Aluminosilicate-containing composition

Abstract

The purpose of the present invention is to provide a composition which is for use in hydraulic materials and attains excellent storage stability. An aluminosilicate-containing composition according to the present invention contains an aluminosilicate, wherein the aluminosilicate is one obtained by reacting an aluminum-containing compound with a silicon-containing compound at a temperature of 30°C or higher in the presence of a water-soluble polymer having at least one functional group selected from among a carboxyl group, a phosphoric acid group, a sulfonic acid group, salts of these, and phosphoric ester groups.

Description

Aluminosilicate-containing composition

[0001] The present invention relates to an aluminosilicate-containing composition. More specifically, it relates to an aluminosilicate-containing composition useful for accelerating the curing of a hydraulic material composition.

[0002] In the production process of ordinary Portland cement, a large amount of CO ２ is emitted. Therefore, in order to reduce the emission of CO ２ Concrete compositions in which cement is replaced with supplementary cementitious materials (Supplementary Cementitious Materials (SCM)) such as fly ash and slag have been proposed. Such SCM concrete has a longer curing time and problems in strength development (especially early strength) compared to ordinary Portland cement (OPC).

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

[0004] Japanese Unexamined Patent Application Publication No. 2022-011743

[0005] As described above, although technologies for improving the strength of conventional concrete have been developed, the conventional compositions have room for improvement in storage stability.

[0006] The present invention has been made in view of the above situation, and an object thereof is to provide a composition having excellent storage stability for use in hydraulic materials.

[0007] The present inventors have conducted various studies on technologies for enhancing the storage stability of compositions used in hydraulic materials. As a result, they have found that a composition containing an aluminosilicate obtained by reacting an aluminum-containing compound and a silicon-containing compound at a temperature of 30°C or higher in the presence of a water-soluble polymer suppresses thickening over time and has excellent storage stability. Based on this finding, the inventors have conceived and reached the present invention, which can successfully solve the above problems.

[0008] The present invention includes the following aluminosilicate-containing compositions, etc.: [1] An aluminosilicate-containing composition, wherein the aluminosilicate is obtained by reacting an aluminum-containing compound and a silicon-containing compound at a temperature of 30°C or higher in the presence of a water-soluble polymer having at least one functional group selected from a carboxyl group, a phosphate group, a sulfonic acid group and salts thereof, and a phosphate ester group. [2] The aluminosilicate-containing composition according to [1], wherein the aluminosilicate has a molar ratio of calcium element to 100 mol% silicon element (Ca / Si) of 50% or less. [3] The aluminosilicate-containing composition according to [1] or [2], wherein the reaction is carried out under pH conditions of 1 to 9. [4] The aluminosilicate-containing composition according to any one of [1] to [3] above, further comprising a polyhydric alcohol alkylene oxide adduct and / or a polyalkyleneimine alkylene oxide adduct. [5] The aluminosilicate-containing composition according to [4] above, wherein the total content of the polyhydric alcohol alkylene oxide adduct and the polyalkyleneimine alkylene oxide adduct is 50% by mass or less with respect to 100% by mass of the total content of the aluminosilicate, aluminum-containing compound and silicon-containing compound. [6] The aluminosilicate-containing composition according to any one of [1] to [5] above, wherein the water-soluble polymer further comprises a (poly)oxyalkylene group. [7] The aluminosilicate-containing composition according to any one of [1] to [6] above, wherein the content of the water-soluble polymer is 5 to 90% by mass with respect to 100% by mass of the total content of the aluminosilicate, aluminum-containing compound and silicon-containing compound. [8] A hydraulic material composition comprising an aluminosilicate-containing composition described in any of [1] to [7] above and a hydraulic material. [9] A method for producing an aluminosilicate-containing composition, the method comprising the step of reacting an aluminum-containing compound and a silicon-containing compound at a temperature of 30°C or higher in the presence of a water-soluble polymer having at least one functional group selected from carboxyl groups, phosphate groups, sulfonic acid groups and salts thereof, and phosphate ester groups.

[0009] The aluminosilicate-containing composition of the present invention has the above-described structure, exhibits excellent storage stability, and can improve work efficiency, making it suitable for use as a hardening accelerator for hydraulic material compositions.

[0010] 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.

[0011] <Aluminosilicate-containing composition> The aluminosilicate-containing composition of the present invention is a composition containing aluminosilicate, wherein the aluminosilicate is obtained by reacting an aluminum-containing compound and a silicon-containing compound at a temperature of 30°C or higher in the presence of a water-soluble polymer (hereinafter also simply referred to as a water-soluble polymer) having at least one functional group selected from carboxyl groups, phosphate groups, sulfonic acid groups and their salts and phosphate ester groups. The inventors have found that carrying out the reaction at the above reaction temperature improves the storage stability of the obtained aluminosilicate-containing composition. This effect is thought to be due to the fact that raising the reaction temperature allows the condensation reaction of the aluminosilicate to proceed sufficiently, and by sufficiently reducing the number of active sites on the surface of the obtained aluminosilicate particles, it is possible to suppress the thickening due to reactions over time at the active sites.

[0012] The aluminosilicate in the aluminosilicate-containing composition of the present invention is not particularly limited as long as it is obtained by reacting an aluminum-containing compound and a silicon-containing compound at a temperature of 30°C or higher in the presence of a water-soluble polymer having at least one functional group selected from a carboxyl group, a phosphate group, a sulfonic acid group, salts thereof, and a phosphate ester group, but it is preferably in a particulate form (aluminosilicate-containing particles). The above aluminosilicate-containing particles may contain other components such as a water-soluble polymer as long as they contain aluminosilicate. The preferred form of the reaction between the above aluminum-containing compound and the silicon-containing compound is the same as the preferred form of step (α) in the method for producing the aluminosilicate-containing composition described below.

[0013] The aluminosilicate contained in the aluminosilicate-containing composition of the present invention is not particularly limited as long as it is a compound having a structure in which part of the silicon atoms in the silicate are replaced by aluminum atoms. For example, the following formula (1); pM １ ２ O·qAl ２ O ３ ·rM ２ O·sSiO ２ ·mH ２ O (1) (In the formula, p, q, r, m, and s represent integers. M １ represents an alkali metal atom, and M ２ represents an alkaline earth metal atom.) can be represented.

[0014] In the aluminosilicate in the aluminosilicate-containing composition of the present invention, the molar ratio of calcium element (Ca / Si) to 100 mol% of silicon element is preferably 50 mol% or less. More preferably, it is 40 mol% or less, still more preferably 30 mol% or less, even more preferably 20 mol% or less, and particularly preferably 10 mol% or less. The form in which the molar ratio of calcium element is 0 mol% is also one of the preferred embodiments of the present invention.

[0015] In the aluminosilicate-containing composition of the present invention, the aluminosilicate preferably has a molar ratio of aluminum element (Al / Si) of 20 mol% or more to 100 mol% silicon element. Preferably, it is 30 to 1000 mol%, more preferably 50 to 300 mol%, even more preferably 70 to 200 mol%, and most preferably 80 to 150 mol%.

[0016] The content of silicon atoms in the aluminosilicate-containing composition of the present invention is preferably 600 mol% or less with respect to 100 mol% of aluminum atoms. The aluminosilicate-containing composition may also contain an aluminum-containing compound and / or a silicon-containing compound, and the content of silicon atoms 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 and the aluminum-containing compound. The content of silicon atoms is more preferably 1 to 500 mol%, even more preferably 10 to 300 mol%, even more preferably 30 to 200 mol%, particularly preferably 50 to 150 mol%, and most preferably 67 to 125 mol%.

[0017] The above-mentioned aluminum-containing compounds and silicon-containing compounds are not particularly limited, but examples include unreacted raw materials 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 above-mentioned silicon-containing compounds include alkali metal salts of metasilicic acid such as sodium metasilicate, and alkali metal salts of silicic acid, such as sodium silicate, potassium silicate, water glass, aluminum silicate, tricalcium silicate, dicalcium silicate, calcium silicate, silicic acid, sodium metasilicate, and / or potassium metasilicate. Preferably, sodium metasilicate, potassium metasilicate, and / or water glass.

[0018] The aluminosilicate content is preferably 0.2 to 40% by mass, based on 100% by mass of the aluminosilicate-containing composition. More preferably, it is 0.5 to 30% by mass, even more preferably 1 to 30% by mass, and particularly preferably 5 to 30% by mass.

[0019] The aluminosilicate-containing particles contained in the aluminosilicate-containing composition of the present invention may be obtained by the above reaction, but it is preferable that the average particle diameter measured by the following measurement method is 10 to 2500 nm. More preferably it is 10 to 800 nm, even more preferably 15 to 700 nm, even more preferably 20 to 600 nm, even more preferably 25 to 500 nm, even more preferably 30 to 400 nm, particularly preferably 40 to 300 nm, and most preferably 50 to 300 nm. <Method for measuring average particle diameter> Using a particle diameter measuring device, the scattering intensity of an aqueous dispersion of the aluminosilicate-containing composition with a solid content of 0.1% by mass is measured by dynamic light scattering, and the Z-average particle diameter is calculated.

[0020] (Water-soluble polymer) The aluminosilicate-containing composition of the present invention may contain an aluminosilicate obtained by reacting an aluminum-containing compound and a silicon-containing compound at a temperature of 30°C or higher in the presence of the water-soluble polymer, but it is preferable that it contains the water-soluble polymer. The content ratio of the water-soluble polymer in the aluminosilicate-containing composition of the present invention is not particularly limited, but it is preferably 0.02 to 25% by mass with respect to 100% by mass of the aluminosilicate-containing composition. If the content ratio of the water-soluble polymer is within the above range, the inhibition of cement nucleation is more sufficiently suppressed, and the strength development performance is better. The content ratio of the water-soluble polymer is more preferably 0.5 to 10% by mass, and particularly preferably 1 to 5% by mass.

[0021] The content of the water-soluble polymer in the aluminosilicate-containing composition of the present invention is preferably 5 to 90% by mass, more preferably 10 to 75% by mass, even more preferably 10 to 50% by mass, and particularly preferably 20 to 50% by mass.

[0022] The content of the water-soluble polymer in the aluminosilicate-containing composition of the present invention is preferably 5 to 90% by mass, based on 100% by mass of the total content of the aluminosilicate, aluminum-containing compound, and silicon-containing compound. More preferably, it is 10 to 75% by mass, even more preferably 10 to 50% by mass, and particularly preferably 20 to 50% by mass. When the aluminum-containing compound and silicon-containing compound are hydrates, their content shall be calculated on an anhydrous basis. The same applies hereinafter.

[0023] The above water-soluble polymer is not particularly limited as long as it has at least one functional group selected from carboxyl groups, phosphate groups, sulfonic acid groups and their salts, and phosphate ester groups, and the insoluble content when 100 g is dissolved in 100 g of water at 20°C is 50 g or less. Among the above functional groups, carboxyl groups, phosphate groups, sulfonic acid groups and their salts are preferred, and carboxyl groups or their salts are more preferred.

[0024] 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, even more preferably 5,000 to 40,000, even more preferably 6,000 to 30,000, and particularly preferably 8,000 to 25,000. The weight-average molecular weight of the above water-soluble polymer can be measured by GPC under the measurement conditions described in the examples.

[0025] 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, and phosphate ester 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 the calcium content in the hydraulic material composition changes to calcium silicate hydrate, calcium aluminate hydrate, or aluminum calcium silicate hydrate, as well as the pozzolanic reaction rate, will be further accelerated, and the strength development will be further improved.

[0026] 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. More preferably, the proportion of structural units derived from monomers having acid groups is 65 to 95 mol%, even more preferably 70 to 95 mol%, and particularly preferably 80 to 95 mol%.

[0027] The water-soluble polymer having a carboxyl group or a salt thereof (hereinafter also referred to as a carboxylic acid-based water-soluble polymer) is not particularly limited, but examples 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. As the unsaturated carboxylic acid monomer, unsaturated monocarboxylic acid monomers and unsaturated dicarboxylic acid monomers are preferred. As the unsaturated monocarboxylic acid monomer, any monomer having one unsaturated group and one group capable of forming a carbanion in the molecule is acceptable, such as (meth)acrylic acid, crotonic acid, tigric acid, 3-methylcrotonic acid, 2-methyl-2-pentenoic 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.

[0028] 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.

[0029] 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 is the following formula (2): -OPO ３ M ３ ２ (2) (wherein, M ３It 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 substituents. There are no particular limitations on the hydrocarbon group which may have substituents, but examples include groups derived from aromatic alcohols and quinones.

