JP7277317B2 - Cement additives, cement admixtures, and cement compositions - Google Patents

Description

The present invention relates to cement additives, cement admixtures, and cement compositions.

Cement compositions generally contain cement, aggregate, and water, and are usually required to have increased fluidity and water reduction.

In recent years, there has been an increasing demand for cement compositions to improve the strength performance of hardened cement compositions.

Early strength improvement performance and long-term strength improvement performance are generally known as representative strength performances of hardened cement compositions.

If the early strength improvement performance is high, the curing period after construction can be shortened, so it can be used for shortening the construction period and labor saving in construction. Such early strength-improving performance can be evaluated, for example, by the strength-improving effect at the one-week level (typically, compressive strength after 7 days). Various investigations have been made so far on cement additives capable of exhibiting such early strength improvement performance (for example, Patent Documents 1 and 2, etc.).

On the other hand, if the long-term strength improvement performance is high, the durability of the cured product of the cement composition is maintained for a long period of time, and it is attracting attention as an indispensable performance for structures that require the maintenance of high strength over many years. performance. Such long-term strength-improving performance can be evaluated, for example, by the strength-improving effect at the 4-week level (typically, compressive strength after 28 days).

Recently, the present applicant has found that 5 moles or more of an alkylene oxide is added to 1 mole of a polyhydric alcohol having a mass-average molecular weight of greater than 3000 as a cement additive that can remarkably improve the strength of a hardened cement composition over a long period of time. A cement additive containing a compound (A) having a structure and an alkanolamine compound (B) has been reported (Patent Document 3).

JP 2011-084459 A JP 2016-222484 A Retable 2017-006995

An object of the present invention is to provide a cement additive capable of remarkably improving the strength of a hardened cement composition over a long period of time. Another object of the present invention is to provide a cement admixture capable of remarkably improving the strength of a hardened cement composition over a long period of time. Another object of the present invention is to provide a cement composition that can remarkably improve the strength of the cured product over a long period of time.

The present applicant has found a cement additive capable of exhibiting long-term strength improvement performance in the invention described in Patent Document 3. Therefore, further investigations were conducted to see if cement additives other than the invention described in Patent Document 3 could exhibit long-term strength improvement performance. As a result, it was found that a cement additive containing a combination of a compound containing a specific structure having a carbonyl group and a hydroxyl group and an alkanolamine compound can markedly improve the strength of a hardened cement composition over a long period of time. was completed.

In addition, the compound containing a specific structure having a carbonyl group and a hydroxyl group used for the above combination found by the present applicant is partially common to the compound used for cement additives that can develop early strength improvement in Patent Document 2, The invention described in Patent Document 2 aims at improving the early strength of the hardened cement composition, and does not discuss the improvement of the long-term strength of the hardened cement composition.

（一般式（１）中、Ｒ^１、Ｒ^２、Ｒ^３は、それぞれ独立に、水素原子または炭素原子数１～１８のアルキル基である。） The cement additive of the present invention is
Contains the following A and B ingredients.
A component: an alkanolamine compound.
Component B: A compound represented by the general formula (1).

(In general formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.)

In a preferred embodiment, the component A is monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, methylethanolamine, methylisopropanolamine, methyldiethanolamine, methyldiisopropanolamine, diethanol At least one selected from the group consisting of isopropanolamine, diisopropanolethanolamine, tetrahydroxyethylethylenediamine, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine and tris(2-hydroxybutyl)amine be.

In a preferred embodiment, the A component is at least one selected from the group consisting of triisopropanolamine, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine and diisopropanolethanolamine.

In a preferred embodiment, in the general formula (1) representing component B, R ¹ is a hydrogen atom, R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ³ is a hydrogen atom or a methyl group. .

（一般式（１）中、Ｒ^１、Ｒ^２、Ｒ^３は、それぞれ独立に、水素原子または炭素原子数１～１８のアルキル基である。）
Ｃ成分：下記のＣ１成分、Ｃ２成分、Ｃ３成分、Ｃ４成分からなる群より選ばれる少なくとも１種。
Ｃ１成分：不飽和ポリアルキレングリコールエーテル系単量体由来の構造単位（Ｉ）と不飽和カルボン酸系単量体由来の構造単位（ＩＩＩ）とを有するポリカルボン酸系重合体である、ポリカルボン酸系分散剤。

（構造単位（Ｉ）中、Ｒ⁴およびＲ⁵は、同一または異なって、水素原子またはメチル基を表し、Ｒ⁶は、水素原子または炭素原子数１～３０の炭化水素基を表し、Ａ^１Ｏは、炭素原子数２～１８のオキシアルキレン基を表し、ｍは、Ａ^１Ｏで表されるオキシアルキレン基の平均付加モル数を表し、ｍは２～３００の数であり、ｘは０～２の整数である。）

（構造単位（ＩＩＩ）中、Ｒ¹⁰～Ｒ¹²は、同一または異なって、水素原子、メチル基、または－（ＣＨ_２）_ｚＣＯＯＭ基を表す。－（ＣＨ_２）_ｚＣＯＯＭ基は－ＣＯＯＸ基または他の－（ＣＨ_２）_ｚＣＯＯＭ基と無水物を形成していても良い。ｚは０～２の整数である。Ｍは、水素原子、アルカリ金属、アルカリ土類金属、アンモニウム基、有機アンモニウム基、または有機アミン基を表す。Ｘは、水素原子、アルカリ金属、アルカリ土類金属、アンモニウム基、有機アンモニウム基、または有機アミン基を表す。）
Ｃ２成分：不飽和ポリアルキレングリコールエステル系単量体由来の構造単位（ＩＩ）と不飽和カルボン酸系単量体由来の構造単位（ＩＩＩ）とを有するポリカルボン酸系重合体である、ポリカルボン酸系分散剤。

（構造単位（ＩＩ）中、Ｒ^７およびＲ^８は、同一または異なって、水素原子またはメチル基を表し、Ｒ^９は、炭素原子数１～３０の炭化水素基を表し、Ａ^２Ｏは、炭素原子数２～１８のオキシアルキレン基を表し、ｎは、Ａ^２Ｏで表されるオキシアルキレン基の平均付加モル数を表し、ｎは２～３００である。）

（構造単位（ＩＩＩ）中、Ｒ¹⁰～Ｒ¹²は、同一または異なって、水素原子、メチル基、または－（ＣＨ_２）_ｚＣＯＯＭ基を表す。－（ＣＨ_２）_ｚＣＯＯＭ基は－ＣＯＯＸ基または他の－（ＣＨ_２）_ｚＣＯＯＭ基と無水物を形成していても良い。ｚは０～２の整数である。Ｍは、水素原子、アルカリ金属、アルカリ土類金属、アンモニウム基、有機アンモニウム基、または有機アミン基を表す。Ｘは、水素原子、アルカリ金属、アルカリ土類金属、アンモニウム基、有機アンモニウム基、または有機アミン基を表す。）
Ｃ３成分：スルホン酸系分散剤。
Ｃ４成分：リン酸系分散剤。 The cement admixture of the present invention contains the following A component and B component, and the following C component.
A component: an alkanolamine compound.
Component B: A compound represented by the general formula (1).

(In general formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.)
C component: at least one selected from the group consisting of the following C1 component, C2 component, C3 component and C4 component.
Component C1: polycarboxylic acid polymer having a structural unit (I) derived from an unsaturated polyalkylene glycol ether-based monomer and a structural unit (III) derived from an unsaturated carboxylic acid-based monomer Acid dispersant.

(in structural unit (I), R ⁴ and R ⁵ are the same or different and represent a hydrogen atom or a methyl group; R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms; A ¹ O represents an oxyalkylene group having 2 to 18 carbon atoms, m represents the average number of added moles of the oxyalkylene group represented by A ¹ O, m is a number of 2 to 300, and x is 0 is an integer between ~2.)

(In structural unit (III), R ¹⁰ to R ¹² are the same or different and represent a hydrogen atom, a methyl group, or a —(CH ₂ ) _z COOM group. —(CH ₂ ) _z COOM group is —COOX group Alternatively, it may form an anhydride with another —(CH ₂ ) _z COOM group, where z is an integer of 0 to 2. M is a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an organic represents an ammonium group or an organic amine group, and X represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an organic ammonium group, or an organic amine group.)
Component C2: polycarboxylic acid-based polymer having a structural unit (II) derived from an unsaturated polyalkylene glycol ester-based monomer and a structural unit (III) derived from an unsaturated carboxylic acid-based monomer Acid dispersant.

(In structural unit (II), R ⁷ and R ⁸ are the same or different and represent a hydrogen atom or a methyl group, R ⁹ represents a hydrocarbon group having 1 to 30 carbon atoms, and A ² O is represents an oxyalkylene group having 2 to 18 carbon atoms, n represents the average number of added moles of the oxyalkylene group represented by A ² O, and n is 2 to 300.)

(In structural unit (III), R ¹⁰ to R ¹² are the same or different and represent a hydrogen atom, a methyl group, or a —(CH ₂ ) _z COOM group. —(CH ₂ ) _z COOM group is —COOX group Alternatively, it may form an anhydride with another —(CH ₂ ) _z COOM group, where z is an integer of 0 to 2. M is a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an organic represents an ammonium group or an organic amine group, and X represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an organic ammonium group, or an organic amine group.)
C3 component: sulfonic acid-based dispersant.
C4 component: phosphate-based dispersant.

（一般式（１）中、Ｒ^１、Ｒ^２、Ｒ^３は、それぞれ独立に、水素原子または炭素原子数１～１８のアルキル基である。） The cement composition of the present invention contains the following components A and B, and cement.
A component: an alkanolamine compound.
Component B: A compound represented by the general formula (1).

(In general formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.)

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a cement additive capable of significantly improving the strength of a hardened cement composition over a long period of time. In addition, it is possible to provide a cement admixture capable of remarkably improving the strength of the hardened cement composition over a long period of time. Furthermore, it is possible to provide a cement composition that can remarkably improve the strength of the cured product over a long period of time.

When the expression "(meth) acrylic" is used in this specification, it means "acrylic and/or methacrylic", and when the expression "(meth) acrylate" is used, "acrylate and/or methacrylate ", and the expression "(meth)allyl" means "allyl and/or methallyl", and the expression "(meth)acrolein" means "acrolein and/or methacrolein". means rain. In addition, the expression "acid (salt)" in this specification means "acid and/or its salt". Salts include, for example, alkali metal salts and alkaline earth metal salts, and specific examples include sodium salts, potassium salts, calcium salts, and the like.

（一般式（１）中、Ｒ^１、Ｒ^２、Ｒ^３は、それぞれ独立に、水素原子または炭素原子数１～１８のアルキル基である。） ≪1. Additives for cement≫
The cement additive of the present invention contains the following A component and B component.
A component: an alkanolamine compound.
Component B: A compound represented by the general formula (1).

(In general formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.)

A component may be only 1 type, and may be 2 or more types. Only one kind of B component may be used, or two or more kinds thereof may be used.

The additive for cement of the present invention exhibits the effect of being able to remarkably improve the strength of the hardened cement composition over a long period of time by containing the A component and the B component.

