Additives for hydraulic compositions for additive manufacturing

Abstract

The present invention addresses the problem of providing an additive or the like having, for example, the effect of improving the laminating property of a hydraulic composition for additive manufacturing. The solution of the present invention is to provide an additive for a hydraulic composition for additive manufacturing, said additive containing a polymer having a structural unit (I) derived from a certain unsaturated polyalkylene glycol ether monomer. The average number of added mol of alkylene oxide in the monomer is preferably 30 mol or more. The polymer can also contain structural units other than the structural unit (I).

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. However, reducing the fluidity of the hydraulic material composition hinders its movement within the hose, so the current situation is that a cure accelerator must be added just before dispensing to reduce the fluidity. Furthermore, 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 a specific polymer is useful for improving lamination properties, and have completed the present invention based on this finding. DETAILED DESCRIPTION OF THE INVENTION

[0013] 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).

[0014] 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.

[0015] (Example of the present invention) The preferred configurations of the additives of the present invention are as described in the following items (1) to (8). (1) An additive for a hydraulic composition for additive manufacturing, comprising a polymer having the following structural unit (I):

[0016] [ka]

[0017] (In the structural unit (I), X is C=O or (CH2) p [p is an integer from 0 to 5], and R 4 O is an oxyalkylene group having 2 to 8 carbon atoms, n is the average number of moles of oxyalkylene groups added and is a number of 15 to 500, and R 5 is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and the remaining R 1 ~R 3 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. (2) The additive according to (1) above, wherein n is 100 to 500. (3) The X is (CH2) p [p is an integer of 0 to 2]. The additive according to (1) or (2) above. (4) The additive according to any one of (1) to (3) above, wherein the polymer contains 50 to 100 parts by weight of the structural unit (I) relative to 100 parts by weight of the polymer. (5) The additive according to any one of (1) to (4) above, wherein the polymer is a copolymer further containing the following structural unit (II):

[0018] [ka]

[0019] (In the structural unit (II), R 6 ~R 8 are the same or different and represent a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or a carboxyl group, and M represents a hydrogen atom or a cationic species. (6) The additive according to any one of (1) to (5), wherein the polymer is a copolymer containing a structural unit derived from an unsaturated monomer having at least one group selected from the group consisting of a sulfonic acid group, a phosphoric acid group, and a salt thereof. (7) A hydraulic composition for additive manufacturing, comprising the additive according to any one of (1) to (6). (8) a step of mixing and stirring a hydraulic composition and the additive described in any one of (1) to (6); A method for producing a hydraulic composition for layered manufacturing, comprising:

[0020] Hereinafter, an additive for a hydraulic composition for layered manufacturing, which contains a polymer having the structural unit (I), will also be referred to as the additive of the present invention. Also, a polymer having the structural unit (I) will also be referred to as the polymer of the present invention.

[0021] The additives of the present invention are excellent in the effect of improving the lamination properties of the hydraulic composition for layered manufacturing.

[0022] Here, improved lamination ability refers to, for example, a high lamination index, which will be described later. Specifically, improved lamination ability refers to the ability of a hydraulic composition, such as mortar or fresh concrete formed from the hydraulic composition, to form a desired height, and to maintain the desired height before the hydraulic composition completely hardens. The additive of the present invention can increase the lamination index of the hydraulic composition for additive manufacturing.

[0023] (additives) The additive of the present invention is used in a hydraulic composition for layered manufacturing. The additive of the present invention is preferably used by being kneaded with a hydraulic composition such as mortar or fresh concrete.

[0024] More specifically, the additive of the present invention comprises a polymer having at least the following structural unit (I). Preferably, the additive of the present invention comprises a polymer having at least the following structural unit (I) as a main component. Here, the term "main component" means that the polymer accounts for 80% by weight or more (preferably 90% by weight or more, more preferably 95% by weight or more) of the additive. More preferably, the additive of the present invention consists of a polymer having at least the following structural unit (I).

[0025] The additive of the present invention can be more specifically limited in its use as a thickener or a layerability improver.

[0026] 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.

