Additives used in hydraulic compositions for additive manufacturing

Abstract

The present invention addresses the problem of providing an additive or the like having, for example, an excellent effect of improving the laminating properties of a hydraulic composition for additive manufacturing. The present invention provides an additive used in a hydraulic composition for additive manufacturing, the additive containing an emulsion that contains a polymer having an acid value of 30 mgKOH / g or more. It is more preferable that said additive contain an emulsion that contains a polymer having an acid value of 100-400 mgKOH / g, and the polymer preferably contains a structural unit having a carboxyl group.

Description

[Technical Field]

[0001] The present invention relates to a technique for producing a hydraulic composition for layered manufacturing, and more particularly to an additive used in a hydraulic composition for layered manufacturing. [Background technology]

[0002] In recent years, additive manufacturing (3D printing) technology has been utilized in the manufacturing industry to create models and parts. These technologies can be categorized into three categories: stereolithography (a method in which UV-curable resin is cured layer by layer to create layers), inkjet printing (a method in which UV-curable resin is sprayed from a printer head while being irradiated with UV light), powdered gypsum printing (a method in which resin or glue is sprayed from a printer head to harden powdered gypsum), powder sintering (a method in which resin or metal powder is baked and solidified with a laser to create layers), and fused deposition modeling (a method in which thermoplastic resin melted by heat is sprayed from a thin nozzle to create layers). The objects created are primarily made of resin, gypsum, and metal. Technology for creating large objects, such as construction components, using hydraulic material compositions has been explored more extensively overseas than in Japan. In Europe, the United States, and China, automated construction machinery is already being used to create large objects, such as detached houses.

[0003] As technologies relating to layered manufacturing using hydraulic compositions, for example, the following Patent Documents 1 to 5 are introduced.

[0004] Patent Document 1 discloses a technology 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 added quick-setting agent 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 on its own, forming a solidified layer in the shape based on the two-dimensional slice data, and the process of forming such solidified layers is repeated to stack them in the vertical direction to form a shape.

[0005] Patent Document 2 introduces a material for creating molds for producing castings using a 3D printer, and discloses a material made of cement, sand, and a water-soluble silicate as an accelerator.

[0006] Patent Document 3 introduces a grout composition that uses a lignin sulfonic acid-based dispersant and a melamine sulfonic acid-based dispersant in combination as a hydraulic material composition.

[0007] Patent Document 4 introduces PC grout as a material that uses a dispersant and a thickener in combination.

[0008] Patent Document 5 discloses a method for producing a hydraulic composition for layered manufacturing using an ionic emulsion-type thickener.

[0009] Hydraulic compositions for additive manufacturing (3D printing) need to have reduced fluidity to achieve their layering properties. Because reducing the fluidity of the hydraulic material composition hinders its movement within the hose, a curing accelerator is typically added immediately before dispensing to reduce the fluidity. Meanwhile, regarding the layering properties themselves, it is currently believed that there are numerous issues that need to be resolved in order to further popularize construction using additive manufacturing. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] Japanese Patent Application Publication No. 10-235623 [Patent Document 2] U.S. Patent No. 8,211,226 [Patent Document 3] Japanese Patent Application Laid-Open No. 2008-247677 [Patent Document 4] Japanese Patent Application Laid-Open No. 2006-290694 [Patent Document 5] Japanese Patent Publication No. 2021-133667 Summary of the Invention [Problem to be solved by the invention]

[0011] The present invention provides an additive or the like that is excellent in the effect of improving the lamination properties of a hydraulic composition for layered manufacturing. [Means for solving the problem]

[0012] As a result of extensive research, the present inventors have found that the addition of an emulsion containing a specific polymer is effective in improving the lamination properties of a hydraulic composition. Based on this finding, the present inventors have completed the present invention described below.

[0013] The preferred configurations of the additives of the present invention are as described in the following items (1) to (9). (1) An additive used in a hydraulic composition for additive manufacturing, An additive containing an emulsion containing a polymer having an acid value of 30 mgKOH / g or more. (2) The additive according to (1) above, which contains an emulsion containing a polymer having an acid value of 100 to 400 mgKOH / g. (3) The additive according to (1) or (2), wherein the polymer contains a structural unit having a carboxyl group. (4) The additive according to (3) above, wherein the structural unit having a carboxyl group is contained in an amount of 10.0 to 60.0 parts by weight per 100 parts by weight of the polymer. (5) The additive according to (3) or (4) above, wherein the polymer is a copolymer further having a hydrophobic structural unit. (6) The additive according to (5) above, wherein the hydrophobic structural unit is contained in an amount of 40.0 to 90.0 parts by weight based on 100 parts by weight of the polymer. (7) The emulsion was adjusted to a concentration of 25% by mass at a shear rate of 10 s at room temperature. -1 The additive according to any one of (1) to (6) above, having a viscosity of 250 mPa·s or less, as measured by a viscosity test. (8) A hydraulic composition for additive manufacturing, comprising the additive according to any one of (1) to (7) and a hydraulic composition. (9) (a) agitating a hydraulic material, an aggregate, and water to obtain a hydraulic composition; and (b) adding and stirring the additive described in any one of (1) to (7) after the step; A method for producing a hydraulic composition for layered manufacturing, comprising: (10) A method for layered manufacturing using a hydraulic composition containing the additive according to any one of (1) to (7). DETAILED DESCRIPTION OF THE INVENTION

[0014] Matters relating to each of the additives of the present invention will be explained in detail below. However, the following description is merely an example for explaining the present invention and is not intended to limit the present invention to the scope of this description. 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 can serve as a legitimate basis for amendment).

[0015] Furthermore, in this specification, the term "X to Y" indicating a range means "X or more and Y or less," and unless otherwise specified, operations and measurements of physical properties are performed at room temperature (20 to 25°C) and a relative humidity of 45 to 55%RH. Furthermore, in this specification, the term "(meth)acrylic" means "acrylic and / or methacrylic," and the term "(meth)acrylate" means "acrylate and / or methacrylate." Furthermore, "weight" and "mass," "parts by weight" and "parts by mass," and "wt%" and "mass%" are treated as synonyms.

[0016] One embodiment of the present invention is an additive for use in a hydraulic composition for additive manufacturing, which contains an emulsion containing a polymer having an acid value of 30 mgKOH / g or more. Hereinafter, the additive will also be referred to as the additive of the present invention or the additive of the present invention. Furthermore, the polymer having an acid value of 30 mgKOH / g or more will also be simply referred to as the polymer of the present invention or the polymer of the present invention.

[0017] The additive of the present invention is effective in improving the lamination property of a hydraulic composition for additive manufacturing. Here, lamination property can be grasped, for example, by the physical property of fluidity after the addition of the additive, and can be evaluated by measuring flow. Good lamination property is defined as a flow value of 150 mm or less in a flow evaluation under the conditions described in the Examples below. Furthermore, the additive of the present invention can significantly reduce the flow value even when added in a small amount.

[0018] The setting time of a hydraulic composition for "additive manufacturing" must be shorter than that of a normal hydraulic composition, and therefore an additive as a curing agent is required. However, if the setting time is extremely short, the mortar or the like will harden before the next layer is dispensed during additive manufacturing, which may reduce the adhesion between the dispensed layer and the newly laminated layer and reduce the strength of the structure. Therefore, good laminateability means ensuring sufficient time for the hydraulic composition to harden.

[0019] One feature of the polymer of the present invention is that it has an acid value of 30 mgKOH / g or more. When the acid value is 30 mgKOH / g or more, the fluidity of the hydraulic composition to which it is added is reduced, resulting in excellent lamination properties. Another feature of the additive of the present invention is that the polymer is contained as an emulsion. When it is in the form of an emulsion, the viscosity can be reduced, improving handleability.

[0020] (additives) The additive of the present invention is used in a hydraulic composition for layered manufacturing. The additive of the present invention is preferably kneaded with a hydraulic composition and used as a hydraulic composition for layered manufacturing.

[0021] More specifically, the additive of the present invention contains an emulsion containing a polymer having an acid value of 30 mgKOH / g or more. In another embodiment, the additive comprises an emulsion containing a polymer having an acid value of 30 mgKOH / g or more. Hereinafter, the polymer having an acid value of 30 mgKOH / g or more will be simply referred to as the polymer of the present invention or the polymer of the present invention.

