WO2019116693A1

WO2019116693A1 - Hydraulic composition additive, and method for preparing hydraulic composition

Info

Publication number: WO2019116693A1
Application number: PCT/JP2018/037436
Authority: WO
Inventors: 章宏古田
Original assignee: 竹本油脂株式会社
Priority date: 2017-12-14
Filing date: 2018-10-05
Publication date: 2019-06-20
Also published as: TWI794310B; TW201927722A; JP7020668B2; JP2019104666A

Abstract

Provided is a hydraulic composition additive that is capable of increasing the initial age of a cured product obtained by curing a prepared hydraulic composition. The hydraulic composition additive contains a compound A represented by formula (1), and/or a salt thereof. (In formula (1), X represents a hydrogen atom or a hydroxy group.)

Description

Additive for hydraulic composition, and method of preparing hydraulic composition

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

A hydraulic composition knead | mixes materials, such as a hydraulic binding material and water, is filled in a formwork, and after making it harden | cure, a formwork is demolded and a hardening body is obtained. Among these, concrete products are produced by kneading materials such as cement, water, aggregates, dispersants, etc., placing them in a mold and curing them. Improving the strength of the early age will lead to the production of more concrete products using the same formwork. For this reason, it is required to shorten the time to reach the strength that can be removed after concrete placement. So far, various additives have been studied, and calcium chloride, inorganic salts such as nitrites and nitrates (for example, Non-Patent Document 1), glycerin, alkanolamines and the like have been disclosed (for example, Patent Documents 1 and 2) ).

JP, 2009-256201, A JP 2011-236127 A

The use of calcium chloride is limited due to the problem of corrosion when it is reinforced concrete, and a large amount of addition may be required for nitrite and nitrate. Alkanolamines and glycerin can also improve the strength of the initial material age, but there is a demand for further improvement of the initial material age.

An object of the present invention is to improve the early strength so as to obtain the strength necessary for demolding in a shorter time. Specifically, it is to secure the demolding strength by curing at a strength of about 24 hours at 20 ° C.

As a result of researches to solve the above-mentioned problems, the present inventors have found that additives for hydraulic compositions containing a specific organic compound are properly suitable. According to the present invention, the following additives for hydraulic composition, and a method of preparing a hydraulic composition are provided.

[1] An additive for a hydraulic composition, which comprises a compound A represented by the following formula (1) and / or a salt thereof.

(However, in the said Formula (1), X shows a hydrogen atom or a hydroxyl group.)

[2] The additive for a hydraulic composition according to [1], further comprising the following compound B:
Compound B: One or more selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethanolamine, diethanolamine, triisopropanolamine, and diisopropanolamine.

[3] The additive for a hydraulic composition according to [1] or [2], further comprising a dispersant for a hydraulic composition.

[4] The additive for a hydraulic composition according to [3], wherein the dispersant for a hydraulic composition is a polycarboxylic acid-based dispersant or an aromatic sulfonic acid-based compound.

[5] The hydraulic binder as set forth in any one of [1] to [4], in the hydraulic composition, the compound A in the hydraulic composition additive. A method of preparing a hydraulic composition, which is added to be contained in a proportion of 0.001 to 1.0 parts by mass with respect to the mass part.

[6] The method for preparing a hydraulic composition according to [5], wherein the ratio of the compound A is 0.05 to 0.8 parts by mass with respect to 100 parts by mass of the hydraulic binder.

The additive for hydraulic composition of the present invention can enhance the strength of the initial age of the cured product obtained by curing the prepared hydraulic composition. For this reason, according to the additive for hydraulic composition of the present invention, it is possible to improve the early strength so as to obtain the strength necessary for demolding 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 appropriate modifications, improvements, and the like can be added to the following embodiments based on the ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. In the following Examples etc., unless otherwise indicated,% means mass%, and a part means mass part.

