Aluminosilicate-containing composition

Abstract

The purpose of the present invention is to provide a composition which has excellent early strength development properties in comparison to conventional compositions. The present invention provides an aluminosilicate-containing composition which contains aluminosilicate and a water-soluble polymer, wherein the aluminosilicate-containing composition additionally contains a metal compound and / or an amine that has a molecular weight of 1,000 or less.

Description

[Technical Field]

[0001] The present invention relates to an aluminosilicate-containing composition, and more particularly to an aluminosilicate-containing composition useful for accelerating the setting of hydraulic material compositions. [Background technology]

[0002] Since the manufacturing process of ordinary Portland cement emits a large amount of CO2, concrete compositions have been proposed in which cement is replaced with supplementary cementitious materials (SCMs) such as fly ash and slag in order to reduce CO2 emissions. Compared to ordinary Portland cement (OPC), this type of SCM concrete has a longer hardening time and has issues with early strength development.

[0003] Regarding technology for improving the early strength of concrete, Patent Document 1 discloses an aluminosilicate-containing composition containing an aluminosilicate and a water-soluble polymer, wherein the aluminosilicate has an average particle diameter of 10 to 2500 nm as measured by a predetermined measurement method. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2022-011743 Summary of the Invention [Problem to be solved by the invention]

[0005] As mentioned above, although technologies have been developed to improve the early strength of concrete, the existing compositions do not have sufficient early strength development, and there has been a demand for the development of compositions with better early strength development. There is also room for the development of compositions that can fully demonstrate early strength development compared to SCM concrete.

[0006] The present invention has been made in view of the above-mentioned circumstances, and has an object to provide a composition that is superior in early strength development to conventional compositions. [Means for solving the problem]

[0007] The present inventors have conducted extensive research into techniques for improving the early strength development of hydraulic material compositions and have found that adding an amine and / or metal compound with a molecular weight of 1,000 or less to a composition containing an aluminosilicate and a water-soluble polymer results in the hydraulic material composition having excellent early strength development. The present inventors have also found that using a composition containing an aluminosilicate and a water-soluble polymer in a hydraulic material composition containing at least one substance selected from the group consisting of substances with latent hydraulic and / or pozzolanic activity and fillers results in a hydraulic material composition having excellent early strength development compared to ordinary cement compositions. The present inventors have thus conceived a method for successfully solving the above problems and have arrived at the present invention.

[0008] The present invention includes the following aluminosilicate-containing compositions, etc. [1] An aluminosilicate-containing composition comprising an aluminosilicate and a water-soluble polymer, the aluminosilicate-containing composition further comprising an amine and / or a metal compound having a molecular weight of 1,000 or less. [2] An aluminosilicate-containing composition comprising an aluminosilicate and a water-soluble polymer, the aluminosilicate-containing composition being used in a hydraulic material composition comprising at least one substance selected from the group consisting of a substance having latent hydraulic activity and / or pozzolanic activity and a filler. [3] The aluminosilicate-containing composition according to [1] or [2] above, wherein the content of the water-soluble polymer is 5 to 100 mass % relative to 100 mass % of the aluminosilicate. [4] The aluminosilicate-containing composition according to any one of [1] to [3] above, wherein the content of the aluminosilicate is 0.01 to 50 mass% relative to 100 mass% of the aluminosilicate-containing composition. [5] The aluminosilicate-containing composition according to any one of [1] to [4] above, wherein the amine is at least one selected from the group consisting of primary amines, secondary amines, and tertiary amines. [6] The aluminosilicate-containing composition according to any one of [1] to [5] above, wherein the total content of the amine and the metal compound is 0.01 to 500 mass% relative to 100 mass% of the aluminosilicate. [7] The aluminosilicate-containing composition according to any one of [1] to [6] above, wherein the substance having latent hydraulic and / or pozzolanic activity is at least one selected from the group consisting of slag, fly ash, clay, metakaolin, silica fume, silica powder, cinder ash, clinker ash, husk ash, bentonite, and calcite clay. [8] The aluminosilicate-containing composition according to any one of [1] to [7] above, wherein the filler is at least one selected from the group consisting of calcium carbonate, ecological calcium carbonate, concrete fines, concrete fines with immobilized carbon dioxide, waste concrete, and gypsum. [9] The aluminosilicate-containing composition according to any one of [1] to [8] above, wherein the aluminosilicate-containing composition has an average particle size of 10 to 2500 nm as measured by the following measurement method. <Method for measuring average particle size> Using a particle size measuring device, the scattering intensity of an aqueous dispersion of the aluminosilicate-containing composition having a solid content of 0.1% by mass is measured by dynamic light scattering, and the average particle size is calculated.

[10] The aluminosilicate-containing composition according to any one of [1] to [9] above, wherein the water-soluble polymer has at least one functional group selected from a carboxyl group, a phosphoric acid group, a sulfonic acid group, and salts thereof, a phosphoric acid ester group, and a hydroxyl group.

[11] The aluminosilicate-containing composition according to any one of the above [1] to

[10] , wherein the water-soluble polymer further has a (poly)oxyalkylene group.

[12] A hydraulic material composition comprising an aluminosilicate, a water-soluble polymer, and at least one selected from the group consisting of a substance having latent hydraulic and / or pozzolanic activity and a filler.

[13] A method for quickly improving the strength of a hydraulically set product, the method comprising the steps of adding the aluminosilicate-containing composition according to any one of [1] to

[11] above to a hydraulic material, and curing the composition obtained in the adding step. [Effects of the Invention]

[0009] The aluminosilicate-containing composition of the present invention has the above-mentioned constitution and is excellent in early strength development, and therefore can be suitably used as a hardening accelerator for hydraulic material compositions. DETAILED DESCRIPTION OF THE INVENTION

[0010] Preferred embodiments of the present invention will be specifically described below, but the present invention is not limited to the following description and can be appropriately modified and applied within the scope of the present invention. A combination of two or more of the individual preferred embodiments of the present invention described below also falls within the scope of the present invention. Furthermore, when the term "the present invention" is used simply in this specification, it refers to matters common to the first and second inventions.

[0011] <Aluminosilicate-containing composition> The aluminosilicate-containing composition of the first aspect of the present invention is characterized by comprising an aluminosilicate and a water-soluble polymer, and further comprising an amine and / or a metal compound having a molecular weight of 1,000 or less. When the aluminosilicate-containing composition contains a metal compound, it is thought that the metal compound will involve cationic metals in the cement hydration reaction, promoting CSH crystal growth from the silicate layer or deforming the shape of the crystals, thereby increasing the heat of hydration and enabling the composition to exhibit excellent early strength development. When the aluminosilicate-containing composition contains an amine having a molecular weight of 1,000 or less, it is believed that the hydration heat generated by hydration increases and excellent early strength development can be achieved by promoting the reaction of the aluminate layer and ferrite layer during the cement hydration reaction, while promoting the growth of CSH crystals from the silicate layer or by deforming the shape of the crystals.

[0012] In the aluminosilicate-containing composition of the first aspect of the present invention, the content of the amine and / or metal compound having a molecular weight of 1,000 or less is not particularly limited, but the total content of the amine and metal compound is preferably 0.01 to 500 mass% relative to 100 mass% of the aluminosilicate, more preferably 1 to 100 mass%, even more preferably 5 to 70 mass%, and particularly preferably 10 to 50 mass%.

[0013] When the aluminosilicate-containing composition of the first aspect of the present invention contains an amine having a molecular weight of 1,000 or less, the content thereof is preferably 0.01 to 500 mass% relative to 100 mass% of the aluminosilicate, more preferably 1 to 100 mass%, even more preferably 5 to 70 mass%, and particularly preferably 10 to 50 mass%.

[0014] When the aluminosilicate-containing composition of the first aspect of the present invention contains a metal compound, the content thereof is preferably 0.001 to 50 mol %, more preferably 0.01 to 50 mol %, still more preferably 0.1 to 50 mol %, and particularly preferably 1 to 50 mol %, relative to 100 mol % in total of the aluminum element, silicon element, and metal compound in the aluminosilicate.

[0015] The amine is not particularly limited as long as it has a molecular weight of 1000 or less, and may be a monovalent amine having one amino group or a polyvalent amine having two or more amino groups, but is preferably a monovalent amine or a divalent amine. The amine may be a primary amine, a secondary amine, or a tertiary amine, but is preferably a tertiary amine. The amine may have a functional group such as a hydroxyl group or a carboxyl group, with a hydroxyl group being preferred as the functional group.

[0016] The amine is represented by the following formula (1):

[0017] [ka] (In the formula, R 1 , R 2 , R 3 are the same or different and represent a hydrocarbon group having 1 to 30 carbon atoms which may have a hydrogen atom or a functional group. 1 , R 2 , R 3 At least one of the groups is a hydrocarbon group having 1 to 30 carbon atoms which may have a functional group. The functional group that the hydrocarbon group may have includes the above-mentioned functional groups and an amino group. When the hydrocarbon group has an amino group, the amine becomes a polyvalent amine.

[0018] R in the above formula (1) 1 , R 2 , R 3 The hydrocarbon group in is not particularly limited, but examples thereof include an aliphatic alkyl group having 1 to 30 carbon atoms, an alicyclic alkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, and an aromatic hydrocarbon group having 6 to 30 carbon atoms.

[0019] Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group (amyl group), an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, an n-icosyl group, an i-propyl group, a sec-butyl group, an i-butyl group, a t-butyl group, a 1-methylbutyl group, a 1-ethylpropyl group, a 2-methylbutyl group, an i-amyl group, a neopentyl group, a 1,2-dimethylpropyl group, a 1,1-dimethylpropyl group, a t-amyl group, a 1,3-dimethylbutyl group, and a 3,3-dimethylbutyl group. aliphatic alkyl groups such as 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, t-octyl group, branched nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, stearyl group, and icosyl group; and alicyclic alkyl groups such as cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclohexylpropyl group, cyclododecyl group, norbornyl group (C7), adamantyl group (C10), and cyclopentylethyl group. The alkyl group having 1 to 30 carbon atoms preferably has 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, even more preferably 1 to 12 carbon atoms, still more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 4 carbon atoms.

[0020] Examples of the alkenyl group include a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a dodecenyl group, an octadecenyl group, and an icosenyl group. Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, a nonynyl group, a decynyl group, a dodecynyl group, an octadecynyl group, and an icosynyl group. The alkenyl group and alkynyl group having 2 to 30 carbon atoms preferably have 2 to 22 carbon atoms, more preferably 2 to 18 carbon atoms, even more preferably 2 to 12 carbon atoms, still more preferably 2 to 8 carbon atoms, and particularly preferably 2 to 4 carbon atoms.

[0021] Examples of aromatic hydrocarbon groups having 6 to 30 carbon atoms include aryl groups such as phenyl, naphthyl, methylphenyl, 1-methoxy-4-methylphenyl, ethylphenyl, propylphenyl, butylphenyl, butylmethylphenyl, dimethylphenyl, diethylphenyl, dibutylphenyl, and biphenyl; and aralkyl groups such as benzyl, 1-phenylethyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, styryl (Ph-CH=C-), cinnamyl (Ph-CH=CHCH-), 1-benzocyclobutenyl, and 1,2,3,4-tetrahydronaphthyl.

[0022] Specific examples of primary amines include monoalkylamines such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine (laurylamine), tridodecylamine, tetradecylamine (myristylamine), pentadecylamine, cetylamine, stearylamine, oleylamine, and cocoalkylamine; and compounds having a functional group such as a hydroxyl group or an amino group in the alkyl group of these monoalkylamines.

[0023] Specific examples of secondary amines include dialkylamines such as dimethylamine, ethylmethylamine, diethylamine, dipropylamine, diisopropylamine, and dibutylamine, as well as compounds having a functional group such as a hydroxyl group or an amino group on the alkyl group of these amines.

