Additive for Resin Condensate and Hydraulic Composition

Abstract

To provide a hydraulic composition additive capable of imparting appropriate air-entraining and flow properties to a hydraulic composition for a long time even if formulation is different.SOLUTION: The hydraulic composition additive contains a polycondensate of a monomer mixture containing compounds represented by formulas (A)-(C).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a phenolic polycondensate and an additive for a hydraulic composition containing the polycondensate. More specifically, the present invention relates to a phenolic polycondensate and an additive for a hydraulic composition containing the polycondensate, which can impart excellent fluidity and air entrainment properties to a hydraulic composition and provide ready-mixed concrete with a stabilized air content.

Background Art

[0002] In the production of concrete as a construction material, efforts to actively utilize industrial by-products such as fly ash and blast furnace slag fine powder for the purpose of effective utilization of resources and reduction of environmental load have been attracting more attention in recent years. In ready-mixed concrete plants (so-called fresh concrete plants) in Japan, although gradually, there are attempts to standardize fresh concrete using fly ash as a measure to suppress alkali-silica reaction. Under these circumstances, the SDGs (Sustainable Development Goals) were adopted at the United Nations Summit in 2015, and this effort is being emphasized, such as setting the goal of considering the global environment and contributing to a circular society in domestic companies and various organizations. Even in the field related to cement and concrete, in response to the above SDGs, there are many solution goals such as constructing a circular society infrastructure by promoting the use of fly ash and blast furnace slag fine powder, strengthening infrastructure in consideration of the recent intensification of natural disasters, and reducing environmental load.

[0003] In the production of concrete using the above fly ash and blast furnace slag fine powder, it is difficult to control the air content at the time of shipment within a predetermined range. In particular, when the product lot of fly ash or blast furnace slag fine powder changes, there is a problem that the amount of the air entraining agent used to obtain a predetermined air content fluctuates greatly. As a countermeasure against these problems, an air entraining agent (AE agent) for fly ash has been proposed so far (for example, Patent Document 1, etc.).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Disclosure of the Invention

Problems to be Solved by the Invention

[0005] However, at the ready-mixed concrete production site, dedicated tanks and instruments are required to measure the AE agent. As a management problem, there are many sites where adding the AE agent for fly ash cannot necessarily be a solution. In addition, since the amount of AE agent used varies greatly depending on the content of unburned carbon contained in fly ash and the like, it is not easy to adjust the air entrainment amount even by using a dedicated AE agent. On the other hand, it is desired that the quality changes such as the slump and air content of ready-mixed concrete be small from the time of shipment from the ready-mixed concrete plant to the placement work at the placement site. However, the number of ready-mixed concrete plants in Japan has been decreasing since 2000, and in conjunction with this decreasing trend in the number of ready-mixed concrete plants, the transportation time from the ready-mixed concrete plant to the placement site has a tendency to become longer. In response to this, in the production of ready-mixed concrete, it is required that the quality such as the slump and air content can be maintained for a long time equivalent to that at the time of shipment.

[0006] The present invention has been made in view of the above situation, and even when the concrete mix such as cement and admixture is different, it is an object of the present invention to provide a new additive for hydraulic compositions that can impart appropriate fluidity and air entrainment to the hydraulic composition for a long time.

Means for Solving the Problems

[0007] ​As a result of intensive studies, the inventors designed a phenolic polycondensate having an air entraining function in a polymer type dispersant, and by applying this to a hydraulic composition, it was found that a desired fluidity and a long-term stable air entraining property can be imparted to the hydraulic composition even when the blending of cement, admixtures, etc. varies variously. Furthermore, the inventors focused on the dynamic surface tension of the above polycondensate, and found that the higher the ability of the polycondensate to lower the dynamic surface tension, the better the ability to keep the air amount in the hydraulic composition constant, and the higher the value of the initial dynamic surface tension of the polycondensate, the better the initial air entraining property in the hydraulic composition, and thus completed the present invention.

[0008] That is, the present invention targets the following [1] to [9]. [1] A polycondensate of a monomer mixture containing a compound A represented by the following formula (A), a compound B represented by the formula (B), and one or more aldehyde compounds C represented by the formula (C), wherein the polycondensate has, in a 1.0 mass% aqueous solution of the polycondensate, the dynamic surface tension value γ t=100ms [mN / m] at a bubble life of 100 ms by the maximum bubble pressure method at 25°C is 65 or less, and the difference Δγ (γ t=100ms - γ t=1000ms ) between the dynamic surface tension value γ t=100ms [mN / m] at a bubble life of 100 ms by the maximum bubble pressure method at 25°C and the dynamic surface tension value γ t=1000ms [mN / m] at the same bubble life of 1000 ms is 1.5 or more, polycondensate.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Advantages of the Invention

[0009] The polycondensate of the present invention and the additive for a hydraulic composition containing the polycondensate impart excellent fluidity and air entrainment to the hydraulic composition even when the formulations of cement, admixtures, etc. vary widely, and can realize the provision of ready-mixed concrete with a stabilized air content. That is, according to the polycondensate of the present invention and the additive for a hydraulic composition containing the polycondensate, regardless of the concrete formulation, the change in the air content is suppressed from the time of shipment from the concrete production plant until the concrete is placed, maintaining the same air entrainment as at the time of factory shipment, and it is possible to provide ready-mixed concrete having appropriate fluidity to the placement site.

Modes for Carrying Out the Invention

[0010] Dispersants (water-reducing agents), which are conventionally used additives for concrete, have been mainly studied in terms of the fluidity of concrete and mortar, and the composition of dispersants has not been studied from the viewpoint of stabilizing the air content. While the present inventors were conducting various studies on polymer-type dispersants, they found that in the polycondensate of a phenolic compound, the substituents bonded to the polycondensate affect the surface-active performance of the polycondensate. And by variously studying the substituents, it was found that a polycondensate having both dispersibility (water-reducing property) and air entrainment can be obtained. Furthermore, the present inventors focused on the dynamic surface tension of the polycondensate. The dynamic surface tension refers to the surface tension that reaches equilibrium over time, that is, the surface tension of a liquid in a moving state, and is considered to be related to the rate at which surfactants, etc. orient toward a newly generated interface. The present inventors have found that, as described below, it is related to the ability to reduce the dynamic surface tension of the polycondensate and the stabilization of the air content in the concrete composition. When the degree of decrease in dynamic surface tension is greater, the increase and decrease in air content are less, and a constant air content can be maintained for a long time. Furthermore, it is related to the initial value of the dynamic surface tension and the initial air entrainment property of the polycondensate. When this initial value is below a predetermined value, it has been found for the first time that the initial (right after mixing) air entrainment property is good. Hereinafter, the polycondensate of the present invention and the additive for hydraulic compositions containing the same will be described in detail.