[0030] The water-soluble polymer having the above-mentioned phosphate group or its salt or phosphate ester group is preferably one that has structural units 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). In particular, the following formula (3);

[0031]

[0032] (In the formula, M ３ 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 R represents a direct bond or a divalent linking group. １ It is more preferable that the structural unit has the structure represented by ( ). １ -O-PO ３ M ３ ２ , R １ The bond positions and number of bonds are not particularly limited, and there may be multiple such bonds.

[0033] Q above １ The linking group is not particularly limited as long as it is a divalent linking group, but it is preferably a divalent hydrocarbon group which may have a heteroatom. More preferably, it is a (poly)oxyalkylene group. Specific and preferred examples of the oxyalkylene group include those similar to the oxyalkylene group described later, and most preferably, it is an oxyethylene group. The average number of moles of (poly)oxyalkylene groups added is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 2, and most preferably 1.

[0034] The above R １Examples 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.

[0035] Specific examples of the above 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 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. Among these, phenoxyethanol phosphate, phenoxydiglycol phosphate, and bis(β-hydroxyethyl)hydroquinone ether diphosphate are preferred, and phenoxyethanol phosphate is more preferred. For the phosphorylation of the above aromatic alcohols and quinones, it is preferable to use phosphoric acid compounds such as phosphoric acid (salt) or polyphosphate (salt).

[0036] 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.

[0037] 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.

[0038] 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.

[0039] The above water-soluble polymer preferably has a (poly)oxyalkylene group in addition to 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. The presence of these groups in the water-soluble polymer further improves the dispersibility of the aluminosilicate, further promotes the hydration reaction and pozzolanic reaction of the cement, and further improves the strength development.

[0040] The above (poly)oxyalkylene group is an alkylene oxide adduct, and examples of such alkylene oxides include C2 to C8 alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, and styrene oxide. More preferably, it is a C2 to C4 alkylene oxide such as ethylene oxide, propylene oxide, and butylene oxide, and even more preferably, it is ethylene oxide or propylene oxide. Furthermore, if the above (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. Furthermore, in order to ensure a balance between hydrophilicity and hydrophobicity, it is preferable that the (poly)alkylene glycol contains oxyethylene groups as an essential component, more preferably 50 mol% or more being oxyethylene groups, and even more preferably 90 mol% or more being oxyethylene groups.

[0041] The average number of moles n added of 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, a decrease in copolymerization reactivity can be suppressed. The average number of moles n added is preferably 2 to 400, more preferably 5 to 300, even more preferably 10 to 200, even more preferably 15 to 150, particularly preferably 20 to 100, and most preferably 30 to 80.

[0042] When 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 (poly)oxyalkylene group-containing monomer is not particularly limited, but is preferably of the following formula (4);

[0043]

[0044] (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. ６ O) 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).

[0045] In the above formula (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 formula (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.

[0046] In the above formula (4), R ５The 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. ２ The most preferred examples are hydrogen atoms or hydrocarbon groups having 1 to 4 carbon atoms.

[0047] 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, and in this case, x is preferably 2. Also, in this case, R ４ It is more preferable that is a methyl group. When y is 1, the compound represented by formula (4) becomes an ester monomer, in which case it is preferable that x is 0. Also in this case, R ４ is more preferably a hydrogen atom or a methyl group, and even more preferably R ４ is a methyl group. In the above formula (4), y is 0 and R ５Compounds in which the atom is a hydrogen atom include (poly)ethylene glycol vinyl ether, (poly)ethylene glycol hydroxybutyl vinyl ether, (poly)ethylene glycol allyl ether, (poly)ethylene glycol metharyl ether, (poly)ethylene glycol 3-methyl-3-butenyl ether, (poly)ethylene (poly)propylene glycol vinyl ether, (poly)ethylene (poly)propylene glycol hydroxybutyl vinyl 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 vinyl ether, (poly)ethylene (poly)butylene glycol hydroxybutyl vinyl 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.

[0048] In the above equation (4), y is 0, and R ５Compounds in which the hydrocarbon group has 1 to 30 carbon atoms include methoxy(poly)ethylene glycol vinyl ether, methoxy(poly)ethylene glycol hydroxybutyl vinyl ether, methoxy(poly)ethylene glycol allyl ether, methoxy(poly)ethylene glycol methallyl ether, methoxy(poly)ethylene glycol 3-methyl-3-butenyl ether, methoxy(poly)ethylene(poly)propylene glycol vinyl ether, methoxy(poly)ethylene(poly)propylene glycol hydroxybutyl vinyl ether, and methoxy(poly)ethylene(poly)propylene glycol allyl ether. Examples include ethers, 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 vinyl ether, methoxy(poly)ethylene(poly)butylene glycol hydroxybutyl vinyl ether, methoxy(poly)ethylene(poly)butylene glycol allyl ether, methoxy(poly)ethylene(poly)butylene glycol metharyl ether, methoxy(poly)ethylene(poly)butylene glycol 3-methyl-3-butenyl ether, and the like.

[0049] In the above equation (4), y is 1, and R ５ Examples of compounds in which the hydrogen atom is present 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.

[0050] In the above equation (4), 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, and ethoxypolyethylene glycol Examples of alkoxy polyalkylene glycol (meth)acrylates include mono(meth)acrylate, ethoxypolypropylene glycol mono(meth)acrylate, ethoxypolybutylene glycol mono(meth)acrylate, ethoxypolyethylene glycol polypropylene glycol mono(meth)acrylate, ethoxypolyethylene glycol polybutylene glycol mono(meth)acrylate, ethoxypolypropylene glycol polybutylene glycol mono(meth)acrylate, and ethoxypolyethylene glycol polypropylene glycol polybutylene glycol mono(meth)acrylate, in which the alkoxy group has 1 to 30 carbon atoms.

[0051] The compound represented by formula (4) above is preferably (poly)ethylene glycol vinyl ether, (poly)ethylene glycol hydroxybutyl vinyl ether, (poly)ethylene glycol metharyl ether, (poly)ethylene glycol 3-methyl-3-butenyl ether, or methoxypolyethylene glycol mono(meth)acrylate.

[0052] Examples of the above-mentioned aromatic group-containing (poly)alkylene glycol monomers include compounds obtained by adding alkylene oxides to aromatic alcohols such as aniline; and, more preferably, compounds obtained by adding alkylene oxides to aromatic alcohols such as phenol, cresol, resorcinol, catechol, hydroquinone, naphthol, and furfuryl alcohol. Among the structural units derived from the above-mentioned aromatic group-containing (poly)alkylene glycol monomers, the following formula (5) is particularly important:

[0053]

[0054] (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 or phosphate ester group. ６ O represents an oxyalkylene group having 2 to 18 carbon atoms, either identical or different. R ８ It is preferable that the structural unit has the following characteristics: ) 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.

[0055] Q above ２ Examples of divalent linking groups in this formula include oxygen atoms, sulfur atoms, halogen atoms, -NH-, and divalent hydrocarbon groups which may have heteroatoms. A divalent hydrocarbon group which may have heteroatoms is 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. ８ The hydrocarbon group having 1 to 30 carbon atoms in the above formula (4) is R ５ This is similar to the hydrocarbon groups with 1 to 30 carbon atoms in R. ８ Hydrogen atoms are preferred as the element. n2 is preferably 5 to 200, more preferably 10 to 150, and even more preferably 12 to 120.

[0056] Preferred aromatic group-containing (poly)alkylene glycol monomers include 2-phenoxyethanol and phenoxy polyethylene glycol.

[0057] 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 formula (4) above, or a polymer having a structural unit derived from a monomer having a carboxyl group and an aromatic group and a structural unit derived from an aromatic group-containing (poly)alkylene glycol monomer. When the carboxylic acid-based water-soluble polymer is a polymer having a structural unit (a) derived from an unsaturated carboxylic acid monomer and a structural unit (b) derived from the compound represented by formula (4) above, it may also have a structural unit (c) derived from other monomers.

[0058] 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 rubonates 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 acids with glycols having 2 to 18 carbon atoms or polyalkylene glycols with 2 to 300 added moles of these glycols.

[0059] (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.

[0060] 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).

[0061] In the above carboxylic acid-based water-soluble polymer, the content of structural unit (a) is preferably 7 to 50% by mass, based on 100% by mass of all structural units. More preferably, it is 10 to 45% by mass, and even more preferably, 12 to 30% by mass. The content of structural unit (a) may be 3 to 30% by mass, or 3.5 to 25% by mass, based on 100% by mass of all structural units. In the above carboxylic acid-based water-soluble polymer, the content of structural unit (b) is preferably 50 to 93% by mass, based on 100% by mass of all structural units. More preferably, it is 55 to 90% by mass, and even more preferably, 70 to 88% by mass. The content of structural unit (b) may be 70 to 97% by mass, or 75 to 96.5% by mass, based on 100% by mass of all structural units. In the above carboxylic acid-based water-soluble polymer, the content of structural unit (c) is preferably 0 to 40% by mass, based on 100% by mass of all 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.

[0062] As polymers having structural units derived from the above-mentioned unsaturated carboxylic acid monomers and structural units derived from the compound represented by formula (4), specifically, as described in Japanese Patent Application Publication No. 9-86990, copolymers comprising (alkoxy)polyalkylene glycol mono(meth)acrylic acid ester monomer (a), (meth)acrylic acid monomer (b) in an amount of 95 to 2% by weight, and other monomers (c) copolymerizable with these monomers; as described in Japanese Patent Application 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 Application Publication No. 2002-121055, 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 a C2 or C3 alkenyl group, and (II) derived from an unsaturated monocarboxylic acid monomer (b), as described in Japanese Patent Application Publication No. 2002-121056, as essential structural units; copolymers comprising an unsaturated polyalkylene glycol ether monomer (I) having a C5 alkenyl group, an unsaturated maleic acid monomer (II), and monomers copolymerizable with these monomers, as described in Japanese Patent Application 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 Application Publication No. 2004-307590.

[0063] 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 the 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 structural units derived from the monomer having a carboxyl group and an aromatic group to structural units represented by the above formula (5) is preferably 0.1 to 9. More preferably 0.25 to 4.

[0064] 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% with respect 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%.

[0065] 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 of the structural unit represented by formula (3) to the structural unit represented by formula (5) (formula (3) / formula (5)) is preferably 0.3 to 4. More preferably 0.4 to 3.5, and even more preferably 0.45 to 3.

[0066] The above-mentioned phosphate-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 listed below. Examples of other aromatic group monomers that can react with aldehyde compounds described later include phenoxy alcohol, phenol, naphthol, aniline, benzene-1,2-diol, benzene-1,2,3-triol, 1,2-dihydroxynaphthalene, and 2,3-dihydroxynaphthalene. The proportion of 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 is not particularly limited, but it is preferably 0 to 50 mol% relative to 100 mol% of the total of structural units having a phosphate (salt) group and / or a phosphate ester group and structural units having a (poly)alkylene glycol chain. More preferably 0 to 40 mol%, even more preferably 0 to 30 mol%, and most preferably 0 mol%.

[0067] 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; glyoxylic acid, benzaldehyde, and paraformaldehyde. Preferably, it is formaldehyde, benzaldehyde, or paraformaldehyde, and most preferably, it is formaldehyde.

[0068] 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);

[0069]

[0070] (In the formula, M ３Q 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 ７ 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. R 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 from 1 to 500. It is indicated by ). In polymers having structural units derived from monomers having aromatic groups, such as the above-mentioned phosphoric acid-based water-soluble polymer, it is preferable that each structural unit derived from the monomer is bonded by a methylene group.

[0071] Specific examples of phosphoric acid-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] An aromatic compound or heteroaromatic compound 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 an 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 (where benzaldehyde is further COOMa, SO ３ Ma, and PO ３It may have an acidic group represented by the formula Ma (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).

[0072] The above-mentioned phosphoric acid-based water-soluble polymer may not have aromatic groups in its structure, and such a form may be, for example, a phosphate group-containing monomer of the following formulas (7) and / or (8);

[0073]

[0074] (In the formula, R ９ , R １１ , R １４ OR represents a hydrogen atom or a methyl group, either identical or distinct. １０ , OR １２ , OR １３ n3, n4, and n5 represent the same or different oxyalkylene groups with 2 to 18 carbon atoms. n3, n4, and n5 represent the same or different numbers from 1 to 30. ３ M in equation (6) ３ This is similar to the above.) Examples include those having a monomer-derived structural unit represented by ).

[0075] 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.

