Method for stabilizing an inorganic binder composition, and inorganic binder composition

Abstract

The present invention provides a method for stabilizing an inorganic binder composition containing a fly ash-containing inorganic binder, comprising (a) providing a dispersant, (b) providing an inorganic binder composition, and (c) mutually grinding and / or mutually mixing the dispersant provided in step (a) and the inorganic binder composition provided in step (b), wherein the dispersant is a phenol resin-based dispersant obtained from the polycondensation of a specific monomer.

Description

Technical Field

[0001] The present invention relates to a method for stabilizing an inorganic binder composition and an inorganic binder composition.

Background Art

[0002] In recent years, in the civil engineering and construction industries, slag and fly ash, which are industrial by-products, have been actively used as inorganic binders for the purpose of effective utilization of resources and reduction of environmental load.

[0003] However, when slag or fly ash is used as at least a part of the inorganic binder, the stability of the obtained inorganic binder composition may decrease.

[0004] In addition, for improving the workability and the like of an inorganic binder composition such as a concrete composition, it is known to use admixtures such as an AE agent (air entraining agent) and a water reducing agent. As such an admixture, a polycarboxylic acid-based polymer is widely known, and in recent years, it is also known to use a phenolic resin-based dispersant obtained by polycondensing a plurality of types of phenolic comonomers and aldehydes.

[0005] Regarding this, for example, International Publication No. 2018 / 147378 pamphlet proposes an admixture containing a phenolic resin-based dispersant obtained by polycondensing a plurality of types of phenolic comonomers and aldehydes and a polycarboxylic acid-based polymer. In International Publication No. 2018 / 147378 pamphlet, such an admixture suppresses the precipitation of colored fine particles contained in the hydraulic composition on the surface of the hardened body and the occurrence of blackening, and also suppresses the delay of coagulation, pre-dinder, and the decrease in initial strength even when a large amount of inorganic powder is contained, and is further excellent in water reducing property.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

[0007] As described above, when fly ash is used as an inorganic binder, especially when fly ash is used in a relatively high proportion, it can be difficult to maintain the stability of the resulting inorganic binder composition.

[0008] In contrast, the present invention aims to provide a method for solving these problems and an inorganic binder composition. [Means for solving the problem]

[0009] As a result of diligent research, the inventors of the present invention have found that the above problems can be solved by a specific phenolic resin-based dispersant obtained by polycondensation of multiple types of phenolic comonomers and aldehydes, and have completed the present invention described below.

[0010] Embodiment 1 A method for stabilizing an inorganic binder composition containing a fly ash-containing inorganic binder, comprising the following steps (a) to (c): (a) To provide a dispersant, (b) To provide the inorganic binder composition, and (c) Mutually grind and / or mutually mix the dispersant provided in step (a) and the inorganic binder composition provided in step (b). Includes, The dispersant is the following monomers (i) to (v): (i) Monomers represented by formula (I) in a molar percentage: [ka] (ii) Monomers represented by formula (II) in b mol%: [ka] (iii) c mol% of the monomer represented by formula (III): [Chemical formula] (iv) d mol% of the monomer represented by formula (IV): [Chemical formula] (v) e mol% of an aldehyde, preferably formaldehyde, paraformaldehyde, metaformaldehyde, or formalin, or a mixture thereof, (wherein, R 1 is H or a C 1~4 alkyl group, or a C 2~5 acyl group, R 2 is H, an alkali metal ion, an alkaline earth metal ion, or a moiety having the following structure: [Chemical formula] R 3 is H, or O-R 2 and R 4 is H, a C 1~4 alkyl group, or a phosphate ester group, R 5 is H, a C 1~18 alkyl group, a polyisobutene moiety, or a sulfonic acid moiety, A1 and A2 are each independently a C x H 2x group, where x = 2 - 5, n = 1 - 350, m = 2 - 300, The molar ratio of a:b:c:d is 0.1 - 2.0:0.1 - 6.0:0.1 - 2.0:0.0 - 0.5, and (the molar ratio of (a + b + c + d):e is 1:10 - 10:1) A phenolic resin - based dispersant obtained from the polycondensation of Embodiment 2 The method according to Embodiment 1, wherein the fly ash content is 70% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less, based on the total dry mass of the inorganic binder. Embodiment 3 The method according to Embodiment 1 or 2, wherein the fly ash conforms to the JIS A 6201:2015 standard. Embodiment 4 The method according to any one of Embodiments 1 to 3, wherein the phenolic resin dispersant is mutually crushed and / or mutually mixed in step (c) in an amount of 0.1 to 5% by mass, preferably 0.5 to 1% by mass, relative to the total dry mass of the inorganic binder. Embodiment 5 The method according to any one of Embodiments 1 to 4, wherein in step (c), the dispersant is mutually ground with the inorganic binder composition using a ball mill or a vertical roll mill. Embodiment 6 The method according to any one of Embodiments 1 to 5, wherein the inorganic binder composition further contains at least one polycarboxylic acid polymer and / or gluconate. Embodiment 7 An inorganic binder composition, the following: (a) 200-700 kg / m 3 fly ash-containing inorganic binder, (b) 700~950 kg / m 3 Fine aggregate, preferably sand, (c) 800~1100 kg / m 3 Coarse aggregate, preferably gravel, and (d) At least one dispersant in an amount of 0.1 to 5% by mass, preferably 0.5 to 1% by mass, relative to the total dry mass of the inorganic binder, and (e) 0.001 to 0.03% by mass of an air-entraining agent relative to the total dry mass of the inorganic binder, Includes, An inorganic binder composition characterized in that the dispersant is a phenol resin-based dispersant obtained by polycondensation of the above monomers (i) to (v). Embodiment 8 The inorganic binder composition according to Embodiment 7, wherein the inorganic binder essentially consists of cement and fly ash. Embodiment 9 The inorganic binder composition according to Embodiment 7, wherein the inorganic binder further comprises cement, fly ash, and steel slag, particularly pulverized blast furnace slag. Embodiment 10 The inorganic binder composition according to Embodiment 8 or 9, wherein the mass ratio of the fly ash to the cement is 1:20 to 1:1, preferably 1:10 to 1:2. Embodiment 11 An inorganic binder composition according to any one of Embodiments 7 to 10, wherein the fly ash conforms to the JIS A 6201:2015 standard. Embodiment 12 An inorganic binder composition according to any one of Embodiments 7 to 11, wherein, when mixed with water at a mass ratio of 0.25 to 0.6 to cement, the decrease in the air content of the inorganic binder composition is 10% or less within the first hour. Embodiment 13 An inorganic binder composition according to any one of embodiments 7 to 12, further comprising at least one polycarboxylic acid polymer and / or gluconate. Embodiment 14 A molded article obtained by mixing an inorganic binder composition according to any one of Embodiments 7 to 12 with water in a mass ratio of water to the cement of 0.29 to 0.6, and then curing the resulting mixture. Embodiment 15 The molded article according to Embodiment 12, wherein the spacing coefficient, as evaluated according to EN 480-11, is less than 200 micrometers, or preferably less than 175 micrometers. [Effects of the Invention]

[0011] According to the method and inorganic binder composition of the present invention, the stability of the obtained inorganic binder composition can be improved even when fly ash is used as the inorganic binder, particularly when fly ash is used in a relatively high proportion as the inorganic binder. [Modes for carrying out the invention]

[0012] A method for improving the stability of an inorganic binder composition containing a fly ash-containing inorganic binder. The present invention provides a method for improving the stability of an inorganic binder composition containing a fly ash-containing inorganic binder, comprising the following steps (a) to (c): (a) To provide a dispersant, (b) To provide an inorganic binder composition, and (c) Mutually grind and / or mutually mix the dispersant provided in step (a) and the inorganic binder composition provided in step (b).