[0022] The additive of the present invention can be used as a thickener or a laminateability improver by limiting its use more specifically. Specifically, it may be a thickener for hydraulic compositions containing an emulsion including a polymer having an acid value of 30 mgKOH / g or more, or may be a laminateability improver for hydraulic compositions containing an emulsion including a polymer having an acid value of 30 mgKOH / g or more.

[0023] A specific method for using the additive of the present invention is, for example, to add it to a hydraulic composition such as mortar or fresh concrete for additive manufacturing and stir it.

[0024] (Additive Manufacturing) In this invention, "additive manufacturing" refers to a technology for manufacturing molded bodies of any shape by layering cross-sectional shapes based on three-dimensional data without using specialized tools such as molds. It is also commonly called "3D printing," "three-dimensional modeling," or "rapid prototyping."

[0025] (Hydraulic composition for additive manufacturing) In the present invention, a "hydraulic composition for additive manufacturing" refers to a hydraulic composition used for additive manufacturing. The hydraulic composition for additive manufacturing includes the additive and hydraulic composition of the present invention. The hydraulic composition includes a hydraulic material and water, preferably a hydraulic material, aggregate (coarse aggregate and / or fine aggregate), and water, and optionally includes other components such as a dispersant and an antifoaming agent. Examples of hydraulic compositions include mortar and fresh concrete. Another aspect of the present invention is a hydraulic composition for additive manufacturing, including an emulsion containing a polymer having an acid value of 30 mgKOH / g or more, a hydraulic material, aggregate, and water.

[0026] The hydraulic composition for additive manufacturing of the present invention preferably contains the additive of the present invention in addition to the hydraulic composition. The hydraulic composition for additive manufacturing preferably contains the additive of the present invention in an amount of 0.01 to 1.0 mass % of the cement, and may contain 0.01 to 0.5 mass %. The additive of the present invention is effective in reducing fluidity even with the addition of a small amount, so that a relatively small amount can be added.

[0027] (hydraulic material) The "hydraulic material" used in the present invention refers to a hydraulic substance, a pozzolanic reactive substance, or a latent hydraulic substance, and preferably contains a hydraulic substance. The hydraulic material may contain 50% by mass or more (up to 100% by mass), 80% by mass or more, or 90% by mass or more of the hydraulic substance. When the hydraulic material contains a pozzolanic reactive substance or a latent hydraulic substance, it is desirable that the hydraulic material further contains cement (or calcium hydroxide) and a stimulant.

[0028] (Hydraulic substance) The "hydraulic material" in the present invention refers to so-called cement, and examples of cement include Portland cement (normal, early-strength, ultra-early-strength, moderate-heat, low-heat, sulfate-resistant, and low-alkali forms of each), various blended cements (blast-furnace cement, silica cement, fly ash cement), white Portland cement, alumina cement, ultra-rapid-hardening cement (1-clinker rapid-hardening cement, 2-clinker rapid-hardening cement, magnesium phosphate cement), cement for grouting, oil well cement, low-heat cement (low-heat blast-furnace cement, low-heat blast-furnace cement mixed with fly ash, high-belite cement), ultra-high-strength cement, cement-based solidification material, and ecocement (cement produced using one or more of municipal waste incineration ash and sewage sludge incineration ash as raw materials). The cement in the present invention may be one type, or two or more types.

[0029] The hydraulic composition is 3 The unit water amount, cement amount, and water / cement ratio per unit are not particularly limited, and since it is used for additive manufacturing purposes, for example, the unit water amount is 50 to 300 kg / m 3 , Cement amount used: 300-500 kg / m3 The water / cement ratio (weight ratio) is preferably 0.1 to 0.5.

[0030] (pozzolanic reactive substances) In the present invention, a "pozzolanic reactive substance" is a substance that does not have hydraulic properties by itself, but gradually combines with components in concrete (e.g., calcium hydroxide produced by cement hydration) to form an insoluble compound (e.g., calcium silicate hydrate). Examples of such substances include natural pozzolana, fly ash, cinder ash, clinker ash, husk ash, metakaolin, and silica fume, with fly ash being preferred. Fly ash can be classified into types I, II, III, and IV, with type II being preferred. The pozzolanic reactive substance is preferably in the form of granules with a particle size of 0.01 to 10 mm.

[0031] (Latent hydraulic substance) The "latent hydraulic substance" in this invention is a substance that does not harden simply by mixing with water, but hardens in the presence of a small amount of a substance called a stimulant, such as slag (blast furnace slag, slowly cooled blast furnace slag, steelmaking slag, etc.). The latent hydraulic substance is preferably in the form of granules with a particle size of 0.01 to 10 mm.

[0032] Examples of the stimulant include an aqueous solution of an alkali metal carbonate, an aqueous solution of an alkali metal fluoride, an aqueous solution of an alkali metal hydroxide, an aqueous solution of an alkali metal aluminate, an aqueous solution of an alkali metal silicate (e.g., water glass), and / or a mixture thereof, and can be added to the composition containing the latent hydraulic material of the present invention.

[0033] (aggregate) The aggregates used in the present invention include gravel (sand), crushed stone, granulated slag, recycled aggregates, etc., as well as refractory aggregates such as silica, clay, zircon, high alumina, silicon carbide, graphite, chromium, chromium-magnesium, and magnesia.

[0034] (dispersant) As the cement dispersant, conventionally known cement dispersants can be used. Examples of the cement dispersant include polyalkylarylsulfonates such as naphthalenesulfonic acid formaldehyde condensates; melamine formalin resin sulfonates such as melamine sulfonic acid formaldehyde condensates; aromatic aminosulfonates such as aminoarylsulfonic acid-phenol-formaldehyde condensates; lignin sulfonates such as lignin sulfonates and modified lignin sulfonates; various sulfonic acid dispersants having sulfonic acid groups in the molecule, such as polystyrene sulfonates; copolymers obtained from polyalkylene glycol mono(meth)acrylate monomers, (meth)acrylic acid monomers, and monomers copolymerizable with these monomers, as described in JP-B-59-18338 and JP-A-7-223852; Examples of suitable dispersants include various polycarboxylic acid dispersants having a (poly)oxyalkylene group and a carboxyl group in the molecule, such as copolymers obtained from unsaturated (poly)alkylene glycol ether monomers, maleic acid monomers, or (meth)acrylic acid monomers, as described in JP-A-236858, JP-A-2001-220417, JP-A-2002-121055, and JP-A-2002-121056; various phosphate dispersants having a (poly)oxyalkylene group and a phosphate group in the molecule, such as copolymers obtained from (alkoxy)polyalkylene glycol mono(meth)acrylates, phosphate monoester monomers, and phosphate diester monomers, as described in JP-A-2006-52381; and the phosphate dispersants described in JP-A-2008-517080. Among these, polycarboxylic acid dispersants are preferred as cement dispersants, as they further enhance the effects of the present invention. The cement dispersant may be of one type only, or of two or more types. The mixing ratio of the cement dispersant is preferably set to, for example, 0.01 to 10 mass% in terms of solid content relative to 100 mass% of cement.

[0035] (Antifoaming agent) Examples of the defoaming agent include polyoxyalkylene alkyl ethers such as diethylene glycol heptyl ether; polyoxyalkylene acetylene ethers; (poly)oxyalkylene fatty acid esters; polyoxyalkylene sorbitan fatty acid esters; polyoxyalkylene alkyl (aryl) ether sulfate ester salts; polyoxyalkylene alkyl phosphate esters; polyoxypropylene polyoxyethylene laurylamine (1 to 20 moles of propylene oxide added, 1 to 20 moles of ethylene oxide added, etc.), and polyoxyalkylene alkylamines such as amines derived from fatty acids obtained from hardened beef tallow to which alkylene oxide has been added (1 to 20 moles of propylene oxide added, 1 to 20 moles of ethylene oxide added, etc.); oxyalkylene-based defoaming agents such as polyoxyalkylene amides; and mineral oil-based, oil-based, fatty acid-based, fatty acid ester-based, alcohol-based, amide-based, phosphate ester-based, metal soap-based, and silicone-based defoaming agents.

