JP7107613B2 - Additive for hydraulic composition - Google Patents

Description

The present invention relates to additives for hydraulic compositions. More particularly, the present invention relates to an additive for hydraulic composition that exhibits excellent dispersibility in the hydraulic composition and has the effect of reducing the viscosity of the hydraulic composition.

Conventionally, a hydraulic composition obtained by kneading various materials such as a hydraulic binder and water is filled in a mold, cured, and then demolded from the mold to produce a hardened body having a desired shape. there is In particular, a concrete composition, which is a type of hydraulic composition, is composed of various materials such as cement, water, aggregate, and dispersant, and these are mixed and kneaded under predetermined conditions. After that, the hardened concrete can be obtained by pouring it into a mold set in advance and hardening it. A concrete hardened body made of such a concrete composition has excellent properties such as strength and durability, and is widely used in various buildings and civil engineering structures making use of these properties.

Hydraulic compositions such as concrete compositions are generally added with additives (additives for hydraulic compositions) in order to improve air entrainment and fluidity during kneading of various materials. . By using the additive, good dispersibility can be maintained even when the hydraulic composition is water-reduced. In addition, it is possible to improve the handleability and workability during kneading and construction. That is, the addition of the additive makes it possible to construct a concrete composition or the like that is excellent in stability over time and workability as well as improving the durability, strength, etc. of the concrete composition.

Here, the hydraulic composition such as the kneaded concrete composition is pressure-fed through the pipe toward the formwork installed at the construction site mainly using a pressure-feeding device such as a pump. Therefore, when the viscosity of the hydraulic composition is high, the transportation speed (pumping speed) of the hydraulic composition that is pumped from a pump or the like and passes through the pipe becomes slow, and the workability and workability may deteriorate. . Furthermore, a large amount of force is required to pump the hydraulic composition, and a pumping device with high pumping performance may be used, or an excessive load may be applied to the pumping device. Furthermore, when the viscosity is high, the hydraulic composition clogs the pipes, which may cause pumping failure.

Therefore, in order to improve the pumpability of the hydraulic composition by a pumping device such as a pump, a structural unit derived from an unsaturated polyalkylene glycol-based monomer, a carboxylic acid-based structural unit, and a carboxylic acid alkyl ester-based structural unit Cement dispersants or concrete admixtures for improving the pumpability of pumps, etc., have been proposed (for example, Patent Document 1-4).

WO2018/088528 WO2018/088529 JP 2018-154711 A JP 2018-154712 A

For example, if the water-cement ratio is increased in order to reduce the viscosity of the hydraulic composition, the strength of the resulting hardened body (concrete hardened body, etc.) of the hydraulic composition is reduced. When the is lowered, the dispersibility during kneading may be affected. Therefore, it has been difficult to strike a good balance between the dispersibility of the hydraulic composition and the reduction of the viscosity of the hydraulic composition.

Therefore, in view of the above circumstances, the additive for hydraulic compositions of the present invention can exhibit excellent dispersibility in hydraulic compositions and an excellent effect of reducing the viscosity of hydraulic compositions in a well-balanced manner. An object of the present invention is to provide an additive for hydraulic compositions.

The inventors of the present application have made intensive research to solve the above problems, and found that by incorporating a specific monomer into a polycarboxylic acid-based dispersant (PCE), it has good dispersibility and a hydraulic composition We have found an additive for hydraulic compositions that can reduce the viscosity of a product.

The additive for hydraulic compositions of the present invention comprises a monomer A having a vinyl group and an acid group in its constituent units and having a mass ratio of 1 to 98% by mass with respect to the total mass, and the following chemical A monomer B represented by 1 and having a mass ratio of 1 to 98% by mass relative to the total mass, and a monomer B represented by Chemical Formula 2 below and having a mass ratio of 1 to 98% by mass relative to the total mass. It is constituted as a copolymer obtained by copolymerizing the monomer C obtained.

Monomer A is unsaturated carboxylic acid and/or its salt, unsaturated sulfonic acid and/or its salt, unsaturated phosphoric acid and/or its salt. For example, unsaturated carboxylic acids include acrylic acid, methacrylic acid, (anhydrous) maleic acid, fumaric acid, crotonic acid, 2-(meth)acryloyloxyethylsuccinic acid and the like. allylsulfonic acid, methallylsulfonic acid, 2-(meth)acrylamido-2-methanesulfonic acid, 2-(meth)acrylamido-2-ethanesulfonic acid, 2-(meth)acrylamido-2-propanesulfonic acid, styrenesulfonic acid acids, etc. Examples of acid-containing monomers such as unsaturated phosphoric acid include 2-((meth)acryloyloxy)ethyl phosphate and the like. Examples of the salts include alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as calcium salts and magnesium salts, and amine salts such as ammonium salts, diethanolamine salts and triethanolamine salts. In particular, it is preferable to use one or more of acrylic acid, methacrylic acid, allylsulfonic acid, methallylsulfonic acid and/or salts thereof as the monomer A.

