Strength improver for hydraulic composition

Abstract

This strength improver for a hydraulic composition is an aqueous dispersion containing (A) a poorly water-soluble polymer having a carboxy group or a salt thereof, (B) an ester compound having a molecular weight of 120 to 500, and (C) water.

Description

Strength improver for hydraulic compositions

[0001] The present invention relates to a strength enhancer for hydraulic compositions, a hydraulic composition, a method for producing a hydraulic composition, and a method for improving the strength of a hydraulic composition.

[0002] Background Technology Conventionally, initial drying of concrete causes cracking, a decrease in strength and density, so measures are taken to prevent drying after demolding during construction. One method to prevent initial drying is to use moist curing with sheets, etc. Another curing method that does not use sheets is to apply a water-retaining curing with a film curing agent after demolding the concrete, thereby preventing drying and ensuring and improving the density of the surface layer, which is related to the durability of the concrete.

[0003] Japanese Patent Publication No. 2014-28729 discloses a film curing agent for preventing initial drying during the curing of concrete, characterized in that it is a material mainly composed of a water-dispersible polyester, which is applied to the exposed surface of the cast concrete after a predetermined hardening period and after the formwork has been removed. Japanese Patent Publication No. 2015-196627 discloses a concrete film coating agent for preventing carbonation and salt damage of concrete, characterized in that it is a material mainly composed of a water-dispersible polyester, which is applied to the exposed surface of the concrete. Japanese Patent Publication No. 2012-116696 discloses a composition for treating the interface or surface of mortar and / or concrete, containing (A) a water-dispersible polyester resin and (B) an acrylic resin emulsion in a mass ratio (A:B) of 1:4 to 4:1. Furthermore, Japanese Patent Publication No. 2021-31337 discloses a cement additive comprising an emulsion (A) containing polymer particles having a glass transition temperature of 35°C to 100°C, and at least one selected from the group consisting of an alkanolamine compound (B) and a retarder (C). In addition, Chinese Patent Application Publication No. 116969730 discloses a microcement coating comprising cement, siliceous additives, hydraulic lime, aqueous acrylic resin, protective colloid, ionic liquid, film-forming agent, plasticizer, coupling agent, metal powder, fiber, and colorant in specific amounts.

[0004] Summary of the Invention In recent years, there has been a growing demand for improved strength performance of cured hydraulic compositions. For example, early strength development is desired from the viewpoint of shortening construction time and improving manufacturing efficiency, and various studies have been conducted. Also, for example, from the viewpoint of improving durability, there is a demand for long-term strength improvement of cured hydraulic compositions. The present invention provides a strength enhancer for hydraulic compositions, a hydraulic composition, a method for producing a hydraulic composition, and a method for improving the strength of a hydraulic composition, which are excellent in early strength development and can maintain excellent strength over a long period of time.

[0005] In one embodiment, the present invention provides a strength enhancer for hydraulic compositions, comprising (A) a poorly water-soluble polymer having a carboxyl group or a salt thereof, (B) an ester compound with a molecular weight of 120 to 500, and (C) an aqueous dispersion containing water.

[0006] Furthermore, in another embodiment, the present invention provides a hydraulic composition in which (A) a poorly water-soluble polymer having a carboxyl group or a salt thereof, (B) an ester compound with a molecular weight of 120 to 500, and (C) water are applied to the surface of a hydraulic composition structure.

[0007] Furthermore, in another embodiment, the present invention provides a method for producing a hydraulic composition, which involves mixing a hydraulic powder with water to obtain a hydraulic composition, and forming a surface layer on the surface of the hydraulic composition containing (A) a poorly water-soluble polymer having a carboxyl group or a salt thereof, and (B) an ester compound with a molecular weight of 120 to 500.

[0008] Furthermore, in another embodiment, the present invention provides a method for improving the strength of a hydraulic composition, comprising applying an aqueous dispersion composition containing (A) a poorly water-soluble polymer having a carboxyl group or a salt thereof, (B) an ester compound with a molecular weight of 120 to 500, and (C) water to the surface of the hydraulic composition and curing the hydraulic composition.

[0009] The present invention provides a strength enhancer for hydraulic compositions, a hydraulic composition, a method for producing a hydraulic composition, and a method for improving the strength of a hydraulic composition, all of which are excellent in early strength development and can maintain excellent strength for a long period of time.

[0010] Modes for Carrying Out the Invention The mechanism by which the strength enhancer for hydraulic compositions of the present invention exhibits excellent early strength development and long-term maintenance of excellent strength is not clear, but it is presumed to be as follows: The ester compound of component (B), with a molecular weight of 120 to 500, interacts with the poorly water-soluble polymer having a carboxyl group or a salt thereof of component (A), reducing entanglement of polymer molecular chains, thereby helping the polymer molecules to efficiently adsorb onto the surface of the hydraulic composition. At the same time, the ester compound itself forms a monolayer-like structure and contributes to moisture retention. In particular, it is presumed that when the molecular weight of component (B) is 120 or more, the amount of component (B) volatilized into the air is reduced, and a synergistic effect of moisture retention is exerted. Furthermore, when the molecular weight of component (B) is 500 or less, it is presumed that both sufficient molecular mobility to interact with component (A) and sufficient molecular mobility to form a monolayer can be ensured, resulting in an excellent moisture retention effect. It is presumed that applying the hydraulic composition strength enhancer of the present invention to the surface of a hydraulic composition, and further to the surface of a hydraulic composition structure, will suppress water evaporation from the hydraulic composition and increase the efficiency of the hydration reaction, thereby contributing to the improvement of the strength of the hydraulic composition. However, the hydraulic composition strength enhancer, hydraulic composition, method for producing a hydraulic composition, and method for improving the strength of a hydraulic composition of the present invention are not limited to the above mechanism.

[0011] In this specification, the expression "(meth)acrylic" means "acrylic and / or methacrylic," and the expression "(meth)acrylate" means "acrylate and / or methacrylate." In addition, the expression "acid (salt)" in this specification means "acid and / or its salt."

[0012] [Strength-improving agent for hydraulic compositions] In exemplary embodiments, the strength-improving agent for hydraulic compositions of the present invention is an aqueous dispersion containing (A) a poorly water-soluble polymer having a carboxyl group or a salt thereof [hereinafter referred to as component (A)], (B) an ester compound with a molecular weight of 120 to 500 [hereinafter referred to as component (B)], and (C) water.

[0013] <Component (A)> Component (A) is a poorly water-soluble polymer having a carboxyl group or a salt thereof. Alternatively, component (A) may be a poorly water-soluble polymer containing a constituent monomer having a carboxyl group or a salt thereof as a constituent monomer. Component (A) can be used in one or more forms. Component (A) may be a polymer having a carboxyl group and a salt of a carboxyl group. The poorly water-soluble polymer in component (A) may be a polymer with a solubility in water of 0.1 g / L or less at 20°C.

[0014] (A) Component preferably contains a polymer having one or more structural units selected from structural units derived from monomers having a carboxyl group and structural units derived from monomers having a salt of a carboxyl group.

[0015] Examples of carboxyl group salts include metal salts, ammonium salts, and organic amine salts. Examples of metal atoms that form metal salts include monovalent metal atoms such as alkali metal atoms such as lithium, sodium, and potassium; divalent metal atoms such as calcium and magnesium; and trivalent metal atoms such as aluminum and iron. Examples of organic amine salts include alkanolamine salts such as ethanolamine salt, diethanolamine salt, and triethanolamine salt, and alkylamine salts such as triethylamine salt. The salts of monomers that form the constituent units of component (A) may be the same as described above.

[0016] (A) Component may be one or more selected from poly(meth)acrylic acid, poly(meth)acrylic acid ester, styrene-acrylic copolymer, polyvinyl acetate, ethylene-vinyl acetate copolymer, polyamide, polyester, styrene-butadiene rubber, isoprene rubber, chloroprene rubber, and natural rubber.

[0017] Component (A) preferably has a carboxylic acid component as a constituent of the molecular main chain, and more preferably has one or more carboxylic acid components selected from polyacrylic acid, polyacrylic acid esters, acrylic acid-acrylic acid ester copolymers, styrene-acrylic copolymers and other acrylic acid copolymers, polyamides, and polyesters as constituent of the molecular main chain.

[0018] Component (A) preferably has a weight average molecular weight (Mw) of 1,000 or more, more preferably 5,000 or more, still more preferably 10,000 or more, and preferably 200,000 or less, more preferably 100,000 or less, still more preferably 50,000 or less, from the viewpoint of enhancing the strength of the hydraulic composition. Alternatively, component (A) preferably has a weight average molecular weight (Mw) of 1,000 or more and 200,000 or less, more preferably 5,000 or more and 100,000 or less, still more preferably 10,000 or more and 50,000 or less, from the viewpoint of enhancing the strength of the hydraulic composition. The weight average molecular weight of component (A) is measured by the GPC method under the conditions of a high-speed GPC apparatus (HLC-8320GPC, Tosoh Corporation), detector: RI, column: G4000PWXL + G2500PWXL (anion), mobile phase: 0.2 M phosphate buffer / acetonitrile = 9 / 1, flow rate: 1.0 mL / min., column temperature: 40°C, and standard substance: polyethylene glycol.

[0019] [Polyester] The polyester of component (A) is preferably a polycondensate of an alcohol and a carboxylic acid compound, more preferably a polycondensate of polyethylene terephthalate, an alcohol, and a carboxylic acid compound, and still more preferably a polycondensate containing an alkylene oxide adduct of bisphenol A, from the viewpoint of further enhancing the strength of the hydraulic composition. The carboxylic acid compound is a general term for organic compounds having a carboxy group (—C(═O)OH), and examples thereof include carboxylic acids.

[0020] <Alcohol> The alcohol that is the origin of the constituent unit of the polyester of component (A) includes, for example, one or more selected from aliphatic diols, aromatic diols, and polyhydric alcohols having a trivalent or higher valency. From the viewpoint of further enhancing the strength of the hydraulic composition, it contains an alkylene oxide adduct of bisphenol A, and preferably contains an alkylene oxide adduct of bisphenol A represented by the following formula (I).

[0021]

[0022] [In the formula, OR １ and R １O is an alkylene oxide, and R １ x is an alkylene group having 2 or 3 carbon atoms, x and y are positive numbers representing the average number of moles of alkylene oxide added, and the sum of x and y is preferably 1 or more, more preferably 1.5 or more, and preferably 16 or less, more preferably 8 or less, and even more preferably 4 or less. Alternatively, the sum of x and y is preferably 1 or more and 16 or less, more preferably 1.5 or more and 8 or less, and even more preferably 1.5 or more and 4 or less.

