JPH06279081A - Production of hardened product of cement mortar concrete - Google Patents

Abstract

PURPOSE:To reduce drying shrinkage without deterioration of strength by admixing a specific compound to starting materials for cement mortar concrete, kneading and applying the mixture. CONSTITUTION:A water-soluble or water-dispersible acetylene alcohol of formula I [R1 is H or formula II (R2, R3 are H or l-8C alkyl; A is 2 to 3 C alkylene; n is 0 to 30) such as propargyl alcohol is added to starting materials for cement mortar concrete including cement, sand, aggregate and water in an amount of 0.5 to 10wt.% to give composition (A). Then, when needed, 50 to 500ppm of a fluorine surfactant and/or 0.05 to 1wt.% of a silicone surfactant are added to the composition to give composition (B). The composition (A) or (B) is kneaded and cast into a mold or frame and aged in a desired manner to produce the hardened cement mortar concrete.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a cement mortar or hardened concrete, which comprises adding a specific amount of a special organic compound to a raw material thereof.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
One of the serious drawbacks of cement mortar and hardened concrete (hereinafter referred to as cement composition) is that dry cracking is likely to occur. This is because the drying shrinkage of cement is large. Therefore, it is desired to reduce the drying shrinkage of the cement composition.

In order to reduce the drying shrinkage of the cement composition, a method of incorporating a latex such as an acrylic latex or a synthetic rubber latex into the cement composition is used, but in this case, the latex is relatively expensive. Since it is necessary to mix a large amount (for example, about 20 to 30% by weight with respect to cement), it is not economically preferable, and a fatal defect that the strength of the cement composition is significantly lowered occurs. Furthermore, the incorporation of large amounts of latex also has the serious drawback of impairing the noncombustibility of the cement composition.

In recent years, organic additives have been sought from another angle. For example, one of them is an alkylene oxide adduct of a specific lower alcohol found by the present inventors.
(Japanese Patent Publication No. 56-51148), it has an excellent effect of reducing shrinkage of cement. However, in order to prevent the dry cracking of the cement composition by using the additive, it was necessary to increase the addition amount to some extent.

It was also disclosed that acetylene glycol or its alkylene oxide adduct is added to the cement in an amount of 0.01 to 0.1% by weight to improve the compression strength. Has not yet been improved in drying shrinkage (JP-A-53-81527).
No. 4,116,706).

[0006]

Under these circumstances, the present inventors do not have the above-mentioned drawbacks, and can reduce the dry cracking of the cement composition with a smaller addition amount, which is effective in reducing shrinkage in cement. As a result of intensive studies on the agent, the present invention has been achieved.

That is, the present invention relates to cement mortar
In the method of kneading a concrete raw material and applying it to produce a hardened body, when the kneading is performed, the following chemical formula 1 is added to the cement.

[Chemical 1] (In the formula, R ₁ is hydrogen or the following Chemical formula 2,

[0007]

[Chemical 2] R ₂ and R ₃ are hydrogen or an alkyl group having 1 to 8 carbon atoms, A
Is a water-soluble or self-water-dispersible acetylene alcohol represented by an alkylene group having 2 to 3 carbon atoms, and n is a number from 0 to 30).
Is a method for producing a hardened cement mortar / concrete, which comprises adding 0.5 to 10% by weight of a compound of the type, or a fluorochemical surfactant and / or a silicone surfactant together.

The compound represented by Chemical Formula 1 of the present invention is acetylene alcohol, acetylene glycol, or acetylene alcohol obtained by reacting acetylene with a formaldehyde or a ketone compound having an alkyl group having 8 or less carbon atoms in the presence of an alkali. These are alkylene oxide adducts of these alcohols. In the case of an acetylene alcohol having an alkyl group having 9 or more carbon atoms, an acetylene glycol, or an alkylene oxide adduct of these alcohols, the shrinkage-reducing effect is lowered, which is not preferable.

