WO2020189631A1 - Additif pour matériaux durcissables à l'eau - Google Patents

Additif pour matériaux durcissables à l'eau Download PDF

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Publication number
WO2020189631A1
WO2020189631A1 PCT/JP2020/011495 JP2020011495W WO2020189631A1 WO 2020189631 A1 WO2020189631 A1 WO 2020189631A1 JP 2020011495 W JP2020011495 W JP 2020011495W WO 2020189631 A1 WO2020189631 A1 WO 2020189631A1
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Prior art keywords
nitrogen
group
additive
cement
meth
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PCT/JP2020/011495
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English (en)
Japanese (ja)
Inventor
太一朗 新井
千紗 小林
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株式会社日本触媒
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Priority to JP2021507342A priority Critical patent/JP7104235B2/ja
Publication of WO2020189631A1 publication Critical patent/WO2020189631A1/fr

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Classifications

    • 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
    • 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
    • C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • E—FIXED CONSTRUCTIONS
    • E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
    • E02D—FOUNDATIONS; EXCAVATIONS; EMBANKMENTS; UNDERGROUND OR UNDERWATER STRUCTURES
    • E02D17/00—Excavations; Bordering of excavations; Making embankments
    • E02D17/20—Securing of slopes or inclines

Definitions

  • the present invention relates to additives for hydraulic materials. More specifically, the present invention relates to additives for hydraulic materials useful for applications such as sprayed mortar and concrete.
  • the spraying method of spraying concrete (mortar) on the construction surface is widely used. ..
  • materials other than the quick-setting admixture hydroaulic material, aggregate, water, additives for hydraulic material, etc.
  • compressed air or a pump is used to reach the nozzle (discharge port). It is pumped, mixed with the quick-setting admixture sent by another pump just before the nozzle, and sprayed onto the construction surface.
  • Patent Document 1 discloses a dust reducing agent composed of a poly (meth) acrylate quaternized product.
  • Patent Documents 2 and 3 disclose spraying materials containing cement concrete containing a quaternary ammonium salt compound.
  • Patent Document 4 discloses a concrete spraying method in which a cationic polymer in an aqueous solution having a cement weight ratio of 0.02% to 0.5% is dissolved in water and mixed with concrete at the time of spraying.
  • Patent Document 5 describes a water-soluble polymer compound obtained by polymerizing an acrylic monomer represented by a predetermined structure or another acrylic monomer represented by a predetermined structure and another copolymerizable therewith.
  • a dust reducing agent for sprayed concrete which is a water-soluble polymer compound obtained by copolymerizing with a monomer, is disclosed.
  • Patent Documents 6 and 7 disclose a sprayed refractory or the like using amine silicate or the like.
  • various additives for hydraulic materials used in the spraying method such as a dust reducing agent are disclosed.
  • the spraying method in addition to reducing dust, in order to reduce the loss (rebound amount) due to rebound when sprayed on the construction surface, the paste content in mortar, concrete, etc. has high adhesiveness to the aggregate. Is required.
  • the additive for hydraulic material used in the conventional spraying method is not sufficient in terms of the adhesiveness of the paste to the aggregate when used in the hydraulic material composition.
  • the present invention has been made in view of the above situation, and an object of the present invention is to provide an additive for a hydraulic material capable of improving the adhesiveness of a paste to an aggregate in mortar, concrete or the like.
  • the present inventor has examined various additives for hydraulic materials used in the spraying method, and found that the additives for hydraulic materials containing nitrogen-containing compounds having a specific nitrogen atom content are mortar, concrete, etc. We have found that the adhesiveness of the paste to the aggregate is improved, and have come up with the idea that the above-mentioned problems can be solved brilliantly, and have reached the present invention.
  • the present invention is an additive for a water-hard material containing a nitrogen-containing compound (A), and the nitrogen-containing compound (A) has a nitrogen atom content ratio of 20% by mass of the nitrogen-containing compound (A).
  • the content is 0% by mass or more
  • the additive for a water-hard material is an additive for a water-hard material used for sprayed concrete applications.
  • the nitrogen-containing compound (A) is preferably polyalkyleneimine.
  • the nitrogen-containing compound (A) preferably has a nitrogen atom content of 21 to 80% by mass with respect to 100% by mass of the nitrogen-containing compound (A).
  • the nitrogen-containing compound (A) preferably has a weight average molecular weight of 10 to 1,000,000.
  • the present invention is also an additive composition for a hydraulic material containing the above-mentioned additive for a hydraulic material and a water reducing agent.
  • the present invention is also a hydraulic material composition containing the above additive for a hydraulic material and a hydraulic material.
  • the hydraulic material composition preferably further contains a water reducing agent.
  • the present invention is also a method in which the additive for a hydraulic material is sprayed onto a construction surface together with the hydraulic material.
  • the additive for hydraulic materials of the present invention has the above-mentioned structure and can improve the adhesiveness of the paste to the aggregate in mortar, concrete, etc., it can be suitably used for sprayed mortar, concrete, etc. it can.
  • the additive for hydraulic materials of the present invention is based on the fact that the content ratio of nitrogen atoms to 100% by mass of the compound is 20.0% by mass or more and the content ratio of nitrogen atoms is 20.0% by mass or more. Since it is sufficiently positively charged, it electrostatically interacts with the surface of a hydraulic material such as a negatively charged cement, and weakly agglomerates molecules such as the hydraulic material to form a hydraulic material composition. Can be imparted with adhesiveness. Further, since the nitrogen-containing compound (A) can suppress an increase in the viscosity of the hydraulic material composition while imparting adhesiveness to the hydraulic material composition, the hydraulic material composition is sprayed at the time of spraying. The influence on the pumping property (hydraulic material composition can pass through the pipe) can be sufficiently suppressed.
  • the content ratio of nitrogen atoms in the nitrogen-containing compound (A) is preferably 21 to 80% by mass. Thereby, the adhesiveness of the hydraulic material composition can be further improved. It is more preferably 23 to 50% by mass, and even more preferably 25 to 40% by mass.