The effect of improving the strength of the cured product of the cement composition over a long period of time (long-term strength improvement effect) expressed by the cement additive of the present invention is preferably the long-term strength improvement effect caused only by the A component and the B It shows a significantly higher synergistic effect than the effect expected from the sum of the long-term strength improvement effect due to the components alone.

The content of the total amount of the A component and the B component in the cement additive of the present invention is preferably 30% by mass to 100% by mass, more preferably 50% by mass to 100% by mass, and further It is preferably 70% to 100% by mass, particularly preferably 80% to 100% by mass, most preferably 85% to 100% by mass. By adjusting the content ratio of the total amount of the A component and the B component in the cement additive of the present invention within the above range, the cement additive of the present invention can maintain the strength of the hardened cement composition for a long period of time. can be improved more significantly over time.

In one embodiment of the cement additive of the present invention, the cement additive of the present invention consists of A component and B component. In this case, the content ratio of the total amount of the A component and the B component in the cement additive is 100% by mass.

In another embodiment of the cement additive of the present invention, the cement additive of the present invention consists of A component, B component and other components. Only one kind of other component may be used, or two or more kinds thereof may be used. In this case, the content of the total amount of component A and component B in the additive for cement of the present invention is preferably 30% by mass to 99.9% by mass, more preferably 50% by mass to 97% by mass. %, more preferably 70% to 95% by mass, particularly preferably 80% to 90% by mass, most preferably 85% to 90% by mass.

In the additive for cement of the present invention, the mass ratio of B component to A component ((mass of B component/mass of A component) × 100%) is preferably 1% to 10000%, more preferably 10% to 5000%, more preferably 25% to 250%, particularly preferably 50% to 100%. By adjusting the mass ratio of the B component to the A component in the cement additive of the present invention within the above range, the cement additive of the present invention maintains the strength of the cured product of the cement composition more significantly over a long period of time. can be improved to

The content of component A in the cement additive of the present invention is preferably 10% by mass to 85% by mass, more preferably 20% by mass to 80% by mass, and still more preferably 30% by mass to 75% by mass. %, particularly preferably 40% by mass to 70% by mass. By adjusting the content of component A in the additive for cement of the present invention within the above range, the additive for cement of the present invention can significantly improve the strength of the cured product of the cement composition over a long period of time. .

The content of component A in the cement additive of the present invention is preferably 0.001% by mass to 0.5% by mass, more preferably 0.003% by mass to 0.3% by mass, relative to cement. % by mass, more preferably 0.007% by mass to 0.1% by mass, and particularly preferably 0.01% by mass to 0.05% by mass. By adjusting the content of component A in the additive for cement of the present invention within the above range for cement, the additive for cement of the present invention increases the strength of the hardened cement composition over a long period of time. can be improved to

The content of component B in the cement additive of the present invention is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 80% by mass, and still more preferably 15% by mass to 70% by mass. %, particularly preferably 20% by mass to 60% by mass. By adjusting the content of component B in the additive for cement of the present invention within the above range, the additive for cement of the present invention can significantly improve the strength of the hardened cement composition over a long period of time. .

The content of component B in the cement additive of the present invention is preferably 0.001% by mass to 0.5% by mass, more preferably 0.003% by mass to 0.3% by mass, relative to cement. % by mass, more preferably 0.007% by mass to 0.1% by mass, and particularly preferably 0.01% by mass to 0.05% by mass. By adjusting the content ratio of component B in the cement additive of the present invention within the above range relative to cement, the cement additive of the present invention maintains the strength of the cured product of the cement composition more significantly over a long period of time. can be improved to

<1-1. A component>
Component A is an alkanolamine compound. Alkanolamine compounds may be used alone or in combination of two or more.

As the alkanolamine compound, any appropriate alkanolamine compound can be adopted as long as the effects of the present invention are not impaired. Examples of such alkanolamine compounds include low-molecular-weight alkanolamine compounds and high-molecular-weight alkanolamine compounds.

Examples of low-molecular alkanolamine compounds include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, methylethanolamine, methylisopropanolamine, methyldiethanolamine, methyldiisopropanolamine, diethanol isopropanolamine, diisopropanol ethanolamine, tetrahydroxyethylethylenediamine, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, tris(2-hydroxybutyl)amine and the like. Among these, preferred low-molecular-weight alkanolamine compounds include triisopropanolamine, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, and diisopropanolethanolamine. Other low-molecular-weight alkanolamine compounds include, for example, monomers having a triisopropanolamine skeleton.

Examples of high-molecular-weight alkanolamine compounds include alkanolamines having a structure in which a portion of the alkanolamine is bound to a polymer. Examples of such high-molecular-weight alkanolamine compounds include polymers having a triisopropanolamine skeleton.

<1-2. B component>
The B component is a compound represented by general formula (1).

In general formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.

In the general formula (1), R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a carbon atom, from the viewpoint that the effects of the present invention can be more expressed. It is an alkyl group having 1 to 6 numbers, more preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, particularly preferably a hydrogen atom.

In the general formula (1), R ² is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a carbon atom, from the viewpoint that the effects of the present invention can be more expressed. It is an alkyl group having 1 to 6 numbers, more preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, particularly preferably a hydrogen atom or a methyl group.

In the general formula (1), R ³ is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom or a carbon atom, in order to further exhibit the effects of the present invention. It is an alkyl group having a number of 1 to 6, more preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, particularly preferably a hydrogen atom or a methyl group, most preferably a hydrogen atom.

Specific examples of component B include hydroxyacetone (in general formula (1), R ¹ is a hydrogen atom, R ² is a hydrogen atom, and R ³ is a hydrogen atom), acetoin (in general formula (1), R ¹ is a hydrogen atom, R ² is a methyl group, R ³ is a hydrogen atom), 3-hydroxy-3-methyl-2-butanone (in general formula (1), R ¹ is a hydrogen atom, R ² is a methyl group, R ³ is a methyl group) and the like.

<1-3. Other Ingredients>
The cement additive of the present invention may contain any appropriate other component within a range that does not impair the effects of the present invention.

When the additive for cement of the present invention contains other components, the content of the other components in the additive for cement of the present invention is preferably 0.1% by mass to 70% by mass, more preferably 3% to 50% by mass, more preferably 5% to 30% by mass, particularly preferably 10% to 20% by mass, most preferably 10% to 15% by mass. By adjusting the content of other components in the additive for cement of the present invention within the above range, the additive for cement of the present invention significantly improves the strength of the hardened cement composition over a long period of time. obtain.

（一般式（１）中、Ｒ^１、Ｒ^２、Ｒ^３は、それぞれ独立に、水素原子または炭素原子数１～１８のアルキル基である。）
Ｃ成分：下記のＣ１成分、Ｃ２成分、Ｃ３成分、Ｃ４成分からなる群より選ばれる少なくとも１種。
Ｃ１成分：不飽和ポリアルキレングリコールエーテル系単量体由来の構造単位（Ｉ）と不飽和カルボン酸系単量体由来の構造単位（ＩＩＩ）とを有するポリカルボン酸系重合体である、ポリカルボン酸系分散剤。

（構造単位（Ｉ）中、Ｒ⁴およびＲ⁵は、同一または異なって、水素原子またはメチル基を表し、Ｒ⁶は、水素原子または炭素原子数１～３０の炭化水素基を表し、Ａ^１Ｏは、炭素原子数２～１８のオキシアルキレン基を表し、ｍは、Ａ^１Ｏで表されるオキシアルキレン基の平均付加モル数を表し、ｍは２～３００の数であり、ｘは０～２の整数である。）

（構造単位（ＩＩＩ）中、Ｒ¹⁰～Ｒ¹²は、同一または異なって、水素原子、メチル基、または－（ＣＨ_２）_ｚＣＯＯＭ基を表す。－（ＣＨ_２）_ｚＣＯＯＭ基は－ＣＯＯＸ基または他の－（ＣＨ_２）_ｚＣＯＯＭ基と無水物を形成していても良い。ｚは０～２の整数である。Ｍは、水素原子、アルカリ金属、アルカリ土類金属、アンモニウム基、有機アンモニウム基、または有機アミン基を表す。Ｘは、水素原子、アルカリ金属、アルカリ土類金属、アンモニウム基、有機アンモニウム基、または有機アミン基を表す。）
Ｃ２成分：不飽和ポリアルキレングリコールエステル系単量体由来の構造単位（ＩＩ）と不飽和カルボン酸系単量体由来の構造単位（ＩＩＩ）とを有するポリカルボン酸系重合体である、ポリカルボン酸系分散剤。

（構造単位（ＩＩ）中、Ｒ^７およびＲ^８は、同一または異なって、水素原子またはメチル基を表し、Ｒ^９は、炭素原子数１～３０の炭化水素基を表し、Ａ^２Ｏは、炭素原子数２～１８のオキシアルキレン基を表し、ｎは、Ａ^２Ｏで表されるオキシアルキレン基の平均付加モル数を表し、ｎは２～３００である。）

（構造単位（ＩＩＩ）中、Ｒ¹⁰～Ｒ¹²は、同一または異なって、水素原子、メチル基、または－（ＣＨ_２）_ｚＣＯＯＭ基を表す。－（ＣＨ_２）_ｚＣＯＯＭ基は－ＣＯＯＸ基または他の－（ＣＨ_２）_ｚＣＯＯＭ基と無水物を形成していても良い。ｚは０～２の整数である。Ｍは、水素原子、アルカリ金属、アルカリ土類金属、アンモニウム基、有機アンモニウム基、または有機アミン基を表す。Ｘは、水素原子、アルカリ金属、アルカリ土類金属、アンモニウム基、有機アンモニウム基、または有機アミン基を表す。）
Ｃ３成分：スルホン酸系分散剤。
Ｃ４成分：リン酸系分散剤。 ≪2. Cement Admixture≫
The cement admixture of the present invention contains the following A component and B component, and the following C component.
A component: an alkanolamine compound.
Component B: A compound represented by the general formula (1).

(In general formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.)
C component: at least one selected from the group consisting of the following C1 component, C2 component, C3 component and C4 component.
Component C1: polycarboxylic acid polymer having a structural unit (I) derived from an unsaturated polyalkylene glycol ether-based monomer and a structural unit (III) derived from an unsaturated carboxylic acid-based monomer Acid dispersant.

(in structural unit (I), R ⁴ and R ⁵ are the same or different and represent a hydrogen atom or a methyl group; R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms; A ¹ O represents an oxyalkylene group having 2 to 18 carbon atoms, m represents the average number of added moles of the oxyalkylene group represented by A ¹ O, m is a number of 2 to 300, and x is 0 is an integer between ~2.)

(In structural unit (III), R ¹⁰ to R ¹² are the same or different and represent a hydrogen atom, a methyl group, or a —(CH ₂ ) _z COOM group. —(CH ₂ ) _z COOM group is —COOX group Alternatively, it may form an anhydride with another —(CH ₂ ) _z COOM group, where z is an integer of 0 to 2. M is a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an organic represents an ammonium group or an organic amine group, and X represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an organic ammonium group, or an organic amine group.)
Component C2: polycarboxylic acid-based polymer having a structural unit (II) derived from an unsaturated polyalkylene glycol ester-based monomer and a structural unit (III) derived from an unsaturated carboxylic acid-based monomer Acid dispersant.

