JP2001019515A - Cement additive and cement composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cement additive capable of attaining excellent dispersibility and dispersion retainability in a small amount of addition thereof by mainly including each specific two polycarboxylic acid-based polymers. SOLUTION: This cement additive is obtained by including a polycarboxylic acid-based polymer X and another polycarboxylic acid-based polymer Y; wherein the polymer X has respective recurring units of formula I, formula II, formula III and formula IV and other recurring unit(s), satisfying the relationships: T>0 and E1>0, and also satisfying at least one of the following requirements: T/(T+E1+E2)>=0.1, S>0, and n>=110; the polymer Y has recurring unit of formula V and recurring unit having COOM5; in the above formulas, R1, R2, R5, R7, R10 to R13 are each H or a 1-30C hydrocarbon group; R3 is H, phenyl or the like; R4, R8 and R9 are each a 1-30C hydrocarbon group; X1, R6, Rx, Ry and Rz are each an alkylene; M1 to M5 are each H, a metal atom, ammonium group or an organic amine group; S, T, E1 and E2 are each the molar ratio in the polymer; (a) is 1-300; n, m and p are each a positive number; and X2 is carbonyl or a 1-3C hydrocarbon group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cement additive and a cement composition having excellent cement dispersibility.

[0002]

2. Description of the Related Art Cement compositions are widely used for applications such as building exterior wall materials and building structures because they provide cured products having excellent strength and durability. Such a cement composition is usually added with a cement additive in order to enhance air entrainment and fluidity. In recent years, its importance has been recognized, and technical innovation has been actively carried out. .

[0003] The duty of cement additives is to reduce the amount of water to be added, to ensure that the cement composition exhibits sufficient dispersibility, to ensure its fluidity and workability, and to improve durability and strength by reducing the amount of water. At the same time, a good cement composition is obtained while maintaining stable dispersibility over time.

[0004] Japanese Patent No. 2741631 discloses that
Component (a) is a copolymer of maleic anhydride and an allyl alkyl ether of a polyalkylene glycol,
A polyether compound or a salt thereof obtained by half-esterification with an alkyl polyalkylene glycol,
As a component (b), there is disclosed a cement dispersant for preventing a decrease in fluidity of a cement composition comprising a salt of a polycarboxylic acid which is a polymer of a monomer such as (meth) acrylic acid. This cement dispersant attempts to maintain stable dispersibility over time by utilizing the fact that the component (a) has a lower adsorption rate to the cement particles than the component (b).

However, in the component (a) of the cement dispersant, since the allyl alkyl ether of the polyalkylene glycol is a monomer having an oxyalkylene group introduced therein, the larger the average number of moles of the oxyalkylene group, the larger the number of moles. The copolymerizability may decrease, and unreacted monomers may remain when producing a copolymer with maleic anhydride. Further, since the carboxyl group or its base derived from maleic anhydride having an action of adsorbing to cement particles is all half-esterified by alkyl polyalkylene glycol, its adsorbability to cement particles is inferior. Furthermore, since the number of oxyalkylene groups, which are the repeating units of the polyalkylene glycol used for half-esterification, is small, hydrophilicity and steric repulsion to cement are not sufficient.

Further, since the hydrophilicity of the salt of the polycarboxylic acid in the component (b) of the cement dispersant and the steric repulsion to the cement are not sufficient, these components (a) and (b) are used in combination. However, the required dispersibility cannot be obtained.

[0007] JP-A-7-267705 discloses that
As the component (a), a copolymer of a polyalkylene glycol mono (meth) acrylate compound and a (meth) acrylic acid compound and / or a salt thereof, and as the component (b), a polyalkylene glycol mono (meth) acrylate A) a copolymer of an allyl ether compound and maleic anhydride;
Or a hydrolyzate thereof, and / or a salt thereof,
As the component (c), a copolymer of a polyalkylene glycol mono (meth) allyl ether-based compound and a maleic acid ester of the polyalkylene glycol-based compound and / or
Or a cement dispersant containing the salt thereof is disclosed.
This cement dispersant attempts to maintain stable dispersibility over time by utilizing the fact that the component (a) has a high adsorption rate to cement particles and the components (b) and (c) are slow. is there.

However, in component (c) of this cement dispersant, since the polyalkylene glycol mono (meth) allyl ether compound is a monomer having an oxyalkylene group introduced, the average number of moles of oxyalkylene group added is small. The larger, the lower its copolymerizability,
When preparing a copolymer with maleic anhydride, unreacted monomers may remain. Further, most of the carboxyl group or its base derived from maleic anhydride having an action of adsorbing to the cement particles is half-esterified by the polyalkylene glycol-based compound, and thus has poor adsorbability to the cement particles. Further, the number of oxyalkylene groups, which are repeating units of the polyalkylene glycol compound used for half esterification, is 10 or less.
The number is 0 or less, and the hydrophilicity and steric rebound to cement are not sufficient.

Further, since the hydrophilicity of the copolymer and the like in the component (a) and the copolymer and the like in the component (b) of the cement dispersant and the steric repulsion to the cement are not sufficient, these (a) ) Component, (b) component and (c)
Necessary dispersibility cannot be obtained even when the components are used together.

[0010]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and is intended to reduce the amount of water to be added to a cement composition while maintaining a high dispersibility and excellent workability. An object of the present invention is to provide a cement additive which is small in amount, is economical, and has excellent cement dispersion holding properties, and a cement composition using the same.

[0011]

SUMMARY OF THE INVENTION The present invention relates to a cement additive comprising a polycarboxylic acid polymer (X) and a polycarboxylic acid polymer (Y) as main components, wherein the polycarboxylic acid polymer is The compound (X) is represented by the following general formula (1);

[0012]

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Wherein R ¹ and R ² are the same or different and each represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms, and a part of the carbon chain of R ¹ and R ² is They may be combined. R ³ is hydrogen, a phenyl group, an alkylphenyl group, a sulfonated phenyl group, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 1 to 30 carbon atoms, an alkoxyl group having 1 to 30 carbon atoms, -OCOR ^4, - X ¹ OR ⁵ , -O
^{(R 6 O) aR 7,} 1 is selected from the group consisting of -CN
Represents a valent organic group. R ⁴ represents a monovalent hydrocarbon group having 1 to 30 carbon atoms. X ¹ represents a divalent hydrocarbon group having 1 to 3 carbon atoms. R ⁵ and R ^{7 each} represent a hydrogen atom or a carbon atom
Represents 30 monovalent hydrocarbon groups. R ⁶ has 2 to 3 carbon atoms
It represents 0 alkylene group, a is, - (R ⁶ O) - in represents the average number of moles of the oxyalkylene group represented by 1
It is a positive number of 300. S represents the abundance (molar ratio) of the repeating unit in the polycarboxylic acid polymer (X). A repeating unit (A) represented by the following general formula (2);

[0014]

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[Wherein, M ¹ and M ² are the same or different and each represents a hydrogen atom, a metal atom, an ammonium group, or an organic amine group. T is a polycarboxylic acid polymer (X)
Represents the abundance (molar ratio) of the repeating unit in the graph. ]
A repeating unit (B) represented by the following general formula (3);

[0016]

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[In the formula, M ³ represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group. R ⁸ represents a monovalent hydrocarbon group having 1 to 30 carbon atoms. R ^X is the same or different and represents an alkylene group having 2 to 18 carbon atoms, and its main constituent is an ethylene group. n it is, - (R ^X O) - in represents the average number of moles of the oxyalkylene group represented by a positive number. E1 represents the abundance (molar ratio) of the repeating unit in the polycarboxylic acid polymer (X). A repeating unit (C) represented by the following general formula (4);

[0018]

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[In the formula, M ⁴ represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group. R ⁹ represents a monovalent hydrocarbon group having 1 to 30 carbon atoms. R ^Y is the same or different and represents an alkylene group having 2 to 18 carbon atoms, and its main body is an alkylene group having 3 or more carbon atoms. m is-
It represents the average number of moles of the oxyalkylene group represented by (R ^Y O)-and is a positive number. E2 represents the abundance (molar ratio) of the repeating unit in the polycarboxylic acid polymer (X). And the other repeating unit (E) [abundance (molar ratio) of the repeating unit in the polycarboxylic acid polymer (X)]
Is represented by S ′. Wherein the polycarboxylic acid polymer (Y) has the following general formula (5):

[0020]

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[Wherein R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are the same or different and each represent a hydrogen atom or a C 1 -C 1
Represents a monovalent hydrocarbon group. X ² is a carbonyl group, or
Represents a divalent hydrocarbon group having 1 to 3 carbon atoms. R ^Z is the same or different and represents an alkylene group having 2 to 18 carbon atoms;
Its main constituent is an ethylene group. p is, - (R ^Z O) - in represents the average number of moles of the oxyalkylene group represented by
It is a positive number. ] Repeating unit represented by (F), and, -COOM ⁵ (M ⁵ represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group.) Are those having a repeating unit (G) with, S, T, E1, E2 and n in the polycarboxylic acid polymer (X) are
It satisfies the requirements of T> 0 and E1> 0, and also has the following (1), (2) and (3); 3) A cement additive that satisfies at least one requirement of n ≧ 110.

The present invention also relates to a cement additive containing a polycarboxylic acid polymer (Q) and a polycarboxylic acid polymer (R) as main components, wherein the polycarboxylic acid polymer (Q) is The cement setting start time is 375-405 minutes, and the polycarboxylic acid polymer (R) has a cement setting start time of 390-420 minutes, and the polycarboxylic acid polymer (Q) The difference between the cement setting start time and the carboxylic acid-based polymer (R) is 5 to 45 minutes.

The present invention is also a cement composition comprising cement, water and the above-mentioned cement additive.
Hereinafter, the present invention will be described in detail.

The cement additive of the present invention contains a polycarboxylic acid polymer (X) and a polycarboxylic acid polymer (Y) as main components. The polycarboxylic acid polymer (X) is
It exhibits sufficient dispersibility to the cement composition from an early stage, and the polycarboxylic acid polymer (Y) is
The polycarboxylic acid-based polymer (X) exhibits cement dispersibility and retention properties. As used herein, the term “cement dispersion retention” means that the cement composition retains stable dispersibility over time.

The above polycarboxylic acid polymer (X) and the above polycarboxylic acid polymer (Y) may be used alone or in combination of two or more. The content of the polycarboxylic acid-based polymer (X) and the polycarboxylic acid-based polymer (Y) in the cement additive is not particularly limited as long as it is a main component. The weight ratio of the polycarboxylic acid polymer (X) and the polycarboxylic acid polymer (Y) in the cement additive is not particularly limited, but is preferably from 99/1 to 1/99. More preferably, it is 90/10 to 10/90,
It is particularly preferably from 80/20 to 20/80, and more preferably from 70/30 to 30/70.

The polycarboxylic acid polymer (X) in the present invention comprises a repeating unit (A), a repeating unit (B),
It has a repeating unit (C), a repeating unit (D) and another repeating unit (E). In the present specification, having a repeating unit means that the repeating unit is present in the polycarboxylic acid polymer when the amount (molar ratio) of the repeating unit in the polycarboxylic acid polymer is not 0. When the abundance (molar ratio) of the repeating unit in the polycarboxylic acid-based polymer is 0, it means that the repeating unit is not present in the polycarboxylic acid-based polymer.

The repeating unit (A) and the other repeating unit (E) adjust the amount of the repeating unit (B), the repeating unit (C) and the repeating unit (D) in the polymer. The repeating unit (B) is a polycarboxylic acid polymer (X)
Has a function of adsorbing to the cement particles,
The repeating unit (C) has a function of exhibiting the dispersibility of the cement composition due to the hydrophilicity and steric repulsion of the oxyalkylene group, and the repeating unit (D)
Has a function of exerting a suitable air entrainment property of the cement composition due to the foam suppressing property of the oxyalkylene group.

The repeating unit (A) in the polycarboxylic acid polymer (X) is represented by the general formula (1). In this specification, the average number of added moles means an average value of the number of moles of the organic group added in 1 mole of the same repeating unit among the repeating units constituting the polymer.

In the case where R ³ is an alkylphenyl group, an alkyl group, an alkenyl group, an alkoxyl group, —X ¹ OR ⁵ and —O (R ⁶ O) aR ⁷ , when the number of carbon atoms exceeds the above-mentioned number, There is a possibility that the hydrophilicity of the polycarboxylic acid polymer (X) is reduced and the dispersibility of the cement composition is deteriorated.

The repeating unit (A) is a repeating unit composed of styrene, α-olefins, alkyl vinyl ethers or vinyl esters, since the production of the polycarboxylic acid polymer (X) is facilitated. Is preferred. When the repeating unit (A) is a repeating unit composed of styrene, R ¹ and R ² are hydrogen atoms, R ³ is a phenyl group, and when the repeating unit is composed of α-olefins, , When R ¹ and R ² are hydrogen atoms, and R ³ is an alkyl group having 1 to 30 carbon atoms and is a repeating unit composed of alkyl vinyl ethers, R ¹ and R ² are hydrogen atoms, said R ³ is an alkoxyl group having 1 to 30 carbon atoms, when a repeating unit consisting of vinyl esters, the R ¹ and R ² is a hydrogen atom, the R ³ is -OCOR ^4.

