Mold release agent for hydraulic composition

Abstract

To provide a form releasing agent for a hydraulic composition capable of producing a hardened body of a hydraulic composition having an excellent surface appearance without exerting influence on the viscosity of the hydraulic composition containing a specific compound, and a method for installing the hydraulic composition.SOLUTION: A form releasing agent for a hydraulic composition is a release agent used for a hydraulic composition form containing a component (A): a specific quaternary salt type compound including a quaternary cationic group and an aromatic anion group or a component (B): two or more kinds of specific amine oxides, wherein the content of aromatic hydrocarbon is 5.0 mass% or less.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a form release agent for a hydraulic composition and a method for placing a hydraulic composition.

Background Art

[0002] Conventionally, a release agent applied to a form for concrete is mainly composed of a liquid water-repellent substance such as mineral oil or animal and vegetable oil, and fatty acids and fatty acid metal salts are blended to enhance the releasability. These fatty acids and fatty acid metal salts enhance the adsorption force to a steel form, and the adhesion to the form is enhanced by being interposed in an oily substance.

[0003] Patent Document 1 discloses a release agent used for a form for a concrete composition using a concrete admixture containing two specific water-soluble low molecular compounds (A) and (B), which contains a silicone compound and / or a fluorine compound. The concrete form release agent of Patent Document 1 can obtain a concrete form release agent that can produce a concrete with excellent surface appearance without adversely affecting the concrete containing an admixture composed of a combination of two specific water-soluble low molecular compounds.

[0004] Also, a rheology modifier that modifies the rheology such as the viscosity and elasticity of an aqueous solution or a hydraulic composition by using a specific compound has been disclosed. Patent Document 2 discloses a rheology modifier containing a specific quaternary salt-type compound containing a quaternary cation group and an aromatic anion group, and an anionic aromatic compound at a specific cation group / (anion group + anionic aromatic compound) molar ratio. Patent Document 3 discloses a rheology modifier containing two or more specific amine oxide compounds represented by the general formula (1), wherein X in the general formula (1) is different for the two or more compounds, and at least one of the two or more compounds has an R in X in the general formula (1) 1 which is a compound having an alkenyl group. The rheology modifier containing the specific compound described in Patent Documents 2 and 3 can modify the rheology such as the viscosity and elasticity of an aqueous solution or a slurry in a wide temperature range. [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-160764 [Patent Document 2] Japanese Patent Application Laid-Open No. 6-808 [Patent Document 3] Japanese Patent Application Laid-Open No. 2020-76022 [Disclosure of the Invention] [Problems to be Solved by the Invention]

[0005] In the hydraulic composition added with the specific compound targeted in Patent Documents 2 and 3, when placing, depending on the mold release agent applied to the formwork, the viscosity of the surface of the hardened body of the hydraulic composition in contact with the formwork surface (mold release agent) decreases, resulting in material separation (bleeding), and the hydraulic composition on the formwork surface may have poor hardening, and therefore, scale may adhere to the formwork. Furthermore, a retardance layer is formed on the surface of the hardened body of the hydraulic composition, the strength of the surface of the hardened body decreases, and the surface of the hardened body turns white or becomes rough, etc., and the finish is also poor.

[0006] The present invention provides a mold release agent for a hydraulic composition and a method for placing a hydraulic composition, which can produce a hardened body of a hydraulic composition having excellent surface appearance without affecting the viscosity of the hydraulic composition containing a specific compound. [Means for Solving the Problems]

[0007] The present invention is a mold release agent used for a formwork of a hydraulic composition containing the following component (A) or the following component (B), It relates to a mold release agent for a hydraulic composition in which the content of aromatic hydrocarbons is 5.0% by mass or less. (A) Component: A compound represented by the following general formula (1A)

[0008] [Chemical formula]

[0009] (In the formula, R 1a is an alkyl group having 10 to 26 carbon atoms or an alkenyl group having 10 to 26 carbon atoms, and R 2a is an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 1 to 22 carbon atoms, or a hydroxyalkyl group having 1 to 22 carbon atoms. R 3a , R 4a are each an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms. Y is an ethylene group or a propylene group. n is a number of 0 or 1. X - represents an anion group derived from an anionic aromatic compound.) (Component (B): Two or more compounds represented by the following general formula (1B), wherein the two or more compounds have different R 1b in the general formula (1B), and at least one of the two or more compounds has R 1b of R 11b or R 12b being an alkenyl group)

[0010]

Chemical formula

[0011] [In the formula, R 1b is a group represented by R 11b or R 12b -[CONH-CH2CH2CH2] m -. R 11b is an alkyl group having 14 to 22 carbon atoms or an alkenyl group having 14 to 22 carbon atoms. R 12b is an alkyl group having 13 to 21 carbon atoms or an alkenyl group having 13 to 21 carbon atoms. m is an integer of 1 to 3. R 2b and R 3b are each independently an alkyl group having 1 to 4 carbon atoms or a group represented by -(C2H4O) p H. p is the average number of added moles. R 2b and R 3bis a number that is 0 or more and 5 or less in total.

[0012] Further, the present invention Aromatic hydrocarbon A formwork for a hydraulic composition type release agent having a content of 5.0% by mass or less is filled with a hydraulic powder, an aggregate, water, and a hydraulic composition containing the component (A) or the component (B) and cured. The present invention relates to a method for placing a hydraulic composition.

Effect of the Invention

[0013] According to the present invention, there are provided a formwork release agent for a hydraulic composition and a method for placing a hydraulic composition, which can produce a cured body of a hydraulic composition having excellent surface appearance without affecting the viscosity of the hydraulic composition containing a specific compound.

