JP6839557B2 - Dispersant for hydraulic composition - Google Patents

Description

The present invention relates to a dispersant for a hydraulic composition containing a novel phenolic polycondensation product. More specifically, polycondensation produced by polycondensing a monomer mixture containing an alkylene oxide adduct of phenols or a derivative thereof, a phosphoric acid ester or sulfate ester derivative of a hydrocarbon-substituted phenol alkylene oxide adduct, and aldehydes. The present invention relates to a dispersant for a water-hard composition containing a substance.

Further, the present invention also includes an aspect of a polycondensation composition having an alkylene oxide adduct of hydroxyethylphenol or a derivative thereof as a monomer mixture in addition to the above-mentioned monomer.

In recent years, as aggregates as concrete materials, there are increasing opportunities to use low-quality aggregates that have not been actively used in the past due to the depletion of high-quality fine aggregates such as river sand. .. A hydraulic composition using such a low-quality fine aggregate tends to have a high viscosity at the time of freshness and a decrease in workability even at a general water powder ratio (W / B). .. Such a problem is likely to occur especially when the amount of impurities such as clay contained in the aggregate is large.
Further, since the aggregate used as a material for a hydraulic composition is a natural product, the content of impurities varies. Therefore, when a conventional polycarboxylic acid-based dispersant is used, the amount of the dispersant required to obtain a certain fluidity varies depending on the type of aggregate used and its origin, etc., and therefore water. In the actual production of the rigid composition, it is necessary to adjust the amount of the dispersant used each time, which complicates various operations. In addition, when a large amount of the above-mentioned low-quality aggregate is used, it is often necessary to increase the amount of the dispersant added in order to secure a certain level of fluidity, which causes an increase in manufacturing cost. ..

To solve such problems, the fluidity is improved by a method of using a conventional polycarboxylic acid-based dispersant in combination with other components, or a method of optimizing the structure of the polycarboxylic acid-based dispersant itself. , Several prior art examples are disclosed that enhance the effectiveness as a polycarboxylic acid-based water reducing agent.
As an example of the combined use of the above-mentioned other components, when using a low-quality aggregate containing a swellable clay (for example, smectite, montmorillonite, etc.), a substance containing an inorganic cation as a clay activity-altering substance (for example, for example). EO / PO plasticizers (ie, polycarboxylic acid-based water reducing agents) that contain substances containing organic cations (eg, tetrabutylammonium bromide, etc.) and polar organic molecules (eg, polyethylene glycol, sodium hexametaphosphate, etc.) There is a proposal to improve the effectiveness of a polycarboxylic acid-based water reducing agent by using it in combination with (Patent Document 1). In addition, when using fine aggregate of low quality, a cationic polymer containing quaternary nitrogen (for example, poly (diallyldimethylammonium) salt, etc.) is used as a high-performance water reducing agent or a high-performance AE water reducing agent (polycarboxylic acid-based water reducing agent). A proposal to improve the fresh state such as concrete viscosity and flow retention by using it in combination with an agent (Patent Document 2). When a clay-containing aggregate is used, a poly-cationic compound (for example, polydiallyldimethylammonium) By using a poly-hydroxyl or hydroxyl carboxylate component (for example, sodium gluconate, etc.) in combination with a polycarboxylate-based dispersant, the dispersant has undergone improvement in maintaining the dose efficiency exhibited in cement mortar. There is a proposal (Patent Document 3).
Furthermore, as a proposal to improve the structure of the polycarboxylic acid-based dispersant itself, a comb-shaped copolymer containing a main hydrocarbon chain and a side chain containing a gem-bisphosphonate group in addition to a carboxy group and a polyoxyalkylene group is used as mineral particles. There is a proposal (Patent Document 4) that has improved the fluidity of the suspension by adopting it as a fluidizing agent for the suspension.

Japanese Patent No. 4491078 Japanese Patent No. 4381923 Japanese Unexamined Patent Publication No. 2011-136844 Japanese Patent No. 5623672

However, the proposals so far have not achieved satisfactory fluidity without being significantly affected by the type of aggregate used and the amount of impurities.
Therefore, with the transition of the aggregates used, there is a demand for a new dispersant for hydraulic compositions that can exhibit a certain fluidity with almost no change in the amount added regardless of the quality of the aggregates. ..
On the other hand, there has been no proposal so far that a phosphoric acid ester or a sulfate ester derivative of a hydrocarbon-substituted phenol alkylene oxide adduct is used as a raw material for an additive for a water-hard composition.

The present invention has been made to improve the performance of a dispersant for a hydraulic composition under the background of the prior art, and has stable dispersibility regardless of the content of impurities in the aggregate. An object of the present invention is to provide a dispersant for a hydraulic composition capable of obtaining a predetermined fluidity without substantially changing the addition amount depending on the type of aggregate.

As a result of diligent studies, the present inventors have used a phosphoric acid ester or a sulfate ester derivative of a hydrocarbon-substituted phenol alkylene oxide adduct, which has not been studied as a material for an additive for a water-hard composition, as a monomer component. By using a phenolic copolymer containing a polycondensation product as an additive for a water-hard composition, desired fluidity is desired regardless of the type and amount of impurities such as clay that can be contained in the aggregate. The present invention has been completed by finding that it is possible to provide a water-hardening composition having the above.

（式中、
Ｒ_３は炭素原子数１乃至２４の炭化水素基を表し、
Ａ_２Ｏは、炭素原子数２乃至４のアルキレンオキシ基を表し、
ｎはアルキレンオキサイドの平均付加モル数であって１乃至１５０の数を表し、
Ｘ_１はリン酸エステル基又は硫酸エステル基を表す。）

（Ｃ） Ｒ_４−ＣＨＯ , ＨＯ（ＣＨ_２Ｏ）_ｒＨ 又は （ＣＨ_２Ｏ）_３

（式中、Ｒ_４は水素原子、カルボキシル基、炭素原子数１乃至１０のアルキル基、炭素原子数２乃至１０のアルケニル基、フェニル基、ナフチル基又はヘテロ環式基を表し、
ｒは１乃至１００の数を表す。） That is, the present invention comprises a monomer mixture containing compound A represented by the following formula (A), compound B represented by the formula (B), and one or more aldehyde compound C represented by the formula (C). The present invention relates to a dispersant for a water-hard composition containing a condensed polycondensation product.