The additive for a hydraulic composition according to an embodiment of the present invention is an additive for a hydraulic composition comprising a compound A represented by the following formula (1) and / or a salt thereof. The additive for a hydraulic composition of the present embodiment can enhance the strength of the initial age of a cured product obtained by curing the prepared hydraulic composition. For this reason, according to the additive for hydraulic composition of the present embodiment, it is possible to improve the early strength so as to obtain the strength necessary for demolding in a shorter time. For example, at 20 ° C., it is also possible to secure demolding strength by curing for about 24 hours.

The compound A represented by the above formula (1) to be used for the additive for hydraulic composition of the present embodiment (hereinafter, also simply referred to as the additive of the present embodiment) is trishydroxymethylaminomethane and / or 2-amino acid. And -2-methyl-1,3-propanediol. Examples of the salt of the compound A include those in which the amino group in the formula (1) is a salt due to an acid or the like.

There is no restriction | limiting in particular about the addition amount at the time of preparing a hydraulic composition using the additive of this embodiment. For example, with respect to the additive of the present embodiment, the compound A in the additive is preferably 0.001 to 1.0 parts by mass, more preferably 100 parts by mass of the hydraulic binder in the hydraulic composition. Is added in a proportion of 0.005 to 0.8 parts by mass, more preferably 0.05 to 0.8 parts by mass. If the amount is too small, the desired effect can not be obtained, and if it is too large, the cost is too high.

It is preferable that the additive of this embodiment contains the following compound B. By containing the compound B, the desired effect can be realized more highly.

As compound B, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethanolamine, diethanolamine, triisopropanolamine and diisopropanolamine can be mentioned. The compound B may be used singly or in combination of two or more.

In the case where the additive of the present embodiment further contains the above-described compound B, the content of the compound B is not particularly limited. For example, when preparing a hydraulic composition using the additive of the present embodiment, the compound B in the additive is preferably 0 based on 100 parts by mass of the hydraulic binder in the hydraulic composition. It is contained in the additive of the present embodiment so that .001 to 1.0 parts by mass, more preferably 0.005 to 0.5 parts by mass, and still more preferably 0.005 to 0.2 parts by mass. Is preferred.

The additive of the present embodiment may further contain a dispersant for hydraulic composition. The dispersant for the hydraulic composition is not particularly limited, but, for example, (1) aromatic sulfonic acid dispersion such as naphthalene dispersant, melamine dispersant, phenol dispersant, lignin dispersant and the like And dispersants such as (2) polycarboxylic acid dispersants and (3) phosphate ester dispersants. Among them, from the viewpoint of securing early strength, those selected from the group consisting of naphthalene type dispersants and polycarboxylic acid type dispersants are preferable.

(A) Examples of naphthalene-based dispersants include naphthalenesulfonic acid-formaldehyde condensates (Mighty 150 (trade name) manufactured by Kao Corporation, Paul Fine 510-AN (trade name) manufactured by Takemoto Oil & Fats Co., Ltd., etc.) . (B) Examples of the melamine based dispersant include melamine sulfonic acid-formaldehyde condensates (Pole Fine MF (trade name) manufactured by Takemoto Oil & Fats Co., Ltd., Accelerate 100 (trade name) manufactured by Nissan Chemical Industries, Ltd., etc.) Be (C) Phenolic dispersants include phenolsulfonic acid-formaldehyde condensates (compounds described in JP-A-46-104919), phenol phosphate-formaldehyde condensates (compounds disclosed in JP-A-2012-504695), etc. Can be mentioned. (D) Examples of lignin-based dispersants include lignin sulfonates (Sun extract (trade name) manufactured by Nippon Paper Chemicals Co., Ltd., Vanillex (trade name), Pearl Rex (trade name), etc.) and the like.

