Method for manufacturing a laminated object, thermosensitive gelling agent, and composition for laminated manufacturing

Abstract

To provide a laminated molded article production method in which the generation of the sagging and collapse of a water curable inorganic composition during lamination is reduced to a practically sufficient level.SOLUTION: Provided is a laminated molded article production method in which lamination molding compositions each contains a water curable inorganic composition and a heat-sensitive gelling agent are laminated, and the lamination molding compositions are made illiquid by heating upon the lamination and / or after the lamination. The heat-sensitive gelling agent comprises: an aqueous medium; a polymer which is dispersed into the aqueous medium; and a nonionic surface active agent which has a cloud point of 30°C or more and an HLB value of 10 to 18. In the heat-sensitive gelling agent, when provided that a penetration resistance value at 17±3°C directly after defoaming is defined as a0 and a penetration resistance value at 17±3°C after microwave heating at 600 W for 30 seconds after the defoaming is defined as a1, a value of the a1 / a0 reaches 15 or more.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a laminated object, a thermosensitive gelling agent, and a composition for laminated manufacturing.

Background Art

[0002] 3D printer construction, which involves building by laminating cement materials using a 3D printer (laminated manufacturing apparatus) based on three-dimensional data of a building, has attracted attention. It is said that using this construction method enables a more free design compared to the conventional method, and can significantly reduce costs through labor saving and shortening of the construction period.

[0003] By the way, although cement materials are widely used as construction materials, they require a considerably long time to solidify. Therefore, attempts have been made to shorten the solidification time. For example, Patent Document 1 describes that an aqueous resin emulsion having a specific chemical structure with thermosensitive gelling ability is added to a water-curable inorganic powder for the purpose of shortening the drying reaction to obtain a soft mortar sheet.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] When laminating a cement material with a 3D printer, sagging and crushing of the cement are inevitable. However, applying the mortar material described in Patent Document 1, which enables shortening of the drying reaction, to a 3D printer cannot solve the above problems. This is because Patent Document 1 only discloses a method effective in the range of heating a mortar material sandwiched between two carrier films to form a film, and the composition is not assumed to stack the cement material in the vertical direction.

[0006] Therefore, an object of the present invention is to provide a method for manufacturing a laminated object by additive manufacturing such as 3D printing, which can reduce the occurrence of sagging and crushing of the water-curable inorganic composition during lamination to a practically sufficient level.

[0007] Another object of the present invention is to provide a material to be contained in a water-curable inorganic composition used for additive manufacturing such as 3D printing, which has excellent defoaming properties, high miscibility with the water-curable inorganic composition, and rapidly becomes non-fluidizable by mixing and heating with the water-curable inorganic composition, and a composition for additive manufacturing using this material.

Means for Solving the Problems

[0008] The present invention provides the following [1] to

[15] .

[0009] [1] A method for manufacturing a laminated object, comprising laminating a composition for additive manufacturing containing a water-curable inorganic composition and a thermosensitive gelling agent, and non-fluidizing the composition for additive manufacturing by heating during and / or after lamination, wherein the thermosensitive gelling agent contains an aqueous medium, a polymer dispersed in the aqueous medium, and a nonionic surfactant having a cloud point of 30°C or higher and an HLB value of 10 to 18, and the thermosensitive gelling agent contains the following formulations (1) to (5) [(1) to (5) are in terms of solid content, and the water content is 18.5% by mass]. (1) 100 parts by mass of mortar (2) 1 part by mass of sodium gluconate (3) 0.5 part by mass of carboxymethyl cellulose (4) 0.1 part by mass of a silicone-based defoaming agent (5) 4.5 parts by mass of the thermosensitive gelling agent The penetration resistance value (needle diameter = 2 mm, piercing speed = 30 mm / min, piercing depth = 10 mm), which is measured after defoaming by introducing 100 g into a cylindrical container with an open top, is When the value at 17 ± 3°C immediately after defoaming is a0 and the value at 17 ± 3°C after microwave heating at 600 W for 30 seconds after defoaming is a1, the thermosensitive gelling agent is such that the value of a1 / a0 is 15 or more. A manufacturing method. According to this manufacturing method, additive manufacturing such as 3D printing becomes possible in a state where the occurrence of sagging and collapse of the water-curable inorganic composition in the laminate is reduced to a practically sufficient level. The thermosensitive gelling agent refers to a material that gels upon heating.

[0010] The thermosensitive gelling agent showing such a penetration resistance value can prevent the occurrence of sagging and collapse of the water-curable inorganic composition in the laminate. In addition, since the composition for additive manufacturing used in the above manufacturing method can be quickly made non-fluid after heating, it also has the characteristic of excellent fluidity when discharged from the nozzle. Further, the composition for additive manufacturing has excellent defoaming properties. For example, bubbles disappear only by applying a slight vibration, and insufficient final strength is prevented. And since the above thermosensitive gelling agent also acts as a binder, the adhesive strength between layers after curing becomes good. That is, according to this manufacturing method, it is also possible to solve problems such as improving the fluidity when discharging the composition for additive manufacturing before curing from the nozzle, improving the defoaming property of the composition for additive manufacturing before curing, and improving the adhesive strength between layers of the composition for additive manufacturing after curing.

[0011] [2] The polymer according to [1], which is at least one selected from the group consisting of a homopolymer or copolymer of a conjugated diene and a homopolymer or copolymer of an ethylenically unsaturated monomer. Such conjugated diene polymers and vinyl polymers are effective as components of the thermosensitive gelling agent.

[0012] [3] The homopolymer or copolymer of the conjugated diene is at least one selected from the group consisting of styrene-butadiene rubber, methyl methacrylate-butadiene rubber, acrylonitrile-butadiene rubber, styrene-butadiene-vinylpyridine rubber, butadiene rubber, and natural rubber, and is the production method according to [2]. Such conjugated diene polymers are particularly effective as components of the thermosensitive gelling agent.

[0013] [4] The nonionic surfactant is polyoxyethylene alkyl ether and / or polyoxyethylene aryl ether, and is the production method according to any one of [1] to [3]. When the above components are used as the nonionic surfactant, the lamination property becomes particularly excellent.

[0014] [5] In the polyoxyethylene alkyl ether, the alkyl moiety is an alkyl having 12 to 20 carbon atoms, and is the production method according to [4].

[0015] [6] In the polyoxyethylene aryl ether, the aryl moiety is an aryl in which at least one of the hydrogen atoms is aralkyl-substituted, and is the production method according to [4].

[0016] When the components of [5] and [6] are used as the nonionic surfactant, the occurrence of sagging and collapse of the water-curable inorganic composition during lamination can be significantly reduced. In addition, the nonionic surfactant of the above components has an excellent balance of hydrophilicity and hydrophobicity, improves the miscibility with the water-curable inorganic composition, prevents the mixing of bubbles, and also has excellent defoaming properties, contributing to the improvement of the final strength.

[0017] [7] The water-hardening inorganic composition is cement defined in JIS R 5210:2019, JIS R 5211:2019, JIS R 5212:2019, JIS R 5213:2019 or JIS R 5214:2019, or mortar or concrete containing the cement, and is the production method according to any one of [1] to [6]. Such cement, mortar or concrete exhibits excellent strength after hardening even when combined with a gelling agent having the above-described characteristics.

[0018] [8] A heat-sensitive gelling agent for a water-hardening inorganic composition to be laminated and shaped, which is composed of an aqueous medium, a carboxy group-containing polymer containing a carboxy group-containing monomer as a monomer unit (however, not containing a group represented by -NHCH2O-) dispersed in the aqueous medium, and a surfactant (however, in the dispersion, the carboxy group may form a salt). The ratio of the carboxy group-containing monomer to all the monomers constituting the carboxy group-containing polymer is 0.1 to 5.0% by mass, and as the surfactant, it contains 0.5 to 3 parts by mass of an anionic surfactant with respect to 100 parts by mass of the carboxy group-containing polymer, and 1 to 8 parts by mass of a nonionic surfactant with a cloud point of 30 to 90 °C with respect to 100 parts by mass of the carboxy group-containing polymer. When the carboxy group forms a salt in the dispersion, part or all of the carboxy group may form a salt, and examples of the salt include alkali metal salts such as sodium salts and calcium salts, alkaline earth metal salts, and ammonium salts.