(A) R ₁ O- [A ₁ O] _m- R ₂

(During the ceremony,
R ₁ represents an aryl group
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 300.
R ₂ represents a hydrogen atom, an alkyl group, or an acyl group having a carbon number of 2 to 24 of 1 to 10 carbon atoms. )

(During the ceremony,
R ₃ represents a hydrocarbon group having 1 to 24 carbon atoms.
A ₂ O represents an alkyleneoxy group having 2 to 4 carbon atoms.
n is the average number of moles of alkylene oxide added and represents a number from 1 to 150.
X ₁ represents a phosphate ester group or a sulfuric acid ester group. )

(C) R _4- CHO, HO (CH ₂ O) _r H or (CH ₂ O) ₃

(In the formula, 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. )

（式中、
Ａ_２Ｏ及びＡ_３Ｏは、それぞれ独立して炭素原子数２乃至４のアルキレンオキシ基を表し、
ｐ及びｑは、アルキレンオキサイドの平均付加モル数であって、それぞれ独立して０乃至３００の数を表し且つｐ＋ｑ≧１であり、
Ｘ_２及びＸ_３はそれぞれ独立して水素原子、リン酸エステル基又は硫酸エステル基を表す。） Further, the present invention is a dispersion for a water-hard composition containing a polycondensation product obtained by polycondensing a monomer mixture containing the compound D represented by the following formula (D) in addition to the above compounds A to C. Also related to agents.

(During the ceremony,
A ₂ O and A ₃ O each independently represent an alkyleneoxy group having 2 to 4 carbon atoms.
p and q are the average number of moles of alkylene oxide added, and each independently represents a number of 0 to 300, and p + q ≧ 1.
X ₂ and X ₃ independently represent a hydrogen atom, a phosphate ester group, or a sulfate ester group, respectively. )

The polycondensation product is the compound A: compound B: compound D = 0.1 to 2: 0.1 to 4: in the molar ratio of the compound A, the compound B and the compound D in the monomer mixture. Compound C is contained in a ratio of 0 to 2 and compound C is contained in a molar ratio with respect to the total molar amount of the compound A, the compound B and the compound D (Compound A + Compound B + Compound D): Compound C = 1 to It is preferably contained in a ratio of 10: 10 to 1.

INDUSTRIAL APPLICABILITY According to the present invention, excellent dispersion stability can be exhibited with respect to a hydraulic composition without significantly changing the amount of impurities added regardless of the type of impurities in the aggregate and the amount thereof, and not only that. Water that has high water reduction, can shorten the kneading time until the hydraulic composition is put into a fluid state, has good stability over time, has low concrete viscosity, and has good workability such as low setting delay. Dispersants for rigid compositions can be provided.

Further, the dispersant for a hydraulic composition of the present invention has an effect of being able to reduce an unfavorable effect that can be caused by the presence of carbon content, typically unburned carbon, contained therein in the hydraulic composition. Play. That is, the dispersant for a hydraulic composition of the present invention can maintain a high water-reducing state even when it is blended as a dispersant for a hydraulic composition in a concrete composition containing fly ash (FA). In particular, in the cured product of the FA compound composition, it is possible to suppress the occurrence of darkening of the surface caused by the floating of unburned carbon on the surface of concrete, and it is possible to provide a cured product having an excellent appearance.

As described above, the dispersant for a hydraulic composition of the present invention can suppress deterioration of the fluidity of a hydraulic composition, which is a concern when impurities such as clay such as clay and bentonite are present.
In the hydraulic composition to which the dispersant for the hydraulic composition of the present invention is applied, impurities include clay and clay.
In the present specification, clay refers to collected fine particles defined as a metal sieve passing portion having a nominal size of 75 μm defined by JIS Z 8801-1.
Further, in the present specification, clay includes not only clay minerals having a layered structure but also clay minerals having no layered structure such as imogolite and allophane. Clay minerals with a layered structure include swelling minerals such as smectite, vermiculite, montmorillonite, bentonite, illite, hectrite, halloysite, mica, and brittle mica; kaolin mineral (kaolinite), serpentine, pyrophyllite, talc, and black. Examples include non-swelling minerals such as light.

Further, the dispersant for a water-hard composition of the present invention includes, in particular, fly ash, coal ash such as cinder ash, clinica ash, bottom ash, silica fume, silica dust, molten silica fine powder, blast furnace slag, volcanic ash, and silicic acid white clay. It is also suitably used for a water-hard composition containing a fine powder of pozzolanate such as diatomaceous earth, metacaolin, silica sol, and precipitated silica.

<Polycondensation product>
The dispersant for a water-hard composition of the present invention includes an alkylene oxide adduct of phenols or a derivative thereof (Compound A), a phosphoric acid ester or a sulfate ester derivative of a polyoxyalkylene hydrocarbon-substituted phenol ether (Compound B), and an aldehyde. It contains a polycondensation product obtained by polycondensing a monomer mixture containing the kind (Compound C).
In the present invention, the term "polycondensation product obtained by polycondensing a monomer mixture" is used.
(1) An embodiment containing a copolymer (copolymer 1) in which all the components of the monomer mixture, that is, all of the compounds A to C are polycondensed.
(2) An embodiment of the monomer mixture containing a copolymer (copolymer 2) in which compound A or compound B and compound C are polycondensed.
(3) An embodiment containing the two types of copolymers (copolymer 1 and copolymer 2) of the above (1) and (2), and (4) the common weight of the above (1) and / or (2). An embodiment comprising at least one of unreacted compounds A to C in addition to the coalescing (copolymer 1 and / or copolymer 2).
In addition to including all of the above, in general, unreacted components generated in each polymerization step and each component (compound A to C) preparation step, for example, an alkylene oxide addition step, and components including by-reactants are also included. Has been done.
Hereinafter, the compounds A to D contained in the monomer mixture will be described in detail.

[Compound A represented by the formula (A)]
Compound A is an alkylene oxide adduct of phenols or a derivative thereof, and has a structure represented by the following formula (A).

(A) R ₁ O- [A ₁ O] _m- R ₂

(During the ceremony,
R ₁ represents an aryl group
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 300.
R ₂ represents a hydrogen atom, an alkyl group, or an acyl group having a carbon number of 2 to 24 of 1 to 10 carbon atoms. )

The compound A is a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to phenols, and a derivative (alkyl ether or fatty acid ester) of the alkylene oxide adduct is also included in the compound A.

The _{aryl group in R 1} is an aromatic hydrocarbon group having 5 to 10 carbon atoms.
Specific examples thereof include a phenyl group and a naphthyl group.
The aryl group may have a substituent, for example, a hydrocarbon group having 1 to 24 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 2 to 10 carbon atoms, and 2 carbon atoms. Examples thereof include 10 to 10 alkoxy groups.