[0024] Specific examples of tertiary amines include trialkylamines such as trimethylamine, triethylamine, tripropylamine, tributylamine, and triamylamine; dialkylarylamines such as dimethylaniline and diethylaniline; triarylamines such as triphenylamine; triaralkylamines such as tribenzylamine; and compounds having functional groups such as hydroxyl groups and amino groups on the alkyl groups and / or aromatic groups of these compounds.

[0025] In one aspect, an embodiment in which the amine has a hydroxyl group is one of the preferred embodiments of the present invention. Specific examples of amines having a hydroxyl group include mono-, di-, and tri-alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, dimethylaminoethanol, ethyldiethanolamine, dimethylaminopropanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, and trishydroxymethylaminomethane. Among these, triisopropanolamine, triethanolamine, diisopropanolamine, ethyldiethanolamine, and dimethylaminoethanol are preferred, and triisopropanolamine is more preferred.

[0026] In one aspect, an embodiment in which the amine is a polyamine is also one of the preferred embodiments of the present invention. Specific examples of polyvalent amines include ethylenediamine, propanediamine, butanediamine, tetramethylethylenediamine, trimethyldiethylenediamine, ethylethylenediamine, diethylethylenediamine, diethylenetriamine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyallylamine, polyethyleneimine, etc. Among these, tetramethylethylenediamine and pentamethyldiethylenetriamine are preferred, and tetramethylethylenediamine is more preferred.

[0027] The molecular weight of the amine may be 1,000 or less, preferably 70-600, more preferably 70-500, and even more preferably 70-300.

[0028] The metal compound is not particularly limited as long as it is a compound containing a metal and is a compound other than the components contained in the aluminosilicate and cement, and examples thereof include inorganic compounds, organic acid salts, and complexes (coordination compounds). The metal element contained in the metal compound is not particularly limited, and examples thereof include monovalent metals such as lithium, sodium, potassium, rubidium, cesium, silver, and copper(I); divalent metals such as magnesium, calcium, barium, iron(II), zinc, copper(II), manganese(II), chromium(II), nickel(II), and cobalt(II); trivalent metals such as iron(III), nickel(III), cobalt(III), aluminum, gallium, chromium(III), zirconium(III), manganese(III), yttrium, lanthanum, cerium(III), and gadolinium; and tetravalent metals such as nickel(IV), cobalt(IV), titanium, zirconium(IV), and manganese(IV). Among these, alkali metals such as lithium and sodium, alkaline earth metals such as magnesium and calcium, zinc, iron, etc. are preferred.

[0029] Examples of the inorganic compound include sulfates, carbonates, halides, nitrates, phosphates, silicates, hydroxides, oxides, sulfides, tellurides, and intermetallic compounds. Among these, sulfates, nitrates, and carbonates are preferred. More preferred are lithium sulfate, sodium sulfate, magnesium sulfate, zinc sulfate, iron sulfate, sodium nitrate, lithium nitrate, magnesium nitrate, zinc nitrate, iron nitrate, sodium carbonate, lithium carbonate, magnesium carbonate, zinc carbonate, and iron carbonate, and even more preferred is sodium sulfate.

[0030] The organic acid salt is not particularly limited as long as it is an organic acid salt containing a metal element, and examples thereof include carboxylates and sulfonates. Examples of the carboxylate include acetate, oxalate, etc. Preferred are acetate, more preferred are sodium acetate, lithium acetate, magnesium acetate, zinc acetate, and iron acetate, and even more preferred is sodium acetate. The complex is not particularly limited as long as it contains a metal element, and examples thereof include ammine complexes, cyano complexes, halogeno complexes, hydroxy complexes, phthalocyanine complexes, porphyrin complexes, carbonyl complexes, salen complexes, ethylenediamine complexes, β-diketone complexes, and β-diketoester complexes.

[0031] The aluminosilicate-containing composition of the second invention is characterized in that it contains an aluminosilicate and a water-soluble polymer, and is used in a hydraulic material composition containing at least one substance selected from the group consisting of a substance having latent hydraulic activity and / or pozzolanic activity and a filler. Substances with latent hydraulic properties do not harden simply by being mixed with water, but harden in the presence of stimulants such as alkalis or sulfates, and change into insoluble hydrates. A substance with pozzolanic activity is one that does not have the property of hardening itself, but easily combines with calcium hydroxide to produce an insoluble, hardening compound. Substances having latent hydraulic and / or pozzolanic activity are substances other than the above-mentioned aluminosilicates. The present inventors have found that by combining an aluminosilicate and a water-soluble polymer with at least one selected from the group consisting of a substance having latent hydraulic property and / or pozzolanic activity and a filler, the hydraulic material composition exhibits superior early strength development compared to when a conventional hardening accelerator is used.

[0032] Specific examples of substances having latent hydraulic properties include slag, oil shale, calcium fly ash, and the like. Specific examples of substances having pozzolanic activity include clay, silicic fly ash, metakaolin, silica fume, silica powder, cinder ash, clinker ash, husk ash, bentonite, calcite clay, pumice, tuff, diatomaceous earth, opal rock, morel, gaizu and other sedimentary rocks, agroforestry waste, masonry waste, decorative stone waste, paper sludge, and glass powder. Preferred materials having latent hydraulic and / or pozzolanic activity are slag, fly ash, clay, metakaolin, silica fume, silica powder, cinder ash, clinker ash, husk ash, bentonite and calcite clay.

[0033] Specific examples of the filler include calcium carbonate, eco-calcium carbonate, concrete fine powder, concrete fine powder with carbon dioxide immobilized thereon, waste concrete, marble powder, gypsum, etc. Among these, calcium carbonate, eco-calcium carbonate, concrete fine powder, concrete fine powder with carbon dioxide immobilized thereon, waste concrete, and gypsum are preferred.

[0034] A preferred embodiment of the second invention is when the aluminosilicate-containing composition is used in a hydraulic material composition containing at least one selected from the group consisting of calcium carbonate, slag, fly ash, eco-calcium carbonate, calcite clay, and gypsum. A more preferred embodiment of the hydraulic material composition is when the hydraulic material composition contains at least one selected from the group consisting of calcium carbonate, eco-calcium carbonate, calcite clay, slag, and gypsum.

[0035] The total content of the substance having latent hydraulic and / or pozzolanic activity and the filler in a hydraulic material composition using the aluminosilicate-containing composition of the second invention is not particularly limited, but is preferably 0.1 to 1000 mass% relative to 100 mass% of cement, more preferably 0.1 to 100 mass%, even more preferably 5 to 80 mass%, even more preferably 8 to 50 mass%, still more preferably 10 to 45 mass%, and particularly preferably 10 to 35 mass%.

[0036] The content of the substance having latent hydraulic and / or pozzolanic activity in the hydraulic material composition is not particularly limited, but is preferably 0 to 1000% by mass relative to 100% by mass of cement, more preferably 0.1 to 100% by mass, even more preferably 5 to 80% by mass, even more preferably 8 to 50% by mass, still more preferably 10 to 45% by mass, and particularly preferably 10 to 35% by mass.

[0037] The content of the filler in the hydraulic material composition is not particularly limited, but is preferably 0 to 1000% by mass relative to 100% by mass of cement, more preferably 0.1 to 100% by mass, even more preferably 1 to 50% by mass, still more preferably 5 to 40% by mass, still more preferably 5 to 30% by mass, and particularly preferably 10 to 20% by mass.

[0038] The aluminosilicate contained in the aluminosilicate-containing composition of the present invention is not particularly limited as long as it is a compound having a structure in which some of the silicon atoms in a silicate are replaced with aluminum atoms. For example, the aluminosilicate may be a compound represented by the following formula (2): p.m. 1 2O·qAl2O3·rSiO2·mH2O (2) (wherein p, q, r, and m represent integers. M 1 represents an alkali metal atom.

[0039] The aluminosilicate-containing composition preferably has an average particle size of 10 to 2500 nm as measured by the following measurement method. When the average particle size of the aluminosilicate is within the above range, it is believed that the rate at which calcium hydroxide contained in the hydraulic material composition changes to calcium silicate hydrate, calcium aluminate hydrate, or aluminum calcium silicate hydrate is improved, thereby accelerating the pozzolanic reaction and enabling more sufficient early strength to be exhibited.

[0040] The average particle size of the aluminosilicate-containing composition is more preferably 10 to 2000 nm, even more preferably 10 to 1000 nm, even more preferably 10 to 800 nm, still more preferably 10 to 500 nm, even more preferably 10 to 400 nm, and particularly preferably 10 to 350 nm.

[0041] The content of silicon atoms in the aluminosilicate-containing composition is preferably 1 to 1000 mol % relative to 100 mol % of aluminum atoms. The aluminosilicate-containing composition may contain an aluminum-containing compound and / or a silicon-containing compound in addition to the aluminosilicate and the water-soluble polymer, and the silicon atom content is based on the total amount of silicon atoms in the aluminosilicate and the silicon-containing compound, and the amount of aluminum atoms is based on the total amount of aluminum atoms in the aluminosilicate. The silicon atom content is more preferably 1 to 800 mol %, further preferably 10 to 250 mol %, and particularly preferably 50 to 150 mol %.

[0042] The aluminum-containing compound and silicon-containing compound are not particularly limited, but examples thereof include unreacted raw materials in the production of an aluminosilicate-containing composition. Examples of the aluminum-containing compound include aluminum sulfate, aluminum nitrate, aluminum chloride, basic aluminum acetate, aluminum formoacetate, and aluminum acetylacetonate, with aluminum sulfate being preferred. Examples of the silicon-containing compound include alkali metal salts of metasilicic acid such as sodium metasilicate, and alkali metal salts of silicic acid, with sodium metasilicate being preferred.

[0043] The content of the aluminosilicate is preferably 0.5 to 50 mass%, more preferably 1 to 50 mass%, even more preferably 5 to 40 mass%, and particularly preferably 5 to 30 mass%, relative to 100 mass% of the aluminosilicate-containing composition.

[0044] The aluminosilicate-containing composition contains water, and the aluminosilicate is dispersed in 100 g of water in an amount of preferably 0.5 to 50 g, more preferably 1 to 50 g, even more preferably 5 to 40 g, and particularly preferably 5 to 30 g.

[0045] The aluminosilicate-containing composition contains a water-soluble polymer, and its content is preferably 0.025 to 90.9% by mass relative to 100% by mass of the aluminosilicate-containing composition. If the content of the water-soluble polymer is within the above range, inhibition of cement nucleation is more sufficiently suppressed, resulting in superior early strength development. The content of the water-soluble polymer is more preferably 0.1 to 50% by mass, even more preferably 0.5 to 30% by mass, and particularly preferably 1 to 20% by mass.

[0046] The content of the water-soluble polymer is preferably 5 to 1000% by mass, more preferably 5 to 100% by mass, still more preferably 10 to 75% by mass, and particularly preferably 20 to 50% by mass, relative to 100% by mass of the total content of the aluminosilicate, aluminum-containing compound, and silicon-containing compound.

[0047] The water-soluble polymer is not particularly limited as long as it has an insoluble content of 50 g or less when 100 g is dissolved in 100 g of water, but it is preferable that the water-soluble polymer has at least one functional group selected from a carboxyl group, a phosphoric acid group, a sulfonic acid group, and salts thereof, a phosphoric ester group, and a hydroxyl group. Among these, a carboxyl group, a phosphoric acid group, a sulfonic acid group, and salts thereof are preferred, and a carboxyl group or a salt thereof is more preferred.

[0048] The weight-average molecular weight of the water-soluble polymer is not particularly limited, but is preferably 1,000 to 100,000. It is more preferably 2,000 to 80,000, even more preferably 3,000 to 50,000, still more preferably 5,000 to 40,000, even more preferably 6,000 to 30,000, and particularly preferably 8,000 to 20,000. The weight-average molecular weight of the water-soluble polymer can be measured by GPC under the measurement conditions described in the Examples.