[0027] (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."

[0028] (Hydraulic composition for additive manufacturing) In the present invention, the "hydraulic composition for additive manufacturing" refers to a hydraulic composition used for additive manufacturing. The hydraulic composition contains a hydraulic material and aggregate (coarse aggregate and / or fine aggregate), and optionally contains other components such as an antifoaming agent and a dispersant. Examples of hydraulic compositions include mortar and fresh concrete.

[0029] 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% by weight relative to the hydraulic substance (cement).

[0030] (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. 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.

[0031] (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.

[0032] (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.

[0033] (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.

[0034] 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.

[0035] (aggregate) The aggregate used in the present invention may be any appropriate aggregate, such as fine aggregate (sand, etc.) or coarse aggregate (crushed stone, etc.). Examples of such aggregate include sand, gravel, crushed stone, granulated slag, recycled aggregate, and refractory aggregate such as silica, clay, zircon, high alumina, silicon carbide, graphite, chromium, chromium-magnesium, and magnesia.

[0036] (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.

[0037] (Structural unit (I)) The polymer in the present invention has the following structural unit (I).

[0038] [ka]

[0039] In the above structural unit (I), X is C=O or (CH2) p [p is an integer from 0 to 5], and R 4 O is an oxyalkylene group having 2 to 8 carbon atoms, n is the average number of moles of oxyalkylene groups added and is a number of 15 to 500, and R 5 is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and the remaining R 1 ~R 3 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. It goes without saying that different types of structural units (I) may be contained in the polymer.

[0040] The X is preferably (CH2). p [p is an integer of 0 to 5], more preferably (CH2) p [p is 0 to 2], more preferably (CH2) p [p is 1] (when p=0, the upper C and lower O of X in the structural unit (I) are directly bonded). 4 O is preferably an oxyalkylene group having 2 to 4 carbon atoms, and more preferably an oxyalkylene group having 2 carbon atoms.

[0041] Furthermore, in terms of the effects of the present invention, the above n may be 20 to 500, 25 to 500, 30 to 500, or 50 to 500, preferably 75 to 500, more preferably 100 to 500, even more preferably 150 to 500, particularly preferably 200 to 500, and most preferably 200 to 400. When n is equal to or greater than the above lower limit, lamination properties are further improved, and when n is equal to or less than the above upper limit, handling properties of the polymer are improved.

[0042] Above R 5 is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and from the viewpoint of the effects of the present invention, is preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.1 ~R 3 are the same or different and each is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group. 1 ~R 3 Among these, at least one may be a hydrocarbon group having 1 to 8 carbon atoms, and one or two may be a hydrocarbon group having 1 to 8 carbon atoms. More specific examples of the hydrocarbon group include linear, branched, or cyclic alkyl groups (for example, linear, branched, or cyclic alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, and 2-ethylhexyl), alkenyl groups, aryl groups, and aralkyl groups, with alkyl groups being preferred, and methyl being particularly preferred.

[0043] The structural unit (I) may be a structural unit 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 unsaturated polyalkylene glycol ester-based monomers and unsaturated polyalkylene glycol ether-based monomers. Among these, the structural unit (I) is preferably a structural unit formed when a carbon-carbon double bond of an unsaturated polyalkylene glycol ester-based monomer and / or an unsaturated polyalkylene glycol ether-based monomer is cleaved, and more preferably a structural unit formed when a carbon-carbon double bond of an unsaturated polyalkylene glycol ether-based monomer is cleaved.

[0044] Examples of the unsaturated polyalkylene glycol ester monomer include polyalkylene glycol monomethacrylate, polyalkylene glycol monoacrylate, alkoxypolyalkylene glycol monomethacrylate, alkoxypolyalkylene glycol monoacrylate, phenoxypolyalkylene glycol monomethacrylate, and phenoxypolyalkylene glycol monoacrylate, of which alkoxypolyalkylene glycol monomethacrylate or alkoxypolyalkylene glycol monoacrylate is preferred, and alkoxypolyalkylene glycol monomethacrylate is more preferred.