[0023] Examples of alkylene oxide adducts of bisphenol A represented by formula (I) include the propylene oxide adduct of bisphenol A [2,2-bis(4-hydroxyphenyl)propane] and the ethylene oxide adduct of bisphenol A. These alkylene oxide adducts of bisphenol A can be used individually or in combination of two or more.

[0024] From the viewpoint of further increasing the strength of the hydraulic composition, the amount of bisphenol A alkylene oxide adduct used is preferably 10 mol% or more, more preferably 30 mol% or more, and 100 mol% or less, out of 100 mol% of the alcohol constituting the polyester of component (A). Alternatively, from the viewpoint of further increasing the hydrophobicity of the coating film, the amount of bisphenol A alkylene oxide adduct used is preferably 10 mol% to 100 mol%, and more preferably 30 mol% to 100 mol%, out of 100 mol% of the alcohol constituting the polyester of component (A). That is, from the viewpoint of further increasing the hydrophobicity of the coating film, the content of constituent units derived from bisphenol A alkylene oxide adduct in component (A) is preferably 10 mol% or more, more preferably 30 mol% or more, and 100 mol% or less, out of 100 mol% of the alcohol-derived constituent units constituting the polyester of component (A). Alternatively, in component (A), the content of constituent units derived from the alkylene oxide adduct of bisphenol A is preferably 10 mol% to 100 mol%, more preferably 30 mol% to 100 mol%, out of 100 mol% of the alcohol-derived constituent units constituting the polyester of component (A), from the viewpoint of further enhancing the hydrophobicity of the coating film. The alcohol constituting the polyester of component (A) also includes ethylene glycol, which constitutes polyethylene terephthalate. In other words, the alcohol-derived constituent units constituting component (A) also include constituent units of component (A) that are derived from ethylene glycol of polyethylene terephthalate. The same applies hereafter to descriptions regarding the amount or content of alcohol and alcohol-derived constituent units constituting the polyester of component (A), unless otherwise specified.

[0025] (A) The alcohols from which the constituent units of the polyester of component (A) are derived may include alcohols other than those corresponding to alkylene oxide adducts of bisphenol A. Examples include aliphatic diols, aromatic diols (excluding those corresponding to alkylene oxide adducts of bisphenol A), and polyhydric alcohols of trihydric or higher hydric value. These alcohols can be used individually or in combination of two or more.

[0026] Aliphatic diols include, for example, one or more selected from ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,10-decanediol, and 1,12-dodecanediol. Aromatic diols include, for example, one or more selected from 1,3-benzenediol, 1,4-benzenediol, 1,3-benzenedimethanol, 1,4-benzenedimethanol, and 4,4'-diphenyldimethanol. Polyhydric alcohols with a valency of three or higher include, for example, trihydric alcohols. For example, glycerin is an example of a polyhydric alcohol with a valency of three or higher.

[0027] <Carboxylic Acid Compounds> The carboxylic acid compounds from which the constituent units of the polyester of component (A) are derived include, for example, one or more selected from aliphatic dicarboxylic acid compounds, aromatic dicarboxylic acid compounds, and polycarboxylic acid compounds with a valency of 3 to 6. These carboxylic acid compounds can be used individually or in combination of two or more. The aliphatic dicarboxylic acid compound may be an aliphatic dicarboxylic acid. The aromatic dicarboxylic acid compound may be an aromatic dicarboxylic acid. The polycarboxylic acid compound with a valency of 3 to 6 may be a polycarboxylic acid with a valency of 3 to 6.

[0028] The number of carbon atoms in the main chain of the aliphatic dicarboxylic acid compound is preferably 3 or more, more preferably 4 or more, and preferably 10 or less, more preferably 8 or less, from the viewpoint of further increasing the strength of the hydraulic composition. Alternatively, the number of carbon atoms in the main chain of the aliphatic dicarboxylic acid compound is preferably 3 to 10, more preferably 4 to 8, from the viewpoint of further increasing the strength of the hydraulic composition. Examples of aliphatic dicarboxylic acid compounds include fumaric acid, maleic acid, oxalic acid, malonic acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanediic acid, succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, or their anhydrides, or their alkyl esters (for example, alkyl groups with 1 to 3 carbon atoms). Examples of substituted succinic acid include dodecyl succinic acid, dodecenyl succinic acid, and octenyl succinic acid. Among the aliphatic dicarboxylic acid compounds mentioned above, one or more selected from the group consisting of fumaric acid, maleic acid, dodecenyl succinic acid or its anhydride, and adipic acid are preferred, with dodecenyl succinic acid or its anhydride being more preferred.

[0029] Examples of aromatic dicarboxylic acid compounds include phthalic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, or their anhydrides, or their alkyl esters (for example, alkyl groups with 1 to 3 carbon atoms). Among these aromatic dicarboxylic acid compounds, from the viewpoint of further increasing the strength of the hydraulic composition, one or more selected from the group consisting of isophthalic acid and terephthalic acid are preferred, with terephthalic acid being more preferred.

[0030] The polycarboxylic acid compound with a valency of 3 to 6 is preferably a tricarboxylic acid. Examples of polycarboxylic acid compounds with a valency of 3 to 6 include trimellitic acid, 2,5,7-naphthalentricarboxylic acid, pyromellitic acid, or acid anhydrides thereof. When a polycarboxylic acid compound is included, from the viewpoint of adjusting physical properties, the alcohol may appropriately contain a monovalent alcohol, and the carboxylic acid compound may appropriately contain a monovalent carboxylic acid compound.

[0031] When the carboxylic acid compound includes an aliphatic dicarboxylic acid compound, the content of aliphatic dicarboxylic acid compound-derived structural units in the carboxylic acid compound-derived structural units of component (A) polyester is, from the viewpoint of further increasing the strength of the hydraulic composition, preferably 1 mol% or more, more preferably 3 mol% or more, even more preferably 5 mol% or more, and preferably 30 mol% or less, and even more preferably 25 mol% or less, per 100 mol% of the carboxylic acid compound-derived structural units. Alternatively, when the carboxylic acid compound includes an aliphatic dicarboxylic acid compound, the content of aliphatic dicarboxylic acid compound-derived structural units in the carboxylic acid compound-derived structural units of component (A) is, from the viewpoint of further increasing the strength of the hydraulic composition, preferably 1 mol% to 30 mol%, more preferably 3 mol% to 25 mol%, and even more preferably 5 mol% to 25 mol%, per 100 mol% of the carboxylic acid compound-derived structural units. This preferred range may be the preferred range when the polyester of component (A) includes structural units derived from aromatic dicarboxylic acid compounds, for example, structural units derived from polyethylene terephthalate. Furthermore, the constituent units of the polyester in component (A) that are derived from carboxylic acid compounds are the constituent units of the polyester in component (A), and also include the constituent units derived from terephthalic acid of polyethylene terephthalate. The same applies hereafter to descriptions regarding the content of constituent units derived from carboxylic acid compounds in the polyester in component (A), unless otherwise specified. In addition, the content of a constituent unit in component (A) may be the amount of compound from which that constituent unit is derived. The same applies hereafter to other constituent units in component (A).

[0032] When the carboxylic acid compound includes an aromatic dicarboxylic acid compound, in the polyester of component (A), the content of constituent units derived from the aromatic dicarboxylic acid compound is preferably 60 mol% or more, more preferably 65 mol% or more, even more preferably 70 mol% or more, even more preferably 75 mol% or more, and preferably 100 mol% or less, more preferably 99 mol% or less, even more preferably 95 mol% or less, and even more preferably 90 mol% or less, from the viewpoint of further increasing the strength of the hydraulic composition. Alternatively, when the carboxylic acid compound includes an aromatic dicarboxylic acid compound, the content of constituent units derived from the aromatic dicarboxylic acid compound in the constituent units derived from the carboxylic acid compound of component (A) is preferably 60 mol% or more and 100 mol% or less, more preferably 65 mol% or more and 99 mol% or less, even more preferably 70 mol% or more and 95 mol% or more, even more preferably 75 mol% or more and 90 mol% or less, from the viewpoint of further increasing the strength of the hydraulic composition.

[0033] (Molar ratio of constituent units derived from carboxylic acid compounds to constituent units derived from alcohol) In the polyester of component (A), the molar ratio of constituent units derived from carboxylic acid compounds to constituent units derived from alcohol [carboxylic acid compound / alcohol] is preferably 0.7 or more, more preferably 0.8 or more, even more preferably 0.9 or more, and preferably 1.5 or less, more preferably 1.3 or less, and even more preferably 1.1 or less, from the viewpoint of further increasing the strength of the hydraulic composition. Alternatively, the molar ratio [carboxylic acid compound / alcohol] is preferably 0.7 or more and 1.5 or less, more preferably 0.8 or more and 1.3 or less, and even more preferably 0.9 or more and 1.1 or less, from the viewpoint of further increasing the strength of the hydraulic composition.

[0034] (Constituent units derived from polyethylene terephthalate) The polyester of component (A) preferably contains constituent units consisting of ethylene glycol and terephthalic acid derived from polyethylene terephthalate. In addition to the constituent units consisting of ethylene glycol and terephthalic acid, polyethylene terephthalate may also contain small amounts of other components such as butanediol and isophthalic acid.

[0035] In recent years, the environmental impact of waste plastics has become a concern, and the recycling of waste plastics is being considered. In this invention, since polyethylene terephthalate, which is the source of the constituent units of the polyester in component (A), is widely used in products such as bottles and films, polyethylene terephthalate (hereinafter also referred to as "recycled PET") that has been manufactured as such products and subsequently discarded is preferably used from the standpoint of environmental issues and cost. The type of recycled material is not particularly limited, as long as it has a certain degree of purity. It may contain small amounts of plastics such as polyethylene or polypropylene as impurities.