[0049] When the water-soluble polymer has at least one functional group selected from a carboxyl group, a phosphate group, a sulfonic acid group, and salts thereof, a phosphate ester group, and a hydroxyl group, and the weight-average molecular weight of the water-soluble polymer is within the above-mentioned preferred range, the functional group adsorbs to the aluminosilicate, and the steric repulsion of the water-soluble polymer disperses the aluminosilicate more thoroughly, thereby more satisfactorily suppressing the aggregation of the aluminosilicate. This increases the rate at which the calcium content in the hydraulic material composition changes to calcium silicate hydrate, calcium aluminate hydrate, or aluminum calcium silicate hydrate, further accelerating the pozzolanic reaction and improving early strength development.

[0050] When the water-soluble polymer has at least one selected from a carboxyl group, a phosphoric acid group, a sulfonic acid group, and salts thereof, the proportion of structural units derived from a monomer having at least one selected from a carboxyl group, a phosphoric acid group, a sulfonic acid group, and salts thereof (hereinafter also referred to as a monomer having an acid group) is preferably 50 to 95 mol % relative to 100 mol % of all structural units. This further improves the adsorption to aluminosilicate. The proportion of structural units derived from a monomer having an acid group is more preferably 65 to 95 mol %, even more preferably 70 to 95 mol %, and particularly preferably 80 to 90 mol %.

[0051] The water-soluble polymer having a carboxyl group or a salt thereof (hereinafter also referred to as a carboxylic acid-based water-soluble polymer) is not particularly limited, but examples thereof include a polymer having a structural unit derived from an unsaturated carboxylic acid-based monomer and a polymer having a structural unit derived from a monomer having a carboxyl group and an aromatic group. Suitable unsaturated carboxylic acid monomers include unsaturated monocarboxylic acid monomers and unsaturated dicarboxylic acid monomers. The unsaturated monocarboxylic acid monomer may be any monomer having one unsaturated group and one group capable of forming a carbanion in the molecule, and examples thereof include (meth)acrylic acid, crotonic acid, tiglic acid, 3-methylcrotonic acid, 2-methyl-2-pentenoic acid, itaconic acid, and the like; and their monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts. The unsaturated dicarboxylic acid monomer may be any monomer having one unsaturated group and two groups capable of forming a carbanion in the molecule, and preferred examples include maleic acid, itaconic acid, mesaconic acid, citraconic acid, fumaric acid, etc., and their monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts, anhydrides, or half esters.

[0052] The monomer having a carboxyl group and an aromatic group may be one or more monomers selected from a benzene compound having a carboxyl group and optionally having a substituent other than the carboxyl group, and a naphthalene compound having a carboxyl group and optionally having a substituent other than the carboxyl group, and is preferably a benzene compound having a carboxyl group and optionally having a substituent other than the carboxyl group. Specifically, it may be one or more monomers selected from hydroxybenzoic acid, benzoic acid, isophthalic acid, oxynaphthoic acid, and isomers thereof, and is preferably one or more monomers selected from hydroxybenzoic acid and benzoic acid, and more preferably hydroxybenzoic acid.

[0053] The water-soluble polymer having a phosphate group or a salt thereof, or a phosphate ester group (hereinafter also referred to as a phosphate-based water-soluble polymer) is not particularly limited, but may be a polymer represented by the following formula (3): -OPO3M 2 2(3) (In the formula, M 2 are the same or different and represent a hydrogen atom, a monovalent metal atom, a divalent metal atom, a trivalent metal atom, an organic amine group, or a hydrocarbon group which may have a substituent. The hydrocarbon group which may have a substituent is not particularly limited, and examples thereof include groups derived from aromatic alcohols and quinones.

[0054] The water-soluble polymer having the above-mentioned phosphate group or its salt, or phosphate ester group preferably has a structural unit derived from a monomer having a phosphate (salt) group and / or a phosphate ester group and an aromatic group (hereinafter also referred to as a phosphate group-containing monomer). Among them, the following formula (4):

[0055] [ka]

[0056] (In the formula, M 2are the same or different and represent a hydrogen atom, a monovalent metal atom, a divalent metal atom, a trivalent metal atom, an organic amine group, or a hydrocarbon group which may have a substituent. 1 represents a direct bond or a divalent linking group. 4 represents a hydrogen atom or a substituent other than a phosphate group or a phosphate ester group. The above Q 1 -OPO3M 2 2. R 4 The bonding position and number of bonds are not particularly limited, and a plurality of these may be present.

[0057] The above Q 1 is not particularly limited as long as it is a divalent linking group, but is preferably a divalent hydrocarbon group which may have a heteroatom. More preferably, it is a (poly)oxyalkylene group. Specific and preferred examples of the oxyalkylene group include the same as the oxyalkylene groups described below, and most preferably, it is an oxyethylene group. The average number of moles added of the (poly)oxyalkylene group is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 2, and most preferably 1.

[0058] Above R 4 Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an aliphatic hydrocarbon group such as an alkenyl group, an alkoxy group, a hydroxyl group, an acyl group, an ether group, an amide group, an ester group, a ketone group, a carboxyl group, a salt of a carboxyl group, a sulfonic acid group, a salt of a sulfonic acid group, and a (poly)alkylene glycol chain-containing group.

[0059] Specific examples of the phosphate group-containing monomer include phosphates of aromatic alcohols and quinones such as phenoxyethanol, phenoxydiglycol, (methoxyphenoxy)ethanol, methylphenoxyethanol, bis(β-hydroxyethyl)hydroquinone ether, nonylphenol, phenol, cresol, resorcinol, catechol, hydroquinone, naphthol, and furfuryl alcohol. Specific examples of the phosphoric acid oxide include phenoxyethanol phosphate, phenoxydiglycol phosphate, (methoxyphenoxy)ethanol phosphate, methylphenoxyethanol phosphate, bis(β-hydroxyethyl)hydroquinone ether phosphate, bis(β-hydroxyethyl)hydroquinone ether diphosphate, and nonylphenol phosphate. Among these, phenoxyethanol phosphate, phenoxydiglycol phosphate, and bis(β-hydroxyethyl)hydroquinone ether diphosphate are preferred, and phenoxyethanol phosphate is more preferred. For the phosphorylation of the aromatic alcohols and quinones, it is preferable to use a phosphoric acid compound such as phosphoric acid (salt) or polyphosphoric acid (salt).

[0060] The water-soluble polymer having a sulfonic acid group or a salt thereof (hereinafter also referred to as a sulfonic acid-based water-soluble polymer) is not particularly limited, but examples thereof include a polymer having a structural unit derived from an unsaturated sulfonic acid-based monomer, a polymer having a structural unit derived from a monomer having a sulfonic acid group and an aromatic group, etc. Examples of the polymer having a structural unit derived from a monomer having a sulfonic acid group and an aromatic group include a naphthalenesulfonic acid formaldehyde condensate, a melaminesulfonic acid formaldehyde condensate, a ligninsulfonic acid, and polystyrene sulfonate.

[0061] The unsaturated sulfonic acid monomer is not particularly limited as long as it has a sulfonic acid (salt) group and an ethylenically unsaturated hydrocarbon group, and examples thereof include 3-(meth)allyloxy-2-hydroxypropanesulfonic acid, 2-(meth)allyloxyethylenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, p-styrenesulfonic acid, α-methyl-p-styrenesulfonic acid, vinylsulfonic acid, vinylsulfamic acid, (meth)allyl sulfonic acid, isoprene sulfonic acid, 4-(allyloxy)benzyl Examples of the acrylic acid include benzenesulfonic acid, 1-methyl-2-propene-1-sulfonic acid, 1,1-dimethyl-2-propene-1-sulfonic acid, 3-butene-1-sulfonic acid, 1-butene-3-sulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamidopropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2-phenylpropanesulfonic acid, 2-((meth)acryloyloxy)ethanesulfonic acid, and 2-(meth)allyloxyethylenesulfonic acid.

[0062] The monomer having a sulfonic acid group and an aromatic group may be one or more monomers selected from a benzene compound having a sulfonic acid group and optionally having a substituent other than the sulfonic acid group, and a naphthalene compound having a sulfonic acid group and optionally having a substituent other than the sulfonic acid group, and is preferably a benzene compound having a sulfonic acid group and optionally having a substituent other than the sulfonic acid group. Specifically, it may be one or more monomers selected from benzenesulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid, alkylnaphthalenesulfonic acid, naphtholsulfonic acid, and isomers thereof, and is preferably one or more monomers selected from benzenesulfonic acid and phenolsulfonic acid, and more preferably phenolsulfonic acid.

[0063] Examples of the water-soluble polymer having a hydroxyl group include polyvinyl alcohol and modified products thereof; hydroxyethyl(meth)acrylic water-soluble polymers; and hydroxypropyl(meth)acrylic water-soluble polymers.

[0064] The water-soluble polymer preferably has at least one functional group selected from a carboxyl group, a phosphoric acid group, a sulfonic acid group and salts thereof, a phosphoric ester group, and a hydroxyl group, and further has a (poly)oxyalkylene group. When the water-soluble polymer has these groups, the dispersibility of the aluminosilicate is further improved, the pozzolanic reaction is further accelerated, and the early strength development is further improved.

[0065] The (poly)oxyalkylene group is an alkylene oxide adduct, and examples of such alkylene oxides include alkylene oxides having 2 to 8 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, and styrene oxide. More preferred are alkylene oxides having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, and butylene oxide, and even more preferred are ethylene oxide and propylene oxide. Furthermore, when the (poly)oxyalkylene group is an adduct of any two or more alkylene oxides selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc., it may be in any form of random addition, block addition, alternating addition, etc. In order to ensure a balance between hydrophilicity and hydrophobicity, it is preferable that the oxyalkylene groups in the (poly)alkylene glycol contain oxyethylene groups as an essential component, more preferably 50 mol % or more of oxyethylene groups, and even more preferably 90 mol % or more of oxyethylene groups.

[0066] The average number of moles n of oxyalkylene groups added is preferably 1 to 500. As this average number of moles added increases, the hydrophilicity of the resulting polymer tends to improve, and dispersibility tends to improve, and when it is 500 or less, a decrease in copolymerization reactivity can be suppressed. The average number of moles n added is preferably 2 to 400, more preferably 5 to 300, even more preferably 10 to 200, still more preferably 15 to 150, particularly preferably 20 to 100, and most preferably 30 to 80.

[0067] When the water-soluble polymer has a (poly)oxyalkylene group, it is preferably a polymer having a structural unit derived from a (poly)oxyalkylene group-containing monomer. The (poly)oxyalkylene group-containing monomer is not particularly limited, but may be selected from the group consisting of the following formula (5):

[0068] [ka]

[0069] (In the formula, R 5 , R 6 and R 7 are the same or different and represent a hydrogen atom or a methyl group. 8 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. (R 9 O) are the same or different and represent an oxyalkylene group. n1 represents the average number of moles of oxyalkylene groups added and is a number from 1 to 500. x represents a number from 0 to 2. y represents 0 or 1.) and a monomer having a (poly)alkylene glycol chain and an aromatic group and / or a heterocyclic aromatic group (hereinafter also referred to as an aromatic group-containing (poly)alkylene glycol monomer).

[0070] In the above formula (5), (R 9 The preferred form of the oxyalkylene group represented by O) is as described above, and the preferred range of n1 is the same as the above n. In the above formula (5), R 5 , R6 and R 7 are the same or different and each is a hydrogen atom or a methyl group. 5 , R 6 is a hydrogen atom, and R 7 is a hydrogen atom or a methyl group.