[0045] Examples of the alkoxypolyalkylene glycol monomethacrylate include methoxypolyethylene glycol-methacrylate, octoxypolyethylene glycol-polypropylene glycol-methacrylate, lauroxypolyethylene glycol-methacrylate, and stearoxypolyethylene glycol-methacrylate, with methoxypolyethylene glycol-methacrylate being preferred.

[0046] Examples of the alkoxypolyalkylene glycol monoacrylate include methoxypolyethylene glycol-acrylate, octoxypolyethylene glycol-polypropylene glycol-acrylate, lauroxypolyethylene glycol-acrylate, and stearoxypolyethylene glycol-acrylate.

[0047] An example of the phenoxypolyalkylene glycol monomethacrylate is phenoxypolyethylene glycol methacrylate.

[0048] An example of the alkoxypolyalkylene glycol monoacrylate is methoxypolyethylene glycol acrylate.

[0049] Examples of the phenoxy polyalkylene glycol monoacrylate include nonylphenoxy polypropylene glycol acrylate and nonylphenoxy polyethylene glycol polypropylene glycol acrylate.

[0050] 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.

[0051] Examples of the polyalkylene glycol monoacrylate include polyethylene glycol monoacrylate and polypropylene glycol monoacrylate.

[0052] Examples of the unsaturated polyalkylene glycol ether monomer include compounds in which 15 to 500 moles of alkylene oxide are added to the hydroxyl groups of any of vinyl alcohol, allyl alcohol, methallyl alcohol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-2-buten-1-ol, 2-methyl-3-buten-1-ol, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, and hydroxybutyl vinyl ether, and preferably 3 The alkylene oxide is preferably a compound obtained by adding 15 to 500 moles (preferably 50 to 500 moles) of alkylene oxide to 3-methyl-3-buten-1-ol, a compound obtained by adding 15 to 500 moles (preferably 50 to 500 moles) of alkylene oxide to allyl alcohol, or a compound obtained by adding 15 to 500 moles (preferably 50 to 500 moles) of alkylene oxide to methallyl alcohol, more preferably a compound obtained by adding 15 to 500 moles of alkylene oxide to allyl alcohol and / or a compound obtained by adding 15 to 500 moles of alkylene oxide to methallyl alcohol. The alkylene oxide is preferably ethylene oxide, propylene oxide, or butylene oxide, and most preferably ethylene oxide.

[0053] (Structural unit (II)) The polymer in the present invention preferably further contains the following structural unit (II) from the viewpoint of improving the adsorption onto hydraulic compositions such as cement.

[0054] [ka]

[0055] In the above structural unit (II), R 6 ~R 8 are the same or different and represent a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or a carboxyl group, and M represents a hydrogen atom or a cationic species (preferably, in terms of the effects of the present invention, M is a cationic species). Needless to say, different types of structural units (II) may be contained in the polymer.

[0056] The above R 6 ~R 8 are the same or different and are preferably a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or a carboxyl group, more preferably a hydrogen atom or a methyl group. More specific examples of the hydrocarbon group include linear, branched, or cyclic alkyl groups (e.g., linear, branched, or cyclic alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, and 2-ethylhexyl), alkenyl groups, aryl groups, and aralkyl groups, among which alkyl groups are preferred, and methyl groups are particularly preferred. Specific examples of the cation species include lithium, sodium, potassium, magnesium, calcium, and aluminum, with sodium being preferred. Two or more types of cation species may be used.

[0057] The structural unit (II) 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, 2-methyleneglutaric acid, and salts thereof. Examples of salts include lithium salts, sodium salts, potassium salts, magnesium salts, calcium salts, and aluminum salts, with sodium salts being preferred. The unsaturated carboxylic acid monomer is preferably acrylic acid (salt), methacrylic acid (salt), maleic acid (salt), or fumaric acid (salt), more preferably acrylic acid (salt) and / or methacrylic acid (salt), even more preferably acrylate and / or methacrylate, and even more preferably sodium acrylate and / or sodium methacrylate. Here, acrylic acid (salt) refers to acrylic acid and / or an acrylic acid salt, and methacrylic acid (salt) refers to methacrylic acid and / or a methacrylic acid salt.