[0036] (polymer) The polymer of the present invention has an acid value of 30 mgKOH / g or more, preferably 50 mgKOH / g or more, more preferably 100 mgKOH / g or more, even more preferably 150 mgKOH / g or more, and most preferably 200 mgKOH / g or more. The upper limit of the acid value is, for example, 500 mgKOH / g or less, preferably 400 mgKOH / g or less, and more preferably 350 mgKOH / g or less. The acid values ​​of the polymer of the present invention are, in order of preference, 30 mgKOH / g or more and 500 mgKOH / g or less, 50 mgKOH / g or more and 500 mgKOH / g or less, 100 mgKOH / g or more and 400 mgKOH / g or less, 150 mgKOH / g or more and 350 mgKOH / g or less, and 200 mgKOH / g or more and 350 mgKOH / g or less.

[0037] The acid value of the polymer in the present disclosure can be determined, for example, by measuring the acid value per gram of polymer solid content (mgKOH / g) according to JIS K0070:1992 using an automatic titrator (product name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.).

[0038] (Structural unit having an acidic functional group) The polymer in the present invention preferably contains one or more structural units having an acidic functional group (also called an acid group). When the polymer contains one or more structural units having an acidic functional group, the acid value of the polymer can be easily controlled to 30 mgKOH / g or more. Examples of the acidic functional group include a carboxyl group, a sulfonic acid group, a phosphate group, a phosphite group, and a hydroxy group. A carboxyl group, a sulfonic acid group, or a phosphate group is preferred, and a carboxyl group is more preferred.

[0039] [ka]

[0040] A specific example of the structural unit having the above acidic functional group is the structural unit represented by the above formula (I). In the above formula (I), R 1 ~R 4 One or more of R 1 ~R 4 are the same or different and are a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms.

[0041] In the above formula (I), preferably R 1 ~R 4 One or two of the groups are acidic functional groups, and more preferably one of the groups is an acidic functional group.

[0042] R other than the above acidic functional groups 1 ~R 4Preferably, two or more of them are hydrogen atoms, more preferably all of them are hydrogen atoms, or two of them are hydrogen atoms and one is an alkyl group (particularly a methyl group). The unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms is preferably an unsubstituted monovalent hydrocarbon group having 1 to 4 carbon atoms. More specific examples of the unsubstituted monovalent hydrocarbon group include linear, branched, or cyclic alkyl groups, alkenyl groups, aryl groups, and aralkyl groups, and are preferably alkyl groups, and particularly preferably a methyl group. The substituted monovalent hydrocarbon group has some or all of the hydrogen atoms substituted with a substituent, and examples of the substituent include alkoxy groups such as methoxy, ethoxy, and (iso)propoxy, and halogen atoms such as fluorine, chlorine, bromine, and iodine.

[0043] The structural unit represented by the formula (I) may be a structural unit formed upon cleavage of a carbon-carbon double bond of an unsaturated acid monomer (an acid group-containing monomer), or may be a structural unit formed upon cleavage of a carbon-carbon double bond of an unsaturated carboxylic acid monomer. Examples of such unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, crotonic acid, tiglic acid, 3-methylcrotonic acid, 2-methyl-2-pentenoic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, and 2-methylene glutaric acid. Acrylic acid, methacrylic acid, maleic acid, or fumaric acid is preferred, acrylic acid or methacrylic acid is more preferred, and methacrylic acid is even more preferred. The structural unit represented by the formula (I) may be present alone or in combination with two or more different types.

[0044] In this specification, the term "acidic functional group" refers to an unneutralized functional group unless otherwise specified.

[0045] (hydrophobic structural unit) The polymer in the present invention is preferably a copolymer containing one or more types of hydrophobic structural units. The presence of the hydrophobic structural units can reduce the effect on dispersibility in hydraulic compositions. The hydrophobic structural units, for example, do not contain hydrophilic functional groups. The hydrophobic structural units, for example, do not contain any functional groups selected from the group consisting of a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphate group or a salt thereof, a phosphite group or a salt thereof, and a hydroxy group.

[0046] [ka]

[0047] A specific example of the hydrophobic structural unit is a structural unit represented by the above formula (II). 5 ~R 8 are the same or different and are a hydrogen atom, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, or -COOM 1 (M 1 is a monovalent hydrocarbon group having 1 to 8 carbon atoms, and preferably R 5 ~R 8 One of them is -COOM 1 and the remaining R 5 ~R 8 is a hydrogen atom or an unsubstituted monovalent hydrocarbon group having 1 to 4 carbon atoms (preferably a methyl group), and more preferably R 5 ~R 8 One of them is -COOM 1 and the remaining R 5 ~R 8 is a hydrogen atom.

[0048] The above M 1is preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and more preferably an ethyl group. Specific examples of the unsubstituted monovalent hydrocarbon group include linear, branched, or cyclic alkyl groups, alkenyl groups, aryl groups, and aralkyl groups, with alkyl groups being preferred, and methyl and ethyl groups being particularly preferred. The substituted monovalent hydrocarbon group is one in which some or all of the hydrogen atoms have been substituted with a substituent, and examples of such substituents include alkoxy groups such as a methoxy group, an ethoxy group, and an (iso)propoxy group.

[0049] The structural unit represented by the above formula (II) may be a structural unit formed when a carbon-carbon double bond of a hydrophobic monomer is cleaved. Examples of the hydrophobic monomer include styrene, acrylic acid esters, and methacrylic acid esters. Preferably, the hydrophobic monomer is an acrylic acid ester or a methacrylic acid ester, and more preferably, an acrylic acid ester. Specific examples of the hydrophobic monomer include methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, and particularly preferably, ethyl acrylate.

[0050] [ka]

[0051] A specific example of the hydrophobic structural unit is a structural unit represented by the formula (III): In the formula (III), X is C=O or (CH2) p [p is an integer from 0 to 5], and R 12 is an (unsubstituted) divalent hydrocarbon group having 2 to 8 carbon atoms (wherein R 12 may be the same or different), m is an integer of 5 to 300, and R 13 is a hydrogen atom or an (unsubstituted) monovalent hydrocarbon group having 1 to 18 carbon atoms, and the remaining R 9 ~R 11 are the same or different and are a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms.

[0052] The above p is preferably an integer of 0 to 2, and more preferably 0. The above X is preferably C=O or (CH2)2, and more preferably C=O. R 12 is preferably a divalent hydrocarbon group having 2 to 4 carbon atoms, more preferably a divalent hydrocarbon group having 2 to 3 carbon atoms, and even more preferably C2H4. 12 may be the same or different, for example, R 12 O may be in a form in which butylene oxide (BO) / propylene oxide (PO) are mixed. In this case, m refers to the total number of moles of each alkylene oxide added (for example, the total number of moles of butylene oxide added and the number of moles of propylene oxide added). The above m is preferably an integer of 5 to 150, more preferably an integer of 7 to 120, and even more preferably an integer of 8 to 90. R 13 is preferably a hydrogen atom or a monovalent hydrocarbon having 1 to 18 carbon atoms, and more preferably hydrogen, CH3, or a stearyl group. 13 may be a hydrogen atom or an (unsubstituted) monovalent hydrocarbon group having 1 to 8 carbon atoms, or may be a hydrogen atom or an (unsubstituted) monovalent hydrocarbon group having 1 to 4 carbon atoms. 9 ~R 11 is preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and more preferably R 9 ~R 11 one of R is a monovalent hydrocarbon group having 1 to 4 carbon atoms (preferably a methyl group), and the remaining R 9 ~R 11 is a hydrogen atom.

[0053] The structural unit represented by the above formula (III) may be a structural unit (structural unit derived from a polyalkylene glycol group-containing monomer) formed when a carbon-carbon double bond of a monomer containing a polyalkylene glycol group (hydroxyl group terminal), an alkoxypolyalkylene glycol group (alkyl group terminal), or a phenoxypolyalkylene glycol group (aryl group terminal) (hereinafter referred to as a polyalkylene glycol group-containing monomer) is cleaved, and examples of the polyalkylene glycol group-containing monomer include polyalkylene glycol monomethacrylate, polyalkylene glycol monoacrylate, alkoxypolyalkylene glycol monomethacrylate, alkoxypolyalkylene glycol monoacrylate, phenoxypolyalkylene glycol monomethacrylate, and phenoxypolyalkylene glycol monoacrylate. Further, as a monomer containing a polyalkylene glycol group other than those mentioned above, a compound in which ethylene oxide is added to the hydroxyl groups of 3-methyl-3-buten-1-ol (isoprenol) (for example, an average number of moles of ethylene oxide added of 50) can be exemplified. Preferred examples of the monomer containing a polyalkylene glycol group or the like are alkoxy polyalkylene glycol mono(meth)acrylate, polyalkylene glycol mono(meth)acrylate, and a compound in which ethylene oxide is added to the hydroxyl groups of 3-methyl-3-buten-1-ol (isoprenol), preferably alkoxy polyalkylene glycol monomethacrylate or alkoxy polyalkylene glycol monoacrylate, more preferably alkoxy polyalkylene glycol monomethacrylate.