[0019] The present inventors have found that for a material for preventing sagging and collapse when added to and used in a water-hardening inorganic composition such as cement or mortar, a heat-sensitive gelling agent that can be quickly made non-fluid by mixing with and heating the water-hardening inorganic composition is effective. Furthermore, the heat-sensitive gelling agent needs to have good miscibility with the water-hardening inorganic composition. However, when used in laminated shaping such as 3D printing and heated to promote solidification, the defoaming property of the heat-sensitive gelling agent is very important.

[0020] That is, when the water-curable inorganic composition contains air bubbles, when heated to cause gelation, the air bubbles rapidly expand and the whole swells into a sponge-like shape, and when solidified in this state, the strength of the shaped article extremely decreases. In laminated shaping such as 3D printing, it is difficult to insert reinforcing bars into the shaped article, so prevention of air bubbles is very important.

[0021] [8] The thermosensitive gelling agent described in [8] is excellent in defoaming property, and even if foamed once, most of the bubbles disappear soon (for example, in about 10 minutes). Further, when incorporated into the water-curable inorganic composition used for laminated shaping such as 3D printing, it has excellent miscibility. And it rapidly becomes non-fluid (gels) by mixing and heating with the water-curable inorganic composition. When the water-curable inorganic composition is heated, the cation concentration (for example, calcium ion concentration) increases, and in addition to deactivating the anionic surfactant, when heated above the cloud point of the nonionic surfactant, the surfactant is deactivated and gelation is considered to occur. Due to the occurrence of gelation, the sagging and collapse of the water-curable inorganic composition during 3D printing (laminated shaping) are reduced to a practically sufficient level.

[0022] [9] The carboxy group-containing polymer is the thermosensitive gelling agent described in [8], which contains an ethylenically unsaturated carboxylic acid monomer as the carboxy group-containing monomer and an aliphatic conjugated diene monomer as monomer units.

[0023]

[10] Further, the thermosensitive gelling agent described in [9], which contains at least one selected from the group consisting of an alkenyl aromatic monomer, a vinyl cyanide monomer, an unsaturated carboxylic acid alkyl ester monomer, a hydroxyalkyl group-containing unsaturated monomer, and an unsaturated carboxylic acid amide monomer as monomer units.

[0024] [9] The carboxy group-containing polymer composed of the monomers described in [9] or

[10] is easy to produce by emulsion polymerization, has excellent physical properties when the composition for laminated shaping obtained by mixing with the water-curable inorganic composition is cured, and also has excellent defoaming property and miscibility.

[0025]

[11] The anionic surfactant is the thermosensitive gelling agent according to any one of [8] to

[10] , which is a sulfonic acid-based anionic surfactant.

[0026]

[12] The nonionic surfactant is the thermosensitive gelling agent according to any one of [8] to

[11] , which is a polyoxyalkylene alkyl ether and / or a polyoxyalkylene aryl ether.

[0027]

[13] The nonionic surfactant is the thermosensitive gelling agent according to any one of [8] to

[12] , which has an HLB value of 11 to 15. In this range, the lower the HLB value, the more excellent the defoaming property tends to be.

[0028]

[14] A composition for additive manufacturing containing the thermosensitive gelling agent according to any one of [8] to

[13] and a water-curable inorganic composition. Since this composition for additive manufacturing can be additively manufactured such as by 3D printing and gelation occurs by heating, the occurrence of sagging and collapse can be suppressed.

[0029]

[15] The water-curable inorganic composition is the cement defined in JIS R 5210:2019, JIS R 5211:2019, JIS R 5212:2019, JIS R 5213:2019 or JIS R 5214:2019, or the mortar or concrete containing the cement, which is the composition for additive manufacturing according to

[14] .

[0030]

[14] Or by using the composition for additive manufacturing according to

[15] , a manufacturing method of a shaped article can be provided. That is, a manufacturing method of a shaped article for additively manufacturing a water-curable inorganic composition, which contains the thermosensitive gelling agent according to any one of [8] to

[13] in the water-curable inorganic composition, and heats the laminate during and / or after lamination to gel the thermosensitive gelling agent, can be provided.

Advantages of the Invention

[0031] According to the present invention, there is provided a method for manufacturing a laminated object by additive manufacturing such as 3D printing, which can reduce the occurrence of sagging and collapse of the water-curable inorganic composition during lamination to a practically sufficient level.

[0032] The present invention also provides a material to be contained in a water-curable inorganic composition used for additive manufacturing such as 3D printing, which has excellent defoaming properties, high miscibility with the water-curable inorganic composition, and rapidly becomes non-fluidizable by mixing with the water-curable inorganic composition and heating, and a composition for additive manufacturing using this material.

Embodiments for Carrying Out the Invention

[0033] The method for manufacturing a laminated object according to the embodiment laminates a composition for additive manufacturing containing a water-curable inorganic composition and a heat-sensitive gelling agent, and non-fluidizes the composition for additive manufacturing by heating during and / or after lamination. (i) The heat-sensitive gelling agent contains an aqueous medium, a polymer dispersed in the aqueous medium, and a nonionic surfactant having a cloud point of 30°C or higher and an HLB value of 10 to 18. (ii) The heat-sensitive gelling agent is a formulation of the following (1) to (5) [(1) to (5) are in terms of solid content, and the water content is 18.5% by mass]. When 100 g of the formulation is introduced into a cylindrical container with an open top, defoamed, and then measured, the penetration resistance value (needle diameter = 2 mm, piercing speed = 30 mm / min, piercing depth = 10 mm) is such that when the value at 17 ± 3°C immediately after defoaming is a0 and the value at 17 ± 3°C after microwave heating at 600 W for 30 seconds after defoaming is a1, the value of a1 / a0 is 15 or more. Note that defoaming can be performed by vibrating the cylindrical container containing the formulation of (1) to (5) so that no visually observable bubbles are generated in the formulation at least at the opening of the cylindrical container. (1) Mortar 100 parts by mass (2) Sodium gluconate 1 part by mass (3) Carboxymethyl cellulose 0.5 part by mass (4) Silicone-based defoaming agent 0.1 part by mass (5) The heat-sensitive gelling agent 4.5 parts by mass

[0034] In some cases, the above-described embodiment may be referred to as the "first embodiment." Also, a nonionic surfactant having a cloud point of 30°C or higher and an HLB value of 10 to 18 may be referred to as "nonionic surfactant 1," and a nonionic surfactant other than nonionic surfactant 1 may be referred to as "nonionic surfactant 2." Examples of the aqueous medium include water, and water may contain water-soluble components (such as ethanol, glycerol, etc.).

[0035] Hereinafter, the first embodiment will be described in detail.

[0036] The thermosensitive gelling agent may be provided as a dispersion (emulsion, latex, etc.) containing the above polymer and nonionic surfactant. In this case, the above polymer may be obtained by emulsion or dispersion polymerization with a nonionic surfactant or a mixture of a nonionic surfactant and other surfactants (anionic surfactant, cationic surfactant, etc.) (Method A), or the above polymer may be emulsion or dispersion polymerized with the above other surfactant and then a nonionic surfactant may be added later (Method B). Alternatively, a nonionic surfactant may be added to the product obtained by Method A (Method C). The nonionic surfactant used in Methods A, B, and C may consist only of nonionic surfactant 1 or may be a mixture of nonionic surfactant 1 and nonionic surfactant 2.

[0037] As the polymer dispersed in the aqueous medium, a polymer having a glass transition temperature (which may be abbreviated as "Tg") measured by a differential scanning calorimeter at a heating rate of 10°C / min of -50 to 35°C can be adopted. Tg can also be -45 to 30°C, -40 to 30°C. As the polymer dispersed in the aqueous medium, a polymer having an elastic modulus (Young's modulus) of 1 to 10 MPa at 25°C can also be adopted. The Young's modulus can be measured in accordance with JIS K 6251:2017. As the polymer dispersed in the aqueous medium, a polymer having a Tg of -50 to 35°C and a Young's modulus of 1 to 10 MPa is preferred, and the polymer may be a crosslinked product or an uncrosslinked product. Such a polymer has properties as an elastomer.

[0038] As the polymer dispersed in the aqueous medium, homopolymers or copolymers of conjugated dienes (which may be abbreviated as "conjugated diene polymers") and homopolymers or copolymers of ethylenically unsaturated monomers (which may be abbreviated as "vinyl polymers") are effective.

