JP7037170B2 - Additives for hydraulic compositions - Google Patents

Description

The present invention relates to an additive for a hydraulic composition, and more particularly to an additive for a hydraulic composition capable of increasing the strength of the initial age of a cured product obtained by curing the prepared hydraulic composition. ..

The hydraulic composition is obtained by kneading a hydraulic binder and a material such as water and then filling the mold, and after curing, the mold is demolded to obtain a cured product. Among them, concrete products are products made by kneading materials such as cement, water, aggregates, and dispersants, placing them in a mold, and hardening them. Improving the strength of the initial age leads to the production of more concrete products using the same formwork, so it is required to shorten the time to reach the strength that can be demolded after concrete placement. For this purpose, various additives have been studied, and inorganic salts such as calcium chloride, nitrite and nitrate (see, for example, Non-Patent Document 1), glycerin, alkanolamine and the like are disclosed (for example, Patent Document). See 1 and 2).

Japanese Unexamined Patent Publication No. 2009-256201 Japanese Unexamined Patent Publication No. 2011-236127

Fumiki Tomozawa et al., "Development and Latest Technology of Concrete Admixtures", CMC Publishing Co., Ltd., 1995

The use of calcium chloride is restricted due to the problem of corrosion of the reinforcing bars of reinforced concrete, and a large amount of nitrite or nitrate may be required. Alkanolamine and glycerin can also improve the strength of the initial age, but further improvement of the strength of the initial age is required.

The problem to be solved by the present invention is to obtain the strength required for demolding in a shorter time without lowering the strength of the cured product of the hydraulic composition at 1 to 2 weeks. That is, the quick strength can be improved, and high compressive strength is ensured by short-time curing such as compression strength 24 hours after water injection and compressive strength 5 hours after heat curing at 20 ° C. It is to be.

As a result of research to solve the above-mentioned problems, the present inventors have found that an additive for a water-hardening composition composed of a specific organic compound is correctly suitable. According to the present invention, the following additives for hydraulic composition are provided.

[1] An additive for a water-hard composition used for a water-hard composition containing a water-hard binder, which comprises a dialkanolamine and a diethylene glycol , wherein the dialkanolamine is a diethanolamine and / or a diisopropanolamine. The mass ratio of the dialkanolamine to the diethyleneglycol (dialkanolamine / diethyleneglycol) is in the range of 0.2 to 100, and the water-hardness binder is kneaded with water and the water-hardness is added. Additive for water-hard composition used when preparing a composition.

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[ 2 ] The additive for a hydraulic composition according to [1 ], which further contains sulfuric acid and / or a sulfonic acid compound.

[ 3 ] The additive for a water-hard composition according to [ 2 ], wherein the sulfonic acid compound is toluenesulfonic acid or methanesulfonic acid.

[ 4 ] The molar ratio of the amine of the dialkanolamine to the acid of the sulfuric acid and the sulfonic acid compound (amine of the dialkanolamine / (acid of the sulfuric acid and the sulfonic acid compound)) is in the range of 0.1 to 2. The additive for a water-hardening composition according to [ 2 ] or [ 3 ].

[ 5 ] The additive for a hydraulic composition according to any one of [1] to [ 4 ], which further contains a dispersant.

The water-hardening composition prepared by using the additive of the present invention enhances the strength of the initial material age of the cured product obtained by curing, and demolds the cured product without reducing the strength of the material age of 1 to 2 weeks. There is an effect that the required strength can be obtained in a shorter time.

Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments. Therefore, it should be understood that the following embodiments can be appropriately modified, improved, or the like based on the ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. In the following examples and the like, unless otherwise specified,% means mass% and parts mean parts by mass.

The additive for a hydraulic composition according to the embodiment of the present invention is an additive for a hydraulic composition used for a hydraulic composition containing a hydraulic binder, and is a hydraulic composition composed of dialkanolamine and diethylene glycol. Additive for use.

