WO2012124716A1 - 水硬性組成物用分散剤 - Google Patents
水硬性組成物用分散剤 Download PDFInfo
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- WO2012124716A1 WO2012124716A1 PCT/JP2012/056493 JP2012056493W WO2012124716A1 WO 2012124716 A1 WO2012124716 A1 WO 2012124716A1 JP 2012056493 W JP2012056493 W JP 2012056493W WO 2012124716 A1 WO2012124716 A1 WO 2012124716A1
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- copolymer
- hydraulic composition
- dispersant
- hydraulic
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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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
- C04B24/121—Amines, polyamines
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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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/12—Nitrogen containing compounds organic derivatives of hydrazine
- C04B24/122—Hydroxy amines
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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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2641—Polyacrylates; Polymethacrylates
- C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
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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
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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
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/34—Flow improvers
-
- 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
- C04B2103/40—Surface-active agents, dispersants
- C04B2103/408—Dispersants
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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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
Definitions
- the present invention relates to a dispersant for a hydraulic composition.
- Dispersants for hydraulic compositions are chemicals used to reduce the amount of unit water required to obtain the required slump by dispersing cement particles and to improve the workability of hydraulic compositions. Admixture.
- Conventional dispersants include naphthamines such as naphthalene sulfonate formaldehyde condensates, polycarboxylic acids such as copolymers of carboxylic acids and monomers having an alkylene glycol chain, and melamines such as melamine sulfonate formaldehyde condensates. The system is known.
- alkanolamine is used in combination with a dispersant in order to develop concrete strength at an early stage.
- Japanese Patent Application Laid-Open No. 2007-31166 has an object to provide a spray material for cement concrete that has a small amount of alkali and excellent initial strength, and the cement concrete contains an acid containing aluminum, sulfur, and alkanolamine.
- a spray material is disclosed.
- known water reducing agents (dispersants) such as lignin sulfonic acid, naphthalene sulfonic acid, and polycarboxylic acid can be used to improve the fluidity of cement concrete. .
- JP 2000-511151A is a salt of an organic or inorganic acid, an alkali or alkaline earth metal salt, with the object of providing a multifunctional mixture that has both hardening acceleration and air carrying properties of a hydraulic composition.
- a multifunctional hydraulic cement composition mixture is disclosed that comprises a cure accelerator and a fatty acid aminosulfonic acid surfactant. And further includes a water weight reducing agent comprising a lignosulfonic acid, polycarboxylic acid, naphthalenesulfonic acid condensate, melamine sulfonic acid condensate, hydroxylated carboxylic acid, or an alkali or alkaline earth metal salt of a carbohydrate.
- composition mixture comprising an early strength enhancing agent comprising an alkanolamine is disclosed.
- triethanolamine or triisopropanolamine is mentioned as the alkanolamine
- calcium lignin sulfonate is mentioned as the water weight reducing agent.
- US-B 5605571 uses a high-performance water-containing agent in combination with a hardening accelerator for hydraulic powder containing a nitric acid or sulfurous acid component, a thiocyanic acid component, an alkanolamine component, and a carboxylic acid component. It is disclosed.
- Japanese Patent Application Laid-Open No. 2002-226245 discloses a concrete mixture and a concrete composition containing a trialkanolamine and a polycarboxylic acid or a salt thereof.
- Japanese Unexamined Patent Publication No. 01-246164 discloses a hydraulic cement admixture containing an amide sulfonate and a water-soluble amino alcohol.
- Japanese Patent Application Laid-Open No. 2002-080250 discloses a setting and hardening accelerator which does not contain an alkali or alkali metal and a chloride, and contains a water-soluble aluminum salt containing a fluoride and an aluminum salt containing a sulfate.
- JP 2002-145651 discloses a cement composition comprising C 2 S or C 3 S and C 3 A and C 4 AF.
- WO-A 2012/008 517 which was distributed on January 19, 2012, discloses a method for producing hydraulic powder.
- the present invention provides water containing N-methyldiethanolamine, and a copolymer containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2).
- the present invention relates to a dispersant for a hard composition.
- R 1 represents a hydrogen atom or a methyl group
- M 1 represents a hydrogen atom or a counter ion forming a salt
- R 2 is a hydrogen atom or a methyl group
- AO is an alkyleneoxy group having 2 to 4 carbon atoms
- l is a number of 0 to 2
- m is a number of 0 or 1
- n is an average added mole number of AO.
- the number is 2 to 300
- R 3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- the present invention also provides N-methyldiethanolamine, a copolymer comprising the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), a hydraulic powder, and an aggregate. And a hydraulic composition containing water and having a weight ratio of water to hydraulic powder (water / hydraulic powder) of 0.20 to 0.50. Furthermore, the present invention provides a hydraulic composition comprising N-methyldiethanolamine, and a copolymer containing the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2).
- the present invention relates to the use of a physical dispersant for improving the fluidity of a hydraulic composition.
- the present invention uses a (meth) acrylic acid-based polycarboxylic acid copolymer, and improves the fluidity while improving the strength of the cured body after 24 hours and 7 days of the hydraulic composition.
- a dispersant for the composition is provided.
- (meth) acrylic acid means “acrylic acid and / or methacrylic acid”.
- the present inventors have determined the strength of the cured product after 24 hours and 7 days after the hydraulic composition. It was found that the initial fluidity, i.e., initial fluidity, of preparing the hydraulic composition was improved as compared with the case where the (meth) acrylic acid-based polycarboxylic acid copolymer was used alone. That is, in order to obtain fluidity equivalent to that when the (meth) acrylic acid-based polycarboxylic acid copolymer is used alone, the amount of the copolymer used can be reduced.
- the fluidity after kneading is improved because adsorption is suppressed and the copolymer buried by crystal growth of the hydraulic powder is reduced. It is effective for copolymers having a phosphate group with a high adsorption rate to the hydraulic powder, and copolymers having a structural unit derived from a dicarboxylic acid having a carboxyl group even if it forms a salt with N-methyldiethanolamine. It is thought that it does not develop. In addition, it is considered that the effects of amines other than N-methyldiethanolamine are inferior because the copolymer does not have an appropriate rate of adsorption onto the hydraulic powder.
- the early strength and fluidity of the hydraulic composition are improved. Specifically, by using a (meth) acrylic acid-based polycarboxylic acid copolymer, the fluidity is further improved while improving the strength of the cured body after 24 hours and 7 days of the hydraulic composition. Dispersants for hydraulic compositions are provided. *
- the amine according to the present invention is N-methyldiethanolamine.
- the fluidity of the hydraulic composition is improved while improving the strength of the cured body after 24 hours and after 7 days of the hydraulic composition. (Also referred to as initial fluidity) can be further improved.
- N-methyldiethanolamine can be used as a salt from the viewpoint of enhancing solubility in water.
- Salts include salts selected from sulfates, acetates, lactates, chlorides, formates, carbonates, silicates and mixtures thereof.
- the copolymer according to the present invention includes a structural unit represented by the general formula (1) [hereinafter referred to as structural unit 1] and a structural unit represented by the general formula (2) [hereinafter referred to as structural unit 2]. including. That is, as an example of the copolymer, acrylic acid or methacrylic acid derived from the structural unit 1, polyalkylene glycol derived from the structural unit 2 and ester of acrylic acid or methacrylic acid, alkyleneoxy group and alkenyl group And those having a constitutional monomer (hereinafter referred to as a monomer (2) as a charcoal monomer derived from the constitutional unit 2). Acrylic acid or methacrylic acid may form a salt.
- a monomer (2) as a charcoal monomer derived from the constitutional unit 2
- Acrylic acid or methacrylic acid may form a salt.
- R 1 is a hydrogen atom or a methyl group, acrylic acid in the case of a hydrogen atom, and methacrylic acid in the case of a methyl group.
- M 1 is a hydrogen atom or a counter ion forming a salt. Examples of the counter ion include alkali metal ions such as sodium ion and potassium ion, alkaline earth metal ions, and ammonium ions.