[0013] Here, the dispersant is a phenol resin-based dispersant obtained from the polycondensation of monomers (i) to (v).

[0014] According to the method of the present invention, when fly ash is used as an inorganic binder, and especially when fly ash is used in a relatively high proportion as an inorganic binder, the stability of the resulting inorganic binder composition can be improved, and in particular, the stability of the air content of the resulting inorganic binder composition can be improved.

[0015] In the method of the present invention, the proportion of fly ash in the fly ash-containing inorganic binder may be 70% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less, 30% by mass or less, or 20% by mass or less, and may also be 1% by mass or more, 5% by mass or more, 10% by mass or more, or 20% by mass or more. Furthermore, the mass ratio of fly ash to cement may be 1:20 to 1:1, preferably 1:10 to 1:2. Examples of inorganic binders other than fly ash include cement, particularly Portland cement. Furthermore, the inorganic binder may essentially consist of cement and fly ash. The inorganic binder composition may include cement, fly ash, and further steel slag, particularly pulverized blast furnace slag.

[0016] The fly ash may conform to the JIS A 6201:2015 standard. Alternatively, the fly ash may be of class F or C according to ASTM C 618.

[0017] The phenolic resin dispersant can be mutually crushed and / or mutually mixed in step (c) in an amount of 0.1 to 5% by mass, preferably 0.5 to 2.0% by mass, more preferably 0.5 to 1.5% by mass, and even more preferably 0.5 to 1.0% by mass, relative to the total dry mass of the inorganic binder.

[0018] In step (c), the dispersant can be mutually ground with the inorganic binder composition using a ball mill or a vertical roll mill.

[0019] In an inorganic binder composition whose workability has been improved by the method of the present invention, when mixed with water at a mass ratio of 0.25 to 0.6 to cement, the decrease in the air content of the inorganic binder composition may be 10% or less within the first hour. Therefore, in this case, the air content of the inorganic binder composition may increase within this first hour.

[0020] The phenolic resin-based dispersant can be used in amounts of 0.1 to 10% by mass, 0.1 to 5% by mass, or 0.5 to 1% by mass, based on solid content relative to the total mass of the inorganic binder.

[0021] An inorganic binder composition whose workability has been improved by the method of the present invention can be molded into a molded article, for example, by mixing this inorganic binder composition with water in a mass ratio of water to inorganic binder of 0.25 to 0.6, and then curing the resulting mixture.

[0022] The inorganic binder composition obtained by the method of the present invention further contains aggregate, thereby forming a concrete composition. Examples of aggregate include fine aggregate and coarse aggregate. Preferred fine aggregates are mountain sand, land sand, river sand, and crushed sand, while preferred coarse aggregates are mountain gravel, land gravel, river gravel, crushed stone, and hard sandstone. Depending on the application, lightweight aggregate may also be used.

[0023] For example, an inorganic binder composition whose stability has been improved by the method of the present invention may include the following: (a) 200-700 kg / m 3 fly ash-containing inorganic binder, (b) 700~950 kg / m 3 Fine aggregate, preferably sand, (c) 800~1100 kg / m 3 Coarse aggregate, preferably gravel, (d) At least one phenolic resin-based dispersant in an amount of 0.1 to 5% by mass, preferably 0.5 to 1% by mass, relative to the total dry mass of the inorganic binder, and (e) an air-entraining agent in an amount of 0.001 to 0.03% by mass relative to the total dry mass of the inorganic binder.

[0024] Furthermore, this inorganic binder composition may include the following: (a) 5 to 95% by mass, preferably 5 to 60% by mass, an inorganic binder containing fly ash, (b) 5 to 85% by mass, preferably 20 to 80% by mass, at least one type of aggregate, (c) Optionally, 0.1 to 10% by mass of other additives, (d) an amount of water, optionally, such that the mass ratio of water to solids is 0.1 to 0.6, preferably 0.2 to 0.5, and particularly 0.2 to 0.35.

[0025] The monomers (i) to (v) used to obtain a phenolic resin-based dispersant by polycondensation are described in detail below.

[0026] monomer(i) Monomer (i) is represented by formula (I): [ka]

[0027] In formula (I), R 1 H or C 1~4 Alkyl alkyl group, or C 2~5 It is an acyl group, R 5 H, C 1~18 The alkyl group, polyisobutene, or sulfonic acid portion, A1 is C x H 2x This is the base, where x = 2 to 5. n = 1 to 350.

[0028] Monomer (i) is a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to phenol or a substituted product thereof, and also includes derivatives of alkylene oxide adducts (alkyl esters or fatty acid esters).

[0029] R 1 C in 1~4 Examples of alkyl groups include methyl, ethyl, propyl, and butyl groups, which may have branched structures (e.g., isopropyl, isobutyl, sec-butyl, tert-butyl) and / or cyclic structures (e.g., cyclopropyl, cyclobutyl).

[0030] R 1Examples of C1-C5 acyl groups in this context include saturated or unsaturated acyl groups (R'(CO)- groups, where R' is a hydrocarbon group with 1-4 carbon atoms). For example, saturated acyl groups with 2-4 carbon atoms include acetic acid, propionic acid, butanoic acid, and pentanoic acid.

[0031] R 5 C in 1~18 Examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl (lauryl), tetradecyl (myristyl), hexadecyl (palmityl), and octadecyl (stearyl) groups, which may have branched structures (e.g., isopropyl, isobutyl, sec-butyl, tert-butyl, neopentyl, etc.) and / or cyclic structures (e.g., cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl, etc.).

[0032] Alkylene oxide (-A1O-) is an alkylene group (C x H 2x It has a group (x = 2 to 5). Therefore, the alkylene oxide may be ethylene oxide, propylene oxide, butylene oxide, and pentene oxide, and these alkylene oxides may be added individually or in combination. When two or more alkylene oxides are added in combination, they may be added in block or random manner.

[0033] In one embodiment, the alkylene group (C) of the alkylene oxide (-A1O-) x H 2xAt least a portion of the alkylene group (C) may be 1 mol% or more, preferably 1 mol% to 20 mol%, more preferably 3 mol% to 20 mol%, having 3 to 5 carbon atoms (x=3 to 5). This percentage may be 1 mol% or more, 5 mol% or more, 10 mol% or more, 20 mol% or more, 25 mol% or more, or 30 mol% or more. Alternatively, this percentage may be less than 100 mol%, 90 mol% or less, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less, 40 mol% or less, 30 mol% or less, or 20 mol% or less. x H 2x If at least some of the carbon atoms in the group have 3 to 5 carbon atoms, the resulting phenolic resin-based dispersant can be made relatively hydrophobic, thereby improving the stability of the resulting inorganic binder composition, especially when fly ash is used as the inorganic binder, particularly when fly ash is used in a relatively high proportion.