[0076] As the above water-soluble polymers, carboxylic acid-based water-soluble polymers, phosphoric acid-based water-soluble polymers, and sulfonic acid-based water-soluble polymers are preferred. 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, methoxypolyethylene glycol mono(meth)acrylate / (meth)acrylic acid copolymer, (poly)ethylene glycol 3-methyl-3-butenyl ether / maleic acid copolymer, and (poly)ethylene glycol 2-methyl-3-propenyl ether / acrylic acid copolymer are more preferred. As phosphoric acid-based water-soluble polymers, polymers having the structure represented by formula (6) above, and polymers having structural units derived from the monomer represented by formula (7) above and structural units derived from the compound represented by formula (4) above are more preferred. As sulfonic acid-based water-soluble polymers, naphthalene sulfonic acid formaldehyde condensate, melamine sulfonic acid formaldehyde condensate, lignin sulfonic acid, polystyrene sulfonate, etc. are more preferred.

[0077] 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.

[0078] (Alkylene Oxide Adducts) The aluminosilicate-containing composition of the present invention preferably contains a polyhydric alcohol alkylene oxide adduct and / or a polyalkyleneimine alkylene oxide adduct (hereinafter also simply referred to as an alkylene oxide adduct). In this case, the alkylene oxide adduct enters between particles in the liquid phase, reducing friction and thereby more effectively suppressing aggregation between particles. The alkylene oxide adduct is not particularly limited as long as it is a compound obtained by adding an alkylene oxide to a polyhydric alcohol or polyalkyleneimine, but it is preferably a compound that does not have a carboxyl group, a phosphate group, a sulfonic acid group and their salts, or a phosphate ester group. The form in which the alkylene oxide adduct is a polyalkyleneimine alkylene oxide adduct is one of the preferred embodiments of the present invention.

[0079] The content of the alkylene oxide adducts is not particularly limited, but it is preferable that the total content of polyhydric alcohol alkylene oxide adducts and polyalkyleneimine alkylene oxide adducts is 50% by mass or less relative to the total content of aluminosilicate, aluminum-containing compounds, and silicon-containing compounds (100% by mass). More preferably, it is 0 to 40% by mass, even more preferably 1 to 30% by mass, and particularly preferably 5 to 15% by mass.

[0080] The above polyhydric alcohol alkylene oxide adduct may be any compound having a structure in which an oxyalkylene group is bonded to a polyhydric alcohol residue, and may or may not have a polymerizable double bond. Furthermore, two or more of the above polyhydric alcohol alkylene oxide adducts may be used in combination. The above polyhydric alcohol residue refers to a group having a structure in which the active hydrogen has been removed from the hydroxyl group of a polyhydric alcohol.

[0081] Of the polyhydric alcohol alkylene oxide adducts mentioned above, those having a polymerizable double bond can be obtained by (1) reacting a compound obtained by adding an alkylene oxide to a polyhydric alcohol with an unsaturated compound such as (meth)acrylic acid or (meth)acrylic acid ester, or an epoxy compound such as (meth)allyl glycidyl ether, or by (2) adding 1 mol or more of glycidol to 1 mol of an unsaturated alcohol or an unsaturated alcohol polyalkylene glycol adduct to generate two or more hydroxyl groups in one molecule, and then adding an alkylene oxide. For those without a polymerizable unsaturated bond, the polyhydric alcohol is not particularly limited as long as it is a compound containing an average of two or more hydroxyl groups in one molecule. A preferred form is a compound in which the polyhydric alcohol residue is composed of three elements: carbon, hydrogen, and oxygen.

[0082] The number of hydroxyl groups in the above polyhydric alcohol is not particularly limited as long as it is 2 or more, but is preferably 3 to 300, more preferably 4 to 100, even more preferably 5 to 50, and particularly preferably 6 to 25.

[0083] Examples of the polyhydric alcohols mentioned above include ethylene glycol, diethylene glycol, diols such as 1,2-propanediol and 1,3-propanediol, polyglycidol, glycerin, polyglycerin, trimethylolethane, trimethylolpropane, 1,3,5-pentatriol, erythritol, pentaerythritol, dipentaerythritol, sorbitol, sorbitan, sorbitol-glycerin condensate, adonitol, arabitol, xylitol, and mannitol. Furthermore, examples of sugars include hexose sugars such as glucose, fructose, mannose, indose, sorbose, gross, talose, tagatose, galactose, allose, psicose, and altrose; pentose sugars such as arabinose, ribulose, ribose, xylose, xylulose, and lyxose; tetrose sugars such as threose, erythrulose, and erythrose; other sugars such as rhamnose, cellobiose, maltose, isomaltose, trehalose, sucrose, raffinose, gentianose, and melegitose; and sugar alcohols and sugar acids (sugars; glucose, sugar alcohols; glucose, sugar acids; gluconic acid). In addition, derivatives such as partially etherified and partially esterified compounds of these exemplary compounds are also suitable. One or more of these can be used. Among these, sorbitol and polyglycerin are preferred. Such compounds lead to the formation of polyhydric alcohol residues in polyhydric alcohol alkylene oxide adducts.

[0084] The above polyalkyleneimine alkylene oxide adduct can be any compound obtained by adding alkylene oxide to the nitrogen atom of the amino group or imino group of the polyalkyleneimine, and may or may not have a polymerizable double bond. Two or more of the above polyalkyleneimine alkylene oxide adducts may also be used in combination. The nitrogen atom of the amino group or imino group to which the alkylene oxide is added must have an active hydrogen atom. The above polyalkyleneimine can be any homopolymer or copolymer of alkyleneimines obtained by polymerizing one or more C2-C8 alkyleneimines such as ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, and 1,1-dimethylethyleneimine by conventional methods. These may be used alone or in combination of two or more. The above polyalkyleneimine chain may have a linear structure, a branched structure, or a three-dimensionally crosslinked structure. Furthermore, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc., may also be used. Such polyalkylene imines typically have a tertiary amino group in their structure, as well as a primary amino group or a secondary amino group (imino group) that has an active hydrogen atom.

[0085] In the alkylene oxide adduct described above, if the average number of added moles of oxyalkylene groups differs, or if there are multiple types of oxyalkylene groups, the adducts may contain different amounts of those oxyalkylene groups. In the present invention, if the average number of added moles or the amount differs, even if the other structures are the same, they will be considered to be of different types. As for the oxyalkylene groups in the alkylene oxide adduct described above, there may be two or more types of oxyalkylene groups in the same adduct, and in this case, the oxyalkylene groups may take any form such as random addition, block addition, or alternating addition, but the form formed by block addition is more preferred. Examples of alkylene oxides that form the oxyalkylene groups described above include the alkylene oxides described in the water-soluble polymers described above. Among these, ethylene oxide is preferred.

[0086] In the above polyalkyleneimine alkylene oxide adduct, it is preferable that the polyalkyleneimine chain is mainly formed of ethyleneimine. In this case, the hydrophilicity of the adduct is improved, and the above effects can be exerted more fully. The proportion of ethylene oxide in the alkylene oxide adduct to the active hydrogen bonded to the amino group of the polyalkyleneimine is preferably 50 to 100 mol%. More preferably 60 mol% or more, even more preferably 70 mol% or more, particularly preferably 80 mol% or more, and most preferably 90 mol% or more. In the above polyalkyleneimine alkylene oxide adduct, the average polymerization number of alkyleneimine per polyalkyleneimine chain is preferably 2 to 300. More preferably 3 to 100, even more preferably 4 to 80, even more preferably 5 to 60, even more preferably 6 to 50, even more preferably 7 to 40, and particularly preferably 8 to 30. The average polymerization number of diethylenetriamine is 2, and the average polymerization number of triethylenetetramine is 3.

[0087] The average number of moles of oxyalkylene groups added to the alkylene oxide adduct described above is not particularly limited, but is preferably greater than 0 and less than or equal to 1000. More preferably it is 1 to 450, even more preferably 5 to 400, and particularly preferably 10 to 300. When the adduct described above is a polyalkylene imine alkylene oxide adduct, the average number of moles of the oxyalkylene groups added to 1 mole of nitrogen atoms having active hydrogen atoms in the polyalkylene imine is preferably 2 to 300. More preferably it is 3 to 100, even more preferably 4 to 80, even more preferably 5 to 60, even more preferably 6 to 50, even more preferably 7 to 40, and particularly preferably 8 to 30.

[0088] The weight-average molecular weight of the alkylene oxide adduct is not particularly limited, but is preferably 100,000 or less. More preferably it is 80 to 30,000, even more preferably 200 to 20,000, and particularly preferably 400 to 15,000.

[0089] (Amine Compounds) The aluminosilicate-containing composition of the present invention preferably contains an amine compound (hereinafter also simply referred to as amine) having a molecular weight of 1000 or less. This further improves the development of strength. The content of the above amine is not particularly limited, but it is preferably 0.01 to 50% by mass based on 100% by mass of the total content of aluminosilicate, aluminum-containing compound and silicon-containing compound. Particularly preferably it is 5 to 25% by mass, and most preferably 5 to 15% by mass.

[0090] The above amine is not particularly limited as long as its molecular weight is 1000 or less, and may be a monohydric amine having one amino group or a polyhydric amine having two or more amino groups, but monohydric or dihydric amines are preferred. Furthermore, the above amine may be a primary amine, a secondary amine, or a tertiary amine, but a tertiary amine is preferred. The above amine may also have a functional group such as a hydroxyl group or a carboxyl group. A hydroxyl group is preferred as the functional group.

[0091] The above amine is represented by the following formula (9);

[0092] (In the formula, R １５ , R １６ , R １７ R represents a hydrocarbon group having 1 to 30 carbon atoms, which may have a hydrogen atom or a functional group, either identical or different. １５ , R １６ , R １７ At least one of the is a hydrocarbon group having 1 to 30 carbon atoms, which may have a functional group. Preferably, the compound is represented by ( ). Examples of functional groups that the hydrocarbon group may have include the functional groups mentioned above and amino groups. When the hydrocarbon group has an amino group, the amine becomes a polyhydric amine.

[0093] R in formula (9) above １５ , R １６ , R １７ The hydrocarbon group in is not particularly limited, but examples include aliphatic alkyl groups having 1 to 30 carbon atoms, alicyclic alkyl groups having 3 to 30 carbon atoms, alkenyl groups having 2 to 30 carbon atoms, alkynyl groups having 2 to 30 carbon atoms, and aromatic hydrocarbon groups having 6 to 30 carbon atoms.

[0094] Examples of the alkyl groups mentioned above include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group (amyl group), n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group, i-propyl group, sec-butyl group, i-butyl group, t-butyl group, 1-methylbutyl group, 1-ethylpropyl group, 2-methylbutyl group, i-amyl group, neopentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, t-amyl group, 1,3-dimethylbutyl group, and 3,3-dimethylbutyl group. Examples include aliphatic alkyl groups such as 2-ethylbutyl group, 2-ethyl-2-methylpropyl group, 1-methylheptyl group, 2-ethylhexyl group, 1,5-dimethylhexyl group, t-octyl group, branched nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, stearyl group, and eicosyl group; and alicyclic alkyl groups such as cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclobutylmethyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, cycloheptyl group, cyclooctyl group, cyclohexylpropyl group, cyclododecyl group, norbornyl group (C7), adamantyl group (C10), and cyclopentylethyl group. The number of carbon atoms in the alkyl group having 1 to 30 carbon atoms is preferably 1 to 22, more preferably 1 to 18, even more preferably 1 to 12, even more preferably 1 to 8, and particularly preferably 1 to 4.

[0095] Examples of the above alkenyl groups include vinyl group, allyl group, 1-butenyl group, 2-butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, dodecenyl group, octadecenyl group, and ecosenyl group. Examples of the above alkynyl groups include ethynyl group, 1-propynyl group, 2-propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octinyl group, noninyl group, decinyl group, dodecinyl group, octadecinyl group, and ecosenyl group. The number of carbon atoms in the above C2 to C30 alkenyl groups and alkynyl groups is preferably 2 to 22, more preferably 2 to 18, even more preferably 2 to 12, even more preferably 2 to 8, and particularly preferably 2 to 4.

[0096] Examples of aromatic hydrocarbon groups having 6 to 30 carbon atoms include aryl groups such as phenyl, naphthyl, methylphenyl, 1-methoxy-4-methylphenyl, ethylphenyl, propylphenyl, butylphenyl, butylmethylphenyl, dimethylphenyl, diethylphenyl, dibutylphenyl, and biphenyl; benzyl, 1-phenylethyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, styryl (Ph-CH=C-), and cinnamyl (Ph-CH=CHCH) groups. ２ Examples include aralkyl groups such as the 1-benzocyclobutenyl group and the 1,2,3,4-tetrahydronaphthyl group.

[0097] Examples of primary amines include monoalkylamines such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine (laurylamine), tridodecylamine, tetradecylamine (myristylamine), pentadecylamine, cetylamine, stearylamine, oleylamine, and cocoalkylamine, as well as compounds having functional groups such as hydroxyl groups and amino groups on these alkyl groups.

