Hydraulic material composition for three-dimensional modeling and additive for hydraulic material

Abstract

[Problem] To provide a hydraulic material composition that has rheological characteristics and that can be used in 3D modeling techniques used in the civil engineering, construction, and factory product fields. [Solution] A hydraulic material composition for 3D modeling containing: a hydraulic material; an aggregate; a nitrogen-containing compound containing a specific proportion of nitrogen atoms; and a dispersant composed of a compound having at least one selected from the group consisting of carboxyl groups, sulfonic acid groups, phosphoric acid groups and salts thereof, and phosphate ester groups.

Description

[Technical field]

[0001] The present invention relates to a hydraulic material composition for three-dimensional modeling, which is mainly used in the fields of civil engineering, construction and factory products, and an additive for hydraulic materials used therein. [Background technology]

[0002] In recent years, 3D modeling technology has been used to create models and parts in the manufacturing industry. The technologies can be classified into photolithography (a method of curing and laminating UV-curable resin one layer at a time), inkjet method (a method of laminating by irradiating UV rays while spraying UV-curable resin from a printer head), powder gypsum modeling (a method of spraying resin or glue from a printer head and solidifying powder gypsum), powder sintering modeling (a method of laminating by baking resin or metal powder with a laser), and fused deposition modeling (a method of laminating by ejecting thermoplastic resin melted by heat from a thin nozzle). The objects created by 3D modeling technology are mainly made of resin, gypsum, and metal, and the technology of creating large objects such as construction materials using hydraulic material compositions has been studied more overseas than in Japan. In Europe, the United States, and China, automatic construction machines are already being used to manufacture large objects at the level of detached houses.

[0003] For example, Patent Document 1 discloses a three-dimensional modeling technique using a hydraulic material composition, in which three-dimensional data created by a computer is cut at a predetermined thickness to create two-dimensional slice data, and mortar mixed with an accelerator is sprayed onto a bed (table) while controlling the movement of a spray nozzle in the vertical and horizontal directions based on the two-dimensional slice data, and the sprayed mortar is allowed to harden by itself to form a solidified layer having a shape based on the two-dimensional slice data, and the solidified layer formation process is repeated to be stacked in the vertical direction to form a model. Patent Document 2 discloses a material for making a mold for producing a casting using a 3D printer, and discloses a material consisting of cement, sand, and a water-soluble silicate as an accelerator.

[0004] On the other hand, as a hydraulic material composition, a material in which a lignin sulfonate-based dispersant and a melamine sulfonate-based dispersant are used in combination is already known as a grout composition or a high-strength concrete composition (Patent Document 3). Also, as a hydraulic material composition, a PC grout material in which a dispersant and a thickener are used in combination is known (Patent Document 4). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 10-235623 [Patent Document 2] U.S. Patent No. 8,211,226 [Patent Document 3] JP 2008-247677 A [Patent Document 4] JP 2006-290694 A DISCLOSURE OF THEINVENTION [Problem to be solved by the invention]

[0006] In the three-dimensional modeling technology, the hydraulic material composition used is mixed, stirred, and extruded by a spray or extrusion nozzle, and then layered. There are various methods for three-dimensional modeling, but regardless of the method used, the hydraulic material composition is required to have appropriate extrudability and layerability.

[0007] However, no conventional hydraulic material composition is known that has sufficient extrudability and lamination properties.

[0008] The present invention has been made in consideration of the above-mentioned current situation, and an object of the present invention is to provide a hydraulic material composition for three-dimensional modeling having good extrudability and lamination property. Another object of the present invention is to provide an additive for hydraulic materials that can obtain a hydraulic material composition having good extrudability and lamination property. [Means for solving the problem]

[0009] The inventors have conducted extensive research into hydraulic material compositions used in three-dimensional modeling, and have come to the conclusion that the above-mentioned problems can be solved by combining a nitrogen-containing compound containing a specific ratio of nitrogen atoms with a dispersant consisting of a compound having at least one selected from the group consisting of a carboxyl group, a sulfonic acid group, a phosphoric acid group and salts thereof, and a phosphoric acid ester group, thereby imparting specific rheological properties, i.e., a certain degree of thixotropy, to the hydraulic material composition and increasing the yield point, thereby completing the present invention.

[0010] That is, the present invention provides: (1) A hydraulic material composition for three-dimensional modeling, comprising a hydraulic material (X), an aggregate (Y), a nitrogen-containing compound (A) and a dispersant (B), wherein the nitrogen-containing compound (A) has a nitrogen atom content of 6.8% by mass or more relative to 100% by mass of the nitrogen-containing compound (A), and the dispersant (B) is a compound having at least one selected from the group consisting of a carboxyl group, a sulfonic acid group, a phosphoric acid group and salts thereof, and a phosphoric acid ester group; (2) The hydraulic material composition for three-dimensional object formation according to the above (1), in which the nitrogen-containing compound (A) is contained in an amount of 0.0001 to 10 parts by mass per 100 parts by mass of the hydraulic material (X); (3) The hydraulic material composition for three-dimensional object formation according to the above (1) or (2), wherein the nitrogen-containing compound (A) is a polymer having a structural unit having an alkylene group and an amino group and / or a structural unit derived from an allylamine monomer; (4) The hydraulic material composition for three-dimensional object formation according to the above (1) or (2), in which the nitrogen-containing compound (A) is contained in an amount of 0.01 to 100,000 parts by mass per 100 parts by mass of the dispersant (B); (5) The hydraulic material composition for three-dimensional object formation according to the above (1) or (2), wherein the dispersant (B) is a polymer having a structural unit derived from at least one monomer selected from the group consisting of an unsaturated carboxylic acid monomer (B1), an unsaturated sulfonic acid monomer (B2), and a phosphoric acid monomer (B3); (6) An additive for hydraulic materials used for three-dimensional modeling applications, comprising a nitrogen-containing compound (A) and a dispersant (B), wherein the nitrogen-containing compound (A) is contained in an amount of 0.01 to 100,000 parts by mass relative to 100 parts by mass of the dispersant (B), the nitrogen-containing compound (A) has a nitrogen atom content of 6.8% by mass or more relative to 100% by mass of the nitrogen-containing compound (A), and the dispersant (B) is a compound having at least one selected from the group consisting of a carboxyl group, a sulfonic acid group, a phosphoric acid group and salts thereof, and a phosphoric acid ester group; (7) A three-dimensional object formed from the hydraulic material composition for three-dimensional object formation according to (1) or (2) above; It is. Effect of the Invention

[0011] The hydraulic material composition of the present invention has the above-mentioned constitution, and since it can impart a certain degree of thixotropy to the hydraulic material composition and increase the yield point, thereby improving extrudability and lamination properties, it can be suitably used for three-dimensional modeling applications. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The preferred embodiments of the present invention are specifically described below, but the present invention is not limited to the following description, and can be appropriately modified and applied within the scope of the present invention. Note that a combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention and is considered to be disclosed in this specification (i.e., it is a legitimate basis for amendment).

[0013] Hereinafter, in this specification, "X to Y" indicating a range means "X or more and Y or less." In this specification, "acid (salt)" means "acid and / or its salt." "(Meth)acrylic" means "acrylic and / or methacrylic." Furthermore, "weight" and "mass," "parts by weight" and "parts by mass," "wt%" and "mass%" are treated as synonyms.

[0014] In the present invention, "three-dimensional modeling" refers to a technology for manufacturing molded bodies of any shape by directly layering a cross-sectional shape based on three-dimensional data without using dedicated tools such as molds. It is also called "additive modeling" or "rapid prototyping."

[0015] The hydraulic material composition of the present invention is also suitable for use as a hydraulic material composition for three-dimensional modeling for construction. In the present invention, "for construction" means that the composition is used for "construction work" (making, partially modifying, removing, or destroying something fixed to the ground), and for example, means that the composition is used for manufacturing buildings such as houses, fences, bridges, structures such as columns of structures, benches, etc.

[0016] The hydraulic material composition of the present invention includes a hydraulic material (X), an aggregate (Y), a nitrogen-containing compound (A), and a dispersant (B), and the additive for the hydraulic material includes the nitrogen-containing compound (A) and the dispersant (B). The hydraulic material composition of the present invention has good extrudability and lamination property as a hydraulic material composition for three-dimensional modeling. Here, the extrudability can be evaluated, for example, by measuring the flow, and the lamination property can be evaluated, for example, by measuring the yield point.

[0017] Good extrudability is 110 mm or more (preferably 180 mm or more, more preferably 200 mm or more, even more preferably 200 mm or more and 250 mm or less, particularly preferably 200 mm or more and less than 230 mm, and most preferably 200 mm or more and 220 mm or less) in the flow evaluation under the conditions described in the examples described later. Good lamination is 200 Pa or more (preferably 300 Pa or more, more preferably 400 Pa or more) in the yield point evaluation under the conditions described in the examples described later when the flow evaluation is adjusted to 200 mm or more and 250 mm or less (preferably 200 mm or more and less than 230 mm, more preferably 200 mm or more and 220 mm or less). Note that the upper limit of the yield point evaluation under these conditions is 2000 Pa or less in practical use.

[0018] The lamination property can also be evaluated, for example, by measuring thixotropy. A suitable thixotropy is a thixotropy evaluation of 300 Pa·s or more (preferably 400 Pa·s or more, more preferably 500 Pa·s or more) under the conditions described in the Examples below when the flow evaluation is adjusted to 200 mm or more and 250 mm or less (preferably 200 mm or more and less than 230 mm, more preferably 200 mm or more and 220 mm or less). Note that the upper limit of the thixotropy evaluation under these conditions is 4000 Pa·s or less in practical use.

[0019] In all of the compositions in the examples, the flow value is 200 mm or more in a flow evaluation under the conditions described in the examples below, and when the flow evaluation is adjusted to 200 mm or more and 250 mm or less (preferably 200 mm or more and less than 230 mm, more preferably 200 mm or more and 220 mm or less), the yield point and thixotropy evaluation under the conditions described in the examples below show a yield point of 200 Pa or more and 2000 Pa or less, and a thixotropy of 300 Pa s or more and 4000 Pa s or less. The predetermined yield point and thixotropy at these predetermined flow values ​​are required to achieve both extrudability and lamination property in three-dimensional modeling.

[0020] <Hydraulic material (X)> The hydraulic material (X) used in the present invention is not particularly limited as long as it has hydraulic or latent hydraulic properties, and examples thereof include Portland cement such as ordinary Portland cement, early strength Portland cement, moderate heat Portland cement, and low heat Portland cement, silica cement, fly ash cement, blast furnace cement, alumina cement, belite-rich cement, and various mixed cements; cement components such as tricalcium silicate, dicalcium silicate, tricalcium aluminate, and tetracalcium ferroaluminate; and latent hydraulic fly ash, silica fume, slag, and lime powder. These may be used alone or in combination of two or more. Among these, ordinary Portland cement is usually used and can be preferably applied.

[0021] The content of the hydraulic material (X) is preferably 15% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less, and even more preferably 25% by mass or more and 70% by mass or less, based on the total mass of the hydraulic material composition. By containing the hydraulic material (X) in the hydraulic material composition within the above range, the desired effect of the present invention is more effectively exhibited.

[0022] <Aggregate (Y)> The aggregate (Y) used in the present invention includes gravel, crushed stone, granulated slag, recycled aggregate, and the like, as well as refractory aggregates such as silica, clay, zircon, high alumina, silicon carbide, graphite, chrome, chromium-magnesium, and magnesia.

[0023] The content of the aggregate (Y) is preferably 10% by mass or more and 90% by mass or less, more preferably 15% by mass or more and 80% by mass or less, and even more preferably 20% by mass or more and 70% by mass or less, based on the total mass of the hydraulic material composition. By including the aggregate (Y) in the hydraulic material composition within the above range, the desired effect of the present invention is more effectively exhibited.