The dialkanolamine used in the additive for the water-hardening composition of the present embodiment (hereinafter, also referred to as the additive of the present embodiment) is diethanolamine and / or diisopropanolamine , and as a reference example , N-alkyldiethanolamine, N- Examples thereof include alkyldiisopropanolamine, and among them, diethanolamine and diisopropanolamine are preferable.

The amount of the dialkanolamine used in the additive of the present embodiment is preferably 0.01 to 1 part by mass, more preferably 0.02 to 0.8 part by mass with respect to 100 parts by mass of the hydraulic binder such as cement. preferable.

As the diethylene glycol used as the additive of the present embodiment, those commercially available as general industrial products can be used.

The amount of diethylene glycol used in the additive of the present embodiment is preferably 0.001 to 1 part by mass, more preferably 0.002 to 0.5 part by mass with respect to 100 parts by mass of the hydraulic binder such as cement. If the amount of diethylene glycol used is too small, there is no effect, and if it is too large, the compressive strength of the material age of about 1 to 4 weeks decreases.

The mass ratio of dialkanolamine to diethylene glycol (dialkanolamine / diethylene glycol) is preferably in the range of 0.2 to 100, and more preferably in the range of 1 to 50.

The additive of the present embodiment preferably further contains a sulfuric acid and / or a sulfonic acid compound. Examples of the sulfonic acid compound include paratoluene sulfonic acid, methane sulfonic acid, benzene sulfonic acid, dodecylbenzene sulfonic acid and the like. Among them, those selected from sulfuric acid, p-toluenesulfonic acid and methanesulfonic acid are preferable. In the present specification, the term "A and / or B" means both "A and B" and "A or B". Therefore, the additive of the present embodiment may further contain sulfuric acid, may further contain a sulfonic acid compound, or may further contain sulfuric acid and a sulfonic acid compound. May be.

Combining a dialkanolamine with a sulfuric acid and / or a sulfonic acid compound means neutralizing the dialkanolamine with a sulfuric acid and / or a sulfonic acid compound. The molar ratio of dialkanolamine to the acid of sulfuric acid and the sulfonic acid compound is not particularly limited. However, the molar ratio of the amine of dialkanolamine to the acid of the sulfuric acid and the sulfonic acid compound (amine of dialkanolamine / (acid of the sulfuric acid and the sulfonic acid compound)) is preferably 0.1 to 2, preferably 0.5 to 2. 1.5 is more preferred.

The additive of the present embodiment preferably further contains a dispersant. Examples of such a dispersant include aromatic sulfonic acid-based dispersants such as naphthalene-based dispersants, phenol-based dispersants, and lignin-based dispersants, polycarboxylic acid-based dispersants, and dispersants such as phosphoric acid ester-based dispersants. Can be mentioned. Among them, as the dispersant, a naphthalene-based dispersant, an aromatic sulfonic acid-based dispersant as a melamine-based dispersant, and a polycarboxylic acid-based dispersant are preferable, and a naphthalene-based dispersant and a naphthalene-based dispersant are preferable from the viewpoint of ensuring quick toughness. A polycarboxylic acid-based dispersant is more preferable.

As the naphthalene-based dispersant, a naphthalene sulfonic acid formaldehyde condensate (Mighty 150 (trade name) manufactured by Kao Corporation, Paul Fein 510-AN (trade name) manufactured by Takemoto Oil & Fats Co., Ltd., etc.) can be used. As the melamine-based dispersant, a melamine sulfonic acid formaldehyde condensate (Paul Fein MF (trade name) manufactured by Takemoto Oil & Fat Co., Ltd., Accelerate 100 (trade name) manufactured by Nissan Chemical Industry Co., Ltd., etc.) can be used. .. Examples of the phenol-based dispersant include a phenol sulfonic acid formaldehyde condensate (compound described in JP-A-46-104919), a phenol phosphate formaldehyde condensate (compound described in JP-A-2012-504695), and the like. Can be used. As the lignin-based dispersant, lignin sulfonate (Sun extract (trade name), Vanillex (trade name), Pearllex (trade name), etc. manufactured by Nippon Paper Chemicals Co., Ltd.) can be used.