Examples of the alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide and butylene oxide, and these alkylene oxides can be added alone or mixed, and when two or more kinds of alkylene oxides are used, they can be added. Either block addition or random addition may be used.

The m is an average molar number of addition of alkylene oxide, 1 to 300, preferably a number from 1 to 150, by increasing the number of moles of added A 1 _O, it can be expected to improve the water-reducing properties.

The _{alkyl group having 1 to 10 carbon atoms in R 2} may have a branched structure or a cyclic structure, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or a cyclopropyl group. , N-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, 1- Examples include adamantyl groups.
Examples of the acyl group having 2 to 24 carbon atoms include a saturated or unsaturated acyl group (R'(CO) -group, R'is a hydrocarbon group having 1 to 23 carbon atoms). For example, saturated acyl groups having 2 to 24 carbon atoms include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid (caproic acid), heptanic acid, octanoic acid (capric acid), nonanoic acid, and decanoic acid (decanoic acid). Capric acid), dodecanoic acid (lauric acid), tetradecanoic (myristic acid), pentadecanoic acid (pentadecic acid), hexadecanoic acid (palmitic acid), heptadecanoic acid (margaric acid), octadecanoic acid (stearic acid), nonadecan acid, eikosan Acrylic groups derived from carboxylic acids and fatty acids such as acids (arachidic acid), docosanoic acid (bechenic acid) and tetracosanoic acid (lignoseric acid), and monounsaturated acyl groups include myristoleic acid, palmitenic acid, oleic acid, Acyl groups derived from monounsaturated fatty acids such as ellaic acid, baxenoic acid, gadrain acid, eicosenoic acid, erucic acid, and nerbonic acid are diunsaturated acyl groups, and diunsaturated acyl groups include linoleic acid, eicosadienoic acid, and docosadienoic acid. Acrylic groups derived from saturated fatty acids, and as triunsaturated acyl groups, triunsaturated fatty acids such as linolenic acid, pinolenic acid, eleostearic acid, meadic acid, dihomo-γ-linolenic acid, and eikosatrienic acid. Examples include the derived acyl group.
Further, preferable R ₂ includes a hydrogen atom and an acetyl group.

The compound A represented by the above formula (A) can be used alone or in combination of two or more. By using two or more kinds of compounds as compound A in combination in the monomer mixture described later, the effect of improving the retention rate of mortar flow can be expected.

（式中、
Ｒ_３は炭素原子数１乃至２４の炭化水素基を表し、
Ａ_２Ｏは、炭素原子数２乃至４のアルキレンオキシ基を表し、
ｎはアルキレンオキサイドの平均付加モル数であって１乃至１５０の数を表し、
Ｘ_１はリン酸エステル基又は硫酸エステル基を表す。） [Compound B represented by the formula (B)]
Compound B has a structure represented by the following formula (B).

(During the ceremony,
R ₃ represents a hydrocarbon group having 1 to 24 carbon atoms.
A ₂ O represents an alkyleneoxy group having 2 to 4 carbon atoms.
n is the average number of moles of alkylene oxide added and represents a number from 1 to 150.
X ₁ represents a phosphate ester group or a sulfuric acid ester group. )

The hydrocarbon groups of R ₃ 1 to 24 carbon atoms in the two alkyl groups of 1 to 24 carbon atoms, an alkenyl group having 2 to 24 carbon atoms, the unsaturated bond of carbon atoms from 4 to 24 Examples thereof include unsaturated aliphatic hydrocarbon groups having the above.
Specific examples of the alkyl group having 1 to 24 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl. Group, n-pentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-octyl group, n-decyl group, 1-adamantyl group, dodecyl group (lauryl group), tetradecyl group (milstyl group), Examples thereof include a hexadecyl group (palmityl group), an octadecyl group (stearyl group), an icosyl group, a docosyl group (behenyl group), and a tetracosyl group.
Specific examples of the alkenyl group having 2 to 24 carbon atoms include 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, and a tridecenyl group. Examples thereof include a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, an eicosenyl group, a docosenyl group, a tetracosenyl group, and the like, which may have a branched structure or a cyclic structure.
Examples of the unsaturated aliphatic hydrocarbon group having two or more unsaturated bonds having 4 to 24 carbon atoms include a decazienyl group, an undecazienyl group, a dodecazienyl group, a tridecazienyl group, a tetradecazienyl group and a pentadecazienyl group. , Hexadecadienyl group, heptadecadienyl group, octadecadienyl group, nonadecadienyl group, icosazienyl group, henikosazienyl group, docosazienyl group, tricosazienyl group, tetracosazienyl group, decatrienyl group, undecatrienyl group , Dodecatrienyl group, Tridecatrienyl group, Tetradecatorienyl group, Pentadecatorienyl group, Hexadecatrienyl group, Heptadecatrienyl group, Octadecatrienyl group, Nonadecatrienyl group, Icosatrienyl group, Examples thereof include a henicosatrienyl group, a docosatrienyl group, a trichosatorienyl group, a tetracosatorienyl group and the like.
Of these, alkyl groups and alkenyl groups having 1 to 10 carbon atoms are preferable.

Examples of the alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide and butylene oxide, and these alkylene oxides can be added alone or mixed, and when two or more kinds of alkylene oxides are used, they can be added. Either block addition or random addition may be used.

Further, n is the average number of moles of alkylene oxide added, and represents a number of 1 to 150, preferably 1 to 80, and more preferably 2 to 40.

When X ₁ represents a phosphoric acid ester group, they are a phosphoric acid monoester and / or a salt thereof, a phosphoric acid diester and / or a salt thereof, or a phosphoric acid triester, or a mixture thereof, and X ₁ is a sulfate. When representing ester groups, they are sulfate monoesters and / or salts thereof, or sulfate diesters, or mixtures thereof.
Examples of the phosphate ester salt or sulfate ester salt include alkali metal salts such as sodium and potassium; Group 2 metal salts such as calcium and magnesium; ammonium salts; and organic ammonium salts such as alkylammonium and alkanolammonium.
As the compound B, a compound synthesized by a known method using a (poly) oxyalkylene alkylphenol with a phosphorylating agent or a sulfate agent may be used.