[0024] <Nitrogen-containing compound (A)> The nitrogen-containing compound (A) has a nitrogen atom content of 6.8 mass% or more relative to 100 mass% of the nitrogen-containing compound (A). The nitrogen atom content of the nitrogen-containing compound (A) is preferably 7 to 70 mass%, more preferably 8 to 50 mass%, and even more preferably 8.5 to 35 mass%, relative to 100 mass% of the nitrogen-containing compound (A). When the nitrogen atom content is in the above preferred range, a certain degree of thixotropy can be imparted to the hydraulic material composition, and the yield point can be further improved.

[0025] In addition, the hydraulic material composition used in the three-dimensional modeling technology is mixed and stirred, then pumped by a pump and extruded by a nozzle. Therefore, it is necessary to have a low viscosity during pumping so that the piping does not get clogged, and after pumping, it is necessary to give the hydraulic composition a high viscosity and a high yield point after being discharged from the nozzle in order to maintain high layerability. The layer extruded by the nozzle of the 3D printer (extrusion device for three-dimensional modeling) needs to have a yield point higher than its own weight or the weight received from the layer stacked on top. Otherwise, the extruded layer will deform and collapse due to external stress, and printing will not be possible.

[0026] The hydraulic material composition used for three-dimensional modeling needs to have a degree of extrudability that allows extrusion through a nozzle, and a high yield point is required as an index of lamination after extrusion. The yield point is defined as the stress required for the target material to change from elasticity to plasticity, and lamination can be improved by increasing the yield point. Here, nozzles for three-dimensional modeling tend to be thinner than those used for normal cement in order to form precise structures. Therefore, hydraulic material compositions for three-dimensional modeling are required to have higher extrudability than hydraulic material compositions for applications other than three-dimensional modeling. In addition, if the water content of the hydraulic material composition is increased in an attempt to achieve high extrudability, the extrudability improves, but the lamination for three-dimensional modeling after extrusion decreases. In other words, it can be said that there is a trade-off between extrudability and lamination. The present inventors have found that, in order to address such a trade-off issue, this trade-off relationship can be resolved by combining a nitrogen-containing compound (A) having a specific nitrogen content with a dispersant (B) having a specific group. Although the mechanism by which the above-mentioned effect is obtained by this constitution is unclear, it is presumed that the interaction between the specific nitrogen-containing compound (A) and the specific dispersant (B) improves lamination property without changing the extrusion property, that is, the fluidity (extrusion property) and lamination property can be exhibited at the same time. However, the above-mentioned mechanism is merely presumed, and the scope of the present invention is not limited by this.

[0027] The content ratio of nitrogen atoms in the nitrogen-containing compound (A) can be calculated from the composition formula of the compound, but when the composition formula is unknown, it can also be measured by elemental analysis. When calculating from the composition formula of the compound, if the nitrogen-containing compound (A) is a polymer (α1) having a structural unit (a1) derived from a nitrogen-containing monomer (A1), it can be calculated from the content ratio of nitrogen atoms in the nitrogen-containing monomer (A1). Specifically, if the nitrogen-containing compound (A) is a polymer (α1) having a structural unit (a1) derived from a nitrogen-containing monomer (A1), the content ratio of nitrogen atoms in the nitrogen-containing monomer (A1) can be used as the content ratio of nitrogen atoms in the nitrogen-containing compound (A).

[0028] The weight average molecular weight of the nitrogen-containing compound (A) is preferably 500 to 1.5 million. This allows the hydraulic material composition to have a certain degree of thixotropy while improving the yield point. In one embodiment, the weight average molecular weight of the nitrogen-containing compound (A) is preferably 1,000 to 1,000,000. This allows the hydraulic material composition to have a certain degree of thixotropy while improving the yield point. The weight average molecular weight of the nitrogen-containing compound (A) is more preferably 3,000 to 800,000, even more preferably 5,000 to 700,000, even more preferably 10,000 to 600,000, even more preferably 50,000 to 500,000, and particularly preferably 100,000 to 400,000.

[0029] In one embodiment, when the nitrogen-containing compound (A) has a structural unit having an alkylene group and an amino group, the weight average molecular weight of the nitrogen-containing compound (A) is preferably 1,000 to 900,000, more preferably 1,100 to 500,000, even more preferably 1,500 to 300,000, particularly preferably 1,600 to 200,000, and most preferably 5,000 to 100,000. In one embodiment, when the nitrogen-containing compound (A) has a structural unit derived from an allylamine monomer, the weight average molecular weight of the nitrogen-containing compound (A) is preferably 3,000 to 1,000,000, more preferably 5,000 to 900,000, even more preferably 10,000 to 800,000, particularly preferably 20,000 to 700,000, and most preferably 50,000 to 500,000.

[0030] The weight average molecular weight of the nitrogen-containing compound (A) is a value measured by the following method.

[0031] <Molecular weight measurement method> The weight average molecular weight and number average molecular weight in the present invention can be measured by a known method using gel permeation chromatography (GPC) with pullulan as a standard substance. The following conditions are adopted as the GPC measurement conditions in the present invention. Measuring device: Shimadzu Corporation Columns used: Showa Denko SHODEX OHpak SB-807HQ (2 units) + SB-806M / HQ (2 units) Eluent: Prepared in 0.5 mol% sodium nitrate and 0.5 mol% acetic acid Standard material: Pullulan P-82 (Wako Pure Chemical Industries, Ltd.) Detector: differential refractometer (Shimadzu Corporation) Flow rate: 0.4ml / min.

[0032] The nitrogen-containing compound (A) is not particularly limited as long as the nitrogen atom content falls within the above range, and examples thereof include polyalkyleneimine and derivatives thereof; and a polymer (α1) (hereinafter also referred to as polymer (α1)) having a structural unit (a1) derived from a nitrogen-containing monomer (A1) having a nitrogen atom content of 6.8 mass% or more.

[0033] The polyalkyleneimine may have a structural unit having an alkylene group and an amino group, and may be represented by the following formula (1) and / or (2):

[0034] [ka]

[0035] (In the formula, R 1 are the same or different and represent an alkylene group having 2 to 6 carbon atoms. Any alkylene group may be used as long as it has a structural unit represented by the following formula: Specific examples of the alkylene group include an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, and an n-hexylene group. The number of carbon atoms in the alkylene group is preferably 2 to 4, more preferably 2 to 3, and most preferably 2.

[0036] Examples of the polyalkyleneimine include polyethyleneimine, polypropyleneimine, and polybutyleneimine, and can be obtained by polymerizing one or more alkyleneimines having 2 to 6 carbon atoms, such as ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, and 1,1-dimethylethyleneimine, by a commonly used method.

[0037] The polyalkyleneimine derivative is not particularly limited as long as the nitrogen atom content and weight average molecular weight satisfy the above ranges. Examples of the polyalkyleneimine derivative include compounds in which the amino groups of polyalkyleneimine are quaternized and compounds in which substituents are introduced into the amino groups or alkylene groups of polyalkyleneimine.

[0038] The quaternizing agent used for the quaternization of the amino group is not particularly limited, but examples thereof include common alkylating agents such as alkyl halides such as methyl chloride, ethyl chloride, methyl bromide, and methyl iodide; and alkyl sulfates such as dimethyl sulfate, diethyl sulfate, and di-n-propyl sulfate. Examples of the substituent include a hydroxyl group, an alkoxy group, a carboxyl group, an acyl group, a sulfonic acid group, a phosphoric acid group, an ether group, a thioether group, a carbonyl group, and an ester group.

[0039] The nitrogen atom-containing monomer (A1) is not particularly limited as long as the nitrogen atom content is 6.8% by mass or more based on 100% by mass of the monomer. Examples of the nitrogen atom-containing monomer (A1) include those represented by the following formulae (3) to (6):

[0040] [ka]

[0041] (In formulas (3) to (6), R 2 ~R 4 are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. X represents a direct bond or a divalent linking group. In formulas (3) and (4), R 5 , R 6 are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. 7 ~R 9 Y may be the same or different and represents a hydrocarbon group having 1 to 12 carbon atoms. - represents an anion.) a monomer represented by any one of the following formulae: a nitrogen-containing heterocyclic group-containing monomer such as an imidazole group, a pyrazole group, an imidazoline group, a triazole group, a tetrazole group, a pyridazine group, a pyrimidine group, a pyrazine group, a purine group, a benzotriazole group, or a pteridine group; a reaction product of an epihalohydrin such as epichlorohydrin with an amine compound described later, and the like.

[0042] R in the above formulas (3) to (6) 2 ~R 4 represents a hydrogen atom or a methyl group, while R 2 , R 3 In the above formulas (3) to (5), R is preferably a hydrogen atom. 4 is preferably a methyl group, and in the above formula (6), R 4 is preferably a hydrogen atom.

[0043] Above R 5 ~R 9 The hydrocarbon group in may have a chain structure or a ring structure, but preferably has a chain structure. When the hydrocarbon group has a chain structure, it may be linear or branched. The hydrocarbon group is preferably an alkyl group, an alkenyl group, or an aryl group, more preferably an alkyl group or an alkenyl group, and even more preferably an alkyl group. The number of carbon atoms in the hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, particularly preferably 1 to 5, and most preferably 1 to 2.

[0044] In the above formulas (3) and (4), R 5 and R 6 At least one of R is preferably a hydrocarbon group having 1 to 12 carbon atoms. 5 and R 6 It is more preferable that both of the above are hydrocarbon groups having a carbon number of 1 to 12. In other words, among the primary to tertiary amino groups, a tertiary amino group is preferable.

[0045] Y in the above formulas (4) to (6) - is not particularly limited, and examples thereof include hydroxide ions; halide ions such as chloride ions, bromide ions, and iodine ions; alkyl sulfate ions such as dimethyl sulfate ions, diethyl sulfate ions, and di-n-propyl sulfate ions; and ions of organic acids such as acetate ions. - is preferably an ion of an organic acid. - is preferably a hydroxide ion, a halide ion, or an alkyl sulfate ion.

[0046] When X in the above formulas (3) to (6) is a divalent linking group, the divalent linking group is not particularly limited, and examples thereof include alkylene groups having 1 to 12 carbon atoms, such as a methylene group, an ethylene group, and a propylene group, and the following formula (7);

[0047] [ka]

[0048] (In the formula, h is 0 or 1, and i represents an integer of 0 to 12.) The following formula (8):

[0049] [ka]

[0050] (In the formula, j represents an integer of 0 to 4.) and the following formula (9);

[0051] [ka]

[0052] (In the formula, k represents an integer of 1 to 10.) Examples of the structure include those represented by the following formula:

[0053] In the above formula (7), i is preferably 1 to 6, and more preferably 1 to 4. In the above formula (8), j is preferably 1 to 4, and more preferably 1 to 2. In the above formula (9), k is preferably 1 to 8, and more preferably 1 to 5.

[0054] X in the above formulas (3) to (5) is preferably an alkylene group having 1 to 12 carbon atoms or a structure represented by the above formula (7) or (9). X in the above formula (6) is preferably an alkylene group having 1 to 12 carbon atoms. The number of carbon atoms in the alkylene group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 or 2. X is a methylene group, and R 2 and R 3 is a hydrogen atom, R 4 When is a hydrogen atom or a methyl group, the monomer represented by any one of the above formulas (3) to (6) is an allylamine monomer having a (meth)allyl group and an amino group. The embodiment in which the nitrogen atom-containing monomer (A1) is an allylamine monomer is one of the preferred embodiments of the present invention.

