JP4987533B2 - Cement admixture - Google Patents

Description

  The present invention relates to a cement admixture. More specifically, the present invention relates to a cement admixture including a copolymer having a polyalkylene glycol ether chain, which can provide a cement composition having excellent early strength.

  Cement admixtures are widely used in cement compositions such as cement paste, mortar and concrete.

  When the cement admixture is used, the fluidity of the cement composition can be increased, and the cement composition can be reduced in water. This water reduction can improve the strength and durability of the cured product.

  In recent years, cement admixtures composed mainly of polycarboxylic acid copolymers have been proposed as cement admixtures. A cement admixture mainly composed of a polycarboxylic acid copolymer (polycarboxylic acid cement admixture) can exhibit high water reduction performance.

  In particular, as a cement admixture that exhibits high dispersibility with a small addition amount and excellent dispersion performance even in the high water reduction rate region, a structural unit derived from an unsaturated polyalkylene glycol ether monomer and an unsaturated monocarboxylic acid type A cement admixture including a polycarboxylic acid-based copolymer having a monomer-derived structural unit has been proposed (Patent Documents 1 to 3).

However, the cement composition using the cement admixture has a problem that the early strength at the level of one day (24 hours) is not sufficient.
JP 2001-220417 A JP 2003-73158 A JP 2002-226245 A

  An object of the present invention is to provide a cement admixture capable of providing a cement composition having high water reduction performance and excellent early strength.

（式（１）中、Ｒ^１、Ｒ^２、およびＲ^３は、それぞれ独立して、水素原子またはメチル基を表し、Ｒ^４は、水素原子または炭素数１〜２０の炭化水素基を表し、Ｒ^ａＯで表されるオキシアルキレン基は、それぞれ同一でも異なっていても良く、Ｒ^ａは炭素数２〜１８のアルキレン基であり、ｍはＲ^ａＯ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、１≦ｍ≦５００であり、Ｘは、炭素数１〜５の２価のアルキレン基または炭素数６〜９の２価のアリーレン基を表し、ｎは０または１である。）

（式（２）中、Ｒ^５は、水素原子、メチル基、または−ＣＨ_２ＣＯＯＭ^２を表し、Ｒ^６およびＲ^７は、それぞれ独立して、水素原子、メチル基、または−ＣＯＯＭ^３を表し、Ｍ^１、Ｍ^２、およびＭ^３は、それぞれ独立して、水素原子、金属原子、アンモニウム基、または有機アンモニウム基を表し、Ｒ^６およびＲ^７は同時に−ＣＯＯＭ^３ではない。また、Ｒ^７が−ＣＯＯＭ^３の場合、Ｒ^７と−ＣＯＯＭ^１が酸無水物基を形成していても良い。） The cement admixture of the present invention is
Comprising a polycarboxylic acid copolymer (A) and an alkanolamine compound (B),
The polycarboxylic acid copolymer (A) comprises a structural unit derived from an unsaturated polyalkylene glycol ether monomer represented by the formula (1) and an unsaturated carboxylic acid monomer represented by the formula (2). And a structural unit derived from a monomer.

(In the formula (1), R ¹ , R ² and R ³ each independently represents a hydrogen atom or a methyl group, R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, The oxyalkylene groups represented by R ^a O may be the same or different, R ^a is an alkylene group having 2 to 18 carbon atoms, and m is the average addition of the oxyalkylene group represented by R ^a O. Represents the number of moles, 1 ≦ m ≦ 500, X represents a divalent alkylene group having 1 to 5 carbon atoms or a divalent arylene group having 6 to 9 carbon atoms, and n is 0 or 1. )

(In formula (2), R ⁵ represents a hydrogen atom, a methyl group, or —CH ₂ COOM ² , and R ⁶ and R ⁷ each independently represent a hydrogen atom, a methyl group, or —COOM ³ . , M ¹ , M ² , and M ³ each independently represent a hydrogen atom, a metal atom, an ammonium group, or an organic ammonium group, and R ⁶ and R ⁷ are not simultaneously —COOM ^3. Also, R ⁷ When R is -COOM ³ , R ⁷ and -COOM ¹ may form an acid anhydride group.)

（式（３）中、Ｒ^１、Ｒ^２、およびＲ^３は、それぞれ独立して、水素原子またはメチル基を表し、Ｒ^４は、水素原子または炭素数１〜２０の炭化水素基を表し、Ｒ^ａＯで表されるオキシアルキレン基は、それぞれ同一でも異なっていても良く、Ｒ^ａは炭素数２〜１８のアルキレン基であり、ｍはＲ^ａＯ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、１≦ｍ≦５００であり、Ｘは、炭素数１〜５の２価のアルキレン基または炭素数６〜９の２価のアリーレン基を表し、ｎは０または１である。）

（式（４）中、Ｒ^５は、水素原子、メチル基、または−ＣＨ_２ＣＯＯＭ^２を表し、Ｒ^６およびＲ^７は、それぞれ独立して、水素原子、メチル基、または−ＣＯＯＭ^３を表し、Ｍ^１、Ｍ^２、およびＭ^３は、それぞれ独立して、水素原子、金属原子、アンモニウム基、または有機アンモニウム基を表し、Ｒ^６およびＲ^７は同時に−ＣＯＯＭ^３ではない。また、Ｒ^７が−ＣＯＯＭ^３の場合、Ｒ^７と−ＣＯＯＭ^１が酸無水物基を形成していても良い。） In a preferred embodiment, the structural unit derived from the unsaturated polyalkylene glycol ether monomer is a structural unit represented by the formula (3), and the structural unit derived from the unsaturated carboxylic acid monomer is represented by the formula: It is a structural unit represented by (4).

(In Formula (3), R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a methyl group, R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, The oxyalkylene groups represented by R ^a O may be the same or different, R ^a is an alkylene group having 2 to 18 carbon atoms, and m is the average addition of the oxyalkylene group represented by R ^a O. Represents the number of moles, 1 ≦ m ≦ 500, X represents a divalent alkylene group having 1 to 5 carbon atoms or a divalent arylene group having 6 to 9 carbon atoms, and n is 0 or 1. )

(In Formula (4), R ⁵ represents a hydrogen atom, a methyl group, or —CH ₂ COOM ² , and R ⁶ and R ⁷ each independently represent a hydrogen atom, a methyl group, or —COOM ³⁾ . , M ¹ , M ² , and M ³ each independently represent a hydrogen atom, a metal atom, an ammonium group, or an organic ammonium group, and R ⁶ and R ⁷ are not simultaneously —COOM ^3. Also, R ⁷ When R is -COOM ³ , R ⁷ and -COOM ¹ may form an acid anhydride group.)

  In a preferred embodiment, the alkanolamine compound (B) is at least one selected from trialkanolamine compounds and tetraalkanolamine compounds.

