbon atoms is preferable, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkenyl group having 2 to 4 carbon atoms are more preferable, and particularly a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, and 2 carbon atoms. Are preferred.
[0035]
Among the components (B1), the nonionic compound of the general formula (2) includes polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyalkylene polystyreneated phenyl ether, polyoxyalkylene polybenzylated phenyl ether. Preferably, polyoxyalkylene (di or tri) styrenated phenyl ether or polyoxyalkylene (di or tri) benzylated phenyl ether is more preferable from the viewpoint of foam stability of fresh concrete, and nonionic of general formula (3) Examples of the ionic compound include polyoxyalkylene alkyl ester and alkoxy polyoxyalkylene alkyl ester, and examples of the nonionic compound represented by the general formula (4) include polyoxyalkylene alkylamine. In addition, a compound having a hydrophobic group such as an organosiloxane instead of the specific alkyl group, alkenyl group, or one or more benzene ring-containing hydrocarbon group having 1 or more benzene rings, such as a silicone-based surfactant. An agent or the like can also be used. As the component (B1), from the viewpoint of product stability, more preferably, the nonionic compound of the general formula (2) is a polyoxyalkylene alkyl ether, and the nonionic compound of the general formula (3) is a polyoxy The alkylene alkyl ester and the nonionic compound of the general formula (4) are polyoxyalkylene alkyl amines, and among these, polyoxyalkylene alkyl ether is particularly preferable.
[0036]
As the component (B1), a nonionic compound represented by the general formula (2) is particularly preferable.
[0037]
Moreover, as a (B2) component, polyoxyalkylene alkyl ether sulfate and polyoxyalkylene alkyl ether carboxylate are preferable. The structure (carbon number, average added mole number, etc.) of these polyoxyalkylene moieties and the carbon number of the alkyl group are the same as in the component (B1).
[0038]
From the viewpoint of aqueous solution properties, (B1) is more preferable than (B2).
[0039]
In the embodiment II in which the component (A) and the component (B) are used in combination, the weight ratio of monoester / (monoester + diester) is preferably from the viewpoint of product stability and fluidity of poor blended concrete. Is 0.5 to 0.95, more preferably 0.65 to 0.95, more preferably 0.7 to 0.95, and particularly preferably 0.7 to 0 from the viewpoint of industrial ease of production. .85. A weight ratio of monoester / (monoester + diester) of less than 0.4 is not preferable from the viewpoint of the pumpability of the aqueous additive solution.
[0040]
Moreover, in Embodiment II which uses (A) component and (B) component together, since the fluidity | liquidity of the poor mixing concrete which (A) component gives improves more, n is 3-35, 5-30 is further more preferable. 8 to 25 are preferable and particularly preferable.
[0026]
Furthermore, from the viewpoint of the fluidity of the poor blended concrete, the weight ratio of (A) / (B) is preferably 99/1 to 10/90, more preferably 90/10 to 30/70, and particularly 80/20 to 45/55 is preferred.
[0041]
<Embodiment III>
In addition to the component (A) and the component (B), the additive for poor blended concrete of the present invention is represented by the general formula (5) from the viewpoint of improving the fluidity retention of the poor blended concrete and further suppressing breathing. One or more types selected from the structural unit derived from the monomer represented, the structural unit derived from the monomer represented by the general formula (6), and the structural unit derived from the monomer represented by the general formula (7) It is preferable to contain the copolymer (C) which has a structural unit of [Hereinafter, it is called (C) component.]. Hereinafter, when (A) component, (B) component, and (C) component are used together in the additive for poor blended concrete of the present invention (substantially effective components are (A) component, (B) component, and (C ) Component) is described as embodiment III.
[0042]
The component (C) is one or more selected from the monomer represented by the general formula (5), the monomer represented by the general formula (6), and the monomer represented by the general formula (7). And a copolymer obtained by polymerizing. As the monomer represented by the general formula (5), an ethylenically unsaturated carboxylic acid ester having an oxyalkylene group or a polyoxyalkylene group having an average addition mole number of 1 to 300 is preferable. Here, the oxyalkylene group may be an oxystyrene group, and the polyoxyalkylene group may include an oxystyrene group or a polyoxystyrene group. Two or more types of the monomer represented by the general formula (5), the monomer represented by the general formula (6), and the monomer represented by the general formula (7) may be used in combination. .
[0043]
[Chemical formula 5]

[0044]
[Where,
R⁶, R⁷: Hydrogen atom or methyl group, respectively
m: number from 0 to 2
R⁸: Hydrogen atom or -COO (AO)_n1Y
p: number of 0 or 1
AO: C2-C4 oxyalkylene group or oxystyrene group
n1: Number of average added moles and a number of 1 to 300
Y: a hydrogen atom or an alkyl or alkenyl group having 1 to 18 carbon atoms
Represents. ]
[0045]
[Chemical 6]