[0058] (Other structural units) The polymer of the present invention may contain structural units other than the above structural units (I) and (II) in the remainder.

[0059] Examples of the remaining structural units include structural units derived from unsaturated monomers having a sulfonic acid group and / or a salt group thereof, structural units derived from unsaturated monomers having a phosphate group and / or a salt group thereof, and structural units derived from (meth)acrylates. Among these, from the viewpoint of improving adsorption to hydraulic compositions such as cement, the polymer of the present invention preferably contains, as the remaining structural units, at least one selected from the group consisting of structural units derived from unsaturated monomers having a sulfonic acid group and / or a salt group thereof and structural units derived from unsaturated monomers having a phosphate group and / or a salt group thereof, and more preferably contains structural units derived from unsaturated monomers having a sulfonic acid group and / or a salt group thereof.

[0060] In this specification, the term "structural unit derived from a monomer" refers to a structural unit formed by polymerization of a monomer, and more specifically, refers to a structure formed by cleavage of a carbon-carbon double bond of a monomer. In addition, in this specification, the term "(meth)acrylate" refers to acrylate and / or methacrylate.

[0061] Examples of the unsaturated monomer having a sulfonic acid group and / or a salt thereof include vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-(methacryloyloxy)ethanesulfonic acid, sulfonic acids represented by the following formula (III) or salts thereof, more preferably 2-acrylamido-2-methylpropanesulfonic acid, sulfonic acids represented by the following formula (III) or salts thereof, and most preferably sodium 3-allyloxy-2-hydroxypropanesulfonate. These unsaturated monomers may be used alone or in combination of two or more.

[0062] The polymer of the present invention may contain the structural unit (I), the structural unit (II), and a structural unit derived from an unsaturated monomer having a sulfonic acid group and / or a salt thereof. Alternatively, the polymer of the present invention may contain the structural unit (I) and a structural unit derived from an unsaturated monomer having a sulfonic acid group or a salt thereof without containing the structural unit (II).

[0063] [ka]

[0064] In the structural unit (III), p is an integer of 1 to 4, q and r are the same or different and are an integer of 0 to 100 (preferably an integer of 0 to 50, more preferably an integer of 0 to 20), and R 9 ,R 10is an oxyalkylene group having 2 to 4 carbon atoms, Y and Z are the same or different and are a hydroxy group, an alkoxyl group having 2 to 4 carbon atoms, a monovalent phosphate group or a monovalent sulfonic acid group, and at least one of Y and Z is a sulfonic acid group.

[0065] Examples of the unsaturated monomer having a phosphate group and / or a salt thereof include hydroxyalkyl (meth)acrylate monophosphate esters or salts thereof, such as hydroxyethyl methacrylate monophosphate ester, hydroxyethyl propyl methacrylate monophosphate ester, and hydroxyethyl butyl methacrylate monophosphate ester.

[0066] The polymer of the present invention may not contain the structural unit (II) but may contain the structural unit (I) and a structural unit derived from the unsaturated monomer that is phosphoric acid and / or a salt thereof.

[0067] Examples of the (meth)acrylate include hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and hydroxybutyl (meth)acrylate, and alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, with hydroxyethyl (meth)acrylate or hydroxypropyl (meth)acrylate being preferred. The polymer of the present invention may contain the structural unit (I), the structural unit (II), and a structural unit derived from the (meth)acrylate.

[0068] (Polymer structure) The polymer of the present invention preferably contains 10.0 to 100.0 parts by weight, more preferably 50.0 to 100.0 parts by weight, even more preferably 75.0 to 99.0 parts by weight, and even more preferably 80.0 to 99.0 parts by weight of the structural unit (I) relative to 100 parts by weight of the polymer. The polymer of the present invention also preferably contains 1.0 to 30.0 parts by weight, more preferably 2.0 to 20.0 parts by weight, even more preferably 2.0 to 15.0 parts by weight, and even more preferably 2.0 to 10.0 parts by weight of the structural unit (II) relative to 100 parts by weight of the polymer. The remaining structural units are contained in the polymer in an amount of, for example, 1.0 to 30.0 parts by weight relative to 100 parts by weight of the polymer of the present invention.