  In a preferred embodiment, the content ratio of the alkanolamine compound (B) is 50% by mass or less based on the total amount of the polycarboxylic acid copolymer (A) and the alkanolamine compound (B). is there.

  According to the present invention, a cement admixture capable of providing a cement composition having high water reduction performance and excellent early strength can be provided.

  Such effects include a polycarboxylic acid copolymer having a structural unit derived from an unsaturated polyalkylene glycol ether monomer and a structural unit derived from an unsaturated carboxylic acid monomer, an alkanolamine compound, Can be expressed in combination. In particular, in the present invention, preferably, an “ether-based” polycarboxylic acid and a “specific” alkanolamine-based compound are used in combination, more preferably an “ether-based” polycarboxylic acid and a “specific amount”. The above-mentioned effect can be further manifested by using in combination with a specific alkanolamine compound.

[Polycarboxylic acid copolymer (A)]
The polycarboxylic acid copolymer (A) used in the present invention comprises a structural unit derived from an unsaturated polyalkylene glycol ether monomer represented by the formula (1) and an unsaturated carboxylic acid represented by the formula (2). And a structural unit derived from an acid monomer. In the present invention, the polycarboxylic acid copolymer (A) may be used alone or in combination of two or more.

式（１）中、Ｒ^１、Ｒ^２、およびＲ^３は、それぞれ独立して、水素原子またはメチル基を表す。Ｒ^４は、水素原子または炭素数１〜２０の炭化水素基を表す。
式（１）中、Ｒ^ａＯで表されるオキシアルキレン基は、それぞれ同一でも異なっていても良い。Ｒ^ａは炭素数２〜１８のアルキレン基である。ｍはＲ^ａＯで表されるオキシアルキレン基の平均付加モル数を表す。１≦ｍ≦５００であり、好ましくは１０≦ｍ≦３００、より好ましくは１５≦ｍ≦１５０、さらに好ましくは２０≦ｍ≦１００である。
式（１）中、Ｘは、炭素数１〜５の２価のアルキレン基または炭素数６〜９の２価のアリーレン基を表す。ｎは０または１である。なお、２価のアリーレン基とは、２個の結合手を有する置換または非置換の芳香族環を意味する。 In the present invention, the unsaturated polyalkylene glycol ether monomer is represented by the formula (1).

In formula (1), R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a methyl group. R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
In formula (1), the oxyalkylene groups represented by R ^a O may be the same or different. R ^a is an alkylene group having 2 to 18 carbon atoms. m represents the average addition mole number of the oxyalkylene group represented by R ^a O. 1 ≦ m ≦ 500, preferably 10 ≦ m ≦ 300, more preferably 15 ≦ m ≦ 150, and further preferably 20 ≦ m ≦ 100.
In formula (1), X represents a C1-C5 bivalent alkylene group or a C6-C9 bivalent arylene group. n is 0 or 1. The divalent arylene group means a substituted or unsubstituted aromatic ring having two bonds.

  The unsaturated polyalkylene glycol ether monomer can be produced by any appropriate method. For example, methods described in JP-A-10-236859 and JP-T-2004-519406 can be mentioned.

  Examples of the unsaturated polyalkylene glycol ether monomer include alkenyl alcohols such as 2-hydroxyethyl vinyl ether, allyl alcohol, hydroxybutyl vinyl ether, methallyl alcohol, and 3-methyl-3-buten-1-ol. An adduct obtained by adding 1 to 500 moles of oxide, or an etherification reaction between a compound having an alkenyl group and a halogen and a terminal alkyl polyalkylene glycol, for example, ether of allyl chloride and methoxypolyethylene glycol Reaction products.

式（２）中、Ｒ^５は、水素原子、メチル基、または−ＣＨ_２ＣＯＯＭ^２を表し、Ｒ^６およびＲ^７は、それぞれ独立して、水素原子、メチル基、または−ＣＯＯＭ^３を表す。
式（２）中、Ｍ^１、Ｍ^２、およびＭ^３は、それぞれ独立して、水素原子、金属原子、アンモニウム基、または有機アンモニウム基を表す。
式（２）中、Ｒ^６およびＲ^７は同時に−ＣＯＯＭ^３ではない。
式（２）中、Ｒ^７が−ＣＯＯＭ^３の場合、Ｒ^７と−ＣＯＯＭ^１が酸無水物基を形成していても良い。 In the present invention, the unsaturated carboxylic acid monomer is represented by the formula (2).

In formula (2), R ⁵ represents a hydrogen atom, a methyl group, or —CH ₂ COOM ² , and R ⁶ and R ⁷ each independently represent a hydrogen atom, a methyl group, or —COOM ³ .
In formula (2), M ¹ , M ² , and M ³ each independently represent a hydrogen atom, a metal atom, an ammonium group, or an organic ammonium group.
In formula (2), R ⁶ and R ⁷ are not simultaneously —COOM ³ .
In Formula (2), when R ⁷ is —COOM ³ , R ⁷ and —COOM ¹ may form an acid anhydride group.

  The unsaturated carboxylic acid monomer can be produced by any appropriate method.

  Examples of the unsaturated carboxylic acid monomer include unsaturated monocarboxylic acid monomers and unsaturated dicarboxylic acid monomers. Examples of the unsaturated monocarboxylic acid monomer include acrylic acid, methacrylic acid, crotonic acid, and monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts thereof. Examples of unsaturated dicarboxylic acid-based monomers include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, mesaconic acid, and monovalent metal salts, divalent metal salts, and ammonium thereof. Salts and organic amine salts. Acrylic acid, methacrylic acid, and salts thereof are preferable, and acrylic acid and salts thereof are more preferable. It is because it is excellent in copolymerizability.

  The total content of the unsaturated polyalkylene glycol ether monomer and the unsaturated carboxylic acid monomer in all the monomers used for producing the polycarboxylic acid copolymer (A). Is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass. When the content ratio is within the above range, the effects of the present invention can be sufficiently exerted.

  In producing the polycarboxylic acid copolymer (A), any appropriate other monomer may be used. For example, styrene, acrylamide, methyl (meth) acrylate, etc. are mentioned. Moreover, the monomer as described in the paragraph 0015 of patent 3683176 is mentioned. These can be preferably used in an amount of 0 to 30% by mass in all monomers used.

  The total amount of the unsaturated polyalkylene glycol ether monomer and the unsaturated carboxylic acid monomer in all the monomers used when the polycarboxylic acid copolymer (A) is produced. When the content is 100% by mass, the proportion of the unsaturated polyalkylene glycol ether monomer is preferably 60 to 96% by mass, more preferably 70 to 95% by mass, still more preferably 80 to 94% by mass, and particularly preferably. Is 84-94 mass%. When the content ratio is within the above range, the effects of the present invention can be sufficiently exerted.

  The polycarboxylic acid copolymer (A) preferably has a structural unit derived from the unsaturated polyalkylene glycol ether monomer and a structural unit derived from the unsaturated carboxylic acid monomer. The polycarboxylic acid copolymer (A) may further have a structural unit derived from the other monomer.

