WO2020115788A1 - Additive for hydraulic compositions, and hydraulic composition - Google Patents
Additive for hydraulic compositions, and hydraulic composition Download PDFInfo
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- WO2020115788A1 WO2020115788A1 PCT/JP2018/044378 JP2018044378W WO2020115788A1 WO 2020115788 A1 WO2020115788 A1 WO 2020115788A1 JP 2018044378 W JP2018044378 W JP 2018044378W WO 2020115788 A1 WO2020115788 A1 WO 2020115788A1
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Classifications
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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
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
Definitions
- the present invention relates to an additive for hydraulic compositions. More specifically, it is possible to reduce the influence of fine particles and clay contained in the aggregate, and to lower the viscosity of the hydraulic composition, which can be suitably used for cement compositions and the like. It relates to an additive for a composition.
- Patent Document 1 by using a specific polycarboxylic acid-based dispersant and an admixture in which a copolymer of a carboxylic acid monomer and a (meth)acrylic acid-based ester is blended, the fluidity of concrete is improved. It has been proposed that material separation resistance can be imparted. And, in Patent Document 1, a specific polycarboxylic acid-based dispersant, which is a raw material component, and a copolymer of a carboxylic acid monomer and a (meth)acrylic acid-based ester are combined to form a one-pack type admixture. It is disclosed that it can be supplied as.
- Patent Document 2 proposes that a concrete having a high filling property and a high fluidity can be obtained by using a specific low-substituted hydroxypropylcellulose.
- ⁇ Coarse aggregates and fine aggregates are used as aggregates to be added to hydraulic compositions.
- natural aggregates such as gravel and sand that are formed from rocks by natural action and are produced from rivers, mountains, the sea, and land, and rocks are artificially crushed with a crusher. The crushed stone and crushed sand obtained by this are used.
- crushed stone and crushed sand with fine particles or clay particles generated when artificially crushing rock to produce crushed stone and crushed sand may be used.
- the problem to be solved by the present invention is to mitigate the influence of the fine particles and clay contained in the aggregate even if the fine particles and the clay attached to the aggregate are not washed off.
- Another object of the present invention is to provide an additive for a hydraulic composition, which can reduce the viscosity of the hydraulic composition.
- the present inventors have found that it is correct and preferable to use an additive for hydraulic composition having a specific polymer. According to the present invention, the following additives for hydraulic compositions are provided.
- a hydraulic composition additive containing the following component A and the following component B.
- Component A a polymer having a structural unit formed from acrylic acid and/or a salt thereof, and having a mass average molecular weight of 1,000 or more and less than 100,000;
- Component B A vinyl copolymer having the following structural unit 1 and structural unit 2 in the molecule, containing 1 to 99% by mass of structural unit 1, and 1 to 99% by mass of structural unit 2.
- Structural unit 1 a structural unit formed from the following monomer 1.
- Structural unit 2 a structural unit formed from a carboxylic acid monomer having a vinyl group in the molecule
- Monomer 1 unsaturated (poly)alkylene glycol represented by the following formula (1):
- R 1 , R 2 and R 3 are the same or different and each represents a hydrogen atom, a methyl group and an organic group represented by —(CH 2 )rCOOM (provided that, among R 1 , R 2 and R 3 , Represents at least one selected from a hydrogen atom or a methyl group)
- R 4 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
- R 5 O represents a hydrocarbon group having 2 to 4 carbon atoms.
- the additive for a hydraulic composition of the present invention even if the fine particles and clay particles attached to the aggregate are not washed off, the effect of the fine particles and clay particles can be mitigated, and further water There is an effect that the viscosity of the hard composition can be lowered.
- the additive for hydraulic composition of the present embodiment is an additive for hydraulic composition containing component A and component B.
- the component A used for the additive for hydraulic composition of the present embodiment is a polymer having a structural unit formed from acrylic acid and/or its salt.
- the type of the acrylate salt is not particularly limited, but examples thereof include alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as calcium salts and magnesium salts, ammonium salts, and diethanolamine salts. And amine salts such as triethanolamine salt. From the viewpoint of easy handling and availability, sodium salts and ammonium salts are preferable, and sodium salts are more preferable.
- the acrylic acid and/or its salt may be only one kind, or may be two or more kinds. ⁇
- the polymer of the component A provided for the additive for hydraulic composition of the present embodiment has a mass average molecular weight of 1,000 or more and less than 100,000, preferably 1,000 or more and less than 70,000, more preferably 1,000 or more and less than 50,000. Yes, and more preferably 1,000 or more and less than 30,000. Even more preferably, it is 1,000 or more and less than 10,000.
- the component B used in the additive for hydraulic composition of the present embodiment is a vinyl copolymer having the structural unit 1 and the structural unit 2 in the molecule.
- the structural unit 1 is formed from the monomer 1.
- the monomer 1 is an unsaturated (poly)alkylene glycol represented by the following formula (1).
- R 1 , R 2 and R 3 are the same or different and each represents at least one selected from a hydrogen atom, a methyl group and an organic group represented by —(CH 2 )rCOOM, provided that R 1 , At least one of R 2 and R 3 represents a hydrogen atom or a methyl group.
- R 4 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Examples of such a hydrocarbon group include a methyl group, an ethyl group, a propyl group, and a butyl group.
- R 5 O represents one or more oxyalkylene groups having 2 to 4 carbon atoms. Examples of such an oxyalkylene group include an oxyethylene group and an oxypropylene group.
- any addition form such as random addition, block addition, and alternate addition may be used.
- p represents an integer of 0 to 5
- q represents 0 or 1
- m represents an integer of 1 to 300
- r represents an integer of 0 to 2
- M represents a hydrogen atom or a metal atom.
- Examples of such a monomer 1 include ⁇ -vinyl- ⁇ -hydroxy(poly)oxybutylene(poly)oxyethylene, ⁇ -allyl- ⁇ -methoxy-(poly)oxyethylene, ⁇ -allyl- ⁇ - Methoxy-(poly)oxyethylene (poly)oxypropylene, ⁇ -allyl- ⁇ -hydroxy-(poly)oxyethylene, ⁇ -allyl- ⁇ -hydroxy-(poly)oxyethylene (poly)oxypropylene, ⁇ -methallyl- ⁇ -hydroxy-(poly)oxyethylene, ⁇ -methallyl- ⁇ -methoxy-(poly)oxyethylene, ⁇ -methallyl- ⁇ -hydroxy-(poly)oxyethylene(poly)oxypropylene, ⁇ -methallyl- ⁇ -acetyl -(Poly)oxyethylene, ⁇ -(3-methyl-3-butenyl)- ⁇ -hydroxy-(poly)oxyethylene, ⁇ -(3-methyl-3-butenyl)-
- Structural unit 2 is formed from a carboxylic acid monomer.
- the carboxylic acid monomer here is a monomer having no ester group or amide group.
- the carboxylic acid monomer has a vinyl group in its molecule.
- Examples of such a carboxylic acid monomer include (meth)acrylic acid, crotonic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, fumaric acid, and salts thereof.
- the salt is not particularly limited, but examples thereof include alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium salt and magnesium salt, ammonium salt, diethanolamine salt, triethanolamine salt and the like. Examples include amine salts. Among them, sodium salt and calcium salt are preferable.
- the vinyl copolymer which is the B component used in the additive for hydraulic composition of the present embodiment, may further include the structural unit 3 as an arbitrary structural unit in the molecule.
- the structural unit 3 may be formed from the monomer 1 and the monomer 3 copolymerizable with the carboxylic acid monomer.
- the monomer 3 is not particularly limited as long as it can be copolymerized with the monomer 1 and the carboxylic acid monomer, and examples thereof include alkyl (meth)acrylate-based monomers such as methyl acrylate, methyl methacrylate and butyl acrylate. And unsaturated amides such as (meth)acrylamide and N,N-dimethyl (meth)acrylamide, unsaturated cyanides such as (meth)acrylonitrile, unsaturated dicarboxylic acids such as maleic acid and fumaric acid, and 1 to 1 carbon atoms.
- alkyl (meth)acrylate-based monomers such as methyl acrylate, methyl methacrylate and butyl acrylate.
- unsaturated amides such as (meth)acrylamide and N,N-dimethyl (meth)acrylamide
- unsaturated cyanides such as (meth)acrylonitrile
- unsaturated dicarboxylic acids such as maleic acid and fumaric acid
- Sulfonic acid type monomers consisting of acids and salts thereof, 2-(methacryloyloxy)ethyl phosphate and bis[2-(methacryloyloxy)ethyl]phosphate and phosphoric acid type monolayers consisting of salts thereof Examples include monomers.
- the constituent unit 1 is contained in an amount of 1 to 99% by mass, preferably 70 to 99% by mass, more preferably 75 to 99% by mass, 80 to 99% by mass is more preferable, 1 to 99% by mass of the constituent unit 2 is contained, 1 to 30% by mass is preferable, 25 to 99% by mass is more preferable, and 1 to 20% by mass is contained. Is more preferable.
- the structural unit 3 is preferably contained in an amount of 0 to 30% by mass, more preferably 0 to 20% by mass, and 0 to 10% by mass. It is more preferred that the content is 0 to 5% by mass, and even more preferred that the content is 0 to 5% by mass.
- the total of the structural unit 1 and the structural unit 2 is preferably 80% by mass or more, more preferably 85% by mass or more, and 90% by mass or more. Is more preferable, and even more preferably 95% by mass or more.
- the mass average molecular weight of the component B used in the additive for hydraulic composition of the present embodiment can be measured by gel permeation chromatography, and is preferably 2000 to 500000 in terms of polyethylene glycol, more preferably 5000 to It is 200,000, and more preferably 10,000 to 100,000.
- Such component B can be obtained by a known radical polymerization reaction.
- it can be manufactured by various methods. Examples of such methods include radical polymerization using water as a solvent, radical polymerization using an organic solvent as a solvent, and solvent-free radical polymerization.
- the reaction temperature in radical polymerization is preferably 0 to 120°C, more preferably 20 to 100°C, and further preferably 50 to 90°C.
- Radical polymerization initiators used for radical polymerization include peroxides such as hydrogen peroxide, ammonium persulfate, sodium persulfate and potassium persulfate, 2,2-azobis(2-amidinopropane) dihydrochloride, 2,2 -Azo-based compounds such as azobis(isobutyronitrile) are mentioned, and the kind thereof is not particularly limited as long as it decomposes at the polymerization reaction temperature and generates radicals.
- a reducing substance such as sulfite or L-ascorbic acid, and further with an amine or the like.
- a chain transfer agent such as 2-mercaptoethanol, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thioglycolic acid, thioglycerin, or thiomalic acid is used to adjust the mass average molecular weight of the resulting component B to a desired range.
- the pressure in the reaction system is not particularly limited, but normal pressure is preferable.
- the concentrations of the A component and the B component are not particularly limited, but the mass% of the A component with respect to the B component is preferably 0.1 to 5 mass %, It is more preferably 0.5 to 4% by mass.
- the hydraulic composition of the present embodiment contains the additive for hydraulic composition of the present embodiment.
- the component A and the component B may be added independently or at the same time.
- the components A and B may be added as powders to the hydraulic composition slurry, or the components A and B may be dispersed or dissolved in a liquid shrinkage reducing agent, a liquid defoaming agent, or the like. In the state, it may be added to the hydraulic composition slurry, and further, the components A and B may be added to the hydraulic composition slurry in a state of being dissolved in water.
- the pH of the 1 mass% aqueous solution of the component B is preferably 2 to 7, and more preferably from the viewpoint of the compatibility between the component A and the component B. Is 2 to 6, and more preferably 2 to 5.
- the hydraulic composition of the present embodiment is prepared using the additive for hydraulic composition of the present embodiment as described above, cement paste, mortar, it is a cement composition such as concrete.
- the cement composition is one in which at least cement is used as the binder, but the cement may be used alone, or the cement and the pozzolanic substance or a fine powder admixture having latent hydraulicity may be used in combination.
- Examples of such cements include various Portland cements such as normal Portland cement, early-strength Portland cement, moderate heat Portland cement, and low heat Portland cement, and various mixed cements such as blast furnace cement, fly ash cement, and silica fume cement.
- the fine powder admixture include blast furnace slag fine powder, silica fume and fly ash.
- the hydraulic composition of the present embodiment also preferably contains an aggregate.
- Any appropriate aggregate such as fine aggregate or coarse aggregate can be adopted as the aggregate.
- fine aggregates include river sand, mountain sand, land sand, silica sand, crushed sand, blast furnace slag fine aggregate
- coarse aggregates include river gravel, mountain gravel, and land gravel. , Crushed stone, blast furnace slag coarse aggregate and the like.
- the aggregate has fine particles and clay, and when used without washing or removing fine particles and clay, the hydraulic composition contains fine particles and clay, but the water of the present embodiment In the hardenable composition, the effects of these fine particles and clay are alleviated, and the viscosity of the hydraulically hardened composition can be lowered.
- the total amount of the components A and B is 0.1 to 2 parts by weight, and 0.1 to 1.5 parts by weight, based on 100 parts by weight of the binder. More preferably, it is 0.1 to 1 part by mass.
- the water binder ratio of 30 to 60% which is easily affected by the fluidity of clay.
- the water binder ratio is a mass part of water relative to 100 mass parts of a binder such as cement in the hydraulic composition, and when the water content is 50 mass parts, the water binder ratio is 50%.
- the hydraulic composition of the present embodiment is, for example, an AE modifier composed of an anionic surfactant, for example, an oxyalkylene antifoaming agent, for example, an oxycarboxylic acid salt, as long as the effect is not impaired.
