JP2007210877A - Dispersant for hydraulic composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dispersant capable of obtaining a hydraulic composition having low viscosity and a small variation in fluidity as a function of a variation in temperature. <P>SOLUTION: The dispersant for the hydraulic composition contains a polycarboxylic acid-based polymer A having a carboxylic acid group and an oxyalkylene group and/or an oxystyrene group such as polymers obtained by copolymerizing a specified monomer 1 such as an ethylenic unsaturated carboxylic acid derivative having a polyoxyalkylene group with a specified monomer 2 such as a (metha) acrylic acid, and a polymer B obtained by copolymerizing the monomer 1, a monophosphate-based monomer 3 and a diphosphate-based monomer 4. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a dispersant for a hydraulic composition and a hydraulic composition containing the dispersant.

  In recent years, the trend toward high durability of concrete, which is a representative hydraulic composition, has been increasing. For such high durability, from the viewpoint of blending concrete, it is fundamental to reduce the ratio of water to cement used in concrete (water cement ratio). When the water-cement ratio is reduced, the viscosity of the resulting hydraulic composition tends to increase and the workability is poor. In the highly water-reduced region, polycarboxylic acid-based cement dispersants having high dispersibility and excellent viscosity reducing properties have been proposed.

  In general, polycarboxylic acid-based dispersants have a temperature dependency in expressing the dispersion effect, and the fluidity of the resulting hydraulic composition increases with time due to a decrease in adsorption rate to the hydraulic powder at low temperatures such as in winter. There is a tendency. This tendency is more likely to occur as the water cement ratio is lower, the unit water amount is smaller, and the stirring time is shorter, and troubles such as separation of coarse aggregates may occur. In the production of ready-mixed concrete, fluctuations in initial fluidity and fluidity retention due to temperature are one of the issues in terms of fluidity management.

  Patent Document 1 discloses a cement admixture excellent in high dispersibility and viscosity reduction in a high water reduction rate region. Patent Document 2 discloses a dispersant for a hydraulic composition that has low mortar viscosity and excellent fluidity against fluctuations in concrete temperature even at a low water / hydraulic powder ratio. Patent Document 3 discloses a cement dispersant composition that can be kneaded with a short period of stirring and having good workability without impairing flow retention and the like for various concrete production conditions. Has been.

In Patent Document 4, a copolymer obtained by polymerizing a monomer having a sulfonic acid group or a phosphoric acid group, a monomer having an oxyalkylene group, and a monomer having a carboxylic acid group is an essential component. It is disclosed that a low-viscosity, high initial fluidity, and high fluidity retention can be obtained by containing a high-performance water reducing agent.
JP 2005-118684 A JP 2004-168635 A JP 2001-316151 A JP 11-79811 A

  However, in each of Patent Documents 1 to 4, there is a limit to the viscosity reduction effect, and a dispersant that is more excellent in viscosity reduction effect is desired.

  The subject of this invention is providing the hydraulic composition excellent in workability | operativity and the dispersing agent from which a hydraulic composition with a low viscosity and few fluidity | liquidity changes with respect to a temperature change is obtained.

The present invention relates to a polycarboxylic acid polymer A having a carboxylic acid group and an oxyalkylene group and / or an oxystyrene group,
Copolymerizing monomer 1 represented by the following general formula (1), monomer 3 represented by the following general formula (3), and monomer 4 represented by the following general formula (4) A polymer B obtained by
Relates to a dispersant for a hydraulic composition.

[In the formula, R ¹ and R ² are each a hydrogen atom or a methyl group, R ³ is a hydrogen atom, or — (CH ₂ ) _q (CO) _p O (AO) _r R ⁴ , and AO has 2 to 4 carbon atoms. An oxyalkylene group or an oxystyrene group, p is a number of 0 or 1, q is a number of 0 to 2, r is an average added mole number of AO, a number of 3 to 300, R ⁴ is a hydrogen atom or a carbon number of 1 Represents an alkyl group of ˜18. ]

[Wherein R ¹¹ is a hydrogen atom or a methyl group, R ¹² is an alkylene group having 2 to 12 carbon atoms, m1 is a number of 1 to 30, M ³ and M ⁴ are a hydrogen atom, an alkali metal or an alkaline earth metal, respectively. Represents. ]

[Wherein R ¹³ and R ¹⁵ are each a hydrogen atom or a methyl group, R ¹⁴ and R ¹⁶ are each an alkylene group having 2 to 12 carbon atoms, m2 and m3 are each a number of 1 to 30 and M ⁵ is Represents a hydrogen atom, an alkali metal or an alkaline earth metal. ]

The present invention also provides a polymer A ′ obtained by copolymerizing the monomer 1 represented by the following general formula (1) and the monomer 2 represented by the following general formula (2). When,
Copolymerizing monomer 1 represented by the following general formula (1), monomer 3 represented by the following general formula (3), and monomer 4 represented by the following general formula (4) A polymer B obtained by
Relates to a dispersant for a hydraulic composition.

[In the formula, R ¹ and R ² are each a hydrogen atom or a methyl group, R ³ is a hydrogen atom, or — (CH ₂ ) _q (CO) _p O (AO) _r R ⁴ , and AO has 2 to 4 carbon atoms. An oxyalkylene group or an oxystyrene group, p is a number of 0 or 1, q is a number of 0 to 2, r is an average added mole number of AO, a number of 3 to 300, R ⁴ is a hydrogen atom or a carbon number of 1 Represents an alkyl group of ˜18. ]

Wherein, R ⁵ to R ⁷ are each a hydrogen atom, a methyl group or ^{_{(CH 2) s COOM 2,}} (CH 2) s COOM 2 is COOM ¹ or another (CH _{²⁾ s} COOM ₂ and anhydrous In this case, M ¹ and M ² of those groups are not present. s represents the number of 0-2. M ¹ and M ² each represent a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkyl ammonium group, a substituted alkyl ammonium group, an alkyl group, a hydroxyalkyl group, or an alkenyl group. ]

[Wherein R ¹¹ is a hydrogen atom or a methyl group, R ¹² is an alkylene group having 2 to 12 carbon atoms, m1 is a number of 1 to 30, M ³ and M ⁴ are a hydrogen atom, an alkali metal or an alkaline earth metal, respectively. Represents. ]

[Wherein R ¹³ and R ¹⁵ are each a hydrogen atom or a methyl group, R ¹⁴ and R ¹⁶ are each an alkylene group having 2 to 12 carbon atoms, m2 and m3 are each a number of 1 to 30 and M ⁵ is Represents a hydrogen atom, an alkali metal or an alkaline earth metal. ]

  The present invention also provides a hydraulic composition containing hydraulic powder, water and the dispersant for hydraulic composition of the present invention, and a method for producing a concrete product comprising the hydraulic composition, in particular, the water. The present invention relates to a method for producing a concrete product in which a mold is filled with a hard composition and molded, and then demolded.

  ADVANTAGE OF THE INVENTION According to this invention, the dispersing agent from which a hydraulic composition with a low viscosity and few fluidity | liquidity changes with respect to a temperature change is obtained, and the hydraulic composition excellent in workability | operativity are provided. Moreover, the concrete product which consists of this hydraulic composition is excellent in the surface aesthetics of a concrete skin surface.

  The inventors of the present invention can obtain a hydraulic composition having a low viscosity and a small change in fluidity with respect to a temperature change when a specific phosphoric acid polymer is blended with a polycarboxylic acid polymer to form a dispersant. As a result, the present invention has been completed.