The repeating unit (B) in the polycarboxylic acid polymer (X) is represented by the general formula (2). The metal atom is not particularly limited, and examples thereof include a monovalent metal atom such as an alkali metal atom such as sodium and potassium; and a divalent metal atom such as calcium and magnesium. These may be used alone or in combination of two or more. The organic amine group is not particularly limited, and includes, for example, an ethanolamine group, a triethylamine group, and the like. These may be used alone,
Two or more kinds may be used in combination.

--COO in the repeating unit (B)
The M ¹ group and the —COOM ² group are present in the cement composition in the M ^{1 group.}
And M ² dissociate to form a carboxy anion, which has an affinity with the surface of the positively charged cement particles, and has a function of adsorbing the polycarboxylic acid polymer (X) to the cement particles. is there. Therefore, M ¹ and M ² are preferably a hydrogen atom or a monovalent metal atom because they are easily dissociated in the cement composition.

The repeating unit (C) in the polycarboxylic acid polymer (X) is represented by the general formula (3). The -COOM ³ has the same function as -COOM ¹ and -COOM ² in the repeating unit (B). When R ⁸ has more than 30 carbon atoms,
The hydrophilicity of the (R ^x O) nR ⁸ group is weakened, and the dispersibility of the cement composition is poor.

In order to prevent the hydrophilicity of the oxyalkylene group from being impaired and to sufficiently exert the dispersibility of the cement composition, R ⁸ has a carbon number of 1 to 1 such as a methyl group, an ethyl group and a propyl group. In order to sufficiently exhibit the dispersibility of the cement composition and to suppress the separation of the compounding material in the cement composition, an n-butyl group, i- A linear saturated hydrocarbon group having 4 to 8 carbon atoms such as a propyl group, a pentyl group, and a hexyl group is preferable. In order to suppress the separation of the compounding material in the cement composition, a carbon atom such as a lauryl group or a stearyl group is used. The linear saturated hydrocarbon groups of the formulas 9 to 18 are preferable, and these are preferably used in appropriate combination.

In the general formula (3),-(R ^X O)-
When two or more oxyalkylene groups represented by the formula (C) are present in the same repeating unit (C), the oxyalkylene group represented by — (R ^X O) — Any additional form may be used.

R ^X is mainly composed of an ethylene group. In the present specification, “mainly” means that when a plurality of oxyalkylene groups are present in a repeating unit, the occupied majority of the oxyalkylene groups is present. In the present invention, in the above R ^X , most of the oxyalkylene groups are ethylene groups, so that the effect of the repeating unit (C) is produced. The existence of the above means that “the majority is occupied”, so that it can be the “subject” in the present specification.

In the above repeating unit (C), when “occupying most” is represented by the number in n, for example, it is preferably n × 0.5 or more, more preferably n × 0.6, and n × 0 0.7 or more, particularly preferably n × 0.8, and most preferably n × 0.9 or more.

In the above R ^X , an oxyalkylene group other than an ethylene group, which is an alkylene group having 3 or more carbon atoms, is
The polycarboxylic acid-based polymer (X) has a function of exhibiting cement dispersing and retaining properties because it suppresses the hydrolysis of oxyalkylene groups in an alkaline cement composition. In order for the group to exhibit the above-described effects, R ^X other than the ethylene group is preferably a group having a small number of carbon atoms, such as a propylene group or a butylene group.

The repeating unit (D) in the polycarboxylic acid polymer (X) is represented by the general formula (4). -COOM ⁴ has the same function as -COOM ¹ and -COOM ² in the repeating unit (B). When the carbon number of R ⁹ exceeds 30,-
And (R ^Y O) mR ⁹ groups hydrophobicity becomes too strong, and so that the dispersibility of the cement composition is poor.

The above R ⁹ is preferably a monovalent hydrocarbon group having 1 to 25 carbon atoms in order to sufficiently exhibit the dispersibility of the cement composition and obtain a cement composition having an appropriate air entrainment. . Still more preferably, a monovalent hydrocarbon group having 3 to 20 carbon atoms, particularly preferably a monovalent hydrocarbon group having 4 to 15 carbon atoms, more preferably a monovalent hydrocarbon group having 4 to 10 carbon atoms. It is.

In the above general formula (4),-(R ^Y O)-
When in represented by oxyalkylene groups are present two or more in the same repeating unit (C) is, - (R ^Y O) - oxyalkylene groups represented by random addition, block addition, alternating addition or the like Any additional form may be used.

The above R ^Y is mainly composed of an alkylene group having 3 or more carbon atoms. As described above, in the present specification, "mainly" means that when a plurality of oxyalkylene groups are present in the repeating unit, the oxyalkylene group accounts for most of the number of the oxyalkylene groups. . In the present invention, in R ^Y , most of the oxyalkylene group is an alkylene group having 3 or more carbon atoms, so that the effect of the repeating unit (D) is produced. In addition, the presence of an alkylene group having 3 or more carbon atoms means that “the majority” is occupied as described above, so that it can be the “subject” in the present specification.

In the above-mentioned repeating unit (D), when “occupying most” is represented by the number in m, for example, m × 0.5 or more is preferable, m × 0.6 or more is preferable, and m × 0.6 or more is preferable. 0.7 or more is particularly preferable, and m × 0.8
The above is most preferred. Among the ^{R Y O, - (R Y} O) m
An oxypropylene group and an oxybutylene group are preferred from the viewpoint of easy synthesis of-.

The other repeating unit (E) in the polycarboxylic acid polymer (X) includes the repeating unit (A), the repeating unit (B), the repeating unit (C), and the repeating unit (E). It is not particularly limited as long as it is a repeating unit constituting the polycarboxylic acid polymer (X) other than D).

In the above-mentioned polycarboxylic acid polymer (X), the repeating unit (A), the repeating unit (B), the repeating unit (C), the repeating unit (D) and the repeating unit (E) are each one kind or Two or more. In the polycarboxylic acid-based polymer (X), the addition form of the repeating unit (A), the repeating unit (B), the repeating unit (C), the repeating unit (D), and the repeating unit (E) may be random addition, block addition. Any form such as addition and alternate addition may be used.

In the polycarboxylic acid polymer (X), S + T + E1 + E2 + S 'is 1. T and E1 in the polycarboxylic acid polymer (X) are represented by T>
0 and E1> 0. T is 0
, The function of adsorbing the polymer to the cement particles by the —COOM ¹ group and the —COOM ² group of the repeating unit (B) disappears, and when E1 is 0, the oxyalkylene in the repeating unit (C) Since the effect of the hydrophilicity of the group and the steric repulsion on the cement particles cannot be exerted, the cement particles cannot be sufficiently dispersed.

Accordingly, the polycarboxylic acid polymer (X) has the above-mentioned repeating unit (B) and the above-mentioned repeating unit (C) as essential repeating units. At least one of the repeating unit (D) and the repeating unit (E)
And it may not have the repeating unit (A), the repeating unit (D) and the repeating unit (E).

When the polycarboxylic acid polymer (X) has the repeating unit (A) and / or the other repeating unit (E), the polycarboxylic acid polymer (X) is (B) It has a repeating unit for adjusting the abundance of the repeating unit (C) and the repeating unit (D) in the polymer. When the polycarboxylic acid polymer (X) has the repeating unit (D), a cement composition containing a cement additive has an appropriate air entrainment.

S, T, E1, E2 and n in the polycarboxylic acid polymer (X) are as follows: (1), (2) and (3); (1) T / (T + E1 + E2) ≧ 0.1 (2) S> 0 (3) At least one of n ≧ 110 is satisfied. Therefore, it may satisfy only one of the requirements of the above (1), (2) or (3), or may satisfy the requirements of the above (1) and (2), It may satisfy the requirements of the above (1) and (3), or may satisfy the requirements of the above (2) and (3). The above (1), (2) and ( It may satisfy the requirement of 3).

In the above requirement (1), T / (T + E
1 + E2) is less than 0.1, the repeating unit (B)
Since the molar ratio of is considerably less, functions to adsorb the polymer by -COOM ¹ and -COOM ² repeating unit (B) has the cement particles may be decreased. Preferably, T / (T + E1 + E2) ≧ 0.3, more preferably, T / (T + E1 + E2) ≧ 0.5, particularly preferably, T / (T + E1 + E2) ≧ 0.7, and most preferably. , T / (T + E1 + E2) ≧ 0.8.

As described above, by satisfying the requirement (1), the amount of the repeating unit (B) becomes a certain amount or more, and the repeating unit (B), which is a repeating unit having a high adsorption function to cement particles, is used. The function can be more fully exhibited. On the other hand, even when the molar ratio of the repeating unit (B) increases and the molar ratio of the repeating unit (C) decreases, the oxyalkylene group in the repeating unit (C) is mainly composed of an oxyethylene group. , The effect can be sufficiently exhibited. Therefore, the polycarboxylic acid polymer (X) can sufficiently disperse the cement particles.

When the requirement (2) is satisfied, the polycarboxylic acid polymer (X) has the repeating unit (B) and the repeating unit (C) as essential repeating units. Together with the repeating unit (A) as an essential repeating unit,
It may have at least one of the repeating unit (D) and the repeating unit (E), and may not have the repeating unit (D) and the repeating unit (E).

In the requirement (2), if S = 0 and S ′ = 0, the polycarboxylic acid polymer (X)
Has no repeating unit for adjusting the abundance of the repeating unit (B), the repeating unit (C) and the repeating unit (D) in the polymer, and the weight average molecular weight (Mw) of the polymer and It becomes difficult to adjust and set the relationship with the unit abundance.

In the above requirement (2), when S ′> 0, the other repeating unit (E) is composed of a monomer having a polyoxyalkylene group, or the repeating unit (A) When a maleic acid-based monomer providing (B) and (C) and a monomer having low copolymerizability are used, a polyoxyalkylene group may be used when producing the polycarboxylic acid-based polymer (X). It is preferable that S> 0 and S ′ = 0 since the unreacted monomer may remain because the copolymerizability of the monomer having the other monomer is low. .

As described above, when the above requirement (2) is satisfied, the repeating unit (A) is present in the polymer. Therefore, the repeating unit (B), the repeating unit (C) and the repeating unit ( The amount of D) present in the polymer can be adjusted, and the weight average molecular weight (M
It is easy to adjust and set the relationship between w) and the abundance of these repeating units, and there is a risk that unreacted monomers may remain when the polycarboxylic acid polymer (X) is produced. And the production of the polymer becomes easier.

N in the polycarboxylic acid polymer (X) is such that S, T, E1 and E2 in the polycarboxylic acid polymer (X) are at least one of the above (1) and (2). When satisfying the requirements, it is preferable to satisfy 300 ≧ n ≧ 1.

If it exceeds 300, it is difficult to prepare an oxyalkylene group in the production of the polycarboxylic acid polymer (X). If it is less than 1, the cement composition may have poor dispersibility. The range of the upper limit of n is more preferably 280 or less, and further preferably 260
Or less, particularly preferably 250 or less, more particularly preferably 230 or less, most preferably
200 or less. Further, the range of the lower limit of n is more preferably 20 or more, and still more preferably 50 or more.
Or more, particularly preferably 80 or more, more preferably 110 or more, and most preferably 1 or more.
30 or more.

In the above requirement (3), if n is less than 110, the oxyalkylene group in the repeating unit (C) in the polycarboxylic acid polymer (X) adsorbed on the cement particles will have an effect on the cement particles. Since the steric repulsion effect may not be sufficiently exerted, the cement composition may have poor dispersibility. Further, n is preferably 300 or less. The upper limit of n is more preferably 280 or less, and particularly preferably 250
Or less, and most preferably 200 or less. Further, the range of the lower limit of n is more preferably 120
The value is particularly preferably 130 or more, and most preferably 140 or more.

As described above, by satisfying the requirement (3), the synergistic effect of the fact that the oxyalkylene group of the repeating unit (C) is mainly composed of an oxyethylene group and that n is 110 or more is obtained. The repeating unit (C) can sufficiently exert the action of causing the cement particles to sterically repel, and the polycarboxylic acid polymer (X) can sufficiently disperse the cement particles.

The polycarboxylic acid polymer (X) has a repeating unit (B) and a repeating unit (C) as essential repeating units. E1, E2 and n satisfy the requirements of T> 0 and E1> 0, and (1), (3) below: (1) T / (T + E1 + E2) ≧ 0.1 (3) n It is preferable that at least one of the requirements of ≧ 110 is satisfied. Thereby, the function of the repeating unit (B) and the repeating unit (C) is sufficiently exhibited, and the polycarboxylic acid polymer (X) can sufficiently disperse the cement particles.

The polycarboxylic acid polymer (X) comprises a repeating unit (A), a repeating unit (B) and a repeating unit (C) as essential repeating units. S, T and E1 in (X)
Preferably satisfies the requirements of S> 0, T> 0, and E1> 0. Thereby, the action of the repeating unit (A), the repeating unit (B) and the repeating unit (C) is sufficiently exhibited, and the polycarboxylic acid polymer (X) can sufficiently disperse the cement particles. It will be. Also, the weight average molecular weight (Mw) of the polymer
And the amounts of the repeating unit (B) and the repeating unit (C) are easily adjusted and set, and when the polycarboxylic acid polymer (X) is produced, the production of the polymer becomes easy. .

