WO2014148549A1 - 水硬性組成物 - Google Patents
水硬性組成物 Download PDFInfo
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- WO2014148549A1 WO2014148549A1 PCT/JP2014/057521 JP2014057521W WO2014148549A1 WO 2014148549 A1 WO2014148549 A1 WO 2014148549A1 JP 2014057521 W JP2014057521 W JP 2014057521W WO 2014148549 A1 WO2014148549 A1 WO 2014148549A1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/10—Accelerators; Activators
Definitions
- the present invention relates to a hydraulic composition, an additive composition for a hydraulic composition, and a method for producing a cured body of the hydraulic composition.
- Concrete may be required to exhibit a certain degree of strength in about one day after kneading hydraulic powder such as cement and water.
- a concrete secondary product is kneaded with materials such as cement, aggregate, water, and a dispersant, placed in various molds, and commercialized through a curing process, that is, a curing process. Since the same formwork is used many times, it is important to develop a high strength in the initial age from the viewpoint of improving the productivity, that is, the rotation rate of the formwork. Therefore, (1) Use early-strength cement as cement, (2) Use various polycarboxylic acid compounds as admixtures to reduce the amount of water in the cement composition, (3) Steam curing as a curing method Measures such as performing are taken.
- Japanese Patent Application Laid-Open No. 2011-162400 discloses one kind selected from glycerin, alkali metal sulfate, and alkali metal thiosulfate for the purpose of obtaining a cured product having a high initial strength even when heat curing energy is reduced.
- a hydraulic composition containing the above inorganic salt A, a naphthalene dispersant, a hydraulic powder, an aggregate, and water and having a specific glycerin and inorganic salt A molar ratio has been proposed. .
- JP-A-61-117142 discloses that a cement composition containing an aldehyde and bisulfite or an addition compound of aldehyde and bisulfite and a water-soluble thiocyanate increases strength after curing. is doing. Summary of invention
- the present invention contains glycerin, hydroxymethanesulfonic acid or a salt thereof, a dispersant, a hydraulic powder, an aggregate, and water, and the content of glycerin is 100 parts by mass of the hydraulic powder. 0.040 parts by mass or more and 0.280 parts by mass or less, and the content of hydroxymethanesulfonic acid or a salt thereof is 0.010 parts by mass or more and 0.420 parts by mass or less with respect to 100 parts by mass of the hydraulic powder. It relates to a hydraulic composition.
- the present invention also includes a hydraulic composition containing glycerin, hydroxymethanesulfonic acid or a salt thereof, and a dispersant, wherein the mass ratio of glycerin / hydroxymethanesulfonic acid is 10/90 or more and 97/3 or less.
- the present invention relates to a physical additive composition.
- the present invention relates to hydraulic powder, aggregate, water, 0.040 parts by mass or more and 0.280 parts by mass or less of glycerin with respect to 100 parts by mass of hydraulic powder, and hydraulic powder 100.
- a step of preparing a hydraulic composition by adding 0.010 parts by mass or more and 0.420 parts by mass or less of hydroxymethanesulfonic acid or a salt thereof, and a dispersant with respect to parts by mass, and an obtained hydraulic composition
- the present invention relates to a method for producing a cured body of a hydraulic composition, the method comprising filling a mold into a mold and curing the process, and demolding the cured hydraulic composition from the mold to obtain a cured body of the hydraulic composition.
- This invention is providing the hydraulic composition which can shorten time until a hardening body reaches
- a hydraulic composition capable of shortening the time until the cured body reaches a required strength without curing by applying heat is provided.
- the hydraulic composition of the present invention can shorten the time until the cured body reaches the required strength.
- the hydraulic composition of the present invention contains glycerin, hydroxymethanesulfonic acid or a salt thereof, a dispersant, a hydraulic powder, aggregate, and water, and a specific amount of glycerin and hydroxymethanesulfonic acid. Or it has the characteristics in containing the salt, and there exists an effect that the time until a hardening body reaches
- alite, alite, ie, C 3 S in the hydraulic powder exhibits strength by crystallization by hydration.
- calcium aluminoferrite that is, calcium-aluminoferrite, that is, C 4 AF hydrates with gypsum contained in the hydraulic powder to produce crystalline ettringite, Ettringite, and develops strength.
- ettringite becomes monosulfate and monosulphate, and further strength is developed. Hydroxymethane sulfonic acid or a salt thereof is considered to improve strength by promoting hydration of C 3 S.
- glycerin is thought to promote C 4 AF to become ettringite.
- a specific amount of glycerin and hydroxymethane sulfonic acid or a salt thereof are used together in the preparation of the hydraulic composition as in the present invention, ettringite whose production is promoted by glycerin is further added, and hydroxymethane sulfonic acid or a salt thereof is further monohydrated. It is thought to promote becoming a sulfate.
- the hydraulic composition of the present invention contains glycerin, hydroxymethanesulfonic acid or a salt thereof, a dispersant, hydraulic powder, aggregate, and water.
- glycerin Commercially available products can be used for glycerin.
- glycerin commercially available refined glycerin, for example, glycerin obtained by transesterification of oil derived from palm can be used. From the viewpoint of shortening the time until the cured product of the hydraulic composition reaches the required strength, purified glycerin is preferable.
- the content of glycerin is 0.040 parts by mass or more and 0.280 parts by mass or less with respect to 100 parts by mass of the hydraulic powder, and a cured product of the hydraulic composition is necessary. From the viewpoint of shortening the time required to reach a sufficient strength, it is preferably 0.050 part by mass or more, more preferably 0.100 part by mass or more, and preferably 0.250 part by mass or less, more preferably 0.8. It is 230 mass parts or less, More preferably, it is 0.200 mass parts or less.
