Method for improving the processability of an inorganic binder composition and an inorganic binder composition

Abstract

[Problem] To provide a method for improving the processability of an inorganic binder composition and an inorganic binder composition. [Solution] The present invention provides a method for improving the processability of an inorganic binder composition, comprising the steps of (a) providing a dispersant, (b) providing an inorganic binder composition, and (c) co-grinding and / or co-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 by polycondensation of a specific monomer.

Description

[Technical Field]

[0001] The present invention relates to a method for improving the processability of an inorganic binder composition and to an inorganic binder composition. [Background technology]

[0002] In recent years, industrial by-products (slag or fly ash) have been actively used as inorganic binders to make resource use more efficient or to reduce their environmental impact.

[0003] However, the use of slag or fly ash as at least part of the inorganic binder sometimes impairs the processability or fluidity of the resulting inorganic binder composition.

[0004] The use of admixtures such as air-entraining agents and water-reducing agents is known to improve the processability of inorganic binder compositions, such as concrete compositions. Polycarboxylic acid polymers are widely known as such admixtures, and the recent use of phenolic resin dispersants obtained through the polycondensation of multiple phenolic comonomers and aldehydes is also known.

[0005] In this regard, Patent Document 1 proposes, for example, a mixture containing a polycarboxylic acid polymer obtained by polycondensation of multiple phenolic comonomers and aldehydes, and a phenolic resin dispersant. According to Patent Document 1, this type of mixture suppresses dark discoloration caused by the separation of colored fine particles (contained in the hydraulic composition) on the surface of the cured product, suppresses setting delay, bleeding and reduction of initial strength despite containing a large amount of inorganic powder, and also has good water-reducing performance. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] International Publication No. 2018 / 147378A1 Pamphlet [Overview of the project] [Problems that the invention aims to solve]

[0007] As described above, when slag is used as an inorganic binder, especially when a relatively high proportion of slag is used, the processability of the resulting inorganic binder composition is sometimes impaired.

[0008] The present invention therefore aims to provide a method and an inorganic binder composition for overcoming such problems. [Means for solving the problem]

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

[0010] Embodiment 1 A method for improving the processability of an inorganic binder composition containing a slag-containing inorganic binder, comprising the following steps (a) to (c): (a) A step of providing a dispersant, (b) the step of providing an inorganic binder composition, (c) A step of co-grinding and / or co-mixing the dispersant provided in step (a) and the inorganic binder composition provided in step (b). The dispersant contains the following monomers (i)~(v): (i) a mol% of formula (I): [ka] monomers represented by (ii) For b mol%, formula (II): [ka] monomers represented by (iii) c mol%, formula (III): [Chemical formula] The monomer represented by (iv) d mole % of the formula (IV): [Chemical formula] The monomer represented by (v) e mole % of an aldehyde, preferably formaldehyde, paraformaldehyde, paraformaldehyde or formalin or a mixture thereof A phenolic resin-based dispersant obtained through polycondensation of In the formula, 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 the following structure: [Chemical formula] The part having R 3 is H or O-R 2 where 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, polyisobutene or a sulfonic acid moiety, A1 and A2 are each independently a C x H 2x group (where x = 2 to 5), n = 1 to 350, m = 2 to 300, The molar ratio of a:b:c:d is 0.1 to 2.0:0.1 to 6.0:0.1 to 2.0:0.0 to 0.5, and (a + b + c + d):e molar ratio is 1:10 to 10:1, method.

[0011] Embodiment 2 The method according to Embodiment 1, wherein the slag content is at least 70% by mass, preferably at least 80% by mass, and particularly at least 85% by mass, based on the total dry mass of the inorganic binder.

[0012] Embodiment 3 The method according to Embodiment 1 or 2, wherein the slag is steel slag, preferably blast furnace slag fine powder, and particularly blast furnace slag fine powder conforming to the JIS A 6206:2013 standard.

[0013] Embodiment 4 The method according to any one of Embodiments 1 to 3, wherein in step (c), the phenolic resin dispersant is co-ground and / or co-mixed 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.

[0014] Embodiment 5 The method according to any one of Embodiments 1 to 4, wherein the dispersant is co-ground with the inorganic binder composition in a ball mill or vertical roll mill in step (c).

[0015] Embodiment 6 The method according to any one of Embodiments 1 to 5, wherein the inorganic binder composition further comprises at least one polycarboxylic acid polymer and / or gluconate.

[0016] Embodiment 7 (a) 280~550 kg / m 3 A slag-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. An inorganic binder composition comprising the above monomers (i) to (v), characterized in that the dispersant is a phenol resin-based dispersant obtained via polycondensation of monomers (i) to (v).

[0017] Embodiment 8 The inorganic binder composition according to Embodiment 7 comprises a substantially cement and slag inorganic binder.

[0018] Embodiment 9 An inorganic binder composition according to Embodiment 7, further comprising fly ash and / or fine calcium carbonate in addition to cement and slag.

[0019] Embodiment 10 An inorganic binder composition according to Embodiment 8 or 9, wherein the mass ratio of slag to cement is 2.3:1 to 6:1, preferably 3:1 to 5:1.

[0020] Embodiment 11 The inorganic binder composition according to any one of Embodiments 7 to 10, wherein the slag is steel slag, preferably blast furnace slag fine powder, and in particular blast furnace slag fine powder conforming to the JIS A 6206:2013 standard.

[0021] Embodiment 12 The inorganic binder composition according to any one of Embodiments 7 to 11, wherein the V-funnel flow time according to JSCE-F 512:1999 is 10 seconds or less when measured 5 minutes after mixing with water at a water-to-inorganic binder mass ratio of 0.25 to 0.6.

[0022] 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.

[0023] Embodiment 14 A molded article obtained by mixing an inorganic binder composition described in any one of Embodiments 7 to 13 with water in a water-to-inorganic binder mass ratio of 0.25 to 0.6, and then curing the resulting mixture. [Effects of the Invention]

[0024] The method and inorganic binder composition of the present invention make it possible to improve the processability of the inorganic binder composition obtained when slag is used as an inorganic binder, particularly when slag is used as an inorganic binder in a relatively high proportion. [Modes for carrying out the invention]

[0025] <<Method for improving the processability of an inorganic binder composition containing a slag-containing inorganic binder>> The present invention provides a method for improving the processability of an inorganic binder composition containing a slag-containing inorganic binder, comprising the following steps (a) to (c): (a) A step of providing a dispersant, (b) the step of providing an inorganic binder composition, (c) A step of co-grinding and / or co-mixing the dispersant provided in step (a) and the inorganic binder composition provided in step (b). Includes.

[0026] Here, the dispersant is a phenol resin-based dispersant obtained through the polycondensation of the following monomers (i) to (v).

[0027] The method of the present invention makes it possible to improve processability and suppress changes in the slump and slump flow over time of an inorganic binder composition obtained when slag is used as an inorganic binder, especially when slag is used as an inorganic binder in a relatively high proportion.

