JP2000319382A - Cement additive and cement composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject additive having high fluidity, excellent workability and capable of exhibiting sufficient bubble-suppressing action, etc., while reducing an amount of water adding to a cement composition by including a specific polymer as a main component. SOLUTION: This cement additive contains a polymer of formulae I to IV [R1 and R2 are each H, a 1-30C monofunctional hydrocarbon or the like; R3 is H, phenyl or the like; S, T, E1 and E2 are each an existing amount (a mol ratio) of a repeating unit in the polymer and S, T and E1 is not 0; M1 to M4 are each H, a metal atom or the like; R8 and R9 are each a 1-30C monofunctional hydrocarbon; RX is a 2-18C alkylene mainly composed of ethylene; RY is a 2-18C alkylene mainly composed of a >=3C alkylene; (m) and (n) are each an average addition mol number of an oxyalkylene group and positive, and (n) is >=110]. preferably, an adding amount of the additive is 0.01-10 wt.% to a total weight of the cement.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cement additive and a cement composition having excellent fluidity and foam suppressing properties.

[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 technological innovation has been actively carried out. . The task of the cement additive is to ensure that the cement composition exhibits sufficient dispersibility even if the amount of water to be added is reduced, and that its fluidity and workability can be ensured. The purpose is to obtain a good cement composition while maintaining appropriate air entrainment.

[0003] US Patent No. 3,563,930 discloses that
A cement composition containing a compound comprising a styrene / maleic anhydride copolymer and a half ester of a styrene / maleic anhydride copolymer is disclosed. However, although this styrene / maleic anhydride copolymer is excellent in air entrainment, since the molecular weight is as low as 500 to 5000, the molecular weight of the half-esterified copolymer is also low, and carboxyl groups per molecule are reduced. When the number of polyalkylene glycol groups is small, the adsorptivity to cement particles is poor, and sufficient dispersibility cannot be obtained.

Japanese Patent Application Laid-Open No. 1-92212 discloses a styrene / maleic anhydride and maleic acid half ester copolymer in which a maleic acid half ester unit is a maleic anhydride unit and a polyalkylene glycol is added. Is disclosed as a fluidity improver for cement compositions. However, in this copolymer, the number of oxyalkylene groups that are repeating units of the polyalkylene glycol is 100 or less, the hydrophilicity and steric repulsion to cement are not sufficient, and the necessary dispersibility cannot be obtained. . Further, the abundance ratio between the maleic anhydride unit and the maleic acid half-ester unit is 1:
3 to 1: 100, and since the ratio of carboxyl groups is relatively small, the adsorptivity to cement particles is poor, and sufficient dispersibility cannot be obtained.

Japanese Patent Application Laid-Open No. 7-216026 discloses a random copolymer in the form of a free acid or salt comprising a specific hydrocarbon monomer, maleic acid monomer and maleic acid half ester monomer. In addition, a cement-like composition fluidizing agent containing a random copolymer in which a maleic acid half-ester monomer is added with a polyalkylene glycol is disclosed. However, this copolymer has no more than 100 oxyalkylene groups, which are repeating units of the polyalkylene glycol, and has insufficient hydrophilicity and steric repulsion, so that necessary dispersibility cannot be obtained. Further, the abundance ratio between the maleic acid monomer and the maleic acid half ester monomer is 5: 1 to 1: 100,
Since the ratio of carboxyl groups is small, the adsorptivity to cement particles is poor, and sufficient dispersibility cannot be obtained.

[0006] Japanese Patent Application Laid-Open No. 8-268741 discloses that an alkylene glycol and / or a polyhydric alcohol and a polyalkylene glycol or a derivative thereof are chemically bonded to a side chain of a polycarboxylic acid or a salt thereof. Although a drying shrinkage-reducing cement dispersant containing a graft polymer is disclosed, this graft polymer is characterized in that the number of oxyalkylene groups which are repeating units of polyalkylene glycol or a derivative thereof is about 12 or less. However, the hydrophilicity and the steric repulsion to the cement are not sufficient, and the necessary dispersibility cannot be obtained. Further, a technique has been disclosed in which a block copolymer of ethylene oxide and propylene oxide having a foam suppressing property for controlling air entrainment is used as a polyalkylene glycol or a derivative thereof. As described above, since sufficient dispersibility cannot be obtained, water cannot be reduced, and durability and strength cannot be improved due to the synergistic action of water reduction and foam suppression.

[0007]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above situation, and has high fluidity and excellent workability while reducing the amount of water added to a cement composition.
It is an object of the present invention to provide a cement additive which has a sufficient air entrainment property by a sufficient foam suppressing action, is small in the amount added, and is excellent in economical efficiency, and a cement composition using the same.