[0054] Examples of the alkoxypolyalkylene glycol monomethacrylate include methoxypolyethylene glycol-methacrylate, octoxypolyethylene glycol-polypropylene glycol-methacrylate, lauroxypolyethylene glycol-methacrylate, and stearoxypolyethylene glycol-methacrylate, of which methoxypolyethylene glycol-methacrylate and stearoxypolyethylene glycol-methacrylate are preferred, and methoxypolyethylene glycol-methacrylate is more preferred due to its ease of availability.

[0055] An example of the phenoxypolyalkylene glycol monomethacrylate is phenoxypolyethylene glycol methacrylate.

[0056] An example of the alkoxypolyalkylene glycol monoacrylate is methoxypolyethylene glycol acrylate.

[0057] Examples of the phenoxy polyalkylene glycol monoacrylate include nonylphenoxy polypropylene glycol acrylate and nonylphenoxy polyethylene glycol polypropylene glycol acrylate.

[0058] Examples of the polyalkylene glycol monomethacrylate include polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polyethylene glycol-propylene glycol monomethacrylate, polyethylene glycol-tetramethylene glycol monomethacrylate, and propylene glycol-polybutylene glycol monomethacrylate, with polypropylene glycol monomethacrylate being preferred.

[0059] Examples of the polyalkylene glycol monoacrylate include polyethylene glycol monoacrylate and polypropylene glycol monoacrylate.

[0060] In a preferred embodiment, the polyalkylene glycol group-containing monomer includes at least one selected from the group consisting of methoxypolyethylene glycol methacrylate, stearoxypolyethylene glycol methacrylate, polypropylene glycol monomethacrylate, and a compound in which ethylene oxide is added to the hydroxyl group of 3-methyl-3-buten-1-ol (isoprenol).

[0061] In a preferred embodiment of the polymer of the present invention, the polymer preferably contains at least a structural unit represented by the above formula (II) as a hydrophobic structural unit, and may further contain a structural unit represented by the above formula (III), in order to further enhance the effects of the present invention.

[0062] (Other structural units) The polymer of the present invention may contain structural units (IV) other than the structural units described above as the remainder. The amount of the other structural units is preferably 5 parts by weight or less (lower limit: 0 parts by weight), more preferably 3 parts by weight or less, and even more preferably 1 part by weight or less, per 100 parts by weight of the polymer.

[0063] (Polymer structure) The polymer of the present invention preferably contains 1.0 to 90.0 parts by weight, more preferably 10.0 to 60.0 parts by weight, even more preferably 20.0 to 60.0 parts by weight, and even more preferably 30.0 to 50.0 parts by weight of a structural unit having an acidic functional group (preferably a structural unit having a carboxyl group) relative to 100 parts by weight of the polymer. By containing the acidic functional group in such a range, it is easy to control the acid value of the polymer within an appropriate range.

[0064] The polymer of the present invention preferably contains 1.0 to 90.0 parts by weight, more preferably 10.0 to 90.0 parts by weight, even more preferably 20.0 to 60.0 parts by weight, and even more preferably 30.0 to 50.0 parts by weight of the structural unit (I) having an acidic functional group, relative to 100 parts by weight of the polymer. The polymer of the present invention also preferably contains 10.0 to 95.0 parts by weight, more preferably 10.0 to 90.0 parts by weight, even more preferably 30.0 to 70.0 parts by weight, and even more preferably 40.0 to 60.0 parts by weight of the hydrophobic structural unit (II), relative to 100 parts by weight of the polymer. The polymer of the present invention also preferably contains 1.0 to 40.0 parts by weight, more preferably 2.0 to 30.0 parts by weight of the hydrophobic structural unit (III), relative to 100 parts by weight of the polymer. The polymer of the present invention preferably contains 10.0 to 90.0 parts by weight, more preferably 40.0 to 90.0 parts by weight, and even more preferably 40.0 to 80.0 parts by weight of the hydrophobic structural unit relative to 100 parts by weight of the polymer. By containing the hydrophobic structural unit in such a range, it is easy to control the emulsion form.

[0065] The polymer of the present invention preferably contains at least a structural unit (I) having an acidic functional group and a hydrophobic structural unit (II). The total content of the structural unit (I) having an acidic functional group and the hydrophobic structural unit (II) in the polymer is preferably 60% by weight or more, more preferably 65% ​​by weight or more.

[0066] The polymer of the present invention is also preferably one consisting essentially of structural unit (I) and hydrophobic structural unit (II) (for example, containing 95.0 parts by weight or more of (I) and (II) per 100 parts by weight of all structural units). When the polymer consists essentially of structural unit (I) and hydrophobic structural unit (II), the polymer preferably contains 1.0 to 80.0 parts by weight, more preferably 3.0 to 60.0 parts by weight, more preferably 5.0 to 50.0 parts by weight, and particularly preferably 10.0 to 50.0 parts by weight of the structural unit (I) having an acidic functional group per 100 parts by weight of the polymer, and 20.0 to 99.0 parts by weight, preferably 30.0 to 98.0 parts by weight, more preferably 50.0 to 95.0 parts by weight, and particularly preferably 50.0 to 90.0 parts by weight of the hydrophobic structural unit (II) per 100 parts by weight of the polymer. Furthermore, when the polymer of the present invention contains a structural unit (I) having an acidic functional group and a hydrophobic structural unit (II) but does not contain a hydrophobic structural unit (III), the ratio of the structural unit (I) having an acidic functional group: the hydrophobic structural unit (II) is preferably 1:99 to 80:20 (weight ratio), more preferably 3:97 to 60:40, and even more preferably 5:95 to 50:50.

[0067] Yet another preferred embodiment is a polymer containing a structural unit (I) having an acidic functional group, a hydrophobic structural unit (II), and a hydrophobic structural unit (III), and more preferably a polymer consisting of or essentially consisting of them (for example, a polymer containing 95.0 parts by weight or more of (I), (II), and (III) per 100 parts by weight of all structural units). In the case of a polymer containing a structural unit (I) having an acidic functional group, a hydrophobic structural unit (II), and a hydrophobic structural unit (III), the polymer contains the structural unit (I) having an acidic functional group in an amount of preferably 10.0 to 90.0 parts by weight, more preferably 20.0 to 60.0 parts by weight, and even more preferably 30.0 to 50.0 parts by weight, per 100 parts by weight of the polymer; the polymer contains the hydrophobic structural unit (II) in an amount of preferably 10.0 to 90.0 parts by weight, more preferably 30.0 to 70.0 parts by weight, and even more preferably 40.0 to 60.0 parts by weight, per 100 parts by weight of the polymer; and the polymer contains the hydrophobic structural unit (III) in an amount of preferably 1.0 to 40.0 parts by weight, and more preferably 2.0 to 30.0 parts by weight, per 100 parts by weight of the polymer.

[0068] Some examples of the polymer in the present invention include, for example, a polymer obtained by polymerizing (I) acrylic acid or methacrylic acid, a polymer obtained by copolymerizing (I) with (II) an alkyl acrylate (having 1 to 8 carbon atoms), and a polymer obtained by copolymerizing (I) and (II) with (III) a monomer containing a polyalkylene glycol group or the like. Among these, a polymer obtained by copolymerizing (I) with (II) an alkyl acrylate (having 1 to 8 carbon atoms) and a polymer obtained by copolymerizing (I) and (II) with (III) a monomer containing a polyalkylene glycol group or the like are preferred, since the effects of the present invention are more effectively exhibited by these polymers.