[0036] If component (A) contains constituent units derived from polyethylene terephthalate, the content of constituent units consisting of ethylene glycol and terephthalic acid derived from polyethylene terephthalate in component (A) is preferably 1 part by mass or more, more preferably 10 parts by mass or more, even more preferably 30 parts by mass or more, and preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less, per 100 parts by mass of constituent units of component (A), from the viewpoint of further increasing the strength of the hydraulic composition. Alternatively, if component (A) contains constituent units derived from polyethylene terephthalate, the content of constituent units consisting of ethylene glycol and terephthalic acid derived from polyethylene terephthalate in component (A) is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 10 parts by mass or more and 45 parts by mass or less, per 100 parts by mass of constituent units of component (A), from the viewpoint of further increasing the strength of the hydraulic composition. The content of constituent units consisting of ethylene glycol and terephthalic acid derived from polyethylene terephthalate may be the total content of constituent units derived from ethylene glycol that constitute polyethylene terephthalate and constituent units derived from terephthalic acid that constitute polyethylene terephthalate.

[0037] (A) In the polyester of component (U Ｂ), and a structural unit (U) composed of ethylene glycol and terephthalic acid derived from polyethylene terephthalate Ｅ ), and the molar ratio [(U Ｂ ) / (U Ｅ ) is preferably 10 / 90 or more, more preferably 20 / 80 or more, still more preferably 30 / 70 or more, even more preferably 35 / 65 or more, and preferably 95 / 5 or less, more preferably 90 / 10 or less, still more preferably 80 / 20 or less, from the viewpoint of further enhancing the strength of the hydraulic composition. Alternatively, the molar ratio [(U Ｂ ) / (U Ｅ ) is preferably 10 / 90 or more and 95 / 5 or less, more preferably 20 / 80 or more and 90 / 10 or less, still more preferably 30 / 70 or more and 80 / 20 or less, even more preferably 35 / 65 or more and 80 / 20 or less, from the viewpoint of further enhancing the strength of the hydraulic composition.

[0038] The polyester used in the present invention may be a polyester modified to such an extent that its properties are not substantially impaired. Specifically, examples of the modified polyester include polyesters grafted or blocked with phenol, urethane, epoxy, etc. by the methods described in JP-A-11-133668, JP-A-10-239903, JP-A-8-20636, etc. Preferred modified polyesters include urethane-modified polyesters obtained by extending polyesters with polyisocyanate compounds.

[0039] (Physical properties of polyester) The softening point of the polyester of component (A) is preferably 85°C or higher, more preferably 90°C or higher, even more preferably 95°C or higher, and preferably 140°C or lower, more preferably 130°C or lower, even more preferably 125°C or lower, even more preferably 120°C or lower, and even more preferably 115°C or lower. Alternatively, this softening point is preferably 85°C or higher and 140°C or lower, more preferably 90°C or higher and 130°C or lower, even more preferably 95°C or higher and 125°C or lower, even more preferably 95°C or higher and 120°C or lower, and even more preferably 95°C or higher and 115°C or lower, from the viewpoint of further increasing the strength of the hydraulic composition.

[0040] (A) The acid value of the polyester component is preferably 2 mg KOH / g or more, more preferably 3 mg KOH / g or more, and even more preferably 5 mg KOH / g or more, from the viewpoint of further increasing the strength of the hydraulic composition, and preferably 40 mg KOH / g or less, more preferably 30 mg KOH / g or less, and even more preferably 20 mg KOH / g or less. Alternatively, from the viewpoint of further increasing the strength of the hydraulic composition, this acid value is preferably 2 mg KOH / g or more and 40 mg KOH / g or less, more preferably 3 mg KOH / g or more and 30 mg KOH / g or less, and even more preferably 5 mg KOH / g or more and 20 mg KOH / g or less.

[0041] (A) The hydroxyl value of the polyester component is preferably 1 mg KOH / g or more, more preferably 2 mg KOH / g or more, even more preferably 5 mg KOH / g or more, even more preferably 10 mg KOH / g or more, and preferably 70 mg KOH / g or less, more preferably 50 mg KOH / g or less, even more preferably 40 mg KOH / g or less, and even more preferably 30 mg KOH / g or less. Alternatively, this hydroxyl value is preferably 1 mg KOH / g or more and 70 mg KOH / g or less, more preferably 2 mg KOH / g or more and 50 mg KOH / g or less, even more preferably 5 mg KOH / g or more and 40 mg KOH / g or less, and even more preferably 10 mg KOH / g or more and 30 mg KOH / g or less, from the viewpoint of further increasing the strength of the hydraulic composition.

[0042] The glass transition temperature of the polyester component (A) is preferably 30°C or higher, more preferably 40°C or higher, even more preferably 50°C or higher, and preferably 80°C or lower, more preferably 70°C or lower, and even more preferably 65°C or lower, from the viewpoint of further increasing the strength of the hydraulic composition. Alternatively, the glass transition temperature is preferably 30°C or higher and 80°C or lower, more preferably 40°C or higher and 70°C or lower, and even more preferably 50°C or higher and 65°C or lower, from the viewpoint of further increasing the strength of the hydraulic composition.

[0043] From the viewpoint of further increasing the strength of the hydraulic composition, the weight-average molecular weight (Mw) of the polyester of component (A) is preferably 1,000 or more, more preferably 5,000 or more, even more preferably 10,000 or more, and preferably 100,000 or less, more preferably 70,000 or less, and even more preferably 50,000 or less. Alternatively, from the viewpoint of further increasing the strength of the hydraulic composition, the weight-average molecular weight (Mw) of the polyester of component (A) is preferably 1,000 or more and 100,000 or less, more preferably 5,000 or more and 70,000 or less, and even more preferably 10,000 or more and 50,000 or less.

[0044] The softening point, acid value, hydroxyl value, glass transition temperature, and weight-average molecular weight of the polyester of component (A) can be measured by the method described in the examples. The softening point, acid value, hydroxyl value, glass transition temperature, and weight-average molecular weight can be adjusted by the raw material monomer composition, molecular weight, catalyst amount, or reaction conditions.

[0045] (Method for producing polyester) The method for producing the polyester of component (A) is not particularly limited, but for example, it can be produced by polycondensing the alcohol and the carboxylic acid compound, further by polycondensing polyethylene terephthalate, the alcohol and the carboxylic acid compound, and further by polycondensing polyethylene terephthalate, the alcohol containing an alkylene oxide adduct of bisphenol A and the carboxylic acid compound. The temperature of the polycondensation reaction is not particularly limited, but from the viewpoint of reactivity and monomer decomposition temperature, it is preferably 210°C to 260°C.

[0046] If the polyester of component (A) contains constituent units derived from polyethylene terephthalate, the amount of polyethylene terephthalate present in the raw material is preferably 4% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 40% by mass or less, out of 100% by mass of the total amount of polyethylene terephthalate, the alcohol, and the carboxylic acid compound. Alternatively, if the polyester of component (A) contains constituent units derived from polyethylene terephthalate, the amount of polyethylene terephthalate present in the raw material is preferably 4% by mass or more and 80% by mass or less, more preferably 10% by mass or more and 70% by mass or less, and even more preferably 20% by mass or more and 40% by mass or less, out of 100% by mass of the total amount of polyethylene terephthalate, the alcohol, and the carboxylic acid compound.

[0047] By adding polyethylene terephthalate during the polycondensation reaction between the alcohol and the carboxylic acid compound, a transesterification reaction occurs, and a polyester can be obtained in which the constituent units of polyethylene terephthalate are incorporated into the constituent units derived from the alcohol and the constituent units derived from the carboxylic acid compound. Polyethylene terephthalate may be present from the start of the polycondensation reaction or added to the reaction system during the polycondensation reaction. From the viewpoint of further increasing the strength of the hydraulic composition, the timing of adding polyethylene terephthalate is preferably when the reaction rate between the alcohol and the carboxylic acid compound is 10% or less, and more preferably when it is 5% or less. The reaction rate refers to the value of Amount of reaction water produced (moles) / Theoretical amount of reaction water produced (moles) × 100.

[0048] For the polycondensation reaction, from the viewpoint of reactivity and cost, a tin(II) compound that does not have a Sn-C bond, such as di(2-ethylhexanoic acid)tin(II), can be used as an esterification catalyst. The amount of esterification catalyst used is preferably 0.01 parts by mass or more, more preferably 0.2 parts by mass or more, preferably 3.0 parts by mass or less, and more preferably 1.5 parts by mass or less, based on 100 parts by mass of the total amount of the alcohol, the carboxylic acid compound, and polyethylene terephthalate. For the polycondensation reaction, from the viewpoint of reactivity and cost, in addition to the catalyst, a pyrogallol derivative such as gallic acid can be used as an esterification co-catalyst. The amount of esterification co-catalyst used is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, even more preferably 0.01 parts by mass or more, preferably 0.50 parts by mass or less, even more preferably 0.20 parts by mass or less, and even more preferably 0.10 parts by mass or less, based on 100 parts by mass of the total amount of the alcohol, the carboxylic acid compound, and polyethylene terephthalate.

[0049] (A) Component (A) is preferably composed of one or more selected from polyester, polyacrylic acid, polyacrylic acid ester, acrylic acid-acrylic acid ester copolymer, and styrene-acrylic copolymer, and is more preferably composed of polyester, from the viewpoint of further increasing the strength of the hydraulic composition.

[0050] Component (A) may be a polymer in which polyester accounts for 100% by mass, from the viewpoint of further increasing the strength of the hydraulic composition, preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, and preferably 100% by mass or less, from the viewpoint of further increasing the strength of the hydraulic composition. Alternatively, from the viewpoint of further increasing the strength of the hydraulic composition, component (A) may be a polymer in which polyester accounts for 100% by mass.

[0051] Component (A) is preferably a polyester containing the alcohol-derived structural units and the carboxylic acid compound-derived structural units. Component (A) may be a poorly water-soluble polymer containing a polyester that, from the viewpoint of further increasing the strength of the hydraulic composition, includes the alcohol-derived structural units and the carboxylic acid compound-derived structural units, wherein the content of aromatic dicarboxylic acid compound-derived structural units in the total amount of carboxylic acid compound-derived structural units contained in the polyester is preferably 60 mol% or more, more preferably 65 mol% or more, even more preferably 70 mol% or more, even more preferably 75 mol% or more, and preferably 100 mol% or less, more preferably 99 mol% or less, even more preferably 95 mol% or less, and even more preferably 90 mol% or less. Alternatively, the content of aromatic dicarboxylic acid compound-derived structural units in the total amount of carboxylic acid compound-derived structural units contained in the polyester is preferably 60 mol% or more and 100 mol% or less, more preferably 65 mol% or more and 99 mol% or less, even more preferably 70 mol% or more and 95 mol% or more and even more preferably 75 mol% or more and 90 mol% or less.

