JP6325849B2 - Air entraining agent for cement composition - Google Patents

Description

  The present invention relates to an air entraining agent for a cement composition, and in particular, while maintaining excellent air entrainment, it is possible to reduce the amount of foaming in a concrete wash water recovery water tank and to improve foaming characteristics. And an air entraining agent for a cement composition.

Concrete that contains fly ash is actively used for civil engineering and construction as an effective use of resources, but this fly ash-containing concrete is improved in workability, long-term strength, durability, water tightness, fluidity, alkali It is widely known that it has many advantages such as reducing aggregate reaction and reducing construction costs.
However, on the other hand, fly ash is known to adsorb an anionic surfactant, which is a known air entraining agent, due to the presence of unburned carbon, and significantly reduce its effect, Therefore, more air entraining agents are added to the concrete containing fly ash than usual.

By the way, in recent years, for the purpose of reducing the environmental load, recycling of sludge water that collects and reuses concrete washing water has been promoted in concrete factories.
However, when sludge water is used, it is often a problem that foaming occurs in the washing water recovery water tank.
For example, as the frequency of concrete production and shipment increases, the amount of washing water for mixers and agitated vehicles will increase further. Therefore, once significant foaming occurs, the foam height in the recovery tank will increase. As a result, there is a case in which it is not possible to smoothly proceed with the work of settling the recovered washing water scheduled for later use for reuse.
In this case, it can be dealt with by adding an antifoaming agent to the recovered water tank, but if the recovered water is used for concrete production, it will be difficult to adjust the air volume. Is imagined.

Also, in the recovery water tank, it is common to perform pump circulation and bubbling for the purpose of facilitating recovery by separating and separating solids and water, so it is necessary for the bubbles to disappear in a shorter time. There has been a demand for suppression of foaming in the recovered water tank and improvement of foam breakage.
The above foaming mainly occurs when various organic compounds (surfactants and dispersants) used in concrete production are brought into the wash water, so more air entrainer is added than usual. The wash water after use of the fly ash-containing concrete produced in particular causes a problem that foaming is likely to occur.

On the other hand, in JP-A-2003-211153 (Patent Document 1), when recovered water from a concrete plant is reused as concrete kneaded water, the recovered water is silicic acid having a BET specific surface area of 30 m ² / g or more. The organic substance removing agent containing calcium hydrate powder or granulated product as an active ingredient is contacted to adsorb the organic substance to the organic substance removing agent, and then the organic substance removing agent is separated, and the recovered water is kneaded. A method of reusing as water is disclosed.

Japanese Patent Laid-Open No. 2003-211153

  However, since the method described in Patent Document 1 removes various organic compounds (surfactants and dispersants) used during concrete production from the washing water, recovery due to these organic compounds is performed. Although it is considered possible to suppress foaming in the water tank, on the other hand, contact of the organic substance removing agent with the washing water and separation work are required, which causes a new problem that work efficiency is lowered.

  Therefore, the present invention is capable of reducing the amount of foaming in the recovered water tank of the concrete washing water and improving the foaming property while maintaining excellent air entrainment, which cannot cause the above-described problems. An object is to provide an air entraining agent for a cement composition.

As a result of intensive studies to solve the above problems, the present inventors have
(A) a fatty acid ester of an adduct obtained by adding an alkylene oxide to a trivalent or higher alcohol having 3 to 10 carbon atoms;
(B) An air entraining agent for a cement composition obtained by mixing a fatty acid ester of a polyalkylene glycol compound at a mass ratio in the range of (A) :( B) = 85: 15 to 99.98: 0.02. As a result, the present inventors have found that excellent air entrainment is maintained, the amount of foaming in the concrete wash water recovery water tank is reduced, and the foam breakage is improved.

That is, the present invention
[1]
(A) a fatty acid ester of an adduct obtained by adding an alkylene oxide to a trivalent or higher alcohol having 3 to 10 carbon atoms;
(B) a fatty acid ester of a polyalkylene glycol compound,
An air entraining agent for a cement composition, wherein the mass ratio of the component (A) to the component (B) is in the range of (A) :( B) = 85: 15 to 99.98: 0.02.
[2] The component (A) and the component (B)
(C) a mixture of an adduct obtained by adding an alkylene oxide to a trivalent or higher alcohol having 3 to 10 carbon atoms, and (D) a polyalkylene glycol compound,
The mixture in which the mass ratio of the component (C) and the component (D) is in the range of (C) :( D) = 85: 15 to 99.98: 0.02 is esterified with a fatty acid or The air entraining agent for cement composition according to the above [1], which is a fatty acid ester mixture obtained by transesterification with a fatty acid alkyl ester,
[3] (E) The air entraining agent for cement composition according to the above [1] or [2], comprising a fatty acid having 8 to 22 carbon atoms,
[4] The air entraining agent for cement composition according to any one of [1] to [3], further comprising (F) another surfactant,
[5] The component (F) is represented by the general formula: R— (OCH ₂ CH ₂ ) _n1 — (OCH ₂ ) _m1 —COOH (wherein R represents an alkyl or alkenyl group having 12 to 24 carbon atoms). N1 represents 0 to 10, and m1 represents 0 or 1.) An alkali metal salt of a carboxylic acid represented by: a lower alkylamine salt of the carboxylic acid, a lower alkanolamine salt of the carboxylic acid, a polyoxy One or more surfactants selected from the group consisting of alkylene alkyl ether sulfates, rosinates, α-olefin sulfonates, polyoxyalkylene alkyl ether phosphates and cocoamphoacetic acid alkali metal salts The air entraining agent for cement composition according to the above [4],
[6] The air entraining agent for cement composition according to any one of [1] to [5], and a high-performance AE water reducing agent, a high-performance water reducing agent, an AE water reducing agent, a water reducing agent, an AE agent, A cement composition containing at least one other concrete additive selected from the group consisting of a foaming agent, an antifoaming agent, a curing agent, a water repellent, a setting accelerator, and a setting retarder;
It is about.
Particularly preferred embodiments of the present invention include (A) a fatty acid ester of an adduct obtained by adding an alkylene oxide to a trivalent or higher alcohol having 3 to 10 carbon atoms,
(B) a fatty acid ester of a polyalkylene glycol compound,
The (B) component is a polyalkylene glycol compound represented by the following formula (3)
Y- [O- (AO) _{n / 2-} H] ₂ (3)
Wherein Y is a linear or branched alkylene group having 1 to 18 carbon atoms (the alkylene group may be substituted with 1 to 8 hydroxyl groups, and is preferably an aromatic ring group, preferably Represents an optionally substituted phenyl group), A represents an ethylene group, a 1,2-propylene group, a 1,2-butylene group or a 2,3-butylene group, and n represents 4 to 80 Represents a fatty acid ester,
The present invention relates to an air entraining agent for a cement composition, wherein the mass ratio of the component (A) to the component (B) is in the range of (A) :( B) = 95: 5 to 99.98: 0.02.