As a polycarboxylic acid based dispersant, a copolymer of monoester of polyalkylene glycol and (meth) acrylic acid and carboxylic acid such as (meth) acrylic acid; unsaturated alcohol having polyalkylene glycol and (meth) acrylic acid Copolymer with carboxylic acid such as acid (for example, JP-A-2007-119337); copolymer of unsaturated alcohol having polyalkylene glycol and dicarboxylic acid such as maleic acid; commercially available polycarboxylic acid-based dispersion A dispersant containing an agent can be used. (Meth) acrylic acid means acrylic acid or methacrylic acid.

As a representative example of the polycarboxylic acid dispersant, a copolymer obtained by polymerizing a monomer (M-1) represented by the following formula (2) and a monomer (M-2) having a carboxylic acid It can be mentioned coalescence.

In equation (2),
R ¹ represents an alkenyl group having 2 to 5 carbon atoms and an unsaturated acyl group having 3 or 4 carbon atoms.
R ² 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 1 to 300 (poly) oxyalkylene group having an average addition mole number composed of one or two or more oxyalkylene groups having 2 to 4 carbon atoms.

As a C2-C5 alkenyl group of R ¹ in Formula (2), a vinyl group, an allyl group, a methallyl group, 3-butenyl group, 2-methyl-1-butenyl group, 3-methyl-1-butenyl group And 2-methyl-3-butenyl group, 3-methyl-3-butenyl group and the like. Moreover, as a C3-C4 unsaturated acyl group of R < ¹ >, an acryloyl group and a methacryloyl group are mentioned. Among them, allyl group, methallyl group, 3-methyl-1-butenyl group, acryloyl group and methacryloyl group are preferable. One or two or more of the constituent units represented by formula (2) may be used.

Examples of R ² in the formula (2) 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 (2) include polyoxyalkylene groups composed of 1 to 300 (poly) oxyalkylene units. Among these, (poly) oxyalkylene groups composed of 1 to 160 oxyethylene units and / or oxypropylene units are preferable.

As a monomer (M-2) having a carboxylic acid which will constitute the above (co) polymer (hereinafter simply referred to as "monomer (M-2)"), (meth) acrylic acid And crotonic acid, dicarboxylic acid, maleic acid, itaconic acid, fumaric acid, succinic acid mono (2- (meth) acryloyloxyethyl) and the like, and salts thereof. Among them, as the monomer (M-2), (meth) acrylic acid, maleic acid, (meth) acrylates and maleates are preferable.

The salt of the monomer (M-2) having a carboxylic acid is not particularly limited, and examples thereof include alkali metal salts such as sodium salt and potassium salt, and alkaline earth metal salts such as calcium salt and magnesium salt. Ammonium salts, amine salts such as diethanolamine salt and triethanolamine salt, and the like.

The dispersant for hydraulic composition used for the additive of the present embodiment is not limited to the (co) polymer etc. described above. For example, when producing a (co) polymer used as a dispersant for hydraulic composition, any other suitable monomer may be used. Examples include styrene, acrylamide, (meth) allyl sulfonic acid and salts thereof.

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

The additive of the present embodiment is added as part of the mixing water when preparing the hydraulic composition. The addition rate thereof is preferably 0.001 to 1.0% by mass, more preferably 0.01 to 0.5% by mass, based on the hydraulic binder.

The hydraulic binder includes cement, ground granulated blast furnace slag, fly ash, gypsum, hemihydrate gypsum, and anhydrous gypsum. Among these, cement is preferred. As cement, in addition to various portland cements such as ordinary portland cement, early strength portland cement, and moderate heat portland cement, various mixed cements such as blast furnace cement, fly ash cement and silica fume cement can be used.

Moreover, as fine aggregate, all known river sand, mountain sand, sea sand, crushed sand, slag sand etc. can be used. Furthermore, as coarse aggregate, any of known river gravel, crushed stone, lightweight aggregate and the like can be used.

Also, other cement dispersants used for preparation of the concrete composition may be used simultaneously. Moreover, as an air content regulator, rosin soap, alkyl aromatic sulfonate, aliphatic alkyl (ether) sulfate, alkyl phosphate ester and the like can be mentioned. Depending on the circumstances, various known antifoam agents can be used.