式（３）中、Ｒ^１、Ｒ^２、およびＲ^３は、それぞれ独立して、水素原子またはメチル基を表す。Ｒ^４は、水素原子または炭素数１〜２０の炭化水素基を表す。
式（３）中、Ｒ^ａＯで表されるオキシアルキレン基は、それぞれ同一でも異なっていても良い。Ｒ^ａは炭素数２〜１８のアルキレン基である。ｍはＲ^ａＯで表されるオキシアルキレン基の平均付加モル数を表す。１≦ｍ≦５００であり、好ましくは１０≦ｍ≦３００、より好ましくは１５≦ｍ≦１５０、さらに好ましくは２０≦ｍ≦１００である。
式（３）中、Ｘは、炭素数１〜５の２価のアルキレン基または炭素数６〜９の２価のアリーレン基を表す。ｎは０または１である。 The structural unit derived from the unsaturated polyalkylene glycol ether monomer is represented by the formula (3).

In formula (3), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a methyl group. R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
In formula (3), the oxyalkylene groups represented by R ^a O may be the same or different. R ^a is an alkylene group having 2 to 18 carbon atoms. m represents the average addition mole number of the oxyalkylene group represented by R ^a O. 1 ≦ m ≦ 500, preferably 10 ≦ m ≦ 300, more preferably 15 ≦ m ≦ 150, and further preferably 20 ≦ m ≦ 100.
In formula (3), X represents a C1-C5 bivalent alkylene group or a C6-C9 bivalent arylene group. n is 0 or 1.

式（４）中、Ｒ^５は、水素原子、メチル基、または−ＣＨ_２ＣＯＯＭ^２を表し、Ｒ^６およびＲ^７は、それぞれ独立して、水素原子、メチル基、または−ＣＯＯＭ^３を表す。
式（４）中、Ｍ^１、Ｍ^２、およびＭ^３は、それぞれ独立して、水素原子、金属原子、アンモニウム基、または有機アンモニウム基を表す。
式（４）中、Ｒ^６およびＲ^７は同時に−ＣＯＯＭ^３ではない。
式（４）中、Ｒ^７が−ＣＯＯＭ^３の場合、Ｒ^７と−ＣＯＯＭ^１が酸無水物基を形成していても良い。 The structural unit derived from the unsaturated carboxylic acid monomer is represented by the formula (4).

In formula (4), R ⁵ represents a hydrogen atom, a methyl group, or —CH ₂ COOM ² , and R ⁶ and R ⁷ each independently represent a hydrogen atom, a methyl group, or —COOM ³ .
In formula (4), M ¹ , M ² , and M ³ each independently represent a hydrogen atom, a metal atom, an ammonium group, or an organic ammonium group.
In formula (4), R ⁶ and R ⁷ are not simultaneously —COOM ³ .
In Formula (4), when R ⁷ is —COOM ³ , R ⁷ and —COOM ¹ may form an acid anhydride group.

  Among all structural units constituting the polycarboxylic acid copolymer (A), the total of structural units derived from the unsaturated polyalkylene glycol ether monomer and structural units derived from the unsaturated carboxylic acid monomer The content of is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass. When the content ratio is within the above range, the effects of the present invention can be sufficiently exerted.

  Among all structural units constituting the polycarboxylic acid copolymer (A), a structural unit derived from the unsaturated polyalkylene glycol ether monomer and a structural unit derived from the unsaturated carboxylic acid monomer. When the total amount is 100% by mass, the proportion of structural units derived from the unsaturated polyalkylene glycol ether monomer is preferably 60 to 96% by mass, more preferably 70 to 95% by mass, and still more preferably 80%. It is -94 mass%, Most preferably, it is 84-94 mass%. When the content ratio is within the above range, the effects of the present invention can be sufficiently exerted.

  The weight average molecular weight (Mw) of the polycarboxylic acid copolymer (A) is preferably 3000 to 100,000, more preferably 5000 to 50000, and still more preferably 7000 to 40000. When the weight average molecular weight of the copolymer is within the above range, the effects of the present invention can be sufficiently exerted.

  The polycarboxylic acid copolymer (A) is preferably prepared by a polymerization reaction, and then adjusted to a pH of 5 to 9, more preferably a pH of 6 to 8. Arbitrary appropriate methods can be employ | adopted for the method of adjusting pH. For example, neutralization can be performed using a compound containing a divalent metal such as magnesium or calcium, or a basic compound such as ammonia or amine. The basic compound used for adjusting the pH is preferably sodium hydroxide or potassium hydroxide, and more preferably sodium hydroxide. As the basic compound, a solid or 100% pure product may be used, or an aqueous solution having any appropriate concentration may be used.

  The polycarboxylic acid copolymer (A) may be unneutralized or neutralized. For example, the carboxylic acid moiety may be an alkali metal salt, alkaline earth metal salt, or amine salt.

[Alkanolamine compound (B)]
Any appropriate alkanolamine compound may be employed as the alkanolamine compound (B) used in the present invention. Preferably, it is at least one selected from trialkanolamine compounds and tetraalkanolamine compounds.

式（５）中、Ｒ^８、Ｒ^９、Ｒ^１０は、それぞれ独立して、炭素数１〜２０の２価のアルキレン基または炭素数６〜３０の２価のアリーレン基を表す。 The trialkanolamine compound is preferably a compound represented by the formula (5).

In formula (5), R < ⁸ >, R <^9> , R < ¹⁰ > represents a C1-C20 bivalent alkylene group or a C6-C30 bivalent arylene group each independently.

Specific examples of trialkanolamine compounds include triethanolamine, hydroxyethyl di- (hydroxypropyl) -amine, di- (hydroxyethyl) -hydroxypropylamine, tri- (hydroxypropyl) -amine, and hydroxyethyl. Di- (hydroxy-n-butyl) -amine, tri- (2-hydroxybutyl) -amine, hydroxybutyl di- (hydroxypropyl) -amine, triisopropanolamine, N, N
-Bis- (2-hydroxybutyl) -N- (2-hydroxypropyl) -amine and the like. Among these, triethanolamine represented by the formula (6) and triisopropanolamine represented by the formula (7) are preferable.

式（８）中、Ｚ、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４は、それぞれ独立して、炭素数１〜２０の２価のアルキレン基または炭素数６〜３０の２価のアリーレン基を表す。 The tetraalkanolamine compound is preferably a compound represented by the formula (8).

In formula (8), Z, R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are each independently a divalent alkylene group having 1 to 20 carbon atoms or a divalent arylene group having 6 to 30 carbon atoms. To express.

Specifically, the tetraalkanolamine-based compound is preferably triisopropanolamine represented by formula (9) or formula (10).