  • the content ratio of nitrogen atoms in the nitrogen-containing compound (A) can be calculated from the composition formula of the compound, but it can also be measured by elemental analysis when the composition formula is unknown.
  • the weight average molecular weight of the nitrogen-containing compound (A) is preferably 10 to 1,000,000. Thereby, the adhesiveness of the hydraulic material composition can be further improved. It is more preferably 3,000 to 800,000, further preferably 5,000 to 700,000, even more preferably 10,000 to 600,000, even more preferably 50,000 to 500,000, and particularly preferably 100,000 to 40,000. It is ten thousand.
  • the weight average molecular weight of the nitrogen-containing compound (A) is a value measured by the following method. ⁇ Molecular weight measurement method> The weight average molecular weight and the number average molecular weight in the present invention can be measured by gel permeation chromatography (GPC) by a known method using pullulan as a standard substance.
  • the following conditions are adopted as the measurement conditions of GPC.
  • Measuring device Column used by Shimadzu Corporation; Showa Denko SHODEX OHpak SB-807HQ (2) + SB-806M / HQ (2) Eluent; 0.5 mol% -sodium nitrate, 0.5 mol% -acetic acid Standard substance; Pullulan P-82 (manufactured by Wako Pure Chemical Industries, Ltd.) Detector; Suggested refractometer (manufactured by Shimadzu Corporation) Flow velocity; 0.4 ml / min.
  • the nitrogen-containing compound (A) is not particularly limited as long as the content ratio of nitrogen atoms satisfies the above range.
  • polyalkyleneimine and its derivatives the content ratio of nitrogen atoms is 20.0% by mass or more.
  • examples thereof include a polymer ( ⁇ 1) having a structural unit (a1) derived from the nitrogen atom-containing monomer (A1) (hereinafter, also referred to as a polymer ( ⁇ 1)).
  • the polyalkyleneimine may have a structural unit having an alkylene group and an amino group, and may have the following formulas (1) and / or (2);
  • R 1 represents the same or different alkylene group having 2 to 6 carbon atoms. It may have a structural unit represented by. Specific examples of the alkylene group include an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, and an n-hexylene group.
  • the number of carbon atoms of the alkylene group is preferably 2 to 4, more preferably 2 to 3, and most preferably 2.
  • polyalkyleneimine examples include polyethyleneimine, polypropyleneimine, polybutyleneimine and the like, such as ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine and 1,1-dimethylethyleneimine. It can be obtained by polymerizing one or more of alkyleneimines having 2 to 6 carbon atoms by a commonly used method.
  • the polyalkyleneimine derivative is not particularly limited as long as the content ratio of nitrogen atom and the weight average molecular weight satisfy the above ranges, and for example, a compound obtained by quaternizing the amino group of polyalkyleneimine or polyalkyleneimine has. Examples thereof include compounds in which a substituent is introduced into an amino group or an alkylene group.
  • the quaternizing agent used for quaternization of the amino group is not particularly limited, but is not particularly limited, but is an alkyl halide such as methyl chloride, ethyl chloride, methyl bromide, methyl iodide; dimethyl sulfate, diethyl sulfate, di-n sulfate.
  • alkylating agents such as alkylsulfuric acid such as propyl
  • substituents include a hydroxyl group, an alkoxy group, a carboxyl group, an acyl group, a sulfonic acid group, a phosphoric acid group, an ether group, a thioether group, a carbonyl group, an ester group and the like.
  • the nitrogen atom-containing monomer (A1) is not particularly limited as long as the nitrogen atom content is 20.0% by mass or more with respect to 100% by mass of the monomer.
  • R 2 to R 5 represent the same or different hydrogen atom or methyl group.
  • X represents the number of 0 or 1.
  • a monomer represented by a total of 3 or less carbon atoms) imidazole group, pyrazole group, imidazoline group, triazole group, tetrazole group, pyridazine group, pyrimidine group, pyrazine group, purine group, benzotriazole group, A nitrogen-containing heterocyclic group-containing monomer such as a pyrazole group; and the like can be mentioned.
  • R 2 to R 5 in the above formula (3) represent a hydrogen atom or a methyl group, but R 2 and R 3 are preferably hydrogen atoms.
  • the monomer represented by the above formula (3) examples include vinylamine, allylamine, N-methylvinylamine, 1-propene-2-amine and the like.
  • the nitrogen-containing heterocyclic group-containing monomer examples include vinyl imidazole, vinyl pyrazole, vinyl imidazoline, vinyl triazole, vinyl tetrazole, vinyl pyridazine, vinyl pyrimidine group, vinyl pyrazine, vinyl purine, vinyl benzotriazole, vinyl pteridine and the like. Can be mentioned.
  • the polymer ( ⁇ 1) having the structural unit (a1) derived from the nitrogen atom-containing monomer (A1) is not particularly limited as long as the content ratio of the nitrogen atom and the weight average molecular weight satisfy the above ranges. Even if it is a homopolymer of the nitrogen atom-containing monomer (A1), it is a copolymer of two or more kinds of nitrogen atom-containing monomer (A1) and other than the nitrogen atom-containing monomer (A1). It may be a copolymer with the monomer (E).
  • the other monomer (E) is not particularly limited, but is a carboxyl group-containing simple substance such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, 2-methyleneglutaric acid, and salts thereof.
  • Vinyl esters such as vinyl acetate; Alkens such as ethylene and propylene; Aromatic vinyl monomers such as styrene; Maleimide derivatives such as maleimide, phenylmaleimide and cyclohexylmaleimide; nitrile group-containing vinyl such as (meth) acrylonitrile System monomers; monomers having a sulfonic acid group such as 3-allyloxy-2-hydroxypropanesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, styrenesulfonic acid, vinylsulfonic acid and salts thereof; Monomers having a phosphonic acid group such as vinyl phosphonic acid and (meth) allyl phosphonic acid; aldehyde group-containing vinyl monomers such as (meth) achlorine; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and butyl vinyl ether Other functional group-containing monomers such as vinyl chloride, vinylidene chlor
  • polyalkylene glycol chain-containing monomers such as monomers having a structure in which 1 to 300 mol of alkylene oxide is added to unsaturated alcohol.
