Two component additive to be used in hydraulic composition for laminate shaping

Abstract

To provide an additive excellent in the effect of improving the pumpability and laminatability of a hydraulic composition for lamination shaping.SOLUTION: There is provided a two-component additive comprising a first additive and a second additive in a separated state, in which the first additive comprises a polymer having the following structural unit (I) and structural unit (II). (In the structural unit (I), X1 is C=O or (CH2)p [p is an integer of 0 to 5], R4O is a 2C to 8C oxyalkylene group, n is an average addition mole number of the oxyalkylene group and is a number from 2 to 100, R5 is hydrogen or a 1C to 8C hydrocarbon group, and the remaining R1 to R3 are identical to or different from each other and represent hydrogen or a 1C to 8C hydrocarbon group. In the structural unit (II), R6 to R8 are identical to or different from each other and represent hydrogen atoms, methyl groups, or COOM2, M1 and M2 represent hydrogen atoms or cationic species, and the second additive is one or more post-additives selected from the group consisting of an accelerator and a thickener.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a two-component 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 of curing and layering UV-curable resin one layer at a time), inkjet printing (a method of spraying UV-curable resin from a printer head while irradiating it with UV light), powdered gypsum printing (a method of spraying resin or glue from a printer head to harden powdered gypsum), powder sintering (a method of baking and solidifying resin or metal powder with a laser), and fused deposition modeling (a method of spraying molten thermoplastic resin from a thin nozzle to layer). The objects created by additive manufacturing are primarily made of resin, gypsum, and metal. Technology for creating large objects, such as construction components, using hydraulic 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 produce large objects, such as those used in single-family homes.

[0003] Examples of technologies related to additive manufacturing using hydraulic compositions include the following Patent Documents 1 to 3. 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, 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, the sprayed mortar is allowed to self-harden, and a solidified layer having a shape based on the two-dimensional slice data is formed, and this solidified layer formation process is repeated to sequentially stack the layers vertically to form a shape.

[0004] Patent Document 2 introduces a material for making molds for producing castings using a 3D printer, and discloses a material made of cement, sand, and a water-soluble silicate as an accelerator. Patent Document 3 discloses a method for producing a hydraulic composition for additive manufacturing using an ionic emulsion-type thickener. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 10-235623 [Patent Document 2] U.S. Patent No. 8,211,226 [Patent Document 3] Japanese Patent Publication No. 2021-133667 Summary of the Invention [Problem to be solved by the invention]

[0006] In three-dimensional modeling techniques, the hydraulic composition used is extruded by a spray or extrusion nozzle or the like, and then layered one by one. For this reason, the ability to resist the weight of the upper layers and maintain the three-dimensional shape even after layering (layerability) is required. Such layerability is a performance required specifically for additive manufacturing, which is not required for conventional self-compacting concrete or the like. Furthermore, in performing additive manufacturing, after mixing and stirring the hydraulic materials in a tank or the like, the obtained hydraulic composition is pumped through a pipe by a pump or the like and extruded by a spray or extrusion nozzle or the like, so the hydraulic composition also needs to be easy to pump, i.e., pumpable.

[0007] Generally, there is a trade-off between the pumpability and stackability of a material. For example, a material with high fluidity and good pumpability is likely to be unable to maintain its stacked shape and to collapse.

[0008] Therefore, additives that improve pumpability and lamination properties are required for hydraulic compositions for additive manufacturing.

[0009] The present invention has been made in view of the above circumstances, and has as its object to provide an additive that is excellent in the effect of improving the pumpability and lamination properties of a hydraulic composition for layered manufacturing. [Means for solving the problem]

[0010] One aspect of the present invention that can solve the above-described problems is a two-component additive used in a hydraulic composition for additive manufacturing, the two-component additive including a first additive and a second additive, wherein the first additive and the second additive are in a separated state, The first additive is a polymer having the following structural unit (I) and the following structural unit (II):

[0011] [ka]

[0012] (Structural unit (I), X 1 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 from 2 to 100, 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.

[0013] [ka]

[0014] (In the structural unit (II), R 6 ~R 8 are the same or different and are a hydrogen atom, a methyl group, or a COOM 2 represents M 1 and M 2 represents a hydrogen atom or a cationic species. Including, the polymer contains structural units derived from an alkyl ester of acrylic acid having 1 to 3 carbon atoms and / or structural units derived from a hydroxyalkyl ester of acrylic acid having 1 to 3 carbon atoms in an amount of 15 parts by weight or less relative to 100 parts by weight of the polymer; The second additive is a two-part additive that is one or more post-additives selected from the group consisting of accelerators and thickeners. [Effects of the Invention]

[0015] The two-component additive according to one embodiment of the present invention is excellent in the effect of improving pumpability and lamination properties when added to a hydraulic composition for layered manufacturing. DETAILED DESCRIPTION OF THE INVENTION

[0016] An embodiment of the present invention will be described below. The embodiment described herein is an example for embodying the technical concept of the present invention and is not intended to limit the present invention. Therefore, all other possible embodiments, methods of use, and operational techniques conceivable by those skilled in the art without departing from the spirit of the present invention are included within the scope and spirit of the present invention, as well as within the scope of the inventions described in the claims and their equivalents. The embodiments described in this specification can be arbitrarily combined to form other embodiments. Combinations of two or more of the individual preferred embodiments of the present invention described below are also preferred embodiments of the present invention and are considered to be disclosed in this specification (i.e., are legal grounds for amendment).

[0017] Furthermore, in this specification, the term "X to Y" indicating a range means "X or more and Y or less." Unless otherwise specified, operations and measurements of physical properties are performed under conditions of room temperature (20 to 25°C) and a relative humidity of 45 to 55%RH. In this specification, the term "(meth)acrylic" means "acrylic and / or methacrylic," and the term "(meth)acrylate" means "acrylate and / or methacrylate." Furthermore, the term "acid (salt)" means "acid and / or its salt."

[0018] In the present specification, the term "structural unit derived from a monomer" means a structural unit formed by polymerization of a monomer, and more specifically, means a structure formed by cleavage of a carbon-carbon double bond in a monomer.

[0019] (Example of the present invention) The preferred embodiments and modes of the present invention are described in the following items (1) to (10).

[0020] (1) A two-component additive used in a hydraulic composition for additive manufacturing, comprising a first additive and a second additive, wherein the first additive and the second additive are in a separated state, The first additive is a polymer having the following structural unit (I) and the following structural unit (II):

[0021] [ka]

[0022] (Structural unit (I), X 1 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 from 2 to 100, 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.

[0023] [ka]

[0024] (In the structural unit (II), R 6 ~R 8 are the same or different and are a hydrogen atom, a methyl group, or a COOM 2 represents M 1 and M 2 represents a hydrogen atom or a cationic species. Including, the polymer contains structural units derived from an alkyl ester of acrylic acid having 1 to 3 carbon atoms and / or structural units derived from a hydroxyalkyl ester of acrylic acid having 1 to 3 carbon atoms in an amount of 15 parts by weight or less relative to 100 parts by weight of the polymer; a two-component additive, wherein the second additive is one or more post-additives selected from the group consisting of accelerators and thickeners; (2) The two-component additive according to (1), wherein n is 5 to 60; (3) The X is (CH2) p [p is an integer of 0 to 2]; (4) The two-component additive according to any one of (1) to (3), wherein the polymer contains 50 to 99 parts by weight of the structural unit (I) per 100 parts by weight of the polymer; (5) The two-component additive according to any one of (1) to (4), wherein the polymer contains 1 to 50 parts by weight of the structural unit (II) per 100 parts by weight of the polymer; (6) The two-component additive according to any one of (1) to (5), wherein the accelerator is selected from the group consisting of sulfates, nitrates, nitrites, thiocyanates, silicates, chlorides, and hydroxides; (7) The two-component additive according to any one of (1) to (6), wherein the thickener is selected from the group consisting of cellulose-based thickeners, polycarboxylic acid-based thickeners, glycol-based thickeners, polyvinyl alcohol-based thickeners, clay-based thickeners, and thickening polysaccharides; (8) The two-component additive according to any one of (1) to (7), wherein the polymer contains 50 to 99 parts by weight of the structural unit (I) and 1 to 50 parts by weight of the structural unit (II) relative to 100 parts by weight of the polymer; (9) A hydraulic composition for additive manufacturing, comprising the two-component additive according to any one of (1) to (8); (10) A method for producing a hydraulic composition for additive manufacturing, comprising: a first step of mixing a hydraulic material, water, and the first additive described in any one of (1) to (8); and a second step of mixing the mixture obtained in the first step with the second additive described in any one of (1) to (8) to obtain a hydraulic composition.

