Aluminosilicate-containing composition and method for producing the same

Abstract

To provide a composition having early strength development of a hydraulic property material composition and capable of suppressing costs.SOLUTION: An aluminosilicate-containing composition involves an aluminosilicate and a water-soluble polymer, wherein the aluminosilicate has an average particle diameter of 10-2500 nm measured by the following measuring method; by using a particle size measurement device, a scattering intensity of an aqueous dispersion of an aluminosilicate-containing composition having a solid content of 0.1 mass% is measured by dynamic light scattering method, and the average particle diameter is calculated.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an aluminosilicate-containing composition and a method for producing the same. More specifically, it relates to an aluminosilicate-containing composition useful as a hardening accelerator for hydraulic material compositions such as precast cement and a method for producing the same. [Background technology]

[0002] In contrast to the cast-in-place method, where formwork is set up at the construction site and concrete is poured, the precast method, in which the basic components of a concrete structure are manufactured in a factory and then brought to the site to assemble the structure, offers advantages such as shorter construction periods and reduced labor costs. In precast concrete construction, concrete is generally poured into formwork, hardened using a method called steam curing, which involves exposing the concrete to high temperature and constant humidity, and then removed from the formwork. In precast concrete construction, early strength development of the concrete is required to shorten the time until formwork removal.

[0003] Various technologies have been developed to improve the early strength of concrete. For example, Patent Document 1 discloses a mortar / concrete admixture containing rapid-hardening Portland cement, at least one of hemihydrate gypsum and anhydrous gypsum, sodium silicate, aluminum sulfate, and silica fume in specific proportions. Patent Document 2 discloses a mortar / concrete admixture containing (A) rapid-hardening Portland cement, (B) at least one of hemihydrate gypsum and anhydrous gypsum, (C) sodium silicate, and (D) aluminum sulfate in specific proportions. Patent Document 3 discloses a cement composition having Al2O3 and SO3 as chemical components and a molar ratio of [SO3] / [Al2O3] of 0.4 to 1.05. Patent Document 4 discloses a method for producing a curing accelerator composition by reaction of a water-soluble calcium compound and a water-soluble silicate compound, wherein the reaction between the water-soluble calcium compound and the water-soluble silicate compound is carried out in the presence of an aqueous solution containing a water-soluble comb-shaped polymer suitable as a plasticizer for a hydraulic binder.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0005] <000​​​​​​​​​​​​​​​In other words, the present invention relates to an aluminosilicate-containing composition comprising an aluminosilicate and a water-soluble polymer, wherein the aluminosilicate is an aluminosilicate-containing composition having an average particle diameter of 10 to 2500 nm, as measured by the following measurement method. <Method for measuring average particle size> Using a particle size analyzer, the scattering intensity of an aqueous dispersion of an aluminosilicate-containing composition with a solid content of 0.1% by mass is measured by dynamic light scattering, and the average particle size is calculated.

[0009] The above water-soluble polymer preferably has at least one functional group selected from carboxyl groups, phosphate groups, sulfonic acid groups and salts thereof, as well as phosphate ester groups and hydroxyl groups.

[0010] The above water-soluble polymer preferably has a weight-average molecular weight of 1,000 to 100,000.

[0011] In the above water-soluble polymer, it is preferable that the proportion of structural units derived from monomers having at least one selected from carboxyl groups, phosphate groups, sulfonic acid groups, and salts thereof is 50 to 95 mol% of the total structural units.

[0012] The above water-soluble polymer preferably further has (poly)oxyalkylene groups.

[0013] The above aluminosilicate-containing composition may also contain an aluminum-containing compound and / or a silicon-containing compound, and the content of the above water-soluble polymer is preferably 5 to 1000% by mass relative to the total content of the aluminosilicate, aluminum-containing compound and silicon-containing compound (100% by mass).

[0014] The silicon atom content in the above aluminosilicate-containing composition is preferably 1 to 1000 mol% per 100 mol% of aluminum atoms.

[0015] The content of the above-mentioned water-soluble polymer is preferably 0.025 to 90.9% by mass based on 100% by mass of the aluminosilicate-containing composition.

[0016] The content of the above-mentioned aluminosilicate is preferably 0.5 to 50% by mass based on 100% by mass of the aluminosilicate-containing composition.

[0017] The above aluminosilicate-containing composition preferably contains water, and the aluminosilicate is dispersed in a quantity of 0.5 to 50 g per 100 g of water.

[0018] The present invention also includes a curing accelerator composition comprising an aluminosilicate, wherein the aluminosilicate 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 analyzer, the scattering intensity of a 0.1% by mass aqueous dispersion of the curing accelerator composition is measured by dynamic light scattering, and the average particle size is calculated.

[0019] Preferably, the above curing accelerator composition further contains a water-soluble polymer.

[0020] The above water-soluble polymer preferably has at least one functional group selected from carboxyl groups, phosphate groups, sulfonic acid groups and salts thereof, as well as phosphate ester groups and hydroxyl groups.

[0021] The above water-soluble polymer preferably further has (poly)oxyalkylene groups.

[0022] The above curing accelerator composition may contain an aluminum-containing compound and / or a silicon-containing compound, and the content of the water-soluble polymer is preferably 5 to 1000% by mass relative to the total content of aluminosilicate, aluminum-containing compound, and silicon-containing compound (100% by mass).

[0023] The silicon atom content in the above curing accelerator composition is preferably 1 to 1000 mol% relative to 100 mol% of aluminum atoms.

[0024] The content of the above-mentioned water-soluble polymer is preferably 0.0025 to 90.9% by mass based on 100% by mass of the curing accelerator composition.

[0025] The content of the above-mentioned aluminosilicate is preferably 10 to 100% by mass relative to 100% by mass of the curing accelerator composition.

[0026] The above curing accelerator composition preferably contains water, and the aluminosilicate is dissolved in 0.05 to 50 g of water per 100 g.

[0027] The present invention also relates to a hydraulic material composition comprising the above-mentioned aluminosilicate-containing composition and / or the above-mentioned hardening accelerator composition and a hydraulic material.

[0028] The above hydraulic material composition is preferably used in precast cement.

[0029] The present invention further relates to a method for producing an aluminosilicate-containing composition, the production method comprising a step (α) of reacting an aluminum-containing compound with a silicon-containing compound in the presence of a water-soluble polymer.

[0030] The amount of water-soluble polymer used in step (α) above is preferably 5 to 1000% by mass relative to 100% by mass of the total amount of aluminum-containing compound and silicon-containing compound used.

[0031] The silicon atom content in the raw materials used in the above step (α) is preferably 1 to 1000 mol% per 100 mol% of aluminum atoms.

[0032] The above step (α) is preferably carried out while stirring in water.

[0033] The present invention further relates to a method for producing a hydraulic material composition, the production method comprising the step (β) of adding the aluminosilicate-containing composition obtained by the above production method to a hydraulic material.

[0034] The present invention further relates to a method for producing a hydraulically hardened product, the production method comprising a step (γ) of hardening the hydraulic material composition obtained by the production method.

[0035] The present invention further relates to a method for rapidly improving the strength of a hydraulically hardened product, the method comprising the steps of adding the aluminosilicate-containing composition and / or hardening accelerator composition to a hydraulic material and hardening the composition obtained in the addition step. [Effects of the Invention]

[0036] The aluminosilicate-containing composition of the present invention has the above-described structure, exhibits excellent early strength development, and can suppress costs, making it suitable for use as a hardening accelerator for hydraulic material compositions such as precast cement. [Modes for carrying out the invention]

[0037] Preferred embodiments of the present invention will be described below in detail, but the present invention is not limited to the following descriptions and can be modified and applied as appropriate without changing the gist of the present invention. Furthermore, embodiments combining two or more of the individual preferred embodiments of the present invention described below also constitute preferred embodiments of the present invention.

[0038] <Aluminosilicate-containing composition> The aluminosilicate-containing composition of the present invention comprises aluminosilicate and a water-soluble polymer, wherein the average particle size of the aluminosilicate, as measured by the above measurement method, is 10 to 2500 nm. It is believed that having an average particle size of aluminosilicate within this range improves 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, thereby promoting the pozzolanic reaction and enabling the development of early strength. The method described in Patent Document 4 enhances the strength of hydraulically hardened products by promoting the hydration reaction of tricalcium silicate in cement using calcium silicate hydrate, and this mechanism differs from the mechanism by which the aluminosilicate-containing composition of the present invention exhibits early strength. In Patent Document 4, the reaction in which calcium silicate hydrate is added increases the amount of heat generated compared to the case without the addition, whereas in the reaction using aluminosilicate in the present invention, no increase in the amount of heat generated is observed. Therefore, when the aluminosilicate-containing composition of the present invention is used as a curing accelerator, the initial rapid increase in heat generation is suppressed, and thus temperature-induced cracking can be suppressed.