  The dispersant for a hydraulic composition of the present invention contains a polymer A and a polymer B. The polymer A is a polycarboxylic acid polymer having a carboxylic acid group and an oxyalkylene group and / or an oxystyrene group. In the polymer A, the oxyalkylene group constitutes a polymer and has a polyalkylene glycol skeleton. The polymer A preferably contains an oxyalkylene group, and the average added mole number of the oxyalkylene group is preferably from 3 to 300, more preferably from 5 to 120. The oxyalkylene group is preferably an oxyalkylene group having 2 to 4 carbon atoms, more preferably an ethyleneoxy group (hereinafter referred to as EO group), and an EO group of 70 mol% or more, more preferably 80 mol% or more, and further 90 mol%. As described above, it is particularly preferable that all AOs are EO groups. Different types of oxyalkylene groups may be included in the repeating unit of the oxyalkylene group, and random addition, block addition, or a mixture thereof may be included. For example, a propyleneoxy group and the like can be included in addition to the EO group.

  As the polymer A, a polymer A ′ obtained by copolymerizing the monomer 1 represented by the following general formula (1) and the monomer 2 represented by the following general formula (2) (Hereinafter referred to as polymer A ′) is preferred.

[In the formula, R ¹ and R ² are each a hydrogen atom or a methyl group, R ³ is a hydrogen atom, or — (CH ₂ ) _q (CO) _p O (AO) _r R ⁴ , and AO has 2 to 4 carbon atoms. An oxyalkylene group or an oxystyrene group, p is a number of 0 or 1, q is a number of 0 to 2, r is an average added mole number of AO, a number of 3 to 300, R ⁴ is a hydrogen atom or a carbon number of 1 Represents an alkyl group of ˜18. ]

Wherein, R ⁵ to R ⁷ are each a hydrogen atom, a methyl group or ^{_{(CH 2) s COOM 2,}} (CH 2) s COOM 2 is COOM ¹ or another (CH _{²⁾ s} COOM ₂ and anhydrous In this case, M ¹ and M ² of those groups are not present. s represents the number of 0-2. M ¹ and M ² each represent a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkyl ammonium group, a substituted alkyl ammonium group, an alkyl group, a hydroxyalkyl group, or an alkenyl group. ]

[Monomer 1]
In monomer 1, R ¹ and R ² in general formula (1) are each a hydrogen atom or a methyl group. R ³ is a hydrogen atom or — (CH ₂ ) _q (CO) _p O (AO) _r R ⁴ , preferably a hydrogen atom. Examples of the alkenyl [(R ¹ ) (R ³ ) C═C (R ² ) — (CH ₂ ) _q —] in the general formula (1) include a vinyl group, an allyl group, and a methallyl group. When p is 0, AO forms an ether bond with (CH ₂ ) _q, and when p is 1, it forms an ester bond. q is 0 to 2, preferably 0 or 1, and more preferably 0. AO is an oxyalkylene group having 2 to 4 carbon atoms or an oxystyrene group, and AO is preferably an oxyalkylene group having 2 to 4 carbon atoms, more preferably an ethyleneoxy group, and an EO group of 70 mol% or more, Further, it is preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably all AO are EO groups. r is the average added mole number of AO, and is a number of 3 to 300, preferably 5 to 120. Moreover, AO is different in an average of r repeating units, and random addition, block addition, or a mixture thereof may be included. For example, AO can contain a propyleneoxy group etc. besides EO group. Monomer 1 is preferably a compound with p = 1 and q = 0. Further, when p = 0, q = 1 is preferable.

  In order for the polymer A ′ to express the initial strength and fluidity of concrete higher, r in the general formula (1) is preferably 50 to 300, more preferably 110 to 300, and r is 200 or less from the viewpoint of polymerizability. Furthermore, since 150 or less, especially 130 or less are preferable, from a comprehensive viewpoint, r is preferably 110 to 200, more preferably 110 to 150, and particularly preferably 110 to 130. From the viewpoint of further reducing the viscosity of the concrete, r in the general formula (1) is preferably 3 to 100, and more preferably 3 to 50.

R ⁴ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, preferably 1 to 12, more preferably 1 to 4, and further preferably 1 or 2, and particularly preferably a methyl group.

  Monomer 1 includes a half-terminated alkyl-capped polyalkylene glycol such as methoxypolyethylene glycol, methoxypolypropylene glycol, methoxypolybutylene glycol, methoxypolystyrene glycol, ethoxypolyethylenepolypropyleneglycol, (meth) acrylic acid, maleic acid (half ) Esterified products, etherified products with (meth) allyl alcohol, and (meth) acrylic acid, maleic acid, and (meth) allyl alcohol adducts having 2 to 4 carbon atoms are preferably used.

  More preferred is an esterified product of alkoxy, particularly methoxypolyethylene glycol and (meth) acrylic acid. Specific examples include ω-methoxypolyoxyalkylene methacrylate and ω-methoxypolyoxyalkylene acrylate, and ω-methoxypolyoxyalkylene methacrylate is more preferable.

When the polymer A ′ is obtained using a plurality of monomers 1 having different r, r represents an average value of the whole polymer. For example, when the polymer A ′ is obtained using x ₁ mol% of a monomer where r = r ₁ and x ₂ mol% of a monomer where r = r ₂ , r is r = (r ₁ x ₁ + r ₂ x ₂ ) / (x ₁ + x ₂ )

[Monomer 2]
In the monomer 2, R ^{5 to} R ⁷ in the general formula (2) are each a hydrogen atom, a methyl group, or (CH ₂ ) _s COOM ² , and (CH ₂ ) _s COOM ² is COOM ¹ or other (CH ₂ ) _s COOM ² and an anhydride may be formed. In that case, M ¹ and M ² of those groups do not exist. s represents the number of 0-2. R ⁵ is preferably a hydrogen atom, and R ⁶ is preferably a methyl group. R ⁷ is preferably a hydrogen atom or (CH ₂ ) _s COOM ² .

M ¹ and M ² are each a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkylammonium group, a substituted alkylammonium group, an alkyl group, a hydroxyalkyl group, or an alkenyl group. M ¹ and M ² are each preferably a hydrogen atom or an alkali metal.

  Specifically, monocarboxylic acid monomers such as (meth) acrylic acid and crotonic acid, dicarboxylic acid monomers such as maleic acid, itaconic acid and fumaric acid, or anhydrides or salts thereof (for example, alkalis) Metal salt, alkaline earth metal salt, ammonium salt, mono-, di-, trialkyl (carbon number 2 to 8) ammonium salt optionally substituted with hydroxyl group) or ester, preferably (meth) acrylic acid, Maleic acid, maleic anhydride, more preferably (meth) acrylic acid or an alkali metal salt thereof. In addition, (meth) acrylic acid means acrylic acid and / or methacrylic acid (hereinafter the same).

  For example, the polymer A ′ is charged with water in a reaction vessel and heated, and the monomer 1 and the monomer 2 are reacted with each other at a constant molar ratio and weight ratio in the presence of a chain transfer agent or the like. It can be produced by aging. Neutralize after aging if necessary.

  The weight ratio (monomer 1 / monomer 2) of the monomer 1 and the monomer 2 used for the production of the polymer A ′ is preferably 97/3 to 3/97, and is preferably 95/5 to 5/95. More preferred is 90/10 to 10/90.