  • these other monomers only one kind may be used alone, or two or more kinds may be used in combination.
  • the ratio of the structural unit (a1) in the polymer ( ⁇ 1) is not particularly limited as long as the content ratio of nitrogen atoms is 20.0% by mass or more with respect to 100% by mass of the polymer ( ⁇ 1).
  • the method for producing the polymer having the structural unit derived from the nitrogen atom-containing monomer (A1) is not particularly limited, but the monomer component containing the nitrogen atom-containing monomer (A1) is polymerized by a commonly used method. Can be obtained by
  • polyalkyleneimine is preferable. More preferably, it is polyethyleneimine.
  • the embodiment in which the nitrogen-containing compound (A) is polyethyleneimine is one of the preferred embodiments of the present invention.
  • the additive for a hydraulic material of the present invention contains the above-mentioned nitrogen-containing compound (A), and may contain two or more kinds of the compound (A).
  • the content of the compound (A) in the additive for hydraulic materials is not particularly limited, but is included in the additive for hydraulic materials.
  • the solid content (that is, non-volatile content) is preferably 5 to 90% by mass based on 100% by mass. It is more preferably 20 to 90% by mass, still more preferably 30 to 75% by mass.
  • the "additive for hydraulic material” refers to an additive added to a hydraulic material composition such as cement paste, mortar, concrete, etc., and only the above nitrogen-containing compound (A). It may be an agent composed of the above-mentioned nitrogen-containing compound (A), or may be an agent containing not only the above-mentioned nitrogen-containing compound (A) but also other additives described later as necessary.
  • the additive for hydraulic materials of the present invention is preferably used in combination with a water reducing agent. That is, the present invention is also an additive composition for a hydraulic material containing an additive for a hydraulic material and a water reducing agent.
  • the proportion of the water reducing agent is preferably 0.4 to 99.99% by mass with respect to 100% by mass of the additive for hydraulic materials. It is more preferably 10 to 99.5% by mass, and even more preferably 50 to 99% by mass.
  • the additive for a hydraulic material of the present invention is preferably used in a hydraulic material composition containing a hydraulic material. That is, a hydraulic material composition containing an additive for a hydraulic material and a hydraulic material is also one of the present inventions. The form in which the hydraulic material composition further contains an aggregate is also one of the preferred embodiments of the present invention.
  • the compounding ratio of the additive for the water-hard material of the present invention for example, the ratio of the nitrogen-containing compound (A) which is an essential component of the present invention (when a plurality thereof is contained, the total amount thereof) is used.
  • the ratio of the nitrogen-containing compound (A) which is an essential component of the present invention when a plurality thereof is contained, the total amount thereof.
  • it is preferably set to 0.0001 to 5% by mass, more preferably 0.0002 to 3% by mass, and further preferably 0.001 to 1% by mass.
  • the solid content can be measured as follows. ⁇ Solid content measurement method> 1.
  • the solid content measurement object is precisely weighed in the aluminum dish precisely weighed in 2.1. 3.
  • the solid content measurement material precisely weighed in 2 is placed in a dryer whose temperature has been adjusted to 130 ° C. under a nitrogen atmosphere for 1.5 hours. After 4.1 hours, remove from the dryer and allow to cool in a desiccator at room temperature for 15 minutes. 5. After 15 minutes, remove from the desiccator and weigh the aluminum dish + the object to be measured.
  • the solid content is measured by subtracting the mass of the aluminum plate obtained in 1 from the mass obtained in 6.5 and dividing by the mass of the solid content measurement product obtained in 2.
  • the water-hardening material is not particularly limited as long as it has water-hardness or latent water-hardness.
  • ordinary Portland cement early-strength Portland cement, moderate heat Portland cement, low heat Portland cement and other Portland cement and silica are used.
  • Cement, fly ash cement, blast furnace cement, alumina cement belite high content cement, various mixed cements; components of cement such as tricalcium silicate, dicalcium silicate, tricalcium aluminate, tetracalcium iron aluminate; latent hydraulic hardness
  • Examples thereof include fly ash, silica fume, slag, lime fine powder and the like having the above. These may be used alone or in combination of two or more.
  • ordinary Portland cement is usually commonly used and can be preferably applied.
  • the above aggregates include silica stone, clayey, zirconite, high alumina, silicon carbide, graphite, chromium, chromemag, magnesia, etc. Fireproof aggregate and the like.
  • the additive for a water-hard material of the present invention may be used in combination with other additives other than the additive for a water-hard material of the present invention in a water-hard material composition, and is usually used as another additive.
  • the cement dispersant (water reducing agent) is not particularly limited, and for example, (i) a polyalkylaryl sulfonate-based dispersant such as naphthalene sulfonic acid formaldehyde condensate; melamine formalin resin such as melamine sulfonic acid formaldehyde condensate, sulfone.
  • a polyalkylaryl sulfonate-based dispersant such as naphthalene sulfonic acid formaldehyde condensate
  • melamine formalin resin such as melamine sulfonic acid formaldehyde condensate, sulfone.
  • Arate-based dispersant Aromatic aminosulfonic acid-based dispersant such as aminoarylsulfonic acid-phenol-formaldehyde condensate; Ligninsulfonate-based dispersant such as ligninsulfonate and modified ligninsulfonate; Various sulfonic acid-based dispersants (water-reducing agents) having a sulfonic acid group in the molecule such as an acid salt-based dispersant; (ii) Polyalkylene glycol mono (meth) acrylate-based monomer, (meth) acrylate-based monomer, and copolymer obtained from a monomer copolymerizable with these monomers; JP-A-10- As described in JP-A-236858, JP-A-2001-220417, JP-A-2002-121055, and JP-A-2002-121056, unsaturated (poly) alkylene glycol ether-based monomer and maleic acid-based single amount.
  • a copolymer obtained from (alkoxy) polyalkylene glycol mono (meth) acrylate, a phosphoric acid monoester-based monomer, and a phosphoric acid diester-based monomer and the like.
  • the additive for hydraulic materials of the present invention is preferably used in combination with a water reducing agent.