Examples of the acetylene alcohol used in the present invention include propargyl alcohol (CH≡C-CH).
₂ OH), methylbutynol [CH≡C-C (CH ₃₎
(OH) CH ₃ ], methylpentinol [CH≡C-C
(CH ₃ ) (OH) C ₂ H ₅ ], dimethylhexinol [CH≡C—C (CH ₃ ) (OH) CH ₂ CH (C
H _{3) 2],} methyl heptylene Nord [CH≡C-C (CH
₃ ) (OH) C ₄ H ₉ ], methyloctinol [CH≡
C—C (CH ₃ ) (OH) C ₅ H ₁₁ ], methylnonanol [CH≡C—C (CH ₃ ) (OH) C ₆ H ₁₃ ], methyldecinol [CH≡C—C (CH ₃ ) (OH) C ₇ H
₁₅ ], methyl undecynol [CH≡C-C (CH ₃ )]
(OH) C ₈ H ₁₇ ], dimethyldecinol [CH≡C-
C (CH ₃ ) (OH) CH ₂ CH (CH ₃ ) C
₅ H ₁₁ ], ethylpentinol [CH≡C—C (C ₂ H
₅ ) (OH) C ₂ H ₅ ], methylethylhexinol [CH≡C—C (C ₂ H ₅ ) (OH) CH ₂ CH (CH
₃ ) CH ₃ ], ethylheptinol [CH≡C-C (C
₂ H ₅ ) (OH) C ₄ H ₉ ], ethyloctinol [C
H≡C—C (C ₂ H ₅ ) (OH) C ₅ H ₁₁ ], ethylnonanol [CH≡C—C (C ₂ H ₅ ) (OH) C
₆ H ₁₃ ], ethyldecinol [CH≡C-C (C
₂ H ₅ ) (OH) C ₇ H ₁₅ ], ethylundecinol [CH≡C—C (C ₂ H ₅ ) (OH) C ₈ H ₁₇ ], methylethyldecinol [CH≡C—C (C ₂ H ₅ ) (O
H) CH ₂ CH (CH ₃ ) C ₅ H ₁₁ ], propylhexynol [CH≡C—C (C ₃ H ₇ ) (OH) C
₃ H ₇ ], methylpropylhexynol [CH≡C-C
_{(C 3 H 7) (OH} ) CH 2 CH (CH 3) CH 3 ],
Propyl heptylene Nord _{[CH≡C-C (C 3 H 7} ) (O
H) C ₄ H ₉ ], propyloctinol [CH≡C-C
_{(C 3 H 7) (OH} ) C 5 H 11 ], propyl nonanol _{[CH≡C-C (C 3 H 7} ) (OH) C 6 H 13 ], propyl deci Nord [CH≡C-C (C ₃ H ₇ ) (OH) C
₇ H ₁₅ ], propyl undecynol [CH≡C-C (C