In the polymer A ′, the average weight ratio (Y _I ) of the monomer 2 to the total monomers for producing the polymer is preferably 1 to 30 (% by weight). The average weight ratio is represented by [total amount of monomer 2 / total amount of all monomers used for the synthesis of polymer A ′] × 100 (% by weight). In order to broaden the versatility of the polymer A ′, it is preferable to use a polymer A ″ produced with an average weight ratio (Y _II ) different from the average weight ratio of the polymer A ′.

Polymer A 'and A''has an average weight ratio (Y _I) and (Y _II) and it is preferably selected two or more differently. The polymers A ′ and A ″ may be the same or different in the types of monomers 1 and 2 used in the production, but it is preferable to use the same type.

  In the present invention, the polymer A ′ is obtained by copolymerizing at least one monomer 1 and at least one monomer 2, and the monomer 1 and the monomer 2 A copolymer mixture in which the molar ratio [monomer 1] / [monomer 2] is changed at least once during the reaction [hereinafter also referred to as copolymer mixture (A)] can be used. Such a copolymer mixture (A) changes the molar ratio [monomer 1] / [monomer 2] of monomer 1 and monomer 2 added to the reaction system at least once during the reaction. Can be manufactured. At that time, it is preferable that the difference between the maximum value and the minimum value of the molar ratio [monomer 1] / [monomer 2] is at least 0.05, particularly 0.05 to 2.5.

The copolymer mixture (A) is obtained by reacting the above monomers 1 and 2 with a molar ratio of preferably [monomer 1] / [monomer 2] = 0.02-4. The molar ratio [monomer 1] / [monomer 2] is changed at least once during the reaction. In the present invention, co-obtained by the copolymer mixture the average weight ratio of the monomer 2 to the total monomers for producing the (A) (X _I) is different from the average weight ratio (X _II) Weight It is preferable to use the coalescence mixture (A ′) in combination. That is, the copolymer mixture (A ′) is prepared by reacting the monomers 1 and 2 with a molar ratio of preferably [monomer 1] / [monomer 2] = 0.02-4. In the obtained copolymer mixture, the molar ratio [monomer 1] / [monomer 2] was changed at least once during the reaction, and the copolymer mixture (A ′) The average weight ratio (X _II ) of the monomer (A2) to the total monomers for production is different from the average weight ratio (X _I ) of the copolymer mixture (A). The average weight ratio is represented by [total amount of monomers (A2) / total amount of monomers] × 100 (% by weight), and preferably in the range of 1 to 30 (% by weight). Hereinafter, this average weight ratio may be referred to as “(A2) ′ average weight ratio”. The average weight ratios (X _I ) and (X _II ) are preferably at least 0.1 (% by weight), more preferably at least 0.5 (% by weight), particularly at least 1.0 (% by weight). Even if the copolymer mixtures (A) and (A ′) are different in the types of monomers 1 and 2 used in the production, the average weight ratios (X _I ) and (X _II ) are As long as they are different, it is preferable to use the same kind of monomers 1 and 2.

In the present invention, as monomer 2 used for polymer A ′, M ¹ and M ^{2 in} general formula (2) are alkyl groups (preferably having 1 to 3 carbon atoms) and hydroxyalkyl groups (preferably having carbon numbers). 2-5) or a polymer using a compound that is an alkenyl group (preferably having 2 to 5 carbon atoms) (hereinafter referred to as polymer A ′ ″) can be used.

  In this case, the preferable structure and type of the monomer 1 used for the production of the polymer A ′ ″ are the same as those described above.

  In the production of the polymer A, particularly the polymer A ', in addition to the monomers 1 and 2, one or more other copolymerizable monomers can be used. Examples of other copolymerizable monomers include allyl sulfonic acid, methallyl sulfonic acid, sulfoethyl methacrylate, alkali metal salts, alkaline earth metal salts, ammonium salts, or amine salts of any of these. (Meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, 2- (meth) acrylamide-2-metasulfonic acid, 2- (meth) acrylamide-2-ethanesulfonic acid, 2- (Meth) acrylamide-2-propanesulfonic acid, styrene, styrenesulfonic acid and the like. Further, as described in Japanese Patent No. 3336456, polyalkylene polyamine and dibasic acid or ester of dibasic acid and lower alcohol having 1 to 4 carbon atoms, acrylic acid or methacrylic acid or acrylic acid or methacrylic acid and carbon A polyamide polyamine monomer obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an amino residue of a polyamide polyamine obtained by condensing an ester with a lower alcohol having 1 to 4 atoms; As described in JP-A-2004-2174, an ester of a polyalkylene polyamine and a dibasic acid and / or a dibasic acid and an alcohol having 1 to 4 carbon atoms, and (meth) acrylic acid and / or (meth) acrylic acid And an unsaturated bond obtained by reacting an ester of alcohol with 1 to 4 carbon atoms A polyamide polyamine monomer obtained by adding an alkylene oxide having 2 to 4 carbon atoms to the amino residue and imino group of a polyamide polyamine, as described in JP-A-2003-335563, a single amount of an amine alkylene oxide adduct And polyalkyleneimine alkylene oxide adduct monomers as described in JP-A No. 2004-342050, poly (polyoxyalkylene) unsaturated monomers as described in JP-A No. 2004-67934, and the like. It is done. The total ratio of the monomers 1 and 2 is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, more preferably 75 to 100 mol%, and more preferably 90 to 100 mol% in all monomers. preferable.

  As the polymer A, particularly the polymer A ′, commercially available products can be used, and specific examples thereof are as follows. Two or more of these may be used in combination.

  Mighty 3000S, Mighty 3000H, Mighty 3000R, Mighty 21LV, Mighty 21VS, Mighty 21HF, Mighty 21HP manufactured by Kao Corp., Aqualock FC600S, FC900 Aqualock manufactured by Nippon Shokubai Co., Ltd. AKM-60F, Marialim EKM-60K, Mariarim Y-40, Degussa's Leo Build SP Series (8LS, 8LSR, 8N, 8S, 8R, 8SE, 8RE, 8SB-S, 8SB-M, 8SB-L, 8SB- LL, 8HE, 8HR, 8SV, 8RV), Leobuild 8000S, 8000E, 8000H, Glenium series (3030NS, 3400NV, 3000NS, 3200HES, 27, 51, 206, C301, C323, C315, ACE28, ACE30, ACE32, ACE38, ACE40 , ACE48, ACE68, ACE327, ACE329, ACE338, SKY501, SKY503, SKY505, SKY528, SKY591, SKY592, SKY593, SKY910 +, SP-8CR, SP-8CN, SP-8N, 8000, SP-8L), Melflux1641, 2453, 2424,2500, Sika's Sikament 1200N, 1100NT, 1100NTR, 1100NT-PWR, 1100NT-PSK, 2300, Sikament686, Sika Viscocrete2100, Sika Viscocrete4100, Sika Viscocrete6100, Sika Viscocrete 20HE, Sika Viscocret e3010, Sika Viscocrete5-500, Sika Viscocrete5-300, Sika Viscocrete5, Sika Viscocrete20SL, Tupole HP-8, Tupole HP-11, Tupole HP-8R, Tupole HP-11R, Tupole HP-11R made by Takemoto Yushi Co., Ltd. Paul HP-11X, Tupole SSP-104, Tupole SSP-116, Tupole HP70, Tupole NV-G1, Tupole NV-G5, Floric's Floric SF500S, Floric SF500SB, Floric SF500H, Floric SF500R, Floric SF500RB, manufactured by GRACE ADVA CAST 570, ADVA Flow 340, ADVA Flow 341, ADVA Flow 355, ADVA Flow 356, ADVA Flow 400, ADVA 100 Superplasticizer, ADVA 140, ADVA 170, ADVA 360 , ADVA 370, ADVA Cast 500, ADVA Cast 530, ADVA Cast 540, ADVA Cast 555, BASF Sokalan series (HP80, 5009X, 5010X, DS3557, R401), Kyunggi Powerflow series (WR, HWR, SR ), Dynamon series made by Mapei, Mapeifluid series (Mapei), Strucuro series made by Fosroc, etc. It is.