According to the present invention, there is provided an air entraining agent for a cement composition capable of maintaining excellent air entrainment and reducing the amount of foaming in a concrete wash water recovery water tank and improving foam breakage.
The air entraining agent for a cement composition of the present invention can be advantageously used especially in concrete containing fly ash to which more air entraining agent is added than usual.
Moreover, when this uses the wash water collect | recovered as sludge water, use of an antifoamer etc. becomes unnecessary and can reduce environmental impact.
Moreover, in the preferable aspect of the air entraining agent of this invention, in addition to (A) component and (B) component, (F) other surfactant is included.
Thereby, air entrainment property and bubble breakability can be optimized, and when it is used as a hardened body, the bubble spacing coefficient is reduced, and the durability of the concrete composition can be improved.

The present invention will be described in more detail.
The air entraining agent for cement composition of the present invention is
(A) a fatty acid ester of an adduct obtained by adding an alkylene oxide to a trivalent or higher alcohol having 3 to 10 carbon atoms;
(B) a fatty acid ester of a polyalkylene glycol compound, and the mass ratio of the component (A) to the component (B) is (A) :( B) = 85: 15 to 99.98: 0. The range is 02.

Hereinafter, the component (A) and the component (B) used in the present invention will be described.
(I) About the component (A) The fatty acid ester of an adduct obtained by adding an alkylene oxide to a trivalent or higher alcohol having 3 to 10 carbon atoms used in the present invention is (C) carbon. An adduct obtained by adding an alkylene oxide to a trivalent or higher alcohol having 3 to 10 atoms can be obtained by esterification with a fatty acid or transesterification with a fatty acid alkyl ester. Esterification or transesterification is usually performed at 80 to 240 ° C. in the presence of an alkali catalyst or an acid catalyst. A reaction solvent may be used, but the reaction proceeds without using a reaction solvent.

The trihydric or higher alcohol having 3 to 10 carbon atoms is preferably a trivalent to 10-valent alcohol having 3 to 10 carbon atoms, and more preferably 3 having 3 to 10 carbon atoms. It is a hexavalent alcohol.
Specific examples of the trivalent or higher alcohol having 3 to 10 carbon atoms include glycerin, diglycerin, triglycerin, trimethylolethane, trimethylolpropane, pentane-1,3,5-triol, erythritol, D -Threitol, L-threitol, pentaerythritol, dipentaerythritol, sorbitol, sorbitan, sorbide, sorbitol and glycerin condensate, xylitol, D-arabinitol, L-arabinitol, adonitol, mannitol, galactitol, D-glucitol, D-iditol, boremitol, perseitol, D-erythro-D-galacto-octitol, cyclitol, inositol, quercitol, D-quercitol, L-quercitol and (-)-pro - Kuerushitoru, and the like.

Examples of the alkylene oxide added to the trivalent or higher alcohol having 3 to 10 carbon atoms are ethylene oxide (EO), 1,2-propylene oxide (PO), 1,2-butylene oxide, and 2, 3-butylene oxide etc. are mentioned,
From the viewpoint of air entrainment, ethylene oxide (EO) and 1,2-propylene oxide (PO) are preferable.
The added mole number of the alkylene oxide added to the trivalent or higher alcohol having 3 to 10 carbon atoms is usually 3 to 1 mole per 1 mole of the trivalent or higher alcohol having 3 to 10 carbon atoms. The range is 100 mol, and in terms of air entrainment, the range of 14 to 60 mol is preferable, and the range of 30 to 60 mol is more preferable.

All the added alkylene oxides can be composed of a single kind of alkylene oxide, but can also be composed of two or more different alkylene oxides. Specifically, it is preferably composed of only EO or two kinds of EO and PO.
The proportion of EO in the added alkylene oxide (molar fraction) is in the range of 80 to 100%, preferably 90 to 100%, and more preferably 90 to 95% in terms of enhancing air entrainment. More preferred.
When the added alkylene oxide is composed of two types of EO and PO, EO and PO can adopt either block addition or random addition, but in terms of air entrainment, EO-PO The block addition is preferred.

An adduct obtained by adding an alkylene oxide to a trivalent or higher alcohol having 3 to 10 carbon atoms as the component (C) can be represented by, for example, the following formula (1).
X- [O- (AO) _{m / p} -H] _p (1)
(In the formula, X represents a residue of a trivalent or higher alcohol having 3 to 10 carbon atoms (a portion other than a hydroxy group), and A represents an ethylene group, a methylethylene group, an ethylethylene group, or 1,2 -Represents a dimethylethylene group, p represents 3 or more, preferably 3 to 10, more preferably 3 to 6, and m represents 3 to 100, preferably 14 to 60, more preferably 30 to 60. )

The fatty acid ester of an alkylene oxide adduct of a trivalent or higher alcohol having 3 to 10 carbon atoms, which is the component (A), is the above component (C), that is, a trivalent or higher alcohol having 3 to 10 carbon atoms. The alkylene oxide adduct can be obtained by esterification with a fatty acid or by transesterification with a fatty acid alkyl ester. Examples of the fatty acid used here include fatty acids having 8 to 22 carbon atoms, and air. In terms of entrainment, higher fatty acids having 12 to 22 carbon atoms and hydroxy fatty acids having 12 to 22 carbon atoms are preferable, and saturated fatty acids having 16 to 18 carbon atoms and unsaturated fatty acids having 16 to 18 carbon atoms are preferable. Of these, unsaturated fatty acids having 16 to 18 carbon atoms are preferred. Most preferred is an unsaturated fatty acid having 18 carbon atoms.
As said fatty acid, although said fatty acid can also be used independently, 2 or more types of said fatty acid can also be mixed and used.