[0039] The average particle size of the above aluminosilicate is preferably 10 to 2000 nm, more preferably 10 to 1000 nm, even more preferably 10 to 800 nm, even more preferably 10 to 500 nm, even more preferably 10 to 250 nm, even more preferably 10 to 200 nm, particularly preferably 10 to 150 nm, and most preferably 10 to 100 nm.

[0040] The above aluminosilicate is not particularly limited as long as it is a compound having a structure in which some of the silicon atoms in the silicate are replaced with aluminum atoms, for example, the following formula (1); pM 1 2O·qAl2O3·rSiO2·mH2O (1) (In the formula, p, q, r, and m represent integers. M 1 ) represents an alkali metal atom. ) can be represented as .

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

[0042] The above-mentioned aluminum-containing compounds and silicon-containing compounds are not particularly limited, but examples include unreacted raw materials used in the production of aluminosilicate-containing compositions. Examples of the above-mentioned aluminum-containing compounds include aluminum sulfate, aluminum nitrate, aluminum chloride, basic aluminum acetate, aluminum formosetate, and aluminum acetylacetonate, with aluminum sulfate being preferred. Examples of the silicon-containing compounds mentioned above 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 aluminosilicate content is preferably 0.5 to 50% by mass, based on 100% by mass of the aluminosilicate-containing composition. More preferably, it is 1 to 50% by mass, even more preferably 5 to 40% by mass, and particularly preferably 5 to 30% by mass.

[0044] The above aluminosilicate-containing composition contains water, and preferably contains 0.5 to 50 g of aluminosilicate dispersed per 100 g of water. More preferably 1 to 50 g, even more preferably 5 to 40 g, and particularly preferably 5 to 30 g.

[0045] The above aluminosilicate-containing composition contains a water-soluble polymer, and its content is preferably 0.025 to 90.9% by mass, based on 100% by mass of the aluminosilicate-containing composition. More preferably, it is 1 to 50% by mass, even more preferably 5 to 40% by mass, and particularly preferably 10 to 20% by mass.

[0046] The content of the above water-soluble polymer is preferably 5 to 1000% by mass, based on 100% by mass of the total content of aluminosilicate, aluminum-containing compound, and silicon-containing compound. More preferably, it is 10 to 500% by mass, even more preferably 50 to 200% by mass, and particularly preferably 75 to 125% by mass.

[0047] The above water-soluble polymer is not particularly limited as long as the insoluble portion when 100g is dissolved in 100g of water is 50g or less, but it is preferable that it has at least one functional group selected from carboxyl groups, phosphate groups, sulfonic acid groups and salts thereof, as well as phosphate ester groups and hydroxyl groups. Preferably, these are carboxyl groups, phosphate groups, sulfonic acid groups, and salts thereof, and more preferably, carboxyl groups or salts thereof.

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

[0049] If the above-mentioned water-soluble polymer has at least one functional group selected from carboxyl groups, phosphate groups, sulfonic acid groups and their salts, as well as phosphate ester groups and hydroxyl groups, and the weight-average molecular weight of the water-soluble polymer is within the above-mentioned preferred range, then the functional group will adsorb to the aluminosilicate, and the steric repulsion of the water-soluble polymer will more sufficiently disperse the aluminosilicate, thereby more sufficiently suppressing the aggregation of the aluminosilicate. As a result, 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, the pozzolanic reaction is more accelerated, and the early development of strength is further improved.

[0050] When the above water-soluble polymer has at least one selected from carboxyl groups, phosphate groups, sulfonic acid groups, and salts thereof, it is preferable that the proportion of structural units derived from monomers having at least one selected from carboxyl groups, phosphate groups, sulfonic acid groups, and salts thereof (hereinafter also referred to as monomers having acid groups) is 50 to 95 mol% of the total structural units. This further improves the adsorption to aluminosilicate. The proportion of structural units derived from monomers having acid groups 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 the carboxyl group or a salt thereof (hereinafter also referred to as a carboxylic acid-based water-soluble polymer) is not particularly limited, but examples include polymers having structural units derived from unsaturated carboxylic acid monomers and polymers having structural units derived from monomers having a carboxyl group and an aromatic group. Suitable unsaturated carboxylic acid monomers include unsaturated monocarboxylic acid monomers and unsaturated dicarboxylic acid monomers. Suitable unsaturated monocarboxylic acid monomers include any monomer having one unsaturated group and one group capable of forming a carbanion in its molecule, such as (meth)acrylic acid, crotonic acid, tigric acid, 3-methylcrotonic acid, 2-methyl-2-pentenoic acid, itaconic acid, etc. Monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts of these are preferred. The above-mentioned unsaturated dicarboxylic acid monomers may be any monomer having one unsaturated group and two groups capable of forming a carbanion within the molecule. Maleic acid, itaconic acid, mesaconic acid, citraconic acid, fumaric acid, etc., or their monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts, their anhydrides, or half-esters are preferred.

[0052] Examples of monomers having a carboxyl group and an aromatic group include one or more monomers selected from benzene compounds having a carboxyl group and which may have substituents other than the carboxyl group, and naphthalene compounds having a carboxyl group and which may have substituents other than the carboxyl group, with benzene compounds having a carboxyl group and which may have substituents other than the carboxyl group being preferred. Specifically, examples include one or more monomers selected from hydroxybenzoic acid, benzoic acid, isophthalic acid, oxynaphthoic acid, and their isomers, with one or more monomers selected from hydroxybenzoic acid and benzoic acid being preferred, and hydroxybenzoic acid being more preferred.

[0053] The water-soluble polymer having the above-mentioned phosphate group or its salt or phosphate ester group (hereinafter also referred to as a phosphate-based water-soluble polymer) is not particularly limited, but the following formula (2); -OPO3M 2 2(2) (In the formula, M 2 It is preferable to have a group represented by ), which may be the same or different, 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 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 (3);

[0055] [Chemical formula]

[0056] (In the formula, M 2 represents, independently or differently, 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. Q 1 represents a direct bond or a divalent linking group. R 1 represents a hydrogen atom or a substituent other than a phosphate group and a phosphate ester group.) is more preferably one having a structural unit represented by the formula. The above Q 1 -OPO3M 2 2, R 1 The bonding position and the number of bonds of are not particularly limited, and a plurality of them 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 hetero atom. More preferably, it is a (poly)oxyalkylene group. Specific examples and preferred examples of the oxyalkylene group are the same as those of the oxyalkylene group described later, and most preferably it is an oxyethylene group. The average addition mole number of the (poly)oxyalkylene group is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 2, and most preferably 1.

[0058] The above R 1 ​​Examples of substituents include alkyl groups having 1 to 10 carbon atoms, aliphatic hydrocarbon groups such as alkenyl groups, alkoxy groups, hydroxyl groups, acyl groups, ether groups, amide groups, ester groups, ketone groups, carboxyl groups, salts of carboxyl groups, sulfonic acid groups, salts of sulfonic acid groups, and (poly)alkylene glycol chain-containing groups.

[0059] Specific examples of the above-mentioned phosphate group-containing monomers include, for example, phenoxyethanol, phenoxydiglycol, (methoxyphenoxy)ethanol, methylphenoxyethanol, bis(β-hydroxyethyl)hydroquinone ether, nonylphenol, phenol, cresol, resorcinol, catechol, hydroquinone, naphthol, and phosphorus oxides of aromatic alcohols and quinones such as furfuryl alcohol. Specific examples of the above-mentioned phosphorus oxides 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. Preferably, the phosphate is phenoxyethanol phosphate, phenoxydiglycol phosphate, or bis(β-hydroxyethyl)hydroquinone ether diphosphate, and more preferably, phenoxyethanol phosphate. For the phosphorylation of the above aromatic alcohols and quinones, it is preferable to use phosphoric acid compounds such as phosphoric acid (salt) or polyphosphate (salt).

