Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y70/00—Materials specially adapted for additive manufacturing
  • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/24—Macromolecular compounds
  • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C04B24/2641—Polyacrylates; Polymethacrylates
  • C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B28—WORKING CEMENT, CLAY, OR STONE
  • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
  • B28B1/00—Producing shaped prefabricated articles from the material
  • B28B1/001—Rapid manufacturing of 3D objects by additive depositing, agglomerating or laminating of material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y70/00—Materials specially adapted for additive manufacturing
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
  • C04B24/24—Macromolecular compounds
  • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C04B24/2688—Copolymers containing at least three different monomers
  • C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
  • C04B28/04—Portland cements
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
  • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
  • C04B40/0039—Premixtures of ingredients
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1802—C2-(meth)acrylate, e.g. ethyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/062—Polyethers
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/00034—Physico-chemical characteristics of the mixtures
  • C04B2111/00181—Mixtures specially adapted for three-dimensional printing (3DP), stereo-lithography or prototyping
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/20—Resistance against chemical, physical or biological attack
  • C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials

Definitions

• the present invention relates to a technology for producing a hydraulic composition for laminate manufacturing, and in particular to an additive used in a hydraulic composition for laminate manufacturing.
• additive manufacturing (3D printing) technology has been used to create models and parts in the manufacturing industry.
• the technology can be categorized into stereolithography (method of curing and laminating UV-curable resin layer by layer), inkjet method (method of layering by irradiating UV rays while spraying UV-curable resin from a printer head), powder Gypsum molding (a method of hardening powder gypsum by spraying resin or glue from a printer head), powder sintering molding (a method of baking and layering resin or metal powder with a laser), hot-melt additive manufacturing (melting with heat from a thin nozzle)
• stereolithography method of curing and laminating UV-curable resin layer by layer
• inkjet method method of layering by irradiating UV rays while spraying UV-curable resin from a printer head
• powder Gypsum molding a method of hardening powder gypsum by spraying resin or glue from a printer head
• powder sintering molding a method of baking and layer
• Modeled bodies are mainly made of resin, gypsum, and metal, and the technology for making large-sized shaped bodies such as construction members using hydraulic material compositions is being studied more overseas than in Japan. In Europe, the United States, and China, we are already manufacturing large-scale models of the level of single-family homes as automatic construction machines.
• Patent Documents 1 to 5 below are introduced as techniques related to lamination molding using a hydraulic composition.
• Patent Document 1 three-dimensional data created by a computer is cut at a predetermined thickness to create two-dimensional slice data, and a spray nozzle is controlled to move vertically and horizontally based on the two-dimensional slice data.
• the mortar mixed with the binder is sprayed onto the bed (table), and the sprayed mortar is allowed to self-harden to form a solidified layer having a shape based on the two-dimensional slice data.
• a technique is disclosed in which layers are sequentially layered in a direction for modeling.
• Patent Document 2 introduces a material for making a mold for manufacturing castings with a 3D printer, and discloses a material consisting of cement, sand, and a water-soluble silicate as an accelerator.
• Patent Document 3 introduces a grout composition that uses both a ligninsulfonic acid-based dispersant and a melamine sulfonic acid-based dispersant as a hydraulic material composition.
• Patent Document 4 introduces a PC grout material as a material that uses both a dispersant and a thickener.
• Patent Document 5 discloses a method for producing a hydraulic composition for laminate molding using an ionic emulsion-type thickener.
• Hydraulic compositions for layered manufacturing (3D printing) need to have reduced fluidity in order to exhibit layering properties. If the fluidity of the hydraulic material composition is reduced, movement in the hose is hindered, so the fluidity is usually reduced by adding a curing accelerator just before discharge. On the other hand, it is currently believed that there are more than a few problems that need to be solved in order to further popularize building by layered manufacturing.
• An object of the present invention is to provide an additive or the like that is excellent in the effect of improving the layerability of a hydraulic composition for layered manufacturing.
• Preferred configurations of the additive, etc. of the present invention are those described in (1) to (9) below.
• An additive used in a hydraulic composition for additive manufacturing An additive containing an emulsion containing a polymer having an acid value of 30 mgKOH/g or more.
• the structural unit having a carboxyl group is contained in an amount of 10.0 to 60.0 parts by weight per 100 parts by weight of the polymer.
• the range “X to Y” means “X or more and Y or less”, and unless otherwise specified, the operation and measurement of physical properties are performed at room temperature (20 to 25 ° C.) / relative humidity 45 to 55 % RH conditions.
• the expression “(meth)acrylic” when used, it means “acrylic and/or methacrylic”, and when the expression “(meth)acrylate” is used, “acrylate and/or or methacrylate”.
• “weight” and “mass”, “parts by weight” and “parts by mass”, and “% by weight” and “% by mass” are treated as synonyms.
• An embodiment of the present invention is an additive used in a hydraulic composition for additive manufacturing, the additive containing an emulsion containing a polymer having an acid value of 30 mgKOH/g or more.
• the above additive is also referred to as the additive in the present invention or the additive of the present invention.
• a polymer having an acid value of 30 mgKOH/g or more is simply referred to as the polymer of the present invention or the polymer of the present invention.
• the additive of the present invention is excellent in the effect of improving the lamination property of the hydraulic composition for lamination molding.
• the lamination property can be grasped, for example, by physical properties of fluidity after addition of additives, and can be evaluated by flow measurement.
• Good lamination property means that the flow value is 150 mm or less in the flow evaluation under the conditions described later in Examples.
• the additive of the present invention can significantly reduce the flow value even when the amount added is small.
• the curing time of the "laminate manufacturing" hydraulic composition must be shorter than that of ordinary hydraulic compositions, so an additive is required as a curing agent.
• the curing time is extremely fast, the mortar, etc., will harden before the next layer is discharged, and the adhesion between the discharged layer and the newly laminated layer will be poor.
• the strength of the structure will decrease due to the decrease in strength. Therefore, good lamination property means that sufficient time is secured until the hydraulic composition hardens.