₃ H ₇ ) (OH) C ₈ H ₁₇ ], methylpropyldecinol [CH≡C—C (C ₃ H ₇ ) (OH) CH ₂ CH (C
H ₃₎ C ₅ H _11], butyl heptylene Nord [CH≡C-C
(C ₄ H ₉ ) (OH) C ₄ H ₉ ], methylbutylhexynol [CH≡C—C (C ₄ H ₉ ) (OH) CH ₂ CH
(CH ₃ ) CH ₃ ], butyloctinol [CH≡C-
C (C ₄ H ₉ ) (OH) C ₅ H ₁₁ ], butylnonanol [CH≡C—C (C ₄ H ₉ ) (OH) C ₆ H ₁₃ ], butyldecinol [CH≡C—C ( C ₄ H ₉ ) (OH) C ₇
H ₁₅ ], butyl undecynol [CH≡C-C (C ₄ H
₉ ) (OH) C ₈ H ₁₇ ], methylbutyldecinol [C
_{H≡C-C (C 4 H 9} ) (OH) CH 2 CH (CH 3)
C ₅ H ₁₁ ], pentyloctinol [CH≡C-C (C
₅ H ₁₁ ) (OH) C ₅ H ₁₁ ], pentylnonanol [C
H≡C—C (C ₅ H ₁₁ ) (OH) C ₆ H ₁₃ ], Pentyldecinol [CH≡C—C (C ₅ H ₁₁ ) (OH) C ₇ H
₁₅ ], pentyl undecynol [CH≡C-C (C ₅ H
₁₁ ) (OH) C ₈ H ₁₇ ], methylpentyldecinol [CH≡C—C (C ₅ H ₁₁ ) (OH) CH ₂ CH (CH
₃ ) C ₅ H ₁₁ ], hexylnonanol [CH≡C-C
_{(C 6 H 13) (OH} ) C 6 H 13 ], hexyl deci Nord _{[CH≡C-C (C 6 H 13} ) (OH) C 7 H 15 ], hexyl undecylenate Nord [CH≡C-C ( C ₆ H ₁₃ ) (O
H) C ₈ H ₁₇ ], methylhexyldecinol [CH≡C
_{-C (C 6 H 13) (} OH) CH 2 CH (CH 3) C 5 H
₁₁ ], heptyldecinol [CH≡C-C (C ₇ H ₁₅ ).
(OH) C ₇ H ₁₅ ], heptyl undecynol [CH≡
C—C (C ₇ H ₁₅ ) (OH) C ₈ H ₁₇ ], methylheptyldecinol [CH≡C—C (C ₇ H ₁₅ ) (OH) CH
₂ CH (CH ₃ ) C ₅ H ₁₁ ], octylundecinol [CH≡C—C (C ₈ H ₁₇ ) (OH) C ₈ H ₁₇ ], methyloctyldecinol [CH≡C—C (C ₈ H ₁₇ ) (O
H) CH ₂ CH (CH ₃ ) C ₅ H ₁₁ ] and the like.