[0039] As the "conjugated diene polymer" used in the first embodiment, styrene-butadiene rubber (hereinafter may be abbreviated as "SBR", and modified products such as carboxy-modified products are also included in SBR), methyl methacrylate-butadiene rubber (hereinafter may be abbreviated as "MBR", and modified products such as carboxy-modified products are also included in MBR), acrylonitrile-butadiene rubber (hereinafter may be abbreviated as "NBR", and modified products such as carboxy-modified products, styrene-modified products, (meth)acrylate ester-modified products are also included in NBR), styrene-butadiene-vinylpyridine rubber (hereinafter may be abbreviated as "VP", and modified products such as carboxy-modified products are also included in VP), butadiene rubber (hereinafter may be abbreviated as "BR", and modified products such as carboxy-modified products are also included in BR) and natural rubber (hereinafter may be abbreviated as "NR", and polyisoprene is also included in NR) are mentioned, and at least one selected from the group consisting of them is mentioned.

[0040] When the above conjugated diene polymer is provided as a dispersion, it is provided as at least one selected from the group consisting of styrene-butadiene rubber emulsion (styrene-butadiene rubber latex), methyl methacrylate-butadiene rubber emulsion (methyl methacrylate-butadiene rubber emulsion latex), acrylonitrile-butadiene rubber emulsion (acrylonitrile-butadiene rubber latex), styrene-butadiene-vinylpyridine rubber emulsion (styrene-butadiene-vinylpyridine rubber latex), butadiene rubber emulsion (butadiene rubber latex) and natural rubber emulsion (natural rubber latex).

[0041] Examples of the conjugated diene polymer include copolymers of an aliphatic conjugated diene monomer (for example, 10 to 80% by mass based on all monomers), an ethylenically unsaturated carboxylic acid monomer (for example, 0.5 to 15% by mass based on all monomers), and other copolymerizable monomers (for example, 5 to 89.5% by mass based on all monomers).

[0042] Examples of the aliphatic conjugated diene monomer include 1,3 - butadiene, 2 - methyl - 1,3 - butadiene, 2,3 - dimethyl - 1,3 - butadiene, 2 - chloro - 1,3 - butadiene, substituted linear conjugated pentadienes, substituted and side - chain conjugated hexadienes, etc., and one or more of these can be used. From the viewpoints of easy industrial production, availability, and cost, the use of 1,3 - butadiene is particularly preferred.

[0043] Examples of the ethylenically unsaturated carboxylic acid monomer include monobasic acids or dibasic acids (anhydrides) such as itaconic acid, acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, etc., and one or more of these can be used.

[0044] Examples of the other monomers include alkenyl aromatic monomers, vinyl cyanide monomers, unsaturated carboxylic acid alkyl ester monomers, unsaturated monomers containing a hydroxyalkyl group, unsaturated carboxylic acid amide monomers, etc.

[0045] Examples of the alkenyl aromatic monomer include styrene, α - methylstyrene, methyl - α - methylstyrene, vinyltoluene, divinylbenzene, etc. These can be used in combination of one or more. From the viewpoints of easy industrial production, availability, and cost, the use of styrene is particularly preferred.

[0046] Examples of vinyl cyanide monomers include monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and α-ethylacrylonitrile. These can be used alone or in combination of two or more. From the viewpoints of easy industrial production, availability, and cost, the use of acrylonitrile or methacrylonitrile is particularly preferred.

[0047] Examples of unsaturated carboxylic acid alkyl ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, glycidyl methacrylate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, dimethyl itaconate, monomethyl fumarate, monoethyl fumarate, 2-ethylhexyl acrylate, etc. These can be used alone or in combination of two or more. From the viewpoints of easy industrial production, availability, and cost, the use of methyl methacrylate is particularly preferred.

[0048] Examples of unsaturated monomers containing a hydroxyalkyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, di-(ethylene glycol) maleate, di-(ethylene glycol) itaconate, 2-hydroxyethyl maleate, bis(2-hydroxyethyl) maleate, 2-hydroxyethyl methyl fumarate, etc. These can be used alone or in combination of two or more.

[0049] Examples of unsaturated carboxylic acid amide monomers include acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N,N-dimethylacrylamide, etc. These can be used alone or in combination of two or more.

[0050] In addition to the above monomers, any of the monomers used in ordinary emulsion polymerization, such as ethylene, propylene, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, etc., can be used.

[0051] Such a conjugated diene polymer may have a carboxy group. In that case, the proportion of the carboxy group-containing monomer to all the monomers constituting the polymer is preferably 0.1 to 5.0% by mass. The proportion of the carboxy group-containing monomer may be 0.5 to 3.5% by mass or 1.0 to 3.0% by mass.

[0052] Examples of the "vinyl polymer" used in the first embodiment include acrylic polymers and / or ethylene copolymers.

[0053] An acrylic polymer means a polymer containing a monomer having a (meth)acryloyl group or a monomer copolymerizable with the monomer as a monomer unit (however, excluding ethylene copolymers according to the following definition). Here, (meth)acryloyl means acryloyl or methacryloyl, and the same applies to similar compounds.

[0054] The acrylic polymer may be provided as an aqueous dispersion. In that case, the monomer as a raw material may be emulsion polymerized to obtain an aqueous dispersion. The aqueous dispersion of the acrylic polymer may be a forced emulsification type aqueous dispersion in which a solution of the acrylic polymer in an organic solvent is dispersed in water and at least a part of the organic solvent is removed.

[0055] As the acrylic polymer, an acrylic rubber having properties as an elastomer can be used. Such an acrylic rubber preferably has a Tg of -40 to 30°C according to the above definition.

[0056] As the acrylic polymer, a copolymer of a low Tg monomer (a monomer having a Tg of 20°C or lower, preferably 0°C or lower according to the above definition when homopolymerized) and a high Tg monomer (a monomer having a Tg of 50°C or higher according to the above definition when homopolymerized) is preferred, and an acrylic polymer having a Tg of -40 to 30°C according to the above definition as a copolymer is more preferred. At least one of the low Tg monomer and the high Tg monomer has the above-mentioned (meth)acryloyl group.

[0057] Examples of the low Tg monomer include acrylic acid esters of linear or branched non-tertiary alcohols having 1 to 12 carbon atoms, and the number of carbon atoms of the non-tertiary alcohol may be 4 to 12, or 4 to 8. Examples of such non-tertiary alcohols include 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 1-hexanol, 2-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 2-ethyl-1-butanol, 3,5,5-trimethyl-1-hexanol, 3-heptanol, 1-octanol, 2-octanol, isooctyl alcohol, 2-ethyl-1-hexanol, 1-decanol, 2-propylheptanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, etc.

[0058] That is, examples of the low Tg monomer include n-butyl acrylate, isobutyl acrylate, hexyl acrylate, 2-ethyl-hexyl acrylate, isooctyl acrylate, caprolactone acrylate, isodecyl acrylate, tridecyl acrylate, lauryl methacrylate, methoxy-polyethylene glycol-monomethacrylate, lauryl acrylate, ethoxy-ethoxyethyl acrylate, ethoxylated-nonyl acrylate.

[0059] Examples of the high-Tg monomer include methacrylic acid esters of linear or branched non-tertiary alcohols having 1 to 2 or 6 to 18 carbon atoms, or acrylic acid esters of cyclic non-tertiary alcohols having 6 to 18 carbon atoms.

[0060] That is, examples of the high-Tg monomer include methyl methacrylate, ethyl methacrylate, stearyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, benzyl methacrylate, 3,3,5-trimethylcyclohexyl acrylate, cyclohexyl acrylate, and propyl methacrylate.

[0061] In addition to the above, examples of the high-Tg monomer include styrene, alkylstyrene (such as methylstyrene), (meth)acrylic acid, (meth)acrylamide, N-alkylacrylamide (such as N-octylacrylamide), N,N-dialkylacrylamide (such as N,N-dimethylacrylamide), and (meth)acrylonitrile.

[0062] The ethylene-based copolymer is a copolymer of ethylene and an ethylenically unsaturated monomer, and examples thereof include ethylene vinyl acetate, ethylene ethyl acrylate, ethylene vinyl ether, and ethylene-α-olefin copolymer.

[0063] The ethylene-based copolymer may be provided as an aqueous dispersion. In that case, an aqueous dispersion can be obtained by emulsion polymerization of the monomer as a raw material.

[0064] As the ethylene-based copolymer, an ethylene-based copolymer having properties as an elastomer can be used. Such an ethylene-based copolymer preferably has a Tg of -40 to 30°C according to the above definition.

[0065] In the first embodiment, regarding the above-mentioned formulations (1) to (5) [(1) to (5) are in terms of solid content, and the water content is 18.5% by mass], a gelling agent is used such that the value of a1 / a0 (30-second value) using a1 after microwave heating at 600 W for 30 seconds is 15 or more.