[0055] Specific examples of the monomer represented by any one of the above formulas (3) to (6) include N,N-dialkylamino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and N,N-diethylaminopropyl (meth)acrylate, as well as monomers obtained by adding a quaternizing agent to the above monomers or neutralized products thereof with an acid such as hydrochloric acid or acetic acid; acrylamide and its derivatives; N,N-dimethylaminoethyl (meth)acrylamide; N,N-dialkylamino group-containing (meth)acrylamides such as N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, and N,N-diethylaminopropyl (meth)acrylamide, and monomers obtained by adding a quaternizing agent to the above monomers, or neutralized products thereof with an acid such as hydrochloric acid or acetic acid; monomethylaminoethyl (meth)acrylate, monoethylaminoethyl (meth)acrylate, monomethylaminopropyl (meth)acrylate, monoethylaminopropyl (meth)acrylate, (meth)acrylamide, p) Monoalkylamino group-containing (meth)acrylates such as 2-(tert-butylamino)ethyl acrylate and their neutralization with acids such as hydrochloric acid and acetic acid; monomethylaminoethyl (meth)acrylamide, monoethylaminoethyl (meth)acrylamide, monomethylaminopropyl (meth)acrylamide, monoethylaminopropyl (meth)acrylamide and their neutralization with acids such as hydrochloric acid and acetic acid; (meth)acrylic acid and alkanolamines such as 2-aminoethyl (meth)acrylate. and their neutralization with acids such as hydrochloric acid, acetic acid, etc.; N,N-diallylalkylamines, and monomers obtained by adding a quaternizing agent thereto, such as diallyldimethylammonium chloride, or their neutralization with acids such as hydrochloric acid, acetic acid, etc.; addition reaction products of unsaturated monomers having a cyclic ether-containing group having 2 to 8 carbon atoms, such as 1-allyloxy-3-dibutylamino-2-ol and 1-allyloxy-3-diethanolamino-2-ol, with an amine compound having 1 to 24 carbon atoms, and their monomers obtained by adding a quaternizing agent thereto, or their neutralization with acids such as hydrochloric acid, acetic acid, etc.;Examples of the monomer include vinylamine, allylamine, N-methylvinylamine, 1-propene-2-amine, and monomers obtained by adding a quaternizing agent to these monomers, or neutralized products of these monomers with an acid such as hydrochloric acid or acetic acid.

[0056] The amine compound having 1 to 24 carbon atoms is not particularly limited as long as it has an amino group and can react with a cyclic ether structure of an unsaturated monomer having a cyclic ether-containing group having 2 to 8 carbon atoms. The number of carbon atoms in the amine compound having 1 to 24 carbon atoms is preferably 1 to 20, more preferably 1 to 16. Examples of the amine compound having 1 to 24 carbon atoms include primary amines and secondary amines, such as (di)alkylamines having 1 to 24 carbon atoms, (di)alkanolamines having 1 to 24 carbon atoms, and alkylalkanolamines having 1 to 24 carbon atoms.

[0057] Preferred examples of the (di)alkylamine having 1 to 24 carbon atoms include methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, pentylamine, dipentylamine, hexylamine, dihexylamine, heptylamine, diheptylamine, octylamine, dioctylamine, dodecylamine, and didodecylamine.

[0058] As the (di)alkanolamine having 1 to 24 carbon atoms, methanolamine, ethanolamine, propanolamine, butanolamine, dimethanolamine, diethanolamine, dipropanolamine, dibutanolamine, hexanolamine and the like are preferred. As the alkylalkanolamine having 1 to 24 carbon atoms, methylethanolamine and the like are preferable.

[0059] Among the monomers represented by any of the above formulas (3) to (6), preferred are N,N-diallylmethylamine and a monomer having a quaternary agent added thereto or a neutralized product thereof with an acid such as hydrochloric acid or acetic acid, diallyldimethylammonium chloride and a monomer having a quaternary agent added thereto or a neutralized product thereof with an acid such as hydrochloric acid or acetic acid, N,N-dialkylamino group-containing (meth)acrylates and a neutralized product thereof with an acid such as hydrochloric acid or acetic acid or a monomer having a quaternary agent added thereto, N,N-dialkylamino group-containing (meth)acrylamides and a neutralized product thereof with an acid such as hydrochloric acid or acetic acid or a monomer having a quaternary agent added thereto, and more preferred are N,N-diallylmethylamine and a monomer having a quaternary agent added thereto or a neutralized product thereof with an acid such as hydrochloric acid or acetic acid.

[0060] The quaternizing agent is not particularly limited, but examples thereof include common alkylating agents such as alkyl halides such as methyl chloride, ethyl chloride, methyl bromide, and methyl iodide; and alkyl sulfates such as dimethyl sulfate, diethyl sulfate, and di-n-propyl sulfate.

[0061] Examples of the nitrogen-containing heterocyclic group-containing monomer include vinylimidazole, vinylpyrazole, vinylimidazoline, vinyltriazole, vinyltetrazole, vinylpyridazine, vinylpyrimidine group, vinylpyrazine, vinylpurine, vinylbenzotriazole, and vinylpteridine.

[0062] The amine compound in the reaction product of the epihalohydrin and the amine compound is preferably a (di)alkylamine having 1 to 24 carbon atoms, more preferably a (di)alkylamine having 1 to 12 carbon atoms, further preferably a (di)alkylamine having 1 to 6 carbon atoms, and most preferably dimethylamine.

[0063] The polymer (α1) having the structural unit (a1) derived from the nitrogen atom-containing monomer (A1) is not particularly limited as long as the nitrogen atom content and weight average molecular weight satisfy the above-mentioned ranges, and may be a homopolymer of the nitrogen atom-containing monomer (A1), a copolymer of two or more kinds of the nitrogen atom-containing monomer (A1), or a copolymer with a monomer (E) other than the nitrogen atom-containing monomer (A1).

[0064] The other monomer (E) is not particularly limited, and examples thereof include carboxyl group-containing monomers such as (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, 2-methylene glutaric acid, and salts thereof; hydroxyl group-containing alkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and α-hydroxymethylethyl (meth)acrylate; alkyl (meth)acrylates which are esters of alkyl groups having 1 to 18 carbon atoms of (meth)acrylic acid such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, and lauryl (meth)acrylate; vinyl esters such as vinyl acetate; alkenes such as ethylene and propylene; aromatic vinyl monomers such as styrene; maleimide, phenylmaleimide, cyclohexyl Examples of the monomers include maleimide derivatives such as maleimide; nitrile group-containing vinyl monomers such as (meth)acrylonitrile; monomers having a sulfonic acid group such as 3-allyloxy-2-hydroxypropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, and vinylsulfonic acid, and salts thereof; monomers having a phosphonic acid group such as vinylphosphonic acid and (meth)allylphosphonic acid; aldehyde group-containing vinyl monomers such as (meth)acrolein; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether; other functional group-containing monomers such as vinyl chloride, vinylidene chloride, and allyl alcohol; polyalkylene glycol chain-containing monomers such as polyalkylene glycol (meth)acrylate, monoalkoxy polyalkylene glycol (meth)acrylate, vinyl alcohol, (meth)allyl alcohol, and isoprenol, which have a structure in which 1 to 300 moles of alkylene oxide are added to an unsaturated alcohol; and the like. As for these other monomers, one type may be used alone, or two or more types may be used in combination.The proportion of structural units derived from the other monomer (E) in the above polymer (α1) may be 10% by mass or less (lower limit: 0% by mass), 5% by mass or less, or 3% by mass or less.

[0065] The proportion of the structural unit (a1) in the polymer (α1) is not particularly limited as long as the nitrogen atom content is 6.8% by mass or more relative to 100% by mass of the polymer (α1), but is preferably 10 to 100% by mass relative to 100% by mass of all structural units, more preferably 20 to 100% by mass, even more preferably 40 to 100% by mass, and particularly preferably 60 to 100% by mass.

[0066] The method for producing the polymer having a structural unit derived from the nitrogen atom-containing monomer (A1) is not particularly limited, but the polymer can be obtained by polymerizing a monomer component containing the nitrogen atom-containing monomer (A1) by a commonly used method.

[0067] The nitrogen-containing compound (A) is preferably a polymer having a structural unit having an alkylene group and an amino group and / or a structural unit derived from an allylamine monomer, a polymer having a structural unit represented by the above formula (6), or a polymer having a structural unit derived from a reaction product of an epihalohydrin and an amine compound. Here, the amino group includes not only a primary amino group (-NH2), but also a secondary amino group as included in the above formula (1), and a tertiary amino group as included in the above formula (2).

[0068] The nitrogen-containing compound (A) is more preferably polyalkyleneimine, polydiallyldimethylammonium chloride, or polyepichlorohydrindimethylamine, and further preferably polyethylenimine or polydiallyldimethylammonium chloride. The embodiment in which the nitrogen-containing compound (A) is polyethylenimine is one of the preferred embodiments of the present invention.

[0069] <Dispersant (B)> The dispersant (B) is a compound having at least one selected from the group consisting of a carboxyl group, a sulfonic acid group, a phosphoric acid group, a salt thereof, and a phosphoric acid ester group. Among the above functional groups, the carboxyl group, the sulfonic acid group, the phosphoric acid group, and a salt thereof are preferred, and the carboxyl group and a salt thereof are more preferred.

[0070] Examples of the above salts include monovalent metal salts such as alkali metals (eg, sodium, potassium, etc.); divalent metal salts such as alkaline earth metals (eg, magnesium, calcium, etc.); ammonium salts; and organic amine salts.

[0071] The dispersant (B) is preferably a polymer having a structural unit derived from a monomer having at least one selected from the group consisting of a carboxyl group, a sulfonic acid group, a phosphoric acid group and their salts, and a phosphoric acid ester group. That is, the dispersant (B) is preferably a polymer having a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid monomer (B1), an unsaturated sulfonic acid monomer (B2), and a phosphoric acid monomer (B3). Hereinafter, the structural unit derived from the unsaturated carboxylic acid monomer (B1) is referred to as "structural unit (b1)", the structural unit derived from the unsaturated sulfonic acid monomer (B2) is referred to as "structural unit (b2)", the structural unit derived from the phosphoric acid monomer (B3) is referred to as "structural unit (b3)", and the structural units (b1) to (b3) may be collectively referred to as "structural unit (b)".

[0072] The unsaturated carboxylic acid monomer (B1) is not particularly limited as long as it has a carboxyl group and / or a salt group thereof and an ethylenically unsaturated hydrocarbon group (unsaturated group), and examples of the unsaturated carboxylic acid monomer (B1) include unsaturated monocarboxylic acid monomers and unsaturated dicarboxylic acid monomers.

[0073] The unsaturated monocarboxylic acid monomer may be a monomer having one unsaturated group and one group capable of forming a carbanion in the molecule, and examples thereof include (meth)acrylic acid, crotonic acid, isocrotonic acid, tiglic acid, 3-methylcrotonic acid, 2-methyl-2-pentenoic acid, α-hydroxyacrylic acid, etc.; monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts thereof; half esters of the below-mentioned unsaturated dicarboxylic acid monomers and alcohols having 1 to 22 carbon atoms or glycols having 2 to 4 carbon atoms; and half amides of unsaturated dicarboxylic acid monomers and amines having 1 to 22 carbon atoms.

[0074] The unsaturated dicarboxylic acid monomer may be any monomer having one unsaturated group and two groups capable of forming a carbanion in the molecule, and examples thereof include maleic acid, itaconic acid, mesaconic acid, citraconic acid, fumaric acid, and the like, as well as their monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts, and their anhydrides. The unsaturated carboxylic acid monomer (B1) is preferably (meth)acrylic acid (salt), maleic acid (salt), or maleic anhydride. More preferably, it is (meth)acrylic acid (salt), and particularly preferably, it is methacrylic acid (salt).