The polycarboxylic acid polymer (X) has a repeating unit (A), a repeating unit (B), a repeating unit (C) and a repeating unit (D) as essential repeating units. S, T, E1 and E2 in the polycarboxylic acid polymer (X) are S> 0, T> 0, E1
> 0 and E2> 0. Thereby, the action of the repeating unit (A), the repeating unit (B), the repeating unit (C) and the repeating unit (D) is sufficiently exerted, and the polycarboxylic acid-based polymer (X) sufficiently disperses the cement particles. Can be dispersed. Further, the relationship between the weight average molecular weight (Mw) of the polymer and the abundance of the repeating unit (B), the repeating unit (C) and the repeating unit (D) can be easily adjusted and set, and the polycarboxylic acid-based polymer can be easily set. When (X) is produced, the production of the polymer becomes easy. Further, the cement composition containing the cement additive has an appropriate air entrainment.

In the repeating unit (C) and the repeating unit (D), na represented by the following formula: na = (n × E1 + mxE2) / (E1 + E2) is an oxyalkylene in the polymer (X). Represents the average number of moles of group added. The na is from 80 to 300 in order that the oxyalkylene group in the repeating unit (C) sufficiently disperses the cement particles and the oxyalkylene group in the repeating unit (D) sufficiently suppresses the foam of the cement composition. Is preferred. More preferably, it is 90 to 250, still more preferably 100 to 2
30, particularly preferably 110 to 200,
Most preferably, it is 120-180.

If E2 is not 0, E1 and E2
Preferably satisfies the relationship of 0.5 ≦ E1 / (E1 + E2) ≦ 0.99. When the molar ratio of the repeating unit (D) is less than 0.5, the molar ratio of the repeating unit (D) is larger than the molar ratio of the repeating unit (C). May not be sufficiently dispersed, and 0.9
When it exceeds 9, since the repeating unit (D) hardly exists, the effect of the oxyalkylene group in the repeating unit (D) cannot be sufficiently exerted, and the foam of the cement composition may not be sufficiently suppressed. is there. More preferably, 0.7 ≦ E1 / (E1 + E2) ≦ 0.9.

As described above, even when the molar ratio of the repeating unit (D) is considerably smaller than the molar ratio of the repeating unit (C), the oxyalkylene group in the repeating unit (D) is replaced by an oxyalkylene group having 3 or more carbon atoms. Since it is a main component, its action can be sufficiently exerted, and the molar ratio of the repeating unit (C) can be set much larger than the molar ratio of the repeating unit (D). The action of the oxyalkylene group mainly comprising the group can be sufficiently exerted.

The weight average molecular weight (Mw) of the polycarboxylic acid polymer (X) in the present invention is preferably 5,000 or more. When it is less than 5000, a function of adsorbing the polymer of the repeating unit (B) to the cement particles,
The effect of sufficiently dispersing the cement particles of the repeating unit (C) may not be sufficiently exhibited. Also, 50
It is preferably 0000 or less. If it exceeds 500,000, the effect of aggregating the cement particles may occur, and the viscosity of the polycarboxylic acid polymer (X) may be too high to make the handling difficult. It is more preferably from 10,000 to 500,000, particularly preferably from 15,000 to 300,000, further preferably from 20,000 to 200,000, and most preferably from 25,000 to 150,000.

In producing the polycarboxylic acid polymer (X) in the present invention, the production method is not particularly limited. For example, the polycarboxylic acid polymer (X)
-1) and polyalkylene glycol (X-2),
A method for producing a polymer for a cement additive to be subjected to an esterification reaction can be applied.

The polycarboxylic acid polymer (X-1) in the above production method is represented by the following general formula (6):

[0069]

Embedded image

[Wherein R ¹ , R ² and R ³ are the same as above. U represents the abundance (molar ratio) of the repeating unit in the polycarboxylic acid polymer (X-1). A repeating unit (H) represented by the following general formula (7);

[0071]

Embedded image

[Wherein V is the abundance (molar ratio) of the repeating unit in the polycarboxylic acid polymer (X-1).
Represents And a repeating unit (J) [polycarboxylic acid polymer (X
The amount (molar ratio) of the repeating unit in -1) is
It is represented by U '. Is a polymer having the formula: Here, the repeating unit (H) forms the repeating unit (A) in the polycarboxylic acid polymer (X), and the repeating unit (I) includes the repeating unit (B) and the repeating unit (C). And a repeating unit (D),
Other repeating units (J) form other repeating units (E). In the polycarboxylic acid polymer (X-1), U + V + U 'is 1.

The weight average molecular weight (Mw) of the polycarboxylic acid polymer (X-1) is preferably 3000 or more. When it is less than 3,000, the polycarboxylic acid-based polymer (X) may not sufficiently exhibit the adsorption and dispersing action on cement particles. Also, 500,000
The following is preferred. If it exceeds 500,000,
There is a possibility of causing the action of coagulating cement particles,
In addition, the viscosity of the polycarboxylic acid polymer (X-1) may be too high to make it difficult to handle. More preferably, it is 8,000 to 300,000, particularly preferably, 10,000 to 200,000, further preferably, 12,000 to 150,000, and most preferably, 15,000 to 100,000.

The polycarboxylic acid polymer (X-1) is not particularly limited as long as it is as described above. For example, a monomer forming the repeating unit (H) and a monomer forming the repeating unit (I) Maleic anhydride as a compound to be
If necessary, a copolymer obtained by copolymerization with a monomer which forms another repeating unit (J) by an ordinary polymerization method may, for example, be mentioned.

The monomer forming the repeating unit (H) is not particularly restricted but includes, for example, styrene; alkyl-substituted styrenes such as methylstyrene, ethylstyrene and propylstyrene; styrenesulfonic acid; ethylene; , Isobutylene, 1-pentene, 1
Α-olefins such as hexene, 1-decene and 1-octadecene; cyclic olefins such as cyclopentene and cyclohexene; dienes such as butadiene, isoprene, 1,3-pentadiene and 2,4-hexadiene; methyl vinyl ether and ethyl Alkyl vinyl ethers such as vinyl ether, propyl vinyl ether, butyl vinyl ether, isopropyl vinyl ether, isobutyl vinyl ether, 1,2-dimethoxyethylene, phenyl vinyl ether, and benzyl vinyl ether; vinyl esters such as vinyl acetate, vinyl propionate, and vinyl butanoate; allyl alcohol , Methallyl alcohol, 3
-Methyl-3-buten-1-ol, 3-methyl-2-
Unsaturated alcohols such as buten-1-ol and 2-methyl-3-buten-2-ol; unsaturated alcohol adducts obtained by etherifying a hydroxyl group of the unsaturated alcohol with a hydrocarbon group having 1 to 30 carbon atoms; vinyl Alcohol has 2 carbon atoms
A vinyl alcohol (poly) alkylene oxide adduct to which 1 to 300 moles of an alkylene oxide of 30 have been added; Poly) alkylene oxide adducts; acrylonitrile, methacrylonitrile and the like. These may be used alone or in combination of two or more.

The monomer forming the other repeating unit (J) is not particularly limited as long as it is other than the monomer forming the repeating unit (H) and the repeating unit (I). For example, the following may be mentioned, and one or more of these may be used.

Unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, citraconic acid and their monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts, or anhydrides thereof; maleic acid, fumaric acid, Unsaturated dicarboxylic acids such as itaconic acid and citraconic acid and C 1-2
Half ester and diester with two alcohols; Half amide and diamide of unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid and citraconic acid with amines having 1 to 22 carbon atoms; alcohols having 1 to 22 carbon atoms Alkyl polyalkylene glycol obtained by adding 1 to 300 moles of oxyalkylene having 2 to 4 carbon atoms to fumaric acid,
Half-esters and diesters with unsaturated dicarboxylic acids such as itaconic acid and citraconic acid; (meth) acrylic acid and monovalent metal salts, ammonium salts and organic amine salts thereof; methoxypolyethylene glycol, ethoxypolyethylene glycol, propoxypolyethylene glycol; Esters of alkoxypolyalkylene glycol such as methoxypolyethylene glycol polypropylene glycol, ethoxypolyethylene glycol polypropylene glycol, propoxypolyethylene glycol polypropylene glycol and (meth) acrylic acid.

Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth)
(Meth) such as butyl acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and glycidyl (meth) acrylate Esters of acrylic acid and alcohol having 1 to 22 carbon atoms; triethylene glycol di (meth)
Acrylate, (poly) ethylene glycol di (meth)
(Poly) alkylene glycol di (meth) acrylates such as acrylate, polypropylene glycol di (meth) acrylate, (poly) ethylene glycol (poly) propylene glycol di (meth) acrylate;
Bifunctional (meth) acrylates such as hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate and trimethylolpropane di (meth) acrylate; (poly) such as triethylene glycol dimaleate and polyethylene glycol dimaleate
Alkylene glycol dimaleates.

Vinyl sulfonate, (meth) allyl sulfonate, 2- (meth) acryloxyethyl sulfonate, 3- (meth) acryloxypropyl sulfonate,
3- (meth) acryloxy-2-hydroxypropylsulfonate, 3- (meth) acryloxy-2-hydroxypropylsulfophenyl ether, 3- (meth) acryloxy-2-hydroxypropyloxysulfobenzoate, 4- (meth) acryloxy Unsaturated sulfonic acids such as butylsulfonate, (meth) acrylamidomethylsulfonic acid, (meth) acrylamidoethylsulfonic acid, 2-methylpropanesulfonic acid (meth) acrylamide, and monovalent and divalent metal salts thereof; Ammonium salts and organic amine salts; alkanediol mono (meth) acrylates such as 1,4-butanediol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, and 1,6-hexanediol mono (meth) acrylate Acri Over preparative like; methyl (meth) 1 Number of carbon and unsaturated monocarboxylic acids as acrylamide
Amides with up to 22 amines; unsaturated amides such as (meth) acrylamide, (meth) acrylalkylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide.

Aminoethyl (meth) acrylate, methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, vinylpyridine, etc. Unsaturated amines; cyanurates such as triallyl cyanurate; allyls such as (meth) allyl alcohol and glycidyl (meth) allyl ether; unsaturated amino compounds such as dimethylaminoethyl (meth) acrylate; polydimethylsiloxane Propylaminomaleamic acid, polydimethylsiloxane aminopropyleneaminomaleamic acid, polydimethylsiloxane-bis- (propylaminomaleamic acid), polydimethylsiloxane-bis- (dipropyleneaminomaleamine De acid), polydimethylsiloxane - (1-propyl-3-acrylate), poly dimethyl siloxane - (1-propyl-3-methacrylate),
Polydimethylsiloxane-bis- (1-propyl-3-
Acrylate), polydimethylsiloxane-bis- (1
-Propyl-3-methacrylate).

Among the polycarboxylic acid-based polymers (X-1), a styrene / maleic anhydride copolymer formed of styrene and maleic anhydride; α-olefin, because it is easily available and inexpensive / Maleic anhydride copolymer; alkyl vinyl ether / maleic anhydride copolymer; vinyl ester / maleic anhydride copolymer. In the above-mentioned alkyl vinyl ether / maleic anhydride copolymer, among alkyl vinyl ethers, a copolymer of a relatively hydrophilic vinyl ether such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether and maleic anhydride is particularly preferable. Among the above-mentioned vinyl ester / maleic anhydride copolymers, particularly preferred are vinyl ester / maleic anhydride copolymers having high hydrophilicity such as vinyl acetate, vinyl propionate and vinyl butanoate.

The above polyalkylene glycol (X-2)
The following general formula ^{(8); HO- (R K} -O) d-R 14 (8) wherein, R ^K are the same or different and each represents an alkylene group having 2 to 18 carbon atoms. d represents the average number of moles of the oxyalkylene group represented by-(R ^K -O)-, and is a positive number. R ¹⁴ represents a hydrocarbon group having 1 to 30 carbon atoms. ] Is represented. The above polyalkylene glycol (X
-2) may be used alone or in combination of two or more.

The above polyalkylene glycol (X-2)
Is not particularly limited as long as it can produce the polycarboxylic acid polymer (X) in the present invention. For example, methanol, ethanol, 2-propanol, 1-butanol, octanol, 2- C1-C30 aliphatic alcohols such as ethyl-1-hexanol, nonyl alcohol, lauryl alcohol, cetyl alcohol, and stearyl alcohol; C3-C30 alicyclic alcohols such as cyclohexanol; phenol, phenylmethanol (Benzyl alcohol), alcohols having a benzene ring such as methylphenol (cresol), p-ethylphenol, dimethylphenol (xylenol), pt-butylphenol, nonylphenol, dodecylphenol, phenylphenol, and naphthol Allyl alcohol, methallyl alcohol, any of alcohols having an alkenyl group of 3-4 carbon atoms such as crotyl alcohol, 2 carbon atoms
And alkoxypolyalkylene glycols to which one or more of the 18 alkylene oxides are added.