[0066] The value of a1 / a0 (30-second value) can be 15 to 350, and further can be 19 to 330. In addition to the value of a1 / a0 (30-second value) using a1 after microwave heating at 600 W for 30 seconds being 15 or more, the value of a2 / a0 (50-second value) using a2 after microwave heating at 600 W for 50 seconds may be 30 or more. The value of a2 / a0 (50-second value) may be 30 to 530, 35 to 530. Further, the value of a3 / a0 (70-second value) using a3 after microwave heating at 600 W for 70 seconds may be 60 or more. The value of a3 / a0 (70-second value) may be 60 to 900, 60 to 880. That is, the value of a1 / a0 (30-second value) is 15 or more and the value of a2 / a0 (50-second value) is 30 or more, the value of a1 / a0 (30-second value) is 15 or more and the value of a3 / a0 (70-second value) is 60 or more, or the value of a1 / a0 (30-second value) is 15 or more, the value of a2 / a0 (50-second value) is 30 or more, and the value of a3 / a0 (70-second value) is 60 or more may be acceptable.

[0067] As the (1) mortar contained in the formulations (1) to (5), "Quick-Drying Cement" manufactured by Kate Chemical Co., Ltd. (https: / / www.monotaro.com / g / 00269134 / ?t.q=%E9%80%9 F%E4%B9%BE%20%E3%82%BB%E3%83%A1%E3%83%B3%E3%83%88) or its equivalent is used. As the (4) silicone-based defoaming agent contained in the formulations (1) to (5), an emulsion-type defoaming agent with 28% active ingredient containing α-(octadecanoyloxy)-ω-hydroxy-poly(oxyethylene), glyceryl monostearate, silicon dioxide, and octamethylcyclotetrasiloxane (for example, "DOWSIL TM SH 5507 Emulsion" manufactured by Dow Corning Toray Co., Ltd. or its equivalent) is used.

[0068] The thermosensitive gelling agent used in the first embodiment contains a nonionic surfactant having a cloud point of 30°C or higher and an HLB value of 10 to 18. Here, the cloud point means the cloud point defined in JIS K 3211:1990, and can be measured, for example, in a 2 mass% aqueous dilution. The HLB value is a value representing the degree of affinity of the surfactant for water and oil (organic compounds insoluble in water), and can be determined by the Griffin method (HLB value = 20 × total sum of the formula weights of the hydrophilic part / molecular weight).

[0069] The cloud point of the nonionic surfactant may be 30 to 100°C, 30 to 98°C, or 40 to 98°C, and the HLB value of the nonionic surfactant may be 11 to 17 or 12 to 17.

[0070] As the nonionic surfactant, polyoxyethylene alkyl ether and / or polyoxyethylene aryl ether can be used. For the polyoxyethylene alkyl ether, (i) it is preferably one in which the alkyl part is an alkyl having 12 to 20 carbon atoms, and for the polyoxyethylene aryl ether, (ii) it is preferably one in which the aryl part is an aryl in which at least one of the hydrogen atoms is aralkyl-substituted. Examples of the nonionic surfactant of (i) include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and polyoxyethylene octyldodecyl ether. Examples of the nonionic surfactant of (ii) include polyoxyethylene distyrenated phenyl ether and polyoxyethylene tribenzyl phenyl ether.

[0071] In the first embodiment, the amount of the nonionic surfactant 1 with respect to 100 parts by mass of the polymer can be 1 to 12 parts by mass, 3 to 10 parts by mass, or 5 to 8 parts by mass.

[0072] As the water-curable inorganic composition in the first embodiment, Portland cement defined in JIS R 5210:2019, blast furnace cement defined in JIS R 5211:2019, silica cement defined in JIS R 5212:2019, fly ash cement defined in JIS R 5213:2019, or eco-cement defined in JIS R 5214:2019, or mortar or concrete containing these cements can be used.

[0073] In the first embodiment, for 100 parts by mass (in terms of solid content) of the water-curable inorganic composition, 1 to 20 parts by mass, 3 to 15 parts by mass, or 3 to 10 parts by mass of the thermosensitive gelling agent can be used.

[0074] In the first embodiment, the thermosensitive gelling agent may contain additives such as an antifoaming agent, a dispersant, an antioxidant, a viscosity modifier, a pH preparation, a preservative, an electrolyte, a filler, a plasticizer, starch, and a coloring pigment, as long as the effects of the present invention are not affected. The solid content concentration of the thermosensitive gelling agent in the first embodiment can be, for example, 30 to 60% by mass, and may be 40 to 50% by mass.

[0075] The thermosensitive gelling agent according to the embodiment is a thermosensitive gelling agent for a water-curable inorganic composition to be laminated and molded, and is composed of an aqueous medium, a carboxy group-containing polymer containing a carboxy group-containing monomer as a monomer unit dispersed in the aqueous medium (however, does not contain a group represented by -NHCH2O-), and a surfactant (however, in the dispersion, the carboxy group may form a salt), and the ratio of the carboxy group-containing monomer to all the monomers constituting the carboxy group-containing polymer is 0.1 to 5.0% by mass. As the surfactant, it contains 0.5 to 3 parts by mass of an anionic surfactant with respect to 100 parts by mass of the carboxy group-containing polymer and 1 to 8 parts by mass of a nonionic surfactant with a cloud point of 30 to 90°C with respect to 100 parts by mass of the carboxy group-containing polymer. In addition, this embodiment may be referred to as the "second embodiment".

[0076] Hereinafter, the second embodiment will be described in detail.

[0077] The carboxy group-containing polymer is dispersed in an aqueous medium, and the anionic surfactant and the nonionic surfactant are usually dissolved in the aqueous medium and have a function of emulsifying and dispersing the carboxy group-containing polymer in the aqueous medium. As the aqueous medium, water may be mentioned, and water may contain water-soluble components (for example, ethanol, glycerol, etc.).

[0078] The carboxy group-containing polymer has a carboxy group in the side chain and / or at the terminal of the polymer molecule, while not having a group represented by -NHCH2O-. Examples of the group represented by -NHCH2O- include -NHCH2OH and -NHCH2OC n H 2n+1 (n is a number from 1 to 4).

[0079] The carboxy group-containing polymer only needs to have a carboxy group, and there is no restriction on the backbone of the main chain. The main chain may be one in which carbon is continuous (for example, a vinyl polymer), or may have a urethane bond (polyurethane), an ester bond (polyester), an ether bond (polyether), or a combination thereof.

[0080] The water-curable inorganic composition containing the carboxy group-containing polymer is heated for gelation during additive manufacturing. The minimum film-forming temperature (MFT) of the carboxy group-containing polymer is arbitrary, but considering the binder properties of the water-curable inorganic composition, the MFT is preferably 0 to 50°C, and may be 5 to 40°C. The value of the glass transition temperature (Tg) generally correlates with the MFT, but the Tg is preferably -20 to 50°C, and may be -15 to 40°C.

[0081] The carboxy group-containing polymer can be obtained by polymerizing monomers, and the proportion of the carboxy group-containing monomer to all the monomers constituting the carboxy group-containing polymer is 0.1 to 5.0% by mass. The proportion of the carboxy group-containing monomer may be 0.5 to 3.5% by mass, or 1.0 to 3.0% by mass. When the proportion of the carboxy group-containing monomer is out of the range of 0.1 to 5.0% by mass, the miscibility with the water-curable inorganic composition deteriorates. When the proportion of the carboxy group-containing monomer is less than 0.1% by mass, the miscibility with the water-curable inorganic composition can be compensated by increasing the amount of the anionic surfactant. However, in that case, the defoaming property is poor, which is not preferable.

[0082] Examples of the carboxy group-containing polymer include polymers containing an ethylenically unsaturated carboxylic acid monomer (corresponding to the carboxy group-containing monomer) and an aliphatic conjugated diene monomer as monomer units. Examples of the ethylenically unsaturated carboxylic acid monomer include monobasic acids or dibasic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid (which may be in the form of anhydrides), and one or more of these can be used. Examples of the aliphatic conjugated diene monomer include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, substituted linear conjugated pentadienes, substituted and side-chain conjugated hexadienes, etc., and one or more of these can be used. From the viewpoints of easy industrial production, availability, and cost, the use of 1,3-butadiene is particularly preferable.

[0083] In addition to the ethylenically unsaturated carboxylic acid monomer and the aliphatic conjugated diene monomer, the carboxy group-containing polymer may contain at least one selected from the group consisting of alkenyl aromatic monomers, vinyl cyanide monomers, unsaturated carboxylic acid alkyl ester monomers, hydroxyalkyl group-containing unsaturated monomers, and unsaturated carboxylic acid amide monomers as monomer units.