[0075] The unsaturated sulfonic acid monomer (B2) is not particularly limited as long as it has a sulfonic acid group and / or a salt group thereof and an ethylenically unsaturated hydrocarbon group (unsaturated group), but it is preferable that the sulfonic acid group and / or the salt group thereof has one or more groups represented by -SO3Z (Z represents a hydrogen atom, a monovalent metal atom, a divalent metal atom, an ammonium group or an organic amine group) in one molecule.

[0076] Examples of the unsaturated sulfonic acid monomer (B2) include unsaturated sulfonic acids such as vinyl sulfonic acid, (meth)allyl sulfonic acid, methallyloxybenzenesulfonic acid, isoprene sulfonic acid, 2-methylpropanesulfonic acid (meth)acrylamide, styrenesulfonic acid, 2-hydroxy-3-allyloxysulfonic acid, sulfoethyl (meth)acrylate ((meth)acryloyloxy)ethanesulfonic acid), sulfopropyl (meth)acrylate, and sulfobutyl (meth)acrylate, as well as their monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts. One or more of these can be used.

[0077] The phosphoric acid monomer (B3) is not particularly limited as long as it has a phosphoric acid (salt) group and / or a phosphoric acid ester group, and may be a monomer represented by the following formula (10): -OPO3M2(10) (In the formula, M may be the same or different and represents 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.) Preferably, one molecule has one or more groups represented by the following formula: embedded image The optionally substituted hydrocarbon group is not particularly limited, and examples thereof include groups derived from aromatic alcohols and quinones, which will be described later. The above M is preferably a hydrogen atom, a monovalent metal atom, or a divalent metal atom, more preferably a monovalent metal atom, and even more preferably sodium.

[0078] The phosphoric acid monomer (B3) preferably further has an aromatic group and / or a heterocyclic aromatic group in the structure. The aromatic group may be a group having an aromatic ring derived from an aromatic compound such as benzene, naphthalene, anthracene, tetracene, or pentacene (a group obtained by removing a hydrogen atom from an aromatic compound), and may have a substituent. The heterocyclic aromatic group may be a group having a heterocyclic aromatic ring derived from a heterocyclic aromatic compound such as furan, thiophene, pyrrole, pyrazole, imidazole, pyridine, pyridazine, pyrimidine, or pyrazine (a group obtained by removing a hydrogen atom from a heterocyclic aromatic compound), and may have a substituent.

[0079] The phosphoric acid monomer (B3) is preferably a phosphoric acid monomer (B3-1) having an aromatic group derived from an aromatic compound, more preferably one having an aryl group.

[0080] The phosphoric acid monomer (B3-1) is preferably a monomer represented by the following formula (11):

[0081] [ka]

[0082] (In the formula, M may be the same or different and represents 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. 10 represents a hydrogen atom or a substituent other than a phosphate group or a phosphate ester group. It is more preferable that the structural unit represented by the above Q 1 -OPO3M 2、 R 10 The bonding position and the number of bonds are not particularly limited, and a plurality of these may be present.

[0083] Above Q 1 is not particularly limited as long as it is a divalent linking group, but is preferably a divalent hydrocarbon group which may have a heteroatom. More preferably, it is a (poly)oxyalkylene group. Specific and preferred examples of the oxyalkylene group include the same as the oxyalkylene group having 2 to 18 carbon atoms in the formula (13) described later, and is most preferably an oxyethylene group. The average number of moles added of the (poly)oxyalkylene group is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 2, and most preferably 1.

[0084] Above R 10Examples of the substituent include an aliphatic hydrocarbon group such as an alkyl group or an alkenyl group having 1 to 10 carbon atoms, an alkoxy group, a hydroxyl group, an acyl group, an ether group, an amide group, an ester group, a ketone group, a carboxyl group, a salt of a carboxyl group, a sulfonic acid group, a salt of a sulfonic acid group, and a (poly)alkylene glycol chain-containing group.

[0085] Specific examples of the phosphoric acid monomer (B3-1) include phosphoric acid oxides of aromatic alcohols and quinones such as phenoxyethanol, phenoxydiglycol, (methoxyphenoxy)ethanol, methylphenoxyethanol, bis(β-hydroxyethyl)hydroquinone ether, nonylphenol, phenol, cresol, resorcinol, catechol, hydroquinone, naphthol, and furfuryl alcohol. Specific examples of the phosphoric acid 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.

[0086] Of these, phenoxyethanol phosphate, phenoxydiglycol phosphate, and bis(β-hydroxyethyl)hydroquinone ether diphosphate are preferred, and phenoxyethanol phosphate is more preferred. For the phosphorylation of the aromatic alcohols and quinones, it is preferable to use a phosphoric acid compound such as phosphoric acid (salt) or polyphosphoric acid (salt).

[0087] When the dispersant (B) is a polymer having a structural unit derived from a monomer having a phosphate ester group, it is preferable that the dispersant further has a structural unit derived from a monomer having a (poly)alkylene glycol chain and an aromatic group and / or a heterocyclic aromatic group (hereinafter also referred to as a (poly)alkylene glycol chain-containing monomer).

[0088] Specific examples of the (poly)alkylene glycol chain-containing monomer include compounds in which alkylene oxide is added to the above-mentioned aromatic alcohols and aromatic amines such as aniline, etc. Preferred are compounds in which alkylene oxide is added to aromatic alcohols such as phenol, cresol, resorcinol, catechol, hydroquinone, naphthol, and furfuryl alcohol.

[0089] Among the structural units derived from the above (poly)alkylene glycol chain-containing monomers, the following formula (12):

[0090] [ka]

[0091] (In the formula, Q 2 R represents a direct bond or a divalent linking group. 11 R represents a hydrogen atom or a substituent other than a phosphate group or a phosphate ester group. 12 O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. 13 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. m represents the average number of moles of oxyalkylene groups added and is a number from 1 to 300. It is preferable that the monomer has a structural unit represented by the following formula:

[0092] Above Q 2 Examples of the divalent linking group in the formula (11) include an oxygen atom, a sulfur atom, a halogen atom, -NH-, and a divalent hydrocarbon group which may have a heteroatom. The divalent hydrocarbon group which may have a heteroatom is Q in the formula (11). 1 The same applies to the divalent hydrocarbon group which may have a heteroatom in Q. 2 is preferably an oxygen atom or -NH-, and more preferably an oxygen atom.

[0093] R 13 The hydrocarbon group having 1 to 30 carbon atoms is R 17The carbon number of the hydrocarbon group is the same as that of the hydrocarbon group having 1 to 30 carbon atoms. 13 is preferably a hydrogen atom.

[0094] R 12 A preferred form of the oxyalkylene group represented by O is the same as the oxyalkylene group in AO of formula (13) described below. m is preferably 5-280, more preferably 5-160, and further preferably 9-120.

[0095] As the monomer having a (poly)alkylene glycol chain and an aromatic group and / or a heterocyclic aromatic group, for example, 2-phenoxyethanol, phenoxypolyethylene glycol, etc. are preferred.

[0096] The polymer having a structural unit derived from a monomer having a phosphate group preferably has a structural unit represented by the above formula (11) and a structural unit represented by the formula (12). In this case, the molar ratio of the structural unit represented by the formula (11) to the structural unit represented by the formula (12) (formula (11) / formula (12)) is preferably 0.3 to 4, more preferably 0.4 to 3.5, and further preferably 0.45 to 3.

[0097] The polymer having structural units derived from the monomer having a phosphate group is preferably a condensation product in which the structural units represented by the formulas (11) and (12) are bonded via a divalent linking group derived from an aldehyde compound, and the structural units derived from the monomer are bonded via a divalent linking group derived from an aldehyde compound.

[0098] Examples of the aldehyde compound include formaldehyde, compounds having an alkyl group having 1 to 5 carbon atoms and an aldehyde group, such as acetaldehyde, propionaldehyde, butanal, glyoxylic acid, benzaldehyde, paraformaldehyde, etc. Preferred are formaldehyde, benzaldehyde, and paraformaldehyde, and most preferred is formaldehyde.

[0099] The polymer having a structural unit derived from the phosphoric acid monomer (B3) may not have an aromatic group or a heterocyclic aromatic group in the structure, and may have a structural unit derived from an unsaturated phosphoric acid monomer (B3-2) having a phosphoric acid (salt) group and / or a phosphoric acid ester group and an ethylenically unsaturated hydrocarbon group (unsaturated group). As the unsaturated phosphoric acid monomer (B3-2), for example, an ester of an unsaturated carboxylic acid and a compound having two or more hydroxyl groups in one molecule, and an ester of phosphoric acid are suitable. Specifically, esters of hydroxyl group-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 1,4-butanediol mono(meth)acrylate with phosphoric acid; esters of polyalkylene glycol mono(meth)acrylates such as polyethylene glycol mono(meth)acrylate and polypropylene glycol mono(meth)acrylate with phosphoric acid, and the like, can be mentioned, and one or more of these can be used.

[0100] As a monomer capable of constituting a polymer, which is a preferred form of the dispersant (B), among the unsaturated carboxylic acid monomer (B1), the unsaturated sulfonic acid monomer (B2) and the phosphoric acid monomer (B3), the unsaturated carboxylic acid monomer (B1) and the unsaturated sulfonic acid monomer (B2) are preferred, and the unsaturated carboxylic acid monomer (B1) is more preferred. The dispersant (B) is preferably a polymer having a structural unit (b1) derived from the unsaturated carboxylic acid monomer (B1), or a polymer having a structural unit (b2) derived from the unsaturated sulfonic acid monomer (B2), and more preferably a polymer having a structural unit (b1) derived from the unsaturated carboxylic acid monomer (B1).

[0101] When the dispersant (B) has a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid monomer (B1), an unsaturated sulfonic acid monomer (B2), and an unsaturated phosphoric acid monomer (B3-2), it further has a structural unit derived from the following formula (13);

[0102] [ka]

[0103] (In the formula, R 14 , R 15 and R 16 R may be the same or different and represents a hydrogen atom or a methyl group. 17 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. (AO) are the same or different and represent an oxyalkylene group. n represents the average number of moles of oxyalkylene groups added and is a number from 1 to 500. p represents a number from 0 to 4. q represents 0 or 1.) It is preferable that the (poly)alkylene glycol monomer (C) has a structural unit (c) represented by the following formula:

[0104] In the above formula (13), AO represents an oxyalkylene group "either the same or different," which means that the n oxyalkylene groups of AO present in the polyalkylene glycol may all be the same or different.

[0105] In the above formula (13), n represents the average number of moles of oxyalkylene groups added and is a number from 1 to 500, preferably from 2 to 300, more preferably from 3 to 250, still more preferably from 10 to 150, and particularly preferably from 20 to 80. The alkylene group constituting the oxyalkylene group preferably has 2 to 18 carbon atoms, more preferably 2 to 10 carbon atoms, further preferably 2 to 8 carbon atoms, and particularly preferably 2 to 4 carbon atoms.

[0106] The (poly)oxyalkylene group represented by (AO)n above is an alkylene oxide adduct, and examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, styrene oxide, etc. Among these, preferred are alkylene oxides having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, and more preferred are ethylene oxide and propylene oxide.

[0107] When the (poly)oxyalkylene group is an adduct of any two or more kinds of alkylene oxides selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide, etc., it may be in any form of random addition, block addition, alternating addition, etc. In order to ensure a balance between hydrophilicity and hydrophobicity, it is preferable that the oxyalkylene group in the polyalkylene glycol has an oxyethylene group as an essential component, more preferably 50 mol % or more of the oxyethylene group, and even more preferably 90 mol % or more of the oxyethylene group.

[0108] R in the above formula (13) 14 ~R 16 are the same or different and each represents a hydrogen atom or a methyl group. 14 , R 15 is a hydrogen atom, and R 16 is a hydrogen atom or a methyl group. More preferably, R 14 , R 15 is a hydrogen atom, and R 16 is a methyl group.