Specific examples of the fatty acid include octanoic acid, nonanoic acid, capric acid, lauric acid, myristic acid, pentasilic acid, palmitic acid, margaric acid, octadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid. Arachidonic acid, α-linolenic acid, eicosapentaenoic acid, docosahexaenoic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid, linoleic acid, eicosadienoic acid, Docosadienoic acid, linolenic acid, pinolenic acid, eleostearic acid, mead acid, dihomo-γ-linolenic acid, eicosatrienoic acid, 2-hydroxydecanoic acid, 2-hydroxylauric acid, 2-hydroxymyristic acid, 2-hydroxy Palmitic acid, 2-hy Droxystearic acid, 2-hydroxyarachidic acid, 2-hydroxybehenic acid, 3-hydroxyhexanoic acid, 3-hydroxyoctanoic acid, 3-hydroxynonanoic acid, 3-hydroxydecanoic acid, 3-hydroxyundecanoic acid, 3- Hydroxylauric acid, 3-hydroxytridecanoic acid, 3-hydroxymyristic acid, 3-hydroxypalmitic acid, 3-hydroxyheptadecanoic acid, 3-hydroxystearic acid, 15-hydroxypentadecanoic acid, 6-hydroxystearic acid, 12- Mention may be made of a mixture of two or more of hydroxy oleic acid and the above fatty acids.
Examples of fatty acid alkyl esters include methyl esters, ethyl esters, propyl esters, butyl esters, and octyl esters of the above fatty acids.

The fatty acid ester of the component (A) can be represented by the following formula (2), for example.
X- [O- (AO) _{m / p} -R] _p (2)
(In the formula, X represents a residue of a trivalent or higher alcohol having 3 to 10 carbon atoms (a portion other than a hydroxy group), and A represents an ethylene group, a methylethylene group, an ethylethylene group, or 1,2 -Represents a dimethylethylene group, R represents a hydrogen atom or a saturated or unsaturated acyl group having 8 to 22 carbon atoms (the acyl group may be substituted with a hydroxy group), and p is 3 or more. And preferably represents 3 to 10, more preferably 3 to 6, and m represents 3 to 100, preferably 14 to 60, more preferably 30 to 60.)

  In addition, when the esterification rate in the compound represented by the above formula (2), that is, the total number of moles of hydroxy groups present in the compound represented by the above formula (1) is 100 (%), The total number of moles of R (acyl group) present in the compound represented by the above formula (2) is 10 to 100 (%), preferably 20 to 80 (%), more preferably 30 to 60. %.

(II) Regarding the component (B) The fatty acid ester of the (B) polyalkylene glycol compound used in the present invention is, for example, (D) esterifying the polyalkylene glycol compound with a fatty acid or a fatty acid alkyl ester. It can be obtained by transesterification.
(D) As a polyalkylene glycol type compound, the polyalkylene glycol type compound represented by the following Formula (3) can be mentioned, for example.
Y- [O- (AO) _{n / 2} -H] ₂ (3)
Wherein Y is a linear or branched alkylene group having 1 to 18 carbon atoms (the alkylene group may be substituted with 1 to 8 hydroxyl groups, and is preferably an aromatic ring group, preferably Represents an optionally substituted phenyl group), A represents an ethylene group, a methylethylene group, an ethylethylene group or a 1,2-dimethylethylene group, and n is 4 to 80, preferably 4 to 60, more preferably 4 to 20.)
As a preferable embodiment of Y, a linear or branched alkylene group having 4 to 18 carbon atoms (the alkylene group may be substituted with 1 to 8 hydroxyl groups, and an aromatic ring group, Preferably, it may be substituted with a phenyl group.) And a linear or branched alkylene group having 1 to 10 carbon atoms (the alkylene group is substituted with 1 to 8 hydroxyl groups). And may be substituted with an aromatic ring group, preferably a phenyl group, and a linear or branched alkylene group having 4 to 10 carbon atoms (the alkylene group is And may be substituted with 1 to 8 hydroxyl groups, and may be substituted with an aromatic ring group, preferably a phenyl group), or a straight or branched carbon atom. 4-10 alkylene group (the alkylene group has 1 to may be substituted with four hydroxyl groups, also aromatic ring group, preferably optionally substituted phenyl group.) Can be mentioned.
Also preferred is an embodiment in which Y is an ethylene group.

The polyalkylene glycol compound represented by the above formula (3) is a linear or branched alkylene glycol having 1 to 18 carbon atoms (the alkylene group may be substituted with 1 to 8 hydroxyl groups). Or may be substituted with an aromatic ring group, preferably a phenyl group)).
Specific alkylene glycols that can be used include, for example, methanediol, ethylene glycol, propylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, Examples include 2,3-butanediol, 1,2-pentanediol, 1,5-pentanediol, neopentyl glycol, hexylene glycol, and styrene glycol.

Examples of the alkylene oxide to be added to the above alkylene glycol include ethylene oxide (EO), 1,2-propylene oxide (PO), 1,2-butylene oxide, 2,3-butylene oxide, and the like. From the viewpoint of properties, ethylene oxide (EO) and 1,2-propylene oxide (PO) are preferable.
The number of moles of alkylene oxide added to the alkylene glycol is usually in the range of 4 to 80 moles per mole of the alkylene glycol, and in the range of 4 to 60 moles in terms of air entrainment. It is more preferable that the amount be in the range of 4 to 20 mol because it is easy to achieve a balance between air entrainment and the foaming suppression effect of washing water.

All the added alkylene oxides can be composed of a single kind of alkylene oxide, but can also be composed of two or more different alkylene oxides. Specifically, it is preferably composed of only EO or two kinds of EO and PO.
The proportion of EO in the added alkylene oxide (molar fraction) is in the range of 80 to 100%, preferably 90 to 100%, and more preferably 90 to 95% in terms of enhancing air entrainment. More preferred.
When the added alkylene oxide is composed of two types of EO and PO, EO and PO can adopt either block addition or random addition, but in terms of air entrainment, EO-PO The block addition is preferred.