<Polymer B>
Polymer B includes monomer 1 represented by the above general formula (1), monomer 3 represented by the following general formula (3), and a single unit represented by the following general formula (4). It is a phosphate ester polymer obtained by copolymerizing a mixed monomer containing the monomer 4.

[Wherein R ¹¹ is a hydrogen atom or a methyl group, R ¹² is an alkylene group having 2 to 12 carbon atoms, m1 is a number of 1 to 30, M ³ and M ⁴ are a hydrogen atom, an alkali metal or an alkaline earth metal, respectively. Represents. ]

[Wherein R ¹³ and R ¹⁵ are each a hydrogen atom or a methyl group, R ¹⁴ and R ¹⁶ are each an alkylene group having 2 to 12 carbon atoms, m2 and m3 are each a number of 1 to 30 and M ⁵ is Represents a hydrogen atom, an alkali metal or an alkaline earth metal. ]

[Monomer 1]
As the monomer 1, those described for the polymer A ′ are used. As a preferable monomer 1 used for the production of the polymer B, R ³ in the general formula (1) is preferably a hydrogen atom, AO is preferably an oxyalkylene group having 2 to 4 carbon atoms, and more preferably includes an EO group. Preferably, the EO group is 70 mol% or more, more preferably 80 mol% or more, further 90 mol% or more, and particularly preferably all AO are EO groups. When p is 0, AO forms an ether bond with (CH ₂ ) _q, and when p is 1, it forms an ester bond. q is a number from 0 to 2, and 0 is preferred. R ⁴ is preferably a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, more preferably 1 to 12, more preferably 1 to 4, and more preferably 1 or 2, and particularly preferably a methyl group. Specific examples include ω-methoxypolyoxyalkylene methacrylate and ω-methoxypolyoxyalkylene acrylate, and ω-methoxypolyoxyalkylene methacrylate is more preferable. Here, r in the formula (1) is 3 to 300, preferably 4 to 120, and more preferably 4 to 80 in terms of the dispersibility of the polymer in the hydraulic composition and the viscosity reducing effect. More preferably, it is 4 to 50, particularly preferably 4 to 30. Moreover, AO is different in an average of r repeating units, and random addition, block addition, or a mixture thereof may be included. AO can also contain a propyleneoxy group etc. besides EO group.

  The monomer 1 used for the production of the polymer B can be obtained, for example, by esterification of alkoxypolyalkylene glycol and (meth) acrylic acid [corresponding to the compound represented by the general formula (2)]. From the viewpoint of the required addition amount and viscosity reduction when the esterified product is used in the dispersant of the present invention, unreacted (meth) acrylic acid is 5% by weight or less with respect to monomer 1 in terms of acid type. 3 wt% or less is more preferable, 1.5 wt% or less is more preferable, and 1 wt% or less is more preferable. Examples of a method for reducing the amount of (meth) acrylic acid remaining during the production of the monomer 1 include topping, steaming, and solvent extraction.

[Monomer 3]
Monomer 3 are the compounds of formula (3), R ¹¹ is a hydrogen atom or a methyl group, R ¹² is an alkylene group having 2 to 12 carbon atoms. m1 is a number from 1 to 30, and M ³ and M ⁴ are each a hydrogen atom, an alkali metal, or an alkaline earth metal. 1-20 are preferable, as for m1 in General formula (3), 1-10 are more preferable, and 1-5 are especially preferable.

  Specific examples include phosphoric acid mono (2-hydroxyethyl) methacrylic acid ester, phosphoric acid mono (2-hydroxyethyl) acrylic acid ester, polyalkylene glycol mono (meth) acrylate acid phosphoric acid ester, and the like. Of these, mono (2-hydroxyethyl) methacrylic acid phosphate is preferable from the viewpoint of ease of production and product quality stability. Further, alkali metal salts, alkaline earth metal salts, ammonium salts, alkylammonium salts and the like of these compounds may be used.

[Monomer 4]
As for the monomer 4, in General formula (4), R <^13> , R <^15> is a hydrogen atom or a methyl group, respectively, R < ¹⁴ >, R < ¹⁶ > is a C2-C12 alkylene group, respectively. m2, m3 is a number of each 1 to 30, M ⁵ represents a hydrogen atom, an alkali metal or alkaline earth metal. M2 and m3 in the general formula (4) are each preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5.

  Specific examples thereof include phosphoric acid di-[(2-hydroxyethyl) methacrylic acid] ester, phosphoric acid di-[(2-hydroxyethyl) acrylic acid] ester, and the like. Among these, di-[(2-hydroxyethyl) methacrylic acid] ester phosphate is preferable from the viewpoint of ease of production and quality stability of the product. Further, alkali metal salts, alkaline earth metal salts, ammonium salts, alkylammonium salts and the like of these compounds may be used.

  Monomers 3 and 4 can be used as a mixed monomer including monomer 3 and monomer 4. Further, as the monomers 3 and 4, phosphate esters obtained by reacting the organic hydroxy compound represented by the general formula (5) with a phosphorylating agent may be used.

  The mixed monomer containing the monomer 3 and the monomer 4 is obtained as a reaction product by reacting, for example, the organic hydroxy compound represented by the general formula (5) with a phosphorylating agent at a predetermined charge ratio. It can also be manufactured.

[Wherein, R ²⁰ represents a hydrogen atom or a methyl group, R ²¹ represents an alkylene group having 2 to 12 carbon atoms, and m4 represents a number of 1 to 30. ]

  1-20 are preferable, as for m4 in General formula (5), 1-10 are more preferable, and 1-5 are especially preferable.

  As a phosphate ester, for example, when producing a mixture of mono (2-hydroxyethyl) methacrylic acid phosphate and di-[(2-hydroxyethyl) methacrylic acid] phosphate, a known technique (for example, JP-A-57) -180618).

  As the mixed monomer including the monomer 3 and the monomer 4, a commercially available product including a monoester and a diester can be used. For example, Phosmer M, Phosmer PE, Phosmer P (Unichemical) , JAMP514, JAMP514P, JMP100 (all Johoku Chemical), light ester P-1M, light acrylate P-1A (all Kyoeisha Chemical), MR200 (Daihachi Chemical), Kayamar (Nippon Kayaku), Ethyleneglycol methacrylate phosphate (Aldrich) Reagent).

  Monomers 3 and 4 are phosphoric acid esters of monomers having an unsaturated bond and a hydroxyl group, and the above-mentioned commercially available products and reaction products include monoester (monomer 3) and diester ( It has been confirmed that compounds other than the monomer 4) are contained. These other compounds are considered to be a mixture of polymerizable and non-polymerizable compounds, but in the present invention, such a mixture (mixed monomer) can be used as it is.

