Admixture, and phenolic resin-based dispersant

Abstract

To provide an admixture for improving the workability of an inorganic binder composition, and a phenolic resin-based dispersant.SOLUTION: An admixture for improving the workability of an inorganic binder composition according to the present invention contains or consists of: 20-80 mass% of at least one dispersant; 10-45 mass% of at least one polycarboxylic acid polymer; 1-20 mass% of a retarder; and optionally, a further additive, with the balance being water up to 100 mass%. The dispersant is a phenolic resin-based dispersant resulting from a specific polycondensation reaction.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an admixture and a phenolic resin-based dispersant. [Background technology]

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

[0003] However, when slag or fly ash is used as at least a part of the inorganic binder, the workability and fluidity of the resulting inorganic binder composition may be reduced.

[0004] It is known that admixtures such as air entraining agents, water reducing agents, etc. are used to improve the workability of inorganic binder compositions such as concrete compositions. Polycarboxylic acid-based polymers are widely known as such admixtures, and in recent years, it has also become known to use phenolic resin-based dispersants obtained by polycondensing multiple types of phenolic comonomers with aldehydes.

[0005] In this regard, for example, Patent Document 1 proposes an admixture containing a phenolic resin dispersant obtained by polycondensing multiple kinds of phenolic comonomers and aldehydes, and a polycarboxylic acid polymer. Patent Document 1 states that such an admixture suppresses the occurrence of blackening due to the precipitation of colored fine particles contained in the hydraulic composition on the surface of the hardened body, and also suppresses the delay in setting, predation, and reduction in early strength even when a large amount of inorganic powder is contained, and further has excellent water reducing properties. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Publication No. 2018 / 147378 Brochure Summary of the Invention [Problem to be solved by the invention]

[0007] As described above, when slag is used as the inorganic binder, particularly when a relatively high proportion of slag is used as the inorganic binder, the workability of the resulting inorganic binder composition may decrease.

[0008] In response to this, an object of the present invention is to provide an admixture and a phenolic resin-based dispersant that solve these problems. [Means for solving the problem]

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

[0010] <Aspect 1> An admixture comprising or consisting of (each in a ratio relative to the total weight of the admixture): (a) 20 to 80% by weight, preferably 50 to 80% by weight, more preferably 64 to 75% by weight, of at least one dispersant, (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 weight, preferably 1 to 10% by weight, of at least one retarder, preferably sodium gluconate; (d) optional further additives, and (e) the balance up to 100% by weight, water; The admixture is characterized in that the dispersant is a phenolic resin-based dispersant obtained by polycondensation of the following monomers (i) to (v): (i) a mol % of a monomer of formula (I): [ka] (ii) b mol % of a monomer of formula (II): [ka] (iii) c mol % of a monomer of formula (III): [ka] (iv) d mol % of a monomer of formula (IV): [ka] (v) e mol % of an aldehyde, preferably formaldehyde, metaformaldehyde, paraformaldehyde, formalin, or a mixture thereof; Where: R 1 is H or C 1 ~C 4 Alkyl group or C 2 ~C 5 Acyl groups, R 2 is H, an alkali metal ion, an alkaline earth metal ion, or a moiety of the structure: [ka] R 3 is H or OR 2 , R 4 , H, C 1 ~C 4 an alkyl group or a phosphate ester group, R 5 , H, C 1 ~C 18 an alkyl group, a polyisobutene, or a sulfonic acid moiety; A 1 and A 2 are independent of each other, 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 to 10:1. <Aspect 2> A 1 and A 2 More than 20 mol% of each of the above is C with X=3 to 5. x H 2x 2. The admixture of embodiment 1, wherein the admixture is a group. <Aspect 3> A 1 and A 2 are ethylene groups. <Aspect 4> A phenolic resin-based dispersant for improving the workability of an inorganic binder composition containing a slag-containing inorganic binder, characterized in that the phenolic resin-based dispersant is obtained by polycondensation of the above monomers (i) to (v). <Aspect 5> A 1 and A 2 More than 20 mol% of each of the above is C with X=3 to 5. x H 2x 5. The phenolic dispersant according to embodiment 4, wherein <Aspect 6> A 1 and A 2 are all ethylene groups. Aspect 7 7. The phenolic resin based dispersant according to any one of aspects 4 to 6, wherein the slag is a steel slag, preferably ground and pulverized blast furnace slag, in particular ground and pulverized blast furnace slag according to the JIS A 6206:2013 standard. <Aspect 8> A phenolic resin-based dispersant according to any one of aspects 4 to 7, wherein the phenolic resin-based dispersant is co-ground and / or co-mixed in an amount of 0.1 to 5% by weight, preferably 0.5 to 1% by weight, based on the total dry weight of the inorganic binder. <Aspect 9> A phenolic resin-based dispersant according to any one of aspects 4 to 8, wherein the phenolic resin-based dispersant is co-ground and / or co-mixed with at least one polycarboxylic acid-based polymer and / or gluconate. Effect of the Invention

[0011] The admixture and phenolic resin-based dispersant of the present invention can improve the workability of the resulting inorganic binder composition even when slag is used as the inorganic binder, particularly when a relatively high proportion of slag is used as the inorganic binder. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Method for improving the workability of an inorganic binder composition containing a slag-containing inorganic binder The method of the present invention for improving the workability of an inorganic binder composition containing a slag-containing inorganic binder comprises the following steps (a) to (c): (a) providing a dispersant; (b) providing an inorganic binder composition; and (c) intergrinding and / or intermixing said dispersant provided in step (a) and said inorganic binder composition provided in step (b).

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

[0014] According to the method of the present invention, even when slag is used as the inorganic binder, particularly when a relatively high proportion of slag is used as the inorganic binder, it is possible to improve the workability of the resulting inorganic binder composition, and in particular to suppress changes in slump and slump flow over time.

[0015] In the method of the present invention, the ratio 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. In addition, an example of the inorganic binder other than slag may be cement, particularly Portland cement. In addition, the inorganic binder may essentially consist of cement and slag. The inorganic binder composition may contain cement, slag, and further 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.