• One feature of the polymer of the present invention is that the acid value is 30 mgKOH/g or more.
• the acid value is 30 mgKOH/g or more, the fluidity of the added hydraulic composition is reduced, resulting in excellent lamination properties.
• one feature of the additive of the present invention is to contain the polymer as an emulsion. Since the viscosity can be reduced as it is an emulsion, the handleability is improved.
• the additive of the present invention is used in a hydraulic composition for laminate manufacturing.
• the additive of the present invention is desirably kneaded with a hydraulic composition and used as a hydraulic composition for lamination molding.
• the additive of the present invention contains an emulsion containing a polymer having an acid value of 30 mgKOH/g or more.
• the additive is an emulsion containing a polymer having an acid value of 30 mgKOH/g or more.
• a polymer having an acid value of 30 mgKOH/g or more is also simply referred to as the polymer of the present invention or the polymer of the present invention.
• the additive of the present invention can be used as a thickener or a lamination improver by more specifically limiting its use. Specifically, it may be a thickener for a hydraulic composition containing an emulsion containing a polymer having an acid value of 30 mgKOH/g or more, and an acid value of 30 mgKOH/g or more. It may also be a lamination improver for hydraulic compositions containing an emulsion containing a polymer.
• a specific method of using the additive of the present invention includes, for example, adding it to a hydraulic composition such as mortar for laminate molding or fresh concrete and stirring it.
• laminate manufacturing refers to a technique for manufacturing molded bodies of arbitrary shapes by layering cross-sectional shapes based on three-dimensional data without using special tools such as molds. It is also commonly referred to as “3D printing”, “stereolithography” or “rapid prototyping”.
• the "hydraulic composition for lamination molding” is a hydraulic composition used for lamination molding.
• a hydraulic composition for additive manufacturing includes the additive and the hydraulic composition of the present invention.
• the hydraulic composition contains a hydraulic material and water, preferably a hydraulic material, aggregate (coarse aggregate and/or fine aggregate) and water, and optionally other components such as a dispersant and an antifoaming agent. including.
• Examples of hydraulic compositions include, for example, mortar and fresh concrete.
• Another aspect of the present invention is a hydraulic composition for additive manufacturing, comprising an emulsion containing a polymer having an acid value of 30 mgKOH/g or more, a hydraulic material, an aggregate, and water.
• the hydraulic composition for additive manufacturing in the present invention preferably contains the additive of the present invention in addition to the hydraulic composition.
• the hydraulic composition for additive manufacturing preferably contains the additive of the present invention in an amount of 0.01 to 1.0% by mass, and may be 0.01 to 0.5% by mass, relative to cement. Since the additive of the present invention is excellent in the effect of lowering the fluidity even when added in a small amount, the amount added can be relatively small.
• the "hydraulic material” used in the present invention is a hydraulic substance or a pozzolanic reactive substance or a latent hydraulic substance, preferably containing a hydraulic substance, wherein 50 mass of the hydraulic substance is contained in the hydraulic material. % or more (upper limit 100% by mass), 80% by mass or more, or 90% by mass or more.
• the hydraulic material contains a pozzolanic reactive substance or latent hydraulic substance, it is desirable that the hydraulic material further contains cement (or calcium hydroxide) and a stimulant.
• the "hydraulic substance” in the present invention is so-called cement, and examples of cement include Portland cement (ordinary, early strength, ultra-early strength, moderate heat, low heat, sulfate resistant and low alkaline types of each), and various mixed cements.
• the cement in the present invention may be of one type or two or more types.
• the hydraulic composition is not particularly limited in terms of the unit water amount per 1 m 3 , the amount of cement used, and the water/cement ratio, and is used for additive manufacturing applications. 300 to 500 kg/m 3 and a water/cement ratio (weight ratio) of 0.1 to 0.5 are preferred.
• the "pozzolanic reactive substance” in the present invention means an insoluble compound (e.g., calcium hydroxide formed by hydration of cement) that gradually combines with components in concrete (for example, calcium hydroxide formed by hydration of cement), although it does not have hydraulic properties by itself.
• it is a substance that forms calcium silicate hydrate), and includes natural pozzolana, fly ash, cinder ash, clinker ash, husk ash, metakaolin or silica fume, preferably fly ash.
• fly ash There are types I, II, III, and IV of fly ash, and type II is preferred. It is desirable that the pozzolanic-reactive material be in the form of particles having a particle size of 0.01 to 10 mm.
• the "latent hydraulic material” in the present invention is a material that does not harden simply by mixing water, but hardens in the presence of a small amount of a substance called a stimulant. slow-cooled blast furnace slag, steelmaking slag, etc.). It is desirable that the latent hydraulic material be in the form of granules having a particle size of 0.01 to 10 mm.
• Stimulants include aqueous solutions of alkali metal carbonates, alkali metal fluorides, alkali metal hydroxides, alkali metal aluminates, alkali metal silicates (e.g. water glass) and/or Mixtures thereof are included and can be added to the composition containing the latent hydraulic material in the present invention.
• Aggregates used in the present invention include, in addition to gravel (sand), crushed stone, granulated slag, recycled aggregate, etc., silica, clay, zircon, high alumina, silicon carbide, graphite, and chromium. refractory aggregates such as chroma, magnesia, and the like.
• cement dispersants include, for example, polyalkylarylsulfonate systems such as naphthalenesulfonic acid formaldehyde condensates; melamine formalin resin sulfonate systems such as melamine sulfonic acid formaldehyde condensates; aminoarylsulfonic acid-phenol-formaldehyde condensates.
• Aromatic aminosulfonate system such as; ligninsulfonate system such as ligninsulfonate and modified ligninsulfonate; various sulfonic acid dispersants having sulfonic acid groups in the molecule such as polystyrenesulfonate; JP-B-59-18338, polyalkylene glycol mono (meth) acrylic acid ester-based monomers, (meth) acrylic acid-based monomers such as those described in JP-A-7-223852, and these Copolymers obtained from monomers and copolymerizable monomers; A (poly)oxyalkylene group in the molecule of a copolymer obtained from an unsaturated (poly)alkylene glycol ether-based monomer, a maleic acid-based monomer, or a (meth)acrylic acid-based monomer as described and various polycarboxylic acid-based dispersants having a carboxyl group; (alkoxy) polyalkylene glycol mono (meth)
• 2008-517080 agents and the like are examples of cement dispersant.