- a commercially available product can be used as hydroxymethanesulfonic acid or a salt thereof.
- the salt include alkali metal salts, alkaline earth metal salts, and ammonium salts, and alkali metal salts are preferable from the viewpoint of shortening the time required for the cured product of the hydraulic composition to reach a required strength.
- the alkali metal salt include sodium salt and potassium salt, and examples of the alkaline earth metal salt include calcium salt.
- the content of hydroxymethanesulfonic acid or a salt thereof is 0.010 parts by mass or more and 0.420 parts by mass or less with respect to 100 parts by mass of the hydraulic powder. From the viewpoint of shortening the time until the cured product reaches the required strength, it is preferably 0.030 parts by mass or more, more preferably 0.050 parts by mass or more, and preferably 0.410 parts by mass or less. More preferably, it is 0.200 mass part or less, More preferably, it is 0.100 mass part or less.
- the total content of glycerin and hydroxymethanesulfonic acid or a salt thereof is hydraulic powder from the viewpoint of shortening the time until the cured product of the hydraulic composition reaches the required strength.
- it is 0.050 mass part or more with respect to 100 mass parts of a body, More preferably, it is 0.100 mass part or more, More preferably, it is 0.130 mass part or more, More preferably, it is 0.180 mass part or more, More preferably Is 0.230 parts by mass or more, and preferably 0.650 parts by mass or less, more preferably 0.500 parts by mass or less, still more preferably 0.400 parts by mass or less, still more preferably 0.330 parts by mass or less, More preferably, it is 0.280 parts by mass or less.
- the mass ratio of glycerin to hydroxymethanesulfonic acid or a salt thereof is glycerin / hydroxymethanesulfone from the viewpoint of shortening the time until the cured product of the hydraulic composition reaches the required strength.
- An acid or a salt thereof preferably 10/90 or more, more preferably 30/70 or more, still more preferably 60/40 or more, still more preferably 65/35 or more, and preferably 97/3 or less, more Preferably it is 95.5 / 4.5 or less, More preferably, it is 90/10 or less, More preferably, it is 85/15 or less.
- the dispersant examples include a naphthalene polymer, a melamine polymer, a phenol polymer, a lignin polymer, a polycarboxylic acid copolymer, and the like. From the viewpoint of shortening the time required for the cured product of the hydraulic composition to reach the required strength, a dispersant selected from naphthalene-based polymers and polycarboxylic acid-based copolymers is preferable, and naphthalene-based polymers are more preferable.
- the dispersant is a dispersant for hydraulic powder.
- naphthalene polymer naphthalene sulfonic acid formaldehyde condensate and a salt thereof, for example, Mighty 150 manufactured by Kao Corporation can be used.
- melamine polymer a melamine sulfonate formaldehyde condensate and a salt thereof such as Mighty 150-V2 manufactured by Kao Corporation can be used.
- phenolic polymer a phenol sulfonic acid formaldehyde condensate and a salt thereof, for example, compounds described in JP-A-49-104919 can be used.
- lignin-based polymers include lignin sulfonic acid and its salts, for example, Ultragin NA manufactured by Borregard, Ultrazine® NA manufactured by Borregaard, Sun Extract manufactured by Nippon Paper Chemical Co., Ltd., SAN® X, Vanillex, VANILLEX, Pearl Rex, PEARLLEX, etc. Can be used.
- polycarboxylic acid-based copolymer examples include a copolymer of a monoester of polyalkylene glycol and (meth) acrylic acid and a carboxylic acid such as (meth) acrylic acid, and a salt thereof, for example, JP-A-8-12397 Or the like can be used.
- a copolymer of unsaturated alcohol having polyalkylene glycol and a carboxylic acid such as (meth) acrylic acid and a salt thereof can be used.
- polycarboxylic acid copolymer a copolymer of an unsaturated alcohol having polyalkylene glycol and a dicarboxylic acid such as maleic acid, a salt thereof, and the like can be used.
- (meth) acrylic acid means a carboxylic acid selected from acrylic acid and methacrylic acid.
- a monomer (1) represented by the following general formula (1) and a monomer (2) represented by the following general formula (2) are polymerized.
- the resulting copolymer can be used.
- a copolymer obtained by polymerizing the monomer (1) represented by the following general formula (1) and the monomer (2) represented by the following general formula (2) is hereinafter referred to as poly It is called carboxylic acid copolymer (I).
- R 4 , R 5 , R 6 hydrogen atom, methyl group, or (CH 2 ) m1 COOM 2
- M 1 and M 2 each represents a number of hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium, alkylammonium, or substituted alkylammonium m1: 0 to 2;
- (CH 2 ) m1 COOM 2 may form an anhydride with COOM 1 .
- AO is preferably an alkyleneoxy group having 2 or 3 carbon atoms, more preferably 2 carbon atoms, that is, an oxyethylene group, from the viewpoint of fluidity of the hydraulic composition.
- N is preferably 9 or more, more preferably 20 or more, still more 50 or more, and even more 70 or more from the viewpoint of improving the strength of the hydraulic composition after 24 hours.
- n is preferably a number of 150 or less and further 130 or less.
- l is preferably 1 or 2.
- l is preferably 0.
- m is preferably 1.
- R 3 is preferably a hydrogen atom from the viewpoint of ease of production of the monomer.
- R 3 is preferably an alkyl group having 1 to 4 carbon atoms from the viewpoint of ease of production of the monomer, and more preferably a methyl group from the viewpoint of water solubility.