  • the hydraulic material composition preferably further contains a water reducing agent, and such a form is one of the preferred embodiments of the present invention.
  • polycarboxylic acid-based water reducing agents are preferable. More preferably, the following equation (4);
  • R 6 to R 8 represent the same or different hydrogen atom or methyl group.
  • R 9 O represents the same or different oxyalkylene group having 2 to 18 carbon atoms.
  • 10 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
  • P represents a number of 0 to 5
  • q is a number of 0 or 1
  • n is an average addition molar of an oxyalkylene group.
  • the structural unit (I) represented by (1 to 300) representing a number and the following formula (5);
  • R 11 to R 13 represent the same or different hydrogen atom, methyl group or-(CH 2 ) m COOZ'group, where m is an integer of 0 to 2.
  • Z' represents a hydrogen atom, a metal atom, an ammonium group, an organic amine group or a hydrocarbon group.
  • Z represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group). It is a polycarboxylic acid-based copolymer having II).
  • the number of carbon atoms of R 9 in the oxyalkylene group R 9 O is preferably 2 to 18, preferably 2 to 8, and more preferably 2 to 4.
  • any two or more kinds of alkylene oxide adducts selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide and the like can be used by any of random addition, block addition, alternating addition and the like.
  • the oxyalkylene group contains an oxyethylene group as an essential component, more preferably 50 mol% or more is an oxyethylene group, and 90 mol% or more. It is more preferably an oxyethylene group.
  • the average number of moles of oxyalkylene groups added is 1 to 300.
  • the larger the average number of moles added the better the hydrophilicity of the obtained polymer, and the more the dispersion performance tends to be improved. If it is 300 or less, it is possible to suppress the decrease in copolymerization reactivity.
  • the average number of added moles n is preferably 5 to 250, and more preferably 10 to 200.
  • R 10 may be a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and the hydrocarbon group having 1 to 30 carbon atoms has a radically polymerizable unsaturated bond. It is preferable not to use an alkyl group having 1 to 30 carbon atoms (aliphatic alkyl group or alicyclic alkyl group), a phenyl group having 6 to 30 carbon atoms, an alkylphenyl group, a phenylalkyl group, or a (alkyl) phenyl group.
  • an alkyl group having 1 to 30 carbon atoms aliphatic alkyl group or alicyclic alkyl group
  • a phenyl group having 6 to 30 carbon atoms an alkylphenyl group, a phenylalkyl group, or a (alkyl) phenyl group.
  • substituted phenyl groups include, an aromatic group having a benzene ring such as a naphthyl group are preferred, since the number of carbon atoms of the hydrocarbon group hydrophobicity increases as increases, the dispersibility decreases, R 10
  • the number of carbon atoms in the case of a hydrocarbon group is preferably 1 to 22, more preferably 1 to 18, further preferably 1 to 12, and particularly preferably 1 to 4. Further, as R 10 , the case of a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms is most preferable.
  • Examples of the monomer forming the structural unit (I) include (poly) ethylene glycol allyl ether, (poly) ethylene glycol metalyl ether, (poly) ethylene glycol 3-methyl-3-butenyl ether, and (poly) ethylene.
  • the polycarboxylic acid-based copolymer may have a structural unit (III) other than the structural unit (I) and (II), and may be used as another monomer forming the structural unit (III).
  • III is not particularly limited as long as it can be copolymerized with the above-mentioned monomer, and is, for example, unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, and citraconic acid, and alcohols having 1 to 30 carbon atoms.
  • Diesters Diamides of unsaturated dicarboxylic acids and amines with 1 to 30 carbon atoms; Alkyl (poly) obtained by adding 1 to 300 mol of an alkylene oxide having 2 to 18 carbon atoms to the alcohol or amine.
  • (Poly) alkylene glycols such as triethylene glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, (poly) ethylene glycol (poly) propylene glycol di (meth) acrylate Di (meth) acrylates; Polyfunctional (meth) acrylates such as hexanediol di (meth) acrylate, trimethylpropantri (meth) acrylate, trimethylpropandi (meth) acrylate; triethylene glycol dimalate, polyethylene glycol (Poly) alkylene glycol dimalates such as zimalate; vinyl sulfonate, (meth) allyl sulfonate, 2- (meth) acryloxyethyl sulfonate, 3- (meth) acryloxypropyl sulfonate, 3- (meth) acryloxy-2 -Hydroxypropyl
  • Amine salts organic ammonium salts
  • amides of unsaturated monocarboxylic acids such as methyl (meth) acrylamide and amines having 1 to 30 carbon atoms
  • styrene ⁇ -methylstyrene, vinyltoluene, p-methylstyrene, etc.
  • Vinyl aromatics alkanediol mono (meth) acrylates such as 1,4-butanediol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, and 1,6-hexanediol mono (meth) acrylate.
  • Dienes such as butadiene, isoprene, 2-methyl-1,3-butadiene, 2-chlor-1,3-butadiene, etc.
  • Unsaturated amides such as (meth) acrylamide, (meth) acrylic alkylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide; unsaturated cyanide such as (meth) acrylonitrile and ⁇ -chloroacrylonitrile Classes; unsaturated esters such as vinyl acetate and vinyl propionate; aminoethyl (meth) acrylate, methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, Unsaturated amines such as dibutylaminoethyl (meth) acrylate, vinylpyridine; divinyl aromatics such as divinylbenzene; cyanurates such as triallyl cyanurate; (meth) allyl alcohol, glycidyl (meth) allyl ether, etc.
  • the unsaturated monocarboxylic acid-based monomer having one carboxy group (or carboxylic acid base) in one molecule as forming the structural unit (I) acrylic acid, methacrylic acid, crotonic acid and theirs are used.
  • Halfamide of the unsaturated dicarboxylic acid and an amine having 1 to 30 carbon atoms an alkyl (poly) alkylene glycol obtained by adding 1 to 300 mol of an alkylene oxide having 2 to 18 carbon atoms to the alcohol or amine and the above-mentioned non-saturated dicarboxylic acid.