[0025] A two-component additive according to one embodiment of the present invention comprises a first additive and a second additive in a separated state. The two-component additive of this embodiment is used by mixing the first additive and the second additive with a hydraulic composition in separate steps. More specifically, the two-component additive of this embodiment is used by mixing a mixture containing a hydraulic material, water, and the first additive with the second additive. That is, the two-component additive of this embodiment brings the first additive and the second additive into contact when used. Therefore, the first additive and the second additive are kept separated so as not to come into contact with each other until use. For example, the first additive and the second additive may be kept packaged in separate containers, bags, etc.

[0026] According to the two-component additive of this embodiment, after mixing and stirring the hydraulic material, water, and first additive in a tank or the like, the resulting mixture has excellent pumpability when pumping through a pipe using compressed air or a pump, etc., and thus a hydraulic composition with excellent pumpability can be obtained. The pumpability can be evaluated by the funnel flow time measured in accordance with the examples described later, and the funnel flow time according to the examples described later is, for example, preferably 13 seconds or less, more preferably 12 seconds or less, even more preferably less than 12 seconds, and even more preferably 11 seconds or less.

[0027] Furthermore, after the mixture is pumped through the pipe, the hydraulic composition is discharged from a nozzle (discharge part) provided at the tip of the pipe and layered to form a target object. According to the two-component additive of this embodiment, the layering property of the hydraulic composition for additive manufacturing can be improved by mixing the second additive with the mixture extruded from the nozzle or by mixing the second additive with the mixture at the tip of the nozzle.

[0028] Here, improved buildability refers to the ability of a hydraulic composition, such as mortar or fresh concrete formed from the hydraulic composition, to build to a desired height and maintain the desired height before the hydraulic composition completely hardens. Specifically, for example, a high yield point, as described below, can be mentioned. The yield point is defined as the stress required for a material to change from elastic to plastic, and a high yield point can improve buildability. The additive of the present invention can increase the yield point of the hydraulic composition for additive manufacturing, thereby improving buildability. The yield point can be measured according to the examples described below. The yield point according to the examples described below is preferably 3,500 Pa or higher, more preferably 3,600 Pa or higher, even more preferably 3,800 Pa or higher, and even more preferably 4,000 Pa or higher.

[0029] (Additive Manufacturing) In this specification, "additive manufacturing" refers to a technology for manufacturing molded bodies of any shape by layering cross-sectional shapes based on 3D data without using specialized tools such as molds. It is also commonly called "3D printing," "three-dimensional modeling," or "rapid prototyping."

[0030] (Hydraulic composition for additive manufacturing) In the present invention, the term "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 may contain other cement admixtures in addition to the additive of the present invention. Examples of other cement admixtures that can be used include antifoaming agents, dispersants, and set retarders. Furthermore, cement admixtures such as glass fibers and metal fibers may be contained. Examples of hydraulic compositions include mortar and fresh concrete.

[0031] The hydraulic composition for additive manufacturing according to this embodiment preferably contains the two-component additive of the present invention in addition to the hydraulic composition. The hydraulic composition for additive manufacturing according to this embodiment preferably contains the first additive in the two-component additive of this embodiment in an amount of 0.01 to 1.0 wt %, more preferably 0.1 to 0.8 wt %, based on the cement ratio. The hydraulic composition for additive manufacturing according to this embodiment preferably contains the second additive in the two-component additive of this embodiment in an amount of 0.01 to 5.0 wt %, more preferably 0.1 to 1.0 wt %, based on the cement ratio.

[0032] In the hydraulic composition for layered manufacturing, the water-cement ratio is, for example, a water / cement ratio (weight ratio) of 0.1 to 0.65.

[0033] (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.

[0034] (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.

[0035] (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.

[0036] (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.

[0037] 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.

[0038] (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.

[0039] (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.

[0040] [First additive] The first additive includes a polymer (i.e., a copolymer) having structural units (I) and (II). The polymer contains 15 parts by weight or less of structural units derived from an alkyl ester of acrylic acid having 1 to 3 carbon atoms and / or structural units derived from a hydroxyalkyl ester of acrylic acid having 1 to 3 carbon atoms, based on 100 parts by weight of the polymer.

[0041] Here, the term "a polymer containing a structural unit derived from an alkyl ester of acrylic acid having 1 to 3 carbon atoms and / or a structural unit derived from a hydroxyalkyl ester of acrylic acid having 1 to 3 carbon atoms" encompasses "a polymer containing a structural unit derived from an alkyl ester of acrylic acid having 1 to 3 carbon atoms", "a polymer containing a structural unit derived from a hydroxyalkyl ester of acrylic acid having 1 to 3 carbon atoms", and "a polymer containing a structural unit derived from an alkyl ester of acrylic acid having 1 to 3 carbon atoms and a structural unit derived from a hydroxyalkyl ester of acrylic acid having 1 to 3 carbon atoms".

[0042] The polymer having the structural unit (I) and the structural unit (II) does not contain any structural units derived from an alkyl ester of acrylic acid having 1 to 3 carbon atoms and does not contain any structural units derived from a hydroxyalkyl ester of acrylic acid having 1 to 3 carbon atoms, or when the polymer contains structural units derived from an alkyl ester of acrylic acid having 1 to 3 carbon atoms and / or structural units derived from a hydroxyalkyl ester of acrylic acid having 1 to 3 carbon atoms, the amount of the structural units derived from an alkyl ester of acrylic acid having 1 to 3 carbon atoms and / or the structural units derived from a hydroxyalkyl ester of acrylic acid having 1 to 3 carbon atoms is 15 parts by weight or less per 100 parts by weight of the polymer.

[0043] Therefore, the first additive (i) comprises a polymer that does not contain structural units derived from an alkyl ester of acrylic acid having 1 to 3 carbon atoms and does not contain structural units derived from a hydroxyalkyl ester of acrylic acid having 1 to 3 carbon atoms, and comprises structural units (I) and structural units (II); or (ii) comprises a polymer that contains structural units (I) and structural units (II) and 15% by weight or less of structural units derived from an alkyl ester of acrylic acid having 1 to 3 carbon atoms and / or structural units derived from a hydroxyalkyl ester of acrylic acid having 1 to 3 carbon atoms. Specific combinations of the form (ii) include: (ii-1) a polymer containing structural units (I), structural units (II), and 15% by weight or less of structural units derived from an alkyl ester of acrylic acid having 1 to 3 carbon atoms; (ii-2) a polymer containing structural units (I), structural units (II), and 15% by weight or less of structural units derived from a hydroxyalkyl ester of acrylic acid having 1 to 3 carbon atoms; and (ii-3) a polymer containing structural units (I), structural units (II), and 15% by weight or less of structural units derived from an alkyl ester of acrylic acid having 1 to 3 carbon atoms and structural units derived from a hydroxyalkyl ester of acrylic acid having 1 to 3 carbon atoms.

[0044] In the two-component additive of this embodiment, the polymer having the structural units (I) and (II) contained in the first additive can improve the pumpability of the hydraulic composition, but it is difficult to maintain the lamination property of the hydraulic composition. Therefore, a method is generally known in which a post-additive is added immediately before discharge from a nozzle after pumping to improve the curing property of the hydraulic composition. The present inventors have found that a specific polymer can significantly improve the effect of the post-added second additive and improve the lamination property of the hydraulic composition. That is, in the two-component additive of this embodiment, when the polymer having the structural units (I) and (II) contained in the first additive does not contain, or contains 15 wt % or less of, structural units derived from alkyl esters of acrylic acid having 1 to 3 carbon atoms and / or structural units derived from hydroxyalkyl esters of acrylic acid having 1 to 3 carbon atoms, the lamination property of the hydraulic composition can be maintained or improved. For example, if the polymer having the structural unit (I) contained in the first additive contains more than 15% by weight of structural units derived from alkyl esters of acrylic acid having 1 to 3 carbon atoms and / or structural units derived from hydroxyalkyl esters of acrylic acid having 1 to 3 carbon atoms, even if the second additive is subsequently added to a hydraulic composition containing the first additive, the second additive will not promote hardening, resulting in poor lamination properties.

[0045] The mechanism by which the two-component additive of this embodiment can achieve improved pumpability and lamination properties is presumed to be as follows: Note that the following mechanism is based on presumption, and the correctness of this presumption does not affect the technical scope of the present invention.