- An example of the monomer (2) is a monoester of polyalkylene glycol and (meth) acrylic acid or an ether obtained by adding an alkylene oxide to an alkenyl alcohol, and has a structure represented by the general formula (2) in the copolymer. What is formed is mentioned.
- AO represents an alkyleneoxy group having 2 to 4 carbon atoms, and preferably has 2 or 3 carbon atoms, more preferably an alkylene having 2 carbon atoms, from the viewpoint of solubility of the copolymer in water. It is an oxy group (ethyleneoxy group).
- n is the average number of moles of AO added and represents a number of 2 to 300.
- l is a number from 0 to 2
- m represents a number of 0 or 1.
- m represents an ether bond
- l is preferably 1 or 2 from the viewpoint of improving the fluidity of the hydraulic composition.
- m is 1, it represents an ester bond, and when m is 1, l is preferably 0 from the viewpoint of the reactivity of the monomer.
- m is preferably 1.
- R 3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when m is 0, R 3 is preferably a hydrogen atom from the viewpoint of production of a monomer. When m is 1, since R 3 may be a hydrogen atom, a transesterification reaction may occur. Therefore, R 3 is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group from the viewpoint of water solubility. preferable.
- the monomer (2) specifically, as an ester of polyalkylene glycol and (meth) acrylic acid, one end-capped alkylene glycol and (meth) acrylic acid ester may be mentioned, and methoxypolyethylene glycol Examples include acrylate, methoxy polyethylene glycol methacrylate, ethoxy polyethylene glycol acrylate, and ethoxy polyethylene glycol methacrylate.
- examples of ethers in which alkylene oxide is added to alkenyl alcohol include allyl alcohol ethylene oxide adduct, methallyl alcohol ethylene oxide adduct, and 3-methyl-3-buten-1-ol ethylene oxide adduct. . From the viewpoint of improving the fluidity of the hydraulic composition and improving the strength after 24 hours, an ester of polyalkylene glycol and (meth) acrylic acid is preferred.
- the copolymer has structural unit 1 and structural unit 2 as structural units, and the proportion of structural unit 1 in the total of structural unit 1 and structural unit 2 is preferably 1 to 99 mol%, and the flow of the hydraulic composition From the viewpoint of improving the property, preferably 40 to 98 mol%, more preferably 50 to 97 mol%, still more preferably 60 to 97 mol%, still more preferably 70 to 90 mol%, still more preferably 70 to 85 mol%. More preferably, it is 72 to 80 mol%.
- the proportion of the structural unit 2 in the total of the structural unit 1 and the structural unit 2 is preferably 1 to 99 mol%, and preferably 2 to 60 mol%, more preferably from the viewpoint of improving the fluidity of the hydraulic composition.
- the total proportion of the structural unit 1 and the structural unit 2 in all the structural units contained in the copolymer is preferably 30 to 100 mol%, more preferably from the viewpoint of improving the initial fluidity of the hydraulic composition. 50 to 100 mol%, more preferably 70 to 100 mol%, more preferably 80 to 100 mol%, and still more preferably substantially 100 mol%.
- Examples of the structural unit other than the structural unit 1 and the structural unit 2 in the copolymer include alkyl esters of unsaturated carboxylic acids.
- the weight average molecular weight of the copolymer is preferably from 1,000 to 200,000, more preferably from 10,000 to 100,000, still more preferably from 20,000 to 80,000, and more preferably from 38,000 to 55,000, from the viewpoint of improving the initial fluidity of the hydraulic composition. Further preferred.
- This weight average molecular weight is measured by a gel permeation chromatography (GPC) method under the following conditions.
- the copolymer can be produced by a polymerization method such as solution polymerization or bulk polymerization using a monomer component and an initiator. It can also be synthesized by a polymer reaction method.
- the polymer reaction method is a method of obtaining a graft copolymer by polymerizing an unsaturated carboxylic acid and then performing an esterification reaction with a polyalkylene glycol compound.
- the obtained copolymer can be neutralized with an alkali agent.
- alkali agent include sodium hydroxide and potassium hydroxide.
- the degree of neutralization of the copolymer is preferably from 0.5 to 1.0, more preferably from 0.5 to 0.9, from the viewpoint of improving the storage stability of the dispersant for hydraulic composition.
- Polymerization initiators used in the production of the copolymer include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; hydrogen peroxide; azo compounds such as azobis-2-methylpropionamidine hydrochloride and azoisobutyronitrile
- peroxide such as benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, and the like can be preferably used.
- Examples of the method for producing the copolymer include solution polymerization methods described in JP-A-62-1119147 and JP-A-7-223852.
- the dispersant for hydraulic composition of the present invention contains N-methyldiethanolamine and the copolymer.
- the weight ratio of the N-methyldiethanolamine (hereinafter also referred to as component (A)) and the copolymer (hereinafter also referred to as component (B)) (component (A) / component (B)) is from 1/20 to 1/1 is preferable, 1/15 to 1/1 is more preferable, 1/10 to 1/1 is still more preferable, 1/5 to 1/1 is still more preferable, and 1/3 to 1/1 is still more preferable preferable.
- the weight ratio in this range is preferable from the viewpoint of improving the strength of the cured body after 24 hours of the hydraulic composition and improving the fluidity of the hydraulic composition.
- the dispersant for a hydraulic composition of the present invention can be used in solid form such as powder or granule, or dissolved or dispersed in a solvent and used in liquid form or paste form.
- the content of the component (A) in the dispersant is preferably 0.1 to 40% by weight, more preferably 0.5 to 30% by weight, and still more preferably from the viewpoint of improving the fluidity of the hydraulic composition. 1.5 to 20% by weight.
- the content of the component (A) in the dispersant is preferably 0.5% by weight or more, more preferably 1.5% by weight or more, from the viewpoint of improving the strength of the cured product after 7 days of the hydraulic composition.
- the content of the component (B) in the dispersant is preferably 0.3% by weight or more, more preferably 5% by weight or more, and still more preferably 10% by weight from the viewpoint of improving the fluidity of the hydraulic composition. From the viewpoint of suppressing the viscosity of the dispersant and improving the handleability at the time of preparing the hydraulic composition, for example, it is preferably 60% by weight or less, more preferably 55% by weight or less, and still more preferably 50% by weight. % Or less. Therefore, the content of the component (B) in the dispersant is preferably 0.3 to 60% by weight, more preferably 5 to 55% from the viewpoint of improving the fluidity of the hydraulic composition and suppressing the viscosity of the dispersant. % By weight, more preferably 10 to 50% by weight.
- the total amount of the component (A) and the component (B) in the dispersant is the viewpoint of improving the fluidity of the hydraulic composition, improving the strength of the cured body after 24 hours and 7 days, and suppressing the viscosity of the dispersant.
- the dispersant for hydraulic composition of the present invention is preferably used in the form of a liquid such as a uniform solution. From the viewpoint of obtaining a uniform liquid with suppressed viscosity, it contains water, and further an aqueous solution. Is more preferable.
- the dispersant of the present invention may be a dispersant containing the component (A), the component (B) and water.
- the dispersant of the present invention is a dispersant containing water
- the content of the component (A) in the dispersant is improved in the fluidity of the hydraulic composition and in the strength of the cured product after 24 hours and 7 days. From this point of view, it is preferably 0.1 to 25% by weight, more preferably 0.5 to 20% by weight, still more preferably 1 to 20% by weight, still more preferably 3 to 10% by weight.
- the content of the component (B) in the dispersant is preferably 1 to 50% by weight from the viewpoint of improving the fluidity of the hydraulic composition. It is preferably 5 to 50% by weight, more preferably 10 to 50% by weight, and still more preferably 15 to 45% by weight.
- the content of water in the dispersant is preferably 25 to 98% by weight, more preferably 30 to 94% by weight from the viewpoint of obtaining a uniform liquid with suppressed viscosity. More preferably, it can be 35 to 89% by weight, and still more preferably 45 to 82% by weight.