[Cement admixture]
The cement admixture of the present invention contains the polycarboxylic acid copolymer (A) and an alkanolamine compound (B). The polycarboxylic acid copolymer (A) in the cement admixture of the present invention may be only one type or two or more types. The said alkanolamine type compound (B) in the cement admixture of this invention may be only 1 type, and 2 or more types may be sufficient as it.

  In the cement admixture of the present invention, the content of the alkanolamine compound (B) is preferably relative to the total amount of the polycarboxylic acid copolymer (A) and the alkanolamine compound (B). Is 50% by mass or less, more preferably 45% by mass or less, and still more preferably 40% by mass or less. The lower limit is preferably 4% by mass or more, more preferably 10% by mass or more. When the content ratio of the alkanolamine compound (B) is within the above range, the effects of the present invention can be sufficiently exerted.

  In the cement admixture of the present invention, the content ratio of the total amount of the polycarboxylic acid copolymer (A) and the alkanolamine compound (B) is arbitrarily appropriate as long as the effects of the present invention are not impaired. Ratios can be adopted. Preferably, it is 50-100 mass%, More preferably, it is 80-100 mass%, More preferably, it is 90-100 mass%, Most preferably, it is 95-100 mass%.

  The cement admixture of the present invention may contain one or more kinds of any appropriate cement dispersant. When the cement dispersant is used, the blending mass ratio between the cement admixture of the present invention and the cement dispersant (cement admixture of the present invention / cement dispersant) is determined by the type and blending conditions of the cement dispersant used. Although not uniquely determined by the difference in test conditions and the like, the mass ratio (mass%) in terms of solid content is preferably 1 to 99/99 to 1, more preferably 5 to 95/95 to 5, More preferably, it is 10-90 / 90-10.

  Examples of the cement dispersant that can be used in combination with the cement admixture of the present invention include the following cement dispersants.

  Polyalkylaryl sulfonate system such as naphthalene sulfonic acid formaldehyde condensate, methyl naphthalene sulfonic acid formaldehyde condensate, anthracene sulfonic acid formaldehyde condensate; melamine formalin resin sulfonate system such as melamine sulfonic acid formaldehyde condensate; amino Aromatic aminosulfonates such as aryl sulfonic acid-phenol-formaldehyde condensates; lignin sulfonates such as lignin sulfonates and modified lignin sulfonates; polystyrene sulfonates; Various sulfonic acid-based dispersants having a sulfonic acid group.

  Polyalkylene glycol mono (meth) acrylic acid ester monomers, (meth) acrylic acid monomers, and their single amounts as described in JP-B-59-18338 and JP-A-7-223852 A copolymer obtained by polymerizing a monomer copolymerizable with a polymer; a polyether compound described in JP-A-7-53645, JP-A-8-208769, JP-A-8-208770; Various polycarboxylic acid dispersants having a (poly) oxyalkylene group and a carboxyl group in the molecule, such as a hydrophilic graft polymer obtained by graft polymerization of an unsaturated carboxylic acid monomer.

  The cement admixture of the present invention may contain any appropriate cement additive (cement additive) as exemplified in the following (1) to (12).

  (1) Water-soluble polymer substance: unsaturated carboxylic acid polymer such as polyacrylic acid (sodium), polymethacrylic acid (sodium), polymaleic acid (sodium), sodium salt of acrylic acid / maleic acid copolymer Nonionic cellulose ethers such as methylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, carboxyethylcellulose, hydroxypropylcellulose; alkylation or hydroxyalkylation of polysaccharides such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose; A hydrophobic substituent having a partial structure of a hydrocarbon chain having 8 to 40 carbon atoms as a part or all of the hydroxyl groups of the fluorinated derivative, and a sulfonic acid group Or a polysaccharide derivative substituted with an ionic hydrophilic substituent having a partial structure thereof as a salt; yeast glucan, xanthan gum, β-1,3-glucan (both linear and branched, Examples include polysaccharides produced by microbial fermentation such as curdlan, paramylon, pachyman, scleroglucan, laminaran, etc .; polyacrylamide; polyvinyl alcohol; starch; starch phosphate ester; sodium alginate, gelatin, molecule A copolymer of acrylic acid having an amino group therein and its quaternary compound;

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

  (3) Curing retarder: oxycarboxylic acid or salt thereof; sugar, sugar alcohol; magnesium silicofluoride; phosphoric acid or salt thereof or boric acid ester; aminocarboxylic acid or salt thereof; alkali-soluble protein; humic acid; Tannic acid; Phenol; Polyhydric alcohol such as glycerol; Aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), and these Phosphonic acid and its derivatives, such as alkali metal salts and alkaline earth metal salts.

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

  (5) Oxyalkylene antifoaming agents: polyoxyalkylenes such as (poly) oxyethylene (poly) oxypropylene adducts; diethylene glycol heptyl ether, polyoxyethylene oleyl ether, polyoxypropylene butyl ether, polyoxyethylene polyoxy Polyoxyalkylene alkyl ethers such as propylene-2-ethylhexyl ether and oxyethyleneoxypropylene adducts to higher alcohols having 12 to 14 carbon atoms; polyoxypropylene phenyl ether, polyoxyethylene nonylphenyl ether, and the like; Oxyalkylene (alkyl) aryl ethers; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 3-methyl Acetylene ethers obtained by addition polymerization of alkylene oxide to acetylene alcohol such as ru-1-butyn-3-ol; (poly) oxyalkylene such as diethylene glycol oleate, diethylene glycol laurate, ethylene glycol distearate Fatty acid esters; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan trioleate, etc., polyoxyalkylene sorbitan fatty acid esters; polyoxypropylene methyl ether sodium sulfate, polyoxyethylene dodecyl phenyl ether sodium sulfate, Polyoxyalkylene alkyl (aryl) ether sulfates; polyoxyethylene stearyl phosphates, Reoxyalkylene alkyl phosphate esters; polyoxypropylene polyoxyethylene laurylamine (1-20 mol addition of propylene oxide, 1-20 mol addition product of ethylene oxide, etc.), derived from fatty acid obtained from cured beef tallow added with alkylene oxide Polyoxyalkylene alkylamines such as amines (propylene oxide 1-20 mol addition, ethylene oxide 1-20 mol addition, etc.); polyoxyalkylene amides; etc.

  (6) Antifoaming agents other than oxyalkylene-based: mineral oil-based antifoaming agents such as coconut oil and liquid paraffin; fat and oil-based antifoaming agents such as animal and vegetable oils, sesame oil, castor oil, and these alkylene oxide adducts; Fatty acid-based antifoaming agents such as stearic acid and these alkylene oxide adducts; fatty acid ester-based antifoaming agents such as glycerin monoricinoleate, alkenyl succinic acid derivatives, sorbitol monolaurate, sorbitol trioleate, and natural wax; octyl Alcohol-based antifoaming agents such as alcohol, hexadecyl alcohol, acetylene alcohol and glycols; Amide-based antifoaming agents such as acrylate polyamines; Phosphate ester-based antifoaming agents such as tributyl phosphate and sodium octyl phosphate; aluminum Stearate, calcium oleate, etc. Genus soap antifoaming agents; dimethylsilicone oils, silicone pastes, silicone emulsions, organic modified polysiloxanes (polyorganosiloxanes dimethylpolysiloxane), fluorosilicone oils, silicone anti-foaming agent; and the like.