On the other hand, the monomer B is a polyalkylene glycol (PAG)-based monomer as shown in Chemical Formula 1 below, such as (poly)ethylene glycol mono(meth)acrylate, (poly)propylene ( Poly)ethylene glycol mono (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy (poly) ethylene (poly) propylene glycol mono (meth) acrylate, butoxy (poly) ethylene glycol mono (meth) acrylate, (poly) ethylene Glycol (poly)butylene glycol vinyl ether, (poly)ethylene glycol monoallyl ether, (poly)ethylene glycol mono(2-methyl-2-propenyl) ether, (poly)ethylene glycol mono(3-methyl-3-butenyl) ether , (poly)ethylene (poly)propylene glycol mono(2-methyl-2-propenyl) ether and the like. One or more of these monomers may be used.

In Chemical Formula 1, R ¹ , R ² and R ³ represent 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 1 having 2 to 4 carbon atoms. or a plurality of oxyalkylene groups, p is an integer of 0-5, q is 0 or 1 , and m is an integer of 1-29.

Monomer C is an aromatic AO adduct (meth)acrylic acid ester and/or an aromatic AO adduct alkenyl ether, as shown in Chemical Formula 2 below, and an aromatic AO adduct (meth) Examples of acrylic acid esters include phenol AO adduct (meth)acrylic acid ester, monostyrenated phenol AO adduct (meth)acrylic acid ester, distyrenated phenol AO adduct (meth)acrylic acid ester, tristyrenated Examples thereof include monomers such as phenol AO adduct (meth)acrylic acid esters and cumylphenol AO adduct (meth)acrylic acid esters. Examples of alkenyl ethers of aromatic AO adducts include α-allyl-ω-(monostyrenated phenoxy)-(poly)oxyethylene, α-allyl-ω-(monostyrenated phenoxy)-(poly)oxyethylene ( Poly)oxypropylene, α-allyl-ω-(distyrenated phenoxy)-(poly)oxyethylene, α-allyl-ω-(distyrenated phenoxy)-(poly)oxyethylene (poly)oxypropylene, α-allyl- ω-(tristyrenated phenoxy)-(poly)oxyethylene, α-allyl-ω-(tristyrenated phenoxy)-(poly)oxyethylene (poly)oxypropylene, α-methallyl-ω-(monostyrenated phenoxy )-(poly)oxyethylene, α-methallyl-ω-(monostyrenated phenoxy)-(poly)oxyethylene (poly)oxypropylene, α-methallyl-ω-(distyrenated phenoxy)-(poly)oxyethylene, α-methallyl-ω-(distyrenated phenoxy)-(poly)oxyethylene (poly)oxypropylene, α-methallyl-ω-(tristyrenated phenoxy)-(poly)oxyethylene, α-methallyl-ω-(tri Styrenated phenoxy)-(poly)oxyethylene (poly)oxypropylene, α-(3-methyl-3-butenyl)-ω-(monostyrenated phenoxy)-(poly)oxyethylene, α-(3-methyl- 3-butenyl)-ω-(monostyrenated phenoxy)-(poly)oxyethylene (poly)oxypropylene, α-(3-methyl-3-butenyl)-ω-(distyrenated phenoxy)-(poly)oxyethylene , α-(3-methyl-3-butenyl)-ω-(distyrenated phenoxy)-(poly)oxyethylene (poly)oxypropylene, α-(3-methyl-3-butenyl)-ω-(tristyrenated phenoxy)-(poly)oxyethylene, α-(3-methyl-3-butenyl)-ω-(tristyrenated phenoxy)-(poly)oxyethylene (poly)oxypropylene, α-(3-methyl-3- butenyl)-ω-cumylphenoxy-(poly)oxyethylene (poly)oxypropylene and the like. In the above, "AO" represents an oxyalkylene group. One or more of these monomers may be used.

In chemical formula 2, R ⁶ , R ⁷ and R ⁸ represent a hydrogen atom or a methyl group, R ⁹ is shown in chemical formula 3 below, and R ¹⁰ O represents one or more oxyalkylene groups having 2 to 4 carbon atoms. , s is an integer of 0 to 5, t is 0 or 1, and n is an integer of 0 to 300.

In Formula 3, R ¹¹ and R ¹² each represent a hydrogen atom or a methyl group, and a represents an integer of 1-3 .

Furthermore, the additive for hydraulic compositions of the present invention comprises a monomer A having a vinyl group and an acid group in its structural units and having a mass ratio of 1 to 98% by mass relative to the total mass, and A monomer B represented by Chemical Formula 4 and having a mass ratio of 1 to 98% by mass relative to the total mass, and a monomer B represented by Chemical Formula 5 below and having a mass ratio of 1 to 98% by mass relative to the total mass. It may be configured as a copolymer obtained by copolymerizing the monomer D contained in.

Here, since the monomer A and the monomer B are the same as those already explained above, detailed explanations thereof are omitted here. In Chemical Formula 4, the symbols of R ¹ , R ² , R ³ , R ⁴ , R ⁵ O, p, q, and m are the same as those described in Chemical Formula 1.