Further, as an example of acetylene glycol,
Butynediol _{(HOCH 2 -C≡C-CH 2 OH} ),
Dimethylhexynediol [CH ₃ C (CH ₃ ) (O
H) -C≡C—C (CH ₃ ) (OH) CH ₃ ], dimethyloctynediol [C ₂ H ₅ C (CH ₃ ) (OH)-
C≡C—C (CH ₃ ) (OH) C ₂ H ₅ ], dimethyldecinediol [C ₃ H ₇ C (CH ₃ ) (OH) —C≡C
_{-C (CH 3) (OH)} C 3 H 7 ], dimethyl de decynediol _{[C 4 H 9 C (CH 3} ) (OH) -C≡C-C
_{(CH 3) (OH) C} 4 H 9 ], tetramethyldecynediol _{[CH 3 CH (CH 3) CH} 2 C (CH 3) (O
H) -C≡C-C (CH ₃ ) (OH) CH ₂ CH (CH
₃ ) CH ₃ ], dimethyltetradecynediol [C ₅ H
₁₁ C (CH ₃ ) (OH) -C≡C-C (CH ₃ ) (O
H) C ₅ H ₁₁ ], dimethyl hexadecyne diol [C _{6
H 13 C (CH 3) (} OH) -C≡C-C (CH 3) (O
H) C ₆ H ₁₃ ], dimethyl octadecine diol [C _{7
H 15 C (CH 3) (} OH) -C≡C-C (CH 3) (O
H) C ₇ H ₁₅ ], dimethyleicosindiol [C ₈ H
₁₇ C (CH ₃ ) (OH) -C≡C-C (CH ₃ ) (O
H) C ₈ H ₁₇ ], tetramethyloctadecine diol [C ₅ H ₁₁ CH (CH ₃ ) CH ₂ C (CH ₃ ) (OH)
_{-C≡C-C (CH 3) (} OH) CH 2 CH (CH 3)
C ₅ H ₁₁ ], diethyloctynediol [C ₂ H ₅ C
(C ₂ H ₅ ) (OH) -C≡C-C (C ₂ H ₅ ) (O
H) C ₂ H ₅ ], diethyldecynediol [C ₃ H ₇ C
(C ₂ H ₅ ) (OH) -C≡C-C (C ₂ H ₅ ) (O
H) C ₃ H ₇ ], diethyl dodecine diol [C ₄ H ₉
C (C ₂ H ₅ ) (OH) -C≡C-C (C ₂ H ₅ ) (O
H) C ₄ H ₉ ], dimethyldiethyldecynediol [C
_{H 3 CH (CH 3) CH} 2 C (C 2 H 5) (OH) -C
≡C—C (C ₂ H ₅ ) (OH) CH ₂ CH (CH ₃ ) C
H ₃ ], diethyltetradecynediol [C ₅ H ₁₁ C
(C ₂ H ₅ ) (OH) -C≡C-C (C ₂ H ₅ ) (O
H) C ₅ H ₁₁ ], diethylhexadecyne diol [C _{6
H 13 C (C 2 H 5} ) (OH) -C≡C-C (C 2 H 5)
(OH) C ₆ H _13], diethyl oct decynediol _{[C 7 H 15 C (C 2} H 5) (OH) -C≡C-C (C 2
_{H 5) (OH) C 7} H 15 ], diethyl Eiko Shinji ol _{[C 8 H 17 C (C 2} H 5) (OH) -C≡C-C (C
₂ H ₅ ) (OH) C ₈ H ₁₇ ], dimethyldiethyl octadecine diol [C ₅ H ₁₁ CH (CH ₃ ) CH ₂ C (C
₂ H ₅ ) (OH) -C≡C-C (C ₂ H ₅ ) (OH) C
_{H 2 CH (CH 3) C} 5 H 11 ], dipropyl decynediol _{[C 3 H 7 C (C 3} H 7) (OH) -C≡C-C
_{(C 3 H 7) (OH} ) C 3 H 7 ], dipropyl de decynediol _{[C 4 H 9 C (C 3} H 7) (OH) -C≡C-
C (C ₃ H ₇ ) (OH) C ₄ H ₉ ], dimethyldipropyldecynediol [CH ₃ CH (CH ₃ ) CH ₂ C (C