[0046] When the polymer having structural units (I) and (II) contained in the first additive contains more than 15 wt% of structural units derived from alkyl esters of acrylic acid having 1 to 3 carbon atoms and / or structural units derived from hydroxyalkyl esters of acrylic acid having 1 to 3 carbon atoms, even if a post-additive is added, the post-additive does not function and lamination properties are not improved. This is thought to be because the structural units derived from alkyl esters of acrylic acid having 1 to 3 carbon atoms and / or structural units derived from hydroxyalkyl esters of acrylic acid having 1 to 3 carbon atoms hydrolyze to produce acrylic acid when kneaded with a hydraulic material. That is, the polymer contained in the first additive generates acrylic acid upon hydrolysis, and the amount increases over time. When mixed with the second additive, the polymer has an excessive dispersing effect, hindering the action of the second additive and preventing improvement in lamination properties.

[0047] The constitution of the first additive according to this embodiment will be explained below.

[0048] (Structural unit (I)) The polymer according to this embodiment has the following structural unit (I).

[0049] [ka]

[0050] In the above structural unit (I), X 1 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 from 2 to 100, 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.

[0051] Above X1 is preferably C=O or (CH2) p [p is an integer of 0 to 2], more preferably (CH2) p [p is 0 to 2 (i.e., p=0, 1, or 2)], and more preferably (CH2) p [p is 1 or 2] (when p=0, X in the structural unit (I) 1 The C at the top and the O at the bottom of the R 4 O is preferably an oxyalkylene group having 2 to 4 carbon atoms, and more preferably an oxyalkylene group having 2 carbon atoms.

[0052] Furthermore, from the viewpoint of the effects of the present invention, the above n may be 3 to 100, 3 to 90, 5 to 85, or 5 to 70, preferably 5 to 60, more preferably 5 to 55, even more preferably 5 to 50, still more preferably 5 to 50, particularly preferably 5 to 40, and most preferably 4 to 25. According to one embodiment, from the viewpoint of the effects of the present invention, n may be 3 to 60, 3 to 45, 3 to 30, 3 to 25, or 5 to 25. When n is equal to or greater than the lower limit, lamination properties are further improved, and when n is equal to or less than the upper limit, pumpability is improved and the polymer is easy to handle.

[0053] 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 3Among 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.

[0054] 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.

[0055] 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.

[0056] Examples of the alkoxypolyalkylene glycol monomethacrylate include methoxypolyethylene glycol-methacrylate and methoxypolyethylene glycol-polypropylene glycol-methacrylate, with methoxypolyethylene glycol-methacrylate being preferred.

[0057] Examples of the alkoxypolyalkylene glycol monoacrylate include methoxypolyethylene glycol-acrylate and methoxypolyethylene glycol-polypropylene glycol-acrylate.

[0058] An example of the phenoxypolyalkylene glycol monomethacrylate is phenoxypolyethylene glycol methacrylate.

[0059] Examples of the phenoxypolyalkylene glycol monoacrylate include phenoxypolyethylene glycol-acrylate and phenoxypolyethylene glycol-polypropylene glycol acrylate.

[0060] Examples of the polyalkylene glycol monomethacrylate include polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polyethylene glycol-polypropylene glycol monomethacrylate, polyethylene glycol-polytetramethylene glycol monomethacrylate, and polyethylene glycol-polybutylene glycol monomethacrylate.

[0061] Examples of the polyalkylene glycol monoacrylate include polyethylene glycol monoacrylate and polypropylene glycol monoacrylate.

[0062] Examples of the unsaturated polyalkylene glycol ether monomer include compounds in which 2 to 100 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. The alkylene oxide is preferably a compound obtained by adding 100 moles or less (preferably 5 to 60 moles) of alkylene oxide to 3-methyl-3-buten-1-ol, a compound obtained by adding 2 to 100 moles (preferably 5 to 60 moles) of alkylene oxide to hydroxybutyl vinyl ether, or a compound obtained by adding 2 to 100 moles (preferably 5 to 60 moles) of alkylene oxide to methallyl alcohol, and more preferably a compound obtained by adding 2 to 100 moles (preferably 5 to 60 moles) of alkylene oxide to 3-methyl-3-buten-1-ol. The alkylene oxide is preferably ethylene oxide, propylene oxide, or butylene oxide, and most preferably ethylene oxide.

[0063] (Structural unit (II)) The polymer according to this embodiment has the following structural unit (II).

[0064] [ka]

[0065] In the above structural unit (II), R 6 ~R 8 are the same or different and are a hydrogen atom, a methyl group, or a COOM 2 represents M 1 and M 2 is a hydrogen atom or a cationic species (preferably, from the viewpoint of the effect of the present invention, M 1 represents a cationic species). It goes without saying that different types of structural units (II) may be contained in the polymer.

[0066] The above R 6 ~R 8 are the same or different and are preferably a hydrogen atom, a methyl group or a COOM 2 and more preferably a hydrogen atom or a methyl group. Specific examples of the cationic species include lithium, sodium, potassium, magnesium, calcium, and aluminum, with sodium being preferred. The cationic species may be two or more types.

[0067] 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, 3-methylcrotonic acid, maleic acid, fumaric 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 acrylic acid and / or methacrylic acid, and particularly preferably acrylic acid. 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.

[0068] (Structural units derived from alkyl esters of acrylic acid having 1 to 3 carbon atoms, structural units derived from hydroxyalkyl esters of acrylic acid having 1 to 3 carbon atoms) The polymer having the structural units (I) and (II) contained in the first additive does not contain structural units derived from an alkyl ester of acrylic acid having 1 to 3 carbon atoms and / or structural units derived from a hydroxyalkyl ester of acrylic acid having 1 to 3 carbon atoms, or, when the polymer contains structural units derived from an alkyl ester of acrylic acid having 1 to 3 carbon atoms and / or structural units derived from a hydroxyalkyl ester of acrylic acid having 1 to 3 carbon atoms, the polymer contains 15 parts by weight or less of the structural units derived from an alkyl ester of acrylic acid having 1 to 3 carbon atoms and / or the structural units derived from a hydroxyalkyl ester of acrylic acid having 1 to 3 carbon atoms, based on 100 parts by weight of the polymer.

[0069] Examples of the alkyl group having 1 to 3 carbon atoms include linear or branched alkyl groups having 1 to 3 carbon atoms, such as methyl, ethyl, n-propyl, and isopropyl.

[0070] Examples of C1-C3 alkyl esters of acrylic acid include methyl acrylate, ethyl acrylate, n-propyl acrylate, and isopropyl acrylate. Examples of C1-C3 hydroxyalkyl esters of acrylic acid include hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxy n-propyl acrylate, and hydroxyisopropyl acrylate.

[0071] (Other structural units) The polymer according to this embodiment may contain structural units other than the structural units (I) and (II) as the remainder.

[0072] Examples of the remaining structural units include structural units derived from unsaturated monomers having a sulfonic acid group and / or a salt thereof, structural units derived from unsaturated monomers having a phosphate group and / or a salt thereof, and structural units derived from (meth)acrylates (excluding structural units derived from C1-3 alkyl esters of acrylic acid and / or structural units derived from C1-3 hydroxyalkyl esters of acrylic acid). Among these, from the viewpoint of improving adsorption to hydraulic compositions such as cement, the polymer according to this embodiment 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 thereof, and structural units derived from unsaturated monomers having a phosphate group and / or a salt thereof, and more preferably contains structural units derived from unsaturated monomers having a sulfonic acid group and / or a salt thereof.

[0073] 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.

[0074] The polymer according to this embodiment may contain the structural unit (I), the structural unit (II), and further the structural unit derived from the unsaturated monomer having a sulfonic acid group and / or a salt thereof.

[0075] [ka]

[0076] In the structural unit (III), p is an integer of 1 to 4, q and r are the same or different and are integers of 0 to 100 (preferably an integer of 0 to 100, more preferably an integer of 0 to 20), and R 9 ,R 10 is 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.

[0077] Examples of the unsaturated monomer having a phosphoric acid 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.

[0078] Examples of the structural units derived from (meth)acrylates (excluding structural units derived from C1-3 alkyl esters of acrylic acid and / or structural units derived from C1-3 hydroxyalkyl esters of acrylic acid) include structural units derived from C4-20 alkyl esters of acrylic acid, structural units derived from C1-20 alkyl esters of methacrylic acid, structural units derived from C4-20 hydroxyalkyl esters of acrylic acid, and structural units derived from C1-20 hydroxyalkyl esters of methacrylic acid.

[0079] Examples of the alkyl group having 1 to 20 carbon atoms include linear or branched alkyl groups having 1 to 3 carbon atoms, such as methyl, ethyl, n-propyl, and isopropyl, and linear or branched alkyl groups such as n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-tetradecyl, and n-octadecyl.