[0034] In other embodiments, the alkylene group (C) of alkylene oxide (-A1O-) x H 2x The group may all have 2 carbon atoms (x=2), that is, it may all be ethylene.

[0035] n is the average number of moles of alkylene oxide added, and represents a number between 1 and 350, 1 and 300, or 1 and 150. Here, n may be 3 or greater.

[0036] Monomer (i) can be used alone or in combination of two or more types.

[0037] monomer(ii) The monomer (ii) is represented by the following formula (II): [ka]

[0038] In formula (II), R 2This is H, alkali metal ions, alkaline earth metal ions, or a portion having the following structure: [ka] R 3 is H, or OR 2 And, R 5 H, C 1~18 The alkyl group, polyisobutene, or sulfonic acid portion, A1 and A2 are independent of each other, C x H 2x This is the base, where x = 2 to 5. n = 1 to 350.

[0039] Monomer (ii) is a phosphate ester derivative of a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to phenol or a substituted compound thereof.

[0040] R 2 Examples of alkali metal ions in this context include sodium, potassium, and R 2 Examples of alkaline earth metal ions in this context include calcium and magnesium.

[0041] R 5 For A1 and n, refer to the description of monomer (i).

[0042] Monomer (ii) can be used alone or in combination of two or more types.

[0043] Monomer (iii) The monomer (iii) is represented by the following formula (III): [ka]

[0044] In formula (III), R 4 H, C 1~4 It is an alkyl group or a phosphate ester group, A1 and A2 are independent of each other, C x H 2x This is the base, where x = 2 to 5. n = 1 to 350, m = 2 to 300.

[0045] Monomer (iii) is a compound in which an alkylene oxide is added to the two hydroxyl groups of hydroxyethylphenol, and also includes derivatives of the alkylene oxide adduct (phosphate ester).

[0046] This hydroxyethylphenol may be o-hydroxyethylphenol, m-hydroxyethylphenol, or p-hydroxyethylphenol. The monomer (iii) is preferably a compound (and its ester derivative) obtained by adding an alkylene oxide having 2 to 5 carbon atoms to o-hydroxyethylphenol.

[0047] By anionizing the end of monomer (iii), that is, by forming a phosphate ester derivative, the mixing time of the mortar can be shortened when added to a hydraulic composition.

[0048] R 4 C 1~4 Regarding the lukyl group, the R of monomer (i) 1 You can refer to the description regarding A1 and A2. For A1 and A2, you can refer to the description regarding A1 of monomer(i). For n, you can refer to the description regarding n1 of monomer(i).

[0049] m represents the average number of moles of alkylene oxide added, and is a number between 2 and 300, 5 and 250, or 5 and 200.

[0050] Monomer (iii) can be used alone or in combination of two or more types.

[0051] monomer(iv) (Monomer (iv) is represented by the following formula (IV): [ka]

[0052] In formula (IV), R 5 H, C 1~18 It is an alkyl group, polyisobutene, or sulfonic acid moiety.

[0053] R 5 For more information, see the description of monomer(i).

[0054] monomer(v) The monomer (v) is an aldehyde, preferably formaldehyde, metaformaldehyde, paraformaldehyde, or formalin, or a mixture thereof.

[0055] Monomer(v) can be used alone or in combination of two or more types.

[0056] Molar ratio of monomers The molar ratio of monomers (i) to (iv), i.e., the molar ratio of a:b:c:d, may be 0.1 to 2.0:0.1 to 6.0:0.1 to 2.0:0.0 to 0.5. In other words, in this case, monomer (iv) is not an essential component and can be omitted. Also, the molar ratio of a:b:c:d may be 0.5 to 1.5:0.5 to 6.0:0.1 to 1.0:0.0 to 0.5, 0.5 to 1.5:0.5 to 6.0:0.1 to 1.0:0.0, or 0.1 to 2.0:0.1 to 6.0:0.1 to 2.0:0.0.

[0057] The molar ratio of monomer (v) to the sum of monomers (i) to (iv), the molar ratio (a+b+c+d):e, may be 1:10 to 10:1. Alternatively, this ratio may be 2:10 to 10:2, or 3:10 to 10:3.

[0058] Polymerization method for obtaining phenolic resin-based dispersants The polymerization method for obtaining the above-mentioned phenol resin-based dispersant by polycondensation of the above-mentioned monomers is not particularly limited.

[0059] Furthermore, there are no particular limitations on the order or method of adding each monomer during polycondensation. For example, the entire amount of all monomers to be reacted can be added all at once before the polycondensation reaction, some of the monomers to be used can be added before the polycondensation reaction and then the remainder can be added dropwise, or some of the monomers to be used can be added before the polycondensation reaction and the remaining monomers can be added after a certain reaction time has elapsed.

[0060] Polycondensates can be obtained, for example, by polycondensing the monomers to be used in the presence of a dehydrating catalyst, either in a solvent-free or solvent-based manner, at a reaction temperature of 80°C to 150°C, under atmospheric pressure to pressurized conditions, for example, 0.001 to 1 MPa (gauge pressure).

[0061] Examples of the above-mentioned dehydration catalysts include hydrochloric acid, perchloric acid, nitric acid, formic acid, methanesulfonic acid, octylsulfonic acid, dodecylsulfonic acid, vinylsulfonic acid, allylsulfonic acid, phenolsulfonic acid, acetic acid, sulfuric acid, diethyl sulfate, dimethyl sulfate, phosphoric acid, oxalic acid, boric acid, benzoic acid, phthalic acid, salicylic acid, pyruvic acid, maleic acid, malonic acid, nitrobenzoic acid, nitrosalicylic acid, p-toluenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid, fluoroacetic acid, thioglycolic acid, mercaptopropionic acid, activated clay, etc. These dehydration catalysts can be used individually or in combination of two or more types.

[0062] Furthermore, when carrying out the polycondensation reaction under a solvent, the solvent can be water, glycol ether compounds such as propylene glycol monomethyl ether (PGME), aromatic compounds such as toluene and xylene, or cyclic aliphatic compounds such as methylcyclohexane. In addition, it is also possible to use a solvent that is suitable as a dehydration catalyst (acid catalyst), such as acetic acid.

[0063] The reaction can preferably be carried out at a temperature of 95°C to 130°C, and the polycondensation reaction can be completed by allowing the reaction to proceed for 3 to 25 hours.

[0064] The polycondensation reaction is preferably carried out under acidic conditions, and it is desirable that the pH of the reaction system be 4 or less.

[0065] In addition to the monomers mentioned above, other monomers that can polycondense with these compounds may be added to the monomer mixture, as long as they do not impair the effects of the present invention.

[0066] After the polycondensation reaction is complete, various known methods can be employed to reduce the content of unreacted monomers (v) (aldehydes, etc.) in the reaction system. For example, methods include making the pH of the reaction system alkaline and heating it to 60-140°C, reducing the pressure of the reaction system (for example, setting the gauge pressure to -0.1 to -0.001 MPa) to volatilize and remove the unreacted monomers (v), and adding small amounts of sodium bisulfite, ethylene urea, and / or polyethyleneimine.

[0067] The dehydration catalyst used in the reaction can be neutralized after the reaction is complete and removed by filtration in the form of a salt. However, even if the catalyst is not removed, the performance of the present invention as a dispersant, as described later, will not be impaired. Methods for removing the catalyst other than filtration include phase separation, dialysis, ultrafiltration, and the use of ion exchangers.

