JP6581369B2 - Hydraulic composition, method for improving initial strength of fly ash-containing hydraulic composition, and additive for fly ash-containing hydraulic composition - Google Patents

Description

  The present invention relates to a hydraulic composition, a method for improving the initial strength of a fly ash-containing hydraulic composition, and an additive for fly ash-containing hydraulic composition.

  Recently, in mortar and concrete containing cement, there is a tendency to replace part of the cement with fly ash generated by coal-fired power generation or the like. This is because it is possible to suppress the amount of heat generated by replacing part of the cement with fly ash, the advantage that fly ash that has been used in the past can be effectively used, and a carbon dioxide emission source in the manufacturing process. This is because there is an advantage that carbon dioxide emissions can be reduced by reducing the amount of cement used.

  However, when part of the cement is replaced with fly ash, there is a problem that the initial strength is reduced (see Patent Document 1).

JP 2002-255616 A

  An object of the present invention is to provide a hydraulic composition containing a pozzolanic reaction-inducing substance and a pozzolanic active substance and having excellent initial strength. Another object of the present invention is to provide a method for improving the initial strength of a fly ash-containing hydraulic composition. Furthermore, it is providing the additive for fly ash containing hydraulic compositions which can improve the initial strength of a fly ash containing hydraulic composition.

  The hydraulic composition of the present invention comprises a pozzolanic reaction-inducing substance, a pozzolanic active substance, and a proton-unbound cationic compound.

  In a preferred embodiment, the mass ratio of the pozzolanic reaction-inducing substance and the pozzolanic active substance (pozzolanic reaction-inducing substance / pozzolanic active substance) is 10/90 to 90/10, the pozzolanic reaction-inducing substance, The content of the proton non-bonded cationic compound is 0.0001 parts by mass to 5.0 parts by mass with respect to 100 parts by mass of the total amount of the pozzolanic active substance and the proton non-bonded cationic compound.

  In a preferred embodiment, the proton non-bonding cationic compound is a quaternary ammonium salt compound.

（一般式（ａ）において、Ｒ^１、Ｒ^２、Ｒ^３は、それぞれ、水素原子、炭素数１〜８のアルキル基、炭素数１〜８のアルケニル基、アリール基、炭素数１〜８のアルキル基で置換されたアリール基のいずれかを表し、Ｒ^４、Ｒ^５は、それぞれ、炭素数１〜６のアルキル基、アリール基を表し、ｌは１以上の整数であり、Ｚ⁻は、ハロゲンイオン、ＣＯＯ⁻、ＯＨ⁻、ＡｌＣｌ_４ ⁻、ＮＯ_２ ⁻、ＮＯ_３ ⁻、ＢＦ_４ ⁻、ＰＦ_６ ⁻、ＡｓＦ_６ ⁻、ＳｂＦ_６ ⁻、ＮｂＦ_６ ⁻、ＴａＦ_６ ⁻、ｐ−ＣＨ_３（Ｃ_６Ｈ_４）ＳＯ_３ ⁻、ＣＨ_３ＳＯ_３ ⁻、ＣＦ_３ＳＯ_３ ⁻、（ＣＦ_３ＳＯ_２）_３Ｃ⁻、Ｃ_４Ｆ_９ＳＯ_３ ⁻、（ＣＦ_３ＳＯ_２）_２Ｎ⁻、（Ｃ_２Ｆ_５ＳＯ_２）_２Ｎ⁻、（ＣＦ_３ＳＯ_２）（ＣＦ_３ＣＯ）Ｎ⁻、（ＣＮ）_２Ｎ⁻のいずれかを表す。）

（一般式（ｂ）において、Ｒ^６、Ｒ^７は、それぞれ、炭素数１〜６のアルキル基を表し、ｍは１以上の整数であり、Ｚ⁻は、ハロゲンイオン、ＣＯＯ⁻、ＯＨ⁻、ＡｌＣｌ_４ ⁻、ＮＯ_２ ⁻、ＮＯ_３ ⁻、ＢＦ_４ ⁻、ＰＦ_６ ⁻、ＡｓＦ_６ ⁻、ＳｂＦ_６ ⁻、ＮｂＦ_６ ⁻、ＴａＦ_６ ⁻、ｐ−ＣＨ_３（Ｃ_６Ｈ_４）ＳＯ_３ ⁻、ＣＨ_３ＳＯ_３ ⁻、ＣＦ_３ＳＯ_３ ⁻、（ＣＦ_３ＳＯ_２）_３Ｃ⁻、Ｃ_４Ｆ_９ＳＯ_３ ⁻、（ＣＦ_３ＳＯ_２）_２Ｎ⁻、（Ｃ_２Ｆ_５ＳＯ_２）_２Ｎ⁻、（ＣＦ_３ＳＯ_２）（ＣＦ_３ＣＯ）Ｎ⁻、（ＣＮ）_２Ｎ⁻のいずれかを表す。）

（一般式（ｃ）において、Ｒ^８は、水素原子、メチル基のいずれかを表し、Ｙは、酸素原子、−ＮＨ−のいずれかを表し、Ｘは、炭素数２〜６のアルキレン基を表し、Ｒ^９、Ｒ^１０、Ｒ^１１は、それぞれ、炭素数１〜８のアルキル基、炭素数１〜８のアルケニル基、アリール基、炭素数１〜８のアルキル基で置換されたアリール基、炭素数１〜８のヒドロキシアルキル基、−ＣＨ_２ＣＨ（Ｒ^１２）−（ＡＯ）_ｐＨのいずれかを表し、Ｒ^１２は、水素原子、メチル基のいずれかを表し、Ａは、炭素数２〜３のアルキレン基を表し、ｎは１以上の整数であり、Ｚ⁻は、ハロゲンイオン、ＣＯＯ⁻、ＯＨ⁻、ＡｌＣｌ_４ ⁻、ＮＯ_２ ⁻、ＮＯ_３ ⁻、ＢＦ_４ ⁻、ＰＦ_６ ⁻、ＡｓＦ_６ ⁻、ＳｂＦ_６ ⁻、ＮｂＦ_６ ⁻、ＴａＦ_６ ⁻、ｐ−ＣＨ_３（Ｃ_６Ｈ_４）ＳＯ_３ ⁻、ＣＨ_３ＳＯ_３ ⁻、ＣＦ_３ＳＯ_３ ⁻、（ＣＦ_３ＳＯ_２）_３Ｃ⁻、Ｃ_４Ｆ_９ＳＯ_３ ⁻、（ＣＦ_３ＳＯ_２）_２Ｎ⁻、（Ｃ_２Ｆ_５ＳＯ_２）_２Ｎ⁻、（ＣＦ_３ＳＯ_２）（ＣＦ_３ＣＯ）Ｎ⁻、（ＣＮ）_２Ｎ⁻のいずれかを表す。）

（一般式（ｄ）において、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６は、それぞれ、炭素数１〜８のアルキル基、炭素数１〜８のアルケニル基、アリール基、炭素数１〜８のアルキル基で置換されたアリール基、炭素数１〜８のヒドロキシアルキル基、−ＣＨ_２ＣＨ（Ｒ^１２）−（ＡＯ）_ｐＨのいずれかを表し、Ｒ^１２は、水素原子、メチル基のいずれかを表し、Ａは、炭素数２〜３のアルキレン基を表し、Ｚ⁻は、ハロゲンイオン、ＣＯＯ⁻、ＯＨ⁻、ＡｌＣｌ_４ ⁻、ＮＯ_２ ⁻、ＮＯ_３ ⁻、ＢＦ_４ ⁻、ＰＦ_６ ⁻、ＡｓＦ_６ ⁻、ＳｂＦ_６ ⁻、ＮｂＦ_６ ⁻、ＴａＦ_６ ⁻、ｐ−ＣＨ_３（Ｃ_６Ｈ_４）ＳＯ_３ ⁻、ＣＨ_３ＳＯ_３ ⁻、ＣＦ_３ＳＯ_３ ⁻、（ＣＦ_３ＳＯ_２）_３Ｃ⁻、Ｃ_４Ｆ_９ＳＯ_３ ⁻、（ＣＦ_３ＳＯ_２）_２Ｎ⁻、（Ｃ_２Ｆ_５ＳＯ_２）_２Ｎ⁻、（ＣＦ_３ＳＯ_２）（ＣＦ_３ＣＯ）Ｎ⁻、（ＣＮ）_２Ｎ⁻のいずれかを表す。） In a preferred embodiment, the quaternary ammonium salt compound is a compound represented by the general formula (a), a compound represented by the general formula (b), a compound represented by the general formula (c), a general formula ( It is at least one selected from the compounds represented by d).

(In the general formula (a), R ¹ , R ² and R ³ are each a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, an aryl group, or an alkyl group having 1 to 8 carbon atoms. Represents an aryl group substituted with an alkyl group, R ⁴ and R ⁵ each represent an alkyl group having 1 to 6 carbon atoms and an aryl group, l is an integer of 1 or more, and Z ⁻ represents Halogen ion, COO ⁻ , OH ⁻ , AlCl ₄ ⁻ , NO ₂ ⁻ , NO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF ₆ ⁻ , TaF ₆ ⁻ , p-CH ₃ ( C ₆ H ₄ ) SO ₃ ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , C ₄ F ₉ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , ( _{C 2 F 5 SO 2) 2} N -, (CF 3 SO 2) ^{_{CF 3 CO) N -, (}} CN) 2 N - represents either).