[0008]

According to the present invention, there is provided a polymer (X)
A cement additive containing, as a main component, the polymer (X) represented by the following general formula (1);

[0009]

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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, —OCOR ⁴ ,
And represents a monovalent organic group selected from the group consisting of (CH ₂ ) aOR ⁵ , —O (R ⁶ O) bR ⁷ , and —CN. R ⁴ is
Represents a monovalent hydrocarbon group having 1 to 30 carbon atoms. R ⁵ and R ⁷
Represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms. a is, - (CH ₂₎ - represents the average molar number of addition of the methylene group represented by the number 1 to 3 positive. R ⁶
Represents an alkylene group having 2 to 30 carbon atoms, and b represents-
(R ⁶ O) - in represents the average number of moles of the oxyalkylene group represented by a positive number from 1 to 300. S represents the abundance (molar ratio) of the repeating unit in the polymer (X). A repeating unit (A) represented by the following general formula (2);

[0011]

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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 polymer (X). A repeating unit (B) represented by the following general formula (3);

[0013]

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[Wherein, 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 polymer (X). And a repeating unit (C) represented by the following general formula (4);

[0015]

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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. m represents the average number in the repeating unit. 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-(R
It represents the average number of moles of the oxyalkylene group represented by ^Y O)-, and is a positive number. E2 represents the abundance (molar ratio) of the repeating unit in the polymer (X). Wherein S, T and E1 are not 0, n is 110 or more, and the weight average molecular weight (Mw) of the polymer (X) is 10,000
The above is the cement additive.

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 comprises a polymer (X)
As a main component. The content of the polymer (X) in the cement additive is not particularly limited as long as it is the main component. The polymer (X) has a repeating unit (A), a repeating unit (B), a repeating unit (C), and a repeating unit (D). The above repeating unit (A)
Is a base of the polymer (X), the repeating unit (B) has a function of adsorbing the polymer (X) to cement particles, and the repeating unit (C) is It has the 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) contains a suitable air of the cement composition due to the foam suppressing property of the oxyalkylene group. It has a function of exhibiting entrainment.

The repeating unit (A) in the present invention is represented by the above general formula (1). In this specification, the average number of added moles means the 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. R ³ is an alkylphenyl group, an alkyl group, an alkenyl group, — (CH ₂ )
In the case of aOR ⁵ and —O (R ⁶ O) bR ⁷ , when the number of carbon atoms exceeds the above-mentioned number, the hydrophilicity of the polymer (X) may be reduced and the dispersibility of the cement composition may be deteriorated. .

The repeating unit (B) in the present invention is represented by the above general formula (2). The metal atom is not particularly limited, and includes, for example, 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 or in combination of two or more.

-COO in the repeating unit (B)
M ¹ group and -COOM ² groups, M ¹ the cement compositions
And M ² are dissociated to generate a carboxy anion and have an affinity with the surface of the positively charged cement particles, and thus have a function of adsorbing the polymer (X) to the cement particles. Therefore, the above 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 present invention is represented by the above general formula (3). The M ³ are those having the same function as the M ¹ and the M ² in the repeating unit (B). When the R ⁸ exceeds 30 carbon atoms, - (R ^X O) hydrophilic nR ⁸ group becomes weak, poor dispersibility of the cement composition. In order not to impair the hydrophilicity of the oxyalkylene group and to sufficiently exhibit the dispersibility of the cement composition, R ⁸ is a methyl group,
A straight-chain saturated hydrocarbon group having 1 to 3 carbon atoms such as an ethyl group and a propyl group is preferable, in order to sufficiently express the dispersibility of the cement composition, and to suppress the separation of the compounding material in the cement composition. For this purpose, a linear saturated hydrocarbon group having 4 to 8 carbon atoms, such as an n-butyl group, an i-propyl group, a pentyl group, and a hexyl group, is preferred, in order to suppress the separation of the compounding material in the cement composition. Is preferably a linear saturated hydrocarbon group having 9 to 18 carbon atoms such as a lauryl group and a stearyl group, and it is preferable to use these in an appropriate combination. The oxyalkylene group represented by-(R ^x O)-in the above general formula (3) has the same repeating unit (C)
When two or more are present, an oxyalkylene group represented by-(R ^X O)-is added by random addition, block addition,
Any addition form such as alternate addition may be used.

The above 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 “occupy most” as described above, so that it can be the “subject” in the present specification.

In the above repeating unit (C), when “occupying the majority” 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
Since the hydrolysis of the oxyalkylene group is suppressed in the alkaline cement composition, the cement composition has a function of maintaining the fluidity of the cement composition. For this purpose, R ^X other than the ethylene group is preferably one having a small number of carbon atoms, such as a propylene group or a butylene group.

The repeating unit (D) in the present invention is represented by the above general formula (4). The M ⁴ has the same function as that of the M ¹ and the M ² in the repeating unit (B). When the carbon number of R ⁹ exceeds 30,-(R
^Y O) The hydrophobicity of the mR ⁹ group becomes too strong, resulting in poor dispersibility of the cement composition. R ⁹ is preferably a monovalent hydrocarbon group having 1 to 25 carbon atoms in order to sufficiently express 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, and more preferably a monovalent hydrocarbon group having 4 to 10 carbon atoms. It is. The above general formula (4)
In - (R ^Y O) - when oxyalkylene groups represented by the presence of two or more in the same repeating unit (C) is, - (R ^Y O) - oxyalkylene group represented by random addition , Block addition, and alternate addition.

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. The presence of a straight-chain saturated hydrocarbon group having 3 or more carbon atoms means that “the majority” is occupied as described above, so that it can be the “main component” in the present specification.

In the above 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-.

