JP3995949B2 - Concrete composition - Google Patents

Description

【００４８】
（式中、Ｒ⁶、Ｒ⁷及びＲ⁸は、同一若しくは異なって、水素原子又はメチル基を表す。Ｒ⁹Ｏは、同一若しくは異なって、炭素数２〜１８のオキシアルキレン基を表す。ａは、オキシアルキレン基の平均付加モル数を表し、２〜３００の数である。Ｒ¹⁰は、水素原子又は炭素数１〜３０の炭化水素基を表す。）で表されるポリオキシアルキレンエステル系構成単位（Ｉ）と、下記一般式（３）；
【００４９】
【化２】

【００５０】
（式中、Ｒ¹¹、Ｒ¹²及びＲ¹³は、同一若しくは異なって、水素原子又はメチル基を表す。Ｍ^１は、水素原子、一価金属、二価金属、アンモニウム又は有機アミンを表す。）で表されるカルボン酸系構成単位（ＩＩ）を有するポリカルボン酸系重合体（Ａ−１）が好ましい。
【００５１】
また上記ポリカルボン酸系重合体としては、下記一般式（４）；
【００５２】
【化３】

【００５３】
（式中、Ｒ¹⁴、Ｒ¹⁵及びＲ¹⁶は、同一若しくは異なって、水素原子又はメチル基を表す。Ｒ¹⁷は、炭素数１〜５の炭化水素基を表す。Ｒ¹⁸Ｏは、同一若しくは異なって、炭素数２〜１８のオキシアルキレン基を表す。ｂは、オキシアルキレン基の平均付加モル数を表し、２〜３００の数である。Ｒ¹⁹は、水素原子又は炭素数１〜３０の炭化水素基を表す。）で表されるポリオキシアルキレンエーテル系構成単位（ＩＩＩ）と、下記一般式（５）；
【００５４】
【化４】