[0016] The slag may be a steel slag, preferably a ground and pulverized blast furnace slag, in particular a ground and pulverized blast furnace slag according to the JIS A 6206:2013 standard.

[0017] The phenolic resin-based dispersant may be co-ground and / or co-mixed in step (c) in an amount of 0.1 to 5% by weight, preferably 0.5 to 1% by weight, based on the total dry weight of the inorganic binder.

[0018] In step (c), the dispersant can be inter-milled with the inorganic binder composition in a ball mill or a vertical roll mill.

[0019] The inorganic binder composition whose workability 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, measured 5 minutes after mixing with water at a mass ratio of water to inorganic binder of 0.25 to 0.6.

[0020] The phenol resin-based dispersant can be used in an amount of 0.1 to 10 mass %, or 0.1 to 5 mass %, calculated as solid content, relative to the total mass of the inorganic binder.

[0021] The inorganic binder composition having improved workability by the method of the present invention can be formed into a molded article, for example, by mixing the 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, which can form a concrete composition. Examples of the aggregate include fine aggregate and coarse aggregate. The fine aggregate is preferably mountain sand, land sand, river sand, and crushed sand, and the coarse aggregate is preferably mountain gravel, land gravel, river gravel, crushed stone, and hard sandstone. Depending on the application, lightweight aggregate can also be used.

[0023] For example, an inorganic binder composition whose workability has been improved by the method of the present invention may comprise: (a) 280-550 kg / m 3 slag-containing inorganic binder, (b) 700-950 kg / m 3 fine aggregate, preferably sand, (c) 800~1100kg / m 3 coarse aggregate, preferably gravel, (d) 0.1 to 5% by weight, preferably 0.5 to 1% by weight, of at least one phenolic resin-based dispersant, based on the total dry weight of the inorganic binder.

[0024] The inorganic binder composition may also include: (a) 5 to 95% by mass, preferably 5 to 60% by mass, of a slag-containing inorganic binder; (b) 5 to 85% by weight, preferably 20 to 80% by weight, of at least one aggregate; (c) optionally, 0.1 to 10% by weight of other additives; (d) optionally water in an amount to provide a water to solids weight ratio of from 0.1 to 0.6, preferably from 0.2 to 0.5, in particular from 0.2 to 0.35.

[0025] The monomers (i) to (v) for obtaining the phenolic resin-based dispersant by polycondensation will be described in detail below.

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

[0027] In formula (I), R 1 is H or C 1 ~C 4 Alkyl group or C 2 ~C 5 Acyl groups, R 5 , H, C 1 ~C 18 an alkyl group, a polyisobutene, or a sulfonic acid moiety; A 1 is C x H 2x Group, where x=2~5, n=1~350.

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

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

[0030] R 1 C in 1 ~C 5The acyl group may be a saturated or unsaturated acyl group (R'(CO)- group, where R' is a hydrocarbon group having 1 to 4 carbon atoms). For example, saturated acyl groups having 2 to 4 carbon atoms include acetic acid, propionic acid, butanoic acid, and pentanoic acid.

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

[0032] Alkylene oxide (-A 1 O-) is an alkylene group (C x H 2x The alkylene oxide may be ethylene oxide, propylene oxide, butylene oxide, or pentene oxide, and these alkylene oxides may be added singly or in a mixed form. When two or more alkylene oxides are added in a mixed form, they may be added in a block form or in a random form.

[0033] In one embodiment, the alkylene oxide (-A 1 O-) alkylene group (C x H 2x At least a portion, for example 20 mol % or more, 25 mol % or more, or 30 mol % or more of the alkylene groups (C ) have 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. x H2x When at least a portion of the carbon atoms in the (alkyl) group is 3 to 5, the resulting phenolic resin-based dispersant can be made relatively hydrophobic, and therefore, when slag is used as the inorganic binder, particularly when slag is used at a relatively high ratio as the inorganic binder, the workability of the resulting inorganic binder composition can be further improved, and in particular, changes in slump and slump flow over time can be further suppressed.

[0034] In another embodiment, the alkylene oxide (-A 1 O-) alkylene group (C x H 2x The x groups may all have 2 carbon atoms (x=2), that is, they may all be ethylene.

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

[0036] The monomer (i) may be used alone or in combination of two or more kinds.

[0037] <Monomer (ii)> The monomer (ii) has the following formula (II): [ka]

[0038] In formula (II), R 2 is H, an alkali metal ion, an alkaline earth metal ion, or a moiety of the structure: [ka] R 3 is H or OR 2 , R 5 , H, C 1 ~C 18 an alkyl group, a polyisobutene, or a sulfonic acid moiety; A 1and A 2 are independent of each other, C x H 2x Group, where x=2~5, n=1~350.

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

[0040] R 2 The alkali metal ion in R may be sodium, potassium, etc. 2 Examples of the alkaline earth metal ion in the above formula include calcium and magnesium.

[0041] R 5 , A 1 For and n, see the description of monomer (i).

[0042] The monomer (ii) may be used alone or in combination of two or more kinds.

[0043] <Monomer (iii)> The monomer (iii) has the following formula (III): [ka]

[0044] In formula (III), R 4 , H, C 1 ~C 4 an alkyl group or a phosphate ester group, A 1 and A 2 are independent of each other, C x H 2x Group, where x=2~5, n=1–350, m=2–300.

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

[0046] This hydroxyethylphenol may be any one of o-hydroxyethyl-phenol, m-hydroxyethyl-phenol, and p-hydroxyethyl-phenol. The monomer (iii) is preferably a compound in which an alkylene oxide having 2 to 5 carbon atoms is added to o-hydroxyethyl-phenol (and its ester derivative).

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

[0048] R 4 C 1 ~C 4 For the alkyl group, R 1 Please refer to the description of A 1 and A 2 Regarding the A of monomer (i), 1 For n, see the description for n in the monomer (i).

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

[0050] The monomer (iii) may be used alone or in combination of two or more kinds.

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

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

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

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

[0055] The monomer (v) may be used alone or in combination of two or more kinds.