[0046]
[Where,
R⁹~ R¹¹: Hydrogen atom, methyl group or (CH₂)_m1COOM²And (CH₂)_m1COOM²Is COOM¹Or other (CH₂)_m1COOM²And may form an anhydride, in which case the M of those groups¹, M²Does not exist.
M¹, M²: Hydrogen atom, alkali metal, alkaline earth metal, ammonium group, alkylammonium group or hydroxyl group-substituted alkylammonium group, respectively
m1: Number from 0 to 2
[0047]
[Chemical 7]

[0048]
Z: hydrogen atom, alkali metal, alkaline earth metal, ammonium group, alkylammonium group or hydroxyl-substituted alkylammonium group
Represents. ]
[0049]
Monomers represented by the general formula (5) include one-end alkyl-capped polyalkylene glycols such as methoxypolyethylene glycol, methoxypolypropylene glycol, methoxypolybutylene glycol, methoxypolystyrene glycol, ethoxypolyethylenepolypropyleneglycol, and (meth) acrylic. Acid, (half) esterified product with maleic acid, etherified product with (meth) allyl alcohol, and (EO) PO and PO adducts to (meth) acrylic acid, maleic acid, (meth) allyl alcohol are preferably used, R⁸Is preferably a hydrogen atom, m is preferably 0, and p is preferably 1. More preferably, it is an esterified product of alkoxy, particularly methoxypolyethylene glycol and (meth) acrylic acid, and still more preferably an esterified product of methoxypolyethylene glycol and methacrylic acid. The esterification may be performed on the monomer, or may be performed after the copolymerization with the monomer of the general formula (6) and / or the monomer of the general formula (7). The average added mole number n1 of the alkylene oxide is in the range of 1 to 300 because it is excellent in fluidity and fluidity retention, and more preferably in the range of 8 to 200, particularly 20 to 150. Y is more preferably an alkyl group or alkenyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group. The alkylene oxide is preferably EO or EO and PO, and particularly preferably EO.
[0050]
Examples of the monomer represented by the general formula (6) include unsaturated monocarboxylic acid monomers such as (meth) acrylic acid and crotonic acid, and unsaturated dicarboxylic acids such as maleic acid, itaconic acid, and fumaric acid. Type monomers, or salts thereof such as alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts, etc., (meth) acrylic acid or alkali metal salts thereof are preferred, and more preferred Is methacrylic acid or an alkali metal salt thereof, particularly preferably methacrylic acid or a sodium salt thereof. Examples of the monomer represented by the general formula (7) include (meth) allylsulfonic acid or a salt thereof such as an alkali metal salt, an alkaline earth metal salt, an ammonium salt, an amine salt, and the like. Is methallylsulfonic acid or its sodium salt.
[0051]
Weight average molecular weight of copolymer of component (C) [gel permeation chromatography method, converted to polyethylene glycol, column: G4000PWXL + G2500PWXL (manufactured by Tosoh Corporation), eluent: 0.2M phosphate buffer / acetonitrile = 7 / 3 (volume ratio)] is preferably 1000 to 200,000, particularly preferably 15,000 to 100,000, in order to obtain sufficient fluidity and fluid retention for the hydraulic powder.
[0052]
(C) A component is the monomer (5) represented by General formula (5), the monomer (6) represented by General formula (6), and the single quantity represented by General formula (7) The body (7) has a molar ratio of (5) / [(6) + (7)] of 99/1 to 1/99, more preferably 60/40 to 1/99, especially 40/60 to 5/95. It is preferable that it is manufactured using. The molar ratio (6) / (7) of the monomer represented by the general formula (6) and the monomer represented by the general formula (7) is preferably 100/0 to 80/20, 0-90 / 10 is preferable.
[0053]
Component (C) can be copolymerized with acrylonitrile, (meth) acrylamide, styrene, alkyl (meth) acrylate (having 1 to 12 carbon atoms which may have a hydroxyl group) ester, styrene sulfonic acid, etc. Various monomers may be used in combination. These can be used in a proportion of preferably 50% by weight or less, more preferably 30% by weight or less, based on all monomers, with 0% by weight being particularly preferred.
[0054]
The copolymer of component (C) can be produced by a known method. For example, there is a solution polymerization method described in JP-A No. 11-157877. In the presence of a polymerization initiator such as ammonium persulfate or hydrogen peroxide in water or a lower alcohol having 1 to 4 carbon atoms, if necessary, sodium sulfite or What is necessary is just to add mercaptoethanol etc. and to make it react at 50-100 degreeC for 0.5 to 10 hours.
[0055]