[0069] The polymer of the present invention preferably contains the structural unit (I) and the structural unit (II) (including those consisting of or essentially consisting of (I) and (II) (for example, 99.0 parts by weight or more of (I) and (II) per 100 parts by weight of all structural units)). In this case, the remaining structural units may be contained in the polymer in an amount of, for example, 1.0 to 20.0 parts by weight, or may be contained in an amount of 1.0 to 10.0 parts by weight per 100 parts by weight of the polymer. Furthermore, in one preferred embodiment, the polymer of the present invention, in addition to containing the structural unit (I) and the structural unit (II), also contains, as the remaining structural units, at least one selected from the group consisting of structural units derived from unsaturated monomers having a sulfonic acid group and / or a salt group thereof, and structural units derived from unsaturated monomers having a phosphoric acid group and / or a salt group thereof.

[0070] The polymer of the present invention preferably contains structural units (I) and structural units derived from unsaturated monomers having a sulfonic acid group and / or a salt thereof (including those consisting of (I) and structural units derived from unsaturated monomers having a sulfonic acid group and / or a salt thereof, or those essentially consisting of (I) and structural units derived from unsaturated monomers having a sulfonic acid group and / or a salt thereof (for example, 99.0 parts by weight or more of (I) and structural units derived from unsaturated monomers having a sulfonic acid group or a salt thereof per 100 parts by weight of all structural units)). In this case, the structural units derived from unsaturated monomers having a sulfonic acid group and / or a salt thereof may be contained in the polymer in a total amount of, for example, 1.0 to 30.0 parts by weight, 5.0 to 30.0 parts by weight, or 10.0 to 25 parts by weight per 100 parts by weight of the polymer.

[0071] Examples of the polymerization in the present invention include copolymerization of (1) a monomer containing a polyalkylene glycol group or the like and (2) an unsaturated carboxylic acid monomer, and copolymerization of (1) a monomer containing a polyalkylene glycol group or the like and an unsaturated monomer having a sulfonic acid group and / or a salt thereof.

[0072] The weight-average molecular weight of the polymer in the present invention, as measured by static light scattering or the method described in the Examples below (preferably the method described in the Examples below), is, for example, 1,000 to 10,000,000, preferably 2,000 to 8,000,000, more preferably 3,000 to 6,000,000, even more preferably 4,000 to 5,000,000, still more preferably 10,000 to 500,000, and particularly preferably 10,000 to 100,000.

[0073] (Polymerization method) The polymerization for obtaining the polymer according to the present invention may be carried out in the presence of a polymerization initiator.

[0074] Examples of polymerization initiators 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 potassium persulfate; and peroxides such as hydrogen peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and ammonium peroxide. In this case, accelerators such as alkali metal sulfites such as sodium bisulfite, metabisulfite, sodium hypophosphite, Fe(II) salts such as Mohr's salt, sodium hydroxymethanesulfinate dihydrate, hydroxylamine hydrochloride, thiourea, L-ascorbic acid (salt), and erythorbic acid (salt) can also be used in combination.

[0075] The polymerization initiators may be used alone or in combination of two or more.

[0076] 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.

[0077] The method for adding the polymerization initiator is not particularly limited, but examples thereof include batch addition, divided addition, and continuous dropwise addition.

[0078] The polymerization reaction may be carried out, as necessary, in the presence of a reducing agent (e.g., sodium bisulfite), 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, mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate, 2-mercaptoethanesulfonic acid, etc.)], 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, etc.

[0079] 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).

[0080] (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 method comprising mixing and stirring a hydraulic composition and the additive of the present invention. Another example includes a method comprising (a) a stirring step of a hydraulic composition and water, and (b) a stirring step of adding the additive of the present invention to the mixture obtained after the stirring step and stirring the mixture. In the method, steps (a) and (b) are carried out independently, with step (b) being carried out after step (a).