[0098] Examples of secondary amines include dialkylamines such as dimethylamine, ethylmethylamine, diethylamine, dipropylamine, diisopropylamine, and dibutylamine, as well as compounds having functional groups such as hydroxyl groups and amino groups on these alkyl groups.

[0099] Examples of tertiary amines include trialkylamines such as trimethylamine, triethylamine, tripropylamine, tributylamine, and triamylamine; dialkylarylamines such as dimethylaniline and diethylaniline; triarylamines such as triphenylamine; trialkylamines such as tribenzylamine; and compounds having functional groups such as hydroxyl groups and amino groups on the alkyl and / or aromatic groups of these compounds.

[0100] In one embodiment, a form in which the above amine has a hydroxyl group is one of the preferred embodiments of the present invention. Specifically, examples of amines having a hydroxyl group include monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, dimethylaminoethanol, ethyldiethanolamine, dimethylaminopropanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, trishydroxymethylaminomethane, and other mono-, di-, and tri-alkanolamines. Among these, triisopropanolamine, triethanolamine, diisopropanolamine, ethyldiethanolamine, and dimethylaminoethanol are preferred, and triisopropanolamine is more preferred.

[0101] In one embodiment, a form in which the amine is a polyhydric amine is also one of the preferred embodiments of the present invention. Specific examples of polyhydric amines include ethylenediamine, propanediamine, butanediamine, tetramethylethylenediamine, trimethyldiethylenediamine, ethylethylenediamine, diethylethylenediamine, diethylenetriamine, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyallylamine, polyethyleneimine, and the like. Among these, tetramethylethylenediamine and pentamethyldiethylenetriamine are preferred, and tetramethylethylenediamine is more preferred.

[0102] The molecular weight of the above amine may be 1000 or less, but is preferably 70 to 600, more preferably 70 to 500, and even more preferably 70 to 300.

[0103] (Functional group-containing compound) The aluminosilicate-containing composition of the present invention preferably contains a compound (hereinafter also referred to as a functional group-containing compound) having a hydroxyl group and two or more functional groups selected from the group consisting of a carboxyl group, a sulfonic acid group, a phosphoric acid group, a phosphite group and salts thereof, and having a molecular weight of 1000 or less. This improves the stability of the aluminosilicate particles.

[0104] The content of the above functional group-containing compound is not particularly limited, but is preferably 0 to 50% by mass based on 100% by mass of the total content of aluminosilicate, aluminum-containing compound, and silicon-containing compound. More preferably it is 1 to 25% by mass, even more preferably 2 to 15% by mass, and particularly preferably 5 to 15% by mass.

[0105] The above-mentioned functional group-containing compounds may be any compound having two or more of the above-mentioned functional groups, but examples include compounds having two or more hydroxyl groups, compounds having a hydroxyl group and a carboxyl group or a salt thereof, compounds having two or more carboxyl groups or a salt thereof, compounds having two or more sulfonic acid groups or a salt thereof, compounds having a hydroxyl group and a sulfonic acid group or a salt thereof, compounds having two or more phosphate groups or a salt thereof, and at least one of these may be used. Specific examples of these compounds are shown below, but as long as the functional group-containing compound has two or more of the above-mentioned functional groups and a molecular weight of 1000 or less, it may fall under the category of compounds with two or more functional groups, for example, it may be a compound that has two or more hydroxyl groups, or a compound that has a hydroxyl group and a carboxyl group or a salt thereof.

[0106] Examples of compounds having two or more hydroxyl groups include sugars, non-sugar polyols, oxocarbonic acids, and the like.

[0107] Compounds having the above-mentioned hydroxyl group and carboxyl group or salt group include derivatives obtained by oxidizing the above-mentioned monosaccharides (oxides of monosaccharides), oxycarboxylic acids other than said oxides, and salts thereof. Examples of the above-mentioned monosaccharide oxides include aldonic acid, aldaric acid, uronic acid, etc. Among these, aldonic acid is preferred.

[0108] The above-mentioned aldonic acid is a sugar acid obtained by oxidizing the aldehyde functional group of an aldose to form a carboxylic acid functional group. Specifically, examples include glyceric acid, xylonic acid, gluconic acid, ascorbic acid, etc., and isomers thereof may also be used. Among these, gluconic acid and its salts are preferred.

[0109] The above-mentioned alduric acid is a sugar acid in which both ends of the aldose are oxidized. Specifically, examples include tartaric acid, mesogalactaric acid, D-glucaric acid, etc., and isomers thereof may also be used. Tartaric acid is preferred among these.

[0110] The above-mentioned uronic acid is a sugar acid obtained by oxidizing the terminal hydroxyl group of an aldose or ketose. Specifically, examples include glucuronic acid, galacturonic acid, iduronic acid, etc., and isomers thereof may also be used.

[0111] Other oxycarboxylic acids besides the oxides of the monosaccharides mentioned above include aliphatic oxycarboxylic acids having 2 to 18 carbon atoms and aromatic oxycarboxylic acids having 6 to 12 carbon atoms.

[0112] Examples of compounds having two or more carboxyl groups or salts thereof include aliphatic dicarboxylic acids having 2 to 6 carbon atoms and salts thereof, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and nosebacic acid; aromatic dicarboxylic acids having 6 to 12 carbon atoms and salts thereof, such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid; and divalent salts of monocarboxylic acids having 1 to 6 carbon atoms, such as formic acid and acetic acid.

[0113] Examples of compounds having two or more sulfonic acid groups or salts thereof include C1-C12 alkanedisulfonic acids such as ethanedisulfonic acid and their salts. Examples of compounds having a hydroxyl group and a sulfonic acid group or salt thereof include C1-C12 hydroxyalkanesulfonic acids such as hydroxymethanesulfonic acid and their salts.

[0114] Examples of compounds having two or more phosphate groups or salts thereof include polyphosphates such as trimetaphosphate, tripolyphosphate, and pyrophosphate, and salts thereof.

[0115] Preferred functional groups are hydroxyl groups, carboxyl groups, and / or salts thereof. Specifically, preferred functional group-containing compounds are those having at least one hydroxyl group and at least one carboxyl group or salt thereof.

[0116] Preferably, the functional group-containing compound is a compound having two or more hydroxyl groups, and is a compound having a hydroxyl group and a carboxyl group or a salt thereof. More preferably, it is a sugar, an oxide of a monosaccharide and its salt, an oxycarboxylic acid other than the derivative thereof and its salt, and even more preferably, a sugar, an aldonic acid, an aldalic acid and its salt, and particularly preferably, glucose, trehalose, sucrose, gluconic acid (salt), tartaric acid (salt).

[0117] The molecular weight of the above functional group-containing compound is 1000 or less, preferably 50 to 500, and more preferably 100 to 400.

[0118] (Metal Compounds) The aluminosilicate-containing composition of the present invention may contain metal compounds containing metal elements other than aluminum and silicon. The content of metal elements other than aluminum and silicon in the aluminosilicate-containing composition of the present invention is not particularly limited, but it is preferably 0 to 30 mol% with respect to 100 mol% of silicon.

[0119] The above-mentioned metal compounds are not particularly limited as long as they are metal-containing compounds other than the components contained in the above-mentioned aluminosilicate and cement, and include inorganic compounds, organic acid salts, complexes (coordination compounds), etc. The metal elements other than aluminum and silicon are not particularly limited, but include, for example, monovalent metals such as lithium, sodium, potassium, rubidium, cesium, silver, and copper(I); divalent metals such as magnesium, calcium, barium, iron(II), zinc, copper(II), manganese(II), chromium(II), nickel(II), and cobalt(II); trivalent metals such as iron(III), nickel(III), cobalt(III), aluminum, gallium, chromium(III), zirconium(III), manganese(III), yttrium, lanthanum, cerium(III), and gadolinium; and tetravalent metals such as nickel(IV), cobalt(IV), titanium, zirconium(IV), and manganese(IV). Preferably, the metal element is alkali metal such as lithium and sodium, alkaline earth metal such as magnesium and calcium, zinc, iron, etc. One preferred embodiment of the present invention is in which the above metal element is at least one element selected from the group consisting of calcium, magnesium, and zinc. More preferably, the above metal element is calcium.

[0120] Examples of the inorganic compounds mentioned above include sulfates, carbonates, halides, nitrates, phosphates, silicates, hydroxides, oxides, sulfides, tellurides, and intermetallic compounds. Among these, sulfates, nitrates, and carbonates are preferred. More preferably are lithium sulfate, sodium sulfate, magnesium sulfate, calcium sulfate, zinc sulfate, iron sulfate, sodium nitrate, lithium nitrate, magnesium nitrate, calcium nitrate, zinc nitrate, iron nitrate, sodium carbonate, lithium carbonate, magnesium carbonate, zinc carbonate, iron carbonate, etc., and even more preferably sodium sulfate, calcium sulfate, and calcium nitrate, with calcium nitrate being particularly preferred.

[0121] The above organic acid salts are not particularly limited as long as they contain a metal element, but examples include carboxylates and sulfonates. Examples of carboxylates include acetates and oxalates. Preferably, they are acetates, more preferably sodium acetate, lithium acetate, magnesium acetate, zinc acetate, and iron acetate, and even more preferably sodium acetate. The above complexes are not particularly limited as long as they contain a metal element, but examples include ammine complexes, cyano complexes, halogeno complexes, hydroxyl complexes, phthalocyanine complexes, porphyrin complexes, carbonyl complexes, salen complexes, ethylenediamine complexes, β-diketone complexes, and β-diketoester complexes.

[0122] The aluminosilicate-containing composition of the present invention may contain other components besides aluminosilicate, water-soluble polymer, aluminum-containing compound, silicon-containing compound, the above-mentioned amine compound, the above-mentioned functional group-containing compound, the above-mentioned metal compound, and the above-mentioned alkylene oxide adduct. The other components are not particularly limited, but examples include defoaming agents, air-enhancing agents, surfactants, etc. The content ratio of the other components is not particularly limited, but it is preferably 0 to 20% by mass based on 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.

[0123] As the above-mentioned surfactant, one or more types of anionic, cationic, nonionic, and amphoteric surfactants, and polymeric surfactants can be used. The above-mentioned anionic surfactant is not particularly limited and includes, for example, polyoxyalkylene alkyl ether sulfate, polyoxyalkylene oleyl ether sodium sulfate, polyoxyalkylene alkylphenyl ether sulfate, alkyl diphenyl ether disulfonate, polyoxyalkylene (mono, di, tri) styrylphenyl ether sulfate, polyoxyalkylene (mono, di, tri) benzylphenyl ether sulfate, alkenyl succinate disalt; alkyl sulfate salts such as sodium dodecyl sulfate, potassium dodecyl sulfate, and ammonium alkyl sulfate; sodium dodecyl polyglycol ether sulfate; 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.

[0124] 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.). Nonionic surfactants equivalent to these can also be used.

[0125] 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 alkenylsuccinate-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.

[0126] Furthermore, in addition to the above-mentioned anionic surfactants, 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.

[0127] 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 Kogyo Seiyaku Co., Ltd.) can also be used. One or more of these can be used.

[0128] 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.

[0129] 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.

[0130] The above polymer surfactants are not particularly limited, and examples of nonionic polymer surfactants include polyvinylpyrrolidone and poly-N-vinylacetamide, and one or more of these can be used. Among the above surfactants, from an environmental perspective, it is preferable to use non-nonylphenyl type surfactants.

[0131] <Method for Producing an Aluminosilicate-Containing Composition> The method for producing an aluminosilicate-containing composition of the present invention includes a step of reacting an aluminum-containing compound and a silicon-containing compound in the presence of a water-soluble polymer at a temperature of 30°C or higher (hereinafter also referred to as step (α)). Specific examples and preferred forms of the water-soluble polymer, aluminum-containing compound, and silicon-containing compound are as described above. The reaction temperature in step (α) may be 30°C or higher, but is preferably 30 to 100°C, more preferably 35 to 95°C, even more preferably 40 to 90°C, even more preferably 40 to 85°C, even more preferably 40 to 80°C, even more preferably 45 to 75°C, and particularly preferably 45 to 60°C. By keeping the reaction temperature below 80°C, the strength development of the resulting composition can be more sufficiently enhanced.

[0132] The above step (α) can be carried out at a reaction temperature of 30°C or higher, but is preferably performed under conditions of pH 1 to 9. This allows for control of the degree of condensation, and by easily controlling the particle size of the alumina silicate-containing particles, further improvement in strength can be expected. The above pH is more preferably 1 to 7, and even more preferably 2 to 5.