- the total amount of the component (A) and the component (B) in the dispersant is the improvement in the fluidity of the hydraulic composition, and the strength of the cured product after 24 hours and 7 days.
- it is preferably 2 to 75% by weight, more preferably 6 to 70% by weight, still more preferably 11 to 65% by weight, and still more preferably 18 to 55% by weight.
- an organic solvent can be used in addition to water.
- the dispersant for a hydraulic composition of the present invention can be used in combination with components other than the components (A) and (B) as necessary.
- components other than the component (A) and the component (B) for example, a dispersant, an air entraining agent (AE agent), an antifoaming agent, a thickener, an early strengthening agent, a retarding agent, etc. can be used in combination. It is.
- the hydraulic composition of the present invention contains N-methyldiethanolamine [component (A)], copolymer [component (B)], hydraulic powder, aggregate, and water.
- Weight ratio of hydraulic powder (weight ratio of water / hydraulic powder, usually abbreviated as W / P, but may be abbreviated as W / C when the powder is cement). 20 to 0.50.
- the weight ratio of water to hydraulic powder is preferably 0.25 or more, more preferably 0.30 or more, from the viewpoint of improving the initial fluidity of the hydraulic composition.
- the weight ratio of water to hydraulic powder is preferably 0.48 or less, and more preferably 0.46 or less, from the viewpoint of the strength of the cured product.
- the weight ratio of water to hydraulic powder is more preferably from 0.25 to 0.48, and further preferably from 0.30 to 0.46, from the viewpoint of improving the initial fluidity of the hydraulic composition and the strength of the cured product. preferable.
- N-methyldiethanolamine and the copolymer the same ones as described above can be used.
- the hydraulic composition of the present invention can be prepared by adding hydraulic powder and aggregate to the above-described dispersant for hydraulic composition as necessary.
- the amount of the component (A), the component (B), the hydraulic powder, the aggregate and the water can be determined from the blending amount at the time of preparing the hydraulic composition.
- the fluidity of the composition can be improved by adding the component (A) and the component (B) according to the present invention to a composition containing hydraulic powder, aggregate, and water. Moreover, since a certain fluidity can be obtained even if the amount used is reduced, the setting delay due to the copolymer can be reduced.
- Component (A) and component (B) may be added to a composition containing hydraulic powder, aggregate and water after they are mixed in advance, or component (A) and component (B) ) Ingredients may be added separately. You may add as a dispersing agent containing (A) component and (B) component mentioned above.
- the hydraulic powder used in the hydraulic composition of the present invention is a powder having physical properties that are cured by a hydration reaction, and examples thereof include cement and gypsum.
- Preferred are ordinary portland cement, belite cement, medium heat cement, early strength cement, ultra-early strength cement, sulfuric acid resistant cement, masonry cement, etc., and blast furnace slag, fly ash, silica fume, stone powder (carbonic acid) Calcium powder) etc. may be added.
- the N-methyldiethanolamine according to the present invention is presumed to act on SO 3 and the aluminate phase (C 3 A and C 4 A) which are minerals in the hydraulic powder.
- the content of SO 3 in the hydraulic powder used in the hydraulic composition of the present invention is 0. From the viewpoint of improving the fluidity of the hydraulic composition and improving the hardening strength after 24 hours and after 7 days. 5 to 6.0% by weight is preferred.
- the SO 3 content in the hydraulic powder used in the hydraulic composition of the present invention is more preferably 1.0 to 4.5% by weight from the viewpoint of improving the fluidity of the hydraulic composition. It is more preferably 0.0 to 4.5% by weight, still more preferably 3.0 to 3.8% by weight.
- the content of SO 3 in the hydraulic powder used in the hydraulic composition of the present invention is 0.5 to 4.5 weight from the viewpoint of improving the curing strength after 24 hours of the hydraulic composition. % Is more preferable, 1.0 to 3.5% by weight is still more preferable, and 1.5 to 3.0% by weight is even more preferable.
- the content of SO 3 in the hydraulic powder used in the hydraulic composition of the present invention is 1.0 to 4.5% by weight from the viewpoint of improving the curing strength after 7 days of the hydraulic composition. Is more preferably 3.0 to 4.5% by weight, still more preferably 3.5 to 4.0% by weight.
- the ratio (weight ratio) of the SO 3 amount in the hydraulic powder to the total amount of C 3 A and C 4 AF in the hydraulic powder used in the hydraulic composition of the present invention is hydraulic. From the viewpoint of improving the fluidity of the composition and the hardening strength after 24 hours and after 7 days, the SO 3 amount / (C 3 A amount + C 4 AF amount) ⁇ 100 is preferably 3.5 to 46.
- the ratio (weight ratio) of the SO 3 amount in the hydraulic powder to the total amount of C 3 A and C 4 AF in the hydraulic powder used in the hydraulic composition of the present invention is the hydraulic composition. From the viewpoint of improving the fluidity of the resin, it is more preferably 10 to 35, further preferably 15 to 33, and still more preferably 20 to 30.
- the ratio (weight ratio) of the SO 3 amount in the hydraulic powder to the total amount of C 3 A and C 4 AF in the hydraulic powder used in the hydraulic composition of the present invention is hydraulic. From the viewpoint of improving the curing strength after 24 hours of the composition, SO 3 amount / (C 3 A amount + C 4 AF amount) ⁇ 100 is more preferably 3.5 to 35, further preferably 10 to 28. 10 to 20 is even more preferable. Further, the ratio (weight ratio) of the SO 3 amount in the hydraulic powder to the total amount of C 3 A and C 4 AF in the hydraulic powder used in the hydraulic composition of the present invention is hydraulic.
- SO 3 amount / (C 3 A amount + C 4 AF amount) ⁇ 100 is more preferably 10 to 35, and further preferably 22 to 33. .
- This ratio is the ratio of the SO 3 amount to the total amount of aluminate phase in the hydraulic powder.
- the hydraulic composition of the present invention contains aggregate.
- the aggregate include fine aggregates such as sand and coarse aggregates such as gravel.
- the hydraulic compositions finally obtained by adding sand, sand and gravel as aggregates to the hydraulic powder are generally called mortar and concrete, respectively.
- the content of aggregate (total of fine aggregate and coarse aggregate) is preferably 1600 to 2000 kg per 1 m 3 of the hydraulic composition from the viewpoint of use in concrete structures and concrete products. 1650 to 1950 kg is more preferable.
- the content of the hydraulic powder is preferably 250 to 800 kg per 1 m 3 of the hydraulic composition, and more preferably 280 to 700 kg.
- the water content is preferably 100 to 200 kg, more preferably 110 to 195 kg per 1 m 3 of the hydraulic composition.
- the fine aggregate when the aggregate consists only of fine aggregate, from the viewpoint of use as mortar, is preferably 100 to 300 parts by weight with respect to 100 parts by weight of the hydraulic powder. 150 to 300 parts by weight is more preferable.
- the total amount of the component (A) and the component (B) with respect to 100 parts by weight of the hydraulic powder is from the viewpoint of improving the fluidity of the hydraulic composition and improving the strength of the cured body.
- 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, more preferably 0.05 to 2 parts by weight, more preferably 0.10 to 0.50 parts by weight, and 0.15 to 0.30 parts by weight is even more preferable.
- the amount of component (A) is 0.0005 to 5 with respect to 100 parts by weight of the hydraulic powder from the viewpoint of improving the fluidity of the hydraulic composition and improving the strength of the cured product after 24 hours and 7 days.
- Parts by weight preferably 0.005 to 2.5 parts by weight, more preferably 0.01 to 1.0 parts by weight, still more preferably 0.01 to 0.3 parts by weight, and 0.03 to 0 parts by weight. More preferable than 1 part by weight.
- the amount of component (A) is preferably 0.02 to 0.3 parts by weight, more preferably 0.04 to 0.3 parts by weight, from the viewpoint of improving the strength of the cured product after 24 hours, and 0.08. Is more preferably 0.25 parts by weight, and still more preferably 0.15 to 0.25 parts by weight.