[0081] After the above steps 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 the above steps).

[0082] <Layered manufactured object and layered manufacturing method> The hydraulic composition of the present invention is suitable for use in layer-by-layer manufacturing. Therefore, the present invention also provides a layer-by-layer manufactured article formed from the hydraulic composition for layer-by-layer manufacturing of the present invention.

[0083] Another embodiment is a method for producing a layered object using the hydraulic material composition of the above embodiment.

[0084] A method for producing a layered object using the hydraulic material composition for layered manufacturing (layered manufacturing method) includes a step of extruding the hydraulic composition of the above embodiment from a nozzle and laminating the hydraulic composition. The layered manufacturing method according to this embodiment preferably includes a step of pressure-feeding the hydraulic composition for layered manufacturing with compressed air, a pump, or the like, and a step of extruding the pressure-fed hydraulic composition for layered manufacturing through a nozzle and laminating the hydraulic composition for layered manufacturing to form a layered object. Since the additive of the present invention can improve the lamination properties without reducing the fluidity of the hydraulic composition, it is preferable to add the additive of the present invention before pressure-feeding the hydraulic composition with compressed air, a pump, or the like. That is, the method for producing an additive manufacturing object using the hydraulic material composition for additive manufacturing (additive manufacturing method) includes the steps of preparing a hydraulic composition for additive manufacturing containing the additive of the present invention, pressurizing the obtained hydraulic composition for additive manufacturing using compressed air, a pump, or the like, and extruding the pressurized hydraulic composition for additive manufacturing from a nozzle to laminate the hydraulic composition for additive manufacturing to form an additive manufacturing object.

[0085] 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.

[0086] 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]

[0087] The present invention will now be described in more detail with reference to 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 weight."

[0088] Example 1 An aqueous solution (B1a) was prepared by dissolving 0.4 parts L-ascorbic acid and 0.8 parts 3-mercaptopropionic acid in 50.0 parts water. A reaction vessel equipped with a thermometer, stirrer, dropping device, nitrogen inlet tube, and reflux condenser was charged with 90.4 parts 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 acrylic acid (AA). The atmosphere inside the reaction vessel was then replaced with nitrogen while stirring. The temperature was raised to 60°C under a nitrogen atmosphere, and 0.9 parts of a 35% aqueous solution of hydrogen peroxide was added. After 30 minutes, the above-mentioned mixed solution (B1a) was added dropwise over 3.5 hours, followed by 25.5 parts of acrylic acid (AA) over 3.0 hours, each at a constant rate. The temperature was maintained at 60°C during this period. 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. The pH of the reaction solution was then neutralized to pH 6.3 using an aqueous sodium hydroxide solution at a temperature below the polymerization reaction temperature. In this way, an aqueous solution containing the target polymer was obtained. The weight-average molecular weight Mw of the polymer was 32,000.

[0089] The weight average molecular weight Mw of the 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.

[0090] <Examples 2 to 29 and Comparative Examples 1 and 2> The polymers of Examples 2 to 29 and Comparative Examples 1 and 2 were obtained by carrying out polymerization according to the formulations shown in Table 1 below, in the same procedure as in Example 1. The molecular weights of these polymers were adjusted by carrying out polymerization while appropriately changing the amount of 3-mercaptopropionic acid added.

[0091] [Table 1]