[0060] The water-soluble polymer having the above-mentioned 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 include polymers having structural units derived from unsaturated sulfonic acid monomers, polymers having structural units derived from monomers having a sulfonic acid group and an aromatic group, etc. Examples of polymers having structural units derived from monomers having a sulfonic acid group and an aromatic group include naphthalene sulfonic acid formaldehyde condensate, melamine sulfonic acid formaldehyde condensate, lignin sulfonic acid, polystyrene sulfonate, etc.

[0061] The above unsaturated sulfonic acid monomers are not particularly limited as long as they have a sulfonic acid (salt) group and an ethylenically unsaturated hydrocarbon group, but examples 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)allylsulfonic acid, isoprenesulfonic acid, 4-(allyloxy) Examples include benzosulfonic 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] Examples of monomers having a sulfonic acid group and an aromatic group include one or more monomers selected from benzene compounds having a sulfonic acid group and which may have substituents other than the sulfonic acid group, and naphthalene compounds having a sulfonic acid group and which may have substituents other than the sulfonic acid group, with benzene compounds having a sulfonic acid group and which may have substituents other than the sulfonic acid group being preferred. Specifically, examples include one or more monomers selected from benzenesulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid, alkylnaphthalenesulfonic acid, naphtholsulfonic acid, and their isomers, with one or more monomers selected from benzenesulfonic acid and phenolsulfonic acid being preferred, and phenolsulfonic acid being more preferred.

[0063] Examples of water-soluble polymers having hydroxyl groups include polyvinyl alcohol and its modified products; hydroxyethyl (meth)acrylic water-soluble polymers; and hydroxypropyl (meth)acrylic water-soluble polymers.

[0064] The above water-soluble polymer preferably has a (poly)oxyalkylene group in addition to a carboxyl group, a phosphate group, a sulfonic acid group and salts thereof, and at least one functional group selected from a phosphate ester group and a hydroxyl group. The presence of these groups in the water-soluble polymer improves the dispersibility of the aluminosilicate, further promotes the pozzolanic reaction, and enhances early strength development.

[0065] The above (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 preferably, alkylene oxides having 2 to 4 carbon atoms, such as ethylene oxide, propylene oxide, and butylene oxide, and even more preferably, ethylene oxide and propylene oxide. Furthermore, if the (poly)oxyalkylene group is any two or more alkylene oxide adducts selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc., it may be in any form such as random addition, block addition, or alternating addition. In order to ensure a balance between hydrophilicity and hydrophobicity, it is preferable that the (poly)alkylene glycol contains an oxyethylene group as an essential component, more preferably 50 mol% or more being oxyethylene groups, and even more preferably 90 mol% or more being oxyethylene groups.

[0066] The average number of moles n added by the oxyalkylene groups is preferably 1 to 500. The larger the average number of moles added, the better the hydrophilicity of the resulting polymer and the better the dispersion performance tends to be. If it is 500 or less, the 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, particularly preferably 15 to 150, and most preferably 20 to 100.

[0067] If the above water-soluble polymer has a (poly)oxyalkylene group, it is preferable that the polymer has structural units derived from a (poly)oxyalkylene group-containing monomer. The monomer containing the (poly)oxyalkylene group is not particularly limited, but the following formula (4);

[0068] [ka]

[0069] (In the formula, R 2 , R 3 and R 4 R represents a hydrogen atom or a methyl group, either identical or distinct. 5 (R) represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. 6O) represents an oxyalkylene group, whether identical or different. 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. Examples include compounds represented by ) and monomers having an (poly)alkylene glycol chain and an aromatic group and / or a heterocyclic aromatic group (hereinafter also referred to as aromatic group-containing (poly)alkylene glycol monomers).

[0070] In the above equation (4), (R 6 The preferred form of the oxyalkylene group represented by O) is as described above, and the preferred range of n1 is the same as that of n above. In equation (4) above, R 2 , R 3 and R 4 These are, either the same or different, a hydrogen atom or a methyl group. Preferably R 2 , R 3 is a hydrogen atom, R 4 This is a hydrogen atom or a methyl group.

[0071] In equation (4) above, R 5 The hydrocarbon group can be a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. Preferably, the hydrocarbon group having 1 to 30 carbon atoms does not have a radically polymerizable unsaturated bond. Suitable hydrocarbon groups include alkyl groups having 1 to 30 carbon atoms (aliphatic alkyl groups or alicyclic alkyl groups), phenyl groups having 6 to 30 carbon atoms, alkylphenyl groups, phenyl alkyl groups, phenyl groups substituted with (alkyl)phenyl groups, and aromatic groups having a benzene ring such as naphthyl groups. However, as the number of carbon atoms in the hydrocarbon group increases, the hydrophobicity increases and the 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, even more preferably 1 to 12, and particularly preferably 1 to 4. 5 The most preferred examples are hydrogen atoms or hydrocarbon groups having 1 to 4 carbon atoms.

[0072] In the above formula (4), x represents a number from 0 to 2, and y represents 0 or 1. When y is 0, the compound represented by formula (4) becomes an ether monomer, in which case x is preferably 2. Also, in this case, R 4 It is more preferable that it be a methyl group. When y is 1, the compound represented by formula (4) becomes an ester monomer, and in this case, x is preferably 0. Also, in this case, R 4 is more preferably a hydrogen atom or a methyl group, and even more preferably R 4 This is a methyl group. In equation (4) above, y is 0, and R 5 Examples of compounds in which the atom is a hydrogen atom include (poly)ethylene glycol allyl ether, (poly)ethylene glycol metharyl ether, (poly)ethylene glycol 3-methyl-3-butenyl ether, (poly)ethylene (poly)propylene glycol allyl ether, (poly)ethylene (poly)propylene glycol metharyl ether, (poly)ethylene (poly)propylene glycol 3-methyl-3-butenyl ether, (poly)ethylene (poly)butylene glycol allyl ether, (poly)ethylene (poly)butylene glycol metharyl ether, and (poly)ethylene (poly)butylene glycol 3-methyl-3-butenyl ether.

[0073] In equation (4) above, y is 0, and R 5Examples of compounds in which the group has 1 to 30 carbon atoms include methoxy(poly)ethylene glycol allyl ether, methoxy(poly)ethylene glycol metharyl ether, methoxy(poly)ethylene glycol 3-methyl-3-butenyl ether, methoxy(poly)ethylene(poly)propylene glycol allyl ether, methoxy(poly)ethylene(poly)propylene glycol metharyl 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 metharyl ether, and methoxy(poly)ethylene(poly)butylene glycol 3-methyl-3-butenyl ether.

[0074] In equation (4) above, y is 1, and R 5 Examples of compounds in which the atom is a hydrogen atom 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 equation (4) above, y is 1, and R 5Compounds in which the hydrocarbon group has 1 to 30 carbon atoms include methoxypolyethylene glycol mono(meth)acrylate, methoxypolypropylene glycol mono(meth)acrylate, methoxypolybutylene glycol mono(meth)acrylate, methoxypolyethylene glycol polypropylene 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 mono(meth)acrylate, ethoxypolypropylene glycol mono(meth)acrylate, ethoxypolybutylene glycol mono(meth)acrylate, ethoxypolyethylene glycol polypropylene glycol mono(meth)acrylate, Examples include alkoxypolyalkylene glycol (meth)acrylates in which the alkoxy group has 1 to 30 carbon atoms, such as 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 formula (4) above is preferably (poly)ethylene glycol metharyl ether, (poly)ethylene glycol 3-methyl-3-butenyl ether, or methoxypolyethylene glycol mono(meth)acrylate.

[0077] Examples of the above-mentioned aromatic group-containing (poly)alkylene glycol monomers include compounds obtained by adding an alkylene oxide to the above-mentioned aromatic alcohols; such as aromatic amines like aniline. Preferably, these 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 above aromatic group-containing (poly)alkylene glycol monomers, the following formula (5);

[0078] [ka]

[0079] (In the formula, Q 2 R represents a direct bond or a divalent linking group. 7 R represents a hydrogen atom or a substituent other than a phosphate base and a phosphate ester group. 6 O represents an oxyalkylene group having 2 to 18 carbon atoms, either identical or different. 8 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. It is preferable that the structural unit has the structure represented by ).