[0071] In the above formula (5), R 8 may be a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and the hydrocarbon group having 1 to 30 carbon atoms is preferably one that does not have a radically polymerizable unsaturated bond, and is preferably an alkyl group having 1 to 30 carbon atoms (aliphatic alkyl group or alicyclic alkyl group), a phenyl group having 6 to 30 carbon atoms, an alkylphenyl group, a phenylalkyl group, a phenyl group substituted with an (alkyl)phenyl group, or an aromatic group having a benzene ring such as a naphthyl group. However, as the number of carbon atoms in the hydrocarbon group increases, the hydrophobicity increases and dispersibility decreases, so R 5 When R is a hydrocarbon group, the number of carbon atoms is preferably 1 to 22, more preferably 1 to 18, still more preferably 1 to 12, and particularly preferably 1 to 4. 5 is most preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.

[0072] In the above formula (5), x represents a number of 0 to 2, and y represents 0 or 1. When y is 0, the compound represented by formula (5) becomes an ether-based monomer, and in this case, x is preferably 2. In addition, in this case, R 7 is more preferably a methyl group. When the above y is 1, the compound represented by formula (5) is an ester-based monomer, and in this case, x is preferably 0. In addition, in this case, R 7 is more preferably a hydrogen atom or a methyl group, and even more preferably R 7 is a methyl group. In the above formula (5), y is 0 and R 8is a hydrogen atom, (poly)ethylene glycol allyl ether, (poly)ethylene glycol methallyl ether, (poly)ethylene glycol 3-methyl-3-butenyl ether, (poly)ethylene (poly)propylene glycol allyl ether, (poly)ethylene (poly)propylene glycol methallyl ether, (poly)ethylene (poly)propylene glycol 3-methyl-3-butenyl ether, (poly)ethylene (poly)butylene glycol allyl ether, (poly)ethylene (poly)butylene glycol methallyl ether, (poly)ethylene (poly)butylene glycol 3-methyl-3-butenyl ether, and the like.

[0073] In the above formula (5), y is 0 and R 8 Examples of the compound in which is a hydrocarbon group having 1 to 30 carbon atoms include methoxy(poly)ethylene glycol allyl ether, methoxy(poly)ethylene glycol methallyl ether, methoxy(poly)ethylene glycol 3-methyl-3-butenyl ether, methoxy(poly)ethylene (poly)propylene glycol allyl ether, methoxy(poly)ethylene (poly)propylene glycol methallyl ether, methoxy(poly)ethylene (poly)propylene glycol 3-methyl-3-butenyl ether, methoxy(poly)ethylene (poly)butylene glycol allyl ether, methoxy(poly)ethylene (poly)butylene glycol methallyl ether, and methoxy(poly)ethylene (poly)butylene glycol 3-methyl-3-butenyl ether.

[0074] In the above formula (5), y is 1 and R 8is a hydrogen atom, examples of which include (poly)alkylene glycol (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polybutylene glycol mono(meth)acrylate, polyethylene glycol polypropylene glycol mono(meth)acrylate, polyethylene glycol polybutylene glycol mono(meth)acrylate, polypropylene glycol polybutylene glycol mono(meth)acrylate, and polyethylene glycol polypropylene glycol polybutylene glycol mono(meth)acrylate.

[0075] In the above formula (5), y is 1 and R 8 is a hydrocarbon group having 1 to 30 carbon atoms, such as methoxypolyethylene glycol mono(meth)acrylate, methoxypolypropylene glycol mono(meth)acrylate, methoxypolybutylene glycol mono(meth)acrylate, methoxypolyethylene glycol polybutylene glycol mono(meth)acrylate, methoxypolypropylene glycol polybutylene glycol mono(meth)acrylate, methoxypolyethylene glycol polypropylene glycol polybutylene glycol mono(meth)acrylate, ethoxypolyethylene glycol Examples of the alkoxypolyalkylene glycol (meth)acrylate include alkoxypolyalkylene glycol (meth)acrylates in which the alkoxy group has 1 to 30 carbon atoms, such as ethoxypolypropylene glycol mono(meth)acrylate, ethoxypolybutylene glycol mono(meth)acrylate, ethoxypolyethylene glycol polypropylene glycol mono(meth)acrylate, ethoxypolyethylene glycol polybutylene glycol mono(meth)acrylate, ethoxypolypropylene glycol polybutylene glycol mono(meth)acrylate, and ethoxypolyethylene glycol polypropylene glycol polybutylene glycol mono(meth)acrylate.

[0076] The compound represented by the above formula (5) is preferably (poly)ethylene glycol methallyl ether, (poly)ethylene glycol 3-methyl-3-butenyl ether, or methoxypolyethylene glycol mono(meth)acrylate.

[0077] The aromatic group-containing (poly)alkylene glycol monomer may be a compound obtained by adding an alkylene oxide to the above-mentioned aromatic alcohol or an aromatic amine such as aniline. Preferred are compounds obtained by adding an alkylene oxide to aromatic alcohols such as phenol, cresol, resorcinol, catechol, hydroquinone, naphthol, and furfuryl alcohol. Among the structural units derived from the aromatic group-containing (poly)alkylene glycol monomer, those having the following formula (6):

[0078] [ka]

[0079] (In the formula, Q 2 represents a direct bond or a divalent linking group. 10 represents a hydrogen atom or a substituent other than a phosphate group or a phosphate ester group. 9 O may be the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. 11 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. n2 represents the average number of moles of oxyalkylene groups added and is a number from 1 to 500.

[0080] The above Q 2 Examples of the divalent linking group in the formula (4) include an oxygen atom, a sulfur atom, a halogen atom, -NH-, and a divalent hydrocarbon group which may have a heteroatom. The divalent hydrocarbon group which may have a heteroatom is Q in the formula (4). 1 The same applies to the divalent hydrocarbon group optionally containing a hetero atom in Q. 2is preferably an oxygen atom or —NH—, and more preferably an oxygen atom. R 11 The hydrocarbon group having 1 to 30 carbon atoms in the above formula (5) is R 8 The hydrocarbon group having 1 to 30 carbon atoms is the same as that in the above. R 11 is preferably a hydrogen atom. n2 is preferably 5 to 200, more preferably 10 to 150, and further preferably 12 to 120.

[0081] As the aromatic group-containing (poly)alkylene glycol monomer, 2-phenoxyethanol, phenoxypolyethylene glycol, etc. are preferred.

[0082] When the above-mentioned carboxylic acid-based water-soluble polymer has a (poly)oxyalkylene group, it is preferably a polymer having a structural unit (a) derived from an unsaturated carboxylic acid-based monomer and a structural unit (b) derived from a compound represented by the above formula (5), or a polymer having a structural unit derived from a monomer having a carboxyl group and an aromatic group and a structural unit derived from an aromatic group-containing (poly)alkylene glycol monomer. When the carboxylic acid-based water-soluble polymer is a polymer having a structural unit (a) derived from an unsaturated carboxylic acid-based monomer and a structural unit (b) derived from a compound represented by the above formula (4), it may also have a structural unit (c) derived from another monomer.

[0083] The other monomers are not particularly limited as long as they are copolymerizable with the unsaturated carboxylic acid monomer and the compound represented by the above formula (5). Examples of such other monomers include diesters of unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, and citraconic acid with alcohols having 1 to 30 carbon atoms; diamides of the above unsaturated dicarboxylic acids with amines having 1 to 30 carbon atoms; diesters of the above unsaturated dicarboxylic acids with alkyl (poly) alkylene glycols in which 1 to 300 moles of alkylene oxide having 2 to 18 carbon atoms are added to the above alcohols or amines; diesters of carboxylic acids with glycols having 2 to 18 carbon atoms or polyalkylene glycols having 2 to 300 moles of these glycols added; esters of unsaturated monocarboxylic acids such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, glycidyl (meth)acrylate, methyl crotonate, ethyl crotonate, propyl crotonate, etc. with alcohols having 1 to 30 carbon atoms; half amides of maleamic acid with glycols having 2 to 18 carbon atoms or polyalkylene glycols having 2 to 300 moles of these glycols added

[0084] (Poly)alkylene glycol di(meth)acrylates such as triethylene glycol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, (poly)ethylene glycol (poly)propylene glycol di(meth)acrylate; polyfunctional (meth)acrylates such as hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane di(meth)acrylate; (poly)alkylene glycol dimaleates such as triethylene glycol dimaleate, polyethylene glycol dimaleate; vinyl sulfonate, (meth)allyl sulfonate, 2-(meth)acryloxyethyl sulfonate, 3-(meth)acryloxypropyl sulfonate, 3-(meth)acryloxy-2-hydroxypropyl sulfonate, 3-(meth)acryloxy-2-hydroxypropyl sulfophenyl ether ... Unsaturated sulfonic acids such as aryloxy-2-hydroxypropyloxysulfobenzoate, 4-(meth)acryloxybutylsulfonate, (meth)acrylamidomethylsulfonic acid, (meth)acrylamidoethylsulfonic acid, 2-methylpropanesulfonic acid (meth)acrylamide, and styrenesulfonic acid, as well as their monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts (organic ammonium salts); amides of unsaturated monocarboxylic acids and amines having 1 to 30 carbon atoms, such as methyl(meth)acrylamide; vinyl aromatics such as styrene, α-methylstyrene, vinyltoluene, and p-methylstyrene; alkanediol mono(meth)acrylates such as 1,4-butanediol mono(meth)acrylate, 1,5-pentanediol mono(meth)acrylate, and 1,6-hexanediol mono(meth)acrylate; dienes such as butadiene, isoprene, 2-methyl-1,3-butadiene, and 2-chloro-1,3-butadiene.

[0085] Unsaturated amides such as (meth)acrylamide, (meth)acrylalkylamide, N-methylol (meth)acrylamide, and N,N-dimethyl (meth)acrylamide; unsaturated cyanides such as (meth)acrylonitrile and α-chloroacrylonitrile; unsaturated esters such as vinyl acetate and vinyl propionate; unsaturated amines such as aminoethyl (meth)acrylate, methylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dibutylaminoethyl (meth)acrylate, and vinylpyridine; divinyl aromatics such as divinylbenzene; cyanurates such as triallyl cyanurate; (methallyl a Examples of the alkyl esters include allyl groups such as alcohol and glycidyl (meth)allyl ether; and siloxane derivatives such as polydimethylsiloxane propylaminomaleamic acid, polydimethylsiloxane aminopropylene aminomaleamic acid, polydimethylsiloxane-bis-(propylaminomaleamic acid), polydimethylsiloxane-bis-(dipropyleneaminomaleamic acid), polydimethylsiloxane-(1-propyl-3-acrylate), polydimethylsiloxane-(1-propyl-3-methacrylate), polydimethylsiloxane-bis-(1-propyl-3-acrylate), and polydimethylsiloxane-bis-(1-propyl-3-methacrylate).

[0086] In the above-mentioned carboxylic acid-based water-soluble polymer, the content of the structural unit (a) is preferably 7 to 50 mass %, more preferably 10 to 45 mass %, and even more preferably 12 to 30 mass %, relative to 100 mass % of all structural units. In the above-mentioned carboxylic acid-based water-soluble polymer, the content of the structural unit (b) is preferably 50 to 93 mass %, more preferably 55 to 90 mass %, and even more preferably 70 to 88 mass %, relative to 100 mass % of all structural units. In the above-mentioned carboxylic acid-based water-soluble polymer, the proportion of the structural unit (c) is preferably 0 to 40% by mass, more preferably 0 to 30% by mass, even more preferably 0 to 20% by mass, particularly preferably 0 to 10% by mass, and most preferably 0% by mass, relative to 100% by mass of all structural units.