(In the general formula (b), R ⁶ and R ⁷ each represents an alkyl group having 1 to 6 carbon atoms, m is an integer of 1 or more, and Z ⁻ is a halogen ion, COO ⁻ , OH ⁻ , AlCl ₄ ⁻ , NO ₂ ⁻ , NO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF ₆ ⁻ , TaF ₆ ⁻ , p-CH ₃ (C ₆ H ₄ ) SO ₃ ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , C ₄ F ₉ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N _{^{-, (CF 3 SO 2)}} (CF 3 CO) N -, (CN) 2 N - represents either).

(In General Formula (c), R ⁸ represents either a hydrogen atom or a methyl group, Y represents either an oxygen atom or —NH—, and X represents an alkylene group having 2 to 6 carbon atoms. R ⁹ , R ¹⁰ and R ¹¹ are each an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, an aryl group, an aryl group substituted with an alkyl group having 1 to 8 carbon atoms, hydroxyalkyl group having 1 to 8 carbon ^{_{atoms, -CH 2 CH (R 12)}} - represents one of the _{(AO) p} ^{H, R 12} represents a hydrogen atom, one of the methyl groups, a is the number of carbon atoms Represents an alkylene group of 2 to 3, n is an integer of 1 or more, and Z ⁻ represents a halogen ion, COO ⁻ , OH ⁻ , AlCl ₄ ⁻ , NO ₂ ⁻ , NO ₃ ⁻ , BF ₄ ⁻ or PF ₆ ^−. , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF ₆ ⁻ , TaF _{6 ^{-, p-CH 3 (C}} 6 H 4) SO 3 -, CH 3 SO 3 -, CF 3 SO 3 -, (CF 3 SO 2) 3 C -, C 4 F 9 SO 3 -, (CF 3 SO _{^{2) 2 N -, (C}} 2 F 5 SO 2) 2 N -, (CF 3 SO 2) (CF 3 CO) N -, (CN) 2 N - represents either).

(In General Formula (d), R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are each an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, an aryl group, or an alkyl group having 1 to 8 carbon atoms. Represents an aryl group substituted with an alkyl group, a hydroxyalkyl group having 1 to 8 carbon atoms, or —CH ₂ CH (R ¹² ) — (AO) _p H, wherein R ¹² represents any of a hydrogen atom and a methyl group; A represents an alkylene group having 2 to 3 carbon atoms, Z ⁻ represents a halogen ion, COO ⁻ , OH ⁻ , AlCl ₄ ⁻ , NO ₂ ⁻ , NO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ^−. , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF ₆ ⁻ , TaF ₆ ⁻ , p-CH ₃ (C ₆ H ₄ ) SO ₃ ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) _{3 ^{C -, C 4 F 9 SO}} 3 -, (C ^{_{3 SO 2) 2 N -,}} (C 2 F 5 SO 2) 2 N -, (CF 3 SO 2) (CF 3 CO) N -, (CN) 2 N - represents either).

  In a preferred embodiment, the pozzolanic reaction-inducing substance is at least one selected from cement, slaked lime, quicklime, and gypsum.

  In a preferred embodiment, the pozzolanic active material is at least one selected from fly ash, silica fume, metakaolin, and blast furnace slag.

The method for improving the initial strength of the fly ash-containing hydraulic composition of the present invention,
A method for improving the initial strength of a fly ash-containing hydraulic composition,
An additive containing a hydraulic material dispersant and a quaternary ammonium salt compound is added to the fly ash-containing hydraulic composition.

  In preferable embodiment, the content rate of the said quaternary ammonium salt compound in the said additive is 0.1 mass%-40 mass%.

  In a preferred embodiment, the hydraulic material dispersant is at least one selected from a polycarboxylic acid copolymer and a sulfonic acid dispersant.

The additive for the fly ash-containing hydraulic composition of the present invention,
A hydraulic material dispersant and a quaternary ammonium salt compound are included, and the content ratio of the quaternary ammonium salt compound is 0.1% by mass to 40% by mass.

  According to the present invention, it is possible to provide a hydraulic composition that includes a pozzolanic reaction-inducing substance and a pozzolanic active substance and has excellent initial strength. Moreover, the method of improving the initial strength of a fly ash containing hydraulic composition can be provided. Furthermore, the additive for fly ash containing hydraulic compositions which can improve the initial strength of a fly ash containing hydraulic composition can be provided.

  In the present specification, the expression “(meth) acryl” means “acryl and / or methacryl”, and the expression “(meth) acrylate” means “acrylate and / or methacrylate”. Means “allyl and / or methallyl”, and “(meth) acrolein” means “acrolein and / or methacrole”. It means "rain". Further, in the present specification, the expression “acid (salt)” means “acid and / or salt thereof”.

  Further, when there is an expression “mass” in the present specification, it may be read as “weight” which is conventionally used as a unit of weight in general.

≪Hydraulic composition≫
The hydraulic composition of the present invention comprises a pozzolanic reaction-inducing substance, a pozzolanic active substance, and a proton-unbound cationic compound. The pozzolanic reaction-inducing substance contained in the hydraulic composition of the present invention may be only one kind or two or more kinds. The pozzolanic active substance contained in the hydraulic composition of the present invention may be only one kind or two or more kinds. The proton non-bonding cationic compound contained in the hydraulic composition of the present invention may be one kind or two or more kinds.

  When a pozzolanic active substance such as fly ash is used as an admixture for mortar or concrete, glassy silica or alumina contained in the pozzolanic active substance is generated by hydration of a pozzolanic reaction inducing substance such as cement. Reacts gradually with calcium hydroxide to produce calcium silicate hydrate and the like. Such a reaction is called a pozzolanic reaction, and the produced hydrate becomes a compound similar to a hydrated product of a pozzolanic reaction-inducing substance such as cement, and can improve durability and water tightness of mortar and concrete.

  The pozzolan reaction-inducing substance is calcium hydroxide or a calcium hydroxide generating substance, and specifically, preferably at least one selected from cement, slaked lime, quicklime, and gypsum. In the manifestation of the effect of the present invention, cement is particularly preferable as the pozzolanic reaction inducing substance. Examples of the cement include Portland cement (ordinary, early strength, very early strength, moderate heat, sulfate-resistant and low alkali type), various mixed cements (blast furnace cement, silica cement, fly ash cement), and white Portland cement. , Alumina cement, super fast cement (1 clinker fast cement, 2 clinker fast cement, magnesium phosphate cement), grout cement, oil well cement, low exothermic cement (low exothermic blast furnace cement, fly ash mixed low exothermic blast furnace Cement, high content belite), ultra-high-strength cement, cement-based solidified material, eco-cement (cement produced from one or more of municipal waste incineration ash and sewage sludge incineration ash).

  The pozzolanic active material is a material containing silica or alumina, and specifically, preferably at least one selected from fly ash, silica fume, metakaolin, and blast furnace slag. In the expression of the effect of the present invention, fly ash is particularly preferable as the pozzolanic active substance.

  As the proton non-bonding cationic compound, any appropriate proton non-bonding cationic compound can be adopted as long as it is a cationic compound in which hydrogen is not bonded to the cationic element as long as the effect of the present invention is not impaired. . Examples of such proton non-bonding cationic compounds include quaternary ammonium salts such as tetraalkylammonium salts, tertiary oxonium salts such as trialkyloxonium salts, and quaternary phosphonium salts such as tetraalkylphosphonium salts. Can be mentioned. Among these non-proton-bonded cationic compounds, a quaternary ammonium salt compound is preferable in that the effect of the present invention can be further expressed.

  The quaternary ammonium salt compound is preferably a compound represented by the general formula (a), a compound represented by the general formula (b), a compound represented by the general formula (c), or a general formula (d). It is at least one selected from the compounds represented.

In the general formula (a), R ¹ , R ² and R ³ are each a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, an aryl group, or an alkyl having 1 to 8 carbon atoms. Represents an aryl group substituted with a group, preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and more preferably a hydrogen atom.

In the general formula (a), R ⁴ and R ⁵ each represent an alkyl group having 1 to 6 carbon atoms or an aryl group, preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group. is there.

  In the general formula (a), l is an integer of 1 or more, and the weight average molecular weight of the compound represented by the general formula (a) is preferably 200 to 100,000, more preferably 500 to 50,000, Preferably it is 500-10000.

In the general formula (a), Z ⁻ represents a halogen ion, COO ⁻ , OH ⁻ , AlCl ₄ ⁻ , NO ₂ ⁻ , NO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF _{6. ^{-, TaF 6 -, p-}} CH 3 (C 6 H 4) SO 3 -, CH 3 SO 3 -, CF 3 SO 3 -, (CF 3 SO 2) 3 C -, C 4 F 9 SO 3 -, ^{_{(CF 3 SO 2) 2 N}} -, (C 2 F 5 SO 2) 2 N -, (CF 3 SO 2) (CF 3 CO) N - represents any of ^-, _(CN) 2 N. Specific examples of the halogen ion include F ⁻ , Cl ⁻ , Br ⁻ and I ⁻ . Z ⁻ is preferably a halogen ion.