- a setting retarder consisting of, for example, a curing accelerator consisting of an alkanolamine, for example a drying shrinkage reducing agent consisting of a polyoxyalkylene alkyl ether, for example an antiseptic consisting of an isothiazoline compound, for example a waterproofing agent consisting of a higher fatty acid derivative,
- a rust preventive agent composed of nitrite can be contained.
- Test Category 1 (polymer of acrylic acid and/or its salt as component A) The polymers of acrylic acid and/or its salt used are summarized in Table 1.
- A-1 Sodium polyacrylate (Aaron T-210 manufactured by Toagosei Co., Ltd.)
- A-2 Polyacrylic acid (polyacrylic acid 5,000 manufactured by Wako Pure Chemical Industries, Ltd.)
- A-3 Polyacrylic acid (polyacrylic acid 25,000 manufactured by Wako Pure Chemical Industries, Ltd.)
- Ar-1 polyacrylic acid (polyacrylic acid 1,000,000 manufactured by Wako Pure Chemical Industries, Ltd.)
- Ar-2 sodium polyacrylate (Aaron A-20P-X manufactured by Toagosei Co., Ltd.)
- Ar-3 Hydroxypropyl methylcellulose (Metronose Hi90SH100000 manufactured by Shin-Etsu Chemical Co., Ltd.)
- d-1 Structural unit formed of sodium acrylate
- d-2 Structural unit formed of acrylic acid
- d-3 Structural unit formed of acrylic acid
- d-4 Structural unit d formed of acrylic acid -5: Structural unit formed from sodium acrylate
- Test Category 2 (Production of vinyl copolymer as component B)
- This monomer mixture aqueous solution and 10% sodium persulfate aqueous solution 24 g are simultaneously added dropwise to the reaction vessel over 4 hours to carry out a radical copolymerization reaction, and further 10% sodium persulfate aqueous solution 6 g is added dropwise over 1 hour.
- the reaction was carried out. Then, the temperature of the reaction system was kept at 60° C. and a radical copolymerization reaction was carried out for 1 hour. Next, the reaction system was cooled to room temperature, an aqueous sodium hydroxide solution was added to adjust the pH to 5, and the concentration was adjusted to 40% with distilled water to obtain a reaction mixture.
- GPC gel permeation chromatography
- This reaction mixture was designated as a vinyl copolymer (B-2).
- This monomer mixture aqueous solution and 10% sodium persulfate aqueous solution 24 g are simultaneously added dropwise to the reaction vessel over 4 hours for radical copolymerization reaction, and further 10% sodium persulfate aqueous solution 6 g is added dropwise over 1 hour.
- the reaction was carried out. Then, the temperature of the reaction system was maintained at 60° C. and a radical copolymerization reaction was carried out for 1 hour. Then, after cooling the reaction system to room temperature, an aqueous sodium hydroxide solution was added to adjust the pH to 4, and the concentration was adjusted to 40% with distilled water to obtain a reaction mixture.
- GPC gel permeation chromatography
- This reaction mixture was designated as vinyl copolymer (B-3).
- the vinyl copolymers produced above are summarized in Table 2.
- Test Category 3 Measurement of mass average molecular weight of A component and B component
- the mass average molecular weights of the component A and the component B were measured by the following method. The results are shown in Tables 1 and 2.
- Detector Differential refractometer (RI) Column: Showa Denko OHpak SB-G+SB-806M HQ+SB-806M HQ Eluent: 50 mM sodium nitrate aqueous solution Flow rate: 0.7 mL/min Column temperature: 40°C Standard material: polyethylene glycol/oxide (PEG/PEO) manufactured by Agilent
- Test Category 4 (confirmation of compatibility) With respect to the compatibility of the solution, the ratio of the component A and the component B shown in Table 4 was sufficiently agitated and mixed when the content of the vinyl copolymer of the component B was 20%, and visually measured according to the following criteria. Distilled water was used to adjust the concentration of the aqueous solution.
- Test Category 5 (Preparation of mortar as hydraulic composition) A mortar mixer conforming to the physical test method of JIS R 5201 cement was used. Using ordinary portland cement (density 3.16 g / cm 3) as a binder, using the Oi aqueous production Rikusuna (density 2.58 g / cm 3) as a fine aggregate, bentonite (reagent manufactured by Wako Pure Chemical Industries stock as clayey (Manufactured by the company) was used. An antifoaming agent (trade name AFK-2 manufactured by Takemoto Yushi Co., Ltd.) was added at a ratio of 0.005 parts by mass to 100 parts by mass of the binder, and the additive for hydraulic composition used in Test Category 4 was kneaded. The mixture was added together with water and the components were kneaded for 240 seconds under the compounding conditions shown in Table 5 to prepare a mortar. The additive and the defoaming agent were regarded as a part of water.
- the components were mixed and the following tests were conducted in an environment in which the material temperature was set to 20 ⁇ 3° C., the room temperature was set to 20 ⁇ 3° C., and the humidity was set to 60% or more.
- the evaluation of the mortar flow of the obtained mortar was carried out by setting the mortar flow without tapping as 240 ⁇ 5 mm.
- the viscosity was evaluated by using a J 14 funnel in accordance with the filling mortar fluidity test method (JSCE-F 541), and those having a short flowing time were evaluated as having low viscosity. The results are shown in Table 6. No visual separation was observed in any mortar.
- Examples 7 and 10 including the A component and the B component increase the addition rate of the additive as compared with Comparative Example 5 in which the A component is not included and only the B component is included. Without it, you can see that the flow-down time has become shorter. As compared with Comparative Example 6 in which polyacrylic acid having a large molecular weight is used, in Example 7 in which polyacrylic acid as the component A is used, the downflow time is significantly shortened without increasing the addition rate of the additive. ..
- Example 10 in which polyacrylic acid as the component A was used did not increase the addition rate of the additive, and the flow-down time was significantly shortened. I understand. Compared to Comparative Example 8 using hydroxypropylmethyl cellulose used as a thickener, Example 8 using polyacrylic acid as the component A has a significantly shorter flow-down time without increasing the addition rate of the additive. I understand that
- the additive for hydraulic composition of the present invention can be used as an additive when preparing a hydraulic composition.
Abstract
The present invention provides an additive for hydraulic compositions, which is capable of decreasing the viscosity of a hydraulic composition, while attenuating the influence of fine particle components or clayey materials contained in an aggregate. An additive for hydraulic compositions, which contains, as a component A, a polymer that has a constituent unit formed from an acrylic acid and/or a salt thereof, while having a mass average molecular weight of 1,000 or more but less than 100,000, and as a component B, a vinyl copolymer that has a constituent unit 1 and a constituent unit 2 in each molecule, with the content of the constituent unit 1 being 1-99% by mass and the content of the constituent unit 2 being 1-99% by mass; and a hydraulic composition.
Description
本発明は、水硬性組成物用添加剤に関する。更に詳細には、骨材に含まれる微粒分や粘土質の影響を緩和するとともに、水硬性組成物の粘性を低くすることが可能であり、セメント組成物などに好適に用いることができる水硬性組成物用添加剤に関する。
The present invention relates to an additive for hydraulic compositions. More specifically, it is possible to reduce the influence of fine particles and clay contained in the aggregate, and to lower the viscosity of the hydraulic composition, which can be suitably used for cement compositions and the like. It relates to an additive for a composition.
従来、モルタルやコンクリートなどの水硬性組成物に対して流動性を付与するために、その調製時に、分散剤としてリグニンスルホン酸系分散剤、ナフタレンスルホン酸系分散剤、メラミンスルホン酸系分散剤やポリカルボン酸系分散剤などが用いられている。近年では、充填性の向上や省力化、施工性の向上のために、さらに流動性を高めた水硬性組成物が使用される機会が多くなり、このような水硬性組成物が求められている。
Conventionally, in order to impart fluidity to a hydraulic composition such as mortar and concrete, at the time of its preparation, a ligninsulfonic acid-based dispersant, a naphthalenesulfonic acid-based dispersant, a melaminesulfonic acid-based dispersant as a dispersant, and Polycarboxylic acid type dispersants and the like are used. In recent years, in order to improve filling property, labor saving, and workability, hydraulic compositions having further improved fluidity are often used, and such hydraulic compositions are required. .
このような水硬性組成物を得るために種々の技術が提案されている。例えば、特許文献１においては、特定のポリカルボン酸系分散剤と、カルボン酸単量体と（メタ）アクリル酸系エステルとの共重合体を配合した混和剤を用いることにより、コンクリートに流動性と材料分離抵抗性を付与できることが提案されている。そして、特許文献１には、原料成分である、特定のポリカルボン酸系分散剤と、カルボン酸単量体と（メタ）アクリル酸系エステルとの共重合体とを組み合わせて一液型混和剤として供給され得ることが開示されている。
Various techniques have been proposed to obtain such a hydraulic composition. For example, in Patent Document 1, by using a specific polycarboxylic acid-based dispersant and an admixture in which a copolymer of a carboxylic acid monomer and a (meth)acrylic acid-based ester is blended, the fluidity of concrete is improved. It has been proposed that material separation resistance can be imparted. And, in Patent Document 1, a specific polycarboxylic acid-based dispersant, which is a raw material component, and a copolymer of a carboxylic acid monomer and a (meth)acrylic acid-based ester are combined to form a one-pack type admixture. It is disclosed that it can be supplied as.
また、特許文献２には、特定の低置換度ヒドロキシプロピルセルロースを用いることにより、高充填性および高流動性のコンクリートが得られることが提案されている。
Further, Patent Document 2 proposes that a concrete having a high filling property and a high fluidity can be obtained by using a specific low-substituted hydroxypropylcellulose.
水硬性組成物に配合される骨材として、粗骨材や細骨材などが用いられている。これらの粗骨材や細骨材として、自然作用により岩石から形成され、川、山、海、陸から産出される砂利、砂等の天然骨材や、岩石をクラッシャなどで人工的に粉砕して得られる砕石及び砕砂が用いられている。
◇Coarse aggregates and fine aggregates are used as aggregates to be added to hydraulic compositions. As these coarse aggregates and fine aggregates, natural aggregates such as gravel and sand that are formed from rocks by natural action and are produced from rivers, mountains, the sea, and land, and rocks are artificially crushed with a crusher. The crushed stone and crushed sand obtained by this are used.
良質な天然骨材が枯渇しつつある中で資源保護の観点や、洗浄の際、環境に与える影響を配慮して、品質として許される範囲内において、天然骨材に付着する微粒分や粘土質を洗い落としたりしないままで使用する場合がある。
While high-quality natural aggregates are being depleted, fine particles and clay that adhere to natural aggregates should be adhered to within the allowable range of quality in consideration of resource protection and the impact on the environment during cleaning. It may be used without washing it off.
また、岩石を人工的に粉砕して砕石及び砕砂を製造する際に発生する微粒分や粘土質が付着したままの砕石及び砕砂を使用する場合もある。
Also, crushed stone and crushed sand with fine particles or clay particles generated when artificially crushing rock to produce crushed stone and crushed sand may be used.
これらの微粒分や粘土質が骨材に付着したままであると、分散剤の添加量が多くなってしまうという問題がある。また、骨材、結合材、分散剤及び消泡剤等が配合された水硬性組成物の粘性が上がってしまうという問題もある。
If these fine particles and clay remain attached to the aggregate, there is a problem that the amount of dispersant added will increase. There is also a problem that the viscosity of a hydraulic composition containing an aggregate, a binder, a dispersant, an antifoaming agent and the like increases.
特許文献１、２に開示された技術では、これらの問題を解決することができなかった。従って、本発明が解決しようとする課題は、骨材に付着した微粒分や粘土質等を洗い落したりしないままであっても、骨材に含まれる微粒分や粘土質の影響を緩和するとともに、水硬性組成物の粘性を低くすることが可能な水硬性組成物用添加剤を提供することにある。
The technologies disclosed in Patent Documents 1 and 2 could not solve these problems. Therefore, the problem to be solved by the present invention is to mitigate the influence of the fine particles and clay contained in the aggregate even if the fine particles and the clay attached to the aggregate are not washed off. Another object of the present invention is to provide an additive for a hydraulic composition, which can reduce the viscosity of the hydraulic composition.
本発明者らは、前記の課題を解決すべく研究した結果、特定の重合体を有する水硬性組成物用添加剤を用いるのが正しく好適であることを見出した。本発明によれば、以下の水硬性組成物用添加剤が提供される。
As a result of research to solve the above problems, the present inventors have found that it is correct and preferable to use an additive for hydraulic composition having a specific polymer. According to the present invention, the following additives for hydraulic compositions are provided.
［１］ 下記のＡ成分と、下記のＢ成分とを含有する水硬性組成物用添加剤。
Ａ成分：アクリル酸及び／又はその塩から形成された構成単位を有し、その質量平均分子量が１０００以上１０００００未満である重合体；
Ｂ成分：分子中に下記の構成単位１及び構成単位２を有し、かつ、構成単位１を１～９９質量％含有し、及び構成単位２を１～９９質量％含有するビニル共重合体；
構成単位１：下記の単量体１から形成された構成単位、
構成単位２：分子中にビニル基を有するカルボン酸単量体から形成された構成単位、
単量体１：下記の式（１）で示される不飽和（ポリ）アルキレングリコール：
（式（１）中、Ｒ１、Ｒ２及びＲ３は同一又は異なり、水素原子、メチル基及び－（ＣＨ２）ｒＣＯＯＭで示される有機基（但し、Ｒ１、Ｒ２及びＲ３のうちの少なくとも１つは水素原子又はメチル基を表す）から選ばれる少なくとも１種を表し、Ｒ４は水素原子又は炭素数１～２０の炭化水素基を表し、Ｒ５Ｏは炭素数２～４のオキシアルキレン基の１種又は２種以上を表し、ｐは０～５の整数を表し、ｑは０又は１を表し、ｍは１～３００の整数を表し、ｒは０～２の整数を表し、Ｍは水素原子又は金属原子を表す。）
[1] A hydraulic composition additive containing the following component A and the following component B.