[0028] In the method of the present invention, the proportion of slag in the slag-containing inorganic binder may be 30% by mass or more, 40% by mass or more, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, 85% by mass or more, 90% by mass or more, or 95% by mass or more, and may be less than 100% by mass, 95% by mass or less, or 80% by mass or less. Examples of inorganic binders other than slag include cement, particularly Portland cement. The inorganic binder can be substantially composed of cement and slag. In addition to cement and slag, the inorganic binder composition may further contain fly ash and / or fine calcium carbonate. The mass ratio of slag to cement may be 2.3:1 to 6:1, preferably 3:1 to 5:1.

[0029] The slag is steel slag, preferably blast furnace slag fine powder, and in particular blast furnace slag fine powder conforming to the JIS A 6206:2013 standard.

[0030] In step (c), the phenolic resin dispersant may be co-ground and / or co-mixed 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.

[0031] The dispersant may be co-ground with the inorganic binder composition in step (c) using a ball mill or vertical roll mill.

[0032] The inorganic binder composition whose processability has been improved by the method of the present invention may have a V-funnel flow time of 10 seconds or less, according to JSCE-F 512:1999, when measured 5 minutes after mixing with water at a water-to-inorganic binder mass ratio of 0.25 to 0.6.

[0033] The phenolic resin dispersant can be used in an amount ranging from 0.1 to 10% by mass or 0.1 to 5% by mass, calculated based on the solid content, relative to the total mass of the inorganic binder.

[0034] An inorganic binder composition with improved processability by the method of the present invention can be molded into a molded article, for example, by mixing the inorganic binder composition and water in a water-to-inorganic binder mass ratio of 0.25 to 0.6, and then curing the resulting mixture.

[0035] The inorganic binder composition obtained by the method of the present invention may further contain aggregates, thereby forming a concrete composition. Examples of aggregates include fine aggregates and coarse aggregates. Mountain sand, land sand, river sand, and fine sand are preferred as fine aggregates, while mountain gravel, land gravel, river gravel, crushed stone, and hard sandstone are preferred as coarse aggregates. Lightweight aggregates can also be used in some applications.

[0036] For example, an inorganic binder composition whose processability has been improved by the method of the present invention, (a) 280~550 kg / m 3 A slag-containing inorganic binder, (b) 700~950 kg / m 3 Fine aggregate, preferably sand, (c) 800~1100 kg / m 3 Coarse aggregate, preferably gravel, (d) 0.1 to 5% by mass, preferably 0.5 to 1% by mass, of at least one phenolic resin-based dispersant relative to the total dry mass of the inorganic binder. It may include.

[0037] Inorganic binder compositions, (a) A slag-containing inorganic binder comprising 5 to 95% by mass, preferably 5 to 60% by mass, (b) At least one type of aggregate in an amount of 5 to 85% by mass, preferably 20 to 80% by mass, (c) If necessary, 0.1 to 10% by mass of other additives, (d) If necessary, water and solids in a water-to-solids mass ratio of 0.1 to 0.6, preferably 0.2 to 0.5, and particularly 0.2 to 0.35. It may also include that.

[0038] The monomers (i) to (v) for obtaining a phenolic resin-based dispersant by polycondensation are described in detail below.

[0039] <Monomer(i)> The monomer (i) is given by formula (I): [ka] It is represented by [this].

[0040] In equation (I), R 1 is 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 The basis (where x = 2 to 5 in the formula), and n = 1 to 350.

[0041] Monomer (i) is C 2~4 The alkylene oxide is a compound obtained by adding an alkylene oxide to a phenol or a substituent thereof, and derivatives of the alkylene oxide adduct (alkyl ester or fatty acid ester) are also included.

[0042] R 1 C represented by 1~4 Examples of alkyl groups include methyl, ethyl, propyl, and butyl groups, which may have branched structures (such as isopropyl, isobutyl, sec-butyl, and tert-butyl groups) and / or cyclic structures (such as cyclopropyl and cyclobutyl groups).

[0043] R 1 C represented by 1~5 Examples of acyl groups include saturated or unsaturated acyl groups (R'(CO)- groups, where R' is C 1~4 Examples include (which are hydrocarbon groups). 2~4 Examples of saturated acyl groups include acetic acid, propionic acid, butanoic acid, and pentanoic acid.

[0044] R5 C represented by 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 (isopropyl, isobutyl, sec-butyl, tert-butyl, and neopentyl groups, etc.) and / or cyclic structures (cyclopropyl, cyclopentyl, cyclohexyl, and 1-adamantyl groups, etc.).

[0045] Alkylene oxide (-A1O-) is an alkylene group (C x H 2x The molecule has a base (where x = 2 to 5). The alkylene oxide can therefore be ethylene oxide, propylene oxide, butylene oxide, or pentene oxide, which can be added individually or in combination. When two or more types of alkylene oxides are added in combination, they can be added in block or random order.

[0046] In one embodiment, the alkylene group (C) of alkylene oxide (-A1O-) x H 2x At least a portion of the alkylene group (C) (20 mol% or more, 25 mol% or more, or 30 mol% or more, etc.) has 3 to 5 carbon atoms (x=3 to 5). This proportion 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, or 40 mol% or less. Therefore, alkylene group (C) x H 2x When at least a portion of the group has 3 to 5 carbon atoms, the resulting phenolic resin-based dispersant can be made relatively hydrophobic, thereby improving processability and further suppressing changes in the slump and slump flow over time of the resulting inorganic binder composition, especially when slag is used as an inorganic binder, particularly when slag is used as an inorganic binder in a relatively high proportion.

[0047] In other embodiments, the alkylene group (C) of alkylene oxide (-A1O-) x H 2x The group can all have two carbon atoms (x=2), and in particular, these can all be ethylene.

[0048] The symbol n represents the average number of moles of alkylene oxide added, and is a number between 1 and 350, 1 and 300, or 1 and 150. Here, n can be 3 or greater.

[0049] Monomer (i) can be used alone or in combination of two or more types.

[0050] <Monomer(ii)> The monomer (ii) is given by the following formula (II): [ka] It is represented by [this].

[0051] In equation (II), R 2 This is H, alkali metal ions, alkaline earth metal ions, or the following structures: [ka] It is a part that has, 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 The basis (where x = 2 to 5 in the formula), and n = 1 to 350.

[0052] Monomer (ii) is C 2~4 It is a phosphate ester derivative of a compound in which alkylene oxide is attached to phenol or a substituent thereof.

[0053] R 2 Examples of alkali metal ions represented by R include sodium and potassium. 2 Examples of alkaline earth metal ions represented by this formula include calcium and magnesium.

[0054] R 5 For A1 and n, please refer to the description related to monomer (i).