• the cement dispersant it is preferable to use a polycarboxylic acid-based dispersant, since the effect of the present invention is exhibited more. Only one type of cement dispersant may be used, or two or more types may be used.
• the mixing ratio of the cement dispersant is preferably set to 0.01 to 10% by mass based on 100% by mass of cement in terms of solid content, for example.
• Antifoaming agents include polyoxyalkylene alkyl ethers such as diethylene glycol heptyl ether; polyoxyalkylene acetylene ethers; (poly)oxyalkylene fatty acid esters; polyoxyalkylene sorbitan fatty acid esters; Sulfuric acid ester salts; polyoxyalkylene alkyl phosphates; polyoxypropylene polyoxyethylene laurylamine (1 to 20 mol of propylene oxide, 1 to 20 mol of ethylene oxide, etc.), obtained from cured beef tallow to which alkylene oxide has been added
• Polyoxyalkylene alkylamines such as amines derived from fatty acids (propylene oxide 1 to 20 mol adducts, ethylene oxide 1 to 20 mol adducts, etc.); , fatty acid-based, fatty acid ester-based, alcohol-based, amide-based, phosphate-based, metal soap-based, and silicone-based antif
• the polymer in the present invention has an acid value of 30 mgKOH/g or more, preferably 50 mgKOH/g or more, more preferably 100 mgKOH/g or more, even more preferably 150 mgKOH/g or more, 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, more preferably 350 mgKOH/g or less.
• the acid value of the polymer in the present invention is, in order of preference, 30 mgKOH/g or more and 500 mgKOH/g or less, 50 mgKOH/g or more and 500 mgKOH/g or less, 100 mgKOH/g or more and 400 mgKOH/g or less, 150 mgKOH/g or more and 350 mgKOH/g or less, and 200 mgKOH/g. /g or more and 350 mgKOH/g or less.
• the acid value of the polymer in the present disclosure is, for example, measured by an automatic titrator (trade name: COM-555, manufactured by Hiranuma Sangyo Co., Ltd.) according to JIS K0070: 1992 per 1 g of polymer solid content (mgKOH/g). It is required by doing.
• the polymer in the present invention desirably contains one or more structural units having an acidic functional group (also referred to as an acid group).
• an acidic functional group also referred to as an acid group.
• the acidic functional group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, a phosphorous acid group, a hydroxy group, etc., preferably a carboxyl group, a sulfonic acid group or a phosphoric acid group, more preferably a carboxyl group. is the base.
• a specific example of the structural unit having an acidic functional group is the structural unit represented by the above formula (I).
• one or more of R 1 to R 4 are acidic functional groups, and the other R 1 to R 4 are the same or different and are hydrogen atoms or unsubstituted groups having 1 to 8 carbon atoms. or a substituted monovalent hydrocarbon group.
• R 1 to R 4 are an acidic functional group, and more preferably one is an acidic functional group.
• R 1 to R 4 other than the above acidic functional groups, preferably two or more of them are hydrogen atoms, more preferably all of them are hydrogen atoms, or two of them are hydrogen atoms, and 1 is an alkyl group (especially 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, aralkyl groups and the like, preferably alkyl groups, and particularly A methyl group is preferred.
• the above-mentioned substituted monovalent hydrocarbon group is one in which some or all of the hydrogen atoms are substituted with a substituent, and as the substituent, an alkoxy group such as a methoxy group, an ethoxy group, a (iso)propoxy group, etc. , a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, and the like.
• the structural unit represented by the above formula (I) may be a structural unit formed when the carbon-carbon double bond of the unsaturated acid monomer (acid group-containing monomer) is cleaved. Furthermore, it may be a structural unit formed when the carbon-carbon double bond of the unsaturated carboxylic acid monomer is cleaved.
• Examples of the unsaturated carboxylic acid monomer include acrylic acid, methacrylic acid, crotonic acid, tiglic acid, 3-methylcrotonic acid, 2-methyl-2-pentenoic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, 2-methyleneglutaric acid, preferably They are acrylic acid, methacrylic acid, maleic acid or fumaric acid, more preferably acrylic acid or methacrylic acid, still more preferably methacrylic acid.
• the structural unit represented by formula (I) may be of one type alone or may be of two or more different types.
• the polymer in the present invention is desirably a copolymer containing one or more hydrophobic structural units.
• the hydrophobic structural unit does not have a hydrophilic functional group, for example.
• the hydrophobic structural unit is, for example, a group consisting of a carboxyl group or its salt group, a sulfonic acid group or its salt group, a phosphoric acid group or its salt group, a phosphorous acid group or its salt group, and a hydroxy group. does not contain any functional groups selected from
• R 5 to R 8 are the same or different and are a hydrogen atom, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, or -COOM 1 (M 1 is a carbon number 1 to 8 monovalent hydrocarbon groups), preferably one of R 5 to R 8 is —COOM 1 and the remaining R 5 to R 8 are hydrogen atoms or unsubstituted 1 having 1 to 4 carbon atoms It is a valent hydrocarbon group (preferably a methyl group), more preferably one of R 5 to R 8 is —COOM 1 and the remaining R 5 to R 8 are hydrogen atoms.
• M 1 above is preferably a methyl group, an ethyl group, a propyl group or a butyl group, more preferably an ethyl group.
• More specific examples of the unsubstituted monovalent hydrocarbon group include linear, branched or cyclic alkyl groups, alkenyl groups, aryl groups, aralkyl groups, etc., preferably alkyl groups, A methyl group and an ethyl group are particularly preferred.
• the above-mentioned substituted monovalent hydrocarbon group is one in which some or all of the hydrogen atoms are substituted with a substituent, and as the substituent, an alkoxy group such as a methoxy group, an ethoxy group, a (iso)propoxy group, etc. etc.