The contents of monomers 3 and 4 in the mixed monomer can be calculated based on the ³¹ P-NMR measurement results.
< ³¹ P-NMR measurement conditions>
・ Inverse-gated-decoupling method
・ Measurement range: 6459.9Hz
・ Pulse delay time 30sec
Observation data point 10336
・ Pulse width (5.833μsec) 35 ° pulse ・ Solvent CD ₃ OH (deuterated methanol) (30% by weight)
・ Number of integration 128

  Under these conditions, the signal of the obtained chart belongs to the following compound, so that it is possible to determine the relative quantitative ratio from the area ratio.

For example, when the organic hydroxy compound is a phosphorous oxide of “2-hydroxyethyl methacrylate”, it can be assigned as follows.
・ 1.8 ppm to 2.6 ppm: phosphoric acid ・ 0.5 ppm to 1.1 ppm: Monomer 3 (monoester)
-0.5 ppm to 0.1 ppm: monomer 4 (diester form)
-1.0 ppm to -0.6 ppm: Triester form -11.1 ppm to -10.9 ppm, -12.4 ppm to -12.1 ppm: Pyrophosphate monoester --12.0 ppm to -11.8 ppm: Pyrophosphate diester -11.2 ppm to -11.1ppm: pyrophosphoric acid, other peaks: unknown

  The phosphoric acid content in the mixed monomer is quantified to determine the contents of monomer 3 and monomer 4. Specifically, the calculation is performed as follows.

  The absolute amount (% by weight) of the phosphoric acid content in the sample is determined by gas chromatography. From the P-NMR results, the relative molar ratio of phosphoric acid, monomer 3 (hereinafter also referred to as mono-isomer), and monomer 4 (hereinafter also referred to as di-isomer) in the sample was determined, and the absolute amount of phosphoric acid was used as a reference. To calculate the absolute amount of the mono and di bodies.

[Phosphoric acid content]
The conditions for gas chromatography are as follows.
Sample: Methylation with diazomethane Example) Methylation by adding 1 to 1.5 cc of diazomethane in diethyl ether to 0.1 g of sample Column: Ultra ALLOY, 15 m × 0.25 mm (inner diameter) × 0.15 μmdf
Carrier gas: He, split ratio 50: 1
Column temperature: 40 ° C. (5 min) (hold) → 10 ° C./min (temperature rise) → 15 min after reaching 300 ° C. Hold inlet temperature: 300 ° C.
Detector temperature: 300 ° C
Under the above conditions, a phosphate-derived peak is detected around 9 minutes, and the phosphate content in the unknown sample can be calculated by a calibration curve method.

[Content of mono- and di-form]
Based on the phosphoric acid content determined above, the total amount of mono- and di-isomers in the reagents used in Examples and the like described below was calculated as follows. The pyrophosphoric acid monoester, pyrophosphoric acid diester, and pyrophosphoric acid were calculated by assigning the decomposition products to phosphoric acid and the monoester compound in consideration of hydrolysis during the polymerization process.
・ Ethyleneglycol methacrylate phosphate (Aldrich reagent): 86.4% by weight
・ Hosmer M: 81.8% by weight
-Light ester P1M: 88.8% by weight

When the charged molar ratio of the monomer is calculated based on the breakdown of the mono- and di-forms from the above results and the NMR results, it is as follows in the case of the polymer B-1 production example described below.
Ω-methoxy polyethylene glycol monomethacrylate (addition mole number of ethylene oxide 23: NK ester M230G manufactured by Shin-Nakamura Chemical Co., Ltd.) = 30 mol%
・ Mono (2-hydroxyethyl) methacrylate = 49 mol%
-Di- (2-hydroxyethyl) phosphate ester = 21 mol%

  Further, as the monomers 3 and 4, a phosphate ester (Y) obtained by reacting the organic hydroxy compound represented by the general formula (5) with a phosphorylating agent can be used.

  1-20 are preferable, as for m4 in General formula (5), 1-10 are more preferable, and 1-5 are especially preferable.

  Phosphoric acid ester (Y) has an organic hydroxy compound and a phosphorylating agent in a ratio defined by the following formula (I) of 2.0 to 4.0, more preferably 2.5 to 3.5, particularly 2.8. What was obtained by making it react on the conditions of -3.2 is preferable.

In the present invention, in the formula (I), the phosphorylating agent is treated as P ₂ O ₅ .n (H ₂ O) for convenience.

  Examples of the phosphorylating agent include orthophosphoric acid, phosphorus pentoxide (anhydrous phosphoric acid), polyphosphoric acid, phosphorus oxychloride and the like, and orthophosphoric acid and phosphorus pentoxide are preferable. These may be used alone or in combination of two or more. The amount of the phosphorylating agent in the reaction of the organic hydroxy compound and the phosphorylating agent can be appropriately determined according to the target phosphate ester composition.

The phosphorylating agent includes phosphorous pentoxide (Z-1) and at least one (Z-2) selected from the group consisting of water, phosphoric acid and polyphosphoric acid (hereinafter referred to as phosphorylating agent (Z)). In this case as well, in the formula (I), phosphorylation containing phosphorus pentoxide (Z-1) and at least one selected from the group consisting of water, phosphoric acid and polyphosphoric acid (Z-2) The agent (Z) is treated as P ₂ O ₅ · n (H ₂ O) for convenience.

Further, the number of moles of the phosphorylating agent defined by the formula (I) means the amount of phosphorous agent introduced into the reaction system as a raw material, particularly the amount of P ₂ O ₅ units derived from the phosphorylating agent (Z) (mole). ). The number of moles of water indicates the amount (mole) of water (H ₂ O) derived from the phosphorylating agent (Z) introduced into the reaction system as a raw material. That is, the reaction system includes water when polyphosphoric acid is represented as (P ₂ O ₅ .xH ₂ O) and orthophosphoric acid is represented as [1/2 (P ₂ O ₅ .3H ₂ O)]. It will contain all the water present in it.

  Moreover, 20-100 degreeC is preferable and, as for the temperature at the time of adding a phosphorylating agent to an organic hydroxy compound, 40-90 degreeC is more preferable. The time required for adding the phosphorylating agent to the reaction system (the time from the start of addition to the end of addition) is preferably 0.1 hour to 20 hours, and more preferably 0.5 hour to 10 hours.

  The temperature of the reaction system after adding the phosphorylating agent is preferably 20 to 100 ° C, more preferably 40 to 90 ° C.

  After completion of the phosphorylation reaction, the produced phosphoric acid condensate (an organic compound having phosphoric acid bond or phosphoric acid) may be reduced by hydrolysis, or the polymer B may be produced without hydrolysis. It is suitable as the monomer.

The polymer B according to the present invention is a phosphate ester polymer obtained by copolymerizing the monomer 1, the monomer 3, and the monomer 4. It is also preferable to use a mixed monomer containing monomer 3 and monomer 4.

  The preferable thing of the monomers 1, 3, and 4 is as above-mentioned, respectively, and the above-mentioned commercial item and reaction product can also be used.