Examples of the polycarboxylic acid-based copolymer include a monoester of polyalkylene glycol and (meth) acrylic acid and a copolymer of a carboxylic acid such as (meth) acrylic acid; an unsaturated alcohol having polyalkylene glycol and (meth). A copolymer with a carboxylic acid such as acrylic acid (for example, JP-A-2007-119337); a copolymer of an unsaturated alcohol having a polyalkylene glycol and a dicarboxylic acid such as maleic acid can be used. In addition, (meth) acrylic acid means acrylic acid or methacrylic acid.

As the polycarboxylic acid-based copolymer, a copolymer obtained by polymerizing a monomer represented by the following formula (1) with a carboxylic acid monomer can be used.

In equation (1)
^R1 represents an alkenyl group having 2 to 5 carbon atoms or an unsaturated acyl group having 3 or 4 carbon atoms.
^R2 represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an aliphatic acyl group having 1 to 22 carbon atoms.
X represents a (poly) oxyalkylene group having an average number of moles of 1 to 300, which is composed of an oxyalkylene group having 2 to 4 carbon atoms.

Examples of the alkenyl group having 2 to 5 carbon atoms of ^R1 in the formula (1) include a vinyl group, an allyl group, a methallyl group, a 3-butenyl group, a 2-methyl-1-butenyl group and a 3-methyl-1-butenyl group. Examples thereof include a group, a 2-methyl-3-butenyl group, a 3-methyl-3-butenyl group and the like. Examples of the unsaturated acyl group having 3 or 4 carbon atoms of R ¹ include an acryloyl group and a methacryloyl group. Among these, an allyl group, a methallyl group, a 3-methyl-1-butenyl group, an acryloyl group, and a methacryloyl group are preferable. One or two or more of these monomers represented by the formula (1) may be used.

Examples of R ² in the formula (1) include 1) a hydrogen atom, 2) an alkyl group having 1 to 22 carbon atoms, and 3) an aliphatic acyl group having 1 to 22 carbon atoms.

Examples of X in the formula (1) include a polyoxyalkylene group composed of 1 to 300 (poly) oxyalkylene units. Of these, a (poly) oxyalkylene group composed of 1 to 160 oxyethylene units and / or oxypropylene units is preferable.

Examples of the carboxylic acid monomer constituting the (co) polymer include (meth) acrylic acid, crotonic acid, and dicarboxylic acid. There are maleic acid, itaconic acid, fumaric acid, succinic acid mono (2- (meth) acryloyloxyethyl) and the like and salts thereof. Of these, (meth) acrylic acid, maleic acid, (meth) acrylic acid salt, and maleic acid salt are preferable.

Examples of the carboxylic acid monomer salt include alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium salt and magnesium salt, ammonium salts, diethanolamine salts and amine salts such as triethanolamine salt. Can be mentioned.

When producing the above (co) polymer, other copolymerizable monomers such as styrene, acrylamide, and (meth) allylsulfonic acid (salt) may be used in combination.

The additive of this embodiment is used when preparing a hydraulic composition. For example, it is used when preparing a hydraulic composition using a hydraulic binder containing cement, water, fine aggregate, coarse aggregate, AE agent and the like.

Examples of the hydraulic binder include cement, blast furnace slag fine powder, fly ash, silica foam and the like. Of these, those containing cement are preferable. As the cement, various Portland cements such as ordinary Portland cement, early-strength Portland cement, and moderate heat Portland cement, as well as various mixed cements such as blast furnace cement, fly ash cement, and silica fume cement can be used.

Further, as the fine aggregate, known river sand, mountain sand, sea sand, crushed sand, slag sand and the like can be used. Further, as the coarse aggregate, known river gravel, crushed stone, lightweight aggregate and the like can be used.

In preparing the water-hardening composition, 1) an air amount adjuster such as rosin soap, alkyl aromatic sulfonate, aliphatic alkyl (ether) sulfate, and alkyl phosphate ester, and 2) dimethylpolysiloxane-based, poly. Antifoaming agents such as alkylene glycol fatty acid ester-based, mineral oil-based, oil-based, oxyalkylene-based, alcohol-based, and amide-based defoaming agents can be used.