In the polymer (X), the repeating unit (A), the repeating unit (B), the repeating unit (C) and the repeating unit (D) are each one or more. As long as the effects of the present invention are not impaired, the polymer (X) may have another repeating unit.
In the polymer (X), the repeating unit (A), the repeating unit (B), the repeating unit (C) and the repeating unit (D) may be added in any form such as random addition, block addition, and alternate addition. There may be.

In the above polymer (X), S + T + E1
+ E2 is 1. S and T in the polymer (X)
And E1 are not zero. Therefore, the polymer (X)
Is the repeating unit (A) and the repeating unit (B)
And the repeating unit (C), and may or may not have the repeating unit (D). When the polymer (X) has the repeating unit (D), the cement composition has appropriate air entrainment.

N in the oxyalkylene group of the repeating unit (C) is 110 or more. When n is less than 110, the oxyalkylene group in the repeating unit (C) in the polymer (X) adsorbed on the cement particles does not sufficiently exhibit a steric repulsion effect on the cement particles. Dispersibility will be inferior. Also,
Since the preparation of the oxyalkylene group becomes difficult, n
Is preferably 300 or less. More preferably, it is 120 to 250, particularly preferably 130 to 250.
200, most preferably 140-180. The oxyalkylene group of the repeating unit (C) is
The synergistic action between the fact that the oxyethylene group is the main component and the fact that n is 110 or more can sufficiently exert the effect of causing the cement particles to rebound sterically.

In the repeating unit (C) and the repeating unit (D), na represented by the following formula: na = (n × E1 + m × E2) / (E1 + E2) is an oxyalkylene in the polymer (X). Represents the average number of moles of group added. The na is 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.

It is preferable that T and E1 satisfy the relationship of 0.005 ≦ E1 / (T + E1) ≦ 0.7. 0.005
When it is less than 1, since the molar ratio of the repeating unit (C) is considerably reduced, the effect of the hydrophilicity of the oxyalkylene group in the repeating unit (C) and the effect of steric repulsion on cement particles may not be sufficiently exhibited, When the ratio exceeds 0.7, the molar ratio of the repeating unit (B) becomes considerably small, so that the polymer (X) of the -COOM ¹ group and the -COOM ² group of the repeating unit (B) is adsorbed on the cement particles. Function may be reduced. More preferably, 0.01 ≦ E1 / (T + E1) ≦ 0.4, particularly preferably, 0.03 ≦ E1 / (T + E1) ≦ 0.3, and most preferably, 0.05 ≦ E1 /. (T + E1) ≦ 0.2. Thus, even when the molar ratio of the repeating unit (C) is smaller than the molar ratio of the repeating unit (B), the oxyalkylene group in the repeating unit (C) is mainly composed of an oxyethylene group, and n is 110 or more. Therefore, the effect can be sufficiently exhibited. Accordingly, since the molar ratio of the repeating unit (B) can be set to be larger than that of the repeating unit (C), the repeating unit (B)
The function of adsorbing the polymer (X) to the cement particles can be more sufficiently exerted.

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 that of the repeating unit (C).
May become strong, and the cement particles may not be sufficiently dispersed. If it exceeds 0.99, 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. More preferably, 0.7 ≦ E1 / (E1 + E2) ≦ 0.9. Thus, even if 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 mainly composed of an oxyalkylene group having 3 or more carbon atoms. for,
Since the effect can be sufficiently exerted and the molar ratio of the repeating unit (C) can be set to be much larger than the molar ratio of the repeating unit (D), the oxyalkylene group mainly composed of an oxyethylene group in the repeating unit (C) Can be sufficiently exerted.

If E2 is not 0, (T + E1) and E2 are: 0.5 ≦ (T + E1) / (T + E1 + E2) ≦ 0.99
It is preferable that the relationship of 9 is satisfied. When it is less than 0.5, the molar ratio of the total of the repeating units (B) and (C) is smaller than the molar ratio of the repeating unit (D). The effect may not be sufficiently exhibited, and the cement particles may not be sufficiently dispersed. If the value exceeds 0.999, the repeating unit (D) hardly exists, so that the effect of the repeating unit (D) may be insufficient. There is a possibility that the cement composition cannot be sufficiently exerted and the foam of the cement composition cannot be sufficiently suppressed. More preferably, 0.7 ≦ (T + E1) / (T + E1 + E2) ≦ 0.99
5 and most preferably 0.9 ≦ (T + E1) / (T + E1 + E2) ≦ 0.99. Thus, as described above, even when the molar ratio of the repeating unit (D) is considerably smaller than the total molar ratio of the repeating units (B) and (C), the action of the repeating unit (D) is not affected. It can be sufficiently exhibited, and the total molar ratio of the repeating units (B) and (C) can be set to be much larger than the molar ratio of the repeating unit (D). Can sufficiently exert the effect of dispersing the cement particles.

The weight average molecular weight (Mw) of the polymer (X) in the present invention is 10,000 or more. If it is less than 10,000, the function of adsorbing the polymer (X) of the repeating unit (B) to the cement particles and the function of sufficiently dispersing the cement particles of the repeating unit (C) cannot be sufficiently exhibited. Further, when the molecular weight of the polymer (X) exceeds 500,000, it is not preferable because an action of aggregating cement particles occurs. The weight average molecular weight (Mw) of the polymer (X) is preferably 500,000 or less, since the viscosity of the polymer (X) becomes too high and handling becomes difficult. It is more preferably from 20,000 to 300,000, particularly preferably from 30,000 to 200,000, and most preferably from 40,000 to 100,000.