  In the copolymerization of the monomers, the molar ratio of the monomer 1 to the monomers 3 and 4 is as follows: monomer 1 / (monomer 3 + monomer 4) = 5/95 to 95/5, Furthermore, 10/90 to 90/10 are preferable. The molar ratio of monomer 1, monomer 3 and monomer 4 is as follows: monomer 1 / monomer 3 / monomer 4 = 5 to 95/3 to 90/1 to 80 (this is This means that the monomer 1 is 5 to 95, the monomer 3 is 3 to 90, and the monomer 4 is 1 to 80 (the total is 100), and further 5 to 96/3 to 80 / 1-60 is preferable. In addition, about the monomer 3 and the monomer 4, a molar ratio and mol% shall be calculated based on an acid type compound (hereinafter the same).

  Moreover, in manufacture of the polymer B, it is preferable that the ratio of the monomer 4 is 1-60 mol% in the whole monomer used for reaction, and also it is 1-30 mol%.

  The molar ratio of monomer 3 to monomer 4 is preferably monomer 3 / monomer 4 = 99/1 to 4/96, more preferably 99/1 to 5/95.

  From the viewpoint of suppressing gelation, it is preferable to use the monomer solution containing monomer 3 and / or monomer 4 for the reaction at a pH of 7 or less.

Hereinafter, more preferable production conditions will be described from the viewpoints of gelation suppression, adjustment of a suitable molecular weight, and performance design of a dispersant for hydraulic composition. From such a viewpoint, at the time of copolymerization, 4 mol% or more, further 6 mol% or more, particularly 8 mol% or more of the chain transfer agent is used with respect to the total number of moles of the monomers 1, 3 and 4. It is preferable. Further, the upper limit of the amount of the chain transfer agent used is preferably 100 mol% or less, more preferably 60 mol% or less, still more preferably 30 mol% or less, based on the total number of moles of the monomers 1, 3 and 4. Most preferably, it can be 15 mol% or less. For more details,
(1) In the case where r of monomer 1 is 3 to 30,
(1-1) When the total molar ratio of the monomers 1, 3 and 4 of the monomer 3 and the monomer 4 is 50 mol% or more, the chain transfer agent is the monomer 1, 3 and 4 It is preferable to use 6 to 100 mol%, particularly 8 to 60 mol%, based on the total of
(1-2) When the molar ratio in the sum of the monomers 1, 3 and 4 of the monomer 3 and the monomer 4 is less than 50 mol%, the chain transfer agent is the monomer 1, 3 and It is preferable to use 4 to 60 mol%, particularly 5 to 30 mol%, based on the total of 4.
(2) When r of monomer 1 used for polymer B is more than 30, the chain transfer agent is used in an amount of 6 to 50 mol%, particularly 8 to 40 mol%, based on monomers 1 to 3. Is preferred.

  The reaction rate of the monomers 3 and 4 is preferably 60% or more, more preferably 70% or more, more preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more. It can be selected from the viewpoint. Here, the reaction rate of the monomers 3 and 4 is calculated by the following equation.

In addition, the ratio (mol%) of the ethylenically unsaturated bond of the monomer 3 and the monomer 4 in the phosphorus-containing compound in the reaction system at the start and end of the reaction is measured by the following ¹ H-NMR. It can be calculated based on the result.
[ ¹ H-NMR conditions]
The polymer B dissolved in water and dried under reduced pressure is dissolved in deuterated methanol at a concentration of 3 to 4% by weight, and ¹ H-NMR is measured. The residual ratio of ethylenically unsaturated bonds is measured by an integral value of 5.5 to 6.2 ppm. In addition, the measurement of ¹ H-NMR uses “Mercury 400 NMR” manufactured by Varian, the number of data points is 42052, the measurement range is 6410.3 Hz, the pulse width is 4.5 μs, the pulse waiting time is 10 S, and the measurement temperature is 25.0 ° C. Perform under conditions.

  In the production of the polymer B, in addition to the monomers 1, 3, and 4, one or more other copolymerizable monomers can be used. Examples of other copolymerizable monomers include allyl sulfonic acid, methallyl sulfonic acid, any of these alkali metal salts, alkaline earth metal salts, ammonium salts, and amine salts. In addition, acrylic monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and the like, and any one or more of alkali metal salts, alkalis Anhydrous compounds such as earth metal salts, ammonium salts, amine salts, methyl esters, ethyl esters and maleic anhydride may also be used. Furthermore, (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, 2- (meth) acrylamide-2-metasulfonic acid, 2- (meth) acrylamide-2-ethanesulfonic acid, Examples include 2- (meth) acrylamide-2-propanesulfonic acid, styrene, styrenesulfonic acid and the like. Furthermore, as described in Japanese Patent No. 3336456, polyalkylene polyamine and dibasic acid or ester of dibasic acid and lower alcohol having 1 to 4 carbon atoms, acrylic acid or methacrylic acid or acrylic acid or methacrylic acid and carbon. A polyamide polyamine monomer obtained by adding an alkylene oxide having 2 to 4 carbon atoms to an amino residue of a polyamide polyamine obtained by condensing an ester with a lower alcohol having 1 to 4 atoms; As described in JP-A-2004-2174, an ester of a polyalkylene polyamine and a dibasic acid and / or a dibasic acid and an alcohol having 1 to 4 carbon atoms, and (meth) acrylic acid and / or (meth) acrylic acid And polyunsaturated bonds obtained by reacting esters of alcohols having 1 to 4 carbon atoms A polyamide polyamine monomer obtained by adding an alkylene oxide having 2 to 4 carbon atoms to the amino residue and imino group of an amide polyamine, a single amount of an amine alkylene oxide adduct as described in JP-A-2003-335563 And polyalkyleneimine alkylene oxide adduct monomers as described in JP-A No. 2004-342050, poly (polyoxyalkylene) unsaturated monomers as described in JP-A No. 2004-67934, and the like. It is done. The total proportion of the monomers 1, 3, and 4 in all monomers is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, particularly preferably 75 to 100 mol%, and more than 95 mol% to 100 Mol%, more preferably 97 to 100 mol%, and particularly preferably 100 mol%.

  Even in the above case, the content of the monomer 2 represented by the above general formula (2) in all monomers used for the production of the polymer B is necessary when used in the dispersant of the present invention. From the viewpoint of addition amount and viscosity reduction, it is preferably 20 mol% or less, more preferably 15 mol% or less, and even more preferably 10% or less, based on all monomers.

  In the production of the polymer B, the monomers are preferably copolymerized in the presence of a predetermined amount of a chain transfer agent. Moreover, you may use the other monomer, polymerization initiator, etc. which can be copolymerized.

  The reaction temperature of the monomers 1, 3 and 4 is preferably 40 to 100 ° C., more preferably 60 to 90 ° C., and the reaction pressure is 101.3 to 111.5 kPa (1 to 1.1 atm) in gauge pressure. 3-106.4 kPa (1-1.05 atm) is preferred.

  The pH of the reaction system can be adjusted with an inorganic acid (phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, etc.), NaOH, KOH, triethanolamine, or the like, if necessary.

  Here, the monomer solution containing the monomer 3 and / or the monomer 4 is preferably a water-containing system (that is, the solvent contains water) for pH measurement. May be measured by adding the required amount of water. From the viewpoint of uniformity of the monomer solution, prevention of gelation, and suppression of performance degradation, the pH is preferably 7 or less, more preferably 0.1 to 6, and further preferably 0.2 to 4.5. Monomer 1 is also preferably used as a monomer solution having a pH of 7 or less. This pH is at 20 ° C.