[0011] <Polycondensate> The polycondensate of the present invention includes an alkylene oxide adduct of a phenolic compound such as phenol or bisphenol A or a derivative thereof (compound A represented by formula (A)), a phosphate ester or sulfate ester derivative of an alkylene oxide adduct of a phenolic compound (compound B represented by formula (B)), and aldehydes (one or more aldehyde compounds C represented by formula (C)). Optionally, it includes other monomer compounds D such as lignin, and further includes other monomers such as an alkylene oxide adduct of hydroxyethylphenol or a derivative thereof. It includes a polycondensate of a monomer mixture, that is, a copolymer obtained by polycondensing these monomer mixtures. Note that the polycondensate in the present invention, that is, the "polycondensate containing a copolymer obtained by polycondensing the monomer mixture" is (1) An embodiment including a copolymer (copolymer 1) in which all of compounds A to C in the monomer mixture are polycondensed, (2) An embodiment including a copolymer (copolymer 2) in which all of compounds A to D in the monomer mixture are polycondensed, (3) An embodiment including a copolymer in which two of compounds A to C in the monomer mixture are polycondensed (copolymer 3), (4) An embodiment including a copolymer (copolymer 4) in which one or two of compounds A to C and compound D in the monomer mixture are polycondensed, (5) An embodiment including two or more of the copolymers among (1) to (4) (6) In addition to one or more of the copolymers of (1) to (4) above, an embodiment containing at least one of the unreacted compounds A to D All of these are included, and in general, components including unreacted components and by-products generated in each polymerization step, each preparation step of each component (compound A to compound D), for example, an alkylene oxide addition step, etc. are also included. Hereinafter, compounds A to D contained in the monomer mixture will be described in detail.

[0012] 《Compound A represented by formula (A)》 Compound A is an alkylene oxide adduct or a derivative thereof of a phenolic compound such as phenol or bisphenol A or a substituted product thereof, and has a structure represented by the following formula (A).

Chemical formula

[0013] The above compound A is a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to a phenolic compound such as phenol or bisphenol A or a substituted product thereof, and derivatives (alkyl esters or fatty acid esters) of the alkylene oxide adduct are also included in compound A. Examples of the alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide, and butylene oxide. These alkylene oxides can be added alone or in combination. When using two or more alkylene oxides, they can be added in either a block or random form.

[0014] That is, the above A 1 Examples of the alkyleneoxy group having 2 to 4 carbon atoms in A 1 O include ethyleneoxy group, propyleneoxy group, and butyleneoxy group. A

[0015] Also, m is the average number of moles of alkyleneoxy group added, representing a number from 1 to 200, preferably from 1 to 150. By increasing the number of moles of addition of A 1 O, an improvement in water repellency can be expected.

[0016] Examples of the hydrocarbon group having 1 to 24 carbon atoms in the above R when n is 1 1 include an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, an unsaturated aliphatic hydrocarbon group having two or more unsaturated bonds and 4 to 24 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 3 to 24 carbon atoms, and the like. Examples of the alkyl group having 1 to 24 carbon atoms 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 (lauryl group), a tetradecyl group (myristyl group), a hexadecyl group (palmityl group), an octadecyl group (stearyl group), an icosyl group, a docosyl group (behenyl group), a tetracosyl group, etc. These may have a branched structure (e.g., isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, neopentyl group, etc.) and / or a cyclic structure (e.g., cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, etc.). Examples of the alkenyl group having 2 to 24 carbon atoms include groups having one carbon-carbon double bond in the alkyl groups having 2 to 24 carbon atoms mentioned as the above alkyl groups. Specifically, an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a dodecenyl group, a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, an octadecenyl group, an eicosenyl group, a docosenyl group, a tetracosenyl group, etc. These may have a branched structure and / or a cyclic structure. Examples of the unsaturated aliphatic hydrocarbon group having two or more unsaturated bonds and having 4 to 24 carbon atoms include a decadienyl group, an undecadienyl group, a dodecadienyl group, a tridecadienyl group, a tetradecadienyl group, a pentadecadienyl group, a hexadecadienyl group, a heptadecadienyl group, an octadecadienyl group, a nonadecadienyl group, an icosadienyl group, a henicosanadienyl group, a docosadienyl group, a tricosadienyl group, a tetracosadienyl group, a decadienyl group, an undecatrienyl group, a dodecatrienyl group, a tridecatrienyl group, a tetradecatrienyl group, a pentadecatrienyl group, a hexadecatrienyl group, a heptadecatrienyl group, an octadecatrienyl group, a nonadecatrienyl group, an icosatrienyl group, a henicosanatrienyl group, a docosatrienyl group, a tricosatrienyl group, a tetracosatrienyl group, etc. Examples of the aryl group having 6 to 20 carbon atoms include, but are not limited to, a phenyl group, a naphthyl group, an anthryl group, and a phenanthryl group. An aralkyl group is an alkyl group substituted with an aryl group. Specific examples of such aryl groups and alkyl groups include the same as those described above. Specific examples of the aralkyl group having 7 to 20 carbon atoms include, but are not limited to, a phenylmethyl group (benzyl group), an α-methylbenzyl group, a 2-phenylethyl group, a 1-methyl-1-phenylethyl group (cumyl group), a 3-phenylpropyl group, and a 2-phenyl-2-propyl group. When n is 2, the above R 1 represents -CH 2 -, -C(CH 3 ) 2 -, or -SO 2 -. In both the case where n is 1 and the case where n is 2, the bonding position of R 1 in the formula (A) is not particularly limited, but it is preferable that it is bonded to the para position with respect to the oxygen atom bonded to the aromatic ring in terms of easily exhibiting the effects of the present invention.

[0017] The alkyl group having 1 to 10 carbon atoms in the above R 2 may have a branched structure and / or a cyclic structure. Specifically, among the groups exemplified as the specific examples of the alkyl group having 1 to 24 carbon atoms in the above R 1 , an alkyl group having 1 to 10 carbon atoms can be mentioned. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, an n-decyl group, a 1-adamantyl group, etc. can be mentioned. Examples of the acyl group having 2 to 24 carbon atoms include a saturated or unsaturated acyl group (R’(CO)- group, where R’ is a hydrocarbon group having 1 to 23 carbon atoms). For example, the number of carbon atoms As for the saturated acyl groups having 2 to 24 carbon atoms, acyl groups derived from carboxylic acids and fatty acids such as acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid (caproic acid), heptanoic acid, octanoic acid (caprylic acid), nonanoic acid, decanoic acid (capric acid), dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), pentadecanoic acid (pentadecyl acid), hexadecanoic acid (palmitic acid), heptadecanoic acid (margaric acid), octadecanoic acid (stearic acid), nonadecanoic acid, eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), and tetracosanoic acid (lignoceric acid) etc. are mentioned. As for the mono-unsaturated acyl groups, acyl groups derived from mono-unsaturated fatty acids such as myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, nervonic acid etc. are mentioned. As for the di-unsaturated acyl groups, acyl groups derived from di-unsaturated fatty acids such as linoleic acid, eicosadienoic acid, docosadienoic acid etc. are mentioned. And as for the tri-unsaturated acyl groups, acyl groups derived from tri-unsaturated fatty acids such as linolenic acid, pinolenic acid, eleostearic acid, mead acid, dihomo-γ-linolenic acid, eicosatrienoic acid etc. are mentioned.

[0018] The compound A represented by the above formula (A) can be used alone or in combination of two or more.

[0019] 《Compound B represented by formula (B)》 Compound B is a phosphate ester derivative or a sulfate ester derivative of an alkylene oxide adduct of a phenolic compound such as phenol or bisphenol A, and has a structure represented by the following formula (B).

Chemical formula

[0020] The above compound B is a phosphate ester derivative or a sulfate ester derivative of a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to a phenolic compound such as phenol or bisphenol A or its substituent. Examples of the above alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide, and butylene oxide. These alkylene oxides can be added alone or in combination, and when two or more alkylene oxides are used, they may be added in a block or random form.