On the other hand, the monomer D is a monomer such as a (meth)acrylic acid cyclic alkyl (ether) ester as shown in Chemical Formula 5 below. Examples of (meth)acrylic acid cyclic alkyl esters include cyclopropyl (meth)acrylate, cyclopentyl (meth)acrylate, 1-methylcyclopentyl (meth)acrylate, 1-ethylcyclopentyl (meth)acrylate, Cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, menthyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate and the like can be mentioned. Examples of (meth)acrylic acid cyclic alkyl ether esters include glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycerol formal (meth)acrylate, solketal (meth)acrylate, and tetrahydropyranol. (Meth)acrylic ester and the like. In particular, it is preferable to use a monomer of cyclohexyl (meth)acrylate or tetrahydrofuryl (meth)acrylate. One or more of these monomers may be used.

In chemical formula 5, R ¹³ represents a hydrogen atom or a methyl group, and R ¹⁴ represents an alkyl group having 3 to 22 carbon atoms containing a cyclic structure (excluding a phenoxy group) or an ether group.

Furthermore, the additive for hydraulic compositions of the present invention includes a monomer A having a vinyl group and an acid group in its constituent units and having a mass ratio of 1 to 97% by mass relative to the total mass, and A monomer B represented by Chemical Formula 6 and having a mass ratio of 1 to 97% by mass relative to the total mass, and a monomer B represented by Chemical Formula 7 below and having a mass ratio of 1 to 97% by mass relative to the total mass. Constituted as a copolymer obtained by copolymerizing a monomer C contained in and a monomer D represented by the following chemical formula 9 and having a mass ratio of 1 to 97% by mass relative to the total mass It doesn't matter if it is.

Here, since the monomer A, the monomer B, the monomer C, and the monomer D are the same as those already explained above, detailed explanations thereof are omitted here. That is, it may constitute an additive for a hydraulic composition containing all of the monomer A, the monomer B, the monomer C, and the monomer D. In Chemical Formula 6, the symbols of R ¹ , R ² , R ³ , R ⁴ , R ⁵ O, p, q, and m are the same as those described in Chemical Formula 1 (or Chemical Formula 4), and Chemical Formula 7 , the codes of R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ O, s, t, and n are the same as those described in Chemical formula 2, and in Chemical formula 8, R ¹¹ , R ¹² , a are the same as those described in Chemical Formula 3, and R ¹³ and R ¹⁴ in Chemical Formula 9 are the same as those described in Chemical Formula 5.

Furthermore, when the additive for a hydraulic composition of the present invention comprises a monomer A, a monomer B, and a monomer C, the value of m in the monomer B is 1 to 29 range, and the value of a in monomer C is preferably in the range of 1-3.

In addition, in the case of the hydraulic composition additive comprising the monomer A, the monomer B, and the monomer C, the mass ratio of the monomer A to the total mass is 1 to 25% by mass. , wherein the mass ratio of the monomer B to the total mass is 65 to 95 mass %, and the mass ratio of the monomer C to the total mass is preferably 1 to 20 mass %.

On the other hand, in the case of the hydraulic composition additive comprising the monomer A, the monomer B, and the monomer D, the mass ratio of the monomer A to the total mass is 1 to 25% by mass. Preferably, the mass ratio of monomer B to the total mass is 65 to 95 mass%, and the mass ratio of monomer D to the total mass is 1 to 10 mass%.

Furthermore, in the case of the additive for hydraulic composition comprising the monomer A, the monomer B, the monomer C, and the monomer D, the mass ratio of the monomer A to the total mass is 1 ~ 25 mass%, the mass ratio of the monomer B to the total mass is 65 to 95 mass%, the mass ratio of the monomer C to the total mass is 1 to 20 mass%, the monomer to the total mass It is preferred that the weight ratio of body D is 1 to 10% by weight.

Other copolymerizable monomers can be used in the method for producing the copolymer of the present invention. Other copolymerizable monomers include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate ( excluding cyclic structures), acrylamide, N,N-dimethyl(meth)acrylamide, styrene, and the like.

Examples of the method for producing the copolymer include a method of polymerizing the vinyl-based monomer in the presence of a radical polymerization initiator having a radical generation site. In the method of polymerizing a vinyl-based monomer in the presence of a radical polymerization initiator having a radical generation site, radicals are generated from a radical generation site such as an azo group by heat or the like, thereby initiating polymerization. becomes. 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, Azo compounds such as 2′-azobis(isobutyronitrile) can be mentioned, and the type is not particularly limited as long as it decomposes at the polymerization reaction temperature to generate radicals. These can also be used as redox initiators in combination with reducing substances such as sulfites and L-ascorbic acid, as well as amines and the like. The amount of the radical polymerization initiator to be used may be appropriately adjusted according to its type.

The radical polymerization reaction can be carried out in various solvents. Among them, a hydraulic composition such as cement is used as an aqueous solution, so it is preferable to perform aqueous solution polymerization using water as a solvent. The aqueous solution polymerization may be a batch system, a continuous system, or a combination of two or more of these.

The reaction temperature in the radical polymerization reaction may be appropriately set according to the type of the radical polymerization initiator, and is not particularly limited, but is preferably 0 to 120° C., more preferably 20 to 100° C., More preferably, it is 50 to 90°C.