Best Mode for Carrying Out the Invention

[0014] [Formwork Release Agent for Hydraulic Composition] As a result of intensive studies, the present inventors have found that the cause of the viscosity reduction is that the aromatic hydrocarbon contained in the release agent is incorporated into the higher-order structure formed by the component (A) or the component (B) in the hydraulic composition, and a single ring or a plurality of rings exhibiting aromaticity break the higher-order structure. As a component of the release agent, by setting the content of the aromatic hydrocarbon to a certain amount or less, it has been found that the properties of the hydraulic composition can be maintained, and the present invention has been achieved. According to the present invention, since a release agent having a content of aromatic hydrocarbon of a certain amount or less that does not adversely affect the higher-order structure is used, the properties of the hydraulic composition can be maintained, and the surface of the cured body of the hydraulic composition after demolding can be kept good. Further, since the formwork coated with the formwork release agent for the hydraulic composition of the present invention is filled with the hydraulic composition containing the component (A) or the component (B) and cured, a cured body of the hydraulic composition having excellent early strength and water resistance can be obtained.

[0015] In the mold release agent for the hydraulic composition of the present invention, the aromatic hydrocarbon is a hydrocarbon composed of a single ring or a plurality of rings (condensed rings) exhibiting aromaticity, and the single ring or the plurality of rings may be substituted with a hydrocarbon group. Specific examples of the aromatic hydrocarbon include one or more selected from benzene, toluene, xylene, trimethylbenzene, naphthalene, and anthracene, and may include isomers.

[0016] From the viewpoint of maintaining viscosity, the content of the aromatic hydrocarbon in the mold release agent for the hydraulic composition of the present invention is 5.0% by mass or less, preferably 2.5% by mass or less, more preferably 1.0% by mass or less, still more preferably 0.5% by mass or less, even more preferably 0.1% by mass or less, and even more preferably 0%. Further, it is preferable that the mold release agent for the hydraulic composition of the present invention does not contain an aromatic hydrocarbon.

[0017] The mold release agent for the hydraulic composition of the present invention may be a mineral oil-based, water-based, silicone-based, or fluorine-based mold release agent.

[0018] In the present invention, the mineral oil-based mold release agent refers to a mold release agent using mineral oil as a base oil. Examples of the mineral oil include one or more selected from kerosene, light oil, spindle oil, transformer oil, machine oil, turbine oil, and motor oil. Examples of the mineral oil include Cosmo Pure Spin E, Cosmo Pure Spin ESP, Hydro HV56, Super High Land SE, Cosmo Pure Safety 10, Cosmo Pure Safety 22, Cosmo Pure Safety 32, Cosmo Pure Safety 46, and Cosmo Pure Safety 68.

[0019] In the present invention, the water-based mold release agent refers to a mold release agent mainly using water as a medium. Examples of the water-based mold release agent include NSH-1507, NSH-1566, NSH-1703, and NSH-2105.

[0020] In the present invention, the silicone-based release agent refers to a release agent based on silicone oil. Examples of the silicone compound include one or more selected from polyalkylphenylsiloxane, alkyl-modified silicone oil, polyether-modified silicone oil, polyalkylsiloxane, polymethylsilsesquioxane, polyalkylhydrogen siloxane, polyalkylalkenyl siloxane, polymethylphenylsiloxane, aralkyl-modified silicone oil, polydimethylsiloxane, alkylaralkyl-modified silicone oil, etc. Among them, from the viewpoint of the peeling effect, one or more selected from the group consisting of polyalkylsiloxane and polydimethylsiloxane are preferable. The silicone compound is TSM6822, TSF4300, TSM621 (all are Momentive Performance Materials Ltd. Japan Co., Ltd.) and other commercially available silicone-based release agents can be used.

[0021] In the present invention, the fluorine-based release agent refers to a release agent containing a fluorine compound. Examples of the fluorine compound used in the release agent of the present invention include one or more selected from polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, ethylene propylene fluoride, and fluorine-containing surfactants. Among them, from the viewpoint of the peeling effect, polytetrafluoroethylene is preferable. As the fluorine compound, commercially available fluorine-based release agents such as the Fluorine Release Series (NeoSci Co., Ltd.) and MacLube (GSI Creos Co., Ltd.) can be used.

[0022] The mold release agent for hydraulic compositions of the present invention may be diluted with organic solvents such as butyl cellosolve, petroleum hydrocarbons (excluding aromatic hydrocarbons), mineral spirits, isopropyl alcohol, cyclohexanone, hexane, butane, propane, etc., or may be an emulsion emulsified in water using an emulsifier such as poly(oxyethylene)=octyl phenyl ether, poly(oxyethylene)=nonyl phenyl ether and other polyoxyalkylene alkyl phenyl ethers, linear alkylbenzene sulfonic acid and its salts, for example, a silicone emulsion. Additionally, it may contain preservatives, water, silica, zinc stearate, pigments, platinum compounds, etc.

[0023] The mold release agent for hydraulic compositions of the present invention may be applied to the mold by spraying in addition to application with a brush or mop. From the viewpoint of releasability, the application amount of the mold release agent for hydraulic compositions of the present invention to the mold is preferably 0.1 g / m 2 or more, more preferably 1 g / m 2 or more, still more preferably 3 g / m 2 or more, even more preferably 5 g / m 2 or more, and preferably 500 g / m 2 or less, more preferably 100 g / m 2 or less, still more preferably 50 g / m 2 or less, even more preferably 25 g / m 2 or less, even more preferably 15 g / m 2 or less.