The cement additive of the present invention is characterized in that the polymer (X) as the main component can sufficiently adsorb to the cement particles and the oxyalkylene group mainly composed of the oxyethylene group of the repeating unit (C) The dispersibility can be improved by suppressing agglomeration of cement particles due to the hydrophilicity of the compound and the steric repulsion effect on the cement particles. Therefore, sufficient fluidity can be imparted to the cement composition even when the amount of water to be added is reduced, and the durability, workability, and strength of the cement composition can be improved by reducing the amount of water. In addition, the cement additive of the present invention can reduce the amount of addition to ensure constant workability in various cement compositions as compared with conventional cement additives, and the cement composition can be used for building exterior walls. Since it is widely used for materials, building structures, and the like, it has excellent economic effects. Further, the oxyalkylene group having 3 or more carbon atoms of the repeating unit (D) in the polymer (X) has a foam-suppressing action to impart appropriate air entrainment to the cement composition, and provides stable strength and durability. A cement hardened material can be obtained. In addition, unlike conventional cement additives, since the foaming property can be imparted to the cement composition without separately adding an antifoaming agent, the work of adding a variety of additives is omitted, and the workability of producing the cement composition is reduced. Can be improved.

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

Polymer (X-1) in the above production method
Is the following general formula (5);

[0040]

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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 following polymer (X-1). And a repeating unit (E) represented by the following general formula (6);

[0042]

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[In the formula, V represents the abundance (molar ratio) of the repeating unit in the following polymer (X-1). And a weight average molecular weight (Mw) of 8000 or more. In the polymer (X-1), U + V is 1. When the weight average molecular weight (Mw) of the polymer (X-1) is less than 8,000, the polymer (X) cannot sufficiently exhibit the adsorption and dispersion of cement particles. In addition, the molecular weight is 50
If it exceeds 0000, it is not preferable because it causes an effect of coagulating cement particles. Since the viscosity of the polymer (X-1) becomes too high and it becomes difficult to handle, the weight average molecular weight (Mw) of the polymer (X─1) is 500000
The following is preferred. More preferably, 1500
0 to 300,000, particularly preferably 25,000
~ 200000, most preferably 35,000 to
100,000. The polymer (X-1) is not particularly limited as long as it is as described above. For example, the polymer (X-1) comprises a monomer that forms the repeating unit (E), maleic anhydride and, if necessary, another monomer. Copolymers obtained by copolymerization by a polymerization method are exemplified.

The monomer forming the repeating unit (E) is not particularly restricted but includes, for example, styrene; alkyl-substituted styrenes such as methylstyrene, ethylstyrene and propylstyrene; styrenesulfonic acid; ethylene;
Propylene, butylene, isobutylene, 1-pentene,
Α such as 1-hexene, 1-decene, 1-octadecene
-Olefins; cyclic olefins such as cyclopentene and cyclohexene; butadiene, isoprene, 1,3
Diene such as pentadiene and 2,4-hexadiene; vinyl esters such as vinyl acetate, vinyl propionate and vinyl butanoate;
Vinyl alcohol (poly) alkylene oxide adduct to which 1 to 300 moles of alkylene oxide of 1 to 30 moles have been added; vinyl alcohol obtained by etherifying terminal hydroxyl groups of the vinyl alcohol (poly) alkylene oxide adduct with a hydrocarbon group having 1 to 30 carbon atoms (Poly) alkylene oxide adducts; allyl alcohol, methallyl alcohol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol An unsaturated alcohol (poly) alkylene oxide adduct obtained by adding 1 to 300 moles of an alkylene oxide having 2 to 30 carbon atoms to an unsaturated alcohol, such as an unsaturated alcohol (poly) alkylene oxide adduct; Unsaturated alcohol (poly) alkyl etherified with 30 hydrocarbon groups Ren'okishido adducts; acrylonitrile, methacrylonitrile, and the like. These may be used alone or in combination of two or more.

Among the above-mentioned polymers (X-1), styrene / maleic anhydride and, if necessary, other monomer (s) formed from styrene / maleic anhydride and
Maleic anhydride copolymer; α-olefin / maleic anhydride copolymer; vinyl acetate / maleic anhydride copolymer are preferred.

The above polyalkylene glycol (X-2)
The following general formula ^{(6); HO- (R Z} -O) d-R 10 (6) : wherein, R ^Z are the same or different and each represents an alkylene group having 2 to 18 carbon atoms. d is, - (R ^Z -O) - in represents the average number of moles of the oxyalkylene group represented by a positive number. R ¹⁰ 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 polymer (X) in the present invention. Examples thereof include methanol, ethanol, 2-propanol and 1-
C1-C30 such as butanol, octanol, 2-ethyl-1-hexanol, nonyl alcohol, lauryl alcohol, cetyl alcohol, and stearyl alcohol
Aliphatic alcohols having 3 to 30 carbon atoms such as cyclohexanol; phenol, phenylmethanol (benzyl alcohol), methylphenol (cresol), p-ethylphenol, dimethylphenol (xylenol), p- t-butylphenol,
Alcohols having a benzene ring such as nonylphenol, dodecylphenol, phenylphenol and naphthol; alcohols having an alkenyl group having 3 to 4 carbon atoms such as allyl alcohol, methallyl alcohol and crotyl alcohol; And alkoxypolyalkylene glycols to which one or more of the alkylene oxides (1) to (18) are added.