[0087] Specific examples of the polymer having a structural unit derived from the unsaturated carboxylic acid monomer and a structural unit derived from the compound represented by the formula (5) include a copolymer comprising an (alkoxy)polyalkylene glycol mono(meth)acrylate monomer (a), 95 to 2% by weight of a (meth)acrylic acid monomer (b), and another monomer (c) copolymerizable with these monomers, as described in JP-A-9-86990; Copolymers containing, as essential structural units, a structural unit (I) derived from an unsaturated polyalkylene glycol ether monomer (a) having an alkenyl group with 5 carbon atoms and a structural unit (II) derived from an unsaturated monocarboxylic acid monomer (b); as described in JP-A-2002-121055, a copolymer containing, as essential structural units, a structural unit (I) derived from an unsaturated polyalkylene glycol ether monomer (a) having an alkenyl group with 4 carbon atoms and a structural unit (II) derived from an unsaturated monocarboxylic acid monomer (b). copolymers containing, as essential structural units, a structural unit (I) derived from an unsaturated polyalkylene glycol ether monomer (a) having an alkenyl group with 2 or 3 carbon atoms and a structural unit (II) derived from an unsaturated monocarboxylic acid monomer (b), as described in JP-A-2002-121056; copolymers consisting of an unsaturated polyalkylene glycol ether monomer (I) having an alkenyl group with 5 carbon atoms, an unsaturated maleic acid monomer (II), and a monomer copolymerizable with these monomers, as described in JP-A-10-236858; and copolymers containing, as essential structural units, a structural unit (A) derived from polyethylene glycol monovinyl ethers, a structural unit (B) derived from an unsaturated carboxylic acid monomer, and a structural unit (C) derived from (hydroxy)alkyl(meth)acrylates, etc., as described in JP-A-2004-307590.

[0088] When the carboxylic acid-based water-soluble polymer is a polymer having a structural unit derived from a monomer having a carboxyl group and an aromatic group and a structural unit derived from an aromatic group-containing (poly)alkylene glycol monomer, it preferably has the structural unit derived from the monomer having a carboxyl group and an aromatic group and a structural unit represented by the formula (6). In this case, the molar ratio (former / latter) of the structural unit derived from the monomer having a carboxyl group and an aromatic group to the structural unit represented by formula (6) is preferably 0.1 to 9, more preferably 0.25 to 4.

[0089] When the carboxylic acid-based water-soluble polymer is a polymer having structural units derived from a monomer having a carboxyl group and an aromatic group and structural units derived from an aromatic group-containing (poly)alkylene glycol monomer, it may have structural units other than the structural units derived from the monomer having a carboxyl group and an aromatic group and the structural units derived from the aromatic group-containing (poly)alkylene glycol monomer. Examples of the other structural units include the structural units derived from the monomer having a sulfonic acid group and an aromatic group, the structural units derived from a monomer having a phosphoric acid (salt) group and / or a phosphoric acid ester group and an aromatic ring group, and the structural units derived from other monomers having aromatic groups, as described below. The proportion of the structural units derived from the monomer having a carboxyl group and an aromatic group and the structural units represented by formula (6) above is not particularly limited, but is preferably 0 to 50 mol % relative to the total of 100 mol % of the structural units derived from the monomer having a carboxyl group and an aromatic group and the structural units represented by formula (6). It is more preferably 0 to 40 mol %, even more preferably 0 to 30 mol %, and most preferably 0 mol %.

[0090] When the phosphoric acid-based water-soluble polymer has a (poly)oxyalkylene group, it preferably has a structural unit represented by the above formula (4) and a structural unit represented by the above formula (6). In this case, the molar ratio of the structural unit represented by formula (4) to the structural unit represented by formula (6) (formula (4) / formula (6)) is preferably 0.3 to 4, more preferably 0.4 to 3.5, and even more preferably 0.45 to 3.

[0091] The phosphoric acid-based water-soluble polymer may have structural units other than the structural units having a phosphoric acid (salt) group and / or a phosphoric acid ester group and the structural units having a (poly)alkylene glycol chain. Examples of the other structural units include the structural units derived from the monomers having a sulfonic acid group and an aromatic group, and the structural units derived from the other monomers having an aromatic group described below. Other monomers having an aromatic group include phenoxy alcohol, phenol, naphthol, aniline, benzene-1,2-diol, benzene-1,2,3-triol, 1,2-dihydroxynaphthalene, and 2,3-dihydroxynaphthalene, which are capable of reacting with the aldehyde compounds described below. The proportion of structural units other than the structural units having a phosphoric acid (salt) group and / or a phosphoric acid ester group and the structural units having a (poly)alkylene glycol chain is not particularly limited, but is preferably 0 to 50 mol %, more preferably 0 to 40 mol %, even more preferably 0 to 30 mol %, and most preferably 0 mol %, relative to 100 mol % of the total of the structural units having a phosphoric acid (salt) group and / or a phosphoric acid ester group and the structural units having a (poly)alkylene glycol chain.

[0092] In the polymer having structural units derived from the above-mentioned monomer having an aromatic group, the structural units are preferably linked via a divalent linking group derived from an aldehyde compound. Examples of the aldehyde compound include formaldehyde; compounds having an alkyl group having 1 to 5 carbon atoms and an aldehyde group, such as acetaldehyde, propionaldehyde, and butanal; glyoxylic acid, benzaldehyde, and paraformaldehyde. Preferred are formaldehyde, benzaldehyde, and paraformaldehyde, and most preferred is formaldehyde.

[0093] For example, the structure in which the structural unit represented by the above formula (4) and the structural unit represented by the above formula (6) are bonded via a divalent linking group derived from an aldehyde compound is represented by the following formula (7):

[0094] [ka]

[0095] (In the formula, M 2 are the same or different and represent a hydrogen atom, a monovalent metal atom, a divalent metal atom, a trivalent metal atom, an organic amine group, or a hydrocarbon group which may have a substituent. 1 , Q 2 are the same or different and represent a direct bond or a divalent linking group. 4 , R 10 R may be the same or different and represent a hydrogen atom or a substituent other than a phosphate group or a phosphate ester group. 9 O may be the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. 11 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. n2 represents the average number of moles of oxyalkylene groups added and is a number from 1 to 500. In the polymer having structural units derived from a monomer having an aromatic group, such as the above-mentioned phosphoric acid-based water-soluble polymer, the structural units derived from each monomer are preferably bonded via a methylene group.

[0096] Specific examples of the phosphoric acid-based water-soluble polymer having a structural unit derived from a monomer having an aromatic group include polycondensation products consisting of the following components C1, C3, and optionally C2, as described in JP-A-2008-517080: [Component C1] Aromatic or heteroaromatic compounds having 5 to 10 carbon or heteroatoms, which contain an average of 1 to 300 oxyethylene and / or oxypropylene groups per molecule bonded to the aromatic or heteroaromatic compound via O or N atoms. [Component C2] Optionally, at least one aromatic compound selected from the group consisting of (C2-1) phenol, (C2-2) phenol ether, (C2-3) naphthol, (C2-4) naphthol ether, (C2-5) aniline, (C2-6) furfuryl alcohol, and (C2-7) an aminoplast-forming agent selected from the group consisting of melamine or a derivative thereof, urea or a derivative thereof, and a carboxamide. [Component C3] an aldehyde selected from the group consisting of formaldehyde, glyoxylic acid, and benzaldehyde, or a mixture thereof, wherein the benzaldehyde may further have an acidic group represented by the formulas COOMa, SO3Ma, and PO3Ma, where M is H, an alkali metal or alkaline earth metal, ammonium, or an organic amine group, and a may be 1 / 2, 1, or 2.

[0097] The phosphoric acid-based water-soluble polymer may not have an aromatic group in its structure, and examples of such a form include a phosphoric acid group-containing monomer represented by the following formula (8) and / or (9):

[0098] [ka]

[0099] (In the formula, R 12 , R 14 , R 17 are the same or different and represent a hydrogen atom or a methyl group. 13 , OR 15 , OR 16 are the same or different and represent an oxyalkylene group having 2 to 18 carbon atoms. 3 , n 4 , n 5 are the same or different and represent a number from 1 to 30. 2 is M in Eq. (7) 2 The same applies to the above.)

[0100] Examples of the phosphoric acid-based water-soluble polymer having no aromatic group in its structure include a polymer having a structural unit derived from a monomer represented by the above formula (8) and / or (9) and a structural unit derived from a compound represented by the above formula (5). Specific examples include copolymers composed of (alkoxy)polyalkylene glycol mono(meth)acrylate monomers and phosphoric acid ester monomers, as described in JP-A-2006-052381.

[0101] The water-soluble polymer is preferably a water-soluble polymer of a carboxylic acid type, a water-soluble polymer of a phosphoric acid type, or a water-soluble polymer of a sulfonic acid type. More preferred carboxylic acid-based water-soluble polymers are (poly)ethylene glycol methallyl ether / acrylic acid copolymer, (poly)ethylene glycol 3-methyl-3-butenyl ether / acrylic acid copolymer, and methoxypolyethylene glycol mono(meth)acrylate / (meth)acrylic acid copolymer. As the phosphoric acid-based water-soluble polymer, a polymer having a structure represented by the above formula (7) is more preferred. As the sulfonic acid-based water-soluble polymer, naphthalene sulfonic acid formaldehyde condensate, melamine sulfonic acid formaldehyde condensate, lignin sulfonic acid, polystyrene sulfonate, etc. are more preferred.

[0102] The method for producing the water-soluble polymer is not particularly limited, but it can be produced by polymerizing the monomer components by a commonly used method.

[0103] The aluminosilicate-containing composition of the present invention may contain other components in addition to the aluminosilicate, water-soluble polymer, aluminum-containing compound, and silicon-containing compound. The other components are not particularly limited, but examples thereof include antifoaming agents, air-entraining agents, surfactants, and the like. The content of the other components is not particularly limited, but is preferably 0 to 20 mass% relative to 100 mass% of the aluminosilicate-containing composition, more preferably 0 to 10 mass%, even more preferably 0 to 5 mass%, and particularly preferably 0 to 1 mass%.

[0104] As the surfactant, one or more of various anionic, cationic, nonionic and amphoteric surfactants, and polymer surfactants can be used. The anionic surfactant is not particularly limited, and examples thereof include polyoxyalkylene alkyl ether sulfate salts, polyoxyalkylene oleyl ether sodium sulfate salts, polyoxyalkylene alkylphenyl ether sulfate salts, alkyl diphenyl ether disulfonate salts, polyoxyalkylene (mono-, di-, tri-)styrylphenyl ether sulfate salts, polyoxyalkylene (mono-, di-, tri-)benzylphenyl ether sulfate salts, alkenyl succinic acid disalts; alkyl sulfate salts such as sodium dodecyl sulfate, potassium dodecyl sulfate, and ammonium alkyl sulfate; sodium dodecyl polyglycol ether sulfate; sodium Examples include thorium sulforisinoate, alkyl sulfonates such as sulfonated paraffin salts, alkyl sulfonates such as sodium dodecylbenzenesulfonate and alkali metal sulfates of alkali phenol hydroxyethylene, high alkyl naphthalene sulfonates, naphthalene sulfonic acid formalin condensates, fatty acid salts such as sodium laurate, triethanolamine oleate, and triethanolamine abietate, polyoxyalkyl ether sulfates, polyoxyethylene carboxylic acid ester sulfates, polyoxyethylene phenyl ether sulfates, succinic acid dialkyl ester sulfonates, and polyoxyethylene alkylaryl sulfates. One or more of these can be used.

[0105] Suitable commercially available anionic surfactants include, for example, Latemul WX, Latemul 118B, Pelex SS-H, Emulgen A-60, B-66, and Levenol WZ (manufactured by Kao Corporation), Newcol 707SF, Newcol 707SN, Newcol 714SF, Newcol 714SN, AB-26S, ABEX-2010, 2020, and 2030, and DSB (manufactured by Rhodia Nikka Co., Ltd.). Surfactants corresponding to these nonionic types can also be used.