[0068] Furthermore, neutralizing the reaction product and diluting it with water improves the ease of measurement and other workability when used as a dispersant. Examples of basic compounds used for neutralization include alkaline hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth hydroxides such as calcium hydroxide, and organic amines such as ammonia, monoethanolamine, diethanolamine, and triethanolamine. One or two of these can be used.

[0069] The final phenol resin-based dispersant obtained is preferably in the range of 1,000 to 50,000, 1,000 to 30,000, 1,000 to 10,000, or 2,000 to 9,000 in terms of weight-average molecular weight (calculated by gel permeation chromatography (hereinafter referred to as "GPC method"), on a polyethylene glycol basis) to improve the stability of the inorganic binder composition, and in particular to improve the stability of the air content of the inorganic binder composition.

[0070] additives In the method of the present invention for improving the stability of an inorganic binder composition containing a fly ash-containing inorganic binder, other additives, such as polycarboxylic acid-based dispersants, particularly polycarboxylic acid ether-based dispersants, can be used in combination with the phenolic resin-based dispersant of the present invention. When such other additives are mixed with the inorganic binder composition by mutual grinding and / or mixing, these other additives can be mixed with the inorganic binder composition simultaneously with the phenolic resin-based dispersant of the present invention, before the phenolic resin-based dispersant of the present invention, or after the phenolic resin-based dispersant of the present invention.

[0071] The blending ratio of the phenol resin-based dispersant and the polycarboxylic acid-based dispersant of the present invention (phenol resin-based dispersant: polycarboxylic acid-based dispersant (mass ratio)) may be 1:99 to 99:1, 1:9 to 3:1, or 1:5 to 1:1. When the phenol resin-based dispersant and the polycarboxylic acid-based dispersant of the present invention are used in combination, they can be used in a range of 0.1 to 10% by mass or 0.1 to 5% by mass, based on the solid content relative to the total mass of the inorganic binder.

[0072] Other additives include at least one other cement or concrete additive selected from the group consisting of other cement dispersants, high-performance AE water-reducing agents, high-performance water-reducing agents, AE water-reducing agents, water-reducing agents, air-entraining agents (AE agents), foaming agents, defoaming agents, setting retarders, setting accelerators, separation reducing agents, thickeners, shrinkage reducing agents, curing agents, water-repellent agents, etc. In particular, gluconates, especially sodium gluconate, can be used as a retarder among the other additives.

[0073] For information on polycarboxylic acid-based dispersants that can be used in this invention, please refer to the description in International Publication No. 2018 / 147378.

[0074] Specifically, the polycarboxylic acid polymer Q that can be used in the present invention is a polycarboxylic acid polymer having structural units having an amino group and an imino group, and / or structural units having an amino group, an imino group and an amide group.

[0075] The polycarboxylic acid polymer Q acts as a dispersant in hydraulic compositions, and its use is expected to result in concrete with less slump loss.

[0076] In the polycarboxylic acid polymer Q described above, structural units having an amino group and an imino group, or structural units having an amino group, an imino group, and an amide group, are structural units derived from a compound having an amino group and an imino group, or a compound having an amino group, an imino group, and an amide group, respectively.

[0077] Furthermore, the compound having an amino group and an imino group, or a compound having an amino group, an imino group and an amide group, is a compound that, in its unit structure, has at least 1 mole each of an amino group which is a primary amine and an imino group which is a secondary amine, and optionally, an amide group (not essential) formed by the condensation of a carboxylic acid with an amino group or an imino group, per mole of unit structure.

[0078] The above-mentioned compounds may be either low-molecular-weight compounds or high-molecular-weight compounds. For example, examples of low-molecular-weight compounds include aliphatic, alicyclic, or aromatic amines such as ethylamine, ethyleneamine, diethylamine, or aniline; heterocyclic amines such as 1-benzofuran-2-ylamine or 4-quinolylamine; aliphatic imines such as hexylidenamine or isopropylidenamine; aliphatic, alicyclic, or aromatic amides such as acetamide, benzamide, or lactam; and compounds derived from hydroxylamine, acid amide, etc., which have an amino group and an imino group, and / or compounds having an amino group, an imino group, and an amide group. Furthermore, adducts obtained by adding oxygen-containing or nitrogen-containing functional groups such as alkylene oxide, halogen-containing (fluorine, bromine, iodine) substituents, etc., to the compounds may also be included. Examples of high-molecular-weight compounds include, for example, compounds obtained by polymerizing one or more of the exemplified compounds that can be derived from the above-mentioned low-molecular-weight compounds, or polyalkylene polyamines or polyamide polyamines.

[0079] The molecular weight of the above compound is 900 to 10,000, preferably 900 to 3,000, and more preferably 900 to 2,000. In this case, the above compound may specifically be polyalkylene polyamine or polyamide polyamine, which may also include those to which polyalkylene oxide has been added.

[0080] In other words, in a preferred embodiment, the structural unit having the amino group and the imino group is preferably a structural unit derived from a polyalkylene polyamine, and the polyalkylene polyamine may include a polyalkylene polyamine to which a polyalkylene oxide has been added.

[0081] Furthermore, the structural units having amino groups, imino groups, and amide groups are preferably structural units derived from polyamide polyamines, and the polyamide polyamine may include polyalkylene polyamines to which polyalkylene oxide has been added.

[0082] Examples of the above-mentioned polyalkylene polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, or mixtures of high molecular weight polyethylene polyamines which are mixtures containing many ethylene units and nitrogen atoms, as well as polymers of cyclic imines such as polyethyleneimine, polypropyleneimine, poly-3-methylpropylimine, and poly-2-ethylpropylimine, and polymers of unsaturated amines such as polyvinylamine and polyallylamine. Furthermore, polyalkylene polyamines may also be copolymers of cyclic imines such as ethyleneimine, propyleneimine, 3-methylpropylimine, and 2-ethylpropylimine, unsaturated amides and imides such as N-vinylacetamide, N-vinylformamide, and N-vinylphthalimide, and unsaturated compounds copolymerizable with these. Examples of unsaturated compounds copolymerizable with cyclic imines, unsaturated amides, unsaturated imides, etc. include dimethylacrylamide, styrene, methyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid, styrene sulfonic acid and their salts, cyclic sulfide compounds such as ethylene sulfide and propylene sulfide, cyclic ethers such as oxetane, mono- or bisalkyloxetane, mono- or bisalkylchloromethyloxetane, tetrahydrofuran, mono- or bisalkyltetrafluorofuran, cyclic formals such as 1,2-dioxofran and trioxofran, and N-substituted alkylimines such as N-methylethyleneimine.

[0083] Furthermore, a polyalkylene polyamine to which polyalkylene oxide has been added is a compound obtained by copolymerizing at least two molecules of the above-mentioned polyalkylene polyamine with at least one molecule of alkylene oxide. The at least two molecules of polyalkylene polyamine constituting such a polyalkylene polyamine-alkylene oxide copolymer may be the same compound or different compounds. Examples of this alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide, and these can be used in combination. Of the above alkylene oxides, ethylene oxide is preferred in terms of improving the water-reducing effect. In a polyalkylene polyamine-alkylene oxide copolymer, if two or more molecules of alkylene oxide are copolymerized for every two molecules of polyalkylene polyamine, the alkylene oxides may form polyoxyalkylene chains through mutual addition polymerization. Alkylene oxide may be used alone or in combination of two or more types. When a polyoxyalkylene chain is formed using two or more types of alkylene oxide, the two or more alkylene oxides constituting the polyoxyalkylene chain may be linked in a block-like manner or randomly linked. Furthermore, if two or more polyoxyalkylene chains are present in one molecule of polyalkylene polyamine copolymer, each polyoxyalkylene chain may be the same or different.