[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 0.1-2.0:0.1-6.0:0.1-2.0:0.0-0.5. In other words, monomer (iv) is not an essential component, and this monomer may not be used. The molar ratio of a:b:c:d may be 0.5-1.5:0.5-6.0:0.1-1.0:0.0-0.5, 0.5-1.5:0.5-6.0:0.1-1.0:0.0, or 0.1-2.0:0.1-6.0:0.1-2.0:0.0.

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

[0058] Polymerization method for obtaining phenolic resin-based dispersant The polymerization method for obtaining the phenolic resin-based dispersant by polycondensing the above monomers is not particularly limited.

[0059] In addition, the order and method of adding each monomer during polycondensation are not particularly limited. For example, all the monomers to be reacted may be added at once before the polycondensation reaction, a part of the monomers to be used may be added before the polycondensation reaction, and the rest may be added dropwise in portions, or a part of the monomers to be used may be added before the polycondensation reaction, and the rest of the monomers may be added after a certain reaction time has elapsed.

[0060] The polycondensate can be obtained, for example, by polycondensing the monomers used in the presence of a dehydration catalyst, without or with a solvent, at a reaction temperature of 80° C. to 150° C., under normal pressure to pressure, for example, 0.001 to 1 MPa (gauge pressure).

[0061] Examples of the dehydration catalyst include hydrochloric acid, perchloric acid, nitric acid, formic acid, methanesulfonic acid, octyl sulfonic 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, paratoluenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid, fluoroacetic acid, thioglycolic acid, mercaptopropionic acid, activated clay, and the like. These dehydration catalysts can be used alone or in combination of two or more.

[0062] When the polycondensation reaction is carried out in a solvent, the solvent may be water, a glycol ether compound such as propylene glycol monomethyl ether (PGME), an aromatic compound such as toluene or xylene, or a cyclic aliphatic compound such as methylcyclohexane. Furthermore, it is also possible to use a solvent that is applicable as the above-mentioned dehydration catalyst (acid catalyst), for example, acetic acid, as the solvent.

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

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

[0065] In addition to the above-mentioned monomers, other monomers capable of polycondensation with these compounds may be blended in the monomer mixture, provided that the effects of the present invention are not impaired.

[0066] After the polycondensation reaction is completed, various known methods can be used to reduce the content of unreacted monomer (v) (aldehyde, etc.) in the reaction system. For example, the pH of the reaction system is made alkaline and heat treatment is performed at 60 to 140°C, the pressure of the reaction system is reduced (for example, the gauge pressure is set to -0.1 to -0.001 MPa) and the unreacted monomer (v) is volatilized and removed, and a small amount of sodium hydrogen sulfite, ethyleneurea and / or polyethyleneimine is added.

[0067] The dehydration catalyst used in the reaction can be neutralized after completion of the reaction and removed in the form of a salt by filtration, but even in an embodiment in which the catalyst is not removed, the performance as a dispersant of the present invention described below is not impaired. Methods for removing the catalyst include, in addition to the above-mentioned filtration, phase separation, dialysis, ultrafiltration, and the use of an ion exchanger.

[0068] In addition, the workability of measurement and the like when used as a dispersant is improved by neutralizing the reaction product and diluting it with water, etc. In this case, examples of basic compounds used for neutralization include alkali hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth hydroxides such as calcium hydroxide, ammonia, and organic amines such as monoethanolamine, diethanolamine, and triethanolamine, and one or two of these may be used.

[0069] The weight average molecular weight of the above-mentioned finally obtained phenolic resin-based dispersant (measured by gel permeation chromatography (hereinafter referred to as "GPC"), calculated as polyethylene glycol) is desirably in the range of 5,000 to 100,000, 10,000 to 80,000, or 15,000 to 35,000 in order to exhibit excellent dispersing performance.

[0070] Additives In the method of the present invention for improving the workability of the inorganic binder composition containing the slag-containing inorganic binder, other additives, such as polycarboxylic acid dispersants, particularly polycarboxylic acid ether dispersants, can be used together with the phenolic resin dispersant of the present invention. When such other additives are interground and / or intermixed with the inorganic binder composition, such other additives can be interground and / or intermixed with the inorganic binder composition at the same time as the phenolic resin dispersant of the present invention, before the phenolic resin dispersant of the present invention, or after the phenolic resin dispersant of the present invention.

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

[0072] The other additives may include at least one other cement or concrete additive selected from the group consisting of other cement dispersants, high-performance air-entraining water-reducing agents, high-performance water-reducing agents, air-entraining water-reducing agents, water-reducing agents, air-entraining agents (AE agents), foaming agents, defoamers, set retarders, set accelerators, separation reducing agents, thickeners, shrinkage reducing agents, curing agents, water repellents, etc. In particular, the other additive may be a gluconate, particularly sodium gluconate, as a retarder.

[0073] For the polycarboxylic acid-based dispersant that can be used in the present invention, the description in Patent Document 1 can be referred to.

[0074] Specifically, the polycarboxylic acid polymer Q that can be used in the present invention is a polycarboxylic acid polymer having 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.

[0075] The polycarboxylic acid polymer Q plays a role as a dispersant for the hydraulic composition, and its use is expected to produce concrete with little slump loss.

[0076] In the polycarboxylic acid polymer Q, the structural unit having an amino group and an imino group, or the structural unit having an amino group, an imino group and an amide group, is a structural unit 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] The compound having an amino group and an imino group, or the compound having an amino group, an imino group and an amide group, is a compound having, in its unit structure, 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 condensation of a carboxylic acid with the amino group or the imino group, per mole of the unit structure.

[0078] The above-mentioned compound may be either a low molecular weight compound or a high molecular weight compound. 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 hexylideneamine or isopropylideneamine, aliphatic, alicyclic or aromatic amides such as acetamide, benzamide or lactam, as well as compounds derived from hydroxylamine, acid amide, etc., and include compounds having an amino group and an imino group, and / or compounds having an amino group, an imino group and an amide group, and may further include adducts obtained by adding oxygen- or nitrogen-containing functional groups such as alkylene oxides, halogen-containing (fluorine, bromine, iodine) substituents, etc., to the compounds. Examples of high molecular weight compounds include compounds obtained by polymerizing one or more of the exemplified compounds that can be derived into the above-mentioned low molecular weight compounds, polyalkylene polyamines, polyamide polyamines, etc.