As the compound B represented by the above formula (B), a compound represented by the following formula can be mentioned.
In the formula, R ₃ , A ₂ O, and n represent the same as those defined in the above formula (B), and Ph represents a phenylene group. Further, 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.
Further, Z represents a polyoxyalkylene alkyl ether residue represented by the formula: R "-O- (A'O) s- (in the formula, R" represents an alkyl group having 1 to 24 carbon atoms, and A'. O represents an oxyalkylene group having 2 to 3 carbon atoms, that is, an oxyethylene group or an oxypropylene group, and s is the average number of moles of the oxyalkylene group A'O, which represents 1 to 100). Representing, when a plurality of Z's exist, they may be the same group or different groups from each other.
-Phosphoric acid monoester and its salt R _3- Ph-O- [A ₂ O] _n- P (= O) (-OM) ₂
-Phosphoric acid diester and its salt [R _3- Ph-O- [A ₂ O] _n- ] ₂ P (= O) (-OM)
[R _3- Ph-O- [A ₂ O] _n- ] (Z-) P (= O) (-OM)
-Phosphate triester [R _3- Ph-O- [A ₂ O] _n- ] ₃ P (= O)
[R _3- Ph-O- [A ₂ O] _n- ] ₂ (Z-) P (= O)
[R _3- Ph-O- [A ₂ O] _n- ] (Z-) ₂ P (= O)
-Sulfuric acid monoester and its salt R _3- Ph-O- [A ₂ O] _n- S (= O) ₂ (-OM)
-Sulfuric acid diester [R _3- Ph-O- [A ₂ O] _n- ] ₂ S (= O) ₂
[R _3- Ph-O- [A ₂ O] _n- ] (Z-) S (= O) ₂

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

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

(C) R _4- CHO, HO (CH ₂ O) _r H or (CH ₂ O) ₃

(During the ceremony,
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. )
In the above formula, 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, and r is 1 to 1 to Represents a number of 100.
The alkyl group, alkenyl group, phenyl group, naphthyl group and heterocyclic group are alkyl groups having 1 to 10 carbon atoms; aryl groups such as phenyl group and naphthyl group; halogen atoms such as chlorine atom and bromine atom; It may be substituted with an arbitrary substituent such as a sulfonic acid functional group such as a sulfo group or a sulfonic acid base; an acyl group such as an acetyl group; a hydroxy group; an amino group; or a carboxyl group.

Compound C includes, for example, formaldehyde, paraformaldehyde, trioxane, glyoxylic acid, acetaldehyde, trichloroacetaldehyde, propionaldehyde, butylaldehyde, isobutylaldehyde, barrelaldehyde, hexylaldehyde, heptanal, octylaldehyde, nonylaldehyde, isononylaldehyde, decylaldehyde, Dodecanal, achlorein, crotonaldehyde, pentenal, hexenal, heptenal, octenal, cinnamaldehyde, benzaldehyde, benzaldehyde sulfonic acid, benzaldehyde disulfonic acid, anisaldehyde, salicylaldehyde, benzylaldehyde [(C ₆ H ₅ ) ₂ C (OH) -CHO ], Naftaldehyde, furfural, etc., among which can be selected from the group consisting of formaldehyde, paraformaldehyde, benzaldehyde or any mixture of two or more thereof.
Compound C can be used as a pure crystalline or powdery substance, or as a hydrate thereof, and can also be used in the form of an aqueous solution such as formalin, in which case the weighing or mixing of the components should be simplified. Can be done.

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

（式中、
Ａ_２Ｏ及びＡ_３Ｏは、それぞれ独立して炭素原子数２乃至４のアルキレンオキシ基を表し、
ｐ及びｑは、アルキレンオキサイドの平均付加モル数であって、それぞれ独立して０乃至３００の数を表し且つｐ＋ｑ≧１であり、
Ｘ_２及びＸ_３はそれぞれ独立して水素原子、リン酸エステル基又は硫酸エステル基を表す。） [Compound D represented by the formula (D)]
Compound D is an alkylene oxide adduct of hydroxyethylphenol or a derivative thereof, and has a structure represented by the following formula (D).

(During the ceremony,
A ₂ O and A ₃ O each independently represent an alkyleneoxy group having 2 to 4 carbon atoms.
p and q are the average number of moles of alkylene oxide added, and each independently represents a number of 0 to 300, and p + q ≧ 1.
X ₂ and X ₃ independently represent a hydrogen atom, a phosphate ester group, or a sulfate ester group, respectively. )

The compound D is a compound in which an alkylene oxide having 2 to 4 carbon atoms is added to at least one or both of a hydroxyethyl group and a phenolic hydroxy group with respect to hydroxyethylphenol, and the alkylene Derivatives of the oxide adduct (phosphate or sulfate) are also included in Compound D.
The hydroxyethylphenol may be any of o-hydroxyethyl-phenol, m-hydroxyethyl-phenol, and p-hydroxyethyl-phenol. Compound A is preferably a compound (and an ester derivative thereof) in which alkylene oxide having 2 to 4 carbon atoms is added to o-hydroxyethyl-phenol.

Examples _{of the alkyleneoxy group having 2 to 4 carbon atoms in A 2} O and A ₃ O include an ethyleneoxy group, a propyleneoxy group and a butyleneoxy group. A ₂ O and A ₃ O may be composed of only one of these, or may contain two or more groups. When two or more groups are contained, the addition form thereof may be either random addition or block addition.
Further, p and q are the average number of moles of alkylene oxide added, and each independently represents a number of 0 to 300, preferably 0 to 60, and p + q ≧ 1. By increasing the number of moles of A ₂ O _and A ₃ O added, improvement in water reduction can be expected.

When X ₂ and X ₃ represent phosphate ester groups, they are phosphate monoesters and / or salts thereof, phosphate diesters and / or salts thereof, or phosphate triesters, or mixtures thereof. _2, if X ₃ represents a sulfate group, which is sulfuric acid monoesters and / or salts thereof, or diesters sulfate, or mixtures thereof.

Examples of the phosphate ester salt or sulfate ester salt include alkali metal salts such as sodium and potassium; Group 2 metal salts such as calcium and magnesium; ammonium salts; and organic ammonium salts such as alkylammonium and alkanolammonium.
By anionizing the ends of compound D, that is, phosphoric acid esterification or sulfate esterification, the kneading time of the mortar can be shortened when added to the hydraulic composition.

The compound D represented by the above formula (D) can be used alone or in combination of two or more. By adding the copolymer using compound D as a monomer component to the hydraulic composition, the resistance to material variable factors is further improved, and good fluidity is obtained regardless of the amount of impurities such as clay. can get.