As a preferable (D) polyalkylene glycol compound, a polyalkylene glycol compound in which Y = A in the above formula (3) (that is, Y and A are an ethylene group, a methylethylene group, an ethylethylene group, or 1,2 -A compound representing a dimethylethylene group.
As the polyalkylene glycol compound, a commercially available polyalkylene glycol compound can be used as it is, but an alkylene glycol having 2 to 4 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,2-butylene). Glycol or 2,3-butylene glycol) by adding alkylene oxide (ethylene oxide (EO), 1,2-propylene oxide (PO), 1,2-butylene oxide or 2,3-butylene oxide) You can also
Examples of commercially available polyalkylene glycol compounds include PEG200, PEG300-PO, PEG400, PEG2000, and the like.

The fatty acid ester as the component (B) can be obtained by esterifying the above component (D), that is, a polyalkylene glycol compound with a fatty acid or transesterifying with a fatty acid alkyl ester.
Examples of the fatty acid include fatty acids having 8 to 22 carbon atoms. From the viewpoint of air entrainment, higher fatty acids having 12 to 22 carbon atoms and hydroxy fatty acids having 12 to 22 carbon atoms are preferable. A saturated fatty acid having 16 to 18 carbon atoms and an unsaturated fatty acid having 16 to 18 carbon atoms are more preferable. Among them, an unsaturated fatty acid having 16 to 18 carbon atoms is preferable. Most preferred is an unsaturated fatty acid having 18 carbon atoms.
As said fatty acid, although said fatty acid can also be used independently, 2 or more types of said fatty acid can also be mixed and used.

Specific examples of the fatty acid include octanoic acid, nonanoic acid, capric acid, lauric acid, myristic acid, pentasilic acid, palmitic acid, margaric acid, octadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid. Arachidonic acid, α-linolenic acid, eicosapentaenoic acid, docosahexaenoic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid, linoleic acid, eicosadienoic acid, Docosadienoic acid, linolenic acid, pinolenic acid, eleostearic acid, mead acid, dihomo-γ-linolenic acid, eicosatrienoic acid, 2-hydroxydecanoic acid, 2-hydroxylauric acid, 2-hydroxymyristic acid, 2-hydroxy Palmitic acid, 2-hy Droxystearic acid, 2-hydroxyarachidic acid, 2-hydroxybehenic acid, 3-hydroxyhexanoic acid, 3-hydroxyoctanoic acid, 3-hydroxynonanoic acid, 3-hydroxydecanoic acid, 3-hydroxyundecanoic acid, 3- Hydroxylauric acid, 3-hydroxytridecanoic acid, 3-hydroxymyristic acid, 3-hydroxypalmitic acid, 3-hydroxyheptadecanoic acid, 3-hydroxystearic acid, 15-hydroxypentadecanoic acid, 6-hydroxystearic acid, 12- Mention may be made of a mixture of two or more of hydroxy oleic acid and the above fatty acids.
Examples of fatty acid alkyl esters include methyl esters, ethyl esters, propyl esters, butyl esters, and octyl esters of the above fatty acids.

The fatty acid ester of the polyalkylene glycol compound as the component (B) can be represented, for example, by the following formula (4).
Y- [O- (AO) _{n / 2} -R] ₂ (4)
Wherein Y is a linear or branched alkylene group having 1 to 18 carbon atoms (the alkylene group may be substituted with 1 to 8 hydroxyl groups, and is preferably an aromatic ring group, preferably Represents an optionally substituted phenyl group), A represents an ethylene group, a methylethylene group, an ethylethylene group or a 1,2-dimethylethylene group, and R represents a hydrogen atom or a saturated or unsaturated group. Represents an acyl group having 8 to 22 carbon atoms (the acyl group may be substituted with a hydroxy group), and n represents 4 to 80, preferably 4 to 60, more preferably 4 to 20. )
As a preferable embodiment of Y, a linear or branched alkylene group having 4 to 18 carbon atoms (the alkylene group may be substituted with 1 to 8 hydroxyl groups, and an aromatic ring group, Preferably, it may be substituted with a phenyl group.) And a linear or branched alkylene group having 1 to 10 carbon atoms (the alkylene group is substituted with 1 to 8 hydroxyl groups). And may be substituted with an aromatic ring group, preferably a phenyl group, and a linear or branched alkylene group having 4 to 10 carbon atoms (the alkylene group is And may be substituted with 1 to 8 hydroxyl groups, and may be substituted with an aromatic ring group, preferably a phenyl group), or a straight or branched carbon atom. 4-10 alkylene group (the alkylene group has 1 to may be substituted with four hydroxyl groups, also aromatic ring group, preferably optionally substituted phenyl group.) Can be mentioned.
Also preferred is an embodiment in which Y is an ethylene group.
An embodiment in which Y = A (that is, Y and A represent an ethylene group, a methylethylene group, an ethylethylene group, or a 1,2-dimethylethylene group) is also preferable.

  In addition, when the esterification rate in the compound represented by the above formula (4), that is, the total number of moles of hydroxy groups present in the compound represented by the above formula (3) is 100 (%), The total number of moles of R (acyl group) present in the compound represented by the above formula (4) is 10 to 100 (%), preferably 20 to 80 (%), more preferably 30 to 60. %.

(III) Combination of Component (A) and Component (B) The mass ratio of the component (A) to the component (B) is (A) :( B) = 85: 15 to 99.98: 0. The range of 02 is preferably 95: 5 to 99.98: 0.02, more preferably 98.5: 1.5 to 99.98: 0. By setting it to 02, the detergency of the washing water can be improved, and most preferably, from 99.0: 1.0 to 99.98: 0.02, the bubbling of the washing water is further suppressed, and the washing water is broken. The sex can be further enhanced.
The mixture of the component (A) and the component (B) can be prepared by mixing the component (A) and the component (B) prepared as described above at a predetermined mass ratio. ) Component and the component (D) can be prepared by esterification with a fatty acid or transesterification with a fatty acid alkyl ester.

The mass ratio in the mixture of the component (C) and the component (D) is in the range of (C) :( D) = 85: 15 to 99.98: 0.02, but suppresses bubbling of washing water. In view of this, the range of 95: 5 to 99.98: 0.02 is preferable, and more preferably, the range of 98.5: 1.5 to 99.98: 0.02 can increase the detergency of washing water. Most preferably, by setting the ratio to 99.0: 1.0 to 99.98: 0.02, it is possible to further suppress foaming of the washing water and further improve the foaming property of the washing water.
Specific examples of fatty acids and preferred fatty acids that can be used for the esterification and fatty acids are the same as the fatty acids and preferred fatty acids described above with respect to esterification of component (A) and esterification of component (B), and specific examples of the fatty acids. Can be used.
Examples of fatty acid alkyl esters that can be used for the transesterification include methyl esters, ethyl esters, propyl esters, butyl esters, and octyl esters of the above fatty acids.