In consideration of the type of hydraulic powder and the like, it is also preferable to use two or more types of copolymers of component (C).
[0056]
In Embodiment III, the specific compounds of component (A) and component (B), the range of the monoester / (monoester + diester) weight ratio, the range of (A) / (B) weight ratio And the like can be appropriately selected from Embodiment I or Embodiment II.
[0057]
The weight ratio of the component (A) to the component (C) is (A) / (C) = 99/1 to 10/90, more preferably 90/10 to 30/70, and particularly 80/20 to 45/55. It is preferable from the viewpoint of the fluid retention effect.
[0058]
<Additives for poor blended concrete>
The poor blended concrete targeted by the present invention is mainly made of hydraulic powder such as cement, fine aggregate and coarse aggregate, and is manufactured by adding the additive of the present invention. Body weight, preferably cement weight is 190-350 kg / m^Three270-330kg / m especially^ThreeHydraulic composition such as cement paste, mortar and concrete. Furthermore, concrete that satisfies the weight of the hydraulic powder and has a water / hydraulic powder ratio of 50 to 70%, more preferably 50 to 65%, and particularly 55 to 65% can be mentioned.
[0059]
The additives for poor blended concrete of the present invention can be used as a viscosity reducing agent or the like because any one of Embodiments I to III can reduce the amount of water and thus has a viscosity reducing effect.
[0060]
In any of Embodiments I to III, the additive for a poor blended concrete of the present invention has component (A) of 0.01 to 7.5 parts by weight, more preferably 0.01 to 100 parts by weight of hydraulic powder. It is preferably used in an amount of 5 parts by weight, more preferably 0.02 to 3 parts by weight, particularly 0.02 to 1 part by weight, from the viewpoint of the dispersibility, fluidity, or viscosity-reducing effect of poor blended concrete.
[0061]
Moreover, (B) component should be used so that it may become 0.01-5 weight part with respect to 100 weight part of hydraulic powder, Furthermore, 0.02-3 weight part, Especially 0.02-1 weight part. However, it is preferable in terms of fluidity of the poor blended concrete.
[0062]
Moreover, (C) component should be used so that it may become 0.01-5 weight part with respect to 100 weight part of hydraulic powder further, 0.05-2 weight part, especially 0.05-1 weight part. However, it is preferable in terms of the fluid retention effect of the poor blended concrete.
[0063]
The weight ratio of the component (A) to the component (B) is (A) / (B) = 99/1 to 10/90, more preferably 90/10 to 30/70, and particularly 80/20 to 45/55. It is preferable from the viewpoint of fluidity of the poor blended concrete.
[0064]
Further, in the additive for poor blended concrete of the present invention, the total amount of the component (A), the component (B) and the component (C) [the component (B) and the component (C) may be 0% by weight, respectively) The proportion of the additive is preferably 5 to 100% by weight, more preferably 10 to 100% by weight, and particularly preferably 20 to 100% by weight in the additive. The ratio of the total amount is 50 to 100% by weight, more preferably 70 to 100% by weight, especially 80% in the total of the components (A), (B), (C) and other components. ~ 100% by weight is preferred.
[0065]
The additive for poor blended concrete of the present invention is preferably used as a solution from the viewpoint of workability. Water or an organic solvent can be used as the solvent, and it is preferably used as an aqueous solution containing water as a solvent from the viewpoint of safety. The total of the components (A), (B) and (C) (hereinafter referred to as an effective component). It is preferable that an aqueous solution having a concentration of 20 wt% or more exhibits a uniform appearance at 20 ° C. Further, the viscosity at 20 ° C. of the aqueous solution is preferably 500 mPa · s or less, more preferably 300 mPa · s or less, further 1 to 300 mPa · s, further 150 mPa · s or less, and further 1 to 150 mPa · s, It is preferable in terms of workability.
[0066]
The additive for poor blended concrete of the present invention may be used in combination with other components, for example, a dispersant having a structure other than the components (A), (B), and (C). The dispersant is not limited as long as it is generally used as an admixture for concrete, but oxycarboxylic acid such as sodium gluconate or a salt thereof, naphthalene sulfonate formaldehyde condensate, melamine sulfonate formaldehyde condensate, Polycarboxylic acid or its ester or its salt, purified lignin sulfonic acid or its salt, polystyrene sulfonate, cement dispersant with phenol skeleton (eg formaldehyde co-polymer with other monomers copolymerizable with phenol sulfonic acid) Condensates), cement dispersants based on aniline sulfonic acid (for example, formaldehyde co-condensates with other monomers co-condensable with aniline sulfonic acid), and so on, what are conventionally called water reducing agents are preferred. Used and fresh concrete bubbles In terms of qualitative, naphthalene sulfonate formaldehyde condensates, melamine sulfonate formaldehyde condensates more preferable.