[Monomer mixture]
In the compound A to C C or the monomer mixture containing the compounds A to D used in the polycondensation product of the present invention, the mixing ratio thereof is not particularly limited, but the compound A, the compound B and the compound are preferable. D is contained in a molar ratio of compound A: compound B: compound D = 0.1 to 2: 0.1 to 4: 0 to 2, and the sum of compound A, compound B and compound D. It is desirable that compound D is contained in a molar ratio of (compound A + compound B + compound D): compound C = 1 to 10: 10 to 1 with respect to the molar amount.
More 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).
When the compounding ratio of the compound D is increased in the monomer mixture, the fluidity can be ensured even when impurities such as clay are mixed in the hydraulic composition, and the setting time can be expected to be shortened. Further, by adjusting the blending ratio of compound B, the water reduction and retention of the hydraulic composition can be adjusted.

[Polycondensation product]
The dispersant for a water-hard composition of the present invention comprises a copolymer obtained by polycondensing the above-mentioned compounds A to C or a monomer mixture containing compounds A to D.
In obtaining the above-mentioned copolymer, the production method and the polymerization method for obtaining the copolymer are not particularly limited.
Further, in the polycondensation, the order of addition and the method of addition of the compounds A to C or the compounds A to D are not particularly limited. For example, the compounds A to C or the compounds A to D are added before the polycondensation reaction. All of the compounds are added all at once, a part of them is added before the polycondensation reaction, and then the rest is added in portions by dropping, or a part of compounds A to D is added before the polycondensation reaction. The rest after a certain reaction time has elapsed may be additionally added, or the like.

The polycondensation product is, for example, compound A to compound C or compound A to compound D in the presence of a dehydration catalyst in the presence of a dehydration catalyst in the presence of a solvent-free or solvent, reaction temperature: 80 ° C. to 150 ° C., normal pressure to pressurized. , For example, obtained by polycondensing at 0.001 to 1 MPa.
Examples of the dehydration catalyst include hydrochloric acid, perchloric acid, nitrate, formic acid, methanesulfonic acid, octylsulfonic acid, dodecylsulfonic acid, vinylsulfonic acid, allylsulfonic acid, phenolsulfonic acid, acetic acid, sulfuric acid, diethyl sulfate, and dimethyl sulfate. Phosic acid, oxalic acid, boric acid, benzoic acid, phthalic acid, salicylic acid, pyruvate, maleic acid, malonic acid, nitrobenzoic acid, nitrosalicylic acid, paratoluenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, trifluoromethanesulfon Examples thereof include acids, fluoroacetic acids, thioglycolic acids, mercaptopropionic acids, active white clay, etc., and these dehydration catalysts can be used alone or in combination of two or more.

When the polycondensation reaction is carried out under a solvent, the solvent includes 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. Etc., and those applicable as the dehydration catalyst (acid catalyst), for example, acetic acid can also be used as a solvent.

The reaction temperature can be preferably carried out at a temperature of 95 ° C. to 130 ° C., and the polycondensation reaction can be completed by reacting for 3 to 25 hours.
The polycondensation reaction is preferably carried out under acidic conditions, and the pH of the reaction system is preferably 4 or less.

Further, in addition to Compounds A to C or Compounds A to D, other monomers that can be polycondensed with these compounds may be added to the monomer mixture as long as the effects of the present invention are not impaired.
Other monomers include cresol, catechol, resorcinol, nonylphenol, methoxyphenol, naphthol, methylnaphthol, butylnaphthol, bisphenol A, aniline, methylaniline, hydroxyaniline, methoxyaniline and / or salicylic acid, and 1 to 300 mol of alkylene. Additives with oxides, phenol, phenoxyacetic acid, methoxyphenol, resorcinol, cresol, bisphenol A, nonylphenol, aniline, methylaniline, N-phenyldiethanolamine, N, N-di (carboxyethyl) aniline, N, N-di ( Carboxymethyl) aniline, phenol sulfonic acid, anthranyl acid and the like can be mentioned.

After the completion of the polycondensation reaction, various conventionally known methods can be adopted in order to reduce the content of the unreacted aldehyde component (Compound C) in the reaction system. For example, a method in which the pH of the reaction system is alkaline and heat treatment is performed at 60 to 140 ° C., a method in which the reaction system is reduced in pressure (-0.1 to -0.001 MPa) to volatilize and remove the aldehyde component, and a small amount of sulfite. Examples include a method of adding sodium bisulfite, ethylene urea and / or polyethyleneimine.
The dehydration catalyst used in the reaction can be neutralized after the reaction is completed and removed by filtration in the form of a salt, but even in the embodiment in which the catalyst is not removed, the dispersion for the water-hard composition of the present invention described later will be described. The performance as an agent is not impaired. Examples of the catalyst removal method include phase separation, dialysis, ultrafiltration, use of an ion exchanger, and the like, in addition to the above filtration.
By neutralizing the reactant and diluting it with water or the like, workability such as weighing in use as a dispersant for a hydraulic composition described later is improved. At this time, the basic compounds used for neutralization include alkaline hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth hydroxides such as calcium hydroxide, ammonia, monoethanolamine, diethanolamine, and triethanolamine. Organic amines such as, etc. are mentioned, and one or a combination of two or more of them is adopted.

The finally obtained copolymer of the present invention in the range of 5,000 to 100,000 in terms of weight average molecular weight (gel permeation chromatography method (hereinafter referred to as "GPC method"), polyethylene glycol equivalent) is suitable. More preferably, the weight average molecular weight is in the range of 10,000 to 80,000, particularly preferably in the range of 15,000 to 50,000 in order to exhibit excellent dispersion performance.
As described above, the "polycondensation product" in the present invention may consist only of a copolymer obtained by polycondensing a monomer mixture containing compounds A to D, but in general, each of them may be used. Unreacted components generated in the polymerization step, alkylene oxide addition step, etc., and components including by-reactants are also included.

<Dispersant for hydraulic composition>
The polycondensation product can be suitably used as a dispersant for a hydraulic composition.
In the present invention, the hydraulic composition refers to a composition containing a powder having a property of being cured by a hydration reaction (hydraulic powder), for example, cement, gypsum, fly ash and the like. When the hydraulic powder is cement, the hydraulic composition is also referred to as a cement composition.

The dispersant for a hydraulic composition of the present invention can also be used in the form of an admixture in which a known and publicly available additive for a hydraulic composition is appropriately adopted and combined according to various uses. Specifically, conventionally known cement dispersants, high-performance AE water-reducing agents, high-performance water-reducing agents, AE water-reducing agents, water-reducing agents, air entraining agents (AE agents), foaming agents, defoaming agents, condensation retarders, etc. At least one other additive selected from the group consisting of a coagulation accelerator, a separation reducing agent, a thickening agent, a shrinkage reducing agent, a curing agent, a water repellent and the like can be blended.