(In structural unit (II), R ⁷ and R ⁸ are the same or different and represent a hydrogen atom or a methyl group, R ⁹ represents a hydrocarbon group having 1 to 30 carbon atoms, and A ² O is represents an oxyalkylene group having 2 to 18 carbon atoms, n represents the average number of added moles of the oxyalkylene group represented by A ² O, and n is 2 to 300.)

(In structural unit (III), R ¹⁰ to R ¹² are the same or different and represent a hydrogen atom, a methyl group, or a —(CH ₂ ) _z COOM group. —(CH ₂ ) _z COOM group is —COOX group Alternatively, it may form an anhydride with another —(CH ₂ ) _z COOM group, where z is an integer of 0 to 2. M is a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an organic represents an ammonium group or an organic amine group, and X represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an organic ammonium group, or an organic amine group.)
C3 component: sulfonic acid-based dispersant.
C4 component: phosphate-based dispersant.

Regarding the A component, <1-1. The description in the section of A component> can be used.

Regarding the B component, <1-2. B Component> section can be referred to.

Since the cement admixture of the present invention contains the A component and the B component, it can remarkably improve the strength of the hardened cement composition over a long period of time.

The effect of improving the strength of the hardened cement composition over a long period of time (long-term strength improvement effect) expressed by the cement admixture of the present invention is preferably the long-term strength improvement effect caused only by the A component and the B component. A significantly higher synergistic effect is shown than the effect expected from the sum of the long-term strength improvement effect caused only by

The content ratio of the total amount of A component, B component and C component in the cement admixture of the present invention is preferably 30% by mass to 100% by mass, more preferably 50% by mass to 100% by mass. , more preferably 70% by mass to 100% by mass, particularly preferably 80% by mass to 100% by mass, and most preferably 85% by mass to 100% by mass. By adjusting the content ratio of the total amount of the A component, the B component and the C component in the cement admixture of the present invention within the above range, the cement admixture of the present invention has a strength of the hardened cement composition can be improved more significantly over the long term.

In one embodiment of the cement admixture of the present invention, the cement admixture of the present invention consists of A component, B component and C component. In this case, the content ratio of the total amount of the A component, the B component and the C component in the cement admixture is 100% by mass.

In another embodiment of the cement admixture of the present invention, the cement admixture of the present invention consists of A component, B component, C component and other components. Only one kind of other component may be used, or two or more kinds thereof may be used. In this case, the content of the total amount of A component, B component and C component in the cement admixture of the present invention is preferably 30% by mass to 99.9% by mass, more preferably 50% by mass to 97% by mass. % by mass, more preferably 70% by mass to 95% by mass, still more preferably 80% by mass to 90% by mass, and particularly preferably 85% by mass to 90% by mass.

In the cement admixture of the present invention, the mass ratio of B component to A component ((mass of B component / mass of A component) × 100%) is preferably 1% to 10000%, more preferably 10 % to 5000%, more preferably 25% to 250%, particularly preferably 50% to 100%. By adjusting the mass ratio of the B component to the A component in the cement admixture of the present invention within the above range, the cement admixture of the present invention significantly improves the strength of the hardened cement composition over a long period of time. can let

The content of component A in the cement admixture of the present invention is preferably 0.1% by mass to 50% by mass, more preferably 1% by mass to 40% by mass, and still more preferably 2% by mass to 30% by mass. % by mass, particularly preferably 3 to 20% by mass. By adjusting the content of component A in the cement admixture of the present invention within the above range, the cement admixture of the present invention can significantly improve the strength of the hardened cement composition over a long period of time.

The content of component A in the cement admixture of the present invention is preferably 0.001% by mass to 0.5% by mass, more preferably 0.003% by mass to 0.3% by mass, relative to cement. %, more preferably 0.007% by mass to 0.1% by mass, and particularly preferably 0.01% by mass to 0.05% by mass. By adjusting the content of component A in the cement admixture of the present invention within the above range relative to cement, the cement admixture of the present invention significantly improves the strength of the hardened cement composition over a long period of time. can let

The content of component B in the cement admixture of the present invention is preferably 0.1% by mass to 50% by mass, more preferably 1% by mass to 40% by mass, and still more preferably 2% by mass to 30% by mass. % by mass, particularly preferably 3 to 20% by mass. By adjusting the content of component B in the cement admixture of the present invention within the above range, the cement admixture of the present invention can significantly improve the strength of the hardened cement composition over a long period of time.

The content of component B in the cement admixture of the present invention is preferably 0.001% by mass to 0.5% by mass, more preferably 0.003% by mass to 0.3% by mass, relative to cement. %, more preferably 0.007% by mass to 0.1% by mass, and particularly preferably 0.01% by mass to 0.05% by mass. By adjusting the content ratio of the B component in the cement admixture of the present invention within the above range for cement, the cement admixture of the present invention significantly improves the strength of the hardened cement composition over a long period of time. can let

The content of component C in the cement admixture of the present invention is preferably 35% to 99% by mass, more preferably 40% to 97% by mass, and still more preferably 45% to 93% by mass. and particularly preferably 50% by mass to 90% by mass. By adjusting the content of the C component in the cement admixture of the present invention within the above range, the cement admixture of the present invention can significantly improve the strength of the hardened cement composition over a long period of time.

The content of C component in the cement admixture of the present invention is preferably 0.01% by mass to 5% by mass, more preferably 0.03% by mass to 1% by mass, relative to cement, It is more preferably 0.07% by mass to 0.5% by mass, and particularly preferably 0.1% by mass to 0.3% by mass. By adjusting the content ratio of the C component in the cement admixture of the present invention within the above range with respect to cement, the cement admixture of the present invention significantly improves the strength of the hardened cement composition over a long period of time. can let

<2-1. C1 component>
Component C1 is a polycarboxylic acid-based polymer having a structural unit (I) derived from an unsaturated polyalkylene glycol ether-based monomer and a structural unit (III) derived from an unsaturated carboxylic acid-based monomer, poly Carboxylic acid dispersant. Only one type of C1 component may be used, or two or more types may be used.

An unsaturated polyalkylene glycol ether-based monomer that provides the structural unit (I) is represented by the general formula (Ia), and an unsaturated carboxylic acid-based monomer that provides the structural unit (III) is represented by the general formula (IIIa). be done.

In structural unit (I) and general formula (Ia), R ⁴ and R ⁵ are the same or different and represent a hydrogen atom or a methyl group.

In structural unit (I) and general formula (Ia), R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. Examples of hydrocarbon groups having 1 to 30 carbon atoms include alkyl groups having 1 to 30 carbon atoms (aliphatic alkyl groups and alicyclic alkyl groups), alkenyl groups having 1 to 30 carbon atoms, and Examples include alkynyl groups of 1 to 30 and aromatic groups of 6 to 30 carbon atoms. R ³ is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, in order to further develop the effects of the present invention It is a hydrogen group, more preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, particularly preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

In structural unit (I) and general formula (Ia), A ¹ O is an oxyalkylene group having 2 to 18 carbon atoms, preferably an oxyalkylene group having 2 to 8 carbon atoms, more preferably carbon It is an oxyalkylene group having 2 to 4 atoms. Further, when AO is any two or more types selected from oxyethylene group, oxypropylene group, oxybutylene group, oxystyrene group, etc., the addition form of A ¹ O is random addition, block addition, alternating Any form such as addition may be used. In order to ensure a balance between hydrophilicity and hydrophobicity, it is preferable that an oxyethylene group is contained as an essential component in the oxyalkylene group, and more than 50 mol% of the entire oxyalkylene group is an oxyethylene group. More preferably, 90 mol % or more of all oxyalkylene groups are oxyethylene groups, and particularly preferably 100 mol % or more of all oxyalkylene groups are oxyethylene groups.

In structural unit (I) and general formula (Ia), m represents the average number of added moles of the oxyalkylene group represented by A ¹ O (sometimes referred to as “chain length”), and is a number from 2 to 300. , preferably a number of 2 to 200, more preferably a number of 5 to 200, still more preferably a number of 8 to 100, particularly preferably a number of 20 to 70, most preferably 40 ~60 numbers. When m is within the above range, the cement admixture of the present invention can remarkably improve the strength of the hardened cement composition over a long period of time.

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

Examples of unsaturated polyalkylene glycol ether-based monomers represented by general formula (Ia) include vinyl alcohol, (meth)allyl alcohol, 3-methyl-3-buten-1-ol, 3-methyl-2 -buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-2-buten-1-ol, 2-methyl-3-buten-1-ol, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether , a compound obtained by adding an average of 1 to 500 mol of an alkylene oxide to any of hydroxybutyl vinyl ether; and preferably a compound obtained by adding an average of 1 to 500 mol of an alkylene oxide to 3-methyl-3-buten-1-ol. is a compound obtained by adding 1 to 500 moles of alkylene oxide on average to methallyl alcohol.

The unsaturated polyalkylene glycol ether-based monomer represented by the general formula (Ia) may be used alone or in combination of two or more.

In structural unit (III) and general formula (IIIa), R ¹⁰ to R ¹² are the same or different and represent a hydrogen atom, a methyl group, or a —(CH ₂ ) _z COOM group. The —(CH ₂ ) _z COOM group may form an anhydride with —COOX group or another —(CH ₂ ) _z COOM group. z is an integer from 0 to 2;

M represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an organic ammonium group, or an organic amine group.

X represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an organic ammonium group, or an organic amine group.

Examples of unsaturated carboxylic acid monomers represented by general formula (IIIa) include monocarboxylic acid monomers such as (meth)acrylic acid and crotonic acid, or salts thereof; maleic acid, itaconic acid, dicarboxylic acid-based monomers such as fumaric acid, or salts thereof; anhydrides of dicarboxylic acid-based monomers such as maleic acid, itaconic acid, fumaric acid, or salts thereof; and the like. Examples of salts used herein include alkali metal salts, alkaline earth metal salts, ammonium salts, organic ammonium salts, organic amine salts and the like.

Alkali metal salts include, for example, lithium salts, sodium salts, potassium salts and the like. Alkaline earth metal salts include, for example, calcium salts and magnesium salts.

Examples of organic ammonium salts include methylammonium salts, ethylammonium salts, dimethylammonium salts, diethylammonium salts, trimethylammonium salts, and triethylammonium salts.

Examples of organic amine salts include ethanolamine salts, diethanolamine salts, triethanolamine salts, monoisopropanolamine salts, diisopropanolamine salts, triisopropanolamine salts, hydroxyethyldiisopropanolamine salts, dihydroxyethylisopropanolamine salts, tetrakis ( and alkanolamine salts such as 2-hydroxypropyl)ethylenediamine and pentakis(2-hydroxypropyl)diethylenetriamine. Among these, diisopropanolamine salts, triisopropanolamine salts, hydroxyethyldiisopropanolamine salts, tetrakis(2-hydroxypropyl)ethylenediamine salts, and pentakis(2-hydroxypropyl)diethylenetriamine salts are preferred, and more preferably, triisopropanolamine salt and hydroxyethyldiisopropanolamine salt.