【００５５】
（式中、Ｒ²⁰及びＲ²¹は、同一若しくは異なって、水素原子、メチル基又は−ＣＯＯＭ³を表す。ただしＲ²⁰及びＲ²¹は、同時に−ＣＯＯＭ³を表さない。Ｒ²²は、水素原子、メチル基又は−ＣＨ₂ＣＯＯＭ⁴を表す。Ｒ²²が−ＣＨ₂ＣＯＯＭ⁴のときＲ²⁰及びＲ²¹は、同一若しくは異なって、水素原子又はメチル基を表す。Ｍ²、Ｍ³及びＭ⁴は、水素原子、一価金属、二価金属、アンモニウム又は有機アミンを表す。）で表されるカルボン酸系構成単位（ＩＶ）を有するポリカルボン酸系重合体（Ａ−２）が好ましい。すなわち上記セメント分散剤は、上記ポリカルボン酸系重合体（Ａ−１）及び／又は上記ポリカルボン酸系重合体（Ａ−２）を含むことが好ましい。
【００５６】
上記ポリカルボン酸系重合体（Ａ−１）及び（Ａ−２）は、上記必須の構成単位（繰り返し単位）を有することを特徴とし、後述の単量体（ｅ）に由来する構成単位（Ｖ）を更に有するものであってもよい。これらの構成単位はそれぞれ１種であってもよく、２種以上であってもよい。
【００５７】
上記ポリカルボン酸系重合体（Ａ−１）は、構成単位（Ｉ）を与える単量体（例えば、後述の単量体（ａ））、構成単位（ＩＩ）を与える単量体（例えば、後述の単量体（ｂ））を必須成分として含む単量体成分を共重合して製造することができる。このような単量体成分は、構成単位（Ｖ）を与える単量体（例えば、後述の単量体（ｅ））を更に含むものでもよい。なお、各構成単位がそれぞれ１種の場合には、各構成単位を与える単量体をそれぞれ１種用いればよく、各構成単位がそれぞれ２種以上の場合には、各構成単位を与える単量体をそれぞれ２種以上用いればよい。
【００５８】
上記ポリカルボン酸系重合体（Ａ−１）を構成する各構成単位の比率としては、質量比で、構成単位（Ｉ）／構成単位（ＩＩ）／構成単位（Ｖ）＝１〜９９／９９〜１／０〜５０であることが好ましい。より好ましくは構成単位（Ｉ）／構成単位（ＩＩ）／構成単位（Ｖ）＝５０〜９９／５０〜１／０〜４９、更に好ましくは構成単位（Ｉ）／構成単位（ＩＩ）／構成単位（Ｖ）＝６０〜９５／４０〜５／０〜３０、最も好ましくは構成単位（Ｉ）／構成単位（ＩＩ）／構成単位（Ｖ）＝７０〜９５／３０〜５／０〜１０である。ただし、構成単位（Ｉ）、構成単位（ＩＩ）及び構成単位（Ｖ）の合計は、１００質量％である。
【００５９】
また上記ポリカルボン酸系重合体（Ａ−１）は、アクリル酸、メタクリル酸、クロトン酸等の不飽和モノカルボン酸系単量体と構成単位（ＩＩ）を与える単量体（例えば、後述の単量体（ｂ））とを必須成分として含む単量体成分を共重合して得られる重合体のカルボキシル基の少なくとも一部に対して、アルコキシポリアルキレングリコールを直接エステル化して製造してもよい。
【００６０】
上記一般式（２）において、Ｒ¹⁰における炭素数１〜３０の炭化水素基としては、炭素原子数１〜３０のアルキル基、炭素原子数６〜３０のフェニル基、アルキルフェニル基、フェニルアルキル基、（アルキル）フェニル基で置換されたフェニル基、ナフチル基等のベンゼン環を有する芳香族基、炭素原子数２〜３０のアルケニル基が好適である。また、オキシアルキレン基の平均付加モル数ａは、２〜３００以下の数であるが、５以上であることが好ましい。より好ましくは１０以上であり、更に好ましくは１５以上であり、最も好ましくは２０以上である。また、最も好ましくは２００以下である。更に、Ｒ¹⁰の炭素原子数としては、１以上であるが、２２以下が好ましい。より好ましくは１８以下であり、更に好ましくは１２以下であり、更に特に好ましくは６以下であり、特に好ましくは５以下であり、最も好ましくは３以下である。
【００６１】
上記一般式（２）におけるオキシアルキレン基Ｒ⁹Ｏの炭素原子数としては、２〜１８が適当であるが、８以下が好ましい。より好ましくは、４以下である。また、構成単位（Ｉ）として１種類となる場合には、親水性と疎水性のバランス確保のため、オキシアルキレン基中にオキシエチレン基を必須として有することが好ましく、より好ましくは５０モル％以上、特に好ましくは６０モル％以上がオキシエチレン基であることである。一方、構成単位（Ｉ）として２種類以上となる場合には、何れか１種類の構成単位（Ｉ）のオキシアルキレン基中にオキシエチレン基を必須として有することが好ましい。
【００６２】
上記構成単位（Ｉ）を与える単量体（ａ）としては、（メタ）アクリル酸、クロトン酸又は脂肪酸の脱水素（酸化）反応物への炭素原子数２〜１８のアルキレンオキシドの付加物、又は、メタノール、エタノール、２−プロパノール、１−ブタノール、１−ペンタノール、１−ヘキサノール、オクタノール、２−エチル−１−ヘキサノール、ノニルアルコール、ラウリルアルコール、セチルアルコール、ステアリルアルコール等の炭素原子数１〜３０の飽和脂肪族アルコール類、アリルアルコール、メタリルアルコール、クロチルアルコール、オレイルアルコール等の炭素原子数３〜３０の不飽和脂肪族アルコール類、シクロヘキサノール等の炭素原子数３〜３０の脂環族アルコール類、フェノール、フェニルメタノール（ベンジルアルコール）、メチルフェノール（クレゾール）、ｐ−エチルフェノール、ジメチルフェノール（キシレノール）、ｐ−ｔ−ブチルフェノール、ノニルフェノール、ドデシルフェノール、フェニルフェノール、ナフトール等の炭素原子数６〜３０の芳香族アルコール類のいずれかに炭素原子数２〜１８のアルキレンオキシドを付加することによって得られるアルコキシポリアルキレングリコール類と、（メタ）アクリル酸又はクロトン酸とのエステル化合物等が好適であるが、一般式（３）において、Ｒ¹⁰が炭化水素基となる場合に相当する、アルコキシポリアルキレングリコール類と、（メタ）アクリル酸又はクロトン酸とのエステル化合物が好ましい。
【００６３】
上記単量体（ａ）の具体的な化学名としては、下記のものが好適である。メトキシポリエチレングリコールモノ（メタ）アクリレート、エトキシポリエチレングリコールモノ（メタ）アクリレート、１−プロポキシポリエチレングリコールモノ（メタ）アクリレート、２−プロポキシポリエチレングリコールモノ（メタ）アクリレート、１−ブトキシポリエチレングリコールモノ（メタ）アクリレート、２−ブトキシポリエチレングリコールモノ（メタ）アクリレート、２−メチル−１−プロポキシポリエチレングリコールモノ（メタ）アクリレート、２−メチル−２−プロポキシポリエチレングリコールモノ（メタ）アクリレート、１−ペンチルオキシポリエチレングリコールモノ（メタ）アクリレート、１−ヘキシルオキシポリエチレングリコールモノ（メタ）アクリレート、シクロヘキシルオキシポリエチレングリコールモノ（メタ）アクリレート、１−オクチルオキシポリエチレングリコールモノ（メタ）アクリレート、２−エチル−１−ヘキシルオキシポリエチレングリコールモノ（メタ）アクリレート、ノニルアルコキシポリエチレングリコールモノ（メタ）アクリレート、ラウリルアルコキシポリエチレングリコールモノ（メタ）アクリレート、セチルアルコキシポリエチレングリコールモノ（メタ）アクリレート、ステアリルアルコキシポリエチレングリコールモノ（メタ）アクリレート、フェノキシポリエチレングリコールモノ（メタ）アクリレート、フェニルメトキシポリエチレングリコールモノ（メタ）アクリレート、メチルフェノキシポリエチレングリコールモノ（メタ）アクリレート、ｐ−エチルフェノキシポリエチレングリコールモノ（メタ）アクリレート、ジメチルフェノキシポリエチレングリコールモノ（メタ）アクリレート、ｐ−ｔ−ブチルフェノキシポリエチレングリコールモノ（メタ）アクリレート、ノニルフェノキシポリエチレングリコールモノ（メタ）アクリレート、ドデシルフェノキシポリエチレングリコールモノ（メタ）アクリレート、フェニルフェノキシポリエチレングリコールモノ（メタ）アクリレート、ナフトキシポリエチレングリコールモノ（メタ）アクリレート、エチレンオキシドを付加させた（メタ）アリルアルコールと（メタ）アクリル酸とのエステル化物、エチレンオキシドを付加させたクロチルアルコールと（メタ）アクリル酸とのエステル化物等の各種アルコキシポリエチレングリコールモノ（メタ）アクリレート類。
【００６４】
メトキシポリプロピレングリコールモノ（メタ）アクリレート、エトキシポリプロピレングリコールモノ（メタ）アクリレート、１−プロポキシポリプロピレングリコールモノ（メタ）アクリレート、２−プロポキシポリプロピレングリコールモノ（メタ）アクリレート、１−ブトキシポリプロピレングリコールモノ（メタ）アクリレート、プロピレンオキシドを付加させた（メタ）アリルアルコールと（メタ）アクリル酸とのエステル化物、プロピレンオキシドを付加させたクロチルアルコールと（メタ）アクリル酸とのエステル化物等の各種アルコキシポリプロピレングリコールモノ（メタ）アクリレート類。
【００６５】
メトキシポリエチレンポリプロピレングリコールモノ（メタ）アクリレート、メトキシポリエチレンポリブチレングリコールモノ（メタ）アクリレート、エトキシポリエチレンポリプロピレングリコールモノ（メタ）アクリレート、エトキシポリエチレンポリブチレングリコールモノ（メタ）アクリレート、１−プロポキシポリエチレンポリプロピレングリコールモノ（メタ）アクリレート、１−プロポキシポリエチレンポリブチレングリコールモノ（メタ）アクリレート、２−プロポキシポリエチレンポリプロピレングリコールモノ（メタ）アクリレート、２−プロポキシポリエチレンポリブチレングリコールモノ（メタ）アクリレート、１−ブトキシポリエチレンポリプロピレングリコールモノ（メタ）アクリレート、１−ブトキシポリエチレンポリブチレングリコールモノ（メタ）アクリレート、エチレンオキシドとプロピレンオキシド又はエチレンオキシドとブチレンオキシドを付加させた（メタ）アリルアルコールと（メタ）アクリル酸とのエステル化物、エチレンオキシドとプロピレンオキシド又はエチレンオキシドとブチレンオキシドを付加させたクロチルアルコールと（メタ）アクリル酸とのエステル化物等の２種類以上のアルキレンオキシドを付加させたアルコールと（メタ）アクリル酸とのエステル化物等の各種アルコキシポリアルキレングリコールモノ（メタ）アクリレート類。
【００６６】
上記一般式（３）で表される構成単位（ＩＩ）を与える単量体（ｂ）としては、アクリル酸、メタクリル酸、クロトン酸及びこれらの金属塩、アンモニウム塩、アミン塩が好適である。特に（メタ）アクリル酸及びこれらの塩が好ましい。
【００６７】
上記ポリカルボン酸系重合体（Ａ−２）は、構成単位（ＩＩＩ）を与える単量体（例えば、後述の単量体（ｃ））、構成単位（ＩＶ）を与える単量体（例えば、後述の単量体（ｄ））を必須成分として含む単量体成分を共重合して製造することができる。このような単量体成分は、構成単位（Ｖ）を与える単量体（例えば、後述の単量体（ｅ））を更に含むものでもよい。
【００６８】
上記ポリカルボン酸系重合体（Ａ−２）を構成する各構成単位の比率は、質量比で、構成単位（ＩＩＩ）／構成単位（ＩＶ）／構成単位（Ｖ）＝１〜９９／９９〜１／０〜５０であることが好ましい。より好ましくは構成単位（ＩＩＩ）／構成単位（ＩＶ）／構成単位（Ｖ）＝５０〜９９／５０〜１／０〜４９、更に好ましくは構成単位（ＩＩＩ）／構成単位（ＩＶ）／構成単位（Ｖ）＝６０〜９５／４０〜５／０〜３０、最も好ましくは構成単位（ＩＩＩ）／構成単位（ＩＶ）／構成単位（Ｖ）＝７０〜９５／３０〜５／０〜１０である。ただし、構成単位（ＩＩＩ）、構成単位（ＩＶ）及び構成単位（Ｖ）の合計は１００質量％である。
【００６９】
また上記ポリカルボン酸系重合体（Ａ−２）は、アリルアルコール、メタリルアルコール、３−メチル−３−ブテン−１−オール、３−メチル−２−ブテン−１−オール、２−メチル−３−ブテン−２−オール等の不飽和アルコールと構成単位（ＩＶ）を与える単量体（例えば、後述の単量体（ｄ））とを必須成分として含む単量体成分を共重合して得られる重合体にアルキレンオキシドを平均２〜３００モル付加するか、又は、平均付加モル数２〜３００のアルコキシポリアルキレングリコールを反応させる方法によっても得ることができる。
【００７０】
上記一般式（４）において、オキシアルキレン基の平均付加モル数ｂは、２〜３００の数であるが、５以上が好ましい。より好ましくは、１０以上であり、更に好ましくは、２０以上であり、特に好ましくは、２５以上である。また、２００以下が特に好ましい。また、Ｒ¹⁹の炭素原子数としては、１以上が好ましい。また、２２以下が好ましい。より好ましくは、１８以下であり、更に好ましくは、１２以下であり、更に特に好ましくは、６以下であり、特に好ましくは、５以下であり、最も好ましくは３以下である。更に、Ｒ¹⁷の炭素原子数としては、１〜５であるが、４以下が好ましい。より好ましくは、３以下であり、特に好ましくは−ＣＨ₂−、−（ＣＨ₂）₂−又は−Ｃ（ＣＨ₃）₂−の構造である。
【００７１】
上記一般式（４）におけるオキシアルキレン基Ｒ¹⁸Ｏの炭素数としては、２〜１８であるが、８以下が好ましい。より好ましくは、４以下である。また、構成単位（ＩＩＩ）として１種類となる場合には、親水性と疎水性のバランス確保のため、オキシアルキレン基中にオキシエチレン基を必須として有することが好ましく、より好ましくは５０モル％以上、特に好ましくは６０モル％以上がオキシエチレン基であることである。
【００７２】
上記一般式（５）で表される構成単位（ＩＶ）を与える単量体（ｄ）としては、アクリル酸、メタクリル酸、クロトン酸及びこれらの金属塩、アンモニウム塩、アミン塩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、シトラコン酸、フマル酸、又は、これらの金属塩、アンモニウム塩、アミン塩等の不飽和ジカルボン酸系単量体が好適である。更に、これらの無水物も用いることができ、無水マレイン酸、無水イタコン酸、無水シトラコン酸が好適である。中でも、Ｒ²⁰、Ｒ²¹及びＲ²²が、同一若しくは異なって、水素原子又はメチル基の場合に相当する、不飽和モノカルボン酸系単量体を用いることが好ましく、特に（メタ）アクリル酸、マレイン酸、無水マレイン酸及びこれらの塩を用いることが好ましい。
【００７３】
本発明で用いることができる構成単位（Ｖ）を与える単量体（ｅ）としては、他の単量体の少なくとも１つと共重合可能な単量体であればよく、下記のものが好適である。
マレイン酸、フマル酸、イタコン酸、シトラコン酸等の不飽和ジカルボン酸類と炭素原子数１〜４のアルコールとのハーフエステル、ジエステル；上記不飽和ジカルボン酸類と炭素原子数１〜３０のアミンとのハーフアミド、ジアミド；上記アルコールやアミンに炭素原子数２〜１８のアルキレンオキシドを１〜５００モル付加させたアルキル（ポリ）アルキレングリコールと上記不飽和ジカルボン酸類とのハーフエステル、ジエステル；上記不飽和ジカルボン酸類と炭素原子数２〜１８のグリコール又はこれらのグリコールの付加モル数２〜３００のポリアルキレングリコールとのハーフエステル、ジエステル。
【００７４】
マレアミド酸と炭素原子数２〜１８のグリコール又はこれらのグリコールの付加モル数２〜３００のポリアルキレングリコールとのハーフアミド；トリエチレングリコールジ（メタ）アクリレート、（ポリ）エチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、（ポリ）エチレングリコール（ポリ）プロピレングリコールジ（メタ）アクリレート等の（ポリ）アルキレングリコールジ（メタ）アクリレート類；ヘキサンジオールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート等の二官能（メタ）アクリレート類；トリエチレングリコールジマレート、ポリエチレングリコールジマレート等の（ポリ）アルキレングリコールジマレート類。
【００７５】
ビニルスルホネート、（メタ）アリルスルホネート、２−（メタ）アクリロキシエチルスルホネート、３−（メタ）アクリロキシプロピルスルホネート、３−（メタ）アクリロキシ−２−ヒドロキシプロピルスルホネート、３−（メタ）アクリロキシ−２−ヒドロキシプロピルスルホフェニルエーテル、３−（メタ）アクリロキシ−２−ヒドロキシプロピルオキシスルホベンゾエート、４−（メタ）アクリロキシブチルスルホネート、（メタ）アクリルアミドメチルスルホン酸、（メタ）アクリルアミドエチルスルホン酸、２−メチルプロパンスルホン酸（メタ）アクリルアミド、スチレンスルホン酸等の不飽和スルホン酸類、並びにそれらの一価金属塩、二価金属塩、アンモニウム塩及び有機アミン塩；アクリル酸、メタクリル酸、クロトン酸等不飽和モノカルボン酸系類、並びにそれらの金属塩、アンモニウム塩、アミン塩。
【００７６】
メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、グリシジル（メタ）アクリレート、メチルクロトネート、エチルクロトネート、プロピルクロトネート等の不飽和モノカルボン酸類と炭素原子数１〜４のアルコールとのエステル；メチル（メタ）アクリルアミドのように不飽和モノカルボン酸類と炭素原子数１〜３０のアミンとのアミド類；スチレン、α−メチルスチレン、ビニルトルエン、ｐ−メチルスチレン等のビニル芳香族類；１，４−ブタンジオールモノ（メタ）アクリレート、１，５−ペンタンジオールモノ（メタ）アクリレート、１，６−ヘキサンジオールモノ（メタ）アクリレート等のアルカンジオールモノ（メタ）アクリレート類；ブタジエン、イソプレン、２−メチル−１，３−ブタジエン、２−クロル−１，３−ブタジエン等のジエン類；（メタ）アクリルアミド、（メタ）アクリルアルキルアミド、Ｎ−メチロール（メタ）アクリルアミド、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド等の不飽和アミド類；（メタ）アクリロニトリル、α−クロロアクリロニトリル等の不飽和シアン類。
【００７７】
酢酸ビニル、プロピオン酸ビニル等の不飽和エステル類；（メタ）アクリル酸アミノエチル、（メタ）アクリル酸メチルアミノエチル、（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸ジメチルアミノプロピル、（メタ）アクリル酸ジブチルアミノエチル、ビニルピリジン等の不飽和アミン類；ジビニルベンゼン等のジビニル芳香族類；トリアリルシアヌレート等のシアヌレート類；（メタ）アリルアルコール、グリシジル（メタ）アリルエーテル等のアリル類；ジメチルアミノエチル（メタ）アクリレート等の不飽和アミノ化合物類；メトキシポリエチレングリコールモノビニルエーテル、ポリエチレングリコールモノビニルエーテル、メトキシポリエチレングリコールモノ（メタ）アリルエーテル、ポリエチレングリコールモノ（メタ）アリルエーテル等のビニルエーテル又はアリルエーテル類。
ポリジメチルシロキサンプロピルアミノマレインアミド酸、ポリジメチルシロキサンアミノプロピレンアミノマレインアミド酸、ポリジメチルシロキサン−ビス−（プロピルアミノマレインアミド酸）、ポリジメチルシロキサン−ビス−（ジプロピレンアミノマレインアミド酸）、ポリジメチルシロキサン−（１−プロピル−３−アクリレート）、ポリジメチルシロキサン−（１−プロピル−３−メタクリレート）、ポリジメチルシロキサン−ビス−（１−プロピル−３−アクリレート）、ポリジメチルシロキサン−ビス−（１−プロピル−３−メタクリレート）等のシロキサン誘導体；２−アクリロイロキシエチルホスフェート、２−メタクリロイロキシエチルホスフェート等の不飽和リン酸エステル類。
【００７８】
ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、ジプロピレントリアミン、トリプロピレンテトラミン、テトラプロピレンペンタミン等のポリアルキレンポリアミンとマロン酸、コハク酸、フマル酸、マレイン酸、アゼライン酸、セバチン酸、又はこれらと炭素数１〜２０のアルコールとのエステル化物等の二塩基酸又は二塩基酸と炭素数１〜２０のアルコールとのエステルとの縮合物に更に（メタ）アクリル酸又は（メタ）アクリル酸と炭素数１〜２０のアルコールとのエステル化物、（メタ）アクリル酸グリシジル、アリルグリシジルエーテル等の不飽和エポキシ化合物等とを特定の割合で縮合させたポリアマイドポリアミンにアルキレンオキシドを特定量付加させた化合物；ポリエチレンイミン、ポリプロピレンイミン等のポリアルキレンイミンの活性水素にエチレンオキシド、プロピレンオキシド等のアルキレンオキシドを付加した化合物と（メタ）アクリル酸又は（メタ）アクリル酸と炭素数１〜２０のアルコールとのエステル化物又は（メタ）アクリル酸グリシジル、アリルグリシジルエーテル等の不飽和エポキシ化物との縮合物等の窒素原子を有するカチオン性単量体。
【００７９】
上記ポリカルボン酸系重合体（Ａ−１）や（Ａ−２）を得るには、重合開始剤を用いて上記単量体成分を重合させればよい。重合は、溶媒中での重合や塊状重合等の方法により行うことができる。溶媒中での重合は回分式でも連続式でも行うことができ、その際使用される溶媒としては、水；メチルアルコール、エチルアルコール、２−プロパノール等の低級アルコール；ベンゼン、トルエン、キシレン、シクロヘキサン、ｎ−ヘキサン等の芳香族又は脂肪族炭化水素；酢酸エチル等のエステル化合物；アセトン、メチルエチルケトン等のケトン化合物の１種又は２種以上が好適である。原料単量体及び得られるポリカルボン酸系重合体（Ａ−１）や（Ａ−２）の溶解性並びにポリカルボン酸系重合体（Ａ−１）や（Ａ−２）の使用時の便宜性からは、水及び炭素原子数１〜４の低級アルコールよりなる群から選ばれた少なくとも１種を用いることが好ましい。その場合、炭素原子数１〜４の低級アルコールの中でも、メチルアルコール、エチルアルコール、２−プロパノール等が特に有効である。
【００８０】
上記ポリカルボン酸系重合体（Ａ−１）や（Ａ−２）を得るために水媒体中で重合を行うときには、重合開始剤としてアンモニウム若しくはアルカリ金属の過硫酸塩又は過酸化水素等の水溶性の重合開始剤を使用することが好ましい。この際、亜硫酸水素ナトリウム、モール塩、アスコルビン酸（塩）、ロンガリット等の促進剤を併用することもできる。また、低級アルコール、芳香族炭化水素、脂肪族炭化水素、エステル化合物又はケトン化合物を溶媒とする重合には、ベンゾイルパーオキシドやラウロイルパーオキシド等のパーオキシド；クメンハイドロパーオキシド等のハイドロパーオキシド；アゾビスイソブチロニトリル等のアゾ化合物等が重合開始剤として用いることが好ましい。この際、アミン化合物等の促進剤を併用することもできる。更に、水−低級アルコール混合溶剤を用いる場合には、上記の種々の重合開始剤又は重合開始剤と促進剤との組み合わせの中から適宜選択して用いることができる。重合温度は、用いる溶媒や重合開始剤により適宜定められるが、通常０〜１２０℃であり、３０℃以上が好ましい。より好ましくは５０℃以上である。また、１００℃以下が好ましい。より好ましくは９５℃以下である。
【００８１】
また塊状重合を行うときには、通常では重合開始剤としてベンゾイルパーオキシドやラウロイルパーオキシド等のパーオキシド；クメンハイドロパーオキシド等のハイドロパーオキシド；アゾビスイソブチロニトリル等のアゾ化合物を用い、５０〜２００℃で行なわれる。
【００８２】
更に得られるポリカルボン酸系重合体（Ａ−１）や（Ａ−２）の分子量調節のために、次亜リン酸（塩）やチオール系連鎖移動剤を併用することもできる。この際に用いられるチオール系連鎖移動剤は、一般式ＨＳ−Ｒ³⁰−Ｅｇ（式中、Ｒ³⁰は、炭素原子数１〜２のアルキル基を表す。Ｅは、−ＯＨ、−ＣＯＯＭ、−ＣＯＯＲ³¹又はＳＯ₃Ｍ基を表す。Ｍは、水素原子、一価金属、二価金属、アンモニウム基又は有機アミン基を表す。Ｒ³¹は、炭素原子数１〜３０のアルキル基を表す。ｇは、１〜２の整数を表す。）で表され、メルカプトエタノール、チオグリセロール、チオグリコール酸、２−メルカプトプロピオン酸、３−メルカプトプロピオン酸、チオリンゴ酸、チオグリコール酸オクチル、３−メルカプトプロピオン酸オクチルが好適である。また、水酸基やカルボキシル基等の官能基をもたない炭素数３以上の炭化水素基をもつチオール化合物を連鎖移動剤として用いてもよい。ブタンチオール、オクタンチオール、デカンチオール、ドデカンチオール、ヘキサデカンチオール、シクロヘキシルメルカプタン、チオフェノールがそのようなチオール化合物として好適である。また、四塩化炭素、四臭化炭素、塩化メチレン、ブロモホルム、ブロモトリクロロエタン等のハロゲン化物；α−メチルスチレンダイマー、α−テルピネン、γ−テルピネン、ジペンテン等の不飽和炭化水素化合物を連鎖移動剤として用いてもよい。これらの１種又は２種以上を用いることができる。また、ポリカルボン酸系重合体（Ａ−１）や（Ａ−２）の分子量調整のためには、単量体（ｅ）として（メタ）アリルスルホン酸（塩）類等の連鎖移動性の高い単量体を用いることも有効である。
【００８３】
上記ポリカルボン酸系重合体（Ａ−１）や（Ａ−２）は、そのままでも用いることができるが、水に対する溶解性が不足するような場合には、水に対する溶解性を向上させて有機溶媒を含まない水媒体液の形態で取り扱うために、更に一価金属及び二価金属の水酸化物、塩化物及び炭素塩等の無機物；アンモニア；有機アミン等（好ましくは水酸化ナトリウム、水酸化カリウム等の一価金属の水酸化物）のアルカリ性物質で中和して得られる重合体塩として用いることが好ましい。
【００８４】
上記ポリカルボン酸系重合体（Ａ−１）や（Ａ−２）の重量平均分子量としては、例えば、ゲルパーミエーションクロマトグラフィー（以下「ＧＰＣ」という）によるポリエチレングリコール換算で、５０００〜１００００００が適当であるが、５０００００以下が好ましい。より好ましくは１００００以上である。また、より好ましくは３０００００以下である。重量平均分子量が５０００未満であると、材料分離低減性能が低下するおそれがあり、１００００００を超えると、分散性能が低下するおそれがある。
【００８５】
（重量平均分子量測定条件）
機種：Ｗａｔｅｒｓ ＬＣＭ１
検出器：Ｗａｔｅｒｓ ４１０ 示差屈折検出器
解析ソフト：Ｗａｔｅｒｓ ＭＩＬＬＥＮＮＩＵＭ Ｖｅｒ．２．１８
溶離液：水１０９９９ｇ、アセトニトリル６００１ｇの混合液に酢酸ナトリウム三水和物１１５．６ｇを溶かし、更に３０％水酸化ナトリウム水溶液でｐＨ６．０に調整した溶離液を用いる。
溶離液流速：０．８ｍｌ／ｍｉｎ
カラム温度：３５℃
カラム：東ソー製 ＴＳＫｇｅｌ ＧｕａｒｄＣｏｌｕｍｎＳＷＸＬ＋Ｇ４０００ＳＷＸＬ＋Ｇ３０００ＳＷＸＬ＋Ｇ２０００ＳＷＸＬ
標準物質：ポリエチレングリコール、重量平均分子量（Ｍｗ）２７２５００、２１９３００、８５０００、４６０００、２４０００、１２６００、４２５０、７１００、１４７０
【００８６】
上記ポリカルボン酸系重合体として、（Ａ−１）や（Ａ−２）以外に、カルボキシル基を側鎖にもつポリオキシアルキレン化合物を用いることもできる。該ポリカルボン酸系重合体は、ポリオキシアルキレン化合物に不飽和カルボン酸系単量体をグラフト重合させることによって得られる。ポリオキシアルキレン化合物としては、ポリエチレングリコール、ポリオキシエチレンポリオキシプロピレンが好適である。また、不飽和カルボン酸系単量体としては、アクリル酸、メタクリル酸、クロトン酸及びこれらの金属塩、アンモニウム塩、アミン塩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、シトラコン酸、フマル酸、又は、これらの金属塩、アンモニウム塩、アミン塩等の不飽和ジカルボン酸系単量体が好適である。更に、これらの無水物も用いることができ、無水マレイン酸、無水イタコン酸、無水シトラコン酸が好適である。中でも、（メタ）アクリル酸、マレイン酸、無水マレイン酸及びこれらの塩を用いることが好ましい。
【００８７】
本発明のコンクリート組成物には、本発明の作用効果を奏する限り、上記のもの以外にも、従来のセメント分散剤、水溶性高分子、空気連行剤、セメント湿潤剤、膨張材、防水剤、遅延剤、急結剤、水溶性高分子物質、増粘剤、凝集剤、乾燥収縮低減剤、強度増進剤、硬化促進剤等を併用してもよい。
【００８８】
本発明のコンクリート組成物においては、アルキルエーテル型陰イオン界面活性剤タイプ、変性ロジン酸化合物系陰イオン界面活性剤タイプ、アルキルスルホン酸化合物系陰イオン界面活性剤タイプ、高アルキルカルボン酸塩系陰イオン界面活性剤タイプ、変性アルキルカルボン酸化合物系陰イオン界面活性剤タイプ等の種々のＡＥ剤、ヴィンソル（商品名、山宗化学社製）又はＭｉｃｒｏ−Ａｉｒ（商品名、マスタービルダーズ社製）等を併用してもよく、本発明の作用効果を減ずるものではない。また、ポリカルボン酸系以外のセメント分散剤、収縮低減剤、分離低減剤、中性化防止剤、膨張剤、防水剤、遅延剤、急結剤、効果促進剤、水溶性高分子、増粘剤、凝集剤、セメント湿潤剤、防錆剤等の他のコンクリート混和剤を併用してもその効果を減ずるものではない。
【００８９】
本発明においてはまた、コンクリート組成物に良質の空気を導入し、耐凍結融解性を向上させる場合には、更にＡＥ剤を含有させることが好ましい。この場合、コンクリート組成物製造時に混練時間を延長して使用するとき、すなわちコンクリート組成物の搬送時に長時間混練し続けるようなときにも、上記コンクリート組成物では連行空気量を安定に保って、その硬化物の耐凍結融解性や、強度、耐久性を優れたものとすることができる。
【００９０】
本発明のセメント組成物は、ポリオキシアルキレン系化合物、セメント、水、細骨材及び粗骨材を必須成分とする製造原料を混合する工程を含むコンクリート組成物の製造方法により製造することができる。この場合、本発明のコンクリート組成物を構成するものすべての製造原料を混合する工程を含むことになる限り、各製造原料の添加方法や順序等は特に限定されるものではない。このようなコンクリート組成物の製造方法は、本発明の好ましい実施形態の一つである。
【００９１】
【実施例】
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されるものではない。なお、特に断りのない限り、「％」は、「質量％」を意味するものとする。
【００９２】
製造例１
温度計、攪拌機、滴下漏斗、窒素導入管及び還流冷却器を備えたガラス製反応容器に水３３９．６ｇを仕込み、攪拌下に反応容器内を窒素置換し、窒素雰囲気下で８０度まで加熱した。次に、メトキシポリエチレングリコールモノメタクリレート（エチレンオキシドの平均付加モル数２５個）３３３．６ｇ、メタクリル酸６６．４ｇ、水１００ｇ、及び連鎖移動剤として３−メルカプトプロピオン酸３．５ｇを混合したモノマー水媒体液５０３．５ｇを４時間、並びにペルオキソ二硫酸アンモニウム４．６ｇを溶かした水溶液４６ｇを５時間かけて滴下した。その後、１時間引き続いて８０度に温度を維持し、重合反応を完結させ、重量平均分子量２３８００の共重合体水媒体液からなる共重合体（１）を得た。
【００９３】
以下の実施例及び比較例で用いた消泡剤の構造を、以下に示す。基本的な構造はアミン又はアルコールにエチレンオキシド及びプロピレンオキシドを付加させたものである。ここで、エチレンオキシドをＥＯとプロピレンオキシドをＰＯと記す。また、ＲａＮは、炭素数１４〜１８の硬化牛脂アミン残基（全アミン価＝２１５．９）である。ＲｂＯは、炭素数１２〜１４の２級アルコール残基である。（消泡剤１）Ｃ₁₂Ｈ₂₅Ｎ（ＥＯ）₇（ＰＯ）₅Ｈ
（消泡剤２）Ｃ₁₂Ｈ₂₅Ｎ（ＥＯ）₇（ＰＯ）₇Ｈ
（消泡剤３）ＲａＮ（ＥＯ）₇（ＰＯ）₇Ｈ
（比較消泡剤１）Ｃ₈Ｈ₁₇Ｏ（ＰＯ）₂₀（ＥＯ）₃Ｈ
（比較消泡剤２）ＲｂＯ（ＥＯ）₉（ＰＯ）₅Ｈ
（比較消泡剤３）Ｃ₁₂Ｈ₂₅Ｎ（ＥＯ）₇（ＰＯ）₃Ｈ
【００９４】
実施例１〜３及び比較例１〜３
＜コンクリート試験＞
コンクリート試験では、製造例１で得た共重合体（１）水溶液を濃度３０％の水酸化ナトリウム水溶液でｐＨ７に調整し、更にイオン交換水で希釈し、固形分濃度４０％に調整したものを使用した。
セメントとして普通ポルトランドセメント（太平洋セメント社製：比重３．１６）、細骨材として大井川水系産陸砂（比重２．６２）、粗骨材として青梅産砕石（比重２．５８）及び水として横須賀市水道水を用い、以下に示す２種類の配合で、練り混ぜ量が４０Ｌとなるようにそれぞれの材料を計量し、可傾式ミキサー（光洋機械産業社製：ＫＹＣベビーミキサー）を用いて材料の混練を行った。ミキサーの回転数は２０回転／分に固定した。
【００９５】
＜配合１＞
単位セメント量：３６０．０ｋｇ／ｍ³
単位水量：１４４．０ｋｇ／ｍ³
単位細骨材量：７６７．１ｋｇ／ｍ³
単位粗骨材量：１０４３．１ｋｇ／ｍ³
水／セメント比：４０％
細骨材率：４２％
【００９６】
＜配合２＞
単位セメント量：３５０．０ｋｇ／ｍ³
単位水量：１６１．０ｋｇ／ｍ³
単位細骨材量：８７７．１ｋｇ／ｍ³
単位粗骨材量：８９９．０ｋｇ／ｍ³
水／セメント比：４６％
細骨材率：４９％
【００９７】
＜混練方法＞
（１）細骨材のみをミキサーに投入し、３０秒間空練りした後、回転を止めた。
（２）セメントを投入し、更に３０秒間空練りした。
（３）回転を止め、減水剤及び消泡剤を含む水（水の全所定量の９５％）を加え、更に９０秒間混練した。
（４）回転を再度止め粗骨材を投入し、更にＡＥ剤を含む水（水の全所定量の５％）を加え、１５０秒間混練した。
（５）得られたコンクリートを一部ミキサーから取り出し、スランプと空気量を測定した。スランプの測定は日本工業規格ＪＩＳ Ａ １１０１に、また空気量の測定は日本工業規格ＪＩＳ Ａ １１２８に準拠して行った。この時点でのスランプ値をＳ１、空気量をＡ１とした。
（６）スランプと空気量の測定に用いたコンクリートをミキサーに戻し５分間混練した後、再度スランプと空気量を測定した。この時点でのスランプ値をＳ２、空気量をＡ２とした。
（７）再度測定に用いたコンクリートを戻し、５分間混練した。得られたコンクリートのスランプと空気量を測定した。この時点でのスランプ値をＳ３、空気量をＡ３とした。
コンクリート試験結果を表１にまとめた。
【００９８】
【表１】