- the amount of the component (B) is preferably 0.0005 parts by weight or more, more preferably 0.005 parts by weight or more with respect to 100 parts by weight of the hydraulic powder, from the viewpoint of improving the fluidity of the hydraulic composition.
- the amount of the component (B) is preferably 5 parts by weight or less, more preferably 2.5 parts by weight or less, with respect to 100 parts by weight of the hydraulic powder from the viewpoint of suppressing the delay in curing of the hydraulic composition. Therefore, the amount of the component (B) is preferably 0.0005 to 5 parts by weight with respect to 100 parts by weight of the hydraulic powder, and more preferably 0% from the viewpoint of improving the fluidity of the hydraulic composition and suppressing curing delay. 0.005 to 2.5 parts by weight is more preferred, 0.05 to 1.0 parts by weight is more preferred, 0.1 to 0.5 parts by weight is still more preferred, and 0.15 to 0.3 parts by weight is more preferred. More preferred is 0.15 to 0.22 parts by weight.
- the weight ratio of the component (A) to the component (B) is the strength of the cured product after 24 hours and 7 days after the hydraulic composition. 1/20 to 1/1 is preferable, 1/15 to 1/1 is more preferable, 1/10 to 1/1 is still more preferable, and 1/10 to 1/1 is more preferable. 5 to 1/1 is still more preferable, and 1/3 to 1/1 is still more preferable.
- the hydraulic composition of the present invention can be produced, for example, by preparing a composition containing the component (A), the component (B) and water in advance and adding the composition to the hydraulic powder and aggregate.
- the hydraulic composition of the present invention can be used as a material for concrete structures and concrete products.
- the hydraulic composition of the present invention improves the compressive strength after 24 hours and after 7 days from contact with water.
- the hydraulic composition of the present invention has a hydraulic powder with low initial age strength after contact with water. Even if the body (blast furnace slag, fly ash, limestone, etc.) is blended, it is equal to or higher than the hydraulic composition not containing the component (A) and / or the component (B), 24 hours after contact with water And the compression strength after 7 days can be obtained.
- the hydraulic composition of the present invention is prepared from ready-mixed concrete, concrete products, self-leveling, refractory, plaster, gypsum slurry, lightweight or heavy concrete, AE, repair, prepacked, for trayy, It is useful in any field of various concrete such as grout, ground improvement, and cold. Furthermore, since the hydraulic composition of the present invention is excellent in fluidity immediately after preparation and develops strength in about 24 hours, it is manufactured by filling the mold and using the same mold many times. It is suitable for concrete secondary products that require a rotation rate. As a hardened body of hydraulic composition using formwork, which is a concrete secondary product, for civil engineering products, various block products for revetment, box culvert products, segment products used for tunnel construction, pier girder products, etc. Examples of building products include building wall products, pillars, beams, and building member products used for floor boards.
- the fluidity is improved as compared with the case where only the copolymer is used. Therefore, even if the amount of the copolymer used is reduced, a certain fluidity can be obtained, so that the setting delay due to the copolymer can be reduced. Moreover, since the fluidity
- liquidity of a hydraulic composition will improve if the addition amount of a copolymer is equivalent, the filling property to a formwork will improve, for example. Furthermore, the compressive strength at the time of hardening 24 hours and 7 days after the wet contact of the hydraulic composition is improved.
- the hydraulic composition of the present invention when the hydraulic composition is cured, energy such as steam heating is not required to accelerate the curing, and a cured body of the hydraulic composition can be produced at an early stage. It becomes possible. This is also excellent in terms of reducing the load on the environment.
- the curing time is 4 to 30 hours, and further 6 to 24 hours even under the curing conditions when the curing temperature is 0 to 40 ° C., further 10 to 40 ° C.
- a cured body having sufficient strength for demolding can be obtained.
- a dispersant for a hydraulic composition comprising N-methyldiethanolamine, and a copolymer containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2).
- R 1 represents a hydrogen atom or a methyl group
- M 1 represents a hydrogen atom or a counter ion forming a salt
- R 2 is a hydrogen atom or a methyl group
- AO is an alkyleneoxy group having 2 to 4 carbon atoms
- l is a number of 0 to 2
- m is a number of 0 or 1
- n is an average added mole number of AO.
- the number is 2 to 300
- R 3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- ⁇ 2> The dispersant for hydraulic composition according to ⁇ 1>, containing 0.1 to 40% by weight of N-methyldiethanolamine and 0.3 to 60% by weight of the copolymer.
- n in the general formula (2) is preferably 2 to 250, more preferably 2 to 200, and still more preferably 2 to 150.
- ⁇ 5> The dispersant for hydraulic composition according to any one of ⁇ 1> to ⁇ 4>, wherein m in the general formula (2) is 1 and l is 0.
- the proportion of the structural unit represented by the general formula (1) in the total of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) is preferably 40 to 98 mol%, More preferably 50 to 97 mol%, more preferably 60 to 97 mol%, more preferably 70 to 90 mol%, still more preferably 70 to 85 mol%, and still more preferably 72 to 80 mol%, ⁇ 1> to ⁇ 5>
- the dispersant for hydraulic compositions according to any one of the above.
- the total proportion of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in all the structural units contained in the copolymer is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, more preferably 70 to 100 mol%, more preferably 80 to 100 mol%, more preferably substantially 100 mol%, for the hydraulic composition according to any one of the above items ⁇ 1> to ⁇ 6> Dispersant.
- ⁇ 8> Any one of the above ⁇ 1> to ⁇ 7>, wherein the copolymer has a weight average molecular weight of preferably 1,000 to 200,000, more preferably 10,000 to 100,000, still more preferably 20,000 to 80,000, and still more preferably 35,000 to 55,000. Dispersant for hydraulic composition.
- the weight ratio of the N-methyldiethanolamine (hereinafter also referred to as component (A)) and the copolymer (hereinafter also referred to as component (B)) is more preferably 1. / 15 to 1/1, more preferably 1/10 to 1/1, still more preferably 1/5 to 1/1, and still more preferably 1/3 to 1/1.
- component (A) / component (B) is more preferably 1. / 15 to 1/1, more preferably 1/10 to 1/1, still more preferably 1/5 to 1/1, and still more preferably 1/3 to 1/1.
- the content of N-methyldiethanolamine in the dispersant is preferably 0.1 to 40% by weight, more preferably 1 to 30% by weight, and still more preferably 3 to 10% by weight. Any of the dispersants for hydraulic compositions.
- the content of the copolymer in the dispersant is preferably from 0.3 to 60% by weight, more preferably from 5 to 55% by weight, still more preferably from 10 to 50% by weight, according to the above ⁇ 1> to ⁇ 10> Any of the dispersants for hydraulic compositions.
- the total amount of N-methyldiethanolamine and the copolymer in the dispersant is preferably 0.4 to 100% by weight, more preferably 6 to 85% by weight, and still more preferably 12 to 60% by weight.
- N-methyldiethanolamine a copolymer containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2), a hydraulic powder, an aggregate and water, A hydraulic composition having a weight ratio of water to hydraulic powder (water / hydraulic powder) of 0.20 to 0.50.
- R 1 represents a hydrogen atom or a methyl group
- M 1 represents a hydrogen atom or a counter ion forming a salt
- R 2 represents a hydrogen atom or a methyl group
- AO represents an alkyleneoxy group having 2 to 4 carbon atoms
- l represents a number of 0 to 2
- m represents a number of 0 or 1
- n represents AO.
- the average number of moles added represents a number of 2 to 300
- R 3 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- the content of SO 3 in the hydraulic powder used in the hydraulic composition is preferably 0.5 to 6.0% by weight, more preferably 1.0 to 4.5% by weight, and still more preferably 2.
- the content of SO 3 in the hydraulic powder used in the hydraulic composition is preferably 0.5 to 4.5% by weight, more preferably 1.0 to 3.5% by weight, still more preferably 1
- the content of SO 3 in the hydraulic powder used in the hydraulic composition is preferably 1.0 to 4.5% by weight, more preferably 3.0 to 4.5% by weight, and still more preferably 1.