In formula ^{(b), R 6, R} 7 each represent an alkyl group having 1 to 6 carbon atoms.

  In the general formula (b), m is an integer of 1 or more, and the weight average molecular weight of the compound represented by the general formula (b) is preferably 1000 to 1000000, more preferably 5000 to 500000, Preferably it is 10,000-100,000.

In the general formula (b), Z ⁻ represents a halogen ion, COO ⁻ , OH ⁻ , AlCl ₄ ⁻ , NO ₂ ⁻ , NO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF _{6. ^{-, TaF 6 -, p-}} CH 3 (C 6 H 4) SO 3 -, CH 3 SO 3 -, CF 3 SO 3 -, (CF 3 SO 2) 3 C -, C 4 F 9 SO 3 -, ^{_{(CF 3 SO 2) 2 N}} -, (C 2 F 5 SO 2) 2 N -, (CF 3 SO 2) (CF 3 CO) N - represents any of ^-, _(CN) 2 N. Specific examples of the halogen ion include F ⁻ , Cl ⁻ , Br ⁻ and I ⁻ . Z ⁻ is preferably a halogen ion.

In the general formula (c), R ⁸ represents either a hydrogen atom or a methyl group.

  In general formula (c), Y represents either an oxygen atom or -NH-.

  In general formula (c), X represents an alkylene group having 2 to 6 carbon atoms.

In the general formula (c), R ⁹ , R ¹⁰ and R ¹¹ are each substituted with an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, an aryl group, or an alkyl group having 1 to 8 carbon atoms. An aryl group, a hydroxyalkyl group having 1 to 8 carbon atoms, or —CH ₂ CH (R ¹² ) — (AO) _p H, wherein R ¹² represents either a hydrogen atom or a methyl group, A represents an alkylene group having 2 to 3 carbon atoms. In the general formula (c), R ⁹ , R ¹⁰ , and R ¹¹ are each preferably an aryl group substituted with an alkyl group having 1 to 8 carbon atoms, an aryl group, or an alkyl group having 1 to 8 carbon atoms. .

  In general formula (c), n is an integer greater than or equal to 1, The weight average molecular weight of the compound represented by general formula (c) becomes like this. Preferably it is 1000-500000, More preferably, it is 5000-100000, Preferably it is 5000-50000.

In the general formula (c), Z ⁻ represents a halogen ion, COO ⁻ , OH ⁻ , AlCl ₄ ⁻ , NO ₂ ⁻ , NO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF _{6. ^{-, TaF 6 -, p-}} CH 3 (C 6 H 4) SO 3 -, CH 3 SO 3 -, CF 3 SO 3 -, (CF 3 SO 2) 3 C -, C 4 F 9 SO 3 -, ^{_{(CF 3 SO 2) 2 N}} -, (C 2 F 5 SO 2) 2 N -, (CF 3 SO 2) (CF 3 CO) N - represents any of ^-, _(CN) 2 N. Specific examples of the halogen ion include F ⁻ , Cl ⁻ , Br ⁻ and I ⁻ . Z ⁻ is preferably a halogen ion.

In the general formula (d), R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, an aryl group, or an alkyl having 1 to 8 carbon atoms. Represents an aryl group substituted with a group, a hydroxyalkyl group having 1 to 8 carbon atoms, or —CH ₂ CH (R ¹² ) — (AO) _p H, wherein R ¹² is a hydrogen atom or a methyl group A represents an alkylene group having 2 to 3 carbon atoms. In the general formula (d), R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each preferably an aryl group substituted with an alkyl group having 1 to 8 carbon atoms, an aryl group, or an alkyl group having 1 to 8 carbon atoms. It is a group.

In the general formula (d), Z ⁻ represents a halogen ion, COO ⁻ , OH ⁻ , AlCl ₄ ⁻ , NO ₂ ⁻ , NO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF _{6. ^{-, TaF 6 -, p-}} CH 3 (C 6 H 4) SO 3 -, CH 3 SO 3 -, CF 3 SO 3 -, (CF 3 SO 2) 3 C -, C 4 F 9 SO 3 -, ^{_{(CF 3 SO 2) 2 N}} -, (C 2 F 5 SO 2) 2 N -, (CF 3 SO 2) (CF 3 CO) N - represents any of ^-, _(CN) 2 N. Specific examples of the halogen ion include F ⁻ , Cl ⁻ , Br ⁻ and I ⁻ . Z ⁻ is preferably a halogen ion.

  In the hydraulic composition of the present invention, the content of the pozzolanic reaction-inducing substance is preferably 10 parts by mass with respect to 100 parts by weight of the total amount of the pozzolanic reaction-inducing substance, the pozzolanic active substance, and the proton non-binding cationic compound. It is -90 mass parts, More preferably, it is 20 mass parts-80 mass parts, More preferably, it is 30 mass parts-70 mass parts, Especially preferably, they are 40 mass parts-60 mass parts. Suppressing heat generation during the curing process by adjusting the content of the pozzolanic reaction-inducing substance within the above range with respect to 100 parts by weight of the total amount of the pozzolanic reaction-inducing substance, pozzolanic active substance and non-proton-binding cationic compound. Can be sufficiently performed, and a cured product with less strain can be obtained, and at the same time, the initial strength can be improved.

  In the hydraulic composition of the present invention, the content of the pozzolanic active substance with respect to 100 parts by weight of the total amount of the pozzolanic reaction inducing substance, the pozzolanic active substance, and the proton non-binding cationic compound is preferably 10 parts by mass to 90 parts by mass. It is a mass part, More preferably, it is 20 mass parts-80 mass parts, More preferably, it is 30 mass parts-70 mass parts, Most preferably, it is 40 mass parts-60 mass parts. By adjusting the content of the pozzolanic active substance within the above range with respect to 100 parts by weight of the total amount of the pozzolanic reaction inducing substance, the pozzolanic active substance and the proton non-bonding cationic compound, sufficient suppression of heat generation during the curing process is achieved. Thus, a cured product with less strain can be obtained, and at the same time, the initial strength can be improved.

  In the hydraulic composition of the present invention, the mass ratio of the pozzolanic reaction-inducing substance and the pozzolanic active substance (pozzolanic reaction-inducing substance / pozzolanic active substance) is preferably 10/90 to 90/10, more preferably 20 / 80 to 80/20, more preferably 30/70 to 70/30, and particularly preferably 40/60 to 60/40. By adjusting the mass ratio of the pozzolanic reaction-inducing substance to the pozzolanic active substance (pozzolanic reaction-inducing substance / pozzolanic active substance) within the above range, it becomes possible to sufficiently suppress heat generation during the curing process, A small amount of cured product can be obtained, and at the same time, the initial strength can be improved.

  In the hydraulic composition of the present invention, the content of the proton non-binding cationic compound is preferably 0 with respect to 100 parts by weight of the total amount of the pozzolanic reaction-inducing substance, the pozzolanic active substance, and the proton non-binding cationic compound. 0.0001 parts by mass to 5.0 parts by mass, more preferably 0.001 parts by mass to 4.0 parts by mass, still more preferably 0.01 parts by mass to 2.0 parts by mass, and particularly preferably. It is 0.05 mass part-1.0 mass part. A hydraulic composition is prepared by adjusting the content of the proton non-bonding cationic compound within the above range with respect to 100 parts by weight of the total amount of the pozzolanic reaction-inducing substance, the pozzolanic active substance and the proton non-bonding cationic compound. When the mold is filled and cured, the initial strength is sufficiently improved, so that a delay in the demolding time can be suppressed and an extension of the construction period can be prevented.

  The hydraulic composition of the present invention may contain any appropriate other component as long as the effects of the present invention are not impaired. Examples of such other components include water, any appropriate aggregate such as fine aggregate (sand, etc.) and coarse aggregate (crushed stone, etc.), a hydraulic material dispersant, and any appropriate other cement. Examples include additives (materials). Among these, the hydraulic composition of the present invention preferably contains water and a hydraulic material dispersant.

  Examples of the aggregate include gravel, crushed stone, granulated slag, and recycled aggregate. Examples of such aggregates include refractory aggregates such as siliceous, clay, zircon, high alumina, silicon carbide, graphite, chromic, chromic, and magnesia. Only one type of aggregate may be used, or two or more types may be used.

  Specifically, the hydraulic material dispersant is preferably at least one selected from a polycarboxylic acid copolymer and a sulfonic acid dispersant. Only one hydraulic material dispersant may be used, or two or more hydraulic material dispersants may be used.

  When the hydraulic composition of the present invention includes a hydraulic material dispersant, the content ratio of the hydraulic material dispersant in the hydraulic composition of the present invention is any suitable content ratio depending on the purpose. Can do. As such a content rate, it is preferably 0.01 to 10 parts by mass, and more preferably 0.02 to 5 parts by mass with respect to 100 parts by mass of the hydraulic composition of the present invention. More preferably, it is 0.05 to 3 parts by mass. By setting it as such a content rate, various favorable effects, such as reduction of unit water amount, an increase in intensity | strength, and an improvement in durability, are brought about. When the content ratio is less than 0.01 parts by mass, sufficient performance may not be exhibited. When the content ratio exceeds 10 parts by mass, the effect that can be achieved substantially reaches its peak and also from the economical aspect. May be disadvantageous.