- the monomer (1) for example, an ester of a polyalkylene glycol and (meth) acrylic acid, an ether obtained by adding an alkylene oxide to an alkenyl alcohol, or the like can be used.
- Monomer (1) is preferably an ester of polyalkylene glycol and (meth) acrylic acid from the viewpoint of polymerizability during polymerization of the copolymer.
- an ester of polyalkylene glycol and (meth) acrylic acid an ester of alkylene glycol and (meth) acrylic acid blocked at one end can be used.
- one or more kinds such as methoxypolyethylene glycol acrylate, methoxypolyethylene glycol methacrylate, ethoxypolyethylene glycol acrylate, and ethoxypolyethylene glycol methacrylate can be used.
- an ether in which an alkylene oxide is added to an alkenyl alcohol an allyl alcohol ethylene oxide adduct or the like can be used.
- an ethylene oxide adduct of methallyl alcohol and an ethylene oxide adduct of 3-methyl-3-buten-1-ol can be used.
- the monomer (2) one or more selected from acrylic acid or a salt thereof, methacrylic acid or a salt thereof, maleic acid or a salt thereof, maleic anhydride, or the like can be used.
- the monomer (2) is preferably methacrylic acid or a salt thereof from the viewpoint of polymerizability at the time of polymerization of the copolymer when m of the monomer (1) is 1.
- m is 0, maleic acid or a salt thereof and maleic anhydride are preferred from the viewpoint of polymerizability at the time of polymerization of the copolymer.
- the content of the dispersant is 0.005 parts by mass with respect to 100 parts by mass of the hydraulic powder from the viewpoint of improving the fluidity of the hydraulic composition and suppressing the curing delay.
- the above is preferable, 0.05 parts by mass or more is more preferable, 0.1 parts by mass or more is more preferable, 2.5 parts by mass or less is preferable, 1.0 parts by mass or less is more preferable, 0.8 parts by mass The following is more preferable.
- the hydraulic powder is a powder that hardens when mixed with water.
- ordinary Portland cement for example, ordinary Portland cement, early-strength Portland cement, ultra-early strength Portland cement, sulfate-resistant Portland cement, low heat Portland cement, white Portland cement, Eco-cement (for example, JIS R5214 etc.) is mentioned.
- a cement selected from ordinary Portland cement, sulfate-resistant Portland cement and white Portland cement is preferable, and ordinary Portland cement is preferably used. More preferred.
- the hydraulic powder may include blast furnace slag, fly ash, silica fume and the like, and may include non-hydraulic fine limestone powder and the like. Silica fume cement or blast furnace cement mixed with cement may be used.
- Aggregates include fine aggregates and coarse aggregates. Fine aggregates are preferably mountain sand, land sand, river sand and crushed sand, and coarse aggregates are preferably mountain gravel, land gravel, river gravel and crushed stone. Depending on the application, lightweight aggregates may be used.
- the term “aggregate” is based on “Concrete Overview” (published on June 10, 1998, published by Technical Shoin).
- Aggregates can be used in the usual ranges used for the preparation of concrete, mortar and the like.
- the amount of coarse aggregate used reduces the expression of the strength of the hydraulic composition and the amount of hydraulic powder such as cement, and improves the filling properties of the formwork and the like.
- the bulk volume is preferably 50% or more, more preferably 55% or more, further preferably 60% or more, more preferably 100% or less, more preferably 90% or less, and still more preferably 80% or less.
- the amount of fine aggregate used is preferably 500 kg / m 3 or more, more preferably 600 kg / m 3 or more, and 700 kg from the viewpoint of improving the filling property to a mold or the like.
- the amount of fine aggregate is preferably from 800 kg / m 3 or more, more preferably 900 kg / m 3 or more, more preferably 1000 kg / m 3 or more, and, 2000 kg / m 3 or less Is preferably 1800 kg / m 3 or less, more preferably 1700 kg / m 3 or less.
- the content of water in the hydraulic composition is preferably 65 parts by mass or less with respect to 100 parts by mass of the hydraulic powder from the viewpoint of shortening the time required for the cured product of the hydraulic composition to reach the required strength. More preferably, it is 60 parts by mass or less, 55 parts by mass or less, and from the viewpoint of improving workability such as ease of kneading of the hydraulic composition and improvement of filling property to the mold at the time of casting.
- the amount is preferably 20 parts by mass or more, more preferably 25 parts by mass or more, and still more preferably 30 parts by mass or more.
- the hydraulic composition can be prepared by mixing glycerin, hydroxymethanesulfonic acid or a salt thereof, a dispersant, hydraulic powder, aggregate, and water. A detailed preparation method will be described in a method for producing a cured body described later.
- the hydraulic composition may further contain other components as long as the effect of the present invention is not affected.
- AE agent retarder, foaming agent, thickener, foaming agent, waterproofing agent, fluidizing agent, antifoaming agent and the like can be mentioned.
- the hydraulic composition of the present invention may be concrete or mortar.
- the hydraulic composition of the present invention is for self-leveling, refractory, plaster, lightweight concrete, heavy concrete, AE, repair, prepacked, prepacked, tremy, tremie, ground improvement, It is useful in any field such as grout, grout, and cold. It is preferable to use it for concrete products such as concrete vibration products and centrifugal molded products from the viewpoint of shortening the time required for the cured body of the hydraulic composition to reach the required strength and enabling early removal from the mold. .
- the additive composition for a hydraulic composition of the present invention contains glycerin, hydroxymethanesulfonic acid or a salt thereof, and a dispersant, and the mass ratio of glycerin / hydroxymethanesulfonic acid is 10/90 to 97/3. It is.