- the total amount of N-methyldiethanolamine and copolymer with respect to 100 parts by weight of the hydraulic powder is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight, still more preferably 0.00.
- N-methyldiethanolamine is preferably 0.0005 to 5 parts by weight, more preferably 0.005 to 2.5 parts by weight, relative to 100 parts by weight of the hydraulic powder.
- the hydraulic composition in any one of>.
- the amount of the copolymer is preferably 0.0005 to 5 parts by weight, more preferably 0.005 to 2.5 parts by weight, still more preferably 0.05 to 1 part by weight based on 100 parts by weight of the hydraulic powder.
- n in the general formula (2) is preferably 2 to 250, more preferably 2 to 200, and still more preferably 2 to 150.
- the proportion of the structural unit represented by the general formula (1) in the total of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) is preferably 40 to 98 mol%, More preferably 50 to 97 mol%, still more preferably 60 to 97 mol%, still more preferably 70 to 90 mol%, still more preferably 70 to 85 mol%, still more preferably 72 to 80 mol%, ⁇ 13
- the total proportion of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in all the structural units contained in the copolymer is preferably 30 to 100 mol%, more preferably The hydraulic composition according to any one of ⁇ 13> to ⁇ 23>, wherein the hydraulic composition is 50 to 100 mol%, more preferably 70 to 100 mol%, further preferably 80 to 100 mol%, and more preferably substantially 100 mol%.
- the weight ratio ((A) component / (B) component) of the N-methyldiethanolamine (hereinafter also referred to as component (A)) and the copolymer (hereinafter also referred to as component (B)) is preferably 1 / 20 to 1/1, more preferably 1/15 to 1/1, still more preferably 1/10 to 1/1, still more preferably 1/5 to 1/1, still more preferably 1/3 to 1 /
- the hydraulic composition contains hydraulic powder, aggregate, and water, and the weight ratio of water to hydraulic powder (water / hydraulic powder) is 0.20 to 0.50.
- the dispersant is an aqueous solution in which alkanolamine and water as necessary are mixed in the copolymer aqueous solution so as to have a content as shown in Table 1, and in the addition pattern b, the aqueous copolymer solution is used. Used as is. However, in comparative product 4, alkanolamine was added to kneaded water as it was.
- the composition of the dispersant of addition pattern a is shown in Table 1.
- preparation of mortar is carried out by first adding pattern b without using alkanolamine, and confirming the amount of copolymer (in terms of pure content) that achieves a target mortar flow of 215 ⁇ 30 mm (except for Comparative Example 4).
- the dispersant of the present invention or the comparative product shown in Table 1 was added so that the amount of the copolymer (in terms of pure content) was the same as that of the addition pattern b.
- the amount of each component added (in terms of pure content) is shown in Table 3.
- the amount of the dispersant in the kneading water is very small, the amount of the kneading water including the amount of the dispersant is defined as W in Table 2.
- the quantitative determination of SO 3 , C 3 A, C 4 AF, etc. in the cement was performed by the following method (the same applies to other examples).
- RINT-2500 manufactured by Rigaku Co., Ltd.
- the measurement conditions were the target CuK ⁇ , the tube current 40 mA, the tube voltage 200 kV, the scanning range 5 to 70 °, 2 ⁇ , the scanning conditions were step scanning, step width The setting was 0.02 ° and the counting time was 2 seconds.
- the compressive strength was measured for each of the addition pattern a or the addition pattern b for one example or comparative example, and a numerical value of [compression strength of addition pattern a] / [compression strength of addition pattern b] ⁇ 100 (in the table) , And expressed as a / b ratio).
- the numerical value of a / b ratio is 100, indicating that there is no change in the compressive strength. The larger the value is, the greater the compressive strength of the additive pattern a is, and the greater the compressive strength is improved by the addition of the dispersant for hydraulic composition. It shows that.
- Example 1 to 4 the addition pattern a using a (meth) acrylic acid-based polycarboxylic acid copolymer and N-methyldiethanolamine is obtained by using only a (meth) acrylic acid-based polycarboxylic acid copolymer. It turns out that fluidity