When using the additive of the present embodiment, other agents can be used in combination as long as the present invention is not impaired. Other agents used in combination with the additive of the present embodiment include other setting accelerators, setting retarders, rust inhibitors, waterproofing agents and the like. Moreover, the method of using the additive according to the present embodiment may be any of a method of adding together with the mixing and mixing water at the time of preparation of the concrete composition, and a method of adding after addition to the concrete composition immediately after mixing.

In the additive of the present embodiment, the compound A and the other components may be previously mixed to form a one-component additive for hydraulic composition.

Next, an embodiment of a method for preparing a hydraulic composition of the present invention will be described. The method of preparing the hydraulic composition of the present embodiment is a method of preparing a hydraulic composition using the additive for hydraulic composition (the additive for hydraulic composition of the present invention) described above. The method for preparing a hydraulic composition according to the present embodiment includes the additive for a hydraulic composition according to the present invention, the compound A in the additive for a hydraulic composition, and the hydraulic binder 100 in the hydraulic composition. In this preparation method, it is added to be contained in a proportion of 0.001 to 1.0 parts by mass with respect to the mass part.

According to the method of preparing a hydraulic composition of the present embodiment, it is possible to improve the early strength so as to obtain the strength necessary for demolding in a shorter time. For example, at 20 ° C., it is also possible to secure demolding strength by curing for about 24 hours.

In the method for preparing a hydraulic composition of the present embodiment, the ratio of the compound A in the additive for hydraulic composition is 0.05 to 0.8 parts by mass with respect to 100 parts by mass of the hydraulic binder. Is preferred.

Hereinafter, in order to make the configuration and effects of the present invention more specifically, examples and the like will be described, but the present invention is not limited to the examples. In the following Examples etc., unless otherwise indicated,% means mass%, and a part means mass part.

Preparation of Additive for Hydraulic Composition (Examples 1 to 7):
As compound A, trishydroxymethylaminomethane (manufactured by ANGUS Co., Ltd.) and 2-amino-2-methyl-1,3-propanediol (Tokyo Kasei Reagent) are prepared. As compound B, AD-1 to AD shown below are prepared. I prepared -5. Compound A and Compound B were previously mixed in the ratio as shown in Table 1, and appropriately diluted with ion exchanged water. Thus, the additive for hydraulic composition of Examples 1 to 7 was produced. The additives for hydraulic composition of Examples 1 to 7 are referred to as EX-1 to EX-7 in Table 1.

In Table 1, the following terms have the following meanings.
a-1: trishydroxymethylaminomethane (manufactured by ANGUS).
a-2: 2-amino-2-methyl-1,3-propanediol (Tokyo Kasei Reagent).
AD-1: Diethylene glycol (Kishida Chemical Reagent).
AD-2: Ethylene glycol (Kishida Chemical Reagent).
AD-3: Triisopropanolamine (Wako Pure Chemical Industries, Ltd.).
AD-4: Triethanolamine (Kishida Chemical Reagent).
AD-5: Glycerin (Wako Pure Chemical Industries, Ltd.).

Preparation of additives for hydraulic composition (Comparative Examples 1 and 2)
Compound B shown in Table 1 was appropriately diluted with ion exchange water to prepare an additive for hydraulic composition of Comparative Examples 1 and 2. The additives for hydraulic composition of Comparative Examples 1 and 2 are referred to as R-1 and R-2 in Table 1, respectively.

The mass average molecular weights of the following copolymers (PC-1) to (PC-3) were measured by gel permeation chromatography. The following copolymers (PC-1) to (PC-3) were used as dispersants for hydraulic compositions of additives for hydraulic compositions in each example.
<Measurement conditions>
Device: 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 aqueous solution of sodium nitrate.
Flow rate: 0.7 mL / min.
Column temperature: 40 ° C.
Sample concentration: Eluant solution with a sample concentration of 0.5% by weight.
Reference materials: polyethylene oxide, polyethylene glycol.