The unsaturated carboxylic acid-based monomer represented by the general formula (IIIa) is preferably (meth)acrylic acid, maleic acid or maleic anhydride from the viewpoint that the effects of the present invention can be further expressed, More preferred are acrylic acid and methacrylic acid.

The unsaturated carboxylic acid-based monomer represented by the general formula (IIIa) may be of one kind, or may be of two or more kinds.

In the polycarboxylic acid-based polymer that is the C1 component, the content ratio of the structural unit (I) to the total structural units constituting the polycarboxylic acid-based polymer is preferably from the viewpoint that the effects of the present invention can be exhibited more 5 mol% to 80 mol%, more preferably 5 mol% to 70 mol%, still more preferably 10 mol% to 60 mol%, particularly preferably 15 mol% to 50 mol%, most preferably It is preferably 20 mol % to 40 mol %.

In the polycarboxylic acid-based polymer that is the C1 component, the content ratio of the structural unit (III) to the total structural units constituting the polycarboxylic acid-based polymer is preferably from the viewpoint that the effects of the present invention can be exhibited more 20 mol% to 95 mol%, more preferably 30 mol% to 95 mol%, still more preferably 40 mol% to 90 mol%, particularly preferably 50 mol% to 85 mol%, most preferably It is preferably 60 mol % to 80 mol %.

In the polycarboxylic acid-based polymer, which is the C1 component, the total content of the structural units (I) and the structural units (III) with respect to all the structural units constituting the polycarboxylic acid-based polymer further enhances the effects of the present invention. It is preferably 50 mol% to 100 mol%, more preferably 60 mol% to 100 mol%, still more preferably 70 mol% to 100 mol%, particularly preferably 80 mol%, in terms of being able to express. ~100 mol %, most preferably 90 mol % to 100 mol %.

The polycarboxylic acid-based polymer, which is the C1 component, may contain structural units (IV) derived from other monomers in addition to the structural units (I) and (III).

Only one kind of other monomer may be used, or two or more kinds thereof may be used.

Other monomers include, for example, hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate; unsaturated monocarboxylic acids such as methyl (meth)acrylate and glycidyl (meth)acrylate; Esters of acids and alcohols having 1 to 30 carbon atoms; various (alkoxy) (poly)alkylene glycol mono(meth)acrylates such as polyethylene glycol mono(meth)acrylate and methoxy(poly)ethylene glycol mono(meth)acrylate (anhydrous) unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid and half esters of alcohols having 1 to 30 carbon atoms; (anhydrous) unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid Diesters of acids and alcohols having 1 to 30 carbon atoms; half amides of the above unsaturated dicarboxylic acids and amines having 1 to 30 carbon atoms; and the above unsaturated dicarboxylic acids and amines having 1 to 30 carbon atoms. Diamides; half esters of alkyl (poly)alkylene glycol obtained by adding 1 to 500 moles of alkylene oxide having 2 to 18 carbon atoms on average to the above alcohol or amine and the above unsaturated dicarboxylic acid; to the above alcohol or amine diesters of alkyl (poly)alkylene glycols to which 1 to 500 moles of alkylene oxides having 2 to 18 carbon atoms are added on average and the above unsaturated dicarboxylic acids; the above unsaturated dicarboxylic acids and glycols having 2 to 18 carbon atoms, or Half esters of these glycols with polyalkylene glycol having an average number of added moles of 2 to 500; the above unsaturated dicarboxylic acids and glycols having 2 to 18 carbon atoms or polyalkylenes having an average number of added moles of 2 to 500 of these glycols; Diesters with glycols; Half amides of maleamic acid with glycols having 2 to 18 carbon atoms or polyalkylene glycols having an average number of added moles of 2 to 500 of these glycols; (poly)ethylene glycol di(meth)acrylates; (poly)alkylene glycol di(meth)acrylates such as (poly)propylene glycol di(meth)acrylate; polyfunctional (meth)acrylates such as hexanediol di(meth)acrylate and trimethylolpropane tri(meth)acrylate; (Poly) alkylene glycol dimalates such as polyethylene glycol dimalate; unsaturated sulfonic acids (salts) such as vinyl sulfonate, (meth) allyl sulfonate, 2-methylpropanesulfonic acid (meth) acrylamide, and styrene sulfonic acid; methyl Amides of unsaturated monocarboxylic acids such as (meth)acrylamide and amines having 1 to 30 carbon atoms; vinyl aromatics such as styrene, α-methylstyrene and vinyltoluene; 1,4-butanediol mono(meth) ) alkanediol mono (meth) acrylates such as acrylates; dienes such as butadiene and isoprene; saturated amides; unsaturated cyanides such as (meth)acrylonitrile; unsaturated esters such as vinyl acetate; unsaturated amines such as aminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and vinylpyridine; divinyl aromatics such as divinylbenzene; allyls such as (meth)allyl alcohol and glycidyl (meth)allyl ether; vinyl ethers such as (methoxy)polyethylene glycol monovinyl ether; (methoxy)polyethylene glycol mono(meth)allyl ether, etc. (Meth) allyl ethers of; and the like.

The content ratio of the structural unit (IV) to the total structural units constituting the polycarboxylic acid-based polymer in the polycarboxylic acid-based polymer that is the C1 component is preferable in that the effects of the present invention can be more expressed. is 0 mol% to 50 mol%, more preferably 0 mol% to 40 mol%, still more preferably 0 mol% to 30 mol%, particularly preferably 0 mol% to 20 mol%, Most preferably 0 mol % to 10 mol %.

Content ratio of the structural unit (I) to all structural units constituting the polycarboxylic acid polymer in the polycarboxylic acid polymer that is the C1 component, relative to all structural units constituting the polycarboxylic acid polymer The content ratio of the structural unit (III), the content ratio of the structural unit (IV) to all the structural units constituting the polycarboxylic acid polymer, the structural unit (I ) and the structural unit (III) can be determined by various structural analyzes (eg, NMR) of the polycarboxylic acid polymer. In addition, even without performing various structural analyzes as described above, the unsaturated polyalkylene glycol ether-based monomer and the unsaturated carboxylic acid-based monomer used when producing the polycarboxylic acid-based polymer that is the C1 component And a structural unit derived from the unsaturated polyalkylene glycol ether-based monomer calculated based on the amount and polymerization rate of other monomers, a structural unit derived from the unsaturated carboxylic acid-based monomer, and the other Based on the content ratio of the structural unit derived from the monomer, the content ratio of the structural unit (I) with respect to the total structural units constituting the polycarboxylic acid-based polymer in the polycarboxylic acid-based polymer that is the C1 component , the content ratio of the structural unit (III) to all the structural units constituting the polycarboxylic acid polymer, the content ratio of the structural unit (IV) to all the structural units constituting the polycarboxylic acid polymer, the polycarboxylic acid The total content ratio of structural units (I) and structural units (III) to all structural units constituting the acid-based polymer may be calculated.

When determining the content ratio of structural units in the polycarboxylic acid-based polymer that is the C1 component, when the structural unit has a salt of a carboxyl group, all the acid moieties of the carboxyl group are converted into sodium salts for calculation. I do.

The weight average molecular weight (Mw) in terms of polyethylene glycol obtained by gel permeation chromatography of the polycarboxylic acid-based polymer, which is the C1 component, is preferably 65000 or more in that the effects of the present invention can be more expressed. , more preferably 65,000 to 1,000,000, still more preferably 67,000 to 800,000, particularly preferably 70,000 to 400,000, and most preferably 75,000 to 200,000.

The polycarboxylic acid-based polymer, which is the C1 component, can be produced by any appropriate method as long as the effects of the present invention are not impaired. The polycarboxylic acid-based polymer, which is the C1 component, can preferably be produced by polymerizing the monomer components in the presence of a polymerization initiator.

<2-2. C2 component>
Component C2 is a polycarboxylic acid polymer having a structural unit (II) derived from an unsaturated polyalkylene glycol ester monomer and a structural unit (III) derived from an unsaturated carboxylic acid monomer, poly Carboxylic acid dispersant. Only one type of C2 component may be used, or two or more types may be used.

An unsaturated polyalkylene glycol ether-based monomer that provides structural unit (II) is represented by general formula (IIa).

In structural unit (II) and general formula (IIa), R ⁷ and R ⁸ are the same or different and represent a hydrogen atom or a methyl group.

In structural unit (II) and general formula (IIa), R ⁹ represents a hydrocarbon group having 1 to 30 carbon atoms. Examples of hydrocarbon groups having 1 to 30 carbon atoms include alkyl groups having 1 to 30 carbon atoms (aliphatic alkyl groups and alicyclic alkyl groups), alkenyl groups having 1 to 30 carbon atoms, and Examples include alkynyl groups of 1 to 30 and aromatic groups of 6 to 30 carbon atoms. R ⁶ is preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 1 to 12 carbon atoms, and further Hydrocarbon groups having 1 to 6 carbon atoms are preferred, and alkyl groups having 1 to 3 carbon atoms are particularly preferred.

In structural unit (II) and general formula (IIa), A ² O is an oxyalkylene group having 2 to 18 carbon atoms, preferably an oxyalkylene group having 2 to 8 carbon atoms, more preferably carbon It is an oxyalkylene group having 2 to 4 atoms. When A ² O is two or more arbitrary groups selected from an oxyethylene group, an oxypropylene group, an oxybutylene group, an oxystyrene group, etc., the addition form of A ² O is random addition or block addition. , alternate addition, or the like. In order to ensure a balance between hydrophilicity and hydrophobicity, it is preferable that an oxyethylene group is contained as an essential component in the oxyalkylene group, and more than 50 mol% of the entire oxyalkylene group is an oxyethylene group. More preferably, 90 mol % or more of all oxyalkylene groups are oxyethylene groups, and particularly preferably 100 mol % or more of all oxyalkylene groups are oxyethylene groups. One type of oxyalkylene group may be used, or two or more types may be used.

In structural unit (II) and general formula (IIa), n represents the average number of added moles of the oxyalkylene group represented by A ² O (sometimes referred to as “chain length”), and is 2 to 300. , preferably 5 to 150, more preferably 10 to 100, even more preferably 15 to 75, and particularly preferably 20 to 50. When n is within the above range, the cement admixture of the present invention can remarkably improve the strength of the hardened cement composition over a long period of time.

As the unsaturated polyalkylene glycol ester-based monomer represented by the general formula (IIa), for example, by adding an alkylene oxide having 2 to 18 carbon atoms to a saturated aliphatic alcohol having 1 to 20 carbon atoms, Esterified products of the obtained alkoxypolyalkylene glycols and (meth)acrylic acid or crotonic acid; Esterified products of alkoxypolyalkylene glycols obtained by adding an alkylene oxide having 2 to 18 carbon atoms and (meth)acrylic acid or crotonic acid; alicyclic alcohols having 3 to 20 carbon atoms such as cyclohexanol To, with alkoxypolyalkylene glycols obtained by adding an alkylene oxide having 2 to 18 carbon atoms, esters of (meth)acrylic acid or crotonic acid; to aromatic alcohols having 6 to 20 carbon atoms, carbon esters of alkoxypolyalkylene glycols obtained by adding alkylene oxides of numbers 2 to 18 with (meth)acrylic acid or crotonic acid; and the like.