A chain transfer agent can be used in the polymerization reaction for the purpose of adjusting the molecular weight. The chain transfer agent is not particularly limited, but the chain transfer agent used in the present invention is not particularly limited as long as it is a compound capable of adjusting the molecular weight of the copolymer, and known chain transfer agents. can be used. Specifically, mercaptoethanol, thioglycerol, thioglycolic acid, mercaptopropionic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate, 2-mercaptoethane Thiol-based chain transfer agents such as sulfonic acid, n-dodecylmercaptan, octylmercaptan, and butylthioglycolate; halides such as carbon tetrachloride, carbon tetrabromide, methylene chloride, bromoform, and bromotrichloroethane; α-methylstyrene dimer, α-terpinene, γ-terpinene, dipentene, unsaturated hydrocarbon compounds such as terpinolene; primary alcohols such as 2-aminopropan-1-ol; secondary alcohols such as isopropanol; phosphorous acid, hypophosphorous acid, and its salts (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionous acid, metabisulfite, and its salts (sodium sulfite, potassium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite , sodium dithionite, potassium dithionite, sodium metabisulfite, potassium metabisulfite, etc.) and salts thereof.

In addition, the method for adding each monomer component used in the radical polymerization reaction to the reaction vessel is not particularly limited. It may be either a method of charging, or a method of charging a part into the reaction vessel at the initial stage of the reaction and dividing or continuously charging the rest into the reaction vessel. Moreover, the radical polymerization initiator and the chain transfer agent may be charged into the reaction vessel from the beginning, may be dropped into the reaction vessel, or may be combined.

For the purpose of the present invention, the weight average molecular weight of the copolymer is suitably in the range of 5000 to 200000, preferably 7000 to 150000, more preferably 7000 to 150000, in terms of polyethylene glycol/polyethylene oxide by gel permeation chromatography (GPC). is between 8,000 and 100,000.

The additive for hydraulic compositions according to the present invention is used in hydraulic compositions containing hydraulic binders for civil engineering, construction, secondary products and the like. Examples of such hydraulic compositions include cement paste, mortar and concrete.

The hydraulic composition additive according to the present invention can be used in combination with existing hydraulic composition additives. Examples of such additives for hydraulic compositions include AE water reducing agents, high-performance AE water reducing agents, AE agents, antifoaming agents, shrinkage reducing agents, thickeners, curing accelerators, and the like.

Various types of hydraulic binders such as ordinary Portland cement, early-strength Portland cement, medium-heat cement, and low-heat Portland cement can be used as the hydraulic binder used in the preparation of the hydraulic composition to which the additive for hydraulic compositions according to the present invention is applied. In addition to Portland cement, various mixed cements such as blast furnace cement, fly ash cement, and silica fume cement can be used. In addition, various admixtures such as ground blast furnace slag, fly ash, silica fume, fine limestone, and expansive agents may be used in combination with the various cements described above.

Aggregates used in the preparation of hydraulic compositions include fine aggregates and coarse aggregates. Examples of fine aggregates include river sand, mountain sand, sea sand, crushed sand, and slag fine aggregate. etc., and examples of coarse aggregate include river gravel, crushed stone, and lightweight aggregate.

According to the additive for hydraulic composition of the present invention, when added to the hydraulic composition, it has excellent dispersibility to uniformly disperse the hydraulic composition and reduces the viscosity of the hydraulic composition. Has an effect. As a result, workability and handling properties when producing a hardened body such as a hardened concrete body from the hydraulic composition are improved, and work efficiency can be improved. Furthermore, it is possible to reduce the load on a pumping device such as a pump, and to suppress the occurrence of clogging of the hydraulic composition in the pipes, thereby reducing the work burden and work cost.

Examples will be given below in order to make the configuration and effects of the present invention more specific, but the present invention is not limited to these Examples. In the following examples and comparative examples, "parts" means parts by weight and "%" means % by weight, unless otherwise specified. "EO" represents an oxyethylene group, and "PO" represents an oxypropylene group.

1. Synthesis of Copolymer (Additive for Hydraulic Composition) As shown in Table 1 below, monomer A, monomer B, monomer C and/or monomer, which are constituent unit species of the copolymer D are combined so that each has a predetermined mass ratio (%), and the synthesis of the copolymers of Examples 1 to 16 (PC-1 to PC-16) and Comparative Examples (R-1 to R-8) is performed. gone. Specific examples of methods for synthesizing copolymers are shown below.

1-1. Synthesis Example 1 (Synthesis of α-methallyl-ω-(monostyrenated phenoxy)-poly(n=30) oxyethylene)
A glass reactor equipped with a dropping funnel, a thermometer, and a stirrer was charged with 330 g of a monostyrenated phenol EO 30 mol adduct and 6.2 g of KOH, and stirred at 120° C. for 120 minutes while introducing dry nitrogen gas. Then, KOH was dissolved and dehydrated. While maintaining the internal liquid at 70° C., 10.0 g of methallyl chloride was slowly added dropwise over 60 minutes. After that, the mixture was reacted at 70° C. for 120 minutes and then at 90° C. for 120 minutes. The resulting precipitate of potassium chloride was removed, other by-products were distilled off under reduced pressure, and the residue was purified to obtain α-methallyl-ω-(monostyrenated phenoxy)-poly(n=30)oxyethylene.