[0052] The solubility of component (A) in water at 20°C is preferably 0 g / L or more, more preferably 0.0001 g / L or more, even more preferably 0.001 g / L or more, and preferably 0.1 g / L or less, more preferably 0.05 g / L or less, and even more preferably 0.01 g / L or less, from the viewpoint of further increasing the strength of the hydraulic composition. Alternatively, the solubility of component (A) in water at 20°C is preferably 0 g / L or more and 0.1 g / L or less, more preferably 0.0001 g / L or more and 0.05 g / L or less, and even more preferably 0.001 g / L or more and 0.01 g / L or less, from the viewpoint of further increasing the strength of the hydraulic composition. This solubility is the maximum mass (g) of component (A) that can dissolve in 1 L of water. The solubility can be measured by the following method. If the solubility of component (A) in 1 L of water at 20°C is within the above range, it can be said that component (A) is a poorly water-soluble polymer.

[0053] [Method for measuring the solubility of component (A) in water at 20°C] Mix 1 g of component (A) thoroughly with 50 g of distilled water at 20°C, let stand for 1 hour, and then centrifuge (3,000 rpm, 5 minutes) to precipitate any undissolved components. Collect 1 mL of the supernatant. Filter this supernatant using a membrane filter (DISMIC 25HP045AN, manufactured by Advantec Corporation), dilute the resulting filtrate 20 times with distilled water, and measure the TOC (mg / L) of the diluted filtrate using a combustion catalyst oxidation method with an online total organic carbon analyzer (TOC-V, manufactured by Shimadzu Corporation) to calculate the solubility of component (A) in water.

[0054] <Component (B)> Component (B) is an ester compound with a molecular weight of 120 to 500. Component (B) can be used in one or more forms. The molecular weight of component (B) is 120 or more, preferably 150 or more, more preferably 200 or more, from the viewpoint of suppressing volatilization over time, and 500 or less, preferably 450 or less, more preferably 400 or less, from the viewpoint of further enhancing interaction with component (A). Alternatively, the molecular weight of component (B) is 120 to 500, preferably 150 to 450, more preferably 200 to 400, from the viewpoint of suppressing volatilization over time and further enhancing interaction with component (A).

[0055] Component (B) is preferably an ester compound having one or more, more preferably two or more, and preferably five or fewer, and more preferably four or fewer ester groups, from the viewpoint of further enhancing the interaction with component (A). Alternatively, component (B) is preferably an ester compound having one to five, more preferably two to five, and even more preferably two to four ester groups, from the viewpoint of further enhancing the interaction with component (A).

[0056] Component (B) may include, for example, one or more selected from aliphatic esters such as monohydric alcohol esters of fatty acids, monohydric alcohol esters of polybasic acids, fatty acid esters of polyhydric alcohols, aromatic esters, and phosphate esters. Examples of aliphatic esters include, for example, one or more selected from 2-ethylhexyl oleate (molecular weight 310.51) and tributyl acetyl citrate (ATBC) (molecular weight 402.48). Examples of aromatic esters may include, for example, one or more selected from diallyl phthalate (molecular weight 246.26), dioctyl phthalate (molecular weight 390.56), diisononyl phthalate (molecular weight 418.61), isodecyl phthalate (molecular weight 446.67), and bis(2-ethylhexyl) phthalate (molecular weight 390.56). (B) Component is preferably one or more selected from aliphatic esters and aromatic esters, and more preferably one or more selected from tributyl acetylcitrate and aromatic diesters, from the viewpoint of further increasing the strength of the hydraulic composition.

[0057] <Component (C)> The strength enhancer for hydraulic compositions of the present invention contains (C) water. Component (C) is water. For example, deionized water, tap water, or purified water can be used. The water can be used as the remainder of the strength enhancer for hydraulic compositions in an amount such that the overall composition of the strength enhancer is 100% by mass.

[0058] <Composition, etc.> The strength enhancer for hydraulic compositions of the present invention contains component (A) in an amount of preferably 19% by mass or more, more preferably 20% by mass or more, even more preferably 25% by mass or more, even more preferably 30% by mass or more, and from the viewpoint of further increasing the strength of the hydraulic composition, preferably 65% ​​by mass or less, more preferably 60% by mass or less, even more preferably 55% by mass or less, and even more preferably 50% by mass or less. Alternatively, the strength enhancer for hydraulic compositions of the present invention contains component (A) in an amount of preferably 19% by mass or more and 65% by mass or less, more preferably 20% by mass or more and 65% by mass or less, even more preferably 20% by mass or more and 60% by mass or less, even more preferably 25% by mass or more and 55% by mass or less, and even more preferably 30% by mass or more and 50% by mass or less, from the viewpoint of further increasing the strength of the hydraulic composition.

[0059] In the strength enhancer for hydraulic compositions of the present invention, the content of component (A) relative to the remainder after removing water from the strength enhancer for hydraulic compositions is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and from the viewpoint of further increasing the strength of the hydraulic composition, preferably 98% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less. Alternatively, in the strength enhancer for hydraulic compositions of the present invention, the content of component (A) relative to the remainder after removing water from the strength enhancer for hydraulic compositions is preferably 60% by mass or more and 98% by mass or less, more preferably 70% by mass or more and 95% by mass or less, and even more preferably 80% by mass or more and 90% by mass or less, from the viewpoint of further increasing the strength of the hydraulic composition.

[0060] The strength enhancer for hydraulic compositions of the present invention contains component (B) in an amount of preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 3% by mass or more, and from the viewpoint of further increasing the strength of the hydraulic composition, preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. Alternatively, the strength enhancer for hydraulic compositions of the present invention contains component (B) in an amount of preferably 1% by mass or more and 20% by mass or less, more preferably 2% by mass or more and 15% by mass or less, and even more preferably 3% by mass or more and 10% by mass or less, from the viewpoint of further increasing the strength of the hydraulic composition.

[0061] In the strength enhancer for hydraulic compositions of the present invention, the content of component (B) relative to the remainder after removing water from the strength enhancer for hydraulic compositions is preferably 2% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, and from the viewpoint of further increasing the strength of the hydraulic composition, preferably 35% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less. Alternatively, in the strength enhancer for hydraulic compositions of the present invention, the content of component (B) relative to the remainder after removing water from the strength enhancer for hydraulic compositions is preferably 2% by mass or more and 35% by mass or less, more preferably 5% by mass or more and 25% by mass or less, and even more preferably 10% by mass or more and 20% by mass or less, from the viewpoint of further increasing the strength of the hydraulic composition.

[0062] In the strength-improving agent for hydraulic compositions of the present invention, the mass ratio of the content of component (B) to the content of component (A) [(B) / (A)] is preferably 0.05 or more, more preferably 0.07 or more, even more preferably 0.10 or more, and from the viewpoint of further increasing the strength of the hydraulic composition, preferably 0.3 or less, more preferably 0.25 or less, and even more preferably 0.20 or less. Alternatively, the mass ratio [(B) / (A)] is preferably 0.05 or more and 0.3 or less, more preferably 0.07 or more and 0.25 or less, and even more preferably 0.10 or more and 0.20 or less, from the viewpoint of further increasing the strength of the hydraulic composition.

[0063] The strength enhancer for hydraulic compositions of the present invention contains, from the viewpoint of further improving the miscibility of component (C) water with the hydraulic composition, preferably 19% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, and from the viewpoint of further improving the strength of the hydraulic composition, preferably 80% by mass or less, more preferably 70% by mass or less, even more preferably 65% ​​by mass or less, and even more preferably 60% by mass or less. Alternatively, the strength enhancer for hydraulic compositions of the present invention contains component (C) in an amount of preferably 19% to 80% by mass, more preferably 19% to 70% by mass, even more preferably 19% to 65% by mass, even more preferably 30% to 70% by mass, even more preferably 40% to 65% by mass, and even more preferably 50% to 60% by mass, from the viewpoint of improving miscibility with the hydraulic composition and the strength of the hydraulic composition.

[0064] In the strength-improving agent for hydraulic compositions of the present invention, the mass ratio of the content of component (C) to the content of component (A) [(C) / (A)] is preferably 0.4 or more, more preferably 0.7 or more, even more preferably 1.0 or more, even more preferably 1.5 or more, and from the viewpoint of further increasing the strength of the hydraulic composition, preferably 3 or less, more preferably 2.5 or less, even more preferably 2.0 or less. Alternatively, the mass ratio [(C) / (A)] is preferably 0.4 or more and 3 or less, more preferably 0.7 or more and 2.5 or less, even more preferably 1.0 or more and 2.0 or less, even more preferably 1.5 or more and 2.0 or less, from the viewpoint of further increasing the strength of the hydraulic composition.

[0065] The strength enhancer for hydraulic compositions of the present invention may be a liquid. The strength enhancer for hydraulic compositions of the present invention may be a liquid strength enhancer for hydraulic compositions.

[0066] The strength enhancer for hydraulic compositions of the present invention may optionally contain one or more known strength enhancers such as amine compounds and inorganic compounds, and organic solvents.

[0067] The strength-enhancing agent for hydraulic compositions of the present invention can be applied, for example, to the exposed surface of concrete after a predetermined hardening period, and then the hydraulic composition can be hardened to obtain a hydraulic composition that exhibits excellent early strength development and can maintain excellent strength for a long period of time. In other words, the strength-enhancing agent for hydraulic compositions of the present invention may be a coating curing agent for improving the strength of hydraulic compositions.

[0068] The hydraulic composition strength improver of the present invention may be a hydraulic composition strength improver comprising component (A), component (B), and component (C). Furthermore, the hydraulic composition strength improver of the present invention may further comprise one or more of the optional components listed in the hydraulic composition strength improver of the present invention. The preferred amounts of component (A), component (B), and component (C) in the hydraulic composition strength improver of the present invention can be applied by substituting the preferred content in the hydraulic composition strength improver with the preferred amounts.

[0069] <Method for Manufacturing Strengthening Agent for Hydraulic Compositions> In an exemplary embodiment, the present invention provides a method for manufacturing a strength improving agent for hydraulic compositions, comprising mixing component (A), component (B), and component (C). This manufacturing method produces the strength improving agent for hydraulic compositions of the present invention, which contains component (A), component (B), and component (C). Specific examples and preferred embodiments of component (A), component (B), and component (C) used in the method for manufacturing the strength improving agent for hydraulic compositions of the present invention are the same as those described in the description of the strength improving agent for hydraulic compositions of the present invention. The matters described in the description of the strength improving agent for hydraulic compositions of the present invention can be applied to the method for manufacturing the strength improving agent for hydraulic compositions of the present invention. In the method for manufacturing the strength improving agent for hydraulic compositions of the present invention, the content of each component and their mass ratios described in the description of the strength improving agent for hydraulic compositions of the present invention can be applied by replacing the content of each component with the amount of mixture.