[0067]
Further, instead of the copolymer of the component (C), an ethylenically unsaturated monomer as described in the claims of JP-A-11-139855 is grafted onto a polyether compound. A polymer can be used.
[0068]
The additive of the present invention according to the above embodiment has good product stability when it is made into an aqueous solution, and when used for poor blended concrete, imparts good fluidity to the poor blended concrete and reduces its viscosity. In addition, since the fresh properties of such poorly blended concrete can be stably expressed, workability and workability when using poorly blended concrete such as pumping, driving and filling into a mold are greatly improved.
[0069]
The additive for poor blended concrete of the present invention can be used in combination with a known additive (material). For example, AE agent, fluidizing agent, retarder, early strengthening agent, accelerator, foaming agent, water retention agent, thickener, waterproofing agent, antifoaming agent, shrinkage reducing agent, water-soluble polymer, interface Examples of the activator include silica powder, blast furnace slag, fly ash, and silica fume.
[0070]
Especially, it is preferable to contain an antifoamer. Antifoaming agents (excluding component (B)) include (1) lower alcohols such as methanol and ethanol, (2) silicones such as dimethyl silicone oil and fluorosilicone oil, and (3) mineral oils and surfactants. (4) trialkyl phosphate esters such as tributyl phosphate, (5) oleic acid, sorbitan oleic acid monoester, polyethylene glycol fatty acid ester, polyethylene glycol / polypropylene glycol fatty acid ester, etc. Examples include fatty acid or fatty acid ester type, (6) polyoxyalkylene type such as polypropylene glycol, polyethylene glycol / polypropylene glycol alkyl ether and the like. Preferably, it is at least one antifoaming agent selected from fatty acid or fatty acid ester antifoaming agent, silicone antifoaming agent, polyoxyalkylene antifoaming agent and trialkyl phosphate ester antifoaming agent. From the viewpoint of mixing stability with the additive for poor blended concrete, more preferably one or more antifoaming agents selected from fatty acid or fatty acid ester antifoaming agents, silicone antifoaming agents, and polyoxyalkylene antifoaming agents. More preferably one or more antifoaming agents selected from fatty acid or fatty acid ester antifoaming agents and silicone antifoaming agents, and particularly preferably silicone antifoaming agents. The amount of the defoaming agent is different from the range of air amount required for the poor blended concrete, but from the viewpoint of the strength and freeze-thaw resistance of the poor blended concrete, the component (A) in the additive of the present invention ( 0.01 to 10 parts by weight is preferable, 0.05 to 5 parts by weight is more preferable, and 0.1 to 3 parts by weight is particularly preferable with respect to 100 parts by weight of the total amount of component B) and component (C).
[0071]
<Poor blended concrete>
The present invention relates to poor blended concrete containing the additive for poor blended concrete of the present invention, hydraulic powder, and water. As described above, the poor blended concrete has a hydraulic powder weight of 190 to 350 kg / m.^ThreeFurther, 220 to 330 kg / m^Three270-330kg / m especially^ThreeW / P is 50 to 70%, more preferably 50 to 65%, especially 55 to 65%, in particular, the weight of the hydraulic powder is 270 to 330 kg / m.^ThreeAnd it is preferable that W / P is 55 to 65%.
[0072]
In the poor blend concrete of the present invention, component (A) is 0.01 to 7.5 parts by weight, further 0.05 to 5 parts by weight, and further 0.02 to 3 parts per 100 parts by weight of the hydraulic powder. It is preferable to contain 0.02 to 1 part by weight, particularly 0.02 to 1 part by weight. Moreover, in the poor blend concrete of this invention, the total amount of (A) component, (B) component, and (C) component is 0.01-10 weight part with respect to 100 weight part of hydraulic powder, Furthermore, 0 It is preferable to contain 0.01 to 7.5 parts by weight, particularly 0.05 to 3 parts by weight.