[0079] The molecular weight of the compound is 900 to 10,000, preferably 900 to 3,000, and more preferably 900 to 2,000. In this case, specific examples of the compound include polyalkylene polyamines and polyamide polyamines, each of which may also include those to which polyalkylene oxides are added.

[0080] That is, in a preferred embodiment, the structural unit having an amino group and an imino group is preferably a structural unit derived from a polyalkylene polyamine, and the polyalkylene polyamine can include a polyalkylene oxide-added polyalkylene polyamine.

[0081] The structural unit having an amino group, an imino group and an amide group is preferably a structural unit derived from a polyamidepolyamine, and the polyamidepolyamine may contain a polyalkylenepolyamine having a polyalkyleneoxide added thereto.

[0082] Examples of the polyalkylene polyamine include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, or a mixture of high molecular weight polyethylene polyamines that are mixtures containing many ethylene units and nitrogen atoms, and the like, as well as cyclic imine polymers such as polyethyleneimine, polypropyleneimine, poly-3-methylpropylimine, and poly-2-ethylpropylimine, and unsaturated amine polymers such as polyvinylamine and polyallylamine. Furthermore, the polyalkylene polyamine may be a copolymer of a cyclic imine such as ethyleneimine, propyleneimine, 3-methylpropylimine, and 2-ethylpropylimine, an unsaturated amide or unsaturated imide such as N-vinylacetamide, N-vinylformamide, and N-vinylphthalimide, and an unsaturated compound copolymerizable therewith. Examples of unsaturated compounds copolymerizable with cyclic imines, unsaturated amides, unsaturated imides, etc. include dimethylacrylamide, styrene, methyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid, styrenesulfonic acid, and salts thereof, cyclic sulfide compounds such as ethylene sulfide and propylene sulfide, cyclic ethers such as oxetane, mono- or bis-alkyl oxetane, mono- or bis-alkyl chloromethyl oxetane, tetrahydrofuran, and mono- or bis-alkyl tetrafluorofuran, cyclic formals such as 1,2-dioxofuran and trioxofuran, and N-substituted alkyl imines such as N-methylethyleneimine.

[0083] The polyalkylene polyamine to which polyalkylene oxide is added is a compound in which at least two molecules of the polyalkylene polyamine and at least one molecule of alkylene oxide are copolymerized. 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 the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, etc., which may be used in combination. Among the alkylene oxides, ethylene oxide is preferred from the viewpoint of improving the water reducing effect. In the polyalkylene polyamine-alkylene oxide copolymer, when two or more molecules of alkylene oxide are copolymerized per two molecules of polyalkylene polyamine, the alkylene oxides may form a polyoxyalkylene chain by addition polymerization with each other. The alkylene oxide may be one kind or two or more kinds, and when a polyoxyalkylene chain is formed using two or more kinds of alkylene oxides, the two or more kinds of alkylene oxides constituting the polyoxyalkylene chain may be bonded in a block form or randomly. When two or more polyoxyalkylene chains are present in one molecule of the polyalkylene polyamine copolymer, the polyoxyalkylene chains may be the same or different.

[0084] In addition, the polyamide polyamine may be a compound obtained by condensation polymerization of the above polyalkylene polyamine with a dibasic acid, a dibasic acid anhydride, a dibasic acid ester, a dibasic acid dihalide, etc., via an amide bond. The dibasic acid may be an aliphatic saturated dibasic acid having 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, sebacic acid, etc., and the dibasic acid anhydride may be an anhydride of the above dibasic acid. The dibasic acid ester may be, for example, a monomethyl ester, monoethyl ester, monobutyl ester, monopropyl ester, dimethyl ester, diethyl ester, dibutyl ester, dipropyl ester, etc., of the above dibasic acid, and the dibasic acid dihalide may be a dichloride, dibromide, diiodide, etc., of the above dibasic acid.

[0085] The polyalkylene oxide-added polyamide polyamine refers to a compound in which an alkylene oxide is added to an amino group, an imino group, or an amide group in one molecule of the polyamide polyamine. Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, etc., which can be used alone or in combination, and when two or more types of alkylene oxides are used, they can be bonded in a block form or randomly.

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

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

[0088] More specifically, the monomer E represented by the above general formula (1) is a polyalkylene glycol monomer having polymerization activity, such as 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; alkoxypolyalkylene glycols having 1 to 22 carbon atoms, such as methoxypolyalkylene glycol, ethoxypolyalkylene glycol, and propoxypolyalkylene glycol; These monomers have a polymerization active group and a polyalkylene glycol as a constituent unit, such as alkoxyalkylene glycol (meth)acrylates made of ethylene glycol and (meth)acrylic acid; alkoxyalkylene glycol unsaturated fatty acid esters made of alkoxypolyalkylene glycol having 1 to 22 carbon atoms and unsaturated fatty acid such as oleic acid; alkoxyalkylene glycol amide compounds formed from α-alkoxy-ω-amino-polyalkylene glycol having a terminal amino group and (meth)acrylic acid or unsaturated fatty acid; and unsaturated aliphatic ethers which are unsaturated aliphatic alcohol alkylene oxide adducts. The constitution of this polyalkylene glycol is formed from alkylene oxide having 2 to 4 carbon atoms, and is composed of a single or mixed addition of ethylene oxide, propylene oxide and / or butylene oxide, and in the case of mixed addition, it may be either random addition or block addition. These polyalkylene glycol monomers having polymerization activity can be used alone or in combination of a plurality of them.

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

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

[0091] Examples of the 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 a condensate of the compound having an amino group and an imino group, or the 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 and a lower alcohol having 1 to 4 carbon atoms. Specifically, production methods thereof are described in Japanese Patent No. 3235002, Japanese Patent No. 3346456, Japanese Patent No. 3740641, Japanese Patent No. 3780456, etc.