[0080] The above Q 2 Examples of divalent linking groups in this formula include oxygen atoms, sulfur atoms, halogen atoms, -NH- groups, and divalent hydrocarbon groups which may have heteroatoms. Divalent hydrocarbon groups which may have heteroatoms are represented by Q in formula (3) above. 1 This is similar to a divalent hydrocarbon group which may have a heteroatom. Q 2 Preferably, it is an oxygen atom, -NH-, and more preferably an oxygen atom. R 8 The hydrocarbon group having 1 to 30 carbon atoms in the above formula (4) is R 5 This is similar to hydrocarbon groups with 1 to 30 carbon atoms in [the relevant context]. R 8 A hydrogen atom is preferred as the atom. n2 is preferably 5 to 200, more preferably 10 to 150, and even more preferably 12 to 120.

[0081] As the above aromatic group-containing (poly)alkylene glycol monomer, 2-phenoxyethanol, phenoxy polyethylene glycol, and the like are preferred.

[0082] When the above carboxylic acid-based water-soluble polymer has a (poly)oxyalkylene group, it is preferable that the polymer has a structural unit (a) derived from an unsaturated carboxylic acid monomer and a structural unit (b) derived from the compound represented by the above formula (4), 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. If the carboxylic acid-based water-soluble polymer is a polymer having structural units (a) derived from an unsaturated carboxylic acid monomer and structural units (b) derived from the compound represented by the above formula (4), it may also have structural units (c) derived from other monomers.

[0083] Other monomers are not particularly limited as long as they can copolymerize with unsaturated carboxylic acid monomers and compounds represented by formula (4) above, but for example, 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 alkyl (poly)alkylene glycols obtained by adding 1 to 300 moles of alkylene oxide having 2 to 18 carbon atoms to the above alcohols or amines with the above unsaturated dicarboxylic acids; Diesters of benzoic acid with glycols having 2 to 18 carbon atoms or polyalkylene glycols with 2 to 300 added moles of these glycols; esters of unsaturated monocarboxylic acids such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, glycidyl (meth)acrylate, methyl crotonate, ethyl crotonate, and propyl crotonate with alcohols having 1 to 30 carbon atoms; halfamides of maleamic acid with glycols having 2 to 18 carbon atoms or polyalkylene glycols with 2 to 300 added moles of these glycols.

[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 dimarates such as triethylene glycol dimarate, polyethylene glycol dimarate; 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, 3-(meth)ac Unsaturated sulfonic acids such as lyloxy-2-hydroxypropyloxysulfobenzoate, 4-(meth)acryloxybutylsulfonate, (meth)acrylamide methylsulfonic acid, (meth)acrylamide ethylsulfonic 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-chlor-1,3-butadiene.

[0085] Unsaturated amides such as (meth)acrylamide, (meth)acrylalkylamide, N-methylol(meth)acrylamide, N,N-dimethyl(meth)acrylamide; unsaturated cyanides such as (meth)acrylonitrile, α-chloroacrylonitrile; unsaturated esters such as vinyl acetate, vinyl propionate; unsaturated amines such as (meth)aminoethyl acrylate, (meth)methylaminoethyl acrylate, (meth)dimethylaminoethyl acrylate, (meth)dimethylaminopropyl acrylate, (meth)dibutylaminoethyl acrylate, vinylpyridine; divinyl aromatics such as divinylbenzene; cyanurates such as triallyl cyanurate; (meth)allyl Examples include allyl compounds such as glycidyl(meth)allyl ether; and siloxane derivatives such as polydimethylsiloxane-propylaminomaleamidoic acid, polydimethylsiloxane-aminopropyleneaminomaleamidoic acid, polydimethylsiloxane-bis-(propylaminomaleamidoic acid), polydimethylsiloxane-bis-(dipropyleneaminomaleamidoic 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 carboxylic acid-based water-soluble polymer, the content of structural unit (a) is preferably 7 to 50% by mass relative to 100% by mass of the total structural units. More preferably, it is 10 to 45% by mass, and even more preferably 12 to 30% by mass. In the above carboxylic acid-based water-soluble polymer, the content of structural unit (b) is preferably 50 to 93% by mass relative to 100% by mass of the total structural units. More preferably, it is 55 to 90% by mass, and even more preferably 70 to 88% by mass. In the above carboxylic acid-based water-soluble polymer, the proportion of structural unit (c) is preferably 0 to 40% by mass relative to 100% by mass of the total structural units. 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.

[0087] Specifically, polymers having structural units derived from the above-mentioned unsaturated carboxylic acid monomers and structural units derived from the compound represented by formula (4) include copolymers consisting of (alkoxy)polyalkylene glycol mono(meth)acrylic acid ester monomer (a), (meth)acrylic acid monomer (b) in an amount of 95-2% by weight, and other monomers (c) copolymerizable with these monomers, as described in Japanese Patent Publication No. 9-86990; and as described in Japanese Patent Publication No. 2001-220417. A copolymer comprising a constituent unit (I) derived from an unsaturated polyalkylene glycol ether monomer (a) having a C5 alkenyl group and a constituent unit (II) derived from an unsaturated monocarboxylic acid monomer (b) as essential constituent units; as described in Japanese Patent Publication No. 2002-121055, a copolymer comprising a constituent unit (I) derived from an unsaturated polyalkylene glycol ether monomer (a) having a C4 alkenyl group and a constituent unit (II) derived from an unsaturated monocarboxylic acid monomer (b) Examples include copolymers containing (II) as an essential structural unit; copolymers containing (I) derived from an unsaturated polyalkylene glycol ether monomer (a) having an alkenyl group with 2 or 3 carbon atoms, and (II) derived from an unsaturated monocarboxylic acid monomer (b), as described in Japanese Patent Publication No. 2002-121056; copolymers comprising an unsaturated polyalkylene glycol ether monomer (I) having an alkenyl group with 5 carbon atoms, an unsaturated maleic acid monomer (II), and monomers copolymerizable with these monomers, as described in Japanese Patent Publication No. 10-236858; and copolymers containing (A) derived from polyethylene glycol monovinyl ethers, (B) derived from an unsaturated carboxylic acid monomer, and (C) derived from (hydroxy)alkyl (meth)acrylates, etc., as essential structural units, as described in Japanese Patent Publication No. 2004-307590.

[0088] When the above 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 is preferable that it has structural units derived from a monomer having a carboxyl group and an aromatic group, and structural units represented by the above formula (5). In this case, the molar ratio (former / latter) of the structural unit derived from the monomer having the carboxyl group and the aromatic group to the structural unit represented by formula (5) is preferably 0.1 to 9. More preferably, it is 0.25 to 4.

[0089] When the above 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 also have other 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 other structural units include the above-mentioned structural units derived from a monomer having a sulfonic acid group and an aromatic group, structural units derived from a monomer having a phosphate (salt) group and / or a phosphate ester group and an aromatic ring group, and structural units derived from other aromatic groups as described later. The ratio of the above-mentioned structural units derived from a monomer having a carboxyl group and an aromatic group to the structural units other than the structural units represented by formula (5) is not particularly limited, but it is preferably 0 to 50 mol% relative to 100 mol% of the total of the above-mentioned structural units derived from a monomer having a carboxyl group and an aromatic group and the structural units represented by formula (5). More preferably 0 to 40 mol%, even more preferably 0 to 30 mol%, and most preferably 0 mol%.

[0090] When the above-mentioned phosphoric acid-based water-soluble polymer has a (poly)oxyalkylene group, it is preferable that it has a structural unit represented by formula (3) and a structural unit represented by formula (5). In this case, the molar ratio (equation (3) / equation (5)) of the structural unit represented by formula (3) to the structural unit represented by formula (5) is preferably 0.3 to 4. More preferably 0.4 to 3.5, and even more preferably 0.45 to 3.

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

[0092] In polymers having structural units derived from monomers having the above-mentioned aromatic groups, it is preferable that the above-mentioned structural units are bonded by divalent linking groups derived from aldehyde compounds. Examples of the above-mentioned aldehyde compounds include formaldehyde; compounds having an alkyl group with 1 to 5 carbon atoms and an aldehyde group, such as acetaldehyde, propionaldehyde, and butanal; and glyoxylic acid, benzaldehyde, and paraformaldehyde. Preferably, formaldehyde, benzaldehyde, and paraformaldehyde are used, with formaldehyde being the most preferred.