Generally, cement dispersants are appropriately combined and used according to concrete production conditions, performance requirements, and the like. The same applies to the cement dispersant of the present invention, which is used alone or as a main agent as a cement dispersant, but as a reforming aid for a cement dispersant having a large slump loss or as an initial water reducing agent. It can be used in combination as a high cement dispersant.
Known cement dispersants include salts of polycarboxylic acid-based copolymers described in Japanese Patent Publication No. 59-18338, Japanese Patent No. 2628486, Japanese Patent No. 2774445, etc., and naphthalene sulfonic acid formarin condensates. Salt, salt of melamine sulfonic acid formalin condensate, lignin sulfonate, sodium gluconate, sugar alcohol can also be mentioned. The compounding ratio of the polycondensation product or copolymer of the present invention to the known cement dispersant is, for example, 1:99 to 99: 1% by mass.

Specific examples of the air entraining agent include anionic air entraining agent, nonionic air entraining agent, and amphoteric air entraining agent.
Examples of the setting retarder include an inorganic setting retarder and an organic setting retarder.
Examples of the accelerator include an inorganic accelerator and an organic accelerator.
Examples of thickeners / separation reducing agents include cellulose-based water-soluble polymers, polyacrylamide-based water-soluble polymers, biopolymers, and nonionic thickeners.
Examples of defoaming agents include nonionic defoaming agents, silicone-based defoaming agents, higher alcohols, and mixtures containing these as main components.

When the dispersant for a water-hardening composition of the present invention is applied to, for example, a cement composition, the component constituting the cement composition is a conventional conventional component for concrete, and cement (for example, ordinary Portland cement, early strength) is used. Portland cement, ultra-fast-strength Portland cement, low-heat / moderate-heat Portland cement or blast furnace cement, etc.), aggregate (ie, fine aggregate and coarse aggregate), admixture (eg silica fume, calcium carbonate powder, blast furnace slag fine powder, frying) Ash, etc.), expansion material and water can be mentioned.
Further, as an admixture other than the dispersant for the hydraulic composition of the present invention, which can be added separately at the time of preparation, the above-mentioned publicly known air entraining agent, coagulation retarder, accelerator, separation reducing agent, thickener, etc. There are antifoaming agents, shrinkage reducing agents and the like, 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 component and the purpose of use.

The amount of the dispersant for a hydraulic composition of the present invention varies depending on the compounding conditions including the above-mentioned concrete material, but when the amount of the cement is increased or when a fine powder of pozzolanate such as fly ash is used in combination. About 0.05 to 5.0% by mass is usually added in terms of solid content with respect to the total mass of cement and fly ash. In order to obtain water reduction and slump flow retention, it is better to add a large amount, but if it is too large, setting delay may occur, and in some cases, curing failure may occur.
The method of use is the same as in the case of a general cement dispersant, and the undiluted solution is added at the time of concrete kneading, or it is diluted with kneading water in advance and added. Alternatively, concrete or mortar may be kneaded and then added, and then uniformly kneaded again.

The present invention will be described below with reference to Examples. However, the present invention is not limited to these Examples and Comparative Examples.

In the examples, the physical characteristics of the sample were measured using the following devices under the following conditions.
(1) GPC (Gel Permeation Chromatography)
<Gel permeation chromatography (GPC) measurement conditions>
Columns: OHpak SB-802.5HQ, OHpak SB-803HQ, OHpak SB-804HQ (manufactured by Showa Denko KK)
Eluent: A mixture of 50 mM sodium nitrate aqueous solution and acetonitrile (volume ratio 80/20)
Detector: differential refractometer, calibration curve: polyethylene glycol

[Example 1: Preparation of compound A]
80 parts of diethylene glycol monophenyl ether (High Solve DPH manufactured by Toho Kagaku Kogyo Co., Ltd.) and 0.2 parts of 96% potassium hydroxide in a stainless steel high-pressure reactor equipped with a thermometer, agitator, pressure gauge, and nitrogen introduction tube. The mixture was charged, the inside of the reaction vessel was replaced with nitrogen, and the mixture was heated to 150 ° C. in a nitrogen atmosphere. Then, 1700 parts of ethylene oxide was introduced into the reactor under safe pressure at 150 ° C. for 10 hours, and then the temperature was maintained for 2 hours to complete the alkylene oxide addition reaction to complete the polyethylene glycol monophenyl ether (EO). The number of added moles = 90) was obtained.
As the 1 molar ethylene oxide adduct of phenol (see No. 2), High Solve EPH manufactured by Toho Chemical Industry Co., Ltd. was used.

[Example 2: Preparation of compound B]
<Preparation of EO adduct>
Preparation of (A) above using p-tert-butylphenol (manufactured by DIC Corporation, PTBP), p-octylphenol (manufactured by DIC Corporation, POP), or cardanol (manufactured by SATYA CASHEW CHEMICALS) as a starting material. The ethylene oxide addition reaction was carried out in the same manner as the method. The number of moles of ethylene oxide added was n as shown in Table 1.
<Adjustment of phosphate ester derivative>
In a glass reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 3 mol of the EO adduct was charged, and 1 mol of anhydrous phosphoric acid was charged at 50 ° C. for 4 hours while performing nitrogen bubbling to react. It was. Then, the aging reaction was carried out at 100 ° C. for 3 hours to terminate the phosphoric acid esterification reaction, and a substituted phenol EO adduct phosphoric acid ester was obtained.
<Adjustment of sulfate ester derivative>
In a glass reaction vessel equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 1 mol of the EO adduct was charged, and 1 mol of chlorosulfonic acid was charged at 40 ° C. over 3 hours under a nitrogen atmosphere, and sulfuric acid was added. The chemical reaction was carried out. Then, it was dehydrochlorinated by nitrogen bubbling for 1 hour to obtain an acidic compound.

[Example 3: Preparation of compound D]
<EO adduct>
A stainless steel high-pressure reactor equipped with a thermometer, agitator, a pressure gauge, and a nitrogen introduction tube was charged with 100 parts of ortho-hydroxyethylphenol (Aldrich's reagent) and 0.3 parts of 96% potassium hydroxide in the reaction vessel. Was replaced with nitrogen and heated to 130 ° C. in a nitrogen atmosphere. Then, 190 parts of ethylene oxide was introduced into the reactor in 4 hours while maintaining 130 ° C. under safe pressure, and then the temperature was maintained for 2 hours to complete the alkylene oxide addition reaction, and the total amount of ortho-hydroxyethylphenol was increased. A 6 molar EO adduct was obtained.