[0021] That is, the above A 2 Examples of the alkyleneoxy group having 2 to 4 carbon atoms in O include an ethyleneoxy group, a propyleneoxy group, and a butyleneoxy group. A 2 O may be composed only of an ethyleneoxy group, a propyleneoxy group, or a butyleneoxy group, or may contain two or more of these groups. When containing two or more groups, their addition forms may be either random addition or block addition. Also, p represents the average number of moles of alkylene oxide added, which is a number from 1 to 200, preferably from 1 to 100, for example, from 1 to 10.

[0022] In one aspect of the polycondensate of the present invention, in compound B, the proportion of the average number of moles of alkylene oxide added p being 1 or less is preferably 90 mol% or less, particularly preferably 20 to 60 mol%. By setting the proportion of the above n being 1 or less within the above numerical range, the value of the dynamic surface tension in a 1.0 mass% aqueous solution of the polycondensate described later can be set within a suitable range, and thus, a polycondensate having excellent air entrainment properties while having water repellency can be obtained.

[0023] When q is 1, the above R 3 Examples of the hydrocarbon group having 1 to 24 carbon atoms in [the above R when q is 1] include an alkyl group having 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, an unsaturated aliphatic hydrocarbon group having two or more unsaturated bonds and 4 to 24 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 3 to 24 carbon atoms, and the like. When q is 2, the above R 3 represents -CH 2 -, -C(CH 3 ) 2 -, or -SO 2 -. Specific examples thereof include the same ones as R 1 . In both the case where q is 1 and the case where q is 2, the bonding position of R 3 in formula (B) is not particularly limited, but it is preferable that it is bonded to the para position with respect to the oxygen atom bonded to the aromatic ring in terms of easily exerting the effects of the present invention.

[0024] When X 1 represents a phosphate group, they are a phosphoric acid monoester and / or its salt, a phosphoric acid diester and / or its salt, or a phosphoric acid triester, or a mixture thereof. When X 1 represents a sulfate group, they are a sulfuric acid monoester and / or its salt, or a sulfuric acid diester, or a mixture thereof. Examples of the above phosphate salt or sulfate salt include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as calcium and magnesium; ammonium salts; organic ammonium salts such as alkylammonium and alkanolammonium. As the above compound B, those synthesized by a known method using a phosphorylating agent or a sulfating agent for (poly)oxyalkylene alkylphenol may be used. Examples of the phosphorylating agent include phosphoric anhydride, phosphoric acid, polyphosphoric acid, phosphorus oxychloride, etc. Examples of the sulfating agent include chlorosulfonic acid, sulfamic acid, direct sulfation using sulfur, etc.

[0025] As the compound B represented by the above formula (B), for example, when q is 1, the compound B can be exemplified by the compounds represented by the following formulas. In the formula, R 3 , A 2 O, n represent the same as those defined in the above formula (B), and Ph represents a phenylene group. Also, M represents a hydrogen atom; an alkali metal atom such as sodium or potassium; an alkaline earth metal atom such as calcium or magnesium; an ammonium group; an organic ammonium group such as an alkylammonium group or an alkanolammonium group. Also, Z represents a polyoxyalkylene alkyl ether residue represented by the formula: R”-O-(A’O)w- (wherein R” represents an alkyl group having 1 to 24 carbon atoms, A’O represents an alkyleneoxy group having 2 to 3 carbon atoms, that is, an ethyleneoxy group or a propyleneoxy group, and w represents the average number of moles of addition of the alkyleneoxy group A’O and represents 1 to 100). When a plurality of Z exist, they may be the same group or different groups from each other. · Monophosphate ester and its salts R 3 -Ph-O-[A 2 O] p -P(=O)(-OM) 2 · Diphosphate ester and its salts [R 3 -Ph-O-[A 2 O] p -] 2 P(=O)(-OM) [R 3 -Ph-O-[A 2 O] p -](Z-)P(=O)(-OM) · Triphosphate ester [R 3 -Ph-O-[A 2 O] p -] 3 P(=O) [R 3 -Ph-O-[A 2 O] p -] 2 (Z-)P(=O) [R3 -Ph-O-[A 2 O] p -](Z-) 2 P(=O) · Monoester sulfate and its salts R 3 -Ph-O-[A 2 O] p -S(=O) 2 (-OM) · Diester sulfate [R 3 -Ph-O-[A 2 O] p -] 2 S(=O) 2 [R 3 -Ph-O-[A 2 O] p -](Z-)S(=O) 2

[0026] Compound B represented by the above formula (B) can be used alone or in combination of two or more.

[0027] 《Compound C represented by formula (C)》 Compound C is an aldehyde and has a structure represented by the following formula (C).

Chemical formula

[0028] Compound C (aldehydes) includes, for example, formaldehyde, paraformaldehyde, trioxane, glyoxylic acid, acetaldehyde, trichloroacetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, hexylaldehyde, heptanal, octylaldehyde, nonylaldehyde, isononylaldehyde, decylaldehyde, dodecanal, acrolein, crotonaldehyde, pentenal, hexenal, heptenal, octenal, cinnamaldehyde, benzaldehyde, benzaldehyde sulfonic acid, benzaldehyde disulfonic acid, anisaldehyde, salicylaldehyde, benzylaldehyde [(C 6 H 5 ) 2 C(OH)-CHO], naphthaldehyde, furfural, etc. Among them, it can be selected from the group consisting of formaldehyde, paraformaldehyde, benzaldehyde or any mixture of two or more of them. Compound C can be used as a pure crystalline or powdery substance, or a hydrate thereof, and can also be used in the form of an aqueous solution such as formalin. In this case, the measurement or mixing of components can be simplified.

[0029] The compound C represented by the above formula (C) can be used alone or in combination of two or more.

[0030] "Other Monomer Compound D" In the polycondensate of the present invention, in addition to the above monomer mixture containing the above Compound A, Compound B, and Compound C, the monomer mixture may contain, within a range not impairing the effects of the present invention, other monomer compound D that can undergo polycondensation with these compounds. Examples of other monomer compound D include lignin, rosin, benzoic acid, phenol, bisphenol A, phenolsulfonic acid, hydroxyethylphenol, and the like.

[0031] "Monomer Mixture" In the monomer mixture containing the above Compound A to Compound C and, if desired, further Compound D used in the polycondensate of the present invention, the mixing ratio is not particularly limited. Preferably, Compound A, Compound B, and Compound D are contained in a molar ratio of Compound A:Compound B:Compound D = 0.1 to 2:0.1 to 4:0 to 2, and with respect to the total molar amount of Compound A, Compound B, and Compound D, Compound C is contained in a molar ratio of (Compound A + Compound B + Compound D):Compound C = 1 to 10:10 to 1. More preferably, Compound A:Compound B:Compound D = 0.5 to 1.5:0.3 to 3.5:0 to 1.0 (molar ratio), or preferably Compound A:Compound B:Compound D = 0.1 to 2:0.1 to 4:0 to 1 (molar ratio), and (Compound A + Compound B + Compound D):Compound C = 2 to 6:10 to 1 (molar ratio). In the polycondensate, by setting the ratios of the above Compound A to Compound C and also Compound D within the above numerical ranges, the value of the dynamic surface tension in a 1.0 mass% aqueous solution of the polycondensate described later can be set within a suitable range.