1-2. Synthesis of Example 1 121.1 g of ion-exchanged water was charged into a 1000 mL round-bottomed flask equipped with a stirrer, a nitrogen inlet tube and a dropping funnel, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was adjusted to 65°C in a hot water bath. . In the reaction system, 3.6 g of sodium allylsulfonate, 262.2 g of α-methacryloyl-ω-methoxy-poly(n=9)oxyethylene, 29.1 g of methacrylic acid ester of monostyrenated phenol EO 10 mol adduct, methacrylic acid A uniformly stirred solution of 68.3 g, 10.8 g of cyclohexyl methacrylate, 8.9 g of methyl acrylate, 9.3 g of 3-mercaptopropionic acid and 95.5 g of deionized water was added dropwise over 2 hours. Furthermore, a solution obtained by diluting 4.3 g of 35% hydrogen peroxide water with 43.5 g of ion-exchanged water was simultaneously added dropwise to the reaction system over 3 hours. held for time. After completion of the reaction, the pH was adjusted to 6 using a 30% aqueous sodium hydroxide solution, and the concentration was adjusted to 40% with deionized water to obtain a reaction mixture. This reaction mixture was analyzed by gel permeation chromatography (GPC) and found to have a mass average molecular weight of 9,000. This reaction mixture was used as a copolymer (PC-1). The copolymer (PC-2) of Example 2 was synthesized in the same manner as in Example 1 above, except that the raw materials and amount charged were changed.

1-3. Synthesis of Example 3 27.0 g of ion-exchanged water was charged into a 1000 mL round-bottomed flask equipped with a stirrer, a nitrogen inlet tube and a dropping funnel, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was adjusted to 65°C in a hot water bath. . In the reaction system, 3.7 g of sodium allylsulfonate, 269.6 g of α-methacryloyl-ω-methoxy-poly(n=9)oxyethylene, 30.0 g of methacrylic acid ester of distyrenated phenol EO 12 mole adduct, and 70 methacrylic acid A uniformly stirred solution of .3 g, 9.0 g of thioglycerol and 95.4 g of deionized water was added dropwise over 2 hours. Furthermore, a solution obtained by diluting 4.5 g of 35% hydrogen peroxide water with 44.8 g of ion-exchanged water was simultaneously added dropwise to the reaction system over 3 hours. held for time. After completion of the reaction, the pH was adjusted to 6 using a 30% aqueous sodium hydroxide solution, and the concentration was adjusted to 40% with deionized water to obtain a reaction mixture. This reaction mixture was analyzed by gel permeation chromatography (GPC) and found to have a mass average molecular weight of 11,000. This reaction mixture was used as a copolymer (PC-3).

1-4. Synthesis of Example 4 152.7 g of ion-exchanged water was charged into a 1000 mL round-bottomed flask equipped with a stirrer, a nitrogen inlet tube and a dropping funnel, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was adjusted to 65°C in a hot water bath. . In the reaction system, α-methacryloyl-ω-methoxy-poly(n=23)oxyethylene 331.5 g, methacrylic acid 45.2 g, tetrahydrofurfuryl acrylate 15.0 g, 3-mercaptopropionic acid 3.9 g, ion exchange A uniformly stirred solution of 248.6 g of water was added dropwise over 2 hours. Furthermore, a solution obtained by diluting 5.8 g of sodium persulfate with 50.1 g of ion-exchanged water was added dropwise to the reaction system over 3 hours at the same time. . After completion of the reaction, the pH was adjusted to 6 using a 30% aqueous sodium hydroxide solution, and the concentration was adjusted to 40% with deionized water to obtain a reaction mixture. This reaction mixture was analyzed by gel permeation chromatography (GPC) and found to have a mass average molecular weight of 24,000. This reaction mixture was used as a copolymer (PC-4). The copolymers (PC-5) to (PC-14) of Examples 5 to 14 were synthesized in the same manner as in Examples 1, 3, and 4 above, except that the raw materials and charging amounts were changed. gone.

1-5. Synthesis of Example 15 In a 1000 mL flask equipped with a stirrer, nitrogen inlet tube and dropping funnel, 188.5 g of deionized water, α-(3-methyl-3-butenyl)-ω-hydroxy-poly(n=53)oxy After 264.2 g of ethylene was charged and uniformly dissolved with stirring, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was adjusted to 65° C. in a hot water bath. 24.3 g of acrylic acid, 15.2 g of α-methallyl-ω-(monostyrenated phenoxy)-poly(n=30)oxyethylene, 15.2 g of tetrahydrofurfuryl acrylate, and 9.1 g of butyl acrylate were mixed with deionized water. A solution diluted with 161.5 g was added dropwise over 3 hours, and 2.9 g of 3.5% hydrogen peroxide was added dropwise to the reaction system over 3 hours. - A solution obtained by diluting 3.1 g of ascorbic acid with 14.7 g of deionized water was added dropwise to the reaction system over 4 hours. Furthermore, the temperature of the reaction system was maintained at 65° C. and aging was carried out for 1 hour. The pH was adjusted to 6 using a 30% sodium hydroxide aqueous solution, and the concentration was adjusted to 40% with deionized water to obtain a reaction mixture. This reaction mixture was analyzed by gel permeation chromatography (GPC) and found to have a mass average molecular weight of 20,000. This reaction mixture was used as a copolymer (PC-15). The copolymer (PC-16) was synthesized in the same manner as in Example 15, except that the raw materials and amount charged were changed.