[0080] Examples of the monomer of the (meth)acrylate-derived structural unit (excluding structural units derived from C1-3 alkyl esters of acrylic acid and / or structural units derived from C1-3 hydroxyalkyl esters of acrylic acid) include alkyl (meth)acrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; and hydroxyalkyl (meth)acrylates such as hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl (meth)acrylate. The polymer according to this embodiment may contain the above structural unit (I), the above structural unit (II), and further the above (meth)acrylate-derived structural unit (excluding structural units derived from C1-3 alkyl esters of acrylic acid and / or structural units derived from C1-3 hydroxyalkyl esters of acrylic acid).

[0081] (Polymer structure) In the two-component additive according to this embodiment, the polymer having the structural unit (I) and the structural unit (II) contained in the first additive preferably contains 1 to 99 parts by weight, and more preferably 1 to 98 parts by weight, of the structural unit (I) relative to 100 parts by weight of the polymer. In the two-component additive according to this embodiment, the polymer having the structural unit (I) and the structural unit (II) contained in the first additive preferably contains 1 to 50 parts by weight, and more preferably 2 to 50 parts by weight, of the structural unit (II) relative to 100 parts by weight of the polymer. In the two-component additive according to this embodiment, the polymer having the structural unit (I) and the structural unit (II) contained in the first additive preferably contains 50 to 99 parts by weight (preferably 50 to 98 parts by weight) of the structural unit (I) and 1 to 50 parts by weight (preferably 2 to 50 parts by weight) of the structural unit (II) relative to 100 parts by weight of the polymer.

[0082] When the polymer contained in the first additive contains structural units derived from an alkyl ester of acrylic acid having 1 to 3 carbon atoms and / or structural units derived from a hydroxyalkyl ester of acrylic acid having 1 to 3 carbon atoms, the polymer preferably contains less than 15 parts by weight of the structural units derived from an alkyl ester of acrylic acid having 1 to 3 carbon atoms and / or the structural units derived from a hydroxyalkyl ester of acrylic acid having 1 to 3 carbon atoms, per 100 parts by weight of the polymer, more preferably 13 parts by weight or less, even more preferably less than 10 parts by weight, particularly preferably 8 parts by weight or less, and most preferably 5 parts by weight or less. When the polymer contained in the first additive contains structural units derived from an alkyl ester of acrylic acid having 1 to 3 carbon atoms and / or structural units derived from a hydroxyalkyl ester of acrylic acid having 1 to 3 carbon atoms, the structural units derived from an alkyl ester of acrylic acid having 1 to 3 carbon atoms and / or the structural units derived from a hydroxyalkyl ester of acrylic acid having 1 to 3 carbon atoms may be contained in an amount of 0.1 part by weight or more, 0.5 part by weight or more, or 1 part by weight or more (for example, 1.0 part by weight or more) relative to 100 parts by weight of the polymer. When the polymer contained in the first additive contains structural units derived from an alkyl ester of acrylic acid having 1 to 3 carbon atoms and / or structural units derived from a hydroxyalkyl ester of acrylic acid having 1 to 3 carbon atoms, the structural units derived from an alkyl ester of acrylic acid having 1 to 3 carbon atoms and / or the structural units derived from a hydroxyalkyl ester of acrylic acid having 1 to 3 carbon atoms may be contained in an amount of less than 15.0 parts by weight, 13.0 parts by weight or less, less than 10.0 parts by weight, 8.0 parts by weight or less, or 0.1 parts by weight or more and 5.0 parts by weight or less, relative to 100 parts by weight of the polymer.

[0083] Thus, according to one embodiment, the two-component additive according to this aspect contains, relative to 100 parts by weight of the polymer having the structural unit (I) and the structural unit (II) contained in the first additive, 50 to 99 parts by weight (e.g., 50.0 to 99.0 parts by weight) of the structural unit (I), 1 to 50 parts by weight (e.g., 1.0 to 50.0 parts by weight) of the structural unit (II), and 15 parts by weight or less (e.g., 15.0 parts by weight or less) of a structural unit derived from an alkyl ester of acrylic acid having 1 to 3 carbon atoms and / or a structural unit derived from a hydroxyalkyl ester of acrylic acid having 1 to 3 carbon atoms. According to one embodiment, the two-component additive according to this aspect contains, relative to 100 parts by weight of the polymer having the structural unit (I) and the structural unit (II) contained in the first additive, 50 to 99 parts by weight (e.g., 50.0 to 99.0 parts by weight) of the structural unit (I), 1 to 50 parts by weight (e.g., 1.0 to 50.0 parts by weight) of the structural unit (II), and 10 parts by weight or less (e.g., 10.0 parts by weight or less) of a structural unit derived from an alkyl ester of acrylic acid having 1 to 3 carbon atoms and / or a structural unit derived from a hydroxyalkyl ester of acrylic acid having 1 to 3 carbon atoms.

[0084] The polymer according to the present invention preferably contains 10.0 to 98.0 parts by weight, more preferably 30.0 to 95.0 parts by weight, even more preferably 50.0 to 90.0 parts by weight, and even more preferably 60.0 to 88.0 parts by weight of the structural unit (I) relative to 100 parts by weight of the polymer. The polymer according to the present invention also preferably contains 1.0 to 50.0 parts by weight, more preferably 2.0 to 45.0 parts by weight, even more preferably 2.0 to 40.0 parts by weight, and even more preferably 2.0 to 35.0 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 15.0 parts by weight relative to 100 parts by weight of the polymer according to the present invention.

[0085] The polymer according to this embodiment 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 1.0 to 10.0 parts by weight per 100 parts by weight of the polymer. The remaining structural units may be 15 parts by weight or less of structural units derived from an alkyl ester of acrylic acid having 1 to 3 carbon atoms and / or structural units derived from a hydroxyalkyl ester of acrylic acid having 1 to 3 carbon atoms per 100 parts by weight of the polymer. Furthermore, in addition to containing the structural unit (I) and the structural unit (II), it is also a preferred embodiment that the polymer according to this embodiment 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.

[0086] According to one embodiment, in the two-component additive according to this aspect, the polymer (i.e., copolymer) having the structural unit (I) and the structural unit (II) contained in the first additive contains 50 to 98 parts by weight (e.g., 50.0 to 98.0 parts by weight) of the structural unit (I) and 1 to 50 parts by weight (e.g., 1.0 to 50.0 parts by weight) of the structural unit (II) relative to 100 parts by weight of the polymer, and does not contain any structural unit derived from an alkyl ester of acrylic acid having 1 to 3 carbon atoms and / or any structural unit derived from a hydroxyalkyl ester of acrylic acid having 1 to 3 carbon atoms.

[0087] The polymer of the present invention preferably contains structural units (I) and (II) and structural units derived from unsaturated monomers having a sulfonic acid group and / or a salt thereof (including those consisting of or essentially consisting of structural units (I) and (II) 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 structural units (I), (II), 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.

[0088] The weight-average molecular weight of the polymer according to this embodiment, as determined 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. When the weight-average molecular weight of the polymer is equal to or less than the upper limit, water solubility is improved and the polymer can be easily added to water, and when the weight-average molecular weight is equal to or greater than the lower limit, the effects of the present invention can be further enhanced.

[0089] (Polymerization method) The polymerization for obtaining the polymer according to the present invention may be carried out in the presence of a polymerization initiator.

[0090] 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.

[0091] The polymerization initiators may be used alone or in combination of two or more.

[0092] 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.

[0093] The method for adding the polymerization initiator is not particularly limited, but examples thereof include batch addition, divided addition, and continuous dropwise addition.

[0094] 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.

[0095] 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).

[0096] [Second additive] The second additive is one or more post-additives selected from the group consisting of accelerators and thickeners, and is added to the mixture after the mixture containing the first additive, the hydraulic material, and water is obtained.

[0097] The accelerator used as the second additive is preferably one or more salt compounds selected from the group consisting of sulfates, nitrates, nitrites, thiocyanates, silicates, chlorides, and hydroxides. The accelerator used as the second additive may also be one or more salt compounds selected from the group consisting of alkali metal salts and alkaline earth metal salts. Examples of the salt compounds include sodium chloride, calcium chloride, aluminum hydroxide, sodium sulfate, potassium sulfate, aluminum sulfate, aluminum potassium sulfate, sodium silicate, calcium nitrate, calcium nitrite, sodium thiocyanate, and calcium thiocyanate. Of these, aluminum sulfate, sodium thiocyanate, calcium chloride, and calcium nitrate are preferred, aluminum sulfate, sodium thiocyanate, and calcium nitrate are more preferred, and aluminum sulfate is particularly preferred. These may be used alone or in combination of two or more.

[0098] The amount of the accelerator is 0.01 to 5.0 parts by weight, preferably 0.05 to 4.5 parts by weight, more preferably 0.1 to 4.0 parts by weight, even more preferably 0.2 to 3.0 parts by weight, and particularly preferably 0.3 to 2.0 parts by weight, relative to 100 parts by weight of cement. When the amount of the accelerator is within the above range, the lamination property of the hydraulic composition is improved.