[Preparation Example 1: Preparation of polycondensation product (No. 1 to 7)]
The raw materials (A) and (B) were charged in a glass reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser at the molar ratios shown in Table 1. This was heated to 70 ° C., and then 98% sulfuric acid was charged in an amount of 1.0 wt% based on the total weight of (A) and (B). Next, the raw materials (C) were collectively charged into the reaction vessel at the molar ratio shown in Table 1, and then the temperature was raised to 105 ° C. When reaching 105 ° C, the pH of the reactants was 2.1 (1% aqueous solution, 20 ° C). The reaction was terminated 6 hours after reaching 105 ° C., 48% caustic soda was charged, and neutralization was performed 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 the polycondensation product was obtained. The polycondensation product was subjected to GPC measurement to determine the weight average molecular weight.
[Preparation Examples 6 to 13: Preparation of polycondensation product (No. 8 to 10)]
The raw materials (A), (B) and (D) were charged in a glass reaction vessel equipped with a stirrer, a thermometer and a reflux condenser at the molar ratios shown in Table 1. This was heated to 70 ° C., and then 98% sulfuric acid was charged in an amount of 1.0 wt% based on the total weight of (A), (B) and (D). Next, the raw materials (C) were collectively charged into the reaction vessel at the molar ratio shown in Table 1, the temperature was raised by the same operation as in the procedure of Cooking Example 1 above, and the mixture was neutralized after the reaction. The solid content was adjusted to 40% to obtain an aqueous solution of the polycondensation product. The polycondensation product was subjected to GPC measurement to determine the weight average molecular weight.

[Comparative Preparation Example 1: Preparation of Polycondensation Product of Comparative Example 1]
The polycondensation product of Comparative Example 1 was prepared according to the following procedure (paragraph [0049] [Preparation of polycondensation product of the present invention B.1] disclosed in Japanese Patent No. 5507809.
First, 1 mol of poly (ethylene oxide) monophenyl ether (1000 g / mol), 2 mol of phenoxyethanol phosphate (or a mixture of 2-phenoxyethanol dihydrogen phosphate and 2-phenoxyethanol hydrogen phosphate), 16.3 mol of water, And 2 mol of H ₂ SO ₄ was placed in a reaction vessel and stirred. 3 mol of formaldehyde in the form of a 37% aqueous solution was added dropwise to the solution thus formed. The polycondensation reaction was completed at 105 ° C. for 5 hours. After completion of the reaction, a 20% aqueous NaOH solution was used to bring the pH of the reaction mixture to 10.5. After an additional 30 minutes at 105 ° C., the mixture was cooled to room temperature and water was added to adjust the solids to about 30% by weight.
In the polycondensation product of Comparative Example 1 thus obtained, the weight average molecular weight Mw measured by GPC was 22,000.

[Comparative Preparation Example 2: Preparation of Polycondensation Product of Comparative Example 2]
The polycondensation product of Comparative Example 2 was prepared according to the following procedure (paragraph [0069] [Example 1.1]) disclosed in Japanese Patent Application Laid-Open No. 2014-503667.
First 2-phenoxyethanol (96%, 16.92 g) was added to a reactor equipped with a jacket and mechanical impeller set at 70 ° C. Polyphosphoric acid ( _{80% in P 2} O ₅ , 9.60 g) was added to the reactor with stirring 2-phenoxyethanol. The mixture was stirred at 80 ° C. for 30 minutes, followed by the supply of polyoxyethylene monophenyl ether (96%, Mn = 5000 g / mol, 200 g). The mixture was then heated to 100 ° C. Concentrated sulfuric acid (96%, 6.10 g), formalin (37%, 9.36 g) and paraformaldehyde (94%, 1.92 g) are added to the mixture and the mixture is heated to 110-115 ° C. , And stirred for 2 hours. The mixture was then cooled to 60 ° C. and 32% by weight aqueous sodium hydroxide solution was added to neutralize the mixture to pH 9.1.
In the polycondensation product of Comparative Example 2 thus obtained, the weight average molecular weight Mw measured by GPC was 22,000.

[Test: Fresh mortar test]
<Mortar combination>
500g of ordinary Portoland cement manufactured by Pacific Cement Co., Ltd. or 500g of the cement and fly ash in total, 1350g of fine aggregate or fine aggregate and clay, etc. [Clay (collected fine particles) or clay (bentonite, kaolinite)] 1350 g, as a dispersant for a water-hard composition, the above-mentioned polycondensation products 1 to 10 or the polycondensation products 1 to 2 of the comparative example [each polycondensation product is 0.20 in terms of solid content with respect to the cement mass. Using 225 g of ion-exchanged water [water / cement ratio (mass ratio) = 0.45] containing [mass% addition (see Table 3)], a mortar was prepared by the procedure described later (see the formulation of mortar in Table 2). ..

The clay (collected fine particles) used in this test is the collected fine particles obtained by collecting components of 75 μm or less from Futtsuyama sand, and the clay (collected fine particles) with a nominal size of 75 μm specified in JIS Z 8801-1 is used as clay (collected fine particles). Used as collected fine particles).
As the clay, the following commercially available products were used.
Bentonite: Reagent (manufactured by Wako Pure Chemical Industries, Ltd.)
Kaolinite: RC-1 (manufactured by Takehara Chemical Industry Co., Ltd.)

<Fresh mortar test>
A fresh mortar test using a mortar according to the formulation shown in Table 2 was carried out in accordance with the provisions of JIS R 5201.
Specifically, kneading water (ion-exchanged water) prepared by adding a dispersant for a water-hard composition (polycondensation products 1 to 10 or polycondensation products 1 to 2 of Comparative Example) in advance is added to powder (ion-exchanged water). In addition to cement or cement and fly ash) and sand (fine aggregate, or fine aggregate and clay, etc.), knead at low speed for 45 to 60 seconds using a high power mixer (manufactured by Maruto Seisakusho Co., Ltd.). It was mixed and allowed to stand for 30 seconds. The kneading time was appropriately selected as a time during which it was confirmed that the mortar was in a fluid state from the start of kneading (the kneading time common to the formulations A to E). The mortar adhering to the wall of the container was scraped off in 20 seconds from the start of standing, and after the end of the standing period, the mixture was kneaded at high speed for 90 seconds to prepare a test mortar.
For the mortar used in the test, in order to avoid the influence of air bubbles in the mortar on the fluidity of the mortar, a defoaming agent (Pronal 753W manufactured by Toho Kagaku Kogyo Co., Ltd.) was used, and the total mass of cement or cement and fly ash was used. The amount of air was adjusted by using the mixture in an amount of 0.01 wt%.