  The polycarboxylic acid copolymer includes an unsaturated carboxylic acid represented by the structural unit (I) derived from the unsaturated polyalkylene glycol monomer (a) represented by the general formula (1) and the general formula (2). And a structural unit (II) derived from the acid monomer (b).

  The structural unit (I) derived from the unsaturated polyalkylene glycol monomer (a) represented by the general formula (1) is specifically represented by the following formula.

  The structural unit (II) derived from the unsaturated carboxylic acid monomer (b) represented by the general formula (2) is specifically represented by the following formula.

In general formula (1) and general formula (I), R ¹ and R ² are the same or different and each represents a hydrogen atom or a methyl group.

In General Formula (1) and General Formula (I), R ³ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. Examples of the hydrocarbon group having 1 to 30 carbon atoms include an alkyl group having 1 to 30 carbon atoms (an aliphatic alkyl group and an alicyclic alkyl group), an alkenyl group having 1 to 30 carbon atoms, and the number of carbon atoms. Examples thereof include an alkynyl group having 1 to 30 carbon atoms and an aromatic group having 6 to 30 carbon atoms. R ³ is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom or a carbon atom having 1 to 12 carbon atoms in that the effects of the present invention can be further exhibited. It is a hydrogen group, more preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

  In general formula (1) and general formula (I), AO is an oxyalkylene group having 2 to 18 carbon atoms, preferably an oxyalkylene group having 2 to 8 carbon atoms, more preferably the number of carbon atoms. 2 to 4 oxyalkylene groups. When AO is any two or more selected from oxyethylene group, oxypropylene group, oxybutylene group, oxystyrene group, etc., the addition form of AO is random addition, block addition, alternating addition, etc. Either form may be sufficient. In order to secure a balance between hydrophilicity and hydrophobicity, it is preferable that the oxyalkylene group contains an oxyethylene group as an essential component, and more than 50 mol% of the entire oxyalkylene group is an oxyethylene group. Preferably, 90 mol% or more of the entire oxyalkylene group is an oxyethylene group.

  In general formula (1) and general formula (I), n represents the average addition mole number of the oxyalkylene group represented by AO, and is 1-500, Preferably it is 2-500, More preferably, 5 It is -500, More preferably, it is 10-300, Most preferably, it is 15-200, Most preferably, it is 20-100.

  In general formula (1) and general formula (I), x is an integer of 0-2.

  In general formula (1) and general formula (I), y is 0 or 1. When y = 0, the unsaturated polyalkylene glycol monomer (a) represented by the general formula (1) is a monomer having an ether structure (unsaturated polyalkylene glycol ether monomer (a1)). ) When y = 1, the unsaturated polyalkylene glycol monomer (a) represented by the general formula (1) is a monomer having an ester structure (unsaturated polyalkylene glycol ester monomer (a1)). ) It is preferable that y = 0 from the viewpoint that the effects of the present invention can be further exhibited.

  As the unsaturated polyalkylene glycol monomer (a) represented by the general formula (1), for example, an alkylene oxide having 2 to 8 carbon atoms is added to a saturated aliphatic alcohol having 1 to 20 carbon atoms. Obtained by polymerizing an alkylene oxide having 2 to 18 carbon atoms with an ester of an alkoxypolyalkylene glycol obtained by this method and (meth) acrylic acid or crotonic acid; a saturated aliphatic alcohol having 1 to 20 carbon atoms Esterified products of polyalkylene glycols and (meth) acrylic acid or crotonic acid; C 3-20 unsaturated aliphatic alcohols such as (meth) allyl alcohol, crotyl alcohol, oleyl alcohol, etc. Alkoxypolyalkylene glycols obtained by adding 2 to 8 alkylene oxides And esterified product of (meth) acrylic acid or crotonic acid; unsaturated alkylene alcohols having 3 to 20 carbon atoms such as (meth) allyl alcohol, crotyl alcohol, oleyl alcohol, etc., and alkylene having 2 to 18 carbon atoms Esterified product of polyalkylene glycol obtained by polymerizing oxide and (meth) acrylic acid or crotonic acid; C3-C20 alicyclic alcohol such as cyclohexanol, C2-C8 alkylene An esterified product of an alkoxypolyalkylene glycol obtained by adding an oxide and (meth) acrylic acid or crotonic acid; an alicyclic alcohol having 3 to 20 carbon atoms such as cyclohexanol; Polyalkylene glycols obtained by polymerizing an alkylene oxide of An esterified product of (meth) acrylic acid or crotonic acid; an alkoxypolyalkylene glycol obtained by adding an alkylene oxide having 2 to 8 carbon atoms to an aromatic alcohol having 6 to 20 carbon atoms, and (meth) acrylic An esterified product with an acid or crotonic acid; a polyalkylene glycol obtained by polymerizing an alkylene oxide having 2 to 18 carbon atoms to an aromatic alcohol having 6 to 20 carbon atoms; and (meth) acrylic acid or crotonic acid; And the like.

  The unsaturated polyalkylene glycol monomer (a) represented by the general formula (1) is preferably an alkoxy polyalkylene glycol of (meth) acrylic acid in that the effects of the present invention can be further exhibited. Esters of vinyl alcohol, (meth) allyl alcohol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, 2- A compound obtained by adding 1 to 500 mol of alkylene oxide to any of methyl-2-buten-1-ol and 2-methyl-3-buten-1-ol; more preferably 3-methyl-3-butene It is a compound obtained by adding 1 to 500 moles of alkylene oxide to -1-ol.

  The unsaturated polyalkylene glycol monomer (a) represented by the general formula (1) may be only one type or two or more types.

In General Formula (2) and General Formula (II), R ^{4 to} R ⁶ are the same or different and each represents a hydrogen atom, a methyl group, or a — (CH ₂ ) _z COOM group. The — (CH ₂ ) _z COOM group may form an anhydride with the —COOX group or other — (CH ₂ ) _z COOM groups. z is an integer of 0-2.

  M represents a hydrogen atom, a monovalent metal atom, a divalent metal atom, an ammonium group, or an organic ammonium group.

  X represents a hydrogen atom, a methyl group, an ethyl group, a monovalent metal atom, a divalent metal atom, an ammonium group, or an organic ammonium group.

  Examples of the unsaturated carboxylic acid monomer (b) represented by the general formula (2) include monocarboxylic acid monomers such as (meth) acrylic acid and crotonic acid or salts thereof; maleic acid, And dicarboxylic acid monomers such as itaconic acid and fumaric acid or salts thereof; anhydrides of dicarboxylic acid monomers such as maleic acid, itaconic acid and fumaric acid or salts thereof; and the like. Examples of the salt herein include alkali metal salts, alkaline earth metal salts, ammonium salts, organic ammonium salts, and organic amine salts. Examples of the alkali metal salt include lithium salt, sodium salt, potassium salt and the like. Examples of alkaline earth metal salts include calcium salts and magnesium salts. Examples of the organic ammonium salt include methyl ammonium salt, ethyl ammonium salt, dimethyl ammonium salt, diethyl ammonium salt, trimethyl ammonium salt, and triethyl ammonium salt. Examples of organic amine salts include alkanolamine salts such as ethanolamine salts, diethanolamine salts, and triethanolamine salts.

  The unsaturated carboxylic acid monomer (b) represented by the general formula (2) is preferably (meth) acrylic acid, maleic acid, maleic anhydride in that the effects of the present invention can be further exhibited. More preferred are acrylic acid and methacrylic acid.

  The unsaturated carboxylic acid monomer (b) represented by the general formula (2) may be only one kind or two or more kinds.

  The total content of the structural unit (I) and the structural unit (II) in the polycarboxylic acid copolymer is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass. %, More preferably 80% by mass to 100% by mass, particularly preferably 90% by mass to 100% by mass, and most preferably 95% by mass to 100% by mass. A hydraulic composition that can exhibit sufficient fluidity even with a small amount of water if the total content of the structural unit (I) and the structural unit (II) in the polycarboxylic acid-based copolymer is adjusted within the above range. It can be a thing.

  The total content of the structural unit (I) and the structural unit (II) in the polycarboxylic acid copolymer is determined by, for example, various structural analyzes (for example, NMR) of the polycarboxylic acid copolymer. I can know. In addition, structural units derived from the various monomers calculated based on the amounts of the various monomers used when producing the polycarboxylic acid-based copolymer without performing the various structural analyzes as described above. The total content of the structural unit (I) and the structural unit (II) in the polycarboxylic acid copolymer may be used. That is, the total of the unsaturated polyalkylene glycol monomer (a) and the unsaturated carboxylic acid monomer (b) in all monomer components used in producing the polycarboxylic acid copolymer. May be treated as the total content ratio of the structural unit (I) and the structural unit (II) in the polycarboxylic acid copolymer.

  The polycarboxylic acid copolymer may contain a structural unit (III) derived from another monomer (c) in addition to the structural unit (I) and the structural unit (II).

