阅读说明：本技术 水硬性组合物用添加剂 (Additive for hydraulic composition ) 是由 古田章宏 大石卓哉 水野多朗 冈田和寿 于 2018-10-05 设计创作，主要内容包括：提供这样一种水硬性组合物用添加剂,其可以增大通过硬化所制备的水硬性组合物而得的硬化体的初期材龄的强度。该水硬性组合物用添加剂是用于包含水硬性结合材料的水硬性组合物的水硬性组合物用添加剂,由二链烷醇胺及二乙二醇构成。(Provided is an additive for hydraulic compositions, which can increase the initial age strength of a cured product obtained by curing a hydraulic composition produced by curing. The additive for hydraulic compositions is used for hydraulic compositions containing hydraulic binding materials and comprises dialkanolamine and diethylene glycol.)

1. An additive for hydraulic compositions, which is used for hydraulic compositions containing a hydraulic binder, comprising a dialkanolamine and diethylene glycol.

2. The additive for hydraulic compositions according to claim 1, wherein the dialkanolamine is diethanolamine and/or diisopropanolamine.

3. The additive for hydraulic compositions according to claim 1 or 2, wherein the mass ratio of the dialkanolamine to the diethylene glycol (dialkanolamine/diethylene glycol) is in the range of 0.2 to 100.

4. The additive for hydraulic compositions according to any one of claims 1 to 3, further comprising a sulfuric acid and/or a sulfonic acid compound.

5. The additive for hydraulic compositions according to claim 4, wherein the sulfonic acid compound is toluenesulfonic acid or methanesulfonic acid.

6. The additive for hydraulic compositions according to claim 4 or 5, wherein the molar ratio of the amine of the dialkanolamine to the sulfuric acid and the acid of the sulfonic acid compound (amine of dialkanolamine/(acid of sulfuric acid and sulfonic acid compound)) is in the range of 0.1 to 2.

7. The additive for hydraulic compositions according to any one of claims 1 to 6, further comprising a dispersant.

Technical Field

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

Background

The hydraulic composition is obtained by kneading a hydraulic binder with a material such as water, filling the mixture into a form, hardening the mixture, and then releasing the form to obtain a hardened body. Among them, the concrete product is produced by kneading materials such as cement, water, aggregate, and a dispersant, pouring the kneaded materials into a form, and hardening the kneaded materials. In order to improve the strength of the initial age, it is necessary to shorten the time required to achieve a strength capable of being demolded after pouring concrete since more concrete products can be produced using the same formwork. For such a purpose, various additives have been studied, and inorganic salts such as calcium chloride, nitrite, and nitrate (see, for example, non-patent document 1), and glycerol, alkanolamines, and the like (see, for example, patent documents 1 and 2) have been disclosed.

Disclosure of Invention

Problems to be solved by the invention

Calcium chloride is limited in use due to the problem of corrosion of the steel reinforcement of reinforced concrete, and nitrite or nitrate is sometimes added in a large amount. The alkanolamine and glycerin can also improve the strength of the initial age, but it is necessary to further improve the strength of the initial age.

The object of the present invention is to obtain a strength required for mold release in a shorter time without reducing the strength of a cured product of a hydraulic composition for 1 to 2 weeks. That is, the early strength can be improved, and a high compressive strength under short-time curing, for example, a compressive strength after 24 hours from water injection at 20 ℃ and a compressive strength after 5 hours under heat curing can be secured.

Means for solving the problems

The present inventors have conducted studies to solve the above problems and found that an additive for hydraulic compositions comprising a specific organic compound is suitable. According to the present invention, the following additive for hydraulic compositions is provided.

[1] An additive for hydraulic compositions, which is used for hydraulic compositions containing a hydraulic binder, comprising a dialkanolamine and diethylene glycol.

[2] The additive for hydraulic compositions according to [1], wherein the dialkanolamine is diethanolamine and/or diisopropanolamine.

[3] The additive for hydraulic compositions according to [1] or [2], wherein a mass ratio of the dialkanolamine to the diethylene glycol (dialkanolamine/diethylene glycol) is in the range of 0.2 to 100.

[4] The additive for hydraulic compositions according to any one of [1] to [3], further comprising a sulfuric acid and/or a sulfonic acid compound.