  • Half-esters with saturated dicarboxylic acids examples thereof include half-esters between the unsaturated dicarboxylic acids and glycols having 2 to 18 carbon atoms or polyalkylene glycols having 2 to 300 additional moles of these glycols.
  • the unsaturated dicarboxylic acid-based monomer having two carboxy groups (or carboxylic acid bases) in one molecule include maleic anhydride, itaconic acid, citraconic acid, fumaric acid, or metal salts, ammonium salts, and organic amines thereof. Examples thereof include salts (organic ammonium salts), and examples of these anhydrides include maleic anhydride, itaconic anhydride, citraconic anhydride and the like.
  • an unsaturated monocarboxylic acid-based monomer is preferable. More preferably, it is acrylic acid or methacrylic acid.
  • the content ratio of the structural unit (I) is preferably 50 to 99% by mass with respect to 100% by mass of all structural units. It is more preferably 60 to 98% by mass, further preferably 70 to 95% by mass, and particularly preferably 80 to 93% by mass.
  • the content ratio of the structural unit (II) in the polycarboxylic acid-based copolymer is preferably 1 to 50% by mass with respect to 100% by mass of the total structural unit. It is more preferably 2 to 40% by mass, further preferably 5 to 30% by mass, and particularly preferably 7 to 20% by mass.
  • the ratio of the structural unit (III) in the copolymer is preferably 0 to 20% by mass with respect to 100% by mass of the total structural unit. It is more preferably 0 to 10% by mass, further preferably 0 to 5% by mass, and particularly preferably 0 to 1% by mass.
  • the polycarboxylic acid-based copolymer preferably has a weight average molecular weight of 1000 to 1000000. It is more preferably 2500 to 500,000, still more preferably 5,000 to 250,000, even more preferably 10,000 to 100,000, and particularly preferably 10,000 to 80,000.
  • the weight average molecular weight of the polycarboxylic acid-based copolymer can be measured by GPC under the measurement conditions described in Examples.
  • the production of the polycarboxylic acid-based copolymer is not particularly limited, but it can be produced by polymerizing a monomer component, and specific examples and preferable examples of the monomer component are as described above.
  • the content ratio of each monomer to 100% by mass of the monomer component is the same as the ratio of each structural unit to 100% by mass of all structural units described above.
  • the quick-setting agent may be any known quick-setting agent and is not particularly limited.
  • the quick-setting agent used may be a powder quick-setting agent, a liquid quick-setting agent, or a slurry-type quick-setting agent.
  • the liquid quick-setting admixture include aluminum sulfate, fluorine, and alkali metals, and those containing these and alkanolamines, and one or more of these can be used.
  • a known water-soluble hydration accelerator can be used as the liquid quick-setting admixture used in the present invention.
  • hydration accelerator examples include organic hydration accelerators such as formic acid or a salt thereof, acetic acid or a salt thereof, and lactic acid or a salt thereof, water glass, nitrate, nitrite, thiosulfate, and thiocyanate. It is possible to use an inorganic hydration accelerator such as a salt.
  • organic hydration accelerator such as formic acid or a salt thereof, acetic acid or a salt thereof, and lactic acid or a salt thereof, water glass, nitrate, nitrite, thiosulfate, and thiocyanate. It is possible to use an inorganic hydration accelerator such as a salt.
  • the powder quick-setting admixture examples include those containing calcium aluminates, sulfates, alkali metal aluminates, alkali metal carbonates, and oxycarboxylic acids, and one or two of these. The above can be used.
  • the defoaming agent is not particularly limited as long as it is a known defoaming agent.
  • mineral oil defoamers such as kerosene and liquid paraffin
  • oil and fat defoamers such as animal and vegetable oils, sesame oil, castor oil and these alkylene oxide adducts
  • fatty acids such as oleic acid, stearic acid and these alkylene oxide adducts.
  • fatty acid esters such as diethylene glycol monolaurate, glycerin monolithinolate, alkenyl succinolate derivative, sorbitol monolaurate, sorbitol trioleate, polyoxyethylene monolaurate, polyoxyethylene sorbitol monolaurate, natural wax, etc.
  • Defoamers such as octyl alcohol, hexadecyl alcohol, acetylene alcohol, glycols, polyoxyalkylene glycol; amide defoamers such as polyoxyalkylene amide and acrylate polyamine; tributyl phosphate, sodium Phosphate defoamers such as octyl phosphate; Metal soap defoamers such as aluminum stearate and calcium oleate; Silicone defoamers such as silicone oil, silicone paste, silicone emulsion, organically modified polysiloxane, fluorosilicone oil, etc.
  • Foaming agents oxyalkylene-based defoaming agents such as polyoxyethylene polyoxypropylene adducts; and the like, and one or more of these can be used.
  • the oxyalkylene defoamer is most preferable.
  • the amount of the defoaming agent used can be reduced, and the compatibility between the defoaming agent and the copolymer is also excellent. Is.
  • the oxyalkylene defoaming agent is not particularly limited as long as it is a compound having an oxyalkylene group in the molecule and having an action of reducing bubbles in an aqueous liquid, but among them, it is represented by the following formula (6). Specific oxyalkylene defoamers are preferred.
  • R 14 and R 16 are the same or different, and have a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 1 to 22 carbon atoms, an alkynyl group having 1 to 22 carbon atoms, and phenyl.
  • R 15 O represents one kind or a mixture of two or more oxyalkylene group having 2 to 4 carbon atoms, in the case of two or more may also be added in a block form are added to the random form.
  • t is the average number of moles of oxyalkylene group added, and represents a number from 0 to 300. When t is zero, never R 14, R 16 are not hydrogen atoms at the same time, T is -O -, - CO 2 -, - SO 4 -, - represent or -NH- groups - PO 4.
  • s represents an integer of 1 or 2, and when R 14 is a hydrogen atom, s is 1.
  • Examples of the oxyalkylene-based defoaming agent represented by the above formula (6) include polyoxyalkylenes such as (poly) oxyethylene (poly) oxypropylene adduct; diethylene glycol heptyl ether, polyoxyethylene oleyl ether, and poly.