[0084] Examples of alkenyl aromatic monomers include styrene, α-methylstyrene, methyl-α-methylstyrene, vinyltoluene, divinylbenzene, etc. These can be used alone or in combination of two or more. From the viewpoints of easy industrial production, availability, and cost, the use of styrene is particularly preferred.

[0085] Examples of vinyl cyanide monomers include monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile, etc. These can be used alone or in combination of two or more. From the viewpoints of easy industrial production, availability, and cost, the use of acrylonitrile or methacrylonitrile is particularly preferred.

[0086] Examples of unsaturated carboxylic acid alkyl ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, glycidyl methacrylate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, dimethyl itaconate, monomethyl fumarate, monoethyl fumarate, 2-ethylhexyl acrylate, etc. These can be used alone or in combination of two or more. From the viewpoints of easy industrial production, availability, and cost, the use of methyl methacrylate is particularly preferred.

[0087] Examples of unsaturated monomers containing a hydroxyalkyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, di-(ethylene glycol) maleate, di-(ethylene glycol) itaconate, 2-hydroxyethyl maleate, bis(2-hydroxyethyl) maleate, 2-hydroxyethyl methyl fumarate, etc. These can be used alone or in combination of two or more.

[0088] Examples of the unsaturated carboxylic acid amide monomers include acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N,N-dimethylacrylamide, etc. These can be used alone or in combination of two or more.

[0089] In addition to the above monomers, any monomers used in ordinary emulsion polymerization, such as ethylene, propylene, vinyl acetate, vinyl propionate, vinyl chloride, vinylidene chloride, etc., can be used.

[0090] In the second embodiment, the carboxy group-containing polymer may be provided as a dispersion (in the state of an emulsion, latex, suspension, etc.) dispersed in an aqueous medium. As the whole heat-sensitive gelling agent, 0.5 to 3 parts by mass of an anionic surfactant is contained with respect to 100 parts by mass of the carboxy group-containing polymer. However, when the carboxy group-containing polymer is provided as a dispersion, it may contain 0.5 to 3 parts by mass of an anionic surfactant with respect to 100 parts by mass of the carboxy group-containing polymer in the state of this dispersion. Alternatively, a dispersion containing an amount of an anionic surfactant less than 0.5 to 3 parts by mass may be prepared, and the anionic surfactant may be added later so that the total amount becomes 0.5 to 3 parts by mass with respect to 100 parts by mass of the carboxy group-containing polymer when adjusting the heat-sensitive gelling agent.

[0091] In the second embodiment, as the entire thermosensitive gelling agent, 1 to 8 parts by mass of a nonionic surfactant having a cloud point of 30 to 90°C is contained with respect to 100 parts by mass of the carboxyl group-containing polymer. However, when the carboxyl group-containing polymer is provided as a dispersion, in the state of this dispersion, it may contain 1 to 8 parts by mass of a nonionic surfactant with respect to 100 parts by mass of the carboxyl group-containing polymer. Alternatively, a dispersion containing an amount of nonionic surfactant less than 1 to 8 parts by mass (it may be a dispersion not containing a nonionic surfactant) is prepared, and when preparing the thermosensitive gelling agent, the nonionic surfactant may be added later so that the total amount becomes 1 to 8 parts by mass with respect to 100 parts by mass of the carboxyl group-containing polymer. However, since the nonionic surfactant has a cloud point of 30 to 90°C, when the nonionic surfactant is added to the system during the synthesis or preparation of the dispersion, only a nonionic surfactant having a cloud point higher than the temperature for synthesis or preparation is added.

[0092] When the carboxyl group-containing polymer is provided as a dispersion, examples of the dispersion include styrene-butadiene latex (including styrene, butadiene, and a carboxyl group-containing monomer as monomer components), chloroprene latex (including chloroprene and a carboxyl group-containing monomer as monomer components), methyl methacrylate-butadiene latex (including methyl methacrylate, butadiene, and a carboxyl group-containing monomer as monomer components), nitrile rubber latex (including acrylonitrile, butadiene, and a carboxyl group-containing monomer as monomer components), polybutadiene latex (including butadiene and a carboxyl group-containing monomer as monomer components), 2-vinylpyridine-styrene-butadiene latex (including 2-vinylpyridine, styrene, butadiene, and a carboxyl group-containing monomer as monomer components), and the like.

[0093] As the dispersion liquid, acrylic ester resin emulsions (including (meth)acrylic acid esters and carboxyl group-containing monomers as monomer components), styrene-acrylic ester resin emulsions (including styrene, (meth)acrylic acid esters, and carboxyl group-containing monomers as monomer components), ethylene-vinyl acetate resin emulsions (including ethylene, vinyl acetate, and carboxyl group-containing monomers as monomer components), ethylene-vinyl acetate-acrylic acid ester copolymer resin emulsions (including ethylene, vinyl acetate, (meth)acrylic acid esters, and carboxyl group-containing monomers as monomer components), etc. can also be used.

[0094] As the dispersion liquid, polyurethane emulsions (emulsions of polyurethanes having carboxyl groups in the side chains or at the terminals) and polyester emulsions (emulsions of polyesters having carboxyl groups in the side chains or at the terminals) can also be mentioned. In the case of these emulsions, carboxyl groups are introduced into the side chains or at the terminals of the polyurethane or polyester.

[0095] When the carboxyl group-containing polymer is provided as the dispersion liquid, its solid content concentration is usually 30 to 60% by mass, and may be 40 to 50% by mass. The average particle diameter of the carboxyl group-containing polymer (the average particle diameter is measured by taking a transmission electron micrograph after staining the copolymer latex with osmium tetroxide, measuring the diameters of 1000 particles using an image analysis processing apparatus (apparatus name: IP-1000PC manufactured by Asahi Kasei Corporation), and by number average) is arbitrary, but can be 80 to 250 nm, and may be 100 to 200 nm, or 120 to 180 nm.

[0096] In the second embodiment, the thermosensitive gelling agent contains a surfactant in addition to the above-described aqueous medium and the carboxy group-containing polymer. As the surfactant, an anionic surfactant in an amount of 0.5 to 3 parts by mass and a nonionic surfactant having a cloud point of 30 to 90°C in an amount of 1 to 8 parts by mass with respect to 100 parts by mass of the carboxy group-containing polymer are included. Although the inclusion of components other than these is not prohibited as the surfactant, since it greatly affects thermosensitive gelation, it is preferably composed only of these components.

[0097] Examples of the anionic surfactant include alkyl sulfate ester-based anionic surfactants such as sodium lauryl sulfate, triethanolamine lauryl sulfate, and ammonium lauryl sulfate; polyoxyethylene alkyl ether sulfate ester salt-based anionic surfactants such as sodium polyoxyethylene lauryl ether sulfate and sodium polyoxyethylene polyoxypropylene alkyl ether sulfate; sulfonic acid-based anionic surfactants such as sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, sodium sulfosuccinate alkyl monoamide disodium, sodium alkyl diphenyl ether disulfonate, and sodium alkanesulfonate; and carboxylic acid-based surfactants such as rosin acid salts and fatty acid salts. Among them, sulfonic acid-based anionic surfactants are preferred.

[0098] The content of the anionic surfactant is 0.5 to 3 parts by mass with respect to 100 parts by mass of the carboxy group-containing polymer, but may be 1.0 to 2.5 parts by mass or 1.0 to 2.0 parts by mass. If the content of the anionic surfactant is less than 0.5 part by mass, the miscibility deteriorates, and if it exceeds 3 parts by mass, the defoaming property decreases and thermosensitive gelation becomes difficult.

[0099] Examples of nonionic surfactants include polyoxyalkylene alkyl ether-based nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene myristyl ether, and polyoxyethylene octyldodecyl ether; and polyoxyalkylene aryl ether-based nonionic surfactants such as polyoxyethylene distyrenated phenyl ether and polyoxyethylene tribenzyl phenyl ether.

[0100] The content of the nonionic surfactant is 1 to 8 parts by mass, preferably 2.0 to 7.5 parts by mass, more preferably 3.0 to 7.0 parts by mass, based on 100 parts by mass of the carboxy group-containing polymer. If the content of the nonionic surfactant is less than 1 part by mass, the miscibility deteriorates. If it exceeds 8 parts by mass, heat-induced gelation becomes difficult and the defoaming property also decreases.