[0069] The weight average molecular weight of the polymer in the present invention, as measured using a static light scattering method, is, for example, 10,000 to 10,000,000, preferably 20,000 to 8,000,000, more preferably 30,000 to 6,000,000, still more preferably 40,000 to 5,000,000, particularly preferably 50,000 to 1,000,000, and most preferably 100,000 to 1,000,000, or 200,000 to 800,000.

[0070] The glass transition temperature of the polymer of the present invention is, from the viewpoint of film-forming properties (shape change of emulsion (collapse of O / W)) and the like, for example, -40°C or higher, preferably -30°C or higher, more preferably -20°C or higher, and particularly preferably -10°C or higher. The upper limit of the glass transition temperature of the polymer of the present disclosure is, for example, 80°C or lower, preferably 75°C or lower, more preferably 65°C or lower, and particularly preferably 50°C or lower. The glass transition temperature can be controlled by the types and compositional ratio of the monomers constituting the polymer. The glass transition temperature is calculated using the glass transition temperature of a homopolymer of the monomer used in the monomer component constituting the polymer. Formula (I): 1 / Tg=Σ(Wm / Tgm) / 100 (I) [In the formula, Wm is the content (mass%) of monomer m in the monomer components constituting the polymer, and Tgm is the glass transition temperature (absolute temperature: K) of a homopolymer of monomer m].

[0071] The pH of the polymer in the present invention is, for example, pH 2.0 to 6.0, more preferably pH 2.0 to 5.0, and even more preferably pH 2.0 to 4.0, as measured in a 10.0% by mass aqueous solution or dispersion at 25.0° C. The aqueous solution or dispersion can be prepared by any known method, such as dissolving or dispersing the polymer in distilled water to a predetermined concentration.

[0072] (emulsion) The polymer-containing emulsion of the present invention is one in which the polymer is coated with an emulsifier to form particles (micelles).

[0073] Examples of such emulsions include O / W type (oil-in-water type), W / O type (water-in-oil type), O / W / O type (oil-in-water-in-oil type), and W / O / W type (water-in-oil-in-water type), with O / W type being preferred.

[0074] Examples of dispersion media for emulsions include water, oil, alcohol, etc., with water being preferred. The solid content (polymer and emulsifier) ​​is 1.0 to 80.0% by mass, preferably 10.0 to 50.0% by mass, and more preferably 20.0 to 40.0% by mass, based on the total mass of the emulsion.

[0075] The viscosity of the emulsion in the present invention is determined by adjusting the emulsion concentration to 25% by mass at a shear rate of 10 s at room temperature (20 to 25°C). -1 The viscosity, measured by the viscosity index (V) is, for example, 500 mPa·s or less, preferably 250 mPa·s or less, more preferably 200 mPa·s or less, even more preferably 100 mPa·s or less, and particularly preferably 50 mPa·s or less. Having an emulsion viscosity below the upper limit makes it easy to handle as an additive and facilitates mixing with the hydraulic material immediately before the nozzle. The lower limit of the viscosity is, for example, 1 mPa·s or more, preferably 5 mPa·s or more, since this facilitates control of the amount added when added immediately before the nozzle.

[0076] The emulsion preferably has a pH of 2.0 to 4.0. The pH of the emulsion can be measured by a known method, such as a method of measuring the pH at 25°C using a pH meter (LAQUA, manufactured by Horiba, Ltd.) in accordance with JIS Z8802:2011.

[0077] The average particle size of the particles (micelles) in the emulsion (emulsion particles) in the present invention may be, for example, 30 nm or more, preferably 50 nm or more, and the upper limit of the average particle size of the emulsion particles may be, for example, 3,000 nm or less, preferably 1,000 nm or less, or 500 nm or less, or 200 nm or less. The average particle size of the particles (micelles) in the emulsion may be 30 nm or more and 3,000 nm or less, 50 nm or more and 1,000 nm or less, 50 nm or more and 500 nm or less, or 50 nm or more and 200 nm or less. The average particle size of the emulsion particles may be the volume average particle size measured using a particle size distribution analyzer (manufactured by Particle Sizing Systems, Inc., trade name: NICOMP Model 380) by dynamic light scattering.

[0078] Examples of emulsifiers used in the production of emulsions include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, amphoteric emulsifiers, polymeric emulsifiers, etc. These emulsifiers may be used alone or in combination of two or more. The emulsifier is preferably present in the emulsion in an amount of 1.0 to 20.0% by mass, preferably 1.0 to 5.0% by mass, based on the total mass of the polymer encapsulated therein.

[0079] The emulsifier is not particularly limited, and examples thereof include anionic emulsifiers (e.g., alkyl sulfate salts such as ammonium dodecyl sulfate and sodium dodecyl sulfate; alkyl sulfonate salts such as ammonium dodecyl sulfonate and sodium dodecyl sulfonate; alkylaryl sulfonate salts such as ammonium dodecyl benzene sulfonate and sodium dodecyl naphthalene sulfonate; polyoxyethylene alkyl sulfate salts (polyoxyethylene alkyl ether sulfate salts); polyoxyethylene alkyl aryl sulfate salts; polyoxyethylene alkyl ether sulfate salts; dialkyl sulfosuccinate salts; aryl sulfonic acid-formalin condensates; fatty acid salts such as ammonium laurate and sodium stearylate, etc.), nonionic emulsifiers (e.g., polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, condensates of polyethylene glycol and polypropylene glycol, etc.), , sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, fatty acid monoglycerides, condensates of ethylene oxide and aliphatic amines, etc.), cationic emulsifiers (e.g., dialkyldimethylammonium salts, ester-type dialkylammonium salts, amide-type dialkylammonium salts, dialkylimidazolinium salts, etc.), amphoteric emulsifiers (e.g., alkyldimethylaminoacetic acid betaine, alkyldimethylamine oxide, alkylcarboxymethylhydroxyethylimidazolinium betaine, alkylamidopropyl betaine, alkylhydroxysulfobetaine, etc.), polymer emulsifiers (e.g., polyvinyl alcohol and modified products thereof; (meth)acrylic acid-based water-soluble polymers; hydroxyethyl(meth)acrylic acid-based water-soluble polymers; hydroxypropyl(meth)acrylic acid-based water-soluble polymers; polyvinylpyrrolidone, etc.), etc., are preferred, and polyoxyethylene alkyl ether sulfates are more preferred.

[0080] Furthermore, as the emulsifier, an emulsifier having a polymerizable group, so-called reactive emulsifier, may be used.

[0081] Examples of reactive emulsifiers include propenyl-alkyl sulfosuccinate salts, (meth)acrylic acid polyoxyethylene sulfonate salts, polyoxyethylene alkylpropenylphenyl ether ammonium sulfate (e.g., manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade names: Aqualon HS-10, Aqualon BC-10, etc.), sulfonate salts of allyloxymethyl alkyloxypolyoxyethylene (e.g., manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10, etc.), sulfonate salts of allyloxymethyl nonylphenoxyethyl hydroxypolyoxyethylene (e.g., manufactured by ADEKA Corporation, trade name: Adeka Reasoap SE-10, etc.), allyloxymethyl alkoxyethyl hydroxypolyoxyethylene sulfate ester salts (e.g., manufactured by ADEKA Corporation, trade name: Adeka Reasoap SE-10, etc.), , trade name: ADEKA REASOAP SR-10, SR-20, SR-30, etc.), bis(polyoxyethylene polycyclic phenyl ether) methacrylated sulfonate salt (e.g., manufactured by Nippon Nyukazai Co., Ltd., trade name: ANTOX MS-60, etc.), allyloxymethylalkoxyethylhydroxypolyoxyethylene (e.g., manufactured by ADEKA Corporation, trade name: ADEKA REASOAP ER-10, ER-20, ER-30, ER-40, etc.), polyoxyethylene alkylpropenylphenyl ether (e.g., manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon RN-20, etc.), allyloxymethylnonylphenoxyethylhydroxypolyoxyethylene (e.g., manufactured by ADEKA Corporation, trade name: ADEKA REASOAP NE-10, NE-20, NE-30, etc.). These reactive emulsifiers may be used alone or in combination of two or more.

[0082] Furthermore, for the purpose of emulsion stability and water retention, polyethylene glycol having an average molecular weight of 4000 or less, polypropylene glycol having an average molecular weight of 4000 or less, etc. may be added to the emulsion. The amount of these additives added may be 5% by mass or less, or 3% by mass or less, based on the solid content of the emulsion.