  • (Poly) oxyalkylene alkyl ethers such as oxypropylene butyl ether, polyoxyethylene polyoxypropylene-2-ethylhexyl ether, oxyethylene oxypropylene adduct to higher alcohols having 12 to 14 carbon atoms; polyoxypropylene phenyl ether, poly (Poly) oxyalkylene (alkyl) aryl ethers such as oxyethylene nonylphenyl ether; 2,4,7,9-tetramethyl-5-decine-4,7-diol, 2,5-dimethyl-3-hexin- Acetylene ethers obtained by addition-polymerizing an alkylene oxide to an acetylene alcohol such as 2,5-diol and 3-methyl-1-butin-3-ol; such as diethylene glycol oleic acid ester, diethylene glycol lauric acid ester, and ethylene glycol distearate ester.
  • the blending ratio of the water reducing agent is preferably 0.01 to 1% by mass with respect to 100% by mass of the total amount of the hydraulic material in terms of solid content. It is more preferably 0.05 to 0.5% by mass, and further preferably 0.07 to 0.3% by mass.
  • the unit water amount, cement usage amount and water / cement ratio per 1 m 3 are not particularly limited, and for example, the unit water amount 100 to 300 kg / m 3 and the cement amount used 300 to 500 kg / m. 3.
  • the water / cement ratio (weight ratio) is preferably 0.35 to 0.6. More preferably, the unit water amount is 140 to 240 kg / m 3 , the cement amount used is 350 to 480 kg / m 3 , and the water / cement ratio (weight ratio) is 0.4 to 0.5.
  • the additive for a hydraulic material of the present invention is not particularly limited as long as it is used in a hydraulic material composition, and can be used for ready-mixed concrete, sprayed concrete, and the like. It is preferably used for sprayed concrete applications.
  • the method of using the additive for hydraulic materials of the present invention in sprayed concrete is also one of the present inventions.
  • the present invention is also a method in which the additive for a hydraulic material of the present invention is sprayed onto a construction surface together with a hydraulic material.
  • the above-mentioned usage method is not particularly limited as long as the additive for hydraulic material of the present invention is sprayed on the construction surface together with the hydraulic material, but a mixture of the additive for hydraulic material and the hydraulic material is sprayed on the construction surface. Is preferable.
  • the above-mentioned usage methods include a step of mixing an additive for a hydraulic material and a hydraulic material, a step of pumping the hydraulic material composition obtained by the mixing step with compressed air, a pump, or the like, and pumped water. It is more preferable to include a step of spraying the hard material composition.
  • the preferred forms of the hydraulic material composition and the like are as described above.
  • the molecular weight of the following polymer was measured as follows. ⁇ Molecular weight measurement (GPC analysis method)> Device: Waters Alliance (2695) Analysis software: Waters, EmPower Professional + GPC option used Column: Tosoh Co., Ltd., TSKguardvolumes ⁇ + TSKgel ⁇ 5000 + ⁇ 4000 + ⁇ 3000 Detectors: Differential Refractometer (RI) Detector (Waters 2414), Multi-Wavelength Visible Ultraviolet (PDA) Detector (Waters 2996) Eluent: 93.98 g of boric acid and 30.4 g of sodium hydroxide dissolved in a mixed solvent of 15076 g of water and 3800 g of acetonitrile Standard material for calibration curve preparation: Polyethylene glycol (peak top molecular weight (Mp) 272,500, 219300, 107000, 50000, 24000, 12600, 7100, 4250, 1470) Calibration curve: It was prepared by a cubic formula based on the Mp value
  • ⁇ Production Example 2 Production of water reducing agent (polycarboxylic acid copolymer ⁇ ) 64.41 parts of ion-exchanged water, 3-methyl-3 in a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, and a recirculation cooler. 272.11 parts of unsaturated alcohol with 50 mol of ethylene oxide added to -buten-1-ol was charged, the temperature was raised to 65 ° C., and then 0.71 part of a 30% aqueous solution of hydrogen peroxide was added to the acrylic acid.
  • water reducing agent polycarboxylic acid copolymer ⁇
  • the temperature was continuously maintained at 60 ° C. for 1 hour to complete the polymerization reaction.
  • Aqueous solution prepared by dissolving in parts was used for 4 hours, 34.85 parts of a 10% aqueous solution of dimethylaminopropylacrylamide quaternary salt (DMAPAA-Q) for 4 hours, and 14.13 parts of a 3.8% aqueous solution of ammonium persulfate in 5 parts. Dropped over time. After that, the temperature was maintained at 80 ° C. for 60 minutes to complete the polymerization reaction, the temperature was lowered to 50 ° C. or lower, and 21.2 parts of a 30% aqueous solution of sodium hydroxide was neutralized from pH 4 to pH 7, and the weight was increased.
  • the polycarboxylic acid copolymer ⁇ of the present invention composed of an aqueous polymer solution having an average molecular weight of 70,000 was obtained.
  • the probe was then penetrated to a depth of 20 mm from the surface of the sample at a rate of 1 mm per second, followed immediately by 1 mm / sec.
  • the probe was pulled out at the speed of, and the maximum load required for the probe to peel off from the mortar was calculated and used as the value of the probe tack test.
  • the unit is N / cm 2 .
  • the maximum load ratio of each system when the maximum load of the system without additives for hydraulic materials was set to 100% was defined as adhesiveness. When the maximum load ratio was 100% or more, it was considered to have high adhesiveness.
  • the mortar test was conducted in an environment where the temperature was 20 ° C. ⁇ 1 ° C. and the relative humidity was 60% ⁇ 15%.
  • C Cement (ordinary Portland cement, manufactured by Taiheiyo Cement)
  • S Fine aggregate (land sand from Oi River)
  • W An ion-exchanged aqueous solution of the sample and the defoaming agent was prepared, and W contained the additive for the water-hard material and the defoaming agent of the following examples, and was sufficiently uniformly dissolved in the ion-exchanged water.
  • a mortar mixer Mater manufactured by Hobart, model number: N-50
  • C and S were put into a kneading container and kneaded at 1st speed for 10 seconds.