[0133] The silicon atom content in the raw materials used in the above step (α) is preferably 20 mol% or more per 100 mol% of aluminum atoms. Preferably it is 30 to 1000 mol%, more preferably 50 to 300 mol%, even more preferably 70 to 200 mol%, and most preferably 80 to 150 mol%. In one embodiment, the silicon atom content is preferably 1 to 500 mol%, more preferably 10 to 300 mol%, even more preferably 30 to 200 mol%, particularly preferably 50 to 150 mol%, and most preferably 67 to 125 mol%.

[0134] The amount of water-soluble polymer used in step (α) above is preferably 5 to 90% 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 75% by mass, even more preferably 10 to 50% by mass, and particularly preferably 20 to 50% by mass. If the aluminum-containing compound and silicon-containing compound are hydrates, their amounts used should be converted to anhydrous forms.

[0135] The above step (α) is not particularly limited as long as the aluminum-containing compound and the silicon-containing compound are reacted at 30°C or higher in the presence of a water-soluble polymer, but it is preferable to carry it out while stirring in water. This makes it possible to set the average particle size of the resulting aluminosilicate-containing particles to a more suitable range. The method of adding the raw materials in the above step (α) is not particularly limited, but it is preferable to mix the water-soluble polymer, the aluminum-containing compound and the silicon-containing compound as aqueous solutions. In addition, the above compounds may be added all at once or sequentially in the above step (α), but it is preferable to dropwise add an aqueous solution containing one or more components of the water-soluble polymer, the aluminum-containing compound and the silicon-containing compound. More preferably, an aqueous solution containing a water-soluble polymer, an aqueous solution containing an aluminum-containing compound and an aqueous solution containing a silicon-containing compound are added dropwise, respectively.

[0136] Step (α) above is preferably carried out in the presence of a polyhydric alcohol alkylene oxide adduct and / or a polyalkyleneimine alkylene oxide adduct. Specific examples and preferred forms of the alkylene oxide adduct are as described above. When the alkylene oxide adduct is used in step (α), the amount used is preferably 0 to 50% by mass relative to 100% by mass of the total amount of the aluminum-containing compound and the silicon-containing compound used. More preferably 0 to 40% by mass, even more preferably 1 to 30% by mass, and particularly preferably 5 to 15% by mass. The method of adding the alkylene oxide adduct in step (α) is not particularly limited, but a dropwise addition of an aqueous solution containing a water-soluble polymer and an alkylene oxide adduct, an aqueous solution containing an aluminum-containing compound, and an aqueous solution containing a silicon-containing compound is preferred.

[0137] If the above aluminosilicate-containing composition contains an amine with a molecular weight of 1000 or less, it is preferable to add the amine in step (α). This results in an aluminosilicate-containing composition with superior early strength development. Specific examples and preferred forms of the amine are as described above. When an amine with a molecular weight of 1000 or less is used in step (α), the amount used is preferably 0.01 to 50% by mass, relative to 100% by mass of the total amount of the aluminum-containing compound and silicon-containing compound used. More preferably, it is 5 to 25% by mass, and even more preferably 5 to 15% by mass. The method of adding the amine in step (α) is not particularly limited, but it is preferable to add an aqueous solution containing a water-soluble polymer and an amine, an aqueous solution containing an aluminum-containing compound, and an aqueous solution containing a silicon-containing compound dropwise, respectively.

[0138] Step (α) above may be carried out in the presence of the functional group-containing compound. This further improves the stability of the aluminosilicate particles obtained. Specific examples and preferred forms of the functional group-containing compound are as described above. When a functional group-containing compound is used in step (α), the amount used is preferably 0 to 50% by mass relative to 100% by mass of the total amount of the aluminum-containing compound and the silicon-containing compound used. More preferably 1 to 25% by mass, even more preferably 2 to 15% by mass, and particularly preferably 5 to 15% by mass. In step (α), there are no particular limitations on the method of adding the functional group-containing compound, but a dropwise addition of an aqueous solution containing a water-soluble polymer, an aqueous solution containing an aluminum-containing compound, an aqueous solution containing a silicon-containing compound, and an aqueous solution containing a functional group-containing compound is preferred.

[0139] Step (α) described above may be carried out in the presence of a metal compound containing metal elements other than aluminum and silicon. Specific examples and preferred forms of the metal compound are as described above. When the metal compound is used in step (α), the amount used is preferably 0.001 to 50 mol% relative to 100 mol% of the total amount of aluminum and silicon elements in the aluminum-containing compound and silicon-containing compound used in step (α). More preferably 0.01 to 50 mol%, even more preferably 0.1 to 50 mol%, and particularly preferably 1 to 50 mol%. When the metal compound is added in step (α), the method of addition is not particularly limited, but a preferred method is to dropwise add an aqueous solution containing an aluminum-containing compound, an aqueous solution containing a silicon-containing compound, and an aqueous solution containing the metal compound to an aqueous solution containing a water-soluble polymer.

[0140] <Hardening Accelerator Composition> The aluminosilicate-containing composition of the present invention can be used as a hardening accelerator in addition to a hydraulic material composition. It can also be used in ultra-high-strength concrete.

[0141] The present invention also comprises an aluminosilicate obtained by reacting an aluminum-containing compound and a silicon-containing compound in the presence of a water-soluble polymer, and is a curing accelerator composition used in hydraulic material compositions. The present invention further comprises aluminosilicate-containing particles having an average particle size of 10 to 2500 nm, wherein the particles contain aluminosilicate and a water-soluble polymer, and is a curing accelerator composition used in hydraulic material compositions. The preferred forms of the aluminosilicate and water-soluble polymer in the above curing accelerator composition are as described above. The present invention also comprises a method for accelerating the curing of hydraulic materials, comprising the steps of adding the above aluminosilicate-containing composition to a hydraulic material composition and curing the composition obtained in the addition step. The preferred forms of the addition step and curing step in the above curing acceleration method are the same as the addition step (β) and curing step (γ) in the method for producing hydraulic material compositions and hydraulic cured products, respectively, described later.

[0142] 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.

[0143] <Hydraulic Material Composition> The present invention is also a hydraulic material composition comprising the aluminosilicate-containing composition and / or hardening accelerator composition of the present invention and a hydraulic material.

[0144] Suitable hydraulic material compositions include those commonly used, such as cement, water, fine aggregate, and coarse aggregate. They may also contain fine powders such as fly ash, blast furnace slag, silica fume, or limestone. Ultra-high-strength concrete refers to what is generally called in the field of cement compositions; that is, concrete in which the hardened product achieves strength equivalent to or higher than 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, particularly 18% by mass or less, particularly 14% by mass or less, and particularly around 12% by mass, it will be concrete with sufficient workability for normal use, and its hardened product will have a strength of 60 N / mm². ２ Furthermore, 80 N / mm２ Furthermore, more than 100 N / mm ２ Furthermore, especially 120 N / mm ２ Furthermore, especially 160 N / mm ２ Furthermore, especially 200 N / mm ２ It will exhibit a compressive strength of more than the above values.

[0145] The above hydraulic material composition may contain calcium carbonate. The type of calcium carbonate is not particularly limited, and it may be light calcium carbonate (produced by a chemical reaction by blowing carbon dioxide into an aqueous calcium hydroxide solution), heavy calcium carbonate (produced by excavating limestone and performing crushing and grinding), or light calcium carbonate (eco calcium carbonate) produced by reacting combustion exhaust gas or carbon dioxide in the atmosphere with calcium. The content ratio of the above calcium carbonate is not particularly limited, but it is preferably 5% by mass or more based on 100% by mass in total of the hydraulic material and calcium carbonate. More preferably, it is 5 - 95% by mass, and still more preferably, it is 5 - 35% by mass. As the hydraulic material containing 5% by mass or more of calcium carbonate, portland limestone cement is suitable, and types containing 5% - 35% by mass of calcium carbonate, types containing 5% - 15% by mass, etc. can be used. The particle size of the calcium carbonate to be used is preferably 5 mm or less in average particle diameter, more preferably 0.3 mm or less, particularly preferably 0.1 mm or less, and most preferably 0.02 mm or less.

[0146] The above hydraulic material composition may also further contain other commonly used cement dispersants and water reducing agents, and multiple combinations are also possible. Other cement dispersants (water reducing agents) are not particularly limited, but examples include the above-mentioned water-soluble polymer compounds, and among them, carboxylic acid-based water-soluble polymers, phosphoric acid-based water-soluble polymers, and sulfonic acid-based water-soluble polymers are suitable. These cement dispersants may be used alone or in combination of two or more.

[0147] 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, AE 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, etc., and one or more of these can be used.

[0148] When using the above-mentioned cement dispersant in combination, the ratio of the mixing mass of the other additives and the above-mentioned cement dispersant cannot be uniquely determined due to differences in the type of cement dispersant used, the formulation, and the test conditions, but it is preferable that the ratio of the mixing mass of the other additives and the above-mentioned cement dispersant be 5 to 95:95 to 5. More preferably, it is 10 to 90:90 to 10.

[0149] 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 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.

[0150] In the hydraulic material composition described above, examples of cement 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 and sewage sludge incineration ash as raw materials). The hydraulic material composition of the present invention may contain only one type of cement or two or more types.

[0151] The above hydraulic material composition preferably contains, in addition to cement, at least one selected from the group consisting of a substance having latent hydraulic properties and / or pozzolanic activity, and a filler other than calcium carbonate. Normally, SCM concrete has a longer hardening time and problems with early strength development than ordinary Portland cement, but the aluminosilicate-containing composition of the present invention exhibits excellent early strength development even for SCM concrete. Therefore, when the above hydraulic material composition contains at least one selected from the group consisting of a substance having latent hydraulic properties and / or pozzolanic activity, and a filler, it is also one of the preferred embodiments of the present invention.

[0152] The total content of substances having latent hydraulic properties and / or pozzolanic activity, as well as fillers, in the above hydraulic material composition is not particularly limited, but is preferably 0.1 to 10,000% by mass per 100% by mass of cement. More preferably 0.1 to 900% by mass, even more preferably 5 to 800% by mass, even more preferably 10 to 500% by mass, even more preferably 20 to 300% by mass, and particularly preferably 30 to 200% by mass.

[0153] In addition to gravel, crushed stone, granulated slag, and recycled aggregate, other aggregates mentioned above include refractory aggregates such as silica, clay, zircon, high alumina, silicon carbide, graphite, chromium, chromomagnesia, and magnesia. In this invention, when limestone crushed stone, which is mainly composed of large-grained calcium carbonate, is used as aggregate, it is treated as being outside the calculation of the calcium carbonate content.

[0154] 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 to 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. ３ It 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).

[0155] The content of the aluminosilicate-containing composition and / or hardening accelerator composition of the present invention in the above hydraulic material composition is not particularly limited, but is preferably 0.2 to 500% by mass with respect to 100% by mass of the total of cement, substances having latent hydraulic and / or pozzolanic activity, and fillers. More preferably it is 0.5 to 100% by mass, even more preferably 1 to 20% by mass, and most preferably 1 to 15% by mass.

[0156] In the above hydraulic material composition, the blending ratio of the aluminosilicate is preferably set to, for example, 0.01 to 5% 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 5% by mass, the effect will substantially plateau, which may be unfavorable from an economic standpoint. More preferably it is 0.3 to 3% by mass, even more preferably 0.5 to 3% by mass, and most preferably 1 to 2% 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. Accurately weigh an aluminum dish. 2. Accurately weigh the solid content sample into the aluminum dish accurately weighed in step 1. 3. Place the solid content sample accurately weighed in step 2 into a drying oven 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. 6. Subtract the mass of the aluminum tray obtained in step 1 from the mass obtained in step 5, and divide by the mass of the sample obtained in step 2 to determine the solid content.

[0157] The aluminosilicate-containing composition and / or hardening accelerator composition of the present invention provides a hydraulic material composition that exhibits excellent early strength development, making it effective for use in 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.

[0158] <Method for Producing Hydraulic Material Composition> 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 an aluminosilicate obtained by reacting an aluminum-containing compound and a silicon-containing compound at a temperature of 30°C or higher in the presence of a water-soluble polymer having at least one functional group selected from carboxyl groups, phosphate groups, sulfonic acid groups and their salts and phosphate ester groups to a hydraulic material composition. The present invention also provides a method for producing a hydraulic material composition, the method of which is to add an aluminosilicate obtained by reacting an aluminum-containing compound and a silicon-containing compound at a temperature of 30°C or higher in the presence of a water-soluble polymer having at least one functional group selected from carboxyl groups, phosphate groups, sulfonic acid groups and their salts and phosphate ester groups to a hydraulic material composition. The present invention provides a method for producing a hydraulic material composition, further comprising the steps of: (α) reacting a water-aluminum-containing compound and a silicon-containing compound at a temperature of 30°C or higher in the presence of a water-soluble polymer having at least one functional group selected from carboxyl groups, phosphate groups, sulfonic acid groups and their salts and phosphate ester groups to obtain an aluminosilicate; and (β) adding the aluminosilicate obtained in step (α) to a hydraulic material composition. The method of adding the aluminosilicate in step (β) is not particularly limited, but it is preferable to disperse the aluminosilicate-containing composition in a solvent such as water before adding it.