[0032] "Polycondensate" The polycondensate used in the present invention comprises a copolymer obtained by polycondensing a monomer mixture containing the above Compound A to Compound C and, if desired, further Compound D. In obtaining the above copolymer, the production methods of Compound A to Compound D and the polymerization method for obtaining the copolymer are not particularly limited. Also, during the polycondensation reaction, the order of addition and the method of addition of the above-mentioned Compound A, Compound B, Compound C, and further Compound D are not particularly limited. For example, the total amounts of Compounds A to D can be added all at once before the polycondensation reaction; a part of Compounds A to D can be added before the polycondensation reaction, and then the remainder can be added dropwise in portions; or a part of Compounds A to D can be added before the polycondensation reaction, and the remainder can be added additionally after a certain reaction time has elapsed. Any of these methods may be used.

[0033] The polycondensate can be obtained, for example, by subjecting Compound A, Compound B, Compound C, and Compound D to polycondensation in the presence of a dehydration catalyst, without a solvent or in a solvent, at a reaction temperature of 80°C to 150°C, under normal pressure to increased pressure, for example, at 0.001 to 1 MPa. Examples of the above-mentioned dehydration catalyst include hydrochloric acid, perchloric acid, nitric acid, formic acid, methanesulfonic acid, octylsulfonic acid, dodecylsulfonic acid, vinylsulfonic acid, allylsulfonic acid, phenolsulfonic acid, acetic acid, sulfuric acid, diethyl sulfate, dimethyl sulfate, phosphoric acid, oxalic acid, boric acid, benzoic acid, phthalic acid, salicylic acid, pyruvic acid, maleic acid, malonic acid, nitrobenzoic acid, nitrosalicylic acid, p-toluenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfonic acid, fluoroacetic acid, thioglycolic acid, mercaptopropionic acid, activated clay, etc. These dehydration catalysts can be used alone or in combination of two or more. When the polycondensation reaction is carried out in a solvent, examples of the solvent include water, glycol ether compounds such as propylene glycol monomethyl ether (PGME), aromatic compounds such as toluene and xylene, and cyclic aliphatic compounds such as methylcyclohexane. Further, those applicable as the above-mentioned dehydration catalyst (acid catalyst), for example, acetic acid can also be used as a solvent. It is possible. The reaction temperature can be, for example, carried out at a temperature of 95°C to 130°C, and the polycondensation reaction can be completed by reacting for about 3 to 25 hours. The polycondensation reaction is preferably carried out under acidic conditions, and preferably the pH of the reaction system is made 4 or less.

[0034] In addition to compound A, compound B, compound C, and optionally compound D, or instead of compound D, other monomers capable of polycondensing with these compounds may be incorporated into the monomer mixture within a range that does not impair the effects of the present invention. Examples of the above other monomers include adducts of cresol, catechol, resorcinol, nonylphenol, methoxyphenol, naphthol, methylnaphthol, butylnaphthol, aniline, methylaniline, hydroxyaniline, methoxyaniline, and / or salicylic acid with 1 to 300 mol of alkylene oxide; phenoxyacetic acid, methoxyphenol, resorcinol, cresol, nonylphenol, aniline, methylaniline, N-phenyldiethanolamine, N,N-di(carboxyethyl)aniline, N,N-di(carboxymethyl)aniline, anthranilic acid, and the like. For example, examples of other monomers include alkylene oxide adducts or derivatives thereof (compound E) of hydroxyethylphenol having a structure represented by the following formula (E).

Chemical formula

[0035] The above compound E is a compound in which alkylene oxide having 2 to 4 carbon atoms is added to at least one, or both, of the hydroxyethyl group or the phenolic hydroxy group in hydroxyethylphenol, and derivatives (phosphate esters, sulfate esters) of the alkylene oxide adduct are also included in compound E. The hydroxyethylphenol may be any of o-hydroxyethyl-phenol, m-hydroxyethyl-phenol, and p-hydroxyethyl-phenol. Compound A is preferably a compound (and its ester derivative) obtained by adding an alkylene oxide having 2 to 4 carbon atoms to o-hydroxyethyl-phenol.

[0036] Examples of the alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide, and butylene oxide. These alkylene oxides can be added alone or in combination, and when using two or more alkylene oxides, they may be added in a block or random form. That is, the above A 3 O and A 4 Examples of the alkyleneoxy group having 2 to 4 carbon atoms in O include an ethyleneoxy group, a propyleneoxy group, and a butyleneoxy group. A 3 O and A 4 O may be composed of only an ethyleneoxy group, a propyleneoxy group, or a butyleneoxy group, or may contain two or more of these groups. When containing two or more groups, their addition forms may be either random addition or block addition. Also, t and u are the average number of moles of alkylene oxide added, and each independently represents a number from 0 to 200, preferably from 0 to 60, and t + u ≥ 1. A 3 O, A 4 Of O By increasing the number of moles of addition, an improvement in water repellency can be expected.

[0037] Also, X 2 , X 3 When represents a phosphate ester group, they are a phosphate monoester and / or its salt, a phosphate diester and / or its salt, or a phosphate triester, or a mixture thereof. Also, X 2 , X 3 When represents a sulfate ester group, they are a sulfate monoester and / or its salt, or a sulfate diester, or a mixture thereof. Examples of the phosphate ester salt or sulfate ester salt include alkali metal salts such as sodium and potassium; alkaline earth metal salts such as calcium and magnesium; ammonium salts; and organic ammonium salts such as alkylammonium and alkanolammonium.

[0038] After completion of the polycondensation reaction, various conventionally known methods can be adopted to reduce the content of the unreacted aldehyde component (Compound C) in the reaction system. For example, a method of making the pH of the reaction system alkaline and performing heat treatment at 60 to 140°C, a method of reducing the pressure of the reaction system (-0.1 to -0.001 MPa) to volatilize and remove the aldehyde component, and a method of adding a small amount of sodium bisulfite, hydrogen peroxide, ethylene urea, and / or polyethyleneimine can be mentioned. The dehydration catalyst used in the reaction can be neutralized after completion of the reaction and removed by filtration in the form of a salt. However, even in a mode where the catalyst is not removed, the performance as an additive for the hydraulic composition of the present invention described later is not impaired. Examples of the method for removing the catalyst include phase separation, dialysis, ultrafiltration, and use of an ion exchanger in addition to the above filtration. In addition, by neutralizing and diluting the reaction product with water or the like, the workability such as weighing in the use as an additive for the hydraulic composition described later is improved. At this time, examples of the basic compound used for neutralization include alkali hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, ammonia, and organic amines such as monoethanolamine, diethanolamine, and triethanolamine. A combination of one or more of these is adopted.

[0039] The weight average molecular weight Mw (gel permeation chromatography method (hereinafter referred to as "GPC method"), polyethylene glycol conversion) of the copolymer finally obtained is preferably in the range of 4,000 to 100,000, more preferably in the range of 8,000 to 50,000, particularly preferably in the range of 8,000 to 45,000, from the viewpoint of exhibiting excellent dispersion performance and making the value of the dynamic surface tension described later fall within a suitable range. As described above, the "condensation polymer" in the present invention may consist only of a copolymer obtained by polycondensing a monomer mixture containing Compound A to Compound C (and optionally Compound D and other monomers). Generally, however, it includes components such as unreacted components and by-products generated in each polymerization step, alkylene oxide addition step, etc.

[0040] The copolymer contained in the condensation polymer of the present invention can have, for example, a structural unit A represented by the following formula (1) and a structural unit B represented by formula (2).