[0109] In the above formula (13), p represents a number from 0 to 4, and q represents 0 or 1. However, when q is 0, p is preferably 1 or 2. In this case, R 16 is more preferably a methyl group. When q is 1, p is preferably 0. In this case, R 16 is more preferably a hydrogen atom or a methyl group. When the above p is 0 and q is 0, AO that is first bonded to the oxygen atom bonded to the carbon-carbon double bond is preferably an oxyalkylene group having 4 carbon atoms. The above p is preferably 0, and an embodiment in which p is 0 and q is 1 is one of the preferred embodiments of the present invention.

[0110] R in the above formula (13) 17 R represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. 17is preferably a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, more preferably a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, even more preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and most preferably a hydrocarbon group having 1 to 3 carbon atoms.

[0111] Examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a 3-pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, an isooctyl group, a 2,3,5-trimethylhexyl group, a 4-ethyl-5-methyloctyl group, a 2-ethylhexyl group, a tetradecyl group, an octadecyl group, linear or branched alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and other cyclic alkyl groups; phenyl, benzyl, phenethyl, o-, m-, or p-tolyl, 2,3-, or 2,4-xylyl, mesityl, naphthyl, anthryl, phenanthryl, biphenylyl, benzhydryl, trityl, and pyrenyl groups, and other aryl groups. Among these, linear, branched, or cyclic alkyl groups are preferred.

[0112] Specific examples of the (poly)alkylene glycol monomer (C) include polyalkylene glycol mono(meth)acrylates such as (poly)ethylene glycol mono(meth)acrylate and (poly)propylene glycol mono(meth)acrylate; alkoxy polyalkylene glycol mono(meth)acrylates such as methoxy(poly)ethylene glycol mono(meth)acrylate and methoxy(poly)propylene glycol mono(meth)acrylate; vinyl alcohol, (meth)allyl alcohol, 3-methyl-3-buten-1-ol (isoprenol), 3-methyl-2-butene ... The alkylene oxide is preferably a compound obtained by adding 1 to 500 moles of alkylene oxide to any one of 2-methyl-3-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-2-buten-1-ol, and 2-methyl-3-buten-1-ol (for example, polyethylene glycol mono(3-methyl-3-butenyl)ether, polyoxyethylene(mono(meth)allyl)ether, etc.); and more preferably a compound obtained by adding 1 to 500 moles of alkylene oxide to 3-methyl-3-buten-1-ol (isoprenol), or (meth)allyl alcohol; and the above-mentioned "alkylene oxide" is preferably ethylene oxide or propylene oxide. Among them, the alkylene oxide is preferably a compound obtained by adding 1 to 500 moles of alkylene oxide to 3-methyl-3-buten-1-ol (isoprenol), or (meth)allyl alcohol.

[0113] The proportion of the structural unit (b) in the dispersant (B) is preferably 1 to 90 mass% relative to 100 mass% of all structural units. The proportion of the structural unit (b) in the dispersant (B) is more preferably 3 to 80 mass%, further preferably 5 to 50 mass%, and particularly preferably 7 to 20 mass%.

[0114] The dispersant (B) preferably contains the structural unit (c) in an amount of 10 to 99 mass % relative to 100 mass % of all structural units. The amount of the structural unit (c) in the dispersant (B) is more preferably 20 to 97 mass %, further preferably 50 to 95 mass %, and particularly preferably 80 to 93 mass %.

[0115] When the dispersant (B) is a polymer, the total content of the structural units (b) and (c) in the polymer is preferably 80 to 100 mass%, more preferably 90 to 100 mass%, and even more preferably 95 to 100 mass%.

[0116] The dispersant (B) preferably has a weight average molecular weight of 1,000 to 1,000,000. More preferably, it is 5,000 to 100,000, even more preferably 7,500 to 70,000, and particularly preferably 10,000 to 40,000. When the dispersant (B) is a polymer having a structural unit (b3) derived from a phosphoric acid monomer (B3), the weight average molecular weight is preferably 3,000 to 100,000. The weight average molecular weight can be measured by the method described in the Examples.

[0117] When the dispersant (B) is a polymer having one or more structural units selected from the structural unit (b1) derived from an unsaturated carboxylic acid monomer (B1), the structural unit (b2) derived from an unsaturated sulfonic acid monomer (B2), and the structural unit (c) derived from a (poly)alkylene glycol monomer (C), the weight average molecular weight is preferably 3,000 to 100,000, more preferably 4,500 to 80,000, even more preferably 6,000 to 70,000, particularly preferably 7,000 to 45,000, and particularly preferably 8,000 to 35,000.

[0118] When the dispersant (B) is a compound having a carboxyl group and / or a salt group thereof, a copolymer having a structural unit (b1) derived from the unsaturated carboxylic acid monomer (B1) and a structural unit (c) derived from the (poly)alkylene glycol monomer (C) is preferred.

[0119] In one embodiment, the dispersant (B) contains a structural unit (b1) derived from an unsaturated carboxylic acid monomer (B1); and a structural unit (c) derived from a (poly)alkylene glycol monomer (C). In this case, for example, the unsaturated carboxylic acid monomer (B1) is (meth)acrylic acid (salt); and the (poly)alkylene glycol monomer (C) is a compound obtained by adding an alkylene oxide to 3-methyl-3-buten-1-ol (isoprenol) (polyethylene glycol mono(3-methyl-3-butenyl)ether); a compound obtained by adding an alkylene oxide to (meth)allyl alcohol (polyoxyethylene(mono(meth)allyl)ether); or a methoxypolyethylene glycol mono(meth)acrylate. In one embodiment, the dispersant (B) contains a structural unit (b2) derived from an unsaturated sulfonic acid monomer (B2) and a structural unit (c) derived from a (poly)alkylene glycol monomer (C). In this case, as an example, the unsaturated sulfonic acid monomer (B2) is 2-((meth)acryloyloxy)ethanesulfonic acid, and the (poly)alkylene glycol monomer (C) is methoxypolyethylene glycol mono(meth)acrylate.

[0120] When the dispersant (B) is a compound having a sulfonic acid group and / or a salt group thereof, specific examples thereof include polyalkylarylsulfonate-based compounds such as naphthalenesulfonic acid formaldehyde condensates, methylnaphthalenesulfonic acid formaldehyde condensates, and anthracenesulfonic acid formaldehyde condensates; melamine formalin resin sulfonate-based compounds such as melamine sulfonic acid formaldehyde condensates; aromatic aminosulfonate-based compounds such as aminoarylsulfonic acid-phenol-formaldehyde condensates; ligninsulfonate-based compounds such as ligninsulfonates and modified ligninsulfonates; and polystyrenesulfonate-based compounds.

[0121] When the dispersant (B) is a compound having at least one selected from the group consisting of a phosphoric acid group, a salt group thereof, and a phosphoric acid ester group, examples of the dispersant include copolymers having a (poly)oxyalkylene group and a phosphoric acid ester group in the molecule, such as copolymers obtained from (alkoxy)polyalkylene glycol mono(meth)acrylates, phosphoric acid monoester monomers, and phosphoric acid diester monomers; polycondensation products consisting of monomers having a (poly)oxyalkylene group, an aromatic group and / or a heterocyclic aromatic group, monomers having a phosphoric acid (salt) group and / or a phosphoric acid ester group, an aromatic group and / or a heterocyclic aromatic group, and an aldehyde compound; and polymers having an aromatic triazine structural unit, a polyalkylene glycol structural unit, and a phosphoric acid ester structural unit.

[0122] The hydraulic material composition and additive for hydraulic material of the present invention contain the nitrogen-containing compound (A) and dispersant (B), and the content ratios thereof are not particularly limited, but the ratio of the nitrogen-containing compound (A) to 100 mass% of the dispersant (B) is preferably 0.01 to 100,000 mass% in terms of solid content. This makes it possible to maintain the fluidity of the hydraulic material composition while improving the thixotropy and increasing the yield point. The ratio of the nitrogen-containing compound (A) in the hydraulic material composition and additive for hydraulic material of the present invention is more preferably 1 to 1000 mass% to 100 mass% of the dispersant (B). A method for measuring the solid content required for solid content conversion will be described later.

[0123] When the dispersant (B) is a compound having a carboxyl group and / or a salt group thereof, and / or a compound having at least one selected from the group consisting of a phosphoric acid group, a salt group thereof, and a phosphoric acid ester group, the ratio of the nitrogen-containing compound (A) to 100 mass% of the dispersant (B) is preferably 0.25 to 2000 mass%. In the above case, the ratio of the nitrogen-containing compound (A) is more preferably 0.25 to 1000 mass%, and even more preferably 0.25 to 100 mass%, to 100 mass% of the dispersant (B). When the dispersant (B) is a compound having a sulfonic acid group and / or a salt group thereof, the ratio of the nitrogen-containing compound (A) to 100 mass% of the dispersant (B) is preferably 1 to 2000 mass%. In the above case, the ratio of the nitrogen-containing compound (A) is more preferably 5 to 2000 mass%, and even more preferably 5 to 1000 mass%, to 100 mass% of the dispersant (B).

[0124] The ratio of the nitrogen-containing compound (A) in the hydraulic material composition and additive for hydraulic material of the present invention is more preferably 1.5 to 100 mass%, particularly preferably 2 to 65 mass%, and most preferably 2.5 to 50 mass% relative to 100 mass% of the dispersant (B). In one embodiment, the ratio of the nitrogen-containing compound (A) in the hydraulic material composition and additive for hydraulic material of the present invention may be 1 to 30 mass%, 1 to 25 mass%, 1 to 20 mass%, 1 to 15 mass%, or 1 to 10 mass% relative to 100 mass% of the dispersant (B). In another embodiment, the ratio of the nitrogen-containing compound (A) in the hydraulic material composition and additive for hydraulic material of the present invention may be 0.5 to 50 mass%, 0.7 to 25 mass%, 1 to 20 mass%, 1.5 to 15 mass%, or 2 to 13 mass% relative to 100 mass% of the dispersant (B).

[0125] In addition, when the dispersant (B) has two or more types of groups (i) to (iii) among (i) carboxyl groups and salt groups thereof, (ii) sulfonic acid groups and salt groups thereof, and (iii) phosphoric acid groups, salt groups thereof, and phosphoric acid ester groups, for example, when it has a carboxyl group and a sulfonic acid group, it is classified as the compound having a larger proportion of these groups.

[0126] In this specification, the solid content can be measured as follows.

[0127] <Solid content measurement method> 1. Accurately weigh the aluminum dish. Accurately weigh the solid content measurement material into the aluminum dish used in 2.1. 3. Place the solid content measured in step 2 in a dryer adjusted to 130°C under a nitrogen atmosphere for one hour. After 4.1 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 accurately weigh the aluminum dish and the sample to be measured. 6. The solid content is calculated by subtracting the mass of the aluminum dish obtained in 1 from the mass obtained in 5 and dividing the result by the mass of the solid content measurement sample obtained in 2.

[0128] The method for producing the polymer having structural units derived from a monomer having at least one selected from the group consisting of a carboxyl group, a sulfonic acid group, a phosphoric acid group, a salt thereof, and a phosphoric ester group is not particularly limited, and the polymer can be obtained by polymerizing a monomer component containing these monomers by a commonly used method.

[0129] In one embodiment, the nitrogen-containing compound (A) comprises one or more polymers selected from the group consisting of a polyalkyleneimine and a polymer (α1) having a structural unit (a1) derived from a nitrogen-containing monomer (A1) represented by the above formula (6); and the dispersant (B) comprises one or more polymers selected from the group consisting of a polymer having a structural unit (b1) derived from an unsaturated carboxylic acid monomer (B1), a polymer having a structural unit (b2) derived from an unsaturated sulfonic acid monomer (B2), and a polymer having a structural unit (c) derived from a (poly)alkylene glycol monomer (C).