  As the monomer (c), any monomer that can be copolymerized with the monomer (a) and the monomer (b) can be appropriately selected and used. Only one type of monomer (c) may be used, or two or more types may be used.

  The content ratio of the structural unit (I) and the structural unit (II) in the polycarboxylic acid-based copolymer is a mass ratio (% by mass), preferably (I) :( II) = 55 to 90:10. To 45, more preferably (I) :( II) = 70 to 90:10 to 30, more preferably (I) :( II) = 75 to 85:15 to 25, Preferably, (I) :( II) = 80 to 85:15 to 20.

  The content ratio of the structural unit (I), the structural unit (II), and the structural unit (III) in the polycarboxylic acid-based copolymer is a mass ratio (% by mass), preferably (I) / (II). / (III) = 55-90 / 10-45 / 0-35, more preferably (I) / (II) / (III) = 70-90 / 10-30 / 0-20, Preferably, (I) / (II) / (III) = 75 to 85/15 to 25/0 to 10, particularly preferably (I) / (II) / (III) = 80 to 85/15. -20 / 0-5.

  In addition, when calculating | requiring the content rate of the structural unit in a polycarboxylic acid-type copolymer, when a structural unit has a carboxyl group, it calculates as it was completely neutralized.

  The mass average molecular weight (Mw) of the polycarboxylic acid copolymer is preferably 1000 to 500,000, more preferably 3000 as the mass average molecular weight (Mw) in terms of polyethylene glycol by gel permeation chromatography (GPC). It is 100,000, More preferably, it is 5000-50000, Most preferably, it is 5000-15000. Since the mass average molecular weight (Mw) of the polycarboxylic acid copolymer falls within the above range, a hydraulic composition capable of exhibiting sufficient fluidity even with a small amount of water can be obtained.

  The polycarboxylic acid copolymer can be produced by any appropriate method. The polycarboxylic acid copolymer is preferably a polymerization initiator for polymerizing a monomer component containing an unsaturated polyalkylene glycol monomer (a) and an unsaturated carboxylic acid monomer (b). It can be made in the presence.

  Unsaturated polyalkylene glycol monomer (a), unsaturated carboxylic acid monomer (b) that can be used in the production of the polycarboxylic acid copolymer, and other monomers (if necessary) The amount of c) used may be appropriately adjusted so that the proportion of structural units derived from each monomer in all structural units constituting the polycarboxylic acid copolymer is as described above. Preferably, as the polymerization reaction proceeds quantitatively, each monomer is added in the same proportion as the proportion of structural units derived from each monomer in all the structural units constituting the polycarboxylic acid copolymer described above. Use it.

  The unsaturated polyalkylene glycol monomer (a) can be synthesized by any appropriate method. For example, it can be synthesized by adding an alkylene oxide to an unsaturated alcohol such as allyl alcohol, methallyl alcohol, 3-methyl-3-buten-1-ol (isoprenol), hydroxyethyl vinyl ether, hydroxybutyl vinyl ether or the like.

  The polymerization of the monomer component can be performed by any appropriate method. Examples thereof include solution polymerization and bulk polymerization. Examples of the solution polymerization method include a batch method and a continuous method. Solvents that can be used for solution polymerization include water; alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, and n-hexane; esters such as ethyl acetate. Compounds; ketone compounds such as acetone and methyl ethyl ketone; cyclic ether compounds such as tetrahydrofuran and dioxane; and the like.

  When the monomer component is polymerized, a water-soluble polymerization initiator, for example, a persulfate such as ammonium persulfate, sodium persulfate, or potassium persulfate; hydrogen peroxide; 2,2′- Azoamidine compounds such as azobis-2-methylpropionamidine hydrochloride, cyclic azoamidine compounds such as 2,2′-azobis-2- (2-imidazolin-2-yl) propane hydrochloride, 2-carbamoylazoisobutyronitrile, etc. Water-soluble azo initiators such as azonitrile compounds of These polymerization initiators include alkali metal sulfites such as sodium hydrogen sulfite, metabisulfites, sodium hypophosphite, Fe (II) salts such as molle salts, sodium hydroxymethanesulfinate dihydrate, hydroxylamine hydrochloride Accelerators such as salt, thiourea, L-ascorbic acid (salt), and erythorbic acid (salt) can also be used in combination. Among these combined forms, a combination of hydrogen peroxide and an accelerator such as L-ascorbic acid (salt) is preferable. These polymerization initiators and accelerators may be used alone or in combination of two or more.

  When performing solution polymerization using a lower alcohol, aromatic hydrocarbon, aliphatic hydrocarbon, ester compound, or ketone compound as a solvent, or when performing bulk polymerization, benzoyl peroxide, lauroyl peroxide may be used as a polymerization initiator. Peroxides such as oxide and sodium peroxide; hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide; azo compounds such as azobisisobutyronitrile; When such a polymerization initiator is used, 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.

  The reaction temperature for the polymerization of the monomer component is appropriately determined depending on the polymerization method, solvent, polymerization initiator, and chain transfer agent used. The reaction temperature is preferably 0 ° C. or higher, more preferably 30 ° C. or higher, further preferably 50 ° C. or higher, preferably 150 ° C. or lower, more preferably 120 ° C. or lower. More preferably, it is 100 ° C. or lower.

  Any appropriate method can be adopted as a method of charging the monomer component into the reaction vessel. As such a charging method, for example, a method in which the entire amount is initially charged into the reaction vessel, a method in which the entire amount is divided or continuously charged into the reaction vessel, a part is initially charged in the reaction vessel, and the rest is put in the reaction vessel. The method of dividing | segmenting or carrying out continuously etc. is mentioned. Specifically, a method in which the total amount of monomer (a) and the total amount of monomer (b) are continuously charged into the reaction vessel, a part of monomer (a) is initially charged into the reaction vessel, A method in which the remainder of the monomer (a) and the entire amount of the monomer (b) are continuously charged into the reaction vessel, a part of the monomer (a) and a part of the monomer (b) in the reaction vessel In the initial stage, and the remainder of the monomer (a) and the remainder of the monomer (b) are alternately fed into the reaction vessel in several divided portions. Furthermore, by changing the charging rate of each monomer into the reaction vessel during the reaction continuously or stepwise, the charging mass ratio per unit time of each monomer is changed continuously or stepwise, You may make it synthesize | combine simultaneously the 2 or more types of copolymer from which the ratio of structural unit (I) and structural unit (II) differs. The polymerization initiator may be charged into the reaction vessel from the beginning, may be dropped into the reaction vessel, or these may be combined according to the purpose.

  In the polymerization of the monomer component, a chain transfer agent can be preferably used. When a chain transfer agent is used, the molecular weight of the resulting copolymer can be easily adjusted. Only one type of chain transfer agent may be used, or two or more types may be used.

  Any appropriate chain transfer agent can be adopted as the chain transfer agent. Examples of such chain transfer agents include thiol chain transfer agents such as mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, and 2-mercaptoethanesulfonic acid; Secondary alcohols such as isopropanol; phosphorous acid, hypophosphorous acid, and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionite, metabisulfite, And lower salts of salts thereof (sodium sulfite, potassium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium dithionite, potassium dithionite, sodium metabisulfite, potassium metabisulfite, etc.) and salts thereof, etc. Is mentioned.

  The produced polycarboxylic acid-based copolymer can be used as it is as a polycarboxylic acid-based copolymer that can be included in the hydraulic composition of the present invention. However, from the viewpoint of handleability, the polycarboxylic acid-based copolymer is used. It is preferable to adjust the pH of the reaction solution after the production of the polymer to 5 or more. However, in order to improve the polymerization rate, it is preferable to perform the polymerization at a pH of less than 5 and adjust the pH to 5 or more after the polymerization. The pH can be adjusted, for example, using an alkaline substance such as an inorganic salt such as monovalent metal or divalent metal hydroxide or carbonate; ammonia; organic amine;

  The produced polycarboxylic acid-based copolymer can be subjected to concentration adjustment, if necessary, with respect to the solution obtained by the production.

  The produced polycarboxylic acid copolymer may be used as it is in the form of a solution, or after neutralization with a divalent metal hydroxide such as calcium or magnesium to obtain a polyvalent metal salt. You may use it by making it dry or carrying | supporting to inorganic powders, such as a silica type fine powder, and making it dry.

  Examples of the sulfonic acid-based dispersant include polyalkylaryl sulfonate-based sulfonic acid-based dispersants such as naphthalene sulfonic acid formaldehyde condensate, methyl naphthalene sulfonic acid formaldehyde condensate and anthracene sulfonic acid formaldehyde condensate; melamine sulfonic acid Melamine formalin sulfonate-based sulfonic acid dispersants such as formaldehyde condensates; Aromatic amino sulfonate-based sulfonic acid dispersants such as aminoaryl sulfonic acid-phenol-formaldehyde condensates; lignin sulfonates, Examples thereof include lignin sulfonate sulfonic acid dispersants such as modified lignin sulfonate; polystyrene sulfonate sulfonic acid dispersants; Only one type of sulfonic acid-based dispersant may be used, or two or more types may be used.