₃ H ₇ ) (OH) -C≡C-C (C ₃ H ₇ ) (OH) C
H ₂ CH (CH ₃ ) CH ₃ ], dipropyltetradecynediol [C ₅ H ₁₁ C (C ₃ H ₇ ) (OH) -C≡C-
_{C (C 3 H 7) (} OH) C 5 H 11 ], dipropyl hexa decynediol _{[C 6 H 13 C (C 3} H 7) (OH) -C
≡C—C (C ₃ H ₇ ) (OH) C ₆ H ₁₃ ], dipropyl octadecine diol [C ₇ H ₁₅ C (C ₃ H ₇ ) (O
_{H) -C≡C-C (C 3} H 7) (OH) C 7 H 15 ], dipropyl Eiko Shinji ol _{[C 8 H 17 C (C 3} H 7)
(OH) -C≡C-C (C 3 H 7) (OH) C
₈ H ₁₇ ], dimethyldipropyl octadecine diol [C ₅ H ₁₁ CH (CH ₃ ) CH ₂ C (C ₃ H ₇ ) (O
_{H) -C≡C-C (C 3} H 7) (OH) CH 2 CH (C
H ₃ ) C ₅ H ₁₁ ], dibutyldodecine diol [C ₄ H
_{9 C (C 4 H 9)} (OH) -C≡C-C (C 4 H 9)
(OH) C ₄ H ₉ ], dimethyldibutyldecynediol [CH ₃ CH (CH ₃ ) CH ₂ C (C ₄ H ₉ ) (OH)
-C≡C-C (C ₄ H ₉ ) (OH) CH ₂ CH (C
H ₃ ) CH ₃ ], dibutyltetradecinediol [C _{5
H 11 C (C 4 H 9} ) (OH) -C≡C-C (C 4 H 9)
(OH) C ₅ H _11], dibutyl hexa decynediol _{[C 6 H 13 C (C 4} H 9) (OH) -C≡C-C (C 4
H ₉ ) (OH) C ₆ H ₁₃ ], dibutyl octadecine diol [C ₇ H ₁₅ C (C ₄ H ₉ ) (OH) -C≡C-C
_{(C 4 H 9) (OH} ) C 7 H 15 ], dibutyl Eiko Shinji ol _{[C 8 H 17 C (C 4} H 9) (OH) -C≡C-
C (C ₄ H ₉ ) (OH) C ₈ H ₁₇ ], dimethyldibutyloctadecinediol [C ₅ H ₁₁ CH (CH ₃ ) CH _{2
C (C 4 H 9) (} OH) -C≡C-C (C 3 H 7) (O
_{H) CH 2 CH (CH 3} ) C 5 H 11 ], dipentyl tetramethyl decynediol _{[C 5 H 11 C (C 5} H 11) (OH) -
C≡C—C (C ₅ H ₁₁ ) (OH) C ₅ H ₁₁ ], dipentylhexadecyne diol [C ₆ H ₁₃ C (C ₅ H ₁₁ ) (O
_{H) -C≡C-C (C 5} H 11) (OH) C 6 H 13 ], dipentyl oct decynediol [C ₇ H ₁₅ C (C
₅ H ₁₁ ) (OH) -C≡C-C (C ₅ H ₁₁ ) (OH) C
₇ H ₁₅ ], dipentyl eicosindiol [C ₈ H ₁₇ C
(C ₅ H ₁₁ ) (OH) -C≡C-C (C ₅ H ₁₁ ) (O
H) C ₈ H _17], dimethyl dipentyl octa decynediol _{[C 5 H 11 CH (CH 3} ) CH 2 C (C 5 H 11)
(OH) -C≡C-C (C 5 H 11) (OH) CH 2 CH
(CH ₃₎ C ₅ H _11] and the like, other methyl butynediol _{[HOCH 2 -C≡C-CH (CH 3} ) OH ], methylpentene Chin diol [HOCH ₂ -C≡C-CH (C
H ₃ ) ₂ OH], methylethylheptindiol [CH
₃ C (C ₂ H ₅ ) (OH) -C≡C-C (CH ₃ ) (O
H) CH ₃ ], trimethyloctynediol [CH ₃ C
_{H (CH 3) CH 2 C} (CH 3) (OH) -C≡C-C
(CH ₃ ) (OH) CH ₃ ] and the like.