[0092] IPN50: Unsaturated polyalkylene glycol ether monomer in which an average of 50 moles of ethylene oxide are added to 3-methyl-3-buten-1-ol PGM25E: methoxypolyethylene glycol monomethacrylate (average number of ethylene oxide added: 25 moles) PGM40E: methoxypolyethylene glycol monomethacrylate (average number of ethylene oxide moles added: 40) MLA20: Unsaturated alcohol obtained by adding an average of 20 moles of ethylene oxide to methallyl alcohol MLA50: Unsaturated alcohol obtained by adding an average of 50 moles of ethylene oxide to methallyl alcohol MLA75: Unsaturated alcohol obtained by adding an average of 75 moles of ethylene oxide to methallyl alcohol ALA75: Unsaturated alcohol obtained by adding an average of 75 moles of ethylene oxide to allyl alcohol ALA150: Unsaturated alcohol obtained by adding an average of 150 moles of ethylene oxide to allyl alcohol ALA250: Unsaturated alcohol obtained by adding an average of 250 moles of ethylene oxide to allyl alcohol MLA100: Unsaturated alcohol obtained by adding an average of 100 moles of ethylene oxide to methallyl alcohol MLA150: Unsaturated alcohol obtained by adding an average of 150 moles of ethylene oxide to methallyl alcohol MLA200: Unsaturated alcohol obtained by adding an average of 200 moles of ethylene oxide to methallyl alcohol MLA250: Unsaturated alcohol obtained by adding an average of 250 moles of ethylene oxide to methallyl alcohol IPN10: Unsaturated polyalkylene glycol ether monomer in which an average of 10 moles of ethylene oxide are added to 3-methyl-3-buten-1-ol MLA10: Unsaturated alcohol obtained by adding an average of 10 moles of ethylene oxide to methallyl alcohol SA: Sodium acrylate SMAA: Sodium methacrylate HEA: 2-hydroxyethyl acrylate HAPS: Sodium 3-allyloxy-2-hydroxy-1-propanesulfonate HPA: Hydroxypropyl acrylate AMPS: sodium 2-acrylamido-2-methylpropanesulfonate.

[0093] [Test Example 1] Flow test A flow test was carried out using the following method, with reference to the contents of JIS R5201: 2015. The flow test and the lamination evaluation test described below were carried out in an environment with a temperature of 20±1°C and a relative humidity of 60±15%RH.

[0094] First, a 10% polymer solution prepared in advance by diluting any of the polymers of Examples 1 to 29 and Comparative Examples 1 and 2 with water, Adekanol LG-299 (manufactured by Adeka Corporation) as an antifoaming agent, and water were mixed to prepare solution (A). Solution (A) was prepared by mixing the 10% polymer solution in an amount such that the result of the flow test below when using solution (A) was 196 mm or more and 204 mm or less, mixing Adekanol LG-299 in an amount that was 5% of the solids content of the 10% polymer solution, and mixing water in an amount such that solution (A) became 331.2 g.

[0095] Next, 690 g of ordinary Portland cement (manufactured by Taiheiyo Cement Corporation) was added to the kettle of a high-power mixer (model CB-34; manufactured by Maruto Seisakusho Co., Ltd.), followed by 1600 g of fine aggregate (Kakegawa sand), and mixing with the mixer was immediately started at low speed. Ten seconds after mixing with the mixer began, solution (A) was added over a 10-second period. Sixty seconds after mixing with the mixer began, a 60-second pause was taken, and during the first 30 seconds of the pause, the kettle was removed, and 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.

[0096] 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:

[0097] 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.

[0098] Flow table: The flow table described in JIS R5201:2015 was used.

[0099] 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).

[0100] [Test Example 2] Lamination evaluation test A single corner of the bottom of a polyethylene bag (200 mm wide, 280 mm long, 0.04 mm thick, Pacol zip-lock bag, 4I, manufactured by Nippon Hightec Co., Ltd.) was cut off in advance to create a discharge bag for discharging the mortar. The shape of the cutout was a right-angled isosceles triangle with a height of 15 mm and a base of 15 mm.