[0159] <Method for Manufacturing Hydraulic Hardened Products> The present invention further relates to a method for manufacturing hydraulic hardened products, the manufacturing method of which includes a step (γ) of hardening the hydraulic material composition of the present invention. The hardening method in the hardening step (γ) is not particularly limited, and may be cured at room temperature or by heat curing such as steam curing. The hardening step (γ) is preferably a step of hardening the hydraulic material composition at 0 to 90°C. The hardening temperature is preferably 5 to 85°C, more preferably 5 to 80°C, even more preferably 5 to 75°C, and particularly preferably 5 to 40°C.

[0160] In the method for producing the hydraulically hardened product described above, it is preferable to carry out the hardening step (γ) under conditions of humidity of 40 to 100%. More preferably, the humidity is 50 to 100%, and even more preferably 60 to 100%.

[0161] 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%.

[0162] 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.

[0163] In the method for producing the hydraulically hardened product described above, it is preferable to perform the hardening step (γ) by steam curing.

[0164] 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.

[0165] 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 80°C, and particularly preferably 40 to 60°C.

[0166] 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 composition and hardening the composition obtained in the addition step. Preferred forms of the addition step and hardening step in the above rapid strength improvement method are the same as the addition step (β) and hardening step (γ) in the method for manufacturing a hydraulic material composition and a hydraulically hardened product, respectively.

[0167] 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".

[0168] <Measurement of Average Particle Size of Aluminosilicate-Containing Particles> The first obtained aqueous dispersion was filtered using Advantec filter paper No. 2 to remove impurities, and the following procedure was performed using the obtained filtrate. Using a particle size analyzer, the scattering intensity of the aqueous dispersion of the aluminosilicate-containing composition with a solid content of 0.1% by mass was measured by dynamic light scattering, and the Z-average particle size was calculated. Apparatus: Malvern Zetasizer Nano Measurement temperature: 20.0°C Solvent: Ion-exchanged water

[0169] <Gel Permeation Chromatography (GPC)> The weight-average molecular weight (Mw) of water-soluble polymers was measured by GPC (gel permeation chromatography) under the following measurement conditions. (GPC Analysis Method) Instrument: Waters Alliance (2695) Analysis software: Empower2 Professional + GPC option, Waters Columns used: TSKguardcolumns SWXL + TSKgel G4000SWXL + G3000SWXL + G2000SWXL, manufactured by Tosoh Corporation Detector: Differential refractometer (RI) detector (Waters 2414), multi-wavelength visible ultraviolet (PDA) detector (Waters 2996) Eluent: Dissolve 115.6 g of sodium acetate trihydrate in a mixed solvent of 10999 g of water and 6001 g of acetonitrile, and further adjust the pH to 6.0 with acetic acid. Standard substances for calibration curve preparation: Polyethylene glycol (peak top molecular weight (Mp) 272500, 219300, 107000, 50000, 24000, 12600, 7100, 4250, 1470) Calibration curve: Prepared using a cubic equation based on the Mp values ​​and elution times of the above standard substances. Flow rate: 1 mL / min Column temperature: 40°C 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)

[0170] (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 with the polymer to separate the polymer portion from the monomer portion and impurity portion, 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)

[0171] (Measurement of suspension viscosity) The aluminosilicate compositions obtained in the following examples were divided into several sealed glass vials. The suspensions were then stored at 40°C in the sealed glass vials without stirring, and the change in solution viscosity over time was monitored. The acceleration coefficients shown in Table 1 were calculated by normalizing the viscosity of the aluminosilicate composition after storage at 40°C for a predetermined period relative to the aluminosilicate immediately after synthesis.

[0172] <Measurement of Heat of Hydration> (Preparation of Paste Sample) The composition of the paste sample is as follows: W: Sample and ion-exchange aqueous solution C: Cement (ordinary Portland cement, manufactured by Taiheiyo Cement Corporation) W / C = 0.4 The cement was placed in an ampoule and put into the apparatus, and the temperature was adjusted to 20°C. Next, the mixture of the prepared sample and ion-exchange aqueous solution was measured into a syringe and injected into the ampoule adjusted to 20°C, and kneaded for 5 minutes to prepare the paste sample. The amount of aluminosilicate composition added was 1.0 wt% of the solid content relative to the powder, and the heat of hydration of the prepared paste sample was measured. The heat of hydration without aluminosilicate was 145 W / g, so it can be seen that samples showing a higher heat of hydration are useful as strength improvers. Heat of hydration measuring device: Microcalorimeter measuring device (manufactured by TA Instruments) Temperature: 20°C

[0173] <Production Example 1> A solution (1a) was prepared by dissolving 0.3 parts of L-ascorbic acid in 191.2 parts of water. A solution (1b) was prepared by dissolving 2.2 parts of 3-mercaptopropionic acid in 13.5 parts of water. A solution (1c) was prepared by dissolving 32.2 parts of acrylic acid (AA) in 8.0 parts of water. In a reaction vessel equipped with a thermometer, stirrer, dropping device, nitrogen inlet tube, and reflux condenser, 30.0 parts of water and 29.8 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 (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 dropwise 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) with a weight-average molecular weight of 20,000 was obtained.

[0174] <Production Example 2> Solution (2a) was prepared by dissolving 0.53 parts of L-ascorbic acid in 191.2 parts of water. Solution (2b) was prepared by dissolving 0.4 parts of 3-mercaptopropionic acid in 4.7 parts of water. Solution (2c) was prepared by dissolving 50.8 parts of acrylic acid (AA) in 12.7 parts of water. 46.8 parts of water and 193.2 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 into a reaction vessel equipped with a thermometer, stirrer, dropping device, nitrogen inlet tube, and reflux condenser. Subsequently, the reaction vessel was purged with nitrogen while stirring, and after raising the temperature to 60°C under a nitrogen atmosphere, 26.3 parts of a 2% aqueous solution of hydrogen peroxide were added. After 30 minutes, the above-mentioned mixed solution (2a) was added dropwise at a constant rate over 4.5 hours, the above-mentioned mixed solution (2b) over 3.5 hours, and the above-mentioned mixed solution (2c) over 3 hours. The temperature was kept constant at 60°C during this time. After the dropwise addition of mixed solution (2a) 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 = 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) with a weight-average molecular weight of 50,000 was obtained.

[0175] <Production Example 3> A solution (3a) was prepared by dissolving 0.13 parts L-ascorbic acid in 13.3 parts water. A solution (3b) was prepared by dissolving 0.21 parts 3-mercaptopropionic acid in 10.2 parts water. A solution (3c) was prepared by dissolving 8.0 parts acrylic acid (AA) in 2.0 parts water. 15.4 parts water and 246.7 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 into a reaction vessel equipped with a thermometer, stirrer, dropping device, nitrogen inlet tube, and reflux condenser. Subsequently, the reaction vessel was purged with nitrogen while stirring, and after raising the temperature to 60°C under a nitrogen atmosphere, 6.7 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 dropwise 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 = 4.0 using an aqueous sodium hydroxide solution at a temperature below the polymerization reaction temperature. In this way, a polymer solution containing copolymer (3) with a weight-average molecular weight of 55,000 was obtained.

[0176] <Production Example 4> A solution (4a) was prepared by dissolving 0.25 parts of L-ascorbic acid in 16.3 parts of water. A solution (4b) was prepared by dissolving 0.96 parts of 3-mercaptopropionic acid in 23.1 parts of water. A solution (4c) was prepared by dissolving 20.3 parts of acrylic acid (AA) in 5.1 parts of water. 5.4 parts of water and 231.3 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 into a reaction vessel equipped with a thermometer, stirrer, dropping device, nitrogen inlet tube, and reflux condenser. Subsequently, the reaction vessel was purged with nitrogen while stirring, and after raising the temperature to 60°C under a nitrogen atmosphere, 12.3 parts of a 2% aqueous solution of hydrogen peroxide were added. After 30 minutes, the above-mentioned mixed solution (4a) was added dropwise at a constant rate over 4.5 hours, the above-mentioned mixed solution (4b) over 3.5 hours, and the above-mentioned mixed solution (4c) over 3 hours. The temperature was kept constant at 60°C during this time. After the dropwise addition of mixed solution (4a) 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 = 6.0 using an aqueous sodium hydroxide solution at a temperature below the polymerization reaction temperature. In this way, a polymer solution containing copolymer (4) with a weight-average molecular weight of 30,000 was obtained.

[0177] <Production Example 5> A solution (5a) was prepared by dissolving 0.54 parts of L-ascorbic acid in 10.2 parts of water. A solution (5b) was prepared by dissolving 4.17 parts of 3-mercaptopropionic acid in 16.7 parts of water. A solution (5c) was prepared by dissolving 33.0 parts of acrylic acid (AA) in 8.3 parts of water. 55.8 parts of water and 172.3 parts of an unsaturated polyalkylene glycol ether monomer (IPN-10), in which an average of 10 moles of ethylene oxide was added to 3-methyl-3-buten-1-ol, were charged into a reaction vessel equipped with a thermometer, stirrer, dropping device, nitrogen inlet tube, and reflux condenser. Subsequently, the reaction vessel was purged with nitrogen while stirring, and after raising the temperature to 60°C under a nitrogen atmosphere, 26.7 parts of a 2% aqueous hydrogen peroxide solution were added. After 30 minutes, the above-mentioned mixed solution (5a) was added dropwise at a constant rate over 4.5 hours, the above-mentioned mixed solution (5b) over 3.5 hours, and the above-mentioned mixed solution (5c) over 3 hours. The temperature was kept constant at 60°C during this time. After the dropwise addition of mixed solution (5a) 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 = 6.0 using an aqueous sodium hydroxide solution at a temperature below the polymerization reaction temperature. In this way, a polymer solution containing copolymer (5) with a weight-average molecular weight of 7,000 was obtained.

[0178] <Production Example 6> A solution (6a) was prepared by dissolving 0.12 parts of L-ascorbic acid in 11.6 parts of water. A solution (6b) was prepared by dissolving 0.91 parts of 3-mercaptopropionic acid in 17.2 parts of water. A solution (6c) was prepared by dissolving 20.5 parts of Light Ester P1M (P1M), manufactured by Kyoeisha Chemical Co., Ltd., in 5.1 parts of water. In a reaction vessel equipped with a thermometer, stirrer, dropping device, nitrogen inlet tube, and reflux condenser, 22.9 parts of water and 231.0 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 was 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, 5.81 parts of a 2% aqueous solution of hydrogen peroxide were added. After 30 minutes, the above-mentioned mixed solution (6a) was added dropwise at a constant rate over 4.5 hours, the above-mentioned mixed solution (6b) over 3.5 hours, and the above-mentioned mixed solution (6c) over 3 hours. The temperature was kept constant at 60°C during this time. After the dropwise addition of mixed solution (6a) 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 = 6.0 using an aqueous sodium hydroxide solution at a temperature below the polymerization reaction temperature. In this way, a polymer solution containing copolymer (6) with a weight-average molecular weight of 38,000 was obtained.

[0179] <Production Example 7> A solution (7a) was prepared by dissolving 0.19 parts of L-ascorbic acid in 19.7 parts of water. In a reaction vessel equipped with a thermometer, stirrer, dropper, nitrogen inlet tube, and reflux condenser, 14.3 parts of water, 225.9 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, and 24.6 parts of maleic acid were charged. Subsequently, the reaction vessel was purged with nitrogen while stirring, and the temperature was raised to 60°C under a nitrogen atmosphere, after which 9.91 parts of a 2% aqueous solution of hydrogen peroxide was added. After 30 minutes, the above mixed solution (7a) was added dropwise at a constant rate over 3 hours. The temperature was kept constant at 60°C during this time. After the dropwise addition of the mixed solution (7a) 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 = 6.0 using an aqueous sodium hydroxide solution at a temperature below the polymerization reaction temperature. In this way, a polymer solution containing copolymer (7) with a weight-average molecular weight of 28,000 was obtained.