  • the surface of the mini slump cone was smoothed after being stabbed with a stab bar, stuffed with mortar to the fullest extent of the mini slump cone, and stabbed with a stab bar 15 times. Then, 3 minutes and 30 seconds after starting the mixer for the first time, the mini slump cone was pulled up vertically, and the diameter of the expanded mortar (the diameter of the longest part (major diameter) and the diameter of the part 90 degrees to the long diameter). ) was measured at two points, and the average value was taken as the mortar flow value.
  • the polycarboxylic acid copolymer obtained in any of Production Examples 1 to 5 was added as a water reducing agent so that the flow value was 230 mm, and an oxyalkylene defoaming agent which was a defoaming agent was added for the amount of air. It was adjusted so that it was less than 3.0%.
  • the mortar obtained in (4) of the above adhesiveness evaluation was poured to the upper surface of the J14 funnel to smooth the upper surface.
  • the rubber stopper was removed to allow the mortar to flow out, and the time from the start of the mortar outflow to the flow down of 1200 g was measured with a stopwatch, and this was taken as the funnel flow-down time (rohto passage time).
  • the funnel flow-down time (rohto passage time). It should be noted that if the increase in the funnel flow time is 15% or less with respect to the funnel flow time of 100% for the mortar to which no additive for hydraulic materials is added, the influence on the pipe passage is sufficiently suppressed. It can be said that if it is less than 10%, it is more sufficiently suppressed.
  • Epomin SP-006 manufactured by Nippon Catalyst Co., Ltd.
  • a nitrogen-containing compound (A) is blended with 0.0001% by weight based on cement, and polycarboxylic acid copolymer ⁇ is blended as a water reducing agent to prepare an admixture for cement.
  • the adhesiveness was 112% and the funnel passage time was 106%.
  • Epomin SP-006 manufactured by Nippon Catalyst Co., Ltd.
  • a nitrogen-containing compound (A) is blended with 0.005% by weight based on cement, and polycarboxylic acid copolymer ⁇ as a water reducing agent is blended to prepare an admixture for cement.
  • the adhesiveness was 126% and the funnel passage time was 104%.
  • Epomin SP-006 manufactured by Nippon Catalyst Co., Ltd.
  • a nitrogen-containing compound (A) is added in an amount of 0.3% by weight based on cement, and a polycarboxylic acid copolymer ⁇ is added as a water reducing agent to prepare an admixture for cement.
  • the adhesiveness was 132% and the funnel passage time was 103%.
  • Epomin SP-006 manufactured by Nippon Catalyst Co., Ltd.
  • a nitrogen-containing compound (A) is blended with 3.0% by weight based on cement, and polycarboxylic acid copolymer ⁇ is blended as a water reducing agent to prepare an admixture for cement.
  • the adhesiveness was 145% and the funnel passage time was 105%.
  • Epomin SP-012 manufactured by Nippon Catalyst Co., Ltd.
  • a nitrogen-containing compound (A) is blended with 0.001% by weight based on cement, and polycarboxylic acid copolymer ⁇ as a water reducing agent is blended to prepare an admixture for cement.
  • the adhesiveness was 123% and the funnel passage time was 103%.
  • Epomin SP-018 manufactured by Nippon Catalyst Co., Ltd.
  • a nitrogen-containing compound (A) is blended with 0.0001% by weight based on cement, and polycarboxylic acid copolymer ⁇ is blended as a water reducing agent to prepare an admixture for cement.
  • the adhesiveness was 121% and the funnel passage time was 100%.
  • Epomin SP-018 manufactured by Nippon Catalyst Co., Ltd.
  • a nitrogen-containing compound (A) was added in an amount of 0.3% by weight based on cement, and a polycarboxylic acid copolymer ⁇ was added as a water reducing agent to prepare an admixture for cement.
  • the adhesiveness was 150% and the funnel passage time was 105%.
  • Epomin SP-018 manufactured by Nippon Catalyst Co., Ltd.
  • a nitrogen-containing compound (A) is blended with 0.5% by weight based on cement, and polycarboxylic acid copolymer ⁇ is blended as a water reducing agent to prepare an admixture for cement.
  • the adhesiveness was 155% and the funnel passage time was 109%.
  • Epomin SP-018 manufactured by Nippon Catalyst Co., Ltd.
  • a nitrogen-containing compound (A) is blended with 3.0% by weight based on cement, and polycarboxylic acid copolymer ⁇ is blended as a water reducing agent to prepare an admixture for cement.
  • the adhesiveness was 172% and the funnel passage time was 106%.
  • Epomin SP-200 manufactured by Nippon Catalyst Co., Ltd.
  • a nitrogen-containing compound (A) is blended with 0.0005% by weight based on cement, and polycarboxylic acid copolymer ⁇ is blended as a water reducing agent to prepare an admixture for cement.
  • the adhesiveness was 130% and the funnel passage time was 105%.
  • Epomin SP-200 manufactured by Nippon Catalyst Co., Ltd.
  • a nitrogen-containing compound (A) is blended with 0.01% by weight based on cement, and polycarboxylic acid copolymer ⁇ is blended as a water reducing agent to prepare an admixture for cement.
  • the adhesiveness was 142% and the funnel passage time was 104%.
  • Epomin HM-2000 manufactured by Nippon Catalyst Co., Ltd.
  • a nitrogen-containing compound (A) is blended with 0.0005% by weight based on cement, and polycarboxylic acid copolymer ⁇ is blended as a water reducing agent to prepare an admixture for cement.
  • the adhesiveness was 126% and the funnel passage time was 102%.
  • Epomin HM-2000 manufactured by Nippon Catalyst Co., Ltd.
  • a nitrogen-containing compound (A) is blended with 0.9% by weight based on cement, and polycarboxylic acid copolymer ⁇ is blended as a water reducing agent to prepare an admixture for cement.
  • the adhesiveness was 175% and the funnel passage time was 112%.
  • Epomin P-1000 manufactured by Nippon Catalyst Co., Ltd.
  • a nitrogen-containing compound (A) is blended with 0.0001% by weight based on cement, and polycarboxylic acid copolymer ⁇ as a water reducing agent is blended to prepare an admixture for cement.