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

  (8) Other surfactants: aliphatic monohydric alcohols having 6-30 carbon atoms in the molecule, such as octadecyl alcohol and stearyl alcohol; 6-30 carbon atoms in the molecule, such as abiethyl alcohol A monocyclic mercaptan having 6 to 30 carbon atoms in the molecule such as dodecyl mercaptan; an alkylphenol having 6 to 30 carbon atoms in the molecule such as nonylphenol; dodecylamine An amine having 6 to 30 carbon atoms in the molecule, such as lauric acid or stearic acid, and a carboxylic acid having 6 to 30 carbon atoms in the molecule, such as ethylene oxide and propylene oxide. Polyalkylene oxide derivatives added in moles or more; alkyl group or alkoxy group substituted Alkyl diphenyl ether sulfonates in which two phenyl groups having a sulfone group may be ether-bonded; various anionic surfactants; various cationic interfaces such as alkylamine acetate and alkyltrimethylammonium chloride Activators; various nonionic surfactants; various amphoteric surfactants;

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

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

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

  (12) Swelling agent: Ettlingite, coal, etc.

  Other arbitrary suitable cement additives (cement additives) include, for example, cement wetting agents, thickeners, separation reducing agents, flocculants, drying shrinkage reducing agents, strength enhancers, self-leveling agents, colorants, An antifungal agent and the like can be mentioned.

  Only one kind of cement additive (cement additive) as mentioned above may be used, or two or more kinds may be used in combination.

  Examples of particularly preferred embodiments of the cement admixture of the present invention include the following (1) to (7).

  (1) <1> A combination comprising two components, the cement admixture of the present invention and <2> an oxyalkylene-based antifoaming agent. Examples of the oxyalkylene-based antifoaming agent include polyoxyalkylenes, polyoxyalkylene alkyl ethers, polyoxyalkylene acetylene ethers and polyoxyalkylene alkylamines, preferably polyoxyalkylene alkylamines. . In addition, the blending mass ratio of the <2> oxyalkylene-based antifoaming agent is preferably in the range of 0.01 to 20% by mass with respect to the cement admixture of <1> the present invention.

  (2) A combination comprising essentially three components, <1> the cement admixture of the present invention, <2> an oxyalkylene antifoaming agent, and <3> an AE agent. Examples of the oxyalkylene-based antifoaming agent include polyoxyalkylenes, polyoxyalkylene alkyl ethers, polyoxyalkylene acetylene ethers and polyoxyalkylene alkylamines, preferably polyoxyalkylene alkylamines. . In addition, the blending mass ratio of the <2> oxyalkylene-based antifoaming agent is preferably in the range of 0.01 to 20% by mass with respect to the cement admixture of <1> the present invention. Moreover, the blending mass ratio of <3> AE agent is preferably in the range of 0.001 to 2% by mass with respect to <1> the cement admixture of the present invention.

  (3) <1> the cement admixture of the present invention, <2> a polyalkylene glycol mono (meth) acryl having a polyoxyalkylene chain in which an alkylene oxide having 2 to 18 carbon atoms is added in an average addition mole number of 2 to 300 A copolymer obtained by polymerizing an acid ester monomer, a (meth) acrylic acid monomer, and a monomer copolymerizable with these monomers (for example, JP-B-59-18338) JP, 7-223852, A), and <3> oxyalkylene type antifoaming agent which requires three components as a combination. Examples of the oxyalkylene-based antifoaming agent include polyoxyalkylenes, polyoxyalkylene alkyl ethers, polyoxyalkylene acetylene ethers and polyoxyalkylene alkylamines, preferably polyoxyalkylene alkylamines. . The blending ratio of <1> the cement admixture of the present invention and <2> copolymer is <1> the mass ratio of the cement admixture of the present invention / <2> copolymer, preferably 5 / 95- 95/5, more preferably 10/90 to 90/10. The blending mass ratio of the <3> oxyalkylene-based antifoaming agent is in the range of 0.01 to 20% by mass with respect to the total amount of the <1> cement admixture of the present invention and the <2> copolymer. preferable.

  (4) A combination comprising two components of <1> the cement admixture of the present invention and <2> a sulfonic acid-based dispersant having a sulfonic acid group in the molecule. Examples of the sulfonic acid-based dispersant include aminosulfonic acid-based compounds such as lignin sulfonate, naphthalene sulfonic acid formalin condensate, melamine sulfonic acid formalin condensate, polystyrene sulfonate, and aminoaryl sulfonic acid-phenol-formaldehyde condensate. A dispersing agent is mentioned. The mixing ratio of <1> the cement admixture of the present invention and <2> the sulfonic acid-based dispersant is preferably the mass ratio of <1> the cement admixture of the present invention / <2> the sulfonic acid-based dispersant, 5/95 to 95/5, more preferably 10/90 to 90/10.

  (5) <1> A combination comprising two components, the cement admixture of the present invention and <2> a material separation reducing agent. Examples of the material separation reducing agent include various thickeners such as nonionic cellulose ethers, a hydrophobic substituent composed of a hydrocarbon chain having 4 to 30 carbon atoms as a partial structure, and an alkylene oxide having 2 to 18 carbon atoms. Examples thereof include compounds having a polyoxyalkylene chain added in an average addition mole number of 2 to 300. The mixing ratio of <1> the cement admixture of the present invention and <2> the material separation reducing agent is the mass ratio of <1> the cement admixture of the present invention / <2> the material separation reducing agent, preferably 10 / It is 90-99.99 / 0.01, More preferably, it is 50 / 50-99.9 / 0.1. The cement admixture in this combination is suitable as high fluidity concrete, self-filling concrete, and self-leveling agent.

  (6) A combination of two components, <1> the cement admixture of the present invention and <2> retarder. Examples of the retarder include oxycarboxylic acids such as gluconic acid (salt) and citric acid (salt), sugars such as glucose, sugar alcohols such as sorbitol, and phosphonic acids such as aminotri (methylenephosphonic acid), Oxycarboxylic acids are preferred. The mixing ratio of <1> the cement admixture of the present invention and <2> retarder is the mass ratio of <1> the cement admixture of the present invention / <2> retarder, and preferably 50/50 to 99.99. 9 / 0.1, more preferably 70/30 to 99/1.

  (7) A combination of two components, <1> the cement admixture of the present invention and <2> an accelerator. Examples of the accelerator include soluble calcium salts such as calcium chloride, calcium nitrite and calcium nitrate, chlorides such as iron chloride and magnesium chloride, formates such as thiosulfate, formic acid and calcium formate, and the like. The blending ratio of <1> the cement admixture of the present invention and <2> accelerator is <1> the mass ratio of the cement admixture of the present invention / <2> accelerator, preferably 10/90 to 99.99. 9 / 0.1, more preferably 20/80 to 99/1.