In the case of acetylene glycol, R in R _1
2, R ₃ groups are not necessarily symmetric with respect to the acetylene group can take different alkyl groups within the carbon number of the alkyl group R _2, R _3. Among these various acetylene alcohols and acetylene glycols, R ₂ and R _{3 in} Chemical formula 1 are hydrogen or a carbon number of 1 to 4 from the viewpoint of shrinkage reduction effect.
It is preferable that the total number of carbon atoms of the alkyl groups R ₂ and R ₃ is within the range of 0-10.

In the chemical formula 1 of the present invention, the following chemical formula 3

[Chemical 3] The alkylene oxide constituting the is ethylene oxide and / or propylene oxide.

In the present invention, n is an alkyl group R
_When the total number of carbon atoms of ₂ and R ₃ is 0-10, the number is 0-30, and when it is 11-32, the number is 2-30. The total carbon number of the alkyl groups R ₂ and R ₃ is 11 to 32.
In the case of acetylene alcohol or acetylene glycol, the compound itself has little solubility in water, and the effect of reducing shrinkage is significantly reduced. Therefore, in the case of acetylene alcohol, at least 2 mol of ethylene oxide should be added on average per mol of the acetylene alcohol, and in the case of acetylene glycol, at least 4 mol of ethylene oxide should be added per mol of the acetylene glycol. is necessary. In some cases, 2 or 4 mol or more of ethylene oxide and propylene oxide may be co-added in a block or random manner before use. When co-adding,
A molar ratio of ethylene oxide / propylene oxide of at least 0.2 is necessary in order to maintain the solubility and affinity in water and exert the shrinkage reducing effect.
Further, the mono- or polyoxyalkylene group to be added to acetylene glycol does not need to be symmetrical to the acetylene group, even if it is added to only one hydroxyl group, or even if the oxyalkylene groups added to both hydroxyl groups are different from each other. Furthermore, the structure of co-addition such as block or random may be different. If the number of n exceeds 30, the effect of reducing shrinkage will be reduced, which is not preferable. When the total number of carbon atoms of the alkyl groups R ₂ and R ₃ is 0 to 10 among the compounds represented by Chemical formula 1 of the present invention, the solubility in water is sufficient even if n is 0, Since it also has a sufficient shrinkage reducing effect, it can be used without adding alkylene oxide. However, since addition of alkylene oxide often improves the shrinkage reducing effect, addition is preferable. In this case, n is preferably a number within the range of 2 to 10 from the viewpoint of shrinkage reduction effect.
Further, among the compounds represented by Chemical formula 1, an alkyl group R ₂
When the total number of carbon atoms of R ₃ and R ₃ is 0 to 10, a propylene oxide added alone is also preferable, and a propylene oxide and ethylene oxide co-added is more preferable from the viewpoint of the shrinkage reducing effect. In this case, the ethylene oxide / propylene oxide molar ratio is preferably in the range of 0 to 5, particularly preferably in the range of 0.2 to 5. In addition, alkylene oxides such as butylene oxide and styrene oxide other than ethylene oxide and propylene oxide may be co-added (usually 50% by weight or less in total oxyalkylene) within a range not impairing the performance.

In the present invention, an excellent shrinkage-reducing effect can be obtained by using one or a mixture of two or more compounds represented by Chemical Formula 1 as an essential component. The combined use of an activator improves the shrinkage reduction effect by a synergistic effect, which is very preferable. There are cation type, nonionic type and anion type in the fluorine-containing surfactant and silicone type surfactant used in combination, respectively, and any of these can be used, but the cation type and nonionic type are effective in reducing shrinkage. Are preferred, and nonionic ones are particularly preferred.

The fluorine-containing surfactant used in the present invention may be a commercially available one and is not particularly limited. A typical example of a cationic fluorine-containing surfactant is a compound having a perfluoroalkyl group having 5 to 18 carbon atoms as a hydrophobic group and a cationic hydrophilic group (for example, a quaternary ammonium base). There is. For example, "Florard FC-134" manufactured by Sumitomo 3M Limited, "Megafuck F-150" manufactured by Dainippon Ink and Chemicals Incorporated.
Other examples include "Surflon S-121" manufactured by Asahi Glass Co., Ltd. and "Stargent 30" manufactured by Neos Co., Ltd.
0 "," F-top EF-123B "manufactured by Tohoku Fertilizer Co., Ltd.,
Examples include "F-top EF-132".