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

[0056] <Monomer(iii)> The monomer (iii) is given by the following formula (III): [ka] It is represented by [this].

[0057] In equation (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 The basis (where x = 2 to 5 in the equation) n = 1 to 350 and m = 2 to 300.

[0058] Monomer (iii) is a compound in which alkylene oxides are added to the two hydroxyl groups of hydroxyethylphenol, and also includes derivatives of the alkylene oxide adduct (phosphate esters).

[0059] Hydroxyethylphenol may be o-hydroxyethylphenol, m-hydroxyethylphenol, or p-hydroxyethylphenol. Monomer (iii) is o-hydroxyethylphenol with C 2~5 It is preferable that the compound (and its ester derivative) has an alkylene oxide added to it.

[0060] Anionization of the monomer (iii), specifically the formation of a phosphate ester derivative, can shorten the mortar mixing time when added to a hydraulic composition.

[0061] R 4 C represented by 1~4 For alkyl groups, please refer to the description of R1 related to monomer (i). For A1 and A2, please refer to the description of A1 related to monomer (i). For n, please refer to the description of n1 related to monomer (i).

[0062] The symbol 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.

[0063] Monomer (iii) may be used alone or in combination of two or more.

[0064] <Monomer (iv)> The monomer (iv) is given by the following formula (IV): [ka] It is represented by [this].

[0065] In equation (IV), R 5 H, C 1~18 It is an alkyl group, polyisobutene, or sulfonic acid moiety.

[0066] R 5 For details, please refer to the description of monomer (i).

[0067] <Monomer(v)> The monomer (v) is an aldehyde, preferably formaldehyde, metaformaldehyde, paraformaldehyde, or formalin, or a mixture thereof.

[0068] Monomer (v) can be used alone or in combination of two or more types.

[0069] <Monomer molar ratio> The molar ratio of monomers (i) to (iv), specifically the molar ratio of a:b:c:d, can be 0.1 to 2.0:0.1 to 6.0:0.1 to 2.0:0.0 to 0.5. Specifically, monomer (iv) is not an essential component and may be used selectively. The molar ratio of a:b:c:d can 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, or 0.1 to 2.0:0.1 to 6.0:0.1 to 2.0:0.0.

[0070] The molar ratio of monomer (i) to monomer (iv) to monomer (v), specifically the molar ratio (a+b+c+d):e, can be 1:10 to 10:1. This ratio can also be 2:10 to 10:2 or 3:10 to 10:3.

[0071] <Polymerization method for obtaining phenolic resin-based dispersants> The polymerization method for obtaining the above-mentioned phenol resin-based dispersant via polycondensation of the above-mentioned monomers is not particularly limited.

[0072] The order and method of adding monomers during polycondensation are not particularly limited. For example, the entire amount of all monomers to be used in the reaction can be added all at once before the polycondensation reaction, or a portion of the monomers to be used can be added and then the remainder added dropwise in batches before the polycondensation reaction, or a portion of the monomers to be used can be added before the polycondensation reaction and the remaining monomers can be added after the reaction has progressed for a certain period of time.

[0073] Polycondensates can be obtained, for example, through the polycondensation of monomers at a reaction temperature of 80°C to 150°C and under atmospheric pressure to elevated pressure such as 0.001 to 1 MPa (gauge pressure), in the presence or absence of a dehydrating catalyst or a solvent.

[0074] Examples of 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, diethylsulfonic acid, dimethylsulfonic acid, 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, and activated clay, which can be used individually or in combination of two or more.

[0075] Examples of solvents that can be used when the polycondensation reaction is carried out in the presence of a solvent include water, glycol ether compounds such as propylene glycol monomethyl ether (PGME), aromatic compounds such as toluene or xylene, and alicyclic compounds such as methylcyclohexane. Any of the above preferred dehydration catalysts (acid catalysts), such as acetic acid, can also be used as a solvent.

[0076] The polycondensation reaction can preferably be carried out at a reaction temperature of 95°C to 130°C, and the reaction can be completed in 3 to 25 hours.

[0077] The polycondensation reaction is preferably carried out under acidic conditions, and the reaction system is preferably adjusted to a pH of 4 or less.

[0078] In addition to the monomer, other monomers that can polycondense with the above monomer may be added, provided that the effects of the present invention are not impaired thereby.

[0079] Various known methods can be used to reduce the content of unreacted monomers (v) (such as aldehydes) in the reaction system after the polycondensation reaction is complete. Examples include heat treatment at 60 to 140°C in an alkaline reaction system pH, volatilization removal of unreacted monomers (v) by setting the gauge pressure to, for example, -0.1 to -0.001 MPa, and further addition of small amounts of sodium bisulfite, ethylene urea, and / or polyethyleneimine.

[0080] The dehydration catalyst used in this reaction can be neutralized after the reaction is complete and filtered out in the form of a salt, but even if the catalyst is not removed, the performance of the dispersant of the present invention will not be impaired, as shown below. Exemplary methods for removing the catalyst, in addition to the filtration described above, include phase separation, dialysis, ultrafiltration, and the use of ion exchangers.

[0081] The reaction product is also neutralized and diluted with water, for example, to improve its processability (such as metering) during use as a dispersant. Examples of basic compounds used for neutralization include alkali hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, and organic amines such as ammonia, monoethanolamine, diethanolamine, and triethanolamine, one or two of which may be used.

[0082] The final phenolic resin-based dispersant should have a weight-average molecular weight (calculated relative to polyethylene glycol by gel permeation chromatography (GPC)) in the range of 5,000 to 100,000, 10,000 to 80,000, or 15,000 to 35,000 to ensure better dispersion performance.

[0083] <Additives> In the method of the present invention for improving the processability of an inorganic binder composition containing a slag-containing inorganic binder, other additives such as polycarboxylic acid-based dispersants, particularly polycarboxylate ether-based dispersants, may be used in combination with the phenol resin-based dispersant of the present invention. When such other additives are co-ground and / or co-mixed with the inorganic binder composition, the other additives may be co-ground and / or co-mixed with the inorganic binder composition simultaneously with or before or after the phenol resin-based dispersant of the present invention.

[0084] The ratio of the phenolic resin-based dispersant and the polycarboxylic acid-based dispersant of the present invention (phenolic 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 used in combination, the phenolic resin-based dispersant and the polycarboxylic acid-based dispersant of the present invention may be used in an amount of 0.1 to 10% by mass or 0.1 to 5% by mass, calculated based on the solid content, relative to the total mass of the inorganic binder.

[0085] Other additives that may be added include at least one other cement or concrete additive selected from the group consisting of 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, concrete hardening retarders, setting accelerators, segregation reducers, thickeners, shrinkage reducers, curing agents, and waterproofing agents. Examples of other additives that may be used in particular include retarders such as gluconate salts, especially sodium gluconate.

[0086] For information on polycarboxylic acid-based dispersants that can be used in the present invention, please refer to the description in Patent Document 1.