[0024] The mold release agent for hydraulic compositions of the present invention is intended for hydraulic compositions containing the above component (A) or the above component (B), more specifically, mortar compositions or concrete compositions containing the above component (A) or the above component (B). Hereinafter, the hydraulic compositions of the present invention will be described.

[0025] Component (A) of the present invention is a compound represented by the general formula (1A). Component (A) of the present invention forms an association pair structure such as a string-like micelle in the composition to be rheologically modified, and exhibits a rheological modification effect by forming the structure.

[0026] In general formula (1A), R 1a From the viewpoint of forming a higher-order structure, it is an alkyl group or alkenyl group having 10 or more carbon atoms, preferably 12 or more carbon atoms, more preferably 14 or more carbon atoms, still more preferably 16 or more carbon atoms, and 26 or less carbon atoms, preferably 24 or less carbon atoms, more preferably 22 or less carbon atoms, more preferably 20 or less carbon atoms, still more preferably 18 or less carbon atoms, and is preferably an alkyl group. In general formula (1A), R 2a From the viewpoint of forming a higher-order structure, it is an alkyl group, alkenyl group, or hydroxyalkyl group having 1 or more carbon atoms and 22 or less carbon atoms, preferably 18 or less carbon atoms, more preferably 14 or less carbon atoms, still more preferably 10 or less carbon atoms, even more preferably 4 or less carbon atoms, and even more preferably 2 or less carbon atoms, and is preferably a hydroxyalkyl group. In general formula (1A), Y is an ethylene group or a propylene group, and n is 0 or 1, preferably 0.

[0027] In general formula (1A), X - is an anion group derived from an anionic aromatic compound. Examples of the anion group derived from an anionic aromatic compound include anion groups derived from one or more anionic aromatic compounds selected from carboxylic acids having an aromatic ring, phosphonic acids having an aromatic ring, and sulfonic acids having an aromatic ring. X -Specifically, examples of the anionic group include those derived from one or more anionic aromatic compounds selected from salicylic acid, p-toluenesulfonic acid, sulfosalicylic acid, benzoic acid, m-sulfobenzoic acid, p-sulfobenzoic acid, 4-sulfophthalic acid, 5-sulfoisophthalic acid, p-phenolsulfonic acid, m-xylene-4-sulfonic acid, cumenesulfonic acid, methyl salicylate, styrenesulfonic acid, and chlorobenzoic acid. From the perspective of the influence on the setting of cement, anionic groups derived from one or more anionic aromatic compounds selected from p-toluenesulfonic acid, p-phenolsulfonic acid, m-xylene-4-sulfonic acid, cumenesulfonic acid, and styrenesulfonic acid are preferred, anionic groups derived from one or more anionic aromatic compounds selected from p-toluenesulfonic acid and m-xylene-4-sulfonic acid are more preferred, and anionic groups derived from p-toluenesulfonic acid are even more preferred.

[0028] Component (B) is two or more compounds represented by the general formula (1B) (hereinafter also referred to as compound (B)), and in the two or more compounds, R 1b is different, and among the two or more compounds, at least one is a compound in which R 1b of R 11b or R 12b is an alkenyl group. Component (B) of the present invention forms a higher-order structure such as a string-like micelle in the composition of the object to be rheologically modified, and exhibits a rheological modification effect by forming the structure.

[0029] Regarding compound (B), the fact that R 1b in the general formula (1B) is different means that, taking the case where there are two types of compound (B) as an example, for example, the following aspects can be mentioned. In the following aspects, among the two types of compound (B), R 11b or R 12b of at least one of the two types of compound (B) is an alkenyl group. (i) One of R 11b or R 12b is an alkyl group, and the other R 11b or R 12bis an alkenyl group. (ii) One of R 11b or R 12b has a different number of carbon atoms from the other R 11b or R 12b . (iii) One of R 1b is R 11b , and the other R 1b is R 12b -[CONH-CH2CH2CH2] m . (iv) Both R 1b are R 12b -[CONH-CH2CH2CH2] m , and one m and the other m are different. (v) A combination of the above (i) to (iv).

[0030] In the general formula (1B), R 1b is a group represented by R 11b or R 12b -[CONH-CH2CH2CH2] m . R 11b is an alkyl group having 14 or more and 22 or less carbon atoms or an alkenyl group having 14 or more and 22 or less carbon atoms. When R 11b is an alkenyl group, the number of carbon atoms is preferably 18 or more and preferably 22 or less. When R 11b is an alkyl group, the number of carbon atoms is preferably 16 or more and preferably 22 or less. R 12b is an alkyl group having 13 or more and 21 or less carbon atoms or an alkenyl group having 13 or more and 21 or less carbon atoms. When R 12b is an alkenyl group, the number of carbon atoms is preferably 17 or more and preferably 21 or less. When R 12b is an alkyl group, the number of carbon atoms is preferably 15 or more and preferably 21 or less. m is preferably 0 or 1. R 2b and R 3bis, independently of each other, preferably an alkyl group having 1 to 2 carbon atoms or -(C2H4O) p is a group represented by H. p is preferably a number from 0 to 3.

[0031] The hydraulic composition of the present invention contains two or more, preferably five or less, more preferably two compounds (B) in which R in the general formula (1B) 1b is different. And among the two or more compounds (B) contained in the hydraulic composition, at least one is R in the general formula (1B) 1b of R 11b or R 12b is a compound having an alkenyl group with 14 to 22 carbon atoms, that is, R in the general formula (1B) 1b in which R 11b is an alkenyl group with 14 to 22 carbon atoms or R 12b is a compound containing an alkenyl group with 13 to 21 carbon atoms.