[0092] From the viewpoint of reducing slump loss, the copolymerization ratio of the above-mentioned monomers E, F and G is preferably in the range of E:F:G=50-90:5-40:5-40 by mass (the total mass ratio of the three monomers E, F and G is 100).

[0093] The method for producing the copolymer is not particularly limited, and for example, a known polymerization method such as solution polymerization or bulk polymerization using a polymerization initiator can be used.

[0094] The polycarboxylic acid polymer Q of the present invention may be a copolymer of the above-mentioned monomers and other monomers copolymerizable with these monomers, as long as the effect of the present invention is not impaired. Examples of copolymerizable monomer components include the following known monomers. (Non)aqueous monomers: styrene, etc.; anionic monomers: vinyl sulfonic acid, styrene sulfonic acid, (meth)acrylic acid phosphate salts, phosphate salts of (meth)acrylic acid alkylene oxide adducts, 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 an amount of about 0 to 20 mass % based on the total mass of monomer E represented by general formula (1), monomer F represented by general formula (2), monomer G, and other monomers.

[0096] In the present invention, the structural unit having an amino group and an imino group and / or the structural unit having an amino group, an imino group and an amide group contained in the polycarboxylic acid polymer Q is a compound having an amino group and an imino group and / or a compound having an amino group, an imino group and an amide group, which is bonded to the polycarboxylic acid polymer Q via a graft bond group or a crosslinking group. 0 Here, the polycarboxylic acid polymer Q may be bonded to 0Polycarboxylic acid polymer Q is not particularly limited as long as it is a polycarboxylic acid polymer having a functional group capable of graft bonding or crosslinking with an acid group, an acid anhydride group, a glycidyl group, an acid ester group, the above-mentioned compounds having amino groups and imino groups, and / or compounds having amino groups, imino groups and amide groups. 0 is a copolymer obtained by copolymerizing, for example, the monomer E and the monomer F, and if necessary, other monomers. Specific examples thereof include a copolymer of maleic anhydride and a polyalkylene glycol monoalkenyl ether, a copolymer of maleic anhydride and an allyl alcohol alkylene oxide adduct monomethyl ether, a copolymer of (meth)acrylic acid and an (alkoxy)polyalkylene glycol (meth)acrylate, a copolymer of (meth)acrylic acid, a glycidyl (meth)acrylate, and an (alkoxy)polyalkylene glycol (meth)acrylate, a copolymer of (meth)acrylic acid, a monomer having a sulfone group, and an (alkoxy)polyalkylene glycol (meth)acrylate, a copolymer of (meth)acrylic acid, a monomer having a phosphoric acid group, and an (alkoxy)polyalkylene glycol (meth)acrylate, and a copolymer of (meth)acrylic acid, a (meth)acrylic acid alkyl ester, and an (alkoxy)polyalkylene glycol (meth)acrylate.

[0097] The polycarboxylic acid copolymer Q used in the present invention preferably has a weight average molecular weight (gel permeation chromatography method, polyethylene glycol equivalent) in the range of 1,000 to 500,000. If it is outside this range, the water reducing ability will be significantly reduced or the desired slump loss reduction effect will not be obtained.

[0098] In the present invention, the reaction liquid containing the polycarboxylic acid copolymer Q produced by the above-mentioned production procedure, etc. may be used as it is for the combination for preparing the admixture for hydraulic composition of the present invention and the admixture for hydraulic composition. In this case, the liquid may contain unreacted components and by-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: (a) 280-550 kg / m 3 slag-containing inorganic binder, (b) 700-950 kg / m 3 fine aggregate, preferably sand, (c) 800~1100kg / m 3 coarse aggregate, preferably gravel, (d) 0.1 to 5% by weight, preferably 0.5 to 1% by weight, of at least one dispersant, based on the total dry weight of the inorganic binder.

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

[0101] According to the inorganic binder composition of the present invention, even when slag is used as the inorganic binder, particularly when a relatively high proportion of slag is used as the inorganic binder, it is possible to improve the workability of the resulting inorganic binder composition, and in particular to suppress changes in slump and slump flow over time.

[0102] For details of the components of the inorganic binder composition of the present invention, usage modes, etc., the description of the method of the present invention for improving the workability of an inorganic binder composition can be referred to.

[0103] <<Molded body>> The molded body of the present invention can be obtained by mixing the inorganic binder composition of the present invention with water in a mass ratio of water to inorganic binder of 0.25 to 0.6, and then curing the resulting mixture.

[0104] For details of each component of the molded product of the present invention, reference can be made to the description of the method of the present invention for improving the workability of an inorganic binder composition.

[0105] <<Molded body>> The molded body of the present invention can be obtained by mixing the inorganic binder composition of the present invention with water in a mass ratio of water to inorganic binder of 0.25 to 0.6, and then curing the resulting mixture.

[0106] For details of each component of the molded product of the present invention, reference can be made to the description of the method of the present invention for improving the workability of an inorganic binder composition.

[0107] <Admixtures and phenolic resin dispersants> The admixture of the present invention comprises or consists of (each in a ratio relative to the total mass of the admixture): (a) 20 to 80% by weight, preferably 50 to 80% by weight, more preferably 64 to 75% by weight, of at least one dispersant, (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 weight, preferably 1 to 10% by weight, of at least one retarder, preferably sodium gluconate; (d) optional further additives, and (e) the balance to 100% by weight, water.

[0108] Here, the dispersant is a phenol resin-based dispersant obtained by polycondensation of the following monomers (i) to (v).

[0109] The phenolic resin-based dispersant of the present invention, i.e., the phenolic resin-based dispersant for improving the workability of the inorganic binder composition containing the slag-containing inorganic binder, is a phenolic resin-based dispersant obtained by polycondensation of the above-mentioned monomers (i) to (v).

[0110] The admixture and phenolic resin-based dispersant of the present invention can be combined with an inorganic binder to obtain an inorganic binder composition. The admixture and phenolic resin-based dispersant of the present invention can improve the workability of the obtained inorganic binder composition, particularly when slag is used as the inorganic binder, even when slag is used at a relatively high rate as the inorganic binder, and can suppress changes in slump and slump flow over time.