Here, the esterification rate in the mixture of the component (A) and the component (B), that is, the total number of moles of hydroxy groups present in the mixture of the component (C) and the component (D) is 100. (%), The total number of moles of fatty acid residues (that is, acyl groups) present in the mixture of the component (A) and the component (B) is 10 to 100 (%), preferably 20 to 80 (%), more preferably 30 to 60%.
Moreover, about the mixture of the said (C) component and the said (D) component, (D) component produced | generated secondary at the time of manufacture of (C) component may be included, (C) component and / or (D) may be further mixed with the mixture of the component (C) and the component (D).

In relation to the components (A) and (B) of the present invention, JP-A-01-157442 discloses a specific polyoxyethylene polyhydric alcohol fatty acid ester, a specific polyoxyethylene glycol fatty acid ester, a specific An air entraining agent for a cement composition comprising a compound A selected from fatty acid esters of polyoxyethylene pentaerythritol and a fatty acid ester of specific polyoxyethylene sorbitan, and a compound B which is a fatty acid having 10 to 30 carbon atoms or a salt thereof. Here, the fatty acid ester of a specific polyoxyethylene polyhydric alcohol, the fatty acid ester of a specific polyoxyethylene pentaerythritol, and the fatty acid ester of a specific polyoxyethylene sorbitan in the above compound A are Corresponding to the component (A) of the invention Are those, fatty acid esters of certain polyoxyethylene glycol is a compound corresponding to component (B) of the present invention.
JP-A-01-157442 discloses that the compound A can be used as a mixture of two or more kinds, but the publication discloses the compound A as a mixture of two kinds. When used, it is different from the air entraining agent of the present invention in that it does not specify what range the mass ratio is.
Japanese Unexamined Patent Publication No. 09-301758 discloses a hydraulic material composition using a polyoxyalkylene derivative that can contain both the component (A) and the component (B) of the present invention. However, this publication differs from the air entraining agent of the present invention in that nothing is specified as to what the mass ratio of the components contained in the polyoxyalkylene derivative is.
Japanese Patent Laid-Open No. 01-157442 and Japanese Patent Laid-Open No. 09-301758 can both reduce the amount of foaming in the concrete wash water recovery water tank and improve the foam breakage. The air-entraining agent of the present invention is also different in that no description or suggestion is given to the mass ratio of the component and the component (B).

(IV) (E) Higher Fatty Acid In a preferred embodiment, the air entraining agent of the present invention may contain (E) a fatty acid having 8 to 22 carbon atoms.
Specific examples of the (E) fatty acid having 8 to 22 carbon atoms include fatty acids used for esterification of the component (C) and the component (D).
The fatty acid is preferably a fatty acid having 12 to 22 carbon atoms and a hydroxy fatty acid having 12 to 22 carbon atoms from the viewpoint of air entrainment, and a saturated fatty acid having 16 to 18 carbon atoms and 16 to 18 carbon atoms. The unsaturated fatty acids are more preferable, and among these, unsaturated fatty acids having 16 to 18 carbon atoms are preferable. Most preferred is an unsaturated fatty acid having 18 carbon atoms.
When the component (E) is added, the mass ratio of the mixture of the component (A) and the component (B) to the component (E) is (A) + (B) :( E) = 99.9: The range is 0.1 to 95.0: 5.0, and the range of 99.9: 0.1 to 97.0: 3.0 is preferable from the viewpoint of the temporal stability of the air amount.
As the (E) fatty acid having 8 to 22 carbon atoms, the above fatty acid can be used alone, or two or more of the above fatty acids can be mixed and used.

  Specific examples of the (E) fatty acid having 8 to 22 carbon atoms include octanoic acid, nonanoic acid, capric acid, lauric acid, myristic acid, pentasilic acid, palmitic acid, margaric acid, octadecanoic acid, stearic acid, and nonadecane. Acid, arachidic acid, behenic acid, lignoceric acid, arachidonic acid, α-linolenic acid, eicosapentaenoic acid, docosahexaenoic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid , Nervonic acid, linoleic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, pinolenic acid, eleostearic acid, mead acid, dihomo-γ-linolenic acid, eicosatrienoic acid, 2-hydroxydecanoic acid, 2-hydroxylauric acid 2-hydroxymyristic acid, 2- Hydroxypalmitic acid, 2-hydroxystearic acid, 2-hydroxyarachidic acid, 2-hydroxybehenic acid, 3-hydroxyhexanoic acid, 3-hydroxyoctanoic acid, 3-hydroxynonanoic acid, 3-hydroxydecanoic acid, 3-hydroxy Undecanoic acid, 3-hydroxylauric acid, 3-hydroxytridecanoic acid, 3-hydroxymyristic acid, 3-hydroxypalmitic acid, 3-hydroxyheptadecanoic acid, 3-hydroxystearic acid, 15-hydroxypentadecanoic acid, 6-hydroxy Mention may be made of stearic acid, 12-hydroxyoleic acid and mixtures of two or more of the above fatty acids.

(V) (F) Other surfactants In a preferred embodiment, the air-entraining agent of the present invention may further contain (F) other surfactants. Other surfactants are anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants, and publicly known and publicly available ones can be used.
By adding the component (F) within the range in which the foaming property can be maintained, the air entrainment property can be improved while maintaining the foaming property.
Moreover, air entrainment can be further improved by combining 2 or more types of the said (F) component.
Specific examples of other surfactants that are the component (F) include those represented by the general formula: R- (OCH
₂ CH ₂ ) _n1- (OCH ₂ ) _m1 -COOH (wherein R represents an alkyl or alkenyl group having 12 to 24 carbon atoms, n1 represents 0 to 10 and m1 represents 0 or 1) ) Alkali metal salts of carboxylic acids, lower alkylamine salts of the carboxylic acids, lower alkanolamine salts of the carboxylic acids, polyoxyalkylene alkyl ether sulfates, rosinates, α-olefin sulfonates , Polyoxyalkylene alkyl ether phosphate ester salt, cocoamphoacetic acid alkali metal salt, and a mixture of two or more of the above surfactants. In terms of air entrainment, tall oil fatty acid soap, alkyl ether sulfate, Sodium α-olefin sulfonate and potassium salt of rosin are preferred.