- the details of glycerin and hydroxymethanesulfonic acid or a salt thereof and the dispersant are the same as those of the hydraulic composition described above.
- the additive composition for hydraulic compositions of the present invention is suitably used for the hydraulic composition of the present invention.
- the additive composition for hydraulic composition may be a liquid composition containing water, for example, an aqueous solution.
- a liquid composition containing water such as an aqueous solution
- the total content of glycerin and hydroxymethanesulfonic acid or a salt thereof and a dispersing agent in the additive composition for hydraulic composition is the hardening of the hydraulic composition.
- it is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more
- an additive for hydraulic composition From the viewpoint of storage stability of the composition, it is preferably 60% by mass or less, more preferably 50% by mass or less.
- the content of water in the additive composition for hydraulic composition is preferably 40% by mass from the viewpoint of storage stability of the additive composition for hydraulic composition. Above, more preferably 50% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, from the viewpoint of shortening the time until the cured product of the hydraulic composition reaches the required strength. More preferably, it is 70 mass% or less.
- the additive composition for hydraulic composition may contain other components as long as the effect of the present invention is not affected.
- the additive composition for hydraulic composition can be prepared by mixing a predetermined amount of glycerin, hydroxymethanesulfonic acid or a salt thereof, and a dispersant. When it is set as the liquid composition containing water, it can prepare by mixing water further.
- the additive composition for a hydraulic composition is preferably 0.05 parts by mass with respect to 100 parts by mass of the hydraulic powder from the viewpoint of shortening the time until the cured product of the hydraulic composition reaches the required strength.
- the additive composition for a hydraulic composition containing glycerin, hydroxymethanesulfonic acid or a salt thereof, and a dispersant is used to improve the strength of the cured hydraulic composition.
- the manufacturing method of the hardening body of the hydraulic composition of this invention is 0.040 mass part or more and 0.280 mass part or less with respect to 100 mass parts of aggregate, water, and hydraulic powder to hydraulic powder.
- a step of preparing a hydraulic composition by adding 0.010 parts by mass or more and 0.420 parts by mass or less of hydroxymethanesulfonic acid or a salt thereof to 100 parts by mass of hydraulic powder.
- the hydraulic powder includes aggregate, water, 0.040 parts by mass or more and 0.280 parts by mass or less of glycerin with respect to 100 parts by mass of the hydraulic powder, and the hydraulic powder 100.
- a hydraulic composition having a step of preparing a hydraulic composition by adding 0.010 parts by mass or more and 0.420 parts by mass or less of hydroxymethanesulfonic acid or a salt thereof and a dispersant with respect to parts by mass.
- a manufacturing method is also provided.
- the hydraulic composition is obtained by adding and mixing aggregate, water, glycerin, hydroxymethanesulfonic acid or a salt thereof, and a dispersant to the hydraulic powder. can get.
- the additive containing glycerin and hydroxymethanesulfonic acid or a salt thereof in advance, the glycerin and hydroxymethanesulfonic acid or a salt thereof, and a dispersing agent It is preferable to use an additive composition for a hydraulic composition.
- glycerin, hydroxymethanesulfonic acid or a salt thereof, a dispersant, hydraulic powder, aggregate and water, glycerin, hydroxymethanesulfonic acid or a salt thereof, water and a dispersant are mixed in advance, It is preferable to mix with hydraulic powder and aggregate. Moreover, it is preferable to mix hydraulic powder and aggregate beforehand. Mixing with hydraulic powder, aggregate, and water can be performed using a mixer such as a mortar mixer or a forced biaxial mixer. It is preferable to use a mixture obtained by adding glycerin and hydroxymethanesulfonic acid or a salt thereof and a dispersant to water. The mixing is preferably performed for 1 minute or more, more preferably 2 minutes or more, and preferably 5 minutes or less, more preferably 3 minutes or less. In preparing the hydraulic composition, the materials and chemicals described in the hydraulic composition and their amounts can be used.
- the uncured hydraulic composition after preparation is filled into the mold, cured, and cured.
- a formwork a formwork for a building, a formwork for a concrete product, and the like can be given.
- the method of filling the mold include a method of directly feeding from a mixer, a method of pumping the hydraulic composition with a pump and introducing it into the mold.
- vibration or centrifugal force may be applied from the viewpoint of improving the filling property.
- the heat curing can be performed by holding the hydraulic composition at a temperature of 50 ° C. or more and 100 ° C. or less. In the present invention, the heat curing can be performed without performing the heat curing under these conditions. From the viewpoint of reducing energy consumption, it is preferable not to include steam curing.
- the curing temperature of the hydraulic composition filled in the mold is preferably 0 ° C. or higher, preferably 10 ° C. or higher, preferably lower than 50 ° C., more preferably 40 ° C. or lower, and further 30 ° C. or lower. preferable.
- air curing at room temperature can be performed.
- the heating curing time is short. It is preferable to carry out for 1 hour or less, more preferably 0.5 hour or less. Moreover, although the time of this heat curing is 0 hour or more, it may be 0 hour. That is, it is not necessary to perform the heat curing under the temperature condition. That is, the present invention can perform the curing of the hydraulic composition filled in the mold under curing conditions in which the time for which the curing temperature is maintained at 50 ° C. or more and 100 ° C. or less is 0 hour or more and 1 hour or less.
- the cured composition of the hydraulic composition is obtained by demolding from the mold.
- the obtained cured product can be used for the uses described in the hydraulic composition.
- the time from contact of water with the hydraulic powder to demolding is 4 hours from the viewpoint of obtaining strength necessary for demolding and improving the production cycle. It is preferably 48 hours or less.