[0111] For details of the respective constituents, modes of use, etc. of the admixture and phenolic resin-based dispersant of the present invention, reference can be made to the description of the method of the present invention for improving the workability of an inorganic binder composition.

[0112] 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 the admixture of the present invention containing the phenolic resin-based dispersant of the present invention and the polycarboxylic acid-based dispersant, or the phenolic resin-based dispersant and the polycarboxylic acid-based dispersant can be added individually during the production of the inorganic binder composition. EXAMPLES

[0113] The present invention will be described below with reference to examples. However, the present invention is not limited to these examples. In the following, "parts" refers to "parts by mass."

[0114] Preparation of phenolic resin dispersant Preparation of Monomers of Formula (I) In a stainless steel high-pressure reactor equipped with a thermometer, a stirrer, a pressure gauge, and a nitrogen inlet tube, 80 parts of diethylene glycol monophenyl ether (HISOLV DPH manufactured by Toho Chemical Industry Co., Ltd.) and 0.2 parts of 96% potassium hydroxide were charged, the inside of the reactor was replaced with nitrogen, and the reactor was heated to 150° C. under a nitrogen atmosphere. Then, while maintaining the temperature at 150° C. under a safe pressure, 1700 parts of ethylene oxide were introduced into the reactor over 10 hours, and the temperature was then maintained for 2 hours to complete the alkylene oxide addition reaction, thereby obtaining polyethylene glycol monophenyl ether (EO addition mole number=90) as a monomer of formula (I).

[0115] Preparation of Monomer of Formula (II) Using p-tert-butylphenol (PTBP, manufactured by DIC Corporation) as a starting material, an alkylene oxide addition reaction was carried out according to the preparation method of the monomer of formula (I) to obtain an alkylene oxide adduct. The number of moles of ethylene oxide added was 6 moles.

[0116] In a glass reaction vessel equipped with a stirrer, a thermometer, and a nitrogen inlet tube, 3 moles of p-tert-butylphenol EO adduct (6 mole adduct) were charged, and 1 mole of phosphoric anhydride was charged over 4 hours at 50°C while bubbling with nitrogen to cause a reaction. Then, an aging reaction was carried out at 100°C for 3 hours to terminate the phosphoric acid esterification reaction, and a phosphoric acid ester of p-tert-butylphenol EO adduct was obtained as a monomer of formula (I).

[0117] (Preparation of Monomer of Formula (III)) In a stainless steel high-pressure reactor equipped with a thermometer, a stirrer, a pressure gauge, and a nitrogen inlet tube, 100 parts of ortho-hydroxyethylphenol (a reagent manufactured by Aldrich) and 0.3 parts of 96% potassium hydroxide were charged, the inside of the reactor was replaced with nitrogen, and the reactor was heated to 130° C. under a nitrogen atmosphere. Then, while maintaining the temperature at 130° C. under a safe pressure, 190 parts of ethylene oxide were introduced into the reactor over 4 hours, and the temperature was then maintained for 2 hours to complete the alkylene oxide addition reaction, thereby obtaining a total of 6 moles of EO adduct of ortho-hydroxyethylphenol as a monomer of formula (III).

[0118] (Preparation of phenolic resin-based dispersant A1) In a glass reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, the raw materials of the monomers of the above 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 charged in an amount of 1.0 mass% relative to the total mass of the monomers of the above formulas (I) to (III). Next, formalin (HCHO) as a monomer of formula (V) was introduced into the reaction vessel in a lump in the molar ratios shown in Table 1, and then the temperature was raised to 105°C. When the temperature reached 105°C, the pH of the reaction product was 2.1 (1% aqueous solution, 20°C). The reaction was terminated 6 hours after the temperature reached 105°C, and 48% caustic soda was charged and neutralized so that the pH of the 1% aqueous solution of the reaction product 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 reaction product was 40%, and an aqueous solution of phenolic resin-based dispersant A1 was obtained as a polycondensation product. The phenol resin-based dispersant A1 was subjected to gel permeation chromatography (GPC) measurement to determine the weight average molecular weight Mw.

[0119] In the present invention, the conditions for gel permeation chromatography (GPC) measurement were as follows: Column: OHpak SB-802.5HQ, OHpak SB-803HQ, OHpak SB-804HQ (Showa Denko K.K.) Eluent: A mixture of 50 mM sodium nitrate aqueous solution and acetonitrile (volume ratio 80 / 20) Detector: differential refractometer, calibration curve: polyethylene glycol.

[0120] (Preparation of phenolic resin-based dispersants A2 to A5) Aqueous solutions of phenolic resin dispersants A2 to A5 were obtained as polycondensation products in the same manner as in the preparation of phenolic resin dispersant A1, except that the types and molar ratios of the raw materials of the monomers of formulas (I) to (III) and (V) were changed as shown in Table 1.

[0121] (Preparation of phenolic resin-based dispersants B1 to B5) Aqueous solutions of phenolic resin dispersants B1 to B5 were obtained as polycondensation products in the same manner as in the preparation of phenolic resin dispersant A1, except that the types and molar ratios of the raw materials of the monomers of formulas (I) to (III) and (V) were changed as shown in Table 1.

[0122] However, in the synthesis of the monomers of the formulae (I) to (III) for the phenolic resin-based dispersants A1 to A5, ethylene oxide (EO) is used as the alkylene oxide (AO) to form a polyethylene glycol group (C x H 2x In the synthesis of the monomers of formulas (I) to (III) for the phenolic resin-based dispersants B1 to B5, a mixture of alkylene oxides was added as alkylene oxide (AO), where x is 2 to 5. x H 2x C where x is 3 to 5 relative to the total number of groups x H 2x The proportion of groups (X=3 to 5 (mol %)) was as shown in Table 1.