[0099] The thickener used as the second additive is preferably one or more selected from the group consisting of cellulose-based thickeners, polycarboxylic acid-based thickeners, glycol-based thickeners, polyvinyl alcohol-based thickeners, clay-based thickeners, and thickening polysaccharides.

[0100] Examples of cellulose-based thickeners include cellulose, methylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, and derivatives thereof (e.g., hydroxypropylmethylether). Examples of polycarboxylic acid-based thickeners include polyacrylamides (e.g., acrylamide homopolymers, acrylamide copolymers), polyacrylic acid esters, polyacrylates (e.g., sodium polyacrylate), polycarboxylic acid ether compounds, and derivatives thereof. Examples of glycol-based thickeners include polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene polyoxypropylene glycol, and derivatives thereof. Examples of polyvinyl alcohol-based thickeners include polyvinyl alcohol and derivatives thereof. Examples of clay-based thickeners include bentonite and montmorillonite. Examples of thickening polysaccharides include thickening polysaccharides derived from natural materials such as guar gum, xanthan gum, diutan gum, welan gum, carrageenan, locust bean gum, tara gum, pectin, gellan gum, alginates (e.g., sodium alginate), and derivatives thereof. Among these, cellulose-based thickeners, polycarboxylic acid-based thickeners, glycol-based thickeners, and thickening polysaccharides are preferred, polycarboxylic acid-based thickeners and glycol-based thickeners are more preferred, polycarboxylic acid-based thickeners are even more preferred, and polycarboxylic acid ether compounds are particularly preferred. These may be used alone or in combination of two or more.

[0101] The polycarboxylic acid ether compound is a polymer obtained by polymerizing a monomer component containing an unsaturated carboxylic acid (salt). Examples of the polycarboxylic acid ether compound include a copolymer of polyethylene glycol monoallyl ether and maleic acid (salt); a copolymer obtained by copolymerizing a monomer component consisting of polyalkylene glycol (meth)allyl ether or polyalkylene glycol (meth)acrylate, an unsaturated sulfonate, and a (meth)acrylate; a copolymer of polyalkylene glycol vinyl ether or polyalkylene glycol (meth)allyl ether and (meth)acrylic acid (salt); a copolymer of polyalkylene glycol (meth)acrylate and (meth)acrylic acid (salt); a copolymer obtained by polymerizing a monomer component containing an unsaturated carboxylic acid (salt) and a monomer having a polyalkylene glycol chain as essential components. Here, as the polycarboxylic acid ether compound, an additive containing an emulsion containing a polymer having an acid value of 30 mgKOH / g or more (hereinafter referred to as "polymer for emulsion" to distinguish it from the polymer contained in the first additive) disclosed in the specification of WO2023 / 162981 is preferably used. The polymer for emulsion, emulsion, and additive containing the same that are preferably used in the two-component additive according to this embodiment will be described below.

[0102] <Polymers for emulsions> The emulsion polymer 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 emulsion polymer, in order of preference, are 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.

[0103] The acid value of the polymer for emulsion can be determined, for example, by measuring the acid value per gram of polymer solids (mgKOH / g) using an automatic titrator (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.) in accordance with JIS K0070:1992.

[0104] (Structural unit having an acidic functional group) The polymer for emulsion preferably contains one or more structural units having an acidic functional group (also referred to as an acid group). When the polymer for emulsion contains one or more structural units having an acidic functional group, it becomes easier to control the acid value of the polymer for emulsion 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.

[0105] [ka]

[0106] A specific example of the structural unit having the above acidic functional group is the structural unit represented by the above formula (IV).

[0107] In the above formula (IV), R 11 ~R 14 One or more of R 11 ~R 14 are the same or different and are a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms.

[0108] In the above formula (IV), preferably R 11 ~R 14 One or two of the groups are acidic functional groups, and more preferably one of the groups is an acidic functional group.

[0109] R other than the above acidic functional groups 11 ~R 14Preferably, two or more of the groups are hydrogen atoms, more preferably all of the groups are hydrogen atoms, or two of the groups 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.

[0110] The structural unit represented by the formula (IV) 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 (IV) may be present alone or in combination with two or more different types.

[0111] In this specification, the term "acidic functional group" refers to an acidic functional group that is not neutralized unless otherwise specified.

[0112] (hydrophobic structural unit) The emulsion polymer 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 the hydraulic composition. 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 hydroxyl group.

[0113] [ka]

[0114] A specific example of the hydrophobic structural unit is a structural unit represented by the above formula (V). 15 ~R 18 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 3 (M 3 is a monovalent hydrocarbon group having 1 to 8 carbon atoms, and preferably R 15 ~R 18 One of them is -COOM 3 and the remaining R 15 ~R 18 is a hydrogen atom or an unsubstituted monovalent hydrocarbon group having 1 to 4 carbon atoms (preferably a methyl group), and more preferably R 15 ~R 18 One of them is -COOM 3 and the remaining R 15 ~R 18 is a hydrogen atom.

[0115] The above M 3is 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.

[0116] The structural unit represented by the above formula (V) 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 include methyl acrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate, and particularly preferably, ethyl acrylate.

[0117] [ka]

[0118] A specific example of the hydrophobic structural unit is a structural unit represented by the above formula (VI). 2 is C=O or (CH2) p [p is an integer from 0 to 5], and R 22 is an (unsubstituted) divalent hydrocarbon group having 2 to 8 carbon atoms (wherein R 22 may be the same or different), m is an integer of 5 to 300, and R 23 is a hydrogen atom or an (unsubstituted) monovalent hydrocarbon group having 1 to 18 carbon atoms, and the remaining R 19 ~R 21 are the same or different and are a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms.

[0119] The above p is preferably an integer of 0 to 2, and more preferably 0. 2 is preferably C=O or (CH2)2, more preferably C=O. 22 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. 22 may be the same or different, for example, R 22 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 23 is preferably a hydrogen atom or a monovalent hydrocarbon having 1 to 18 carbon atoms, and more preferably hydrogen, CH3, or a stearyl group. 23 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. 19 ~R 21 is preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and more preferably R 19 ~R 21 one of R is a monovalent hydrocarbon group having 1 to 4 carbon atoms (preferably a methyl group), and the remaining R 19 ~R 21 is a hydrogen atom.

[0120] The structural unit represented by the above formula (VI) 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.

[0121] 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.

[0122] An example of the phenoxypolyalkylene glycol monomethacrylate is phenoxypolyethylene glycol methacrylate.

[0123] An example of the alkoxypolyalkylene glycol monoacrylate is methoxypolyethylene glycol acrylate.

[0124] Examples of the phenoxy polyalkylene glycol monoacrylate include nonylphenoxy polypropylene glycol acrylate and nonylphenoxy polyethylene glycol polypropylene glycol acrylate.

[0125] 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.

[0126] Examples of the polyalkylene glycol monoacrylate include polyethylene glycol monoacrylate and polypropylene glycol monoacrylate.

[0127] 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).

[0128] (Other structural units) The emulsion polymer may contain structural units other than those described above as the remainder, and 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 emulsion polymer.

[0129] (Configuration of polymer for emulsion) The polymer for emulsion 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) per 100 parts by weight of the polymer for emulsion. By containing the acidic functional group in such a range, it is easy to control the acid value of the polymer for emulsion within an appropriate range.

[0130] The polymer for emulsion preferably contains the hydrophobic structural unit (VI) in an amount of 1.0 to 40.0 parts by weight, more preferably 2.0 to 30.0 parts by weight, per 100 parts by weight of the polymer for emulsion. The polymer for emulsion preferably contains the hydrophobic structural unit (VI) in an amount of 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, per 100 parts by weight of the polymer for emulsion. By including the hydrophobic structural unit (VI) in such a range, it is easy to control the emulsion form.

[0131] The polymer for emulsion 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 (IV) having an acidic functional group, per 100 parts by weight of the polymer for emulsion. The polymer for emulsion 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 (V). The polymer for emulsion 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 (VI), per 100 parts by weight of the polymer for emulsion. The polymer for emulsion preferably contains 10.0 to 90.0 parts by weight of the hydrophobic structural unit, more preferably 40.0 to 90.0 parts by weight, and even more preferably 40.0 to 80.0 parts by weight, per 100 parts by weight of the polymer for emulsion. By containing the hydrophobic structural unit in such a range, it is easy to control the emulsion form.

[0132] The polymer for emulsion preferably contains at least the structural unit (IV) having an acidic functional group and the hydrophobic structural unit (V). The total content of the structural unit (IV) having an acidic functional group and the hydrophobic structural unit (V) in the polymer for emulsion is preferably 60% by weight or more, more preferably 65% ​​by weight or more.