  The cement admixture of the present invention may be manufactured by any suitable method. For example, the method of adding the said alkanolamine type compound (B) and arbitrary appropriate other components as needed to the aqueous solution of the said polycarboxylic acid type copolymer (A) is mentioned.

[Cement composition]
The cement admixture of the present invention can be used by adding to a cement composition such as cement paste, mortar or concrete.

  Any appropriate cement composition may be adopted as the cement composition. For example, what contains cement, water, an aggregate, and an antifoamer is mentioned.

  Any appropriate cement can be adopted as the cement. For example, Portland cement (ordinary, early strength, very early strength, moderate heat, sulfate resistance and low alkali type of each), various mixed cements (blast furnace cement, silica cement, fly ash cement), white Portland cement, alumina cement, Super fast cement (1 clinker fast cement, 2 clinker fast cement, magnesium phosphate cement), grout cement, oil well cement, low heat cement (low heat blast furnace cement, fly ash mixed low heat blast furnace cement, belite High-content cement), ultra-high-strength cement, cement-based solidified material, and eco-cement (cement produced from one or more of municipal waste incineration ash and sewage sludge incineration ash). Further, fine powder such as blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica powder, limestone powder, or gypsum may be added.

  Any appropriate aggregate can be adopted as the aggregate. Examples include gravel, crushed stone, granulated slag, and recycled aggregate. In addition, refractory aggregates such as siliceous, clay, zircon, high alumina, silicon carbide, graphite, chromium, chromic, magnesia, etc. can be used.

  Any appropriate antifoaming agent can be adopted as the antifoaming agent. For example, the antifoaming agent described in paragraphs [0041] to [0042] of Japanese Patent No. 3683176 can be mentioned.

In the above cement composition, the blending amount and unit water amount per 1 m ³ of concrete are preferably 100 to 185 kg / m ³ , water / unit water amount, for example, in order to produce high durability and high strength concrete. The cement ratio is 10 to 70% by mass, more preferably the unit water amount is 120 to 175 kg / m ³ and the water / cement ratio is 20 to 65% by mass.

  The addition amount when adding the cement admixture of the present invention to the cement composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 8% by mass when the total amount of cement is 100% by mass. %, More preferably 0.1 to 5% by mass. There exists a possibility that it may be inferior to the performance as a cement composition as the said addition amount is less than 0.01 mass%. If the amount added exceeds 10% by mass, the economy may be inferior.

  What is necessary is just to mix | blend said each component with arbitrary appropriate methods, and to adjust the said cement composition. For example, the method of kneading in a mixer is mentioned.

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

<Weight average molecular weight>
Detector: Japan Waters 410 Differential refraction detector Analysis software: Japan Waters Millenium Ver. 3.21
Eluent: Eluent prepared by dissolving 115.6 g of sodium acetate trihydrate in a mixed solution of 10999 g of water and 6001 g of acetonitrile, and further adjusting the pH to 6 with acetic acid. Eluent flow rate: 0.8 ml / min
Column temperature: 40 ° C
Column: manufactured by Tosoh Corporation, TSK Guard Column SWXL + TSKgel G4000SWXL + G3000SWXL + G2000SWXL
Standard substance: polyethylene glycol, peak top molecular weight (Mp) = 272500, 219300, 85000, 46000, 24000, 12600, 4250, 7100, 1470
Calibration curve order: cubic equation

<Concrete test condition A>
(1) Materials used Cement: Ordinary Portland cement (manufactured by Taiheiyo Cement)
Coarse aggregate: Ome hard sandstone crushed fine aggregate: Kimitsu mountain sand, Chiba Prefecture (2) Unit amount (kg / m ³ )
W / C = 36.0
s / a = 47.2
Air = 25.5
Water = 165.0
Cement = 458.3
Stone = 929.7
Sand = 821.7
(3) Mixer used Taiheiyo Kiko TM55 (55 liter forced mixing van type mixer)
Kneading amount = 30 liters (4) Kneading method / measuring method Cement, coarse aggregate and fine aggregate were put into a mixer indoors adjusted to a temperature of 20 ° C. and a humidity of 60%, and kneaded for 10 seconds. . Next, water containing cement admixture was added, and after kneading for 120 seconds, the concrete was discharged. The flow value and air volume of the obtained concrete were measured. The flow value and the air amount were measured in accordance with JIS-A-1101,1128. A sample for compressive strength test was prepared, and the compressive strength after 24 hours was measured.
Specimen preparation: 100 mm × 200 mm Paper specimen molds 3 each Specimen curing: Temperature 20 ° C., humidity 60%, constant temperature and humidity air curing (after 24 hours)
Specimen polishing: Specimen surface polishing (using a specimen polishing finisher)
Compressive strength measurement: Automatic compressive strength meter (Maekawa Seisakusho)

<Concrete test condition B>
(1) Materials used Cement: Ordinary Portland cement (equipped with equal amounts of cement from Taiheiyo Cement, Sumitomo Osaka Cement, and Ube Mitsubishi Cement)
Coarse aggregate: Ome hard sandstone crushed fine aggregate: Kimitsu mountain sand and Oigawa water system land sand (2) Unit amount (kg / m ³ )
W / C = 30.0
s / a = 47.0
Air = 30.0
Water = 172.0
Cement = 573.3
Stone = 866.0
Sand = 750.5
(3) Mixer used Taiheiyo Kiko TM55 (55 liter forced mixing van type mixer)
Kneading amount = 30 liters (4) Kneading method / measuring method In a room adjusted to a temperature of 10 ° C and a humidity of 60%, water containing fine aggregate, cement, and cement admixture is put into the mixer to make the mortar uniform. After kneading until it was, coarse aggregate was added and kneaded for 90 seconds. After that, the concrete was discharged. The flow value and air volume of the obtained concrete were measured. The flow value and the air amount were measured in accordance with JIS-A-1101,1128. A sample for compressive strength test was prepared, and the compressive strength after 24 hours was measured.
Specimen preparation: 100 mm × 200 mm Paper specimen molds 3 each Specimen curing: Temperature 10 ° C., humidity 60%, constant temperature and humidity air curing (after 24 hours)
Specimen polishing: Specimen surface polishing (using a specimen polishing finisher)
Compressive strength measurement: Automatic compressive strength meter (Maekawa Seisakusho)

<Alkanolamine compound (B)>
TEA represented by formula (6), TIPA represented by formula (7), HEEDA represented by formula (9), and HPEDA represented by formula (10) were used.