The alkoxypolyalkylene glycols are not particularly restricted but include, for example, the following. Methoxy polyethylene glycol, methoxy polyethylene glycol (poly) propylene glycol, methoxy polyethylene glycol (poly) butylene glycol, methoxy polyethylene glycol (poly)
Propylene glycol (poly) butylene glycol, methoxy polypropylene glycol, methoxy polypropylene glycol (poly) ethylene glycol, methoxy polybutylene glycol, methoxy polybutylene glycol (poly) ethylene glycol, ethoxy polyethylene glycol, ethoxy polyethylene glycol (poly) propylene glycol, ethoxy Polyethylene glycol (poly) butylene glycol, ethoxy polyethylene glycol (poly) propylene glycol (poly)
Butylene glycol, ethoxy polypropylene glycol, ethoxy polypropylene glycol (poly) ethylene glycol, ethoxy polybutylene glycol, ethoxy polybutylene glycol (poly) ethylene glycol, propoxy polyethylene glycol, propoxy polyethylene glycol (poly) propylene glycol,
Propoxy polyethylene glycol (poly) butylene glycol, propoxy polyethylene glycol (poly)
Propylene glycol (poly) butylene glycol, propoxy polypropylene glycol, propoxy polypropylene glycol (poly) ethylene glycol, propoxy polybutylene glycol, propoxy polybutylene glycol (poly) ethylene glycol.

Butoxy polyethylene glycol, butoxy polyethylene glycol (poly) propylene glycol, butoxy polyethylene glycol (poly) butylene glycol, butoxy polyethylene glycol (poly)
Propylene glycol (poly) butylene glycol, butoxy polypropylene glycol, butoxy polypropylene glycol (poly) ethylene glycol, butoxy polybutylene glycol, butoxy polybutylene glycol (poly) ethylene glycol, pentoxy polyethylene glycol, pentoxy polyethylene glycol (poly) propylene glycol , Pentoxy polyethylene glycol (poly) butylene glycol, pentoxy polyethylene glycol (poly) propylene glycol (poly) butylene glycol, pentoxy polypropylene glycol, pentoxy polypropylene glycol (poly) ethylene glycol, pentoxy polybutylene glycol, pentoxy poly Butylene glycol (poly) ethylene glycol Hexoxy polyethylene glycol, hexoxy polyethylene glycol (poly) propylene glycol, hexoxy polyethylene glycol (poly) butylene glycol, hexoxy polyethylene glycol (poly) propylene glycol (poly) butylene glycol, hexoxy polypropylene glycol, hexoxy polypropylene glycol ( Poly) ethylene glycol, hexoxypolybutylene glycol,
Hexoxypolybutylene glycol (poly) ethylene glycol, octoxy polyethylene glycol, octoxy polyethylene glycol (poly) propylene glycol, octoxy polyethylene glycol (poly) butylene glycol, octoxy polyethylene glycol (poly) propylene glycol (poly) butylene glycol , Octoxypolypropylene glycol, octoxypolypropylene glycol (poly) ethylene glycol, octoxypolybutylene glycol, octoxypolybutylene glycol (poly) ethylene glycol.

Decanoxy polyethylene glycol, decanoxy polyethylene glycol (poly) propylene glycol, decanoxy polyethylene glycol (poly) butylene glycol, decanoxy polyethylene glycol (poly) propylene glycol (poly) butylene glycol, decanoxy Polypropylene glycol, decanoxy polypropylene glycol (poly) ethylene glycol, decanoxy polybutylene glycol, decanoxy polybutylene glycol (poly) ethylene glycol, dodecanoloxypolyethylene glycol, dodecanoloxypolyethylene glycol (poly) propylene glycol, Dodecanoloxy polyethylene glycol (poly) butylene glycol, dodecanoloxy polyethylene glycol (poly) propylene glycol (Poly) butylene glycol, dodecanoloxy polypropylene glycol, dodecanoloxy polypropylene glycol (poly) ethylene glycol, dodecanoloxypolybutylene glycol, dodecanoloxypolybutylene glycol (poly) ethylene glycol, hexadecanoloxypolyethylene glycol , Hexadecanoxy polyethylene glycol (poly) propylene glycol, hexadecanoloxy polyethylene glycol (poly) butylene glycol, hexadecanoloxy polyethylene glycol (poly) propylene glycol (poly) butylene glycol, hexadecanoloxy polypropylene glycol, Hexadecanoloxy polypropylene glycol (poly) ethylene glycol, hexadecanoloxypolybutylene glycol, hexadecanol Polybutylene glycol (poly) ethylene glycol, octadecanoxy polyethylene glycol, octadecanoxy polyethylene glycol (poly) propylene glycol, octadecanoxy polyethylene glycol (poly) butylene glycol, octadecanoxy polyethylene glycol (poly) propylene Glycol (poly) butylene glycol, octadecanoxy polypropylene glycol,
Octadecanoxy polypropylene glycol (poly) ethylene glycol, octadecanoxy polybutylene glycol, octadecanoxy polybutylene glycol (poly) ethylene glycol.

Phenoxy polyethylene glycol, phenoxy polyethylene glycol (poly) propylene glycol, phenoxy polyethylene glycol (poly) butylene glycol, phenoxy polyethylene glycol (poly) propylene glycol (poly) butylene glycol, phenoxy polypropylene glycol, phenoxy polypropylene glycol (poly) ethylene Glycol, phenoxypolybutylene glycol, phenoxypolybutylene glycol (poly) ethylene glycol, phenylmethoxy polyethylene glycol, phenylmethoxy polyethylene glycol (poly) propylene glycol, phenylmethoxy polyethylene glycol (poly) butylene glycol, phenylmethoxy polyethylene glycol (poly Propylene glycol (poly) butylene glycol, phenyl methoxy polypropylene glycol, phenyl methoxy polypropylene glycol (poly) ethylene glycol, phenyl methoxy polybutylene glycol, phenyl methoxy polybutylene glycol (poly) ethylene glycol, methyl phenoxy polyethylene glycol, methyl phenoxy polyethylene glycol ( Poly) propylene glycol, methylphenoxypolyethylene glycol (poly) butylene glycol, methylphenoxypolyethylene glycol (poly) propylene glycol (poly) butylene glycol, methylphenoxypolypropylene glycol, methylphenoxypolypropylene glycol (poly) ethylene glycol, methylphenoxypolybute Glycol, methylphenoxy polybutylene glycol (poly)
Ethylene glycol, p-ethylphenoxy polyethylene glycol, p-ethylphenoxy polyethylene glycol (poly) propylene glycol, p-ethylphenoxy polyethylene glycol (poly) butylene glycol, p-ethylphenoxypolyethylene glycol (poly) propylene glycol (poly) butylene glycol P-ethylphenoxy polypropylene glycol, p-ethylphenoxy polypropylene glycol (poly) ethylene glycol, p-ethylphenoxypolybutylene glycol, p-ethylphenoxypolybutylene glycol (poly) ethylene glycol.

Dimethyl phenoxy polyethylene glycol, dimethyl phenoxy polyethylene glycol (poly) propylene glycol, dimethyl phenoxy polyethylene glycol (poly) butylene glycol, dimethyl phenoxy polyethylene glycol (poly) propylene glycol (poly) butylene glycol, dimethyl phenoxy polypropylene glycol, dimethyl phenoxy Polypropylene glycol (poly) ethylene glycol, dimethylphenoxypolybutylene glycol, dimethylphenoxypolybutylene glycol (poly) ethylene glycol, pt-butylphenoxypolyethylene glycol, pt-butylphenoxypolyethylene glycol (poly) propylene glycol, p- t-butylphenoxypolyester Len glycol (poly) butylene glycol, pt-butylphenoxy polyethylene glycol (poly) propylene glycol (poly) butylene glycol, pt-butylphenoxy polypropylene glycol, pt-butylphenoxy polypropylene glycol (poly) ethylene glycol, pt-butylphenoxypolybutylene glycol, pt-butylphenoxypolybutylene glycol (poly) ethylene glycol, nonylphenoxypolyethylene glycol, nonylphenoxypolyethylene glycol (poly)
Propylene glycol, nonylphenoxypolyethylene glycol (poly) butylene glycol, nonylphenoxypolyethylene glycol (poly) propylene glycol (poly) butylene glycol, nonylphenoxypolypropylene glycol, nonylphenoxypolypropylene glycol (poly) ethylene glycol, nonylphenoxypolybutylene glycol, nonyl Phenoxypolybutylene glycol (poly) ethylene glycol, dodecylphenoxypolyethylene glycol, dodecylphenoxypolyethylene glycol (poly) propylene glycol, dodecylphenoxypolyethylene glycol (poly) butylene glycol, dodecylphenoxypolyethylene glycol (poly) propylene glycol (poly) butylene glycol Lumpur, dodecyl phenoxy polypropylene glycol, dodecyl phenoxy polypropylene glycol (poly) ethylene glycol dodecyl phenoxy polybutylene glycol, dodecyl phenoxy polybutylene glycol (poly) ethylene glycol.

Phenylphenoxypolyethylene glycol, phenylphenoxypolyethylene glycol (poly) propylene glycol, phenylphenoxypolyethylene glycol (poly) butylene glycol, phenylphenoxypolyethylene glycol (poly) propylene glycol (poly) butylene glycol, phenylphenoxypolypropylene glycol, phenylphenoxy Polypropylene glycol (poly) ethylene glycol, phenylphenoxy polybutylene glycol, phenylphenoxy polybutylene glycol (poly) ethylene glycol, naphthoxy polyethylene glycol, naphthoxy polyethylene glycol (poly) propylene glycol, naphthoxy polyethylene glycol (poly)
Butylene glycol, naphthoxy polyethylene glycol (poly) propylene glycol (poly) butylene glycol, naphthoxy polypropylene glycol, naphthoxy polypropylene glycol (poly) ethylene glycol, naphthoxy polybutylene glycol, naphthoxy polybutylene glycol (poly) ethylene glycol,
Methallyloxypolyethylene glycol, methallyloxypolyethylene glycol (poly) propylene glycol, methallyloxypolyethylene glycol (poly) butylene glycol, methallyloxypolyethylene glycol (poly) propylene glycol (poly) butylene glycol, methallyloxypolypropylene glycol,
Methallyloxypolypropylene glycol (poly) ethylene glycol, methallyloxypolybutylene glycol, methallyloxypolybutylene glycol (poly) ethylene glycol, allyloxypolyethylene glycol, allyloxypolyethylene glycol (poly) propylene glycol, allyloxypolyethylene glycol ( Poly) butylene glycol, allyloxy polyethylene glycol (poly) propylene glycol (poly)
Butylene glycol, allyloxy polypropylene glycol, allyloxy polypropylene glycol (poly) ethylene glycol, allyloxy polybutylene glycol, allyloxy polybutylene glycol (poly) ethylene glycol.

In the method for producing the polycarboxylic acid polymer (X) in the present invention, the esterification reaction includes
A normal esterification method can be used, and is not particularly limited. For example, the reaction can be performed using an esterification catalyst in a solvent and appropriately setting reaction conditions such as reaction time and reaction temperature.

The esterification catalyst is not particularly restricted but includes, for example, acids such as sulfuric acid and p-toluenesulfonic acid; and tertiary amines such as triethylamine, triethanolamine and pyridine. These may be used alone or in combination of two or more.

The above polyalkylene glycol (X
-2) and the above-mentioned polycarboxylic acid polymer (X-1) may be subjected to an esterification reaction. For the alkoxidation of the polyalkylene glycol (X-2), for example, metal hydrides such as sodium hydride and calcium hydride; alkali metals such as sodium; organic metals such as n-butyllithium, methyllithium, and phenyllithium Or the like can be used. Furthermore,
After the esterification reaction, if necessary, some or all of the carboxyl groups in the polymer may be converted to a salt form.

In producing the polycarboxylic acid-based polymer (X), the repeating unit (C) has a polymer having an oxyalkylene group having a large average number of added moles which exerts the effect of hydrophilicity and steric repulsion to cement. In order to produce the union, an oxyalkylene group is introduced into a monomer by an esterification reaction, and a production method of copolymerizing the oxyalkylene group with another monomer is used. The monomer forming the repeating unit (C) may be unreacted and remain due to low copolymerizability with the monomer.

Therefore, the polycarboxylic acid polymer (X-1) and the polyalkylene glycol (X-2) are not used for copolymerizing a monomer having an oxyalkylene group having a large average addition mole number. ) Is preferably applied to a method for producing a polymer for a cement additive to be subjected to an esterification reaction. Thereby, the polycarboxylic acid polymer (X
-1) Since the maleic anhydride group in the repeating unit (I) is easily esterified with the polyalkylene glycol (X-2) having a large number of moles of the oxyalkylene group, the esterification time is shortened and the production efficiency is reduced. It is possible to produce a polycarboxylic acid polymer (X) having an oxyalkylene group having a large average number of moles added to the repeating unit (C) without the risk of unreacted monomers remaining. .

The polycarboxylic acid polymer (Y) in the present invention has a repeating unit (F) and a repeating unit (G) having —COOM ⁵ . The repeating unit (F) has a function of exhibiting the dispersibility of the cement composition over time due to the hydrophilicity and steric repulsion of the oxyalkylene group, and the repeating unit (G) having -COOM ⁵ is , Polycarboxylic acid polymer (Y)
Has a function of adsorbing water on cement particles.

The repeating unit (F) in the polycarboxylic acid polymer (Y) is represented by the general formula (5). When R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are monovalent hydrocarbon groups, when the number of carbon atoms exceeds 30, the hydrophilicity of the polycarboxylic acid polymer (Y) decreases, and There is a possibility that the dispersion retention is inferior. R ¹³ is the same as R ⁸ in the repeating unit (C) of the polycarboxylic acid polymer (X).
Is similar to

In the general formula (5),-(R ^ZO )-
In the case of the oxyalkylene group represented exists two or more in the same repeating unit (F) is, - (R ^Z O) - oxyalkylene groups represented by random addition, block addition, alternating addition or the like Any additional form may be used.
R ^Z is mainly composed of an ethylene group, and is the same as R ^X in the repeating unit (C) of the polycarboxylic acid polymer (X).