When the component (F) is added, the mass ratio of the mixture of the component (A) and the component (B) to the component (F) is (A) + (B) :( F) = 99: 1 to The range is 1:99, and the range of 80:20 to 20:80 is preferable from the viewpoint of the temporal stability of the air amount.
The component (F) can be used alone, but it is preferable to use it as a mixture of two or more from the viewpoint of the stability over time of the air amount and the durability.
The air entraining agent of the present invention can be applied to all cement concrete, but when applied to concrete containing fly ash, the effect of improving the durability of the cured product can be further enhanced.
One factor contributing to the durability improvement effect is that the bubble spacing coefficient of the concrete can be reduced. This is because, when the air entraining agent of the present invention is used, a large number of bubbles having a small diameter are entrained in the concrete. It is speculated that it is retained without being lost after curing.

In relation to the component (F) of the present invention, JP-A-08-059320 discloses alkyl sulfonates, alkylaryl sulfonates, higher alcohol sulfates similar to the component (F) of the present invention, And an air entraining agent for cement compositions containing one or more salts selected from rosinates.
However, the air entraining agent for cement composition described in Japanese Patent Application Laid-Open No. 08-059320 is a fatty acid based on a lower alkylamine salt or a lower alkanolamine salt that does not belong to the components (A) and (B) of the present invention. It is completely different in that a surfactant is contained as an essential component and in addition, a component corresponding to the component (A) of the present invention is not contained.

The present invention also relates to a cement composition containing at least one of the above-mentioned air entraining agents and other concrete additives.
Specific examples of the above other concrete additives include high performance AE water reducing agent, high performance water reducing agent, AE water reducing agent, water reducing agent, AE agent, foaming agent, antifoaming agent, curing agent, water repellent, and setting accelerator. Examples thereof include an agent and a setting retarder.
The cement composition of the present invention can provide a cured product that maintains excellent air entrainment, and in addition, when the washing water of the cement composition is recovered, the amount of foaming is reduced. Can be improved and the foamability can be improved.

EXAMPLES Next, although an Example demonstrates this invention still in detail, this invention is not limited to an Example.
<(C) Production of an adduct obtained by adding an alkylene oxide to a trivalent or higher alcohol having 3 to 10 carbon atoms>
Production Example 1
A stainless steel autoclave equipped with a nitrogen inlet tube, a stirrer, and a thermometer was charged with 591 parts of glycerin and 5.3 parts of 96% caustic potash. The reaction vessel was sealed and the inside of the system was purged with nitrogen, and then the temperature was raised to 130 ° C. Thereafter, 3904 parts of ethylene oxide were introduced over 10 hours, and after completion of the introduction, aging was performed for 1 hour at the same temperature to obtain 4438 parts of a 14 mol EO adduct of glycerin.

Production Example 2
In the same procedure as in Production Example 1, 2024 parts of ethylene oxide was introduced over 8 hours to 708 parts of 14 mol EO adduct of glycerin and 5.7 parts of 96% caustic potash, and 60 mol EO adduct 2683 of glycerin was introduced. Got a part.

Production Example 3
In the same procedure as in Production Example 1, 2620 parts of ethylene oxide was introduced over 6 hours to 1871 parts of sorbit D and 9.2 parts of 96% caustic potash to obtain 4430 parts of a 6-mol EO adduct of sorbitol. .

Production Example 4
In the same procedure as in Production Example 1, 3039 parts of ethylene oxide was introduced over 10 hours to 1257 parts of 6 mol EO adduct of sorbitol and 4.1 parts of 96% caustic potash, and 30 mol EO adduct 4223 of sorbitol. Got a part.

Production Example 5
In the same procedure as in Production Example 1, 1866 parts of ethylene oxide was introduced over 6 hours to 860 parts of 6 mol EO adduct of sorbitol and 4.6 parts of 96% caustic potash, and then aged at the same temperature for 1 hour. did. Next, 224 parts of propylene oxide was introduced over 2 hours and then aged for 3 hours at the same temperature to obtain 2913 parts of 28 mol EO2PO adduct (block addition) of sorbitol.

Production Example 6
In the same procedure as in Production Example 1, 2086 parts of ethylene oxide was introduced over 8 hours to 622 parts of 6 mol EO adduct of sorbitol and 4.6 parts of 96% caustic potash, and then aged at the same temperature for 1 hour. did. Next, after introducing 243 parts of propylene oxide over 2 hours, the mixture was aged at the same temperature for 3 hours to obtain 2896 parts of 40 mol EO3PO adduct (block addition) of sorbitol.

Production Example 7 Production of Polyalkylene Glycol (BG20EO2PO) In the same procedure as in Production Example 1, 232 parts of 1,4-butanediol and 5.8 parts of 96% caustic potash were charged with 2269 parts of ethylene oxide over 8 hours. After the introduction, the mixture was aged at the same temperature for 1 hour. Next, after introducing 299 parts of propylene oxide over 2 hours and aging for 3 hours at the same temperature, 2760 parts of a 20-mol EO2PO adduct (block addition) of 1,4-butanediol was obtained.

Production Example 8
(D) Polyalkylene glycol compounds (PEG200, PEG400, PEG2000, PEG300) were added to the adduct obtained by adding alkylene oxide to (C) trivalent or higher alcohol having 3 to 10 carbon atoms, which was produced in Production Examples 1 to 6. -PO or BG20EO2PO produced in Production Example 7) was mixed to prepare compositions C1 to C8 and compositions X1 to X2, which were a mixture of component (C) and component (D).
Table 1 summarizes the type of component (C), the type of component (D) and the ratio of component (D) ((D) ratio (mass%)) used in each composition.
In addition, the ratio ((D) ratio (mass%)) of (D) component shown in Table 1 was determined by the LC analysis method mentioned later.
In addition, in the case of component (C), “number of added moles” in Table 1 indicates the number of moles of ethylene oxide (EO) and propylene oxide (PO) used per mole of alcohol used. In the case of component (D), in the case of PEG200, PEG400, PEG2000 and PEG300-PO, the number of moles of ethylene oxide (EO) used when it is assumed that 1 mole of the compound is produced by addition of alkylene oxide In the case of BG20EO2PO, the number of moles of ethylene oxide (EO) and the number of moles of propylene oxide (PO) used per mole of 1,4-butanediol used. Show.