[0032] In the present invention, there are two compounds (B). Among the two compounds (B) including the above (i) to (v), one is preferably a compound in which R in the general formula (1B) 1b is R 11b and has an alkenyl group with 14 to 22 carbon atoms. That is, as the hydraulic composition of the present invention, there is a hydraulic composition containing two compounds represented by the general formula (1B), and the two compounds have different R in the general formula (1B) 1b and among the two compounds, one is a compound in which R in the general formula (1B) 1b is R 11b and R 11b is an alkenyl group.

[0033] As the hydraulic composition of the present invention, R in the general formula (1B) 1b is R 11b or R 12b -[CONH-CH2CH2CH2] m -represented group (where R 11b is an alkenyl group with 14 to 22 carbon atoms, R 12bA compound (11B) which is an alkenyl group having 13 to 21 carbon atoms), and R in the general formula (1B) is different from the compound (11B). 1b Examples thereof include a rheology modifier containing a compound (12B) which is different from the compound (11B). Specifically, examples thereof include a rheology modifier containing a compound (11B) represented by the following general formula (11B) and a compound (12B) represented by the following general formula (12B).

[0034]

Chemical formula

[0035] 〔In the formula, m1 and m2 are each independently an integer of 0 or more and 3 or less. R 11b When m1 is 0, it is an alkenyl group having 14 to 22 carbon atoms, and when m1 is 1 to 3, it is an alkenyl group having 13 to 21 carbon atoms. R 12b When m2 is 0, it is an alkyl group having 14 to 22 carbon atoms or an alkenyl group having 14 to 22 carbon atoms, and when m2 is 1 to 3, it is an alkyl group having 13 to 21 carbon atoms or an alkenyl group having 13 to 21 carbon atoms. However, when m1 and m2 are the same number, the alkenyl group of R 12b is a different alkenyl group from R 11b . R 21b and R 31b are each independently an alkyl group having 1 to 4 carbon atoms or a group represented by -(C2H4O) p1 H. p1 is the average number of moles added, and is a number of 0 or more and 5 or less in total of R 21b and R 31b . R 22b and R 32b are each independently an alkyl group having 1 to 4 carbon atoms or a group represented by -(C2H4O) p2 H. p2 is the average number of moles added, and is a number of 0 or more and 5 or less in total of R 22b and R 32b .〕

[0036] In general formula (11B), R 11b preferably has 17 or more carbon atoms and preferably 22 or fewer carbon atoms. In general formula (11B), m1 is preferably 0 or 1, more preferably 0.

[0037] In general formula (12B), when m2 is 0 and R 12b is an alkyl group, R 12b preferably has 16 or more carbon atoms and preferably 22 or fewer carbon atoms. In general formula (12B), when m2 is 0 and R 12b is an alkenyl group, R 12b preferably has 18 or more carbon atoms and preferably 22 or fewer carbon atoms. In general formula (12B), when m2 is 1 to 3 and R 12b is an alkyl group, R 12b preferably has 15 or more carbon atoms and preferably 21 or fewer carbon atoms. In general formula (11B), when m2 is 1 to 3 and R 12b is an alkenyl group, R 12b preferably has 17 or more carbon atoms and preferably 21 or fewer carbon atoms. In general formula (11B), R 12b is preferably an alkyl group. In general formula (11B), m2 is preferably 0 or 1.

[0038] In general formula (11B), R 21b , and R 31b are each independently preferably an alkyl group having 1 or 2 carbon atoms or a group represented by -(C2H4O) p1 H, more preferably an alkyl group having 1 or 2 carbon atoms. In general formula (11B), p1 is preferably a number of 0 or more and 3 or less. In general formula (12B), R 22b , and R 32b are each independently preferably an alkyl group having 1 or 2 carbon atoms or a group represented by -(C2H4O) p2A group represented by H, more preferably an alkyl group having 1 or 2 carbon atoms. In the general formula (12B), p2 is preferably a number of 0 or more and 3 or less. When m1 and m2 are the same number, the alkenyl group of R 12b is an alkenyl group different from R 11b .

[0039] Preferred compounds (B) of the present invention include a compound (13B) represented by the following general formula (13B) and a compound (12B) represented by the following general formula (12B).

[0040]

Chemical formula

[0041] 〔In the formula, m2 is an integer of 0 or more and 3 or less. R 13b is an alkenyl group having 14 or more and 22 or less carbon atoms. R 12b is an alkyl group having 14 or more and 22 or less carbon atoms or an alkenyl group having 14 or more and 22 or less carbon atoms when m2 is 0, and is an alkyl group having 13 or more and 21 or less carbon atoms or an alkenyl group having 13 or more and 21 or less carbon atoms when m2 is 1 to 3. R 22b and R 32b are each independently an alkyl group having 1 or more and 4 or less carbon atoms or a group represented by -(C2H4O) p2 H. p2 is the average number of added moles, and the total of R 22b and R 32b is a number of 0 or more and 5 or less. R 23b and R 33b are each independently an alkyl group having 1 or more and 4 or less carbon atoms or a group represented by -(C2H4O) p3 H. p3 is the average number of added moles, and the total of R 23b and R 33b is a number of 0 or more and 5 or less. 〕

[0042] The compound (13B) represented by the general formula (13B) corresponds to the compound in which m1 is 0 in the general formula (11B). R in the general formula (13B) 13b , R 23b and R 33b preferred embodiments are the same as those of the general formula (11B). Also in this combination, the preferred embodiments of the compound (12B) are the same as described above.