• the structural unit represented by the above formula (II) may be a structural unit formed when the carbon-carbon double bond of a hydrophobic monomer is cleaved.
• a hydrophobic monomer for example, styrene, acrylic acid ester, methacrylic acid ester, etc., preferably acrylic acid ester or methacrylic acid ester, more preferably acrylic acid ester, specifically methyl acrylate, ethyl acrylate , butyl acrylate, and 2-ethylhexyl acrylate, and ethyl acrylate is particularly preferred.
• X is C ⁇ O or (CH 2 ) p [p is an integer of 0 to 5]
• R 12 is a (unsubstituted) divalent hydrocarbon group having 2 to 8 carbon atoms.
• R 12 may be the same or different
• m is an integer of 5 to 300
• R 13 is a hydrogen atom or a (unsubstituted) 1 having 1 to 18 carbon atoms It is a valent hydrocarbon group in which the remaining R 9 to R 11 are the same or different and are a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms.
• the above p is preferably an integer from 0 to 2, and more preferably 0.
• R 12 is preferably a C 2-4 divalent hydrocarbon group, more preferably a C 2-3 divalent hydrocarbon group, still more preferably C 2 H 4 .
• R 12 may be the same or different, and for example, R 12 O may be a mixture of butylene oxide (BO)/propylene oxide (PO).
• m refers to the total number of added moles of each alkylene oxide (for example, the total number of added moles of butylene oxide and the number of added moles of propylene oxide).
• R 13 is preferably a hydrogen atom or a monovalent hydrocarbon having 1 to 18 carbon atoms, more preferably hydrogen, CH 3 or a stearyl group.
• R 13 may be a hydrogen atom or a (unsubstituted) monovalent hydrocarbon group having 1 to 8 carbon atoms, or a hydrogen atom or a (unsubstituted) monovalent hydrocarbon group having 1 to 4 carbon atoms, good too.
• the remaining R 9 to R 11 are preferably a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, more preferably one of R 9 to R 11 is a monovalent hydrocarbon group having 1 to 4 carbon atoms. group (preferably methyl group) and the remaining R 9 to R 11 are hydrogen atoms.
• the structural unit represented by the above formula (III) is 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 a structural unit formed when the carbon-carbon double bond is cleaved (a structural unit derived from a polyalkylene glycol group-containing monomer).
• polyalkylene glycol group-containing monomer examples include polyalkylene glycol monomethacrylate, polyalkylene glycol monoacrylate, alkoxypolyalkylene glycol monomethacrylate, alkoxypolyalkylene glycol monoacrylate, phenoxypolyalkyleneglycol monomethacrylate, phenoxy polyalkylene glycol monoacrylate and the like.
• a monomer containing a polyalkylene glycol group other than the above a compound obtained by adding ethylene oxide to the hydroxyl group of 3-methyl-3-buten-1-ol (isoprenol) (for example, the average number of added moles of ethylene oxide is 50). can also be mentioned as an example.
• Polyalkylene glycol group-containing monomers are preferably alkoxypolyalkylene glycol mono (meth) acrylate, polyalkylene glycol mono (meth) acrylate, hydroxyl group of 3-methyl-3-buten-1-ol (isoprenol) It is a compound to which ethylene oxide is added, preferably an alkoxypolyalkylene glycol monomethacrylate or an alkoxypolyalkylene glycol monoacrylate, more preferably an alkoxypolyalkylene glycol monomethacrylate.
• alkoxypolyalkylene glycol monomethacrylates examples include methoxypolyethyleneglycol-methacrylate, octoxypolyethyleneglycol-polypropyleneglycol-methacrylate, lauroxypolyethyleneglycol-methacrylate, and stearoxypolyethyleneglycol-methacrylate, preferably methoxypolyethyleneglycol- They are methacrylate and stearoxypolyethyleneglycol-methacrylate, and methoxypolyethyleneglycol-methacrylate is more preferable from the viewpoint of easy availability.
• phenoxypolyalkylene glycol monomethacrylate examples include phenoxypolyethylene glycol-methacrylate.
• alkoxypolyalkylene glycol monoacrylate examples include methoxypolyethylene glycol-acrylate.
• phenoxypolyalkylene glycol monoacrylate examples include nonylphenoxypolypropyleneglycol-acrylate and nonylphenoxypolyethyleneglycol-polypropyleneglycol acrylate.
• polyalkylene glycol monomethacrylate examples include polyethylene glycol-monomethacrylate, polypropylene glycol-monomethacrylate, polyethylene glycol-propylene glycol-monomethacrylate, polyethylene glycol-tetramethylene glycol-monomethacrylate, propylene glycol-polybutylene glycol-monomethacrylate. and preferably polypropylene glycol-monomethacrylate.
• polyalkylene glycol monoacrylate examples include polyethylene glycol-monoacrylate and polypropylene glycol-monoacrylate.
• the polyalkylene glycol group-containing monomer is methoxypolyethyleneglycol-methacrylate, stearoxypolyethyleneglycol-methacrylate, polypropyleneglycol-monomethacrylate and 3-methyl-3-buten-1-ol (isoprenol). It contains at least one selected from the group consisting of compounds in which ethylene oxide is added to a hydroxyl group.
• a preferred embodiment of the polymer of the present invention preferably contains at least a structural unit represented by the above formula (II) as a hydrophobic structural unit, since the effect of the present invention is further exhibited, and further the above It may contain a structural unit represented by formula (III).
• the polymer in the present invention can contain structural units (IV) other than the structural units described above in the remainder.
• the other structural unit is preferably 5 parts by weight or less (lower limit of 0 parts by weight), more preferably 3 parts by weight or less, and 1 part by weight or less with respect to 100 parts by weight of the polymer. Even more preferred.
• the polymer in the present invention contains a structural unit having an acidic functional group (preferably a structural unit having a carboxyl group) with respect to 100 parts by weight of the polymer, preferably 1.0 to 90.0 parts by weight, more preferably It is desirable to include 10.0 to 60.0 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.