[0130] <Hydraulic material compositions and additives for hydraulic materials> The hydraulic material composition of the present invention contains a hydraulic material (X), an aggregate (Y), a nitrogen-containing compound (A) and a dispersant (B), and the hydraulic material additive composition of the present invention contains a nitrogen-containing compound (A) and a dispersant (B). The hydraulic material additive may contain two or more kinds of the nitrogen-containing compound (A) and the dispersant (B). The content of the nitrogen-containing compound (A) in the hydraulic material additive (when two or more kinds of the nitrogen-containing compound (A) and the dispersant (B) are contained, the total content) is not particularly limited, but is preferably 5 to 100% by mass in 100% by mass of the solid content (i.e., non-volatile content) in the hydraulic material additive. It is more preferably 20 to 99% by mass, and even more preferably 30 to 95% by mass.

[0131] In this specification, the term "hydraulic material additive" refers to an additive added to a hydraulic material composition such as cement paste, mortar, or concrete, and may be an agent consisting of only the nitrogen-containing compound (A) and dispersant (B), or may contain not only the nitrogen-containing compound (A) and dispersant (B) but also other additives, as described below, as necessary.

[0132] The hydraulic material composition of the present invention contains a hydraulic material (X) and a nitrogen-containing compound (A), and the content ratios thereof are not particularly limited, but the ratio of the nitrogen-containing compound (A) to 100% by mass of the hydraulic material (X) is preferably 0.0001 to 10% by mass. This can improve the thixotropy of the hydraulic material composition and increase the yield point. In the hydraulic material composition of the present invention, the content of the nitrogen-containing compound (A) is preferably 0.0005 to 1% by mass, more preferably 0.001 to 0.5% by mass, even more preferably 0.001 to 0.3% by mass, particularly preferably 0.001 to 0.2% by mass, and particularly preferably 0.001 to 0.1% by mass, to 100% by mass of the hydraulic material (X).

[0133] In the hydraulic material composition, the mixing ratio of the additive for hydraulic material of the present invention is preferably set so that the total ratio of the nitrogen-containing compound (A) and dispersant (B), which are essential components of the present invention, is 0.0101 to 11 mass% based on 100 mass% of the total amount of the hydraulic material, calculated as solid content. In the hydraulic material composition of the present invention, the total content of the nitrogen-containing compound (A) and dispersant (B) is more preferably 0.0525 to 2 mass%, further preferably 0.055 to 1 mass%, particularly preferably 0.06 to 0.7 mass%, and most preferably 0.08 to 0.5 mass%, based on 100 mass% of the hydraulic material (X).

[0134] In the hydraulic material composition of the present invention, additives other than the nitrogen-containing compound (A) and dispersant (B) of the present invention may be used in combination. Examples of the additives include water-soluble polymeric substances, retarders, quick-setting agents, early-strength agents / accelerators, mineral oil-based defoamers, oil-based defoamers, fatty acid-based defoamers, fatty acid ester-based defoamers, oxyalkylene-based defoamers, alcohol-based defoamers, amide-based defoamers, phosphate ester-based defoamers, metal soap-based defoamers, silicone-based defoamers, air-enhancing agents, surfactants, waterproofing agents, rust inhibitors, preservatives, crack reducing agents, expanding agents, cement wetting agents, thickeners, separation reducing agents, flocculants, drying shrinkage reducing agents, strength enhancing agents, self-leveling agents, colorants, and mold inhibitors.

[0135] The above-mentioned quick-setting agent is not particularly limited as long as it is a known quick-setting agent. The quick-setting agent used may be a powder quick-setting agent, a liquid quick-setting agent, or a slurry type quick-setting agent. Examples of liquid quick-setting agents include aluminum sulfate, fluorine, and alkali metals, and further, those containing these and alkanolamines, and one or more of these can be used. In addition, a known water-soluble hydration accelerator can be used for the liquid quick-setting agent used in the present invention. Examples of the hydration accelerator include organic hydration accelerators such as formic acid or its salts, acetic acid or its salts, and lactic acid or its salts, and inorganic hydration accelerators such as water glass, nitrates, nitrites, thiosulfates, and thiocyanates. Examples of powder quick-setting agents include those containing calcium aluminates, sulfates, alkali metal aluminates, alkali metal carbonates, and oxycarboxylic acids, and one or more of these can be used.

[0136] The above-mentioned defoaming agent is not particularly limited as long as it is a known defoaming agent. For example, mineral oil-based defoaming agents such as kerosene and liquid paraffin; oil-based defoaming agents such as animal and vegetable oils, sesame oil, castor oil, and alkylene oxide adducts thereof; fatty acid-based defoaming agents such as oleic acid, stearic acid, and alkylene oxide adducts thereof; fatty acid ester-based defoaming agents such as diethylene glycol monolaurate, glycerin monoricinoleate, alkenylsuccinic acid derivatives, sorbitol monolaurate, sorbitol trioleate, polyoxyethylene monolaurate, polyoxyethylene sorbitol monolaurate, and natural wax; fatty acid ester-based defoaming agents such as octyl alcohol, hexadecyl alcohol, acetylene alcohol, glyceryl ester ... Alcohol-based defoamers such as choline and polyoxyalkylene glycol; amide-based defoamers such as polyoxyalkylene amide and acrylate polyamine; phosphate-based defoamers such as tributyl phosphate and sodium octyl phosphate; metal soap-based defoamers such as aluminum stearate and calcium oleate; silicone-based defoamers such as silicone oil, silicone paste, silicone emulsion, organic modified polysiloxane and fluorosilicone oil; oxyalkylene-based defoamers such as polyoxyethylene polyoxypropylene adduct; and the like. One or more of these can be used. Among the above-listed defoamers, oxyalkylene-based defoamers are most preferred. When the copolymer for cement admixture of the present invention is used in combination with an oxyalkylene-based defoamer, the amount of defoamer used can be reduced, and the compatibility between the defoamer and the copolymer is also excellent. The oxyalkylene defoaming agent is not particularly limited as long as it is a compound having an oxyalkylene group in the molecule and having the effect of reducing bubbles in an aqueous liquid. Among them, a specific oxyalkylene defoaming agent represented by the following formula (14) is preferred. R 17 {-W-(R 18 O)u1-R 19}u2 (14) In the above formula (14), R 17 , R 19are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 1 to 22 carbon atoms, an alkynyl group having 1 to 22 carbon atoms, a phenyl group, or an alkylphenyl group (the alkyl group in the alkylphenyl group has 1 to 22 carbon atoms). 18 O represents one or a mixture of two or more oxyalkylene groups having 2 to 4 carbon atoms, and when two or more types are used, they may be added in a block or random manner. u1 represents the average number of moles of oxyalkylene groups added and is a number from 0 to 300. When u1 is 0, R 17 , R 19 are not simultaneously hydrogen atoms, W represents a -O-, -CO2-, -SO4-, -PO4- or -NH- group; u2 represents an integer of 1 or 2, R 17 When is a hydrogen atom, u2 is 1.

[0137] Examples of the oxyalkylene-based defoaming agent represented by the above formula (14) include polyoxyalkylenes such as (poly)oxyethylene (poly)oxypropylene adducts; (poly)oxyalkylene alkyl ethers such as diethylene glycol heptyl ether, polyoxyethylene oleyl ether, polyoxypropylene butyl ether, polyoxyethylene polyoxypropylene-2-ethylhexyl ether, and oxyethylene oxypropylene adducts to higher alcohols having 12 to 14 carbon atoms; (poly)oxyalkylene (alkyl)aryl ethers such as polyoxypropylene phenyl ether and polyoxyethylene nonyl phenyl ether; and addition polymerization of alkylene oxides to acetylene alcohols such as 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,5-dimethyl-3-hexyne-2,5-diol, and 3-methyl-1-butyne-3-ol. (poly)oxyalkylene fatty acid esters such as diethylene glycol oleate, diethylene glycol laurate, ethylene glycol distearate, etc.; (poly)oxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan trioleate, etc.; (poly)oxyalkylene alkyl (aryl) ether sulfate salts such as polyoxypropylene methyl ether sodium sulfate, polyoxyethylene dodecylphenol ether sodium sulfate, etc.; (poly)oxyalkylene alkyl phosphates such as (poly)oxyethylene stearyl phosphate, etc.; (poly)oxyalkylene alkyl amines such as polyoxyethylene laurylamine, etc.; and the like, and one or more of these can be used.

[0138] In the above hydraulic material composition, 1 m 3 The unit water amount, cement usage amount and water / cement ratio per unit are not particularly limited. For example, the unit water amount is 100 to 300 kg / m 3 , Cement amount used: 300-500kg / m 3 The water / cement ratio (weight ratio) is preferably 0.35 to 0.6. More preferably, the unit water content is 140 to 240 kg / m3 , Cement amount used: 350-480kg / m 3 , the water / cement ratio (weight ratio) is 0.4 to 0.5.

[0139] <Three-dimensional object and three-dimensional modeling method> The hydraulic material composition of the present invention is suitable for use in three-dimensional modeling, particularly for three-dimensional modeling, and is also suitable for use in three-dimensional modeling for construction. Thus, the present invention also provides a three-dimensional object formed from the hydraulic material composition for three-dimensional modeling of the present invention.

[0140] The method for producing a three-dimensional object using the hydraulic material composition for three-dimensional object fabrication of the present invention (three-dimensional object fabrication method) includes a step of extruding the hydraulic material composition of the present invention from a nozzle and laminating the hydraulic material composition. The three-dimensional object fabrication method according to the present invention preferably includes a step of kneading a hydraulic material (X), an aggregate (Y), a nitrogen-containing compound (A) and a dispersant (B), a step of pumping the kneaded hydraulic material composition with compressed air or a pump, etc., and a step of extruding the pumped hydraulic material composition from a nozzle and laminating the hydraulic material composition to form a three-dimensional object.

[0141] A nozzle (discharge part) is provided at the tip of the pressure-feeding pipe for the hydraulic material composition of the present invention. The diameter of the nozzle is not particularly limited, but may be appropriately set depending on the size of the aggregate (Y) used and the width of the laminated hydraulic material composition. For example, if the size of the aggregate (Y) is 5 mm or less and the laminated width is 50 mm or less, the diameter of the nozzle is preferably 8 to 15 mm. The shape of the nozzle is not particularly limited, but examples include a circle, an ellipse, a rectangle, a cross, and a star, and a brim may be provided around the nozzle for the purpose of providing smoothness to the surface of the discharged hydraulic material composition.

[0142] When the hydraulic material composition discharged from the nozzle is laminated to form a shape, the nozzle may be moved vertically or horizontally to form a shape. For example, it is preferable to fix the nozzle to a robot arm or a portal plotter and control the movement of the nozzle by computer control. A method is possible in which the three-dimensional data created by the computer is cut at a predetermined thickness to create two-dimensional slice data, and the hydraulic material composition is discharged from the nozzle while controlling the horizontal movement of the spray nozzle in the vertical, horizontal, and diagonal directions based on the two-dimensional slice data, and the nozzle is moved vertically to repeatedly laminate the composition in sequence to form a shape. The nozzle movement speed is not particularly limited and can be changed depending on the width of the layer. EXAMPLES

[0143] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In addition, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".