[0101] In the second embodiment, the cloud point of the nonionic surfactant is 30 to 90°C, preferably 30 to 85°C, 40 to 90°C, 40 to 85°C, 50 to 90°C, or 50 to 85°C. Since the cloud point of the nonionic surfactant correlates with the temperature of heat-induced gelation, it is preferable to determine the cloud point of the nonionic surfactant to be used according to the temperature at which the water-curable inorganic composition added with the carboxy group-containing polymer is laminated. For example, in the case of lamination outdoors at a high temperature (such as in summer), a nonionic surfactant having a cloud point on the high temperature side, such as 40 to 90°C or 50 to 90°C, is preferably used. In the case of lamination outdoors at a low temperature (such as in winter), a nonionic surfactant having a cloud point on the low temperature side, such as 30 to 80°C, 30 to 70°C, or 30 to 60°C, is preferably used.

[0102] In the second embodiment, the HLB value of the nonionic surfactant is preferably in the range of 11 to 15, more preferably 12 to 14. As the HLB increases, the defoaming property tends to decrease.

[0103] In the second embodiment, the thermosensitive gelling agent only needs to contain the above-mentioned aqueous medium, carboxyl group-containing polymer, and surfactant, and may contain additives such as defoamers, dispersants, antioxidants, viscosity modifiers, pH agents, preservatives, electrolytes, fillers, plasticizers, starch, and coloring pigments as long as the effects of the present invention are not affected. The solid content concentration of the thermosensitive gelling agent can be, for example, 30 to 60% by mass, and may be 40 to 50% by mass.

[0104] To obtain the thermosensitive gelling agent, each component contained therein may be mixed. However, since it contains a nonionic surfactant having a cloud point of 30 to 90°C, it is preferable to mix at a temperature below the cloud point of the nonionic surfactant contained.

[0105] Note that a production example in the case where a carboxyl group-containing polymer containing a carboxyl group-containing monomer as a monomer unit is provided as a latex will be described below. In this case, a latex is obtained in a state containing an aqueous medium, a carboxyl group-containing polymer, and an anionic surfactant, which are required for the thermosensitive gelling agent.

[0106] The latex can be produced by emulsion polymerization of a monomer component containing an ethylenically unsaturated carboxylic acid monomer, an aliphatic conjugated diene monomer, and other copolymerizable monomers in an aqueous medium together with a surfactant.

[0107] As the other copolymerizable monomers, at least one selected from the group consisting of alkenyl aromatic monomers, vinyl cyanide monomers, unsaturated carboxylic acid alkyl ester monomers, hydroxyalkyl group-containing unsaturated monomers, and unsaturated carboxylic acid amide monomers can be used. Specific examples of the monomers are as described above, and the above-mentioned anionic surfactant can be used as the surfactant.

[0108] As methods for adding monomer components and other components during emulsion polymerization, for example, a batch addition method, a divided addition method, a continuous addition method, and a power feed method can be mentioned. Among these, it is preferable to adopt the continuous addition method (hereinafter, sometimes referred to as "continuous addition"). Furthermore, the continuous addition may be performed multiple times.

[0109] Emulsion polymerization is usually carried out using a polymerization initiator, and a chain transfer agent may be used for purposes such as molecular weight adjustment.

[0110] Examples of the polymerization initiator include water-soluble polymerization initiators such as lithium persulfate, potassium persulfate, sodium persulfate, and ammonium persulfate; oil-soluble polymerization initiators such as cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, diisopropylbenzene hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide. These can be used alone or in combination of two or more. In particular, it is preferable to select from potassium persulfate, sodium persulfate, cumene hydroperoxide, and t-butyl hydroperoxide. The blending amount of the polymerization initiator is not particularly limited, but is appropriately adjusted in consideration of combinations such as the monomer composition, the pH of the polymerization reaction system, and other additives.

[0111] Examples of the chain transfer agent include alkyl mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and n-stearyl mercaptan; xanthogen compounds such as dimethyl xanthogen disulfide and diisopropyl xanthogen disulfide; thiuram compounds such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, and tetramethylthiuram monosulfide; phenolic compounds such as 2,6-di-t-butyl-4-methylphenol and styrenated phenol; allyl compounds such as allyl alcohol; halogenated hydrocarbon compounds such as dichloromethane, dibromomethane, and carbon tetrabromide; vinyl ethers such as α-benzyloxystyrene, α-benzyloxyacrylonitrile, and α-benzyloxyacrylamide; and chain transfer agents such as triphenylethane, pentaphenylethane, acrolein, methacrolein, thioglycolic acid, thiomalic acid, 2-ethylhexyl thioglycolate, terpinolene, and α-methylstyrene dimer. These can be used alone or in combination of two or more. The blending amount of the chain transfer agent can be appropriately adjusted in consideration of combinations of other additives and the like.

[0112] By mixing the above-described thermosensitive gelling agent and the water-curable inorganic composition, a composition for additive manufacturing can be obtained and used for additive manufacturing such as 3D printing. Then, by heating the laminate during and / or after lamination, the thermosensitive gelling agent causes gelation, preventing sagging and collapse of the composition for additive manufacturing. The heating may be performed, for example, so that the composition for additive manufacturing reaches, for example, 40 to 100°C, and may be 50 to 90°C. The heating means is arbitrary, and examples include blowing hot air, irradiating far-infrared rays, irradiating a heating electric lamp, irradiating microwaves, and blowing superheated steam.

[0113] In the second embodiment, the mixing ratio of the thermosensitive gelling agent and the water-curable inorganic composition can be, for example, 1 to 15 parts by mass in terms of solid content of the thermosensitive gelling agent with respect to 100 parts by mass of the water-curable inorganic composition, and may be 3 to 10 parts by mass.

[0114] In the second embodiment, as the water-curable inorganic composition, Portland cement defined in JIS R 5210:2019, blast furnace cement defined in JIS R 5211:2019, silica cement defined in JIS R 5212:2019, fly ash cement defined in JIS R 5213:2019, or eco-cement defined in JIS R 5214:2019, or mortar or concrete containing these cements can be used.

Examples

[0115] Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to the following examples.

[0116] (Copolymer 1) Into a pressure-resistant polymerization reactor, 95 parts by mass of polymerization water, 7.2 parts by mass of styrene, 2.3 parts by mass of 1,3-butadiene, 1.2 parts by mass of acrylic acid, 0.5 parts by mass of fumaric acid, 2 parts by mass of hydroxyethyl acrylate, 6 parts by mass of cyclohexene, 0.03 parts by mass of t-dodecyl mercaptan, 0.9 parts by mass of sodium dodecylbenzenesulfonate, and 0.3 parts by mass of sodium hydrogen carbonate were charged and stirring was started. 1 part by mass of potassium persulfate was added and the temperature inside the reactor was raised to 70°C, and 19.5 parts by mass of styrene, 5.3 parts by mass of 1,3-butadiene, and 0.06 parts by mass of t-dodecyl mercaptan were continuously added over 150 minutes. After the addition of each monomer and other compounds was completed, immediately 28.0 parts by mass of styrene, 34 parts by mass of 1,3-butadiene, and 0.36 parts by mass of t-dodecyl mercaptan were continuously added over 360 minutes. Then, the temperature inside the polymerization reactor was raised to 85°C and polymerization was terminated when the polymerization conversion rate exceeded 98%. Next, the pH was adjusted to 7.0 with an aqueous sodium hydroxide solution, and steam distillation was performed to remove unreacted monomers and other low-boiling compounds, obtaining an emulsion containing copolymer 1.

[0117] (Copolymer 2) Into a pressure-resistant polymerization reactor, 90 parts by mass of polymerization water, 0.16 parts by mass of sodium hydrogen carbonate, 0.6 parts by mass of sodium dodecylbenzenesulfonate, 5.2 parts by mass of styrene, 2.7 parts by mass of 1,3-butadiene, 0.1 parts by mass of methyl methacrylate, 4 parts by mass of cyclohexene, 1.2 parts by mass of acrylic acid, 1 part by mass of hydroxyethyl acrylate, and 0.5 parts by mass of fumaric acid were charged and stirring was started. 1 part by mass of potassium persulfate was added and the temperature inside the reactor was raised to 68 °C, and 66.3 parts by mass of styrene, 23 parts by mass of 1,3-butadiene, 1 part by mass of t-dodecyl mercaptan, and 0.5 parts by mass of sodium dodecylbenzenesulfonate were continuously added over 450 minutes. Then, polymerization was terminated when the polymerization conversion rate exceeded 98%. Next, the pH was adjusted to 7.0 with an aqueous sodium hydroxide solution, and steam distillation was performed to remove unreacted monomers and other low-boiling compounds, obtaining an emulsion containing copolymer 2.