[0070] <Hydraulic Composition> In exemplary embodiments, the present invention provides a hydraulic composition in which an aqueous dispersion composition comprising (A) a poorly water-soluble polymer having a carboxyl group or a salt thereof [component (A)], (B) an ester compound having a molecular weight of 120 to 500 [component (B)], and (C) water [component (C)] is applied to the surface of a hydraulic composition structure. Alternatively, the hydraulic composition of the present invention may be a hydraulic composition in which an aqueous dispersion composition comprising components (A), (B), and (C) is applied to the surface of a hydraulic composition structure containing hydraulic powder and water. Examples of how the aqueous dispersion composition is "applied" to the surface of the hydraulic composition structure include coating or spraying. From the viewpoint of improving strength, the hydraulic composition structure used here may be a structure made by hardening hydraulic powder containing aggregate.

[0071] In this specification, "applying the aqueous dispersion composition to a surface" means performing one or more of the following treatments: applying the aqueous dispersion composition to the surface of a cured structure, applying it to the surface of a molded body before curing, or applying it to a surface layer during the formation of a structure.

[0072] The hydraulic composition of the present invention may be a hydraulic composition having a surface layer containing component (A) and component (B). Alternatively, the hydraulic composition of the present invention may be a hydraulic composition in which the strength-improving agent for hydraulic compositions of the present invention is applied to the surface of the hydraulic composition structure. Specific examples and preferred embodiments of component (A), component (B), and the strength-improving agent for hydraulic compositions used in the hydraulic composition of the present invention are the same as those described for the strength-improving agent for hydraulic compositions of the present invention. The matters described for the strength-improving agent for hydraulic compositions and its manufacturing method of the present invention can be applied to the hydraulic composition of the present invention.

[0073] <Hydraulic Powder> The hydraulic powder used in the hydraulic composition of the present invention is a powder that hardens when mixed with water, and examples include ordinary Portland cement, rapid-hardening Portland cement, ultra-rapid-hardening Portland cement, sulfate-resistant Portland cement, low-heat Portland cement, white Portland cement, and eco-cement (e.g., JIS R 5214). Among these, from the viewpoint of strength development, one or more cements selected from rapid-hardening Portland cement, ordinary Portland cement, sulfate-resistant Portland cement, and white Portland cement are preferred, and one or more cements selected from rapid-hardening Portland cement and ordinary Portland cement are more preferred. The hydraulic powder may also contain blast furnace slag, fly ash, silica fume, calcined clay, anhydrous gypsum, etc., and may also contain non-hydraulic limestone fine powder, etc. As the hydraulic powder, blast furnace cement, fly ash cement, silica fume cement, or calcined clay mixed cement, which are mixtures of cement with blast furnace slag, fly ash, silica fume, calcined clay, etc., may be used. It may also contain clay such as bentonite. The hydraulic compositions obtained by adding sand and gravel as aggregates to these powders are generally called mortar, concrete, etc., respectively.

[0074] <Aggregate> The hydraulic composition of the present invention may optionally contain aggregate. The aggregate may be one or more types of aggregate selected from fine aggregate and coarse aggregate. Fine aggregate may be those specified in JIS A0203-2014, number 2311. For example, fine aggregate may be river sand, land sand, mountain sand, sea sand, lime sand, silica sand and crushed sand thereof, blast furnace slag fine aggregate, ferronickel slag fine aggregate, lightweight fine aggregate (artificial and natural), and recycled fine aggregate. Coarse aggregate may be those specified in JIS A0203-2014, number 2312. For example, coarse aggregate may be river gravel, land gravel, mountain gravel, sea gravel, lime gravel, crushed stone thereof, blast furnace slag coarse aggregate, ferronickel slag coarse aggregate, lightweight coarse aggregate (artificial and natural), and recycled coarse aggregate. Fine aggregate and coarse aggregate may be mixed together or used as a single type.

[0075] A surface layer containing component (A) and component (B) can be formed by applying an aqueous dispersion composition containing component (A), component (B), and component (C) to the surface of a hydraulic composition. Methods for applying the aqueous dispersion composition to the surface of the hydraulic composition include, for example, coating or spraying. Specifically, the aqueous dispersion composition can be attached to the surface of the hydraulic composition using a roller, a hand pump sprayer, or a sprayer. The aqueous dispersion composition containing component (A), component (B), and component (C) may be the strength enhancer for hydraulic compositions of the present invention. Therefore, the content of component (A), the content of component (B), the content of component (C), and the mass ratio of these contents [(B) / (A)] in the aqueous dispersion composition are the same as those described for the strength enhancer for hydraulic compositions of the present invention.

[0076] The aqueous dispersion composition containing component (A), component (B), and component (C), and furthermore, the strength enhancer for hydraulic compositions of the present invention, are preferably 100 g / m² from the viewpoint of further increasing the strength of the hydraulic composition. ２ More preferably 150 g / m ２ In addition to the above, and from the standpoint of working time and cost, a preferable 250 g / m² is preferred. ２ More preferably, 200 g / m ２ The following is how it is applied to the surface of the hydraulic composition. Alternatively, the aqueous dispersion composition, and even more so the strength enhancer for the hydraulic composition of the present invention, is preferably 100 g / m² from the viewpoint of further increasing the strength of the hydraulic composition and from the viewpoint of work time and cost. ２ More than 250g / m ２ More preferably, 150 g / m ２ More than 200g / m ２ The following is how to apply it to the surface of the hydraulic composition.

[0077] In the hydraulic composition of the present invention, the mass percentage of water content to hydraulic powder content (water / hydraulic powder ratio (W / P)) is preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 45% by mass or less, and preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, from the viewpoint of further increasing the strength of the hydraulic composition. Alternatively, the mass percentage (water / hydraulic powder ratio (W / P)) is preferably 10% by mass or more and 60% by mass or less, more preferably 20% by mass or more and 50% by mass or less, and even more preferably 30% by mass or more and 45% by mass or less, from the viewpoint of further increasing the strength of the hydraulic composition. Here, the water / hydraulic powder ratio (W / P) is the mass percentage (mass%) of water and hydraulic powder in the hydraulic composition, and is calculated as (water / hydraulic powder) × 100. The water / hydraulic powder ratio is calculated based on the amount of powder that hardens through a hydration reaction. Furthermore, if the hydraulic powder is cement, the W / P ratio may be expressed as W / C. In addition to powders that harden through a hydration reaction, such as cement, if the hydraulic powder includes powders with pozzolanic properties, powders with latent hydraulic properties, and stone powder (calcium carbonate powder), the amounts of these are also included in the amount of hydraulic powder in this invention. Furthermore, if the powder that hardens through a hydration reaction contains a high-strength admixture, the amount of the high-strength admixture is also included in the amount of hydraulic powder. This also applies to other parts of mass related to the mass of the hydraulic powder.

[0078] In the hydraulic composition of the present invention, the mass percentage of the hydraulic powder content to the aggregate content is preferably 60% by mass or less, more preferably 45% by mass or less, even more preferably 30% by mass or less, and even more preferably 25% by mass or less, from the viewpoint of further improving workability during concrete placement, and preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, from the viewpoint of further improving durability. The mass percentage of the hydraulic powder content to the aggregate content is calculated as (hydraulic powder content / aggregate content) × 100.

[0079] Aggregates may be used within the normal range used in the preparation of concrete, mortar, etc. When the hydraulic composition is concrete, the amount of coarse aggregate used is preferably 50% or more of the bulk volume, more preferably 55% or more, even more preferably 60% or more, and preferably 100% or less, more preferably 90% or less, and even more preferably 80% or less, from the viewpoint of the properties of the concrete. The bulk volume is 1 m³ of concrete. ３ This is the ratio of the volume of coarse aggregate (including voids) within the composition. Furthermore, when the hydraulic composition is concrete, the amount of fine aggregate used is preferably 500 kg / m³ from the viewpoint of further enhancing durability. ３ More preferably 600 kg / m ３ More preferably 700 kg / m ３ In addition, preferably 1,000 kg / m ３ More preferably, 900 kg / m ３ The following applies. Furthermore, when the hydraulic composition is mortar, the amount of fine aggregate used is preferably 800 kg / m³. ３ More preferably 900 kg / m ３ More preferably, 1,000 kg / m ３ In addition, preferably 2,000 kg / m ３ More preferably, 1,800 kg / m ３ More preferably, 1,700 kg / m ３ The following applies:

[0080] The hydraulic composition of the present invention may optionally contain other components in addition to the above components, such as retarders, thickeners, air-entraining agents, waterproofing agents, fluidizing agents, rapid strengthening agents, defoaming agents, compatibilizers, preservatives, etc. Examples of rapid strengthening agents include compounds selected from alkali metal or alkaline earth metal hydrochlorides, sulfates, nitrates, nitrites, cyanates, thiocyanates, thiosulfates, and formates; organic compounds selected from alkanolamines, glycerin derivatives, formaldehyde derivatives, and catechol derivatives; and nanoparticles of Portland cement hydration products (C-S-H, calcium carbonate, and calcium hydroxide).

[0081] The hydraulic composition of the present invention may use concrete or mortar. The hydraulic composition of the present invention is useful in any of the following fields: self-leveling, refractories, plaster, lightweight or heavy concrete, air entrainment, repair, pre-packed, tremie, ground improvement, grouting, and cold weather applications.

[0082] [Method for Producing a Hydraulic Composition] In an exemplary embodiment, the present invention provides a method for producing a hydraulic composition, comprising mixing hydraulic powder with water to obtain a hydraulic composition, and forming a surface layer on the surface of the hydraulic composition containing (A) a poorly water-soluble polymer having a carboxyl group or a salt thereof [component (A)] and (B) an ester compound with a molecular weight of 120 to 500 [component (B)]. Furthermore, the method for producing a hydraulic composition of the present invention may involve mixing aggregate with the hydraulic powder.