[0101] For each of the polymers of Examples 1 to 29 and Comparative Examples 1 and 2, mortar was kneaded and the above-mentioned flow test was carried out, and then the laminateability index was evaluated according to the following procedure. (1) Mortar (flow test result: 196mm to 204mm) was poured into a discharge bag and the weight before discharge was measured. Here, since there is a trade-off between fluidity and stackability, in the stackability evaluation test, the flow value was set to 196mm to 204mm. (2) The extrusion bag was lifted and manually squeezed to extrude the material at a speed of one rotation per 10 seconds around the sides of a 100 mm square. The extrusion was then rotated three times to stack three layers. The same extrusion process was repeated once more to produce a total of two stacks. After extrusion was complete, the weight of the extrusion bag was measured, and the extrusion volume was calculated using the following formula: Discharge amount (kg) = Weight of discharge bag before discharge (kg) - Weight of discharge bag after discharge (kg) (3) When it was confirmed that the discharge amount was within the range of 0.45 kg to 0.55 kg, the height of the laminate was evaluated. The height (mm) was measured at eight points, namely, the four corners and the center of each side of the laminate, for a total of 16 height points (since there were two laminates), and the average was calculated. (4) As an index of stackability, the stackability index calculated by the following formula was defined. Lamination index = average height of 16 points (mm) ÷ discharge amount (kg) Here, a higher value of the stackability index means higher stackability. The stackability index is preferably, for example, 30 or more, 35 or more, 40 or more, 42 or more, or 45 or more.

[0102] The lamination index for each of the Examples and Comparative Examples evaluated according to the above is shown in the right column of Table 1 above.

[0103] The results in Table 1 suggest that the use of the additive of the present invention can significantly improve the lamination properties of the hydraulic composition for layered manufacturing. Furthermore, it is understood that n (average number of moles of oxyalkylene groups added) of the structural unit (I) of the present invention is preferably 20 or more, 25 or more, 40 or more, 50 or more, 75 or more, 100 or more, 150 or more, 200 or more, or 250 or more, and preferably falls within a larger numerical range.

[0104] This application is based on Japanese Patent Application No. 2022-141353, filed on September 6, 2022, the disclosure of which is hereby incorporated by reference in its entirety.

Claims

1. The polymer includes a polymer having the following structural unit (I) and the following structural unit (II): The polymer contains 50.0 to 99.0 parts by weight of the structural unit (I) and 1.0 to 30.0 parts by weight of the structural unit (II) relative to 100 parts by weight of the polymer. 【Chemistry 1】 (In the structural unit (I), X is C═O or (CH ２ ) ｐ [p is an integer from 0 to 5], and R ４ O is an oxyalkylene group having 2 to 8 carbon atoms, n is the average number of moles of oxyalkylene groups added and is a number of 40 to 500, and R ５ is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and the remaining R １ ~R ３ are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. 【Chemistry 2】 (In the structural unit (II), R 6 to R 8 may be the same or different and represent a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or a carboxyl group, and M represents a hydrogen atom or a cation species.)

2. A polymer having the following structural unit (I): the polymer contains 50.0 to 99.0 parts by weight of the structural unit (I) relative to 100 parts by weight of the polymer; The additive for a hydraulic composition for layered manufacturing, wherein the polymer further contains 1.0 to 30.0 parts by weight of a structural unit derived from an unsaturated monomer having at least one selected from the group consisting of a sulfonic acid group, a phosphoric acid group, and a salt group thereof, relative to 100 parts by weight of the polymer. 【Chemistry 1】 (In the structural unit (I), X is C═O or (CH 2 ) p [p is an integer of 0 to 5], R 4 O is an oxyalkylene group having 2 to 8 carbon atoms, n is the average number of moles of oxyalkylene groups added and is a number of 15 to 500, R 5 is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and the remaining R 1 to R 3 are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms.)

3. The additive described in claim 1 or 2, wherein n is a number from 50 to 500.

4. The additive according to claim 1 or 2, wherein n is a number from 100 to 500.

5. The X is (CH ２ ) ｐ The additive according to claim 1 or 2, wherein p is an integer of 0 to 2.

6. The additive according to claim 2, wherein the polymer is a copolymer further comprising the following structural unit (II): 【Chemistry 2】 (In the structural unit (II), R ６ ~R ８ are the same or different and represent a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or a carboxyl group, and M represents a hydrogen atom or a cation species.

7. An additive described in claim 1 or 2, which is a stackability improver.

8. A hydraulic composition for additive manufacturing, comprising the additive according to claim 1 or 2.

9. a step of mixing and stirring the hydraulic composition and the additive according to claim 1 or 2; A method for producing a hydraulic composition for layered manufacturing, comprising:

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