1-6. Synthesis of Comparative Example 1 In a 1000 mL round-bottomed flask equipped with a stirrer, a nitrogen inlet tube and a dropping funnel, 494.8 g of deionized water, α-methacryloyl-ω-methoxy-poly(n=9)oxyethylene 284.1 g, methacryl 66.6 g of acid, 8.9 g of 3-mercaptopropionic acid, and 3.5 g of sodium allylsulfonate were charged and dissolved uniformly with stirring. and Then, 6.9 g of sodium persulfate diluted with 34.5 g of deionized water was added to the reaction system to initiate the polymerization reaction. The temperature of the reaction system was kept at 60° C. and the polymerization reaction was carried out for 2 hours. Thereafter, 2.6 g of sodium persulfate diluted with 20.31 g of ion-exchanged water was added to the reaction system, and the temperature of the reaction system was maintained at 60° C. for 2 hours to carry out a polymerization reaction. The pH was adjusted to 6 using a 30% sodium hydroxide aqueous solution, and the concentration was adjusted to 40% with deionized water to obtain a reaction mixture. This reaction mixture was analyzed by gel permeation chromatography (GPC) and found to have a mass average molecular weight of 12,000. This reaction mixture was used as a copolymer (R-1).

1-7. Synthesis of Comparative Example 2
152.7 g of ion-exchanged water was introduced into a 1000 mL round-bottomed flask equipped with a stirrer, a nitrogen inlet tube and a dropping funnel, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was adjusted to 70° C. in a hot water bath. 331.6 g of α-methacryloyl-ω-methoxy-poly(n=23)oxyethylene, 45.2 g of methacrylic acid, 3.5 g of 3-mercaptopropionic acid, and 248.6 g of ion-exchanged water were uniformly stirred into the reaction system. The solution was added dropwise over 2 hours. Furthermore, a solution obtained by diluting 5.78 g of sodium persulfate with 24.51 g of ion-exchanged water was added dropwise to the reaction system over 3 hours at the same time. . After completion of the reaction, the pH was adjusted to 6 using a 30% aqueous sodium hydroxide solution, and the concentration was adjusted to 40% with deionized water to obtain a reaction mixture. This reaction mixture was analyzed by gel permeation chromatography (GPC) and found to have a mass average molecular weight of 25,000. This reaction mixture was used as a copolymer (R-2). Copolymers (R-3) to (R-6) were synthesized in the same manner as in Comparative Example 1, except that the raw materials and amounts charged were changed.

1-8. Synthesis of Comparative Example 7 In a 1000 mL flask equipped with a stirrer, a nitrogen inlet tube and a dropping funnel, 201.2 g of deionized water, α-(3-methyl-3-butenyl)-ω-hydroxy-poly(n=53)oxy After charging 361.0 g of ethylene and uniformly dissolving it with stirring, the atmosphere was replaced with nitrogen, and the temperature of the reaction system was adjusted to 65° C. in a hot water bath. A solution of 31.39 g of acrylic acid and 11.8 g of butyl acrylate diluted with 157.0 g of deionized water was added dropwise over 3 hours, and at the same time, 2.83 g of 3.5% hydrogen peroxide water was added to the reaction system over 3 hours. At the same time, a solution of 3.1 g of 3-mercaptopropionic acid and 3.1 g of L-ascorbic acid diluted with 15.1 g of deionized water was added dropwise to the reaction system over 4 hours. Furthermore, the temperature of the reaction system was maintained at 65° C. and aging was carried out for 1 hour. The pH was adjusted to 6 using a 30% sodium hydroxide aqueous solution, and the concentration was adjusted to 40% with deionized water to obtain a reaction mixture. This reaction mixture was analyzed by gel permeation chromatography (GPC) and found to have a mass average molecular weight of 34,000. This reaction mixture was used as a copolymer (R-7). Copolymer (R-8) was synthesized in the same manner as in Comparative Example 7, except that the raw materials and amount charged were changed.

1-9. Measurement of Weight Average Molecular Weight of Copolymer The weight average molecular weight of the copolymer was measured by gel permeation chromatography under the following measurement conditions.
<Measurement conditions>
Apparatus: Shodex GPC-101
Column: Showa Denko OHpak SB-G + SB-806M HQ + SB-806M HQ
Detector: differential refractometer (RI)
Eluent: 50 mM aqueous sodium nitrate solution Flow rate: 0.7 mL/min Column temperature: 40°C
Sample concentration: Eluent solution with a sample concentration of 0.5% by weight. It was adjusted and measured by NMR at 300 MHz to confirm that each monomer was polymerized.