[0144] <Measurement of weight average molecular weight of dispersant (B)> The weight average molecular weight was measured under the following measurement conditions. Equipment: Waters Alliance (2695) Analysis software: Waters, Empower2 Professional + GPC option Columns used: Tosoh Corporation, TSKguard columns SWXL + TSKgel G4000SWXL + G3000SWXL + G2000SWXL Detector: Refractometer (RI) detector (Waters 2414), multi-wavelength visible-ultraviolet (PDA) detector (Waters 2996) Eluent: 115.6 g of sodium acetate trihydrate dissolved in a mixed solvent of 10,999 g of water and 6,001 g of acetonitrile, and the pH was adjusted to 6.0 with acetic acid. · Standard substance for calibration curve preparation: polyethylene glycol (peak top molecular weight (Mp) 272500, 219300, 107000, 50000, 24000, 12600, 7100, 4250, 1470) · Calibration curve: Prepared by 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 · Injection volume of standard substance sample solution: 100 μL (eluent solution with polymer concentration of 0.1 mass%) · Injection volume of polymer sample solution: 100 μL (eluent solution with polymer concentration of 0.5 mass%).

[0145] <GPC analysis conditions (analysis of polymer)> In the obtained RI chromatogram, the flat and stable parts of the baseline immediately before and after the elution of the polymer were connected by a straight line, and the polymer was detected and analyzed. However, when the peaks of monomers and monomer-derived impurities partially overlapped with the polymer peak and were measured, they were vertically divided at the deepest concave part of the overlapping part between them to separate the polymer part from the monomer part and the impurity part, and the molecular weight and molecular weight distribution of only the polymer part were calculated. When there was no concave part, they were calculated together. The pure polymer content was calculated as follows from the ratio of the peak areas by the RI detector. Pure polymer content = (polymer peak area) / (polymer peak area + peak area of monomer or impurity) <Rheological evaluation by rheometer> (1) Apparatus: Rotational rheometer RST rheometer manufactured by Brook field (2) Outline of the apparatus: Consists of a probe, a sample stage, and a stress detector, and has a mechanism for detecting the stress applied to the probe while rotating the probe while changing the speed. Probe for rheological measurement test: Vane Spindle VT-60-30 (3) Evaluation method: The mortar prepared (mixed) as described below was transferred to a 1000 mL death cup and placed on the sample stage, and immediately after mixing, the rotation speed of the probe was increased from 0 rpm to 120 rpm over 60 seconds, and then decreased from 120 rpm to 0 rpm over another 60 seconds. In the obtained time vs. stress plot, the area enclosed by the stress curve obtained when the rotation speed was increased and the stress curve obtained when the rotation speed was decreased was quantified and used as a measure of thixotropy.

[0146] <Yield point evaluation using a rheometer> (1) Equipment: Brookfield RST rheometer (2) Overview of the device: A probe for yield point detection tests consisting of a probe, a sample stage, and a stress detector. The probe is rotated at a constant speed and has a mechanism for detecting the stress applied to the probe. Probe for yield point detection tests: Vane Spindle VT-60-30 (3) Evaluation method: The mortar prepared (mixed) as described below was transferred to a 1000 mL desscup and placed on the sample stage, and left to stand for 5 minutes after mixing. Next, the stirring was continued for 30 seconds, the probe rotation speed was increased from 0 rpm to 5 rpm, and stirring was continued for another 30 seconds at 5 rpm. The maximum value of the obtained time vs. stress plot was defined as the yield point.

[0147] <Dispersibility evaluation> The mortar test was carried out under an environment of 20°C ± 1°C and 60% ± 15% relative humidity. The mortar mix was C / S / W = 690 / 1600 / 331.2 (g). however, C: Cement (ordinary Portland cement, manufactured by Taiheiyo Cement Corporation) S: Fine aggregate (Oigawa River land sand) W: Aqueous ion exchange solution of sample (additive for hydraulic materials) and defoamer The W contained additives for hydraulic materials and antifoaming agents listed in Tables 1 to 6 below, and was dissolved sufficiently and uniformly in ion-exchanged water. Adekanol LG-299 (manufactured by Adeka) was used as the antifoaming agent, and was added so as to be 5 mass% of the solid content of the dispersant (B). Using a mortar mixer (Hobart mixer, model number: N-50), C and S were charged into a kneading container and kneaded at first speed for 10 seconds. While further kneading at first speed, W was charged over 10 seconds. 60 seconds after the start of kneading, the mixer was stopped, and the mortar was scraped off for 30 seconds. Then, kneading was further carried out at second speed for 60 seconds to prepare mortar. This mortar was used for the following dispersibility evaluation, the above-mentioned thixotropy evaluation, and yield point evaluation.

[0148] The mortar obtained as described above was half-filled into a mini-slump cone (JIS micro concrete slump cone, upper end inner diameter 50 mm, lower end inner diameter 100 mm, height 150 mm) placed on a flow measuring board (60 cm x 60 cm), and poked 15 times with a ramming rod. The mortar was further filled to the top of the mini-slump cone and poked 15 times with a ramming rod, and the surface of the mini-slump cone was smoothed. After that, 3 minutes and 30 seconds after the mixer was first started, the mini-slump cone was pulled up vertically, and the diameter of the spread mortar (the diameter of the longest part (long diameter) and the diameter of the part at 90 degrees to the long diameter) was measured at two points, and the average value was taken as the mortar flow value. The air content was adjusted to less than 3.0% by adding an oxyalkylene-based defoaming agent (Adekanol LG-299 (manufactured by Adeka)).

[0149] <Regarding nitrogen-containing compound (A)> As the nitrogen-containing compound (A), the following compound was prepared. Polyethyleneimine (Epomin® P-1000 (molecular weight: 70,000, amine value: 18) Polydiallyldimethylammonium chloride Product code 52237 (SIGMA-ALDRICH) (Molecular weight: 200,000~350,000) Polydiallyldimethylammonium chloride Product code 409022 (SIGMA-ALDRICH) (Molecular weight: <100,000) Polyethyleneimine (Epomin® SP-006 (molecular weight: 600, amine value: 20) Polyethyleneimine (Epomin® SP-012 / Nippon Shokubai Co., Ltd.) (molecular weight: 1,200, amine value: 19) Polyethyleneimine (Epomin (registered trademark) SP-018 / manufactured by Nippon Shokubai Co., Ltd.) (molecular weight: 1,800, amine value: 19).

[0150] The nitrogen atom content of polyethyleneimine is 32.5% by mass relative to 100% by mass of polyethyleneimine (because the nitrogen atom content of the polyethyleneimine monomer is 32.5% by mass relative to 100% by mass of the monomer). Also, the nitrogen atom content of polydiallyldimethylammonium chloride is 8.6% by mass relative to 100% by mass of polydiallyldimethylammonium chloride (because the nitrogen atom content of the polydiallyldimethylammonium chloride monomer is 8.6% by mass relative to 100% by mass of the monomer).

[0151] <Production of Dispersant (B-1)> An aqueous solution (B1a) was prepared by dissolving 0.4 parts of L-ascorbic acid and 0.8 parts of 3-mercaptopropionic acid in 50.0 parts of water.

[0152] A reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet tube, and a reflux condenser was charged with 90.4 parts of water, 191.0 parts of an unsaturated polyalkylene glycol ether monomer (IPN-50) in which an average of 50 moles of ethylene oxide were added to 3-methyl-3-buten-1-ol, and 0.3 parts of acrylic acid (AA). The atmosphere in the reaction vessel was then replaced with nitrogen while stirring, and the temperature was raised to 60°C under a nitrogen atmosphere, after which 0.9 parts of a 35% aqueous hydrogen peroxide solution was added. After 30 minutes, the above mixed solution (B1a) was added dropwise over 3.5 hours, and 25.5 parts of acrylic acid (AA) was added dropwise over 3.0 hours at a constant rate, while the temperature was kept constant at 60°C.

[0153] After the dropwise addition of the mixed solution (B1a) was completed, the temperature was maintained at 60°C for 1 hour to terminate the polymerization reaction. After that, the pH of the reaction solution was neutralized to pH=6.3 using an aqueous sodium hydroxide solution at a temperature below the polymerization reaction temperature. In this way, an aqueous polymer solution containing copolymer (B-1) was obtained. The weight average molecular weight Mw of the obtained copolymer (B-1) was 32,000.

[0154] <Production of Dispersant (B-2)> A solution (B2a) was prepared by dissolving 2.3 parts of ammonium persulfate in 75.2 parts of water. A solution (B2b) was prepared by dissolving 40.0 parts of 2-(methacryloyloxy)ethanesulfonic acid in 40.0 parts of water. A solution (B2c) was prepared by dissolving 160.0 parts of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added: 23) and 0.7 parts of 3-mercaptopropionic acid in 68.9 parts of water. A reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet tube, and a reflux condenser was charged with 112.9 parts of water, and then the inside of the reaction vessel was replaced with nitrogen under stirring. After heating to 80°C under a nitrogen atmosphere, the above-mentioned mixed solution (B2a) was added dropwise at a constant rate over 5 hours, and the above-mentioned mixed solutions (B2b) and (B2c) were added dropwise over 4 hours. The temperature during this period was kept constant at 80°C. After the dropwise addition of the mixed solution (B2a) was completed, the temperature was maintained at 80° C. for 1 hour to terminate the polymerization reaction. Thereafter, 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 to obtain the copolymer (B-2) of the present invention consisting of an aqueous polymer solution having a weight average molecular weight of 30,000.

[0155] <Production of Dispersant (B-3)> A solution (B3a) was prepared by dissolving 1.5 parts of ammonium persulfate in 28.5 parts of water. A solution (B3b) was prepared by dissolving 72.3 parts of polyethylene glycol mono(3-methyl-3-butenyl)ether (average number of moles of ethylene oxide added: 50), 22.5 parts of acrylic acid, and 1.8 parts of 3-mercaptopropionic acid in 64.6 parts of water. 83.6 parts of water was charged into a reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet tube, and a reflux condenser, and then the inside of the reaction vessel was replaced with nitrogen while stirring. After the temperature was raised to 80°C under a nitrogen atmosphere, the above-mentioned mixed solution (B3a) was dropped at a constant rate over 4 hours and the above-mentioned mixed solution (B3b) was dropped over 3 hours. The temperature during this time was kept constant at 80°C. After the dropwise addition of the mixed solution (B3a) was completed, the temperature was maintained at 80°C for 1 hour, and the polymerization reaction was completed. Thereafter, 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 to obtain a copolymer (B-3) of the present invention consisting of an aqueous polymer solution having a weight average molecular weight of 13,000.

[0156] <Production of Dispersant (B-4)> A solution (B4a) was prepared by dissolving 0.3 parts of L-ascorbic acid in 29.7 parts of water. A solution (B3b) was prepared by dissolving 21.4 parts of acrylic acid in 8.6 parts of water. A solution (B3c) was prepared by dissolving 0.78 parts of 3-mercaptopropionic acid in 29.2 parts of water. A reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet tube, and a reflux condenser was charged with 158.6 parts of unsaturated alcohol obtained by adding 50 moles of ethylene oxide to methallyl alcohol, followed by nitrogen replacement under stirring, and then heating to 65°C under a nitrogen atmosphere, followed by adding 0.8 parts of a 30% aqueous solution of hydrogen peroxide. The above-mentioned mixed solution (B4a) was added dropwise at a constant rate over 3.5 hours, and the above-mentioned mixed solution (B4b) and mixed solution (B4c) were added dropwise over 3 hours. The temperature during this period was kept constant at 65°C. After the dropwise addition of the mixed solution (B4a) was completed, the temperature was maintained at 65°C for 1 hour to terminate the polymerization reaction. Thereafter, 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 to obtain the copolymer (B-4) of the present invention consisting of an aqueous polymer solution having a weight average molecular weight of 27,800.