[5] The additive for hydraulic compositions according to [4], wherein the sulfonic acid compound is toluenesulfonic acid or methanesulfonic acid.

[6] The additive for hydraulic compositions according to [4] or [5], wherein the molar ratio of the amine of the dialkanolamine to the sulfuric acid and the acid of the sulfonic acid compound (amine of dialkanolamine/(acid of sulfuric acid and sulfonic acid compound)) is in the range of 0.1 to 2.

[7] The additive for hydraulic compositions according to any one of [1] to [6], further comprising a dispersant.

ADVANTAGEOUS EFFECTS OF INVENTION

The hydraulic composition prepared using the additive of the present invention has the following effects: the strength of the cured product obtained by curing at the initial age is increased, and the strength required for mold release can be obtained in a shorter time without lowering the strength of the cured product at 1 to 2 weeks of age.

Detailed Description

Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments. Therefore, it is to be understood that the following embodiments may be appropriately modified, improved, and the like according to the common general 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 stated, "%" represents "% by mass" and "parts" represent "parts by mass".

The additive for hydraulic compositions according to the embodiment of the present invention is an additive for hydraulic compositions used for hydraulic compositions containing a hydraulic binder, and is an additive for hydraulic compositions comprising a dialkanolamine and diethylene glycol.

Examples of dialkanolamines used as the additive for hydraulic compositions of the present embodiment (hereinafter also referred to as the additive of the present embodiment) include: diethanolamine, diisopropanolamine, N-alkyldiethanolamine, and N-alkyldiisopropanolamine, among which diethanolamine and diisopropanolamine are preferable.

The amount of dialkanolamine 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, relative to 100 parts by mass of a hydraulic binder such as cement.

As the diethylene glycol used as the additive in the present embodiment, a commercially available industrial product 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, and more preferably 0.002 to 0.5 part by mass, relative to 100 parts by mass of a hydraulic binder such as cement. If the amount of diethylene glycol used is too small, no effect is obtained, and if it is too large, the compressive strength of the product aged about 1 to 4 weeks is lowered.

The mass ratio of dialkanolamine to diethylene glycol (dialkanolamine/diethylene glycol) is preferably in the range of 0.2 to 100, 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: p-toluenesulfonic acid, methanesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, and the like. Among them, preferred is a compound selected from sulfuric acid, p-toluenesulfonic acid and methanesulfonic acid. In the present specification, the case of "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.

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

The additive of the present embodiment preferably further contains a dispersant. Examples of such a dispersant include: aromatic sulfonic acid dispersants such as naphthalene dispersants, phenol dispersants, and lignin dispersants; a polycarboxylic acid-based dispersant; and dispersants such as phosphate dispersants. Among these, from the viewpoint of ensuring early strength, preferred are aromatic sulfonic acid-based dispersants such as naphthalene-based dispersants and melamine-based dispersants, and polycarboxylic acid-based dispersants, and more preferred are naphthalene-based dispersants and polycarboxylic acid-based dispersants.

As the naphthalene-based dispersant, a naphthalenesulfonic acid formaldehyde condensate ("マイテイ 150" (trade name) manufactured by Kao corporation, or "ポールファイン 510-AN" (trade name) manufactured by bamboo oil and fat Co., Ltd) or the like can be used. As the melamine-based dispersant, a melamine sulfonic acid formaldehyde condensate ("ポールファイン MF" (trade name) manufactured by bamboo oil and fat Co., Ltd., or "アクセリート 100" (trade name) manufactured by Nissan chemical industry Co., Ltd.) or the like can be used. As the phenolic dispersant, a phenolsulfonic acid formaldehyde condensate (a compound described in Japanese patent application laid-open No. 46-104919, etc.) or a phenolphosphoric acid formaldehyde condensate (a compound described in Japanese patent application laid-open No. 2012-504695), etc. can be used. As the lignin-based dispersant, lignosulfonate ("サンエキス" (trade name), "バニレックス" (trade name), "パールレックス" (trade name), etc., manufactured by japan paper chemical corporation, etc., can be used.