[0083] (Method for producing emulsion) The method for producing the emulsion containing the polymer is not particularly limited, but for example, the emulsion may be produced by emulsion polymerization of the monomer components that are the raw materials for the polymer in a solvent.

[0084] Examples of the solvent include aqueous solvents such as water and solvents containing water [for example, a mixed solvent of water and alcohol (e.g., C1-4 alcohol such as methanol or ethanol)]. Among these, it is preferable that the solvent contains water as the main component. Here, "main component" refers to a solvent in which the water content is 95% by mass or more (up to 100% by mass), preferably 98% by mass or more, or 99% by mass or more. One or more solvents may be used in combination.

[0085] The method for emulsion polymerization of the monomer components is not particularly limited, but examples thereof include a method in which the monomer components are polymerized by dropping them into a solvent containing an emulsifier, a method in which the monomer components that have been emulsified in advance with an emulsifier are polymerized by dropping them into a solvent, etc. Specific examples of the emulsifier include those listed above.

[0086] One or more kinds of emulsifiers may be used. The emulsifier may be a non-reactive emulsifier or a reactive emulsifier, but from the viewpoint of emulsion particle stability, a non-reactive emulsifier is preferred, and a non-reactive anionic emulsifier is more preferred.

[0087] The amount of the solvent may be appropriately determined taking into consideration the amount of nonvolatile matter contained in the resulting emulsion.

[0088] The polymerization may be carried out in the presence of a polymerization initiator.

[0089] Examples of the polymerization initiator include azo compounds such as azobisisobutyronitrile, 2,2-azobis(2-methylbutyronitrile), 2,2-azobis(2,4-dimethylvaleronitrile), 2,2-azobis(2-diaminopropane) hydrochloride, 4,4-azobis(4-cyanovaleric acid), and 2,2-azobis(2-methylpropionamidine); persulfates such as ammonium persulfate and potassium persulfate; and peroxides such as hydrogen peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and ammonium peroxide.

[0090] The polymerization initiators may be used alone or in combination of two or more.

[0091] The amount of the polymerization initiator used may be appropriately set depending on the type of polymerization initiator, etc., and is not particularly limited. For example, it may be 0.05 parts by weight or more, preferably 0.1 parts by weight or more, and may be, for example, 2 parts by weight or less, preferably 1 part by weight or less, relative to 100 parts by weight of the monomer component.

[0092] The method for adding the polymerization initiator is not particularly limited, but examples thereof include batch addition, divided addition, and continuous dropwise addition.

[0093] The polymerization reaction may be carried out, if necessary, in the presence of a reducing agent (e.g., sodium hydrogen sulfite), a decomposing agent for the polymerization initiator (e.g., a transition metal salt such as ferrous sulfate), a chain transfer agent [e.g., a compound having a thiol group (e.g., tert-dodecyl mercaptan)], a pH buffer, a chelating agent, etc. The atmosphere during polymerization is not particularly limited, but may be an inert gas such as nitrogen gas from the viewpoint of polymerization efficiency.

[0094] The polymerization temperature is not particularly limited, but may be, for example, 50 to 100°C, preferably 60 to 95°C. The polymerization temperature may be constant or may be changed during the polymerization reaction. The polymerization time is not particularly limited and may be set appropriately depending on the progress of the polymerization reaction, but may be, for example, 1 hour or more (for example, 1 to 24 hours), preferably about 2 to 12 hours (for example, 2 to 9 hours).

[0095] (Hydraulic composition for additive manufacturing) The hydraulic composition for additive manufacturing of the present invention may be mortar or fresh concrete for additive manufacturing. Examples of methods for producing the hydraulic composition for additive manufacturing include (a) a process of stirring a hydraulic material and water, preferably a hydraulic material, aggregate, and water, to obtain a hydraulic composition, and (b) a process of adding the additive of the present invention to the hydraulic composition obtained in the process and stirring the mixture. In the production method, steps (a) and (b) are performed independently, with step (b) being performed after step (a). The hydraulic material, aggregate, and water may be added sequentially and stirred, or may be added all at once and stirred. The order of addition of the hydraulic material, aggregate, and water is not particularly important. Furthermore, the additive in step (b) may be added after diluting the additive in emulsion form with water or the like. The stirring time in step (b) is appropriately set to a time that ensures uniform mixing and is as short as possible, for example, 3 to 180 seconds.

[0096] After step (b) in the manufacturing method, the fresh concrete is desirably layered on top of another fresh concrete immediately (for example, within 0 to 300 seconds after step (b)).

[0097] <Layered manufactured object and layered manufacturing method> The hydraulic composition for additive manufacturing of the present invention (hereinafter also referred to as hydraulic material composition) is suitable for use in additive manufacturing. Therefore, the present invention also provides an additively manufactured product formed from the hydraulic material composition for additive manufacturing of the present invention.

[0098] Another embodiment is a method for producing a layered object using the hydraulic material composition of the above embodiment.

[0099] Another embodiment is a method for producing an additive manufacturing method, comprising: adding an emulsion containing a polymer having an acid value of 30 mgKOH / g or more to a composition containing a hydraulic material and water to obtain a mixture; and producing an additive manufacturing method using the mixture.

[0100] The method for producing an additive manufacturing object using a hydraulic material composition for additive manufacturing (additive manufacturing method) is not particularly limited, and may include, for example, the steps of: pumping a composition containing a hydraulic material and water (optionally containing aggregate and other additives) to the nozzle tip of a 3D printer using compressed air or a pump, extruding the pumped composition from the nozzle, adding the additive of the present invention from a separate line, and further mixing to prepare a hydraulic material composition for additive manufacturing, and laminating the composition to form an additive manufacturing object; or, for example, the method may include the steps of pumping a composition containing a hydraulic material and water (optionally containing aggregate and other additives) to the nozzle tip of a 3D printer using compressed air or a pump, adding the additive of the present invention from a separate line, mixing using a mixing mechanism installed in a tube at the nozzle tip, and extruding the resulting composition from the nozzle and laminating it to form an additive manufacturing object.

[0101] A nozzle (discharge part) is usually provided at the tip of the pressure-feeding pipe for the hydraulic material composition for additive manufacturing. The diameter of the nozzle is not particularly limited, but may be set appropriately depending on the size of the aggregate used and the width over which the hydraulic material composition for additive manufacturing is to be layered. For example, if the aggregate size is 5 mm or less and the layering width is 50 mm or less, the nozzle diameter is preferably 8 to 15 mm. The shape of the nozzle is not particularly limited, but examples include circular, elliptical, rectangular, cross, and star shapes. A brim may be provided around the nozzle to impart smoothness to the surface of the discharged hydraulic material composition.

[0102] When building a structure by layering the hydraulic material composition for additive manufacturing dispensed from a nozzle, the nozzle may be moved vertically or horizontally to form the structure. For example, it is preferable to fix the nozzle to a robot arm or a portal plotter and control the nozzle movement by computer. A possible method involves cutting computer-generated 3D data at a predetermined thickness to create 2D slice data, discharging the hydraulic material composition for additive manufacturing from the nozzle while controlling the horizontal movement of the spray nozzle in vertical, horizontal, or diagonal directions based on the 2D slice data, and then moving the nozzle vertically to repeatedly layer the material. The nozzle movement speed is not particularly limited and can be varied depending on the width of the layer. [Example]

[0103] The present invention will now be described in more detail based on examples, but the present invention is not limited to these examples. In the following, unless otherwise specified, "parts" means parts by weight and "%" means "% by mass."