[0133] The polymer for emulsions is also preferably one consisting essentially of the structural unit (IV) and the hydrophobic structural unit (V) (for example, 95.0 parts by weight or more of (IV) and (V) per 100 parts by weight of all structural units). When the polymer for emulsions is one consisting essentially of the structural unit (IV) and the hydrophobic structural unit (V), the content of the structural unit (IV) having an acidic functional group is preferably 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, per 100 parts by weight of the polymer for emulsions. The content of the hydrophobic structural unit (IV) is also preferably 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, per 100 parts by weight of the polymer for emulsions. Furthermore, when the emulsion polymer contains a structural unit (VI) having an acidic functional group and a hydrophobic structural unit (V), and does not contain a hydrophobic structural unit (VI), the weight ratio of the structural unit (IV) having an acidic functional group: the hydrophobic structural unit (V) is preferably 1:99 to 80:20, more preferably 3:97 to 60:40, and even more preferably 5:95 to 50:50.

[0134] Yet another preferred embodiment is a polymer for emulsions containing a structural unit (IV) having an acidic functional group, a hydrophobic structural unit (V), and a hydrophobic structural unit (VI), 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 (IV), (V), and (VI) per 100 parts by weight of all structural units). When the polymer for emulsion contains a structural unit (IV) having an acidic functional group, a hydrophobic structural unit (V), and a hydrophobic structural unit (VI), the polymer contains the structural unit (IV) 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 for emulsion; the polymer contains the hydrophobic structural unit (V) 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 for emulsion; and the polymer contains the hydrophobic structural unit (VI) 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 for emulsion.

[0135] Some examples of emulsion polymers include (i) polymerized using acrylic acid or methacrylic acid, (ii) copolymerized using alkyl acrylate (having 1 to 8 carbon atoms) in addition to (i), and (iii) copolymerized using a monomer containing a polyalkylene glycol group or the like in addition to (i) and (ii). Among these, the copolymerized using alkyl acrylate (having 1 to 8 carbon atoms) in addition to (i) and the copolymerized using a monomer containing a polyalkylene glycol group or the like in addition to (i) and (ii) are preferred because they further enhance the effects of the present invention.

[0136] The weight-average molecular weight of the emulsion polymer is, for example, 10,000 to 10,000,000, preferably 20,000 to 8,000,000, more preferably 30,000 to 6,000,000, even 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. The weight-average molecular weight can be measured, for example, by the method described in the Examples.

[0137] The glass transition temperature of the emulsion polymer is, from the viewpoint of film-forming properties (change in emulsion shape (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 emulsion 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 that constitute the emulsion 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 (wt%) 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].

[0138] The pH of the emulsion polymer is, for example, 2.0 to 6.0, more preferably 2.0 to 5.0, and even more preferably 2.0 to 4.0, as a 10.0 wt % aqueous solution or dispersion at 25.0° C. The aqueous solution or dispersion can be prepared by any known appropriate method, such as dissolving or dispersing the emulsion polymer in distilled water to a predetermined concentration.

[0139] <Emulsion containing emulsion polymer> An emulsion containing an emulsion polymer is one in which the emulsion polymer is covered with an emulsifier to form particles (micelles).

[0140] 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.

[0141] Examples of dispersion media for emulsions include water, oil, alcohol, etc., with water being preferred. The solid content (polymer for emulsion and emulsifier) ​​is 1.0 to 80.0 wt %, preferably 10.0 to 50.0 wt %, and more preferably 20.0 to 40.0 wt %, based on the total weight of the emulsion.

[0142] The viscosity of the emulsion was measured at a shear rate of 10 s at room temperature (20-25°C) when adjusted to a concentration of 25% by weight. -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.

[0143] 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.

[0144] The average particle size of the particles (micelles) in the emulsion (emulsion particles) 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) using a dynamic light scattering method.

[0145] 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 weight, preferably 1.0 to 5.0% by weight, based on the total weight of the emulsion polymer contained therein.

[0146] 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.

[0147] Furthermore, as the emulsifier, an emulsifier having a polymerizable group, so-called reactive emulsifier, may be used.

[0148] 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.

[0149] 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 weight or less, or 3% by weight or less, based on the solid content of the emulsion.

[0150] (Method for producing emulsion) The method for producing the emulsion containing the polymer for emulsion is not particularly limited. For example, the emulsion may be produced by emulsion polymerization of the monomer components that are the raw materials for the polymer for emulsion in a solvent.

[0151] 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 weight or more (up to 100% by weight), preferably 98% by weight or more, or 99% by weight or more. One or more solvents may be used in combination.

[0152] 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.

[0153] 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.

[0154] The amount of the solvent may be appropriately determined taking into consideration the amount of nonvolatile matter contained in the resulting emulsion.

[0155] The polymerization may be carried out in the presence of a polymerization initiator.

[0156] 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.

[0157] The polymerization initiators may be used alone or in combination of two or more.

[0158] 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.

[0159] The method for adding the polymerization initiator is not particularly limited, but examples thereof include batch addition, divided addition, and continuous dropwise addition.

[0160] The polymerization reaction may be carried out, as 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, etc.

[0161] 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).

[0162] As described above, according to one embodiment, the emulsion polymer having an acid value of 30 mgKOH / g or more is a polycarboxylic acid ether compound and may be a polycarboxylic acid thickener. An emulsion containing a polymer (emulsion polymer) having an acid value of 30 mgKOH / g or more is preferably used as the second additive of the two-part additive according to this embodiment. That is, according to one embodiment, the second additive in the two-part additive according to this embodiment is an additive containing an emulsion containing a polymer having an acid value of 30 mgKOH / g or more.

[0163] The amount of the thickener is 0.0005 to 2.0 parts by weight, preferably 0.001 to 1.0 part by weight, more preferably 0.005 to 0.5 parts by weight, even more preferably 0.008 to 0.3 parts by weight, and particularly preferably 0.01 to 0.1 part by weight, relative to 100 parts by weight of cement. If the amount of the thickener is within the above range, the lamination property of the hydraulic composition is improved.

[0164] According to one embodiment, the two-component additive according to this aspect is a two-component additive used in a hydraulic composition for additive manufacturing, comprising a first additive and a second additive, wherein the first additive and the second additive are in a separated state, and the first additive comprises a copolymer having a structural unit (I) and a structural unit (II), wherein the copolymer contains 50 to 99 parts by weight (e.g., 50.0 to 99.0 parts by weight) of the structural unit (I) and 1 to 50 parts by weight (e.g., 1.0 to 50.0 parts by weight) of the structural unit (II) relative to 100 parts by weight of the copolymer; and the copolymer contains 15 parts by weight or less (e.g., 15 parts by weight or less) of a structural unit derived from an alkyl ester of acrylic acid having 1 to 3 carbon atoms and / or a structural unit derived from a hydroxyalkyl ester of acrylic acid having 1 to 3 carbon atoms. The second additive is one or more post-additives selected from the group consisting of accelerators and thickeners; the accelerator is one or more salt compounds selected from the group consisting of sulfates, nitrates, nitrites, thiocyanates, silicates, chlorides, and hydroxides (preferably sulfates, more preferably aluminum sulfate); the thickener is one or more selected from the group consisting of cellulose-based thickeners, polycarboxylic acid-based thickeners, glycol-based thickeners, polyvinyl alcohol-based thickeners, clay-based thickeners, and thickening polysaccharides (preferably polycarboxylic acid-based thickeners, more preferably polycarboxylic acid polyether-based compounds, even more preferably an additive containing an emulsion containing a polymer having an acid value of 30 mgKOH / g or more), and it is a two-component additive.

[0165] The second additive is preferably added immediately before the hydraulic composition, such as mortar or fresh concrete for additive manufacturing, is discharged from the nozzle.

[0166] (Method for producing 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 a method for producing the hydraulic composition for additive manufacturing include a method for producing a hydraulic composition for additive manufacturing, which includes: (a) a first step of mixing a hydraulic material, water, and a first additive; and (b) a second step of mixing a second additive with the mixture obtained in the first step to obtain a hydraulic composition.

[0167] In the above-mentioned manufacturing method, steps (a) and (b) are carried out independently, with step (b) being carried out after step (a). In steps (a) and (b), additives other than the first additive and the second additive (e.g., dispersants, antifoaming agents) may be added as needed. The hydraulic material, water, and first additive may be added sequentially and stirred, or may be added all at once and stirred. The order in which the hydraulic material, water, and first additive are added is not particularly important. In this case, the dispersant and antifoaming agent may be added together with the first additive, or may be added separately.