- Examples 5 to 11 Furthermore, on the basis of Example 5 (corresponding to Example 4 in Table 3), when the total amount of dispersant was changed (Examples 6 and 7), when the amount of alkanolamine added was changed (Examples) For 8 to 11), the mortar fluidity and mortar strength were measured in the same manner as in Example 1. The results are shown in Table 4. The mortar was prepared in the same manner as in Example 1.
- Example 12 to 17 After adding dihydrate gypsum and hemihydrate gypsum to cement clinker containing 4 wt% C 3 A and 9 wt% C 4 AF as the aluminate phase, it is pulverized to a brane value of 3300 ⁇ 100 cm 2 / g.
- a cement having a composition of SO 3 amount and [SO 3 amount / (C 3 A amount + C 4 AF amount)] ⁇ 100 shown in Table 6 was prepared. Then, using these cements, mortar was prepared in the same manner as in Example 1 under the blending conditions shown in Table 5.
- the weight ratio (W / C) of water to hydraulic powder is 0.40 (40% by weight).
- the fine aggregate is 175 parts by weight with respect to 100 parts by weight of the hydraulic powder.
- the mortar fluidity and the mortar strength were measured in the same manner as in Example 1 when the alkanolamine and the copolymer were used in combination and when only the copolymer was used. The results are shown in Table 6.
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Abstract
Description
水硬性組成物用の分散剤は、セメント粒子を分散させることにより、所要のスランプを得るのに必要な単位水量を減少させ、水硬性組成物の作業性等を向上させるために用いる化学混和剤である。分散剤には、従来、ナフタレンスルホン酸ホルムアルデヒド縮合物等のナフタレン系やカルボン酸とアルキレングリコール鎖を有する単量体との共重合体等のポリカルボン酸系、メラミンスルホン酸ホルムアルデヒド縮合物等のメラミン系等が知られている。
本発明は、N-メチルジエタノールアミンと、下記一般式(1)で表される構成単位と下記一般式(2)で表される構成単位とを含有する共重合体とを含有する水硬性組成物用分散剤に関する。
さらに、本発明は、N-メチルジエタノールアミンと、上記一般式(1)で表される構成単位と上記一般式(2)で表される構成単位とを含む共重合体とを含有する水硬性組成物用分散剤の、水硬性組成物の流動性を向上するための使用に関する。
背景技術においては、(メタ)アクリル酸系のポリカルボン酸系共重合体を使用する水硬性組成物に、早期強度向上の為のアミン化合物として特開2007-31166の実施例及び特表2000-511151の配合例で挙げられているジエタノールアミン、トリエタノールアミン及びトリイソプロパノールアミンを併用した場合には、水硬性組成物の流動性がポリカルボン酸系共重合体単独で用いた時よりも低下する傾向があることがわかった。これらのアミン化合物を用いてポリカルボン酸系共重合体単独で用いた時と同等の流動性を得るには、例えば、ポリカルボン酸系共重合体の使用量を増やす方法が挙げられる。しかし、前記共重合体の量を増やすと水硬性組成物の凝結遅延が促進される傾向があり、早期強度向上の為にはむしろ前記共重合体の量を低減することが望まれる。
本発明に係るアミンは、N-メチルジエタノールアミンである。前記メチルジエタノールアミンを(メタ)アクリル酸系のポリカルボン酸系共重合体に併用することで、水硬性組成物の24時間後及び7日後の硬化体の強度を向上しつつ水硬性組成物の流動性(初期流動性ともいう)をさらに向上することができる。
本発明に係る共重合体は、上記一般式(1)で表される構成単位〔以下、構成単位1という〕と上記一般式(2)で表される構成単位〔以下、構成単位2という〕を含む。すなわち、共重合体の一例としては、構成単位1の由来となるアクリル酸又はメタクリル酸と、構成単位2の由来となるポリアルキレングリコールとアクリル酸もしくはメタクリル酸のエステル又はアルキレンオキシ基とアルケニル基を有するエーテル〔以下、構成単位2の由来となる炭単量体を単量体(2)という〕とを構成単量体とするものが挙げられる。アクリル酸又メタクリル酸は塩を形成していてもよい。
る可能性があるので、R3は炭素数1~4のアルキル基が好ましく、さらに水溶性の観点からメチル基がより好ましい。
[GPC条件]
装置:高速GPC装置 HLC-8320GPC(東ソー)
カラム:G4000PWXL+G2500PWXL(東ソー)
溶離液:0.2Mリン酸バッファー/CH3CN=9/1
流量:1.0mL/min
カラム温度:40℃
検出:示差屈折検出器(RI)
サンプルサイズ:0.5mg/mL
標準物質:ポリエチレングリコール換算
本発明の水硬性組成物用分散剤は、N-メチルジエタノールアミンと前記共重合体とを含有する。前記N-メチルジエタノールアミン〔以下、(A)成分ともいう〕と前記共重合体〔以下、(B)成分ともいう〕の重量比((A)成分/(B)成分)は、1/20~1/1が好ましく、1/15~1/1がより好ましく、1/10~1/1が更に好ましく、1/5~1/1がより更に好ましく、1/3~1/1がより更に好ましい。この範囲の重量比は、水硬性組成物の24時間後の硬化体の強度の向上と、水硬性組成物の流動性の向上の観点から好ましい。
本発明の水硬性組成物は、N-メチルジエタノールアミン〔(A)成分〕と、共重合体〔(B)成分〕と、水硬性粉体と、骨材と、水とを含有し、水と水硬性粉体の重量比(水/水硬性粉体の重量比、通常W/Pと略記されるが、粉体がセメントの場合、W/Cと略記されることがある。)が0.20~0.50である。水と水硬性粉体の重量比は、水硬性組成物の初期流動性の向上の観点から、0.25以上が好ましく、0.30以上がより好ましい。また、水と水硬性粉体の重量比は硬化体の強度の観点から、0.48以下が好ましく、0.46以下がより好ましい。水と水硬性粉体の重量比は、水硬性組成物の初期流動性の向上と硬化体の強度の観点から、0.25~0.48がより好ましく、0.30~0.46が更に好ましい。N-メチルジエタノールアミン及び共重合体は、前述したものと同様のものを用いることができる。また、本発明の水硬性組成物は、前記の水硬性組成物用分散剤に水硬性粉体と骨材とを必要に応じて水を加えて調製することができる。(A)成分、(B)成分、水硬性粉体、骨材及び水の量は、水硬性組成物の調製時の配合量から求めることができる。
<1>
N-メチルジエタノールアミンと、下記一般式(1)で表される構成単位と下記一般式(2)で表される構成単位とを含む共重合体とを含有する水硬性組成物用分散剤。
N-メチルジエタノールアミンを0.1~40重量%、前記共重合体を0.3~60重量%含有する前記<1>の水硬性組成物用分散剤。
N-メチルジエタノールアミンと前記共重合体の重量比(N-メチルジエタノールアミン/共重合体)が1/20~1/1である前記<1>又は前記<2>の水硬性組成物用分散剤。
一般式(2)のnが、好ましくは2~250、より好ましくは2~200、更に好ましくは2~150である前記<1>~<3>のいずれかの水硬性組成物用分散剤。
一般式(2)のmが1であり、lが0である前記<1>~<4>のいずれかの水硬性組成物用分散剤。
一般式(1)で表される構成単位及び一般式(2)で表される構成単位の合計中の一般式(1)で表される構成単位の割合が、好ましくは40~98モル%、より好ましくは
50~97モル%、更に好ましくは60~97モル%、更に好ましくは70~90モル%、更に好ましくは70~85モル%、より更に好ましくは72~80モル%である前記<1>~<5>のいずれかの水硬性組成物用分散剤。
共重合体が含む全構成単位中、一般式(1)で表される構成単位と一般式(2)で表される構成単位の合計の割合が、好ましくは30~100モル%、より好ましくは50~100モル%、更に好ましくは70~100モル%、更に好ましくは80~100モル%、更に好ましくは実質100モル%である前記<1>~<6>のいずれかの水硬性組成物用分散剤。
共重合体の重量平均分子量が、好ましくは1000~200000、より好ましくは10000~100000、更に好ましくは20000~80000、より更に好ましくは35000~55000である前記<1>~<7>のいずれかの水硬性組成物用分散剤。