[0106] As the anionic surfactant, and as the reactive surfactant, one or more of reactive anionic surfactants, sulfosuccinate-type reactive anionic surfactants, alkenyl succinate-type reactive anionic surfactants, etc. can be used. Commercially available sulfosuccinate-type reactive anionic surfactants include Latemul S-120, S-120A, S-180, and S-180A (all trade names, manufactured by Kao Corporation), Eleminol JS-2 (trade name, manufactured by Sanyo Chemical Industries, Ltd.), and Adeka Reasop SR-10, SR-20, and SR-30 (manufactured by ADEKA Corporation). Commercially available alkenyl succinate reactive anionic surfactants include Latemul ASK (trade name, manufactured by Kao Corporation). Furthermore, sulfate esters (salts) having an allyl group such as (meth)acrylic acid polyoxyethylene sulfonate salts (e.g., "Eleminol RS-30" manufactured by Sanyo Chemical Industries, Ltd., "Antox MS-60" manufactured by Nippon Nyukazai Co., Ltd.), sulfonate salts of allyloxymethylalkyloxypolyoxyethylene (e.g., "Aqualon KH-10" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), polyoxyalkylene alkenyl ether ammonium sulfate (e.g., "Latemul PD-104" manufactured by Kao Corporation), and aromatic hydrocarbon compounds having a 1-propenyl group, a polyoxyethylene group, and an ammonium sulfate salt group (e.g., "Aqualon BC-10" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) can also be used.

[0107] Furthermore, the anionic surfactants may further include the following reactive surfactants. Sulfoalkyl (C1-C4) ester salt surfactants of aliphatic unsaturated carboxylic acids having 3 to 5 carbon atoms, for example, (meth)acrylic acid sulfoalkyl ester salt surfactants such as 2-sulfoethyl (meth)acrylate sodium salt and 3-sulfopropyl (meth)acrylate ammonium salt; aliphatic unsaturated dicarboxylic acid alkyl sulfoalkyl diester salt surfactants such as sulfopropyl maleic acid alkyl ester sodium salt, sulfopropyl maleic acid polyoxyethylene alkyl ester ammonium salt, and sulfoethyl fumaric acid polyoxyethylene alkyl ester ammonium salt.

[0108] The nonionic surfactant is not particularly limited, and examples thereof include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, sorbitan aliphatic esters, polyoxyethylene sorbitan aliphatic esters, aliphatic monoglycerides such as glycerol monolaurate, polyoxyethylene oxypropylene copolymers, condensation products of ethylene oxide with aliphatic amines, amides, or acids, triisopropanolamine, and Jeffamines. Reactive nonionic surfactants such as allyloxymethylalkoxyethylhydroxypolyoxyethylene (e.g., "ADEKA REASOAP ER-20" manufactured by ADEKA Corporation), polyoxyalkylene alkenyl ethers (e.g., "LATEMUL PD-420" and "LATEMUL PD-430" manufactured by Kao Corporation), and aromatic compounds having a 1-propenyl group and a polyoxyethylene group (e.g., "Aqualon RN-20" manufactured by Daiichi Seiyaku Co., Ltd.) can also be used. One or more of these surfactants can be used.

[0109] The cationic surfactant is not particularly limited, and examples thereof include dialkyldimethylammonium salts, ester-type dialkylammonium salts, amide-type dialkylammonium salts, and dialkylimidazolinium salts, and one or more of these can be used.

[0110] The amphoteric surfactant is not particularly limited, and examples thereof include alkyldimethylaminoacetic acid betaine, alkyldimethylamine oxide, alkylcarboxymethylhydroxyethylimidazolinium betaine, alkylamidopropyl betaine, and alkylhydroxysulfobetaine, and one or more of these can be used.

[0111] The polymer surfactant is not particularly limited, and examples of nonionic polymer surfactants include polyvinylpyrrolidone and poly-N-vinylacetamide, and one or more of these can be used. Among the above surfactants, from an environmental point of view, it is preferable to use non-nonylphenyl surfactants.

[0112] <Method for producing aluminosilicate-containing composition> The method for producing the aluminosilicate-containing composition of the present invention is not particularly limited, but it is preferable to produce it by reacting an aluminum-containing compound with a silicon-containing compound in the presence of a water-soluble polymer. The present invention also relates to a method for producing an aluminosilicate-containing composition, which method includes a step (α) of reacting an aluminum-containing compound with a silicon-containing compound in the presence of a water-soluble polymer. Specific examples and preferred forms of the water-soluble polymer, aluminum-containing compound and silicon-containing compound are as described above.

[0113] The above step (α) is not particularly limited as long as it involves reacting an aluminum-containing compound with a silicon-containing compound in the presence of a water-soluble polymer, but is preferably carried out in water with stirring. This allows the average particle size of the resulting aluminosilicate to fall within a more suitable range. The method for adding the raw materials in the above step (α) is not particularly limited, but it is preferable to mix the water-soluble polymer, aluminum-containing compound, and silicon-containing compound as aqueous solutions. In the step (α), the compounds may be added all at once or successively, but it is preferable to add the remaining components dropwise to an aqueous solution containing one or two of the water-soluble polymer, aluminum-containing compound, and silicon-containing compound. More preferred is a method in which an aqueous solution containing an aluminum-containing compound and an aqueous solution containing a silicon-containing compound are added dropwise to an aqueous solution containing a water-soluble polymer.

[0114] When the aluminosilicate-containing composition contains an amine and / or a metal compound having a molecular weight of 1000 or less, it is preferable to add the amine and / or the metal compound in step (α). In the step (α), the method for adding the amine and / or metal compound is not particularly limited. When the amine is added, a preferred method is to dropwise add an aqueous solution containing an aluminum-containing compound and an aqueous solution of a silicon-containing compound to an aqueous solution containing a water-soluble polymer and an amine. In the step (α), when the metal compound is added, a method is preferred in which an aqueous solution containing an aluminum-containing compound, an aqueous solution containing a silicon-containing compound, and an aqueous solution containing the metal compound are added dropwise to an aqueous solution containing a water-soluble polymer.

[0115] The amount of the water-soluble polymer used in step (α) is preferably 5 to 1000% by mass, more preferably 10 to 500% by mass, even more preferably 10 to 75% by mass, and particularly preferably 20 to 50% by mass, relative to 100% by mass of the total amount of the aluminum-containing compound and the silicon-containing compound used.

[0116] The silicon atom content in the raw material used in step (α) is preferably 1 to 1000 mol %, more preferably 10 to 800 mol %, even more preferably 50 to 500 mol %, and particularly preferably 50 to 300 mol %, relative to 100 mol % of aluminum atoms.

[0117] When an amine having a molecular weight of 1,000 or less is used in the above step (α), the amount used is preferably 0.01 to 500 mass% relative to 100 mass% of the aluminosilicate to be produced, more preferably 1 to 100 mass%, even more preferably 5 to 70 mass%, and particularly preferably 10 to 50 mass%.

[0118] When the metal compound is used in step (α), the amount used is preferably 0.001 to 50 mol %, more preferably 0.01 to 50 mol %, still more preferably 0.1 to 50 mol %, and particularly preferably 1 to 50 mol %, relative to 100 mol % of the total of aluminum element and silicon element in the aluminum-containing compound and silicon-containing compound used in step (α).

[0119] The reaction temperature in the above step (α) is not particularly limited, but is preferably 10 to 90°C, and more preferably 20 to 80°C.

[0120] <Curing accelerator composition> The aluminosilicate-containing composition of the present invention can be used as a hardening accelerator in hydraulic material compositions including cement paste, mortar, concrete, etc. It can also be used in ultra-high strength concrete.

[0121] The present invention also provides a curing accelerator composition comprising an aluminosilicate, a water-soluble polymer, and an amine and / or metal compound having a molecular weight of 1,000 or less. The present invention also relates to a hardening accelerator composition that contains an aluminosilicate and a water-soluble polymer and is used in a hydraulic material composition that contains at least one substance selected from the group consisting of a substance having latent hydraulic activity and / or pozzolanic activity and a filler. The preferred forms of the aluminosilicate, water-soluble polymer, amine having a molecular weight of 1000 or less, and metal compound in the curing accelerator composition are as described above. The present invention also provides a method for accelerating the hardening of a hydraulic material, comprising the steps of adding the above-described aluminosilicate-containing composition to a hydraulic material and hardening the composition obtained in the adding step. The preferred forms of the adding step and the curing step in the above-mentioned hardening acceleration method are the same as the adding step (β) in the method for producing a hydraulic material composition and the curing step (γ) in the method for producing a hydraulically hardened product, respectively, which will be described later.

[0122] The curing accelerator composition may contain an aluminum-containing compound and / or a silicon-containing compound and the other components described above, and specific examples and preferred forms thereof are as described above.

[0123] The preferred ranges of the content ratios of the aluminosilicate, water-soluble polymer, amine having a molecular weight of 1,000 or less, metal compound, and other components in the curing accelerator composition are the same as the preferred ranges of the content ratios of these components in the aluminosilicate-containing composition described above.

[0124] <Hydraulic material composition> The present invention also relates to a hydraulic material composition comprising the aluminosilicate-containing composition and / or the hardening accelerator composition of the present invention and a hydraulic material. The hydraulic material composition is preferably a commonly used composition containing cement, water, fine aggregate, coarse aggregate, etc. Alternatively, it may contain fine powder of fly ash, blast furnace slag, silica fume, limestone, etc. The term "ultra-high strength concrete" refers to what is generally called in the field of cement compositions, that is, concrete whose hardened product has the same or higher strength as conventional concrete even when the water-cement ratio is lower than that of conventional concrete. For example, even when the water-cement ratio is 25% by mass or less, further 20% by mass or less, particularly 18% by mass or less, particularly 14% by mass or less, and particularly about 12% by mass, the concrete has workability that does not hinder normal use, and the hardened product has a strength of 60 N / mm 2 Above, an additional 80N / mm 2 Above that, even more than 100N / mm 2Above, especially 120N / mm 2 Above, especially 160N / mm 2 Above 200N / mm 2 This will result in a compressive strength of the above.

[0125] The hydraulic material composition may further contain other commonly used cement dispersants and water-reducing agents, and a combination of these is also possible. The other cement dispersants (water-reducing agents) are not particularly limited, but include the above-mentioned water-soluble polymer compounds, and among these, carboxylic acid-based water-soluble polymers, phosphoric acid-based water-soluble polymers, and sulfonic acid-based water-soluble polymers are preferred. These cement dispersants may be used alone or in combination of two or more.

[0126] The hydraulic material composition of the present invention may further contain other additives, if necessary. Examples of other additives include water-soluble polymeric substances, polymer emulsions, retarders, early-strengthening agents / accelerators, antifoaming agents, air-entraining agents, other surfactants, waterproofing agents, rust inhibitors, expanding agents, cement wetting agents, thickeners, separation-reducing agents, flocculants, drying shrinkage-reducing agents, strength enhancers, self-leveling agents, colorants, and mildew inhibitors. One or more of these may be used.

[0127] When the cement dispersant is used in combination, the mixing ratio cannot be uniquely determined due to differences in the type, blending, and test conditions of the cement dispersant used, but the blending mass ratio of the other additives and the cement dispersant is preferably 5-95:95-5, and more preferably 10-90:90-10.

[0128] The hydraulic material composition can be used for various hydraulic materials, i.e., cement compositions such as cement and gypsum, as well as other hydraulic materials. Specific examples of hydraulic compositions containing such hydraulic materials and water, and further containing fine aggregate (sand, etc.) or coarse aggregate (crushed stone, etc.), as needed, include cement paste, mortar, concrete, plaster, etc. Among these hydraulic compositions, preferred are cement compositions using cement as the hydraulic material, and a cement composition containing the aluminosilicate-containing composition and / or the hardening accelerator composition, and cement also constitutes one aspect of the present invention.