[0043] In the hydraulic composition of the present invention, the mass ratio of the compound (12B) / compound (11B) is preferably 5 / 95 or more, more preferably 25 / 75 or more, still more preferably 40 / 60 or more, and preferably 95 / 5 or less, more preferably 75 / 25 or less, still more preferably 60 / 40 or less, from the viewpoint of obtaining a rheology-modifying effect, such as high viscoelasticity, in a wider temperature range.

[0044] In the hydraulic composition of the present invention, the mass ratio of the compound (12B) / compound (13B) is preferably 5 / 95 or more, more preferably 25 / 75 or more, still more preferably 40 / 60 or more, and preferably 95 / 5 or less, more preferably 75 / 25 or less, still more preferably 60 / 40 or less, from the viewpoint of obtaining a rheology-modifying effect, such as high viscoelasticity, in a wider temperature range.

[0045] The hydraulic composition of the present invention contains a hydraulic powder and water. The hydraulic powder is a powder having physical properties that harden by a hydration reaction, and examples thereof include cement and gypsum. Examples of the cement include ordinary Portland cement, early-strength Portland cement, ultra-early-strength Portland cement, sulfate-resistant Portland cement, low-heat Portland cement, white Portland cement, and eco-cement (e.g., JIS R5214, etc.). Among these, a cement selected from ordinary Portland cement, sulfate-resistant Portland cement, and white Portland cement is preferred, and ordinary Portland cement is more preferred.

[0046] In addition, the hydraulic powder such as cement may include powders having pozzolanic action and / or latent hydraulicity such as blast furnace slag, fly ash, silica fume, and powders such as stone powder (calcium carbonate powder). For example, blast furnace slag cement, fly ash cement, silica fume cement, etc. may be used.

[0047] From the viewpoint of strength development property, the water / hydraulic powder ratio [the mass ratio of water and hydraulic powder in the slurry (mass of water / mass of hydraulic powder × 100), usually abbreviated as W / C.] of the hydraulic composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 35% by mass or more, and preferably 150% by mass or less, more preferably 100% by mass or less, still more preferably 80% by mass or less, even more preferably 70% by mass or less, even more preferably 55% by mass or less, and such ratios can be used. In addition, when the hydraulic powder includes powders selected from powders having properties of hardening by a hydration reaction such as cement, powders having pozzolanic action, powders having latent hydraulicity, and stone powder (calcium carbonate powder), in the present invention, their amounts are also included in the amount of the hydraulic powder. Further, when the powder having properties of hardening by a hydration reaction contains a high-strength admixture, the amount of the high-strength admixture is also included in the amount of the hydraulic powder. This is the same for other parts by mass related to the mass of the hydraulic powder.

[0048] When the hydraulic composition of the present invention contains the component (A), the content of the component (A) is preferably 0.2 part by mass or more, more preferably 0.3 part by mass or more, still more preferably 0.5 part by mass or more, and preferably 5 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 2 parts by mass or less, even more preferably 1.5 parts by mass or less, even more preferably 1 part by mass or less, even more preferably 0.8 part by mass or less, from the viewpoint of expressing sufficient viscoelasticity, based on 100 parts by mass of the hydraulic powder.

[0049] When the hydraulic composition of the present invention contains the component (B), from the viewpoint of expressing sufficient viscoelasticity, the content of the component (B) is preferably 0.1 part by mass or more, more preferably 0.2 part by mass or more, still more preferably 0.3 part by mass or more, and preferably 5 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 2 parts by mass or less, even more preferably 1.5 parts by mass or less, even more preferably 1 part by mass or less, even more preferably 0.8 part by mass or less, based on 100 parts by mass of the hydraulic powder.

[0050] The hydraulic composition of the present invention may contain aggregates. Examples of the aggregates include aggregates selected from fine aggregates and coarse aggregates. Examples of the fine aggregates include those defined by No. 2311 in JIS A0203 - 2014. Examples of the fine aggregates include river sand, land sand, mountain sand, sea sand, lime sand, silica sand, and crushed sand thereof, blast furnace slag fine aggregate, ferronickel slag fine aggregate, lightweight fine aggregate (artificial and natural), and recycled fine aggregate. Examples of the coarse aggregates include those defined by No. 2312 in JIS A 0203 - 2014. For example, the coarse aggregates include river gravel, land gravel, mountain gravel, sea gravel, lime gravel, crushed stone thereof, blast furnace slag coarse aggregate, ferronickel slag coarse aggregate, lightweight coarse aggregate (artificial and natural), and recycled coarse aggregate. The fine aggregates and coarse aggregates may be used by mixing those of different types, or a single type may be used.

[0051] When the hydraulic composition of the present invention is concrete, that is, when it is a hydraulic composition containing the component (A) or (B), hydraulic powder, coarse aggregate, fine aggregate, and water, from the viewpoints of expressing the strength of the hydraulic composition and reducing the amount of hydraulic powder such as cement, and improving the filling property into a formwork, etc., the bulk volume is preferably 50% or more, more preferably 55% or more, still more preferably 60% or more, and preferably 100% or less, more preferably 90% or less, still more preferably 80% or less. The bulk volume is the ratio of the volume (including voids) of the coarse aggregate in 1 m 3 of the concrete. In addition, when the hydraulic composition of the present invention is concrete, that is, in the case of a hydraulic composition containing component (A) or component (B), hydraulic powder, coarse aggregate, fine aggregate, and water, the amount of fine aggregate used is preferably 500 kg / m 3 or more, more preferably 600 kg / m 3 or more, still more preferably 700 kg / m 3 or more, and preferably 1000 kg / m 3 or less, more preferably 900 kg / m 3 or less. When the hydraulic composition of the present invention is mortar, that is, in the case of a hydraulic composition containing component (A) or component (B), hydraulic powder, fine aggregate, and water, the amount of fine aggregate used is preferably 800 kg / m 3 or more, more preferably 900 kg / m 3 or more, still more preferably 1000 kg / m 3 or more, and preferably 2000 kg / m 3 or less, more preferably 1800 kg / m 3 or less, still more preferably 1700 kg / m 3 or less.