Production of copolymer (PC-1):
First, as raw materials for producing the copolymer (PC-1), 165.5 g of ion-exchanged water, 133.4 g of α-methacryloyl-ω-methoxy-poly (n = 45) oxyethylene, 22.2 g of methacrylic acid, 3 -Prepare 1.6 g of mercaptopropionic acid. The prepared raw material was charged into a reaction vessel (hereinafter, the same one was used) equipped with a thermometer, a stirrer, a dropping funnel, and a nitrogen introduction tube, and uniformly dissolved while being stirred. Thereafter, the atmosphere of the reaction system in which each component described above was dissolved was replaced with nitrogen, and the temperature of the reaction system was adjusted to 65 ° C. by a water bath. Next, 27.3 g of 1.0% hydrogen peroxide water was added, and the temperature was maintained at 65 ° C. for 6 hours to complete the polymerization reaction. Thereafter, a 30% aqueous sodium hydroxide solution was added to adjust to pH 6, and the concentration was adjusted to 40% with ion exchanged water to obtain a reaction mixture. It was 35000 when the mass mean molecular weight of the obtained reaction mixture was measured. This reaction mixture was designated as copolymer (PC-1).

Production of copolymer (PC-2):
41.4 g of ion-exchanged water was charged into a reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, and a nitrogen inlet tube, the atmosphere was replaced with nitrogen while stirring, and the temperature of the reaction system was adjusted to 70 ° C. with a hot water bath. 188.0 g of deionized water, 188.0 g of α-methacryloyl-ω-methoxy-poly (n = 130) oxyethylene, 12.0 g of methacrylic acid, 2.0 g of sodium methallyl sulfonate, 4.0 g of 3-mercaptopropionic acid The aqueous solution in which was dissolved was added dropwise over 3 hours. At the same time, an aqueous solution in which 3.0 g of ammonium persulfate was dissolved 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. Thereafter, a 30% aqueous sodium hydroxide solution was added to adjust to pH 6, and the concentration was adjusted to 40% with ion exchanged water to obtain a reaction mixture. It was 45000 when the mass mean molecular weight of the obtained reaction mixture was measured. This reaction mixture was designated as copolymer (PC-2).

Production of copolymer (PC-3):
117.0 g of ion-exchanged water, 98.2 g of α- (3-methyl-3-butenyl) -ω-hydroxy-poly (n = 53) oxyethylene were equipped with a thermometer, a stirrer, a dropping funnel, and a nitrogen inlet tube The mixture was charged into a reaction vessel and uniformly dissolved with stirring. Thereafter, the atmosphere of the dissolved reaction system was replaced with nitrogen, and the temperature of the reaction system was adjusted to 70 ° C. with a warm water bath. Next, 7.9 g of 3.5% hydrogen peroxide water was added dropwise over 3 hours. At the same time, an aqueous solution in which 9.5 g of acrylic acid was dissolved in 47.2 g of ion-exchanged water was dropped over 3 hours. At the same time, an aqueous solution in which 0.6 g of L-ascorbic acid and 0.6 g of 3-mercaptopropionic acid were dissolved in 5.0 g of ion-exchanged water was dropped over 4 hours. Thereafter, the temperature was maintained at 70 ° C. for 2 hours to complete the polymerization reaction. Thereafter, a 30% aqueous sodium hydroxide solution was added to adjust to pH 6, and the concentration was adjusted to 40% with ion exchanged water to obtain a reaction mixture. It was 46000 when the mass mean molecular weight of the obtained reaction mixture was measured. This reaction mixture was designated as copolymer (PC-3).