【００９９】
表１について、説明する。ＡＥ剤において、Ｍｉｃｒｏ−Ａｉｒ（商品名）とは、マスタービルダーズ社製のＡＥ剤である。添加量（質量％／Ｃ）とは、セメント固形分に対する質量割合である。空気量（％）とは、コンクリート組成物における容積％である。
【０１００】
＜混和剤との相溶性試験＞
消泡剤（１）〜（３）を所定量共重合体（１）の水溶液に加え、水酸化ナトリウム水溶液でｐＨを調整し、更に固形分をイオン交換水で４０％に調整した。得られた水溶液の様子をまず室温にて観察した後、４３℃に保った恒温室内に放置し、１日後及び６ヶ月後の様子を観察した。
比較消泡剤（１）及び（２）の場合は、共重合体（１）の水溶液を水酸化ナトリウムでｐＨ７に調整した水溶液に対して、所定量添加した。イオン交換水で固形分を４０％に調整した後、上記と同様の操作を行い、水溶液の様子を観察した。結果を表２にまとめた。
（外観の評価基準）
◎：均一で透明
△：白濁
×：層分離
【０１０１】
【表２】

【０１０２】
表２について、以下に説明する。消泡剤の構造において、ＲａＮは、炭素数１４〜１８の硬化牛脂アミン残基（全アミン価＝２１５．９）であり、ＲｂＯは、炭素数１２〜１４の２級アルコール残基である。固形分濃度（％）とは、水溶液における固形分の質量％である。
【０１０３】
【発明の効果】
本発明のコンクリート組成物は、上述の構成よりなり、コンクリート組成物製造時の混練時間延長にともなう空気量増加がなく、連行空気量を安定に保つことができると共に、強度及び耐久性に優れた硬化物を形成することができるものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a concrete composition. Specifically, the present invention relates to a concrete composition that contains cement, water, fine aggregate, and coarse aggregate as essential components and gives a cured product having excellent strength and durability.
[0002]
[Prior art]
A concrete composition is manufactured by mixing cement, water, fine aggregate, and coarse aggregate, and gives a cured product that is superior in strength and durability to paste and mortar among cement compositions. Widely and suitably used for applications such as outer wall materials and building structures. In such a concrete composition, reducing the unit water content contained in the concrete composition will improve the performance of the cured product. However, in the recent concrete industry, there is a strong demand for improvement in the strength and durability of concrete buildings. Therefore, reduction of unit water volume is an important issue.
[0003]
Such a concrete composition is usually added with an admixture for enhancing air entrainment and fluidity. The task of the admixture in the concrete composition is to exhibit sufficient dispersibility even when the concrete composition is reduced in water, ensuring its fluidity and workability, realizing durability and strength improvement due to water reduction, and at the same time In other words, a stable concrete dispersibility is maintained and a good concrete composition is obtained. In recent years, the importance of such admixtures has been recognized, and technological innovation has been actively conducted. In particular, many polycarboxylic acid-based dispersants have been studied because they exhibit higher water reduction performance than conventional naphthalene-based dispersants. When such a dispersant is used, the air entrainment property is increased and the bubble diameter is increased. Therefore, in order to improve the freeze-thaw property by entraining fine high-quality bubbles, an AE agent is used in combination. ing.
[0004]
However, when a polycarboxylic acid-based dispersant and an AE agent are used in combination, if the concrete is continuously kneaded, the amount of entrained air gradually increases, which makes it difficult to obtain a desired concrete strength. Although it is possible to temporarily reduce the amount of entrained air using a conventional antifoaming agent, this case also results in an increase in the amount of entrained air as kneading continues. In addition, it is difficult to add an antifoaming agent immediately before placing the concrete in consideration of workability on site, and therefore it is required to add an antifoaming agent during concrete production. In particular, when the addition of an AE agent is indispensable as a countermeasure for freezing and thawing, or when kneading is continued for a long time during transportation, the problem of an increase in the amount of entrained air is serious.
[0005]
By the way, it has been studied to use an alkylene oxide adduct of a specific compound in a concrete composition or the like.
JP-A-60-27638 discloses a molecular length of 6,000 to 2,000,000 obtained by adding 20 to 300 moles of an alkylene oxide, which always contains ethylene oxide and propylene oxide, to one active hydrogen to an amine compound. Cement dispersion containing polyethylene polyol or polyether polyol derivative as an essential component, and polyethylene imine, ethylene diamine or diethylene triamine added with ethylene oxide and propylene oxide, or styrene oxide in addition thereto as an essential component Agents are disclosed.
[0006]
WO17128 Pamphlet (2000) relates to a mixture comprising a liquefying agent of polycarboxylate for inorganic building materials such as cement and a butoxylated polyalkylenepolyamine or a salt thereof used for deaeration. As the butoxylated polyalkylene polyamine or a salt thereof, a butylene oxide adduct of polyethyleneimine is disclosed.
[0007]
Japanese Patent Application Laid-Open No. 63-11557 discloses adjustment of the amount of entrained air used when mixing ethylene oxide derivative (I) of primary amine and water-soluble polycarboxylic acid polymer (II) at a specific mass ratio in cement mortar or concrete kneading. Regarding the method, ethylene oxide adducts of laurylamine are disclosed as ethylene oxide derivatives (I) of primary amines.
[0008]
JP-A-8-73250 discloses a polyalkylene oxide obtained by adding 10 to 1000 mol of alkylene oxide to a monohydric alcohol, monohydric mercaptan, alkylphenol, amine or carboxylic acid having 6 to 30 carbon atoms in the molecule. A hydraulic composition comprising a water-soluble polymer (a) comprising a derivative, a high-performance water reducing agent (b) and a hydraulic powder (c), an ethylene oxide adduct of a mixture of stearyl alcohol and cetanol, an ethylene oxide of nonylphenol and A propylene oxide adduct, an ethylene oxide adduct of dodecyl mercaptan, an ethylene oxide adduct of palmityl alcohol, an ethylene oxide adduct of dodecylamine, an ethylene oxide adduct of lauric acid, and the like are disclosed.
[0009]
However, in these techniques, since it has not been sufficiently studied to keep the amount of entrained air in the concrete composition stable, in addition to exhibiting excellent performance in this respect, it has excellent strength and durability. There was room to devise the structure of the alkylene oxide adduct so as to provide a concrete composition exhibiting performance.
[0010]
[Problems to be solved by the invention]
The present invention has been made in view of the above situation, there is no increase in the amount of air accompanying the kneading time extension during the production of the concrete composition, the amount of entrained air can be kept stable, and the strength and durability are excellent. It is an object of the present invention to provide a concrete composition.
[0011]
[Means for solving the problems]
While the inventors have studied an admixture that keeps the amount of entrained air in a concrete composition stable, a polyoxyalkylene compound has an action as an antifoaming agent, and a concrete composition containing such a compound. Focused on exhibiting excellent performance in strength and durability. In such a concrete composition, an admixture containing a polyoxyalkylene compound is added and mixed with water, cement, fine aggregate, coarse aggregate, etc., but the polyoxyalkylene compound is a molecule. When the ratio of the number of moles added between the oxyethylene group and the oxyalkylene group having 3 or more carbon atoms in the oxyalkylene group of the polyoxyalkylene compound is specified, In addition to stabilizing the alkylene compound without being separated in the admixture, hydrophilicity is expressed by the oxyethylene group, and hydrophobicity is expressed by the oxyalkylene group having 3 or more carbon atoms and the defoaming property is maintained. I found. That is, in the past, it was thought that a highly hydrophobic antifoaming agent in a concrete composition would be good. However, if a polyoxyalkylene compound is specified as described above, bubbles generated by an AE agent or the like are effectively removed. It has been found that it is possible to suppress the increase in the amount of air accompanying the kneading time extension at the time of producing the concrete composition, and to solve the above-mentioned problems in an excellent manner. Further, as the polyoxyalkylene compound, those having an aliphatic hydrocarbon group in which 5 or more carbon atoms are continuously bonded in the molecule are suitable, or the oxyethylene group and carbon in the oxyalkylene group It has been found that when the ratio of the number of added moles with an oxyalkylene group of 3 or more is set more appropriately, the above-mentioned effects can be fully exhibited, and the present invention has been achieved.
[0012]
That is, the present invention is a concrete composition comprising a polyoxyalkylene compound, water, cement, fine aggregate and coarse aggregate as essential components, wherein the polyoxyalkylene compound isThe following general formula (1);
X-[(AO) n-R ¹ ] K (1)
(In the formula, X represents an amine residue, and has an aliphatic hydrocarbon group in which 8 or more carbon atoms are continuously bonded in the molecule. R ¹ Are the same or different and each represents a hydrogen atom, a hydrocarbon group, -Y-NR ² R ^Three , -COR ^Four Or -CH ₂ CH ₂ NHCO-R ^Five Represents. Y represents an alkylene group having 1 to 10 carbon atoms. R ² And R ^Three Are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. R ^Four And R ^Five Represents a hydrocarbon group having 1 to 30 carbon atoms or a group having at least one carboxyl group or sulfonyl group or a salt thereof. AO is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. n is the same or different and represents the average number of added moles of the oxyalkylene group, and is 1 to 300. k is 1 to 300. the above0.15 <u / (u + v) <0.65 where u is the total number of added oxyethylene groups in the oxyalkylene group, and v is the total number of added oxyalkylene groups having 3 or more carbon atoms.1 <u + v <300 is satisfied. The concrete composition is further represented by a polyoxyalkylene ester structural unit (I) represented by the following general formula (2) and a general formula (3) described later. A polycarboxylic acid polymer (A-1) having a carboxylic acid structural unit (II)It is a concrete composition.
The present invention is described in detail below.
[0013]
First, the polyoxyalkylene compound in the concrete composition of the present invention will be described.
The polyoxyalkylene compound in the present invention has at least one nitrogen atom in the molecule and has an oxyalkylene group. The oxyalkylene group includes an oxyethylene group and an oxyalkylene having 3 or more carbon atoms. The group is essential. In the present invention, one or more of such polyoxyalkylene compounds can be used. The polyoxyalkylene compound may have a plurality of oxyalkylene groups and / or a plurality of oxyalkylene groups (polyalkylene glycol chains) in which two or more alkylene oxides are added. is there.
[0014]
The polyoxyalkylene compound may be used by neutralizing nitrogen atoms with an inorganic acid such as hydrochloric acid, sulfuric acid, or nitric acid, or an acidic substance such as acetic acid, propionic acid, or (meth) acrylic acid. When such a polyoxyalkylene compound and a polycarboxylic acid polymer having a free carboxyl group, which will be described later, are blended, the free carboxyl group of the polycarboxylic acid polymer is reduced by a nitrogen atom in the polyoxyalkylene compound. Since it is neutralized to form a salt, the water solubility is improved, and the storage stability of the blended product of the polyoxyalkylene compound and the polycarboxylic polymer in the aqueous medium is very good.
[0015]
The oxyalkylene group in the polyoxyalkylene compound is 0.15 <u / (u + v) where u is the total number of added oxyethylene groups and v is the total number of added oxyalkylene groups having 3 or more carbon atoms. ) <0.65 is satisfied. If it is 0.65 or more, the hydrophilicity becomes strong and the defoaming property becomes insufficient, and it becomes necessary to increase the amount of the polyoxyalkylene compound added. If it is 0.15 or less, the defoaming property is maintained. In any case, the strength of the cured product will be reduced. The value of u / (u + v) is preferably more than 0.35. That is, it is preferable that u and v satisfy the relationship of 0.35 <u / (u + v) <0.65. More preferably, it exceeds 0.4.
In the present invention, when the polyoxyalkylene compound has a plurality of oxyalkylene groups, it does not mean that each individual oxyalkylene group satisfies the above relationship, but the oxyethylene group in all oxyalkylene groups. When the total number of added moles is u and the total number of added moles of oxyalkylene groups having 3 or more carbon atoms is v, it means that the relationship of 0.15 <u / (u + v) <0.65 is satisfied.
[0016]
In the oxyalkylene group, the oxyalkylene group having 3 or more carbon atoms preferably has 8 or less carbon atoms. More preferably, it is 6 or less, and more preferably 4 or less. In addition, as an addition form of an oxyalkylene group in which two or more types of alkylene oxide, that is, ethylene oxide and an alkylene oxide having 3 or more carbon atoms are added, any of random addition, block addition, alternating addition, etc. There may be. As a preferable form, an oxyethylene group-an oxyalkylene group having 3 or more carbon atoms is added in a block form.
[0017]
In the polyoxyalkylene compound, the average addition mole number of the oxyalkylene group is preferably 1 to 300. More preferably, it is 2 or more, More preferably, it is 5 or more, Most preferably, it is 10 or more. Moreover, 200 or less is preferable. More preferably, it is 100 or less, More preferably, it is 50 or less, Most preferably, it is 40 or less. The average added mole number means an average value of the number of moles of oxyalkylene groups added in one mole of the polyalkylene glycol chain of the polyoxyalkylene compound. In addition, in the polyoxyalkylene compound, the addition form of the oxyalkylene group in which two or more kinds of alkylene oxides are added may be any of random, block, and alternate additions. The polyoxyalkylene compound preferably has a form in which an oxyalkylene group is added to a compound residue having active hydrogen as described later. In this case, the addition form includes an oxyethylene group and 3 carbon atoms. A form in which the above oxyalkylene groups are added in block form is preferred.
[0018]
The polyoxyalkylene compound has carbon atoms in the molecule.8It is preferable to have at least one aliphatic hydrocarbon group bonded continuously. As the number of continuously bonded carbon atoms in such an aliphatic hydrocarbon group,,10 or more are more preferable. Moreover, 30 or less are more preferable and 22 or less are still more preferable.
[0019]
As the polyoxyalkylene compound in the present invention, the following general formula (1);
X-[(AO) n-R¹] K (1)
(In the formula, X represents a compound residue having active hydrogen. R¹Are the same or different and each represents a hydrogen atom, a hydrocarbon group, -Y-NR²R^Three, -COR^FourOr -CH₂CH₂NHCO-R^FiveRepresents. Y represents an alkylene group having 1 to 10 carbon atoms. R²And R^ThreeAre the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. R^FourAnd R^FiveRepresents a hydrocarbon group having 1 to 30 carbon atoms or a group having at least one carboxyl group or sulfonyl group or a salt thereof. AO is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. n is the same or different and represents the average number of added moles of the oxyalkylene group, and is 1 to 300. k is 1 to 300. When the total number of added oxyethylene groups in the oxyalkylene group is u and the total number of added oxyalkylene groups having 3 or more carbon atoms is v, 0.15 <u / (u + v) <0.65, 1 <U + v <300 is satisfied. k is 1 to 300. It is preferable to use a compound represented by In the polyoxyalkylene compound represented by the general formula (1), a group represented by X and / or R¹The group represented by has a nitrogen atom.
[0020]
In the general formula (1), X is a compound residue having active hydrogen.(Residue of amine)The tableAnd having an aliphatic hydrocarbon group in which 8 or more carbon atoms are continuously bonded in the molecule.The compound residue having active hydrogen means a group having a structure obtained by removing active hydrogen from a compound having active hydrogen, but is not particularly limited to a group formed by reaction with a compound having active hydrogen. Absent. In the polyoxyalkylene compound, the compound residue having active hydrogen may be one type or two or more types. As such a group,Residues of amines having a structure in which active hydrogen is removed from the amino group of the aminesoPreferably there is. Further, the form of the compound residue having active hydrogen may be any of a chain, branched, and three-dimensionally crosslinked structure.
In a preferred form of the compound residue having the active hydrogen,As the amine residue, a residue having a structure obtained by removing active hydrogen from a monovalent amine or polyvalent amine is preferable.Ru.
[0021]
In the general formula (1), R¹Are the same or different and each represents a hydrogen atom, a hydrocarbon group, -Y-NR²R^Three, -COR^FourOr -CH₂CH₂NHCO-R^FiveRepresents. Examples of the hydrocarbon group include linear or branched alkyl groups having 1 to 30 carbon atoms; phenyl groups having 6 to 30 carbon atoms, alkylphenyl groups, phenylalkyl groups, phenyl groups substituted with (alkyl) phenyl groups, and naphthyl groups. An aromatic group having a benzene ring such as an alkenyl group having 2 to 30 carbon atoms and an alkynyl group having 2 to 30 carbon atoms is preferable. Moreover, although carbon number of a hydrocarbon group is 1 or more, since a polyoxyalkylene type compound has high defoaming performance, 2 or more are preferable. More preferably, it is 5 or more. Moreover, 30 or less is preferable. More preferably, it is 22 or less, More preferably, it is 18 or less. Furthermore, among the hydrocarbon groups, straight chain, branched alkyl groups, and alkenyl groups are particularly preferable.
[0022]