[0052] The hydraulic composition of the present invention can contain a dispersant. Examples of the dispersant include one or more dispersants selected from lignin sulfonic acid polymers, polycarboxylic acid polymers, naphthalene sulfonic acid polymers, melamine polymers, and phenol polymers. From the viewpoint of dispersibility, preferably one or more dispersants selected from polycarboxylic acid polymers, lignin sulfonic acid polymers, and naphthalene sulfonic acid polymers, and more preferably one or more dispersants selected from lignin sulfonic acid polymers and polycarboxylic acid polymers.

[0053] Examples of the naphthalene sulfonic acid polymer include naphthalene sulfonic acid formaldehyde condensates (such as Mytei 150 manufactured by Kao Corporation); examples of the melamine polymer include melamine sulfonate formaldehyde condensates (such as Mytei 150-V2 manufactured by Kao Corporation); examples of the phenol polymer include phenol sulfonic acid formaldehyde condensates (such as the compounds described in JP-A-49-104919); examples of the lignin sulfonic acid polymer include lignin sulfonates (such as Pozolith No. 70 manufactured by BASF, Ultrazin NA manufactured by Borregaard, Sun Extract, Vanilex, Pearllex, etc. manufactured by Nippon Paper Chemicals Co., Ltd.). These can be used.

[0054] Examples of the polycarboxylic acid polymer include copolymers of polyalkylene glycol and a monoester of (meth)acrylic acid and a carboxylic acid such as (meth)acrylic acid (such as the compounds described in JP-A-8-12397), copolymers of an unsaturated alcohol having polyalkylene glycol and a carboxylic acid such as (meth)acrylic acid, copolymers of an unsaturated alcohol having polyalkylene glycol and a dicarboxylic acid such as maleic acid, and the like. Here, (meth)acrylic acid means a carboxylic acid selected from acrylic acid and methacrylic acid.

[0055] When the hydraulic composition of the present invention contains a dispersant, the content of the dispersant is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.3 parts by mass or more, and preferably 2 parts by mass or less, more preferably 1.5 parts by mass or less, still more preferably 1 part by mass or less, from the viewpoint of obtaining high fluidity, based on 100 parts by mass of the hydraulic powder.

[0056] The hydraulic composition of the present invention can further contain other components in addition to the above components. For example, defoamers, AE agents, retarders, foaming agents, thickeners, foaming agents, waterproof agents, fluidizing agents, early strength agents, etc. can be mentioned. Examples of early strength agents include compounds selected from hydrochlorides, sulfates, nitrates, nitrites, cyanates, thiocyanates, thiosulfates, and formates of alkali metals and alkaline earth metals, or organic compounds selected from alkanolamines, glycerin derivatives, formaldehyde derivatives, and catechol derivatives, and nanoparticles of hydration products (C-S-H and calcium hydroxide) of Portland cement.

[0057] Since the hydraulic composition of the present invention is excellent in water separation resistance, it is effective in applications that require pumpability and material separation resistance. Therefore, the hydraulic composition of the present invention is suitable for use in high-fluidity concrete, non-segregating underwater concrete, lightweight high-fluidity concrete, permeable concrete, in-situ lining method (ECL method), and SENS method.

[0058] [Method for placing hydraulic composition] The present invention relates to a method for placing a hydraulic composition, which comprises filling a formwork coated with a form release agent for a hydraulic composition having an aromatic hydrocarbon content of 5.0% by mass or less with a hydraulic powder, an aggregate, water, and a hydraulic composition containing the above component (A) or the above component (B), and curing the mixture. The form release agent for a hydraulic composition is the form release agent for a hydraulic composition of the present invention described above, and the embodiments described for the form release agent for a hydraulic composition of the present invention can be appropriately applied. The hydraulic composition is the hydraulic composition of the present invention described above, and the embodiments described for the hydraulic composition of the present invention can be appropriately applied.

[0059] The method for placing the hydraulic composition of the present invention preferably includes the following steps 1 to 4. Step 1: A step of kneading component (A) or component (B), water, and a hydraulic powder to obtain the hydraulic composition of the present invention. Step 2: A step of filling the hydraulic composition obtained in Step 1 into a mold coated with the mold release agent for the hydraulic composition of the present invention having an aromatic hydrocarbon content of 5.0% by mass or less. Step 3: A step of curing the hydraulic composition filled in the mold obtained in Step 2. Step 4: A step of demolding the cured body obtained in Step 3 from the mold.

[0060] Step 1 may be a step of preparing a hydraulic composition by mixing the component (A) or the component (B), optionally a dispersant, a hydraulic powder, water, and optionally an aggregate. Further, in Step 1, the content of each component in the hydraulic composition of the present invention described above can be applied by reading it as a mixing amount.

[0061] In Step 2, the mold release agent for the hydraulic composition of the present invention may be applied to the mold by spraying with a spray in addition to application with a brush or a mop. These mold release agents can also be used as lubricating oils. Also, the application amount of the mold release agent for the hydraulic composition of the present invention to the mold is preferably 0.5 g / m 2 or more, more preferably 1 g / m 2 or more, still more preferably 3 g / m 2 or more, even more preferably 5 g / m 2 or more, and preferably 500 g / m 2 or less, more preferably 100 g / m 2 or less, still more preferably 50 g / m 2 or less, even more preferably 25 g / m 2 or less, even more preferably 15 g / m 2 or less. Also, examples of the method of filling the mold include a method of directly charging from a mixer and a method of pumping the hydraulic composition and introducing it into the mold.