As a typical example of the nonionic fluorine-containing surfactant, a perfluoroalkyl group having 5 to 18 carbon atoms is used as a hydrophobic group, and from this and a nonionic hydrophilic group (for example, an ethylene oxide adduct). There is a compound. For example, “Florard FC-17” manufactured by Sumitomo 3M Limited
0C "," Megafuck F "manufactured by Dainippon Ink and Chemicals, Inc.
-142D "," F-144D "," F-171 "," F-177 "
", Surflon S-141" manufactured by Asahi Glass Co., Ltd., "Stargent 200", "251" manufactured by Neos Co., Ltd.
Tohoku Fertilizer Co., Ltd. “F-top EF-121”, “EF-
122A, EF-122B, EF-122C, EF-122A3
And so on. As a typical example of the anionic fluorine-containing surfactant, a perfluoroalkyl group having 5 to 18 carbon atoms is used as a hydrophobic group, and anionic hydrophilic group (for example, sulfonic acid group, carboxylic acid group, phosphoric acid group) is used. And ester groups). This includes "Florard FC-95", "FC-98" manufactured by Sumitomo 3M Limited,
"FC-126", "FC-128", Dainippon Ink and Chemicals, Inc.
"Megafuck F-110", "F-113", "F"
-120 "," F-812 "," F-191 ", Asahi Glass Co., Ltd.
"Surflon S-111", "S-112", "S-1"
13 "," Stargent 100 "manufactured by Neos Co.,
"150", "F-top EF-102" manufactured by Tohoku Fertilizer Co., Ltd.
, `` EF-103 '', `` EF-112 '', `` EF-123A '', `` E
F-123B ”and the like. In addition to the above, cationic, anionic and nonionic fluorine-containing surfactants are available from Daikin Industries, Ltd., Kanto Denka Co., Ltd., Du Pont,
It is also commercially available from ICI, Hoechst and CIBA-GEIGY, and these can also be used as the fluorine-containing surfactant of the present invention.

As the silicone-based surfactant used in the present invention, polysiloxane is used as a hydrophobic group, a cationic hydrophilic group (for example, a fourth ammonium base), and a nonionic hydrophilic group (for example, alkylene group). There are compounds having an anionic hydrophilic group (for example, sulfate ester salt, phosphate ester salt, carboxylate salt, etc.). In Japan, Toray Silicone Co., Ltd., Shin-Etsu Silicone Co., Ltd., Toshiba Silicone Co., Ltd.
Various products are commercially available from, for example, and these various products can be used in the present invention.

The cement used in the present invention is a conventional ordinary cement,
Portland-based cements such as early strength and mixed cements are mentioned, and these are not particularly limited.

In the present invention, the addition amount of the compound represented by Chemical formula 1 varies depending on the carbon number of the alkyl group and the carbon number of the alkylene group, but is usually 0.5 to 10% by weight with respect to the cement. If the addition amount is less than 0.5% by weight, the effect of reducing shrinkage is low, while if it exceeds 10% by weight, the strength of the cement composition is about 2/3 or less as compared with that of the additive-free composition, which is not practical. A particularly preferred amount of addition is 1 to 4% by weight.

When the compound represented by Chemical formula 1 is used in combination with the fluorine-based surfactant and / or the silicone-based surfactant, the effect of reducing shrinkage is increased by a synergistic effect. In this case, the addition amount of the compound represented by Chemical formula 1 is 0.5 to 10% by weight with respect to the cement, the fluorine-based surfactant is 50 to 500 ppm with respect to the weight of the cement, and the silicone-based surfactant is 0.05 to 0.05% with respect to the cement. It is 1% by weight.

The means for adding the compound used in the present invention is as follows:
It is the same as in the case of a commonly used cement admixture. For example, it is possible to employ a means of previously mixing an appropriate amount of the compound with kneading water, or adding an appropriate amount of the compound when kneading a mixture of cement, aggregate and water.

The compound represented by Chemical formula 1 can be used in combination with other components (optional components). Such optional components include metal chlorides such as calcium chloride and sodium chloride, metal sulfates such as sodium sulfate,
Well-known cement hardening accelerators such as organic amines such as triethanolamine, well-known cement hardening retarders such as alcohols, sugars, starch, glycerin and sodium polyphosphate, well-known reinforcing bars such as sodium nitrite and calcium nitrite. Anticorrosion agent, lignin sulfonic acid, oxycarboxylic acid,
Various known cement dispersants such as naphthalene sulfonic acid formalin condensate, melamine sulfonic acid formalin condensate, known cement pastes such as carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl starch, phosphorylated starch, sodium alginate, etc. There are things.