[0083] Specific examples and preferred embodiments of component (A) and component (B) used in the method for producing the hydraulic composition of the present invention are the same as those described in the Strength Enhancer for Hydraulic Composition of the present invention, and specific examples and preferred embodiments of hydraulic powder and aggregate are the same as those described in the Hydraulic Composition of the present invention. In the method for producing the hydraulic composition of the present invention, the hydraulic powder is mixed so that the W / P ratio is within the range described in the Hydraulic Composition of the present invention. The amount of aggregate used (mixing amount) and the mass percentage of the hydraulic powder content to the aggregate content are also within the range described in the Hydraulic Composition of the present invention. The matters described in the Strength Enhancer for Hydraulic Composition of the present invention, its production method, and hydraulic composition can be applied to the method for producing the hydraulic composition of the present invention. In the method for producing the hydraulic composition of the present invention, the content of each component and their mass ratios described in the Hydraulic Composition of the present invention can be applied by replacing the content of each component with the mixing amount.

[0084] The method for producing the hydraulic composition of the present invention may be, for example, a method for producing a hydraulic composition that involves mixing hydraulic powder and water to obtain a hydraulic composition, and then applying an aqueous dispersion composition containing components (A), (B), and (C) of the present invention to the surface of the hydraulic composition. The method for producing the hydraulic composition of the present invention may also be a method for producing a hydraulic composition that involves mixing hydraulic powder and water to obtain a hydraulic composition, and then applying a strength-improving agent for hydraulic compositions of the present invention to the surface of the hydraulic composition. It is preferable that the method for producing the hydraulic composition of the present invention involves applying an aqueous dispersion composition containing components (A), (B), and (C), or a strength-improving agent for hydraulic compositions of the present invention, to the surface of the hydraulic composition and then curing the hydraulic composition.

[0085] In the method for producing the hydraulic composition of the present invention, specifically, the aqueous dispersion composition containing component (A), component (B), and component (C), and furthermore, the strength enhancer for the hydraulic composition of the present invention, are preferably 100 g / m² from the viewpoint of further increasing the strength of the hydraulic composition. ２ More preferably 150 g / m ２ In addition to the above, and from the viewpoint of labor costs, a preferable 250 g / m² is preferred. ２ More preferably, 200 g / m ２ The following is applied to the surface of the hydraulic composition. Alternatively, in the method for producing the hydraulic composition of the present invention, the aqueous dispersion composition, and furthermore, the strength enhancer for the hydraulic composition of the present invention, is preferably 100 g / m² from the viewpoint of further increasing the strength of the hydraulic composition and from the viewpoint of labor costs. ２ More than 250g / m ２ More preferably, 150 g / m ２ More than 200g / m ２ The following is how to apply it to the surface of the hydraulic composition.

[0086] In the method for producing the hydraulic composition of the present invention, the method for applying the aqueous dispersion composition containing component (A), component (B), and component (C), and further the strength enhancer for the hydraulic composition of the present invention, to the surface of the hydraulic composition includes, for example, coating or spraying. Specifically, this includes coating the surface of the hydraulic composition with a brush or mop, or spraying with a sprayer.

[0087] In the method for producing the hydraulic composition of the present invention, the hydraulic composition and water may be mixed using a mixer such as a mortar mixer or a forced twin-screw mixer. The mixing time is preferably 1 minute or more, more preferably 2 minutes or more, and preferably 5 minutes or less, and more preferably 3 minutes or less.

[0088] In the method for producing the hydraulic composition of the present invention, for example, the method may include filling a mold with a mixture obtained by mixing hydraulic powder and water to obtain a molded body of the hydraulic composition, and applying a water dispersion composition containing components (A), (B), and (C), preferably the strength enhancer for the hydraulic composition of the present invention, to the exposed surface of the molded body and hardening it. Examples of molds used in the method for producing the hydraulic composition of the present invention include building molds and concrete product molds. Methods for filling the mold include, for example, directly pouring the mixture from a mixer, and introducing the hydraulic composition into the mold by pumping it.

[0089] In the method for producing the hydraulic composition of the present invention, for example, when filling a mold with the hydraulic composition of the present invention and curing it, the hardening can be accelerated by heat curing. Here, heat curing may be, for example, by holding the hydraulic composition at a temperature of 40°C to 80°C to accelerate the hardening.

[0090] The hardened hydraulic composition can be demolded to obtain a hardened body of the hydraulic composition of the present invention. It is preferable that the hardened body of the hydraulic composition has sufficient compressive strength upon demolding. The compressive strength upon demolding is preferably equal to or greater than the strength specified in, for example, "Commentary Table 8.8.1 of the 2023 Japan Society of Civil Engineers Standard Specifications [Construction Edition]".

[0091] Examples of hardened hydraulic compositions using concrete product formwork include, for civil engineering products, concrete piles, concrete poles, various block products for revetments, box culvert products, segment products used in tunnel construction, bridge pier girders, etc., and for architectural products, curtain wall products, columns, beams, and building component products used in floor slabs, etc.

[0092] In the present invention, in the preparation of the hydraulic composition, the time from contacting the hydraulic powder with water to demolding is preferably, for example, 16 hours or more and 72 hours or less, from the viewpoint of obtaining the strength necessary for demolding and improving the manufacturing cycle.

[0093] <Method for improving the strength of a hydraulic composition> In an exemplary embodiment, the present invention provides a method for improving the strength of a hydraulic composition, comprising applying an aqueous dispersion composition containing (A) a poorly water-soluble polymer having a carboxyl group or a salt thereof, (B) an ester compound with a molecular weight of 120 to 500, and (C) water to the surface of the hydraulic composition and curing the hydraulic composition.

[0094] Specific examples and preferred embodiments of components (A), (B), and (C) used in the method for improving the strength of the hydraulic composition of the present invention are the same as those described in the Strength Enhancer for Hydraulic Compositions of the present invention, and specific examples and preferred embodiments of hydraulic powder and aggregate are the same as those described in the Hydraulic Composition of the present invention. In the method for improving the strength of the hydraulic composition of the present invention, the hydraulic powder is mixed so that the W / P ratio is within the range described in the Hydraulic Composition of the present invention. The amount of aggregate used (mixing amount) and the mass percentage of the hydraulic powder content to the aggregate content are also within the range described in the Hydraulic Composition of the present invention. In the method for improving the strength of the hydraulic composition of the present invention, the content of each component and their mass ratios described in the Hydraulic Composition of the present invention can be appropriately applied by replacing the content of each component with the mixing amount. The matters described in the Strength Enhancer for Hydraulic Compositions and its manufacturing method, as well as the hydraulic composition and its manufacturing method, can be applied to the method for improving the strength of the hydraulic composition of the present invention. In the method for improving the strength of the hydraulic composition of the present invention, the preparation of the hydraulic composition may be the same as in the embodiment described in the method for producing the hydraulic composition of the present invention.

[0095] The following are examples of embodiments of the present invention. The matters described in the descriptions of the strength enhancer for hydraulic compositions, hydraulic compositions, methods for producing hydraulic compositions, and methods for improving the strength of hydraulic compositions of the present invention can be appropriately applied to these embodiments.

[0096] <1> A strength enhancer for hydraulic compositions, comprising (A) a poorly water-soluble polymer having a carboxyl group or a salt thereof, (B) an ester compound with a molecular weight of 120 to 500, and (C) an aqueous dispersion containing water.

[0097] <2> The strength enhancer for hydraulic compositions according to <1>, wherein the mass ratio of the content of component (B) to the content of component (A) [(B) / (A)] is 0.05 or more and 0.3 or less.

[0098] <3> The strength enhancer for hydraulic compositions according to <1> or <2> above, wherein the mass ratio of the content of component (C) to the content of component (A) [(C) / (A)] is 0.4 or more and 3 or less.

[0099] <4> The strength improver for hydraulic compositions according to any one of <1> to <3> above, wherein component (A) is one or more selected from poly(meth)acrylic acid, poly(meth)acrylic acid ester, styrene-acrylic copolymer, polyvinyl acetate, ethylene-vinyl acetate copolymer, polyamide, polyester, styrene-butadiene rubber, isoprene rubber, chloroprene rubber, and natural rubber.

[0100] <5> A strength enhancer for hydraulic compositions according to any one of <1> to <4> above, wherein polyester accounts for 30% by mass or more and 100% by mass or less of the component (A).

[0101] <6> The strength enhancer for hydraulic compositions according to any one of <1> to <5> above, wherein the component (A) is a polyester containing alcohol-derived structural units and carboxylic acid-derived structural units, and the content of aromatic dicarboxylic acid-derived structural units in the total amount of carboxylic acid-derived structural units contained in the polyester is 60 mol% or more.

[0102] <7> The strength enhancer for hydraulic compositions according to any one of <4> to <6> above, wherein the polyester contains constituent units derived from polyethylene terephthalate.

[0103] <8> The strength enhancer for hydraulic compositions according to any one of <4> to <7> above, wherein the polyester is a polycondensate of a compound containing an alkylene oxide adduct of bisphenol A.

[0104] <9> A strength enhancer for hydraulic compositions according to any one of <1> to <8> above, wherein the weight-average molecular weight (Mw) of component (A) is 1,000 or more and 200,000 or less.

[0105] <10> The component (A) is a strength enhancer for hydraulic compositions according to any one of <1> to <9> above, wherein the solubility in water at 20°C is 0.1 g / L or less.

[0106] <11> The (B) component is a strength enhancer for hydraulic compositions according to any one of <1> to <10> above, having two to five ester groups.

[0107] <12> The strength enhancer for hydraulic compositions according to any of <1> to <11> above, wherein component (B) is one or more selected from aliphatic esters and aromatic esters.

[0108] <13> A strength enhancer for hydraulic compositions according to any one of <1> to <12> above, wherein the content of component (A) is 19% by mass or more and 65% by mass or less.

[0109] <14> A strength enhancer for hydraulic compositions according to any one of <1> to <13> above, wherein the content of component (B) is 1% by mass or more and 20% by mass or less.

[0110] <15> A strength enhancer for hydraulic compositions according to any one of <1> to <14> above, wherein the content of component (C) is 19% by mass or more and 65% by mass or less.

[0111] <16> A hydraulic composition in which a water dispersion composition comprising (A) a poorly water-soluble polymer having a carboxyl group or a salt thereof, (B) an ester compound with a molecular weight of 120 to 500, and (C) water is applied to the surface of a hydraulic composition structure.

[0112] <17> The hydraulic composition according to <16> above, wherein the hydraulic composition structure is a structure obtained by hardening hydraulic powder containing aggregate.