[0073]
Examples of the cement include ordinary Portland cement, early-strength Portland cement, ultra-early-strength Portland cement, and eco-cement (for example, JIS R5214). The poor-mixed concrete of the present invention may include blast furnace slag, fly ash, silica fume and the like as hydraulic powder other than cement, and may include non-hydraulic fine limestone powder and the like. Silica fume cement or blast furnace cement mixed with cement may be used.
[0074]
Moreover, the poor-mixed concrete of the present invention may contain an aggregate. Examples of the aggregate include fine aggregate and coarse aggregate. The fine aggregate is preferably mountain sand, land sand, river sand and crushed sand, and the coarse aggregate is preferably mountain gravel, land gravel, river gravel and crushed stone. Depending on the application, lightweight aggregates may be used. The term “aggregate” is based on “Concrete Overview” (published on June 10, 1998, published by Technical Shoin).
[0075]
【The invention's effect】
According to the present invention, it is possible to obtain an additive for poor blended concrete having good additive workability and stable entrained air amount, fluidity and fluidity retention in a fresh state of the blended concrete (immediately after kneading to the end of casting). It is done.
【Example】
In the following, in the production examples of each component, what is simply described as% means weight%.
[0076]
<(A) component>
(A) component used for the Example and the comparative example is as Table 1, and these were manufactured according to the following manufacture examples A-1 to A-2.
[0077]
(1) Production Example A-1
In a reaction vessel equipped with a stirrer, 500 g (0.44 mol) of an EO adduct of oleyl alcohol (average addition mole number 20, hydroxyl value 49.9) was charged, and the atmosphere was replaced with nitrogen while stirring to obtain a nitrogen atmosphere. It heated to about 80 degreeC and the water | moisture content was removed under pressure reduction. After returning to normal pressure and about 40 ° C., 21.5 g (0.15 mol) of commercially available phosphoric anhydride (purity 98%) was added. The addition of phosphoric anhydride was carried out in three portions. After the addition, the liquid temperature was adjusted to 65 to 75 ° C., and aging was performed for about 6 hours. The acid value 1 of the reaction product is measured, and tap water and 48% -water so that the neutralization degree is 0.5 to 1.0 with respect to the acid value 1 and the concentration is 20% by weight. It adjusted with potassium oxide aqueous solution and (A) component a-1 in Table 1 was obtained. Moreover, although a-2 was manufactured according to this method, after aging after addition of phosphoric anhydride, 26.1 g of tap water was added, the liquid temperature was adjusted to about 80 ° C., and about The hydrolysis reaction was performed for 4 hours.
[0078]
(2) Production Example A-2
In a reaction vessel equipped with a stirrer, 500 g (0.44 mol) of an EO adduct of oleyl alcohol (average addition mole number 20, hydroxyl value 49.9) was charged, and the atmosphere was replaced with nitrogen while stirring to obtain a nitrogen atmosphere. It heated to about 80 degreeC and the water | moisture content was removed under pressure reduction. After normal pressure and about 60 ° C., 9.40 g (0.08 mol) of phosphoric acid (purity 85%) is added dropwise. After becoming completely uniform, 26.2 g (0.18 mol) of commercially available phosphoric anhydride (purity 98%) was added. The addition of phosphoric anhydride was carried out in three portions. After the addition, the liquid temperature was adjusted to 65 to 75 ° C., and aging was performed for about 6 hours. 26.8 g of tap water was added, the liquid temperature was adjusted to about 80 ° C., and the mixture was further reacted for about 4 hours.
[0079]
The acid value 1 of the reaction product is measured, and tap water and 48% -water so that the neutralization degree is 0.5 to 1.0 and the concentration is 20% by weight with respect to the acid value 1. It adjusted with potassium oxide aqueous solution and (A) component a-3 in Table 1 was obtained. In the same manner, (A) components a-4, 5, 6, 7, and 8 were obtained.
[0080]
Here, the acid value of the reaction product was determined as follows.