[0087] Specifically, the polycarboxylic acid polymer Q that can be used in the present invention has 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.

[0088] Polycarboxylic acid polymer Q functions as a dispersant for hydraulic compositions, and its use can be expected to result in concrete with less slump loss.

[0089] Structural units having amino groups and imino groups, as well as structural units having amino groups, imino groups, and amide groups in polycarboxylic acid polymer Q, are derived from compounds having amino groups and imino groups, and compounds having amino groups, imino groups, and amide groups, respectively.

[0090] Compounds having an amino group and an imino group, and compounds having an amino group, an imino group and an amide group, are compounds that, per mole of unit structure, contain at least 1 mole each of an amino group (primary amine) and an imino group (secondary amine), and in some cases also contain an amide group (not essential) formed by the condensation of a carboxylic acid with an amino group or an imino group.

[0091] The above compounds may be either low molecular weight or high molecular weight compounds. Examples of low molecular weight compounds include, for example, 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; or hydroxylamines or acid amides (other than aliphatic, alicyclic, or aromatic amides) such as acetamide, benzamide, or lactam; and compounds having amino and imino groups derived from adducts obtained by adding oxygen-containing or nitrogen-containing functional groups or halogen-containing (fluorine, bromine, iodine) substituents, such as alkylene oxides, to the above compounds, and / or compounds having amino, imino, and amide groups. Examples of high molecular weight compounds include compounds that can be derived from the above low molecular weight compounds by polymerizing one or more of the compounds listed as examples, as well as polyalkylene polyamines and polyamide polyamines.

[0092] The molecular weight of the above compounds is 900 to 10,000, preferably 900 to 3,000 and more preferably 900 to 2,000. Specific examples of the above compounds in this case are polyalkylene polyamines or polyamide polyamines that may contain their alkylene oxide adducts.

[0093] Specifically, in preferred embodiments, the structural units having amino and imino groups are preferably derived from polyalkylene polyamines, and such polyalkylene polyamines may include polyalkylene oxide adducts of polyalkylene polyamines.

[0094] Structural units having amino groups, imino groups, and amide groups can preferably be derived from polyamide polyamines, and such polyamide polyamines may include polyalkylene oxide adducts of polyalkylene polyamines.

[0095] Examples of polyalkylene polyamines include mixtures of high molecular weight polyethylene polyamines, such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, or mixtures containing a large amount of ethylene units and nitrogen atoms; cyclic imine polymers such as polyethyleneimine, polypropyleneimine, poly-3-methylpropylimine, and poly-2-ethylpropylimine; and unsaturated amine polymers such as polyvinylamine and polyallylamine. Polyalkylene polyamines can also be copolymers of cyclic imines (such as ethyleneimine, propyleneimine, 3-methylpropylimine, and 2-ethylpropylimine), unsaturated amides (such as N-vinylacetamide, N-vinyl versate, and N-vinylphthalimide), or unsaturated imides with unsaturated compounds copolymerizable with the above. For example, unsaturated compounds that can be copolymerized with cyclic imines, unsaturated amides, or unsaturated imides 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 bis-alkyloxetane, mono- or bis-alkylchloromethyloxetane, tetrahydrofuran and mono- or bis-alkyltetrafluorofuran, cyclic formals such as 1,2-dioxofran and trioxofran, and N-substituted alkylimines such as N-methylethyleneimine.

[0096] Polyalkylene oxide adducts of polyalkylene polyamines are compounds 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 the polyalkylene polyamine-alkylene oxide copolymer may be the same compound or different compounds. Examples of alkylene oxides that can be used in combination include ethylene oxide, propylene oxide, and butylene oxide. From the viewpoint of improving the water-reducing effect, ethylene oxide is preferred. When two or more molecules of alkylene oxide are copolymerized for each of the two molecules of polyalkylene polyamine in the polyalkylene polyamine-alkylene oxide copolymer, polyoxyalkylene chains in which the alkylene oxides are added and polymerized together may be formed. One type of alkylene oxide may be used, or two or more types may be used. When a polyoxyalkylene chain is formed using two or more types of alkylene oxides, the two or more alkylene oxides constituting the polyoxyalkylene chain may be linked in a block-like manner or randomly. If there are two or more polyoxyalkylene chains per molecule of polyalkylene polyamine copolymer, the polyoxyalkylene chains may be identical or different from each other.

[0097] Examples of polyamide polyamines include compounds formed by the polycondensation of the above-mentioned polyalkylene polyamine via an amide bond with a dibasic acid, dibasic acid anhydride, dibasic acid ester, or dibasic acid dihalide. Examples of dibasic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. 2~10Examples include aliphatic saturated dibasic acids, and dibasic acid anhydrides include the anhydrides of the dibasic acids mentioned above. 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 dibasic acids mentioned above, and examples of dibasic acid dihalides include dichlorides, dibromids, and diiodides of the dibasic acids mentioned above.

[0098] Polyalkylene oxide adducts of polyamide polyamines are compounds obtained by adding an alkylene oxide to an amino group, imino group, or amide group in each 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 can be bonded in a block-like or random manner.

[0099] Preferably, examples of polycarboxylic acid polymers Q that can be used in the present invention include polymers having the following: copolymer units obtained by copolymerizing a monomer mixture containing a monomer represented by the following general formula (1) ("monomer E") and a monomer represented by the following general formula (2) ("monomer F"), structural units having the above-mentioned amino group and imino group, and / or structural units having the above-mentioned amino group, imino group, and amide group. This type of polymer can be obtained by copolymerizing monomer E represented by the following general formula (1) and monomer F represented by the following general formula (2) with a monomer having the above-mentioned amino group and imino group structural unit or a monomer having the above-mentioned amino group, imino group, and amide group structural unit ("monomer G").

[0100] The following general formula (1) [ka] In monomer E represented by R 11 , R 12, R 13 and R 14 Each of these is independently a hydrogen atom or C 1~22 The hydrocarbon group is represented, where X represents -COO-, -CON< or -(CH2)bO-, and AO represents C 2~4 This represents an alkylene oxide group. The symbol 'a' represents the average number of moles of alkylene oxide to be added, which is a number between 1 and 200, preferably between 30 and 150. If X is -(CH2)bO-, then 'b' represents a number between 1 and 20.