The above-mentioned 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, decanoloxypolybutylene glycol, decanoloxypolybutylene 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.

Dimethylphenoxy polyethylene glycol, dimethylphenoxy polyethylene glycol (poly) propylene glycol, dimethylphenoxypolyethylene glycol (poly) butylene glycol, dimethylphenoxypolyethylene glycol (poly) propylene glycol (poly) butylene glycol, dimethylphenoxypolypropylene glycol, dimethylphenoxy 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.

The esterification reaction in the production method of the present invention may be a usual esterification method, and is not particularly limited. For example, the reaction time and the reaction temperature may be determined by using an esterification catalyst in a solvent. The reaction can be performed by appropriately setting reaction conditions such as the above. 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. Further, the polyalkylene glycol (X-2) obtained by alkoxidation and the polymer (X-1) may be subjected to an esterification reaction. In the alkoxidation of the polyalkylene glycol (X-2), metal hydrides such as sodium hydride and calcium hydride; alkali metals such as sodium; and organic metals such as n-butyl lithium, methyl lithium and phenyl lithium are used. Can be used. Further, 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 polymer (X),
In order to produce a polymer having a large average number of moles of oxyalkylene group added, a conventional production method is used in which an oxyalkylene group is introduced into a monomer by an esterification reaction and this is copolymerized with another monomer. And unreacted monomer may remain because of low copolymerizability between the monomer having the oxyalkylene group introduced therein and the other monomer. By using the method for producing a polymer for a cement additive of the present invention, the maleic anhydride group in the repeating unit (F) of the polymer (X-1) is a polyalkylene glycol having a large addition mole number of an oxyalkylene group ( Since the esterification is easily performed with X-2), the esterification time is shortened to increase the production efficiency, and there is no possibility that unreacted monomers remain.
The polymer (X) having an oxyalkylene group having an average addition mole number of 110 or more can be produced.

The cement additive of the present invention may contain, in addition to the above-mentioned polymer (X) as a main component, those which improve the fluidity, foam suppressing property, etc. of the cement composition. The cement additive of the present invention can be used in combination with a commonly used cement dispersant. Known cement dispersants used in combination include, for example, lignin sulfonic acid salt; polyol derivative; naphthalene sulfonic acid formalin condensate; melamine sulfonic acid formalin condensate; polystyrene sulfonic acid salt; aminoaryl sulfonic acid as disclosed in JP-A-1-113419; An aminosulfonic acid such as a phenol-formaldehyde condensate; a copolymer of a polyalkylene glycol mono (meth) acrylate compound and a (meth) acrylic compound as the component (a) as disclosed in JP-A-7-267705. As a component (b), a copolymer of a polyalkylene glycol mono (meth) allyl ether-based compound and maleic anhydride and / or a hydrolyzate thereof and / or a salt thereof, as a component (c) Polyalkylene glycol mono (meth) ant Dispersing agent for cement comprising a copolymer of an ether compound and a maleic acid ester of a polyalkylene glycol compound and / or a salt thereof, and polyalkylene glycol ester of (meth) acrylic acid as component A as disclosed in Japanese Patent Publication No. 2508113 And (meth) acrylic acid (salt) copolymer,
A concrete admixture comprising a specific polyethylene glycol polypropylene glycol compound as the B component and a specific surfactant as the C component, JP-A-62-2169.
50 (poly) glycol (meth) acrylic acid polyethylene (propylene) glycol ester or polyethylene (propylene) glycol mono (meth) allyl ether, (meth) allyl sulfonic acid (salt), (meth) acrylic acid (salt) As described in JP-A-1-226557, polyethylene (propylene) glycol ester of (meth) acrylic acid, (meth) allylsulfonic acid (salt),
Copolymer of (meth) acrylic acid (salt), Tokuho 5
From polyethylene (propylene) glycol ester of (meth) acrylic acid, (meth) allylsulfonic acid (salt) or p- (meth) allyloxybenzenesulfonic acid (salt) or (meth) acrylic acid (salt) as in 36376 A copolymer of polyethylene glycol mono (meth) allyl ether and maleic acid (salt) as disclosed in JP-A-4-149056, a polyethylene glycol ester of (meth) acrylic acid as disclosed in JP-A-5-170501, (Meth) allylsulfonic acid (salt), (meth) acrylic acid (salt), alkanediol mono (meth) acrylate, polyalkylene glycol mono (meth) acrylate, α, β-unsaturated monomer having an amide group in the molecule Copolymer consisting of a polymer, polyethylene glycol mono (JP-A-6-191918) (Meth) allyl ether, polyethylene glycol mono (meth) acrylate, (meth)
Alkyl acrylate, (meth) acrylic acid (salt), (meth) allyl sulfonic acid (salt) or p-
A copolymer comprising (meth) allyloxybenzenesulfonic acid (salt), a copolymer of alkoxypolyalkylene glycol monoallyl ether and maleic anhydride, or a hydrolyzate or a salt thereof as disclosed in JP-A-5-43288; As disclosed in JP-B-58-38380, a copolymer comprising polyethylene glycol monoallyl ether, maleic acid, and a monomer copolymerizable with these monomers, or a salt or ester thereof, as in JP-B-59-18338. A polyalkylene glycol mono (meth) acrylate monomer, a (meth) acrylate monomer, and a copolymer comprising a monomer copolymerizable with these monomers,
Copolymers of (meth) acrylic acid esters having a sulfonic acid group and, if necessary, monomers copolymerizable therewith, or salts thereof as disclosed in JP-A-62-119147, or alkoxypolyesters as disclosed in JP-A-6-271347. Esterification reaction product of a copolymer of alkylene glycol monoallyl ether and maleic anhydride with a polyoxyalkylene derivative having an alkenyl group at a terminal, JP-A-6-29855
5, esterification product of a copolymer of an alkoxypolyalkylene glycol monoallyl ether and maleic anhydride and a polyoxyalkylene derivative having a hydroxyl group at a terminal, and 3-methyl-3 as disclosed in JP-A-62-68806.
An alkenyl ether-based monomer obtained by adding ethylene oxide or the like to a specific unsaturated alcohol such as buten-1-ol, an unsaturated carboxylic acid-based monomer and a monomer copolymerizable with these monomers. Polycarboxylic acids (salts) such as polymers and salts thereof; and the like. These may be used alone or in combination of two or more. When the above cement dispersant is used in combination, the ratio of the blending weight of the cement additive of the present invention and the above 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 listed.