[0084] Polyamide polyamines include compounds obtained by condensation polymerization of the above-mentioned polyalkylene polyamines with dibasic acids, dibasic acid anhydrides, dibasic acid esters, and dibasic acid dihalides via amide bonds. Dibasic acids include aliphatic saturated dibasic acids with a total of 2 to 10 carbon atoms, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. Dibasic acid anhydrides include the anhydrides of these dibasic acids. Examples of dibasic acid esters include monomethyl esters, monoethyl esters, monobutyl esters, monopropyl esters, dimethyl esters, diethyl esters, dibutyl esters, and dipropyl esters of the above-mentioned dibasic acids. Dibasic acid dihalides include dichlorides, dibrominateds, and diiodides of the above-mentioned dibasic acids.

[0085] Furthermore, polyamide polyamines with added polyalkylene oxides refer to compounds in which alkylene oxides are added to the amino, imino, and amide groups of one molecule of the above-mentioned polyamide polyamine. Examples of alkylene oxides include ethylene oxide, propylene oxide, and butylene oxide, which can be used individually or in combination. When two or more alkylene oxides are used, they may be bonded in a block-like manner or randomly.

[0086] The polycarboxylic acid polymer Q used in the present invention can preferably be a polymer having a copolymer unit obtained by copolymerizing a monomer mixture containing a monomer represented by the following general formula (1) (hereinafter referred to as monomer E) and a monomer represented by the following general formula (2) (hereinafter referred to as monomer F), and a structural unit having an amino group and an imino group, and / or a structural unit having an amino group, an imino group and an amide group. Such a polymer can be obtained by copolymerizing monomer E represented by the following general formula (1) and monomer F represented by general formula (2) with a structural unit having an amino group and an imino group, or a monomer having a structural unit having an amino group, an imino group and an amide group (hereinafter referred to as monomer G).

[0087] In monomer E represented by the following general formula (1), R 11 , R 12 , R 13 , R 14 Each of these independently represents a hydrogen atom and a hydrocarbon group having 1 to 22 carbon atoms, where X represents -COO-, -CON<, or -(CH2)bO-, and AO represents an alkylene oxide group having 2 to 4 carbon atoms. a is the average number of added moles of alkylene oxide, representing a number from 1 to 200, more preferably from 30 to 150. If X is -(CH2)bO-, then b represents a number from 1 to 20. [ka]

[0088] More specifically, the monomer E represented by the above general formula (1) is a polymeric polyalkylene glycol monomer, for example; alkenyl ethers formed from (alkoxy)alkylene glycols and alkenyl ethers having 3 to 8 carbon atoms, such as polyalkylene glycol monoallyl ether, alkylene glycol monoalkenyl ether, methoxypolyalkylene glycol monoallyl ether, and methoxyalkylene glycol monoalkenyl ether; and alkoxy polyalkylene glycols having 1 to 22 carbon atoms, such as methoxypolyalkylene glycol, ethoxypolyalkylene glycol, and propoxypolyalkylene glycol. These monomers have polymerization-active groups and polyalkylene glycol as constituent units, such as: alkoxyalkylene glycol (meth)acrylates consisting of ylene glycol and (meth)acrylic acid; alkoxyalkylene glycol unsaturated fatty acid esters consisting of alkoxy polyalkylene glycols with 1 to 22 carbon atoms and unsaturated fatty acids such as oleic acid; alkoxyalkylene glycolamide compounds formed from α-alkoxy-ω-amino-polyalkylene glycols having terminal amino groups and (meth)acrylic acid or unsaturated fatty acids; and unsaturated aliphatic ethers which are unsaturated aliphatic alcohol alkylene oxide adducts. The composition of these polyalkylene glycols is formed from alkylene oxides with 2 to 4 carbon atoms, consisting of the addition of ethylene oxide, propylene oxide and / or butylene oxide alone or in combination, and in the case of mixed addition, it may be either random addition or block addition. These polymerization-active polyalkylene glycol monomers can be used alone or in combination.

[0089] Furthermore, in monomer F represented by the general formula (2) below, R 15 , R 16 , R 17 , R 18 These are, independently, a hydrogen atom, a hydrocarbon group with 1 to 22 carbon atoms, -(CH2)c-COOM, -COOM, and -COOR. 19(R19 represents a hydrocarbon group with 1 to 22 carbon atoms, -(CH2)c-COOM, -COOM, or a glycidyl group.) or represents a glycidyl group, or R 15 and R 16 , or R 17 and R 1 8 combines with the >C=C< group in formula (2) to form an acid anhydride. c represents a number from 1 to 20. M represents a hydrogen atom, alkali metal, alkaline earth metal, ammonium, or alkanolamine. [ka]

[0090] More specifically, the monomer F represented by the general formula (2) above includes unsaturated fatty acids and their ester derivatives such as maleic acid, maleic anhydride, itaconic acid, methacrylic acid, acrylic acid, dialkyl maleate, alkyl methacrylate, and alkyl acrylate, as well as glycidyl compounds such as glycidyl methacrylate, glycidyl acrylate, and glycidyl allyl ether. These may be in acid form or neutralized form, and sodium, potassium, calcium, magnesium, ammonium ions, alkanolamines, etc., may be used for neutralization. These acids or neutralized salts may be used individually or as a mixture of several.

[0091] Examples of monomers G having a structural unit having an amino group and an imino group, or a structural unit having an amino group, an imino group and an amide group, include the aforementioned compound having an amino group and an imino group, or a condensate of the aforementioned compound having an amino group, an imino group and an amide group with acrylic acid, methacrylic acid, or an ester formed from acrylic acid or methacrylic acid with a lower alcohol having 1 to 4 carbon atoms. Specifically, methods for producing such products are described in Japanese Patent Publication No. 3235002, Japanese Patent Publication No. 3346456, Japanese Patent Publication No. 3740641, Japanese Patent Publication No. 3780456, etc.

[0092] The copolymerization ratio of monomers E, F, and G is preferably in the range of E:F:G = 50-90:5-40:5-40 in terms of mass ratio (where the sum of the mass ratios of the three monomers E, F, and G is 100) in terms of reducing slump loss.

[0093] The method for producing the copolymer is not particularly limited; for example, known polymerization methods such as solution polymerization or bulk polymerization using polymerization initiators can be employed.

[0094] The polycarboxylic acid polymer Q of the present invention may be copolymerized with other monomers that are copolymerizable with these monomers, in addition to the monomers described above, as long as the effects of the present invention are not impaired. Examples of copolymerizable monomer components include the following known ones: (non)aqueous monomers: styrene, etc.; anionic monomers: vinyl sulfonic acid, styrene sulfonic acid, (meth)acrylic acid phosphate salts, (meth)acrylic acid alkylene oxide adduct phosphate salts, etc.; amide monomers: acrylamide, alkylene oxide adducts of acrylamide, etc.; amine monomers: polyalkylene polyimine compounds, etc.; polyalkylene glycol monomers: mono or diesters of polyalkylene glycol and maleic anhydride, esters of polyalkylene glycol and itaconic acid, etc.