The —COOM ⁵ in the repeating unit (G) having —COOM ⁵ is the same as the —COOM ⁵ in the repeating unit (B) of the polycarboxylic acid polymer (X).
Those having the same functions as the ^first and -COOM ^2.

The repeating unit (F) and the above-mentioned —COO
No particular limitation is imposed on the weight ratio in the repeating the polycarboxylic acid polymer with units (G) (Y) in having a M ^5, is preferably 1-99 / 99-1. When the proportion of the repeating unit (F) is smaller than 1/99 and the proportion of the repeating unit (G) is larger, the effect of hydrophilicity of the oxyalkylene group in the repeating unit (F) and steric repulsion to cement particles may not be exhibited. When the proportion of the repeating unit (F) is larger than 99/1 and the proportion of the repeating unit (G) is smaller than 99/1, the function of adsorbing the polymer to the cement particles may be reduced, and the cement dispersibility may be deteriorated. There is a possibility that. It is more preferably from 99 to 50/1 to 50, and particularly preferably 9 to 50/1.
5 to 60/5 to 40, most preferably 95 to 7
0/5 to 30.

The above-mentioned polycarboxylic acid polymer (Y) may optionally contain the above-mentioned repeating unit (F) and the above-mentioned —COO.
M ⁵ may have a repeating unit (G) other than the other repeating units (K) having a.

The above-mentioned polycarboxylic acid polymer (Y) is not particularly limited as long as it is as described above, but is preferably a polyalkylene glycol ester (meth) acrylate polymer and / or an adduct of an unsaturated alcohol polyalkylene glycol. It is preferably a polymer.

The above (meth) acrylic acid polyalkylene glycol ester-based polymer includes the following general formula (9):

[0103]

Embedded image

(Wherein, R ¹⁵ represents a hydrogen atom or a methyl group; M ⁶ is the same as the above M ⁵ ); and a repeating unit (L) represented by the following general formula (10):

[0105]

Embedded image

[Wherein, R ¹⁶ represents a hydrogen atom or a methyl group. R ¹⁷ represents a monovalent hydrocarbon group having 1 to 30 carbon atoms. R ^L is the same or different and represents an alkylene group having 2 to 18 carbon atoms, and its main constituent is an ethylene group. q is
- (R ^L O) - in represents the average number of moles of the oxyalkylene group represented by a positive number from 1 to 300. And a repeating unit (M) represented by the formula:

The above R ¹⁷ is the same as the above R ¹³ . The formula in (10) - (R ^L O) - oxyalkylene groups represented by the in the above general formula (5) - is in the same as the oxyalkylene group represented - (R ^Z O) . The above R ^L is the same as the above R ^Z.

In the polyalkylene glycol ester (meth) acrylate polymer having the repeating unit (L) and the repeating unit (M), R ¹⁶ is represented by-(R ^LO )-due to a steric hindrance effect. It is preferable that the oxyalkylene group to be used is a methyl group, since the oxyalkylene group is less likely to be hydrolyzed and the cement dispersibility is improved.

The number of carbon atoms of R ¹⁷ is set so as not to impair the hydrophilicity of the oxyalkylene group, to sufficiently exert the cement dispersion holding property, and to suppress the separation of the compounding material in the cement composition. In order to do, it is preferably 1 to 10, more preferably 1 to 5,
Particularly preferably, it is 1-3.

The above q indicates that the oxyalkylene group in the repeating unit (M) in the polyalkylene glycol ester (meth) acrylate adsorbed on the cement particles exerts a sufficient steric repulsion effect on the cement particles. In order to demonstrate sufficient cement dispersion retention,
Preferably, it is 10 to 250, more preferably 2
It is 0 to 200, particularly preferably 25 to 150.

The unsaturated alcohol polyalkylene glycol adduct-based polymer includes the following general formula (11):

[0112]

Embedded image

(Wherein M ⁷ and M ⁸ are the same as the above M ⁵ ); and a repeating unit (N) represented by the following general formula (12):

[0114]

Embedded image

[In the formula, R ¹⁸ represents a hydrogen atom or a methyl group. R ¹⁹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms. r is 1 or 2. R ^M is the same or different and represents an alkylene group having 2 to 18 carbon atoms;
Its main constituent is an ethylene group. s is, - (R ^M O) - in represents the average number of moles of the oxyalkylene group represented by
It is a positive number from 1 to 300. ] Having a repeating unit (O) represented by the formula:

The above R ¹⁹ is the same as the above R ¹³ . The formula in (12) - (R ^M O) - oxyalkylene groups represented by the in the above general formula (5) - is in the same as the oxyalkylene group represented - (R ^Z O) . The above R ^M is the same as the above R ^Z.

[0117] The repeating unit (N) and the repeating having units (O) unsaturated alcohol-polyalkylene glycol adduct polymers is, - (R ^M O) - oxyalkylene groups represented by the above by an ether bond Since the oxyalkylene group is present in the repeating unit (O) in a bonded state, the oxyalkylene group is not easily hydrolyzed.

When the above r is 1, the unsaturated alcohol polyalkylene glycol adduct polymer having the repeating unit (N) and the repeating unit (O) is
(Meth) allyl alcohol-based polymer, wherein r is 2
When R ¹⁸ is a methyl group, the polymer is an isoprene alcohol-based polymer.

[0119] In the above (meth) allyl alcohol polymer, the R ¹⁸ is, - (R ^M O) - since it is possible to sufficiently exhibit the effects possessed by the oxyalkylene group represented by is a hydrogen atom Is preferred. Also,
In the (meth) allyl alcohol-based polymer and the isoprene alcohol-based polymer, the s is such that the oxyalkylene group in the repeating unit (O) in the polymer adsorbed on the cement particles has a sufficient steric repulsion to the cement particles. In order to exhibit the effect and exhibit sufficient cement dispersion holding property, it is preferably from 10 to 250, more preferably from 20 to 200, and most preferably from 25 to 200.
１５０150.

The weight average molecular weight (Mw) of the polycarboxylic acid polymer (Y) in the present invention is preferably 5,000 or more. If it is less than 5000, -COOM
^{Since the} function of adsorbing the polymer of the repeating unit (G) having ⁵ to the cement particles and the effect of sufficiently dispersing the cement particles of the repeating unit (F) may not be sufficiently exhibited, the cement dispersion retention May not be fully exhibited. Moreover, it is preferable that it is 500,000 or less. If it exceeds 500,000, the action of aggregating the cement particles may occur, and the viscosity of the polycarboxylic acid polymer (Y) may be too high to make it difficult to handle. More preferably, 1000
0 to 400,000, particularly preferably 15,000
３００300,000, more preferably 1800
0 to 200,000, most preferably 20,000
１００100,000.

In producing the polycarboxylic acid-based polymer (Y) in the present invention, the production method is not particularly limited. For example, the polycarboxylic acid-based polymer (Y) has a monomer forming the repeating unit (F) and -COOM ⁵ . Repeating unit (G)
A method for producing a polymer for a cement additive, which is subjected to copolymerization by a usual polymerization method, using a monomer that forms a polymer and, if necessary, a monomer that forms another repeating unit (K). Can be.

The monomer forming the repeating unit (F) is not particularly limited, and examples thereof include an esterified product of the above-mentioned alkoxypolyalkylene glycols and (meth) acrylic acid; Number 2
Unsaturated alcohol (poly) alkylene oxide adduct to which 1 to 300 moles of alkylene oxide of 1 to 30 moles have been added; the terminal hydroxyl group of the unsaturated alcohol (poly) alkylene oxide adduct is etherified with a hydrocarbon group having 1 to 30 carbon atoms And unsaturated alcohol (poly) alkylene oxide adducts. These may be used alone,
More than one species may be used in combination.

The monomer forming the repeating unit (G) having -COOM ⁵ is not particularly restricted but includes, for example, unsaturated monobasic acids such as (meth) acrylic acid, maleic acid and maleic anhydride; Saturated dibasic acids and the like; monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts and the like of the above-mentioned unsaturated monobasic acids and the above-mentioned unsaturated dibasic acids. These may be used alone or in combination of two or more.

The monomer forming the other repeating unit (K) includes the above repeating unit (F) and the above
It is not particularly limited as long as it is a monomer other than the monomer that forms the repeating unit (G) having COOM ^5, and examples thereof include the following, and one or more of these can be used.

Unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, citraconic acid and their monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts, or anhydrides thereof; Carbon number 1
Half esters and diesters with 22 alcohols;
Half amides and diamides of the unsaturated dicarboxylic acids and amines having 1 to 22 carbon atoms; alkyl polyalkylene glycols obtained by adding 1 to 300 moles of oxyalkylene having 2 to 4 carbon atoms to these alcohols and amines, Half esters and diesters with saturated dicarboxylic acids;
Half-esters and diesters of the unsaturated dicarboxylic acids and glycols having 2 to 4 carbon atoms or polyalkylene glycols having 2 to 300 moles of these glycols to be added; triethylene glycol di (meth) acrylate, (poly) ethylene glycol diester (Poly) alkylene glycol di (meth) acrylates such as (meth) acrylate, polypropylene glycol di (meth) acrylate, (poly) ethylene glycol (poly) propylene glycol di (meth) acrylate; hexanediol di (meth) acrylate, Bifunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate and trimethylolpropane di (meth) acrylate; triethylene glycol dimaleate, polyethylene glycol dimale (Poly) alkylene glycol dimaleate such as theft.

Vinyl sulfonate, (meth) allyl sulfonate, 2- (meth) acryloxyethyl sulfonate, 3- (meth) acryloxypropyl sulfonate,
3- (meth) acryloxy-2-hydroxypropylsulfonate, 3- (meth) acryloxy-2-hydroxypropylsulfophenyl ether, 3- (meth) acryloxy-2-hydroxypropyloxysulfobenzoate, 4- (meth) acryloxy Unsaturated sulfonic acids such as butylsulfonate, (meth) acrylamidomethylsulfonic acid, (meth) acrylamidoethylsulfonic acid, 2-methylpropanesulfonic acid (meth) acrylamide and styrenesulfonic acid, and monovalent metal salts and divalent salts thereof Metal salts, ammonium salts and organic amine salts; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
(Meth) acrylic acid such as 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, methyl crotonate, and glycidyl (meth) acrylate, having 1 to 22 carbon atoms
With an alcohol; unsaturated monocarboxylic acids such as methyl (meth) acrylamide and C 1-2
Amides with two amines; vinyl aromatics such as styrene, α-methylstyrene, vinyltoluene and p-methylstyrene.

Alkanediol mono (meth) acrylates such as 1,4-butanediol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate and 1,6-hexanediol mono (meth) acrylate; butadiene , Isoprene, 2-methyl-1,3
-Dienes such as butadiene and 2-chloro-1,3-butadiene; unsaturated such as (meth) acrylamide, (meth) acrylalkylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide and the like. Amides; unsaturated cyanates such as (meth) acrylonitrile and α-chloroacrylonitrile; vinyl acetate;
Unsaturated esters such as vinyl propionate; (meth)
Unsaturated amines such as aminoethyl acrylate, methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, and vinylpyridine; Divinyl aromatics such as divinylbenzene; cyanurates such as triallyl cyanurate; (meth) allyl alcohol, glycidyl (meth)
Allyls such as allyl ether; unsaturated amino compounds such as dimethylaminoethyl (meth) acrylate.

Vinyl ethers or allyl ethers such as methoxypolyethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, methoxypolyethylene glycol mono (meth) allyl ether, polyethylene glycol mono (meth) allyl ether; polydimethylsiloxane propylaminomaleamic acid; Polydimethylsiloxane aminopropylene aminomaleamic acid, polydimethylsiloxane-bis- (propylaminomaleamic acid), polydimethylsiloxane-bis- (dipropyleneaminomaleamic acid), polydimethylsiloxane- (1-propyl-3)
-Acrylate), polydimethylsiloxane- (1-propyl-3-methacrylate), polydimethylsiloxane-bis- (1-propyl-3-acrylate), polydimethylsiloxane-bis- (1-propyl-3-methacrylate), etc. A siloxane derivative.

The cement additive of the present invention may further comprise, in addition to the above-mentioned polycarboxylic acid-based polymer (X) and polycarboxylic acid-based polymer (Y), dispersibility of the cement composition,
It may also include those that improve the foam-suppressing properties and the like. The cement additive of the present invention can be used in combination with a commonly used cement dispersant.