As the unsaturated polyalkylene glycol ester-based monomer represented by the general formula (IIa), esters of alkoxypolyalkylene glycols of (meth)acrylic acid are preferable in that the effects of the present invention can be further expressed. is.

The unsaturated polyalkylene glycol ester-based monomer represented by the general formula (IIa) may be used alone or in combination of two or more.

Regarding the structural unit (III) derived from the unsaturated carboxylic acid-based monomer and the unsaturated carboxylic acid-based monomer (IIIa) providing the structural unit (III), these descriptions are described in the above description of the C1 component. can be used.

In the polycarboxylic acid-based polymer, which is the C2 component, the content ratio of the structural unit (II) to the total structural units constituting the polycarboxylic acid-based polymer is preferably 5 mol% to 95 mol%, more preferably 10 mol% to 90 mol%, still more preferably 20 mol% to 80 mol%, particularly preferably 30 mol% to 70 mol%, most It is preferably 40 mol % to 60 mol %.

In the polycarboxylic acid-based polymer, which is the C2 component, the content ratio of the structural unit (III) to the total structural units constituting the polycarboxylic acid-based polymer is preferably 5 mol% to 95 mol%, more preferably 10 mol% to 90 mol%, still more preferably 20 mol% to 80 mol%, particularly preferably 30 mol% to 70 mol%, most preferably It is preferably 40 mol % to 60 mol %.

In the polycarboxylic acid-based polymer, which is the C2 component, the total content of the structural units (II) and the structural units (III) with respect to all the structural units constituting the polycarboxylic acid-based polymer can further enhance the effects of the present invention. It is preferably 50 mol% to 100 mol%, more preferably 60 mol% to 100 mol%, still more preferably 70 mol% to 100 mol%, particularly preferably 80 mol%, in terms of being able to express. ~100 mol %, most preferably 90 mol % to 100 mol %.

The polycarboxylic acid polymer that is the C2 component may contain structural units (IV) derived from other monomers in addition to the structural units (II) and (III).

For other monomers and structural units (IV) derived from other monomers, the above description of other monomers and structural units (IV) derived from other monomers in the description of the C1 component. can be used.

The content ratio of structural units (IV) to all structural units constituting the polycarboxylic acid-based polymer in the polycarboxylic acid-based polymer that is the C2 component is preferable in that the effects of the present invention can be more expressed. is 0 mol% to 50 mol%, more preferably 0 mol% to 40 mol%, still more preferably 0 mol% to 30 mol%, particularly preferably 0 mol% to 20 mol%, Most preferably 0 mol % to 10 mol %.

Content ratio of structural unit (II) to all structural units constituting the polycarboxylic acid polymer in the polycarboxylic acid polymer that is the C2 component, relative to all structural units constituting the polycarboxylic acid polymer The content ratio of the structural unit (III), the content ratio of the structural unit (IV) with respect to all structural units constituting the polycarboxylic acid polymer, the structural unit (II) with respect to all structural units constituting the polycarboxylic acid polymer ) and the structural unit (III) can be determined by various structural analyzes (eg, NMR) of the polycarboxylic acid polymer. In addition, even without performing various structural analyzes as described above, the unsaturated polyalkylene glycol ester-based monomer and the unsaturated carboxylic acid-based monomer used when producing the polycarboxylic acid-based polymer that is the C2 component And a structural unit derived from the unsaturated polyalkylene glycol ester monomer calculated based on the amount and polymerization rate of other monomers and a structural unit derived from the unsaturated carboxylic acid monomer and the other Based on the content ratio of the structural unit derived from the monomer, the content ratio of the structural unit (II) to the total structural units constituting the polycarboxylic acid polymer in the polycarboxylic acid polymer that is the C2 component , the content ratio of the structural unit (III) to all the structural units constituting the polycarboxylic acid polymer, the content ratio of the structural unit (IV) to all the structural units constituting the polycarboxylic acid polymer, the polycarboxylic acid The total content ratio of structural units (II) and (III) to all structural units constituting the acid-based polymer may be calculated.

When determining the content ratio of structural units in the polycarboxylic acid-based polymer that is the C2 component, if the structural unit has a salt of a carboxyl group, all the acid moieties of the carboxyl group are converted into sodium salts for calculation. I do.

The weight average molecular weight (Mw) in terms of polyethylene glycol obtained by gel permeation chromatography of the polycarboxylic acid-based polymer, which is the C2 component, is preferably 3000 or more in that the effects of the present invention can be further expressed. , more preferably 5,000 to 1,000,000, still more preferably 10,000 to 500,000, particularly preferably 20,000 to 300,000, and most preferably 30,000 to 200,000.

The polycarboxylic acid-based polymer, which is the C2 component, can be produced by any appropriate method as long as the effects of the present invention are not impaired. The polycarboxylic acid-based polymer, which is the C2 component, can preferably be produced by polymerizing the monomer components in the presence of a polymerization initiator.

<2-3. C3 component>
The C3 component is a sulfonic acid-based dispersant. Only one kind of C3 component may be used, or two or more kinds thereof may be used.

The sulfonic acid-based dispersant is a dispersant that exhibits dispersibility in cement mainly by electrostatic repulsion caused by the sulfonic acid group, and any appropriate sulfonic acid-based dispersant can be used, is preferably a compound having an aromatic group in. Examples of sulfonic acid-based dispersants include polyalkylarylsulfonate-based sulfonic acid-based dispersants such as naphthalenesulfonic acid-formaldehyde condensates, methylnaphthalenesulfonic acid-formaldehyde condensates, and anthracene sulfonic acid-formaldehyde condensates; melamine sulfonic acid; melamine formalin resin sulfonate-based sulfonic acid-based dispersants such as formaldehyde condensates; aromatic aminosulfonate-based sulfonic acid-based dispersants such as aminoarylsulfonic acid-phenol-formaldehyde condensates; Lignin sulfonate-based sulfonic acid-based dispersants such as modified lignin sulfonate; polystyrene sulfonate-based sulfonic acid-based dispersants; alkenyl ether-based monomers and unsaturated sulfonic acid-based monomers obtained by adding ethylene oxide or the like to unsaturated alcohols a polymer obtained from a monomer containing a monomer or a salt thereof; and the like.

<2-4. C4 component>
The C4 component is a phosphoric acid-based dispersant. Only one type of C4 component may be used, or two or more types may be used.

Any suitable phosphoric acid-based dispersant having a phosphoric acid group in the molecule can be used as the phosphoric acid-based dispersant. Phosphoric acid-based dispersants described in Table 2008-517080 and the like.

（一般式（１）中、Ｒ^１、Ｒ^２、Ｒ^３は、それぞれ独立に、水素原子または炭素原子数１～１８のアルキル基である。） ≪3. Cement composition≫
The cement composition of the present invention contains the following components A and B, and cement.
Component A: A compound having a structure in which 5 mol or more of alkylene oxide is added to 1 mol of alcohol.
Component B: A compound represented by the general formula (1).

(In general formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.)

A component may be only 1 type, and may be 2 or more types. Only one kind of B component may be used, or two or more kinds thereof may be used.

By containing the A component and the B component, the cement composition of the present invention can significantly improve the strength of the cured product over a long period of time.

The effect that the strength of the hardened material can be improved over a long period of time (long-term strength improvement effect) expressed by the cement composition of the present invention is preferably due to the long-term strength improvement effect caused only by the A component and the B component only. Compared to the effect expected from the sum of the long-term strength improvement effect, it shows a remarkably high synergistic effect.

Regarding the A component, <1-1. The description in the section of A component> can be used.

Regarding the B component, <1-2. B Component> section can be referred to.

Only one type of cement may be used, or two or more types may be used. Any appropriate cement can be adopted as the cement. Such cements include, for example, Portland cement (ordinary, early strength, ultra-early strength, moderate heat, sulfate resistant, and low alkali type of each), various mixed cements (blast furnace cement, silica cement, fly ash cement) , white Portland cement, alumina cement, ultra fast hardening cement (1 clinker fast hardening cement, 2 clinker fast hardening cement, magnesium phosphate cement), grouting cement, oil well cement, low heat generating cement (low heat generating blast furnace cement, fly ash mixture low-heat-generation blast-furnace cement, belite-rich cement), ultra-high-strength cement, cement-based solidifying material, eco-cement (cement manufactured from one or more types of municipal waste incineration ash and sewage sludge incineration ash), etc. .

The cement composition of the present invention may contain aggregate. Only one kind of aggregate may be used, or two or more kinds thereof may be used. Any appropriate aggregate such as fine aggregate (such as sand) and coarse aggregate (such as crushed stone) can be adopted as the aggregate. Examples of such aggregate include gravel, crushed stone, water granulated slag, and recycled aggregate. Such aggregates also include refractory aggregates such as silicatic, clay, zircon, high alumina, silicon carbide, graphite, chromium, chromamag, and magnesia.

The cement composition of the present invention may contain any suitable admixture. Examples of admixtures include blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, ground granulated blast furnace slag, and expansion agents.

The cement composition of the present invention may be prepared by blending the constituent components by any suitable method. For example, a method of kneading the components in a mixer can be used.

The cement composition of the present invention may be prepared by independently blending A component, B component, cement, and if necessary other components, or may be prepared by independently blending A component and B component. It may be prepared by blending additives for cement, cement, and, if necessary, other components. Moreover, <<2. When the C component described in the section "Cement admixture" is blended, the cement composition of the present invention is obtained by independently blending the A component, B component, C component, cement, and, if necessary, other components. It may be prepared by blending the cement additive of the present invention containing A component and B component, C component, cement, and other components as necessary. Alternatively, it may be prepared by blending the cement admixture of the present invention containing A component, B component and C component, cement, and, if necessary, other components.

The content of component A in the cement composition of the present invention is preferably 0.001% by mass to 0.5% by mass, more preferably 0.003% by mass to 0.3% by mass, relative to cement. %, more preferably 0.007% by mass to 0.1% by mass, and particularly preferably 0.01% by mass to 0.05% by mass. By adjusting the content of component A in the cement composition of the present invention within the above range, the cement composition of the present invention can significantly improve the strength of the cured product over a long period of time.

The content of component B in the cement composition of the present invention is preferably 0.001% by mass to 0.5% by mass, more preferably 0.003% by mass to 0.3% by mass, relative to cement. %, more preferably 0.007% by mass to 0.1% by mass, and particularly preferably 0.01% by mass to 0.05% by mass. By adjusting the content of the B component in the cement composition of the present invention within the above range, the cement composition of the present invention can remarkably improve the strength of the cured product over a long period of time.