When using the additive of the present embodiment, a coagulation accelerator, a coagulation retarder, a rust preventive agent, a waterproof agent and the like can be used in combination within a target range. Further, the method of using the additive of the present embodiment may be either a method of adding the additive together with the kneading water at the time of preparing the concrete composition, a method of adding the additive to the concrete composition immediately after kneading, or the like.

The additive of the present embodiment is preferably a one-component multifunctional admixture in which various components are mixed in advance.

In the step of filling the mold with the hydraulic composition using the additive of the present embodiment, curing and curing, the obtained hydraulic composition is filled in the mold and cured. Examples of the formwork include formwork for buildings and formwork for concrete products. Examples of the method of filling the hydraulic composition into the mold include a method of directly charging the hydraulic composition from a mixer and a method of pumping the hydraulic composition into the mold.

Heat curing can be performed to accelerate the curing of the hydraulic composition. The heat curing is carried out by holding the hydraulic composition at a temperature of 40 ° C. or higher and 80 ° C. or lower.

Hereinafter, examples and the like will be given in order to make the configuration and effect of the present invention more specific, but the present invention is not limited to the examples. In the following examples and the like, unless otherwise specified,% means mass% and parts mean parts by mass.

Preparation of Additives for Hydraulic Composition (Examples 1 to 14):
Dialkanolamine, diethylene glycol (DEG), ion-exchanged water and the like were blended in the proportions shown in Table 1 to prepare an aqueous solution of an additive for a water-hard composition.

In Table 1, the following terms have the following meanings.
DEA: Diethanolamine.
DIPA: Diisopropanolamine.
DEF: Diethylene glycol.
MSA: Methanesulfonic acid.
PTS: Paratoluenesulfonic acid / monohydrate.
TEA: Triethanolamine (reagent).
TIPA: Triisopropanolamine (reagent).
A / B: Mass ratio of dialkanolamine / diethylene glycol.
A / C: Amine ratio of dialkanolamine / (acid of sulfuric acid and sulfonic acid compound).

The mass average molecular weight of the copolymer (dispersant) obtained by the polymerization shown in the following example was measured by gel permeation chromatography.
(Measurement condition)
Equipment: Shodex GPC-101 (manufactured by Showa Denko).
Column: OHpak SB-G + SB-806M HQ + SB-806M HQ (manufactured by Showa Denko).
Detector: Differential refractometer (RI).
Eluent: 50 mM sodium nitrate aqueous solution.
Flow rate: 0.7 mL / min.
Column temperature: 40 ° C.
Sample concentration: Eluent solution with a sample concentration of 0.5% by weight.
Standard material: polyethylene oxide, polyethylene glycol.

-Manufacturing of dispersant (PC-1):
First, ion-exchanged water 165.5 g, α-methacryloyl-ω-methoxy-poly (n = 45) oxyethylene 133.4 g, methacrylic acid 22.2 g, and 3-mercaptopropionic acid 1.6 g were added to a thermometer, agitator, and the like. It was placed in a reaction vessel equipped with a dropping funnel and a nitrogen introduction tube (hereinafter, the same was used), and the mixture was uniformly dissolved with stirring. Then, the atmosphere of the reaction system in which each of the above-mentioned components was dissolved was replaced with nitrogen, and the temperature of the reaction system was set to 65 ° C. in a water bath. Next, 27.3 g of 1.0% hydrogen peroxide solution was added, and then the temperature was maintained at 65 ° C. for 6 hours to complete the polymerization reaction. Then, a 30% aqueous sodium hydroxide solution was added to adjust the pH to 6, and the concentration was adjusted to 40% with ion-exchanged water to obtain a reaction mixture. The mass average molecular weight of the obtained reaction mixture was measured and found to be 35,000. This reaction mixture was used as a dispersant (PC-1).