The reaction product was dissolved in ethanol / water (70% by volume / 30% by volume), and a 0.5 mol / l potassium hydroxide aqueous solution (reagent) was used as a titration standard solution. ) And measured by multi-stage titration. The acid value 1 and acid value 2 of the reaction product are subsequently measured. The acid value 3 is measured using a sample different from the acid value 1 and acid value 2. The measurement is started in the same manner as the acid value 1, and after the titration of the acid value 1 is completed, about 20 ml of 1M calcium chloride aqueous solution is quickly added to the measurement solution. There may be some titration end points, but the last end point is the titration end point with an acid number of 3.
[0081]
(Calculation method of monoester ratio)
[0082]
³¹Phosphoric acid monoester, phosphoric acid diester, pyrophosphoric acid monoester, pyrophosphoric acid diester, phosphoric acid triester, pyrophosphoric acid and phosphoric acid contained in component (A) were quantified and calculated by P-NMR measurement (internal standard Trimethyl phosphate is used as a sample). Here, UNITY INOVA 300 (Varian) was used as the measurement apparatus, and the measurement conditions were a pulse width of 90 ° pulse (17.2 μs) and a waiting time of 30 s (more than 5 times t1). In order to improve spectral resolution, as a pretreatment, 2 volumes of heavy methanol is added to 1 volume of a 20 wt% aqueous solution sample, and the neutralization degree is 1.0 with respect to the acid value 3 of the sample measured above. Was added in a 20 wt% aqueous solution of potassium hydroxide. The molecular weight of the polyoxyalkylene alkyl ether was determined from each hydroxyl value.
[0083]
<(B) component>
(B) component used for the Example and the comparative example is as Table 2, and can be obtained with the manufacturing method of common nonionic compounds, such as a nonionic surfactant. Production Example B-1 shows a production method of polyoxyalkylene alkyl ether b-1.
[0084]
Production Example B-1
268 g of oleyl alcohol (hydroxyl value 209 mgKOH / g) and 0.56 g of potassium hydroxide were charged into a pressure vessel (3 liters), stirred and decompressed, and then purged with nitrogen. After heating up to 110 degreeC, it dehydrated at 2.7 kPa for 30 minutes. The temperature was raised to 155 ° C., 881.0 g of EO was reacted at a pressure of 0.02 to 0.4 MPa, and then aging was performed for 30 minutes. After cooling to 80 ° C. and subjecting to a reduced pressure treatment at 1.3 kPa for 15 minutes, 0.60 g of acetic acid was added at the same temperature (80 ° C.) for neutralization to obtain b-1.
[0085]
<(C) component>
(C) component used for the Example and the comparative example is as Table 3, and these were manufactured according to the following manufacture examples C-1 to C-3.
[0086]
(1) Production Example C-1
Into a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introducing tube and a reflux condenser, 366 parts by weight of water was charged, and nitrogen substitution was performed. Subsequently, after raising the temperature to 80 ° C. in a nitrogen atmosphere, a mixture of 898 parts by weight of methanol EO (average addition mole number 120) adduct / 60% aqueous solution of methacrylic acid monoester and 34.4 parts by weight of methacrylic acid; Three liquids, 62.3 parts by weight of a 5% -2-mercaptoethanol aqueous solution and 68.4 parts by weight of a 5% -ammonium persulfate aqueous solution, were dropped simultaneously, and the dripping was completed over 90 minutes for all three liquids. Next, after aging at the same temperature for 1 hour, 22.8 parts by weight of 5% -ammonium persulfate aqueous solution was added dropwise over 30 minutes, and after the addition, the mixture was aged at the same temperature for 2 hours. Further, after neutralizing by adding 23.3 parts by weight of 48% -aqueous sodium hydroxide solution, 8.0 parts by weight of 35% -hydrogen peroxide water was added, the temperature was raised to 90 ° C., and After being held for a period of time, it was cooled to obtain a copolymer (sodium salt, degree of neutralization 70%) c-1 having a weight average molecular weight of 53,000. Further, c-4 was produced in the same manner as c-1 except that methanol EO (average addition mole number: 18) adduct / methacrylic acid monoester was used in the molar ratio shown in Table 3.
[0087]
(2) Production Example C-2
Methanol was charged with 70 mol of water in a glass reaction vessel equipped with a thermometer, stirrer, dropping funnel, nitrogen inlet tube and reflux condenser, purged with nitrogen while stirring, and heated to 75 ° C. under a nitrogen atmosphere. EO (average addition mole number 120) adduct / methacrylic acid monoester 0.1 mol, methyl acrylate 0.7 mol and methacrylic acid 0.2 mol mixed and dissolved, 20% -ammonium persulfate aqueous solution 0. 05 mol (in terms of effective amount, hereinafter the same for the aqueous solution of this production example) and 0.1 mol of a 20% -2-mercaptoethanol aqueous solution were dropped together over 2 hours. Next, 0.02 mol of 20% -ammonium persulfate aqueous solution was added dropwise over 30 minutes, followed by aging at the same temperature (75 ° C.) for 1 hour. After the aging, the temperature was raised to 95 ° C., and 0.2% of 35% -hydrogen peroxide solution was added dropwise over 30 minutes. After aging at the same temperature (95 ° C.) for 2 hours, a 48% -sodium hydroxide aqueous solution 0.07 Mole was added to obtain a copolymer c-2 having a weight average molecular weight of 40,000.