[0062] In Step 3, the hydraulic composition filled in the mold obtained in Step 2 is cured. In Step 3, for example, as the curing condition, the time for which the hydraulic composition is maintained at a curing temperature of 50°C or higher is preferably 1 hour or more, and preferably 24 hours or less, more preferably 20 hours or less. When curing is performed by maintaining the hydraulic composition filled in the mold at 50°C or higher, it can be performed by autoclave curing or heat curing with steam or the like. Also in Step 3, the hydraulic composition may be cured without steam curing. When preparing the hydraulic composition in the case of manufacturing a mortar or concrete product without steam curing, the time from when water comes into contact with the cement until demolding is preferably 4 hours or more and 48 hours or less from the viewpoints of productivity and strength. In this case, the temperature is preferably 0°C or higher, more preferably 5°C or higher, and preferably 45°C or lower, more preferably 40°C or lower. Heating and / or cooling within this temperature range can be appropriately performed.

[0063] In Step 4, the cured body obtained in Step 3 is demolded from the mold. Step 3 and Step 4 can be continuously performed under a series of temperature controls. Demolding of the cured body can conform to a known method. In the present invention, the time from the start of preparation of the hydraulic composition until demolding, that is, the time from when water comes into contact with the hydraulic powder until the start of demolding, is preferably 4 hours or more, more preferably 5 hours or more, and preferably 48 hours or less, more preferably 40 hours or less from the viewpoints of productivity and strength.

[0064] The cured body of the hydraulic composition obtained by the placing method of the hydraulic composition of the present invention is suitable for high-fluidity concrete, non-segregating underwater concrete, lightweight high-fluidity concrete, permeable concrete, in-situ lining method (ECL method), and SENS method.

Examples

[0065] The following were used for the mold release agent for the hydraulic composition, component (A), and component (B).

[0066] <Preparation of Mold Release Agent for Hydraulic Composition> To the following mold release agents 1 to 4, the aromatic hydrocarbons described in Tables 1, 2, 4, and 5 were added so as to have the contents described in Tables 1, 2, 4, and 5, and a mold release agent for a hydraulic composition was prepared. The original contents of the aromatic hydrocarbons in mold release agents 1 to 4 were 0% by mass. Release agent 1: silicone-based release agent, "TSM6822" manufactured by Momentive Performance Materials Japan LLC Release agent 2: fluorine-based release agent, "Release 310" manufactured by Neos Co., Ltd. Release agent 3: mineral oil-based release agent, "Hydro HV56" manufactured by Cosmo Oil Lubricants Co., Ltd. Release agent 4: mineral oil-based release agent, "Super Hi-Land SE" manufactured by ENEOS Co., Ltd.

[0067] <Component (A)> A-1: Dimethylhydroxyethylalkyl (C16 - C18) ammonium p-toluenesulfonate, manufactured by Kao Corporation

[0068] <Component (B)> · Compound (11B) 11B-1: Oleyl dimethylamine oxide (in the general formula (11B), R 11b : alkenyl group with 18 carbon atoms (oleyl group), m1: 0, R 21b : methyl group, R 31b : methyl group) · Compound (12B) 12B-1: Oleylamidopropyldimethylamine oxide (in the general formula (12B), R 12b : alkenyl group with 18 carbon atoms (oleyl group), m2: 1, R 22b : methyl group, R 32b : methyl group)

[0069] [Evaluation of Viscosity Change] Water, a dispersant (CAD-90: manufactured by Kao Corporation) were added to cement so that the water / hydraulic powder ratio (W / C) was 45% by mass, and the mixture was kneaded for 30 seconds. Then, component (A) or component (B) was added and kneaded for 60 seconds to prepare a cement paste. The viscosity of the cement paste immediately after preparation was measured using a B-type viscometer (manufactured by RION Co., Ltd., VISCOTESTER VT-04E, rotor No. 1, rotation speed: 62.5 rpm). Also, 400 ml of the cement paste immediately after preparation was added to a 400 mL disposable cup container coated with the mold release agent described in Table 1 at a rate of 10 g / m 2 and stirred at high speed for 30 seconds with a hand mixer. The viscosity of the cement paste mixed with the mold release agent was measured using a B-type viscometer (manufactured by RION Co., Ltd., VISCOTESTER VT-04E, rotor No. 1, rotation speed: 62.5 rpm). In this evaluation, it is preferable that the viscosity be maintained at 7000 mPa·s or more. The results are shown in Tables 1 and 2.

[0070] [Table 1]

[0071] [Table 2]

[0072] In Tables 1 and 2, the contents of the (A) component and the (B) component are the contents (parts by mass) with respect to 100 parts by mass of the hydraulic powder.

[0073] [Preparation of Concrete] The concrete mix is shown in Table 3. The concrete was prepared by mixing cement (C), fine aggregate, and coarse aggregate, adding water (W), a dispersant, and, if necessary, an antifoaming agent, kneading for 90 seconds, and then adding the (A) component or the (B) component and kneading for 60 seconds. The concrete prepared by this method was highly viscous high-flow concrete with a slump flow of 650 ± 50 mm and an air content of 4.5 ± 1.5% after 5 minutes.

[0074] [Placing of Concrete] This concrete was filled into a 10 cm × 10 cm × 40 cm steel mold coated with the mold release agents shown in Tables 4 and 5 at a rate of 10 g / m 2 and cured, and then demolded 30 hours later.