- the method for producing a cured body of the hydraulic composition of the present invention since the curing of the hydraulic composition is promoted, it is possible to shorten the time from preparation of the hydraulic composition to demolding.
- each “content” of glycerin, hydroxymethanesulfonic acid or a salt thereof, a dispersant, and water in the section of the hydraulic composition can be read as “mixing amount” or “addition amount”.
- Embodiments of the present invention are exemplified below.
- ⁇ 1> Contains glycerin, hydroxymethanesulfonic acid or a salt thereof, a dispersant, a hydraulic powder, an aggregate, and water, and the content of glycerin is 0 with respect to 100 parts by mass of the hydraulic powder. 0.040 parts by mass or more and 0.280 parts by mass or less, and the content of hydroxymethanesulfonic acid or a salt thereof is 0.010 parts by mass or more and 0.420 parts by mass or less with respect to 100 parts by mass of the hydraulic powder. , Hydraulic composition.
- the content of glycerin is 0.040 parts by mass or more, preferably 0.050 parts by mass or more, more preferably 0.100 parts by mass or more, and 0.280 with respect to 100 parts by mass of the hydraulic powder.
- the hydraulic composition according to the above ⁇ 1> which is not more than part by mass, preferably not more than 0.250 part by mass, more preferably not more than 0.230 part by mass, and further preferably not more than 0.200 part by mass.
- the content of hydroxymethanesulfonic acid or a salt thereof is preferably 0.030 parts by mass or more, more preferably 0.050 parts by mass or more, and 0.420 parts by mass with respect to 100 parts by mass of the hydraulic powder. Part or less, preferably 0.410 part by weight or less, more preferably 0.200 part by weight or less, and still more preferably 0.100 part by weight or less, the hydraulic composition according to ⁇ 1> or ⁇ 2>.
- the total content of glycerin and hydroxymethanesulfonic acid or a salt thereof is preferably 0.050 part by mass or more, more preferably 0.100 part by mass or more, further preferably 100 parts by mass of the hydraulic powder. Is 0.130 parts by mass or more, more preferably 0.180 parts by mass or more, still more preferably 0.230 parts by mass or more, and preferably 0.650 parts by mass or less, more preferably 0.500 parts by mass or less.
- the mass ratio of glycerin / hydroxymethanesulfonic acid or a salt thereof is preferably 10/90 or more, more preferably 30/70 or more, still more preferably 60/40 or more, still more preferably 65/35 or more, and Any of the above ⁇ 1> to ⁇ 4>, preferably 97/3 or less, more preferably 95.5 / 4.5 or less, still more preferably 90/10 or less, and even more preferably 85/15 or less.
- the hydraulic composition as described.
- dispersant is one or more dispersants selected from naphthalene polymers and polycarboxylic acid copolymers, preferably naphthalene polymers.
- the hydraulic composition as described.
- the water content is preferably 65 parts by mass or less, more preferably 60 parts by mass or less, 55 parts by mass or less, and preferably 20 parts by mass or more, more preferably 100 parts by mass of the hydraulic powder.
- Glycerin, hydroxymethanesulfonic acid or a salt thereof, and a dispersant, and a mass ratio of glycerin / hydroxymethanesulfonic acid is 10/90 or more, preferably 30/70 or more, more preferably 60/40. Or more, more preferably 65/35 or more, and 97/3 or less, preferably 95.5 / 4.5 or less, more preferably 90/10 or less, still more preferably 85/15 or less, preferably ⁇
- An additive composition for hydraulic composition which is used for the hydraulic composition according to any one of 1> to ⁇ 7>.
- the hydraulic powder With respect to 100 parts by mass of the hydraulic powder, it is preferably 0.05 parts by mass or more, more preferably 0.10 parts by mass or more, still more preferably 0.13 parts by mass or more, and even more preferably 0.18 parts by mass. Part or more, more preferably 0.23 part by weight or more, and preferably 0.50 part by weight or less, more preferably 0.40 part by weight or less, still more preferably 0.33 part by weight or less, still more preferably 0.
- dispersant according to ⁇ 10> or ⁇ 11>, wherein the dispersant is one or more dispersants selected from naphthalene polymers and polycarboxylic acid copolymers, preferably naphthalene polymers.
- a method for producing a cured product of a hydraulic composition is one or more dispersants selected from naphthalene polymers and polycarboxylic acid copolymers, preferably naphthalene polymers.
- ⁇ 13> The cured product of the hydraulic composition according to any one of ⁇ 10> to ⁇ 12>, wherein the amount of water added is 20 parts by mass or more and 65 parts by mass or less with respect to 100 parts by mass of the hydraulic powder. Manufacturing method.
- the production of a hydraulic composition comprising the step of preparing a hydraulic composition by adding hydroxymethanesulfonic acid or a salt thereof in an amount of not more than mass parts, more preferably not more than 0.100 mass parts, and a dispersant.
- Glycerin, hydroxymethanesulfonic acid or a salt thereof, and a dispersant are included, and the mass ratio of glycerin / hydroxymethanesulfonic acid is 10/90 or more, preferably 30/70 or more, more preferably 60/40. More preferably, the hydraulic composition is 65/35 or more and 97/3 or less, preferably 95.5 / 4.5 or less, more preferably 90/10 or less, and still more preferably 85/15 or less.
- Use of the additive composition for improving the strength of the cured hydraulic composition are examples The following examples describe the practice of the present invention. The examples are illustrative of the invention and are not intended to limit the invention.