When the cement composition of the present invention contains the C component, the content of the C component in the cement composition of the present invention is preferably 0.01% by mass to 5% by mass, more preferably 0.01% by mass to 5% by mass, relative to cement. is 0.03% by mass to 1% by mass, more preferably 0.07% by mass to 0.5% by mass, and particularly preferably 0.1% by mass to 0.3% by mass. By adjusting the content of C component in the cement composition of the present invention within the above range, various favorable effects such as reduction in unit water content, increase in strength, and improvement in durability are brought about.

In the cement composition of the present invention, any appropriate values can be set for the unit water amount per 1 m ³ of the cement composition, the amount of cement used, and the water/cement ratio. As such values, the unit water amount is preferably 100 kg/m ³ to 250 kg/m ³ , the cement amount used is preferably 200 kg/m ³ to 800 kg/m ³ , and the water/cement ratio (mass ratio) = 0.1 to 0.7, more preferably, the unit water amount is 120 kg/m ³ to 185 kg/m ³ , the cement amount used is 250 kg/m ³ to 800 kg/m ³ , and the water/cement ratio ( mass ratio) = 0.12 to 0.65. As described above, the cement composition of the present invention can be used in a wide range from poor to rich blends, and can be used for both high-strength concrete with a large unit cement amount and poor blend concrete with a unit cement amount of 300 kg / m ³ or less. It is valid.

The cement composition of the present invention may contain any appropriate additive as long as the effects of the present invention are not impaired. Only one kind of such additives may be used, or two or more kinds thereof may be used. Such additives include, for example, water-soluble polymer substances, polymer emulsions, early strengthening agents/accelerators, retarders, AE agents, antifoaming agents, crack reducing agents, surfactants, waterproofing materials, and rust preventives. agents, expanding agents, cement wetting agents, thickeners, segregation reducing agents, flocculants, drying shrinkage reducing agents, strength enhancers, self-leveling agents, coloring agents, antifungal agents and the like.

Examples of water-soluble polymer substances include nonionic cellulose ethers such as methyl cellulose, ethyl cellulose and carboxymethyl cellulose; polysaccharides produced by microbial fermentation such as yeast glucan, xanthan gum and β-1.3 glucans; polyethylene glycol. polyoxyalkylene glycols such as polyacrylamide;

Polymer emulsions include, for example, polymers of various vinyl monomers such as alkyl (meth)acrylates.

Examples of early strengthening agents and accelerators include soluble calcium salts such as calcium chloride, calcium nitrite, calcium nitrate, calcium bromide and calcium iodide; chlorides such as iron chloride and magnesium chloride; sulfate; potassium hydroxide. carbonates; thiosulfates; formic acid and formates such as calcium formate;

Examples of retarders include oxycarboxylic acids such as gluconic acid, tartaric acid, glucoheptonic acid, arabonic acid, malic acid, and citric acid, or salts thereof; keto acids such as pyruvic acid, oxoglutaric acid, or salts thereof; glucose, fructose, and galactose. , mannose, xylose, arabinose, ribose, isomerized sugar, maltose, sucrose, lactose, raffinose, dextrin; glycerin, xylitol, D-arabinitol, L-arabinitol, ribitol, boremitol, perseitol, erythritol, sorbitol, mannitol , galactitol, D-threitol, L-threitol, D-iditol, D-glycidol, D-erythro-D-galacto-octitol and other sugar alcohols; phosphonic acids and derivatives thereof such as aminotri(methylenephosphonic acid); is mentioned.

Examples of AE agents include resin soaps, saturated or unsaturated fatty acids, sodium hydroxystearate, lauryl sulfate, ABS (alkylbenzenesulfonic acid), alkanesulfonates, polyoxyethylene alkyl (phenyl) ethers, polyoxyethylene alkyl (phenyl) Ether sulfates or salts thereof, polyoxyethylene alkyl (phenyl) ether phosphates or salts thereof, protein materials, alkenylsulfosuccinic acids, α-olefin sulfonates.

Examples of antifoaming agents include oxyalkylene antifoaming agents, mineral oil antifoaming agents, fat and oil antifoaming agents, fatty acid antifoaming agents, fatty acid ester antifoaming agents, alcohol antifoaming agents, and amide antifoaming agents. antifoaming agents, phosphate ester antifoaming agents, metallic soap antifoaming agents, and silicone antifoaming agents. Examples of oxyalkylene antifoaming agents include polyoxyalkylene alkyl ethers such as diethylene glycol heptyl ether; polyoxyalkylene acetylene ethers; (poly)oxyalkylene fatty acid esters; polyoxyalkylene sorbitan fatty acid esters; Alkyl (aryl) ether sulfate salts; polyoxyalkylene alkyl phosphates; polyoxypropylene polyoxyethylene laurylamine (propylene oxide 1 to 20 mol adduct, ethylene oxide 1 to 20 mol adduct, etc.), alkylene oxide added polyoxyalkylenealkylamines such as amines derived from fatty acids obtained from cured beef tallow (1 to 20 mol of propylene oxide, 1 to 20 mol of ethylene oxide, etc.); and polyoxyalkyleneamides.

Crack reducing agents include, for example, polyoxyalkyl ethers.

Examples of surfactants include various anionic surfactants; various cationic surfactants such as alkyltrimethylammonium chloride; various nonionic surfactants; and various amphoteric surfactants.

Waterproof agents include, for example, fatty acids (salts), fatty acid esters, fats and oils, silicones, paraffins, asphalts, and waxes.

Rust inhibitors include, for example, nitrites, phosphates, and zinc oxide.

Examples of expansive materials include ettringite-based expansive materials and coal-based expansive materials.

The types, combinations, blending amounts, etc. of other components can be appropriately set according to the purpose.

The content of the additive in the cement composition of the present invention is preferably 0% by mass to 50% by mass, more preferably 0% by mass to 10% by mass, and still more preferably 0% by mass in terms of solid content. % to 1% by mass, particularly preferably 0% to 0.1% by mass.

The cement composition of the present invention can be effective for, for example, ready-mixed concrete, concrete for secondary concrete products, centrifugal molding concrete, vibration compaction concrete, steam cured concrete, shotcrete, and the like.

The cement composition of the present invention includes, for example, medium-flow concrete (concrete with a slump value of 22 to 25 cm), high-flow concrete (concrete with a slump value of 25 cm or more and a slump flow value of 50 to 70 cm), and self-compacting concrete. It can also be effective for mortar and concrete that require high fluidity, such as self-leveling materials.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, parts means parts by mass, and % means % by mass.

<Conditions for weight average molecular weight analysis>
Regarding the weight average molecular weight of polyethylene glycol, if it is a commercially available product and is published on a catalog or website, the value is used unless otherwise specified (for example, "actual value" etc.) in Examples and Comparative Examples. Adopted (when publication on catalogs and websites uses other expressions such as "average molecular weight", that value was adopted).
- Columns used: TSKguardcolumnα+TSKgelα-5000+TSKgelα-4000+TSKgelα-3000 manufactured by Tosoh Corporation were used by connecting one column each.
Eluent: 62.4 g of sodium dihydrogen phosphate 2H ₂ O, 143.3 g of disodium hydrogen phosphate 12H ₂ O, dissolved in 7794.3 g of ion-exchanged water, acetonitrile: 2000 g was used.
Detector: Viscotek triple detector "Model 302 Light Scattering Detector", 90° scattering angle for normal light scattering, 7° scattering angle for low angle light scattering, 18 μL as cell volume, 670 nm as wavelength.
Standard sample: Polyethylene glycol SE-8 (Mw=107000) manufactured by Tosoh Corporation was used, and the device constant was determined with dn/dC of 0.135 ml/g and a refractive index of the eluent of 1.333.
Standard sample of injection amount: 100 μL of the solution dissolved in the above eluent so that the polymer concentration was 0.2 vol % was injected.
Sample: 100 μL of the solution dissolved in the above eluent so that the polymer concentration was 1.0 vol % was injected.
・Flow rate: 0.8 ml/min
・Column temperature: 40°C

<Measurement of flow value, air content, and 28-day compressive strength>
(Measurement of flow value and air volume)
Ordinary Portland cement (manufactured by Taiheiyo Cement Co., Ltd.) is used as cement, land sand from the Oi River water system is used as fine aggregate, crushed stone from Aomi is used as coarse aggregate, component A and/or component B is used, water reducing agent is used, and tap water is used as kneading water. : 382 kg/m ³ , water: 172 kg/m ³ , fine aggregate: 796 kg/m ³ , coarse aggregate: 930 kg/m ³ , fine aggregate ratio (fine aggregate/fine coarse aggregate + coarse aggregate) ( volume ratio): 47%, and a cement composition was prepared with a water/cement ratio (mass ratio) of 0.45.
In addition, the materials used for the measurement, the forced kneading mixer, and the measuring instruments were adjusted under the atmosphere of the above measurement temperature so that the temperature of the cement composition reached the measurement temperature of 20°C. It was carried out under the atmosphere of the measurement temperature. In addition, in order to avoid the influence of air bubbles in the cement composition on the fluidity of the cement composition, an oxyalkylene antifoaming agent is used as necessary so that the air content is 4.5 ± 0.5%. adjusted to
Under the above conditions, concrete was produced using a forced kneading mixer with a kneading time of 90 seconds, and the flow value and air content were measured. The flow value and air content were measured according to Japanese Industrial Standards (JIS-A-1101, 1128). In addition, the amount of the A component and/or the B component and the C component added was such that the flow value was 375 mm to 425 mm.
(28 days compressive strength)
After measuring the flow value and the amount of air, a sample for compressive strength test was prepared, and the compressive strength after 28 days was measured under the following conditions.
Specimen creation: 100 mm × 200 mm
Specimen curing (28 days): Temperature about 20°C, humidity 60%, constant temperature and humidity air curing for 24 hours, then curing in water for 27 days Specimen polishing: Specimen surface polishing (specimen polishing finishing machine used)
Compressive strength measurement: Automatic compressive strength measuring instrument (Mayekawa Seisakusho)
(28-day compressive strength ratio, 28-day compressive strength synergistic effect)
The "28-day compressive strength ratio" in the table refers to the 28-day compressive strength (p (N/mm ² )) measured in Comparative Example 1, which is 100, in other examples and comparative examples. It represents the ratio of compressive strength (q (N/mm ² )), that is, 100×(q/p) (%).
In addition, the "28-day compressive strength synergistic effect" in the table means that in the example in which the A component and the B component were used together, the 28-day compressive strength ratio in the corresponding comparative example when only the A component used was used -100)% and (the 28-day compressive strength ratio in the corresponding comparative example when only the B component used -100)% is X%, and (the A component and the B component were used together It is (YX)% when the 28-day compressive strength ratio -100)% in the example is Y%. , indicates that the synergistic effect of improving the compressive strength on the 28th is large.