• an acidic functional group preferably a structural unit having a carboxyl group
• the polymer in the present invention preferably contains 1.0 to 90.0 parts by weight, more preferably 10.0 to 90 parts by weight, of the structural unit (I) having an acidic functional group, per 100 parts by weight of the polymer. .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.
• the polymer in the present invention preferably contains 10.0 to 95.0 parts by weight, more preferably 10.0 to 90.0 parts by weight of the hydrophobic structural unit (II) per 100 parts by weight of the polymer. It is desirable to include 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.
• the polymer in the present invention preferably contains 1.0 to 40.0 parts by weight, more preferably 2.0 to 30 parts by weight, of the hydrophobic structural unit (III) with respect to 100 parts by weight of the polymer. It is desirable to include .0 parts by weight. Further, the polymer in the present invention preferably contains 10.0 to 90.0 parts by weight, more preferably 40.0 to 90.0 parts by weight of the hydrophobic structural unit with respect to 100 parts by weight of the polymer. It is desirable to contain 40.0 to 80.0 parts by weight. By including the hydrophobic structural unit in such a range, it is easy to control the emulsion form.
• the polymer in the present invention preferably contains at least a structural unit (I) having an acidic functional group and a hydrophobic structural unit (II).
• the total content of the structural unit (I) having an acidic functional group and the hydrophobic structural unit (II) in the polymer is preferably 60% by weight or more, more preferably 65% by weight or more.
• the polymer in the present invention consists of or substantially consists of structural unit (I) and hydrophobic structural unit (II) (for example, 95.5 parts of (I) and (II) per 100 parts by weight of all structural units). 0 parts by weight or more) is also desirable.
• the polymer consists or substantially consists of the structural unit (I) and the hydrophobic structural unit (II)
• the structural unit (I) having the above acidic functional group is added to 100 parts by weight of the polymer.
• the hydrophobic structural unit (II) based on 100 parts by weight of the polymer 50.0 to 95.0 parts by weight, particularly preferably 50.0 to 90.0 parts by weight.
• Still another preferred embodiment is a polymer comprising structural units (I) having an acidic functional group, hydrophobic structural units (II) and hydrophobic structural units (III), consisting of or substantially consisting of them (for example, 95.0 parts by weight or more of (I), (II) and (III) are contained relative to 100 parts by weight of all structural units).
• the structural unit (I) having an acidic functional group is added to the polymer
• the structural unit (I) having an acidic functional group is added to the polymer
• the structural unit (I) having an acidic functional group is added to the polymer
• the structural unit (I) having an acidic functional group is added to the polymer
• the structural unit (I) having an acidic functional group is added to the polymer
• the structural unit (I) having an acidic functional group is added to the polymer
• the structural unit (I) having an acidic functional group is added to the polymer
• the structural unit (I) having an acidic functional group is added to the polymer
• the hydrophobic structural unit (I) having an acidic functional group is added to the polymer
• the hydrophobic structural unit (I) having an acidic functional group is added to the polymer
• the hydrophobic structural unit (I) having an acidic functional group is added to the polymer
• the hydrophobic structural unit (I) having an acidic functional group is added to the polymer
• polymer in the present invention examples include (I) those polymerized using acrylic acid or methacrylic acid, and (II) alkyl (having 1 to 8 carbon atoms) acrylate in addition to (I). and those copolymerized using (III) polyalkylene glycol group-containing monomers in addition to the above (I) and (II), among which the effect of the present invention is further exhibited. Therefore, in addition to (I), (II) alkyl (having 1 to 8 carbon atoms) copolymerized using acrylate, in addition to (I) and (II), (III) polyalkylene glycol A copolymer obtained by copolymerizing a group-containing monomer is preferable.
• the weight average molecular weight of the polymer in the present invention is, for example, 10,000 to 10,000,000, preferably 20,000 to 8,000,000, more preferably 20,000 to 8,000,000, as a weight average molecular weight using a static light scattering method. is 30,000 to 6,000,000, still more preferably 40,000 to 5,000,000, particularly preferably 50,000 to 1,000,000, most preferably 100,000 ⁇ 1,000,000 and 200,000 to 800,000.
• the glass transition temperature of the polymer in the present invention is, for example, -40°C or higher, preferably -30°C or higher, more preferably - 20° C. or higher, particularly preferably ⁇ 10° C. or higher.
• the upper limit of the glass transition temperature of the polymer of the present disclosure is, for example, 80° C. or lower, preferably 75° C. or lower, more preferably 65° C. or lower, and particularly preferably 50° C. or lower.
• the glass transition temperature can be controlled by the kind and composition ratio of the monomers constituting the polymer.
• the glass transition temperature is the glass transition temperature of the homopolymer of the monomers used in the monomer component that constitutes the polymer.
• the pH of the polymer in the present invention is, for example, pH 2.0 to 6.0, more preferably pH 2.0 to 5.0, as a 10.0% by mass aqueous solution or aqueous dispersion at 25.0°C. 0, and more preferably pH 2.0 to 4.0.
• the above aqueous solution or aqueous dispersion can be prepared by a known suitable method such as dissolving or dispersing the above polymer in distilled water so as to have a predetermined concentration.
• the emulsion containing the polymer in the present invention is obtained by covering the polymer with an emulsifier to form particles (micelles).
• O / W type oil-in-water type
• W / O type water-in-oil type
• O / W / O type oil-in-water type
• W / O / W type oil-in-water type
• W / O / W type oil-in-water type medium water type
• Dispersion media for emulsions include water, oil, alcohol, etc. Water is preferably used.
• the solid content (polymer and emulsifier) is 1.0 to 80.0% by weight, preferably 10.0 to 50.0% by weight, more preferably 20.0 to 40.0% by weight, based on the total weight of the emulsion. %included.
• the viscosity of the emulsion in the present invention is, for example, 500 mPa s or less, preferably 250 mPa s or less, as a viscosity at a shear rate of 10 s ⁇ 1 at room temperature (20 to 25 ° C.) when adjusted to a concentration of 25% by mass. It is more preferably 200 mPa ⁇ s or less, still more preferably 100 mPa ⁇ s or less, and particularly preferably 50 mPa ⁇ s or less.