[0101] The monomer E represented by general formula (1) is, more specifically, a polymerizable polyalkylene glycol monomer having polymerization-active groups and having polyalkylene glycol as a structural unit, and includes the following: C such as polyalkylene glycol monoallyl ether, alkylene glycol monoalkenyl ether, methoxypolyalkylene glycol monoallyl ether, and methoxyalkylene glycol monoalkenyl ether. 3~8 Alkenyl ethers formed from alkenyl ethers and (alkoxy)alkylene glycols, (meth)acrylic acid, and C such as methoxypolyalkylene glycol, ethoxypolyalkylene glycol, or propoxypolyalkylene glycol. 1~22 Alkoxyalkylene glycol (meth)acrylate formed from alkoxy polyalkylene glycol, C 1~22 Alkoxyalkylene glycol unsaturated fatty acid esters formed from alkoxy polyalkylene glycols and unsaturated fatty acids such as oleic acid; alkoxyalkylene glycol amide 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 structure of this polyalkylene glycol consists of ethylene oxide, propylene oxide and / or butylene oxide added alone or in combination. 2~4Formed from alkylene oxides, the addition by combination can be random or block. These polyalkylene glycol monomers, which possess polymerization activity, can be used alone or in combination.

[0102] The following general formula (2) [ka] In monomer F represented by R 15 , R 16 , R 17 and R 18 These are, independently, hydrogen atoms and C 1~22 Hydrocarbon group, -(CH2)c-COOM, -COOM, -COOR 19 (Here, R 19 C 1~22 (representing a hydrocarbon group, -(CH2)c-COOM, -COOM, or glycidyl group) or a glycidyl group, or R 15 and R 16 Or R 17 and R 18 It combines with the >C=C< group in formula (2) to form an oxyhydride. The symbol c represents a number from 1 to 20. M represents a hydrogen atom, alkali metal, alkaline earth metal, ammonium, or alkanolamine.

[0103] Further specific examples of monomer F represented by the general formula (2) above include unsaturated aliphatic acids and their ester derivatives such as maleic acid, maleic anhydride, itaconic acid, methacrylic acid, acrylic acid, dialkylmaleate esters, alkyl methacrylate esters, and alkyl acrylate esters, as well as glycidyl compounds such as glycidyl methacrylate, glycidyl acrylate, and glycidyl allyl ether. These can be in acidic or neutralized form, and in the case of neutralization, for example, sodium, potassium, calcium, magnesium, ammonium ions, and alkanolamines can be used. These acids or neutralized salts can be used alone or in combination.

[0104] Examples of monomer 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 condensates of the above-mentioned compounds having an amino group and an imino group, or the above-mentioned compounds having an amino group, an imino group, and an amide group, with acrylic acid, methacrylic acid, or esters formed from acrylic acid or methacrylic acid and C1-4 lower alcohols. The method for producing these is specifically disclosed in, for example, Japanese Patent No. 3235002, Japanese Patent No. 3346456, Japanese Patent No. 3740641, and Japanese Patent No. 3780456.

[0105] From the perspective of reducing slump loss, the copolymerization ratio of monomer E, monomer F, and monomer G should be within the range of E:F:G = 50-90:5-40:5-40 (the sum of the mass ratios of the three monomers E, F, and G is 100).

[0106] The method for producing the copolymer is not particularly limited, and known polymerization methods such as solution polymerization or bulk polymerization using a polymerization initiator can be employed.

[0107] The polycarboxylic acid polymer Q of the present invention can be obtained by copolymerizing other monomers copolymerizable with the above monomers, in addition to the above monomers, as long as the effects of the present invention are not impaired thereby. Examples of such monomer components include the following known copolymerizable monomer components: (non)aqueous monomers such as styrene; anionic monomers such as vinyl sulfonic acid, styrene sulfonic acid, (meth)acrylic acid phosphate salts and (meth)acrylic acid-alkylene oxide adduct phosphate salts; amide monomers such as acrylamide and acrylamide-alkylene oxide adducts; amine monomers such as polyalkylene polyimine compounds; polyalkylene glycol monomers such as mono- or di-esters of polyalkylene glycol and maleic anhydride, and esters of polyalkylene glycol and itaconic acid.

[0108] These additional monomers may 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 the additional monomers.

[0109] The above-mentioned compounds having an amino group and an imino group, and / or the above-mentioned compounds having an amino group, an imino group, and an amide group, bond to the polycarboxylic acid polymer Qo via graft-bonding groups or crosslinking groups to generate 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 in the polycarboxylic acid polymer Q of the present invention. Here, the polycarboxylic acid polymer Qo is not particularly limited, however, it is a polycarboxylic acid polymer having functional groups that can be graft-bonded or crosslinked with the above-mentioned compounds having an amino group and an imino group, such as acid groups, acid anhydride groups, glycidyl groups, and acid ester groups, and / or compounds having an amino group, an imino group, and an amide group. Polycarboxylic acid polymers Qo can be prepared, for example, by copolymerization of the aforementioned monomers E and F and optionally additional monomers. Specific examples of polycarboxylic acid polymers Qo include copolymers of maleic anhydride and polyalkylene glycol monoalkenyl ethers, copolymers of maleic anhydride and allyl alcohol-alkylene oxide adduct monomethyl ethers, 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, monomers having sulfone groups and (alkoxy) polyalkylene glycol (meth)acrylate, copolymers of (meth)acrylic acid, monomers having phosphate groups and (alkoxy) polyalkylene glycol (meth)acrylate, and copolymers of (meth)acrylic acid, (meth)acrylate alkyl esters and (alkoxy) polyalkylene glycol (meth)acrylate.

[0110] The polycarboxylic acid copolymer Q used in this invention should have a weight-average molecular weight (calculated using polyethylene glycol as a reference by gel permeation chromatography) in the range of 1,000 to 500,000. If the molecular weight is outside this range, the water-reducing performance will be significantly impaired, or the desired effect on reducing slump loss will not be achieved.

[0111] In the present invention, the reaction solution containing the polycarboxylic acid copolymer Q produced as described above can be used, for example, as an admixture for the hydraulic composition in the present invention, or in combination for the preparation of the admixture for the hydraulic composition in the present invention. In such cases, the solution may contain, in addition to the polycarboxylic acid copolymer Q, unreacted components and by-products (which are, for example, produced in various polymerization steps, grafting steps, crosslinking steps, and alkylene oxide addition steps).

[0112] <<Inorganic Binder Composition>> The inorganic binder composition of the present invention, (a) 280~550 kg / m 3 A slag-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. Includes.

[0113] Here, the dispersant is a phenol resin-based dispersant obtained by polycondensation of the following monomers (i) to (v).

[0114] The inorganic binder composition of the present invention improves processability and, in particular when slag is used as the inorganic binder, especially when slag is used as the inorganic binder in a relatively high proportion, it is possible to suppress changes in slump and slump flow over time.

[0115] For details regarding the features and embodiments of the inorganic binder composition of the present invention, please refer to the disclosure relating to the method of the present invention for improving the processability of the inorganic binder composition.

[0116] <<Molded products>> The molded article of the present invention is obtained by mixing the inorganic binder composition of the present invention with water in a water-to-inorganic binder mass ratio of 0.25 to 0.6, and then curing the resulting mixture.

[0117] For further details regarding the characteristics of the molded articles of the present invention, please refer to the disclosures relating to the method of the present invention for improving the processability of inorganic binder compositions.