[0118] (Copolymer 3) Saiatex NA-106 (acrylonitrile-butadiene latex) manufactured by Nippon A&R Co., Ltd. was used as copolymer 3.

[0119] (Copolymer 4) 2.0 parts by mass of sodium dodecylbenzenesulfonate was added to J-9049 (carboxylic acid-unmodified styrene-butadiene latex) manufactured by Nippon A&R Co., Ltd. to obtain copolymer 4.

[0120] (Copolymer 5) Into a pressure-resistant polymerization reactor, 0.8 parts by mass of itaconic acid, 0.04 parts by mass of sodium alkyl diphenyl ether disulfonate, 0.24 parts by mass of rosin oil, 1.4 parts by mass of sodium β-naphthalenesulfonic acid formalin condensate, and 100 parts by mass of polymerization water were charged and stirring was started, and the temperature inside the reactor was raised to 67°C. When the temperature reached 67°C, 0.33 parts by mass of potassium persulfate was added. Immediately after the addition of potassium persulfate was completed, 9.6 parts by mass of 1,3-butadiene, 14.2 parts by mass of methyl methacrylate, 0.06 parts by mass of t-dodecyl mercaptan, 0.012 parts by mass of rosin oil, and 0.06 parts by mass of sodium β-naphthalenesulfonic acid formalin condensate were continuously added over 100 minutes. After the addition was completed, the reaction was continued for 80 minutes, and then 20.4 parts by mass of 1,3-butadiene, 31.0 parts by mass of methyl methacrylate, 0.14 parts by mass of t-dodecyl mercaptan, 0.027 parts by mass of rosin oil, and 0.14 parts by mass of sodium β-naphthalenesulfonic acid formalin condensate were continuously added over 270 minutes. After the addition was completed, stirring was continued for 90 minutes, and then 0.2 parts by mass of itaconic acid, 0.01 parts by mass of rosin oil, and 0.05 parts by mass of sodium β-naphthalenesulfonic acid formalin condensate were added. Further, 6 parts by mass of 1,3-butadiene, 17.8 parts by mass of methyl methacrylate, 0.1 parts by mass of t-dodecyl mercaptan, 0.05 parts by mass of rosin oil, and 0.35 parts by mass of sodium β-naphthalenesulfonic acid formalin condensate were continuously added over 120 minutes. Then, the polymerization was terminated when the polymerization conversion rate reached 98% or more. Next, the pH was adjusted to 7.0 with potassium hydroxide, and steam distillation was performed to remove unreacted monomers and other low-boiling compounds, obtaining an emulsion containing copolymer 5.

[0121] (Copolymer 6) SiaTex SR-110 (carboxylic acid-modified styrene-butadiene latex) manufactured by Nippon A&R Co., Ltd. was used as copolymer 6.

[0122] (Copolymer 7) In a pressure-resistant polymerization reactor, 90 parts by mass of polymerization water, 6.0 parts by mass of styrene, 4.0 parts by mass of 1,3-butadiene, 1.0 part by mass of methyl methacrylate, 1.0 part by mass of hydroxyethyl acrylate, 2.0 parts by mass of fumaric acid, 2 parts by mass of cyclohexene, 0.15 part by mass of sodium dodecylbenzenesulfonate, and 0.3 part by mass of sodium hydrogen carbonate were charged under a nitrogen atmosphere, and stirring was started. 1 part by mass of potassium persulfate was added, and the temperature inside the reactor was raised to 70°C. 54.0 parts by mass of styrene, 29.0 parts by mass of 1,3-butadiene, 3.0 parts by mass of methyl methacrylate, 0.47 part by mass of t-dodecyl mercaptan, and 0.1 part by mass of sodium dodecylbenzenesulfonate were continuously added over 420 minutes. After the addition of each monomer and other compounds was completed, 0.1 part by mass of t-dodecyl mercaptan was immediately added, and the reaction was carried out for 150 minutes while maintaining the temperature at 70°C. Then, the temperature inside the polymerization reactor was raised to 85°C, and the polymerization was terminated when the polymerization conversion rate exceeded 98%. Next, the pH was adjusted to 7.0 with an aqueous sodium hydroxide solution, and steam distillation was performed to remove unreacted monomers and other low-boiling compounds, obtaining an emulsion containing copolymer 7.

[0123] (Acrylic copolymer 1) In a pressure-resistant polymerization reactor, 105 parts by mass of polymerization water, 5.2 parts by mass of styrene, 4.6 parts by mass of 2-ethylhexyl acrylate, 1.5 parts by mass of itaconic acid, 0.2 part by mass of ethylene glycol dimethacrylate, 0.3 part by mass of sodium dodecylbenzenesulfonate, and 0.3 part by mass of sodium hydrogen carbonate were charged under a nitrogen atmosphere, and stirring was started. 1 part by mass of potassium persulfate was added, and the temperature inside the reactor was raised to 70°C. 45.8 parts by mass of styrene, 40.6 parts by mass of 2-ethylhexyl acrylate, 2.1 parts by mass of ethylene glycol dimethacrylate, 0.7 part by mass of sodium dodecylbenzenesulfonate, and 10 parts by mass of polymerization water were continuously added over 300 minutes. Then, the polymerization was terminated when the polymerization conversion rate exceeded 98%. Next, for the obtained emulsion, the pH was adjusted to 7.0 with an aqueous sodium hydroxide solution, and steam distillation was performed to remove unreacted monomers and other low-boiling compounds, obtaining acrylic copolymer 1.

[0124] (Examples 1 to 14, Comparative Examples 1 to 3) For 100 parts by mass of Copolymers 1 to 7, the nonionic surfactant described in Table 1 was added in the amount described in the same table and used as a thermosensitive gelling agent. In Example 14, Sumiflex 510HQ manufactured by Sumitomo Chemical Tex Co., Ltd. was used.

[0125] (Comparative Examples 4 to 8) Copolymers 2 to 5 and Acrylic Copolymer 1 without addition of nonionic surfactant were used as thermosensitive gelling agents.

[0126] (Comparative Example 9) A commercially available latex for mortar mixing (L-3642E manufactured by Nippon A&R Co., Ltd.) was used as a gelling agent.

[0127] (Comparative Examples 10 to 11) Commercially available mortar (“Quick-drying Cement” manufactured by Kate Chemical Co., Ltd.) was used, and no thermosensitive gelling agent was used. In Comparative Example 11, 1 part by mass of sodium gluconate, which is a setting retarder, was added to 100 parts by mass of the mortar.

[0128]

Table 1

[0129]

Table 2

[0130] [Penetration Resistance Value] The following formulations (1) to (5) [where (1) to (5) are in terms of solid content and the moisture content is 18.5% by mass] were introduced into a cylindrical container with an open top in an amount of 100 g. (1) Mortar (“Quick-drying Cement” manufactured by Kate Chemical Co., Ltd.) 100 parts by mass (2) Sodium gluconate 1 part by mass (3) Carboxymethyl cellulose 0.5 part by mass (4) Silicone-based antifoaming agent (“DOWSIL” manufactured by Dow Corning Toray Co., Ltd.) TM0.1 part by mass of "SH 5507 Emulsion" (5) 4.5 parts by mass of the gelling agent in Examples 1 to 2 and Comparative Examples 1 to 2 Next, the bottom surface of the cylindrical container was tapped with a spatula for 1 minute to defoam. After defoaming, the penetration resistance value (needle diameter = 2 mm, piercing speed = 30 mm / min, piercing depth = 10 mm) was measured at 17°C. When measuring, the maximum value was read, and 5 measurements were taken at 5 locations for 1 sample to obtain the average value. The average value obtained at this time was designated as a0. The defoamed product was heated with a 600 W microwave for 30 seconds, cooled together with the container in ice water at 2 - 5°C to bring the content to 17°C, and the average value of the penetration resistance value was obtained in the same manner as above at the same temperature. The average value obtained at this time was designated as a1. Table 1 shows a0, a1, and a1 / a0.