Y represents an alkylene group having 1 to 10 carbon atoms, and the number of carbon atoms is preferably 2 or more, and more preferably 8 or less. R above²And R^ThreeRepresents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and when there is no aliphatic hydrocarbon group having 5 or more carbon atoms bonded to X or AO in the general formula (1), R²And R^ThreeThe number of carbon atoms in the hydrocarbon group is preferably 5 or more. More preferably, it is 8 or more, More preferably, it is 10 or more. Moreover, 22 or less is preferable. Conversely, when an aliphatic hydrocarbon group in which 5 or more carbon atoms are continuously bonded to X or AO is present, R²And R^ThreeIs preferably a hydrogen atom. R^FourAnd R^FiveRepresents a hydrocarbon group having 1 to 30 carbon atoms or at least one carboxyl group or sulfonyl group or a group having a salt thereof, and X or AO in the general formula (1) has 5 or more carbon atoms. When there is no aliphatic hydrocarbon group bonded continuously, a hydrocarbon group having 5 or more carbon atoms is preferred. Conversely, when an aliphatic hydrocarbon group in which 5 or more carbon atoms are continuously bonded to X or AO is present, at least one carboxyl group or sulfonyl group or a group having a salt thereof is used. Preferably there is. Of the hydrocarbon groups, straight chain, branched alkyl groups and alkenyl groups are particularly preferred.
[0023]
The AO represents an oxyalkylene group having 2 to 18 carbon atoms, and the number of carbon atoms is preferably 8 or less. More preferably, it is 6 or less, More preferably, it is 4 or less. The addition form of the oxyethylene group and the oxyalkylene group having 3 or more carbon atoms may be any of random, block, and alternate additions. A more preferable form is a block shape. U and v represent the total number of added moles of oxyethylene groups and the total number of added moles of oxyalkylene groups having 3 or more carbon atoms, respectively. 0.15 <u / (u + v) <0.65, 1 < It is preferable to satisfy the relationship of u + v <300. (U + v) is more preferably greater than 5, and still more preferably greater than 10. Also, it is preferably less than 200, more preferably less than 150, still more preferably less than 100, particularly preferably less than 80, and most preferably less than 50. U / (u + v) with respect to the total number of added moles of alkylene oxide (u + v) of the total number of added moles u of oxyethylene groups is more preferably more than 0.2, still more preferably more than 0.35. In the general formula (1), the average added mole number n is [(AO) n-R.¹] The average value of the number of moles of the oxyalkylene group added in 1 mole of the same unit among the units represented by
[0024]
The k is 1 to 300, but 200 or less is preferable. More preferably, it is 100 or less. When k is 2 or more, that is, X is-[(AO) n-R¹When a plurality of groups represented by the above are bonded,-[(AO) n-R¹] May be the same or different.
[0025]
When the polyoxyalkylene compound in the general formula (1) has at least one aliphatic hydrocarbon group in which 5 or more carbon atoms are continuously bonded in the molecule, in the general formula (1) R constituting a polyoxyalkylene compound¹, X, R¹In at least one of the structures represented by -AO and AO, there will be an aliphatic hydrocarbon group in which 5 or more carbon atoms are continuously bonded. Further, such an aliphatic hydrocarbon group is more preferably one in which 8 or more carbon atoms are continuously bonded. Further, 10 or more are more preferable. Moreover, 30 or less are preferable. More preferably, it is 22 or less.
[0026]
The molecular weight of the polyoxyalkylene compound in the present invention is preferably 10,000 or less. More preferably, it is 5000 or less. Moreover, it is preferable that it is 100 or more. More preferably, it is 200 or more.
[0027]
Examples of the compound represented by the general formula (1) include (di) methylamine, (di) ethylamine, (di) propylamine, (di) butylamine, (di) pentylamine, (di) hexylamine, (di) ) Heptylamine, (di) octylamine, (di) nonylamine, (di) decaamine, (di) undecamine, (di) dodecamine, (di) tetradecamine, (di) pentadecamine, (di) hexadecamine (Di) heptadecamine, (di) octadecamine, (di) nonadecamine, (di) primary amine having a branched alkyl group having 1 to 30 carbon atoms, such as icosamine, the same type of alkyl group, Or secondary amines having different types of alkyl groups; primary amines derived from fatty acids obtained from coconut oil, primary amines derived from oleic acid, obtained from soybean oil A straight-chain, branched alkyl group having 1 to 30 carbon atoms such as a primary amine derived from fatty acid, a primary amine derived from fatty acid obtained from beef tallow, a primary amine derived from fatty acid obtained from hardened beef tallow, and different Primary amines mixed with various alkyl groups; secondary amine derived from fatty acid obtained from coconut oil, secondary amine derived from oleic acid, secondary amine derived from fatty acid obtained from soybean oil, fatty acid obtained from beef tallow Secondary amines derived from secondary amines derived from fatty acids derived from hardened beef tallow, etc., which have linear and branched alkyl groups of 1 to 30 carbon atoms and mixed with different types of alkyl groups; C6-C30 phenyl group, alkylphenyl group, phenylalkyl group, phenyl group substituted with (alkyl) phenyl group, aromatic group having benzene ring such as naphthyl group, carbon number Primary or secondary amines having -30 alkenyl groups and alkynyl groups having 2 to 30 carbon atoms; amines such as alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; ethylene oxide and 3 to 18 carbon atoms Adducts obtained by adding an alkylene oxide of
[0028]
Among the compounds represented by the general formula (1), the compounds having 2 or more nitrogen atoms include polyalkylene polyamines such as ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, dipropylenetriamine, and tetrapropylenepentamine. Fatty acids such as acetic acid, propionic acid, butyric acid, valeric acid, lauric acid, stearic acid, oleic acid, fatty acids obtained from coconut oil, fatty acids obtained from soybean oil, fatty acids obtained from beef tallow, fatty acids obtained from hardened tallow Of ethyleneamide and C3-C18 alkylene oxide obtained by dehydration condensation with ethylene; ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, dipropylenetriamine, tetrapropylenepentamine, etc. Lialkylene polyamines and fatty acids obtained from acetic acid, propionic acid, butyric acid, valeric acid, lauric acid, stearic acid, oleic acid, coconut oil, fatty acids obtained from soybean oil, fatty acids obtained from beef tallow, fatty acids obtained from hardened tallow Imidazolines obtained by further dehydrating amide amines obtained by dehydration condensation with fatty acids such as ethylene oxide and C3-C18 alkylene oxide adducts; ethylene diamine, propylene diamine, diethylene triamine, triethylene tetramine, dipropylene triamine , Ethylene oxide of polyalkylene polyamines such as tetrapropylenepentamine and alkylene oxide adducts having 3 to 18 carbon atoms; ethylene diamine, propylene diamine, diethylene to be modified with a hydrocarbon group having 1 to 30 carbon atoms Obtained by polymerization of polyalkylene polyamines such as amine, triethylenetetramine, dipropylenetriamine, and tetrapropylenepentamine, and ethylene oxide and adducts having 3 to 18 carbon atoms; alkyleneimine such as ethyleneimine and propyleneimine Polyethyleneimine, polypropyleneimine and other polyalkyleneimines ethylene oxide and C3-C18 alkylene oxide adducts; polymerizing ethyleneimine and propyleneimine alkyleneimine modified with C1-30 hydrocarbon groups Polyalkyleneimines such as polyethyleneimine and polypropyleneimine obtained by addition of ethylene oxide and alkylene oxide adducts having 3 to 18 carbon atoms; primary amines and secondary amines having 1 to 30 carbon atoms. Ethylene oxide and alkylene oxide adducts having 3 to 18 carbon atoms of alkylaminopropylamines such as those obtained by adding acrylonitrile to a amine and then reducing it are preferred.
[0029]
Moreover, as a nitrogen atom containing polyoxyalkylene type compound in this invention, the compound described below is also suitable.
Amines having amino groups introduced into polyoxyalkylenes obtained by adding ethylene oxide and alkylene oxides having 3 to 18 carbon atoms to monohydric alcohols having a hydrocarbon group having 1 to 30 carbon atoms; hydroxyl groups at both ends Polyoxyethylene polyoxyalkylenes having amino groups introduced into them; polyoxyalkylenes obtained by adding ethylene oxide and alkylene oxides having 3 to 18 carbon atoms to polyhydric alcohols having 3 or more hydroxyl groups in the molecule Amines having amino groups introduced therein; amines having amino groups introduced into polyoxyalkylenes obtained by adding ethylene oxide and alkylene oxides having 3 to 18 carbon atoms to alcohols having an acetylene group in the molecule.
Various methods for introducing an amino group are conceivable, but a method of converting a hydroxyl group itself to an amino group with various amination reagents and a method of adding an alkyleneimine such as ethyleneimine or propyleneimine to the hydroxyl group are suitable. is there.
[0030]
Examples of the monohydric alcohol having a hydrocarbon group having 1 to 30 carbon atoms include methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, octanol, lauryl alcohol, cetyl alcohol, stearyl alcohol, and 12 to 14 carbon atoms. Linear and branched saturated alcohols such as: allyl alcohol, methallyl alcohol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl Unsaturated alcohols such as -3-buten-2-ol and oleyl alcohol; aromatic alcohols such as phenol, nonylphenol and benzyl alcohol are preferred.
[0031]
Examples of polyoxyethylene polyoxyalkylenes having hydroxyl groups at both ends include AB block types such as polyoxyethylene polyoxypropylene and polyoxyethylene polyoxybutylene; polyoxyethylene polyoxypropylene polyoxyethylene, polyoxypropylene ABA block types such as polyoxyethylene polyoxypropylene and polyoxyethylene polyoxybutylene polyoxyethylene are preferred.
[0032]
As the polyhydric alcohol having 3 or more hydroxyl groups in the molecule, trimethylolpropane, pentaerythritol, polyglycerin and sorbitol are preferable.
[0033]
Examples of alcohols having an acetylene group in the molecule include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 3-methyl 1-butyn-3-ol is preferred.
[0034]
In addition, in the above polyoxyalkylene compounds, when an aliphatic hydrocarbon group in which 5 or more carbon atoms are continuously bonded is not contained in the molecule, carbon is added during or after synthesis. Aliphatic hydrocarbon groups can also be introduced as appropriate by adding a part of alkylene oxide having 5 or more or reacting with alkyl halide having 5 or more carbon atoms.
[0035]
Further, a compound obtained by further adding an alkylene oxide such as ethylene oxide or an alkylene imine such as ethylene imine to the terminal functional group of the polyoxyalkylene compound described so far is also the present invention. Can be used as a polyoxyalkylene compound.
[0036]
Furthermore, compounds obtained by reacting acid functional anhydrides such as acetic anhydride and butyric anhydride with the terminal functional groups of the polyoxyalkylene compounds described so far can also be used as the polyoxyalkylene compounds in the present invention. it can.
[0037]
Further, as the polyoxyalkylene compound in the present invention, the following compounds are also suitable.
A compound in which the polyoxyalkylene compound described above and a compound having two or more carboxyl groups are ester-bonded leaving at least one carboxyl group; the above polyoxyalkylene compound; a carboxyl group; A compound having a sulfonyl group and an ester bond leaving at least one sulfonyl group; the polyoxyalkylene compound and a compound having two or more carboxyl groups having at least one carboxyl group A compound in which an amide bond is left; a compound in which the polyoxyalkylene compound and a compound having a carboxyl group and a sulfonyl group are amide-bonded leaving at least one sulfonyl group.
In such a polyoxyalkylene compound, the remaining carboxyl group or sulfonyl group is a metal salt such as sodium salt or calcium salt neutralized with a base such as sodium hydroxide or calcium hydroxide, ammonium salt, amine Salt may be used.
[0038]
Examples of the compound having two or more carboxyl groups include unsaturated dicarboxylic acids such as maleic acid, fumaric acid, phthalic acid, and itaconic acid, and metal salts, ammonium salts, and amine salts thereof; succinic acid, malonic acid, and glutaric acid. , Saturated dicarboxylic acids such as adipic acid and their metal salts, ammonium salts, amine salts; low molecular weight polymers of unsaturated monocarboxylic acids or unsaturated dicarboxylic acids such as acrylic acid oligomers, methacrylic acid oligomers, maleic acid oligomers, and the like; Their metal salts, ammonium salts and amine salts are preferred.
[0039]
The polyoxyalkylene compound can be obtained, for example, by reacting a hydroxyl group-terminated polyoxyalkylene compound with an acid anhydride such as maleic anhydride or succinic anhydride in the absence of a solvent or in a suitable solvent. Can do. At this time, it is preferable to use an appropriate base catalyst. In addition, it can also be obtained by esterification by a dehydration reaction between a polyoxyalkylene compound having a hydroxyl group at the end and a carboxylic acid, or by an ester exchange reaction between a polyoxyalkylene compound having a hydroxyl group at the end and an ester compound. .
[0041]
Next, other essential components in the concrete composition of the present invention will be described.
Examples of the cement in the present invention include Portland cement (ordinary, early strength, ultra-early strength, moderate heat, sulfate resistant and low alkali type), various mixed cements (blast furnace cement, silica cement, fly ash cement), white Portland cement. Cement, alumina cement, super fast cement (1 clinker fast cement, 2 clinker fast cement, magnesium phosphate cement), grout cement, oil well cement, low heat cement (low heat blast furnace cement, fly ash mixed low heat heat type) Blast furnace cement, cement with high belite content), ultra-high-strength cement, cement-based solidified material, eco-cement (cement manufactured using one or more of municipal waste incineration ash and sewage sludge incineration ash), and Blast furnace slag, fly ash, cinder ash Clinker ash, husk ash, silica fume, silica powder, a fine powder and gypsum limestone powder may be added. These may be used alone or in combination of two or more.
[0042]
As the fine aggregate in the present invention, sand is suitable, and as the coarse aggregate, in addition to gravel, crushed stone, granulated slag, recycled aggregate, etc., siliceous, clay, zircon, high alumina, carbonized Refractory aggregates such as silicon, graphite, chrome, chromia, and magnesia can be used. These may be used alone or in combination of two or more.
[0043]
In the concrete composition of the present invention, 1 m^ThreeAs unit water amount per unit, amount of cement used, amount of coarse aggregate, and water / cement ratio, unit water amount 100 to 185 kg / m^Three, Use cement amount 250-800kg / m^Three, Unit coarse aggregate amount 500-1500kg / m^ThreeThe water / cement ratio (mass ratio) is preferably 0.1 to 0.7. Unit water volume is 120kg / m^ThreeThe above is more preferable, and 175 kg / m^ThreeThe following is more preferable. The amount of cement used is 270 kg / m^ThreeMore preferably, 800 kg / m^ThreeThe following is more preferable. Unit coarse aggregate amount is 600kg / m^ThreeMore preferably, more preferably 800 kg / m^ThreeOr more and 1300 kg / m^ThreeThe following is more preferable, and further preferably 1200 kg / m^ThreeIt is as follows. The water / cement ratio (mass ratio) is more preferably 0.2 or more, and more preferably 0.65 or less. The concrete composition of the present invention can be used widely from poor blending to rich blending, high-strength concrete having a large unit cement amount, and the unit cement amount is 300 kg / m.^ThreeIt is effective for any of the following poorly blended concrete.
[0044]
The blending ratio of the polyoxyalkylene compound in the concrete composition of the present invention is preferably 0.0001% by mass or more and 1.0% by mass or less of the cement mass. If the above blending ratio is less than 0.0001% by mass, the performance may be insufficient, and even if a large amount exceeding 1.0% by mass is used, the effect is practically peaked and is economical. May be disadvantageous. More preferably, it is 0.0005 mass% or more, More preferably, it is 0.001 mass% or more. More preferably, it is 0.5 mass% or less, More preferably, it is 0.1 mass% or less, and what is necessary is just to add the quantity used as such a ratio. By this addition, various preferable effects such as reduction in unit water amount, increase in strength, and improvement in durability are brought about.
[0045]
The concrete composition of the present invention preferably also contains a cement dispersant, so that a concrete composition having a stable entrained air amount can be obtained during the kneading of the concrete composition. In addition, a concrete composition having a stable entrained air amount can be obtained even when left standing after kneading. Conventionally, what is mixed as a defoaming component in a cement dispersant has poor solubility in water, and there is a problem that the defoaming component is separated during storage when mixed with a cement dispersant solution. Since the polyoxyalkylene compound in is highly hydrophilic, it is relatively uniform even in the cement dispersant liquid, and can be stably stored without separation. Thus, it is one of the preferable embodiments of the present invention that the concrete composition contains the polyoxyalkylene compound and the cement dispersant as essential components.
[0046]
The cement dispersant is not particularly limited as long as it can exhibit water-reducing performance in the concrete composition. One or two or more kinds of cement dispersants can be used. The polycarboxylic acid heavy polymer having a polyalkylene glycol in the side chain can be used. Coalescence is preferred. Such a polycarboxylic acid polymer can be an essential component of a cement dispersant, and is called a polycarboxylic acid cement dispersant or a water reducing agent. Such a cement dispersant may be composed only of the polycarboxylic acid-based polymer or may contain other components, but it is preferable that the cement dispersant is mainly composed of the polycarboxylic acid-based polymer.
As the polycarboxylic acid polymer, the following general formula (2);
[0047]
[Chemical 1]