[0118] <<Molded products>> The molded article of the present invention is obtained by mixing the inorganic binder composition of the present invention with water in a water-to-inorganic binder mass ratio of 0.25 to 0.6, and then curing the resulting mixture.

[0119] For further details regarding the characteristics of the molded articles of the present invention, please refer to the disclosures relating to the method of the present invention for improving the processability of inorganic binder compositions.

[0120] <<Admixtures and phenolic resin-based dispersants>> The blend of the present invention comprises or consists of the following (each in proportion to the total mass of the blend): (a) At least one dispersant in an amount of 20-80% by mass, preferably 50-80% by mass, more preferably 64-75% by mass, (b) 10 to 45% by mass, preferably 15 to 40% by mass, more preferably 15 to 35% by mass of at least one polycarboxylic acid polymer, (c) 1 to 20% by mass, preferably 1 to 10% by mass, at least one retarder, preferably sodium gluconate. (d) Optional additional additives, and (e) Remaining amount, water (amount that is 100% by mass in total).

[0121] Here, the dispersant is a phenol resin-based dispersant obtained by polycondensation of the following monomers (i) to (v).

[0122] The phenolic resin-based dispersant of the present invention, which improves the processability of inorganic binder compositions containing slag-containing inorganic binders, is obtained by polycondensation of the above monomers (i) to (v).

[0123] An inorganic binder composition can be obtained by combining the admixture and phenolic resin-based dispersant of the present invention with an inorganic binder. The admixture and phenolic resin-based dispersant of the present invention improve processability and suppress changes in slump and slump flow over time in the obtained inorganic binder composition, especially when slag is used as the inorganic binder, particularly when slag is used as the inorganic binder in a relatively high proportion.

[0124] For details regarding the characteristics and embodiments of the use of the admixture and phenolic resin-based dispersant of the present invention, please refer to the disclosure relating to the method of the present invention for improving the processability of inorganic binder compositions.

[0125] When the phenolic resin-based dispersant of the present invention is used in combination with a polycarboxylic acid-based dispersant, this combination can be used as a mixture of the present invention (containing the phenolic resin-based dispersant and the polycarboxylic acid-based dispersant of the present invention), and for example, the phenolic resin-based dispersant and the polycarboxylic acid-based dispersant of the present invention can be added individually during the production of an inorganic binder composition. [Examples]

[0126] The present invention will be illustrated by the following embodiments. However, the present invention is by no means limited by these embodiments. In the following embodiments, "part" means "parts by mass".

[0127] <<Preparation of phenolic resin-based dispersant>> (Preparation of monomers represented by formula (I)) 80 parts of diethylene glycol monophenyl ether (Hisolve DPH, manufactured by Toho Chemical Industry Co., Ltd.) and 0.2 parts of 96% potassium hydroxide were introduced into a stainless steel high-pressure reactor equipped with a thermometer, stirrer, pressure gauge, and nitrogen supply pipe. The reactor was purged with nitrogen, and the contents were heated to 150°C in the resulting nitrogen atmosphere. While maintaining the system at a temperature of 150°C and a safe pressure, 1,700 parts of ethylene oxide were introduced into the reactor over 10 hours, and the temperature was maintained for 2 hours to complete the alkylene oxide addition reaction, yielding polyethylene glycol monophenyl ether (moles of added EO: 90) as a monomer represented by formula (I).

[0128] (Preparation of monomers represented by formula (II)) Using p-tert-butylphenol (PTBP, manufactured by DIC) as the starting material, an ethylene oxide addition reaction was carried out according to the monomer preparation method represented by formula (I) to obtain an alkylene oxide adduct. 6 moles of ethylene oxide were added.

[0129] Three moles of p-tert-butylphenol-EO adduct (6 moles adduct) were introduced into a glass reactor equipped with a stirrer, thermometer, and nitrogen supply pipe. One mole of anhydrous phosphoric acid was introduced into the reactor over 4 hours at 50°C while supplying nitrogen, and the reaction was carried out. Subsequently, an aging reaction was carried out at 100°C for 3 hours to complete the phosphate ester reaction, yielding the phosphate ester of the p-tert-butylphenol-EO adduct as a monomer represented by formula (I).

[0130] (Preparation of monomers represented by formula (III)) 100 parts of ortho-hydroxyethylphenol (Aldrich reagent) and 0.3 parts of 96% potassium hydroxide were introduced into a stainless steel high-pressure reactor equipped with a thermometer, stirrer, pressure gauge, and nitrogen supply tube. The reactor was purged with nitrogen, and the contents were heated to 130°C in the resulting nitrogen atmosphere. While maintaining the system at a temperature of 130°C and a safe pressure, 190 parts of ethylene oxide were introduced into the reactor over 4 hours, and the temperature was maintained for 2 hours to complete the alkylene oxide addition reaction, yielding an EO adduct of ortho-hydroxyethylphenol (totaling 6 moles) as a monomer represented by formula (III).

[0131] <<Preparation of phenolic resin-based dispersant A1>> The monomer raw materials represented by formulas (I) to (III) above were introduced into a glass reactor equipped with a stirrer, thermometer, and reflux condenser in the molar ratios shown in Table 1. The contents were heated to 70°C, and then 98% sulfuric acid was introduced in an amount of 1.0% by mass relative to the total mass of the monomers represented by formulas (I) to (III) above. Next, formalin (HCHO), as the monomer represented by formula (V), was introduced into the reactor all at once in the molar ratio shown in Table 1, and then the contents were heated to 105°C. When the temperature reached 105°C, the pH of the reaction mixture was 2.1 (1% aqueous solution, 20°C). The reaction was completed 6 hours after the temperature reached 105°C, and 48% sodium hydroxide was introduced to neutralize the reaction solution (in the form of a 1% aqueous solution) to a pH in the range of 5.0 to 7.5. Next, the reaction product was adjusted to a solid content concentration of 40% by adding a suitable amount of water to obtain an aqueous solution of phenol resin-based dispersant A1 in the form of a polycondensate. The weight-average molecular weight Mw of phenol resin-based dispersant A1 was measured by gel permeation chromatography (GPC).

[0132] The conditions for permeation chromatography (GPC) in this invention are as follows: Columns: OHpak SB-802.5HQ, OHpak SB-803HQ, and OHpak SB-804HQ (manufactured by Showa Denko Corporation) Eluent: A mixture of 50 mM aqueous sodium nitrate solution and acetonitrile (volume ratio 80 / 20) Detector: Differential refractive index meter, calibration curve: polyethylene glycol

[0133] <<Preparation of phenolic resin-based dispersants A2 to A5>> Except for changing the types and molar ratios of the raw materials of the monomers of formulas (I) to (III) and (V) as shown in Table 1, aqueous solutions of phenolic resin-based dispersants A2 to A5 were obtained in the form of polycondensates in the same manner as the preparation of phenolic resin-based dispersant A1.