-Manufacturing of dispersant (PC-2):
41.4 g of ion-exchanged water was charged in a reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, and a nitrogen introduction tube, the atmosphere was replaced with nitrogen while stirring, and the temperature of the reaction system was set to 70 ° C. in a warm water bath. In 188.0 g of ion-exchanged water, α-methacryloyl-ω-methoxy-poly (n = 130)
An aqueous solution in which 188.0 g of oxyethylene, 12.0 g of methacrylic acid, 2.0 g of sodium methallyl sulfonate and 4.0 g of 3-mercaptopropionic acid were dissolved was added dropwise over 3 hours. At the same time, an aqueous solution prepared by dissolving 3.0 g of ammonium persulfate in 26.0 g of ion-exchanged water was added dropwise over 4 hours, and then the temperature was maintained at 70 ° C. for 1 hour to complete the polymerization reaction. Then, a 30% aqueous sodium hydroxide solution was added to adjust the pH to 6, and the concentration was adjusted to 40% with ion-exchanged water to obtain a reaction mixture. The mass average molecular weight of the obtained reaction mixture was measured and found to be 45,000. This reaction mixture was used as a dispersant (PC-2).

-Manufacturing of dispersant (PC-3):
It was charged in a reaction vessel equipped with 72.0 g of ion-exchanged water, a thermometer, a stirrer, a dropping funnel, and a nitrogen introduction tube, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was set to 70 ° C. in a warm water bath. Next, an aqueous solution prepared by dissolving 147.7 g of α-methacryloyl-ω-hydroxy-oxypropylene poly (n = 68) oxyethylene, 135.0 g of ion-exchanged water, 16.4 g of methacrylic acid and 1.0 g of mercaptoethanol was added. Dropped over time. At the same time, an aqueous solution prepared by dissolving 2.5 g of sodium persulfate in 22.9 g of ion-exchanged water was added dropwise over 4 hours. Then, the temperature was maintained at 70 ° C. for 1 hour to complete the polymerization reaction. Then, a 30% aqueous sodium hydroxide solution was added to adjust the pH to 6, and the concentration was adjusted to 40% with ion-exchanged water to obtain a reaction mixture. The mass average molecular weight of the obtained reaction mixture was measured and found to be 50,000. This reaction mixture was used as a dispersant (PC-3).

-Manufacturing of dispersant (PC-4):
117.0 g of ion-exchanged water with 98.2 g of α- (3-methyl-3-butenyl) -ω-hydroxy-poly (n = 53) oxyethylene was provided with a thermometer, agitator, a dropping funnel, and a nitrogen introduction tube. It was charged into a reaction vessel and dissolved uniformly with stirring. Then, the atmosphere of the reaction system in which each of the above-mentioned components was dissolved was replaced with nitrogen, and the temperature of the reaction system was set to 70 ° C. in a warm water bath. Next, 7.9 g of 3.5% hydrogen peroxide solution was added dropwise over 3 hours, and at the same time, an aqueous solution prepared by dissolving 9.5 g of acrylic acid in 47.2 g of ion-exchanged water was added dropwise over 3 hours. At the same time, an aqueous solution prepared by dissolving 0.6 g of L-ascorbic acid and 0.6 g of 3-mercaptopropionic acid in 5.0 g of ion-exchanged water was added dropwise over 4 hours. Then, the temperature was maintained at 70 ° C. for 2 hours to complete the polymerization reaction. Then, a 30% aqueous sodium hydroxide solution was added to adjust the pH to 6, and the concentration was adjusted to 40% with ion-exchanged water to obtain a reaction mixture. The mass average molecular weight of the obtained reaction mixture was measured and found to be 46000. This reaction mixture was used as a dispersant (PC-4).

Preparation of hydraulic composition (Examples 15 to 28 and Comparative Examples 1 to 6):
The hydraulic composition was prepared by the following method. 55L forced twin-screw mixer with ordinary Portland cement (Pacific cement, Ube-Mitsubishi cement, Sumitomo Osaka Cement, 3 brands equal volume mixture, specific gravity = 3.16), fine aggregate (Oigawa water-based sand, specific gravity = 2) .58) and coarse aggregate (crushed stone from Okazaki, specific gravity = 2.66) were sequentially added at the ratios shown in Table 2 and kneaded for 10 seconds. After that, the dispersant and defoamer (AFK-2 (trade name) manufactured by Takemoto Oil & Fat Co., Ltd.) were added to the cement to 0 so that the target slump was 18 ± 2.0 cm and the air volume was 2.0% or less. An amount of .005% was added to the kneading water, the dispersant and the defoaming agent were regarded as a part of the kneading water, and the mixture was added together with the kneading water and kneaded for 90 seconds. The results are summarized in Table 3.