[0088]
(3) Production Example C-3
A copolymer c-3 was obtained according to Example 8 of JP-A-2001-180998. However, instead of the monomer (A-IV) in the publication, methanol EO (average addition mole number 120) adduct / methacrylic acid monoester was used.
[0089]
Example 1
The poor blended concrete was prepared using the (A) component in Table 1, the (B) component in Table 2, and the (C) component in Table 3 as shown in Tables 5 to 7 with respect to the concrete blends in Table 4. Was evaluated. The results are shown in Tables 5-7.
[0090]
(1) State of aqueous solution
The state of the aqueous solution of the additive [the aqueous solution in which the total concentration of the components (A), (B), and (C) is 20% by weight) was visually observed after standing at 20 ° C. for 24 hours. When the aqueous solution was uniform, the viscosity at 20 ° C. was measured using Programmable Viscometer DVII + (manufactured by Brookfield), and the state of the aqueous solution was evaluated according to the following criteria. If this evaluation is Δ, ○, or ◎, an additive having aqueous solution properties that are not problematic in pumping property and the like can be provided.
A: The viscosity is 150 mPa.s. less than s
○: Viscosity of 150 mPa.s s to 300 mPa.s less than s
Δ: Viscosity of 300 mPa · s or more and 500 mPa.s less than s
X: Viscosity is 500 mPa.s s or more, or non-uniform aqueous solution
[0091]
(2) Concrete test
(2-1) Concrete mixing (mixing)
W: Tap water
C: Ordinary Portland cement (Pacific cement), density = 3.16 g / cm^Three
S1: Seto Inland sea sand, surface dry specific gravity = 2.56g / cm^Three
S2: Joyo mountain sand, surface dry specific gravity = 2.56 g / cm^Three
G: Crushed stone from Ibaraki, surface dry specific gravity = 2.64 g / cm^Three
The above materials were used in the preparation of the concrete blends I-III in Table 4.
[0092]
(2-2) Evaluation method
An aqueous additive solution [aqueous solution in which the total concentration of the (A) component, the (B) component, and the (C) component is 20% by weight) was added to tap water (mixed water) in the concrete composition shown in Table 4. At this time, as necessary, as an antifoaming agent, fatty acid ester antifoaming agent Foam Rex 797 (manufactured by Nikka Chemical Co., Ltd.) and silicone antifoaming agent Antifoam 013B (manufactured by Dow Corning Asia Ltd .; polyorganosiloxane type) Was added.
[0093]
Subsequently, gravel, about half the amount of sand, cement, and the remaining sand were put into a biaxial forced mixer (made by IHI) in this order. After empty kneading for 10 seconds, the above kneaded water was quickly stirred and added uniformly, and kneaded for 90 seconds. The slump flow was measured for the obtained concrete. At that time, the additive amount was adjusted so that the concrete blend I was slump 15 cm ± 1.5 cm, the concrete blend II was slump 21 cm ± 1.5 cm, and the concrete blend III was slump 18 cm ± 1.5 cm.
[0094]
(3) Stability of concrete fluidity over time
In the above (2), the manufactured concrete is stored in a square container (commonly known as a kneaded plate) and is slumped with concrete after 30 minutes, 60 minutes, and 90 minutes after concrete mixing (based on JIS A 1101). ) Were measured respectively. However, the kneading was performed using a scoop before measurement.
[0095]
(4) Measurement of air volume
The air amount measurement method was measured by a test method (JIS-A1118 method) based on the volume of air amount of fresh concrete. At that time, the amount of air immediately after kneading (initial air amount) is 4.5 ± 1.5% by volume for all three types of concrete blending, and the air bubble entrainer Mighty AE-03 (manufactured by Kao Corporation) and defoaming It adjusted with the agent (Antifoam E-20: Kao Co., Ltd. product). Air stability was measured from 30 minutes, 60 minutes, and 90 minutes immediately after kneading. The smaller the difference with respect to the initial air amount, the better the air stability.
[0096]
(5) Breathing rate
The breathing rate was measured according to JIS-A1123 method.
[0097]
[Table 1]