- glycerin "Purified glycerin" (manufactured by Kao Corporation) ⁇ Sodium hydroxymethanesulfonate> Reagent (manufactured by Tokyo Chemical Industry Co., Ltd.) Purity: 97.0% by mass or more
- ⁇ Manufacture of additive composition for hydraulic composition Glycerin, sodium hydroxymethanesulfonate, a dispersant and water are mixed so that the ratio of the addition amounts shown in Table 2 and Table 3 is reached, and the total amount of glycerin, sodium hydroxymethanesulfonate and the dispersant is 35% by mass.
- the additive composition for hydraulic compositions which is an aqueous solution was prepared.
- glycerin and / or hydroxymethanesulfonic acid may be referred to as “early strong agent” for convenience.
- Hydraulic compositions (mortar) of Test Groups 1 to 6 having different mixing ratios of water, hydraulic powder, and aggregate were prepared.
- the mixing ratio of hydraulic powder, aggregate and water in Test Groups 1 to 6 was set to the ratio shown in Table 1.
- a mortar mixer manufactured by Dalton Co., Ltd., a universal mixing stirrer, model: 5DM-03- ⁇
- each test group was charged with a predetermined amount of hydraulic powder and aggregate shown in Table 1, and 10 kneaded.
- the blending amount of the dispersant is a hydraulic composition in which only the dispersant is added as the additive composition for the hydraulic composition, that is, Comparative Example 1-1, Comparative Example 2-1 and Comparative Examples 3 to 6.
- the hydraulic composition was adjusted so that the mortar flow value was in the range of 180 to 200 mm and the target air entrainment amount was 2 ⁇ 1%.
- Table 1 shows the necessary demolding strength and the time required for the hydraulic composition to which the early strengthening agent of each test group is not added.
- the hydraulic composition to which no early strengthening agent is added is the hydraulic composition of Comparative Example 1-1, Comparative Example 2-1, and Comparative Examples 3 to 6.
- the arrival time was calculated by the following formula: 12 + ⁇ (required demolding strength * ⁇ 12 hour strength) / [(24 hour strength ⁇ 12 hour strength) / 12] ⁇ . * 40 N / mm 2 in test group 1
- Necessary demolding strength is empirically said to be general in order to prevent product damage during demolding, to prevent deformation in prestressed products and prestressed concrete, and to prevent breakage during lifting and transport. It has been broken.
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Abstract
Description
背景技術
発明の要約
発明の詳細な説明
水硬性組成物の初期硬化において、水硬性粉体中のエーライト、alite、すなわちC3Sは水和により結晶化することにより強度が発現する。また、カルシウムアルミノフェライト、calcium-aluminoferrite、すなわち、C4AFは水硬性粉体に含まれている石膏とともに水和し結晶性のエトリンガイト、Ettringiteを生成して、強度が発現する。さらに系中のカルシウムが消費されるとエトリンガイトがモノサルフェート、monosulphateとなって、さらに強度が発現する。
ヒドロキシメタンスルフォン酸又はその塩はC3Sの水和を促進することにより、強度を向上すると考えられる。一方、グリセリンはC4AFがエトリンガイトになることを促進すると考えられる。
本発明のように特定量のグリセリンとヒドロキシメタンスルフォン酸又はその塩を水硬性組成物の調製の際に併用すると、グリセリンにより生成が促進されたエトリンガイトを、更にヒドロキシメタンスルフォン酸又はその塩がモノサルフェートになることを促進すると考えられる。その結果、グリセリンとヒドロキシメタンスルフォン酸又はその塩のそれぞれの強度向上効果が相乗的に発現し強度向上が加速され、硬化体が必要な硬度に到達するまでの時間を短縮することができると考えられる。