[Production Example 1]: Production of polymer (1) as a dispersant A glass reactor equipped with a Dimroth condenser, a stirrer with a Teflon (registered trademark) stirring blade and a stirring seal, a nitrogen introduction tube, and a temperature sensor. 80.0 parts of ion-exchanged water was charged into a vessel, and heated to 70° C. while stirring at 250 rpm and introducing nitrogen at 200 mL/min. Next, a mixed solution of 133.4 parts of methoxypolyethylene glycol monomethacrylate (average number of added moles of ethylene oxide: 9), 26.6 parts of methacrylic acid, 1.53 parts of mercaptopropionic acid and 106.7 parts of deionized water was added dropwise over 4 hours, and at the same time, a mixed solution of 1.19 parts of ammonium persulfate and 50.6 parts of deionized water was added dropwise over 5 hours. After completion of dropping, the temperature was maintained at 70° C. for 1 hour to complete the polymerization reaction. Then, it was neutralized with an aqueous sodium hydroxide solution to obtain an aqueous solution of polymer (1) having a weight average molecular weight of 100,000.

[Production Example 2]: Production of polymer (2) as a dispersant A glass reactor equipped with a Dimroth condenser, a Teflon (registered trademark) stirring blade and a stirrer with a stirring seal, a nitrogen introduction tube, and a temperature sensor. In a container, ethylene oxide is added to the hydroxyl group of 3-methyl-3-buten-1-ol (isoprenol) (average number of added moles of ethylene oxide: 50) (hereinafter referred to as IPN-50) (80% aqueous solution) 198 .2 parts, 0.32 parts of acrylic acid, 12.47 parts of hydrogen peroxide water (2% aqueous solution), and 44.75 parts of ion-exchanged water were charged, and stirred at 250 rpm, while introducing nitrogen at 200 mL/min. It was warmed to °C. Next, a mixed solution consisting of 27.12 parts of acrylic acid and 108.5 parts of ion-exchanged water was added dropwise over 3 hours, and at the same time, 0.74 parts of L-ascorbic acid, 1.61 parts of 3-mercaptopropionic acid, and ion A mixed solution of 86.31 parts of exchanged water was added dropwise over 3 hours and 30 minutes. After completion of dropping, the temperature was maintained at 58° C. for 1 hour to complete the polymerization reaction. Then, it was neutralized with an aqueous sodium hydroxide solution to obtain an aqueous solution of polymer (2) having a weight average molecular weight of 140,000.

[Production Example 3]: Production of phosphoric acid-based dispersant A condensation reaction is carried out according to the method described in Japanese Patent Application Publication No. 2008-517080, and polyethylene glycol (average number of added moles of ethylene oxide: 20 mol) monophenyl ether and phenoxyethanol phosphate by condensation with formaldehyde, polyethylene glycol (average number of added moles of ethylene oxide: 20 moles) containing a condensate with a ratio of monophenyl ether and phenoxyethanol phosphate of 30/70 (mol%) and a weight average molecular weight (Mw) of 25000 An aqueous solution of phosphoric acid-based dispersant (3) was obtained.

[Production Example 4]: Production of polymer (4) as a dispersant A copolymerization reaction was carried out according to the method described in Japanese Patent Publication No. 2004-519406 to obtain an unsaturated poly(ethylene oxide) added with an average of 50 mol of ethylene oxide to methallyl alcohol. An aqueous solution of polymer (4) having a copolymer composition ratio of alkylene glycol ether and sodium acrylate of 85/15 (mass %), 19/81 (mol %) and a weight average molecular weight (Mw) of 32,000 was obtained.

[Production Example 5]: Production of dispersant (5) Mighty 150 (manufactured by Kao Corporation) was used as the dispersant (5).

[Production Example 6]: Production of Dispersant (6) Master Pozzolith No. 8 (manufactured by BASF Japan) was used as a dispersant (6).

[Examples 1a to 3a]: Additives for cement (1) to (3)
TIPA (triisopropanolamine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and acetoin (manufactured by Tokyo Chemical Industry Co., Ltd.) were blended under the conditions shown in Table 1 to prepare cement additives (1) to (3).

[Examples 4a to 6a]: Additives for cement (4) to (6)
EDIPA (diisopropanolethanolamine, manufactured by Aldrich) and acetoin (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were blended under the conditions shown in Table 1 to prepare cement additives (4) to (6).

[Examples 7a to 9a]: Additives for cement (7) to (9)
Cement additives (7) to (9) were prepared by blending TIPA (triisopropanolamine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and hydroxyacetone (manufactured by Tokyo Chemical Industry Co., Ltd.) under the conditions shown in Table 1. .

[Examples 10a to 12a]: Additives for cement (10) to (12)
EDIPA (diisopropanolethanolamine, manufactured by Aldrich) and hydroxyacetone (manufactured by Tokyo Chemical Industry Co., Ltd.) were blended under the conditions shown in Table 1 to prepare cement additives (10) to (12).

[Examples 13a to 15a]: Additives for cement (13) to (15)
TIPA (triisopropanolamine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and acetoin (manufactured by Tokyo Chemical Industry Co., Ltd.) were blended under the conditions shown in Table 1 to prepare cement additives (13) to (15).

[Examples 16a to 18a]: Additives for cement (16) to (18)
EDIPA (diisopropanolethanolamine, manufactured by Aldrich) and acetoin (manufactured by Tokyo Chemical Industry Co., Ltd.) were blended under the conditions shown in Table 1 to prepare cement additives (16) to (18).

[Examples 19a to 21a]: Additives for cement (19) to (21)
Cement additives (19) to (21) were prepared by blending TIPA (triisopropanolamine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and hydroxyacetone (manufactured by Tokyo Chemical Industry Co., Ltd.) under the conditions shown in Table 1. .

[Examples 22a to 24a]: Additives for cement (22) to (24)
EDIPA (diisopropanolethanolamine, manufactured by Aldrich) and hydroxyacetone (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were blended under the conditions shown in Table 1 to prepare cement additives (22) to (24).

[Example 25a]: Cement additive (25)
TIPA (triisopropanolamine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and acetoin (manufactured by Tokyo Chemical Industry Co., Ltd.) were blended under the conditions shown in Table 1 to prepare a cement additive (25).

[Example 26a]: Cement additive (26)
TIPA (triisopropanolamine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and hydroxyacetone (manufactured by Tokyo Chemical Industry Co., Ltd.) were blended under the conditions shown in Table 1 to prepare a cement additive (26).

[Example 27a]: Additive for cement (27)
EDIPA (diisopropanolethanolamine, manufactured by Aldrich) and acetoin (manufactured by Tokyo Chemical Industry Co., Ltd.) were blended under the conditions shown in Table 1 to prepare a cement additive (27).

[Example 28a]: Cement additive (28)
EDIPA (diisopropanolethanolamine, manufactured by Aldrich) and hydroxyacetone (manufactured by Tokyo Chemical Industry Co., Ltd.) were blended under the conditions shown in Table 1 to prepare additive for cement (28).

[Example 29a]: Cement additive (29)
EDIPA (diisopropanolethanolamine, manufactured by Aldrich) and acetoin (manufactured by Tokyo Chemical Industry Co., Ltd.) were blended under the conditions shown in Table 1 to prepare a cement additive (29).

[Examples 1b to 3b]: Cement admixtures (1) to (3)
TIPA (triisopropanolamine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), acetoin (manufactured by Tokyo Chemical Industry Co., Ltd.), and the polymer (1) obtained in Production Example 1 were blended under the conditions shown in Table 2 and mixed with cement. Agents (1) to (3) were prepared.

[Examples 4b to 6b]: Cement admixtures (4) to (6)
EDIPA (diisopropanolethanolamine, manufactured by Aldrich), acetoin (manufactured by Tokyo Chemical Industry Co., Ltd.), and the polymer (1) obtained in Production Example 1 were blended under the conditions shown in Table 2 to form a cement admixture (4). (6) were prepared.

[Examples 7b to 9b]: Cement admixtures (7) to (9)
TIPA (triisopropanolamine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), hydroxyacetone (manufactured by Tokyo Chemical Industry Co., Ltd.), and the polymer (1) obtained in Production Example 1 were blended under the conditions shown in Table 2 to produce cement. Admixtures (7)-(9) were prepared.

[Examples 10b to 12b]: Cement admixtures (10) to (12)
EDIPA (diisopropanolethanolamine, manufactured by Aldrich), hydroxyacetone (manufactured by Tokyo Chemical Industry Co., Ltd.), and the polymer (1) obtained in Production Example 1 were blended under the conditions shown in Table 2 to obtain a cement admixture (10 ) to (12) were prepared.

[Examples 13b to 15b]: Cement admixtures (13) to (15)
TIPA (triisopropanolamine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), acetoin (manufactured by Tokyo Chemical Industry Co., Ltd.), and the polymer (1) obtained in Production Example 1 were blended under the conditions shown in Table 2 and mixed with cement. Agents (13)-(15) were prepared.

[Examples 16b to 18b]: Cement admixtures (16) to (18)
EDIPA (diisopropanolethanolamine, manufactured by Aldrich), acetoin (manufactured by Tokyo Chemical Industry Co., Ltd.), and the polymer (1) obtained in Production Example 1 were blended under the conditions shown in Table 2 to prepare a cement admixture (16). (18) was prepared.

[Examples 19b to 21b]: Cement admixtures (19) to (21)
TIPA (triisopropanolamine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), hydroxyacetone (manufactured by Tokyo Chemical Industry Co., Ltd.), and the polymer (1) obtained in Production Example 1 were blended under the conditions shown in Table 2 to produce cement. Admixtures (19)-(21) were prepared.

[Examples 22b to 24b]: Cement admixtures (22) to (24)
EDIPA (diisopropanolethanolamine, manufactured by Aldrich), hydroxyacetone (manufactured by Tokyo Chemical Industry Co., Ltd.), and the polymer (1) obtained in Production Example 1 were blended under the conditions shown in Table 2 to obtain a cement admixture (22 ) to (24) were prepared.

[Example 25b]: Cement admixture (25)
TIPA (triisopropanolamine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), acetoin (manufactured by Tokyo Chemical Industry Co., Ltd.), and the polymer (2) obtained in Production Example 2 were blended under the conditions shown in Table 2 and mixed with cement. Agent (25) was prepared.

[Example 26b]: Cement admixture (26)
TIPA (triisopropanolamine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), hydroxyacetone (manufactured by Tokyo Chemical Industry Co., Ltd.), and the phosphoric acid-based dispersion (3) obtained in Production Example 3 were blended under the conditions shown in Table 2. to prepare a cement admixture (26).

[Example 27b]: Cement admixture (27)
EDIPA (diisopropanolethanolamine, manufactured by Aldrich), acetoin (manufactured by Tokyo Chemical Industry Co., Ltd.), and the polymer (4) obtained in Production Example 4 were blended under the conditions shown in Table 2 to form a cement admixture (27). was prepared.

[Example 28b]: Cement admixture (28)
The cement admixture (28 ) was prepared.

[Example 29b]: Cement admixture (29)
EDIPA (diisopropanolethanolamine, manufactured by Aldrich), acetoin (manufactured by Tokyo Chemical Industry Co., Ltd.), and the dispersant (6) obtained in Production Example 6 were blended under the conditions shown in Table 2 to produce a cement admixture (29). was prepared.