  In the present invention, the pH at 20 ° C. of the reaction solution collected during the reaction (from the start of the reaction to the end of the reaction) is defined as the pH during the reaction. It is preferable to start the reaction under conditions that clearly show that the pH during the reaction is 7 or less (monomer ratio, solvent, other components, etc.).

  When the reaction system is non-aqueous, it can be measured by adding an amount of water capable of measuring pH to the reaction system.

In the production method of the polymer B, the monomers 1, 3 and 4 are usually reacted under the consideration of other conditions if they are reacted under the conditions exemplified in the following (1) and (2). The pH inside is considered to be 7 or less.
(1) A monomer solution having a pH of 7 or less containing all of the monomers 1, 3, and 4 is used for the copolymerization reaction of the monomers 1, 3, and 4.
(2) The copolymerization reaction of the monomers 1, 3, and 4 is started at pH 7 or less. That is, the reaction is started after the reaction system containing the monomers 1, 3 and 4 is brought to pH 7 or lower.

[Chain transfer agent]
The chain transfer agent has a function of causing a chain transfer reaction in radical polymerization (a reaction in which a growing polymer radical reacts with another molecule to move a radical active site). It is a substance to be added, and is preferably used in the polymerization from the viewpoints of suppressing gelation, adjusting the suitable molecular weight, and designing the performance of the dispersant for hydraulic composition.

  Examples of chain transfer agents include thiol chain transfer agents and halogenated hydrocarbon chain transfer agents, and thiol chain transfer agents are preferred.

As the thiol chain transfer agent, those having a —SH group are preferable, and in particular, the general formula HS—R—Eg (wherein R represents a hydrocarbon-derived group having 1 to 4 carbon atoms, and E is − OH, —COOM, —COOR ′ or —SO ₃ M group, M represents a hydrogen atom, monovalent metal, divalent metal, ammonium group or organic amine group, and R ′ represents an alkyl having 1 to 10 carbon atoms. In which g represents an integer of 1 to 2, for example, mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, Examples include octyl thioglycolate, octyl 3-mercaptopropionate, and the like from the viewpoint of chain transfer effect in a copolymerization reaction including monomers 1 to 3. Mercaptoethanol are preferable, more preferably mercaptopropionic acid. These 1 type (s) or 2 or more types can be used.

  Examples of the halogenated hydrocarbon chain transfer agent include carbon tetrachloride and carbon tetrabromide.

  Examples of other chain transfer agents include α-methylstyrene dimer, terpinolene, α-terpinene, γ-terpinene, dipentene, 2-aminopropan-1-ol and the like. A chain transfer agent can use 1 type (s) or 2 or more types.

[Polymerization initiator]
In the production method of the polymer B, it is preferable to use a polymerization initiator. In particular, the polymerization initiator is 5 mol% or more, further 7 to 50 mol% based on the total number of moles of the monomers 1, 3 and 4. In particular, it is preferable to use 10 to 30 mol%.

  Examples of aqueous polymerization initiators include ammonium persulfate salt or alkali metal salt, hydrogen peroxide, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis (2-methylpropionamide) dihydrate, etc. These water-soluble azo compounds can be used. In addition, an accelerator such as sodium bisulfite and an amine compound can be used in combination with the polymerization initiator.

[solvent]
Production of the polymer B can be carried out by a solution polymerization method, and the solvent used in that case contains water or water and methyl alcohol, ethyl alcohol, isopropyl alcohol acetone, methyl ethyl ketone, or the like. Examples of the solvent include hydrous solvents. In view of handling and reaction equipment, water is preferred. Particularly when an aqueous solvent is used, it is preferable that the monomer solution containing the monomer 3 and / or the monomer 4 has a pH of 7 or less, more preferably 0.1 to 6, particularly 0.2 to 4. It is preferable to carry out a copolymerization reaction by using it from the viewpoint of uniformity (handleability) of the monomer mixture, monomer reaction rate, and crosslinking by hydrolysis of a pyro compound of a phosphoric acid compound.

  An example of the manufacturing method of the polymer B is shown. A predetermined amount of water is charged into a reaction vessel, the atmosphere is replaced with an inert gas such as nitrogen, and the temperature is raised. Prepare monomer 1, monomer 3, monomer 4, chain transfer agent mixed and dissolved in water, and polymerization initiator dissolved in water for 0.5 to 5 hours. Drip into the reaction vessel. At that time, each monomer, chain transfer agent and polymerization initiator may be dropped separately, or a mixed solution of monomers can be charged in a reaction vessel in advance and only the polymerization initiator can be dropped. is there. That is, the chain transfer agent, the polymerization initiator, and other additives may be added as an additive solution separately from the monomer solution, or may be added to the monomer solution after being added. From the viewpoint of stability, it is preferable to supply the reaction system as an additive solution separately from the monomer solution. In any case, the pH of the solution containing the monomer 3 and / or the monomer 4 is preferably 7 or less. Further, the copolymerization reaction is preferably performed with an acid agent or the like while maintaining the pH at 7 or less, and preferably aging is performed for a predetermined time. The polymerization initiator may be added dropwise at the same time as the monomer, or may be added in portions, but it is preferable to add in portions in terms of reducing unreacted monomers. For example, in the total amount of the polymerization initiator to be finally used, 1/2 to 2/3 polymerization initiator is added simultaneously with the monomer, and the remainder is aged for 1 to 2 hours after the completion of the monomer dropping, It is preferable to add. If necessary, it is further neutralized with an alkali agent (such as sodium hydroxide) after completion of ripening to obtain the phosphate ester polymer according to the present invention. This production example is suitable as a method for producing the polymer B according to the present invention.

  The total amount of the monomers 1, 3 and 4 and other copolymerizable monomers in the reaction system is preferably 5 to 80% by weight, more preferably 10 to 65% by weight, and particularly preferably 20 to 50% by weight. .

  The polymer B preferably has a weight average molecular weight (Mw) of 10,000 to 150,000. This polymer B has a Mw of 10,000 or more, preferably 12,000 or more, more preferably 13,000 or more, more preferably 14,000 or more, from the viewpoint of the expression of the dispersion effect and the viscosity reduction effect. Particularly preferably, it is 15,000 or more, and it is 150,000 or less, preferably 130,000 or less, more preferably from the viewpoints of high molecular weight by crosslinking, suppression of gelation and performance in terms of dispersion effect and viscosity reduction effect. 120,000 or less, more preferably 110,000 or less, particularly preferably 100,000 or less, and from the viewpoints of both, preferably 12,000 to 130,000, more preferably 13,000 to 120,000, More preferably, it is 14,000-110,000, Most preferably, it is 15,000-100,000. It is preferable to have Mw in this range and Mw / Mn is 1.0 to 2.6. Here, Mn is a number average molecular weight.