Component A: a polymer having a structural unit formed from acrylic acid and/or a salt thereof, and having a mass average molecular weight of 1,000 or more and less than 100,000;
Component B: A vinyl copolymer having the following structural unit 1 and structural unit 2 in the molecule, containing 1 to 99% by mass of structural unit 1, and 1 to 99% by mass of structural unit 2.
Structural unit 1: a structural unit formed from the following monomer 1.
Structural unit 2: a structural unit formed from a carboxylic acid monomer having a vinyl group in the molecule,
Monomer 1: unsaturated (poly)alkylene glycol represented by the following formula (1):
(In the formula (1), R 1 , R 2 and R 3 are the same or different and each represents a hydrogen atom, a methyl group and an organic group represented by —(CH 2 )rCOOM (provided that, among R 1 , R 2 and R 3 , Represents at least one selected from a hydrogen atom or a methyl group), R 4 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R 5 O represents a hydrocarbon group having 2 to 4 carbon atoms. Represents one or more oxyalkylene groups, p represents an integer of 0 to 5, q represents 0 or 1, m represents an integer of 1 to 300, and r represents an integer of 0 to 2. , M represents a hydrogen atom or a metal atom.)
Ａ成分：アクリル酸及び／又はその塩から形成された構成単位を有し、その質量平均分子量が１０００以上１０００００未満である重合体；
Ｂ成分：分子中に下記の構成単位１及び構成単位２を有し、かつ、構成単位１を１～９９質量％含有し、及び構成単位２を１～９９質量％含有するビニル共重合体；
構成単位１：下記の単量体１から形成された構成単位、
構成単位２：分子中にビニル基を有するカルボン酸単量体から形成された構成単位、
単量体１：下記の式（１）で示される不飽和（ポリ）アルキレングリコール：
Component A: a polymer having a structural unit formed from acrylic acid and/or a salt thereof, and having a mass average molecular weight of 1,000 or more and less than 100,000;
Component B: A vinyl copolymer having the following structural unit 1 and structural unit 2 in the molecule, containing 1 to 99% by mass of structural unit 1, and 1 to 99% by mass of structural unit 2.
Structural unit 1: a structural unit formed from the following monomer 1.
Structural unit 2: a structural unit formed from a carboxylic acid monomer having a vinyl group in the molecule,
Monomer 1: unsaturated (poly)alkylene glycol represented by the following formula (1):
［２］ 前記Ｂ成分が、更に、下記の構成単位３を０～３０質量％含有するビニル共重合体である前記［１］に記載の水硬性組成物用添加剤。
構成単位３：前記単量体１及び前記カルボン酸単量体と共重合可能な単量体３から形成された構成単位 [2] The additive for hydraulic composition according to the above [1], wherein the component B is a vinyl copolymer further containing 0 to 30% by mass of the following structural unit 3.
Structural unit 3: Structural unit formed from the monomer 1 and the monomer 3 copolymerizable with the carboxylic acid monomer
構成単位３：前記単量体１及び前記カルボン酸単量体と共重合可能な単量体３から形成された構成単位 [2] The additive for hydraulic composition according to the above [1], wherein the component B is a vinyl copolymer further containing 0 to 30% by mass of the following structural unit 3.
Structural unit 3: Structural unit formed from the monomer 1 and the monomer 3 copolymerizable with the carboxylic acid monomer
［３］ 前記Ｂ成分に対する、前記Ａ成分の質量％が０．１～５質量％である前記［１］又は［２］に記載の水硬性組成物用添加剤。
[3] The additive for hydraulic composition according to the above [1] or [2], wherein the mass% of the A component is 0.1 to 5 mass% with respect to the B component.
［４］ 前記Ａ成分の質量平均分子量が１０００以上１００００未満である前記［１］～［３］のいずれかに記載の水硬性組成物用添加剤。
[4] The additive for hydraulic compositions according to any one of [1] to [3], wherein the mass average molecular weight of the component A is 1,000 or more and less than 10,000.
［５］ 前記［１］～［４］のいずれかに記載の水硬性組成物用添加剤を含有する水硬性組成物。
[5] A hydraulic composition containing the additive for hydraulic compositions according to any one of [1] to [4] above.
［６］ 更に、結合材を含有する前記［５］に記載の水硬性組成物。
[6] The hydraulic composition according to the above [5], which further contains a binder.
［７］ 前記結合材１００質量部に対する、前記Ａ成分と前記Ｂ成分の合計の質量部が０．１～２質量部である前記［６］に記載の水硬性組成物。
[7] The hydraulic composition according to the above [6], wherein the total amount by mass of the component A and the component B is 0.1 to 2 parts by mass relative to 100 parts by mass of the binder.
本発明の水硬性組成物用添加剤によれば、骨材に付着した微粒分や粘土質等を洗い落したりしないままであっても、微粒分や粘土質の影響を緩和できるとともに、更に水硬性組成物の粘性を低くできるという効果がある。
According to the additive for a hydraulic composition of the present invention, even if the fine particles and clay particles attached to the aggregate are not washed off, the effect of the fine particles and clay particles can be mitigated, and further water There is an effect that the viscosity of the hard composition can be lowered.
以下、本発明の実施形態について説明する。しかし、本発明は以下の実施形態に限定されるものではない。したがって、本発明の趣旨を逸脱しない範囲で、当業者の通常の知識に基づいて、以下の実施形態に対し適宜変更、改良等が加えられ得ることが理解されるべきである。なお、以下の実施例等において、別に記載しない限り、％は質量％を、また部は質量部を意味する。
An embodiment of the present invention will be described below. However, the present invention is not limited to the following embodiments. Therefore, it should be understood that modifications and improvements can be appropriately made to the following embodiments based on ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. In the following examples and the like, unless otherwise stated,% means% by mass, and part means part by mass.
本実施形態の水硬性組成物用添加剤は、Ａ成分と、Ｂ成分とを含有する水硬性組成物用添加剤である。
The additive for hydraulic composition of the present embodiment is an additive for hydraulic composition containing component A and component B.
本実施形態の水硬性組成物用添加剤に供するＡ成分は、アクリル酸及び／又はその塩から形成された構成単位を有する重合体である。ここで、アクリル酸塩の種類は、特に制限されるものではないが、例えば、ナトリウム塩やカリウム塩等のアルカリ金属塩、カルシウム塩やマグネシウム塩等のアルカリ土類金属塩、アンモニウム塩、ジエタノールアミン塩やトリエタノールアミン塩等のアミン塩等が挙げられる。取扱いやすさや入手のしやすさの観点から、好ましくはナトリウム塩、アンモニウム塩であり、より好ましくはナトリウム塩である。また、アクリル酸及び／又はその塩は、１種のみであってもよいし、２種以上であってもよい。・
The component A used for the additive for hydraulic composition of the present embodiment is a polymer having a structural unit formed from acrylic acid and/or its salt. Here, the type of the acrylate salt is not particularly limited, but examples thereof include alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as calcium salts and magnesium salts, ammonium salts, and diethanolamine salts. And amine salts such as triethanolamine salt. From the viewpoint of easy handling and availability, sodium salts and ammonium salts are preferable, and sodium salts are more preferable. Moreover, the acrylic acid and/or its salt may be only one kind, or may be two or more kinds.・
本実施形態の水硬性組成物用添加剤に供するＡ成分の重合体は、質量平均分子量が１０００以上１０００００未満であり、好ましくは、１０００以上７００００未満であり、より好ましくは、１０００以上５００００未満であり、更に好ましくは１０００以上３００００未満である。更により好ましくは１０００以上１００００未満である。
The polymer of the component A provided for the additive for hydraulic composition of the present embodiment has a mass average molecular weight of 1,000 or more and less than 100,000, preferably 1,000 or more and less than 70,000, more preferably 1,000 or more and less than 50,000. Yes, and more preferably 1,000 or more and less than 30,000. Even more preferably, it is 1,000 or more and less than 10,000.
本実施形態の水硬性組成物用添加剤に供するＢ成分は、分子中に構成単位１及び構成単位２を有するビニル共重合体である。
The component B used in the additive for hydraulic composition of the present embodiment is a vinyl copolymer having the structural unit 1 and the structural unit 2 in the molecule.
構成単位１は、単量体１から形成される。単量体１は、下記式（１）で表される不飽和（ポリ）アルキレングリコールである。
The structural unit 1 is formed from the monomer 1. The monomer 1 is an unsaturated (poly)alkylene glycol represented by the following formula (1).
式（１）中、Ｒ１、Ｒ２及びＲ３は同一又は異なり、水素原子、メチル基及び－（ＣＨ２）ｒＣＯＯＭで示される有機基から選ばれる少なくとも１種を表し、但し、Ｒ１、Ｒ２及びＲ３のうちの少なくとも１つは水素原子又はメチル基を表す。Ｒ４は水素原子又は炭素数１～２０の炭化水素基を表す。このような炭化水素基として、メチル基、エチル基、プロピル基、及びブチル基等が挙げられる。Ｒ５Ｏは炭素数２～４のオキシアルキレン基の１種又は２種以上を表す。このようなオキシアルキレン基として、オキシエチレン基、オキシプロピレン基等が挙げられる。２種以上のオキシアルキレン基の場合、ランダム付加、ブロック付加、交互付加等のいずれの付加形態であってもよい。ｐは０～５の整数を表し、ｑは０又は１を表し、ｍは１～３００の整数を表し、ｒは０～２の整数を表し、Ｍは水素原子又は金属原子を表す。
In the formula (1), R 1 , R 2 and R 3 are the same or different and each represents at least one selected from a hydrogen atom, a methyl group and an organic group represented by —(CH 2 )rCOOM, provided that R 1 , At least one of R 2 and R 3 represents a hydrogen atom or a methyl group. R 4 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Examples of such a hydrocarbon group include a methyl group, an ethyl group, a propyl group, and a butyl group. R 5 O represents one or more oxyalkylene groups having 2 to 4 carbon atoms. Examples of such an oxyalkylene group include an oxyethylene group and an oxypropylene group. In the case of two or more kinds of oxyalkylene groups, any addition form such as random addition, block addition, and alternate addition may be used. p represents an integer of 0 to 5, q represents 0 or 1, m represents an integer of 1 to 300, r represents an integer of 0 to 2, and M represents a hydrogen atom or a metal atom.
このような単量体１としては、例えば、α－ビニル－ω－ヒドロキシ（ポリ）オキシブチレン（ポリ）オキシエチレン、α－アリル－ω－メトキシ－（ポリ）オキシエチレン、α－アリル－ω－メトキシ－（ポリ）オキシエチレン（ポリ）オキシプロピレン、α－アリル－ω－ヒドロキシ－（ポリ）オキシエチレン、α－アリル－ω－ヒドロキシ－（ポリ）オキシエチレン（ポリ）オキシプロピレン、α－メタリル－ω－ヒドロキシ－（ポリ）オキシエチレン、α－メタリル－ω－メトキシ－（ポリ）オキシエチレン、α－メタリル－ω－ヒドロキシ－（ポリ）オキシエチレン（ポリ）オキシプロピレン、α－メタリル－ω－アセチル－（ポリ）オキシエチレン、α－（３－メチル－３－ブテニル）－ω－ヒドロキシ－（ポリ）オキシエチレン、α－（３－メチル－３－ブテニル）－ω－ブトキシ－（ポリ）オキシエチレン、α－（３－メチル－３－ブテニル）－ω－ヒドロキシ－（ポリ）オキシエチレン（ポリ）オキシプロピレン、α－（３－メチル－３－ブテニル）－ω－アセチル－（ポリ）オキシエチレン（ポリ）オキシプロピレン、α－アクリロイル－ω－ヒドロキシ－（ポリ）オキシエチレン、α－アクリロイル－ω－メトキシ－（ポリ）オキシエチレン、α－アクリロイル－ω－ブトキシ－（ポリ）オキシエチレン、α－アクリロイル－ω－メトキシ－（ポリ）オキシエチレン（ポリ）オキシプロピレン、α－メタクリロイル－ω－ヒドロキシ－（ポリ）オキシエチレン、α－メタクリロイル－ω－メトキシ－（ポリ）オキシエチレン、α－メタクリロイル－ω－ブトキシ－（ポリ）オキシエチレン、α－アクリロイル－ω－メトキシ－（ポリ）オキシエチレン（ポリ）オキシプロピレン、α－メタクリロイル－ω－ヒドロキシ－（ポリ）オキシエチレン（ポリ）オキシプロピレン、α－メタクリロイル－ω－アセチル－（ポリ）オキシエチレン（ポリ）オキシプロピレン、マレイン酸やフマル酸、イタコン酸等の不飽和ジカルボン酸と（ポリ）オキシエチレンとのモノエステル、マレイン酸やフマル酸、イタコン酸等の不飽和ジカルボン酸と（ポリ）オキシエチレン（ポリ）オキシプロピレンとのモノエステルが挙げられる。
Examples of such a monomer 1 include α-vinyl-ω-hydroxy(poly)oxybutylene(poly)oxyethylene, α-allyl-ω-methoxy-(poly)oxyethylene, α-allyl-ω- Methoxy-(poly)oxyethylene (poly)oxypropylene, α-allyl-ω-hydroxy-(poly)oxyethylene, α-allyl-ω-hydroxy-(poly)oxyethylene (poly)oxypropylene, α-methallyl- ω-hydroxy-(poly)oxyethylene, α-methallyl-ω-methoxy-(poly)oxyethylene, α-methallyl-ω-hydroxy-(poly)oxyethylene(poly)oxypropylene, α-methallyl-ω-acetyl -(Poly)oxyethylene, α-(3-methyl-3-butenyl)-ω-hydroxy-(poly)oxyethylene, α-(3-methyl-3-butenyl)-ω-butoxy-(poly)oxyethylene , Α-(3-methyl-3-butenyl)-ω-hydroxy-(poly)oxyethylene (poly)oxypropylene, α-(3-methyl-3-butenyl)-ω-acetyl-(poly)oxyethylene( Poly)oxypropylene, α-acryloyl-ω-hydroxy-(poly)oxyethylene, α-acryloyl-ω-methoxy-(poly)oxyethylene, α-acryloyl-ω-butoxy-(poly)oxyethylene, α-acryloyl -Ω-methoxy-(poly)oxyethylene (poly)oxypropylene, α-methacryloyl-ω-hydroxy-(poly)oxyethylene, α-methacryloyl-ω-methoxy-(poly)oxyethylene, α-methacryloyl-ω- Butoxy-(poly)oxyethylene, α-acryloyl-ω-methoxy-(poly)oxyethylene(poly)oxypropylene, α-methacryloyl-ω-hydroxy-(poly)oxyethylene(poly)oxypropylene, α-methacryloyl- ω-acetyl-(poly)oxyethylene (poly)oxypropylene, monoesters of unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid with (poly)oxyethylene, maleic acid, fumaric acid, itaconic acid etc. Mention may be made of monoesters of unsaturated dicarboxylic acids and (poly)oxyethylene (poly)oxypropylene.