Chemical formula

[0041] As a preferred embodiment of the method for producing the above condensation polymer, an embodiment including the following steps (1) to (3) can be mentioned. The method for producing a condensation polymer including the following steps (1) to (3) is also an object of the present invention. Step (1): A step of heating a mixture containing Compound A represented by the above formula (A) and Compound B represented by the following formula (B) to a first set temperature. Step (2): A step of adding one or more aldehyde compounds C represented by the above formula (C) to the mixture and heating it from the first set temperature to a second set temperature over 1.5 hours to 12 hours. Step (3): A step of maintaining at the second set temperature for 2 hours to 24 hours. The above first set temperature can be 50°C to 80°C, and the second set temperature can be 100°C to 130°C. In step (2), the time for increasing the temperature from the first set temperature to the second set temperature can preferably be 1.5 to 9 hours, and in step (3), the time for maintaining the second set temperature can preferably be 3 to 16 hours.

[0042] When the monomer mixture further contains the above-mentioned (D) monomer compound D in addition to compound A, compound B, and compound C, step (1) may be changed to step (1-1) of heating a mixture containing compound A represented by the above formula (A), compound B represented by the above formula (B), and the above-mentioned (D) monomer compound D to the first set temperature. Furthermore, when the monomer mixture contains other monomers, the other monomers may be added together with the (D) monomer compound D or in place of the (D) monomer compound D in step (1-1).

[0043] [Dynamic surface tension] Generally, the dynamic surface tension value γ of a polymer (copolymer, polycondensate) and the difference Δγ in γ at different measurement times are considered to change depending on the ratio of hydrophobic groups / hydrophobic groups in the polymer, the molecular weight of the polymer, the ratio of adsorbable groups in the polymer, the ratio of groups having a neutralized salt structure, and further the steric hindrance caused by substituents to the polymer backbone. In the present invention, the selection of monomers (such as compound A and compound B) constituting the polycondensate, the ratio of hydrophobic groups / hydrophilic groups in these monomers (the presence / type of substituents of the phenyl group, the added molar number of alkyleneoxy groups, etc.), the type and ratio of substituents in the monomers (the bulkiness of the substituents causes steric hindrance), the ratio of adsorbable groups and neutralized salt structures in these monomers (the selection of phosphate ester salts or sulfate ester salts), and further the production conditions of the polycondensate are considered to affect the numerical values of the suitable dynamic surface tension value γ and the difference Δγ described below.

[0044] In the present invention, the dynamic surface tension is determined by the maximum bubble pressure method. The maximum bubble pressure method is a method of measuring the maximum pressure required to release bubbles generated at the tip of a probe immersed in the liquid to be measured, and obtaining the surface tension of the liquid from this maximum pressure. Specifically, while continuously generating bubbles at the tip of the probe, the maximum pressure is measured. At this time, from the point when a new bubble surface is generated at the tip of the probe until the maximum bubble pressure (the point when the radius of curvature of the bubble is equal to the radius of the tip portion of the probe) is reached, the time is called the lifetime (referred to as the bubble lifetime). The basic principle of the maximum bubble pressure method is based on the Young-Laplace equation. Bubbles (interfaces) are continuously generated from a probe (capillary) with a radius r inserted into a liquid, and the surface tension is obtained from the pressure (maximum bubble pressure) applied to the bubble when the radius of the bubble becomes the same as the radius r of the probe by the following equation. Surface tension γ = ΔP × r / 2 [mN / m] (ΔP is the difference between the maximum bubble pressure and the minimum bubble pressure (atmospheric pressure)) This dynamic surface tension can be measured, for example, using a commercially available dynamic surface tensiometer (such as "Portable Dynamic Surface Tensiometer SITA t100", manufactured by Eihiro Seiki Co., Ltd., etc.).

[0045] In the present invention, a 1% by mass aqueous solution of the polycondensate is used as the measurement object of the dynamic surface tension, and the dynamic surface tension value γ t=100ms [mN / m] at a bubble lifetime of 100 ms by the maximum bubble pressure method and the difference Δγ between this initial value and the dynamic surface tension value γ t=1000ms [mN / m] at a bubble lifetime of 1000 ms are taken as the evaluation objects. Note that the dynamic surface tension at the time when the bubble lifetime is short corresponds to the dynamic surface tension in a very initial state that is closer to the flowing state. From the viewpoint of the measurement accuracy, in the present invention, the measurement time (bubble lifetime) of the initial value is set to 100 ms. The present invention relates to the difference Δγ (γ t=100ms [mN / m] and the dynamic surface tension value γ t=1000ms [mN / m] at a bubble lifetime of 1000 ms) between the dynamic surface tension value γ t=100ms -γ t=1000msThe present invention relates to a hydraulic composition containing the above polycondensate, wherein the difference Δγ in the dynamic surface tension value is 1.5 or more, preferably 2.0 or more, more preferably 4.5 or more. That is, by making the degree of decrease in dynamic surface tension larger, it is possible to have excellent air entrainment (stabilizing the air volume and having little increase or decrease in the air volume) while having water-reducing properties. Also, the dynamic surface tension value γ at a foam life of 100 ms t=100ms is 65 (mN / m) or less, preferably 60 (mN / m) or less, more preferably 57 (mN / m) or less. In this case, the polycondensate can be quickly oriented at the interface of the bubbles, and the initial air entrainment can be made good.

[0046] <Additive for hydraulic composition> The additive for a hydraulic composition of the present invention can be used in the form of a so-called admixture by appropriately combining and using known and publicly available additives for hydraulic compositions according to various applications. Specifically, at least one other additive selected from the group consisting of conventionally known cement dispersants, high-performance AE water reducers, high-performance water reducers, AE water reducers, water reducers, air entraining agents (AE agents), foaming agents, defoaming agents, setting retarders, setting accelerators, segregation reducing agents, thickeners, shrinkage reducing agents, curing agents, water repellents, etc. can be blended. In the present invention, the hydraulic composition refers to a composition containing a powder (hydraulic powder) having the property of hardening by a hydration reaction, such as cement, gypsum, fly ash, blast furnace slag, etc. When the hydraulic powder is cement, the hydraulic composition is also referred to as a cement composition.

[0047] Generally, cement dispersants are appropriately combined and used according to the manufacturing conditions and performance requirements of concrete, etc. The same applies to the additive for a hydraulic composition of the present invention. It can be used alone as a cement dispersant or as a main agent, but can also be used in combination as a modifying aid for a cement dispersant with a large slump loss or as a cement dispersant with high initial water-reducing properties. For example, known cement dispersants include salts of polycarboxylic acid copolymers described in Japanese Patent Publication No. Sho 59-18338, Japanese Patent No. 2628486, Japanese Patent No. 2774445, etc., and salts of naphthalene sulfonic acid formalin condensates, salts of melamine sulfonic acid formalin condensates, lignin sulfonates, sodium gluconate, and sugar alcohols. The blending ratio of the polycondensate of the present invention and a known cement dispersant is, for example, 1:99 to 99:1% by mass.

[0048] Specific examples of the air-entraining agent include anionic air-entraining agents, nonionic air-entraining agents, and amphoteric air-entraining agents. Examples of the setting retarder include inorganic setting retarders and organic setting retarders. More specifically, oxycarboxylic acids such as gluconic acid, glucoheptonic acid, tartaric acid, citric acid, malic acid, and arabic acid and their salts; saccharides such as sucrose; and inorganic compounds such as zinc oxide, zinc chloride, silicofluoride, and silicofluoride salts can be mentioned. Examples of the accelerator include inorganic accelerators and organic accelerators. Examples of the thickener / segregation reducer include cellulose-based water-soluble polymers, polyacrylamide-based water-soluble polymers, biopolymer-based thickeners such as dutangum, welangum, and xanthan gum, and nonionic thickeners such as polyethylene glycol and polyalkylene oxide. Examples of the defoaming agent include nonionic defoaming agents, silicone defoaming agents, higher alcohols, and mixtures mainly composed of these.