[0123] [Table 1]

[0124] Preparation of polycarboxylic acid dispersant Q1 In a reaction vessel equipped with a stirrer, 103g (1.00 mol) of diethylenetriamine and 97.3g (0.67 mol) of adipic acid were charged and mixed by stirring under a nitrogen atmosphere by introducing nitrogen. The temperature was raised to 150°C, and the reaction was continued for 20 hours until the acid value reached 22 while removing the water of the reaction product accompanying the polycondensation. Next, 1.1g of hydroquinone methyl ether and 27.5g (0.32 mol) of methacrylic acid were charged and reacted at the same temperature (150°C) for 10 hours. As a result, 187g of polyamide polyamine (melting point 122°C, acid value 23) was obtained together with a total of 42g of reaction distillate water.

[0125] The entire amount of this polyamidepolyamine 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 gradually introduced over 4 hours, and the mixture was aged for 2 hours. As a result, 680 g of polyamidepolyamine EO adduct (solid content 60%) was obtained.

[0126] A reaction vessel equipped with a stirrer was charged with 180 g of water, and nitrogen was introduced to create a nitrogen atmosphere within the synthesis system, and the temperature was raised to 80°C. In addition, 150g of water, 98.2g of the above polyamide polyamine EO adduct, 72.0g of methacrylic acid, and a mixture of 60.9g of short chain methoxy polyethylene glycol monomethacrylate (short chain MPEGM, molecular weight 1000) and 183g of long chain methoxy polyethylene glycol monomethacrylate (long chain MPEGM, molecular weight 2000) (the calculated blending ratio when methacrylic acid is a sodium salt is polyamide polyamine EO adduct: methacrylic acid: short chain MPEGM: long chain MPEGM = 15 mass%: 23 mass%: 15 mass%: 47 mass% (total 100 mass%)) and 66.4g of a 5% aqueous solution of thioglycolic acid were each dropped into the synthesis system over 2 hours, and 123g of a 5% aqueous solution of sodium persulfate was dropped into the synthesis system over 3 hours. After that, the mixture was aged for 2 hours and cooled. Thereafter, the mixture was neutralized to pH 7 with a 48% NaOH aqueous solution to obtain 1,029 g of polycarboxylic acid dispersant Q-1. According to GPC molecular weight measurement, this polycarboxylic acid dispersant Q1 had a weight average molecular weight Mw of 46,000.

[0127] Preparation of polycarboxylic acid dispersant Q2 A reaction vessel equipped with a stirrer was charged with 314 g of water, and nitrogen was introduced to create a nitrogen atmosphere in the synthesis system, and the temperature was raised to 80° C. In addition, three liquids, namely a mixture of 61 g of water, 6.0 g of acrylic acid, 18.7 g of methacrylic acid, 169 g of methoxypolyethylene glycol monomethacrylate (MPEGM, molecular weight approximately 2000), 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, were simultaneously dropped into the synthesis system over a period of 2 hours.

[0128] After the completion of the dropping, 42.7g of polyamide polyamine EO adduct obtained in the same manner as in the preparation of polycarboxylic acid dispersant Q1 was dropped over 30 minutes, and 39.2g of 5% ammonium persulfate aqueous solution was dropped over 1 hour. The solid contents were expressed in mass ratio, and the ratio was polyamide polyamine EO adduct / acids (total of acrylic acid and methacrylic acid):MPEGM:MPEGA=6% by mass:8% by mass:43% by mass:43% by mass (total 100% by mass). After that, the mixture was aged for 2 hours, cooled, and neutralized with 48% NaOH aqueous solution to pH 6, to obtain 1,000g of polycarboxylic acid dispersant Q2. According to GPC molecular weight measurement, this polycarboxylic acid dispersant Q2 had a weight average molecular weight Mw of 42,000.

[0129] Preparation of admixture 1 Using the dispersants obtained as described above (phenolic resin-based dispersant B1, and polycarboxylic acid-based dispersants Q1 and Q2), admixtures having the compositions shown in Table 2 below were prepared.

[0130] [Table 2]

[0131] Preparation and evaluation of concrete composition 1 A concrete composition conforming to JIS A 1138 was prepared with the mix proportions shown in Table 3. As can be seen from Table 3, the ratio of ground granulated blast furnace slag (BS) to the total of cement (C) and ground granulated blast furnace slag (BS) (C / (C+BS)) was 75% (=354 / (118+354)). A twin-shaft forced mixer with a nominal capacity of 100 liters was used for mixing, and the concrete production volume for each batch was 50 liters x 1 batch. [Table 3]

[0132] The concrete compositions thus prepared were evaluated for 5 to 90 minutes after preparation. The evaluation was performed as follows.

[0133] Slump and slump flow The slump and slump flow of the concrete compositions were evaluated in accordance with JIS A 1101:2020 and JIS A 1150:2020.

[0134] <Air volume> The air content of the concrete composition was evaluated in accordance with JIS A 1128:2019.

[0135] <O-funnel flow time and V-funnel flow time> In accordance with the "Draft method for testing high-fluidity concrete using a funnel: JSCE F-512", the amount of air in the concrete composition was evaluated for the O-funnel flow time and the V-funnel flow time.

[0136] <Congealing time> The setting time of the concrete composition was measured in accordance with JIS A 1147.

[0137] <Crushing strength> Specimens for compressive strength tests were prepared in accordance with JIS A 1132, and crushing strength was measured in accordance with JIS A 1108.

[0138] The evaluation results for each concrete composition are shown in Table 4.

[0139] [Table 4]

[0140] As shown in Table 4, concrete composition B1-1 using the phenolic resin-based dispersant B1 of the present invention had stable properties over time and maintained an appropriate air content compared to concrete composition A using polycarboxylic acid-based dispersants Q1 and Q2.

[0141] Preparation of admixtures 2 Using the dispersants obtained as described above (phenolic resin-based dispersants A1 and B1, and polycarboxylic acid-based dispersants Q1 and Q2), admixtures having the compositions shown in Table 5 below were prepared.

[0142] [Table 5]

[0143] <<Concrete Preparation and Evaluation 2>> A concrete composition conforming to JIS A 1138 was prepared with the mix proportions shown in Table 6. As can be seen from Table 6, the ratio of ground granulated blast furnace slag (BS) to the total of cement (C) and ground granulated blast furnace slag (BS) (C / (C+BS)) was 65% (=307 / (165+307)). The mixing method used was a twin-shaft forced mixer with a nominal capacity of 100 liters, with the concrete production volume for each batch being 50 liters x 1 batch. [Table 6]

[0144] The concrete compositions thus prepared were subjected to the following evaluations.