[LC analysis method]
Analyzer: LC-20A (manufactured by Shimadzu Corporation)
Detector: ELSD-LTII (manufactured by Shimadzu Corporation)
Mobile phase: Water / acetonitrile (Binary Gradient)
Stationary phase: Kinetex 2.6u HILIC 100A (Phenomenex, 150 mm x 4.6 mm)
Calibration curve compounds: PEG200, PEG400, PEG2000, PEG4000

Examples 1 to 12 and Comparative Examples 1 to 2
A stainless steel autoclave with a nitrogen inlet tube, a stirrer, and a thermometer was charged with any of the compositions C1 to C8 and X1 to X2 shown in Table 1 and a fatty acid. Next, 0.3% by mass of 96% caustic potash was charged with respect to the total amount of charged raw materials, and the reaction system was purged with nitrogen, and then heated to 220 ° C. while introducing nitrogen at normal pressure. Thereafter, the dehydration reaction is continued at the same temperature until the acid value of the reaction product becomes 3.5 or less, and LC measurement is performed together. Unreacted (C) and (D) are below the lower limit of quantitation. The reaction was terminated, and mixtures of Examples 1 to 12 and Comparative Examples 1 and 2 (component (A) + component (B)) were obtained.
The type of composition used, the type of fatty acid used, and the molar ratio of the fatty acid used ((C) component and (D) of the fatty acid when the number of moles of all hydroxy groups present in the component is 1) The molar ratios used) are summarized in Table 3.

Test Example 1: Fresh mortar test A mortar was prepared according to JIS R 5201 according to the mortar formulation shown in Table 2 below and subjected to a mortar test. In this test, trial kneading was performed, and the amounts of the mixtures used in Examples 1 to 11 and Comparative Examples 1 and 2 were adjusted so that the amount of air in the mortar was 7.0 to 9.0%. Each air entrainer is weighed as part of the kneading water.
Specifically, a high-power mixer (manufactured by Maruto Manufacturing Co., Ltd.) is used for kneading mortar. First, kneading water and cement are kneaded at low speed for 30 seconds, then sand is added and kneaded at low speed for 30 seconds. mixed. Then, after kneading at high speed for 30 seconds, stirring was stopped and the mixture was allowed to stand for 90 seconds. The mortar adhering to the wall of the container was scraped off in 15 seconds from the start of standing, and after standing, kneading was performed at high speed for 60 seconds.
The mortar flow was measured using a JIS flow cone. The total mass method was adopted for the measurement of the air amount, and the air amount was calculated by the following formula from the result of measurement using a graduated cylinder. Air amount (%) = [1- (Mortar mass) / (Mortar mass at 0% of air amount determined from formulation)] × 100
In the test of washing water foaming property and foam breaking property, 100 g of tap water was added to 50 g of the mortar prepared in the above procedure and stirred well, and then the sludge was settled using a centrifuge (4400 rpm × 10 minutes). It was. 80 ml of the supernatant liquid from which sludge was removed was placed in a 200 ml graduated cylinder with a stopper. The measuring cylinder was tightly sealed, shaken for 30 seconds, allowed to stand, and the bubble height from immediately after the shaking until 90 seconds was recorded.
The results obtained are shown in Table 3.
“Usage amount” in Table 3 indicates the usage amount (solid content conversion) of the mixture of each example or comparative example with respect to cement when the mortar air amount is 7.0 to 9.0%.

Test Example 2: Concrete test An air entraining agent for concrete tests was prepared by combining any of the mixtures listed in Table 3 with various surfactants (one or two of F1 to F7).
Table (1 or 2 types of F1 to F7) and ratio (mass% of surfactant (F) when the mass of the air entraining agent is 100% (in terms of solid content)) It was summarized in 5.
Add 1.0% of the air-entraining agent and AE water reducing agent (Sea Cament J: Nippon Seika Co., Ltd., density 1.05 g / cm ³ ) prepared as above to the total amount of cement and fly ash. The prepared kneading water was added to cement, fly ash, fine aggregate and coarse aggregate, and kneaded for 90 seconds using a 55 liter forced biaxial mixer. Concrete was discharged and various measurements shown below were performed. Table 4 shows unit amounts of each material of the concrete subjected to the test.
For concrete after kneading, measure the slump and slump flow according to the procedure of JIS A 1101 and JIS A 1150, measure the air amount immediately after kneading and after 30 minutes according to the procedure of JIS A 1128, and visually confirm the state of the concrete did.
The fresh concrete produced by the above procedure was filled in a plastic mold of φ10 cm × 20 cm and cured to prepare a specimen. The central part of the specimen was cut to about φ10 × 1-2 cm, polished on both sides, and then used for measuring the bubble spacing coefficient of the hardened concrete. The test method was determined according to ASTM C 457-98 “Microscopical Determination of Parameters of the Air-Void System in Hardened Concrete”.
In the test for foaming property and defoaming property of washing water, wet screening mortar that passed through a mesh with a mesh size of 5 mm was collected from the concrete produced by the above procedure using a vibrator, and 100 g of tap water was added to 50 g of this mortar. After stirring well, the sludge was settled using a centrifuge (4400 rpm × 10 minutes). 80 ml of the supernatant liquid from which sludge was removed was placed in a 200 ml graduated cylinder with a stopper. The measuring cylinder was tightly sealed, shaken for 30 seconds, allowed to stand, and the bubble height from immediately after the shaking until 90 seconds was recorded.
As an index of resistance to freezing and thawing, the bubble spacing coefficient is 200 μm or less (Concrete Handbook: Japan Concrete Institute, ACI recommended value) or 250 to 300 μm or less (Concrete Science and Technology: Sankaido; Murata Jiro et al. ). However, these values are recommended values. Depending on the environmental conditions of the placed concrete, the resistance to freezing and thawing is good even if it is larger than this value, or the resistance is severe even in a severe environment. It may be inferior.
The results are shown in Table 5.