[0134] <<Preparation of phenolic resin-based dispersants B1 to B5>> Except for changing the types and molar ratios of the raw materials of the monomers of formulas (I) to (III) and (V) as shown in Table 1, aqueous solutions of phenolic resin-based dispersants B1 to B5 were obtained in the form of polycondensates in the same manner as the preparation of phenolic resin-based dispersant A1.

[0135] However, ethylene oxide (EO) was used as the alkylene oxide (AO) to add a polyethylene glycol group (C x H 2x group, where x = 2) to synthesize the monomers of formulas (I) to (III) for phenolic resin-based dispersants A1 to A5, while a mixture of alkylene oxides was added as the alkylene oxide (AO) to synthesize the monomers of formulas (I) to (III) for phenolic resin-based dispersants B1 to B5. Table 1 shows the ratio of the C x H 2x group with x being 3 to 5 (X = 3 to 5 (mol%)) to the total amount of the C x H 2x group which was 2 to 5.

[0136]

Table 1

[0137] <<Preparation of polycarboxylic acid-based dispersant Q1>> 103 g (1.00 mol) of diethylenetriamine and 97.3 g (0.67 mol) of adipic acid were introduced into a stirring reactor, nitrogen was introduced, and the contents were stirred and mixed in the resulting nitrogen atmosphere. The contents were heated to 150°C and reacted for 20 hours until the acid value reached 22, while removing the reaction product water associated with polycondensation. Next, 1.1 g of hydroquinone methyl ether and 27.5 g (0.32 mol) of methacrylic acid were introduced, and the contents were reacted at the same temperature (150°C) for 10 hours. As a result, 42 g (total) of water was removed from the reaction, and 187 g of polyamide polyamine (melting point: 122°C, acid value: 23) was obtained.

[0138] All of the polyamide polyamine was dissolved in 272 g of water, and the solution was heated to a temperature of 50°C. At the same temperature (50°C), 220 g of ethylene oxide (corresponding to 3.0 moles relative to the total amount of amino residue containing unreacted amino groups) was gradually introduced over 4 hours, and the contents were then aged for 2 hours. This yielded 680 g of polyamide polyamine-EO adduct (60% solids).

[0139] 180g of water was introduced into a stirring reactor, nitrogen was introduced to create a nitrogen atmosphere in the synthesis system, and the contents were heated to 80°C. The following were added dropwise to the synthesis system over 3 hours: 150 g of water, 98.2 g of the above polyamide polyamine-EO adduct, 72.0 g of methacrylic acid, 60.9 g of short-chain methoxypolyethylene glycol monomethacrylate (short-chain MPEGM, molecular weight: 1,000), and 183 g of long-chain methoxypolyethylene glycol monomethacrylate (long-chain MPEGM, molecular weight: 2,000) (when methacrylic acid was used in the form of a sodium salt, the proportion of components added was calculated as polyamide polyamine-EO adduct: 15% by mass, methacrylic acid: 23% by mass, short-chain MPEGM: 15% by mass, and long-chain MPEGM: 47% by mass (total 100% by mass)), and 66.4 g of 5% aqueous thioglycolic acid, followed by 123 g of 5% aqueous sodium persulfate, which were added dropwise over 3 hours. The contents were then aged for 2 hours and cooled. Next, the product was neutralized to pH 7 with a 48% NaOH aqueous solution to obtain 1,029 g of polycarboxylic acid-based dispersant Q1. The weight-average molecular weight Mw of polycarboxylic acid-based dispersant Q1 was 46,000, as measured by GPC.

[0140] <<Preparation of polycarboxylic acid-based dispersant Q2>> 314 g of water was introduced into a stirring reactor, nitrogen was introduced to create a nitrogen atmosphere in the synthesis system, and the contents were heated to 80°C. The following three solutions were simultaneously added dropwise to the synthesis system over 2 hours: 61 g of water, 6.0 g of acrylic acid, 18.7 g of methacrylic acid, a mixture of 169 g of methoxypolyethylene glycol monomethacrylate (MPEGM, molecular weight: approximately 2000) and 169 g of methoxypolyethylene glycol monoacrylate (MPEGA, molecular weight: approximately 1000), 78.4 g of a 5% aqueous solution of ammonium thioglycolate, and 78.4 g of a 5% aqueous solution of ammonium persulfate.

[0141] After adding the solution, 42.7 g of polyamide polyamine EO adduct, obtained in the same manner as the preparation of polycarboxylic acid dispersant Q1 described above, was added dropwise over 30 minutes, and 39.2 g of 5% ammonium persulfate aqueous solution was added dropwise over 1 hour. Expressed as a mass ratio of solids, the proportions were as follows: polyamide polyamine EO adduct: 6% by mass, acid (total of acrylic acid and methacrylic acid): 8% by mass, MPEGM: 43% by mass and MPEGA: 43% by mass (total 100% by mass). The contents were then aged for 2 hours, cooled, and neutralized to pH 6 with 48% NaOH aqueous solution to obtain 1,000 g of polycarboxylic acid dispersant Q2. The weight-average molecular weight Mw of polycarboxylic acid dispersant Q2 was 42,000 as measured by GPC.

[0142] <<Mixture preparation 1>> A mixture having the composition shown in Table 2 below was prepared using the dispersants obtained as described above (phenol resin-based dispersant B1 and polycarboxylic acid-based dispersants Q1 and Q2).

[0143] [Table 2]

[0144] <<Preparation and Evaluation of Concrete Composition 1>> Concrete compositions were prepared using the formulations shown in Table 3, in accordance with JIS A 1138. Table 3 shows that the ratio of blast furnace slag powder to the total of cement (C) and blast furnace slag powder (BS) (C / (C+BS)) was 75% (=354 / (118+354)). The materials were mixed using a twin-screw forced mixing mixer (nominal capacity 100 liters), and the amount of concrete produced in each batch was 50 liters / batch.

[0145] [Table 3]

[0146] The prepared concrete composition was evaluated within the time range of 5 minutes to 90 minutes after its generation. The composition was evaluated as follows.

[0147] <Slump and slump flow> The concrete composition was evaluated for slump and slump flow in accordance with JIS A 1101:2020 and JIS A 1150:2020, respectively.

[0148] <Air content> The concrete composition was evaluated for air content in accordance with JIS A 1128:2019.

[0149] <O-funnel flow time and V-funnel flow time> The air content of the concrete composition was evaluated based on the O-funnel flow time and V-funnel flow time in accordance with "Test of High-Flow Concrete Fluidity Using Funnel (draft): JSCE F-512".

[0150] <Setting time> The setting time of the concrete composition was measured in accordance with JIS A 1147.

[0151] <Compressive strength> Compressive strength test specimens were prepared in accordance with JIS A 1132, and the compressive strength was measured in accordance with JIS A 1108.