[0049] When the additive for the hydraulic composition of the present invention is applied to, for example, a cement composition, the components constituting the cement composition are components conventionally used for concrete, and include cement (for example, ordinary Portland cement, early-strength Portland cement, ultra-early-strength Portland cement, low-heat / medium-heat Portland cement, or blast furnace cement, etc.), aggregates (that is, fine aggregates and coarse aggregates), admixtures (for example, silica fume, calcium carbonate powder, blast furnace slag fine powder, fly ash, etc.), expansive agents, and water.

[0050] Among them, the additive for hydraulic compositions of the present invention is preferably used in hydraulic compositions (cement compositions) containing fly ash or fine blast furnace slag powder as admixtures. Fly ash mainly consists of silica (SiO 2 ) and alumina (Al 2 O 3 ). In JIS A 6201, the standards are defined for Types I to IV (JIS A6201) based on the particle size and flow value. It is said that there is a relationship between the amount of unburned carbon contained in fly ash and the amount of air-entraining agent used, and an increase in the amount of unburned carbon tends to result in an increase in the amount of air-entraining agent used. Generally, the amount of unburned carbon is said to be correlated with the methylene blue adsorption amount of fly ash. Fine blast furnace slag powder is a by-product produced during the purification of iron in a blast furnace and mainly consists of calcium oxide (CaO), silica (SiO 2 ), and alumina (Al 2 O 3 ). The standards are defined in JIS A 6206.

[0051] In addition, as admixtures that can be separately added during formulation with admixtures other than the additive for hydraulic compositions of the present invention, there are the above-mentioned publicly known and commonly used air-entraining agents, setting retarders, accelerators, separation reducers, thickeners, defoamers, shrinkage reducers, etc., and these can also be appropriately blended. The blending ratio of each of these components can be appropriately determined according to the type of selected components and the purpose of use.

[0052] The addition amount of the additive for hydraulic compositions of the present invention varies depending on the blending conditions including the above-mentioned concrete materials. When used in combination with pozzolanic fine powder such as fly ash, it is usually added in an amount of about 0.05 to 5.0% by mass in terms of solid content based on the cement mass or the total mass of cement and fly ash. To obtain water-reducing property and slump flow retention property, the larger the addition amount, the better. However, if it is too much, it may cause setting retardation and, in some cases, poor hardening. The usage method is the same as that of general cement dispersants. It can be added as a stock solution during concrete mixing, or diluted in mixing water in advance and then added. Alternatively, it can be added after the concrete or mortar has been kneaded, and then kneaded uniformly again.

Examples

[0053] The present invention will be described by the following examples. However, the present invention is not limited in any way by these examples and comparative examples.

[0054] In addition, the physical property measurements of the samples were carried out using the following apparatus under the following conditions. (1) GPC (gel permeation chromatography) <Gel Permeation Chromatography (GPC) Measurement Conditions> Column: OHpak SB-802.5HQ, OHpak SB-803HQ, OHpak SB-804HQ (manufactured by Showa Denko K.K.) Eluent: A mixed solution of 50 mM sodium nitrate aqueous solution and acetonitrile (volume ratio 80 / 20) Detector: Differential refractometer, Calibration curve: Polyethylene glycol (2) NMR (nuclear magnetic resonance spectrum) <Measurement of the number of moles of introduced phosphate groups> Manufactured by JEOL Ltd., JNM-ECZ400S. Nuclide: 31P, Solvent: Heavy water, Sample concentration: 15 wt%, Number of integration times: 512 times. The molar ratio of phosphate groups in the phosphate groups and the polycondensate is calculated by comparing the integral values. <Measurement of the number of moles of introduced sulfate groups: Epton method> Weigh about 0.3 g of the sample into a 100 mL volumetric flask and make it up to the mark with water. Accurately measure 10 mL of the stirred and homogeneous aqueous solution into a measuring cylinder. Then add 20 mL of chloroform, 25 mL of methylene blue, and 20 mL of cation standard solution (0.004 mol / L benzethonium chloride solution), shake to make it homogeneous, and separate it into a dark blue upper layer and a colorless lower layer. While appropriately stirring the cylinder, titrate with an anion solution (0.004 mol / L sodium lauryl sulfate aqueous solution), and take the point where the colors of the upper and lower layers show the same blue as the end point. [Chemical formula]

[0055] ≪Method for Producing Polycondensate≫ [Production Example 1: Preparation of Compound (A)] 80 parts of diethylene glycol monophenyl ether (Hysorb DPH manufactured by Toho Chemical Industry Co., Ltd.) and 0.2 part of 96% potassium hydroxide were charged into a stainless steel high-pressure reactor equipped with a thermometer, a stirrer, a pressure gauge, and a nitrogen inlet tube. The inside of the reaction vessel was purged with nitrogen and heated to 150°C under a nitrogen atmosphere. Then, 406 parts of ethylene oxide were introduced into the reactor over 10 hours while maintaining 150°C under a safe pressure, and the temperature was maintained for another 2 hours to complete the alkylene oxide addition reaction, obtaining polyethylene glycol monophenyl ether (number of moles of added EO = 23). Following this procedure, various starting materials were used, such as p-tert-butylphenol, bisphenol A, and cardanol, and the number of moles of ethylene oxide added was varied to prepare various polyalkylene glycol monophenyl ether derivatives shown in Table 2.

[0056] [Production Example 2: Preparation of Compound (B) (Phosphate Ester Derivative)] 3 moles of the EO adduct of p-tert-butylphenol were charged into a glass reaction vessel equipped with a stirrer, a thermometer, and a nitrogen inlet tube. While performing nitrogen bubbling, 1 mole of phosphoric anhydride was charged over 4 hours at 50°C and allowed to react. Then, a ripening reaction was carried out at 100°C for 3 hours to complete the phosphorylation reaction, obtaining the phosphate ester of the EO adduct of p-tert-butylphenol. In the same manner as the phosphate ester of the EO adduct of p-tert-butylphenol, phosphate esters of the EO adducts of phenol and bisphenol A were obtained.

[0057] [Production Example 3: Preparation of Compound (B) (Sulfate Ester Derivative)] Into a glass reaction vessel equipped with a stirrer, a thermometer, and a nitrogen inlet tube, 1 mol of an EO adduct of p-tert-butylphenol and 0.05 mol of urea were charged, and the temperature was raised while performing nitrogen bubbling. The temperature was raised from 30 °C to 95 °C over 30 minutes, and during that time, 1.05 mol of sulfamic acid was gradually charged. Then, an aging reaction was carried out at 95 °C for 3 hours and then at 120 °C for 5 hours. Thereafter, neutralization was carried out with a 25% aqueous ammonium solution to terminate the sulfuric acid esterification reaction, and an EO adduct sulfate of p-tert-butylphenol was obtained. Regarding the purity of the obtained sulfate compound, confirmation was carried out by the above-mentioned Epton measurement.