[0131] [Laminability] Regarding Examples 1 to 13 and Comparative Examples 1 to 2 to which the gelling agent was added, and Comparative Examples 3 to 4 to which the gelling agent was not added, a food processing squeezing bag and a squeezer were used, and extrusion was performed into a string shape with a width of about 10 mm under the condition that the diameter of the aperture of the squeezer was 10 mm. After extruding about 100 mm, when heating, it was heated with a 600 W microwave heating device for 20 seconds, then folded back and laminated, and an experiment was conducted to see how many layers could be formed without dripping or breaking of the layers. When 10 or more layers could be formed, it was marked as ◎, when 7 - 9 layers could be formed, it was marked as 〇, when 4 - 6 layers could be formed, it was marked as △, and when 3 or fewer layers were formed, it was marked as ×.

[0132] In addition, for the composition for laminated molding in the examples, the final curing strength and the adhesive strength between layers were good. Also, just by applying a slight vibration (such as tapping with a spatula) to the container containing the composition for laminated molding, the bubbles disappeared. Also, the dischargeability from the nozzle of the composition for laminated molding before curing was good.

[0133] (Copolymer A) Into a pressure-resistant polymerization reactor equipped with a stirrer, 150 parts by mass of polymerization water and the initial addition components described in Table 3 were charged all at once, the temperature was raised to 75°C, and the continuous addition components described in Table 3 were continuously added for 8 hours to carry out a polymerization reaction. Polymerization was terminated when the polymerization conversion rate exceeded 98%. Subsequently, the pH was adjusted to 7 using sodium hydroxide, and steam distillation was performed to remove unreacted monomers and other low-boiling compounds, obtaining a latex containing copolymer A. Note that this copolymer A corresponds to a carboxyl group-containing polymer in which the proportion of the carboxyl group-containing monomer to all monomers is 0.1 to 5.0% by mass. Table 3 shows the particle diameters of the latex particles.

[0134] (Copolymers B - I) Copolymers B - I were obtained in the same manner as copolymer A, except that the components were changed to those described in Table 3. Note that copolymers B - F and H correspond to carboxyl group-containing polymers in which the proportion of the carboxyl group-containing monomer to the monomers is 0.1 to 5.0% by mass. Copolymer G is a carboxyl group-containing polymer, but the proportion of the carboxyl group-containing monomer to all monomers exceeds 5.0% by mass. Copolymer I is a polymer having no carboxyl group. Table 3 shows the average particle diameters of the latex particles.

[0135] [Table 3]

[0136] (Examples 21 - 30) Latexes containing copolymers A, B, C, E, F, and H shown in Table 4 and the nonionic surfactant shown in the same table were mixed at the ratios shown in the same table to prepare a thermosensitive gelling agent. Then, the properties were measured according to the following method, and the results are shown in Table 4.

[0137] (Comparative Examples 21 - 26) Latexes containing copolymers A, D, G, and I shown in Table 5 and the nonionic surfactant shown in the same table were mixed at the ratios shown in the same table to prepare a thermosensitive gelling agent. Then, the properties were measured according to the following method, and the results are shown in Table 5.

[0138] (Mortar Mixability and Heat-Sensitive Gelation) 100 g of quick-drying cement for household chemicals and 1.0 g of sodium gluconate were weighed into a 200 mL poly cup and stirred well. Next, 24.4 g of a heat-sensitive gelling agent adjusted to a solid content of 45% and 6.3 g of water were added and stirred well. The poly cup was immersed in boiling water and heated for 10 minutes. Note that sodium gluconate is a setting retarder, and without its addition, it would set immediately after heating. The evaluation criteria were as follows. [Evaluation Criteria] Mortar mixability: Good = 〇, Thickening = △, Setting = × Heat-sensitive gelation: Setting = 〇, Fluidity present = ×

[0139] (Defoaming Property) 200 g of a heat-sensitive gelling agent adjusted to a solid content of 45% was weighed into a 1000 mL graduated cylinder. 800 mL of air was blown into the latex over 35 seconds. The volume of the foam was read. The smaller the foaming volume 10 minutes after air injection, the better the defoaming property.

[0140]

Table 4

[0141]

Table 5

Claims

1. A method for producing an layered object, comprising: layering a composition for layered modeling, the composition containing a water-setting inorganic composition and a thermosensitive gelling agent; and heating the composition for layered modeling during and / or after the layering to make the composition non-fluid, The thermosensitive gelling agent comprises an aqueous medium, a polymer dispersed in the aqueous medium, and a nonionic surfactant having a cloud point of 30 to 98° C. and an HLB value of 12 to 17, the nonionic surfactant being present in an amount of 3 to 10 parts by mass relative to 100 parts by mass of the polymer; The thermosensitive gelling agent is The following blends of (1) to (5) [(1) to (5) are calculated as solid contents, and the water content is 18.5% by mass] were mixed together. (1) Mortar 100 parts by weight (2) Sodium gluconate 1 part by mass (3) Carboxymethyl cellulose 0.5 parts by mass (4) Silicone-based defoaming agent: 0.1 parts by mass (5) The heat-sensitive gelling agent: 4.5 parts by mass 100 g of the mixture was introduced into a cylindrical container with an open top, degassed, and then the penetration resistance (needle diameter = 2 mm, piercing speed = 30 mm / min, piercing depth = 10 mm) was measured. The method for producing a thermosensitive gelling agent in which the nonionic surfactant is deactivated by heating, the value of a1 / a0 being 15 or more, where a0 is the value at 17±3°C immediately after degassing and a1 is the value at 17±3°C after microwave heating at 600 W for 30 seconds after degassing.

2. The method according to claim 1, wherein the polymer has a glass transition temperature of -50 to 35°C.

3. The method according to claim 1, wherein the polymer is at least one selected from the group consisting of homo- or copolymers of conjugated dienes and homo- or copolymers of ethylenically unsaturated monomers.

4. The method according to claim 3, wherein the homo- or copolymer of the conjugated diene is at least one selected from the group consisting of styrene-butadiene rubber, methyl methacrylate-butadiene rubber, acrylonitrile-butadiene rubber, styrene-butadiene-vinylpyridine rubber, butadiene rubber, and natural rubber.

5. The method according to claim 3, wherein the conjugated diene homopolymer or copolymer has a carboxy group, and the ratio of the carboxy group-containing monomer to the total monomers constituting the conjugated diene homopolymer or copolymer is 0.1 to 5.0 mass%.

6. The method according to claim 1 , wherein the nonionic surfactant is a polyoxyethylene alkyl ether and / or a polyoxyethylene aryl ether.

7. The method according to claim 6, wherein the polyoxyethylene alkyl ether has an alkyl moiety having 12 to 20 carbon atoms.

8. The method according to claim 6, wherein the aryl moiety of the polyoxyethylene aryl ether is an aryl in which at least one hydrogen atom is substituted with an aralkyl.

9. The hydraulic inorganic composition is a cement defined in JIS R 5210:2019, JIS R 5211:2019, JIS R 5212:2019, JIS R 5213:2019 or JIS R 5214:2019, or a mortar or concrete containing the cement. The manufacturing method according to claim 1.

10. The thermosensitive gelling agent is used in an amount of 1 to 20 parts by mass per 100 parts by mass (solid content equivalent) of the water-setting inorganic composition; The method according to claim 1 , wherein the thermosensitive gelling agent has a solid content concentration of 30 to 60% by mass.

11. A method for reducing sagging or crushing of the water-setting inorganic composition during lamination by laminating a composition for lamination containing a water-setting inorganic composition and a thermosensitive gelling agent, and non-fluidizing the composition for lamination by heating during lamination, comprising: The thermosensitive gelling agent comprises an aqueous medium, a polymer dispersed in the aqueous medium, and a nonionic surfactant having a cloud point of 30 to 98° C. and an HLB value of 12 to 17, the nonionic surfactant being present in an amount of 3 to 10 parts by mass relative to 100 parts by mass of the polymer; The thermosensitive gelling agent is The following blends of (1) to (5) [(1) to (5) are calculated as solid contents, and the water content is 18.5% by mass] were mixed together. (1) Mortar 100 parts by weight (2) Sodium gluconate 1 part by mass (3) Carboxymethyl cellulose 0.5 parts by mass (4) Silicone-based defoaming agent: 0.1 parts by mass (5) The heat-sensitive gelling agent: 4.5 parts by mass 100 g of the mixture was introduced into a cylindrical container with an open top, degassed, and then the penetration resistance (needle diameter = 2 mm, piercing speed = 30 mm / min, piercing depth = 10 mm) was measured. The method for producing a thermosensitive gelling agent in which the nonionic surfactant is deactivated by heating, the value of a1 / a0 being 15 or more, where a0 is the value at 17±3°C immediately after degassing and a1 is the value at 17±3°C after microwave heating at 600 W for 30 seconds after degassing.

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