Preparation of hydraulic composition (Examples 8 to 17 and Comparative Examples 3 to 5):
Preparation of the hydraulic composition was performed by the following method. 55L forced twin screw mixer with ordinary portland cement (Pacific Cement Co., Ltd., Ube Mitsubishi Cement Co., Ltd., Sumitomo Osaka Cement Co., Ltd., 3 brands equivalent mixing, specific gravity = 3.16), fine aggregate (Oikawa water system sand, specific gravity = 2 .57) and coarse aggregate (Okazaki Crushed Stone, specific gravity = 2.66) were sequentially introduced at the ratio shown in Table 2 and air-kneaded for 10 seconds. Thereafter, an additive for a hydraulic composition and an antifoaming agent (AFK-2 (trade name) manufactured by Takemoto Yushi Co., Ltd.) so that the target slump is 18 ± 2.5 cm and the air content is 2.0% or less, The mixture was added with mixing and mixing water, and mixed for 90 seconds to prepare a hydraulic composition. About the addition amount (addition rate) of the additive for hydraulic composition, it was as having described in Table 3. Moreover, the antifoamer was made into the ratio of 0.002% with respect to cement.

Slump: The hydraulic composition immediately after mixing was measured according to JIS-A1150.
Air content: The concrete composition immediately after mixing was measured according to JIS-A1128.
Compressive strength: Based on JIS-A1132, three pieces of cylindrical steel formwork (diameter at the bottom: 100 mm, height 200 mm) were each filled with concrete by two-layer filling method. Thereafter, curing in air (20 ° C.) was performed in a room at 20 ° C. to harden the concrete. Twenty-four hours after the preparation of the concrete, the hardened 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 determined. Furthermore, after preparing another three samples in the same manner as above and removing them from the samples in the same manner, they were aged in water at 20 ° C. for 14 days, and the 14 days strength of the samples was measured according to JIS-A1108. The average value of three test specimens was determined. Each result is shown in Table 3.

In Table 3, the following terms have the following meanings. In addition, about the thing which overlaps with the term shown in Table 1, the description is abbreviate | omitted.
Addition rate: The dispersant for hydraulic composition ("dispersant" in Table 3) indicates the proportion (% by mass) of the mass relative to the cement in the form. For additives, the ratio (mass%) of mass to cement at solid content is shown.
Dispersant: A dispersant for hydraulic composition shown in the column of "type" in Table 3 is shown.
Additive: The additive for hydraulic composition shown in the column of “type” in Table 3 is shown.
NFS: Naphthalene sulfonic acid-formaldehyde condensate (Pole Fine 510AN (trade name) manufactured by Takemoto Yushi Co., Ltd.).

(result)
In Examples 8 to 17, it was confirmed that the use of the additive containing the compound A shows higher values in any of the 24-hour strength and the 14-day strength as compared with Comparative Examples 3 to 5.

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

Claims

The additive for hydraulic composition which contains the compound A shown by following formula (1), and / or its salt.

(However, in the said Formula (1), X shows a hydrogen atom or a hydroxyl group.)
Furthermore, the additive for hydraulic composition of Claim 1 containing the following compound B.
Compound B: One or more selected from the group consisting of ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethanolamine, diethanolamine, triisopropanolamine, and diisopropanolamine.
The additive for a hydraulic composition according to claim 1, further comprising a dispersant for a hydraulic composition.
The additive for hydraulic composition according to claim 3, wherein the dispersant for hydraulic composition is a polycarboxylic acid type dispersant or an aromatic sulfonic acid type compound.
An additive for a hydraulic composition according to any one of claims 1 to 4, wherein 100 parts by mass of the hydraulic binder in the hydraulic composition contains the compound A in the additive for a hydraulic composition. A method of preparing a hydraulic composition, which is added to be contained in a proportion of 0.001 to 1.0 parts by mass with respect to the above.
The method for preparing a hydraulic composition according to claim 5, wherein the proportion of the compound A is 0.05 to 0.8 parts by mass with respect to 100 parts by mass of the hydraulic binder.