構成単位２は、カルボン酸単量体から形成される。ここでのカルボン酸単量体とはエステル基やアミド基を持たない単量体である。カルボン酸単量体は、その分子中にビニル基を有する。このようなカルボン酸単量体として、例えば、（メタ）アクリル酸、クロトン酸、（無水）マレイン酸、（無水）イタコン酸、フマル酸及びこれらの塩などが挙げられる。塩としては、特に制限するものではないが、例えば、ナトリウム塩、カリウム塩などのアルカリ金属塩、カルシウム塩、マグネシウム塩などのアルカリ土類金属塩、アンモニウム塩、ジエタノールアミン塩、トリエタノールアミン塩等のアミン塩などが挙げられる。なかでもナトリウム塩とカルシウム塩が好ましい。
Structural unit 2 is formed from a carboxylic acid monomer. The carboxylic acid monomer here is a monomer having no ester group or amide group. The carboxylic acid monomer has a vinyl group in its molecule. Examples of such a carboxylic acid monomer include (meth)acrylic acid, crotonic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, fumaric acid, and salts thereof. The salt is not particularly limited, but examples thereof include alkali metal salts such as sodium salt and potassium salt, alkaline earth metal salts such as calcium salt and magnesium salt, ammonium salt, diethanolamine salt, triethanolamine salt and the like. Examples include amine salts. Among them, sodium salt and calcium salt are preferable.
本実施形態の水硬性組成物用添加剤に供するＢ成分であるビニル共重合体は、更に分子中に、任意の構成単位として、構成単位３を含んでいても良い。構成単位３は、単量体１及びカルボン酸単量体と共重合可能な単量体３から形成されてもよい。
The vinyl copolymer, which is the B component used in the additive for hydraulic composition of the present embodiment, may further include the structural unit 3 as an arbitrary structural unit in the molecule. The structural unit 3 may be formed from the monomer 1 and the monomer 3 copolymerizable with the carboxylic acid monomer.
単量体３は、単量体１及びカルボン酸単量体と共重合可能であれば特に制限されないが、例えば、アクリル酸メチル、メチルメタクリレート、ブチルアクリレート等のアルキル（メタ）アクリレート系単量体や、（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド等の不飽和アミド類、（メタ）アクリロニトリル等の不飽和シアン類、マレイン酸やフマル酸等の不飽和ジカルボン酸と炭素数１～２２のアルキル基若しくはアルケニル基のアルコールとのモノエステルや、マレイン酸やフマル酸等の不飽和ジカルボン酸と（ポリ）アルキレングリコールや炭素数１～２２のアルキル基若しくはアルケニル基のアルコールとのジエステルとなる不飽和ジカルボン酸ジエステル類、不飽和カルボン酸や不飽和ジカルボン酸と炭素数が１～２２であるアミンとのモノアミドやジアミドとなるアミド単量体類、不飽和カルボン酸や不飽和ジカルボン酸と炭素数が１～２２であるアミンとのモノアミドやジアミドとなるアミド単量体類、アルキルジカルボン酸とポリエチレンポリアミンを縮合させたものの活性水素を持つ窒素原子にエチレンオキシドやプロピレンオキシドを付加させたものと（メタ）アクリル酸との反応物や、不飽和カルボン酸や不飽和ジカルボン酸と炭素数が１～２２であるアミンとのモノアミドやジアミドとなるアミド単量体類、アルキルジカルボン酸とポリエチレンポリアミンを縮合させたものの活性水素を持つ窒素原子にエチレンオキシドやプロピレンオキシドを付加させたものとグリシジル（メタ）アクリレートと反応させたものである、ポリアミドポリアミン単量体類、（メタ）アリルスルホン酸やビニルスルホン酸及びそれらの塩などからなるスルホン酸系単量体類、リン酸２－（メタクリロイルオキシ）エチルやリン酸－ビス［２―（メタクリロイルオキシ）エチル］およびそれらの塩などからなるリン酸系単量体類等が挙げられる。
The monomer 3 is not particularly limited as long as it can be copolymerized with the monomer 1 and the carboxylic acid monomer, and examples thereof include alkyl (meth)acrylate-based monomers such as methyl acrylate, methyl methacrylate and butyl acrylate. And unsaturated amides such as (meth)acrylamide and N,N-dimethyl (meth)acrylamide, unsaturated cyanides such as (meth)acrylonitrile, unsaturated dicarboxylic acids such as maleic acid and fumaric acid, and 1 to 1 carbon atoms. A monoester of an alkyl or alkenyl group of 22 with an alcohol, or a diester of an unsaturated dicarboxylic acid such as maleic acid or fumaric acid with a (poly)alkylene glycol or an alcohol of an alkyl or alkenyl group of 1 to 22 carbon atoms Unsaturated dicarboxylic acid diesters, unsaturated carboxylic acids, and monoamides of unsaturated carboxylic acids and unsaturated dicarboxylic acids with amines having 1 to 22 carbon atoms, amide monomers to be diamides, unsaturated carboxylic acids and unsaturated dicarboxylic acids Amide monomers that become monoamides or diamides with amines having 1 to 22 carbon atoms, those obtained by adding ethylene oxide or propylene oxide to the nitrogen atom having active hydrogen, which is obtained by condensing an alkyldicarboxylic acid and polyethylene polyamine. Reaction products with (meth)acrylic acid, amide monomers that form monoamides or diamides of unsaturated carboxylic acids or unsaturated dicarboxylic acids with amines having 1 to 22 carbon atoms, alkyldicarboxylic acids and polyethylene polyamines Polyamide polyamine monomers, (meth)allyl sulfonic acid or vinyl sulfone, which are obtained by reacting glycidyl (meth)acrylate with ethylene oxide or propylene oxide added to a condensed nitrogen atom having active hydrogen. Sulfonic acid type monomers consisting of acids and salts thereof, 2-(methacryloyloxy)ethyl phosphate and bis[2-(methacryloyloxy)ethyl]phosphate and phosphoric acid type monolayers consisting of salts thereof Examples include monomers.
本実施形態の水硬性組成物用添加剤に供するＢ成分においては、構成単位１を１～９９質量％含み、７０～９９質量％含むのが好ましく、７５～９９質量％含むのがより好ましく、８０～９９質量％含むのが更に好ましく、構成単位２を１～９９質量％含み、１～３０質量％含むのが好ましく、２５～９９質量％含むのがより好ましく、１～２０質量％含むのが更に好ましい。また、本実施形態の水硬性組成物用添加剤に供するＢ成分においては、構成単位３を０～３０質量％含むのが好ましく、０～２０質量％含むのがより好ましく、０～１０質量％含むのが更に好ましく、０～５質量％含むのが更により好ましい。
In the B component used for the additive for hydraulic composition of the present embodiment, the constituent unit 1 is contained in an amount of 1 to 99% by mass, preferably 70 to 99% by mass, more preferably 75 to 99% by mass, 80 to 99% by mass is more preferable, 1 to 99% by mass of the constituent unit 2 is contained, 1 to 30% by mass is preferable, 25 to 99% by mass is more preferable, and 1 to 20% by mass is contained. Is more preferable. Further, in the B component used for the additive for hydraulic composition of the present embodiment, the structural unit 3 is preferably contained in an amount of 0 to 30% by mass, more preferably 0 to 20% by mass, and 0 to 10% by mass. It is more preferred that the content is 0 to 5% by mass, and even more preferred that the content is 0 to 5% by mass.
本実施形態の水硬性組成物用添加剤に供するＢ成分においては、構成単位１、構成単位２の合計が８０質量％以上であることが好ましく、８５質量％以上がより好ましく、９０質量％以上であることが更に好ましく、９５質量％以上であることが更により好ましい。
In the component B used for the additive for hydraulic composition of the present embodiment, the total of the structural unit 1 and the structural unit 2 is preferably 80% by mass or more, more preferably 85% by mass or more, and 90% by mass or more. Is more preferable, and even more preferably 95% by mass or more.
本実施形態の水硬性組成物用添加剤に供するＢ成分の質量平均分子量は、ゲルパーミエーションクロマトグラフィーで測定することができ、好ましくはポリエチレングリコール換算で２０００～５０００００であり、より好ましくは５０００～２０００００であり、更に好ましくは１００００～１０００００である。
The mass average molecular weight of the component B used in the additive for hydraulic composition of the present embodiment can be measured by gel permeation chromatography, and is preferably 2000 to 500000 in terms of polyethylene glycol, more preferably 5000 to It is 200,000, and more preferably 10,000 to 100,000.
このようなＢ成分は、公知のラジカル重合反応により得ることができる。例えば、各種方法で製造することができる。これには、溶媒に水を使用したラジカル重合、溶媒に有機溶媒を使用したラジカル重合、無溶媒のラジカル重合による方法が挙げられる。ラジカル重合における反応温度は、好ましく０～１２０℃であり、より好ましくは２０～１００℃であり、更に好ましくは５０～９０℃である。ラジカル重合に使用するラジカル重合開始剤は、過酸化水素、過硫酸アンモニウム、過硫酸ナトリウム、過硫酸カリウム等の過酸化物や、２，２－アゾビス（２－アミジノプロパン）二塩酸塩、２，２－アゾビス（イソブチロニトリル）等のアゾ系化合物が挙げられ、重合反応温度下において分解し、ラジカル発生するものであれば、その種類は特に制限されない。これらは、亜硫酸塩やＬ－アスコルビン酸等の還元性物質、更にはアミン等と組み合わせ、レドックス開始剤として使用することもできる。得られるＢ成分の質量平均分子量を所望の範囲とするため、２－メルカプトエタノール、２－メルカプトプロピオン酸、３－メルカプトプロピオン酸、チオグリコール酸、チオグリセリン、チオリンゴ酸等の連鎖移動剤を使用することもできる。これらのラジカル重合開始剤や還元性物質、連鎖移動剤は、それぞれ単独で使用しても２種類以上を併用してもよい。反応系内の圧力は特に限定されないが、常圧が好ましい。
Such component B can be obtained by a known radical polymerization reaction. For example, it can be manufactured by various methods. Examples of such methods include radical polymerization using water as a solvent, radical polymerization using an organic solvent as a solvent, and solvent-free radical polymerization. The reaction temperature in radical polymerization is preferably 0 to 120°C, more preferably 20 to 100°C, and further preferably 50 to 90°C. Radical polymerization initiators used for radical polymerization include peroxides such as hydrogen peroxide, ammonium persulfate, sodium persulfate and potassium persulfate, 2,2-azobis(2-amidinopropane) dihydrochloride, 2,2 -Azo-based compounds such as azobis(isobutyronitrile) are mentioned, and the kind thereof is not particularly limited as long as it decomposes at the polymerization reaction temperature and generates radicals. These can be used as a redox initiator in combination with a reducing substance such as sulfite or L-ascorbic acid, and further with an amine or the like. A chain transfer agent such as 2-mercaptoethanol, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thioglycolic acid, thioglycerin, or thiomalic acid is used to adjust the mass average molecular weight of the resulting component B to a desired range. You can also These radical polymerization initiators, reducing substances, and chain transfer agents may be used alone or in combination of two or more kinds. The pressure in the reaction system is not particularly limited, but normal pressure is preferable.
本実施形態の水硬性組成物用添加剤においては、Ａ成分とＢ成分の濃度は特に制限されないが、Ｂ成分に対する、Ａ成分の質量％が０．１～５質量％であるのが好ましく、０．５～４質量％であるのがより好ましい。
In the additive for hydraulic composition of the present embodiment, the concentrations of the A component and the B component are not particularly limited, but the mass% of the A component with respect to the B component is preferably 0.1 to 5 mass %, It is more preferably 0.5 to 4% by mass.
次に、本実施形態の水硬性組成物について説明する。本実施形態の水硬性組成物は、本実施形態の水硬性組成物用添加剤を含む。
Next, the hydraulic composition of the present embodiment will be described. The hydraulic composition of the present embodiment contains the additive for hydraulic composition of the present embodiment.