[0104] Example 1 A flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser was charged with 453 g of deionized water and 64 g of a 20% aqueous solution of an emulsifier (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Hitenol LA-10). A pre-emulsion consisting of 30 g of deionized water, 32 g of a 20% aqueous solution of an emulsifier (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Hitenol LA-10), 322 g of ethyl acrylate, 234 g of methacrylic acid, and 832 g of a 10% aqueous solution of methyl polyethylene glycol (90) monomethacrylate (NOF Corporation, trade name: Blemmer PME-4000) was prepared in the dropping funnel. 73 g of this pre-emulsion was added to the flask, and the temperature was raised to 72°C while gently blowing in nitrogen gas. Polymerization was initiated by adding 2.3 g of a 5.0% aqueous solution of sodium bisulfite and 8 g of a 1.0% aqueous solution of ammonium persulfate to the flask. Next, the remainder of the pre-emulsion for dropping and 144 g of a 1.0% aqueous solution of ammonium persulfate were added dropwise uniformly to the flask over 120 minutes. After the dropwise addition was completed, the contents of the flask were maintained at 72°C for 60 minutes and then cooled to terminate the polymerization reaction. The resulting reaction solution was cooled to room temperature and then filtered through a 300 mesh (JIS mesh, the same applies hereinafter) wire mesh to obtain an emulsion with a non-volatile content (solid content) of 29.6 mass%.

[0105] The emulsion particles contained in the resin emulsion had an average particle diameter of 136 nm and a glass transition temperature (Tg) of 14°C for the entire emulsion particles. In addition, the emulsion (1) was diluted with water to a concentration of 25%, and the resulting liquid was subjected to a shear rate of 10 s -1 The viscosity was 33 mPa·s at room temperature.

[0106] <Examples 2 to 16> The emulsions of Examples 2 to 16 were obtained in the same manner as in Example 1, except that the monomer components (ethyl acrylate, methacrylic acid, methyl polyethylene glycol (90) monomethacrylate) and their compositional ratios, etc. used in Example 1 were changed to the monomer components (acid group-containing monomer (a), hydrophobic monomer (b) providing a structural unit represented by formula (II) (hydrophobic group monomer (b) in the Table), polyalkylene glycol group-containing monomer (c) ((alkoxy)polyalkylene glycol group-containing monomer (c) in the Table)) and their compositional ratios (mass ratio) (a:b:c), etc. shown in Tables 1 to 3 below.

[0107] Details of the polymers / emulsions of Examples 1-16 are shown in Tables 1-3 below. In Examples 12 to 16, polyethylene glycol (PEG1000) was added to impart water retention (1% by mass of the solid content of the emulsion; polyethylene glycol was added after the emulsion was obtained in the same manner as in the manufacturing example of Example 1).

[0108] [Table 1]

[0109] [Table 2]

[0110] [Table 3]

[0111] The product names or abbreviations listed in Tables 1 to 3 have the following meanings: MAA: methacrylic acid EA: Ethyl acrylate EO: Ethylene oxide PO: Propylene oxide BO: Butylene oxide Blenmer® PME-4000: Methoxypolyethylene glycol (90) monomethacrylate Blenmar® PSE-1300: stearoxy polyethylene glycol (30) monomethacrylate Blenmar® PP-800: Polypropylene glycol (13) monomethacrylate Blenmar® PE-350: Polyethylene glycol (8) monomethacrylate Blenmar® 10PPB-500B: Propylene glycol polybutylene glycol (6) monomethacrylate IPN-50: 3-methyl-3-buten-1-ol (isoprenol) with ethylene oxide added to the hydroxyl groups with an average of 50 moles. Hitenol® LA-10: Polyoxyethylene alkyl ether ammonium sulfate Adeka Reasoap® SR-10: Ether sulfate type ammonium salt

[0112] <Particle size> In this specification, the average particle size of emulsion particles means the volume average particle size measured using a particle size distribution analyzer (manufactured by Particle Sizing Systems, trade name: NICOMP Model 380) by dynamic light scattering.

[0113] <Solid content (non-volatile content)> The solid content of the emulsion means the value calculated by weighing 1 g of the emulsion, drying it in a hot air dryer at 110°C for 1 hour, and taking the resulting residue as the nonvolatile content, based on the formula: nonvolatile content in emulsion (mass %) = ([mass of residue] ÷ [1 g of emulsion]) × 100 (%).

[0114] <Method for measuring molecular weight (1)> The weight average molecular weight of the polymer was measured (in terms of polystyrene) using gel permeation chromatography (for example, manufactured by Tosoh Corporation, product number: HLC-8120GPC, columns: TSKgel G-5000HXL and TSKgel GMHXL-L in series).

[0115] <ph> The pH was measured at 25°C using a pH meter (LAQUA, manufactured by Horiba Ltd.) in accordance with JIS Z8802:2011.

[0116] <tg> In this specification, the glass transition temperature of a resin is determined by the glass transition temperature of a homopolymer of a monomer used in a monomer component constituting the resin, using the formula: 1 / Tg=Σ(Wm / Tgm) / 100 (wherein Wm is the content (mass%) of monomer m in the monomer components constituting the resin, and Tgm is the glass transition temperature (absolute temperature: K) of a homopolymer of monomer m.) This refers to the temperature calculated based on the Fox equation, In this specification, unless otherwise specified, the glass transition temperature of the polymer constituting the emulsion particles means the glass transition temperature determined based on Fox.

[0117] The glass transition temperature of the entire emulsion particle having multiple resin layers obtained by multistage emulsion polymerization or the like is the glass transition temperature calculated according to the Fox equation using the glass transition temperatures of the homopolymers of all monomer components used as raw materials for all resin layers in the multistage emulsion polymerization. For monomers with unknown glass transition temperatures, such as special monomers and multifunctional monomers, if the total amount of monomers with unknown glass transition temperatures in the monomer component is 10% by mass or less, the glass transition temperature is calculated using only monomers with known glass transition temperatures. If the total amount of monomers with unknown glass transition temperatures in the monomer component exceeds 10% by mass, the glass transition temperature of the resin can be calculated using differential scanning calorimetry (DSC), differential thermal analysis (DTA), thermomechanical analysis (TMA), or other methods.

[0118] The glass transition temperatures are, for example, 105°C for a homopolymer of methyl methacrylate, -70°C for a homopolymer of 2-ethylhexyl acrylate, -24°C for a homopolymer of ethyl acrylate, -56°C for a homopolymer of n-butyl acrylate, 83°C for a homopolymer of cyclohexyl methacrylate, 107°C for a homopolymer of tert-butyl methacrylate, 55°C for a homopolymer of 2-hydroxyethyl methacrylate, 95°C for a homopolymer of acrylic acid, 130°C for a homopolymer of methacrylic acid, and 100°C for a homopolymer of styrene.

[0119] <Acid value> The acid value (mgKOH / g) per 1 g of resin solid content was measured using an automatic titrator (product name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.) in accordance with JIS K0070:1992.

[0120] <Production of polymers for dispersants> A glass reaction vessel equipped with a thermometer, a dispensing valve, a dropping funnel, a nitrogen inlet tube, and a reflux condenser was charged with 21.6 g of ion-exchanged water and 206.4 g of unsaturated polyalkylene glycol ether (IPN-50) prepared by adding an average of 50 moles of ethylene oxide (EO) to isoprenol. The temperature was raised to 60°C, and 15.6 g of 1% aqueous hydrogen peroxide solution was added. Next, an aqueous solution prepared by diluting 42.8 g of acrylic acid with 42.8 g of ion-exchanged water was added dropwise over 3 hours. Simultaneously, an aqueous solution prepared by dissolving 0.1 g of L-ascorbic acid and 2.0 g of 3-mercaptopropionic acid in 358.4 g of ion-exchanged water was added dropwise over 3.5 hours. After the addition was completed, stirring was continued for 1 hour to complete the polymerization reaction. The reaction solution was then adjusted to pH 6 using a 30% aqueous sodium hydroxide solution at a temperature below the polymerization reaction temperature, yielding an aqueous solution of a dispersant polymer with a weight-average molecular weight (Mw) of 18,000. The weight average molecular weight of the dispersant polymer was measured by the following molecular weight measurement method (2).