[0075]

Table 3

[0076] · Cement: Ordinary Portland Cement manufactured by Taiheiyo Cement Corporation · Fine aggregate: New fine sand from the Ibi River: Coarse sand from the Ibi River: Crushed sand from Kojima = 39%: 21%: 40% · Coarse aggregate: Limestone crushed stone from Torigata · Dispersant: "Mytei 21EG" manufactured by Kao Corporation

[0077] Regarding the concrete filled in the formwork, the surface appearance of the hardened concrete was evaluated as follows. The results are shown in Tables 4 and 5.

[0078] [Evaluation of surface appearance] The surface appearance of the hardened concrete was visually observed on the concrete surface removed from the formwork after hardening and judged according to the following criteria. The results are shown in Tables 4 and 5. Grade A: There are less than 10 defects or spots with a diameter of 3 mm or more in the range of 10 × 40 cm on the concrete surface Grade B: There are 10 or more and less than 20 defects or spots with a diameter of 3 mm or more in the range of 10 × 40 cm on the concrete surface. Grade C: There are 20 or more and less than 30 defects or spots with a diameter of 3 mm or more in the range of 10 × 40 cm on the concrete surface. Grade D: There are 30 or more and less than 40 defects or spots with a diameter of 3 mm or more in the range of 10 × 40 cm on the concrete surface. Grade E: There are 40 or more defects or spots with a diameter of 3 mm or more in the range of 10 × 40 cm on the concrete surface.

[0079]

Table 4

[0080]

Table 5

[0081] In Tables 4 and 5, the contents of the (A) component and the (B) component are the contents (parts by mass) with respect to 100 parts by mass of the hydraulic powder.

[0082] When a form release agent having an aromatic hydrocarbon content of 5.0% by mass or less was applied as in the examples of Tables 1, 2, 4, and 5, no decrease in viscosity was observed, and a smooth and aesthetically pleasing concrete surface was obtained. On the other hand, when a form release agent having an aromatic hydrocarbon content exceeding 5.0% by mass was applied as in the comparative example, the viscosity of the paste component decreased, and the surface of the hardened concrete was rough, resulting in concrete with poor aesthetics.

Claims

A mold release agent for a formwork used for a hydraulic composition containing the following component (B), A mold release agent for a formwork for a hydraulic composition, wherein the content of aromatic hydrocarbons is 5.0% by mass or less. Component (B): Two or more compounds represented by the following general formula (1B), wherein the two or more compounds have different Rs in the general formula (1B) １ｂ and at least one of the two or more compounds has an alkenyl group as R １ｂ of R １１ｂ or R １２ｂ in the general formula (1B). 【Chemical 2】 [In the formula, R １ｂ is a group represented by R １１ｂ or R １２ｂ -[CONH-CH ２ CH ２ CH ２ . ｍ R １１ｂ is an alkyl group having 14 to 22 carbon atoms or an alkenyl group having 14 to 22 carbon atoms. R １２ｂ is an alkyl group having 13 to 21 carbon atoms or an alkenyl group having 13 to 21 carbon atoms. m is an integer of 1 or more and 3 or less. R ２ｂ and R ３ｂ are each independently an alkyl group having 1 to 4 carbon atoms or a group represented by -(C ２ H ４ O) ｐ H. p is the average number of moles of addition, and the total of R ２ｂ and R ３ｂ is a number of 0 or more and 5 or less.] **Claim 2** The mold release agent for a formwork for a hydraulic composition according to claim 1, which is a mineral oil-based, water-based, silicone-based, or fluorine-based mold release agent. **Claim 3** A placing method for a hydraulic composition, wherein a formwork coated with a mold release agent for a formwork for a hydraulic composition, in which the content of aromatic hydrocarbons is 5.0% by mass or less, is filled with a hydraulic composition containing a hydraulic powder, an aggregate, water, and the following component (B) and cured. Component (B): Two or more compounds represented by the following general formula (1B), wherein the two or more compounds have different Rs in the general formula (1B) １ｂ and among the two or more compounds, at least one has an alkenyl group as R １ｂ in R １１ｂ or R １２ｂ of the compound 【Chemical Formula 4】 [wherein, R １ｂ is a group represented by R １１ｂ or R １２ｂ - [CONH-CH ２ CH ２ CH ２ . R ｍ is an alkyl group having 14 to 22 carbon atoms or an alkenyl group having 14 to 22 carbon atoms. R １１ｂ is an alkyl group having 13 to 21 carbon atoms or an alkenyl group having 13 to 21 carbon atoms. m is an integer of 1 or more and 3 or less. R １２ｂ and R ２ｂ and R ３ｂ are each independently an alkyl group having 1 to 4 carbon atoms or a group represented by -(C ２ H ４ O) ｐ H. p is the average number of moles added, and is a number of 0 or more and 5 or less in total of R ２ｂ and R ３ｂ .] **Claim 4** The placing method for a hydraulic composition according to claim 3, wherein the mold release agent for a formwork for a hydraulic composition is a mineral oil-based, water-based, silicone-based, or fluorine-based mold release agent. **Claim 5** The coating amount of the formwork release agent for the hydraulic composition on the formwork is 0.1 g / m ２ or more and 500 g / m ２ or less. The placing method of the hydraulic composition according to claim 3 or 4. **Claim 6** The placing method for a hydraulic composition according to any one of claims 3 to 5, wherein the hydraulic composition is for high-flow concrete, for non-segregating underwater concrete, for lightweight high-flow concrete, for permeable concrete, for the in-situ lining method (ECL method), or for the SENS method.

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