[Production Example 1]: Production of copolymer (I) In a glass reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux condenser, 403.0 g of ion-exchanged water, 3-methyl-3 -An ethylene oxide 50 mol adduct of buten-1-ol was added in an amount of 1263.8 g of an 80 mass% aqueous solution and 1.8 g of acrylic acid, and the temperature was raised to 58 ° C while introducing nitrogen. Subsequently, a mixed solution of 3.3 g of 30% hydrogen peroxide water and 41.7 g of ion-exchanged water was added, and then a mixed solution of 70.1 g of acrylic acid and 17.5 g of ion-exchanged water was added in 3 hours. -A mixed solution of 1.3 g of ascorbic acid, 2.7 g of 3-mercaptopropionic acid and 194.9 g of ion-exchanged water was added dropwise over 3.5 hours. After the dropwise addition, stirring was further continued at 58 ° C. for 1 hour to complete the polymerization reaction. After cooling, an aqueous sodium hydroxide solution was added to obtain an aqueous solution of copolymer (i) having a pH of 6.5 and a weight average molecular weight of 35,000.

[Production Example 2]: Production of copolymer (b) In a glass reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux condenser, 100.2 g of ion-exchanged water and an average of methallyl alcohol 194.1 g of unsaturated polyalkylene glycol ether to which 50 mol of ethylene oxide was added and 0.35 g of acrylic acid were charged, the inside of the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 58 ° C. under a nitrogen atmosphere. While maintaining the inside of the reaction vessel at 58 ° C., 8.6 g of 2% aqueous hydrogen peroxide solution was added. An acrylic acid aqueous solution consisting of 11.8 g of acrylic acid and 22.4 g of ion-exchanged water was dropped over 3 hours while maintaining the inside of the reaction vessel at 58 ° C., and at the same time, L-ascorbine was added to 36.93 g of ion-exchanged water. An aqueous solution in which 0.22 g of acid and 0.35 g of 3-mercaptopropionic acid were dissolved was dropped over 3.5 hours. Thereafter, the temperature was maintained at 58 ° C. for 2 hours, and then the polymerization reaction was completed. After cooling, an aqueous sodium hydroxide solution was added to obtain an aqueous solution of a copolymer (b) having a pH = 6 and a weight average molecular weight of 37000.

[Production Example 3]: Production of copolymer (c) In a glass reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux condenser, ion-exchanged water 546.0 g, 3-methyl-3 -800.0 g of unsaturated polyalkylene glycol ether obtained by adding 50 mol of ethylene oxide on average to buten-1-ol and 83.0 g of maleic acid were heated to 65 ° C, and then 2.4 g of 30% aqueous hydrogen peroxide solution Was added. Thereto, an aqueous solution in which 0.9 g of L-ascorbic acid was dissolved in 39.1 g of ion-exchanged water was dropped over 1 hour. Thereafter, the polymerization reaction was completed by aging at 65 ° C. for 1 hour. After cooling, an aqueous solution of sodium hydroxide was added to obtain an aqueous solution of copolymer (c) having a pH = 8 and a weight average molecular weight of 30000.

[Production Example 4]: Production of copolymer (d) In a glass reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux condenser, 363.8 g of ion-exchanged water, 3-methyl-3 -2219.1g of 80 mass% aqueous solution of 50-mole ethylene oxide adduct of buten-1-ol and 3.1g of acrylic acid were charged, and it heated up to 58 degreeC, introducing nitrogen. Subsequently, a mixed solution of 5.5 g of 30% hydrogen peroxide water and 61.2 g of ion-exchanged water was added, and then a mixed solution of 118.1 g of acrylic acid and 29.5 g of ion-exchanged water was added in 3 hours. -A mixed solution of 2.1 g of ascorbic acid, 4.4 g of 3-mercaptopropionic acid and 283.1 g of ion-exchanged water was added dropwise over 3.5 hours. After the dropwise addition, stirring was further continued at 58 ° C. for 1 hour to complete the polymerization reaction. After cooling, an aqueous sodium hydroxide solution was added to obtain an aqueous solution of copolymer (d) having pH = 6.5 and a weight average molecular weight of 35,000.

[Production Example 5]: Production of copolymer (e) In a glass reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux condenser, 72.3 g of ion-exchanged water, 3-methyl-3 -Charged 127.7 g of ethylene oxide 50 mol adduct of buten-1-ol, and heated to 58 ° C while introducing nitrogen. Subsequently, after adding 0.7 g of 30% hydrogen peroxide, a mixture of 8.9 g of acrylic acid and 15.5 g of hydroxyethyl acrylate was added in 3 hours, and 0.3 g of L-ascorbic acid and 3-mercaptopropion. A mixed solution of 1.0 g of acid and 26.6 g of ion-exchanged water was added dropwise over 3.5 hours. After the dropwise addition, stirring was further continued at 58 ° C. for 1 hour to complete the polymerization reaction. After cooling, an aqueous solution of sodium hydroxide was added to obtain an aqueous solution of a copolymer (e) having a pH of 5.5 and a weight average molecular weight of 25,000.

[Production Example 6]: Production of Comparative Copolymer (I) 400 g of distilled water was charged into a glass reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux condenser, and nitrogen was stirred. The temperature was raised to 80 ° C. while introducing. Subsequently, a mixed solution of polyethylene glycol methyl ether methacrylate 50% aqueous solution (manufactured by Aldrich) 1223.8 g, acrylic acid 48.1 g, distilled water 48.1 g, 3-mercaptopropionic acid 5.1 g in 4 hours, and 197.9 g of an aqueous solution in which 0.2 g of L-ascorbic acid was dissolved and 199.7 g of an aqueous solution in which 2.0 g of 30% aqueous hydrogen peroxide was dissolved were added dropwise over 5 hours. After the dropwise addition, stirring was further continued at 80 ° C. for 1 hour to complete the polymerization reaction. An aqueous solution of a comparative copolymer (i) having a weight average molecular weight of 30000 was obtained.

[Example 1]
A cement admixture (1) was obtained using the copolymer (I) obtained in Production Example 1 and the alkanolamine compound TIPA under the blending conditions shown in Table 1.
Using the cement admixture (1), the flow value, air amount, and compressive strength (after 24 hours) were measured. The measurement results are shown in Table 2.

[Example 2]
A cement admixture (2) was obtained using the copolymer (I) obtained in Production Example 1 and the alkanolamine compound TIPA under the blending conditions shown in Table 1.
Using the cement admixture (2), the flow value, the air amount, and the compressive strength (after 24 hours) were measured. The measurement results are shown in Table 2.

Example 3
A cement admixture (3) was obtained using the copolymer (I) obtained in Production Example 1 and the alkanolamine compound TEA under the blending conditions shown in Table 1.
Using the cement admixture (3), the flow value, air amount, and compressive strength (after 24 hours) were measured. The measurement results are shown in Table 2.