• the lower limit of the viscosity is desirably, for example, 1 mPa ⁇ s or more, preferably 5 mPa ⁇ s or more, since the amount added immediately before the nozzle can be easily controlled.
• the above emulsion has a pH of 2.0 to 4.0.
• a known method can be used for measuring the pH of the emulsion. For example, a method of measuring at 25°C using a pH meter (LAQUA manufactured by Horiba, Ltd.) in accordance with JIS Z8802:2011 can be used.
• the average particle size of the particles (micelles) (emulsion particles) in the emulsion in the present invention may be, for example, 30 nm or more, preferably 50 nm or more, and the upper limit of the average particle size of the emulsion particles is, for example, 3 ,000 nm or less, preferably 1,000 nm or less, or the like, 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 is the volume-average particle size measured using a particle size distribution analyzer [Particle Sizing Systems, trade name: NICOMP Model 380] using the dynamic light scattering method. diameter.
• emulsifiers used in the production of emulsions include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, amphoteric emulsifiers, polymer emulsifiers, and the like. may be used together.
• the emulsifier is desirably present in the emulsion at 1.0 to 20.0% by weight, preferably 1.0 to 5.0% by weight, based on the total weight of the polymer contained therein.
• emulsifiers include, but are not limited to, anionic emulsifiers (e.g., alkylsulfate salts such as ammonium dodecylsulfate and sodium dodecylsulfate; alkylsulfonate salts such as ammonium dodecylsulfonate and sodium dodecylsulfonate; ammonium dodecylbenzenesulfonate, sodium Alkyl aryl sulfonate salts such as dodecyl naphthalene sulfonate; polyoxyethylene alkyl sulfate salts (polyoxyethylene alkyl ether sulfates); polyoxyethylene alkyl aryl sulfate salts; polyoxyethylene alkyl ether sulfates; dialkyl sulfosuccinates; - formalin condensates; fatty acid salts such as ammonium laurylate and sodium stea
• an emulsifier having a polymerizable group a so-called reactive emulsifier may be used.
• reactive emulsifiers include propenyl-alkyl sulfosuccinate salts, (meth)acrylic acid polyoxyethylene sulfonate salts, polyoxyethylene alkyl propenyl phenyl ether ammonium sulfate [for example, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon HS-10, Aqualon BC-10, etc.], allyloxymethylalkyloxypolyoxyethylene sulfonate salt [for example, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon KH-10, etc.], allyloxymethylnonylphenoxy Sulfonate salts of ethyl hydroxypolyoxyethylene [for example, manufactured by ADEKA Corporation, trade name: Adekari Soap SE-10, etc.], allyloxymethylalkoxyethylhydroxypolyoxyethylene sulfate salts [
• polyethylene glycol with an average molecular weight of 4000 or less, polypropylene glycol with an average molecular weight of 4000 or less, or the like may be added to the emulsion.
• the amount of these additives added may be 5% by mass or less, or 3% by mass or less, relative to the solid content of the emulsion.
• the method for producing the emulsion containing the polymer is not particularly limited, but for example, the emulsion may be produced by emulsion polymerization of the monomer component, which is the raw material of the polymer, in a solvent.
• solvents examples include aqueous solvents such as water and solvents containing water [eg, mixed solvents of water and alcohols (eg, C1-4 alcohols such as methanol and ethanol)].
• the solvent preferably contains water as a main component.
• the main component means that the content of water in the solvent is 95% by mass or more (upper limit of 100% by mass), preferably 98% by mass or more and 99% by mass or more. You may use a solvent in combination of 1 type(s) or 2 or more types.
• the method of emulsion polymerization of the monomer component is not particularly limited, but for example, a method of polymerizing by dropping the monomer component into a solvent containing an emulsifier, or a method of dropping a monomer component previously emulsified with an emulsifier into a solvent. and the like. Examples of specific emulsifiers are those listed above.
• 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. .
• the amount of solvent may be appropriately set in consideration of the amount of nonvolatile matter contained in the obtained emulsion.
• the polymerization may be carried out in the presence of a polymerization initiator.
• polymerization initiators examples include azobisisobutyronitrile, 2,2-azobis(2-methylbutyronitrile), 2,2-azobis(2,4-dimethylvaleronitrile), 2,2-azobis ( 2-diaminopropane) hydrochloride, 4,4-azobis (4-cyanovaleric acid), azo compounds such as 2,2-azobis (2-methylpropionamidine); persulfates such as ammonium persulfate and potassium persulfate; Hydrogen peroxide, benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, and peroxides such as ammonium peroxide.
• the polymerization initiator may be used alone or in combination of two or more.
• the amount of the polymerization initiator to be used may be appropriately set according to the type of polymerization initiator and the like, and is not particularly limited. It may be 0.1 part by weight or more, for example, 2 parts by weight or less, preferably 1 part by weight or less.
• the method of adding the polymerization initiator is not particularly limited, but examples include batch charging, divided charging, and continuous dropping.
• 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 thiol group compound (eg, tert-dodecylmercaptan)] pH buffer, chelating agent, or the like.
• the atmosphere during polymerization is not particularly limited, but may be an inert gas such as nitrogen gas from the viewpoint of polymerization efficiency.
• the polymerization temperature is not particularly limited, it 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 appropriately set according to the progress of the polymerization reaction. time).
• the hydraulic composition for lamination molding in the present invention may be mortar or fresh concrete for lamination molding.
• a method for producing the hydraulic composition for laminate manufacturing for example, (a) a step of stirring a hydraulic material and water, preferably a hydraulic material, an aggregate and water to obtain a hydraulic composition, and (b) the A manufacturing method including a step of adding the additive of the present invention to the hydraulic composition obtained in the step and stirring.
• the (a) step and the (b) step in the manufacturing method are performed independently, and the (b) step is performed after the (a) step.
• the hydraulic material, aggregate and water may be added sequentially and stirred, or may be added all at once and stirred.
• the order of addition of the hydraulic material, the aggregate and the water is not particularly limited.