[0113] <18> A method for producing a hydraulic composition, comprising mixing hydraulic powder with water to obtain a hydraulic composition, and forming a layer on the surface of the hydraulic composition containing (A) a poorly water-soluble polymer having a carboxyl group or a salt thereof, and (B) an ester compound having a molecular weight of 120 or more and 500 or less.

[0114] <19> The method for producing the hydraulic composition according to <18> above, wherein the method for forming the layer is coating or spraying.

[0115] <20> A method for improving the strength of a hydraulic composition, comprising applying an aqueous dispersion composition containing (A) a poorly water-soluble polymer having a carboxyl group or a salt thereof, (B) an ester compound with a molecular weight of 120 to 500, and (C) water to the surface of the hydraulic composition and curing the hydraulic composition.

[0116] <21> The amount of the aqueous dispersion composition applied to the surface of the hydraulic composition is 100 g / m ２ More than 250g / m ２ The method for improving the strength of the hydraulic composition described in <20> above is as follows:

[0117] <22> A method for improving the strength of a hydraulic composition according to <20> or <21>, wherein the curing is performed at a temperature of 40°C or higher and 80°C or lower.

[0118] Examples The components used in the preparation of the strength improvers for hydraulic compositions in the Examples and Comparative Examples are shown below. <Component (A)> ・(A-1): Poorly water-soluble polymer produced in Production Example 1 below, solubility (1 L of water at 20°C) 0.009 g / L ・(A-2): Poorly water-soluble polymer produced in Production Example 2 below, solubility (1 L of water at 20°C) 0.008 g / L ・(A-3): A mixture of (A-1) and acrylic polymer (Sika Antisol-250W, manufactured by Sika), (A-1): Acrylic polymer = 4.18:1 (mass ratio), polyester mass in the total (A) component = 80.7% by mass, solubility (1 L of water at 20°C) 0.023 g / L ・(A-4): (A-1) and acrylic polymer (Sika A mixture of Antisol-250W (manufactured by Sika), (A-1):acrylic polymer = 0.46:1 (mass ratio), polyester mass in the total (A) component = 31.7% by mass, solubility (1 L of water at 20°C) 0.012 g / L. The solubility of components (A-1) to (A-4) at 20°C was measured according to the following procedure.

[0119] [Method for measuring the solubility of component (A) in water at 20°C] 1 g of component (A) was thoroughly mixed with 50 g of distilled water at 20°C and allowed to stand for 1 hour. Undissolved components were precipitated by centrifugation (3,000 rpm, 5 minutes), and 1 mL of the supernatant was collected. This supernatant was filtered using a membrane filter (DISMIC 25HP045AN, manufactured by Advantec Corporation), and the resulting filtrate was diluted 20-fold with distilled water. The TOC (mg / L) of the diluted filtrate was measured using a combustion catalyst oxidation method with an online total organic carbon analyzer (TOC-V, manufactured by Shimadzu Corporation) to calculate the solubility of component (A) in water. For the solubility of (A-3) and (A-4), the solid obtained by drying Antisol 250W at 105°C for 2 hours was mixed with distilled water together with (A-1) according to the ratio shown for (A-3) or (A-4). Subsequently, the solubility was measured by performing the same procedure as described above.

[0120] <(B) Components> ・(B-1): Diallyl phthalate, molecular weight 246.3, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・(B-2): Bis(2-ethylhexyl) phthalate, molecular weight 390.6, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・(B-3): Tributyl o-acetylcitrate, molecular weight 402.5, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. <(B') Components> ・(B'-1): Dimethyl oxalate, molecular weight 118.1, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・(B'-2): Sorbitan trioleate, molecular weight 957.5, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0121] <Method for producing component (A)> Component (A-1) and component (A-2) listed in Table 1 were produced according to the manufacturing methods described in Manufacturing Example 1 and Manufacturing Example 2 below. The monomer composition and physical properties of component (A-1) and component (A-2) are shown in Table 1.

[0122]

[0123] (1) Production Example 1 (Production of Polyester (A-1)) The alcohol, terephthalic acid, and polyethylene terephthalate (UNIFI, 100% Post Consumer rPETResin / 500 Mesh Filtered / Round / Bright / 0.68IV / Crystallized) shown in Table 1 were placed in a 5-liter four-necked flask equipped with a thermometer, thermocouple, stainless steel stirring rod, fall-flow condenser, and nitrogen inlet tube, and heated to 120°C. Then, the esterification catalyst shown in Table 1 was added at 120°C, and the temperature was rapidly increased to 235°C. After reaching 235°C, the temperature was maintained for 4 hours, and the reaction system was thoroughly stirred. After a 4-hour reaction, the temperature was lowered to 185°C, then dodecenyl succinic anhydride was added. The temperature was then raised to 220°C at 10°C / 30 minutes, and the mixture was reacted at 220°C and 100 torr for approximately 2 hours until the softening point shown in Table 1 was reached to produce polyester (A-1).

[0124] (2) Production Example 2 (Production of Polyester (A-2)) The components shown in Table 1 were placed in a 5-liter four-necked flask equipped with a thermometer, thermocouple, stainless steel stirring rod, fall-flow condenser, and nitrogen inlet tube. The esterification catalyst shown in Table 1 was added under a nitrogen atmosphere, and the temperature was raised to 215°C over 3 hours. After reaching 215°C, the temperature was maintained for 5 hours. Subsequently, the pressure was reduced to 8.0 kPa for 1 hour, and the reaction was carried out until the softening point shown in Table 1 was reached to produce polyester (A-2).

[0125] (3) Method for measuring the softening point and glass transition point of polyester (i) Using a softening point flow tester (Shimadzu Corporation, "CFT-500D"), 1 g of the sample was heated at a heating rate of 6°C / min while a load of 1.96 MPa was applied by a plunger and extruded from a nozzle with a diameter of 1 mm and a length of 1 mm. The amount of plunger descent of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was defined as the softening point. The results are shown in Table 1. (ii) Using a glass transition point differential scanning calorimeter (TA Instruments Japan Co., Ltd., "Q-100"), 0.01 to 0.02 g of the sample was weighed into an aluminum pan, heated to 200°C, and then cooled to 0°C at a cooling rate of 10°C / min. Next, the heat quantity was measured while heating to 150°C at a heating rate of 10°C / min. The glass transition temperature was defined as the temperature at the intersection of the baseline extension below the maximum endothermic peak temperature and the tangent line representing the maximum slope from the peak's rising portion to its peak. The results are shown in Table 1.

[0126] (4) Method for measuring the acid value and hydroxyl value of polyester The acid value and hydroxyl value of polyester were measured according to the method of JIS K 0070:1992. However, the measurement solvent was changed from a mixed solvent of ethanol and ether specified in JIS K 0070:1992 to a mixed solvent of acetone and toluene (acetone:toluene = 1:1 (volume ratio)). The results are shown in Table 1.

[0127] (5) Method for measuring the weight-average molecular weight of polyesters The weight-average molecular weight of polyesters was determined by measuring the molecular weight distribution using the gel permeation chromatography (GPC) method shown below. The weight-average molecular weight of polyester A-1 was 13,023, and the weight-average molecular weight of polyester A-2 was 41,567. (i) Preparation of sample solution The sample was dissolved in tetrahydrofuran at 25°C to a concentration of 0.5 g / 100 mL. This solution was then filtered using a fluororesin filter with a pore size of 0.2 μm (Toyo Roshi Co., Ltd., "DISMIC-25JP") to remove undissolved material and obtain the sample solution. (ii) Measurement of weight-average molecular weight Using the following measuring apparatus and analytical column, tetrahydrofuran was flowed as the eluent at a flow rate of 1 mL / min, and the column was stabilized in a constant temperature bath at 40°C. 100 μL of the sample solution was injected therein and the measurement was performed. The weight-average molecular weight of the sample was calculated based on a calibration curve prepared in advance. The calibration curve at this time included several types of monodisperse polystyrene "A-500" (5.0 x 10 ２ ), “A-1000” (1.01×10 ３ ), “A-2500” (2.63×10 ３ ), “A-5000” (5.97×10 ３ ), “F-1” (1.02×10 ３ ), “F-2” (1.81×10 ４ ), “F-4” (3.97×10 ４ ), “F-10” (9.64×10 ４ ), “F-20” (1.90×10 ５ ), “F-40” (4.27×10 ５ ), “F-80” (7.06×10 ５ ), “F-128” (1.09×10 ６ The following samples were prepared using the following as standard samples (manufactured by Tosoh Corporation): Measurement device: "HLC-8220CPC" (manufactured by Tosoh Corporation) Analytical column: "GMHXL" + "G3000HXL" (manufactured by Tosoh Corporation)

[0128] (6) Method for measuring the solid content of polyester aqueous dispersions 2.0 g of polyester aqueous dispersion was weighed onto an aluminum dish and left to stand in a constant temperature drying oven at 105°C for 2 hours to evaporate the water and dry it. The amount of solids in the aqueous dispersion was calculated from the difference in weight before and after drying.

[0129] <Method for producing strength improvers for hydraulic compositions> Strength improvers for hydraulic compositions (M-1) to (M-9), (m-2) to (m-5) were prepared according to the following production examples of strength improvers for hydraulic compositions (M-1) to (M-9), (m-2) to (m-5), respectively, containing components (A), (B), and (C) as shown in Table 2.

[0130] (1) Example of production of strength improver (M-1) for hydraulic composition in Example 1 A 5-liter three-necked flask equipped with a reflux tubing, stirrer, and thermocouple was placed in it and 400 g of polyester (A-1). The mixture was heated to 60°C while stirring at 200 rpm until polyester (A-1) was completely dissolved in the methyl ethyl ketone. The resulting polyester (A-1) solution was cooled to 50°C, and 80 g of (B) diallyl phthalate and 9.1 g of dimethylaminoethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added. Then, 800 g of (C) water at 50°C was added while stirring. Subsequently, a distillation tube and trap were placed in a 5-liter container to allow for the distillation of methyl ethyl ketone, and the pressure was reduced to 80-150 torr using a vacuum pump at 40°C until the concentration of methyl ethyl ketone was 100 ppm or less. Finally, the mixture was filtered through a 150-mesh wire mesh to obtain an aqueous dispersion of polyester (A-1), which is the strength enhancer for hydraulic compositions (M-1). The solid content of the obtained aqueous dispersion was measured using the method described in "(6) Method for measuring the solid content of polyester aqueous dispersion" above. The solid content of the strength enhancer for hydraulic compositions (M-1) was 45.2% by mass. The water content contained in the strength enhancer for hydraulic compositions (M-1) was calculated from the solid content of the strength enhancer for hydraulic compositions (M-1). The results are shown in Table 2. The water content contained in the strength enhancers for hydraulic compositions of other examples and comparative examples was calculated using the same method.