(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 emulsion: 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; Saccharides such as molasses; sugar alcohols such as sorbitol; magnesium silicofluoride; phosphoric acid and salts or borates thereof; aminocarboxylic acids and salts thereof; alkali-soluble proteins; humic acid; tannic acid; Polyhydric alcohols such as glycerin;
Phosphonic acids such as aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and their alkali metal salts and alkaline earth metal salts And its derivatives.

(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 defoamer: kerosene, liquid paraffin, etc. (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-based 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) Metallic soap-based defoamers: 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 (alkylbenzene sulfonic acid), LAS (linear alkylbenzene sulfonic 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 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 agent: fatty acid (salt), fatty acid ester, oil and fat, 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
For cement, mortar, concrete, etc.
It can be used. As the above cement composition
There is no particular limitation, for example, cement, water, fine aggregate, coarse bone
A commonly used material including materials and the like can be used. The above sema
Is not particularly limited, for example, normal, fast, super
Portland cement of early strength, moderate heat, white color, etc .; aluminum
Na cement, fly ash cement, blast furnace cement,
Mixed Portland cement such as silica cement
Can be 1m concrete of the above cement^Three Distribution per hit
The total amount and the unit water amount are not particularly limited.
100-185kg / m^Three , Water / cement ratio = 10
Preferably, it is 70%. More preferably, unit water
120-175Kg / m ^Three , Water / cement ratio = 20-
65%.

The method and amount of addition of the cement additive of the present invention are not particularly limited, but the amount of the polymer (X) in the present invention is preferably 0.01 to 10% by weight based on the total weight of cement. %. If the amount is less than 0.01% by weight, the dispersibility of the cement composition may be inferior. If the amount exceeds 10% by weight, the economic efficiency is inferior. In addition, the said weight% is a value of solid content conversion.

The cement composition to which the cement additive of the present invention is added exhibits excellent dispersibility and excellent fluidity, and can improve workability, durability and strength of the cement composition by reducing water. . Further, since the amount of water to be added is small and the air has an appropriate air entrainment property, a hardened cement material having a stable strength can be obtained, and its durability can be excellent. The above cement composition is also one of the present invention.

[0072]

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.

Synthesis Examples 1 and 2 In a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser, SMA-, a styrene / maleic anhydride copolymer manufactured by Elf Atochem, was added. 10
2.5 g of 00P (trade name) and 20 g of dehydrated tetrahydrofuran were charged, and the styrene / maleic anhydride copolymer was dissolved. Next, dehydrated tetrahydrofuran 20
g of a polyalkylene glycol of the type and amount shown in Table 1 was added to 0.04 g of sodium hydride to separately prepare methoxypolyethylene glycol alkoxide. The methoxypolyethylene glycol alkoxide solution was reacted at room temperature. It was dropped into the container. 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, thereby obtaining a polymer (1).
And (2) were obtained, respectively. Table 1 shows the values of n, m, na, S, T, E1, and E2 and the weight average molecular weight (Mw) of the obtained polymer. Note that SM
The weight average molecular weight (Mw) of A-1000P (trade name) after being converted to a styrene / sodium maleate type polymer using sodium hydroxide was 10,000.

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)
Was appropriately selected and used. 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.

Comparative Synthesis Examples 1 to 3 Comparative polymers (1) and (2) were prepared in the same manner as in Synthesis Examples 1 and 2, except that the kind and amount of polyalkylene glycol and the amount of sodium hydride were as shown in Table 1. )-(3)
Was obtained respectively. N, m, in the obtained comparative polymer
Table 1 shows the values of na, S, T, E1, and E2 and the weight average molecular weight (Mw) of the comparative polymer.