[0048]
(Wherein R⁶, R⁷And R⁸Are the same or different and each represents a hydrogen atom or a methyl group. R⁹O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. a represents the average addition mole number of an oxyalkylene group, and is a number of 2 to 300. R^TenRepresents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. And a polyoxyalkylene ester structural unit (I) represented by the following general formula (3);
[0049]
[Chemical 2]

[0050]
(Wherein R¹¹, R¹²And R¹³Are the same or different and each represents a hydrogen atom or a methyl group. M¹Represents a hydrogen atom, a monovalent metal, a divalent metal, ammonium or an organic amine. The polycarboxylic acid polymer (A-1) having a carboxylic acid structural unit (II) represented by
[0051]
Moreover, as said polycarboxylic acid-type polymer, following General formula (4);
[0052]
[Chemical 3]

[0053]
(Wherein R¹⁴, R¹⁵And R¹⁶Are the same or different and each represents a hydrogen atom or a methyl group. R¹⁷Represents a hydrocarbon group having 1 to 5 carbon atoms. R¹⁸O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. b represents the average addition mole number of an oxyalkylene group, and is a number of 2 to 300. R¹⁹Represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. And a polyoxyalkylene ether structural unit (III) represented by the following general formula (5);
[0054]
[Formula 4]

[0055]
(Wherein R²⁰And R^{twenty one}Are the same or different and are a hydrogen atom, a methyl group, or -COOM.^ThreeRepresents. However, R²⁰And R^{twenty one}At the same time -COOM^ThreeDoes not represent. R^{twenty two}Is a hydrogen atom, a methyl group or —CH₂COOM^FourRepresents. R^{twenty two}Is -CH₂COOM^FourWhen R²⁰And R^{twenty one}Are the same or different and each represents a hydrogen atom or a methyl group. M², M^ThreeAnd M^FourRepresents a hydrogen atom, a monovalent metal, a divalent metal, ammonium or an organic amine. The polycarboxylic acid polymer (A-2) having a carboxylic acid structural unit (IV) represented by That is, the cement dispersant preferably contains the polycarboxylic acid polymer (A-1) and / or the polycarboxylic acid polymer (A-2).
[0056]
The polycarboxylic acid polymers (A-1) and (A-2) have the above essential structural units (repeating units), and are structural units derived from the monomer (e) described later ( V) may further be included. Each of these structural units may be one kind or two or more kinds.
[0057]
The polycarboxylic acid-based polymer (A-1) is a monomer that provides the structural unit (I) (for example, a monomer (a) described later), a monomer that provides the structural unit (II) (for example, It can be produced by copolymerizing a monomer component containing the monomer (b)) described below as an essential component. Such a monomer component may further contain a monomer that gives the structural unit (V) (for example, a monomer (e) described later). In addition, when each structural unit is 1 type, it is sufficient to use one type of monomer that provides each structural unit. When there are 2 or more types of structural units, a single amount that provides each structural unit. What is necessary is just to use 2 or more types of bodies, respectively.
[0058]
The ratio of each structural unit constituting the polycarboxylic acid polymer (A-1) is, by mass ratio, structural unit (I) / structural unit (II) / structural unit (V) = 1 to 99/99. It is preferable to be 1/0 to 50. More preferably, the structural unit (I) / the structural unit (II) / the structural unit (V) = 50 to 99/50 to 1/0 to 49, and more preferably the structural unit (I) / the structural unit (II) / the structural unit. (V) = 60 to 95/40 to 5/0 to 30, most preferably the structural unit (I) / the structural unit (II) / the structural unit (V) = 70 to 95/30 to 5/0 to 10. . However, the total of the structural unit (I), the structural unit (II) and the structural unit (V) is 100% by mass.
[0059]
The polycarboxylic acid polymer (A-1) is a monomer that provides an unsaturated monocarboxylic acid monomer such as acrylic acid, methacrylic acid, or crotonic acid, and a structural unit (II) (for example, described later). It can be produced by directly esterifying an alkoxypolyalkylene glycol with respect to at least a part of a carboxyl group of a polymer obtained by copolymerizing a monomer component containing the monomer (b)) as an essential component. Good.
[0060]
In the general formula (2), R^TenAs the hydrocarbon group having 1 to 30 carbon atoms, the alkyl group having 1 to 30 carbon atoms, the phenyl group having 6 to 30 carbon atoms, the alkylphenyl group, the phenylalkyl group, and the (alkyl) phenyl group are substituted. An aromatic group having a benzene ring such as a phenyl group or a naphthyl group, or an alkenyl group having 2 to 30 carbon atoms is preferable. The average addition mole number a of the oxyalkylene group is 2 to 300 or less, and preferably 5 or more. More preferably, it is 10 or more, More preferably, it is 15 or more, Most preferably, it is 20 or more. Most preferably, it is 200 or less. In addition, R^TenThe number of carbon atoms is 1 or more, preferably 22 or less. More preferably, it is 18 or less, More preferably, it is 12 or less, More preferably, it is 6 or less, Especially preferably, it is 5 or less, Most preferably, it is 3 or less.
[0061]
Oxyalkylene group R in the general formula (2)⁹As the number of carbon atoms of O, 2 to 18 is appropriate, but 8 or less is preferable. More preferably, it is 4 or less. Moreover, when it becomes one type as the structural unit (I), it is preferable to have an oxyethylene group as an essential component in the oxyalkylene group in order to ensure a balance between hydrophilicity and hydrophobicity, and more preferably 50 mol% or more. Particularly preferably, 60 mol% or more is an oxyethylene group. On the other hand, when there are two or more types of structural units (I), it is preferable to have an oxyethylene group as an essential component in the oxyalkylene group of any one of the structural units (I).
[0062]
As the monomer (a) giving the structural unit (I), an adduct of an alkylene oxide having 2 to 18 carbon atoms to the dehydrogenation (oxidation) reaction product of (meth) acrylic acid, crotonic acid or fatty acid, Or 1 carbon atom such as methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, octanol, 2-ethyl-1-hexanol, nonyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol -30 saturated aliphatic alcohols, allyl alcohol, methallyl alcohol, crotyl alcohol, oleyl alcohol, etc., C3-30 unsaturated aliphatic alcohols, cyclohexanol, etc., C3-30 fats Cyclic alcohols, phenol, phenylmethanol (benzyl alcohol) ), Methylphenol (cresol), p-ethylphenol, dimethylphenol (xylenol), pt-butylphenol, nonylphenol, dodecylphenol, phenylphenol, naphthol, or any other aromatic alcohol having 6 to 30 carbon atoms An ester compound of an alkoxypolyalkylene glycol obtained by adding an alkylene oxide having 2 to 18 carbon atoms to (meth) acrylic acid or crotonic acid is suitable, but in the general formula (3), R^TenAn ester compound of an alkoxypolyalkylene glycol and (meth) acrylic acid or crotonic acid corresponding to the case where is a hydrocarbon group is preferred.
[0063]
As specific chemical names of the monomer (a), the following are suitable. Methoxy polyethylene glycol mono (meth) acrylate, ethoxy polyethylene glycol mono (meth) acrylate, 1-propoxy polyethylene glycol mono (meth) acrylate, 2-propoxy polyethylene glycol mono (meth) acrylate, 1-butoxy polyethylene glycol mono (meth) acrylate 2-butoxypolyethylene glycol mono (meth) acrylate, 2-methyl-1-propoxypolyethylene glycol mono (meth) acrylate, 2-methyl-2-propoxypolyethylene glycol mono (meth) acrylate, 1-pentyloxypolyethylene glycol mono ( (Meth) acrylate, 1-hexyloxypolyethylene glycol mono (meth) acrylate, cyclohexyloxypolyethylene Glycol mono (meth) acrylate, 1-octyloxypolyethylene glycol mono (meth) acrylate, 2-ethyl-1-hexyloxypolyethylene glycol mono (meth) acrylate, nonylalkoxypolyethyleneglycol mono (meth) acrylate, laurylalkoxypolyethyleneglycolmono (Meth) acrylate, cetylalkoxypolyethyleneglycol mono (meth) acrylate, stearylalkoxypolyethyleneglycolmono (meth) acrylate, phenoxypolyethyleneglycolmono (meth) acrylate, phenylmethoxypolyethyleneglycolmono (meth) acrylate, methylphenoxypolyethyleneglycolmono ( (Meth) acrylate, p-ethylphenoxypolyethyleneglycol Mono (meth) acrylate, dimethylphenoxypolyethylene glycol mono (meth) acrylate, pt-butylphenoxypolyethylene glycol mono (meth) acrylate, nonylphenoxypolyethylene glycol mono (meth) acrylate, dodecylphenoxypolyethylene glycol mono (meth) acrylate, Phenylphenoxypolyethylene glycol mono (meth) acrylate, naphthoxypolyethylene glycol mono (meth) acrylate, esterified product of (meth) allyl alcohol and (meth) acrylic acid to which ethylene oxide is added, crotyl alcohol to which ethylene oxide is added Various alkoxy polyethylene glycol mono (meth) acrylates such as esterified products with (meth) acrylic acid.
[0064]
Methoxy polypropylene glycol mono (meth) acrylate, ethoxy polypropylene glycol mono (meth) acrylate, 1-propoxy polypropylene glycol mono (meth) acrylate, 2-propoxy polypropylene glycol mono (meth) acrylate, 1-butoxy polypropylene glycol mono (meth) acrylate , Various types of alkoxypolypropylene glycol mono ((ester) of (meth) allyl alcohol and propylene oxide and (meth) acrylic acid, ester of crotyl alcohol and propylene oxide and (meth) acrylic acid) (Meth) acrylates.
[0065]
Methoxypolyethylenepolypropyleneglycol mono (meth) acrylate, methoxypolyethylenepolybutyleneglycolmono (meth) acrylate, ethoxypolyethylenepolypropyleneglycolmono (meth) acrylate, ethoxypolyethylenepolybutyleneglycolmono (meth) acrylate, 1-propoxypolyethylenepolypropyleneglycolmono ( (Meth) acrylate, 1-propoxypolyethylene polybutylene glycol mono (meth) acrylate, 2-propoxypolyethylenepolypropylene glycol mono (meth) acrylate, 2-propoxypolyethylenepolybutylene glycol mono (meth) acrylate, 1-butoxypolyethylenepolypropylene glycol mono ( (Meth) acrylate, 1-butoxypoly Tylene polybutylene glycol mono (meth) acrylate, esterified product of (meth) allyl alcohol and (meth) acrylic acid with addition of ethylene oxide and propylene oxide or ethylene oxide and butylene oxide, addition of ethylene oxide and propylene oxide or ethylene oxide and butylene oxide Alkoxypolyalkylene glycol mono (meth) acrylates such as esterified products of alcohol and (meth) acrylic acid to which two or more alkylene oxides such as esterified products of crotyl alcohol and (meth) acrylic acid added are added Kind.
[0066]
As the monomer (b) that gives the structural unit (II) represented by the general formula (3), acrylic acid, methacrylic acid, crotonic acid, and metal salts, ammonium salts, and amine salts thereof are preferable. Particularly preferred are (meth) acrylic acid and salts thereof.
[0067]
The polycarboxylic acid-based polymer (A-2) includes a monomer that gives the structural unit (III) (for example, a monomer (c) described later) and a monomer that gives the structural unit (IV) (for example, It can be produced by copolymerizing a monomer component containing the monomer (d) described below as an essential component. Such a monomer component may further contain a monomer that gives the structural unit (V) (for example, a monomer (e) described later).
[0068]
The ratio of each structural unit which comprises the said polycarboxylic acid type polymer (A-2) is mass ratio, and structural unit (III) / structural unit (IV) / structural unit (V) = 1-99 / 99- It is preferable that it is 1 / 0-50. More preferably, the structural unit (III) / the structural unit (IV) / the structural unit (V) = 50 to 99/50 to 1/0 to 49, and more preferably the structural unit (III) / the structural unit (IV) / the structural unit. (V) = 60 to 95/40 to 5/0 to 30, most preferably the structural unit (III) / the structural unit (IV) / the structural unit (V) = 70 to 95/30 to 5/0 to 10. . However, the sum total of structural unit (III), structural unit (IV), and structural unit (V) is 100 mass%.
[0069]
The polycarboxylic acid polymer (A-2) includes allyl alcohol, methallyl alcohol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl- A monomer component containing an unsaturated alcohol such as 3-buten-2-ol and a monomer (for example, monomer (d) described later) that gives structural unit (IV) as an essential component is copolymerized. It can also be obtained by adding an average of 2 to 300 moles of alkylene oxide to the resulting polymer or reacting an alkoxypolyalkylene glycol having an average number of moles of addition of 2 to 300.
[0070]
In the general formula (4), the average addition mole number b of the oxyalkylene group is a number of 2 to 300, but 5 or more is preferable. More preferably, it is 10 or more, More preferably, it is 20 or more, Most preferably, it is 25 or more. Moreover, 200 or less is especially preferable. R¹⁹The number of carbon atoms is preferably 1 or more. Moreover, 22 or less is preferable. More preferably, it is 18 or less, More preferably, it is 12 or less, More preferably, it is 6 or less, Especially preferably, it is 5 or less, Most preferably, it is 3 or less. In addition, R¹⁷The number of carbon atoms is from 1 to 5, preferably 4 or less. More preferably, it is 3 or less, particularly preferably —CH.₂-,-(CH₂)₂-Or -C (CH_Three)₂-Structure.
[0071]
Oxyalkylene group R in the general formula (4)¹⁸The carbon number of O is 2-18, but 8 or less is preferable. More preferably, it is 4 or less. In addition, when it is one kind as the structural unit (III), it is preferable to have an oxyethylene group as an essential component in the oxyalkylene group in order to ensure a balance between hydrophilicity and hydrophobicity, more preferably 50 mol% or more. Particularly preferably, 60 mol% or more is an oxyethylene group.
[0072]
Examples of the monomer (d) which gives the structural unit (IV) represented by the general formula (5) include acrylic acid, methacrylic acid, crotonic acid, and unsaturated monomonomers such as metal salts, ammonium salts, and amine salts thereof. Carboxylic acid monomers: Maleic acid, itaconic acid, citraconic acid, fumaric acid, or unsaturated dicarboxylic acid monomers such as metal salts, ammonium salts, and amine salts thereof are suitable. Furthermore, these anhydrides can also be used, and maleic anhydride, itaconic anhydride, and citraconic anhydride are preferred. Above all, R²⁰, R^{twenty one}And R^{twenty two}Are preferably the same or different and corresponding to the case of a hydrogen atom or a methyl group, it is preferable to use unsaturated monocarboxylic acid monomers, and in particular, (meth) acrylic acid, maleic acid, maleic anhydride and salts thereof Is preferably used.
[0073]
The monomer (e) that gives the structural unit (V) that can be used in the present invention may be any monomer that can be copolymerized with at least one of the other monomers. is there.
Half esters and diesters of unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid and citraconic acid and alcohols having 1 to 4 carbon atoms; half of the above unsaturated dicarboxylic acids and amines having 1 to 30 carbon atoms Amides and diamides: Half esters and diesters of alkyl (poly) alkylene glycols obtained by adding 1 to 500 moles of alkylene oxides having 2 to 18 carbon atoms to the above alcohols and amines; and the above unsaturated dicarboxylic acids; Ester and diester of a glycol having 2 to 18 carbon atoms or a polyalkylene glycol having 2 to 300 addition moles of these glycols.
[0074]
Half amides of maleamic acid and glycols having 2 to 18 carbon atoms or polyalkylene glycols having 2 to 300 addition moles of these glycols; triethylene glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate (Poly) alkylene glycol di (meth) acrylates such as polypropylene glycol di (meth) acrylate and (poly) ethylene glycol (poly) propylene glycol di (meth) acrylate; hexanediol di (meth) acrylate, trimethylolpropane tri Bifunctional (meth) acrylates such as (meth) acrylate and trimethylolpropane di (meth) acrylate; (poly) alkylene groups such as triethylene glycol dimaleate and polyethylene glycol dimaleate Call dimaleate class.
[0075]
Vinyl sulfonate, (meth) allyl sulfonate, 2- (meth) acryloxyethyl sulfonate, 3- (meth) acryloxypropyl sulfonate, 3- (meth) acryloxy-2-hydroxypropyl sulfonate, 3- (meth) acryloxy-2 -Hydroxypropylsulfophenyl ether, 3- (meth) acryloxy-2-hydroxypropyloxysulfobenzoate, 4- (meth) acryloxybutylsulfonate, (meth) acrylamidomethylsulfonic acid, (meth) acrylamidoethylsulfonic acid, 2- Unsaturated sulfonic acids such as methylpropane sulfonic acid (meth) acrylamide and styrene sulfonic acid, and monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts thereof; acrylic acid, methacrylic acid, croto Acid and unsaturated monocarboxylic acid-based compounds, and their metal salts, ammonium salts, amine salts.
[0076]
Unsaturated monocarboxylic acids such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, glycidyl (meth) acrylate, methyl crotonate, ethyl crotonate, propyl crotonate and the like and those having 1 to 4 carbon atoms Esters with alcohols; Amides of unsaturated monocarboxylic acids and amines having 1 to 30 carbon atoms such as methyl (meth) acrylamide; Vinyl aromas such as styrene, α-methylstyrene, vinyltoluene, p-methylstyrene Alkanediol mono (meth) acrylates such as 1,4-butanediol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate; butadiene , Isoprene, 2-methyl-1, -Dienes such as butadiene and 2-chloro-1,3-butadiene; Unsaturation such as (meth) acrylamide, (meth) acrylalkylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, etc. Amides; unsaturated cyanides such as (meth) acrylonitrile and α-chloroacrylonitrile.