Example 4
A cement admixture (4) was obtained using the copolymer (I) obtained in Production Example 1 and the alkanolamine compound HPEDA under the blending conditions shown in Table 1.
Using the cement admixture (4), the flow value, air amount, and compressive strength (after 24 hours) were measured. The measurement results are shown in Table 2.

Example 5
A cement admixture (5) was obtained using the copolymer (I) obtained in Production Example 1 and the alkanolamine compound HEEDA under the blending conditions shown in Table 1.
Using the cement admixture (5), the flow value, air volume, and compressive strength (after 24 hours) were measured. The measurement results are shown in Table 2.

Example 6
A cement admixture (6) was obtained using the copolymer (b) obtained in Production Example 2 and the alkanolamine compound TIPA under the blending conditions shown in Table 1.
Using the cement admixture (6), the flow value, air amount, and compressive strength (after 24 hours) were measured. The measurement results are shown in Table 2.

Example 7
A cement admixture (7) was obtained using the copolymer (c) obtained in Production Example 3 and the alkanolamine compound TIPA under the blending conditions shown in Table 1.
Using the cement admixture (7), the flow value, air amount, and compressive strength (after 24 hours) were measured. The measurement results are shown in Table 2.

[Comparative Example 1]
Cement admixture (C1) was obtained using the copolymer (I) obtained in Production Example 1 and no alkanolamine compound under the blending conditions shown in Table 1.
Using the cement admixture (C1), the flow value, air amount, and compressive strength (after 24 hours) were measured. The measurement results are shown in Table 2.

[Comparative Example 2]
A cement admixture (C2) was obtained using the comparative copolymer (I) obtained in Production Example 4 and no alkanolamine compound under the blending conditions shown in Table 1.
Using the cement admixture (C2), the flow value, air amount, and compressive strength (after 24 hours) were measured. The measurement results are shown in Table 2.

[Comparative Example 3]
A cement admixture (C3) was obtained using the comparative copolymer (I) obtained in Production Example 4 and the alkanolamine compound HPEDA under the blending conditions shown in Table 1.
Using the cement admixture (C3), the flow value, the amount of air, and the compressive strength (after 24 hours) were measured. The measurement results are shown in Table 2.

[Comparative Example 4]
A cement admixture (C4) was obtained using the copolymer (b) obtained in Production Example 2 and no alkanolamine compound under the blending conditions shown in Table 1.
Using the cement admixture (C4), the flow value, the amount of air, and the compressive strength (after 24 hours) were measured. The measurement results are shown in Table 2.

[Comparative Example 5]
A cement admixture (C5) was obtained using the copolymer (c) obtained in Production Example 3 and no alkanolamine compound under the blending conditions shown in Table 1.
Using the cement admixture (C5), the flow value, the air amount, and the compressive strength (after 24 hours) were measured. The measurement results are shown in Table 2.

Example 8
Cement admixture (8) using the copolymer (d) obtained in Production Example 2, the copolymer (e) obtained in Production Example 3, and the alkanolamine compound TIPA under the blending conditions shown in Table 1. Got.
Using the cement admixture (8), the flow value, air amount, and compressive strength (after 24 hours) were measured. The measurement results are shown in Table 2.

Example 9
Cement admixture (9) using the copolymer (d) obtained in Production Example 2, the copolymer (e) obtained in Production Example 3, and the alkanolamine compound TIPA under the blending conditions shown in Table 1. Got.
Using the cement admixture (9), the flow value, air amount, and compressive strength (after 24 hours) were measured. The measurement results are shown in Table 2.

[Comparative Example 6]
A cement admixture using the copolymer (d) obtained in Production Example 2 and the copolymer (e) obtained in Production Example 3 without using an alkanolamine compound under the blending conditions shown in Table 1. (C6) was obtained.
Using the cement admixture (C6), the flow value, air amount, and compressive strength (after 24 hours) were measured. The measurement results are shown in Table 2.

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

Claims (2)

Comprising a polycarboxylic acid copolymer (A) and an alkanolamine compound (B),
The polycarboxylic acid copolymer (A) comprises a structural unit derived from an unsaturated polyalkylene glycol ether monomer represented by the formula (1) and an unsaturated carboxylic acid monomer represented by the formula (2). Having a structural unit derived from a monomer,
The unsaturated polyalkylene glycol ether monomer represented by the formula (1) is an adduct obtained by adding 1 to 500 mol of alkylene oxide to 3-methyl-3-buten-1-ol,
The alkanolamine compound (B) is at least one selected from trialkanolamine compounds and tetraalkanolamine compounds,
The content ratio of the alkanolamine compound (B) is 50% by mass or less based on the total amount of the polycarboxylic acid copolymer (A) and the alkanolamine compound (B).
Cement admixture.

(In the formula (1), R ¹ , R ² and R ³ each independently represents a hydrogen atom or a methyl group, R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, The oxyalkylene groups represented by R ^a O may be the same or different, R ^a is an alkylene group having 2 to 18 carbon atoms, and m is the average addition of the oxyalkylene group represented by R ^a O. Represents the number of moles, 1 ≦ m ≦ 500, X represents a divalent alkylene group having 1 to 5 carbon atoms or a divalent arylene group having 6 to 9 carbon atoms, and n is 0 or 1. )

(In formula (2), R ⁵ represents a hydrogen atom, a methyl group, or —CH ₂ COOM ² , and R ⁶ and R ⁷ each independently represent a hydrogen atom, a methyl group, or —COOM ³ . , M ¹ , M ² , and M ³ each independently represent a hydrogen atom, a metal atom, an ammonium group, or an organic ammonium group, and R ⁶ and R ⁷ are not simultaneously —COOM ^3. Also, R ⁷ When R is -COOM ³ , R ⁷ and -COOM ¹ may form an acid anhydride group.) The structural unit derived from the unsaturated polyalkylene glycol ether monomer is a structural unit represented by the formula (3), and the structural unit derived from the unsaturated carboxylic acid monomer is represented by the formula (4). The cement admixture according to claim 1, which is a structural unit.

(In Formula (3), R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a methyl group, R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, The oxyalkylene groups represented by R ^a O may be the same or different, R ^a is an alkylene group having 2 to 18 carbon atoms, and m is the average addition of the oxyalkylene group represented by R ^a O. Represents the number of moles, 1 ≦ m ≦ 500, X represents a divalent alkylene group having 1 to 5 carbon atoms or a divalent arylene group having 6 to 9 carbon atoms, and n is 0 or 1. )

(In Formula (4), R ⁵ represents a hydrogen atom, a methyl group, or —CH ₂ COOM ² , and R ⁶ and R ⁷ each independently represent a hydrogen atom, a methyl group, or —COOM ³⁾ . , M ¹ , M ² , and M ³ each independently represent a hydrogen atom, a metal atom, an ammonium group, or an organic ammonium group, and R ⁶ and R ⁷ are not simultaneously —COOM ^3. Also, R ⁷ When R is -COOM ³ , R ⁷ and -COOM ¹ may form an acid anhydride group.)