前記N-メチルジエタノールアミン〔以下、(A)成分ともいう〕と前記共重合体〔以下、(B)成分ともいう〕の重量比((A)成分/(B)成分)が、より好ましくは1/15~1/1、更に好ましくは1/10~1/1、より更に好ましくは1/5~1/1、より更に好ましくは1/3~1/1である前記<1>~<8>のいずれかの水硬性組成物用分散剤。
分散剤中のN-メチルジエタノールアミンの含有量が、好ましくは0.1~40重量%、より好ましくは1~30重量%、更に好ましくは3~10重量%である前記<1>~<9>のいずれかの水硬性組成物用分散剤。
分散剤中の共重合体の含有量が、好ましくは0.3~60重量%、より好ましくは5~55重量%、更に好ましくは10~50重量%である前記<1>~<10>のいずれかの水硬性組成物用分散剤。
分散剤中のN-メチルジエタノールアミンと共重合体の合計量が、好ましくは0.4~100重量%、より好ましくは6~85重量%、更に好ましくは12~60重量%である前記<1>~<11>のいずれかの水硬性組成物用分散剤。
N-メチルジエタノールアミン、下記一般式(1)で表される構成単位と下記一般式(2)で表される構成単位とを含む共重合体、水硬性粉体、骨材及び水を含有し、水と水硬性粉体の重量比(水/水硬性粉体)が0.20~0.50である水硬性組成物。
水と水硬性粉体の重量比が、より好ましくは0.25~0.48、更に好ましくは0.30~0.46である前記<13>の水硬性組成物。
水硬性組成物に用いられる水硬性粉体中のSO3の含有量が、好ましくは0.5~6.0重量%、より好ましくは1.0~4.5重量%、更に好ましくは2.0~4.5重量%である前記<13>又は<14>の水硬性組成物。
水硬性組成物に用いられる水硬性粉体中のSO3の含有量が、好ましくは0.5~4.5重量%、より好ましくは1.0~3.5重量%が、更に好ましくは1.5~3.0重量%である前記<13>又は<14>の水硬性組成物。
水硬性組成物に用いられる水硬性粉体中のSO3の含有量が、好ましくは1.0~4.5重量%、より好ましくは3.0~4.5重量%、更に好ましくは1.5~3.0重量%である前記<13>又は<14>の水硬性組成物。
水硬性粉体100重量部に対して、N-メチルジエタノールアミンと共重合体の合計量が、好ましくは0.001~10重量部、より好ましくは0.01~5重量部、更に好ましくは0.05~2重量部である前記<13>~<17>のいずれかの水硬性組成物。
N-メチルジエタノールアミンの量が、水硬性粉体100重量部に対して、好ましくは0.0005~5重量部、更に好ましくは0.005~2.5重量部である前記<13>~<18>のいずれかの水硬性組成物。
共重合体の量が、水硬性粉体100重量部に対して、好ましくは0.0005~5重量部、更に好ましくは0.005~2.5量部、更に好ましくは0.05~1.0量部、更に好ましくは0.1~0.5量部である前記<13>~<19>のいずれかの水硬性組成物。
一般式(2)のnが、好ましくは2~250、より好ましくは2~200、更に好ましくは2~150である前記<13>~<20>のいずれかの水硬性組成物。
一般式(2)のmが1であり、lが0である前記<13>~<21>のいずれかの水硬性組成物。
一般式(1)で表される構成単位及び一般式(2)で表される構成単位の合計中の一般式(1)で表される構成単位の割合は、好ましくは40~98モル%、より好ましくは50~97モル%、更に好ましくは60~97モル%、更に好ましくは70~90モル%、更に好ましくは70~85モル%、より更に好ましくは72~80モル%である前記<13>~<22>のいずれかの水硬性組成物。
共重合体が含む全構成単位中、一般式(1)で表される構成単位と一般式(2)で表される構成単位の合計の割合が、好ましくは30~100モル%、より好ましくは50~100モル%、更に好ましくは70~100モル%、更に好ましくは80~100モル%、更に好ましくは実質100モル%である前記<13>~<23>のいずれかの水硬性組成物。
共重合体の重量平均分子量が、好ましくは1000~200000、より好ましくは10000~100000、更に好ましくは20000~80000が、より更に好ましくは35000~55000である前記<13>~<24>のいずれかの水硬性組成物。
前記N-メチルジエタノールアミン〔以下、(A)成分ともいう〕と前記共重合体〔以下、(B)成分ともいう〕の重量比((A)成分/(B)成分)が、好ましくは1/20~1/1、より好ましくは1/15~1/1、更に好ましくは1/10~1/1、より更に好ましくは1/5~1/1、より更に好ましくは1/3~1/1である前記<13>~<25>のいずれかの水硬性組成物。
<1>~<12>の水硬性組成物用分散剤の、水硬性組成物の流動性向上のための使用。
水硬性組成物が、水硬性粉体、骨材及び水を含有し、水と水硬性粉体の重量比(水/水硬性粉体)が0.20~0.50である、水硬性組成物用分散剤の前記<27>の水硬性組成物の流動性向上のための使用。
実施例
<製造例1>
攪拌機付きガラス製反応容器(四つ口フラスコ)に水114gを仕込み、撹拌しながら窒素置換をし、窒素雰囲気中で80℃まで昇温した。60重量%のω-メトキシポリエチレングリコールモノメタクリレート(エチレンオキシドの平均付加モル数120:エステル純度100%)水溶液300g、メタクリル酸(試薬:和光純薬工業株式会社製)11.5g、及び3-メルカプトプロピオン酸1.2gを混合溶解した水溶液と、過硫酸アンモニウム1.9gを水45gに溶解した水溶液の2者を、それぞれ1.5時間かけて上記反応容器中に滴下した。その後、80℃で1時間熟成し、更に過硫酸アンモニウム0.8gを水15gに溶解した水溶液を30分かけて滴下し、引き続き80℃で1.5時間熟成した。熟成終了後に40℃以下に冷却した後、48%水酸化ナトリウム水溶液9.6gで中和し、重量平均分子量54000の共重合体を得た(中和度0.7)。その後、水を用いて固形分20重量%に調整した。単量体1/[単量体1+単量体2]は80モル%である。
攪拌機付きガラス製反応容器(四つ口フラスコ)に、水333.7g、および3-メチル-3-ブテン-1-オールにエチレンオキサイドを平均50モル付加した不飽和ポリアルキレングリコールエーテルを463.9g仕込み、攪拌しながら窒素置換をし、窒素雰囲気下60℃まで昇温した。そこに30%過酸化水素水溶液2.43gを滴下した。滴下後、アクリル酸62.7gを水37.3gに溶解した水溶液と、L-アスコルビン酸0.94g、3-メルカプトプロピオン酸2.44g、水96.6gを混合溶解した水溶液の2者を、それぞれ3.0時間及び3.5時間かけて上記反応容器中に滴下した。その後、60℃で1時間熟成した。熟成終了後に40℃以下に冷却した後、48%水酸化ナトリウム水溶液で中和し、重量平均分子量62000の共重合体を得た(中和度0.7)。その後、水を用いて固形分45重量%に調整した。単量体1/[単量体1+単量体2]は81モル%である。
攪拌機付きガラス製反応容器(四つ口フラスコ)に水333gを仕込み、撹拌しながら窒素置換をし、窒素雰囲気中で80℃まで昇温した。ω-メトキシポリエチレングリコールモノメタクリレート(エチレンオキシドの平均付加モル数23:NKエステルM230G、新中村化学工業株式会社製)300g、メタクリル酸(試薬:和光純薬工業株式会社製)69.7g、及び3-メルカプトプロピオン酸6.3gを水200gに混合溶解した水溶液と、過硫酸アンモニウム12.3gを水45gに溶解した水溶液の2者を、それぞれ1.5時間かけて上記反応容器中に滴下した。その後、80℃で1時間熟成し、更に過硫酸アンモニウム4.9gを水15gに溶解した水溶液を30分かけて滴下し、引き続き80℃で1.5時間熟成した。熟成終了後に40℃以下に冷却した後、48%水酸化ナトリウム水溶液50.2gで中和し、重量平均分子量43000の共重合体を得た(中和度0.7)。その後、水を用いて固形分20重量%に調整した。単量体1/[単量体1+単量体2]は75モル%である。
攪拌機付きガラス製反応容器(四つ口フラスコ)に水395gを仕込み、撹拌しながら窒素置換をし、窒素雰囲気中で80℃まで昇温した。ω-メトキシポリエチレングリコールモノメタクリレート(エチレンオキシドの平均付加モル数23:NKエステルM230G、新中村化学工業株式会社製)261g、ホスマーM〔2-ヒドロキシエチルメタクリレートモノリン酸エステルと2-ヒドロキシエチルメタクリレートジリン酸エステルとの混合物、ユニケミカル株式会社製)〕67.3g、及びメルカプトプロピオン酸4.3gを水141gに混合溶解した水溶液と、過硫酸アンモニウム8.0gを水45gに溶解した水溶液の2者を、それぞれ1.5時間かけて上記反応容器中に滴下した。その後、80℃で1時間熟成し、更に過硫酸アンモニウム1.8gを水10gに溶解した水溶液を30分かけて滴下し、引き続き80℃で1.5時間熟成した。熟成終了後に40℃以下に冷却した後、30%水酸化ナトリウム水溶液66gで中和し、分子量37000の共重合体を得た。その後、水を用いて固形分20重量%に調整した。
(1)モルタルの調製
表2に示す配合条件で、モルタルミキサー(株式会社ダルトン製 万能混合撹拌機 型式:5DM-03-γ)を用いて、セメント(C)、細骨材(S)を投入し空練りを10秒行い、分散剤を含む練り水(W)を加えた。この際、空気連行量が2%以下になるよう消泡剤を添加した。そして、モルタルミキサーの低速回転(63rpm)にて60秒間、更に高速回転(128rpm)にて120秒間本混練りしてモルタルを調製した。
また、表中の記号は以下のものである。
・M-DEA:N-メチルジエタノールアミン(日本乳化剤株式会社製、アミノアルコールMDA)
・TiPA:トリイソプロパノールアミン(和光純薬工業株式会社製、試薬)
・TEA:トリエタノールアミン(和光純薬工業株式会社製、試薬)
・DEA:ジエタノールアミン(和光純薬工業株式会社製、試薬)
・リグニンスルホン酸系:リグニンスルホン酸系分散剤(Borregaard Industries Ltd.、Ultrazine NAS、有効分濃度20重量%の水溶液)
・ナフタレン系:ナフタレン系分散剤(花王株式会社製、マイテイ150、有効分濃度40重量%の水溶液)
・マレイン酸系:マレイン酸系のポリカルボン酸系分散剤(日油株式会社製、マリアリムAKM-60F、有効分濃度60重量%の水溶液)