[0058] [Production Example 4: Preparation of polycondensates (No. 1 to No. 14, Ratio 1 to Ratio 4)] Into a glass reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, Compound A, Compound B (and Compound D) were charged in the molar ratios shown in Table 2. This was heated to 70 °C, and then 2.0 wt% of 98% sulfuric acid was charged based on the total mass of Compound A and B (and Compound D). Then, Compound C: aldehydes were charged all at once into the reaction vessel in the molar ratios shown in Table 2, and then the temperature was raised to 105 °C. The time required to reach from 70 °C to 105 °C was set for each example (see Table 1 below, [A]). When 105 °C was reached, the pH of the reaction product was 2.1 (1% aqueous solution, 20 °C). After reaching 105 °C, the reaction was carried out for a predetermined time for each example (see Table 1 below, [B]). After the reaction was completed, 48% caustic soda was charged into the reaction vessel, and neutralization was carried out so that the pH of a 1% aqueous solution of the reaction product was in the range of 5.0 to 7.5. Thereafter, an appropriate amount of water was added so that the solid content of the reaction product was 35%, and an aqueous solution of the polycondensate was obtained. GPC measurement was carried out on this polycondensate to determine the weight average molecular weight Mw. The results obtained are shown in Table 2.

[0059]

Table 1

[0060] ≪Measurement of dynamic surface tension≫ The measurement of the dynamic surface tension of the polycondensates prepared in each production example was carried out according to the following procedure. Using the "Portable Dynamic Surface Tensiometer SITA t100" manufactured by Eihiro Seiki Co., Ltd., the dynamic surface tension of a 1.0 mass% aqueous solution of the above polycondensate was measured at a measurement temperature of 25°C and a bubble generation interval in the range of 0.015 seconds to 50 seconds. Before the measurement, the dynamic surface tension was measured using ultrapure water, and it was confirmed that it was 72 mN / m (25°C) at any bubble lifetime. Dynamic surface tension γ at bubble lifetimes of 100 ms and 1000 ms t=100ms and γ t=1000ms , as well as, γ t=100ms and γ t=1000ms The difference Δγ between them is shown in Table 2.

[0061]

Table 2

[0062] [Fresh Mortar Test] According to the provisions of JIS R 5201, mortars (M1 ) to (M4) were prepared with the mortar mixtures shown in Table 3 below, and a fresh mortar test was carried out. The above polycondensate (additive for each hydraulic composition) [usage amount: addition amount based on the mass of powder (B): (M1) 0.28 mass%, (M2) 0.25 mass%, (M3) 0.27 mass%, (M4) 0.30 mass% respectively unified] was weighed as part of the mixing water. Specifically, the mixing water (ion-exchanged water) prepared by adding the above polycondensate (additive for hydraulic composition) (No. 1 to 14 or ratio 1 to 4) in advance was added to the powder [cement, cement and fly ash (FA-A or FA-B whose unburned carbon amount is evaluated as different from the methylene blue adsorption amount), or cement and blast furnace slag] and fine aggregate [sand], and using a high-power mixer (manufactured by Maruto Seisakusho Co., Ltd.), it was kneaded at a low speed for 60 seconds and left standing for 30 seconds. The kneading time is defined as the time when it can be confirmed that the mortar has become a fluid state from the start of kneading. The mortar adhering to the wall of the container was scraped off 20 seconds after the start of standing, and after the standing was completed, it was then kneaded at a high speed for 90 seconds to prepare the test mortar. The mortar used in the test was mixed with an antifoaming agent (Pronal 753W manufactured by Toho Chemical Industry Co., Ltd.) to avoid the influence of air bubbles in the mortar on the fluidity of the mortar, and the air content was adjusted so that the air content immediately after remixing was around 10% by mass.

[0063]

Table 3

[0064] ≪(1) Measurement of air content≫ The air content of the test mortar was measured immediately after the completion of mixing (0 minutes) and 30 minutes after the completion of mixing (30 minutes). The total mass method was adopted for the measurement of the air content, and the air content (% by mass) was calculated by the following formula from the measurement results using a graduated cylinder. In addition, the difference (loss value) between the air content at 0 minutes and the air content after 30 minutes was calculated. Air content (% by mass) = [1 - (mortar mass) / (mortar mass at 0% air content determined from the formulation)] × 100 Considering the concrete transportation time from the actual concrete production site to the actual construction site, from the perspective of maintaining the quality to maintain the same air content as at the time of shipment, in this evaluation the loss value of the air content is preferably less than 3% by mass, more preferably less than 2% by mass. Also, as described above, the air content of the mortar is adjusted to around 10% by mass (6 - 12% by mass), but within the above adjustment range, the initial value (0 minutes) is preferably 8.5% by mass or more, more preferably 9.5% by mass or more, and even more preferably 10% by mass or more. In the case of concrete, the air content at the time of shipment is adjusted to approximately 3.0% - 6.0% by mass. The obtained results are shown together in Tables 4 to 7.

[0065] ≪(2) Evaluation of fluidity: Measurement of mortar flow≫ Regarding the test mortar immediately after the kneading was completed (0 minutes) and 30 minutes after the completion (30 minutes), a mini slump cone (a conical cylinder with an upper inner diameter of 50 mm, a lower inner diameter of 100 mm, and a height of 150 mm) compliant with JIS A 1171 "Test Methods for Polymer Cement Mortar" was used to measure the spread of the mortar (flow value: mm). Also, the difference (loss value) between the mortar flow value at 0 minutes and the mortar flow value after 30 minutes was calculated. From the perspective of quality retention, it is preferable that the loss value of fluidity in this evaluation is less than 40 mm, and more preferably less than 20 mm. The obtained results are shown together in Tables 4 to 7.

[0066] ≪(3) Mortar Appearance Evaluation≫ The appearance of the test mortar immediately after the kneading was completed (0 minutes) was visually observed and evaluated according to the following criteria. The obtained results are shown together in Tables 4 to 7. <Appearance Evaluation> ◎··· No surface bubbles of the mortar are visually confirmed. ○··· Slight surface bubbles of the mortar are visually confirmed. △··· Obvious surface bubbles of the mortar are visually confirmed. ×··· Obvious surface bubbles of the mortar are visually present, and water has seeped around its outer periphery.

[0067]

Table 4

[0068]

Table 5

[0069]

Table 6

[0070]

Table 7

[0071] As shown in Table 2 and Tables 4 to 7, for Mortars (M1) to (M4) using the polycondensates (additives for hydraulic compositions) of No. 1 to No. 14 where the difference Δγ between the dynamic surface tension at a foam life of 100 ms and the dynamic surface tension at a foam life of 1000 ms in a 1.0 mass% aqueous solution is 2.0 or more, regardless of the type of powder such as fly ash or blast furnace slag, the loss value of the air amount was less than 3 mass%, and the loss value of fluidity was less than 40 mm. That is, it was confirmed that the polycondensate (additive for hydraulic composition) of the present invention can impart not only appropriate fluidity but also air entrainment to fresh mortar for a long time even when the formulation of cement, admixture, etc. is different. Further, all of the above No. 1 to No. 14 have a dynamic surface tension γ at a foam life of 100 ms of 60 mN / m or less and satisfy an initial value (0 minutes) of the air amount of 8.5 mass% or more, and are also excellent in controlling air entrainment at the initial stage of mixing. Furthermore, in terms of their appearance, surface bubbles were not visually confirmed, or if confirmed, they were extremely few, and they were also excellent in mortar appearance. In particular, for Mortars (M1), (M2), and (M4) using the polycondensates (additives for hydraulic compositions) of No. 1 to No. 2, 7 to 14 where the difference Δγ in the dynamic surface tension is 4.5 or more, the air loss value of the amount became less than 2 mass%, and even in the case of Mortar (M3) using fly ash FA - B with a larger unburned carbon amount than the methylene blue adsorption amount, the loss of the air amount was suppressed to around 2%, and it was confirmed that a fresh mortar with little variation in the air amount can be obtained. On the other hand, for Mortars (M1) to (M4) using the polycondensates of Ratio 1 to Ratio 4 where the difference Δγ in the dynamic surface tension is 2.0 or less, the loss value of the air amount exceeded 3 mass%, and the loss value of fluidity also exceeded 40 mm, resulting in difficulty in imparting stable fluidity and air entrainment to fresh mortar for a long time. Also, in terms of their appearance, surface bubbles were prominently confirmed, and they were inferior in mortar appearance. As described above, by setting the values of the predetermined dynamic surface tension (γ, Δγ), the air content of the mortar is controlled to a good value, and in addition, it is confirmed that bubbles hardly move on the mortar surface (resulting in excellent surface appearance), proving that the polycondensate (additive for hydraulic composition) of the present invention can achieve good air entrainment and excellent retention.