[0093] For example, the form in which the structural unit represented by formula (3) and the structural unit represented by formula (5) are linked by a divalent linking group derived from an aldehyde compound is shown in formula (6);

[0094] [ka]

[0095] (In the formula, M 2 Q represents, either identically or differently, 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 R represents a direct bond or a divalent linking group, whether identical or different. 1 R represents a hydrogen atom or a substituent other than a phosphate base and a phosphate ester group, whether identical or different. 6 O represents an oxyalkylene group having 2 to 18 carbon atoms, either identical or different. 8 n² 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 between 1 and 500. In polymers having structural units derived from monomers having aromatic groups, such as the above-mentioned phosphoric acid-based water-soluble polymers, it is preferable that each monomer-derived structural unit is bonded by a methylene group.

[0096] Specifically, examples of phosphate-based water-soluble polymers having structural units derived from monomers with aromatic groups include polycondensation products consisting of the following components C1, C3, and optionally C2, as described in Japanese Patent Publication No. 2008-517080. [Component C1] Aromatic compounds or heteroaromatic compounds having 5 to 10 carbon atoms or heteroatoms, wherein the aromatic compound or heteroaromatic compound contains an average of 1 to 300 oxyethylene and / or oxypropylene groups per molecule, bonded to the aromatic compound or heteroaromatic compound via an O atom or N atom. [Component C2] At least one aromatic compound as an optional component, 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 its derivatives, urea or its derivatives, and carboxamide. [Component C3] An aldehyde selected from the group consisting of formaldehyde, glyoxylic acid, and benzaldehyde, or mixtures thereof (wherein benzaldehyde may further have an acidic group represented by the formula 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 above-mentioned phosphate-based water-soluble polymer may not have aromatic groups in its structure. For example, such a form may be a phosphate group-containing monomer represented by the following formulas (7) and / or (8);

[0098] [ka]

[0099] (In the formula, R 9 , R 11 , R 14 OR represents a hydrogen atom or a methyl group, either identical or different. 10 , OR 12 , OR 13 This represents an oxyalkylene group having 2 to 18 carbon atoms, which may be identical or different. 3 , n 4 , n 5 These represent numbers from 1 to 30, either identical or different. 2 M in equation (6) 2 This is similar to the above. Examples include those having a monomer-derived structural unit represented by ).

[0100] Examples of phosphoric acid-based water-soluble polymers that do not have aromatic groups in their structure include polymers having structural units derived from monomers represented by formula (7) and / or (8) and structural units derived from compounds represented by formula (4). Specifically, examples include copolymers consisting of (alkoxy)polyalkylene glycol mono(meth)acrylic acid ester monomers and phosphoric acid ester monomers, as described in Japanese Patent Application Publication No. 2006-052381.

[0101] Preferred water-soluble polymers include carboxylic acid-based water-soluble polymers, phosphate-based water-soluble polymers, and sulfonic acid-based water-soluble polymers. As carboxylic acid-based water-soluble polymers, (poly)ethylene glycol metharyl 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 are more preferred. As the phosphoric acid-based water-soluble polymer, a polymer having the structure represented by the above formula (6) is more preferred. As sulfonic acid-based water-soluble polymers, naphthalene sulfonic acid formaldehyde condensate, melamine sulfonic acid formaldehyde condensate, lignin sulfonic acid, polystyrene sulfonate, and the like are more preferred.

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

[0103] The aluminosilicate-containing composition of the present invention may contain other components besides aluminosilicate, water-soluble polymer, aluminum-containing compound, and silicon-containing compound. Other ingredients are not particularly limited, but examples include defoaming agents, air-enhancing agents, surfactants, etc. The content ratio of other components is not particularly limited, but it is preferably 0 to 20% by mass relative to 100% by mass of the aluminosilicate-containing composition. More preferably it is 0 to 10% by mass, even more preferably 0 to 5% by mass, and particularly preferably 0 to 1% by mass.

[0104] As the surfactants mentioned above, one or more types of anionic, cationic, nonionic, and amphoteric surfactants, as well as polymeric surfactants, can be used. The above-mentioned anionic surfactants are not particularly limited and include, for example, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene oleyl ether sodium sulfates, polyoxyalkylene alkylphenyl ether sulfates, alkyl diphenyl ether disulfonates, polyoxyalkylene (mono, di, tri) styrylphenyl ether sulfates, polyoxyalkylene (mono, di, tri) benzylphenyl ether sulfates, alkenyl succinate disalts; alkyl sulfate salts such as sodium dodecyl sulfate, potassium dodecyl sulfate, and ammonium alkyl sulfate; sodium dodecyl polyglycol ether sulfate; and Examples include thorium sulforisinoates; alkyl sulfonates such as sulfonated paraffin salts; alkyl sulfonates such as sodium dodecylbenzene sulfonate and alkali metal sulfates of alkali phenol hydroxyethylene; high alkylnaphthalene sulfonates; naphthalene sulfonic acid formalin condensates; fatty acid salts such as sodium laurate, triethanolamine oleate, and triethanolamine abietate; polyoxyalkyl ether sulfates; polyoxyethylene carboxylic acid sulfates; polyoxyethylene phenyl ether sulfates; dialkyl succinate 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, Perex SS-H, Emulgen A-60, B-66, Revenol WZ (manufactured by Kao Corporation), Newcol 707SF, Newcol 707SN, Newcol 714SF, Newcol 714SN, AB-26S, ABEX-2010, 2020, 2030, and DSB (manufactured by Rhodia Nikka Co., Ltd.). In addition, surfactants equivalent to these nonionic types can also be used.

[0106] As the above-mentioned anionic surfactant, one or more types of reactive surfactants can be used, such as reactive anionic surfactants, sulfosuccinate-type reactive anionic surfactants, and alkenylsuccinate-type reactive anionic surfactants. Examples of 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), Eleminor JS-2 (trade name, manufactured by Sanyo Chemical Industries), and Adekarya Soap SR-10, SR-20, and SR-30 (manufactured by ADEKA Corporation). Examples of commercially available alkenyl succinate-type reactive anionic surfactants include Latemul ASK (trade name, manufactured by Kao Corporation). Furthermore, sulfate esters (salts) having an allyl group, such as polyoxyethylene sulfonate (meth)acrylate salts (e.g., "Eleminol RS-30" manufactured by Sanyo Chemical Industries, Ltd., "Antox MS-60" manufactured by Nippon Emulsifier Co., Ltd.), sulfonate salts of allyloxymethylalkyloxypolyoxyethylene (e.g., "Aqualon KH-10" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), ammonium polyoxyalkylene alkenyl ether 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 base (e.g., "Aqualon BC-10" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) can also be used.

[0107] Furthermore, in addition to the above-mentioned anionic surfactant, the following surfactants can also be used as reactive surfactants. Sulfoalkyl (1-4 carbon atoms) ester salt type surfactants of aliphatic unsaturated carboxylic acids having 3-5 carbon atoms, for example, (meth)acrylate sulfoalkyl ester salt type surfactants such as 2-sulfoethyl (meth)acrylate sodium salt and 3-sulfopropyl (meth)acrylate ammonium salt; aliphatic unsaturated dicarboxylic acid alkyl sulfoalkyl diester salt type surfactants such as sulfopropyl maleate alkyl ester sodium salt, sulfopropyl maleate polyoxyethylene alkyl ester ammonium salt, and sulfoethyl fumarate polyoxyethylene alkyl ester ammonium salt.

[0108] The above nonionic surfactants are not particularly limited and include, for example, 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. In addition, reactive nonionic surfactants such as allyloxymethyl alkoxyethyl hydroxypolyoxyethylene (e.g., "ADEKA Soap 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 can be used.

[0109] The cationic surfactants mentioned above are not particularly limited and include, for example, dialkyldimethylammonium salts, ester-type dialkylammonium salts, amide-type dialkylammonium salts, dialkylimidazolinium salts, and one or more of these can be used.

[0110] The above amphoteric surfactants are not particularly limited, and examples include alkyldimethylaminoacetic acid betaine, alkyldimethylamine oxide, alkylcarboxymethylhydroxyethylimidazolinium betaine, alkylamidopropyl betaine, alkylhydroxysulfobetaine, and the like, and one or more of these can be used.

[0111] The above-mentioned polymeric surfactant is not particularly limited, and examples of nonionic polymeric surfactants include polyvinylpyrrolidone and poly-N-vinylacetamide, and one or more of these can be used. Among the surfactants mentioned above, non-nonylphenyl type surfactants are preferable from an environmental perspective.