[0180] <Production Example 8> A solution (8a) was prepared by dissolving 0.09 parts of L-ascorbic acid in 18.1 parts of water. A solution (8b) was prepared by dissolving 0.56 parts of 3-mercaptopropionic acid in 10.7 parts of water. A solution (8c) was prepared by dissolving 7.9 parts of acrylic acid (AA) in 5.3 parts of water. In a reaction vessel equipped with a thermometer, stirrer, dropping device, nitrogen inlet tube, and reflux condenser, 8.7 parts of water and 246.7 parts of an 80% aqueous solution of an unsaturated polyalkylene glycol ether monomer (MLA-200) obtained by adding an average of 200 moles of ethylene oxide to 2-methyl-3-propen-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, 4.5 parts of a 2% aqueous solution of hydrogen peroxide were added. After 30 minutes, the above-mentioned mixed solution (8a) was added dropwise at a constant rate over 4.5 hours, the above-mentioned mixed solution (8b) over 3.5 hours, and the above-mentioned mixed solution (8c) over 3 hours. The temperature was kept constant at 60°C during this time. After the addition of mixed solution (8a) 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 = 6.0 using an aqueous sodium hydroxide solution at a temperature below the polymerization reaction temperature. In this way, a polymer solution containing copolymer (8) with a weight-average molecular weight of 32,000 was obtained.

[0181] <Production Example 9> Solution (9a) was prepared by dissolving 1.8 parts sodium persulfate in 33.8 parts water. Solution (9b) was prepared by dissolving 122.2 parts methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added: 23) (MPG-23), 3.8 parts 3-mercaptopropionic acid, and 37.8 parts methacrylic acid (MAA) in 69.6 parts water. 131.0 parts water was charged into a reaction vessel equipped with a thermometer, stirrer, dropping device, 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 (9a) was added dropwise at a constant rate over 5 hours, and the above-mentioned mixed solution (9b) 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 (9a) was completed, 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 (9) with a weight-average molecular weight of 8,000 was obtained.

[0182] <Example 1> 47.2 g of aluminum sulfate 14-18 hydrate (solids content 53.9%) was dissolved in 54.6 g of deionized water to obtain solution (A1). Next, 42.4 g of sodium metasilicate 9 hydrate (solids content 42.9%) was dissolved in 78.8 g of deionized water to obtain solution (B1). Next, 25.7 g of copolymer (1) (solids content 40%) and 6.82 g of triisopropanolamine (solids content 80%) were dissolved in 44.5 g of deionized water to obtain solution (C1). 100.0 g of deionized water was poured into a glass container equipped with a stirring device and stirred. Solutions (A1), (B1), and (C1) were then slowly added dropwise to the mixture at 50°C over approximately 180 minutes each to obtain aluminosilicate composition (1). The composition of the aluminosilicate composition (1) was 10.9% total of aluminosilicate, aluminum sulfate, and sodium metasilicate, 2.7% copolymer, and 1.4% triisopropanolamine. The solid content concentration of the aluminosilicate composition was 14.8%, and the average Z particle size was 430 nm.

[0183] <Example 2> 45.7 g of aluminum sulfate 14-18 hydrate (solids content 53.9%) was dissolved in 52.9 g of deionized water to obtain solution (A2). Next, 32.8 g of sodium metasilicate 9 hydrate (solids content 42.9%) was dissolved in 61.0 g of deionized water to obtain solution (B2). Next, 22.8 g of copolymer (1) (solids content 40%), 6.05 g of triisopropanolamine (solids content 80%), and 6.05 g of polyethyleneimine ethylene oxide copolymer (manufactured by Nippon Shokubai Co., Ltd., obtained by adding ethylene oxide (EO) equivalent to 20 moles per mole of nitrogen atoms of polyethyleneimine (SP-006: manufactured by Nippon Shokubai)) (solids content 80%) were dissolved in 66.3 g of deionized water to obtain solution (C2). Furthermore, 1.94 g of sodium gluconate was dissolved in 4.52 g of deionized water to obtain solution (D2). Aluminosilicate composition (2) was obtained by filling a glass container equipped with a stirring device with 100.0 g of deionized water and stirring, and then slowly adding solutions (A2), (B2), (C2), and (D2) dropwise to it over approximately 60 minutes at 30°C. The composition of aluminosilicate composition (2) was 9.9% total of aluminosilicate, aluminum sulfate, and sodium metasilicate, 2.4% copolymer, 1.2% triisopropanolamine, 1.2% polyethyleneimine ethylene oxide, and 0.5% sodium gluconate. The solid content concentration in the aluminosilicate composition was 15.2%, and the average Z particle size was 100 nm.

[0184] <Example 3> 45.7 g of aluminum sulfate 14-18 hydrate (solids content 53.9%) was dissolved in 52.9 g of deionized water to obtain solution (A3). Next, 32.8 g of sodium metasilicate 9 hydrate (solids content 42.9%) was dissolved in 61.0 g of deionized water to obtain solution (B3). Next, 22.8 g of copolymer (1) (solids content 40%), 6.05 g of triisopropanolamine (solids content 80%), and 6.05 g of polyethyleneimine ethylene oxide copolymer (solids content 80%) were dissolved in 66.3 g of deionized water to obtain solution (C3). Furthermore, 1.94 g of sodium gluconate was dissolved in 4.52 g of deionized water to obtain solution (D3). Aluminosilicate composition (3) was obtained by filling a glass container equipped with a stirring device with 100.0 g of deionized water and stirring, and then slowly adding solutions (A3), (B3), (C3), and (D3) dropwise to it over approximately 60 minutes at 50°C. The composition of aluminosilicate composition (3) was 9.9% total of aluminosilicate, aluminum sulfate, and sodium metasilicate, 2.4% copolymer, 1.2% triisopropanolamine, 1.2% polyethyleneimine ethylene oxide, and 0.5% sodium gluconate. The solid content concentration in the aluminosilicate composition was 15.2%, and the average Z particle size was 220 nm.

[0185] <Example 4> 45.7 g of aluminum sulfate 14-18 hydrate (solids content 53.9%) was dissolved in 52.9 g of deionized water to obtain solution (A4). Next, 32.8 g of sodium metasilicate 9 hydrate (solids content 42.9%) was dissolved in 61.0 g of deionized water to obtain solution (B4). Next, 22.8 g of copolymer (1) (solids content 40%), 6.05 g of triisopropanolamine (solids content 80%), and 6.05 g of polyethyleneimine ethylene oxide copolymer (solids content 80%) were dissolved in 66.3 g of deionized water to obtain solution (C4). Furthermore, 1.94 g of sodium gluconate was dissolved in 4.52 g of deionized water to obtain solution (D4). Aluminosilicate composition (4) was obtained by filling a glass container equipped with a stirring device with 100.0 g of deionized water and stirring, and then slowly adding solutions (A4), (B4), (C4), and (D4) dropwise to it at 70°C for approximately 60 minutes each. The composition of aluminosilicate composition (4) was 9.9% total of aluminosilicate, aluminum sulfate, and sodium metasilicate, 2.4% copolymer, 1.2% triisopropanolamine, 1.2% polyethyleneimine ethylene oxide, and 0.5% sodium gluconate. The solid content concentration in the aluminosilicate composition was 15.2%, and the average Z particle size was 650 nm.

[0186] <Example 5> 45.7 g of aluminum sulfate 14-18 hydrate (solids content 53.9%) was dissolved in 52.9 g of deionized water to obtain solution (A5). Next, 32.8 g of sodium metasilicate 9 hydrate (solids content 42.9%) was dissolved in 61.0 g of deionized water to obtain solution (B5). Next, 22.8 g of copolymer (1) (solids content 40%), 6.05 g of triisopropanolamine (solids content 80%), and 6.05 g of polyethyleneimine ethylene oxide copolymer (solids content 80%) were dissolved in 66.3 g of deionized water to obtain solution (C5). Furthermore, 1.94 g of sodium gluconate was dissolved in 4.52 g of deionized water to obtain solution (D5). Aluminosilicate composition (5) was obtained by filling a glass container equipped with a stirring device with 100.0 g of deionized water and stirring, and then slowly adding solutions (A5), (B5), (C5), and (D5) dropwise to it at 90°C for approximately 60 minutes each. The composition of aluminosilicate composition (5) was 9.9% total of aluminosilicate, aluminum sulfate, and sodium metasilicate, 2.4% copolymer, 1.2% triisopropanolamine, 1.2% polyethyleneimine ethylene oxide, and 0.5% sodium gluconate. The solid content concentration in the aluminosilicate composition was 15.2%, and the average Z particle size was 770 nm.

[0187] <Example 6> 51.5 g of aluminum sulfate 14-18 hydrate (solids content 53.9%) was dissolved in 59.6 g of deionized water to obtain solution (A6). Next, 37.0 g of sodium metasilicate 9 hydrate (solids content 42.9%) was dissolved in 68.7 g of deionized water to obtain solution (B6). Next, 27.3 g of copolymer (1) (solids content 40%) and 6.7 g of polyethyleneimine ethylene oxide copolymer (solids content 80%) were dissolved in 49.2 g of deionized water to obtain solution (C6). 100.0 g of deionized water was poured into a glass container equipped with a stirring device and stirred. Solutions (A6), (B6), and (C6) were then slowly added dropwise to the mixture at 50°C over approximately 60 minutes each to obtain aluminosilicate composition (6). The composition of the aluminosilicate composition (6) was 10.9% total of aluminosilicate, aluminum sulfate, and sodium metasilicate, 2.7% copolymer, and 1.3% polyethyleneimine ethylene oxide. The solid content concentration in the aluminosilicate composition was 15.0%, and the average Z particle size was 530 nm.

[0188] <Example 7> 51.5 g of aluminum sulfate 14-18 hydrate (solids content 53.9%) was dissolved in 59.6 g of deionized water to obtain solution (A7). Next, 37.0 g of sodium metasilicate 9 hydrate (solids content 42.9%) was dissolved in 68.7 g of deionized water to obtain solution (B7). Next, 27.3 g of copolymer (1) (solids content 40%) and 5.5 g of polyethylene glycol (molecular weight 400, Fujifilm Wako Pure Chemical Industries, Ltd.) were dissolved in 50.4 g of deionized water to obtain solution (C7). 100.0 g of deionized water was poured into a glass container equipped with a stirring device and stirred. Solutions (A7), (B7), and (C7) were then slowly added dropwise to the mixture at 50°C over approximately 60 minutes each to obtain aluminosilicate composition (7). The composition of the aluminosilicate composition (7) was 10.9% total of aluminosilicate, aluminum sulfate, and sodium metasilicate, 2.7% copolymer, and 1.4% polyethylene glycol. The solid content concentration in the aluminosilicate composition was 15.0%, and the average Z particle size was 540 nm.

[0189] <Example 8> 51.5 g of aluminum sulfate 14-18 hydrate (solids content 53.9%) was dissolved in 59.6 g of deionized water to obtain solution (A8). Next, 37.0 g of sodium metasilicate 9 hydrate (solids content 42.9%) was dissolved in 68.7 g of deionized water to obtain solution (B8). Next, 27.3 g of copolymer (1) (solids content 40%) and 5.5 g of polyethylene glycol (molecular weight 2000, Fujifilm Wako Pure Chemical Industries, Ltd.) were dissolved in 50.4 g of deionized water to obtain solution (C8). 100.0 g of deionized water was poured into a glass container equipped with a stirring device and stirred. Solutions (A8), (B8), and (C8) were then slowly added dropwise to the mixture at 50°C over approximately 60 minutes each to obtain aluminosilicate composition (8). The composition of the aluminosilicate composition (8) was 10.9% total of aluminosilicate, aluminum sulfate, and sodium metasilicate, 2.7% copolymer, and 1.4% polyethylene glycol. The solid content concentration in the aluminosilicate composition was 15.0%, and the average Z particle size was 690 nm.

[0190] <Example 9> 51.5 g of aluminum sulfate 14-18 hydrate (solids content 53.9%) was dissolved in 59.6 g of deionized water to obtain solution (A9). Next, 37.0 g of sodium metasilicate 9 hydrate (solids content 42.9%) was dissolved in 68.7 g of deionized water to obtain solution (B9). Next, 27.3 g of copolymer (1) (solids content 40%) and 5.5 g of polyethylene glycol (molecular weight 10000, Fujifilm Wako Pure Chemical Industries, Ltd.) were dissolved in 50.4 g of deionized water to obtain solution (C9). 100.0 g of deionized water was poured into a glass container equipped with a stirring device and stirred. Solutions (A9), (B9), and (C9) were then slowly added dropwise to the mixture at 50°C over approximately 60 minutes each to obtain aluminosilicate composition (9). The composition of the aluminosilicate composition (9) was 10.9% total of aluminosilicate, aluminum sulfate, and sodium metasilicate, 2.7% copolymer, and 1.4% polyethylene glycol. The solid content concentration in the aluminosilicate composition was 15.0%, and the average Z particle size was 620 nm.