[0095] These other monomers can be used in amounts of approximately 0 to 20% by mass relative to the total mass of monomer E represented by general formula (1), monomer F represented by general formula (2), monomer G, and other monomers.

[0096] Furthermore, in the present invention, the structural units having amino groups and imino groups, and / or structural units having amino groups, imino groups and amide groups, contained in the polycarboxylic acid polymer Q may be obtained by bonding the compounds having amino groups and imino groups, and / or compounds having amino groups, imino groups and amide groups to the polycarboxylic acid polymer Q0 via graft bonding groups or crosslinking groups. Here, the polycarboxylic acid polymer Q0 is not particularly limited as long as it is a polycarboxylic acid polymer having functional groups that can be graft-bonded or crosslinked with the compounds having amino groups and imino groups, and / or compounds having amino groups, imino groups and amide groups, such as acid groups, acid anhydride groups, glycidyl groups, acid ester groups, etc. Polycarboxylic acid polymer Q0 is a copolymer obtained by copolymerizing monomer E and monomer F, and other monomers as needed. Specifically, examples include copolymers of maleic anhydride and polyalkylene glycol monoalkenyl ether, copolymers of maleic anhydride and allyl alcohol alkylene oxide adduct monomethyl ether, copolymers of (meth)acrylic acid and (alkoxy) polyalkylene glycol (meth)acrylate, copolymers of (meth)acrylic acid, glycidyl (meth)acrylate and (alkoxy) polyalkylene glycol (meth)acrylate, copolymers of (meth)acrylic acid, monomer having a sulfone group and (alkoxy) polyalkylene glycol (meth)acrylate, copolymers of (meth)acrylic acid, monomer having a phosphate group and (alkoxy) polyalkylene glycol (meth)acrylate, and copolymers of (meth)acrylic acid, alkyl (meth)acrylate and (alkoxy) polyalkylene glycol (meth)acrylate.

[0097] The polycarboxylic acid copolymer Q used in this invention preferably has a weight-average molecular weight (calculated by gel permeation chromatography, in terms of polyethylene glycol) in the range of 1,000 to 500,000. If it falls outside this range, the water-reducing properties decrease significantly, or the desired slump loss reduction effect cannot be obtained.

[0098] In this invention, the reaction solution containing the polycarboxylic acid copolymer Q produced by the above-described manufacturing procedure may be used as is in the preparation of the admixture for hydraulic compositions and the combination for preparing the admixture for hydraulic compositions. In this case, the solution may contain unreacted components and by-reaction products generated in each polymerization step, grafting step, crosslinking step, alkylene oxide addition step, etc., in addition to the polycarboxylic acid copolymer Q.

[0099] Inorganic binder composition The inorganic binder composition of the present invention comprises the following: (a) 200-700 kg / m 3 fly ash-containing inorganic binder, (b) 700~950 kg / m 3 Fine aggregate, preferably sand, (c) 800~1100 kg / m 3 Coarse aggregate, preferably gravel, (d) At least one dispersant in an amount of 0.1 to 5% by mass, preferably 0.5 to 1% by mass, relative to the total dry mass of the inorganic binder, and (e) an air-entraining agent in an amount of 0.001 to 0.03% by mass relative to the total dry mass of the inorganic binder.

[0100] Here, the dispersant is a phenol resin-based dispersant obtained from the polycondensation of monomers (i) to (v).

[0101] According to the inorganic binder composition of the present invention, when fly ash is used as the inorganic binder, and especially when fly ash is used in a relatively high proportion as the inorganic binder, the stability of the resulting inorganic binder composition can be improved, and in particular, the stability of the air content of the resulting inorganic binder composition can be improved.

[0102] For details regarding the components and usage embodiments of the inorganic binder composition of the present invention, please refer to the description of the method of the present invention for improving the stability of the inorganic binder composition.

[0103] Molded body The molded article of the present invention is obtained by mixing the inorganic binder composition of the present invention with water at a mass ratio of water to cement of 0.29 to 0.6, and then curing the resulting mixture.

[0104] Such molded articles may have a spacing coefficient, as evaluated according to EN 480-11, of less than 200 micrometers, or preferably less than 175 micrometers.

[0105] For details regarding the components of the molded article of the present invention, refer to the description of the method of the present invention for improving the stability of an inorganic binder composition.

[0106] Admixtures and phenolic resin-based dispersants The admixture of the present invention comprises or consists of the following (each in proportion to the total mass of the admixture): (a) At least one dispersant in an amount of 1 to 20% by mass, preferably 5 to 15% by mass, more preferably 8 to 13% by mass, (b) 10 to 45% by mass, preferably 15 to 40% by mass, more preferably 20 to 30% by mass, of at least one polycarboxylic acid polymer, (c) At least one retarder, preferably sodium gluconate, in an optional amount of 1 to 20% by mass, preferably 1 to 10% by mass. (d) 0.05 to 0.2% by mass of a defoaming agent, and (e) Further additives as desired, and (f) Water, with the remainder up to 100% by mass.

[0107] Here, the dispersant is a phenol resin-based dispersant obtained from the polycondensation of monomers (i) to (v).

[0108] The phenolic resin-based dispersant of the present invention, that is, the phenolic resin-based dispersant for improving the stability of an inorganic binder composition containing a fly ash-containing inorganic binder, is a phenolic resin-based dispersant obtained by polycondensation of monomers (i) to (v).

[0109] The admixture and phenol resin-based dispersant of the present invention can be combined with an inorganic binder to obtain an inorganic binder composition. According to the admixture and phenol resin-based dispersant of the present invention, even when fly ash is used as the inorganic binder, particularly when fly ash is used in a relatively high proportion as the inorganic binder, the stability of the resulting inorganic binder composition can be improved, and in particular, the stability of the air content of the resulting inorganic binder composition can be improved.

[0110] For details regarding the composition and usage embodiments of the admixture and phenol resin-based dispersant of the present invention, please refer to the description of the method of the present invention for improving the stability of inorganic binder compositions.

[0111] When the phenolic resin-based dispersant of the present invention is used in combination with a polycarboxylic acid-based dispersant, it can be used as an admixture containing the phenolic resin-based dispersant and the polycarboxylic acid-based dispersant of the present invention, or the phenolic resin-based dispersant and the polycarboxylic acid-based dispersant can be added individually during the production of an inorganic binder composition. [Examples]

[0112] The present invention will be described below with reference to examples. However, the present invention is not limited in any way by these examples. In the following, "parts" refers to "parts by mass".

[0113] Preparation of phenolic resin-based dispersants Preparation of monomers of formula (I) In a stainless steel high-pressure reactor equipped with a thermometer, stirrer, pressure gauge, and nitrogen inlet tube, 80 parts of diethylene glycol monophenyl ether (HighSolve DPH, manufactured by Toho Chemical Industry Co., Ltd.) and 0.2 parts of 96% potassium hydroxide were charged. The reaction vessel was purged with nitrogen, and the mixture was heated to 150°C under a nitrogen atmosphere. Then, while maintaining the temperature at 150°C under safe pressure, 1700 parts of ethylene oxide were introduced into the reactor over 10 hours. After that, the temperature was maintained for 2 hours to complete the alkylene oxide addition reaction, yielding polyethylene glycol monophenyl ether (number of moles of EO added = 90) as the monomer of formula (I).