[0112] <Method for producing an 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, the method comprising 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 water-soluble polymers, aluminum-containing compounds, and silicon-containing compounds are as described above.

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

[0114] The amount of water-soluble polymer used in step (α) above is preferably 5 to 1000% by mass, relative to 100% by mass of the total amount of aluminum-containing compound and silicon-containing compound used. More preferably it is 10 to 500% by mass, even more preferably 50 to 200% by mass, and particularly preferably 75 to 125% by mass.

[0115] The silicon atom content in the raw materials used in the above step (α) is preferably 1 to 1000 mol% per 100 mol% of aluminum atoms. More preferably 10 to 800 mol%, even more preferably 50 to 500 mol%, and particularly preferably 50 to 300 mol%.

[0116] The reaction temperature in step (α) described above is not particularly limited, but is preferably 10 to 90°C. More preferably 20 to 80°C.

[0117] <Curing accelerator composition> The aluminosilicate-containing composition of the present invention can be used as a hardening accelerator in addition to hydraulic material compositions including cement paste, mortar, and concrete. It can also be used in ultra-high-strength concrete.

[0118] The present invention also includes a curing accelerator composition comprising an aluminosilicate, wherein the aluminosilicate has an average particle size of 10 to 2500 nm as measured by the above measurement method. The preferred form of the aluminosilicate and the preferred range of average particle size are as described above.

[0119] The above curing accelerator composition may further contain a water-soluble polymer. Specific examples and preferred forms of the above-mentioned water-soluble polymers are as described above. The above-mentioned curing accelerator composition may also contain an aluminum-containing compound and / or a silicon-containing compound, and other components as described above. Specific examples and preferred forms are as described above.

[0120] The preferred range of the content ratios of aluminosilicate, water-soluble polymer, and other components in the above-mentioned curing accelerator composition is the same as the preferred range of their content ratios in the above-mentioned aluminosilicate-containing composition, except as described below.

[0121] If the above curing accelerator composition contains a water-soluble polymer, its content is preferably 0.025 to 90.9% by mass, based on 100% by mass of the curing accelerator composition. More preferably, it is 1 to 50% by mass, even more preferably 5 to 40% by mass, and particularly preferably 10 to 20% by mass.

[0122] The aluminosilicate content in the above curing accelerator composition is preferably 0.05 to 50% by mass, based on 100% by mass of the curing accelerator composition. More preferably, it is 1 to 40% by mass, even more preferably 2 to 40% by mass, and particularly preferably 5 to 30% by mass.

[0123] <Hydraulic material composition> The present invention also relates to a hydraulic material composition comprising the aluminosilicate-containing composition and / or hardening accelerator composition of the present invention and a hydraulic material. The hydraulic material composition described above is preferably one that is commonly used and contains cement, water, fine aggregate, coarse aggregate, etc. It may also contain fine powders such as fly ash, blast furnace slag, silica fume, or limestone. Ultra-high-strength concrete refers to concrete that is commonly known as such in the field of cement compositions, meaning concrete in which the hardened product achieves the same or higher strength as conventional concrete even with a lower water-cement ratio. For example, even with a water-cement ratio of 25% by mass or less, even 20% by mass or less, especially 18% by mass or less, especially 14% by mass or less, and especially around 12% by mass, it will still have workability that does not hinder normal use, and the hardened product will have a strength of 60 N / mm². 2 Furthermore, 80 N / mm 2 In addition to the above, an additional 100 N / mm 2 In particular, 120 N / mm 2 In particular, 160 N / mm 2 In particular, 200 N / mm 2 This demonstrates the above compressive strength.

[0124] The content of the aluminosilicate-containing composition and / or hardening accelerator composition of the present invention is not particularly limited, but is preferably 2% by mass or more and 50% by mass or less of 100% by mass of solid content (i.e., non-volatile content) in the cement additive. More preferably 3% by mass or more and 40% by mass or less, even more preferably 4% by mass or more and 35% by mass or less, and particularly preferably 5% by mass or more and 30% by mass or less.

[0125] The above-mentioned hydraulic material composition may further contain other commonly used cement dispersants or water-reducing agents, and multiple combinations are also possible. The other cement dispersants (water-reducing agents) are not particularly limited, but include the water-soluble polymer compounds mentioned above, among which 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 individually or in combination of two or more types.

[0126] Furthermore, the hydraulic material composition of the present invention may contain other additives as needed. Examples of other additives include water-soluble polymers, polymer emulsions, retarders, early-strengthening agents / accelerators, defoamers, 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, antifungal agents, blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, gypsum, etc., and one or more of these can be used.

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

[0128] The above hydraulic material composition can be used with various hydraulic materials, namely cement compositions such as cement and gypsum, and other hydraulic materials. Specific examples of hydraulic compositions containing such hydraulic materials and water, and further optionally containing fine aggregate (sand, etc.) or coarse aggregate (crushed stone, etc.), include cement paste, mortar, concrete, and plaster. Among these hydraulic compositions, cement compositions using cement as the hydraulic material are most preferred, and a cement composition containing the above aluminosilicate-containing composition and / or the above hardening accelerator composition, along with cement, is also one of the present inventions.

[0129] In the hydraulic material composition described above, the cement may include Portland cement (ordinary, rapid-hardening, ultra-rapid-hardening, 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 (1-clinker rapid-hardening cement, 2-clinker rapid-hardening cement, magnesium phosphate cement); grout cement; oil well cement; low-heat cement (low-heat blast furnace cement, fly ash-mixed low-heat blast furnace cement, beelite-high content cement); ultra-high-strength cement; cement-based solidifying agent; eco-cement (cement manufactured using one or more of municipal solid waste incineration ash, sewage sludge incineration ash, etc. as raw materials), as well as those to which fine powders such as blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, limestone powder, or gypsum are added. The cement contained in the hydraulic material composition of the present invention may be only one type or two or more types. In addition to gravel, crushed stone, granulated slag, and recycled aggregates, other aggregates mentioned above include refractory aggregates such as silica, clay, zircon, high alumina, silicon carbide, graphite, chromium, chromium-magnesium, and magnesia.

[0130] In the above hydraulic material composition, 1 m 3 The unit water content, cement usage, and water / cement ratio are not particularly limited; for example, a unit water content of 100-185 kg / m³. 3 , amount of cement used: 250-800 kg / m 3 Preferably, the water / cement ratio (by weight) is 0.12 to 0.74. More preferably, the unit water content is 120 to 175 kg / m³. 3 , amount of cement used: 270-800 kg / m 3 The water / cement ratio (by weight) is 0.15 to 0.65. Thus, the hydraulic material composition of the present invention can be used in a wide range of mixes, from lean to rich, and is suitable for high-strength concrete with a high unit cement content, and for concrete with a unit cement content of 300 kg / m³. 3It is effective for any of the following lean mix concretes. Furthermore, the hydraulic material composition of the present invention can be used well even in regions with relatively high water loss rates, i.e., in regions with low water / cement ratios such as water / cement ratio (weight ratio) = 0.15 to 0.5 (preferably 0.15 to 0.4).

[0131] In the above hydraulic material composition, the blending ratio of the aluminosilicate is preferably set to, for example, 0.01 to 1% by mass based on solid content relative to 100% by mass of the total cement mass. If it is less than 0.01% by mass, the performance may not be sufficient, and conversely, if it exceeds 1% by mass, the effect will substantially plateau, which may be unfavorable from an economic standpoint. More preferably it is 0.05 to 0.5% by mass, and even more preferably 0.1 to 0.4% by mass. In this specification, the solid content can be measured as follows. In this specification, the solid content can be measured as follows. <Method for measuring solid content> 1. Weigh the aluminum tray accurately. 2.1 The solid content sample is accurately weighed into the aluminum pan prepared in step 2.1. 3. Place the solids measured in step 2 into a dryer heated to 130°C under a nitrogen atmosphere for 1 hour. 4. After 1 hour, remove from the dryer and allow to cool in a desiccator at room temperature for 15 minutes. 5. After 15 minutes, remove from the desiccator and weigh the aluminum tray and the sample. The solid content is measured by subtracting the mass of the aluminum tray obtained in step 1 from the mass obtained in step 6.5, and then dividing by the mass of the solid content sample obtained in step 2.