A-1 to A-3, B-1 to B-10, C-1 to C-8, D-1 to D- 6 , and MA and BA shown in Table 1 above are the following monomers showing each body.
A-1: methacrylic acid A-2: sodium allylsulfonate A-3: acrylic acid B-1: α-methacryloyl-ω-methoxy-poly (n = 9) oxyethylene B-2: α-methacryloyl-ω- Methoxy-poly (n = 23) oxyethylene B-3: hydroxyethyl methacrylate B-4: α-methallyl-ω-hydroxy-poly (n = 25) oxyethylene B-5: hydroxyethyl acrylate B-6: α- methacryloyl-ω-methoxy-poly (n = 45) oxyethylene B-7: α-methacryloyl-ω-methoxy-poly (n = 68) oxyethylene B-8: α-methacryloyl-ω-hydroxy-oxypropylene poly ( n=113) oxyethylene B-9: α-(3-methyl-3-butenyl)-ω-hydroxy-poly(n=53) oxyethylene B-10: α-methallyl-ω-hydroxy-poly(n= 70) Oxyethylene C-1: methacrylic acid ester of monostyrenated phenol EO 10 mol adduct C-2: methacrylic acid ester of distyrenated phenol EO 12 mols adduct C-3: methacrylic acid of tristyrenated phenol EO 15 mols adduct Ester C-4: methacrylic acid ester of cumylphenol EO 23 mol adduct C-5: methacrylic acid ester of monostyrenated phenol EO 20 mol adduct C-6: α-methallyl-ω-(monostyrenated phenoxy)-poly (n = 30) Oxyethylene C-7: Methacrylic acid ester of tristyrenated phenol EO 23 mol PO 4 mol adduct C-8: Methacrylic acid ester of distyrenated phenol EO 23 mol adduct D-1: Cyclohexyl methacrylate D-2 : Tetrahydrofurfuryl acrylate D-3: Dicyclopentanyl methacrylate D-4: Tetrahydrofurfuryl methacrylate D-5: Cyclohexyl acrylate D-6: Dicyclopentanyl methacrylate MA: Methyl acrylate BA: Acrylic Butyl acid

Here, in Examples 1 to 16 (PC-1 to PC-16), although Example 3 (PC-3) contains the monomer C (C-2), the constituent unit species of the monomer D On the other hand, Example 4 (PC-4) contains the monomer D (D-2) but does not contain the constituent unit species of the monomer C. Furthermore, although Examples 6 and 8 (PC-6, PC-8) contain monomer C (C-4 or C-5), as in Example 3, the constituent unit species of monomer D is It does not contain Examples other than the above contain both monomer C and monomer D.

As described above, Examples 1 to 16 (PC-1 to PC-16) contain at least one of the structural unit species of monomer C and monomer D. On the other hand, Comparative Examples do not contain any of the structural unit species of the monomer C and the monomer D.

2. Mortar composition 2-1. Preparation of mortar composition (water cement ratio = 40%)
Under the compounding conditions described in Table 2, the above 1. was added to a mortar mixer conforming to JIS R5201. Predetermined amount of copolymer (additive) (Examples 1 to 11, Comparative Examples 1 to 3) prepared by synthesizing the copolymer of, 0.2 g of polyether antifoaming agent, water (Gamagori City Waterworks) Add ordinary Portland cement (manufactured by Taiheiyo Cement) for 30 seconds while stirring at a low speed with a mixer, and fine aggregate (Oigawa water system land sand, excluding those that remain in a 2.5 mm sieve) for the following 30 minutes. Seconds were added and kneaded for 180 seconds to prepare mortar compositions (Application Examples 1 to 11, Comparative Application Examples 1 to 3). The additive amount (%) of the additive relative to the mass of cement is shown in Table 4 below together with the test results. The copolymer (additive) and polyether antifoaming agent were part of the water.

2-2. Preparation of mortar composition (water cement ratio = 30%)
2-1 above. Similarly, under the compounding conditions described in Table 3, a mortar mixer conforming to JIS R5201 was added to the above 1. Predetermined amount of copolymer (additive) (Examples 12 to 16, Comparative Examples 4 to 8) prepared by synthesizing the copolymer of, 0.2 g of polyether antifoaming agent, water (Gamagori City Waterworks) Then, while stirring the mixer at a low speed, moderate heat Portland cement (manufactured by Ube Mitsubishi Cement) is added for 30 seconds, and fine aggregates (land sand produced in the Oi River water system, excluding those that remain in a 2.5 mm sieve) are added as follows. and kneaded for 180 seconds to prepare mortar compositions (Application Examples 12 to 16, Comparative Application Examples 4 to 8). The additive amount (%) of the additive relative to the mass of cement is shown in Table 4 below together with the test results. The copolymer (additive) and polyether antifoaming agent were part of the water.

3. Mortar flow test and J ₁₄ funnel flow down test For the mortar compositions prepared above (Application Examples 1 to 16, Comparative Application Examples 1 to 8), the mortar flow immediately after kneading (0 min) and after 30 min from the completion of kneading ( mm) and _J14 funnel run-down time (s) were measured respectively.
Mortar flow value (mm): Performed according to JIS R 5201 except that tapping was not performed.
J14 funnel flow down time (s): Measured in accordance with the Japan Society of Civil Engineers Concrete Standard Specifications JSCE- _F541 "Test Method for Fluidity of Filling Mortar".