<Measurement of mortar flow and calculation of liquidity retention rate and liquidity volatility>
Regarding the test mortar immediately after kneading and the test mortar after 30 minutes have passed, a mini slump cone (upper end inner diameter 50 mm, lower end inner diameter 100 mm, height 150 mm) conforming to JIS A 1171 "Test method for polymer cement mortar". ) Was used to measure the spread (flow value) of the mortar.
The results obtained are shown in Table 3.

For the test mortars of Formulation A, Formulation C and Formulation E, the rate of change of the flow value immediately after kneading and the flow value after 30 minutes had passed as the fluidity retention rate was calculated by the following formula.
Liquidity retention rate (%) = [Flow value after 30 minutes / Flow value immediately after kneading] x 100
The results obtained are shown in Table 3.

In addition, for test mortars with the same dispersant for hydraulic composition (and the amount used thereof), clay or clay or clay or mortar without clay (blended A mortar) has a flow value as a fluidity fluctuation rate. The rate of change in the flow value of the mortar (formulation B to formulation E) when clay was added was calculated by the following formula. It can be evaluated that the closer the fluidity volatility (%) is to 100%, the better the result is that the change in fluidity due to the inclusion of clay or clay is small.
Liquidity volatility (%) = [Flow value when clay or clay is added (blending B to E) / Flow value when clay or clay is not added (blending A)] x 100
The results obtained are shown in Table 3.

<Measurement of curability (exothermic peak)>
The test mortar prepared in Formulation A was filled in a plastic container having a diameter of 10 cm and a height of 12 cm, and this was placed in the center of a simple heat insulating box made of urethane foam. The internal temperature of the mortar was measured using a wire diameter: 0.1 mm) and NTB-201A.
Then, from the history of the internal temperature of the mortar, the time to reach the maximum temperature (heat generation peak time: minutes (h: m)) was confirmed.
The results obtained are shown in Table 3.

<Evaluation of the appearance of the cured mortar>
Following the procedure of the previous <Fresh mortar test>, the test mortar prepared in Formulation E was filled in a triple mold manufactured by Maruto Seisakusho Co., Ltd., and after 24 hours, it was demolded to obtain a cured mortar. ..
The cured mortar obtained by the above procedure was photographed on the casting surface (4 cm × 16 cm), and the casting surface (surface photograph) was divided into 1 square 5 mm × 5 mm, for a total of 256 squares. The number of squares in which darkening occurred was counted among the 256 squares to calculate the darkening area ratio (rounded to the first decimal place), and the appearance (blackening) was evaluated according to the following criteria.
Evaluation 1: Darkened area ratio on the surface of the cured product = 5.0% or more 2: Darkened area ratio on the surface of the cured product = 3.0 to 4.9% or more 3: Darkened area ratio on the surface of the cured product = 1. 0-2.9% or more 4: Darkening area ratio on the surface of the cured product = less than 1.0% The obtained results are shown in Table 3.

As shown in Table 3, comparing Formulation A with Formulation B to Formulation D, the hydraulic composition dispersant containing the polycondensation product of the present invention contains clay (formulation B) and bentonite in the fine aggregate. Even when (formulation C) or kaolinite (formulation D) is mixed, it is confirmed that the mortar flow value fluctuates less and high fluidity can be maintained as compared with the formulation A which does not contain these clays and the like.
Further, as the formulation E, even when fly ash is used as the hydraulic powder in the formulation in which bentonite is mixed, the fluctuation of the mortar flow value is small, and the flow value is maintained even after 30 minutes, and the fluidity is retained. It was also confirmed that it was excellent in the above, and further, it was confirmed that the darkening of the appearance of the cured product was suppressed as compared with the hydraulic composition dispersant containing the polycondensation product of the comparative example.
On the other hand, in the hydraulic composition dispersant containing the polycondensation product of Comparative Example 1 and Comparative Example 2 which does not contain the copolymer of the present invention, the mortar flow value greatly fluctuates (decreases) depending on the blending of clay and clay. ), And the flow value after 30 minutes also dropped significantly. In addition, in the system using fly ash together, the darkening of the surface of the cured product was conspicuous.

Further, in compound B (a derivative of a phosphoric acid ester or a sulfate ester of a hydrocarbon-substituted phenol EO adduct), the appearance of the cured product was improved by having a substituent on the phenyl group. It was also confirmed that the appearance of the cured product was further improved by increasing the chain length of the substituted alkyl group.

Further, in compound D (alkylene oxide adduct of hydroxyethylphenol), it was confirmed that the fluctuation of the mortar flow value can be further reduced in the formulations B to E by using the copolymer containing the compound D (Example). 8-10).

Claims (4)

Polycondensation by polycondensing a monomer mixture containing compound A represented by the following formula (A), compound B represented by the formula (B), and one or more aldehyde compound C represented by the formula (C). A dispersant for a water-hard composition containing a product.

(A) R ₁ O- [A ₁ O] _m- R ₂

(During the ceremony,
R ₁ represents an aryl group
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 300.
R ₂ represents a hydrogen atom, an alkyl group, or an acyl group having a carbon number of 2 to 24 of 1 to 10 carbon atoms. )

(During the ceremony,
R ₃ represents a hydrocarbon group having 1 to 24 carbon atoms.
A ₂ O represents an alkyleneoxy group having 2 to 4 carbon atoms.
n is the average number of moles of alkylene oxide added and represents a number from 1 to 150.
X ₁ represents a phosphate ester group or a sulfuric acid ester group. )

(C) R _4- CHO, HO (CH ₂ O) _r H or (CH ₂ O) ₃

(In the formula, 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. ) The dispersant for a hydraulic composition according to claim 1, wherein the monomer mixture further contains a compound D represented by the following formula (D).

(During the ceremony,
A ₃ O and A ₄ O each independently represent an alkyleneoxy group having 2 to 4 carbon atoms.
p and q are the average number of moles of alkylene oxide added, and each independently represents a number of 0 to 300, and p + q ≧ 1.
X ₂ and X ₃ independently represent a hydrogen atom, a phosphate ester group, or a sulfate ester group, respectively. ) The monomer mixture
The compound A, the compound B and the 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.
Compound C is contained in a molar ratio of (Compound A + Compound B + Compound D): Compound C = 1 to 10: 10 to 1 with respect to the total molar amount of Compound A, Compound B and Compound D.
The dispersant for a hydraulic composition according to claim 1 or 2. The dispersant for a hydraulic composition according to any one of claims 1 to 3, wherein the monomer mixture contains two or more kinds of compounds A represented by the formula (A).