The above-mentioned cement dispersant is not particularly limited, and examples thereof include the following. Lignin sulfonic acid salt; polyol derivative; naphthalene sulfonic acid formalin condensate; melamine sulfonic acid formalin condensate; polystyrene sulfonic acid salt;
Aminosulfonic acid compounds such as aminoarylsulfonic acid-phenol-formaldehyde condensate as described in JP-A-9 / 9; (a) as described in JP-A-7-267705
As a component, a copolymer of a polyalkylene glycol mono (meth) acrylate compound and a (meth) acrylic compound and / or a salt thereof, and as a component (b), a polyalkylene glycol mono (meth) allyl ether (C) a copolymer of a system compound and maleic anhydride and / or a hydrolyzate thereof and / or a salt thereof;
Patent No. 2508113 describes a cement dispersant containing, as a component, a copolymer of a polyalkylene glycol mono (meth) allyl ether-based compound and a maleic acid ester of a polyalkylene glycol-based compound and / or a salt thereof; As a component A, a copolymer of a polyalkylene glycol ester of (meth) acrylic acid and (meth) acrylic acid (salt), as a component B, a specific polyethylene glycol polypropylene glycol compound,
Concrete admixture comprising a specific surfactant as the component C; polyethylene (propylene) glycol ester of (meth) acrylic acid or polyethylene (propylene) glycol mono (meth) allyl as described in JP-A-62-216950. Ether, (meth) allylsulfonic acid (salt), and (meth) acrylic acid (salt)
A copolymer consisting of

As described in JP-A 1-222657, polyethylene (propylene) glycol ester of (meth) acrylic acid, (meth) allyl sulfonic acid (salt),
And a copolymer consisting of (meth) acrylic acid (salt); as described in JP-B-5-36377, polyethylene (propylene) glycol ester of (meth) acrylic acid, (meth) allylsulfonic acid (salt) or p- (meth) allyloxybenzenesulfonic acid (salt), and
Copolymer of (meth) acrylic acid (salt);
Copolymers of polyethylene glycol mono (meth) allyl ether and maleic acid (salt) as described in JP-A-149056; polyethylene glycol esters of (meth) acrylic acid as described in JP-A-5-170501, (Meth) allylsulfonic acid (salt), (meth) acrylic acid (salt), alkanediol mono (meth) acrylate, polyalkylene glycol mono (meth) acrylate, and α, β-unsaturated having an amide group in the molecule Copolymers composed of monomers; polyethylene glycol mono (meth) allyl ether, polyethylene glycol mono (meth) acrylate, alkyl (meth) acrylate, (meth) acrylic acid as described in JP-A-6-191918 (Salt), and (meth) allylsulfonic acid (salt) or Copolymer of p- (meth) allyloxybenzenesulfonic acid (salt); JP-A-5-432
No. 88, a copolymer of an alkoxypolyalkylene glycol monoallyl ether and maleic anhydride, or a hydrolyzate thereof, or a salt thereof; a polyethylene glycol monomer as described in JP-B-58-38380. Copolymers consisting of allyl ether, maleic acid, and monomers copolymerizable with these monomers, or salts or esters thereof.

As described in JP-B-59-18338, polyalkylene glycol mono (meth) acrylate monomers, (meth) acrylic monomers, and
Copolymers composed of monomers copolymerizable with these monomers; (meth) acrylic acid esters having a sulfonic acid group as described in JP-A-62-119147, and copolymerizable therewith if necessary. Copolymer consisting of various monomers or a salt thereof; a copolymer of alkoxypolyalkylene glycol monoallyl ether and maleic anhydride as described in JP-A-6-271347, and having an alkenyl group at a terminal Esterification reaction product with a polyoxyalkylene derivative; a copolymer of an alkoxypolyalkylene glycol monoallyl ether and maleic anhydride as described in JP-A-6-298555, and a polyoxyalkylene derivative having a hydroxyl group at a terminal. Esterification product of 3-methyl-3-butene-1- as described in JP-A-62-68806. Alkenyl ether-based monomer, unsaturated carboxylic acid-based monomer obtained by adding ethylene oxide or the like to a specific unsaturated alcohol such as alcohol, and a copolymer comprising a monomer copolymerizable with these monomers. Coalescing, or
Polycarboxylic acids (salts) such as salts thereof. These cement dispersants may be used alone or in combination of two or more.

When the above cement dispersant is used in combination,
The weight ratio of the cement additive of the present invention to the cement dispersant is preferably 5 to 95:95 to 5. More preferably, it is 10-90: 90-10.

Further, the cement additive of the present invention can be used in combination with other cement additives. The other cement additives are not particularly limited, for example,
Other known cement additives (materials) such as those shown below are included.

(1) Water-soluble polymer: unsaturated carboxylic acid polymerization such as polyacrylic acid (sodium), polymethacrylic acid (sodium), polymaleic acid (sodium), and sodium salt of acrylic acid / maleic acid copolymer object;
Polyoxyethylene or polyoxypropylene polymers such as polyethylene glycol and polypropylene glycol or copolymers thereof; methylcellulose,
Nonionic cellulose ethers such as ethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, carboxyethylcellulose, and hydroxypropylcellulose; yeast glucan, xanthan gum, β-1,3 glucans (either linear or branched) Polysaccharides produced by microbial fermentation, such as curdlan, baramiron, bakiman, scleroglucan, laminaran, etc.); polyacrylamide; polyvinyl alcohol; starch; starch phosphate; sodium alginate; gelatin; Acrylic acid copolymer having an amino group therein and a quaternary compound thereof.

(2) Polymer emulsions: copolymers of various vinyl monomers such as alkyl (meth) acrylate and the like. (3) retarders: gluconic acid, glucoheptonic acid, arabonic acid, malic acid or citric acid, and oxycarboxylic acids such as inorganic salts or organic salts such as sodium, potassium, calcium, magnesium, ammonium, and triethanolamine; Acids; monosaccharides such as glucose, fructose, galactose, saccharose, xylose, apiose, ribose, isomerized sugars, oligosaccharides such as disaccharides and trisaccharides, oligosaccharides such as dextrin, and polysaccharides such as dextran; Sugars such as molasses; sugar alcohols such as sorbitol; magnesium silicofluoride; phosphoric acid and salts or borate esters thereof; aminocarboxylic acids and salts thereof; alkali-soluble proteins; humic acid; tannic acid; Polyhydric alcohol; aminotri (methylene phosphonic acid) 1-hydroxyethylidene--1,
1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and phosphonic acids such as alkali metal salts and alkaline earth metal salts thereof, and derivatives thereof.

(4) Early strength agent / promoter: calcium chloride,
Calcium nitrite, calcium nitrate, calcium bromide,
Soluble calcium salts such as 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) Mineral oil-based antifoaming agents: kerosene, liquid paraffin and the like. (6) Oil-based antifoaming agents: animal and vegetable oils, sesame oil, castor oil, alkylene oxide adducts thereof and the like. (7) Fatty acid antifoaming agents: oleic acid, stearic acid, alkylene oxide adducts thereof and the like. (8) Fatty acid ester antifoaming agents: glycerin monoricinoleate, alkenyl succinic acid derivatives, sorbitol monolaurate, sorbitol trioleate, natural wax and the like.

(9) Oxyalkylene-based antifoaming agents: polyoxyalkylenes such as (poly) oxyethylene (poly) oxypropylene adduct; diethylene glycol heptyl ether, polyoxyethylene oleyl ether;
(Poly) oxyalkyl ethers such as polyoxypropylene butyl ether, polyoxyethylene polyoxypropylene 2-ethylhexyl ether, and oxyethyleneoxypropylene adducts to higher alcohols having 12 to 14 carbon atoms; polyoxypropylene phenyl ether, polyoxy (Poly) oxyalkylene (alkyl) aryl ethers such as ethylene nonylphenyl ether; 2,4,7,9-tetramethyl-5-decyne-
4,7-diol, 2,5-dimethyl-3-hexyne-
Acetylene ethers obtained by addition-polymerizing an alkylene oxide to acetylene alcohol such as 2,5-diol and 3-methyl-1-butyn-3-ol; diethylene glycol oleate, diethylene glycol laurate, ethylene glycol distearate and the like. (Poly) oxyalkylene fatty acid esters;
(Poly) oxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan trioleate; (poly) oxy such as sodium polyoxypropylene methyl ether sulfate and sodium polyoxyethylene dodecyl phenol ether sulfate Alkylene alkyl (aryl) ether sulfates; (poly)
(Poly) such as oxyethylene stearyl phosphate
Oxyalkylene alkyl phosphates; (poly) oxyalkylene alkylamines such as polyoxyethylene laurylamine; polyoxyalkylene amide;

(10) Alcohol antifoaming agents: octyl alcohol, hexadecyl alcohol, acetylene alcohol, glycols and the like. (11) Amide-based antifoaming agent: acrylate polyamine and the like. (12) Phosphate ester antifoam: tributyl phosphate,
Sodium octyl phosphate and the like.

(13) Metal soap-based defoaming agents: aluminum stearate, calcium oleate and the like. (14) silicone antifoaming agent: dimethyl silicone oil,
Silicone paste, silicone emulsion, organically modified polysiloxane (polyorganosiloxane such as dimethylpolysiloxane), fluorosilicone oil and the like.

(15) AE agent: resin soap, saturated or unsaturated fatty acid, sodium hydroxystearate, lauryl sulfate, ABS (alkylbenzenesulfonic acid), LAS (linear alkylbenzenesulfonic acid),
Alkane sulfonate, polyoxyethylene alkyl (phenyl) ether, polyoxyethylene alkyl (phenyl) ether sulfate or salt thereof, polyoxyethylene alkyl (phenyl) ether phosphate or salt thereof, protein material, alkenyl sulfosuccinic acid, α- Olefin sulfonates and the like.

(16) Other surfactants: 6 to 3 molecules per molecule such as octadecyl alcohol and stearyl alcohol.
Aliphatic monohydric alcohol having 0 carbon atoms, alicyclic monohydric alcohol having 6 to 30 carbon atoms in a molecule such as abiethyl alcohol, 6 to 30 carbon atoms in a molecule such as dodecyl mercaptan, etc. Monovalent mercaptans having atoms, nonylphenols and the like, alkylphenols having 6 to 30 carbon atoms in the molecule, dodecylamines and the like having 6 to 30 carbon atoms in the molecule, molecules such as lauric acid and stearic acid Polyalkylene oxide derivatives in which an alkylene oxide such as ethylene oxide or propylene oxide is added in an amount of 10 mol or more to a carboxylic acid having 6 to 30 carbon atoms therein; and may have an alkyl group or an alkoxyl group as a substituent. Alkyl diphenyl ether in which two phenyl groups having a sulfone group are ether-bonded Rusuruhon acid salts; various anionic surfactants; alkylamine acetates, various cationic surfactants such as alkyl trimethyl ammonium chloride; and various nonionic surfactants; various amphoteric surfactants.

(17) Waterproofing agents: fatty acids (salts), fatty acid esters, oils and fats, silicone, paraffin, asphalt,
Wax and the like. (18) Rust inhibitors: nitrites, phosphates, zinc oxide and the like. (19) Crack reducing agents: polyoxyalkyl ethers; alkanediols such as 2-methyl-2,4-pentanediol and the like. (20) Expansive materials: ettringite, coal, etc.

Other known cement additives (materials) include cement wetting agents, thickening agents, separation reducing agents, flocculants,
Drying shrinkage reducing agent, strength enhancer, self-leveling agent, rust inhibitor, color difference agent, fungicide, blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, gypsum, etc. be able to. These known cement additives (materials) may be used alone or in combination of two or more.

The cement additive of the present invention is capable of sufficiently adsorbing the polycarboxylic acid polymer (X) to the cement particles, and has a hydrophilic property and a cement property that an oxyalkylene group mainly composed of an oxyethylene group has. By the steric repulsion effect on the particles, the dispersibility can be improved by suppressing the aggregation of the cement particles. Further, since the oxyalkylene group mainly composed of the oxyethylene group of the polycarboxylic acid polymer (Y) is hardly hydrolyzed even in a cement alkali having a pH of about 12, the action of the oxyalkylene group is exerted with time. can do.

As described above, the polycarboxylic acid-based polymer (X) having excellent dispersibility of the cement composition and the polycarboxylic acid-based polymer (Y) capable of exhibiting the action of the oxyalkylene group with the lapse of time. ) Can be used in combination to exert an excellent cement dispersion retention property by the synergistic action of these.

Therefore, the cement additive of the present invention can impart sufficient dispersibility to the cement composition even if the amount of water to be added is small, and can reduce the water content of the cement composition. Since it is excellent in dispersion retention, the durability, workability, and strength of the cement composition can be improved.

In addition, the cement additive of the present invention can reduce the amount of addition in order to secure constant workability in various cement compositions over time, as compared with the conventional cement additive. Since the composition is widely used for applications such as building exterior wall materials and building structures, the composition has excellent economic effects.

The second cement additive of the present invention contains a polycarboxylic acid polymer (Q) and a polycarboxylic acid polymer (R) as main components. The polycarboxylic acid polymer (Q) and the polycarboxylic acid polymer (R) may be used alone or in combination of two or more.
The content of the polycarboxylic acid-based polymer (Q) and the polycarboxylic acid-based polymer (R) in the cement additive is not particularly limited as long as it is a main component. The weight ratio of the polycarboxylic acid-based polymer (Q) and the polycarboxylic acid-based polymer (R) in the cement additive is not particularly limited as long as the effects of the second present invention are exhibited.

The polycarboxylic acid polymer (Q) had a cement setting time of 375-405 minutes, and the polycarboxylic acid polymer (R) had a cement setting time of 390-420 minutes. The difference in the cement setting start time between the polycarboxylic acid polymer (Q) and the polycarboxylic acid polymer (R) is 5 to 45 minutes.