• the additive in the step (b) may be added after further diluting the additive in emulsion form with water or the like.
• the stirring time in the step (b) is appropriately set so that the mixture can be uniformly mixed and is as short as possible.
• the fresh concrete is desirably laminated on another fresh concrete immediately (for example, 0 to 300 seconds after the (b) step).
• the hydraulic composition for layered manufacturing of the present invention (hereinafter also referred to as a hydraulic material composition) is suitable for use in layered manufacturing. Therefore, according to the present invention, there is also provided a layered product formed from the hydraulic material composition for layered manufacturing of the present invention.
• Another embodiment is a method of manufacturing a laminate-molded article using the hydraulic material composition of the above embodiment.
• Another embodiment is adding an emulsion comprising a polymer having an acid value of 30 mgKOH/g or more to a composition comprising a hydraulic material and water to obtain a mixture, and laminating using the mixture
• the method for producing a laminate-molded article using the hydraulic material composition for laminate manufacturing is not particularly limited, but for example, a hydraulic material and water (optionally aggregate, other additives A step of pumping a composition containing) to the nozzle tip of a 3D printer with compressed air or a pump, etc., extruding the pumped composition from the nozzle, adding the additive of the present invention from another line, and further mixing a step of preparing a hydraulic material composition for lamination molding by doing so, and laminating the composition to form a lamination-molded article.
• a hydraulic material and water optionally aggregate, other additives
• a step of pumping a composition containing a hydraulic material and water (optionally including aggregates and other additives) to the nozzle tip of a 3D printer by compressed air or a pump or the like, and from another line the present invention adding the additives of and mixing by a mixing mechanism installed in a tube at the tip of the nozzle, extruding the resulting composition from the nozzle and stacking to form a laminate product.
• a nozzle (discharging part) is usually provided at the tip of the pressure feeding pipe for the hydraulic material composition for additive manufacturing.
• the diameter of the nozzle is not particularly limited, it may be appropriately set depending on the size of the aggregate to be used and the width for laminating the hydraulic material composition for lamination molding. For example, if the aggregate size is 5 mm or less and the lamination 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 may be circular, elliptical, rectangular, cross-shaped, star-shaped, or the like.
• a flange may be provided around the nozzle.
• the nozzle When laminating the hydraulic material composition for lamination molding discharged from the nozzle to form a model, the nozzle may be moved vertically or horizontally to form a model using the hydraulic material composition for lamination molding. .
• 2D slice data is created by cutting 3D data created by a computer at a predetermined thickness, and the spray nozzle is controlled to move vertically, horizontally, diagonally, etc. based on the 2D slice data.
• a hydraulic material composition for lamination molding may be ejected from a nozzle, and the nozzle may be moved in the vertical direction to repeat and successively laminate for modeling.
• the movement speed of the nozzle is not particularly limited, and can be changed depending on the width of the layers to be laminated.
• Example 1 In a flask equipped with a dropping funnel, stirrer, nitrogen gas inlet tube, thermometer and reflux condenser, 453 g of deionized water and 20% of an emulsifier [manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Hytenol LA-10]. 64 g of aqueous solution was charged.
• a dropping funnel was charged with 30 g of deionized water, 32 g of a 20% aqueous solution of emulsifier [manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Hytenol LA-10], 322 g of ethyl acrylate, 234 g of methacrylic acid, and methyl polyethylene glycol (90) monomethacrylate.
• a pre-emulsion consisting of 832 g of a 10% aqueous solution of [NOF Corporation, trade name: Blemmer PME-4000] was prepared, 73 g of which was added to the flask, and the temperature was raised to 72 ° C. while gently blowing nitrogen gas.
• the emulsion particles contained in the resin emulsion had an average particle diameter of 136 nm, and the glass transition temperature (Tg) of the entire emulsion particles was 14°C. Further, the viscosity of the liquid prepared by diluting the emulsion (1) with water so that the concentration was 25% was 33 mPa ⁇ s at a shear rate of 10 s ⁇ 1 at room temperature.
• Examples 2 to 16 The monomer components (ethyl acrylate, methacrylic acid, methyl polyethylene glycol (90) monomethacrylate) used in Example 1 and their composition ratios are shown in Tables 1 to 3 below.
• Each emulsion of Examples 2 to 16 was obtained in the same manner as in Example 1.
• Examples 1-16 Details of the polymers/emulsions of Examples 1-16 are provided in Tables 1-3 below.
• polyethylene glycol PEG 1000
• Example 12 to 16 polyethylene glycol (PEG 1000) was added to impart water retention (1% by mass relative to the solid content of the emulsion, and the emulsion was obtained in the same manner as in Example 1. after adding polyethylene glycol.).
• the average particle size of the emulsion particles is measured using a particle size distribution analyzer (manufactured by Particle Sizing Systems, trade name: NICOMP Model 380) based on the dynamic light scattering method. mean the volume average particle size.
• the weight average molecular weight of the polymer is measured using gel permeation chromatography [for example, manufactured by Tosoh Corporation, product number: HLC-8120GPC, column: TSKgel G-5000HXL and TSKgelGMHXL-L used in series] (polystyrene converted).
• ⁇ pH> The pH was measured at 25° C. using a pH meter (LAQUA, manufactured by Horiba, Ltd.) in accordance with JIS Z8802:2011.
• Wm is the content (% by mass) of the monomer m in the monomer component constituting the resin
• Tgm is the glass transition temperature (absolute temperature: K) of a homopolymer of the monomer m].
• K glass transition temperature
• the glass transition temperature of the entire emulsion particles having a plurality of resin layers obtained by multistage emulsion polymerization or the like is the total monomer component used as the raw material for all the resin layers used during multistage emulsion polymerization. It means the glass transition temperature obtained based on the Fox equation using the glass transition temperature of the homopolymer of the monomers.
• the total amount of monomers with unknown glass transition temperatures in the monomer components is the mass fraction. is 10% by mass or less, the glass transition temperature is determined using only monomers whose glass transition temperatures are known.