  Examples of other cement additives (materials) include other cement additives (materials) exemplified in the following (1) to (12). Such other cement additives (materials) may be only one kind or two or more kinds.

(1) Water-soluble polymer substances: nonionic cellulose ethers such as methylcellulose, ethylcellulose, carboxymethylcellulose; polysaccharides produced by microbial fermentation such as yeast glucan, xanthan gum, β-1.3 glucans; polyethylene glycol, etc. Polyoxyalkylene glycols; polyacrylamide and the like.

(2) Polymer emulsion: Copolymers of various vinyl monomers such as alkyl (meth) acrylate.

(3) Curing retarder: oxycarboxylic acid or salt thereof such as gluconic acid, glucoheptonic acid, alabonic acid, malic acid, citric acid; sugar and sugar alcohol; polyhydric alcohol such as glycerin; aminotri (methylenephosphonic acid) Phosphonic acid and its derivatives.

(4) Early strengthening agents / accelerators: soluble calcium salts such as calcium chloride, calcium nitrite, calcium nitrate, calcium bromide and calcium iodide; chlorides such as iron chloride and magnesium chloride; sulfates; potassium hydroxide; Sodium hydroxide; carbonate; thiosulfate; formate such as formic acid and calcium formate; alkanolamine; alumina cement; calcium aluminate silicate.

(5) Oxyalkylene-based antifoaming agent: polyoxyalkylenes such as (poly) oxyethylene (poly) oxypropylene adducts; polyoxyalkylene alkyl ethers such as diethylene glycol heptyl ether; polyoxyalkylene acetylene ethers; ) Oxyalkylene fatty acid esters; polyoxyalkylene sorbitan fatty acid esters; polyoxyalkylene alkyl (aryl) ether sulfate salts; polyoxyalkylene alkyl phosphate esters; polyoxypropylene polyoxyethylene laurylamine (propylene oxide 1-20) Mole additions, ethylene oxide 1-20 mol adducts, etc.), fatty acid-derived amines obtained from cured beef tallow added with alkylene oxide (propylene oxide 1-20 mol) Additionally, polyoxyalkylene alkyl amines ethylene oxide 20 mol adduct) or the like; polyoxyalkylene amide.

(6) Antifoaming agents other than oxyalkylene type: Mineral oil type, fat type, fatty acid type, fatty acid ester type, alcohol type, amide type, phosphate ester type, metal soap type, silicone type and the like.

(7) AE agent: resin soap, saturated or unsaturated fatty acid, sodium hydroxystearate, lauryl sulfate, ABS (alkylbenzene sulfonic acid), alkane sulfonate, polyoxyethylene alkyl (phenyl) ether, polyoxyethylene alkyl (phenyl) ether Sulfate ester or a salt thereof, polyoxyethylene alkyl (phenyl) ether phosphate ester or a salt thereof, protein material, alkenyl sulfosuccinic acid, α-olefin sulfonate and the like.

(9) Waterproofing agent: fatty acid (salt), fatty acid ester, fats and oils, silicon, paraffin, asphalt, wax and the like.

(10) Rust inhibitor: nitrite, phosphate, zinc oxide and the like.

(11) Crack reducing agent: polyoxyalkyl ether and the like.

(12) Expansion material: Ettlingite, coal, etc.

  Other known cement additives (materials) include cement wetting agents, thickeners, separation reducing agents, flocculants, drying shrinkage reducing agents, strength enhancers, self-leveling agents, rust preventives, colorants, and antifungal agents. An agent etc. can be mentioned.

In the hydraulic composition of the present invention, any appropriate value can be set as the unit water amount per 1 m ³ and the water / (fly ash + cement) ratio. As such values, preferably, the unit water amount is 100 kg / m ^{3 to} 200 kg / m ³ , and the water / (fly ash + cement) ratio (mass ratio) = 0.1 to 0.7, preferably, the unit water amount is ^{120kg / m 3 ~180kg / m 3} , water / (fly ash + cement) ratio (mass ratio) is a = 0.3 to 0.6.

  The hydraulic composition of the present invention can be effective for ready mixed concrete, concrete for concrete secondary products, concrete for centrifugal molding, concrete for vibration compaction, steam-cured concrete, shotcrete, and the like. The cement composition of the present invention includes medium-fluidity concrete (concrete with a slump value of 22 to 25 cm), high-fluidity concrete (concrete with a slump value of 25 cm or more and a slump flow value of 50 to 70 cm), self-filling concrete, self It can also be effective for mortar and concrete that require high fluidity, such as leveling materials.

  The hydraulic composition of the present invention may be prepared by blending the constituent components by any appropriate method. For example, the method etc. which knead | mix a structural component in a mixer are mentioned.

≪Method for improving initial strength of fly ash-containing hydraulic composition, additive for fly ash-containing hydraulic composition≫
The method for improving the initial strength of the fly ash-containing hydraulic composition of the present invention is a method for improving the initial strength of the fly ash-containing hydraulic composition, and the fly ash-containing hydraulic composition includes a hydraulic material dispersant. And an additive comprising a quaternary ammonium salt compound. By such a method, the initial strength of the fly ash-containing hydraulic composition can be improved.

  The fly ash-containing hydraulic composition preferably includes fly ash, cement, and water, and further includes aggregate as necessary.

  In the fly ash-containing hydraulic composition, the content of fly ash with respect to the total amount of fly ash and cement is a mass ratio, preferably 10% to 90%, more preferably 20% to 80%. More preferably, it is 30% to 70%, and particularly preferably 35% to 65%.

Any appropriate value can be set as the unit water amount per 1 m ³ and the water / (fly ash + cement) ratio of the hydraulic composition containing fly ash. As such values, preferably, the unit water amount is 100 kg / m ^{3 to} 200 kg / m ³ , and the water / (fly ash + cement) ratio (mass ratio) = 0.1 to 0.7, preferably, the unit water amount is ^{120kg / m 3 ~180kg / m 3} , water / (fly ash + cement) ratio (mass ratio) is a = 0.3 to 0.6.

  In the method for improving the initial strength of the fly ash-containing hydraulic composition of the present invention, an additive containing a hydraulic material dispersant and a quaternary ammonium salt compound is added to the fly ash-containing hydraulic composition. Such an additive preferably includes a hydraulic material dispersant and a quaternary ammonium salt compound, and the content of the quaternary ammonium salt compound is 0.1% by mass to 40% by mass. The agent is an additive for fly ash-containing hydraulic composition of the present invention.

  That is, in the method for improving the initial strength of the fly ash-containing hydraulic composition of the present invention, the fly ash-containing hydraulic composition additive of the present invention is preferably added to the fly ash-containing hydraulic composition.

  In the additive containing the hydraulic material dispersant and the quaternary ammonium salt compound, the content of the quaternary ammonium salt compound is preferably 0.1% by mass to 40% by mass, more preferably 1.0% by mass to It is 20 mass%, More preferably, it is 2.0 mass%-15 mass%, Most preferably, it is 5.0 mass%-10 mass%. By adjusting the content ratio of the quaternary ammonium salt compound in the additive containing the hydraulic material dispersant and the quaternary ammonium salt compound within the above range, the initial strength of the fly ash-containing hydraulic composition is effectively improved. be able to.

  In the additive containing the hydraulic material dispersant and the quaternary ammonium salt compound, the content ratio of the hydraulic material dispersant is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 40% by mass. Yes, more preferably 10% by mass to 30% by mass, and particularly preferably 15% by mass to 25% by mass. By adjusting the content ratio of the hydraulic material dispersant in the additive containing the hydraulic material dispersant and the quaternary ammonium salt compound within the above range, the initial strength of the fly ash-containing hydraulic composition is effectively improved. be able to.

  The additive containing a hydraulic material dispersant and a quaternary ammonium salt compound may contain any appropriate other component as long as the effects of the present invention are not impaired.

  In the fly ash-containing hydraulic composition additive of the present invention, the content of the quaternary ammonium salt compound is 0.1% by mass to 40% by mass, preferably 1.0% by mass to 20% by mass, More preferably, it is 2.0 mass%-15 mass%, More preferably, it is 5.0 mass%-10 mass%. By adjusting the content ratio of the quaternary ammonium salt compound in the fly ash-containing hydraulic composition additive of the present invention within the above range, the initial strength of the fly ash-containing hydraulic composition can be effectively improved. it can.

  In the fly ash-containing hydraulic composition additive of the present invention, the content ratio of the hydraulic material dispersant is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, More preferably, it is 10 mass%-30 mass%, Most preferably, it is 15 mass%-25 mass%. By adjusting the content ratio of the hydraulic material dispersant in the fly ash-containing hydraulic composition additive of the present invention within the above range, the fluidity of the hydraulic composition can be improved, and fly ash The initial strength of the contained hydraulic composition can be effectively improved.

  The additive for a fly ash-containing hydraulic composition of the present invention can contain any appropriate other component as long as the effects of the present invention are not impaired.