The above-mentioned cement setting start time is defined as the mortar containing the polymer in accordance with JIS R using a Vicat needle device.
It means the setting start time of cement as measured according to 5201. The mortar was 400 g of Pacific Portland Cement (trade name, manufactured by Taiheiyo Co., Ltd.),
800 g of Toyoura standard sand is kneaded with a mortar mixer at low speed for 30 seconds, and then 240 g of water containing the polymer is kneaded with cement so that the solids content% with respect to the cement weight of the polymer is 0.12. It is prepared by throwing into a mixture with sand and kneading at a high speed for 3 minutes.

The polycarboxylic acid polymer (Q) and the polycarboxylic acid polymer (R) are not particularly limited as long as they are polycarboxylic acid polymers satisfying the above requirements. A polycarboxylic acid-based polymer or the like in which an element related to a cement setting start time in the polymer is appropriately set so as to satisfy the above conditions may be used.

The factors relating to the cement setting onset time in the above polymer are not particularly limited. For example, the structure of the repeating unit in the polymer, the average number of moles of the oxyalkylene group in the repeating unit, and the presence of the repeating unit amount,
Factors related to the properties of the polymer, such as the weight average molecular weight (Mw) of the polymer, may be mentioned.

As the polycarboxylic acid polymer (R), the repeating unit (L) represented by the general formula (9) and the repeating unit (M) represented by the general formula (10) are used. (Meth) acrylic acid polyalkylene glycol ester-based polymer.

In the polyalkylene glycol ester (meth) acrylate polymer having the repeating unit (L) and the repeating unit (M), R ¹⁶ is preferably a methyl group. The carbon number of R ¹⁷ is preferably 1 to 10, more preferably 1 to 10.
To 5, and particularly preferably 1 to 3. Further, the above q is preferably 10 to 250, more preferably 20 to 200, and particularly preferably 25 to 1
50.

The cement additive according to the second aspect of the present invention comprises, in addition to the above-mentioned polycarboxylic acid-based polymer (Q) and polycarboxylic acid-based polymer (R), a dispersibility of a cement composition, It may also include those that improve the foam-suppressing properties and the like. The cement additive of the second aspect of the present invention can be used in combination with the above-mentioned commonly used cement dispersant.

Further, the second cement additive of the present invention comprises:
It can also be used in combination with other cement additives. The other cement additives are not particularly limited,
For example, other known cement additives (materials) as described above can be used.

The cement additive of the second aspect of the present invention has sufficient cement dispersing and retaining properties, whereby the durability, workability and strength of the cement composition can be improved.

The cement additive of the present invention can be used in addition to a cement composition such as cement paste, mortar, concrete and the like. The cement composition is not particularly limited, and examples thereof include commonly used cement compositions including cement, water, fine aggregate, coarse aggregate and the like.

The cement is not particularly limited, and includes, for example, portland cements of ordinary, fast strength, super fast strength, moderate heat, white color, etc .; mixed portland cements such as alumina cement, fly ash cement, blast furnace cement, silica cement, etc. Is mentioned.

1 m of concrete of the above cement^Three Hit
Although there is no particular limitation on the blending amount and unit water amount of
Water quantity 100 to 185 kg / m^Three , Water / cement ratio = 1
Preferably it is 0-70%. More preferably,
120-175Kg / m ^Three , Water / cement ratio = 2
0 to 65%.

The method and amount of the cement additive of the present invention are not particularly limited. Therefore, as an addition method, the components constituting the cement additive of the present invention may be added simultaneously or separately. Further, it may be added at once, or may be added in several times. The amount of addition is preferably such that the total amount of the polycarboxylic acid-based polymer in the present invention is 0.01 to 10% by weight based on the total weight of cement. When the content is less than 0.01% by weight, the cement dispersion holding property may be inferior,
If it exceeds 10% by weight, economic efficiency will be poor. In addition, the said weight% is a value of solid content conversion.

The cement composition to which the cement additive of the present invention has been added exhibits sufficient dispersibility and excellent fluidity, and also has excellent cement dispersibility and retention. Workability and strength can be improved.

Further, since the amount of water to be added is small, the air entrainment is moderate, and the cement dispersion and retention properties are excellent, a hardened cement having a stable strength can be obtained. Excellent. The above cement composition is also one of the present invention.

[0166]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

In the examples, the weight average molecular weight (Mw) of the polymer was measured under the following conditions. Measurement model: Millenium system (product name, W
detectors) Detector: 410RI detector (trade name, Waters)
Column used: TSK-GEL G4000SWXL, T
SK-GEL G3000SWXL or TSK-GEL
G2000SWXL (both trade names, manufactured by Tosoh Corporation)
Were used in series in the order of G4000, G3000, and G2000. Eluent used: 1765 g of acetonitrile, 3235 g of water
And 34 g of sodium acetate trihydrate with acetic acid at pH 6.0.
Was used. Flow rate: 1.0 ml / min Measurement temperature: 25 ° C. Standard sample: weight average molecular weight (Mw) of 170,000
85,000, 46000, 26000, 12600, 7
100 polyethylene glycols were used.

Production Example 1 Ethyl vinyl ether / ethyl vinyl ether was placed in a glass reactor equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser.
4 g of a maleic anhydride copolymer (having a molar ratio of ethyl vinyl ether and maleic anhydride of 0.5 / 0.5),
Then, 24.0 g of dehydrated tetrahydrofuran was charged to dissolve the ethyl vinyl ether / maleic anhydride copolymer. Next, 0.2 g of sodium hydride was added to a solution in which 8.0 g of methoxypolyethylene glycol (average number of moles of ethylene oxide added: 25) was dissolved in 24.0 g of dehydrated tetrahydrofuran to separately prepare a methoxypolyethylene glycol alkoxide solution. The alkoxide solution was added dropwise to the reaction vessel at room temperature. After the dropwise addition, the reaction was continued for 24 hours while maintaining the reaction temperature at 55 ° C.
After completion of the reaction, tetrahydrofuran was distilled off with an evaporator, and water and a 30% aqueous sodium hydroxide solution were added.
The solution was adjusted to pH 7.0 to obtain a polycarboxylic acid polymer (X1).

Production Example 2 Ethyl vinyl ether / maleic anhydride copolymer (4 g) and dehydrated tetrahydrofuran (40 g) were charged into the same glass reaction vessel as in Production Example 1, and the ethyl vinyl ether / maleic anhydride copolymer was dissolved. . Then, methoxypolyethylene glycol (average number of moles of ethylene oxide added 25) 1 was added to 40 g of dehydrated tetrahydrofuran.
0.4 g of sodium hydride is added to a solution in which 6.0 g is dissolved.
Was added to separately prepare a methoxypolyethylene glycol alkoxide solution, and this alkoxide solution was dropped into the reaction vessel at room temperature. After the dropwise addition, the reaction was continued for 24 hours while maintaining the reaction temperature at 55 ° C. After completion of the reaction, tetrahydrofuran was distilled off with an evaporator, and water and a 30% aqueous sodium hydroxide solution were added to adjust the solution to pH 7.0 to obtain a polycarboxylic acid polymer (X2).

Production Example 3 In a glass reaction vessel similar to that of Production Example 1, 4 g of ethyl vinyl ether / maleic anhydride copolymer and 61 g of dehydrated tetrahydrofuran were charged, and the ethyl vinyl ether / maleic anhydride copolymer was dissolved. . Then, methoxypolyethylene glycol (average number of moles of ethylene oxide added 25) 2 was added to 61 g of dehydrated tetrahydrofuran.
Sodium hydride 0.68 was added to the solution in which 6.6 g was dissolved.
g was added to separately prepare a methoxypolyethylene glycol alkoxide solution, and this alkoxide solution was dropped into the reaction vessel at room temperature. After the dropwise addition, the reaction was continued for 24 hours while maintaining the reaction temperature at 55 ° C. After completion of the reaction, tetrahydrofuran was distilled off using an evaporator, and the residue was mixed with water at 30%.
An aqueous sodium hydroxide solution was added to adjust the solution to pH 7.0.
To obtain a polycarboxylic acid polymer (X3).

Production Example 4 In a glass reaction vessel similar to that of Production Example 1, 4 g of ethyl vinyl ether / maleic anhydride copolymer and 40 g of dehydrated tetrahydrofuran were charged, and the ethyl vinyl ether / maleic anhydride copolymer was dissolved. . Next, methoxypolyethylene glycol (average number of moles of ethylene oxide added 150) 1 was added to 40 g of dehydrated tetrahydrofuran.
To a solution in which 5.6 g was dissolved, 0.07% of sodium hydride was added.
g was added to separately prepare a methoxypolyethylene glycol alkoxide solution, and this alkoxide solution was dropped into the reaction vessel at room temperature. After the dropwise addition, the reaction was continued for 24 hours while maintaining the reaction temperature at 55 ° C. After completion of the reaction, tetrahydrofuran was distilled off using an evaporator, and the residue was mixed with water at 30%.
An aqueous sodium hydroxide solution was added to adjust the solution to pH 7.0.
To obtain a polycarboxylic acid polymer (X4).

Production Example 5 In a glass reaction vessel similar to that of Production Example 1, 4 g of ethyl vinyl ether / maleic anhydride copolymer and 40 g of dehydrated tetrahydrofuran were charged, and the ethyl vinyl ether / maleic anhydride copolymer was dissolved. . Next, methoxypolyethylene glycol (average number of moles of ethylene oxide added 150) 1 was added to 40 g of dehydrated tetrahydrofuran.
To a solution in which 5.6 g and 0.6 g of butoxy polypropylene glycol (average number of moles of propylene oxide added: 20) were dissolved, 0.09 g of sodium hydride was added to separately prepare a methoxypolyethylene glycol alkoxide / butoxy polypropylene glycol alkoxide solution. This alkoxide solution was added dropwise to the reaction vessel at room temperature. After the dropwise addition, the reaction was continued for 24 hours while maintaining the reaction temperature at 55 ° C. After completion of the reaction, tetrahydrofuran was distilled off using an evaporator, and water and a 30% aqueous sodium hydroxide solution were added to adjust the solution to pH 7.0 to obtain a polycarboxylic acid polymer (X5).

Production Example 6 4 g of a styrene / maleic anhydride copolymer (having a styrene / maleic anhydride molar ratio of 0.5 / 0.5) was placed in the same glass reactor as in Production Example 1, and , 32 g of dehydrated tetrahydrofuran, and charged with ethyl vinyl ether /
The maleic anhydride copolymer was dissolved. Next, methoxypolyethylene glycol (average number of moles of ethylene oxide added 150) 1 was added to 32 g of dehydrated tetrahydrofuran.
To a solution in which 3.1 g is dissolved, add 0.07
g was added to separately prepare a methoxypolyethylene glycol alkoxide solution, and this alkoxide solution was dropped into the reaction vessel at room temperature. After the dropwise addition, the reaction was continued for 24 hours while maintaining the reaction temperature at 55 ° C. After completion of the reaction, tetrahydrofuran was distilled off using an evaporator, and the residue was mixed with water at 30%.
An aqueous sodium hydroxide solution was added to adjust the solution to pH 7.0.
To obtain a polycarboxylic acid polymer (X6).

Production Example 7 A glass reaction vessel similar to that of Production Example 1 was charged with 4 g of a styrene / maleic anhydride copolymer and 32 g of dehydrated tetrahydrofuran, and the ethyl vinyl ether / maleic anhydride copolymer was dissolved. Then, 0.09 g of sodium hydride was added to a solution obtained by dissolving 13.1 g of methoxypolyethylene glycol (average mole number of ethylene oxide 150) and 0.6 g of butoxy polypropylene glycol (average mole number of propylene oxide 20) in 32 g of dehydrated tetrahydrofuran. Was added to separately prepare a methoxypolyethylene glycol alkoxide / butoxypolypropylene glycol alkoxide solution, and this alkoxide solution was dropped into the reaction vessel at room temperature. After the dropwise addition, the reaction was continued for 24 hours while maintaining the reaction temperature at 55 ° C. After completion of the reaction, tetrahydrofuran was distilled off using an evaporator, and water and a 30% aqueous sodium hydroxide solution were added to adjust the solution to pH 7.0 to obtain a polycarboxylic acid polymer (X7).

In the polycarboxylic acid polymers (X1) to (X7) obtained in Production Examples 1 to 7, S, T, E1,
Table 1 shows values of E2, T / (T + E1 + E2) and n, and the weight average molecular weight (Mw) of the polymer.

[0176]

[Table 1]

Production Example 8 100.6 g of water was placed in the same glass reaction vessel as in Production Example 1.
And the inside of the reaction vessel was replaced with nitrogen under stirring, and heated to 80 ° C. in a nitrogen atmosphere. Next, 121.2 g of methoxypolyethylene glycol monomethacrylate (average number of moles of added ethylene oxide: 25) and 1 methacrylic acid
3.8 g, mercaptopropionic acid 0.7 g and water 3
An aqueous mixture solution consisting of 3.5 g and 24 g of a 5% aqueous ammonium persulfate solution were each added dropwise over 4 hours. After completion of the dropwise addition, 5 g of a 5% ammonium persulfate aqueous solution was further added dropwise over 1 hour. Thereafter, the reaction temperature was maintained at 80 ° C.
The reaction was continued for a period of time to complete the polymerization reaction. After completion of the reaction, neutralize the solution with a 30% aqueous sodium hydroxide solution,
A polycarboxylic acid polymer (Y1) was obtained.