[0121] <Method for measuring molecular weight (2)> The weight average molecular weight of the dispersant polymer was measured by GPC (gel permeation chromatography) under the following conditions. Device name: Waters Alliance e2695 Columns used: TSKguard column α + TSKgel α-5000 + TSKgel α-4000 + TSKgel α-3000 manufactured by Tosoh Corporation were connected together. Eluent: A solution prepared by dissolving 62.4 g of sodium dihydrogen phosphate·2H2O and 143.3 g of disodium hydrogen phosphate·12H2O in 7794.3 g of ion-exchanged water and mixing this with 2000 g of acetonitrile was used. Detector: Refractometer (RI) detector (Waters 2414) Standard material for creating calibration curve: Polyethylene oxide (MW 255,000, 200,000, 107,000, 72,500, 44,900, 31,440, 21,300, 11,840, 6,450, 4,020, 1,470) manufactured by GL Sciences Calibration curve: A cubic equation was prepared based on the Mw values ​​and elution times of the above standard substances. -Drop-in amount Samples and standard samples: 100 μL of a solution prepared by dissolving the polymer in the eluent so that the polymer concentration was 1.0 vol % was injected. ·Flow rate: 0.5ml / min Column temperature: 40℃ Measurement time: 90 minutes

[0122] [Test Example 1] Paste flow test The test was conducted in accordance with the contents of JIS R5201:2015 using the following method. Solution (A) was prepared by mixing 23.4 g of a 10% aqueous solution of dispersant polymer, which had been diluted with water in advance, 11.7 g of 1% water-dispersed Adekanol LG-299 (manufactured by Adeka Corporation) as an antifoaming agent, and 198.9 g of water. After adding 900 g of ordinary Portland cement (manufactured by Taiheiyo Cement Corporation) to the kettle of a Hobart mixer (model number N-50; manufactured by Hobart Corporation), solution (A) was added, and mixing in the mixer was immediately started at low speed. The time from the addition of solution (A) is referred to below as the elapsed time after water injection.

[0123] 1350g of ISO sand was added 30 seconds after the mixer started mixing, and then a certain amount of sand was added over the next 30 seconds. The mixing speed was then changed to high speed and mixing continued for another 30 seconds. There was then a 90-second pause, and during the first 60 seconds of the pause, the kettle was removed and the mortar adhering to the kettle and paddle was scraped off using a paddle and spatula. After the pause, the mixture was mixed at high speed for 60 seconds.

[0124] After this kneading, a liquid (adjusted so that the total weight of the additive, including the weight of the water, was 66.6 g) prepared by diluting a predetermined amount (listed in Table 4 below as % by mass relative to the amount of cement) of additive (any of the emulsions of Examples 1 to 16 or the hardening accelerator (aluminum sulfate) of Comparative Example 2) with water was added, and the mixture was stirred at low speed for an additional 30 seconds to prepare a mortar (in Comparative Example 1, the predetermined amount of additive was not added, so only 66.6 g of water was added).

[0125] The flow value of each mortar mixed above was measured using a truncated cone (bottom diameter 100 mm, top diameter 70 mm, height 60 mm). The detailed conditions for measuring the flow value are as follows:

[0126] Cone installation: Before use, the cone was visually inspected to ensure there was no dirt, scratches, or dents. The inner surface of the cone and the top surface of the flow table were wiped clean with a wet cloth or similar.

[0127] Flow table: The flow table described in JIS R5201:2015 was used.

[0128] Sample filling method: The cone was placed on a horizontally placed flat plate, and the sample was packed in two layers of approximately equal volume. Each layer was leveled with a tamping rod, and then poked evenly 25 times to ensure no bias. When tamping each layer, the tamping rod was pierced to a depth that almost reached the previous layer. Finally, if necessary, any shortfalls were made up and the surface was leveled. The cone was immediately removed vertically, and allowed to fall a total of 15 times at a frequency of once per second. After the mortar had spread, the length in the direction where it was recognized to be the maximum and the length perpendicular to this were measured, and the average value was recorded as flow (mm).

[0129] The results of the flow tests are set forth in Table 4 below.

[0130] [Table 4]

[0131] [Test Example 2] Penetration resistance test After mixing the mortar using the method described in the flow test above, a penetration resistance test was conducted on the mixed material in accordance with JIS R5201:2015 (Example 1, Comparative Example 2). The penetration resistance value (N / mm) was measured at each elapsed time (minutes) after water was poured into the mortar (at the time when solution (A) was added). 2 ) was measured.

[0132] The results of the penetration resistance tests are set forth in Table 5 below.

[0133] [Table 5]

[0134] From the results in Table 4, it was confirmed that Examples 1 to 16 according to the present invention (emulsions containing a polymer having an acid value within a specific range) significantly reduced the flow value of the mortar compared to Comparative Example 1. Furthermore, it was confirmed that Examples 1 to 15, which had an acid value of 63 KOH / g or more, reduced the flow value of the mortar more significantly than Example 16, and furthermore reduced the flow value of the mortar to the same extent as Comparative Example 2 (hardening accelerator: aluminum sulfate), which added in a much larger amount.

[0135] Therefore, it can be understood that the present invention is excellent in the effect of improving the lamination properties of the hydraulic composition for layered manufacturing.

[0136] Furthermore, the results in Table 5 confirm that Example 1 according to the present invention shows a significantly slower increase in penetration resistance value after water injection than Comparative Example 2, demonstrating that the time until the mortar hardens can be maintained sufficiently.

[0137] If the mortar hardens too quickly, the mortar will harden before the next layer is ejected during additive manufacturing, which will reduce the adhesion between the layer that has been ejected and the newly added layer, resulting in a decrease in the strength of the structure.

[0138] Therefore, the present invention is expected to prevent a decrease in the adhesion between layers and, ultimately, the strength of the structure, by ensuring sufficient time for the mortar to harden. This also shows that the present invention is highly effective in improving the lamination properties of hydraulic compositions for additive manufacturing.

[0139] This application is based on Japanese Patent Application No. 2022-29627, filed on February 28, 2022, the disclosure of which is incorporated by reference in its entirety.< / tg> < / ph>

Claims

1. An additive used in a hydraulic composition for additive manufacturing, The emulsion contains a polymer having an acid value of 30 mg KOH / g or more, The molecular weight of the polymer is 50,000 to 1,000,000, The polymer has a structural unit represented by the following formula (I): 【Chemistry 1】 In the above formula (I), one or more of R 1 to R 4 are acidic functional groups, and the remaining R 1 to R 4 are the same or different and are hydrogen atoms or unsubstituted or substituted monovalent hydrocarbon groups having 1 to 8 carbon atoms; and A hydrophobic structural unit represented by the following formula (II): 【Chemistry 2】 In the above formula (II), R 5 to R 8 are the same or different and each include a hydrogen atom, a monovalent hydrocarbon group having 1 to 8 carbon atoms which is unsubstituted or alkoxy-substituted, or —COOM 1 (M 1 is a monovalent hydrocarbon group having 1 to 8 carbon atoms); The polymer contains 1.0 to 60.0 parts by weight of the structural unit represented by formula (I) relative to 100 parts by weight of the polymer, and 30.0 to 95.0 parts by weight of the structural unit represented by formula (II) relative to 100 parts by weight of the polymer.

2. 2. The additive according to claim 1, comprising an emulsion containing a polymer having an acid value of 100 to 400 mg KOH / g.

3. The additive described in claim 1, wherein the acidic functional group is a carboxyl group.

4. Further, as a hydrophobic structural unit, a structural unit represented by the following formula (III): 【Transformation 3】 In formula (III), X is C═O or (CH 2 ) p [p is an integer of 0 to 5], R 12 is an (unsubstituted) divalent hydrocarbon group having 2 to 8 carbon atoms (wherein R 12 may be the same or different), m is an integer of 5 to 300, R 13 is a hydrogen atom or an (unsubstituted) monovalent hydrocarbon group having 1 to 18 carbon atoms, and the remaining R 9 to R 11 are the same or different and are a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms; The additive of claim 1 comprising:

5. The additive according to claim 4, comprising 1.0 to 40.0 parts by weight of the hydrophobic structural unit (III) relative to 100 parts by weight of the polymer.

6. The emulsion was adjusted to a concentration of 25% by mass at a shear rate of 10 s at room temperature. －１ 2. The additive according to claim 1, wherein the viscosity of the additive is 250 mPa·s or less according to

7. A hydraulic composition for layered manufacturing, comprising the additive according to any one of claims 1 to 6 and a hydraulic composition.

8. A method for producing a hydraulic composition for additive manufacturing, comprising: (a) a step of stirring a hydraulic material, an aggregate, and water to obtain a hydraulic composition; and (b) a step of adding an additive according to any one of claims 1 to 6 after the step of stirring the hydraulic composition.

9. A method for layered manufacturing using a hydraulic composition containing the additive according to any one of claims 1 to 6.

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