The test results of the mortar compositions with a water-cement ratio of 40% (Application Examples 1 to 11 and Comparative Application Examples 1-3) are shown in Table 4 below, and the concrete compositions with a water-cement ratio of 30% (Application Examples 12 to 16 and Comparative Application Examples 4 to 8) are shown in Table 5 below.

As is clear from the results shown in Tables 4 and 5, the concrete compositions (Application Examples 1 to 16) prepared by adding the additives for hydraulic compositions of the present invention (Examples 1 to 16) , for the concrete compositions of Comparative Application Examples 1 to 8, both immediately after kneading (0 min) and after 30 min, the mortar composition (hydraulic composition) was determined from the slump flow value and J ₁₄ funnel flow time value. Viscosity improvement is observed. Therefore, it was confirmed that the transportability during pressure feeding by a pump or the like is excellent.

Claims (6)

a monomer A having a vinyl group and an acid group in its constituent units and having a mass ratio of 1 to 98% by mass with respect to the total mass;
A monomer B represented by the following chemical formula 1 and having a mass ratio of 1 to 98% by mass with respect to the total mass;
An additive for a hydraulic composition constituted by a copolymer obtained by copolymerizing a monomer C represented by the following chemical formula 2 and contained in a mass ratio of 1 to 98% by mass with respect to the total mass.

(where R ¹ , R ² and R ³ represent 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 1 having 2 to 4 carbon atoms or represents a plurality of oxyalkylene groups, p represents an integer of 0 to 5, q represents 0 or 1, and m represents an integer of 1 to 29 )

(However, R ⁶ , R ⁷ and R ⁸ represent a hydrogen atom or a methyl group, R ⁹ is represented by Chemical Formula 3 below, and R ¹⁰ O represents one or more oxyalkylene groups having 2 to 4 carbon atoms. , s represents an integer of 0 to 5, t represents 0 or 1, and n represents an integer of 0 to 300)

(where R ¹¹ and R ¹² represent a hydrogen atom or a methyl group, and a represents an integer of 1 to 3) a monomer A having a vinyl group and an acid group in its constituent units and having a mass ratio of 1 to 98% by mass with respect to the total mass;
A monomer B represented by the following chemical formula 4 and having a mass ratio of 1 to 98% by mass with respect to the total mass,
An additive for a hydraulic composition comprising a copolymer obtained by copolymerizing a monomer D represented by the following chemical formula 5 and contained in a mass ratio of 1 to 98% by mass with respect to the total mass.

(where R ¹ , R ² and R ³ represent 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 1 having 2 to 4 carbon atoms or represents a plurality of oxyalkylene groups, p represents an integer of 0 to 5, q represents 0 or 1, and m represents an integer of 1 to 300)

(However, R ¹³ represents a hydrogen atom or a methyl group, and R ¹⁴ represents an alkyl group having 3 to 22 carbon atoms containing a cyclic structure (excluding a phenoxy group) or an ether group.) a monomer A having a vinyl group and an acid group in its constituent units and having a mass ratio of 1 to 97% by mass with respect to the total mass;
A monomer B represented by the following chemical formula 6 and having a mass ratio of 1 to 97% by mass with respect to the total mass,
A monomer C represented by the following chemical formula 7 and having a mass ratio of 1 to 97% by mass with respect to the total mass and a monomer C represented by the chemical formula 9 below and having a mass ratio of 1 to 97% by mass relative to the total mass Hydraulic composition additive constituted as a copolymer obtained by copolymerizing the monomer D contained in.

(where R ¹ , R ² and R ³ represent 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 1 having 2 to 4 carbon atoms or represents a plurality of oxyalkylene groups, p represents an integer of 0 to 5, q represents 0 or 1, and m represents an integer of 1 to 29 )

(However, R ⁶ , R ⁷ and R ⁸ represent a hydrogen atom or a methyl group, R ⁹ is represented by Chemical Formula 8 below, and R ¹⁰ O represents one or more oxyalkylene groups having 2 to 4 carbon atoms. , s is an integer of 0 to 5, t is 0 or 1, and n is an integer of 0 to 300)

(However, R ¹¹ and R ¹² represent a hydrogen atom or a methyl group, and a represents an integer of 1 to 3.)

(However, R ¹³ represents a hydrogen atom or a methyl group, and R ¹⁴ represents an alkyl group having 3 to 22 carbon atoms containing a cyclic structure or an ether group.) The mass ratio of the monomer A to the total mass is 1 to 25% by mass,
The mass ratio of the monomer B to the total mass is 65 to 95% by mass,
4. The additive for hydraulic composition according to claim 1 , wherein the mass ratio of said monomer C to the total mass is 1 to 20% by mass . The mass ratio of the monomer A to the total mass is 1 to 25% by mass,
The mass ratio of the monomer B to the total mass is 65 to 95% by mass,
4. The additive for hydraulic composition according to claim 2 , wherein the weight ratio of said monomer D to the total weight is 1 to 10% by weight. The mass ratio of the monomer A to the total mass is 1 to 25% by mass,
The mass ratio of the monomer B to the total mass is 65 to 95% by mass,
The mass ratio of the monomer C to the total mass is 1 to 20% by mass,
4. The additive for hydraulic composition according to claim 3, wherein the mass ratio of said monomer D to the total mass is 1 to 10% by mass.