The method of applying the kneaded product of mortar or concrete to which the compound shown in Chemical formula 1 is added may be the same as the conventional method, such as trowel coating, filling in a mold, spray coating, pouring with a caulking gun, and the like. Can be taken. Also,
The curing method may be any of air dry curing, wet air curing, underwater curing, heating accelerated curing (steam curing, autoclave curing, etc.), or these methods may be used in combination.

[0024]

The present invention will be described below with reference to examples, but the present invention is not limited thereto. Example 1 Various acetylene alcohols obtained by reacting acetylene with formaldehyde or a ketone compound in the presence of alkali, acetylene glycol, or alkylene oxide adducts thereof were appropriately selected. The shrinkage reduction rate of the cured mortar obtained by adding these compounds as pure components at a ratio of 3.5% by weight to cement was measured by the dial gauge method of JIS A 1129, and the strength was determined by JIS R 5201. It measured and obtained the result of Table 1 (1) and Table 1 (2). The amount of mixed air was measured for concrete according to JIS A1128.

Regarding the mixing ratio, in the case of mortar, the water / cement ratio is 65%, and the sand / cement ratio is 200%, and in the case of concrete, the unit cement amount is 300 kg / m ³ ,
The water / cement ratio was 60% and the fine aggregate ratio was 44%. In Tables 1 (1) and 1 (2), EO represents ethylene oxide and PO represents propylene oxide.

[0026]

[Table 1 (1)]

[0027]

[Table 1 (2)]

Example 2 A test was conducted in the same manner as in Example 1 except that the compound of No. 3 in Example 1 was used and the addition amount was changed, and the results shown in Table 2 were obtained.

[0029]

[Table 2]

Example 3 The compound No. 3 in Example 1 was used in an amount of 2.0% by weight with respect to ordinary Portland cement, various fluorine-containing surfactants were used in an amount of 200 ppm with respect to the cement, or silicone-based surfactants were used in the cement. On the other hand, the shrinkage ratio, the air content and the strength were measured in the same manner as in Example 1 by using 0.1% by weight together, and the results in Table 3 were obtained.

[0031]

[Table 3]

Example 4 The compound of No. 11 in Example 1 was added to cement at 2.0.
% By weight, and Surflon S- as a fluorochemical surfactant
141 and SH 3747 as a silicone-based surfactant were tested in the same manner as in Example 1 while changing the addition amount, and the results in Table 4 were obtained.

[0033]

[Table 4]

[0034]

When the compound represented by Chemical formula 1 is added to the cement in an amount of 0.5 to 10% by weight, a drastic reduction in drying shrinkage is achieved as compared with the case where no addition is made. In addition, the noncombustibility of the cement composition is less likely to be impaired, and the cement composition does not significantly decrease in strength even at a high addition amount (for example, about several%).

Claims (2)

[Claims] 1. A method for producing a hardened product by kneading cement mortar / concrete raw materials and applying the raw material to the cement, when the kneading is performed, the following chemical formula 1 is applied to the cement. (In the formula, R ₁ is hydrogen or the following Chemical formula 2, R ₂ and R ₃ are hydrogen or an alkyl group having 1 to 8 carbon atoms, A
Is a water-soluble or self-water-dispersible acetylene alcohol represented by an alkylene group having 2 to 3 carbon atoms, and n is a number from 0 to 30).
A method for producing a hardened cement mortar / concrete, characterized by comprising adding 0.5 to 10% by weight of a rutile compound. 2. A method for producing a hardened product by kneading cement mortar / concrete raw materials and applying the same to the cement when the kneading is carried out. (In the formula, R ₁ is hydrogen or the following Chemical formula 2, R ₂ and R ₃ are hydrogen or an alkyl group having 1 to 8 carbon atoms, A
Is a water-soluble or self-water-dispersible acetylene alcohol represented by an alkylene group having 2 to 3 carbon atoms, and n is a number from 0 to 30).
A method for producing a hardened cement mortar / concrete, which comprises adding 0.5 to 10% by weight of a fluorine-based compound, and further adding a fluorine-based surfactant and / or a silicone-based surfactant.