In Table 5, “Use amount” indicates the use amount (mass%, solid content conversion) of the air entraining agent with respect to the powder, and F1 to F7 mean the following.
F1: sodium soap of tall oil fatty acid F2: polyoxyethylene (4.5) sodium lauryl ether acetate (manufactured by Kao, Kao Akipo RLM-45NV)
F3: Sodium polyoxyethylene alkyl ether sulfate (manufactured by Toho Chemical Co., Ltd., Scope W-181S)
F4: sodium α-olefin sulfonate (manufactured by Lion, Lipolane LB-400)
F5: Potassium salt of rosin acid (manufactured by Toho Chemical Co., Ltd., Spiel K-20P)
F6: Polyoxyethylene (7) alkenyl (C18) sodium ether phosphate (manufactured by Toho Chemical Co., Ltd., Phosphanol RD-720)
F7: Amino acid-based amphoteric surfactant (manufactured by Toho Chemical Co., Ltd., ovazoline 552)

結果：
実施例１３ないし２４の組成物、即ち、（Ａ）成分と該（Ｂ）成分との質量比が、（Ａ
）：（Ｂ）＝８５：１５ないし９９．９８：０．０２の範囲内となる混合物を用いる組成物は、何れも優れた空気連行性を維持すると共にコンクリート洗浄水の回収水槽における泡立ちの発生量を低減し及び泡切れ性を改善したのに対して、（Ｂ）成分との質量比が、０．０２未満（検出限界以下）の混合物を用いる比較例３の組成物は、（Ｆ）成分を添加したのも拘わらず、上記に比して劣った結果しか示さなかった。
また、（Ｆ）成分を添加した場合、使用量を少なくしても、同程度の効果が維持される傾向にあった（実施例１３と実施例１４との比較、実施例１８と実施例１９との比較）。
（Ｆ）成分の２種の混合物を用いた実施例２３及び２４は、硬化前から硬化後における空気量低下の程度が小さかった。
気泡間隔係数（μｍ）の数値は、以下のような順番となることが分った。
（Ｆ）成分を含まない組成物＞１種の（Ｆ）成分を含む組成物＞２種の（Ｆ）成分を含む組成物

result:
The compositions of Examples 13 to 24 , that is, the mass ratio of the component (A) to the component (B) is (A
) :( B) = 85: 15 to 99.98: 0.02: All the compositions using the mixture maintain excellent air entrainment and generate foam in the concrete wash water recovery tank. The composition of Comparative Example 3 using a mixture having a mass ratio with the component (B) of less than 0.02 (below the detection limit), while reducing the amount and improving the foaming property, is (F) Despite the addition of ingredients, it showed only inferior results compared to the above.
Further, when the component (F) was added, the same level of effect tended to be maintained even when the amount used was reduced (comparison between Example 13 and Example 14 , Example 18 and Example 19). And comparison).
In Examples 23 and 24 using the two types of mixtures of the component (F), the degree of decrease in the amount of air after curing was small.
It was found that the numerical values of the bubble spacing coefficient (μm) were in the following order.
Composition containing no component (F)> Composition containing one type of component (F)> Composition containing two types of component (F)

Claims (8)

(A) a fatty acid ester of an adduct obtained by adding an alkylene oxide to a trivalent or higher alcohol having 3 to 10 carbon atoms;
(B) a fatty acid ester of a polyalkylene glycol compound,
The (B) component is a polyalkylene glycol compound represented by the following formula (3)
Y- [O- (AO) _{n / 2-} H] ₂ (3)
Wherein Y is a linear or branched alkylene group having 1 to 18 carbon atoms (the alkylene group may be substituted with 1 to 8 hydroxyl groups, and is preferably an aromatic ring group, preferably Represents an optionally substituted phenyl group), A represents an ethylene group, a 1,2-propylene group, a 1,2-butylene group or a 2,3-butylene group, and n represents 4 to 80 Represents a fatty acid ester,
An air entraining agent for a cement composition, wherein a mass ratio of the component (A) to the component (B) is in the range of (A) :( B) = 95: 5 to 99.98: 0.02. The component (A) and the component (B)
(C) a fatty acid ester of a mixture of an adduct obtained by adding alkylene oxide to a trivalent or higher alcohol having 3 to 10 carbon atoms and (D) a polyalkylene glycol compound,
The mass ratio of the component (C) to the component (D) is in the range of (C) :( D) = 95: 5 to 99.98: 0.02 .
The air entraining agent for cement composition according to claim 1, which is a fatty acid ester mixture. In the component (A), the addition number of alkylene oxide is in the range of 30 to 60 mol,
In the component (B), n represents 4 to 20.
The air entrainment agent for cement compositions according to claim 1 or 2. The component (A) is
(A) The fatty acid ester of an adduct obtained by adding ethylene oxide (EO) and 1,2-propylene oxide (PO) to a trivalent or higher valent alcohol having 3 to 10 carbon atoms. The air entraining agent for cement composition according to claim 1. (E) The air entrainment agent for cement compositions according to any one of claims 1 to 4, comprising a fatty acid having 8 to 22 carbon atoms. Furthermore, (F) The air entrainment agent for cement compositions of any one of Claim 1 thru | or 5 containing other surfactant. The component (F) is represented by the general formula: R— (OCH ₂ CH ₂ ) _n1 — (OCH ₂ ) _m1 —COOH (wherein R represents an alkyl group or alkenyl group having 12 to 24 carbon atoms, and n1 Represents 0 to 10, and m1 represents 0 or 1.) Alkali metal salt of carboxylic acid represented by: lower alkylamine salt of carboxylic acid, lower alkanolamine salt of carboxylic acid, polyoxyalkylene alkyl ether It is one or more surfactants selected from the group consisting of sulfate ester salts, rosinates, α-olefin sulfonates, polyoxyalkylene alkyl ether phosphate esters and cocoamphoacetic acid alkali metal salts. Item 7. An air entraining agent for a cement composition according to Item 6 . The air entraining agent for cement composition according to any one of claims 1 to 7 , and a high performance AE water reducing agent, a high performance water reducing agent, an AE water reducing agent, a water reducing agent, an AE agent, a foaming agent, and an antifoaming agent. A cement composition comprising at least one other concrete additive selected from the group consisting of an agent, a curing agent, a water repellent, a setting accelerator, and a setting retarder.