本発明の水硬性組成物は、グリセリンと、ヒドロキシメタンスルフォン酸又はその塩と、分散剤と、水硬性粉体と、骨材と、水とを含有する。
R1、R2:水素原子、又はメチル基
l:0以上2以下の数
m:0又は1の数
AO:炭素数2以上4以下のアルキレンオキシ基
n:AOの平均付加モル数であり、5以上150以下の数
R3:水素原子、又は炭素数1以上4以下のアルキル基
を表す。〕
R4、R5、R6:水素原子、メチル基、又は(CH2)m1COOM2
M1、M2:水素原子、アルカリ金属、アルカリ土類金属(1/2原子)、アンモニウム、アルキルアンモニウム、又は置換アルキルアンモニウム
m1:0以上2以下の数
を表す。なお、(CH2)m1COOM2はCOOM1と無水物を形成していてもよい。〕
本発明の水硬性組成物用添加剤組成物は、グリセリンと、ヒドロキシメタンスルフォン酸又はその塩と、分散剤を含有し、グリセリン/ヒドロキシメタンスルフォン酸の質量比が、10/90~97/3である。グリセリンとヒドロキシメタンスルフォン酸又はその塩と分散剤の詳細は、それぞれ前述の水硬性組成物と同様である。本発明の水硬性組成物用添加剤組成物は、本発明の水硬性組成物に好適に用いられる。
本発明の水硬性組成物の硬化体の製造方法は、水硬性粉体に、骨材と、水と、水硬性粉体100質量部に対し0.040質量部以上、0.280質量部以下のグリセリンと、水硬性粉体100質量部に対し0.010質量部以上、0.420質量部以下のヒドロキシメタンスルフォン酸又はその塩を添加し、水硬性組成物を調製する工程と、得られた水硬性組成物を型枠に充填し硬化させる工程と、硬化した水硬性組成物を型枠から脱型して水硬性組成物の硬化体を得る工程とを有する。なお、本発明により、水硬性粉体に、骨材と、水と、水硬性粉体100質量部に対し0.040質量部以上、0.280質量部以下のグリセリンと、水硬性粉体100質量部に対し0.010質量部以上、0.420質量部以下のヒドロキシメタンスルフォン酸又はその塩と、分散剤とを添加し、水硬性組成物を調製する工程を有する、水硬性組成物の製造方法もまた提供される。
<1> グリセリンと、ヒドロキシメタンスルフォン酸又はその塩と、分散剤と、水硬性粉体と、骨材と、水とを含有し、グリセリンの含有量が水硬性粉体100質量部に対し0.040質量部以上、0.280質量部以下であり、ヒドロキシメタンスルフォン酸又はその塩の含有量が水硬性粉体100質量部に対し0.010質量部以上、0.420質量部以下である、水硬性組成物。
実施例
次の実施例は本発明の実施について述べる。実施例は本発明の例示について述べるものであり、本発明を限定するためではない。
<グリセリン>
「精製グリセリン」(花王株式会社製)
<ヒドロキシメタンスルフォン酸ナトリウム>
試薬(東京化成株式会社製) 純度:97.0質量%以上
<分散剤(1)>
ナフタレンスルフォン酸ホルマリン縮合物〔マイテイ150、MIGHTY150(花王株式会社製)、固形分40質量%、表中の添加量は固形分換算の添加量〕
<分散剤(2)>
メトキシポリエチレングリコールモノメタクリレート/メタクリル酸共重合体のナトリウム塩の水溶液〔一般式(1)において、R1が水素原子、R2がメチル基、lが0、mが1、AOがエチレンオキシ基、nが120、R3がメチル基である単量体(1)と、一般式(2)において、R4及びR5が共に水素原子、R6がメチル基、M1が水素原子である単量体(2)との共重合体のナトリウム塩の水溶液、単量体(1)/単量体(2)の質量比は94/6、固形分40質量%、表中の添加量は固形分換算の添加量〕
<水硬性粉体>
セメント(C):普通ポルトランドセメント〔太平洋セメント株式会社製の普通ポルトランドセメント/住友大阪セメント株式会社製の普通ポルトランドセメント=1/1、質量比〕、密度3.16g/cm3
<骨材>
細骨材(S):城陽産、山砂、FM(粗粒率、Finess modulus)=2.67、密度2.56g/cm3
<水>
水道水(W)
表2及び表3に示す添加量の比になるように、グリセリン、ヒドロキシメタンスルフォン酸ナトリウム、分散剤及び水を混合し、グリセリン、ヒドロキシメタンスルフォン酸ナトリウム及び分散剤の合計量が35質量%の水溶液である水硬性組成物用添加剤組成物を調製した。なお、以下、グリセリン及び/又はヒドロキシメタンスルフォン酸を、便宜的に「早強剤」として示す場合もある。
水、水硬性粉体、骨材の配合比の異なる試験群1~6の水硬性組成物(モルタル)を調製した。試験群1~6における水硬性粉体、骨材、水の配合比は、表1に示す比に設定した。
モルタルミキサー、株式会社ダルトン社製、万能混合撹拌機、型式:5DM-03-γを用いて、各試験群において表1に示す所定量の水硬性粉体、骨材を投入し空練りを10秒行い、表2及び表3に示す添加量になるように水硬性組成物用添加剤組成物を含んだ練り水を加え、低速回転にて60秒、更に高速回転にて120秒間本混練りし、水硬性組成物を得た。
なお、分散剤の配合量は、水硬性組成物用添加剤組成物として分散剤のみを添加した水硬性組成物、即ち、比較例1-1、比較例2-1及び比較例3~6の水硬性組成物のモルタルフロー値が180~200mmの範囲、目標空気連行量2±1%となるように調整した。
(フロー試験)
調製した水硬性組成物を、JIS R 5201に基づき、直ちにフローコーン、flowconeに2層詰めし、フローコーン、flow coneを正しく上の方に取り去り、最大と認める方向と、これに直角な方向の長さを測定し、これらの平均値を算出した。尚、JIS R 5201記載の落下運動は行っていない。
得られた水硬性組成物について、以下に示す試験法にしたがって、脱型時の圧縮強度を評価した。評価結果を表2、3に示す。
(1)硬化体の強度の評価
JIS A 1132に基づき、底面の直径が5cm、高さが10cmの円柱型プラスチックモールドの型枠に、二層詰め方式によりモルタルを充填し、20℃の室内にて大気中で養生を行い硬化させた。各モルタルそれぞれに対して型枠4個に充填した。モルタル調製から12時間後に2個の型枠、24時間後に2個の型枠の硬化したモルタルを型枠から脱型して硬化体を得た。そして、12時間後、24時間後、それぞれの硬化体について、JIS A 1108に基づいて硬化体の圧縮強度を測定し、2個の平均値を算出した。
得られた12時間後強度と24時間強度の比例計算より、脱型時に必要な圧縮強度の到達に必要な所要養生時間、すなわち、到達時間を算出した。脱型時に必要な圧縮強度は、以下、必要脱型強度ともいう。