-Slump: The hydraulic composition immediately after kneading was measured according to JIS-A1150.
-Amount of air: The concrete composition immediately after kneading was measured according to JIS-A1128.
-Compressive strength: Based on JIS-A1132, concrete specimen molding formwork made of cylindrical tin (trade name "Summit Mold", manufactured by Sumitomo Corporation, bottom diameter of formwork: 100 mm, height of formwork: 200 mm) Each of the three formwork was filled with concrete by a two-layer packing method. Then, it was cured in the air (20 ° C.) in a room at 20 ° C. to harden the concrete. Twenty-four hours after the preparation of the concrete, the cured specimen was removed from the mold to obtain a specimen. The 24-hour strength of the specimen was measured based on JIS-A1108, and the average value of three specimens was obtained. Further, another specimen was prepared by the same method as above, demolded in the same manner, cured in water at 20 ° C. for 14 days, and the 14-day strength of the specimen was measured based on JIS-A1108. , The average value of 3 specimens was calculated.

-Heat curing compressive strength: Based on JIS-A1132, concrete specimen molding formwork made of columnar tin (trade name "Summit Mold" manufactured by Sumitomo Corporation, bottom diameter of formwork: 100 mm, height of formwork: 200 mm ), Each of the three formwork was filled with concrete by a two-layer packing method. Then, the upper part of the filled concrete was leveled and capped with polyethylene wrap. The specimen was cured in the air (20 ° C.) for 2 hours after water injection, then transferred to an incubator heated to 65 ° C., and cured for another 3 hours. After a predetermined curing time, the cured specimen was removed from the mold to obtain a specimen. The 5-hour intensity of the specimen was measured based on JIS-A1108, and the average value of the three specimens was obtained. The results are shown in Table 3.

In Table 3, the following terms have the following meanings. The explanation of the terms that overlap with those shown in Table 1 will be omitted. In Comparative Examples 2 to 6, each additive was used as a reagent.
Addition rate: Addition rate (%) as it is to cement.
NA: Naphthalene sulfonic acid formaldehyde condensate (Paul Fein 510-AN (trade name) manufactured by Takemoto Oil & Fats Co., Ltd., concentration 40%).

(result)
In Examples 15 to 28, by using an additive containing dialkanolamine and diethylene glycol, higher values were obtained in both 24-hour intensity, 14-day intensity, and 5-hour intensity as compared with Comparative Examples 1 to 6. It was confirmed to show.

The additive for a hydraulic composition of the present invention can be used as an additive when preparing a hydraulic composition.

Claims (5)

An additive for a water-hard composition used for a water-hard composition containing a water-hard binder, which comprises a dialkanolamine and a diethylene glycol , wherein the dialkanolamine is a diethanolamine and / or a diisopropanolamine, and The mass ratio of the dialkanolamine to the diethylene glycol (dialkanolamine / diethylene glycol) is in the range of 0.2 to 100, and the water-hardening binder is kneaded with water to obtain the water-hardening composition. Additive for water-hard composition used in preparation. The additive for a hydraulic composition according to claim 1 , further containing sulfuric acid and / or a sulfonic acid compound. The additive for a water-hard composition according to claim 2 , wherein the sulfonic acid compound is toluenesulfonic acid or methanesulfonic acid. The molar ratio of the amine of the dialkanolamine to the acid of the sulfuric acid and the sulfonic acid compound (amine of the dialkanolamine / (acid of the sulfuric acid and the sulfonic acid compound)) is in the range of 0.1 to 2. The additive for a water-hardening composition according to claim 2 or 3 . The additive for a hydraulic composition according to any one of claims 1 to 4 , further comprising a dispersant.