[0152] Table 4 shows the evaluation results for the concrete compositions of each formulation.

[0153]

Table 4

[0154] Table 4 shows that the concrete composition B1-1 obtained using the phenolic resin-based dispersant B1 of the present invention has more stable properties over time and maintains a more suitable amount of air compared to the concrete compositions A obtained using the polycarboxylic acid-based dispersants Q1 and Q2.

[0155] <<Mixture Preparation 2>> A mixture having the composition shown in Table 5 below was prepared using the dispersants (phenolic resin-based dispersants A1 and B1 and polycarboxylic acid-based dispersants Q1 and Q2) obtained as described above.

[0156]

Table 5

[0157] <<Concrete Preparation and Evaluation 2>> According to JIS A 1138, a concrete composition was produced using the formulation shown in Table 6. Table 6 shows that the ratio of blast furnace slag fine powder to the total of cement (C) and blast furnace slag fine powder (BS) (C / (C + BS)) was 65% (= 307 / (165 + 307)). The materials were kneaded using a twin-screw forced mixing mixer (nominal capacity 100 liters), and the amount of concrete produced per batch was 50 liters / batch.

[0158]

Table 6

[0159] The prepared concrete composition was evaluated as follows.

[0160] <Slump and Slump Flow> The concrete composition was evaluated for slump and slump flow according to JIS A 1101:2020 and JIS A 1150:2020, respectively.

[0161] <Air Content> The concrete composition was evaluated for air content according to JIS A 1128.

[0162] <O-Funnel Flow Time and V-Funnel Flow Time> The air content of the concrete composition was evaluated based on the O-funnel flow-down time and the V-funnel flow-down time in accordance with "Test of High-Flow Concrete Fluidity Using Funnel (draft): JSCE F-512".

[0163] <Sensory Evaluation of Handling> The softness of the concrete composition was evaluated by sensory evaluation using a scoop. 5: Very soft 4: Soft 3: Somewhat soft 2: Hard 1: Very hard

[0164] Table 7 shows the results of the evaluation for the concrete compositions of each formulation.

[0165]

Table 7

[0166] Table 6 shows that the concrete composition B1-2 obtained using the phenolic resin-based dispersant B1 of the present invention has more stable properties over time and maintains a more suitable amount of air compared to the concrete composition A obtained using the phenolic resin-based dispersant A.

[0167] Ethylene oxide (EO) was used as an alkylene oxide (AO) to add a polyethylene glycol group (C x H 2x group, where x = 2) to synthesize a monomer for the phenolic resin-based dispersant A1, while a mixture of alkylene oxides was added as the alkylene oxide (AO) to synthesize a monomer for the phenolic resin-based dispersant B1. The ratio of the C x H 2x group with x = 3 - 5 (X = 3 - 5 (mol%)) to the total amount of the C x H 2x group with x = 2 - 5 was 0 mol% for the phenolic resin-based dispersant A1, but 20 mol% for the phenolic resin-based dispersant B1.

Claims

1. A method for improving the processability of an inorganic binder composition containing a slag-containing inorganic binder, comprising the following steps (a) to (c): (a) A step of providing a dispersant, (b) the step of providing the inorganic binder composition, (c) A step of co-grinding and / or co-mixing the dispersant provided in step (a) and the inorganic binder composition provided in step (b). The dispersant includes the following monomers (i) to (v): (i) a mol% of formula (I): 【Chemistry 1】 monomers represented by (ii) For b mol%, formula (II): 【Chemistry 2】 monomers represented by (iii) c mol%, formula (III): 【Transformation 3】 monomers represented by Formula (IV) of (iv) d mol%: 【Chemistry 4】 monomers represented by (v) e mol% of an aldehyde, preferably formaldehyde, metaformaldehyde, paraformaldehyde, or formalin, or a mixture thereof. It is a phenol resin-based dispersant obtained by polycondensation, During the ceremony, 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 the following structures: 【Transformation 5】 It is a part that has, 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, polyisobutene or a sulfonic acid moiety, A １ and A ２ Each of them is independent of C ｘ H ２ｘ The basis (where x = 2 to 5 in the equation) 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, according to this method.

2. The method according to claim 1, wherein the slag content is at least 70% by mass, preferably at least 80% by mass, and particularly at least 85% by mass, based on the total dry mass of the inorganic binder.

3. The method according to claim 1 or 2, wherein the slag is steel slag, preferably blast furnace slag fine powder, and more particularly blast furnace slag fine powder conforming to JIS A 6206:2013 standard.

4. The method according to claim 1 or 2, wherein the phenolic resin dispersant is co-ground and / or co-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 the dispersant is co-ground with the inorganic binder composition in a ball mill or vertical roll mill in step (c).

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

7. (a) 280-550kg / m ３ A slag-containing inorganic binder, (b) 700-950kg / m ３ Fine aggregate, preferably sand, (c) 800-1100kg / m ３ Coarse aggregate, preferably gravel, (d) A 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. In an inorganic binder composition containing the following monomers (i) to (v): (i) a mol% of formula (I): 【Transformation 6】 monomers represented by (ii) For b mol%, formula (II): 【Transformation 7】 monomers represented by (iii) c mol%, formula (III): 【Transformation 8】 monomers represented by Formula (IV) of (iv) d mol%: 【Chemistry 9】 monomers represented by (v) e mol% of an aldehyde, preferably formaldehyde, metaformaldehyde, paraformaldehyde, or formalin, or a mixture thereof. It is a phenol resin-based dispersant obtained by polycondensation, During the ceremony, 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 the following structures: 【Chemistry 10】 It is a part that has, 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, polyisobutene, or sulfonic acid portion, A １ and A ２ Each of them is independent of C ｘ H ２ｘ The basis (where x = 2 to 5 in the equation) 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 An inorganic binder composition characterized by having a molar ratio of (a+b+c+d):e of 1:10 to 10:

1.

8. The inorganic binder composition according to claim 7, wherein the inorganic binder is substantially composed of cement and slag.

9. The inorganic binder composition according to claim 7, further comprising fly ash and / or fine calcium carbonate in addition to the cement and slag.

10. The inorganic binder composition according to claim 8 or 9, wherein the mass ratio of slag to cement is 2.3:1 to 6:1, preferably 3:1 to 5:

1.

11. The inorganic binder composition according to claim 7 or 8, wherein the slag is steel slag, preferably blast furnace slag fine powder, and more particularly blast furnace slag fine powder conforming to JIS A 6206:2013 standard.

12. The inorganic binder composition according to claim 7 or 8, wherein the V-funnel flow time according to JSCE-F 512:1999 is 10 seconds or less when measured 5 minutes after mixing with water at a water-to-inorganic binder mass ratio of 0.25 to 0.

6.

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 water-to-inorganic binder mass ratio of 0.25 to 0.6, and then curing the resulting mixture.

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