[0077]
Unsaturated esters such as vinyl acetate and vinyl propionate; aminoethyl (meth) acrylate, methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, (meth ) Unsaturated amines such as dibutylaminoethyl acrylate and vinyl pyridine; divinyl aromatics such as divinylbenzene; cyanurates such as triallyl cyanurate; allyls such as (meth) allyl alcohol and glycidyl (meth) allyl ether ; Unsaturated amino compounds such as dimethylaminoethyl (meth) acrylate; methoxypolyethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, methoxypolyethylene glycol mono (meth) allyl ether, polyethylene glycol Mono (meth) vinyl or allyl ethers such as allyl ether.
Polydimethylsiloxanepropylaminomaleamic acid, polydimethylsiloxaneaminopropylaminomaleamic acid, polydimethylsiloxane-bis- (propylaminomaleamic acid), polydimethylsiloxane-bis- (dipropylaminomaleamic acid), polydimethyl Siloxane- (1-propyl-3-acrylate), polydimethylsiloxane- (1-propyl-3-methacrylate), polydimethylsiloxane-bis- (1-propyl-3-acrylate), polydimethylsiloxane-bis- (1 Siloxane derivatives such as (propyl-3-methacrylate); unsaturated phosphate esters such as 2-acryloyloxyethyl phosphate and 2-methacryloyloxyethyl phosphate.
[0078]
Polyalkylene polyamines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine and malonic acid, succinic acid, fumaric acid, maleic acid, azelaic acid, sebacic acid Or a condensate of a dibasic acid such as an esterified product of these with an alcohol having 1 to 20 carbon atoms or an ester of a dibasic acid and an alcohol having 1 to 20 carbon atoms with (meth) acrylic acid or (meth) A specific amount of alkylene oxide to a polyamide polyamine obtained by condensing an esterified product of acrylic acid and an alcohol having 1 to 20 carbon atoms, an unsaturated epoxy compound such as glycidyl (meth) acrylate and allyl glycidyl ether at a specific ratio. Added compounds; Esterified products of (meth) acrylic acid or (meth) acrylic acid and alcohols having 1 to 20 carbon atoms with compounds obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to active hydrogen of polyalkyleneimines such as reethyleneimine and polypropyleneimine Or a cationic monomer having a nitrogen atom such as a condensate with an unsaturated epoxidized product such as glycidyl (meth) acrylate and allyl glycidyl ether.
[0079]
In order to obtain the polycarboxylic acid polymer (A-1) or (A-2), the monomer component may be polymerized using a polymerization initiator. The polymerization can be performed by a method such as polymerization in a solvent or bulk polymerization. Polymerization in a solvent can be carried out either batchwise or continuously. The solvent used here is water; lower alcohols such as methyl alcohol, ethyl alcohol, 2-propanol; benzene, toluene, xylene, cyclohexane, One or more of aromatic or aliphatic hydrocarbons such as n-hexane; ester compounds such as ethyl acetate; ketone compounds such as acetone and methyl ethyl ketone are preferred. Solubility of raw material monomers and polycarboxylic acid polymers (A-1) and (A-2) to be obtained, and convenience when using polycarboxylic acid polymers (A-1) and (A-2) From the viewpoint of properties, it is preferable to use at least one selected from the group consisting of water and lower alcohols having 1 to 4 carbon atoms. In that case, among lower alcohols having 1 to 4 carbon atoms, methyl alcohol, ethyl alcohol, 2-propanol and the like are particularly effective.
[0080]
When the polymerization is carried out in an aqueous medium in order to obtain the polycarboxylic acid polymers (A-1) and (A-2), water or an aqueous solution such as ammonium or alkali metal persulfate or hydrogen peroxide as a polymerization initiator. It is preferable to use a polymerizable polymerization initiator. In this case, an accelerator such as sodium bisulfite, Mole salt, ascorbic acid (salt), Rongalite and the like can be used in combination. For polymerization using a lower alcohol, aromatic hydrocarbon, aliphatic hydrocarbon, ester compound or ketone compound as a solvent, peroxides such as benzoyl peroxide and lauroyl peroxide; hydroperoxides such as cumene hydroperoxide; azo It is preferable to use an azo compound such as bisisobutyronitrile as a polymerization initiator. In this case, an accelerator such as an amine compound can be used in combination. Furthermore, when a water-lower alcohol mixed solvent is used, it can be appropriately selected from the above-mentioned various polymerization initiators or combinations of polymerization initiators and accelerators. Although superposition | polymerization temperature is suitably determined with the solvent and polymerization initiator to be used, it is 0-120 degreeC normally and 30 degreeC or more is preferable. More preferably, it is 50 ° C. or higher. Moreover, 100 degrees C or less is preferable. More preferably, it is 95 degrees C or less.
[0081]
When bulk polymerization is carried out, usually a peroxide such as benzoyl peroxide or lauroyl peroxide; a hydroperoxide such as cumene hydroperoxide; an azo compound such as azobisisobutyronitrile is used as the polymerization initiator; Performed at ° C.
[0082]
Furthermore, hypophosphorous acid (salt) and a thiol chain transfer agent can be used in combination for adjusting the molecular weight of the resulting polycarboxylic acid polymer (A-1) or (A-2). The thiol chain transfer agent used in this case has a general formula HS-R.³⁰-Eg (wherein R³⁰Represents an alkyl group having 1 to 2 carbon atoms. E is -OH, -COOM, -COOR³¹Or SO_ThreeM group is represented. M represents a hydrogen atom, a monovalent metal, a divalent metal, an ammonium group or an organic amine group. R³¹Represents an alkyl group having 1 to 30 carbon atoms. g represents the integer of 1-2. And mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, octyl thioglycolate, and octyl 3-mercaptopropionate are preferred. Moreover, you may use the thiol compound which has a C3-C3 or more hydrocarbon group which does not have functional groups, such as a hydroxyl group and a carboxyl group, as a chain transfer agent. Butanethiol, octanethiol, decanethiol, dodecanethiol, hexadecanethiol, cyclohexyl mercaptan, thiophenol are suitable as such thiol compounds. In addition, halides such as carbon tetrachloride, carbon tetrabromide, methylene chloride, bromoform and bromotrichloroethane; unsaturated hydrocarbon compounds such as α-methylstyrene dimer, α-terpinene, γ-terpinene and dipentene as chain transfer agents It may be used. These 1 type (s) or 2 or more types can be used. In order to adjust the molecular weight of the polycarboxylic acid polymer (A-1) or (A-2), the monomer (e) has a chain transfer property such as (meth) allylsulfonic acid (salt). It is also effective to use a high monomer.
[0083]
The polycarboxylic acid-based polymers (A-1) and (A-2) can be used as they are, but in the case where the solubility in water is insufficient, the solubility in water is improved and organic In order to handle it in the form of a solvent-free aqueous medium, further, inorganic substances such as monovalent and divalent metal hydroxides, chlorides and carbon salts; ammonia; organic amines (preferably sodium hydroxide, hydroxide) It is preferably used as a polymer salt obtained by neutralizing with an alkaline substance (a monovalent metal hydroxide such as potassium).
[0084]
The weight average molecular weight of the polycarboxylic acid polymer (A-1) or (A-2) is, for example, 5000 to 1000000 in terms of polyethylene glycol by gel permeation chromatography (hereinafter referred to as “GPC”). However, 500,000 or less is preferable. More preferably, it is 10,000 or more. More preferably, it is 300,000 or less. If the weight average molecular weight is less than 5,000, the material separation reduction performance may be lowered, and if it exceeds 1,000,000, the dispersion performance may be lowered.
[0085]
(Weight average molecular weight measurement conditions)
Model: Waters LCM1
Detector: Waters 410 differential refraction detector
Analysis software: Waters MILLENNIUM Ver. 2.18
Eluent: An eluent prepared by dissolving 115.6 g of sodium acetate trihydrate in a mixed solution of 10999 g of water and 6001 g of acetonitrile and adjusting the pH to 6.0 with a 30% aqueous sodium hydroxide solution is used.
Eluent flow rate: 0.8ml / min
Column temperature: 35 ° C
Column: Tosoh TSKgel GuardColumnSWXL + G4000SWXL + G3000SWXL + G2000SWXL
Reference material: polyethylene glycol, weight average molecular weight (Mw) 272500, 219300, 85000, 46000, 24000, 12600, 4250, 7100, 1470
[0086]
In addition to (A-1) and (A-2), a polyoxyalkylene compound having a carboxyl group in the side chain can also be used as the polycarboxylic acid polymer. The polycarboxylic acid polymer is obtained by graft polymerization of an unsaturated carboxylic acid monomer to a polyoxyalkylene compound. As the polyoxyalkylene compound, polyethylene glycol and polyoxyethylene polyoxypropylene are suitable. Moreover, as unsaturated carboxylic acid monomers, acrylic acid, methacrylic acid, crotonic acid and their metal salts, ammonium salts, amine salts and other unsaturated monocarboxylic acid monomers; maleic acid, itaconic acid, Citraconic acid, fumaric acid, or unsaturated dicarboxylic acid monomers such as metal salts, ammonium salts, and amine salts thereof are preferable. Furthermore, these anhydrides can also be used, and maleic anhydride, itaconic anhydride, and citraconic anhydride are preferred. Among them, it is preferable to use (meth) acrylic acid, maleic acid, maleic anhydride and salts thereof.
[0087]
In the concrete composition of the present invention, as long as the effects of the present invention are exhibited, in addition to the above, conventional cement dispersant, water-soluble polymer, air entraining agent, cement wetting agent, expansion material, waterproofing agent, A retarder, quick setting agent, water-soluble polymer substance, thickener, flocculant, drying shrinkage reducer, strength enhancer, curing accelerator and the like may be used in combination.
[0088]
In the concrete composition of the present invention, the alkyl ether type anionic surfactant type, the modified rosin acid compound type anionic surfactant type, the alkyl sulfonic acid compound type anionic surfactant type, the high alkyl carboxylate type anionic surfactant type are used. Various AE agents such as ionic surfactant type, modified alkyl carboxylic acid compound type anionic surfactant type, Vinsol (trade name, manufactured by Yamaso Chemical Co., Ltd.) or Micro-Air (trade name, manufactured by Master Builders), etc. May be used in combination, and does not reduce the effects of the present invention. Also, cement dispersants other than polycarboxylic acids, shrinkage reducing agents, separation reducing agents, neutralization inhibitors, swelling agents, waterproofing agents, retarders, quick setting agents, effect accelerators, water-soluble polymers, thickening agents Even if other concrete admixtures such as an agent, a flocculant, a cement wetting agent, and a rust preventive agent are used in combination, the effect is not reduced.
[0089]
In the present invention, it is preferable to further contain an AE agent when high-quality air is introduced into the concrete composition to improve freeze-thaw resistance. In this case, when the kneading time is extended during the production of the concrete composition, that is, when the kneading is continued for a long time during the transport of the concrete composition, the entrained air amount is kept stable in the concrete composition, The freeze-thaw resistance, strength, and durability of the cured product can be made excellent.
[0090]
The cement composition of the present invention can be produced by a method for producing a concrete composition including a step of mixing production raw materials containing polyoxyalkylene compounds, cement, water, fine aggregate and coarse aggregate as essential components. . In this case, as long as it includes the step of mixing all the manufacturing raw materials constituting the concrete composition of the present invention, the adding method and order of the respective manufacturing raw materials are not particularly limited. Such a method for producing a concrete composition is one of the preferred embodiments of the present invention.
[0091]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. Note that “%” means “mass%” unless otherwise specified.
[0092]
Production Example 1
A glass reaction vessel equipped with a thermometer, stirrer, dropping funnel, nitrogen inlet tube and reflux condenser was charged with 339.6 g of water, the inside of the reaction vessel was purged with nitrogen under stirring, and heated to 80 ° C. under a nitrogen atmosphere. . Next, a monomer aqueous medium in which 333.6 g of methoxypolyethylene glycol monomethacrylate (average number of added moles of ethylene oxide of 25), 66.4 g of methacrylic acid, 100 g of water, and 3.5 g of 3-mercaptopropionic acid as a chain transfer agent are mixed. 503.5 g of the liquid was added dropwise over 4 hours, and 46 g of an aqueous solution in which 4.6 g of ammonium peroxodisulfate had been dissolved was added dropwise over 5 hours. Thereafter, the temperature was maintained at 80 ° C. for 1 hour to complete the polymerization reaction, and a copolymer (1) composed of a copolymer aqueous medium having a weight average molecular weight of 23800 was obtained.
[0093]
The structure of the antifoaming agent used in the following examples and comparative examples is shown below. The basic structure is the addition of ethylene oxide and propylene oxide to an amine or alcohol. Here, ethylene oxide is described as EO and propylene oxide as PO. RaN is a cured tallow amine residue having 14 to 18 carbon atoms (total amine value = 215.9). RbO is a secondary alcohol residue having 12 to 14 carbon atoms. (Antifoaming agent 1) C₁₂H_{twenty five}N (EO)₇(PO)_FiveH
(Antifoaming agent 2) C₁₂H_{twenty five}N (EO)₇(PO)₇H
(Antifoaming agent 3) RaN (EO)₇(PO)₇H
(Comparative antifoam 1) C₈H₁₇O (PO)₂₀(EO)_ThreeH
(Comparative antifoam 2) RbO (EO)₉(PO)_FiveH
(Comparative antifoam 3) C₁₂H_{twenty five}N (EO)₇(PO)_ThreeH
[0094]
Examples 1-3 and Comparative Examples 1-3
<Concrete test>
In the concrete test, the aqueous solution of copolymer (1) obtained in Production Example 1 was adjusted to pH 7 with a 30% aqueous sodium hydroxide solution, further diluted with ion-exchanged water, and adjusted to a solid content concentration of 40%. used.
Ordinary Portland cement (made by Taiheiyo Cement Co., Ltd .: specific gravity 3.16) as cement, Oikawa water-based land sand (specific gravity 2.62) as fine aggregate, Ome crushed stone (specific gravity 2.58) as coarse aggregate and Yokosuka as water Using city tap water, weigh each material so that the mixing amount is 40L with the following two types of blending, and use a tilting mixer (manufactured by Koyo Machine Industries Co., Ltd .: KYC Baby Mixer) Kneading was performed. The rotation speed of the mixer was fixed at 20 rotations / minute.
[0095]
<Formulation 1>
Unit cement amount: 360.0kg / m^Three
Unit water volume: 144.0 kg / m^Three
Unit fine aggregate amount: 767.1 kg / m^Three
Unit coarse aggregate amount: 1043.1 kg / m^Three
Water / cement ratio: 40%
Fine aggregate rate: 42%
[0096]
<Formulation 2>
Unit cement amount: 350.0kg / m^Three
Unit water volume: 161.0kg / m^Three
Unit fine aggregate amount: 877.1kg / m^Three
Unit coarse aggregate amount: 899.0 kg / m^Three
Water / cement ratio: 46%
Fine aggregate rate: 49%
[0097]
<Kneading method>
(1) Only the fine aggregate was put into the mixer, and after kneading for 30 seconds, the rotation was stopped.
(2) Cement was added and further kneaded for 30 seconds.
(3) The rotation was stopped, water containing a water reducing agent and an antifoaming agent (95% of the total predetermined amount of water) was added, and the mixture was further kneaded for 90 seconds.
(4) The rotation was stopped again and the coarse aggregate was added, and further water containing AE agent (5% of the total predetermined amount of water) was added and kneaded for 150 seconds.
(5) A part of the obtained concrete was taken out of the mixer, and the slump and the amount of air were measured. The slump was measured in accordance with Japanese Industrial Standard JIS A 1101, and the amount of air was measured in accordance with Japanese Industrial Standard JIS A 1128. The slump value at this time is S1, and the air amount is A1.
(6) The concrete used for the measurement of the slump and the air amount was returned to the mixer and kneaded for 5 minutes, and then the slump and the air amount were measured again. The slump value at this time is S2, and the air amount is A2.
(7) The concrete used for the measurement was returned and kneaded for 5 minutes. The obtained concrete slump and air amount were measured. The slump value at this time is S3, and the air amount is A3.
The concrete test results are summarized in Table 1.
[0098]
[Table 1]