[0157] <Production of Dispersant (B-5)> A solution (B5a) was prepared by dissolving 2.3 parts of ammonium persulfate in 20.7 parts of water. A solution (B5b) was prepared by dissolving 158 parts of methoxypolyethylene glycol monomethacrylate (average mole number of ethylene oxide added: 25), 42.0 parts of methacrylic acid, and 1.5 parts of 3-mercaptopropionic acid in 50.0 parts of water. A reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet tube, and a reflux condenser was charged with 170.0 parts of water, and then the reaction vessel was replaced with nitrogen under stirring, and the temperature was raised to 80°C under a nitrogen atmosphere. The above-mentioned mixed solution (B5a) was then dropped at a constant rate over 5 hours, and the above-mentioned mixed solution (B5b) was then dropped at a constant rate over 4 hours. The temperature during this time was kept constant at 80°C. After the dropwise addition of the mixed solution (B5a) was completed, the temperature was maintained at 80°C for 1 hour, and the polymerization reaction was completed. Thereafter, 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 to obtain a copolymer (B-5) of the present invention consisting of an aqueous polymer solution having a weight average molecular weight of 28,600.

[0158] Example (1)-1 and Comparative Example (1)-1, and Example (1)-2 and Comparative Example (1)-2 Polyethyleneimine (Nippon Shokubai Co., Ltd., Epomin P-1000) was used as the nitrogen-containing compound (A), and the copolymer (B-1) synthesized in the above synthesis example was used as the dispersant (B) in the proportions shown in Tables 1 and 2 to prepare additives for hydraulic materials. The prepared additives for hydraulic materials were evaluated for dispersibility, thixotropy, and yield point by the above-mentioned method. The results of calculating the thixotropy and yield point of Example (1)-1, assuming that Comparative Example (1)-1 is 100%, are shown in Table 1. The results of calculating the thixotropy and yield point of Example (1)-2, assuming that Comparative Example (1)-2 is 100%, are shown in Table 2. In the following Tables 1 to 8, "addition amount (% / cement)" refers to the mass % (solid content equivalent) of the additive when the cement mass is 100 mass%.

[0159] The mortar using the additive for hydraulic materials of Example (1)-1 had a flow value of 200 mm or more and less than 230 mm, and when the flow evaluation was adjusted to 200 mm or more and less than 230 mm, the yield point was 200 Pa or more and less than 2000 Pa, and the thixotropy was 300 Pa·s to 4000 Pa·s. The mortar using the additive for hydraulic materials of Example (1)-2 had a flow value of 200 mm or more and less than 230 mm (more specifically, 200 mm or more and less than 220 mm), and when the flow evaluation was adjusted to 200 mm or more and less than 230 mm (more specifically, 200 mm or more and less than 220 mm), the yield point was 300 Pa or more and less than 2000 Pa, and the thixotropy was 400 Pa·s to 4000 Pa·s.

[0160] [Table 1]

[0161] [Table 2]

[0162] Example (2)-1 and Comparative Example (2)-1, and Example (2)-2 and Comparative Example (2)-2 Polydiallyldimethylammonium chloride (manufactured by SIGMA-ALDRICH, product code 522376) was used as the nitrogen-containing compound (A) and the copolymer (B-1) synthesized in the above synthesis example was used as the dispersant (B) in the proportions shown in Tables 3 and 4 to prepare additives for hydraulic materials. The prepared additives for hydraulic materials were evaluated for dispersibility, thixotropy, and yield point by the above-mentioned method. The results of calculating the thixotropy and yield point of Example (2)-1 with Comparative Example (2)-1 set to 100% are shown in Table 3. The results of calculating the thixotropy and yield point of Example (2)-2 with Comparative Example (2)-2 set to 100% are shown in Table 4.

[0163] The mortar using the additive for hydraulic materials of Example (2)-1 had a flow value of 200 mm or more and 250 mm or less, and when the flow evaluation was adjusted to 200 mm or more and 250 mm or less, the yield point was 200 Pa or more and the thixotropy was 300 Pa s or more. The mortar using the additive for hydraulic materials of Example (2)-2 had a flow value of 200 mm or more and less than 230 mm (more specifically, 200 mm or more and 220 mm or less), and when the flow evaluation was adjusted to 200 mm or more and less than 230 mm (more specifically, 200 mm or more and 220 mm or less), the yield point was 300 Pa or more and 2000 Pa or less and the thixotropy was 400 Pa s or more and 4000 Pa s or less.

[0164] [Table 3]

[0165] [Table 4]

[0166] Example (3)-1 and Comparative Example (3)-1 Polyethyleneimine (Epomin P-1000, manufactured by Nippon Shokubai Co., Ltd.) was used as the nitrogen-containing compound (A), and the copolymer (B-2) synthesized in the above synthesis example was used as the dispersant (B) in the proportions shown in Table 5 to prepare an additive for hydraulic materials. The prepared additive for hydraulic materials was evaluated for dispersibility, thixotropy, and yield point by the above-mentioned method. The thixotropy and yield point of Example (3)-1 were calculated by taking the thixotropy and yield point of Comparative Example (3)-1 as 100%. The results are shown in Table 5. In addition, the mortar using the additive for hydraulic materials in Example (3)-1 had a flow value of 200 mm or more and less than 230 mm (more specifically, 200 mm or more and 220 mm or less), and when adjusted so that the flow evaluation was 200 mm or more and less than 230 mm (more specifically, 200 mm or more and 220 mm or less), the yield point was 300 Pa or more and 2000 Pa or less, and the thixotropy was 400 Pa s or more and 4000 Pa s or less.

[0167] [Table 5]

[0168] Examples (4)-1 to (4)-10 and Comparative Examples (4)-1 and (4)-2 Compound A shown in Table 6 below was used as the nitrogen-containing compound (A), and copolymer (B-3) synthesized in the above synthesis example was used as the dispersant (B) in the proportions shown in Table 6 to prepare additives for hydraulic materials. The prepared additives for hydraulic materials were evaluated for dispersibility, thixotropy, and yield point by the above-mentioned method. The thixotropy and yield point of Examples (4)-1 to (4)-10 and Comparative Example (4)-2 were calculated with Comparative Example (4)-1 as 100%. The results are shown in Table 6.

[0169] The mortar using the hydraulic material additives of Examples (4)-1 to (4)-10 had a flow value of 200 mm or more and less than 230 mm (more specifically, 200 mm or more and 220 mm or less), and when adjusted so that the flow evaluation was 200 mm or more and less than 230 mm (more specifically, 200 mm or more and 220 mm or less), the yield point was 400 Pa or more and 2000 Pa or less, and the thixotropy was 500 Pa s or more and 4000 Pa s or less.

[0170] [Table 6]

[0171] Examples (5)-1 to (5)-3 and Comparative Example (5)-1 Compound A shown in Table 7 below was used as the nitrogen-containing compound (A), and copolymer (B-4) synthesized in the above Synthesis Example was used as the dispersant (B) in the proportions shown in Table 7 to prepare additives for hydraulic materials. The prepared additives for hydraulic materials were evaluated for dispersibility, thixotropy, and yield point by the above-mentioned method. The thixotropy and yield point of Examples (5)-1 to (5)-3 were calculated by taking Comparative Example (5)-1 as 100%. The results are shown in Table 7.

[0172] The mortar using the hydraulic material additives of Examples (5)-1 to (5)-3 had a flow value of 200 mm or more and less than 230 mm (more specifically, 200 mm or more and 220 mm or less), and when adjusted so that the flow evaluation was 200 mm or more and less than 230 mm (more specifically, 200 mm or more and 220 mm or less), the yield point was 400 Pa or more and 2000 Pa or less, and the thixotropy was 500 Pa s or more and 4000 Pa s or less.

[0173] [Table 7]

[0174] Example (6)-1 and Comparative Example (6)-1 Compound A shown in Table 8 below was used as the nitrogen-containing compound (A) and copolymer (B-5) synthesized in the above synthesis example was used as the dispersant (B) in the proportions shown in Table 8 to prepare an additive for hydraulic materials. The prepared additive for hydraulic materials was evaluated for dispersibility, thixotropy, and yield point by the above-mentioned method. The thixotropy and yield point of Example (6)-1 were calculated by taking Comparative Example (6)-1 as 100%. The results are shown in Table 8.

[0175] The mortar using the additive for hydraulic materials in Example (6)-1 had a flow value of 200 mm or more and less than 230 mm (more specifically, 200 mm or more and 220 mm or less), and when adjusted so that the flow evaluation was 200 mm or more and less than 230 mm (more specifically, 200 mm or more and 220 mm or less), the yield point was 200 Pa or more and 2000 Pa or less, and the thixotropy was 300 Pa s or more and 4000 Pa s or less.

[0176] [Table 8]

[0177] From all the above examples, it was confirmed that the addition of compound A increases the thixotropy and yield point of the mortar. The improvement in thixotropy and yield point by the addition of compound A makes it suitable for 3D printing (three-dimensional modeling).

[0178] This application is based on Japanese Patent Application No. 2021-120005, filed on July 20, 2021, the disclosure of which is incorporated by reference in its entirety into this specification. [Industrial Applicability]

[0179] The hydraulic material composition of the present invention can be used as a material for three-dimensional modeling, and can be used to easily produce products in the fields of civil engineering and construction.

Claims

1. A hydraulic material composition for three-dimensional object formation, comprising a hydraulic material (X), an aggregate (Y), a nitrogen-containing compound (A) and a dispersant (B), The nitrogen-containing compound (A) has a nitrogen atom content of 6.8% by mass or more relative to 100% by mass of the nitrogen-containing compound (A), The nitrogen-containing compound (A) is represented by the following formula (1) and / or (2): 【Chemistry 1】 (In the formula, R 1 s are the same or different and each represents an alkylene group having 2 to 6 carbon atoms.) is a polyalkyleneimine having a structural unit represented by The hydraulic material composition for three-dimensional object formation, wherein the dispersant (B) is a compound having at least one selected from the group consisting of a carboxyl group, a sulfonic acid group, a phosphoric acid group, a group of salts thereof, and a phosphoric acid ester group.

2. The hydraulic material composition for three-dimensional modeling according to claim 1, wherein the nitrogen-containing compound (A) is polyethyleneimine.

3. 3. The hydraulic material composition for three-dimensional object formation according to claim 1, wherein the nitrogen-containing compound (A) is contained in an amount of 0.0001 to 10 parts by mass per 100 parts by mass of the hydraulic material (X).

4. 3. The hydraulic material composition for three-dimensional object formation according to claim 1, wherein the nitrogen-containing compound (A) is contained in an amount of 0.01 to 100,000 parts by mass per 100 parts by mass of the dispersant (B).

5. 3. The hydraulic material composition for three-dimensional object formation according to claim 1, wherein the dispersant (B) is a polymer having a structural unit derived from at least one monomer selected from the group consisting of an unsaturated carboxylic acid monomer (B1), an unsaturated sulfonic acid monomer (B2), and a phosphoric acid monomer (B3).

6. An additive for hydraulic materials used for three-dimensional modeling applications, comprising a nitrogen-containing compound (A) and a dispersant (B), The nitrogen-containing compound (A) is contained in an amount of 0.01 to 100,000 parts by mass relative to 100 parts by mass of the dispersant (B), The nitrogen-containing compound (A) has a nitrogen atom content of 6.8% by mass or more relative to 100% by mass of the nitrogen-containing compound (A), The nitrogen-containing compound (A) is represented by the following formula (1) and / or (2): 【Chemistry 1】 (In the formula, R 1 s are the same or different and each represents an alkylene group having 2 to 6 carbon atoms.) is a polyalkyleneimine having a structural unit represented by The dispersant (B) is an additive for hydraulic materials used for three-dimensional modeling applications, which is a compound having at least one selected from the group consisting of a carboxyl group, a sulfonic acid group, a phosphoric acid group, a group of salts thereof, and a phosphoric acid ester group.

7. A three-dimensional object formed from the hydraulic material composition for three-dimensional object formation according to claim 1 or 2.

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