  In the method for improving the initial strength of the fly ash-containing hydraulic composition of the invention, the amount of the additive containing the hydraulic material dispersant and the quaternary ammonium salt compound added to the fly ash-containing hydraulic composition is fly ash and cement. Is preferably 0.01% to 10%, more preferably 0.05% to 5%, still more preferably 1.0% to 3%, in particular by mass ratio with respect to the total amount of Preferably, it is 1.5% to 2.5%. The initial strength of the fly ash-containing hydraulic composition is effectively adjusted by adjusting the amount of the additive containing the hydraulic material dispersant and the quaternary ammonium salt compound to the fly ash-containing hydraulic composition within the above range. Can be improved.

  Regarding the hydraulic material dispersant and the quaternary ammonium salt compound, the above description can be used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. Unless otherwise specified, parts and% in the examples are based on mass.

<Measurement of flow value>
The flow value was measured according to the flow test measurement method specified in JIS R-5201.

<Measurement of compressive strength>
The hydraulic compositions prepared in the examples and comparative examples were filled into a cylindrical shape having a diameter of 50 mm and a height of 100 mm, left standing at 30 ° C. for 24 hours, and then demolded to prepare a specimen for measuring compressive strength. The compressive strength was measured using a compression tester in accordance with Japan Society of Civil Engineers standard JSCE-G 505-1999.

[Production Example 1]: Production of polycarboxylic acid-based copolymer In a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube, and a reflux condenser, 209.0 g of ion-exchanged water was charged. The reaction apparatus was purged with nitrogen under stirring and heated to 58 ° C. Next, 444.8 g of unsaturated polyalkylene glycol ether (MBO-50) obtained by adding an average of 50 mol of ethylene oxide (EO) to 3-methyl-3-buten-1-ol was dissolved in 111.2 g of ion-exchanged water. An aqueous solution and an aqueous solution obtained by diluting 85.2 g of acrylic acid with 43.1 g of ion-exchanged water were added dropwise over 5 hours. At the same time, an aqueous solution in which 0.94 g of L-ascorbic acid and 8.0 g of 3-mercaptopropionic acid were dissolved in 48.9 g of ion-exchanged water, and an aqueous solution in which 4.9 g of ammonium persulfate was dissolved in 44.0 g of ion-exchanged water. It was dripped over 5 hours. After completion of the dropwise addition, stirring was continued at 58 ° C. for 1 hour to complete the polymerization reaction, thereby obtaining an aqueous solution of a polycarboxylic acid copolymer having a mass average molecular weight (Mw) of 9200.

[Production Example 2]: Mortar formulation As shown in Table 1, water, cement, fly ash (FA), and sand were blended to prepare mortar.

[Example 1]
As shown in Table 2, the mortar of Formulation 1 obtained in Production Example 2, the polycarboxylic acid copolymer obtained in Production Example 1, poly (2-hydroxypropyldimethylammonium chloride) of Mw = 8000, It put into the mortar mixer and obtained the hydraulic composition (1).
The results are shown in Table 2.
Further, the polycarboxylic acid copolymer obtained in Production Example 1 and the dimethylamine epichlorohydrin condensate of Mw = 8000 were mixed in advance at the blending ratio shown in Table 2 to obtain additive (1), and in the mortar mixer The hydraulic composition (1) was also obtained by adding the additive (1) to the mortar of the formulation 1 obtained in Production Example 2 at the formulation ratio shown in Table 2.

[Example 2]
A hydraulic composition (2) was obtained in the same manner as in Example 1 except that the blending ratio was changed as shown in Table 2. Moreover, additive (2) was obtained.
The results are shown in Table 2.

Example 3
Except that the dimethylamine epichlorohydrin condensate with Mw = 8000 was replaced with the dimethylaminetrimethylamine epichlorohydrin condensate with Mw = 500, and the mixing ratio was changed as shown in Table 2, the same procedure as in Example 1 was carried out. 3) was obtained. Moreover, additive (3) was obtained.
The results are shown in Table 2.

Example 4
As shown in Table 2, the mortar of Formulation 1 obtained in Production Example 2, the polycarboxylic acid copolymer obtained in Production Example 1, and the cyclized polymer of diallyldimethylammonium chloride having Mw = 20000 were obtained. The mixture was put into a mixer to obtain a hydraulic composition (4).
The results are shown in Table 2.
In addition, the polycarboxylic acid copolymer obtained in Production Example 1 and a cyclized polymer of diallyldimethylammonium chloride with Mw = 20000 were mixed in advance to obtain additive (4), and this additive was added in a mortar mixer. The hydraulic composition (4) was also obtained by adding (4) to the mortar of Formulation 1 obtained in Production Example 2.

Example 5
As shown in Table 2, the mortar of Formulation 1 obtained in Production Example 2, the polycarboxylic acid copolymer obtained in Production Example 1 and tetramethylammonium chloride were introduced into a mortar mixer, and the hydraulic composition (5) was obtained.
The results are shown in Table 2.
In addition, the polycarboxylic acid copolymer obtained in Production Example 1 and tetramethylammonium chloride were mixed in advance at the blending ratio shown in Table 2 to obtain an additive (5). In the mortar mixer, this additive ( The hydraulic composition (5) was obtained also by adding 5) to the mortar of the mixing | blending 1 obtained by manufacture example 2 by the mixing | blending ratio shown in Table 2.

Example 6
A hydraulic composition (6) was obtained in the same manner as in Example 5 except that tetramethylammonium chloride was replaced with tetraethylammonium chloride and the blending ratio was changed as shown in Table 2. Moreover, the additive (6) was obtained.
The results are shown in Table 2.

Example 7
As shown in Table 2, a hydraulic composition (7) was obtained in the same manner as in Example 6 except that the blending ratio was changed. Moreover, the additive (7) was obtained.
The results are shown in Table 2.

Example 8
A hydraulic composition (8) was obtained in the same manner as in Example 6 except that tetraethylammonium chloride was replaced with tetraethylammonium bromide. Moreover, the additive (8) was obtained.
The results are shown in Table 2.

Example 9
A hydraulic composition (9) was obtained in the same manner as in Example 7 except that tetraethylammonium chloride was replaced with tetraethylammonium bromide. In addition, additive (9) was obtained.
The results are shown in Table 2.

[Comparative Example 1]
Except not using the dimethylamine epichlorohydrin condensate of Mw = 8000, it carried out similarly to Example 1 and obtained the hydraulic composition (C1). Moreover, the additive (C1) was obtained.
The results are shown in Table 2.

[Comparative Example 2]
As shown in Table 2, the mortar of Formulation 2 obtained in Production Example 2 and the polycarboxylic acid copolymer obtained in Production Example 1 were introduced into a mortar mixer to obtain a hydraulic composition (C2). It was.
The results are shown in Table 2.
Further, the polycarboxylic acid copolymer obtained in Production Example 1 was used as an additive (C2), and in a mortar mixer, this additive (C2) was obtained in Production Example 2 at a blending ratio shown in Table 2. The hydraulic composition (C2) was also obtained by adding to the obtained mortar of Formulation 2.

[Comparative Example 3]
As shown in Table 2, the mortar of Formulation 2 obtained in Production Example 2, the polycarboxylic acid copolymer obtained in Production Example 1, and the dimethylamine epichlorohydrin condensate of Mw = 8000 were put into a mortar mixer. A hydraulic composition (C3) was obtained.
The results are shown in Table 2.
Further, the polycarboxylic acid copolymer obtained in Production Example 1 and the dimethylamine epichlorohydrin condensate of Mw = 8000 were mixed in advance at the blending ratio shown in Table 2 to obtain an additive (C3). The hydraulic composition (C3) was also obtained by adding the additive (C3) to the mortar of the formulation 2 obtained in Production Example 2 at the formulation ratio shown in Table 2.

  The hydraulic composition of the present invention is suitably used for cement compositions such as cement paste, mortar and concrete.

Claims (7)

Including a pozzolanic reaction-inducing substance, a pozzolanic active substance, a proton non-bonding cationic compound, a hydraulic material dispersant,
The pozzolanic active substance is fly ash,
The proton-unbonded cationic compound is a quaternary ammonium salt compound;
The quaternary ammonium salt compound is at least one selected from a compound represented by the general formula (a), a compound represented by the general formula (b), and a compound represented by the general formula (d),
The hydraulic material dispersant is at least one selected from a polycarboxylic acid copolymer and a sulfonic acid dispersant;
Hydraulic composition.

(In the general formula (a), R ¹ , R ² and R ³ are each a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, an aryl group, or an alkyl group having 1 to 8 carbon atoms. Represents an aryl group substituted with an alkyl group, R ⁴ and R ⁵ each represent an alkyl group having 1 to 6 carbon atoms and an aryl group, l is an integer of 1 or more, and Z ⁻ represents Halogen ion, COO ⁻ , OH ⁻ , AlCl ₄ ⁻ , NO ₂ ⁻ , NO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF ₆ ⁻ , TaF ₆ ⁻ , p-CH ₃ ( C ₆ H ₄ ) SO ₃ ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , C ₄ F ₉ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , ( _{C 2 F 5 SO 2) 2} N -, (CF 3 SO 2) ^{_{CF 3 CO) N -, (}} CN) 2 N - represents either).