また、同じ試験群で、早強剤を添加しない水硬性組成物の到達時間を100とした場合の、各水硬性組成物の到達時間の相対値である相対時間を求めた。早強剤を添加しない水硬性組成物は、比較例1-1、比較例2-1及び比較例3~6の水硬性組成物である。相対時間の数値が小さいほど、必要脱型強度に到達する所要養生時間の短縮効果に優れることを意味する。
各試験群の早強剤を添加しない水硬性組成物の必要脱型強度及び到達時間を表1に示す。早強剤を添加しない水硬性組成物は、比較例1-1、比較例2-1及び比較例3~6の水硬性組成物である。
ことがわかる。一般的に、モルタル硬化体においては、凝結が始まり強度を示すようになれば、一定強度までは、時間と強度の増加量には比例関係が成り立つといわれている。一定強度とは、例えばW/Cが25までのときは、60N/mm2程度である。本発明では、具体的には、到達時間は、12+{(必要脱型強度*-12時間強度)/[(24時間強度-12時間強度)/12]}の計算式により計算した。
*試験群1では40N/mm2
試験群1、2:遠心成型の高強度パイル製品、脱型強度=40N/mm2
試験群3:振動製品の小物製品、必要脱型強度=8N/mm2
試験群4:振動製品の中物製品、必要脱型強度=10N/mm2
試験群5:振動製品の大物製品、必要脱型強度=15N/mm2
試験群6:遠心成型のパイル製品、必要脱型強度=40N/mm2
必要脱型強度は、脱型時の製品損傷の防止のためや、プレストレス製品、prestressed concreteでは変形防止のためや、吊り上げ運搬時の破損防止のために、経験的に上記が一般的と言われている。
Claims (14)
- グリセリンと、ヒドロキシメタンスルフォン酸又はその塩と、分散剤と、水硬性粉体と、骨材と、水とを含有し、グリセリンの含有量が水硬性粉体100質量部に対し0.040質量部以上、0.280質量部以下であり、ヒドロキシメタンスルフォン酸又はその塩の含有量が水硬性粉体100質量部に対し0.010質量部以上、0.420質量部以下である、水硬性組成物。
- グリセリン/ヒドロキシメタンスルフォン酸又はその塩の質量比が、10/90以上、97/3以下である、請求項1記載の水硬性組成物。
- グリセリンとヒドロキシメタンスルフォン酸又はその塩の合計の含有量が、水硬性粉体100質量部に対し、0.050質量部以上、0.650質量部以下である、請求項1又は2記載の水硬性組成物。
- 分散剤が、ナフタレン系重合体及びポリカルボン酸系共重合体から選ばれる一種以上の分散剤である、請求項1~3の何れか1項記載の水硬性組成物。
- 分散剤が、ナフタレン系重合体である、請求項1~4の何れか1項記載の水硬性組成物。
- 水の含有量が、水硬性粉体100質量部に対し、20質量部以上、65質量部以下である、請求項1~5の何れか1項記載の水硬性組成物。
- 請求項1~6の何れか1項記載の水硬性組成物に用いる水硬性組成物用添加剤組成物であって、
グリセリンと、ヒドロキシメタンスルフォン酸又はその塩と、分散剤を含有し、グリセリン/ヒドロキシメタンスルフォン酸の質量比が、10/90以上、97/3以下である、水硬性組成物用添加剤組成物。 - 水硬性粉体に、骨材と、水と、水硬性粉体100質量部に対し0.040質量部以上、0.280質量部以下のグリセリンと、水硬性粉体100質量部に対し0.010質量部以上、0.420質量部以下のヒドロキシメタンスルフォン酸又はその塩と、分散剤とを添加し、水硬性組成物を調製する工程と、得られた水硬性組成物を型枠に充填し硬化させる工程と、硬化した水硬性組成物を型枠から脱型して水硬性組成物の硬化体を得る工程とを有する水硬性組成物の硬化体の製造方法。
- 蒸気養生を含まない請求項8記載の水硬性組成物の硬化体の製造方法。
- 分散剤が、ナフタレン系重合体及びポリカルボン酸系共重合体から選ばれる一種以上の分散剤である請求項8又は9に記載の水硬性組成物の硬化体の製造方法。
- 分散剤が、ナフタレン系重合体である請求項8~10の何れか1項記載の水硬性組成物の硬化体の製造方法。
- 水の添加量が、水硬性粉体100質量部に対し、20質量部以上、65質量部以下である請求項8~11の何れか1項記載の水硬性組成物の硬化体の製造方法。
- グリセリンと、ヒドロキシメタンスルフォン酸又はその塩と、分散剤を含有する水硬性組成物用添加剤組成物の、水硬性組成物硬化体の強度を向上するための使用。
- グリセリンと、ヒドロキシメタンスルフォン酸又はその塩と、分散剤を含有し、グリセリン/ヒドロキシメタンスルフォン酸の質量比が、10/90以上、97/3以下である水硬性組成物用添加剤組成物の、水硬性組成物硬化体の強度を向上するための使用。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61117142A (ja) * | 1984-11-08 | 1986-06-04 | 藤沢薬品工業株式会社 | セメント組成物 |
WO2011081115A1 (ja) * | 2009-12-28 | 2011-07-07 | 花王株式会社 | 水硬性組成物用早強剤 |
JP2012201577A (ja) * | 2011-03-28 | 2012-10-22 | Kao Corp | 水硬性組成物の硬化体の製造方法 |
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EP2128110B1 (de) * | 2008-05-29 | 2016-08-17 | Sika Technology AG | Zusatzmittel für hydraulische Bindemittel mit langer Verarbeitungszeit und hoher Frühfestigkeit |
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JPS61117142A (ja) * | 1984-11-08 | 1986-06-04 | 藤沢薬品工業株式会社 | セメント組成物 |
WO2011081115A1 (ja) * | 2009-12-28 | 2011-07-07 | 花王株式会社 | 水硬性組成物用早強剤 |
JP2012201577A (ja) * | 2011-03-28 | 2012-10-22 | Kao Corp | 水硬性組成物の硬化体の製造方法 |
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JP2023151146A (ja) * | 2022-03-31 | 2023-10-16 | 住友大阪セメント株式会社 | コンクリート組成物の製造方法、及び、コンクリートの製造方法 |
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