水硬性組成物用添加剤の水硬性組成物に対する添加方法は、Ａ成分とＢ成分とをそれぞれ独立して添加してもよく、また同時に添加してもよい。Ａ成分及びＢ成分は、粉末として水硬性組成物スラリーに添加してもよく、また、Ａ成分及びＢ成分を液体の収縮低減剤や液体の消泡剤等に分散させた状態又は溶解させた状態で水硬性組成物スラリーに添加してもよく、更に、Ａ成分及びＢ成分を水に溶解させた状態で水硬性組成物スラリーに添加してもよい。
As a method of adding the additive for hydraulic composition to the hydraulic composition, the component A and the component B may be added independently or at the same time. The components A and B may be added as powders to the hydraulic composition slurry, or the components A and B may be dispersed or dissolved in a liquid shrinkage reducing agent, a liquid defoaming agent, or the like. In the state, it may be added to the hydraulic composition slurry, and further, the components A and B may be added to the hydraulic composition slurry in a state of being dissolved in water.
なお、Ｂ成分であるビニル共重合体を水溶液として用いる場合は、Ａ成分とＢ成分との相溶性の観点から、Ｂ成分の１質量％水溶液のｐＨが好ましくは２～７であり、より好ましくは２～６であり、更に好ましくは２～５である。
When the vinyl copolymer as the component B is used as an aqueous solution, the pH of the 1 mass% aqueous solution of the component B is preferably 2 to 7, and more preferably from the viewpoint of the compatibility between the component A and the component B. Is 2 to 6, and more preferably 2 to 5.
本実施形態の水硬性組成物は以上説明したような本実施形態の水硬性組成物用添加剤を使用して調製したものであり、セメントペースト、モルタル、コンクリート等のセメント組成物であることが好ましい。セメント組成物は、結合材として、少なくともセメントを使用したものであるが、セメントを単独で使用してもよく、また、セメントとポゾラン物質や潜在水硬性をもつ微粉末混和材料を併用してもよい。このようなセメントとしては、普通ポルトランドセメント、早強ポルトランドセメント、中庸熱ポルトランドセメント、低熱ポルトランドセメント等の各種ポルトランドセメント、高炉セメント、フライアッシュセメント、シリカフュームセメント等の各種混合セメントが挙げられる。また、微粉末混和材料としては、高炉スラグ微粉末、シリカフューム、フライアッシュ等が挙げられる。
The hydraulic composition of the present embodiment is prepared using the additive for hydraulic composition of the present embodiment as described above, cement paste, mortar, it is a cement composition such as concrete. preferable. The cement composition is one in which at least cement is used as the binder, but the cement may be used alone, or the cement and the pozzolanic substance or a fine powder admixture having latent hydraulicity may be used in combination. Good. Examples of such cements include various Portland cements such as normal Portland cement, early-strength Portland cement, moderate heat Portland cement, and low heat Portland cement, and various mixed cements such as blast furnace cement, fly ash cement, and silica fume cement. Examples of the fine powder admixture include blast furnace slag fine powder, silica fume and fly ash.
本実施形態の水硬性組成物は、骨材を含むことも好ましい。骨材としては、細骨材や粗骨材などの任意の適切な骨材を採用し得る。このような骨材のうち、細骨材としては、川砂、山砂、陸砂、珪砂、砕砂、高炉スラグ細骨材などが挙げられ、粗骨材としては、川砂利、山砂利、陸砂利、砕石、高炉スラグ粗骨材などが挙げられる。
The hydraulic composition of the present embodiment also preferably contains an aggregate. Any appropriate aggregate such as fine aggregate or coarse aggregate can be adopted as the aggregate. Among such aggregates, fine aggregates include river sand, mountain sand, land sand, silica sand, crushed sand, blast furnace slag fine aggregate, and coarse aggregates include river gravel, mountain gravel, and land gravel. , Crushed stone, blast furnace slag coarse aggregate and the like.
骨材には、微粒分や粘土質が付着し、微粒分や粘土質を洗い落としたりしないままで使用した場合、水硬性組成物中に微粒分や粘土質が含まれるが、本実施形態の水硬性組成物は、これらの微粒分や粘土質の影響が緩和されるとともに、水硬性組成物の粘性を低くすることができる。
The aggregate has fine particles and clay, and when used without washing or removing fine particles and clay, the hydraulic composition contains fine particles and clay, but the water of the present embodiment In the hardenable composition, the effects of these fine particles and clay are alleviated, and the viscosity of the hydraulically hardened composition can be lowered.
本実施形態の水硬性組成物においては、結合材１００質量部に対する、Ａ成分とＢ成分の合計の質量部が０．１～２質量部であるのが好ましく、０．１～１．５質量部であるのがより好ましく、０．１～１質量部であるのが更に好ましい。
In the hydraulic composition of the present embodiment, it is preferable that the total amount of the components A and B is 0.1 to 2 parts by weight, and 0.1 to 1.5 parts by weight, based on 100 parts by weight of the binder. More preferably, it is 0.1 to 1 part by mass.
本実施形態の水硬性組成物においては、粘土質の流動性への影響を受けやすい水結合材比３０～６０％で使用されることが好ましい。なお、水結合材比とは、水硬性組成物中のセメントなどの結合材１００質量部に対する水の質量部であり、水が５０質量部となる場合は水結合材比が５０％となる。
In the hydraulic composition of the present embodiment, it is preferable to use the water binder ratio of 30 to 60%, which is easily affected by the fluidity of clay. The water binder ratio is a mass part of water relative to 100 mass parts of a binder such as cement in the hydraulic composition, and when the water content is 50 mass parts, the water binder ratio is 50%.
本実施形態の水硬性組成物は、効果が損なわれない範囲内で、適宜、例えば、陰イオン界面活性剤からなるＡＥ調整剤、例えば、オキシアルキレン系の消泡剤、例えば、オキシカルボン酸塩からなる凝結遅延剤、例えば、アルカノールアミンからなる硬化促進剤、例えば、ポリオキシアルキレンアルキルエーテルからなる乾燥収縮低減剤、例えば、イソチアゾリン系化合物からなる防腐剤、例えば、高級脂肪酸誘導体からなる防水剤、例えば、亜硝酸塩からなる防錆剤等を含有させることができる。
The hydraulic composition of the present embodiment is, for example, an AE modifier composed of an anionic surfactant, for example, an oxyalkylene antifoaming agent, for example, an oxycarboxylic acid salt, as long as the effect is not impaired. A setting retarder consisting of, for example, a curing accelerator consisting of an alkanolamine, for example a drying shrinkage reducing agent consisting of a polyoxyalkylene alkyl ether, for example an antiseptic consisting of an isothiazoline compound, for example a waterproofing agent consisting of a higher fatty acid derivative, For example, a rust preventive agent composed of nitrite can be contained.
試験区分１（Ａ成分としてのアクリル酸及び／又はその塩の重合体）
用いたアクリル酸及び／又はその塩の重合体を表１にまとめて示す。 Test Category 1 (polymer of acrylic acid and/or its salt as component A)
The polymers of acrylic acid and/or its salt used are summarized in Table 1.
用いたアクリル酸及び／又はその塩の重合体を表１にまとめて示す。 Test Category 1 (polymer of acrylic acid and/or its salt as component A)
The polymers of acrylic acid and/or its salt used are summarized in Table 1.
表１において、
Ａ－１：ポリアクリル酸ナトリウム（東亞合成株式会社製アロンＴ－２１０）
Ａ－２：ポリアクリル酸（和光純薬工業株式会社製ポリアクリル酸５，０００）
Ａ－３：ポリアクリル酸（和光純薬工業株式会社製ポリアクリル酸２５，０００）
Ａｒ－１：ポリアクリル酸（和光純薬工業株式会社製ポリアクリル酸１，０００，０００）
Ａｒ－２：ポリアクリル酸ナトリウム（東亞合成株式会社製アロンＡ－２０Ｐ－Ｘ）
Ａｒ－３：ヒドロキシプロピルメチルセルロース（信越化学工業社製メトローズＨｉ９０ＳＨ１０００００）
ｄ－１：アクリル酸ナトリウムから形成された構成単位
ｄ－２：アクリル酸から形成された構成単位
ｄ－３：アクリル酸から形成された構成単位
ｄ－４：アクリル酸から形成された構成単位
ｄ－５：アクリル酸ナトリウムから形成された構成単位 In Table 1,
A-1: Sodium polyacrylate (Aaron T-210 manufactured by Toagosei Co., Ltd.)
A-2: Polyacrylic acid (polyacrylic acid 5,000 manufactured by Wako Pure Chemical Industries, Ltd.)
A-3: Polyacrylic acid (polyacrylic acid 25,000 manufactured by Wako Pure Chemical Industries, Ltd.)
Ar-1: polyacrylic acid (polyacrylic acid 1,000,000 manufactured by Wako Pure Chemical Industries, Ltd.)
Ar-2: sodium polyacrylate (Aaron A-20P-X manufactured by Toagosei Co., Ltd.)
Ar-3: Hydroxypropyl methylcellulose (Metronose Hi90SH100000 manufactured by Shin-Etsu Chemical Co., Ltd.)
d-1: Structural unit formed of sodium acrylate d-2: Structural unit formed of acrylic acid d-3: Structural unit formed of acrylic acid d-4: Structural unit d formed of acrylic acid -5: Structural unit formed from sodium acrylate
Ａ－１：ポリアクリル酸ナトリウム（東亞合成株式会社製アロンＴ－２１０）
Ａ－２：ポリアクリル酸（和光純薬工業株式会社製ポリアクリル酸５，０００）
Ａ－３：ポリアクリル酸（和光純薬工業株式会社製ポリアクリル酸２５，０００）
Ａｒ－１：ポリアクリル酸（和光純薬工業株式会社製ポリアクリル酸１，０００，０００）
Ａｒ－２：ポリアクリル酸ナトリウム（東亞合成株式会社製アロンＡ－２０Ｐ－Ｘ）
Ａｒ－３：ヒドロキシプロピルメチルセルロース（信越化学工業社製メトローズＨｉ９０ＳＨ１０００００）
ｄ－１：アクリル酸ナトリウムから形成された構成単位
ｄ－２：アクリル酸から形成された構成単位
ｄ－３：アクリル酸から形成された構成単位
ｄ－４：アクリル酸から形成された構成単位
ｄ－５：アクリル酸ナトリウムから形成された構成単位 In Table 1,
A-1: Sodium polyacrylate (Aaron T-210 manufactured by Toagosei Co., Ltd.)
A-2: Polyacrylic acid (polyacrylic acid 5,000 manufactured by Wako Pure Chemical Industries, Ltd.)
A-3: Polyacrylic acid (polyacrylic acid 25,000 manufactured by Wako Pure Chemical Industries, Ltd.)
Ar-1: polyacrylic acid (polyacrylic acid 1,000,000 manufactured by Wako Pure Chemical Industries, Ltd.)
Ar-2: sodium polyacrylate (Aaron A-20P-X manufactured by Toagosei Co., Ltd.)
Ar-3: Hydroxypropyl methylcellulose (Metronose Hi90SH100000 manufactured by Shin-Etsu Chemical Co., Ltd.)
d-1: Structural unit formed of sodium acrylate d-2: Structural unit formed of acrylic acid d-3: Structural unit formed of acrylic acid d-4: Structural unit d formed of acrylic acid -5: Structural unit formed from sodium acrylate
試験区分２（Ｂ成分としてのビニル共重合体の製造）
Test Category 2 (Production of vinyl copolymer as component B)
・製造例１｛ビニル共重合体（Ｂ－１）の製造｝
蒸留水２５０ｇ、α－（３－メチル－３－ブテニル）－ω－ヒドロキシ－ポリ（ｎ＝５０）オキシエチレン３３０ｇを温度計、撹拌機、滴下ロート、窒素導入管を備えた反応容器（以下、同様のものを使用した）に仕込み、攪拌しながら均一に溶解した後、雰囲気を窒素置換し、反応系の温度を温水浴にて６５℃に保持した。次に、１％過酸化水素水１６ｇを３時間かけて滴下し、それと同時にイオン交換水８０ｇにアクリル酸３０ｇを均一に溶解させた水溶液を３時間かけて滴下し、それと同時にイオン交換水１４ｇにＬ－アスコルビン酸２ｇとチオグリコール酸３ｇを溶解させた水溶液を４時間かけて滴下した。その後、２時間、反応系の温度を６５℃に維持し、重合反応を終了した。その後、反応系に３０％水酸化ナトリウム水溶液を加えて、ｐＨ３に調整し、イオン交換水にて濃度を４０％に調整して反応混合物を得た。この反応混合物をゲルパーミエーションクロマトグラフィー（ＧＰＣ）にて分析したところ、質量平均分子量３５０００であった。この反応物をビニル共重合体（Ｂ－１）とした。 Production Example 1 {Production of vinyl copolymer (B-1)}
250 g of distilled water and 330 g of α-(3-methyl-3-butenyl)-ω-hydroxy-poly(n=50)oxyethylene were placed in a reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, and a nitrogen introducing tube (hereinafter, The same was used), and the solution was uniformly dissolved with stirring, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was maintained at 65° C. in a warm water bath. Next, 16 g of 1% hydrogen peroxide solution was added dropwise over 3 hours, and at the same time, an aqueous solution in which 30 g of acrylic acid was uniformly dissolved in 80 g of ion exchanged water was added over 3 hours, and at the same time, 14 g of ion exchanged water was added. An aqueous solution in which 2 g of L-ascorbic acid and 3 g of thioglycolic acid were dissolved was added dropwise over 4 hours. Then, the temperature of the reaction system was maintained at 65° C. for 2 hours to complete the polymerization reaction. Then, a 30% sodium hydroxide aqueous solution was added to the reaction system to adjust the pH to 3, and the concentration was adjusted to 40% with ion-exchanged water to obtain a reaction mixture. When the reaction mixture was analyzed by gel permeation chromatography (GPC), the mass average molecular weight was 35,000. This reaction product was designated as a vinyl copolymer (B-1).