・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、重量比)、密度3.16g/cm3、SO3量2.67重量%、〔SO3/(C3A+C4AF)〕×100=15.8
・細骨材(S):城陽産、山砂、FM=2.67、密度2.56g/cm3
水と水硬性粉体の重量比(W/C)は0.40(40重量%)である。細骨材は水硬性粉体100重量部に対して175重量部である。
そして、試料の水硬性粉体2.7gに0.3gの標準物質『α-コランダム(Al2O3)』を添加し、標準物質のピーク面積を基準として、Rietveld解析ソフトにて定量した。Rietveld解析ソフトは(株)リガク製のPDXL Ver.1.8を使用した。これにより、表2で用いたセメント中の含有量は、C3Sが61.9重量%、C2Sが15.8重量%、C3Aが8.5重量%、C4AFが8.4重量%、SO3量2.67重量%であった。
モルタルについて、以下に示す試験法にしたがって、モルタルフロー及び硬化強度をそれぞれ評価した。評価結果を表3に示した。
モルタルフローはJIS R5201に従って測定を行った。なお、JIS R5201記載の落下運動は行っていない。モルタルフローは、1つの実施例又は比較例について、添加パターンa又は添加パターンbのそれぞれについて測定し、〔添加パターンaのモルタルフロー値〕/〔添加パターンbのモルタルフロー値〕×100の数値(表中、a/b比と表記する)で流動性を評価した。a/b比の数値が100でモルタルフローに変化がないことを示し、100より大きいほど添加パターンaのモルタルフローが大きくなり、水硬性組成物用分散剤の添加による流動性の向上効果が大きいことを示す。
JIS A 1132に基づき、円柱型プラモールド(底面の直径:5cm、高さ10cm)の型枠5個に、それぞれ二層詰め方式によりモルタルを充填し、20℃の室内にて気中(20℃)養生を行い硬化させた。モルタル調製から24時間後に硬化した供試体を型枠から脱型し供試体を得た。これらの供試体の内、3個の24時間後の圧縮強度を測定した。さらに残りの2個の供試体は7日まで20℃で水中養生を行い、7日後の圧縮強度を測定した。供試体の圧縮強度はJIS A1108に基づいて測定し、供試体3個(24時間後)又は2個(7日後)の平均値を求めた。圧縮強度は、1つの実施例又は比較例について、添加パターンa又は添加パターンbのそれぞれについて測定し、〔添加パターンaの圧縮強度〕/〔添加パターンbの圧縮強度〕×100の数値(表中、a/b比と表記する)で圧縮強度を評価した。a/b比の数値が100で圧縮強度に変化がないことを示し、100より大きいほど添加パターンaの圧縮強度が大きくなり、水硬性組成物用分散剤の添加による圧縮強度の向上効果が大きいことを示す。
さらに、実施例5(表3中の実施例4に相当)を基準として、分散剤全体の添加量を変えた場合(実施例6及び7)、アルカノールアミンの添加量を変えた場合(実施例8~11)について、モルタル流動性とモルタル強度を実施例1と同様に測定した。結果を表4に示した。なお、モルタルの調製は実施例1と同様に行った。セメント(C)は表2と同じもの(構成、出所)を採用したが、製品ロットが表2とは異なるものであり、本実施例で用いたセメント中の含有量は、実施例1等と同様の定量法により、C3Sが60.6重量%、C2Sが17.2重量%、C3Aが7.9重量%、C4AFが8.8重量%、SO3量2.71重量%、〔SO3/(C3A+C4AF)〕×100は16.2であった。
アルミネート相としてC3Aを4重量%、C4AFを9重量%含有するセメントクリンカーに、二水石膏と半水石膏を添加後、ブレーン値が3300±100cm2/gになるよう粉砕し、表6に示したSO3量及び〔SO3量/(C3A量+C4AF量)〕×100の組成のセメントを調製した。そして、これらのセメントを用いて、表5に示す配合条件で、実施例1と同様にモルタルを調製した。水と水硬性粉体の重量比(W/C)は0.40(40重量%)である。細骨材は水硬性粉体100重量部に対して175重量部である。アルカノールアミン及び共重合体を併用した場合と、共重合体のみを用いた場合について、モルタル流動性とモルタル強度を実施例1と同様に測定した。結果を表6に示した。
Claims (17)
- 分散剤中のN-メチルジエタノールアミンの含有量が、0.1~40重量%である請求項1~3のいずれかに記載の水硬性組成物用分散剤。
- 分散剤中の共重合体の含有量が、0.3~60重量%である請求項1~4のいずれかの水硬性組成物用分散剤。
- N-メチルジエタノールアミンを0.1~40重量%、前記共重合体を0.3~60重量%含有する請求項1記載の水硬性組成物用分散剤。
- N-メチルジエタノールアミンと前記共重合体の重量比(N-メチルジエタノールアミン/共重合体)が1/20~1/1である請求項1~4のいずれかに記載の水硬性組成物用分散剤。
- 分散剤中のN-メチルジエタノールアミンと共重合体の合計量が、0.4~100重量%である請求項1~5のいずれかに記載の水硬性組成物用分散剤。
- N-メチルジエタノールアミンの含有量が水硬性粉体100重量部に対して0.0005~5重量部である、請求項7記載の水硬性組成物。
- N-メチルジエタノールアミンと前記共重合体の含有量が水硬性粉体100重量部に対して、0.001~10重量部である請求項7又は8記載の水硬性組成物。
- N-メチルジエタノールアミンと前記共重合体の重量比(N-メチルジエタノールアミン/共重合体)が1/20~1/1である請求項7~9のいずれかに記載の水硬性組成物。
- N-メチルジエタノールアミンと前記共重合体の重量比(N-メチルジエタノールアミン/共重合体)が1/10~1/1である請求項7~10のいずれかに記載の水硬性組成物。
- 分散剤中のN-メチルジエタノールアミンの含有量が、0.1~40重量%である水硬性組成物用分散剤の請求項12記載の使用。
- 分散剤中の共重合体の含有量が、0.3~60重量%である水硬性組成物用分散剤の請求項12記載の使用。
- N-メチルジエタノールアミンを0.1~40重量%、前記共重合体を0.3~60重量%含有する水硬性組成物用分散剤の請求項12記載の使用。
- N-メチルジエタノールアミンと前記共重合体の重量比(N-メチルジエタノールアミン/共重合体)が1/20~1/1である水硬性組成物用分散剤の請求項12~15のいずれかに記載の使用。
- 分散剤中のN-メチルジエタノールアミンと共重合体の合計量が、0.4~100重量%である請求項12~16のいずれかに記載の使用。
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- 2012-03-14 US US14/005,190 patent/US9353004B2/en active Active
- 2012-03-14 MX MX2013009775A patent/MX2013009775A/es active IP Right Grant
- 2012-03-14 EP EP12757577.7A patent/EP2687497B1/en active Active
- 2012-03-14 RU RU2013145947/03A patent/RU2586121C2/ru active
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US20160107935A1 (en) * | 2013-06-19 | 2016-04-21 | Kao Corporation | Liquid dispersant composition for gypsum |
RU2656053C2 (ru) * | 2013-06-19 | 2018-05-30 | Йосино Джипсум Ко., Лтд. | Жидкая диспергирующая композиция для гипса |
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JPWO2017033590A1 (ja) * | 2015-08-25 | 2018-04-26 | 株式会社日本触媒 | セメント用添加剤、セメント組成物、およびセメント用添加剤用原料 |
JP2018138515A (ja) * | 2015-08-25 | 2018-09-06 | 株式会社日本触媒 | セメント組成物 |
US10294157B2 (en) | 2015-08-25 | 2019-05-21 | Nippon Shokubai Co., Ltd. | Cement additive, cement composition, and cement additive raw material |
JP2017075076A (ja) * | 2015-10-16 | 2017-04-20 | 株式会社日本触媒 | セメント用添加剤およびセメント組成物 |
Also Published As
Publication number | Publication date |
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RU2586121C2 (ru) | 2016-06-10 |
MY158382A (en) | 2016-09-26 |
EP2687497A1 (en) | 2014-01-22 |
MX2013009775A (es) | 2013-09-26 |
JP5848633B2 (ja) | 2016-01-27 |
US20140005305A1 (en) | 2014-01-02 |
EP2687497A4 (en) | 2014-10-01 |
JP2012206928A (ja) | 2012-10-25 |
RU2013145947A (ru) | 2015-04-20 |
US9353004B2 (en) | 2016-05-31 |
EP2687497B1 (en) | 2018-08-08 |
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