[Examples 1c to 29c]
Cement compositions (1) to (29) were prepared according to the formulations shown in Table 3, and the flow value and 28-day compressive strength were measured. Table 3 shows the results. Even if the A component, B component, and C component are blended individually, even if the A component and the B component are blended as cement additives (1) to (29), the A component and Similar results were obtained even when the B component and the C component were blended as cement admixtures (1) to (29).

[Comparative Example 1c]
A cement composition (C-1) was prepared according to the formulation shown in Table 4, and the flow value and 28-day compressive strength were measured. Table 4 shows the results. Cement composition (C-1) is a cement composition that does not contain A component and B component.

[Comparative Examples 2c to 7c]
Cement compositions (C-2) to (C-7) were prepared according to the formulations shown in Table 4, and the flow value and 28-day compressive strength were measured. Table 4 shows the results. In addition, even when the B component and the C component are blended individually, even when the B component is blended as cement additives (C-2) to (C-7), the B component and the C component was blended as cement admixtures (C-2) to (C-7), similar results were obtained.

[Comparative Examples 8c to 11c]
Cement compositions (C-8) to (C-11) were prepared according to the formulations shown in Table 4, and the flow value and 28-day compressive strength were measured. Table 4 shows the results. Even when the A component and the C component are blended individually, even when the A component is blended as cement additives (C-8) to (C-11), the A component and the C component Similar results were obtained even when blended as cement admixtures (C-8) to (C-11).

[Comparative Examples 12c to 14c]
Cement compositions (C-12) to (C-14) were prepared according to the formulations shown in Table 4, and the flow value and 28-day compressive strength were measured. Table 4 shows the results. In addition, even when dihydroxyacetone and C component are blended individually, even when dihydroxyacetone is blended as cement additives (C-12) to (C-14), dihydroxyacetone and C component Similar results were obtained even when blended as cement admixtures (C-12) to (C-14).

[Comparative Example 15c]
A cement composition (C-15) was prepared according to the formulation shown in Table 4, and the flow value and 28-day compressive strength were measured. Table 4 shows the results. Even when the A component, dihydroxyacetone, and C component are blended individually, even when the A component and dihydroxyacetone are blended as a cement additive (C-15), the A component and dihydroxyacetone Similar results were obtained even when the C component was blended as a cement admixture (C-15).

As shown in Tables 3 and 4, when the 28-day compressive strength of Comparative Example 1c is 100%, the 28-day compressive strength ratio of Example 1c using the A component and the B component is 121%, and 121%- A strength improvement effect equivalent to 100%=21% can be expressed. On the other hand, the strength improvement effect caused by the A component (TIPA) used in Example 1c is 105% as a 28-day compressive strength ratio as shown in Comparative Example 8c, and the B used in Example 1c The strength improvement effect due to the component (acetoin) is 107% as a 28-day compressive strength ratio as shown in Comparative Example 2c, and the simple sum of these effects is (105% + 107%) - 100 = 12%. is. Thus, a significant synergistic effect of strength improvement (significant increase from 12% to 21%) is seen in Example 1c. A significant synergistic effect of strength improvement is similarly observed for other Examples 2c to 29c.

Further, in Comparative Examples 12c to 15c using dihydroxyacetone, which does not correspond to the B component used in the present invention, no significant synergistic effect of strength improvement is observed.

[Examples 30a to 32a]: Additives for cement (30) to (32)
A cement additive ( 30) to (32) were prepared.

[Examples 33a to 35a]: Additives for cement (33) to (35)
EDIPA (diisopropanolethanolamine, manufactured by Aldrich) and 3-hydroxy-3-methyl-2-butanone (manufactured by Tokyo Chemical Industry Co., Ltd.) were blended under the conditions shown in Table 5 to obtain cement additives (33) to ( 35) was prepared.

[Examples 36a to 38a]: Additives for cement (36) to (38)
A cement additive ( 36)-(38) were prepared.

[Examples 39a to 41a]: Additives for cement (39) to (41)
EDIPA (diisopropanolethanolamine, manufactured by Aldrich) and 3-hydroxy-3-methyl-2-butanone (manufactured by Tokyo Chemical Industry Co., Ltd.) were blended under the conditions shown in Table 5 to obtain additives for cement (39) to ( 41) was prepared.

[Examples 30b to 32b]: Cement admixtures (30) to (32)
TIPA (triisopropanolamine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 3-hydroxy-3-methyl-2-butanone (manufactured by Tokyo Chemical Industry Co., Ltd.), Polymer (1) obtained in Production Example 1 is shown. Cement admixtures (30) to (32) were prepared by blending under the conditions of 6.

[Examples 33b to 35b]: Cement admixtures (33) to (35)
EDIPA (diisopropanolethanolamine, manufactured by Aldrich), 3-hydroxy-3-methyl-2-butanone (manufactured by Tokyo Chemical Industry Co., Ltd.), the polymer (1) obtained in Production Example 1 under the conditions shown in Table 6. By blending, cement admixtures (33) to (35) were prepared.

[Examples 36b to 38b]: Cement admixtures (36) to (38)
TIPA (triisopropanolamine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 3-hydroxy-3-methyl-2-butanone (manufactured by Tokyo Chemical Industry Co., Ltd.), Polymer (1) obtained in Production Example 1 is shown. Cement admixtures (36) to (38) were prepared by blending under the conditions of 6.

[Examples 39b to 41b]: Cement admixtures (39) to (41)
EDIPA (diisopropanolethanolamine, manufactured by Aldrich), 3-hydroxy-3-methyl-2-butanone (manufactured by Tokyo Chemical Industry Co., Ltd.), the polymer (1) obtained in Production Example 1 under the conditions shown in Table 6. By blending, cement admixtures (39) to (41) were prepared.

[Examples 30c to 41c]
Cement compositions (30) to (41) were prepared according to the formulations shown in Table 7, and the flow value and 28-day compressive strength were measured. The results are shown in Table 7. Even when the A component, B component, and C component are blended individually, even when the A component and the B component are blended as cement additives (30) to (41), the A component and Similar results were obtained even when the B component and the C component were blended as cement admixtures (30) to (41).

[Comparative Examples 16c to 18c]
Cement compositions (C-16) to (C-18) were prepared according to the formulations shown in Table 8, and the flow value and 28-day compressive strength were measured. Table 8 shows the results. In addition, even when 3-hydroxy-3-methyl-2-butanone and C component are blended individually, 3-hydroxy-3-methyl-2-butanone is added to cement additives (C-16) to ( C-18), or when 3-hydroxy-3-methyl-2-butanone and C component are blended as cement admixtures (C-16) to (C-18) , gave similar results.

As shown in Tables 7 and 8, when the 28-day compressive strength of Comparative Example 1c is 100%, the 28-day compressive strength ratio of Example 30c using the A component and the B component is 121%, and 121%- A strength improvement effect equivalent to 100%=21% can be expressed. On the other hand, the strength improvement effect due to the A component (TIPA) used in Example 30c is 105% as a 28-day compressive strength ratio as shown in Comparative Example 8c, and the B used in Example 30c The strength improvement effect caused by the component (3-hydroxy-3-methyl-2-butanone) is 107% as a 28-day compressive strength ratio as shown in Comparative Example 16c, and the simple sum of these effects is ( 105%+107%)−100=12%. Thus, a significant synergistic effect of strength improvement (significant increase from 12% to 21%) is seen in Example 30c. A significant synergistic effect of strength improvement is similarly observed for other Examples 31c to 41c.

The cement additive of the present invention is suitably used in cement compositions such as mortar and concrete.

Claims (6)

A cement additive containing the following A component and B component ,
An additive for cement, wherein the mass ratio of component B to component A ((mass of component B/mass of component A)×100%) in the additive for cement is 1% to 10000%.
A component: an alkanolamine compound.
Component B: A compound represented by the general formula (1).

(In general formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.) The A component is monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, methylethanolamine, methylisopropanolamine, methyldiethanolamine, methyldiisopropanolamine, diethanolisopropanolamine, diisopropanolethanol. amine, tetrahydroxyethylethylenediamine, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, and tris(2-hydroxybutyl)amine, according to claim 1 Cement additive as described. The A component according to claim 2, wherein the A component is at least one selected from the group consisting of triisopropanolamine, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine and diisopropanolethanolamine. Additive for cement. Claims 1 to 3, wherein R ¹ is a hydrogen atom, R ² is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ³ is a hydrogen atom or a methyl group in the general formula (1) representing the B component. Cement additive according to any one of the above. A cement admixture comprising the following A component and B component, and the following C component.
A component: an alkanolamine compound.
Component B: A compound represented by the general formula (1).

(In general formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.)
C component: at least one selected from the group consisting of the following C1 component, C2 component, C3 component and C4 component.
Component C1: polycarboxylic acid polymer having a structural unit (I) derived from an unsaturated polyalkylene glycol ether-based monomer and a structural unit (III) derived from an unsaturated carboxylic acid-based monomer Acid dispersant.

(In structural unit (I), R ⁴ and R ⁵ are the same or different and represent a hydrogen atom or a methyl group, R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, A ¹ O represents an oxyalkylene group having 2 to 18 carbon atoms, m represents the average number of added moles of the oxyalkylene group represented by A ¹ O, m is a number of 2 to 300, and x is 0 is an integer between ~2.)

(In structural unit (III), R ¹⁰ to R ¹² are the same or different and represent a hydrogen atom, a methyl group, or a —(CH ₂ ) _z COOM group. —(CH ₂ ) _z COOM group is —COOX group. Alternatively, it may form an anhydride with another —(CH ₂ ) _z COOM group, where z is an integer of 0 to 2. M is a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an organic represents an ammonium group or an organic amine group, and X represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an organic ammonium group, or an organic amine group.)
Component C2: polycarboxylic acid-based polymer having a structural unit (II) derived from an unsaturated polyalkylene glycol ester-based monomer and a structural unit (III) derived from an unsaturated carboxylic acid-based monomer Acid dispersant.

(In structural unit (II), R ⁷ and R ⁸ are the same or different and represent a hydrogen atom or a methyl group, R ⁹ represents a hydrocarbon group having 1 to 30 carbon atoms, and A ² O is represents an oxyalkylene group having 2 to 18 carbon atoms, n represents the average number of added moles of the oxyalkylene group represented by A ² O, and n is 2 to 300.)

(In structural unit (III), R ¹⁰ to R ¹² are the same or different and represent a hydrogen atom, a methyl group, or a —(CH ₂ ) _z COOM group. —(CH ₂ ) _z COOM group is —COOX group. Alternatively, it may form an anhydride with another —(CH ₂ ) _z COOM group, where z is an integer of 0 to 2. M is a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an organic represents an ammonium group or an organic amine group, and X represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an organic ammonium group, or an organic amine group.)
C3 component: sulfonic acid-based dispersant.
C4 component: phosphate-based dispersant. A cement composition comprising the following A component and B component ,
A cement composition, wherein the mass ratio of B component to A component ((mass of B component/mass of A component)×100%) in the cement composition is 1% to 10000%.
A component: an alkanolamine compound.
Component B: A compound represented by the general formula (1).

(In general formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.)