Production Example 9 In a glass reaction vessel similar to that of Production Example 1, 3-methyl-3 was added.
An unsaturated alcohol 50 obtained by adding ethylene oxide so that the average number of moles added to buten-1-ol becomes 35;
g, 6.4 g of maleic acid and 24.2 g of water were charged and heated to 60 ° C. with stirring. Subsequently, 14.3 g of a 6% aqueous solution of ammonium persulfate was added dropwise over 3 hours. afterwards,
The reaction was continued for 1 hour while maintaining the reaction temperature at 60 ° C. to complete the polymerization reaction. After completion of the reaction, the solution was neutralized with a 30% aqueous sodium hydroxide solution to obtain a polycarboxylic acid polymer (Y2).

Polycarbo obtained according to Production Examples 8 and 9
Of p in acid-based polymers (Y1) and (Y2),
A repeating unit (F) having a xyalkylene group and -C
OOM ^Five Of a repeating unit (G) having a carboxylic acid
Abundance (molar ratio) in the system polymer (Y), and
Table 2 shows the weight average molecular weight (Mw) of the polymer.

[0180]

[Table 2]

Examples 1 to 9 The polycarboxylic acid polymers (X1) to (X7) obtained in Production Examples 1 to 7 and the polycarboxylic acid polymer (Y1) obtained in Production Examples 8 and 9 And (Y2) were blended and used in the following mortar test. Pacific Portland Cement 600g, Toyoura Standard Sand 6
00 g was kneaded with a mortar mixer at low speed for 30 seconds. Next, 210 g of water containing a polymer of the type shown in Table 3 was put into the mixture of the cement and sand that had been kneaded, and kneaded at high speed for 3 minutes to form a mortar (1) to
(9) was prepared respectively. The polymer was blended so that the solid content% by weight with respect to the cement weight became the value shown in Table 3.

According to the following method, the obtained mortars (1) to (9) are allowed to stand, and after pouring for 5 minutes, 30 minutes and 60 minutes.
The flow value after 90 minutes and the flow value after 90 minutes and the entrained air amount (volume%) after 5 minutes from the water injection were evaluated. The results are shown in Table 3. In the preparation of each mortar, the kneading and kneading conditions using a mortar mixer were made uniform, and each mortar after water injection was allowed to stand at a constant temperature and humidity.

[0183]Evaluation method  (1) Flow value Morta after 5 minutes, 30 minutes, 60 minutes and 90 minutes after water injection
Is placed on a table with a diameter of 55 mm and a height of 50 mm
Into a hollow cylindrical container, then the hollow cylindrical container
After vertically lifting the mortar spread on the table
Measure the diameter in two directions, and calculate the average
Value (mm). The larger the flow value, the higher the mortar flow
High mobility and high dispersibility.

(2) Amount of entrained air The volume of the mortar 5 minutes after the injection was 500 m
The weight at the time of 1 was measured, and the entrained air amount (volume%) was calculated from the specific gravity of the used raw material.

Comparative Examples 1 to 9 The polycarboxylic acid polymers (X1) to (X7) obtained in Production Examples 1 to 7 and the polycarboxylic acid polymer (Y1) obtained in Production Examples 8 and 9 And (Y2) were used alone, and a mortar test shown below was performed.
Comparative mortars (1) to () were prepared in the same manner as in Examples 1 to 9 except that the polymer used to prepare the mortar was changed to the type shown in Table 3 and the solid content% by weight relative to the cement weight. 9) was prepared respectively. Comparative mortars (1) to (9) obtained by the methods shown in Examples 1 to 9
5 minutes, 30 minutes, 60 minutes, and 90 minutes after the water injection, the flow value was evaluated. The results are shown in Table 3.

[0186]

[Table 3]

In Table 3, the entrained air amount (volume%) was evaluated for mortars (3), (5), (6), (7) and (9), but not for other mortars.
The difference in flow value (mm) is the difference between the flow value after 5 minutes and 90 minutes after water injection.

As apparent from Table 3, in the mortar tests of Comparative Examples 1 to 9, the polycarboxylic acid polymer (X
In the comparative mortars (1) to (7) using each of 1) to (X7) alone, except for the comparative mortar (3) having a low flow value 5 minutes after the water injection, the difference in the flow value was −16.
To -45 mm, and the flow value was significantly negative in each case, resulting in flow loss. In the comparative mortars (8) and (9) using the polycarboxylic acid polymers (Y1) and (Y2) alone, the difference in the flow value was +34.
And +79 mm, and no flow loss occurred, but the difference between the flow values after 5 minutes and 90 minutes was large.

On the other hand, in the mortar tests of Examples 1 to 9, in mortars (1) to (9), polycarboxylic acid polymers (X1) to (X7), polycarboxylic acid polymer (Y1) and The mortar (3) using the polycarboxylic acid polymer (X3) in which T was 0 was used by blending half the amount of each of Comparative Examples 1 to 9 in which (Y2) was used alone. Except for the above, the difference between the flow values was not negative, and there was no flow loss, resulting in excellent cement dispersion retention. In the mortar (3), the flow loss was small, but the value was small.

In mortars (1) to (9), except for mortar (3), polycarboxylic acid polymer (Y1)
And mortars (Y2) alone were used, and the flow value was increased 5 minutes after water injection with a smaller total amount of addition than mortars (8) and (9). It turned out that it was excellent in retention.

Example 10 The setting time (minutes) of cement setting of the polycarboxylic acid polymers (X4) and (Y1) obtained in Production Examples 4 and 8 was measured by the following method. The results are shown in Table 4. Pacific ordinary Portland cement (brand name)
400 g and 800 g of Toyoura standard sand were kneaded with a mortar mixer (trade name: N-50, manufactured by Tesco Corporation) at a low speed for 30 seconds. Next, 240 g of water containing the polymer was added to the mixture of the cement and sand that had been kneaded, and kneaded at high speed for 3 minutes to prepare a mortar. The polymer was blended so that the weight percentage of solid content relative to the weight of cement was 0.12. The prepared mortar was measured using a Vicat needle device (trade name: Hydraulic Vicat needle device, manufactured by West Japan Testing Machine Co., Ltd.) in accordance with JIS R5201 to obtain a cement setting start time (minute) of the polymer. Table 4 shows the difference in the cement setting start time (minute) between the polycarboxylic acid polymer (X4) and (Y1) in the mortar (4) obtained in Example 4. Table 4 shows the results of the mortar test obtained in Example 4.

[0192]

[Table 4]

As apparent from Table 4, the onset time of cement setting of one polycarboxylic acid polymer was 375 to 40.
5 minutes, the other polycarboxylic acid-based polymer had a cement setting start time of 390 to 420 minutes, and the difference in the cement setting start time of the used polycarboxylic acid-based polymer was 5 to 4 minutes.
In the case of 5 minutes, there was no flow loss, and the result was excellent in cement dispersion retention.

[0194]

As described above, the cement additive of the present invention has the above-mentioned structure, so that the amount of water to be added to the cement composition is small while the dispersibility is high and the workability is excellent. It is excellent in economy, has a suitable air entrainment due to the foam suppressing action, and can provide a cement composition excellent in cement dispersion retention,
The durability, workability and strength of the cement composition can be improved. Since the cement additive of the second present invention is capable of providing a cement composition having excellent cement dispersion holding properties, it is possible to improve the durability, workability, and strength of the cement composition. Things. INDUSTRIAL APPLICABILITY The cement composition of the present invention is excellent in dispersibility, has an appropriate air entrainment property, and is excellent in cement dispersion holding properties, so that it is possible to obtain a hardened cement material having stable strength.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) // C04B 103: 40 (72) Inventor Hirokatsu Kawakami 5-8 Nishiomibashicho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. (72) Inventor Takeshi Kenta 5-8 Nishiburi-cho, Suita-shi, Osaka F-term in Nippon Shokubai Co., Ltd. 4G012 PA04 PB32 PC03 4J002 BE041 BG072 BH011 BH021 BH022 GL00

Claims (7)

[Claims] 1. A cement additive containing a polycarboxylic acid polymer (X) and a polycarboxylic acid polymer (Y) as main components, wherein the polycarboxylic acid polymer (X) has the following general formula: Formula (1): [Wherein, R ¹ and R ² are the same or different and each represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms;
A part of the carbon chain of ¹ and R ² may be bonded. R ³
Is hydrogen, a phenyl group, an alkylphenyl group, a sulfonated phenyl group, an alkyl group having 1 to 30 carbon atoms,
30 alkenyl group, an alkoxyl group having 1 to 30 carbon ^{atoms, -OCOR 4, -X 1 OR 5} , -O (R 6 O) aR
⁷ represents a monovalent organic group selected from the group consisting of -CN. R ⁴ represents a monovalent hydrocarbon group having 1 to 30 carbon atoms. X ¹ represents a divalent hydrocarbon group having 1 to 3 carbon atoms.
R ⁵ and R ⁷ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms. R ⁶ represents an alkylene group having 2 to 30 carbon atoms, a represents an average addition mole number of the oxyalkylene group represented by — (R ⁶ O) —, and is a positive number of 1 to 300. S represents the abundance (molar ratio) of the repeating unit in the polycarboxylic acid polymer (X). A repeating unit (A) represented by the following general formula (2); [Wherein, M ¹ and M ² are the same or different and each represent a hydrogen atom, a metal atom, an ammonium group, or an organic amine group. T represents the abundance (molar ratio) of the repeating unit in the polycarboxylic acid polymer (X). A repeating unit (B) represented by the following general formula (3): [Wherein, M ³ represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group. R ⁸ is 1 having 1 to 30 carbon atoms.
Represents a monovalent hydrocarbon group. R ^X is the same or different and represents an alkylene group having 2 to 18 carbon atoms, and its main constituent is an ethylene group. n it is, - (R ^X O) - in represents the average number of moles of the oxyalkylene group represented by a positive number. E
1 represents the abundance (molar ratio) of the repeating unit in the polycarboxylic acid polymer (X). A repeating unit (C) represented by the following general formula (4): [In the formula, M ⁴ represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group. R ⁹ is 1 having 1 to 30 carbon atoms.
Represents a monovalent hydrocarbon group. R ^Y is the same or different and represents an alkylene group having 2 to 18 carbon atoms, and its main body is an alkylene group having 3 or more carbon atoms. m ^is- (RYO)-
Represents the average number of added moles of the oxyalkylene group represented by, and is a positive number. E2 represents the abundance (molar ratio) of the repeating unit in the polycarboxylic acid polymer (X). And the other repeating unit (E) [polycarboxylic acid polymer (X)
The abundance (molar ratio) of the repeating unit in the compound is represented by S '. Wherein the polycarboxylic acid-based polymer (Y) has the following general formula (5): [In the formula, R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are the same or different and each represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms. X ² is a carbonyl group or a group having 1 to 3 carbon atoms.
Represents a divalent hydrocarbon group. R ^Z is the same or different and represents an alkylene group having 2 to 18 carbon atoms, and its main constituent is an ethylene group. p is, - (R ^Z O) - in represents the average number of moles of the oxyalkylene group represented by a positive number. A repeating unit (F) represented by the formula:
OM ⁵ (where M ⁵ represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group), having a repeating unit (G) having S, T in the polycarboxylic acid polymer (X). , E1, E2 and n are T> 0,
And (1) T / (T + E1 + E2) ≧ 0.1 (2) S> 0 (3) n ≧ 110, wherein at least one of the requirements is satisfied. 2. The polycarboxylic acid-based polymer (X) comprises:
The repeating unit (B) and the repeating unit (C) are essential repeating units, and T, E1, E2, and n in the polycarboxylic acid polymer (X) are such that T> 0,
And satisfying the requirement of E1> 0 and satisfying at least one of the following (1) and (3); (1) T / (T + E1 + E2) ≧ 0.1 (3) n ≧ 110 The cement additive according to claim 1, wherein 3. The polycarboxylic acid polymer (X) comprises:
The repeating unit (A), the repeating unit (B) and the repeating unit (C) are essential repeating units, and S, T and E in the polycarboxylic acid-based polymer (X) are used.
The cement additive according to claim 1, wherein 1 satisfies the requirements of S> 0, T> 0, and E1> 0. 4. The polycarboxylic acid polymer (X) comprises:
The recurring unit (A), the recurring unit (B), the recurring unit (C) and the recurring unit (D) are essential recurring units, and the polycarboxylic acid-based polymer (X)
S, T, E1 and E2 in S> 0, T> 0, E
2. The cement additive according to claim 1, wherein the requirements of 1> 0 and E2> 0 are satisfied. 5. A cement additive containing a polycarboxylic acid polymer (Q) and a polycarboxylic acid polymer (R) as main components, wherein the polycarboxylic acid polymer (Q) is cement-set. The start time is 375 to 405 minutes, and the polycarboxylic acid polymer (R) has a cement setting start time of 3 minutes.
90 to 420 minutes, and a difference in cement setting start time between the polycarboxylic acid polymer (Q) and the polycarboxylic acid polymer (R) is 5 to 45 minutes. Additive. 6. The polycarboxylic acid polymer (R)
The cement additive according to claim 5, which is a poly (alkylene glycol) acrylate (meth) acrylate polymer. 7. The cement, water and claim 1, 2,
A cement composition comprising the cement additive according to 3, 4, 5, or 6.