[0098]
[Table 2]

[0099]
[Table 3]

[0100]
[Table 4]

[0101]
[Table 5]

[0102]
[Table 6]

[0103]
[Table 7]

[0104]
The addition amount in Tables 5 to 7 is the weight percent of cement with respect to the total amount of component (A), component (B), component (C), and other components. The components used in Comparative Examples 1-1 to 1-3 are as follows.
* Lignin sulfonic acid Na salt (1): Ultrazine NAS, manufactured by Boleguard, desugared (1% or less)
* Lignin sulfonate Na salt (2) Pearl Rex CP, manufactured by Nippon Paper Industries Co., Ltd.
* Polycarboxylate-based dispersant: Mighty 3000S, manufactured by Kao Corporation

Claims (8)

A phosphoric acid monoester having a group represented by the following general formula (1) or a salt thereof (hereinafter referred to as a monoester form) and a phosphoric acid diester having a group represented by the following general formula (1) Including a diester of pyrophosphoric acid) or a salt thereof (hereinafter referred to as a diester form) [hereinafter referred to as a component (A) combining a monoester form and a diester form]
(B1) An alkyl group or an alkenyl group having 8 to 26 carbon atoms or a hydrocarbon group having 6 to 35 carbon atoms having one or more benzene rings and an oxyalkylene group having 2 to 4 carbon atoms, and an average added mole number And a nonionic compound having a polyoxyalkylene group having 3 to 400, and (B2) an alkyl group or alkenyl group having 8 to 26 carbon atoms or a hydrocarbon group having 6 to 35 carbon atoms having one or more benzene rings And an ionic compound comprising a polyoxyalkylene group having an average addition mole number of 5 to 400 (phosphoric acid having a group represented by the general formula (1)) One or more compounds selected from (excluding esters or salts thereof) (hereinafter referred to as component (B));
The structural unit derived from the monomer represented by the general formula (5), the structural unit derived from the monomer represented by the general formula (6), and the structural unit derived from the monomer represented by the general formula (7) A copolymer having one or more structural units selected from the units (C) [hereinafter referred to as component (C)],
An additive for poor blended concrete containing
The weight ratio of monoester form and diester is Ri 0.4 to 0.95 der in monoester / (monoester + diester)
The weight ratio of the component (A) and the component (C) is (A) / (C) = 90 / 10-30 / 70.
Additive for poor blended concrete.
R ¹ —O (AO) _n — (1)
[Wherein, R ¹ is an alkyl group or alkenyl group having 8 to 22 carbon atoms, or a hydrocarbon group having two or more benzene rings, AO is an oxyalkylene group having 2 to 4 carbon atoms, and n is an average added mole number. The number of 1-50 exists. ]

[Where,
R ⁶ and R ⁷ are each a hydrogen atom or a methyl group
m: number from 0 to 2
R ⁸ : hydrogen atom or —COO (AO) _n1 Y
p: number of 0 or 1
AO: C2-C4 oxyalkylene group or oxystyrene group
n1: Number of average added moles and a number of 1 to 300
Y: a hydrogen atom or an alkyl or alkenyl group having 1 to 18 carbon atoms
Represents. ]

[Where,
R ^{9 to} R ¹¹ are each a hydrogen atom, a methyl group or (CH ₂ ) _m1 COOM ² , and (CH ₂ ) _m1 COOM ² forms an anhydride with COOM ¹ or other (CH ₂ ) _m1 COOM ^2. In this case, M ¹ and M ² of these groups are not present.
M ¹ and M ² : hydrogen atom, alkali metal, alkaline earth metal, ammonium group, alkylammonium group or hydroxyl group-substituted alkylammonium group, respectively
m1: Number from 0 to 2

Z: hydrogen atom, alkali metal, alkaline earth metal, ammonium group, alkylammonium group or hydroxyl-substituted alkylammonium group
Represents. ] Nonionic compounds, the general formula (2), the compound represented by claims in formula (3) and the compound represented by the general formula least one compound selected from compounds represented by (4) 1 The additive for poor blend concrete as described.
R ² —O— (AO) _p —R (2)
R ³ —COO— (AO) _q —R ⁴ (3)
R ⁵ —NH _(2-t) [(AO) _s —H] _t (4)
[Wherein R ² , R ³ and R ⁵ are each an alkyl group or alkenyl group having 8 to 26 carbon atoms or a hydrocarbon group having 6 to 35 carbon atoms having one or more benzene rings, and R and R ⁴ are A hydrogen atom, an alkyl or alkenyl group having 1 to 26 carbon atoms or a hydrocarbon group having 6 to 35 carbon atoms having one or more benzene rings, AO is an oxyalkylene group having 2 to 4 carbon atoms, p, q and s Is the average number of moles added, and is a number from 3 to 400, and t is 1 or 2. ] The additive for poor blended concrete according to claim 1 or 2 , further comprising an antifoaming agent. 1m weight of hydraulic powder per ³ in 190~350kg / m ^3, water / hydraulic powder ratio is 50% to 70% (by weight) any claim 1-3 for use in poor compounding concrete is The additive for poor blended concrete according to claim 1. The additive for poor blended concrete according to any one of claims 1 to 4, comprising two or more types of copolymers of component (C). A poor blended concrete comprising the additive for poor blended concrete according to any one of claims 1 to 5 , a hydraulic powder, and water. The poor-mixed concrete according to claim 6 , comprising 0.01 to 7.5 parts by weight of the monoester body and the diester body in total with respect to 100 parts by weight of the hydraulic powder. The poor blended concrete according to claim 6 or 7 , wherein the weight of the hydraulic powder per 1 m ³ is 190 to 350 kg / m ³ and the water / hydraulic powder ratio is 50 to 70% (weight ratio).