(In the general formula (b), R ⁶ and R ⁷ each represents an alkyl group having 1 to 6 carbon atoms, m is an integer of 1 or more, and Z ⁻ is a halogen ion, COO ⁻ , OH ⁻ , AlCl ₄ ⁻ , NO ₂ ⁻ , NO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF ₆ ⁻ , TaF ₆ ⁻ , p-CH ₃ (C ₆ H ₄ ) SO ₃ ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , C ₄ F ₉ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N _{^{-, (CF 3 SO 2)}} (CF 3 CO) N -, (CN) 2 N - represents either).

(In General Formula (d), R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are each an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, an aryl group, or an alkyl group having 1 to 8 carbon atoms. Represents an aryl group substituted with an alkyl group, a hydroxyalkyl group having 1 to 8 carbon atoms, or —CH ₂ CH (R ¹² ) — (AO) _p H, wherein R ¹² represents any of a hydrogen atom and a methyl group; A represents an alkylene group having 2 to 3 carbon atoms, Z ⁻ represents a halogen ion, COO ⁻ , OH ⁻ , AlCl ₄ ⁻ , NO ₂ ⁻ , NO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ^−. , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF ₆ ⁻ , TaF ₆ ⁻ , p-CH ₃ (C ₆ H ₄ ) SO ₃ ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) _{3 ^{C -, C 4 F 9 SO}} 3 -, (C ^{_{3 SO 2) 2 N -,}} (C 2 F 5 SO 2) 2 N -, (CF 3 SO 2) (CF 3 CO) N -, (CN) 2 N - represents either). The polycarboxylic acid copolymer is an unsaturated polyalkylene glycol monomer (a) -derived structural unit (I) represented by the general formula (1) and an unsaturated compound represented by the general formula (2). The hydraulic composition according to claim 1, comprising a structural unit (II) derived from a carboxylic acid monomer (b).

(In General Formula (1), R ¹ and R ² are the same or different and each represents a hydrogen atom or a methyl group; R ³ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms; , An oxyalkylene group having 2 to 18 carbon atoms, n represents an average addition mole number of the oxyalkylene group represented by AO, 1 to 500, x is an integer of 0 to 2, y Is 0 or 1.)

(In General Formula (2), R ^{4 to} R ⁶ are the same or different and each represents a hydrogen atom, a methyl group, or — (CH ₂ ) _z COOM group, and — (CH ₂ ) _z COOM group represents a —COOX group. Or other — (CH ₂ ) _z COOM group may form an anhydride, z is an integer of 0 to 2, and M is a hydrogen atom, a monovalent metal atom, a divalent metal atom, an ammonium group. X represents an hydrogen atom, a methyl group, an ethyl group, a monovalent metal atom, a divalent metal atom, an ammonium group, or an organic ammonium group.   The mass ratio of the pozzolanic reaction-inducing substance and the pozzolanic active substance (pozzolanic reaction-inducing substance / pozzolanic active substance) is 10/90 to 90/10, the pozzolanic reaction-inducing substance, the pozzolanic active substance, and the proton The water according to claim 1 or 2, wherein the content of the proton non-bonding cationic compound is 0.0001 parts by mass to 5.0 parts by mass with respect to 100 parts by mass of the total amount of the non-bonding cationic compound. Hard composition.   The hydraulic composition according to any one of claims 1 to 3, wherein the pozzolanic reaction-inducing substance is at least one selected from cement, slaked lime, quicklime, and gypsum. A method for improving the initial strength of a fly ash-containing hydraulic composition,
To the fly ash-containing hydraulic composition, an additive containing a hydraulic material dispersant and a quaternary ammonium salt compound is added ,
The hydraulic material dispersant is at least one selected from a polycarboxylic acid copolymer and a sulfonic acid dispersant,
The quaternary ammonium salt compound is at least one selected from a compound represented by the general formula (a), a compound represented by the general formula (b), and a compound represented by the general formula (d) .
A method for improving the initial strength of a fly ash-containing hydraulic composition.

(In the general formula (a), R ¹ , R ² and R ³ are each a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, an aryl group, or an alkyl group having 1 to 8 carbon atoms. Represents an aryl group substituted with an alkyl group, R ⁴ and R ⁵ each represent an alkyl group having 1 to 6 carbon atoms and an aryl group, l is an integer of 1 or more, and Z ⁻ represents Halogen ion, COO ⁻ , OH ⁻ , AlCl ₄ ⁻ , NO ₂ ⁻ , NO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF ₆ ⁻ , TaF ₆ ⁻ , p-CH ₃ ( C ₆ H ₄ ) SO ₃ ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , C ₄ F ₉ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , ( _{C 2 F 5 SO 2) 2} N -, (CF 3 SO 2) _{^{CF 3 CO) N -, (}} CN) 2 N - represents either).

(In the general formula (b), R ⁶ and R ⁷ each represents an alkyl group having 1 to 6 carbon atoms, m is an integer of 1 or more, and Z ⁻ is a halogen ion, COO ⁻ , OH ⁻ , AlCl ₄ ⁻ , NO ₂ ⁻ , NO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF ₆ ⁻ , TaF ₆ ⁻ , p-CH ₃ (C ₆ H ₄ ) SO ₃ ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , C ₄ F ₉ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N _{^{-, (CF 3 SO 2)}} (CF 3 CO) N -, (CN) 2 N - represents either).

(In General Formula (d), R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are each an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, an aryl group, or an alkyl group having 1 to 8 carbon atoms. Represents an aryl group substituted with an alkyl group, a hydroxyalkyl group having 1 to 8 carbon atoms, or —CH ₂ CH (R ¹² ) — (AO) _p H , wherein R ¹² represents any of a hydrogen atom and a methyl group; A represents an alkylene group having 2 to 3 carbon atoms, Z ⁻ represents a halogen ion, COO ⁻ , OH ⁻ , AlCl ₄ ⁻ , NO ₂ ⁻ , NO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ^−. , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF ₆ ⁻ , TaF ₆ ⁻ , p-CH ₃ (C ₆ H ₄ ) SO ₃ ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) _{3 ^{C -, C 4 F 9 SO}} 3 -, (C _{^{3 SO 2) 2 N -,}} (C 2 F 5 SO 2) 2 N -, (CF 3 SO 2) (CF 3 CO) N -, (CN) 2 N - represents either).   The method for improving the initial strength of the fly ash-containing hydraulic composition according to claim 5, wherein a content ratio of the quaternary ammonium salt compound in the additive is 0.1% by mass to 40% by mass. A hydraulic material dispersant and a quaternary ammonium salt compound,
The hydraulic material dispersant is at least one selected from a polycarboxylic acid copolymer and a sulfonic acid dispersant,
The quaternary ammonium salt compound is at least one selected from a compound represented by the general formula (a), a compound represented by the general formula (b), and a compound represented by the general formula (d),
The content of the quaternary ammonium salt compound is 0.1% by mass to 40% by mass,
Additive for hydraulic composition containing fly ash.

(In the general formula (a), R ¹ , R ² and R ³ are each a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, an aryl group, or an alkyl group having 1 to 8 carbon atoms. Represents an aryl group substituted with an alkyl group, R ⁴ and R ⁵ each represent an alkyl group having 1 to 6 carbon atoms and an aryl group, l is an integer of 1 or more, and Z ⁻ represents Halogen ion, COO ⁻ , OH ⁻ , AlCl ₄ ⁻ , NO ₂ ⁻ , NO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF ₆ ⁻ , TaF ₆ ⁻ , p-CH ₃ ( C ₆ H ₄ ) SO ₃ ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , C ₄ F ₉ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , ( _{C 2 F 5 SO 2) 2} N -, (CF 3 SO 2) _{^{CF 3 CO) N -, (}} CN) 2 N - represents either).

(In the general formula (b), R ⁶ and R ⁷ each represents an alkyl group having 1 to 6 carbon atoms, m is an integer of 1 or more, and Z ⁻ is a halogen ion, COO ⁻ , OH ⁻ , AlCl ₄ ⁻ , NO ₂ ⁻ , NO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF ₆ ⁻ , TaF ₆ ⁻ , p-CH ₃ (C ₆ H ₄ ) SO ₃ ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , C ₄ F ₉ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (C ₂ F ₅ SO ₂ ) ₂ N _{^{-, (CF 3 SO 2)}} (CF 3 CO) N -, (CN) 2 N - represents either).

(In General Formula (d), R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are each an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, an aryl group, or an alkyl group having 1 to 8 carbon atoms. Represents an aryl group substituted with an alkyl group, a hydroxyalkyl group having 1 to 8 carbon atoms, or —CH ₂ CH (R ¹² ) — (AO) _p H , wherein R ¹² represents any of a hydrogen atom and a methyl group; A represents an alkylene group having 2 to 3 carbon atoms, Z ⁻ represents a halogen ion, COO ⁻ , OH ⁻ , AlCl ₄ ⁻ , NO ₂ ⁻ , NO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ^−. , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF ₆ ⁻ , TaF ₆ ⁻ , p-CH ₃ (C ₆ H ₄ ) SO ₃ ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) _{3 ^{C -, C 4 F 9 SO}} 3 -, (C _{^{3 SO 2) 2 N -,}} (C 2 F 5 SO 2) 2 N -, (CF 3 SO 2) (CF 3 CO) N -, (CN) 2 N - represents either).