[0191] <Example 10> 47.2 g of aluminum sulfate 14-18 hydrate (solids content 53.9%) was dissolved in 54.6 g of deionized water to obtain solution (A12). Next, 42.4 g of sodium metasilicate 9 hydrate (solids content 42.9%) was dissolved in 78.8 g of deionized water to obtain solution (B12). Next, 25.7 g of copolymer (2) (solids content 40%) and 6.82 g of triisopropanolamine (solids content 80%) were dissolved in 44.5 g of deionized water to obtain solution (C12). 100.0 g of deionized water was poured into a glass container equipped with a stirring device and stirred. Solutions (A12), (B12), and (C12) were then slowly added dropwise to the mixture at 50°C over approximately 180 minutes each to obtain aluminosilicate composition (12). The composition of the aluminosilicate composition (12) was 10.9% total of aluminosilicate, aluminum sulfate, and sodium metasilicate, 2.7% copolymer, and 1.4% triisopropanolamine. The solid content concentration of the aluminosilicate composition was 14.8%, and the average Z particle size was 530 nm.

[0192] <Example 11> 47.2 g of aluminum sulfate 14-18 hydrate (solids content 53.9%) was dissolved in 54.6 g of deionized water to obtain solution (A13). Next, 42.4 g of sodium metasilicate 9 hydrate (solids content 42.9%) was dissolved in 78.8 g of deionized water to obtain solution (B13). Next, 25.7 g of copolymer (3) (solids content 40%) and 6.82 g of triisopropanolamine (solids content 80%) were dissolved in 44.5 g of deionized water to obtain solution (C13). 100.0 g of deionized water was poured into a glass container equipped with a stirring device and stirred. Solutions (A13), (B13), and (C13) were then slowly added dropwise to the mixture at 50°C over approximately 180 minutes each to obtain aluminosilicate composition (13). The composition of the aluminosilicate composition (13) was 10.9% total of aluminosilicate, aluminum sulfate, and sodium metasilicate, 2.7% copolymer, and 1.4% triisopropanolamine. The solid content concentration of the aluminosilicate composition was 14.8%, and the average Z particle size was 630 nm.

[0193] <Example 12> 47.2 g of aluminum sulfate 14-18 hydrate (solids content 53.9%) was dissolved in 54.6 g of deionized water to obtain solution (A14). Next, 42.4 g of sodium metasilicate 9 hydrate (solids content 42.9%) was dissolved in 78.8 g of deionized water to obtain solution (B14). Next, 25.7 g of copolymer (4) (solids content 40%) and 6.82 g of triisopropanolamine (solids content 80%) were dissolved in 44.5 g of deionized water to obtain solution (C14). 100.0 g of deionized water was poured into a glass container equipped with a stirring device and stirred. Solutions (A14), (B14), and (C14) were then slowly added dropwise to the mixture at 50°C over approximately 180 minutes each to obtain aluminosilicate composition (14). The composition of the aluminosilicate composition (14) was 10.9% in total of aluminosilicate, aluminum sulfate, and sodium metasilicate, 2.7% of copolymer, and 1.4% of triisopropanolamine. The solid content concentration of the aluminosilicate composition was 14.8%, and the average Z particle size was 330 nm.

[0194] <Example 13> 47.2 g of aluminum sulfate 14-18 hydrate (solids content 53.9%) was dissolved in 54.6 g of deionized water to obtain solution (A15). Next, 42.4 g of sodium metasilicate 9 hydrate (solids content 42.9%) was dissolved in 78.8 g of deionized water to obtain solution (B15). Next, 25.7 g of copolymer (5) (solids content 40%) and 6.82 g of triisopropanolamine (solids content 80%) were dissolved in 44.5 g of deionized water to obtain solution (C15). 100.0 g of deionized water was poured into a glass container equipped with a stirring device and stirred. Solutions (A15), (B15), and (C15) were then slowly added dropwise to the mixture at 50°C over approximately 180 minutes each to obtain aluminosilicate composition (15). The composition of the aluminosilicate composition (15) was 10.9% total of aluminosilicate, aluminum sulfate, and sodium metasilicate, 2.7% copolymer, and 1.4% triisopropanolamine. The solid content concentration of the aluminosilicate composition was 14.8%, and the average Z particle size was 370 nm.

[0195] <Example 14> 47.2 g of aluminum sulfate 14-18 hydrate (solids content 53.9%) was dissolved in 54.6 g of deionized water to obtain solution (A16). Next, 42.4 g of sodium metasilicate 9 hydrate (solids content 42.9%) was dissolved in 78.8 g of deionized water to obtain solution (B16). Next, 25.7 g of copolymer (6) (solids content 40%) and 6.82 g of triisopropanolamine (solids content 80%) were dissolved in 44.5 g of deionized water to obtain solution (C16). 100.0 g of deionized water was poured into a glass container equipped with a stirring device and stirred. Solutions (A16), (B16), and (C16) were then slowly added dropwise to the mixture at 50°C for approximately 180 minutes each to obtain aluminosilicate composition (16). The composition of the aluminosilicate composition (16) was 10.9% in total of aluminosilicate, aluminum sulfate, and sodium metasilicate, 2.7% of copolymer, and 1.4% of triisopropanolamine. The solid content concentration of the aluminosilicate composition was 14.8%, and the Z-average particle size was 260 nm.

[0196] <Example 15> 47.2 g of aluminum sulfate 14-18 hydrate (solids content 53.9%) was dissolved in 54.6 g of deionized water to obtain solution (A17). Next, 42.4 g of sodium metasilicate 9 hydrate (solids content 42.9%) was dissolved in 78.8 g of deionized water to obtain solution (B17). Next, 25.7 g of copolymer (7) (solids content 40%) and 6.82 g of triisopropanolamine (solids content 80%) were dissolved in 44.5 g of deionized water to obtain solution (C17). 100.0 g of deionized water was poured into a glass container equipped with a stirring device and stirred. Solutions (A17), (B17), and (C17) were then slowly added dropwise to the mixture at 50°C for approximately 180 minutes each to obtain aluminosilicate composition (17). The composition of the aluminosilicate composition (17) was 10.9% total of aluminosilicate, aluminum sulfate, and sodium metasilicate, 2.7% copolymer, and 1.4% triisopropanolamine. The solid content concentration of the aluminosilicate composition was 14.8%, and the average Z particle size was 330 nm.

[0197] <Example 16> 47.2 g of aluminum sulfate 14-18 hydrate (solids content 53.9%) was dissolved in 54.6 g of deionized water to obtain solution (A18). Next, 42.4 g of sodium metasilicate 9 hydrate (solids content 42.9%) was dissolved in 78.8 g of deionized water to obtain solution (B18). Next, 25.7 g of copolymer (8) (solids content 40%) and 6.82 g of triisopropanolamine (solids content 80%) were dissolved in 44.5 g of deionized water to obtain solution (C18). 100.0 g of deionized water was poured into a glass container equipped with a stirring device and stirred. Solutions (A18), (B18), and (C18) were then slowly added dropwise to the mixture at 50°C for approximately 180 minutes each to obtain aluminosilicate composition (18). The composition of the aluminosilicate composition (18) was 10.9% total of aluminosilicate, aluminum sulfate, and sodium metasilicate, 2.7% copolymer, and 1.4% triisopropanolamine. The solid content concentration of the aluminosilicate composition was 14.8%, and the average Z particle size was 290 nm.

[0198] <Example 17> 47.2 g of aluminum sulfate 14-18 hydrate (solids content 53.9%) was dissolved in 54.6 g of deionized water to obtain solution (A19). Next, 42.4 g of sodium metasilicate 9 hydrate (solids content 42.9%) was dissolved in 78.8 g of deionized water to obtain solution (B19). Next, 25.7 g of copolymer (9) (solids content 40%) and 6.82 g of triisopropanolamine (solids content 80%) were dissolved in 44.5 g of deionized water to obtain solution (C18). 100.0 g of deionized water was poured into a glass container equipped with a stirring device and stirred. Solutions (A19), (B19), and (C19) were then slowly added dropwise to the mixture at 50°C over approximately 180 minutes each to obtain aluminosilicate composition (19). The composition of the aluminosilicate composition (19) was 10.9% in total, consisting of aluminosilicate, aluminum sulfate, and sodium metasilicate, 2.7% of copolymer, and 1.4% of triisopropanolamine. The solid content concentration of the aluminosilicate composition was 14.8%, and the average Z particle size was 590 nm.

[0199] <Comparative Example 1> 202.7 g of aluminum sulfate 14-18 hydrate (solids content 53.9%) was dissolved in 343.6 g of deionized water to obtain solution (A10). Next, 181.7 g of sodium metasilicate 9 hydrate (solids content 42.9%) was dissolved in 793.9 g of deionized water to obtain solution (B10). Next, 93.6 g of copolymer (1) (solids content 40%) and 46.8 g of triisopropanolamine (solids content 40%) were dissolved in 414.6 g of deionized water to obtain solution (C10). A glass container equipped with a stirring device was filled with a solution prepared by dissolving 23.4 g of copolymer (1) (40% solids) and 11.7 g of triisopropanolamine (40% solids) in 88.1 g of deionized water, and the mixture was stirred. Solutions (A10), (B10), and (C10) were then slowly added dropwise to the mixture over approximately 60 minutes at 20°C to obtain aluminosilicate composition (10). The composition of aluminosilicate composition (10) consisted of a total of 8.5% aluminosilicate, aluminum sulfate, and sodium metasilicate, 2.1% copolymer, and 1.1% triisopropanolamine. The solids content in the aluminosilicate composition was 11.7%, and the average Z particle size was 110 nm.

[0200] <Comparative Example 2> 56.7 g of aluminum sulfate 14-18 hydrate (solid content 53.9%) was dissolved in 65.5 g of deionized water to obtain solution (A11). Next, 40.7 g of sodium metasilicate 9 hydrate (solid content 42.9%) was dissolved in 75.6 g of deionized water to obtain solution (B11). Next, 30.0 g of copolymer (1) (solid content 40%) was dissolved in 31.5 g of deionized water to obtain solution (C11). 100.0 g of deionized water was poured into a glass container equipped with a stirring device and stirred. Solutions (A11), (B11), and (C11) were then slowly added dropwise to the mixture over approximately 60 minutes at 20°C to obtain aluminosilicate composition (11). The composition of the aluminosilicate composition (11) was 12.0% in total, consisting of aluminosilicate, aluminum sulfate, and sodium metasilicate, and 3.0% copolymer. The solid content concentration in the aluminosilicate composition was 15.0%, and the average Z particle size was 230 nm.

[0201]

Claims

1. A composition containing an aluminosilicate, wherein the aluminosilicate is obtained by reacting an aluminum-containing compound and a silicon-containing compound at a temperature of 30°C or higher in the presence of a water-soluble polymer having at least one functional group selected from a carboxyl group, a phosphate group, a sulfonic acid group and salts thereof, and a phosphate ester group.

2. The aluminosilicate-containing composition according to claim 1, wherein the aluminosilicate has a molar ratio of calcium element (Ca / Si) of 50% or less to 100 mol% silicon element.

3. The aluminosilicate-containing composition according to claim 1 or 2, wherein the reaction is carried out under conditions of pH 1 to 9.

4. The aluminosilicate-containing composition according to any one of claims 1 to 3, further comprising a polyhydric alcohol alkylene oxide adduct and / or a polyalkyleneimine alkylene oxide adduct.

5. The aluminosilicate-containing composition according to claim 4, wherein the total content of the polyhydric alcohol alkylene oxide adduct and the polyalkyleneimine alkylene oxide adduct is 50% by mass or less with respect to 100% by mass of the total content of the aluminosilicate, aluminum-containing compound and silicon-containing compound.

6. The aluminosilicate-containing composition according to any one of claims 1 to 5, wherein the water-soluble polymer further comprises a (poly)oxyalkylene group.

7. The aluminosilicate-containing composition according to any one of claims 1 to 6, wherein the content of the water-soluble polymer is 5 to 90% by mass with respect to 100% by mass of the total content of aluminosilicate, aluminum-containing compound and silicon-containing compound.

8. A hydraulic material composition comprising an aluminosilicate-containing composition according to any one of claims 1 to 7 and a hydraulic material.

9. A method for producing an aluminosilicate-containing composition, the method comprising the step of reacting an aluminum-containing compound and a silicon-containing compound at a temperature of 30°C or higher in the presence of a water-soluble polymer having at least one functional group selected from a carboxyl group, a phosphate group, a sulfonic acid group and salts thereof, and a phosphate ester group.

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