[0076]

[Table 1]

In Table 1, methoxypolyethylene glycol (150), methoxypolyethylene glycol (25)
Means that the average number of moles of ethylene oxide added is 1
Methoxypolyethylene glycol which is 50 or 25, and butoxypolypropylene glycol (20)
Butoxy polypropylene glycol having an average number of moles of propylene oxide of 20.

Synthesis of Polycarboxylic Dispersant (PC1) Water 24 was placed in the same glass reaction vessel as used in the synthesis example.
25 g was charged, the inside of the reaction vessel was replaced with nitrogen under stirring, and heated to 95 ° C. in a nitrogen atmosphere. Next, 790 g of methoxypolyethylene glycol monomethacrylate having an average addition mole number of ethylene oxide of 10, 189 g of methacrylic acid, 26 g of sodium methacrylate and 1 part of water
A 500 g mixture aqueous solution and a 10% ammonium persulfate aqueous solution 75 g were each added dropwise over 4 hours. After dropping, 20 g of a 10% aqueous ammonium persulfate solution
Was added dropwise over 1 hour. Thereafter, the reaction temperature was maintained at 95 ° C., and the reaction was continued for 1 hour 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-based dispersant (PC1) having a weight average molecular weight (Mw) of 35,000.

Synthesis of Polycarboxylic Acid Dispersant (PC2) In the same glass reaction vessel as used in Synthesis Examples 1 and 2, 3-methyl-3-buten-1-ol was added with an average number of moles of 35. 50 g of unsaturated alcohol to which ethylene oxide has been added, 6.4 g of maleic acid and water 2
4.2 g 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. Thereafter, the reaction temperature was maintained at 60 ° C., and the reaction was continued for 1 hour to complete the polymerization reaction. After the reaction,
The solution was neutralized with a 30% aqueous sodium hydroxide solution to obtain a polycarboxylic acid-based dispersant (PC2) having a weight average molecular weight (Mw) of 33,400.

Synthesis of Polycarboxylic Dispersant (PC3) 2.5 g of SMA-1000P (trade name) was replaced with 2 g of an ethyl vinyl ether / maleic anhydride copolymer, and methoxypolyethylene glycol (150) was used as a polyalkylene glycol. Synthesis Example 1 except that 8 g was used and the amount of sodium hydride was changed from 0.04 g to 0.034 g.
And the weight average molecular weight (Mw) was 6300.
Thus, a polycarboxylic acid-based dispersant (PC3) was obtained.

Example 1 Pacific Normal Portland Cement (Pacific) 600
g, Toyoura standard sand 600g with mortar mixer (trade name:
N-50, manufactured by Tesco Corporation) at low speed for 30 seconds. Then, 210 g of water containing a polymer of the type shown in Table 2 was put into the mixture of the cement and sand which had been kneaded, and kneaded at high speed for 3 minutes to make mortar (1) to (1).
4) 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 2. In addition, in preparation of each mortar, the kneading | mixing and kneading | mixing conditions by a mortar mixer were made uniform. The obtained mortars (1) to (14) were evaluated by the following methods. Table 2 shows the results.
It described in.

[0082]Evaluation method  (1) Flow value Each of the prepared mortars (1) to (14) was
55mm diameter, 50mm height hollow cylinder placed on a bull
And then hold this hollow cylindrical container vertically.
After raising the mortar spread on the table
The measurement was made in two directions, and the average value was the flow value (mm).
And The higher the flow value, the higher the fluidity of the mortar
It is shown that. (2) Entrained air volume For each of the prepared mortars (1) to (14),
Then, the weight when the volume is 500 ml is measured and used.
The entrained air volume (% by volume) was calculated from the specific gravity of the raw material.

[0083]

[Table 2]

Comparative Example 1 A comparative mortar was prepared in the same manner as in Example 1 except that the polymer used for preparing the mortar was changed to the type shown in Table 3 and the solid content% by weight relative to the cement weight. 1) ~
(6) was prepared respectively. According to the method shown in Example 1, the obtained comparative mortars (1) to (6) were respectively evaluated. The results are shown in Table 3.

[0085]

[Table 3]

As is clear from Table 2, mortar (1) using polymers (1) and (2) in which n is 150 at 0.2% by weight (solid content) based on the weight of cement.
And (8) indicate that the flow values are 90 mm and 92 m, respectively.
m, indicating a sufficient fluidity. On the other hand, as apparent from Table 3, comparative polymers (1) and (2) in which n is 25
Comparative mortars (1), (3) and (5) using each of (2) and (3) at 0.2% by weight (solid content) with respect to the cement weight have a polymer E1 molar ratio of 0.15. ~ 0.4
Despite being as high as 5, the flow value was 61 to 65 mm, and the fluidity was poor. Also, using the comparative polymers (1), (2), and (3) in which n is 25, the flow value was 90 ± 5 mm as in the mortar (1) and (8).
However, as is apparent from the comparative mortars (2), (4) and (6), the polymer was added in an amount of 0.4 to 0.6% by weight (solid content) based on the weight of cement. And about two to three times the amount of cement additive was required, resulting in poor economic efficiency. Further, as is clear from Table 2, mortars (8) to (14) using the polymer (2) having the repeating unit (D) in which m is 20.
Has an air entrainment amount of 4.2 to 5.6% by volume, which is smaller than that of a mortar using a polymer having no repeating unit (D), and is an appropriate air entrainment amount.