[0131] (2) Example of production of strength improver for hydraulic composition (M-2) in Example 2 (B) An aqueous dispersion of polyester (A-1), which is the strength improver for hydraulic composition (M-2), was produced in the same manner as in the production example of the strength improver for hydraulic composition (M-1) in (1), except that the amount of diallyl phthalate added was 48 g. The solid content of the obtained strength improver for hydraulic composition (M-2) was 44.9% by mass.

[0132] (3) Example of production of strength improver for hydraulic composition (M-3) in Example 3 (B) An aqueous dispersion of polyester (A-1), which is the strength improver for hydraulic composition (M-3), was produced in the same manner as in the example of production of the strength improver for hydraulic composition (M-1) in (1), except that diallyl phthalate was changed to bis(2-ethylhexyl) phthalate. The solid content of the obtained strength improver for hydraulic composition (M-3) was 43.7% by mass.

[0133] (4) Example of production of strength improver for hydraulic composition (M-4) in Example 4 (B) An aqueous dispersion (M-4) of polyester (A-1), which is the strength improver for hydraulic composition (M-4), was produced in the same manner as in the example of production of the strength improver for hydraulic composition (M-1) in (1), except that diallyl phthalate was changed to tributyl acetylcitrate. The solid content of the obtained strength improver for hydraulic composition (M-4) was 44.5% by mass.

[0134] (5) Production example of strength enhancer for hydraulic composition (M-5) of Example 5 A water dispersion of polyester (A-2), which is the strength enhancer for hydraulic composition (M-5), was produced in the same manner as the production example of the strength enhancer for hydraulic composition (M-1) in (1), except that polyester (A-1) was changed to polyester (A-2). The solid content of the obtained strength enhancer for hydraulic composition (M-5) was 45.0% by mass.

[0135] (6) Example of preparation of strength improver for hydraulic composition (M-6) in Example 6 75 g of strength improver for hydraulic composition (M-1) (polyester content 37.65% by mass) and 25 g of commercially available acrylic concrete curing agent (water dispersion (acrylic polymer content 27% by mass), Sika Antisol-250W, manufactured by Sika) were mixed at room temperature and 200 rpm for 10 minutes to prepare strength improver for hydraulic composition (M-6) in Example 6.

[0136] (7) Example of preparation of strength improver for hydraulic composition (M-7) in Example 7 25 g of strength improver for hydraulic composition (M-1) (polyester content 37.65% by mass) and 75 g of commercially available acrylic concrete curing agent (water dispersion (acrylic polymer content 27% by mass), Sika Antisol-250W, manufactured by Sika) were mixed at room temperature and 200 rpm for 10 minutes to prepare the strength improver for hydraulic composition (M-7) in Example 7.

[0137] (8) Example of production of strength improver for hydraulic composition (M-8) in Example 8 (B) An aqueous dispersion of polyester (A-1), which is the strength improver for hydraulic composition (M-8), was produced in the same manner as in the example of production of strength improver for hydraulic composition (M-1) in (1), except that the amount of diallyl phthalate added was 200 g. The solid content of the obtained strength improver for hydraulic composition (M-8) was 45.4% by mass.

[0138] (9) Example of production of strength improver for hydraulic composition (M-9) in Example 9 (B) An aqueous dispersion of polyester (A-1), which is the strength improver for hydraulic composition (M-9), was produced in the same manner as in the example of production of the strength improver for hydraulic composition (M-1) in (1), except that the amount of diallyl phthalate added was 12 g. The solid content of the obtained strength improver for hydraulic composition (M-9) was 45.6% by mass.

[0139] (10) Example of production of strength improver for hydraulic composition (m-2) in Comparative Example 2 (B) An aqueous dispersion of polyester (A-1), which is the strength improver for hydraulic composition (m-2), was produced in the same manner as the production example of the strength improver for hydraulic composition (M-1) in (1), except that diallyl phthalate was not added. The solid content of the obtained strength improver for hydraulic composition (m-2) was 40.1% by mass.

[0140] (11) Examples of production of strength improvers for hydraulic compositions (m-4, m-5) in Comparative Examples 4 and 5 (B) An aqueous dispersion of polyester (A-1), which is the strength improver for hydraulic compositions (m-4) or (m-5), was produced in the same manner as in the example of production of the strength improver for hydraulic compositions (M-1) in (1), except that diallyl phthalate was replaced with dimethyl oxalate or sorbitan trioleate, respectively. The solid content of the obtained strength improvers for hydraulic compositions (m-4) or (m-5) was 43.8% by mass and 44.5% by mass, respectively.

[0141] <Method for Manufacturing Hydraulic Composition> The mass ratio of water to cement (W / C) is 42% by mass (42 parts by mass of water per 100 parts by mass of cement). The fine aggregate is 300 parts by mass per 100 parts by mass of cement. The AE water-reducing agent is 1 part by mass per 100 parts by mass of cement. The components used are as follows: ・W: Mixing water (tap water (Wakayama City tap water)) ・C: Ordinary Portland cement (a mixture of cement manufactured by Taiheiyo Cement Corporation and Sumitomo Osaka Cement Corporation in a mass ratio of 50 / 50, specific gravity 3.16 g / cm³) ３ ) ・S: Fine aggregate (mountain sand, from Joyo, specific gravity 2.50 g / cm³) ３ ) ・AE water-reducing agent (Mighty 1000S, manufactured by Kao Corporation)

[0142] <Method for measuring compressive strength> The above mortar was poured into a triple-type formwork conforming to JIS R 5201, and left to stand for approximately 1 to 2 hours until the water on the surface of the mortar disappeared. After confirming the disappearance of the water, 200 g / m of the strength improver for hydraulic compositions shown in Table 2 was added. ２The specified amount was applied to the exposed mortar surface using a brush. The specimens were left to stand for one day under conditions of 20°C and 60% humidity, after which the mortar specimens were removed from the formwork. To prevent moisture loss from surfaces other than those coated with the hydraulic composition strength enhancer, the surfaces other than those coated with the hydraulic composition strength enhancer were immediately covered with aluminum tape after removal. After the aluminum tape treatment, the specimens were left to stand in a constant temperature and humidity chamber at 20°C and 60% humidity, and compressive strength tests were conducted after 7 and 28 days. For the compression test, a bending strength test was first performed on the mortar bar in accordance with JIS R 5201, and then, as described in JIS R 5201, a compressive strength test was performed on both folded sections of the three specimens after the bending strength test. The strength values ​​were the average of six measurements. The results are shown in Table 2. In Comparative Example 1, after confirming the disappearance of floating water, no coating was applied, and the mortar specimen was left to stand for one day at 20°C and 60% humidity before demolding. The subsequent operations were carried out in the same manner as described above. In Comparative Example 3, (B) diallyl phthalate was applied at a rate of 200 g / m². ２ The procedure was the same as described above, except that the amount of the coating was applied to the exposed mortar surface using a brush.

[0143]

Claims

1. A strength enhancer for hydraulic compositions, comprising (A) a poorly water-soluble polymer having a carboxyl group or a salt thereof, (B) an ester compound with a molecular weight of 120 to 500, and (C) water, in an aqueous dispersion.

2. The strength enhancer for hydraulic compositions according to claim 1, wherein the mass ratio of the content of component (B) to the content of component (A) [(B) / (A)] is 0.05 or more and 0.3 or less.

3. The strength enhancer for hydraulic compositions according to claim 1 or 2, wherein component (B) has two to five ester groups.

4. The strength enhancer for hydraulic compositions according to any one of claims 1 to 3, wherein component (A) is one or more selected from poly(meth)acrylic acid, poly(meth)acrylic acid ester, styrene-acrylic copolymer, polyvinyl acetate, ethylene-vinyl acetate copolymer, polyamide, polyester, styrene-butadiene rubber, isoprene rubber, chloroprene rubber, and natural rubber.

5. A strength enhancer for hydraulic compositions according to any one of claims 1 to 4, wherein polyester accounts for 30% by mass or more and 100% by mass or less of the component (A).

6. The strength enhancer for hydraulic compositions according to any one of claims 1 to 5, wherein the component (A) is a polyester containing alcohol-derived structural units and carboxylic acid-derived structural units, and the content of aromatic dicarboxylic acid-derived structural units in the total amount of carboxylic acid-derived structural units contained in the polyester is 60 mol% or more.

7. The strength enhancer for hydraulic compositions according to any one of claims 1 to 6, wherein the mass ratio of the content of component (C) to the content of component (A) [(C) / (A)] is 0.4 or more and 3 or less.

8. Strength enhancer for hydraulic compositions according to any one of claims 1 to 7, wherein the content of component (A) is 19% by mass or more and 65% by mass or less.

9. Strength enhancer for hydraulic compositions according to any one of claims 1 to 8, wherein the content of component (B) is 1% by mass or more and 20% by mass or less.

10. Strength enhancer for hydraulic compositions according to any one of claims 1 to 9, wherein the content of component (C) is 19% by mass or more and 65% by mass or less.

11. The strength enhancer for hydraulic compositions according to any one of claims 1 to 10, wherein the weight-average molecular weight (Mw) of component (A) is 1,000 or more and 200,000 or less.

12. The strength enhancer for hydraulic compositions according to any one of claims 1 to 11, wherein component (A) has a solubility of 0.1 g / L or less in water at 20°C.

13. A hydraulic composition in which a water dispersion composition containing (A) a poorly water-soluble polymer having a carboxyl group or a salt thereof, (B) an ester compound with a molecular weight of 120 to 500, and (C) water is applied to the surface of a hydraulic composition structure.

14. A method for producing a hydraulic composition, comprising mixing hydraulic powder with water to obtain a hydraulic composition, and forming a layer on the surface of the hydraulic composition containing (A) a poorly water-soluble polymer having a carboxyl group or a salt thereof, and (B) an ester compound having a molecular weight of 120 to 500.

15. A method for improving the strength of a hydraulic composition, comprising applying an aqueous dispersion composition containing (A) a poorly water-soluble polymer having a carboxyl group or a salt thereof, (B) an ester compound with a molecular weight of 120 to 500, and (C) water to the surface of the hydraulic composition and curing the hydraulic composition.

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