[0114] Preparation of monomers of formula (II) Using p-tert-butylphenol (PTBP, manufactured by DIC Corporation) as the starting material, an alkylene oxide addition reaction was carried out according to the method for preparing the monomer of formula (I) to obtain an alkylene oxide adduct. The number of moles of ethylene oxide added was 6 moles.

[0115] Three moles of the p-tert-butylphenol EO adduct (6 mole adduct) were charged into a glass reaction vessel equipped with a stirrer, thermometer, and nitrogen inlet tube. One mole of phosphoric anhydride was charged at 50°C over 4 hours while nitrogen bubbling was performed, and the reaction was carried out. Subsequently, the reaction was aged at 100°C for 3 hours to complete the phosphate esterification reaction, yielding the phosphate ester of the p-tert-butylphenol EO adduct as the monomer of formula (I).

[0116] Preparation of monomers of formula (III) In a stainless steel high-pressure reactor equipped with a thermometer, stirrer, pressure gauge, and nitrogen inlet tube, 100 parts of ortho-hydroxyethylphenol (Aldrich reagent) and 0.3 parts of 96% potassium hydroxide were charged. The reaction vessel was purged with nitrogen and heated to 130°C under a nitrogen atmosphere. Then, while maintaining the temperature at 130°C under safe pressure, 190 parts of ethylene oxide were introduced into the reactor over 4 hours. The temperature was then maintained for 2 hours to complete the alkylene oxide addition reaction, yielding a total of 6 moles of ortho-hydroxyethylphenol EO adduct as the monomer of formula (III).

[0117] Preparation of phenol resin-based dispersant A1 In a glass reaction vessel equipped with a stirrer, thermometer, and reflux condenser, the starting materials for each monomer of formulas (I) to (III) were charged in the molar ratios shown in Table 1. The temperature was raised to 70°C, and then 98% sulfuric acid was added at a concentration of 1.0% by mass relative to the total mass of the monomers of formulas (I) to (III). Next, formalin (HCHO) as the monomer of formula (V) was introduced into the reaction vessel all at once in the molar ratio shown in Table 1, and the temperature was then raised to 105°C. At 105°C, the pH of the reactants was 2.1 (1% aqueous solution, 20°C). Six hours after reaching 105°C, the reaction was terminated, and 48% caustic soda was added to neutralize the reactants so that the pH of the 1% aqueous solution was in the range of 5.0 to 7.5. Then, an appropriate amount of water was added so that the solid content of the reactants was 40%, and an aqueous solution of phenol resin-based dispersant A1 as a polycondensation product was obtained. Gel permeation chromatography (GPC) was performed on this phenol resin-based dispersant A1 to determine its weight-average molecular weight Mw.

[0118] Furthermore, the conditions for gel permeation chromatography (GPC) measurement in relation to this invention were as follows: Columns: OHpak SB-802.5HQ, OHpak SB-803HQ, OHpak SB-804HQ (manufactured by Showa Denko Corporation) Eluent: Mixture of 50 mM sodium nitrate aqueous solution and acetonitrile (volume ratio 80 / 20) Detector: Differential refractometer, Calibration curve: Polyethylene glycol.

[0119] Preparation of phenol resin-based dispersants A2 to A5 Aqueous solutions of phenol resin-based dispersants A2 to A5 were obtained as polycondensation products in the same manner as the preparation of phenol resin-based dispersant A1, except that the types and molar ratios of the monomer raw materials in formulas (I) to (III) and (V) were changed as shown in Table 1.

[0120] Preparation of phenolic resin-based dispersants C1-C5 Aqueous solutions of phenol resin-based dispersants C1 to C5 as polycondensation products were obtained in the same manner as the preparation of phenol resin-based dispersant A1, except that the types and molar ratios of the monomer raw materials in formulas (I) to (III) and (V) were changed as shown in Table 1.

[0121] However, in the synthesis of monomers of formulas (I) to (III) for phenol resin dispersants A1 to A5, ethylene oxide (EO) is used as alkylene oxide (AO) and polyethylene glycol group (C x H 2x In contrast to the addition of x=2 in the previous example, in the synthesis of monomers of formulas (I) to (III) for phenol resin dispersants C1 to C5, a mixture of alkylene oxides was added as alkylene oxide (AO). Here, x is 2 to 5 C x H 2x C where x is 3 to 5 for the sum of the bases x H 2x The proportion of the groups (X = 3 to 5 (mol%)) was as shown in Table 1.

[0122] [Table 1]

[0123] Preparation of polycarboxylic acid-based dispersant Q1 In a reaction vessel equipped with a stirrer, 103 g (1.00 mol) of diethylenetriamine and 97.3 g (0.67 mol) of adipic acid were charged and stirred and mixed under a nitrogen atmosphere by introducing nitrogen. The temperature was raised to 150°C and the reaction was carried out for 20 hours, removing water, a reaction product associated with condensation polymerization, until the acid value reached 22. Next, 1.1 g of hydroquinone methyl ether and 27.5 g (0.32 mol) of methacrylic acid were charged and the reaction was carried out at the same temperature (150°C) for 10 hours. This yielded 187 g of polyamide polyamine (melting point 122°C, acid value 23) along with a total of 42 g of reaction distillate water.

[0124] The entire amount of this polyamide polyamine was dissolved in 272 g of water and heated to 50°C. At the same temperature (50°C), 220 g of ethylene oxide (equivalent to 3.0 moles relative to the total amino residues, including unreacted amino groups) was sequentially introduced over 4 hours, and the mixture was aged for 2 hours. This yielded 680 g of polyamide polyamine EO adduct (60% solids).

[0125] 180g of water was placed in a reaction vessel equipped with a stirrer, nitrogen was introduced to create a nitrogen atmosphere within the synthesis system, and the temperature was raised to 80°C. Furthermore, 150 g of water, 98.2 g of the above polyamide polyamine EO adduct, 72.0 g of methacrylic acid, and a mixture of 60.9 g of short-chain methoxypolyethylene glycol monomethacrylate (short-chain MPEGM, molecular weight 1000) and 183 g of long-chain methoxypolyethylene glycol monomethacrylate (long-chain MPEGM, molecular weight 2000) (the ratio of the mixture calculated when methacrylic acid is the sodium salt is polyamide polyamine EO adduct:methacrylic acid:short-chain MPEGM:long-chain MPEGM = 15% by mass:23% by mass:15% by mass:47% by mass (total 100% by mass)) and 66.4 g of a 5% aqueous solution of thioglycolic acid were each added dropwise to the synthesis system over 2 hours, and 123 g of a 5% aqueous solution of sodium persulfate was added dropwise to the synthesis system over 3 hours. After that, the mixture was aged for 2 hours and then cooled. Subsequently, the solution was neutralized to pH 7 with a 48% NaOH aqueous solution to obtain 1,029 g of polycarboxylic acid-based dispersant Q-1. According to GPC molecular weight measurement, the weight-average molecular weight Mw of this polycarboxylic acid-based dispersant Q1 was 46,000.