[0099]
Table 1 will be described. In the AE agent, Micro-Air (trade name) is an AE agent manufactured by Master Builders. The addition amount (mass% / C) is a mass ratio with respect to the cement solid content. The amount of air (%) is the volume% in the concrete composition.
[0100]
<Compatibility test with admixture>
Defoamers (1) to (3) were added in a predetermined amount to the aqueous solution of copolymer (1), the pH was adjusted with an aqueous sodium hydroxide solution, and the solid content was further adjusted to 40% with ion-exchanged water. The state of the obtained aqueous solution was first observed at room temperature, then left in a constant temperature room maintained at 43 ° C., and the state after 1 day and 6 months was observed.
In the case of comparative antifoaming agents (1) and (2), a predetermined amount of the aqueous solution of copolymer (1) was added to an aqueous solution adjusted to pH 7 with sodium hydroxide. After adjusting the solid content to 40% with ion-exchanged water, the same operation as described above was performed, and the state of the aqueous solution was observed. The results are summarized in Table 2.
(Evaluation criteria for appearance)
A: Uniform and transparent
Δ: cloudiness
×: Layer separation
[0101]
[Table 2]

[0102]
Table 2 will be described below. In the structure of the antifoaming agent, RaN is a cured tallow amine residue having 14 to 18 carbon atoms (total amine value = 215.9), and RbO is a secondary alcohol residue having 12 to 14 carbon atoms. Solid content concentration (%) is the mass% of the solid content in aqueous solution.
[0103]
【The invention's effect】
The concrete composition of the present invention has the above-described configuration, does not increase the amount of air accompanying the kneading time extension during the production of the concrete composition, can keep the entrained air amount stable, and has excellent strength and durability. A cured product can be formed.

Claims (3)

A concrete composition comprising polyoxyalkylene compounds, water, cement, fine aggregate and coarse aggregate as essential components,
The polyoxyalkylene compound has the following general formula (1):
X - [(AO) ^{n-R 1]} k (1)
(In the formula, X represents an amine residue and has an aliphatic hydrocarbon group in which 8 or more carbon atoms are continuously bonded in the molecule. R ¹ may be the same or different. , A hydrogen atom, a hydrocarbon group, —Y—NR ² R ³ , —COR ⁴ or —CH ₂ CH ₂ NHCO—R ⁵ , where Y represents an alkylene group having 1 to 10 carbon atoms, R ² and R ³ are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and R ⁴ and R ⁵ are each a hydrocarbon group having 1 to 30 carbon atoms or at least one carboxyl group or sulfonyl group. Or AO is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms, n is the same or different and represents the average number of added moles of the oxyalkylene group; -300, k is 1-3. 0. The total molar number of addition of oxyethylene group in the oxyalkylene group and u, when the total addition molar number of 3 or more oxyalkylene group having a carbon and v, 0.15 <u / (u + v) <0 .65 , 1 <u + v <300).)
The concrete composition further includes the following general formula (2):

(.A wherein, R ^6, R ⁷ and R ⁸ are the same or different, .R ⁹ O represents a hydrogen atom or a methyl group, the same or different and each represents an oxyalkylene group having 2 to 18 carbon atoms Represents the average number of added moles of the oxyalkylene group, and is a number from 2 to 300. R ¹⁰ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. Structural unit (I) and the following general formula (3);

(In the formula, R ¹¹ , R ¹² and R ¹³ are the same or different and represent a hydrogen atom or a methyl group. M ¹ represents a hydrogen atom, a monovalent metal, a divalent metal, ammonium or an organic amine.) The concrete composition characterized by including the polycarboxylic acid type polymer (A-1) which has carboxylic acid type structural unit (II) represented by these. The polyoxyalkylene compounds, u and v are 0.35 <u / (u + v ) < claim 1 concrete composition, wherein a satisfies 0.65 relations. The concrete composition according to claim 1 or 2, wherein the concrete composition further contains an AE agent.