[0132] The aluminosilicate-containing composition and / or hardening accelerator composition of the present invention provides a hydraulic material composition that exhibits excellent early strength development and can therefore 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.

[0133] 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 production method to a hydraulic material. The present invention further relates to a method for producing a hydraulic material composition, the production method comprising the step (β) of adding the aluminosilicate-containing composition of the present invention or the aluminosilicate-containing composition obtained by the production method to a hydraulic material. The method of adding the aluminosilicate-containing composition in step (β) described above is not particularly limited, but it is preferable to disperse the aluminosilicate-containing composition in a solvent such as water before adding it.

[0134] The present invention further relates to a method for producing a hydraulically hardened product, wherein the production method includes a step (γ) of hardening the hydraulic material composition of the present invention or the hydraulic material composition obtained by the production method. The above curing step (γ) is preferably a step of curing the hydraulic material composition 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 85°C, and particularly preferably 40 to 80°C.

[0135] In the method for producing the hydraulically hardened product described above, it is preferable to carry out the hardening step (γ) under conditions of 40 to 100% humidity. More preferably, the humidity is 50 to 100%, and even more preferably 60 to 100%.

[0136] The above curing process (γ) may be carried out in one step or in two or more steps, but it is preferable to carry it out in two steps. It is preferable to carry out the first step under conditions of a temperature of 15 to 30°C and a humidity of 40 to 60%, and the second step under conditions of a temperature of 40 to 90°C and a humidity of 60 to 100%.

[0137] The method for producing the hydraulically hardened product described above preferably includes a step of pouring the hydraulic material composition into a mold, and it is preferable to perform the hardening step (γ) after the step of pouring into the mold.

[0138] In the method for producing the hydraulically hardened product described above, it is preferable to perform the hardening step (γ) by steam curing.

[0139] In the method for producing the hydraulically hardened product described above, it is preferable to carry out the hardening step (γ) for 1 to 10 hours. More preferably, it is 1.5 to 8 hours, and even more preferably 2 to 6 hours.

[0140] The present invention also relates to a method for curing a hydraulic material composition comprising the above-mentioned aluminosilicate-containing composition and / or the above-mentioned curing 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 85°C, and particularly preferably 40 to 80°C.

[0141] The present invention further relates to a method for rapidly improving the strength of a hydraulically hardened product, the method comprising the steps of adding the aluminosilicate-containing composition to a hydraulic material and hardening the composition obtained in the addition step. The preferred configurations of the additive step and the curing step in the above-described method for early strength improvement are the same as those of the additive step (β) and water in the method for manufacturing a hydraulic material composition, and the curing step (γ) in the method for manufacturing a hardened product, respectively. [Examples]

[0142] 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 mass" and "%" means "percent mass".

[0143] <Measurement of average particle size of aluminosilicate> The first aqueous dispersion was filtered using Advantec's filter paper No. 2 to remove impurities, and the following operations were performed using the resulting filtrate. Using a particle size analyzer, the scattering intensity of an aqueous dispersion of an 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: Deionized water

[0144] <Gel Permeation Chromatography (GPC)> The weight-average molecular weight (Mw) of water-soluble polymers was measured using GPC (gel permeation chromatography) under the following measurement conditions. (GPC analysis method) Equipment: Waters Alliance (2695) Analysis software: Empower2 Professional + GPC option from Waters. Columns used: TSKguardcolumnsSWXL + TSKgel G4000SWXL + G3000SWXL + G2000SWXL (manufactured by Tosoh Corporation) Detectors: Differential refractometer (RI) detector (Waters 2414), multi-wavelength visible ultraviolet (PDA) detector (Waters 2996) Eluent: A mixture of 10999g water and 6001g acetonitrile in which 115.6g of sodium acetate trihydrate was dissolved, and then the pH was adjusted to 6.0 with acetic acid. Standard materials for creating calibration curves: Polyethylene glycol (peak top molecular weight (Mp): 272500, 219300, 107000, 50000, 24000, 12600, 7100, 4250, 1470) Calibration curve: Created as a cubic equation based on the Mp value and elution time of the above standard substance. 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 polymer concentration of 0.5% by mass)

[0145] (GPC analysis conditions (polymer analysis)) In the obtained RI chromatogram, the regions that were flat and stable at the baseline immediately before and immediately after polymer elution were connected by straight lines to detect and analyze the polymer. However, if the peaks of monomers or monomer-derived impurities partially overlapped with the polymer peak, the polymer portion was vertically split at the deepest recess of the overlapping region to separate it from the monomer and impurity portions, and the molecular weight and molecular weight distribution of only the polymer portion were calculated. If there was no recess, the calculations were performed together. The polymer purity was calculated from the ratio of peak areas measured by the RI detector as follows. Polymer purity = (polymer peak area) / (polymer peak area + monomer and impurity peak area)

[0146] <Early Strength Assessment> (Mortar test) Preparation of mortar samples: The mortar test was conducted under conditions of 20°C ± 1°C and 60% ± 15% relative humidity. The mortar mix was C / S / W = 535 / 1350 / 214 (g). however, C: Cement (ordinary Portland cement, manufactured by Taiheiyo Cement Corporation) S: Fine aggregate (standard sand for cement strength testing, manufactured by the Cement Association) W: Ion-exchange aqueous solution of sample and defoamer For W, the additives and defoamers obtained in the following examples and comparative examples were dissolved uniformly and thoroughly in ion-exchanged water. Using a mortar mixer (Hobart mixer, model number: N-50), S and W were added to the mixing container and mixed at speed 1 for 40 seconds. While continuing to mix at speed 1, C was added over 20 seconds. 60 seconds after the start of mixing, the speed was changed to 2 and mixed for another 30 seconds. The mixer was then stopped, the mortar was scraped off for 30 seconds, and it was allowed to stand for 60 seconds. After that, mixing was performed again at speed 2 for 60 seconds to prepare the mortar. The air content was adjusted to less than 3.0% by adding an oxyalkylene-based defoaming agent.

[0147] (Measurement of compressive strength) After mixing, samples for compressive strength testing were prepared, and the compressive strength after steam curing was measured under the following conditions. Specimen preparation: 50mm x 100mm Specimen curing (room temperature curing): The specimens were cured in a constant temperature and humidity air at 20°C and 50% humidity for 12 hours. Specimen curing (steam curing): After curing in a constant temperature and humidity air at 20°C and 50% humidity for 4 hours, the specimens were further cured in a constant temperature and humidity oven at 80°C and 98% humidity for 6 hours. Specimen polishing: Surface polishing of the specimen (using a specimen polishing machine) Compression strength measurement: Automatic compression strength measuring instrument (Maekawa Manufacturing Co., Ltd.)

[0148] <Manufacturing Example 1> A solution (1a) was prepared by dissolving 0.3 parts of L-ascorbic acid in 78.1 parts of water. A solution (1b) was prepared by dissolving 2.9 parts of 3-mercaptopropionic acid in 17.9 parts of water. A solution (1c) was prepared by dissolving 32.8 parts of acrylic acid (AA) in 8.2 parts of water. In a reaction vessel equipped with a thermometer, stirrer, dropping device, nitrogen inlet tube, and reflux condenser, 43.3 parts of water and 302.8 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 were charged. Subsequently, the reaction vessel was purged with nitrogen while stirring, and after raising the temperature to 60°C under a nitrogen atmosphere, 13.8 parts of a 2% aqueous solution of hydrogen peroxide were added. After 30 minutes, the above-mentioned mixed solution (1a) was added dropwise at a constant rate over 4.5 hours, the above-mentioned mixed solution (1b) over 3.5 hours, and the above-mentioned mixed solution (1c) over 3 hours. The temperature was kept constant at 60°C during this time. After the addition of mixed solution (1a) was completed, the temperature was maintained at 60°C for 1 hour to complete the polymerization reaction. Subsequently, the pH of the reaction solution was neutralized to pH=7.0 using an aqueous sodium hydroxide solution at a temperature below the polymerization reaction temperature. In this way, a polymer solution containing copolymer (1) was obtained.