As the polycarboxylic acid-based copolymer, a copolymer of a monoester of Polyalkylene glycol (Polyalkylene glycol) and (meth) acrylic acid and a carboxylic acid such as (meth) acrylic acid; copolymers of unsaturated alcohols having polyalkylene glycol and carboxylic acids such as (meth) acrylic acid (e.g., Japanese patent laid-open publication No. 2007-119337); copolymers of unsaturated alcohols having polyalkylene glycols and dicarboxylic acids such as maleic acid, and the like. 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) and a carboxylic acid monomer can be used.

[ chemical formula 1]

R¹－O－X－R²(1)

In the formula (1), the reaction mixture is,

R¹represents an alkenyl group having 2 to 5 carbon atoms or an unsaturated acyl group having 3 or 4 carbon atoms.

R²Represents 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 addition mole number of 1 to 300 composed of an Oxyalkylene group (Oxyalkylene group) having 2 to 4 carbon atoms.

As R in formula (1)¹The alkenyl group having 2 to 5 carbon atoms of (a) includes: vinyl, allyl, methyl allyl, 3-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl etc.. In addition, as R¹Examples of the unsaturated acyl group having 3 or 4 carbon atoms include: acryl and methacryl. Of these, allyl, methallyl, 3-methyl-1-butenyl, acryloyl, and methacryloyl are preferable. One or two or more of the monomers represented by the formula (1) may be used.

As R in formula (1)²Examples thereof 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 formula (1) include: polyoxyalkylene composed of 1 to 300 (poly) oxyalkylene units. Among them, preferred is a (poly) oxyalkylene group consisting of 1 to 160 oxyethylene units and/or oxypropylene units.

Examples of the carboxylic acid monomers constituting the (co) polymer include: (meth) acrylic acid, crotonic acid, dicarboxylic acid, maleic acid, itaconic acid, fumaric acid, succinic acid mono (2-methacryloyloxyethyl) ester, and the like, and salts thereof. Among them, (meth) acrylic acid, maleic acid, (meth) acrylate, and maleate are preferable.

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

In the production of the above (co) polymer, other monomers capable of copolymerization, for example, styrene, acrylamide, (meth) allylsulfonic acid (salt), etc., may be used in combination.

The additive of the present embodiment is used for preparing a hydraulic composition. For example, it can be used in the production of a hydraulic composition using a hydraulic binder containing cement, water, fine aggregate, coarse aggregate, an AE agent, or the like.

Examples of the hydraulic binder include: cement, blast furnace slag micropowder, fly ash, silica fume and the like. Among them, a hydraulic binder containing cement is preferable. As the cement, various mixed cements such as blast furnace cement, fly ash cement, and silica cement can be used in addition to various portland cements such as ordinary portland cement, early strength portland cement, and moderate heat portland cement.

As the fine aggregate, any of well-known river sand, mountain sand, sea sand, crushed sand, ore sand, and the like can be used. As the coarse aggregate, any of well-known river sand, crushed stone, lightweight aggregate, and the like can be used.

In addition, in the preparation of hydraulic compositions, 1) air quantity regulators such as rosin soaps, alkyl aromatic sulfonates, aliphatic alkyl (ether) sulfates, alkyl phosphate esters, and the like; 2) dimethyl polysiloxane, polyalkylene glycol fatty acid ester, mineral oil, oil and fat, alkylene oxide, alcohol, and amide defoaming agents.

When the additive of the present embodiment is used, a setting accelerator, a setting retarder, an antirust agent, a water repellent, and the like may be used in combination within a desired range. The additive of the present embodiment may be used in any of the following ways: a method of adding together with kneading water at the time of preparing a concrete composition; and a method of adding the concrete composition immediately after kneading.

The additive of the present embodiment is preferably a multifunctional admixture in which various components are mixed in advance to form a single liquid type.

In the step of filling the hydraulic composition using the additive of the present embodiment in a form and curing the hydraulic composition to cure the hydraulic composition, the hydraulic composition obtained is filled in a form and cured. Examples of the template include: forms for buildings, and forms for concrete products. Examples of the method for filling the hydraulic composition into the form include: a method of directly charging the mixture from a mixer, or a method of introducing the hydraulic composition into the mold by pumping the hydraulic composition.

Heat curing may be performed to promote hardening of the hydraulic composition. The hydraulic composition is maintained at a temperature of 40 to 80 ℃ for heat curing.