[0072] As described above, the polycondensate and the additive for hydraulic composition of the present invention can maintain a high level of water reduction not only for the cement composition but also for the hydraulic composition containing admixtures such as fly ash and blast furnace slag, and can impart good air entrainment to the hydraulic composition for a long time. Therefore, according to the present invention, regardless of the concrete mix, it is possible to provide ready-mixed concrete at the placing site that maintains the same air entrainment as that at the time of factory shipment and has appropriate fluidity for the concrete composition.

Claims

1. A polycondensate of a monomer mixture containing compound A represented by the following formula (A), compound B represented by formula (B), and one or more aldehyde compounds C represented by formula (C), wherein in compound B represented by the following formula (B), the proportion of p being 1 or less is 20 to 90 mol%, in a 1.0 mass% aqueous solution of the polycondensate, the polycondensate Dynamic surface tension value γ at 100 ms of foam life by the maximum bubble pressure method at 25°C ｔ＝１００ｍｓ [mN / m] is 65 or less, and Dynamic surface tension value γ at a foam life of 100 ms by the maximum bubble pressure method at 25°C ｔ＝１００ｍｓ [mN / m] and the difference Δγ (γ ｔ＝１０００ｍｓ [mN / m]) between the dynamic surface tension value γ at the same foam life of 1000 ms ｔ＝１００ｍｓ - γ ｔ＝１０００ｍｓ ) is 1.5 or more. Polycondensate 【Chemical 1】 (wherein n represents 1 or 2, when n represents 1, R １ represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms, A １ O represents an alkyleneoxy group having 2 to 4 carbon atoms, m is the average number of moles of alkylene oxide added and represents a number from 1 to 200, R ２ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 24 carbon atoms, when n represents 2, R １ represents -CH ２ -, -C(CH ３ ) ２ -, or -SO ２ -, and A １ O represents an alkyleneoxy group having 2 to 4 carbon atoms, m is the average number of moles of alkylene oxide added and represents a number from 1 to 200, R ２ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 24 carbon atoms.) [Chemical 2] (wherein q represents 1 or 2, when q represents 1, R ３ represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms, A ２ O represents an alkyleneoxy group having 2 to 4 carbon atoms, p is the average number of moles of alkylene oxide added and represents a number from 1 to 200, X １ represents a phosphate ester group or a sulfate ester group, when q represents 2, R ３ represents -CH ２ -, -C(CH ３ ) ２ -, or -SO ２ -, and A ２ O represents an alkyleneoxy group having 2 to 4 carbon atoms, p is the average number of moles of alkylene oxide added and represents a number from 1 to 200, X １ represents a phosphate ester group or a sulfate ester group.) 【Chemical Formula 3】 (wherein, R ４ represents a hydrogen atom, a carboxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a naphthyl group or a heterocyclic group, r represents a number from 1 to 100.)

2. The polycondensate according to claim 1, wherein the monomer mixture further contains at least one other monomer compound D selected from the group consisting of (D) lignin, rosin, benzoic acid, phenol, bisphenol A, phenolsulfonic acid, and hydroxyethylphenol.

3. The polycondensate according to claim 1 or claim 2, wherein in compound B represented by the formula (B), the proportion of p being 1 or less is 20 to 60 mol%. The polycondensate according to claim 1 or claim 2.

4. The dynamic surface tension value γ ｔ＝１００ｍｓ at the bubble lifetime of 100 ms is 60 or less, The polycondensate according to any one of claims 1 to 3.

5. The difference Δγ (γ ｔ＝１００ｍｓ −γ ｔ＝１０００ｍｓ ) in the dynamic surface tension value is 2.0 or more, The polycondensate according to any one of claims 1 to 4.

6. An additive for a hydraulic composition, comprising the polycondensate according to any one of claims 1 to 5.

7. A method for producing a polycondensate of a monomer mixture containing compound A represented by the following formula (A), compound B represented by formula (B), and one or more aldehyde compounds C represented by formula (C), wherein in compound B represented by the following formula (B), the proportion of p being 1 or less is 20 to 90 mol%, A step (1) of heating a mixture containing compound A represented by the following formula (A) and compound B represented by the following formula (B) to a first set temperature, Step (1) of raising the temperature of the mixture to a first set temperature, Adding one or more aldehyde compounds C represented by the above formula (C) to the mixture and raising the temperature from the first set temperature to a second set temperature over 1.5 hours to 12 hours (step (2)), A step (3) of maintaining at the second set temperature for 2 hours to 24 hours comprising, wherein the first set temperature is 50°C to 80°C and the second set temperature is 100°C to 130°C. Method for producing a polycondensate. 【Chemical Formula 4】 (In the formula, n represents 1 or 2, When n represents 1, R １ represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms, A １ O represents an alkyleneoxy group having 2 to 4 carbon atoms, m is the average number of moles of alkylene oxide added and represents a number from 1 to 200, R ２ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 24 carbon atoms, When n represents 2, R １ represents -CH ２ -, -C(CH ３ ) ２ -, or -SO ２ -, and A １ O represents an alkyleneoxy group having 2 to 4 carbon atoms, m is the average number of moles of alkylene oxide added and represents a number from 1 to 200, R ２ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an acyl group having 2 to 24 carbon atoms.) [Chemical Formula 5] (In the formula, q represents 1 or 2, When q represents 1, R ３ represents -CH ２ -, -C(CH ３ ) ２ -, or -SO ２ -, and A ２ O represents an alkyleneoxy group having 2 to 4 carbon atoms, p is the average number of moles of alkylene oxide added and represents a number from 1 to 200, X １ represents a phosphate ester group or a sulfate ester group, When q represents 2, R ３ represents an alkylene group having 1 to 3 carbon atoms, A ２ O represents an alkyleneoxy group having 2 to 4 carbon atoms, p is the average number of moles of alkylene oxide added and represents a number from 1 to 200, X １ represents a phosphate ester group or a sulfate ester group.) 【Chemical Formula 6】 (wherein, R ４ is a hydrogen atom, a carboxyl group, an alkyl group having 1 to 10 carbon atoms, a carbon atom represents an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a naphthyl group or a heterocyclic group, r represents a number from 1 to 100.)

8. The monomer mixture further contains at least one other monomer compound D selected from the group consisting of (D) lignin, rosin, benzoic acid, phenol, bisphenol A, phenolsulfonic acid and hydroxyethylphenol, The above step (1) is a step (1-1) of heating a mixture containing the compound A represented by the above formula (A), the compound B represented by the above formula (B) and the above (D) monomer compound D to a first set temperature, The method for producing a polycondensate according to claim 7.

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