[0149] <Manufacturing Example 2> A solution (2a) was prepared by dissolving 1.8 parts of sodium persulfate in 33.8 parts of water. A solution (2b) was prepared by dissolving 122.2 parts of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added: 23) (MPG-23), 3.8 parts of 3-mercaptopropionic acid, and 37.8 parts of methacrylic acid (MAA) in 69.6 parts of water. 131.0 parts of water were placed in a reaction vessel equipped with a thermometer, stirrer, dropper, nitrogen inlet tube, and reflux condenser. Subsequently, the reaction vessel was purged with nitrogen while stirring, and the temperature was raised to 93°C under a nitrogen atmosphere. Then, the above-mentioned mixed solution (2a) was added dropwise at a constant rate over 5 hours, and the above-mentioned mixed solution (2b) was added dropwise at a constant rate over 4 hours. The temperature was kept constant at 93°C during this time. After the dropwise addition of mixed solution (2a) was complete, the temperature was maintained at 93°C for 1 hour to complete the polymerization reaction. Subsequently, the pH of the reaction solution was neutralized to pH=5.0 using an aqueous sodium hydroxide solution at a temperature below the polymerization reaction temperature. In this way, a polymer solution containing copolymer (2) was obtained.

[0150] <Manufacturing Example 3> A solution (3a) was prepared by dissolving 0.3 parts of L-ascorbic acid in 191.2 parts of water. A solution (3b) was prepared by dissolving 2.2 parts of 3-mercaptopropionic acid in 13.5 parts of water. A solution (3c) was prepared by dissolving 32.2 parts of acrylic acid (AA) in 8.0 parts of water. In a reaction vessel equipped with a thermometer, stirrer, dropping device, nitrogen inlet tube, and reflux condenser, 30.0 parts of water and 209.8 parts of an 80% aqueous solution of an unsaturated polyalkylene glycol ether monomer (IPN-50) obtained by adding an average of 50 moles of ethylene oxide to 3-methyl-3-buten-1-ol were charged. Subsequently, the reaction vessel was purged with nitrogen while stirring, and after raising the temperature to 60°C under a nitrogen atmosphere, 12.8 parts of a 2% aqueous solution of hydrogen peroxide were added. After 30 minutes, the above-mentioned mixed solution (3a) was added dropwise at a constant rate over 4.5 hours, the above-mentioned mixed solution (3b) over 3.5 hours, and the above-mentioned mixed solution (3c) over 3 hours. The temperature was kept constant at 60°C during this time. After the addition of mixed solution (3a) was completed, the temperature was maintained at 60°C for 1 hour to complete the polymerization reaction. Subsequently, the pH of the reaction solution was neutralized to pH=7.0 using an aqueous sodium hydroxide solution at a temperature below the polymerization reaction temperature. In this way, a polymer solution containing copolymer (3) was obtained.

[0151] Table 1 shows the monomer composition and weight-average molecular weight of copolymers (1) to (3) obtained in the above production examples 1 to 3.

[0152] [Table 1]

[0153] <Example 1> 9.28 g of aluminum sulfate 14-18 hydrate (solids content 53.9%) was dissolved in 40.7 g of deionized water, and 15.6 g of copolymer (1) (solids content 55%) was added and mixed to obtain solution (A1). Next, 8.31 g of sodium metasilicate 9 hydrate (solids content 42.9%) was dissolved in 41.7 g of deionized water to obtain solution (B1). Solution (A1) was stirred at room temperature, and solution (B1) was slowly added dropwise over approximately 10 minutes to obtain aluminosilicate composition (1). The average particle size of the aluminosilicate was 51 nm.

[0154] <Example 2> 9.28 g of aluminum sulfate 14-18 hydrate (solids content 53.9%) was dissolved in 40.7 g of deionized water, and 19.0 g of copolymer (2) (solids content 45%) was added and mixed to obtain solution (A2). Next, 8.31 g of sodium metasilicate 9 hydrate (solids content 42.9%) was dissolved in 41.7 g of deionized water to obtain solution (B2). Solution (A2) was stirred at room temperature, and solution (B2) was slowly added dropwise over approximately 10 minutes to obtain aluminosilicate composition (2). The average particle size of the aluminosilicate was 270 nm.

[0155] <Example 3> 9.28 g of aluminum sulfate 14-18 hydrate (solids content 53.9%) was dissolved in 40.7 g of deionized water, and 21.4 g of copolymer (3) (solids content 40%) was added and mixed to obtain solution (A3). Next, 8.31 g of sodium metasilicate 9 hydrate (solids content 42.9%) was dissolved in 41.7 g of deionized water to obtain solution (B3). Solution (A3) was stirred at room temperature, and solution (B3) was slowly added dropwise over approximately 10 minutes to obtain aluminosilicate composition (3). The average particle size of the aluminosilicate was 32 nm.

[0156] <Comparative Example 1> 9.28 g of aluminum sulfate 14-18 hydrate (solids content 53.9%) was dissolved in 40.7 g of deionized water to obtain solution (A4). Next, 8.31 g of sodium metasilicate 9 hydrate (solids content 42.9%) was dissolved in 41.7 g of deionized water to obtain solution (B4). Solution (A4) was stirred at room temperature, and solution (B4) was slowly added dropwise over approximately 10 minutes to obtain aluminosilicate composition (4). The average particle size of the aluminosilicate was 2550 nm.

[0157] The compressive strength was measured using the method described above, with the aluminosilicate compositions (1) to (3) obtained in Examples 1 to 3 as cement admixtures, the aluminosilicate composition (4) and copolymer (1) prepared in the absence of copolymer as Comparative Example 1, and the copolymers (1) to (3) obtained in Production Examples 1 to 3 as Comparative Examples 2 to 4, in the proportions shown in Table 2. In addition, the compressive strength was measured in Comparative Example 5 without the addition of cement admixtures. The results are shown in Table 2. The strength ratio is expressed as a ratio with Comparative Example 2.

[0158] [Table 2]

Claims

1. A curing accelerator composition comprising an aluminosilicate and a water-soluble polymer, The aluminosilicate is a curing accelerator composition characterized in that its average particle size, as measured by the following measurement method, is 10 to 500 nm. <Method for measuring average particle size> Using a particle size analyzer, the scattering intensity of an aqueous dispersion of an aluminosilicate-containing composition with a solid content of 0.1% by mass is measured by dynamic light scattering, and the average particle size is calculated.

2. The curing accelerator composition according to claim 1, characterized in that 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, as well as a phosphate ester group and a hydroxyl group.

3. The curing accelerator composition according to claim 2, characterized in that the water-soluble polymer further has (poly)oxyalkylene groups.

4. The curing accelerator composition according to any one of claims 1 to 3, characterized in that the content of the water-soluble polymer is 0.025 to 90.9% by mass with respect to 100% by mass of the aluminosilicate-containing composition.

5. Contains aluminosilicate, The aluminosilicate is characterized by having an average particle size of 10 to 500 nm, as measured by the following measurement method, as a curing accelerator composition (excluding those containing aqueous colloidal silica). <Method for measuring average particle size> Using a particle size analyzer, the scattering intensity of a 0.1% by mass aqueous dispersion of the curing accelerator composition is measured by dynamic light scattering, and the average particle size is calculated.

6. The curing accelerator composition according to claim 5, further characterized in that it comprises a water-soluble polymer.

7. The curing accelerator composition according to claim 6, characterized in that 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, as well as a phosphate ester group and a hydroxyl group.

8. The curing accelerator composition according to claim 7, characterized in that the water-soluble polymer further has (poly)oxyalkylene groups.

9. The curing accelerator composition may contain an aluminum-containing compound and / or a silicon-containing compound, and the content of the water-soluble polymer is 5 to 1000% by mass with respect to 100% by mass of the total content of aluminosilicate, aluminum-containing compound and silicon-containing compound, as described in any one of 6 to 8.

10. The curing accelerator composition according to any one of 5 to 9, characterized in that the content of silicon atoms in the curing accelerator composition is 1 to 1000 mol% with respect to 100 mol% of aluminum atoms.

11. A hydraulic material composition characterized by comprising a hardening accelerator composition according to any one of claims 1 to 10 and a hydraulic material.

12. A method for producing the curing accelerator composition according to any one of Claims 1 to 4, The method for producing a curing accelerator composition is characterized by comprising a step (α) of mixing an aluminum-containing compound and a silicon-containing compound as an aqueous solution and reacting them in the presence of a water-soluble polymer.

13. A method for rapidly improving the strength of a hydraulically hardened material, The method is characterized by comprising the steps of adding a curing accelerator composition according to any one of claims 1 to 10 to a hydraulic material and curing the composition obtained in the addition step, thereby improving the early strength of a hydraulically cured product.

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