[0087]

Since the cement additive of the present invention has the above-mentioned constitution, it has high flowability and excellent workability while having a small amount of water added to the cement composition, and has a sufficient foam suppressing effect. It is possible to provide a cement composition which has an appropriate air entrainment property and has a small amount of addition and is excellent in economic efficiency. ADVANTAGE OF THE INVENTION The cement composition of this invention is excellent in dispersibility, has moderate air entrainment, and can obtain a hardened cement material of stable strength.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C04B 103: 32 (72) Inventor Takeshi Kenta 5-8 Nishiomiboricho, Suita-shi, Osaka Japan F term in catalyst (reference) 4J002 CH051 FD200 FD310 GL00 4J005 AA12 BD02 BD05 BD06

Claims (5)

[Claims] 1. A cement additive containing a polymer (X) as a main component, wherein the polymer (X) is represented by the following general 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, -OCOR 4, - (CH 2}} ) a
Represents a monovalent organic group selected from the group consisting of OR ⁵ , —O (R ⁶ O) bR ⁷ , and —CN. R ⁴ has 1 to 3 carbon atoms
Represents a monovalent hydrocarbon group of 0. R ⁵ and R ⁷ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms. a
Is, - (CH ₂₎ - represents the average molar number of addition of the methylene group represented by the number 1 to 3 positive. R ⁶ has 2 carbon atoms
Represents a 30 alkylene group, b is, - (R ⁶ O) - in represents the average number of moles of the oxyalkylene group represented by
It is a positive number from 1 to 300. S represents the abundance (molar ratio) of the repeating unit in the 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 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 polymer (X). A repeating unit (C) represented by the formula:
And 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. m represents the average number in the repeating unit. ^RY are the same or different and each have 2 to 2 carbon atoms.
Represents an alkylene group of 18 and is mainly composed of an alkylene group having 3 or more carbon atoms. m is, - (R ^Y O) - in represents the average number of moles of the oxyalkylene group represented by a positive number. E2 represents the abundance (molar ratio) of the repeating unit in the polymer (X). Wherein S, T and E1 are not 0, n is 110 or more, and the weight average molecular weight of the polymer (X) is 10,000 or more. A cement additive characterized by the fact that: 2. The cement additive according to claim 1, wherein T and E1 satisfy a relationship of 0.005 ≦ E1 / (T + E1) ≦ 0.7. 3. If E2 is not zero, E1 and E2
The cement additive according to claim 1, wherein the following condition is satisfied: 0.5 ≦ E1 / (E1 + E2) ≦ 0.99. 4. A polymer (X) for a cement additive, which is represented by the following general 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, -OCOR 4, - (CH 2}} ) a
Represents a monovalent organic group selected from the group consisting of OR ⁵ , —O (R ⁶ O) bR ⁷ , and —CN. R ⁴ has 1 to 3 carbon atoms
Represents a monovalent hydrocarbon group of 0. R ⁵ and R ⁷ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms. a
Is, - (CH ₂₎ - represents the average molar number of addition of the methylene group represented by the number 1 to 3 positive. R ⁶ has 2 carbon atoms
Represents a 30 alkylene group, b is, - (R ⁶ O) - in represents the average number of moles of the oxyalkylene group represented by
It is a positive number from 1 to 300. S represents the abundance (molar ratio) of the repeating unit in the 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 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 polymer (X). A repeating unit (C) represented by the formula:
And 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. m represents the average number in the repeating unit. ^RY are the same or different and each have 2 to 2 carbon atoms.
Represents an alkylene group of 18 and is mainly composed of an alkylene group having 3 or more carbon atoms. m is, - (R ^Y O) - in represents the average number of moles of the oxyalkylene group represented by a positive number. E2 represents the abundance (molar ratio) of the repeating unit in the polymer (X). Wherein S, T and E1 are not 0, n is 110 or more, and the weight average molecular weight is 1
In producing the polymer (X) of 0000 or more,
The following general formula (5): 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 following polymer (X-1). A repeating unit (E) represented by the formula:
And the following general formula (6): [In the formula, V represents the abundance (molar ratio) of the repeating unit in the following polymer (X-1). A polymer having a repeating unit (F) represented by] the polymer has a weight-average molecular weight of 8000 or more and (X-1), the following general formula ^{(6); HO- (R Z} -O) d-R ¹⁰ (6) [wherein, R ^Z is the same or different and represents an alkylene group having 2 to 18 carbon atoms. d is, - (R ^Z -O) - in represents the average number of moles of the oxyalkylene group represented by a positive number. R ¹⁰ represents a hydrocarbon group having 1 to 30 carbon atoms. A polyalkylene glycol (X-2)
To a polymer for cement additives, which is subjected to an esterification reaction. 5. A cement composition comprising cement, water, and the cement additive according to claim 1, 2 or 3.