[0145] Slump and slump flow The slump and slump flow of the concrete compositions were evaluated in accordance with JIS A 1101:2020 and JIS A 1150:2020.

[0146] <Air volume> The air content of the concrete composition was evaluated in accordance with JIS A 1128. <O-funnel flow time and V-funnel flow time> In accordance with the "Funnel-based Flow Test Method for High-Fluidity Concrete (Draft): JSCE F-512", the air content of the concrete composition was evaluated for the O-funnel flow time and the V-funnel flow time.

[0147] Handling Sensory Evaluation Using a shovel, the softness of the concrete composition was evaluated sensorily according to the following criteria. 5. Very soft 4. Soft 3. Slightly soft 2. Hard 1 Very hard.

[0148] The evaluation results for each concrete composition are shown in Table 7.

[0149] [Table 7]

[0150] As shown in Table 6, concrete composition B1-2 using the phenolic resin-based dispersant B1 of the present invention had stable properties over time and maintained an appropriate air content compared to concrete composition A using the phenolic resin-based dispersant A of the present invention.

[0151] In the synthesis of the monomer for the phenolic resin-based dispersant A1, ethylene oxide (EO) was used as the alkylene oxide (AO) to obtain a polyethylene glycol group (C x H 2x In the synthesis of the monomer for the phenolic resin dispersant B1, a mixture of alkylene oxides was added as alkylene oxide (AO), where x is 2 to 5. x H 2x C where x is 3 to 5 relative to the total number of groups x H 2x The proportion of the group (X=3 to 5 (mol %)) was 0 mol % for the phenol resin dispersant A1, whereas it was 20 mol % for the phenol resin dispersant B1.

Claims

1. An admixture comprising or consisting of (each in a ratio relative to the total weight of the admixture): (a) 20 to 80% by weight, preferably 50 to 80% by weight, more preferably 64 to 75% by weight, of at least one dispersant; (b) 10 to 45% by weight, preferably 15 to 40% by weight, more preferably 15 to 35% by weight, of at least one polycarboxylic acid-based polymer; (c) 1 to 20% by weight, preferably 1 to 10% by weight, of at least one retarder, preferably sodium gluconate; (d) optional further additives, and (e) the balance to 100% by weight, water; The admixture is characterized in that the dispersant is a phenolic resin-based dispersant obtained by polycondensation of the following monomers (i) to (v): (i) a mol % of monomers of formula (I): 【Chemistry 1】 (ii) b mol % of monomers of formula (II): 【Chemistry 2】 (iii) c mol % of a monomer of formula (III): 【Chemistry 3】 (iv) d mol % of monomers of formula (IV): 【Chemistry 4】 (v) e mol % of an aldehyde, preferably formaldehyde, metaformaldehyde, paraformaldehyde, formalin, or a mixture thereof; Where: R １ is H or C １ ~C ４ Alkyl group, or C ２ ~C ５ Acyl groups, R ２ is H, an alkali metal ion, an alkaline earth metal ion, or a moiety of the structure: 【Chemistry 5】 R ３ is H or O-R ２ , R ４ is H, C １ ~C ４ an alkyl group or a phosphate ester group, R ５ is H, C １ ~C １８ an alkyl group, a polyisobutene, or a sulfonic acid moiety; A １ and A ２ are independent of each other, C ｘ H ２ｘ Groups, 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 from 1:10 to 10:

1.

2. A １ and A ２ 20 mol % or more of each of the above is C with X = 3 to 5 ｘ H ２ｘ The admixture of claim 1 which is a group.

3. A １ and A ２ 3. The admixture of claim 1 or 2, wherein all of are ethylene groups.

4. A phenolic resin-based dispersant for improving the workability of an inorganic binder composition containing a slag-containing inorganic binder, characterized in that the phenolic resin-based dispersant is obtained by polycondensation of the following monomers (i) to (v): (i) a mol % of monomers of formula (I): 【Chemistry 6】 (ii) b mol % of monomers of formula (II): 【Chemistry 7】 (iii) c mol % of a monomer of formula (III): 【Chemistry 8】 (iv) d mol % of monomers of formula (IV): 【Chemistry 9】 (v) e mol % of an aldehyde, preferably formaldehyde, metaformaldehyde, paraformaldehyde, formalin, or a mixture thereof; Where: R １ is H or C １ ~C ４ Alkyl group, or C ２ ~C ５ Acyl groups, R ２ is H, an alkali metal ion, an alkaline earth metal ion, or a moiety of the structure: 【Chemistry 10】 R ３ is H or O-R ２ , R ４ is H, C １ ~C ４ an alkyl group or a phosphate ester group, R ５ is H, C １ ~C １８ an alkyl group, a polyisobutene, or a sulfonic acid moiety; A １ and A ２ are independent of each other, C ｘ H ２ｘ Groups, 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 from 1:10 to 10:

1.

5. A １ and A ２ 20 mol % or more of each of the above is C with X = 3 to 5 ｘ H ２ｘ The phenolic resin dispersant according to claim 4, wherein the phenolic resin dispersant is a group.

6. A １ and A ２ The phenolic resin dispersant according to claim 4 or 5, wherein all of the groups are ethylene groups.

7. 6. A phenolic resin-based dispersant according to claim 4 or 5, wherein the slag is a steel slag, preferably a ground and pulverized blast furnace slag, in particular a ground and pulverized blast furnace slag according to the JIS A 6206:2013 standard.

8. 6. The phenolic resin-based dispersant according to claim 4 or 5, wherein the phenolic resin-based dispersant is co-ground and / or co-mixed in an amount of 0.1 to 5% by weight, preferably 0.5 to 1% by weight, based on the total dry weight of the inorganic binder.

9. A phenolic dispersant according to claim 4 or 5, wherein the phenolic dispersant is interground and / or intermixed with at least one polycarboxylic acid polymer and / or gluconate salt.

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