[0168] For example, in step (a), when producing a hydraulic composition for additive manufacturing, the first additive, hydraulic material, other cement admixtures, and water may be mixed at once, or the first additive and hydraulic material may be mixed together and then the other cement admixtures and water may be mixed, or the hydraulic material, other cement admixtures, and water may be mixed together and then the first additive may be added, or water and the first additive may be mixed together and then the hydraulic material may be added.

[0169] In the step (b), the second additive may be added as an accelerator and / or thickener as is, or may be added after being dispersed or dissolved in a dispersion medium such as water. For example, when the second additive is in the form of an emulsion, the emulsion may be further diluted with water or the like before being added. The stirring time in the step (b) is appropriately set to a time that allows uniform mixing and is as short as possible, and is, for example, 3 to 180 seconds.

[0170] After step (b) in the manufacturing method, it is desirable that the fresh concrete be layered on top of another fresh concrete immediately (for example, within 0 to 300 seconds after step (b)).

[0171] <Layered manufactured object and layered manufacturing method> The hydraulic composition of this embodiment 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 this embodiment.

[0172] Another embodiment is a method for producing a layered object using the hydraulic composition of the above embodiment.

[0173] A method for producing an additive manufacturing object using a hydraulic composition for additive manufacturing (additive manufacturing method) is not particularly limited, and may include, for example, the steps of: pumping a composition (mixture) containing a hydraulic material, water, and a first additive (optionally containing aggregate and other additives) to the nozzle tip of a 3D printer using compressed air or a pump, extruding the pumped composition (mixture) from the nozzle, adding a second additive from a separate line, and further mixing to prepare a hydraulic composition for additive manufacturing, and laminating the composition to form an additive manufacturing object; or, for example, the steps of pumping a composition (mixture) containing a hydraulic material, water, and a first additive (optionally containing aggregate and other additives) to the nozzle tip of a 3D printer using compressed air or a pump, adding a second additive 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.

[0174] A nozzle (discharge part) is usually provided at the tip of the pressure-transfer pipe for the hydraulic composition for additive manufacturing. The diameter of the nozzle is not particularly limited, but may be appropriately set depending on the size of the aggregate used and the width over which the hydraulic composition for additive manufacturing is to be layered. For example, if the size of the aggregate 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, and a brim may be provided around the nozzle to impart smoothness to the surface of the discharged hydraulic composition.

[0175] When building a structure by layering the hydraulic composition for additive manufacturing dispensed from a nozzle, the hydraulic composition for additive manufacturing may be moved vertically or horizontally. 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 three-dimensional data created by a computer at a predetermined thickness to create two-dimensional slice data, discharging the hydraulic 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 two-dimensional slice data, and then moving the nozzle vertically to repeatedly layer and build the structure. The nozzle movement speed is not particularly limited and can be varied depending on the width of the layer. [Example]

[0176] The effects of the present invention will be explained using the following examples and comparative examples. In the examples, the units "parts" and "%" are sometimes used, but unless otherwise specified, they represent "parts by weight" or "% by weight." Unless otherwise specified, each operation is carried out at room temperature (25°C).

[0177] [Production Example 1] A glass reaction vessel equipped with a Dimroth condenser, a stirrer with Teflon (registered trademark) stirring blades and stirring seal, a nitrogen inlet tube, and a temperature sensor was charged with 161.8 parts of a product obtained by adding ethylene oxide to the hydroxyl groups of 3-methyl-3-buten-1-ol (isoprenol) (average number of moles of ethylene oxide added: 10) (hereinafter referred to as IPN-10), 1.06 parts of acrylic acid, 12.79 parts of hydrogen peroxide (5 wt% aqueous solution), and 32.84 parts of ion-exchanged water, and the reaction solution in the reactor was heated to 58°C while stirring at 250 rpm and introducing nitrogen at a rate of 200 mL / min. Next, a mixed solution consisting of 52.08 parts acrylic acid and 52.08 parts ion-exchanged water was added dropwise to the reaction solution in the reactor over 3 hours. Simultaneously, a mixed solution consisting of 0.77 parts L-ascorbic acid, 1.66 parts 3-mercaptopropionic acid, and 21.93 parts ion-exchanged water was added dropwise over 3 hours and 30 minutes. After the completion of the addition, the temperature was maintained at 58°C for 1 hour to complete the polymerization reaction. The reaction solution in the reactor was then neutralized with aqueous sodium hydroxide solution to obtain a polymer. The weight-average molecular weight (Mw) of the obtained polymer was 12,000.

[0178] 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 materials for creating calibration curves: 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: Created using a cubic equation based on the Mw values ​​and elution times of the above standard materials. -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.

[0179] [Production Examples 2 to 9 and Comparative Production Examples 1 to 4] Production Examples 2 to 9 and Comparative Production Examples 1 to 4 were produced in the same manner as Production Example 1, except that the types and amounts of monomers and the amount of mercaptopropionic acid in Production Example 1 were changed as shown in the following Table 1. The molecular weight of the polymer was adjusted by appropriately changing the amount of 3-mercaptopropionic acid added during polymerization.

[0180] [Production Example 10] A flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser was charged with 453 parts of deionized water and 64 parts of a 20 wt % aqueous solution of an emulsifier (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Hitenol LA-10). A pre-emulsion consisting of 30 parts of deionized water, 32 parts of a 20 wt % aqueous solution of an emulsifier (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Hitenol LA-10), 322 parts of ethyl acrylate, 234 parts of methacrylic acid, and 832 parts of a 10 wt % aqueous solution of methyl polyethylene glycol (90) monomethacrylate (NOF Corporation, trade name: Blemmer PME-4000) was prepared in the dropping funnel. 73 parts of the pre-emulsion was added to the flask, and the temperature was raised to 72°C while slowly blowing in nitrogen gas. Polymerization was initiated by adding 2.3 parts of a 5.0 wt % aqueous solution of sodium hydrogen sulfite and 8 parts of a 1.0 wt % aqueous solution of ammonium persulfate to the flask. Next, the remainder of the pre-emulsion for dropping and 144 parts of a 1.0 wt % aqueous solution of ammonium persulfate were added dropwise uniformly into 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 liquid 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 wt %.

[0181] 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% by weight, and the resulting liquid was subjected to a shear rate of 10 s -1 The viscosity of the emulsion was 33 mPa·s at room temperature. The emulsion viscosity was 33 mPa·s and the pH of the emulsion was 2.6. The weight average molecular weight of the polymer contained in the emulsion was 400,000 and the acid value of the polymer was 231 mgKOH / g. These physical properties were measured by the following methods.

[0182] <Particle size> The average particle size of emulsion particles refers to 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.

[0183] <Solid content (non-volatile content)> The solid content of the emulsion is determined 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, using the formula: nonvolatile content in emulsion (% by weight) = ([weight of residue] ÷ [1 g of emulsion]) × 100 (%).

[0184] <Method for measuring molecular weight of polymer in emulsion> 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).

[0185] <ph> The pH was measured at 25°C using a pH meter (LAQUA, manufactured by Horiba Ltd.) in accordance with JIS Z8802:2011.

[0186] <tg> The glass transition temperature of a resin is calculated using the glass transition temperature of a homopolymer of a monomer used in the monomer component constituting the resin, using the formula: 1 / Tg=Σ(Wm / Tgm) / 100 (wherein Wm is the content (wt%) 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.

[0187] 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 monomers 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 weight fraction of the monomers with unknown glass transition temperatures in the monomer composition is 10 wt% or less, the glass transition temperature is calculated using only the monomers with known glass transition temperatures. If the total weight fraction of the monomers with unknown glass transition temperatures in the monomer composition exceeds 10 wt%, 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.

[0188] 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.

[0189] <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.

[0190] The composition ratios and molecular weights of the polymers obtained in Production Examples 1 to 9 and Comparative Production Examples 1 to 4 are shown in Table 1. Hereinafter, the polymers of Production Examples 1 to 9 and Comparative Production Examples 1 to 4 are used as first additives to be added to cement. The emulsion obtained in Production Example 10 is used as a post-additive (second additive) as a polycarboxylic acid-based thickener.

[0191] [Table 1]

[0192] <Evaluation of pumpability> A mortar funnel flow test was carried out to evaluate the pumpability when the obtained Production Examples 1 to 9 and Comparative Production Examples 1 to 4 were used as the first additive. Mortar that flowed without clogging and in a short time was judged to have excellent pumpability. Specifically, when the funnel flow time test method described below was 13.0 seconds or less, it was judged to have excellent pumpability. The specific method for the funnel flow test is described below.

[0193] The mortar funnel flow test was carried out under an environment of 20°C ± 1°C temperature and 60% ± 15% relative humidity.