[0129] In the hydraulic material composition, examples of cement include Portland cement (normal, early strength, extra early strength, moderate heat, sulfate-resistant, and their respective low-alkali forms); various blended cements (blast furnace cement, silica cement, fly ash cement); white Portland cement; alumina cement; ultra-rapid-hardening cement (one-clinker rapid-hardening cement, two-clinker rapid-hardening cement, magnesium phosphate cement); cement for grout; oil well cement; low-heat cement (low-heat blast furnace cement, fly ash-blended low-heat blast furnace cement, belite-rich cement); ultra-high-strength cement; cement-based solidifying material; and ecocement (cement produced from one or more of municipal waste incineration ash and sewage sludge incineration ash). The hydraulic material composition of the present invention may contain only one type of cement, or two or more types.

[0130] The hydraulic material composition preferably contains, in addition to cement, at least one selected from the group consisting of substances having latent hydraulic activity and / or pozzolanic activity and fillers. Normally, SCM concrete has a longer hardening time than ordinary Portland cement and has problems with early strength development, but the aluminosilicate-containing composition of the present invention has excellent early strength development even compared to SCM concrete. Therefore, the technical significance of the present invention is more effectively realized when the hydraulic material composition contains at least one selected from the group consisting of substances having latent hydraulic activity and / or pozzolanic activity and fillers.

[0131] The total content of the substance having latent hydraulic and / or pozzolanic activity and the filler in the hydraulic material composition is not particularly limited, but is preferably 0.1 to 10,000 mass% relative to 100 mass% of cement, more preferably 0.1 to 900 mass%, even more preferably 5 to 800 mass%, even more preferably 10 to 500 mass%, still more preferably 20 to 300 mass%, and particularly preferably 30 to 200 mass%.

[0132] Examples of the above aggregate include gravel, crushed stone, granulated slag, recycled aggregate, and also refractory aggregate such as silica, clay, zircon, high alumina, silicon carbide, graphite, chromium, chromium-magnesium, and magnesia.

[0133] In the above hydraulic material composition, 1 m 3 The unit water amount, cement amount used, and water / cement ratio per unit are not particularly limited. For example, the unit water amount is 100 to 185 kg / m 3 , cement amount used: 250-800 kg / m 3 The water / cement ratio (weight ratio) is preferably 0.12 to 0.74. More preferably, the unit water content is 120 to 175 kg / m. 3 , cement amount used: 270-800 kg / m 3 The water / cement ratio (weight ratio) is 0.15 to 0.65. As described above, the hydraulic material composition of the present invention can be used in a wide range of mixes from lean to rich, and can be used in high-strength concrete with a large unit cement content, and in concrete with a unit cement content of 300 kg / m 3 The hydraulic material composition of the present invention is effective for any of the following lean concretes. The hydraulic material composition of the present invention can also be used effectively in a region with a relatively high water reduction rate, that is, a region with a low water / cement ratio (weight ratio) of 0.15 to 0.5 (preferably 0.15 to 0.4).

[0134] The content of the aluminosilicate-containing composition and / or hardening accelerator composition of the present invention in the hydraulic material composition is not particularly limited, but is preferably 0.1 to 10 mass %, more preferably 0.2 to 5 mass %, and even more preferably 0.2 to 3 mass %, relative to 100 mass % of the total of the cement, the substance having latent hydraulic and / or pozzolanic activity, and the filler.

[0135] In the hydraulic material composition, the blending ratio of the aluminosilicate is preferably set to, for example, 0.01 to 1 mass% in terms of solid content relative to 100 mass% of the total cement mass. If it is less than 0.01 mass%, the performance may be insufficient, while if it exceeds 1 mass%, the effect may substantially plateau, which may be disadvantageous from an economic standpoint. It is more preferably 0.05 to 0.5 mass%, and even more preferably 0.1 to 0.4 mass%. In this specification, the solid content can be measured as follows. In this specification, the solid content can be measured as follows. <Solid content measurement method> 1. Accurately weigh the aluminum dish. Accurately weigh the solid content measurement material into the aluminum dish that was accurately weighed in 2.1. 3. Place the solid content measured in step 2 in a dryer adjusted to 130°C under a nitrogen atmosphere for 1 hour. After 4.1 hours, remove from the oven and allow to cool in a desiccator at room temperature for 15 minutes. 5. After 15 minutes, remove from the desiccator and accurately weigh the aluminum dish and the sample. 6. Subtract the mass of the aluminum dish obtained in 1 from the mass obtained in 5, and divide the result by the mass of the solids measurement sample obtained in 2 to measure the solids content.

[0136] The hydraulic material composition obtained by using the aluminosilicate-containing composition and / or hardening accelerator composition of the present invention has excellent early strength development, and therefore can be effectively applied to precast cement (precast concrete). The use of the hydraulic material composition of the present invention in precast cement is one of the preferred embodiments of the present invention. The aluminosilicate-containing composition and / or hardening accelerator composition of the present invention also exhibits excellent early strength development even when SCM such as fly ash or slag is used, and can therefore be effectively applied to SCM concrete.

[0137] The method for producing the hydraulic material composition of the present invention is not particularly limited, but it is preferable to produce it by adding the aluminosilicate-containing composition of the present invention or the aluminosilicate-containing composition obtained by the above-mentioned production method to a hydraulic material. The present invention also relates to a method for producing a hydraulic material composition, which includes a step (β) of adding the aluminosilicate-containing composition of the present invention or the aluminosilicate-containing composition obtained by the above-mentioned method to a hydraulic material. The method for adding the aluminosilicate-containing composition in the step (β) is not particularly limited, but it is preferable to add the aluminosilicate-containing composition after dispersing it in a solvent such as water.

[0138] The present invention also relates to a method for producing a hydraulically set product, which method includes a step (γ) of hardening the hydraulic material composition of the present invention or the hydraulic material composition obtained by the method. The curing method in the curing step (γ) is not particularly limited, and room temperature curing or steam curing may be used. The hardening step (γ) is preferably a step of hardening the hydraulic material composition at -20 to 90°C. The hardening temperature is preferably 5 to 85°C, more preferably 5 to 80°C, even more preferably 5 to 75°C, and particularly preferably 5 to 40°C.

[0139] In the method for producing a hydraulically set product, the curing step (γ) is preferably carried out under conditions of a humidity of 40 to 100%, more preferably 50 to 100%, and even more preferably 60 to 100%.

[0140] The curing step (γ) may be carried out in one stage or in two or more stages, but is preferably carried out in two stages. The first stage is preferably carried out under conditions of a temperature of 15 to 30°C and a humidity of 40 to 60%, and the second stage is preferably carried out under conditions of a temperature of 40 to 90°C and a humidity of 60 to 100%.

[0141] The method for producing the hydraulically set product preferably includes a step of pouring the hydraulic material composition into a formwork, and the hardening step (γ) is preferably carried out after the step of pouring into the formwork.

[0142] In the method for producing the hydraulically set product, the hardening step (γ) is preferably carried out by steam curing.

[0143] In the method for producing a hydraulically set product, the curing step (γ) is preferably carried out for 1 to 10 hours, more preferably 1.5 to 8 hours, and even more preferably 2 to 6 hours.

[0144] The present invention also relates to a method for curing a hydraulic material composition containing the aluminosilicate-containing composition and / or the hardening accelerator composition and a hydraulic material at 15 to 90°C. The curing temperature is preferably 20 to 85°C, more preferably 30 to 85°C, even more preferably 35 to 80°C, and particularly preferably 40 to 60°C.

[0145] The present invention also provides a method for rapidly improving the strength of a hydraulically set product, the method comprising the steps of adding the aluminosilicate-containing composition to a hydraulic material and curing the composition obtained in the adding step. The preferred forms of the adding step and the curing step in the above-mentioned method for improving early strength are the same as the adding step (β) in the method for producing a hydraulic material composition and the curing step (γ) in the method for producing a hydraulically cured product, respectively. [Example]

[0146] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means "parts by weight" and "%" means "% by mass."

[0147] <Measurement of Average Particle Size of Aluminosilicate-Containing Composition> First, the obtained aqueous dispersion was filtered using filter paper No. 2 manufactured by Advantec Co., Ltd. to remove impurities, and the obtained filtrate was used to carry out the following operations. Using a particle size measuring device, the scattering intensity of an aqueous dispersion of the aluminosilicate-containing composition with a solid content of 0.1% by mass was measured by dynamic light scattering, and the Z-average particle size was calculated. Equipment: Malvern Zetasizer Nano Measurement temperature: 20.0℃ Measurement solvent: ion-exchanged water

[0148] <Gel Permeation Chromatography (GPC)> The weight average molecular weight (Mw) of the water-soluble polymer was measured by GPC (gel permeation chromatography) under the following measurement conditions. (GPC analysis method) Equipment: Waters Alliance (2695) Analysis software: Waters Empower2 Professional + GPC option Columns used: Tosoh Corporation, TSKguard columns SWXL + TSKgel G4000SWXL + G3000SWXL + G2000SWXL Detector: Differential Refractometer (RI) detector (Waters 2414), Multi-wavelength Visible Ultraviolet (PDA) detector (Waters 2996) Eluent: 115.6 g of sodium acetate trihydrate dissolved in a mixed solvent of 10,999 g of water and 6,001 g of acetonitrile, and the pH was adjusted to 6.0 with acetic acid. Standard material for creating a calibration curve: polyethylene glycol (peak top molecular weight (Mp) 272,500, 219,300, 107,000, 50,000, 24,000, 12,600, 7,100, 4,250, 1,470) Calibration curve: A cubic equation was prepared based on the Mp values ​​and elution times of the above standard substances. Flow rate: 1mL / min Column temperature: 40℃ Measurement time: 45 minutes Standard substance sample solution injection volume: 100 μL (eluent solution with polymer concentration of 0.1% by mass) Polymer sample solution injection volume: 100 μL (eluent solution with a polymer concentration of 0.5% by mass)

[0149] (GPC analysis conditions (polymer analysis)) In the obtained RI chromatogram, the flat and stable parts of the baseline just before and just after the polymer elution were connected with a straight line to detect and analyze the polymer. However, if the peaks of the monomer or monomer-derived impurities were measured to overlap with the polymer peak, the peak was vertically divided at the deepest point of the overlapping part with the polymer to separate the polymer part from the monomer part and impurity part, and the molecular weight and molecular weight distribution of only the polymer part were calculated. If there was no recess, they were calculated together. The pure polymer content was calculated as follows from the ratio of peak areas measured by an RI detector. Pure polymer content = (polymer peak area) / (polymer peak area + peak area of ​​monomers and impurities)

[0150] <Production Example 1> A solution (1a) was prepared by dissolving 0.3 parts of L-ascorbic acid in 191.2 parts of water. A solution (1b) was prepared by dissolving 2.2 parts of 3-mercaptopropionic acid in 13.5 parts of water. A solution (1c) was prepared by dissolving 32.2 parts of acrylic acid (AA) in 8.0 parts of water. A reaction vessel equipped with a thermometer, stirrer, dropping device, nitrogen inlet tube, and reflux condenser was charged with 30.0 parts of water and 209.8 parts of an 80% aqueous solution of an unsaturated polyalkylene glycol ether monomer (IPN-50) in which an average of 50 moles of ethylene oxide were added to 3-methyl-3-buten-1-ol. The temperature was raised to 60°C under a nitrogen atmosphere, and 12.8 parts of a 2% aqueous solution of hydrogen peroxide was added. Next, the above-mentioned mixed solutions (1a), (1b), and (1c) were mixed, and the pH of the reaction solution was neutralized to pH 7.0 using aqueous sodium hydroxide at a temperature below the polymerization reaction temperature. In this way, a polymer solution containing copolymer (1) was obtained. The weight-average molecular weight was 15,000.