• the glass transition temperature of the resin can be determined by differential scanning calorimetry (DSC), differential calorimetry ( DTA), thermomechanical analysis (TMA), or the like.
• the glass transition temperature is, 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, and ⁇ 24° C. for a homopolymer of n-butyl acrylate. ⁇ 56° C., 83° C. for cyclohexyl methacrylate homopolymer, 107° C. for tert-butyl methacrylate homopolymer, 55° C. for 2-hydroxyethyl methacrylate homopolymer, 95° C. for acrylic acid homopolymer, methacrylic It is 130° C. for an acid homopolymer and 100° C. for a styrene homopolymer.
• Unsaturated polyalkylene glycol ether obtained by adding an average of 50 moles of ethylene oxide (EO) to 21.6 g of ion-exchanged water and isoprenol in a glass reaction vessel equipped with a thermometer, a vending machine, a dropping funnel, a nitrogen inlet tube and a reflux condenser. 206.4 g of (IPN-50) was charged, heated to 60° C., and then 15.6 g of 1% aqueous hydrogen peroxide solution was added. Next, an aqueous solution prepared by diluting 42.8 g of acrylic acid with 42.8 g of deionized water was added dropwise over 3 hours.
• EO ethylene oxide
• an aqueous solution prepared by dissolving 0.1 g of L-ascorbic acid and 2.0 g of 3-mercaptopropionic acid in 358.4 g of ion-exchanged water was added dropwise over 3.5 hours. After the dropwise addition was completed, stirring was continued for 1 hour to complete the polymerization reaction. Thereafter, the reaction solution was adjusted to pH 6 with a 30% aqueous solution of sodium hydroxide at a temperature not higher than the polymerization reaction temperature to obtain an aqueous solution of a dispersant polymer having a weight average molecular weight (Mw) of 18,000. The weight average molecular weight of the dispersant polymer was measured by the following molecular weight measurement method (2).
• Detector differential refractometer (RI) detector (Waters 2414) Standard material for creating a calibration curve: polyethylene oxide manufactured by GL Sciences (Mw 255000, 200000, 107000, 72500, 44900, 31440, 21300, 11840, 6450, 4020, 1470)
• Calibration curve Created by a cubic equation based on the Mw value and elution time of the standard substance. - Amount of injection sample and standard material: 100 ⁇ L of the solution dissolved in the above eluent so that the polymer concentration was 1.0 vol % was injected. ⁇ Flow rate: 0.5 ml/min ⁇ Column temperature: 40°C ⁇ Measurement time: 90 minutes
• Paste flow test A test was performed by the following method in accordance with the contents of JIS R5201:2015. 23.4 g of a 10% aqueous solution of dispersant polymer that had been diluted with water in advance, 11.7 g of 1% water-dispersed Adekanol LG-299 (manufactured by Adeka Co., Ltd.) as an antifoaming agent, and 198.9 g of water were mixed. , to prepare solution (A).
• a predetermined amount (listed in % by mass relative to the amount of cement in Table 4 below) of an additive (emulsion of any of Examples 1 to 16 or a hardening accelerator (aluminum sulfate) of Comparative Example 2) was added.
• a liquid diluted with water (the additive was adjusted to a total of 66.6 g together with the weight of water) was added, and the mixture was stirred at a low speed for 30 seconds to prepare a mortar (in Comparative Example 1, , only 66.6 g of water will be added, since there is no addition of the above given amount of additive).
• the flow value was measured using a truncated conical flow cone (lower diameter 100 mm, upper diameter 70 mm, height 60 mm). The detailed conditions for measuring the flow value are as described below.
• the cone was visually confirmed to be free of dirt, scratches and dents before use.
• the inner surface of the cone and the upper surface of the flow table were wiped clean with a wet cloth in advance.
• Sample filling method The cone was placed on a flat plate placed horizontally, and the sample was divided into two layers of approximately equal amount and packed. Each layer was leveled with a ram and then poked evenly 25 times. The depth of the plunger when piercing each layer was set so that it almost reached the previous layer. Finally, if necessary, the shortfall was compensated and the surface was smoothed. Immediately remove the cone in the vertical direction, give a total of 15 falling motions at a frequency of once per second, and measure the length in the direction recognized as the maximum after the mortar spreads and the length in the direction perpendicular to this. , the mean value was recorded as flow (mm).
• Examples 1 to 16 according to the present invention can significantly reduce the mortar flow value compared to Comparative Example 1. confirmed.
• Examples 1 to 15 having an acid value of 63 KOH/g or more it was confirmed that the mortar flow value was significantly reduced compared to Example 16, and Comparative Example 2 (hardening acceleration agent: aluminum sulfate) to reduce the mortar flow value to the same extent.
• the present invention is excellent in the effect of improving the lamination property of the hydraulic composition for lamination molding.
• Example 1 According to the present invention, the increase in the penetration resistance value after water injection was remarkably gradual compared to Comparative Example 2, and the time until the mortar hardened was shown to be adequately maintained.
• the mortar will harden before the next layer is dispense during additive manufacturing, resulting in poor adhesion between the dispense-completed layer and the newly laminated layer. is lowered, and the strength of the structure is lowered.
• the present invention does not reduce the adhesion between layers and the strength of the structure by keeping the time until the mortar hardens sufficiently. It can be understood that the effect of improving the lamination property of the composition is excellent.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Ceramic Engineering (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Structural Engineering (AREA)
• Manufacturing & Machinery (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Inorganic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Mechanical Engineering (AREA)
• Civil Engineering (AREA)
• Composite Materials (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=87765899

Family Applications (1)

Country Status (4)

Cited By (1)

Citations (17)

Family Cites Families (1)

• 2023
  • 2023-02-21 US US18/835,271 patent/US20250162944A1/en active Pending
  • 2023-02-21 JP JP2024503173A patent/JP7810784B2/ja active Active
  • 2023-02-21 EP EP23759982.4A patent/EP4488338A4/en active Pending
  • 2023-02-21 WO PCT/JP2023/006248 patent/WO2023162981A1/ja not_active Ceased

Patent Citations (17)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events