蒸留水２５０ｇ、α－（３－メチル－３－ブテニル）－ω－ヒドロキシ－ポリ（ｎ＝５０）オキシエチレン３３０ｇを温度計、撹拌機、滴下ロート、窒素導入管を備えた反応容器（以下、同様のものを使用した）に仕込み、攪拌しながら均一に溶解した後、雰囲気を窒素置換し、反応系の温度を温水浴にて６５℃に保持した。次に、１％過酸化水素水１６ｇを３時間かけて滴下し、それと同時にイオン交換水８０ｇにアクリル酸３０ｇを均一に溶解させた水溶液を３時間かけて滴下し、それと同時にイオン交換水１４ｇにＬ－アスコルビン酸２ｇとチオグリコール酸３ｇを溶解させた水溶液を４時間かけて滴下した。その後、２時間、反応系の温度を６５℃に維持し、重合反応を終了した。その後、反応系に３０％水酸化ナトリウム水溶液を加えて、ｐＨ３に調整し、イオン交換水にて濃度を４０％に調整して反応混合物を得た。この反応混合物をゲルパーミエーションクロマトグラフィー（ＧＰＣ）にて分析したところ、質量平均分子量３５０００であった。この反応物をビニル共重合体（Ｂ－１）とした。 Production Example 1 {Production of vinyl copolymer (B-1)}
250 g of distilled water and 330 g of α-(3-methyl-3-butenyl)-ω-hydroxy-poly(n=50)oxyethylene were placed in a reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, and a nitrogen introducing tube (hereinafter, The same was used), and the solution was uniformly dissolved with stirring, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was maintained at 65° C. in a warm water bath. Next, 16 g of 1% hydrogen peroxide solution was added dropwise over 3 hours, and at the same time, an aqueous solution in which 30 g of acrylic acid was uniformly dissolved in 80 g of ion exchanged water was added over 3 hours, and at the same time, 14 g of ion exchanged water was added. An aqueous solution in which 2 g of L-ascorbic acid and 3 g of thioglycolic acid were dissolved was added dropwise over 4 hours. Then, the temperature of the reaction system was maintained at 65° C. for 2 hours to complete the polymerization reaction. Then, a 30% sodium hydroxide aqueous solution was added to the reaction system to adjust the pH to 3, and the concentration was adjusted to 40% with ion-exchanged water to obtain a reaction mixture. When the reaction mixture was analyzed by gel permeation chromatography (GPC), the mass average molecular weight was 35,000. This reaction product was designated as a vinyl copolymer (B-1).
・製造例２｛ビニル共重合体（Ｂ－２）の製造｝
蒸留水１５０ｇを反応容器に仕込み、雰囲気を窒素置換し、窒素雰囲気下にて反応系の温度を６０℃に保持した。次に蒸留水１５０ｇ、メタクリル酸２０ｇ、α－ヒドロキシ－ω－メタクリロイル－ポリ（ｎ＝２）プロピレンポリ（ｎ＝１１３)オキシエチレン３２０ｇ、ヒドロキシエチルアクリレート１０ｇ、及び３－メルカプトプロピオン酸３．５ｇを均一混合し、単量体混合物水溶液を調整した。この単量体混合物水溶液と１０％過硫酸ナトリウム水溶液２４ｇとを４時間かけて反応容器に同時に滴下してラジカル共重合反応を行い、更に、１０％過硫酸ナトリウム水溶液６ｇを１時間かけて滴下して反応を行った。その後、反応系の温度を６０℃に保持して１時間、ラジカル共重合反応を行った。次いで、反応系を室温まで冷却した後、水酸化ナトリウム水溶液を加えて、ｐＨ５に調整し、蒸留水にて濃度を４０％に調整して反応混合物を得た。この反応混合物をゲルパーミエーションクロマトグラフィー（ＧＰＣ）にて分析したところ、質量平均分子量４３０００であった。この反応混合物をビニル共重合体（Ｂ－２）とした。 Production Example 2 {Production of vinyl copolymer (B-2)}
150 g of distilled water was charged into the reaction vessel, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was maintained at 60° C. under a nitrogen atmosphere. Next, 150 g of distilled water, 20 g of methacrylic acid, 320 g of α-hydroxy-ω-methacryloyl-poly(n=2) propylene poly(n=113)oxyethylene, 10 g of hydroxyethyl acrylate, and 3.5 g of 3-mercaptopropionic acid. The mixture was uniformly mixed to prepare an aqueous monomer mixture solution. This monomer mixture aqueous solution and 10% sodium persulfate aqueous solution 24 g are simultaneously added dropwise to the reaction vessel over 4 hours to carry out a radical copolymerization reaction, and further 10% sodium persulfate aqueous solution 6 g is added dropwise over 1 hour. The reaction was carried out. Then, the temperature of the reaction system was kept at 60° C. and a radical copolymerization reaction was carried out for 1 hour. Next, the reaction system was cooled to room temperature, an aqueous sodium hydroxide solution was added to adjust the pH to 5, and the concentration was adjusted to 40% with distilled water to obtain a reaction mixture. When the reaction mixture was analyzed by gel permeation chromatography (GPC), the mass average molecular weight was 43,000. This reaction mixture was designated as a vinyl copolymer (B-2).
蒸留水１５０ｇを反応容器に仕込み、雰囲気を窒素置換し、窒素雰囲気下にて反応系の温度を６０℃に保持した。次に蒸留水１５０ｇ、メタクリル酸２０ｇ、α－ヒドロキシ－ω－メタクリロイル－ポリ（ｎ＝２）プロピレンポリ（ｎ＝１１３)オキシエチレン３２０ｇ、ヒドロキシエチルアクリレート１０ｇ、及び３－メルカプトプロピオン酸３．５ｇを均一混合し、単量体混合物水溶液を調整した。この単量体混合物水溶液と１０％過硫酸ナトリウム水溶液２４ｇとを４時間かけて反応容器に同時に滴下してラジカル共重合反応を行い、更に、１０％過硫酸ナトリウム水溶液６ｇを１時間かけて滴下して反応を行った。その後、反応系の温度を６０℃に保持して１時間、ラジカル共重合反応を行った。次いで、反応系を室温まで冷却した後、水酸化ナトリウム水溶液を加えて、ｐＨ５に調整し、蒸留水にて濃度を４０％に調整して反応混合物を得た。この反応混合物をゲルパーミエーションクロマトグラフィー（ＧＰＣ）にて分析したところ、質量平均分子量４３０００であった。この反応混合物をビニル共重合体（Ｂ－２）とした。 Production Example 2 {Production of vinyl copolymer (B-2)}
150 g of distilled water was charged into the reaction vessel, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was maintained at 60° C. under a nitrogen atmosphere. Next, 150 g of distilled water, 20 g of methacrylic acid, 320 g of α-hydroxy-ω-methacryloyl-poly(n=2) propylene poly(n=113)oxyethylene, 10 g of hydroxyethyl acrylate, and 3.5 g of 3-mercaptopropionic acid. The mixture was uniformly mixed to prepare an aqueous monomer mixture solution. This monomer mixture aqueous solution and 10% sodium persulfate aqueous solution 24 g are simultaneously added dropwise to the reaction vessel over 4 hours to carry out a radical copolymerization reaction, and further 10% sodium persulfate aqueous solution 6 g is added dropwise over 1 hour. The reaction was carried out. Then, the temperature of the reaction system was kept at 60° C. and a radical copolymerization reaction was carried out for 1 hour. Next, the reaction system was cooled to room temperature, an aqueous sodium hydroxide solution was added to adjust the pH to 5, and the concentration was adjusted to 40% with distilled water to obtain a reaction mixture. When the reaction mixture was analyzed by gel permeation chromatography (GPC), the mass average molecular weight was 43,000. This reaction mixture was designated as a vinyl copolymer (B-2).
・製造例３｛ビニル共重合体（Ｂ－３）の製造｝
蒸留水１５０ｇを反応容器に仕込み、雰囲気を窒素置換し、窒素雰囲気下にて反応系の温度を６０℃に保持した。次に蒸留水１５０ｇ、メタクリル酸３５ｇ、α－メトキシ－ω－メタクリロイル－ポリ（ｎ＝２３)オキシエチレン３００ｇ、アクリル酸メチル５ｇ、及び３－メルカプトプロピオン酸３．５ｇを均一混合し、単量体混合物水溶液を調整した。この単量体混合物水溶液と１０％過硫酸ナトリウム水溶液２４ｇとを４時間かけて反応容器に同時に滴下してラジカル共重合反応を行い、更に、１０％過硫酸ナトリウム水溶液６ｇを１時間かけて滴下して反応を行った。その後、反応系の温度を６０℃に保持して１時間、、ラジカル共重合反応を行った。次いで、反応系を室温まで冷却した後、水酸化ナトリウム水溶液を加えて、ｐＨ４に調整し、蒸留水にて濃度を４０％に調整して反応混合物を得た。この反応混合物をゲルパーミエーションクロマトグラフィー（ＧＰＣ）にて分析したところ、質量平均分子量４３０００であった。この反応混合物をビニル共重合体（Ｂ－３）とした。以上製造したビニル共重合体について、表２にまとめて示した。 Production Example 3 {Production of vinyl copolymer (B-3)}
150 g of distilled water was charged into the reaction vessel, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was maintained at 60° C. under a nitrogen atmosphere. Next, 150 g of distilled water, 35 g of methacrylic acid, 300 g of α-methoxy-ω-methacryloyl-poly(n=23)oxyethylene, 5 g of methyl acrylate, and 3.5 g of 3-mercaptopropionic acid were uniformly mixed to obtain a monomer. An aqueous mixture was prepared. This monomer mixture aqueous solution and 10% sodium persulfate aqueous solution 24 g are simultaneously added dropwise to the reaction vessel over 4 hours for radical copolymerization reaction, and further 10% sodium persulfate aqueous solution 6 g is added dropwise over 1 hour. The reaction was carried out. Then, the temperature of the reaction system was maintained at 60° C. and a radical copolymerization reaction was carried out for 1 hour. Then, after cooling the reaction system to room temperature, an aqueous sodium hydroxide solution was added to adjust the pH to 4, and the concentration was adjusted to 40% with distilled water to obtain a reaction mixture. When the reaction mixture was analyzed by gel permeation chromatography (GPC), the mass average molecular weight was 43,000. This reaction mixture was designated as vinyl copolymer (B-3). The vinyl copolymers produced above are summarized in Table 2.
蒸留水１５０ｇを反応容器に仕込み、雰囲気を窒素置換し、窒素雰囲気下にて反応系の温度を６０℃に保持した。次に蒸留水１５０ｇ、メタクリル酸３５ｇ、α－メトキシ－ω－メタクリロイル－ポリ（ｎ＝２３)オキシエチレン３００ｇ、アクリル酸メチル５ｇ、及び３－メルカプトプロピオン酸３．５ｇを均一混合し、単量体混合物水溶液を調整した。この単量体混合物水溶液と１０％過硫酸ナトリウム水溶液２４ｇとを４時間かけて反応容器に同時に滴下してラジカル共重合反応を行い、更に、１０％過硫酸ナトリウム水溶液６ｇを１時間かけて滴下して反応を行った。その後、反応系の温度を６０℃に保持して１時間、、ラジカル共重合反応を行った。次いで、反応系を室温まで冷却した後、水酸化ナトリウム水溶液を加えて、ｐＨ４に調整し、蒸留水にて濃度を４０％に調整して反応混合物を得た。この反応混合物をゲルパーミエーションクロマトグラフィー（ＧＰＣ）にて分析したところ、質量平均分子量４３０００であった。この反応混合物をビニル共重合体（Ｂ－３）とした。以上製造したビニル共重合体について、表２にまとめて示した。 Production Example 3 {Production of vinyl copolymer (B-3)}
150 g of distilled water was charged into the reaction vessel, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was maintained at 60° C. under a nitrogen atmosphere. Next, 150 g of distilled water, 35 g of methacrylic acid, 300 g of α-methoxy-ω-methacryloyl-poly(n=23)oxyethylene, 5 g of methyl acrylate, and 3.5 g of 3-mercaptopropionic acid were uniformly mixed to obtain a monomer. An aqueous mixture was prepared. This monomer mixture aqueous solution and 10% sodium persulfate aqueous solution 24 g are simultaneously added dropwise to the reaction vessel over 4 hours for radical copolymerization reaction, and further 10% sodium persulfate aqueous solution 6 g is added dropwise over 1 hour. The reaction was carried out. Then, the temperature of the reaction system was maintained at 60° C. and a radical copolymerization reaction was carried out for 1 hour. Then, after cooling the reaction system to room temperature, an aqueous sodium hydroxide solution was added to adjust the pH to 4, and the concentration was adjusted to 40% with distilled water to obtain a reaction mixture. When the reaction mixture was analyzed by gel permeation chromatography (GPC), the mass average molecular weight was 43,000. This reaction mixture was designated as vinyl copolymer (B-3). The vinyl copolymers produced above are summarized in Table 2.