[0151] <Synthesis Example 1> A solution of 101.0 g of aluminum sulfate 14-18 hydrate dissolved in 172.0 g of ion-exchanged water was designated solution (A1), and a solution of 46.8 g of copolymer (1) (solid content 40%) dissolved in 69.1 g of ion-exchanged water was designated solution (B1). Next, 90.9 g of sodium metasilicate nonahydrate was dissolved in 397.0 g of ion-exchanged water, designated solution (C1). 11.7 g of copolymer (1) (solid content 40%) was added to 111.5 g of water at room temperature and stirred, and solutions (A1), (B1), and (C1) were mixed to obtain aluminosilicate composition (1). The average particle size of the aluminosilicate-containing composition was 90 nm.

[0152] <Synthesis Examples 2-3> In each of Synthesis Examples 2 and 3, aluminum sulfate 14-18 hydrate, copolymer (1), and sodium metasilicate 9 hydrate were charged in amounts such that the Si / Al ratio was as shown in Table 1, and a synthesis reaction was carried out in the same manner as in Synthesis Example 1 to obtain aluminosilicate-containing compositions (2) and (3), respectively. The average particle diameters of the resulting aluminosilicate-containing compositions are shown in Table 1.

[0153] <Synthesis Example 4> A solution of 24.7 g of aluminum sulfate 14-18 hydrate dissolved in 41.8 g of ion-exchanged water was designated solution (A2), and 1.4 g of copolymer (1) (solid content 40%) and 1.4 g of triethanolamine (solid content 40%) were added and mixed to create solution (B2). Next, 22.1 g of sodium metasilicate nonahydrate was dissolved in 50.9 g of ion-exchanged water to create solution (C2). At room temperature, 5.7 g of copolymer (1) (solid content 40%) and 5.7 g of triethanolamine (solid content 40%) were added to 62.5 g of water and stirred. Solutions (A2), (B2), and (C2) were mixed to obtain aluminosilicate-containing composition (4). The average particle size of the aluminosilicate-containing composition was 310 nm.

[0154] <Synthesis Examples 5 to 17> In each of Synthesis Examples 5 to 17, aluminum sulfate 14-18 hydrate, copolymer (1), and the amine compound and sodium metasilicate nonahydrate shown in Table 1 below were charged in amounts such that the Si / Al ratio was as shown in Table 1, and a synthesis reaction was carried out in the same manner as in Synthesis Example 4 to obtain aluminosilicate compositions (5) to (17), respectively. The average particle diameter of each of the obtained aluminosilicate-containing compositions is shown in Table 1.

[0155] <Synthesis Example 18> A solution of 23.5 g of aluminum sulfate 14-18 hydrate dissolved in 40.0 g of ion-exchanged water was designated solution (A3), and a solution of 11.4 g of copolymer (1) (solid content 40%) dissolved in 48.0 g of ion-exchanged water was designated solution (B3). Next, 21.1 g of sodium metasilicate nonahydrate was dissolved in 48.5 g of ion-exchanged water, designated solution (C3). Next, a solution of 4.0 g of zinc sulfate (solid content 56.0%) dissolved in 20.0 g of ion-exchanged water was designated solution (D3). 2.85 g of copolymer (1) (solid content 40%) was added to 27.2 g of water at room temperature and stirred. Solutions (A3), (B3), (C3), and (D3) were mixed to obtain aluminosilicate-containing composition (18). The average particle size of the aluminosilicate-containing composition was 65 nm.

[0156] <Synthesis Examples 19-26> In each of Synthesis Examples 19 to 26, aluminum sulfate 14-18 hydrate, copolymer (1), and the metal compounds and sodium metasilicate nonahydrate shown in Table 1 below were charged in amounts such that the Si / Al ratios were as shown in Table 1, and a synthesis reaction was carried out in accordance with a method similar to Synthesis Example 18 to obtain aluminosilicate-containing compositions (19) to (26), respectively. The average particle size of each of the obtained aluminosilicate-containing compositions is as shown in Table 1. However, the metal compounds are expressed as molar ratios when the inorganic salts containing aluminum sulfate 14-18 hydrate, sodium metasilicate nonahydrate, and metal compounds are taken as 100 mol %.

[0157] <Synthesis Example 27> 104.8 g of copolymer (1) (solid content 40%) was adjusted to pH 8 with 30 wt% sodium hydroxide solution, and this was designated solution (E1). Next, 105.0 g of calcium nitrate tetrahydrate was dissolved in 66.4 g of ion-exchanged water to prepare a solution designated solution (E2). 95.9 g of sodium metasilicate nonahydrate was dissolved in 179.8 g of ion-exchanged water to prepare solution (3). Solution (E1) was heated to 75°C, and (E1) and (E2) were added dropwise over 18 minutes under a nitrogen atmosphere to obtain calcium silicate composition (27). The average particle size of the calcium silicate composition was 280 nm.

[0158] [Table 1]

[0159] The descriptions in Table 1 are as follows: TEA: Triethanolamine TIPA: Triisopropanolamine DIPA: Diisopropanolamine TMEDA: Tetramethylethylenediamine EDEA: Ethyldiethanolamine DMAE: Dimethylaminoethanol 1DMA2P: 1-dimethylamino-2-propanol In addition, wt% / particle in Table 1 represents the ratio relative to 100% by mass of the aluminosilicate particles.

[0160] The obtained aluminosilicate-containing compositions (1) to (26) and calcium silicate composition (27) were used to carry out various tests. The results are shown in Tables 3 to 6. <Early strength evaluation> (Mortar test) Mortar sample preparation: The mortar test was carried out under an environment of 20°C ± 1°C and 60% ± 15% relative humidity. The mortar mix is ​​shown in Table 2. however, C: Cement (ordinary Portland cement, manufactured by Taiheiyo Cement Corporation) LS: Heavy calcium carbonate (Softon 3200, Marutosha) CC: Calcined clay (Hyogo Clay Co., Ltd.) BFS: Blast furnace slag powder (Spirits 4000, manufactured by Nippon Steel Cement Co., Ltd.) g: Gypsum (Merck, calcium sulfate dihydrate) S: Fine aggregate (standard sand for cement strength testing, manufactured by the Cement Association) W: Ion-exchange aqueous solution of sample and antifoaming agent B: Powder (materials other than S and W) W contained the additives for hydraulic materials and the antifoaming agent obtained in the following Examples and Comparative Examples, and was dissolved thoroughly and uniformly in ion-exchanged water. Using a mortar mixer (Hobart mixer, model number: N-50), S and W were added to a mixing vessel and mixed at first speed for 30 seconds. While mixing at first speed, C was added over 15 seconds. 60 seconds after mixing began, the speed was changed to second speed and mixed for an additional 30 seconds. The mixer was then stopped, the mortar was scraped off for 30 seconds, and the mixture was allowed to stand for 60 seconds. After that, mixing was continued for an additional 60 seconds at second speed to prepare mortar. The air content was adjusted to less than 3.0% by adding an oxyalkylene antifoaming agent.

[0161] [Table 2]

[0162] (Compression strength measurement) After kneading, a sample for a compressive strength test was prepared, and the compressive strength was measured under the following conditions. The results are shown in Tables 3 to 6. Test specimen creation: 50mm x 100mm Test specimen curing (room temperature curing): The test specimen was cured at a constant temperature and humidity of 20°C and 50% for 24 hours. Test specimen curing (underwater curing): After 24 hours of constant temperature and humidity air curing at a temperature of 20°C and a humidity of 50%, the test specimen was further cured in water at a temperature of 20°C for 27 days. Specimen polishing: Specimen surface polishing (using a specimen polishing finishing machine) Compressive strength measurement: Automatic compressive strength measuring device (manufactured by Maekawa Manufacturing Co., Ltd.)

[0163] <Measurement of calorific value of hydration> (Preparation of paste sample) The compositions of the paste samples are shown in Tables 3 to 6 below, where: W: Sample and ion-exchanged aqueous solution C: Cement (ordinary Portland cement, manufactured by Taiheiyo Cement Corporation) W / C=0.4 Aluminosilicate-containing compositions (1) to (26) Calcium silicate composition (27) The amounts of additives added in Tables 3 to 6 are the ratios relative to 100% by mass of powder (components other than fine aggregate in mortar). The cement was placed in an ampoule and placed in the device, which was then adjusted to a temperature of 20°C. The mixture of the prepared sample and ion-exchanged aqueous solution was then measured into a syringe and poured into the ampoule, which had been adjusted to a temperature of 20°C, and kneaded for 5 minutes to prepare a paste sample. The heat release values ​​of the prepared paste samples were measured under the following conditions. Hydration calorific value measuring device: Microcalorimeter measuring device (manufactured by TA Instruments) Temperature: 20℃ The results are shown in Tables 3 to 6.

[0164] Table 3

[0165] Table 4

[0166] Table 5

[0167] Table 6

Claims

1. An aluminosilicate-containing composition comprising an aluminosilicate and a water-soluble polymer, the aluminosilicate-containing composition further comprises an amine and / or a metal compound having a molecular weight of 1000 or less; the metal compound is at least one selected from the group consisting of lithium sulfate, sodium sulfate, magnesium sulfate, zinc sulfate, iron sulfate, sodium nitrate, lithium nitrate, magnesium nitrate, zinc nitrate, iron nitrate, sodium carbonate, sodium acetate, lithium acetate, magnesium acetate, zinc acetate, and calcium nitrate; An aluminosilicate-containing composition having an average particle size of 10 to 500 nm as measured by the following method. <Method for measuring average particle size> Using a particle size measuring device, the scattering intensity of an aqueous dispersion of the aluminosilicate-containing composition having a solids content of 0.1% by mass is measured by dynamic light scattering, and the average particle size is calculated.

2. The aluminosilicate-containing composition according to claim 1, which is used in a hydraulic material composition containing at least one substance selected from the group consisting of substances having latent hydraulic and / or pozzolanic activity and fillers.

3. 3. The aluminosilicate-containing composition according to claim 1, wherein the content of the water-soluble polymer is 5 to 100% by mass relative to 100% by mass of the aluminosilicate.

4. 3. The aluminosilicate-containing composition according to claim 1, wherein the content of the aluminosilicate is 0.01 to 50 mass% relative to 100 mass% of the aluminosilicate-containing composition.

5. 2. The aluminosilicate-containing composition according to claim 1, wherein the amine is at least one selected from the group consisting of primary amines, secondary amines, and tertiary amines.

6. 2. The aluminosilicate-containing composition according to claim 1, wherein the total content of the amine and the metal compound is 0.01 to 500 mass% relative to 100 mass% of the aluminosilicate.

7. 3. The aluminosilicate-containing composition according to claim 2, wherein the substance having latent hydraulic and / or pozzolanic activity is at least one selected from the group consisting of slag, fly ash, clay, metakaolin, silica fume, silica powder, cinder ash, clinker ash, husk ash, bentonite, and calcite clay.

8. 3. The aluminosilicate-containing composition according to claim 2, wherein the filler is at least one selected from the group consisting of calcium carbonate, eco-calcium carbonate, concrete fines, concrete fines with immobilized carbon dioxide, waste concrete, and gypsum.

9. 3. The aluminosilicate-containing composition according to claim 1, wherein the water-soluble polymer has at least one functional group selected from the group consisting of a carboxyl group, a phosphoric acid group, a sulfonic acid group and salts thereof, a phosphoric acid ester group, and a hydroxyl group.

10. The aluminosilicate-containing composition according to claim 9 , wherein the water-soluble polymer further has a (poly)oxyalkylene group.

11. A hydraulic material composition comprising the aluminosilicate-containing composition of claim 1 and at least one selected from the group consisting of substances having latent hydraulic and / or pozzolanic activity and fillers.

12. A method for quickly improving the strength of a hydraulically set product, comprising: The method for improving the early strength of a hydraulically set product comprises the steps of adding the aluminosilicate-containing composition according to claim 1 or 2 to a hydraulic material and curing the composition obtained in the adding step.

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