[0194] Before mixing the mortar, a rubber stopper was placed at the bottom of a J14 funnel (top inner diameter 70 mm, bottom inner diameter 14 mm, height 392 mm) specified in the Japan Society of Civil Engineers standard JSCE-F541, and the funnel was supported vertically on a stand. An electronic balance was then placed below the bottom of the J14 funnel to measure the amount of mortar that had flowed out.

[0195] The mortar mix was C / S / W = 900 / 1350 / 270 (g). however, C: Cement (ordinary Portland cement, manufactured by Taiheiyo Cement Corporation) S: Fine aggregate (Kakegawa sand) W: Sample (first additive: ion-exchange aqueous solution of the polymer and antifoaming agent obtained in Production Examples 1 to 9 and Comparative Production Examples 1 to 4) The W mixture contained the polymers and antifoaming agents obtained in Production Examples 1 to 9 and Comparative Production Examples 1 to 4 listed in Tables 2 and 3 below, dissolved thoroughly and uniformly in ion-exchanged water. Adekanol LG-299 (manufactured by Adeka) was used as the antifoaming agent, and was included at 0.007% by weight of the cement addition amount. Using a mortar mixer (Hobart mixer, model number: N-50), C and S were added to a mixing vessel and mixed at first speed for 10 seconds. While further mixing at first speed, W was added over 10 seconds.

[0196] The mortar obtained as described above was half-filled into a mini-slump cone (JIS microconcrete slump cone, upper inner diameter 50 mm, lower inner diameter 100 mm, height 150 mm) placed on a flow measurement board (60 cm × 60 cm) and rammed 15 times with a ramming rod. Further mortar was filled to the brim of the mini-slump cone and rammed 15 times with a ramming rod, after which the surface of the mini-slump cone was smoothed. Four minutes after the initial start of the mixer, the mini-slump cone was lifted vertically, and the diameter of the expanded mortar (the diameter of the longest part (major axis) and the diameter at a 90-degree angle to the major axis) was measured at two points. The average of these measurements was taken as the mortar flow value. If the flow value was between 278 mm and 282 mm, the flow time described below was measured. If the flow value was outside the aforementioned range, the amount of the first additive was changed and the test was repeated from the beginning.

[0197] <Funnel flow time> When the flow value fell within the above range, the mortar was recovered and poured into the J14 funnel up to the top surface 6.5 minutes after the mixer was first started, and the top surface was smoothed. The mortar was left to stand for 8 minutes after the mixer was first started, at which point the rubber stopper was removed to allow the mortar to flow out. The time from the start of the mortar flow until 1,200 g had flowed out was measured with a stopwatch, and this value was taken as the funnel flow time. The results of the funnel flow time are shown in Tables 2 and 3.

[0198] <Evaluation of lamination> The obtained Production Examples 1 to 9 and Comparative Production Examples 1 to 4 were used as the first additive, and the post-additives (second additives) listed in Tables 4 and 5 below were used to evaluate the lamination properties, and the yield point of the mortar was evaluated using a rheometer.

[0199] The yield point evaluation of the mortar using a rheometer was carried out under an environment of a temperature of 20°C ± 1°C and a relative humidity of 60% ± 15%.

[0200] The mortar mix was C / S / W = 690 / 1600 / 331.2 (g). however, C: Cement (ordinary Portland cement, manufactured by Taiheiyo Cement Corporation) S: Fine aggregate (Kakegawa sand) W: Sample (first additive: ion-exchange aqueous solution of the polymer and antifoaming agent obtained in Production Examples 1 to 7 and Comparative Production Examples 1 to 4) The W mixture contained the polymers and antifoaming agents obtained in Production Examples 1 to 9 and Comparative Production Examples 1 to 4 listed in Tables 2 and 3 below, dissolved uniformly in ion-exchanged water. Adekanol LG-299 (manufactured by Adeka) was used as the antifoaming agent, and was added at 0.007% by weight of the cement addition amount. Using a mortar mixer (Hobart mixer, model number: N-50), C and S were added to a mixing vessel and mixed at first speed for 10 seconds. While mixing at first speed, W was added over 10 seconds. The mixer was stopped 60 seconds after mixing began, and the mortar was scraped off for 30 seconds. Mixing was then continued at second speed for an additional 60 seconds to prepare the mortar. When a post-additive (second additive; aluminum sulfate or the polycarboxylic acid thickener obtained in Production Example 10) was added, the mixture was mixed at second speed for 60 seconds, and then a 27 wt % aqueous solution of the post-additive was added over 5 seconds while continuing to stir at second speed. The mixture was then mixed at second speed for an additional 25 seconds, after which the yield point was evaluated as described below. When no post-additive (second additive) was added, the mixture was mixed at second speed for 60 seconds, and then the yield point was evaluated as described below.

[0201] <Yield point evaluation using a rheometer> (1) Apparatus: Brookfield RST rheometer (2) Overview of the device: A probe for yield point detection tests consisting of a probe, a sample stage, and a stress detector. The probe is rotated at a constant speed and has a mechanism that can detect the stress applied to the probe. Probe for yield point detection tests: Vane Spindle VT-60-30 (3) Evaluation method: Prepared and evaluated as follows: The (mixed) mortar sample was transferred to a 1000 mL descup, placed on the sample stage, and left to stand for 10 minutes after pouring water. Next, the probe rotation speed was increased from 0 rpm to 5 rpm over 30 seconds, and stirring continued at 5 rpm for another 30 seconds. The maximum stress value in the obtained time vs. stress plot was defined as the yield point.

[0202] The amount of the first additive added was changed until the yield point was between 390 [Pa] and 410 [Pa]. If the yield point was between 390 [Pa] and 410 [Pa], the material was mixed again with the new amount of the first additive. The second additive was added at the end of the mixing process using the method described above. The yield point was evaluated after adding the second additive. The yield point values ​​are shown in the table. A value of 3500 Pa or higher was considered to be high and to have excellent lamination properties. The yield point results are shown in Tables 4 and 5.

[0203] [Table 2]

[0204] [Table 3]

[0205] [Table 4]

[0206] [Table 5]

[0207] From the above results, it was found that, among mortar compositions with equivalent flow values ​​(fluidity), the mortar composition using the two-component additive of the Example had superior pumpability, a higher yield point, and superior lamination properties compared to the cement composition using the two-component additive of the Comparative Example.< / tg> < / ph>

Claims

1. A two-component additive for use in a hydraulic composition for additive manufacturing, the two-component additive comprising a first additive and a second additive, the first additive and the second additive being in a separated state, The first additive is a polymer having the following structural unit (I) and the following structural unit (II): 【Chemical 1】 (In the structural unit (I), X １ 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 from 2 to 100, 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 ~R ８ are the same or different and are a hydrogen atom, a methyl group, or COOM ２ represents M １ and M ２ represents a hydrogen atom or a cationic species. Including, the polymer contains 15 parts by weight or less of a structural unit derived from an alkyl ester of acrylic acid having 1 to 3 carbon atoms and / or a structural unit derived from a hydroxyalkyl ester of acrylic acid having 1 to 3 carbon atoms, based on 100 parts by weight of the polymer; A two-component additive, wherein the second additive is one or more post-additives selected from the group consisting of accelerators and thickeners.

2. 2. The two-component additive according to claim 1, wherein n is 5 to 60.

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

4. 3. The two-component additive according to claim 1, wherein the polymer contains 50 to 99 parts by weight of the structural unit (I) per 100 parts by weight of the polymer.

5. 3. The two-component additive according to claim 1, wherein the polymer contains 1 to 50 parts by weight of the structural unit (II) per 100 parts by weight of the polymer.

6. 3. The two-part additive of claim 1 or 2, wherein the accelerator is selected from the group consisting of sulfates, nitrates, nitrites, thiocyanates, silicates, chlorides, and hydroxides.

7. 3. The two-component additive according to claim 1, wherein the thickener is selected from the group consisting of cellulose-based thickeners, polycarboxylic acid-based thickeners, glycol-based thickeners, polyvinyl alcohol-based thickeners, clay-based thickeners, and thickening polysaccharides.

8. The two-component additive according to claim 1 or 2, wherein the polymer contains 50 to 99 parts by weight of the structural unit (I) and 1 to 50 parts by weight of the structural unit (II) relative to 100 parts by weight of the polymer.

9. A hydraulic composition for additive manufacturing, comprising the two-component additive according to claim 1 or 2.

10. A first step of mixing a hydraulic material, water, and the first additive according to claim 1 or 2; a second step of mixing the second additive according to claim 1 or 2 with the mixture obtained in the first step to obtain a hydraulic composition; A method for producing a hydraulic composition for layered manufacturing, comprising:

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