表２において、
＊１：Ｂ成分であるビニル共重合体の種類
＊２：構成単位１を形成することとなる単量体１の種類
＊３：構成単位２を形成することとなるカルボン酸単量体の種類
＊４：構成単位３を形成することとなる単量体３の種類
割合：単位は質量％
単量体（ｅ－１）～（ｅ－４）：下記の表３にまとめて示した式（１）で示される単量体
単量体（ｆ－１）：アクリル酸
単量体（ｆ－２）：メタクリル酸
単量体（ｇ－１）：アククリル酸メチル In Table 2,
*1: Kind of vinyl copolymer that is the B component *2: Kind of monomer 1 that forms the structural unit 1 *3: Kind of carboxylic acid monomer that forms the structural unit 2 *4: Kind ratio of the monomer 3 that forms the structural unit 3: Unit is% by mass
Monomers (e-1) to (e-4): Monomers represented by the formula (1) shown in Table 3 below (f-1): Acrylic acid monomers (f -2): Methacrylic acid monomer (g-1): Methyl acrylate
＊１：Ｂ成分であるビニル共重合体の種類
＊２：構成単位１を形成することとなる単量体１の種類
＊３：構成単位２を形成することとなるカルボン酸単量体の種類
＊４：構成単位３を形成することとなる単量体３の種類
割合：単位は質量％
単量体（ｅ－１）～（ｅ－４）：下記の表３にまとめて示した式（１）で示される単量体
単量体（ｆ－１）：アクリル酸
単量体（ｆ－２）：メタクリル酸
単量体（ｇ－１）：アククリル酸メチル In Table 2,
*1: Kind of vinyl copolymer that is the B component *2: Kind of monomer 1 that forms the structural unit 1 *3: Kind of carboxylic acid monomer that forms the structural unit 2 *4: Kind ratio of the monomer 3 that forms the structural unit 3: Unit is% by mass
Monomers (e-1) to (e-4): Monomers represented by the formula (1) shown in Table 3 below (f-1): Acrylic acid monomers (f -2): Methacrylic acid monomer (g-1): Methyl acrylate
表３において、
ＥＯ：オキシエチレン基
ＰＯ：オキシプロピレン基
ＥＯ（１１３）＋ＰＯ（２）：ＥＯ １１３ｍｏｌとＰＯ ２ｍｏｌで合計１１５ｍｏｌ付加したもの In Table 3,
EO: oxyethylene group PO: oxypropylene group EO(113)+PO(2): EO 113 mol and PO 2 mol, a total of 115 mol added.
ＥＯ：オキシエチレン基
ＰＯ：オキシプロピレン基
ＥＯ（１１３）＋ＰＯ（２）：ＥＯ １１３ｍｏｌとＰＯ ２ｍｏｌで合計１１５ｍｏｌ付加したもの In Table 3,
EO: oxyethylene group PO: oxypropylene group EO(113)+PO(2): EO 113 mol and PO 2 mol, a total of 115 mol added.
試験区分３（Ａ成分、Ｂ成分の質量平均分子量の測定）
Ａ成分及びＢ成分の質量平均分子量を以下の方法により測定した。結果を表１、２に示す。 Test Category 3 (Measurement of mass average molecular weight of A component and B component)
The mass average molecular weights of the component A and the component B were measured by the following method. The results are shown in Tables 1 and 2.
Ａ成分及びＢ成分の質量平均分子量を以下の方法により測定した。結果を表１、２に示す。 Test Category 3 (Measurement of mass average molecular weight of A component and B component)
The mass average molecular weights of the component A and the component B were measured by the following method. The results are shown in Tables 1 and 2.
［Ａ成分の質量平均分子量の測定］
Ａ成分であるアクリル酸及び／又はその塩の重合体の質量平均分子量の測定は、ゲルパーミエーションクロマトグラフィー－多角度光散乱法（ＧＰＣ－ＭＡＬＳ法）及び／またはゲルパーミエーションクロマトグラフィー法（ＧＰＣ法）にて行い、条件を以下のものとした。なお、ポリアクリル酸の質量平均分子量が５００，０００を超えるとＧＰＣ法では測定できなかったので、質量平均分子量が５００，０００を超えたものはＧＰＣ－ＭＡＬＳ法を用いた。なお、Ａ－３とＡｒ－１にてＧＰＣ－ＭＡＬＳ法とＧＰＣ法に分子量の差は±３％以内であり同一であるとみなした。 [Measurement of mass average molecular weight of component A]
The mass average molecular weight of the polymer of acrylic acid and/or its salt as the component A is measured by gel permeation chromatography-multi-angle light scattering method (GPC-MALS method) and/or gel permeation chromatography method (GPC). Method) and the conditions were as follows. When the mass average molecular weight of polyacrylic acid exceeded 500,000, it could not be measured by the GPC method. Therefore, the GPC-MALS method was used for those whose mass average molecular weight exceeded 500,000. The difference in molecular weight between GPC-MALS method and GPC method between A-3 and Ar-1 was within ±3%, and they were considered to be the same.
Ａ成分であるアクリル酸及び／又はその塩の重合体の質量平均分子量の測定は、ゲルパーミエーションクロマトグラフィー－多角度光散乱法（ＧＰＣ－ＭＡＬＳ法）及び／またはゲルパーミエーションクロマトグラフィー法（ＧＰＣ法）にて行い、条件を以下のものとした。なお、ポリアクリル酸の質量平均分子量が５００，０００を超えるとＧＰＣ法では測定できなかったので、質量平均分子量が５００，０００を超えたものはＧＰＣ－ＭＡＬＳ法を用いた。なお、Ａ－３とＡｒ－１にてＧＰＣ－ＭＡＬＳ法とＧＰＣ法に分子量の差は±３％以内であり同一であるとみなした。 [Measurement of mass average molecular weight of component A]
The mass average molecular weight of the polymer of acrylic acid and/or its salt as the component A is measured by gel permeation chromatography-multi-angle light scattering method (GPC-MALS method) and/or gel permeation chromatography method (GPC). Method) and the conditions were as follows. When the mass average molecular weight of polyacrylic acid exceeded 500,000, it could not be measured by the GPC method. Therefore, the GPC-MALS method was used for those whose mass average molecular weight exceeded 500,000. The difference in molecular weight between GPC-MALS method and GPC method between A-3 and Ar-1 was within ±3%, and they were considered to be the same.
［測定条件］
［ＧＰＣ－ＭＡＬＳ法］
検出器：示差屈折率計（ＲＩ）、多角度光散乱検出器（ＭＡＬＳ）
カラム：昭和電工社製ＯＨｐａｋ ＳＢ－８０７ ＨＱ＋ＳＢ－８０６Ｍ ＨＱ
溶離液：０．１Ｍトリス緩衝液（ｐＨ＝０．９、０．１Ｍ塩化カリウム添加）／アセトニトリル混合溶媒（混合体積比：７／３）
流速：０．５ｍＬ／分
カラム温度：４０℃ [Measurement condition]
[GPC-MALS method]
Detector: differential refractometer (RI), multi-angle light scattering detector (MALS)
Column: Showa Denko OHpak SB-807 HQ+SB-806M HQ
Eluent: 0.1 M Tris buffer (pH=0.9, 0.1 M potassium chloride added)/acetonitrile mixed solvent (mixing volume ratio: 7/3)
Flow rate: 0.5 mL/min Column temperature: 40°C
［ＧＰＣ－ＭＡＬＳ法］
検出器：示差屈折率計（ＲＩ）、多角度光散乱検出器（ＭＡＬＳ）
カラム：昭和電工社製ＯＨｐａｋ ＳＢ－８０７ ＨＱ＋ＳＢ－８０６Ｍ ＨＱ
溶離液：０．１Ｍトリス緩衝液（ｐＨ＝０．９、０．１Ｍ塩化カリウム添加）／アセトニトリル混合溶媒（混合体積比：７／３）
流速：０．５ｍＬ／分
カラム温度：４０℃ [Measurement condition]
[GPC-MALS method]
Detector: differential refractometer (RI), multi-angle light scattering detector (MALS)
Column: Showa Denko OHpak SB-807 HQ+SB-806M HQ
Eluent: 0.1 M Tris buffer (pH=0.9, 0.1 M potassium chloride added)/acetonitrile mixed solvent (mixing volume ratio: 7/3)
Flow rate: 0.5 mL/min Column temperature: 40°C
［ＧＰＣ法］
検出器：示差屈折計（ＲＩ）
カラム：昭和電工社製ＯＨｐａｋ ＳＢ－Ｇ＋ＳＢ－８０６Ｍ ＨＱ＋ＳＢ－８０６Ｍ ＨＱ
溶離液：５０ｍＭ硝酸ナトリウム水溶液
流速：０．７ｍＬ／分
カラム温度：４０℃
標準物質：アジレント社製ポリアクリル酸ナトリウム [GPC method]
Detector: Differential refractometer (RI)
Column: Showa Denko OHpak SB-G+SB-806M HQ+SB-806M HQ
Eluent: 50 mM sodium nitrate aqueous solution Flow rate: 0.7 mL/min Column temperature: 40°C
Standard material: Agilent sodium polyacrylate
検出器：示差屈折計（ＲＩ）
カラム：昭和電工社製ＯＨｐａｋ ＳＢ－Ｇ＋ＳＢ－８０６Ｍ ＨＱ＋ＳＢ－８０６Ｍ ＨＱ
溶離液：５０ｍＭ硝酸ナトリウム水溶液
流速：０．７ｍＬ／分
カラム温度：４０℃
標準物質：アジレント社製ポリアクリル酸ナトリウム [GPC method]
Detector: Differential refractometer (RI)
Column: Showa Denko OHpak SB-G+SB-806M HQ+SB-806M HQ
Eluent: 50 mM sodium nitrate aqueous solution Flow rate: 0.7 mL/min Column temperature: 40°C
Standard material: Agilent sodium polyacrylate
［Ｂ成分の質量平均分子量の測定］
Ｂ成分であるビニル共重合体の質量平均分子量の測定は、ゲルパーミエーションクロマトグラフィー法（ＧＰＣ）にて行い、条件を以下のものとした。 [Measurement of mass average molecular weight of component B]
The weight average molecular weight of the vinyl copolymer as the component B was measured by gel permeation chromatography (GPC), and the conditions were as follows.
Ｂ成分であるビニル共重合体の質量平均分子量の測定は、ゲルパーミエーションクロマトグラフィー法（ＧＰＣ）にて行い、条件を以下のものとした。 [Measurement of mass average molecular weight of component B]
The weight average molecular weight of the vinyl copolymer as the component B was measured by gel permeation chromatography (GPC), and the conditions were as follows.
［測定条件］
検出器：示差屈折計（ＲＩ）
カラム：昭和電工社製ＯＨｐａｋ ＳＢ－Ｇ＋ＳＢ－８０６Ｍ ＨＱ＋ＳＢ－８０６Ｍ ＨＱ
溶離液：５０ｍＭ硝酸ナトリウム水溶液
流速：０．７ｍＬ／分
カラム温度：４０℃
標準物質：アジレント社製ポリエチレングリコール／酸化物（ＰＥＧ／ＰＥＯ） [Measurement condition]
Detector: Differential refractometer (RI)
Column: Showa Denko OHpak SB-G+SB-806M HQ+SB-806M HQ
Eluent: 50 mM sodium nitrate aqueous solution Flow rate: 0.7 mL/min Column temperature: 40°C
Standard material: polyethylene glycol/oxide (PEG/PEO) manufactured by Agilent
検出器：示差屈折計（ＲＩ）
カラム：昭和電工社製ＯＨｐａｋ ＳＢ－Ｇ＋ＳＢ－８０６Ｍ ＨＱ＋ＳＢ－８０６Ｍ ＨＱ
溶離液：５０ｍＭ硝酸ナトリウム水溶液
流速：０．７ｍＬ／分
カラム温度：４０℃
標準物質：アジレント社製ポリエチレングリコール／酸化物（ＰＥＧ／ＰＥＯ） [Measurement condition]
Detector: Differential refractometer (RI)
Column: Showa Denko OHpak SB-G+SB-806M HQ+SB-806M HQ
Eluent: 50 mM sodium nitrate aqueous solution Flow rate: 0.7 mL/min Column temperature: 40°C
Standard material: polyethylene glycol/oxide (PEG/PEO) manufactured by Agilent
試験区分４（相溶性の確認）
溶液の相溶性を、Ｂ成分のビニル共重合体を２０％としたときの、表４に示すＡ成分とＢ成分の比率で十分撹拌混合し、目視により以下の基準で測定を行った。水溶液の濃度調整には蒸留水を用いた。 Test Category 4 (confirmation of compatibility)
With respect to the compatibility of the solution, the ratio of the component A and the component B shown in Table 4 was sufficiently agitated and mixed when the content of the vinyl copolymer of the component B was 20%, and visually measured according to the following criteria. Distilled water was used to adjust the concentration of the aqueous solution.
溶液の相溶性を、Ｂ成分のビニル共重合体を２０％としたときの、表４に示すＡ成分とＢ成分の比率で十分撹拌混合し、目視により以下の基準で測定を行った。水溶液の濃度調整には蒸留水を用いた。 Test Category 4 (confirmation of compatibility)
With respect to the compatibility of the solution, the ratio of the component A and the component B shown in Table 4 was sufficiently agitated and mixed when the content of the vinyl copolymer of the component B was 20%, and visually measured according to the following criteria. Distilled water was used to adjust the concentration of the aqueous solution.