  • the adhesiveness was 124% and the funnel passage time was 103%.
  • Epomin P-1000 manufactured by Nippon Catalyst Co., Ltd.
  • a nitrogen-containing compound (A) is blended with 0.005% by weight based on cement, and polycarboxylic acid copolymer ⁇ is blended as a water reducing agent to prepare an admixture for cement.
  • the adhesiveness was 157% and the funnel passage time was 103%.
  • Epomin P-1000 manufactured by Nippon Catalyst Co., Ltd.
  • a nitrogen-containing compound (A) is added in an amount of 1.8% by weight based on cement, and a polycarboxylic acid copolymer ⁇ is added as a water reducing agent to prepare an admixture for cement.
  • the adhesiveness was 158% and the funnel passage time was 115%.
  • Epomin SP-012 manufactured by Nippon Catalyst Co., Ltd.
  • a nitrogen-containing compound (A) is blended with 0.5% by weight based on cement, and polycarboxylic acid copolymer ⁇ is blended as a water reducing agent to prepare an admixture for cement.
  • the adhesiveness was 135% and the funnel passage time was 109%.
  • Epomin P-1000 manufactured by Nippon Catalyst Co., Ltd.
  • a nitrogen-containing compound (A) is blended with 0.001% by weight based on cement, and polycarboxylic acid copolymer ⁇ is blended as a water reducing agent to prepare an admixture for cement.
  • the adhesiveness was 175% and the funnel passage time was 106%.
  • Epomin SP-018 manufactured by Nippon Catalyst Co., Ltd.
  • a nitrogen-containing compound (A) is blended with 0.005% by weight based on cement, and a polycarboxylic acid copolymer ⁇ is blended as a water reducing agent to prepare an admixture for cement.
  • the adhesiveness was 126% and the funnel passage time was 107%.
  • Epomin SP-200 manufactured by Nippon Catalyst Co., Ltd.
  • a nitrogen-containing compound (A) is added in an amount of 0.3% by weight based on cement, and a polycarboxylic acid copolymer ⁇ is added as a water reducing agent to prepare an admixture for cement.
  • the adhesiveness was 138% and the funnel passage time was 109%.
  • Epomin SP-012 manufactured by Nippon Catalyst Co., Ltd.
  • a nitrogen-containing compound (A) was added in an amount of 1.8% by weight based on cement, and a polycarboxylic acid copolymer ⁇ was added as a water reducing agent to prepare an admixture for cement.
  • the adhesiveness was 146% and the funnel passage time was 108%.
  • Epomin SP-018 manufactured by Nippon Catalyst Co., Ltd.
  • a nitrogen-containing compound (A) is blended with 0.005% by weight based on cement, and a polycarboxylic acid copolymer ⁇ is blended as a water reducing agent to prepare an admixture for cement.
  • the adhesiveness was 129% and the funnel passage time was 106%.
  • Epomin SP-018 manufactured by Nippon Catalyst Co., Ltd.
  • a nitrogen-containing compound (A) is blended with 0.9% by weight based on cement, and a polycarboxylic acid copolymer ⁇ is blended as a water reducing agent to prepare an admixture for cement.
  • the adhesiveness was 162% and the funnel passage time was 109%.
  • the cause of stickiness in mortar is that the cationic nitrogen atom in the additive molecule interacts with anions such as silicate ions and hydroxide ions in cement minerals to form a weak network in the system. Can be guessed. Therefore, it is considered that the higher the nitrogen content of the nitrogen-containing compound is, the better the adhesiveness is. Therefore, the same effect as that of Examples 1 to 23 is obtained for molecules having a structure other than the polyalkyleneimine described in Examples 1 to 23. Can be expected.

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Abstract

La présente invention concerne un additif pour matériaux durcissables à l'eau, qui peut améliorer l'adhérence d'un composant pâteux à un agrégat dans du mortier, du béton ou similaire. La présente invention concerne un additif pour matériaux durcissables à l'eau, qui contient un composé contenant de l'azote (A), l'additif étant caractérisé en ce que le composé contenant de l'azote (A) a une teneur en atomes d'azote supérieure ou égale à 20 % en masse par rapport à 100 % en masse du composé contenant de l'azote (A), et est également caractérisé en ce qu'il peut être utilisé dans du béton projeté.
PCT/JP2020/011495 2019-03-20 2020-03-16 Additif pour matériaux durcissables à l'eau WO2020189631A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0699169B2 (ja) * 1984-09-12 1994-12-07 藤沢薬品工業株式会社 コンクリート混和剤
WO2007086507A1 (fr) * 2006-01-26 2007-08-02 Sika Ltd. Agent de dispersion de ciment
JP2008094708A (ja) * 2006-09-11 2008-04-24 Nippon Shokubai Co Ltd セメント混和剤及びセメント組成物
JP2015536294A (ja) * 2012-10-31 2015-12-21 コンストラクション リサーチ アンド テクノロジー ゲーエムベーハーＣｏｎｓｔｒｕｃｔｉｏｎ Ｒｅｓｅａｒｃｈ ＆ Ｔｅｃｈｎｏｌｏｇｙ ＧｍｂＨ 優れた凍結融解安定性を有するアルカリ活性化アルミノケイ酸塩結合材

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0699169B2 (ja) * 1984-09-12 1994-12-07 藤沢薬品工業株式会社 コンクリート混和剤
WO2007086507A1 (fr) * 2006-01-26 2007-08-02 Sika Ltd. Agent de dispersion de ciment
JP2008094708A (ja) * 2006-09-11 2008-04-24 Nippon Shokubai Co Ltd セメント混和剤及びセメント組成物
JP2015536294A (ja) * 2012-10-31 2015-12-21 コンストラクション リサーチ アンド テクノロジー ゲーエムベーハーＣｏｎｓｔｒｕｃｔｉｏｎ Ｒｅｓｅａｒｃｈ ＆ Ｔｅｃｈｎｏｌｏｇｙ ＧｍｂＨ 優れた凍結融解安定性を有するアルカリ活性化アルミノケイ酸塩結合材

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