[0126] Preparation of admixture 1 Using the dispersants obtained as described above (phenol resin-based dispersants A1 and C1, and polycarboxylic acid-based dispersant Q1), admixtures with the compositions shown in Table 2 below were prepared.

[0127] [Table 2]

[0128] Preparation and evaluation of concrete compositions 1 Concrete compositions conforming to JIS A 1138 were prepared using the mix designs shown in Table 3. As can be seen from Table 3, the ratio of fly ash fine powder to the total amount of cement (C) and fly ash fine powder (FA) (C / (C+FA)) was 70% (=265 / (114+265)). The mixing method used was a twin-screw forced mixer with a nominal capacity of 100 liters, with a concrete production volume of 50 liters per batch.

[0129] [Table 3]

[0130] The prepared concrete compositions were evaluated over a period of time from 0 to 60 minutes after preparation. The evaluation was carried out as follows.

[0131] Slump and slump flow The slump and slump flow of the concrete composition were evaluated in accordance with JIS A 1101:2020 and JIS A 1150:2020.

[0132] Air volume The air content of the concrete composition was evaluated in accordance with JIS A 1128:2019.

[0133] The evaluation results for each concrete composition mix are shown in Table 4.

[0134] [Table 4]

[0135] As shown in Table 4, concrete compositions using the phenolic resin-based dispersants A1 and C1 of the present invention, and particularly the phenolic resin-based dispersant C1 of the present invention, exhibited a higher amount of air retention in the concrete composition compared to concrete composition A using the polycarboxylic acid-based dispersant Q1, while maintaining stable properties over time and preserving an appropriate amount of air.

Claims

1. A method for stabilizing an inorganic binder composition containing a fly ash-containing inorganic binder, comprising the following steps (a) to (c): (a) To provide a dispersant, (b) To provide the inorganic binder composition, and (c) Mutually grind and / or mutually mix the dispersant provided in step (a) and the inorganic binder composition provided in step (b). Includes, The dispersant is the following monomers (i) to (v): (i) Monomers represented by formula (I) in a mol%: 【Chemistry 1】 (ii) Monomers represented by formula (II) in b mol%: 【Chemistry 2】 (iii) Monomers represented by formula (III) in c mol%: 【Transformation 3】 (iv) Monomers represented by formula (IV) in d mol%: 【Chemistry 4】 (v) e mol% of an aldehyde, preferably formaldehyde, metaformaldehyde, paraformaldehyde, or formalin, or a mixture thereof. (In the formula, R １ is H or C １～４ Alkyl alkyl group, or C ２～５ It is an acyl group, R ２ This is H, alkali metal ions, alkaline earth metal ions, or a portion having the following structure: 【Transformation 5】 R ３ is H, or O-R ２ And, R ４ H, C １～４ It is an alkyl group or a phosphate ester group, R ５ is H, C １～１８ an alkyl group, a polyisobutene moiety, or a sulfonic acid moiety, A １ and A ２ They are independent of each other, C ｘ H ２ｘ This is the base, where x = 2 to 5. n=1 to 350, m=2 to 300, The molar ratio of a:b:c:d is 0.1-2.0:0.1-6.0:0.1-2.0:0.0-0.5, and The molar ratio of (a + b + c + d):e is between 1:10 and 10:

1. A method for obtaining a phenol resin-based dispersant from polycondensation.

2. The method according to claim 1, wherein the fly ash content is 70% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less, based on the total dry mass of the inorganic binder.

3. The method according to claim 1 or 2, wherein the fly ash conforms to the JIS A 6201:2015 standard.

4. The method according to claim 1 or 2, wherein the phenolic resin dispersant is mutually crushed and / or mutually mixed in step (c) in an amount of 0.1 to 5% by mass, preferably 0.5 to 1% by mass, relative to the total dry mass of the inorganic binder.

5. The method according to claim 1 or 2, wherein in step (c), the dispersant is mutually ground with the inorganic binder composition using a ball mill or a vertical roll mill.

6. The method according to claim 1 or 2, wherein the inorganic binder composition further contains at least one polycarboxylic acid polymer and / or gluconate.

7. An inorganic binder composition, the following: (a) 200-700kg / m ３ fly ash-containing inorganic binder, (b) 700-950kg / m ３ Fine aggregate, preferably sand, (c) 800-1100kg / m ３ Coarse aggregate, preferably gravel, and (d) At least one dispersant in an amount of 0.1 to 5% by mass, preferably 0.5 to 1% by mass, relative to the total dry mass of the inorganic binder, and (e) 0.001 to 0.03% by mass of an air-entraining agent with respect to the total dry mass of the inorganic binder, Includes, The dispersant is the following monomers (i) to (v): (i) Monomers represented by formula (I) in a mol%: 【Transformation 6】 (ii) Monomers represented by formula (II) in b mol%: 【Transformation 7】 (iii) Monomers represented by formula (III) in c mol%: 【Transformation 8】 (iv) Monomers represented by formula (IV) in d mol%: 【Chemistry 9】 (v) e mol% of an aldehyde, preferably formaldehyde, metaformaldehyde, paraformaldehyde, or formalin, or a mixture thereof. (In the formula, R １ is H or C １～４ Alkyl alkyl group, or C ２～５ It is an acyl group, R ２ This is H, alkali metal ions, alkaline earth metal ions, or a portion having the following structure: 【Chemistry 10】 R ３ is H, or O-R ２ And, R ４ H, C １～４ It is an alkyl group or a phosphate ester group, R ５ H, C １～１８ The alkyl group, the polyisobutene portion, or the sulfonic acid portion, A １ and A ２ They are independent of each other, C ｘ H ２ｘ This is the base, where x = 2 to 5. n=1 to 350, m=2 to 300, The molar ratio of a:b:c:d is 0.1-2.0:0.1-6.0:0.1-2.0:0.0-0.5, and The molar ratio of (a + b + c + d):e is between 1:10 and 10:

1. An inorganic binder composition characterized by being a phenol resin-based dispersant obtained by polycondensation.

8. The inorganic binder composition according to claim 7, wherein the inorganic binder essentially consists of cement and fly ash.

9. The inorganic binder composition according to claim 7, wherein the inorganic binder further comprises cement, fly ash, and steel slag, particularly pulverized blast furnace slag.

10. The inorganic binder composition according to claim 8 or 9, wherein the mass ratio of the fly ash to the cement is 1:20 to 1:1, preferably 1:10 to 1:

2.

11. The inorganic binder composition according to claim 7 or 8, wherein the fly ash conforms to the JIS A 6201:2015 standard.

12. The inorganic binder composition according to claim 7 or 8, wherein, when mixed with water at a mass ratio of 0.25 to 0.6 to cement, the decrease in the air content of the inorganic binder composition is 10% or less within the first hour.

13. The inorganic binder composition according to claim 7 or 8, further comprising at least one polycarboxylic acid polymer and / or gluconate.

14. A molded article obtained by mixing the inorganic binder composition according to claim 7 or 8 with water in a mass ratio of water to the cement of 0.29 to 0.6, and then curing the resulting mixture.

15. The molded article according to claim 14, wherein the spacing coefficient evaluated according to EN 480-11 is less than 200 micrometers, or preferably less than 175 micrometers.

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