相溶性の判定基準
Ａ：沈殿や沈降を判別できない程度であった
Ｂ：薄い濁りが確認された
Ｃ：沈殿や沈降が確認された Criteria for compatibility A: Precipitation or sedimentation was indistinguishable B: Light turbidity was confirmed C: Precipitation or sedimentation was confirmed
Ａ：沈殿や沈降を判別できない程度であった
Ｂ：薄い濁りが確認された
Ｃ：沈殿や沈降が確認された Criteria for compatibility A: Precipitation or sedimentation was indistinguishable B: Light turbidity was confirmed C: Precipitation or sedimentation was confirmed
試験区分５（水硬性組成物としてのモルタルの調製）
ＪＩＳ Ｒ ５２０１セメントの物理試験方法に準拠したモルタルミキサを用いた。結合材として普通ポルトランドセメント（密度３．１６ｇ／ｃｍ３）を用い、細骨材として大井川水系産陸砂（密度２．５８ｇ／ｃｍ３）を用い、粘土質としてベントナイト（試薬 和光純薬工業株式会社製）を用いた。結合材１００質量部に対し０．００５質量部の割合で消泡剤（竹本油脂社製の商品名ＡＦＫ－２）を添加すると共に、試験区分４で使用した水硬性組成物用添加剤を練り混ぜ水と共に投入し、表５に記載の配合条件下で、２４０秒間、成分を練混ぜてモルタルを調製した。なお、添加剤および消泡剤は水の一部とみなした。 Test Category 5 (Preparation of mortar as hydraulic composition)
A mortar mixer conforming to the physical test method of JIS R 5201 cement was used. Using ordinary portland cement (density 3.16 g / cm 3) as a binder, using the Oi aqueous production Rikusuna (density 2.58 g / cm 3) as a fine aggregate, bentonite (reagent manufactured by Wako Pure Chemical Industries stock as clayey (Manufactured by the company) was used. An antifoaming agent (trade name AFK-2 manufactured by Takemoto Yushi Co., Ltd.) was added at a ratio of 0.005 parts by mass to 100 parts by mass of the binder, and the additive for hydraulic composition used in Test Category 4 was kneaded. The mixture was added together with water and the components were kneaded for 240 seconds under the compounding conditions shown in Table 5 to prepare a mortar. The additive and the defoaming agent were regarded as a part of water.
ＪＩＳ Ｒ ５２０１セメントの物理試験方法に準拠したモルタルミキサを用いた。結合材として普通ポルトランドセメント（密度３．１６ｇ／ｃｍ３）を用い、細骨材として大井川水系産陸砂（密度２．５８ｇ／ｃｍ３）を用い、粘土質としてベントナイト（試薬 和光純薬工業株式会社製）を用いた。結合材１００質量部に対し０．００５質量部の割合で消泡剤（竹本油脂社製の商品名ＡＦＫ－２）を添加すると共に、試験区分４で使用した水硬性組成物用添加剤を練り混ぜ水と共に投入し、表５に記載の配合条件下で、２４０秒間、成分を練混ぜてモルタルを調製した。なお、添加剤および消泡剤は水の一部とみなした。 Test Category 5 (Preparation of mortar as hydraulic composition)
A mortar mixer conforming to the physical test method of JIS R 5201 cement was used. Using ordinary portland cement (density 3.16 g / cm 3) as a binder, using the Oi aqueous production Rikusuna (density 2.58 g / cm 3) as a fine aggregate, bentonite (reagent manufactured by Wako Pure Chemical Industries stock as clayey (Manufactured by the company) was used. An antifoaming agent (trade name AFK-2 manufactured by Takemoto Yushi Co., Ltd.) was added at a ratio of 0.005 parts by mass to 100 parts by mass of the binder, and the additive for hydraulic composition used in Test Category 4 was kneaded. The mixture was added together with water and the components were kneaded for 240 seconds under the compounding conditions shown in Table 5 to prepare a mortar. The additive and the defoaming agent were regarded as a part of water.
成分の練混ぜ及び以下の試験は材料温度を２０±３℃に設定し、室温を２０±３℃に設定し、湿度を６０％以上に設定した環境下で行った。得られたモルタルのモルタルフローの評価は、タッピングなしのモルタルフローとし、２４０±５ｍｍを目標に行った。粘性の評価は、充填モルタル流動性試験方法（ＪＳＣＥ－Ｆ ５４１）に準拠して、Ｊ１４ロートを用いて測定し、流下時間の短いものを粘性が低いと評価した。結果を表６に示す。なお、どのモルタルにおいても目視による分離は確認されなかった。
The components were mixed and the following tests were conducted in an environment in which the material temperature was set to 20±3° C., the room temperature was set to 20±3° C., and the humidity was set to 60% or more. The evaluation of the mortar flow of the obtained mortar was carried out by setting the mortar flow without tapping as 240±5 mm. The viscosity was evaluated by using a J 14 funnel in accordance with the filling mortar fluidity test method (JSCE-F 541), and those having a short flowing time were evaluated as having low viscosity. The results are shown in Table 6. No visual separation was observed in any mortar.
表６において、
※１：結合材１００質量部に対する、（Ａ）成分と（Ｂ）成分の合計の質量部（固形分） In Table 6,
*1: 100 parts by weight of binder, total parts by weight of component (A) and component (B) (solid content)
※１：結合材１００質量部に対する、（Ａ）成分と（Ｂ）成分の合計の質量部（固形分） In Table 6,
*1: 100 parts by weight of binder, total parts by weight of component (A) and component (B) (solid content)
（結果）
表６に示すように、Ａ成分を含まないでＢ成分のみを含有する比較例５に比べて、Ａ成分及びＢ成分を含む実施例７、実施例１０は、添加剤の添加率を増加させることなく、流下時間が短くなっていることが分かる。分子量の大きなポリアクリル酸を用いる比較例６に比べて、Ａ成分のポリアクリル酸を用いる実施例７は、添加剤の添加率を増加させることなく、流下時間が著しく短くなっていることが分かる。分子量の大きなポリアクリル酸塩を用いる比較例７に比べて、Ａ成分のポリアクリル酸を用いる実施例１０は、添加剤の添加率を増加させることなく、流下時間が著しく短くなっていることが分かる。増粘剤として使用されるヒドロキシプロピルメチルセルロースを用いる比較例８に比べて、Ａ成分のポリアクリル酸を用いる実施例８は、添加剤の添加率を増加させることなく、流下時間が著しく短くなっていることが分かる。 (result)
As shown in Table 6, Examples 7 and 10 including the A component and the B component increase the addition rate of the additive as compared with Comparative Example 5 in which the A component is not included and only the B component is included. Without it, you can see that the flow-down time has become shorter. As compared with Comparative Example 6 in which polyacrylic acid having a large molecular weight is used, in Example 7 in which polyacrylic acid as the component A is used, the downflow time is significantly shortened without increasing the addition rate of the additive. .. Compared to Comparative Example 7 in which a polyacrylic acid salt having a large molecular weight was used, Example 10 in which polyacrylic acid as the component A was used did not increase the addition rate of the additive, and the flow-down time was significantly shortened. I understand. Compared to Comparative Example 8 using hydroxypropylmethyl cellulose used as a thickener, Example 8 using polyacrylic acid as the component A has a significantly shorter flow-down time without increasing the addition rate of the additive. I understand that
表６に示すように、Ａ成分を含まないでＢ成分のみを含有する比較例５に比べて、Ａ成分及びＢ成分を含む実施例７、実施例１０は、添加剤の添加率を増加させることなく、流下時間が短くなっていることが分かる。分子量の大きなポリアクリル酸を用いる比較例６に比べて、Ａ成分のポリアクリル酸を用いる実施例７は、添加剤の添加率を増加させることなく、流下時間が著しく短くなっていることが分かる。分子量の大きなポリアクリル酸塩を用いる比較例７に比べて、Ａ成分のポリアクリル酸を用いる実施例１０は、添加剤の添加率を増加させることなく、流下時間が著しく短くなっていることが分かる。増粘剤として使用されるヒドロキシプロピルメチルセルロースを用いる比較例８に比べて、Ａ成分のポリアクリル酸を用いる実施例８は、添加剤の添加率を増加させることなく、流下時間が著しく短くなっていることが分かる。 (result)
As shown in Table 6, Examples 7 and 10 including the A component and the B component increase the addition rate of the additive as compared with Comparative Example 5 in which the A component is not included and only the B component is included. Without it, you can see that the flow-down time has become shorter. As compared with Comparative Example 6 in which polyacrylic acid having a large molecular weight is used, in Example 7 in which polyacrylic acid as the component A is used, the downflow time is significantly shortened without increasing the addition rate of the additive. .. Compared to Comparative Example 7 in which a polyacrylic acid salt having a large molecular weight was used, Example 10 in which polyacrylic acid as the component A was used did not increase the addition rate of the additive, and the flow-down time was significantly shortened. I understand. Compared to Comparative Example 8 using hydroxypropylmethyl cellulose used as a thickener, Example 8 using polyacrylic acid as the component A has a significantly shorter flow-down time without increasing the addition rate of the additive. I understand that
本発明の水硬性組成物用添加剤は、水硬性組成物を調製する際の添加剤として利用することができる。
The additive for hydraulic composition of the present invention can be used as an additive when preparing a hydraulic composition.
The additive for hydraulic composition of the present invention can be used as an additive when preparing a hydraulic composition.
Claims (7)
- 下記のＡ成分と、下記のＢ成分とを含有する水硬性組成物用添加剤。
Ａ成分：アクリル酸及び／又はその塩から形成された構成単位を有し、その質量平均分子量が１０００以上１０００００未満である重合体；
Ｂ成分：分子中に下記の構成単位１及び構成単位２を有し、かつ、構成単位１を１～９９質量％含有し、及び構成単位２を１～９９質量％含有するビニル共重合体；
構成単位１：下記の単量体１から形成された構成単位、
構成単位２：分子中にビニル基を有するカルボン酸単量体から形成された構成単位、
単量体１：下記の式（１）で示される不飽和（ポリ）アルキレングリコール：
Component A: a polymer having a structural unit formed from acrylic acid and/or a salt thereof, and having a mass average molecular weight of 1,000 or more and less than 100,000;
Component B: a vinyl copolymer having the following structural unit 1 and structural unit 2 in the molecule, containing 1 to 99% by mass of structural unit 1, and 1 to 99% by mass of structural unit 2;
Structural unit 1: a structural unit formed from the following monomer 1.
Structural unit 2: a structural unit formed from a carboxylic acid monomer having a vinyl group in the molecule,
Monomer 1: unsaturated (poly)alkylene glycol represented by the following formula (1):
- 前記Ｂ成分が、更に、下記の構成単位３を０～３０質量％含有するビニル共重合体である請求項１に記載の水硬性組成物用添加剤。
構成単位３：前記単量体１及び前記カルボン酸単量体と共重合可能な単量体３から形成された構成単位 The additive for hydraulic compositions according to claim 1, wherein the component B is a vinyl copolymer further containing 0 to 30% by mass of the following structural unit 3.
Structural unit 3: Structural unit formed from the monomer 1 and the monomer 3 copolymerizable with the carboxylic acid monomer - 前記Ｂ成分に対する、前記Ａ成分の質量％が０．１～５質量％である請求項１又は２に記載の水硬性組成物用添加剤。 The additive for hydraulic compositions according to claim 1 or 2, wherein the mass% of the A component is 0.1 to 5 mass% with respect to the B component.
- 前記Ａ成分の質量平均分子量が１０００以上１００００未満である請求項１～３のいずれか１項に記載の水硬性組成物用添加剤。 The additive for hydraulic compositions according to any one of claims 1 to 3, wherein the weight average molecular weight of the component A is 1,000 or more and less than 10,000.
- 請求項１～４のいずれかに１項に記載の水硬性組成物用添加剤を含有する水硬性組成物。 A hydraulic composition containing the additive for hydraulic composition according to any one of claims 1 to 4.
- 更に、結合材を含有する請求項５に記載の水硬性組成物。 The hydraulic composition according to claim 5, further comprising a binder.
- 前記結合材１００質量部に対する、前記Ａ成分と前記Ｂ成分の合計の質量部が０．１～２質量部である請求項６に記載の水硬性組成物。
The hydraulic composition according to claim 6, wherein the total amount by mass of the component A and the component B is 0.1 to 2 parts by mass relative to 100 parts by mass of the binder.
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| JP2020558691A JP7103691B2 (en) | 2018-12-03 | 2018-12-03 | Additives for hydraulic compositions and hydraulic compositions |
| PCT/JP2018/044378 WO2020115788A1 (en) | 2018-12-03 | 2018-12-03 | Additive for hydraulic compositions, and hydraulic composition |
| TW108100093A TWI777016B (en) | 2018-12-03 | 2019-01-02 | Additive for hydraulic composition and hydraulic composition |
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| JPH0931458A (en) * | 1995-07-24 | 1997-02-04 | Fujisawa Pharmaceut Co Ltd | Water reducing agent for clayey soil added with cement |
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| JP6339819B2 (en) * | 2013-03-21 | 2018-06-06 | 株式会社日本触媒 | Additives used in hydraulic compositions |
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2018
- 2018-12-03 WO PCT/JP2018/044378 patent/WO2020115788A1/en active Application Filing
- 2018-12-03 JP JP2020558691A patent/JP7103691B2/en active Active
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2019
- 2019-01-02 TW TW108100093A patent/TWI777016B/en active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000086315A (en) * | 1998-09-07 | 2000-03-28 | Kao Corp | Additive for hydraulic composition |
| JP2010163325A (en) * | 2009-01-16 | 2010-07-29 | Kao Corp | Dispersant composition for hydraulic composition |
| JP2015182917A (en) * | 2014-03-24 | 2015-10-22 | 竹本油脂株式会社 | Multifunctional admixture for concrete |
| JP2017160076A (en) * | 2016-03-09 | 2017-09-14 | 株式会社日本触媒 | Additive for hydraulic composition, and concrete composition |
| JP2018095537A (en) * | 2016-12-16 | 2018-06-21 | 花王株式会社 | Method for producing hardened body of hydraulic composition |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI777016B (en) | 2022-09-11 |
| JP7103691B2 (en) | 2022-07-20 |
| TW202021928A (en) | 2020-06-16 |
| JPWO2020115788A1 (en) | 2021-09-27 |
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