Mw and Mn of the polymer B are those measured by gel permeation chromatography (GPC) method under the following conditions. In addition, Mw / Mn of the phosphate ester type polymer in the present invention is calculated based on the peak of the polymer.
[GPC conditions]
Column: G4000PWXL + G2500PWXL (Tosoh)
Eluent: 0.2M phosphate buffer / CH ₃ CN = 9/1
Flow rate: 1.0mL / min
Column temperature: 40 ° C
Detection: RI
Sample size: 0.2mg / mL
Reference material: Polyethylene glycol equivalent

  The phosphate ester polymer satisfying Mw / Mn as described above has an appropriate branched structure by suppressing cross-linking by the monomer 3 which is a diester body, and has a structure in which adsorbing groups are densely present in the molecule. It is thought to form. Further, since the degree of dispersion Mw / Mn is controlled within a predetermined range, it approaches a system in which molecules of the same size are monodispersed, so that it is considered possible to increase the amount of adsorption on the adsorption target substance (for example, cement particles). Satisfying both of these conditions makes it possible to densely pack the substance to be adsorbed, such as cement particles, and is estimated to be effective in achieving both a dispersibility and a viscosity reducing effect. Mw / Mn can be controlled by adjusting the amount of the chain transfer agent, for example. When the amount of the chain transfer agent is increased, Mw / Mn tends to decrease.

  Further, in the chart pattern showing the molecular weight distribution obtained by the GPC method under the above conditions, the area having a molecular weight of 100,000 or more is 5% or less of the total area of the chart, so that dispersibility (required addition amount reduction) It is more preferable in terms of the viscosity reducing effect.

  The Mw / Mn of the phosphate ester polymer according to the present invention as described above is 1.0 from the viewpoint of ensuring practical production ease, dispersibility, viscosity reduction effect, and versatility with respect to materials and temperature. From the viewpoint of achieving both dispersibility and viscosity reduction effect, 2.6 or less is preferable, more preferably 2.4 or less, more preferably 2.2 or less, still more preferably 2.0 or less, particularly preferably. From the viewpoint of combining the above two points, it is preferably 1.0 to 2.4, more preferably 1.0 to 2.2, more preferably 1.0 to 2.0, and particularly preferably. Is 1.0 to 1.8.

<Dispersant for hydraulic composition>
The dispersant of the present invention contains a polymer A and a polymer B. Although the blending ratio can be arbitrarily adjusted depending on the purpose of use, the weight ratio of the polymer A and the polymer B (polymer A / polymer B) is preferably Polymer A / Polymer B) = 95/5 to 5/95, more preferably 90/10 to 10/90, still more preferably 80/20 to 20/80. Further, from the viewpoint of improving the viscosity reduction effect, the ratio of the polymer A is preferably small, (polymer A / polymer B) = 70/30 to 15/85, more preferably 60/40 to 15/85. More preferably, it is 50 / 50-20 / 80.

  In order to express the effect of further reducing the viscosity while maintaining the effect of low temperature dependence, it is necessary to use a polymer A ′ having a total average addition mole number r of AO of monomer 1 of 3 to 100. preferable.

  In order to obtain a quick hardening effect in addition to the viscosity reduction effect with less temperature dependence, it is necessary to use a polymer A ′ having a total average addition mole number r of AO of monomer 1 of 50 to 300. preferable.

  Further, the fluidity retention can be controlled by the copolymerization ratio of the polymer A (especially the polymer A ′) and / or the polymer B. That is, the fluidity retention can be improved by increasing the content of the monomer 1 of the polymer A (particularly the polymer A ′) and / or the polymer B.

  For example, as shown in Table 1, the polymer used in the present invention has the number of moles of AO added to the monomer 1 used for the polymer A ′ or B, and 4 types of a-1, a-2, b-1 and b-2 in the charged molar ratio (mol%) of monomer 2 or (total of monomer 3 and monomer 4) with respect to the total charged amount Can be classified into groups. Within the same group, it is preferable to change the charged molar ratio of monomer 2 (total of monomer 3 and monomer 4) depending on the number of moles of AO added to monomer 1. The a-1 and b-1 groups are excellent in fluidity immediately after kneading with a low addition amount, and can mainly bear the performance of viscosity reduction. The a-2 and b-2 groups have a slower adsorption rate to the hydraulic substance than the a-1 and b-1 groups, but the fluidity is obtained over time, and is mainly responsible for fluid retention. be able to.

  When the polymer A ′ is selected from the a-1 group, it is preferable that the polymer B is selected from the b-1 group from the viewpoint of further reducing the viscosity. Furthermore, it is preferable to further use the polymer B selected from the group b-2 from the viewpoint of less temperature dependence and improving fluidity retention.

  When the polymer A ′ is selected from the a-2 group, it is preferable to select the polymer B from the b-1 group from the viewpoint of viscosity reduction effect and temperature dependency. Furthermore, it is preferable to further use the polymer B selected from the group b-2 from the viewpoint of improving fluidity retention.

  The dispersant of the present invention can be obtained, for example, by mixing an aqueous solution containing the polymer A and an aqueous solution containing the polymer B. From the viewpoint of workability, it is preferably liquid.

  The dispersant of the present invention has a solid content concentration of 0.02 to 1 part by weight, more preferably 0.04 to 0.4 part by weight, based on 100 parts by weight of the hydraulic powder. It is preferable that the solid content concentration of the combined B is 0.02 to 1 part by weight, and more preferably 0.04 to 0.4 part by weight because the temperature dependency is small and the viscosity reducing effect is compatible.

  The dispersant of the present invention can also contain other additives (materials). For example, resin soap, saturated or unsaturated fatty acid, sodium hydroxystearate, lauryl sulfate, alkylbenzene sulfonic acid (salt), alkane sulfonate, polyoxyalkylene alkyl (phenyl) ether, polyoxyalkylene alkyl (phenyl) ether sulfate (salt) ), Polyoxyalkylene alkyl (phenyl) ether phosphates (salts), protein materials, AE agents such as alkenyl succinic acid and α-olefin sulfonate; oxy such as gluconic acid, glucoheptonic acid, alabonic acid, malic acid, citric acid Delayers such as carboxylic acids, dextrins, monosaccharides, oligosaccharides, polysaccharides, etc .; foaming agents; thickeners; silica sand; AE water reducing agents; calcium chloride, calcium nitrite, calcium nitrate , Cal bromide Soluble calcium salts such as um, calcium iodide, chlorides such as iron chloride and magnesium chloride, sulfates, potassium hydroxide, sodium hydroxide, carbonates, thiosulfates, formic acid (salts), alkanolamines, etc. Strong agent or accelerator; foaming agent; waterproofing agent such as resin acid (salt), fatty acid ester, oil, fat, silicone, paraffin, asphalt, wax; blast furnace slag; fluidizing agent; dimethylpolysiloxane series, polyalkylene glycol fatty acid ester series Anti-foaming agents such as mineral oils, fats and oils, oxyalkylenes, alcohols, amides, etc .; antifoaming agents; fly ash; melamine sulfonic acid formalin condensates, aminosulfonic acids, polymaleic acid, etc. Agent: Silica fume; Anticorrosive agent such as nitrite, phosphate, zinc oxide; Methyl cellulose, Hydroxyethyl cell Cellulose series such as loose, natural products such as β-1,3-glucan, xanthan gum, synthetic system such as polyacrylic acid amide, polyethylene glycol, EO adduct of oleyl alcohol, or a reaction product of this with vinylcyclohexene diepoxide And water-soluble polymers such as alkyl emulsions such as alkyl (meth) acrylates. In the total solid content of the dispersant, the total concentration of the polymer A and the polymer B is preferably 0.02 to 1% by weight, more preferably 0.04 to 0.4% by weight.

<Hydraulic composition>
The hydraulic powder used in the hydraulic composition that is the target of the dispersant of the present invention is a powder having physical properties that is cured by a hydration reaction, and examples thereof include cement and gypsum. Preferred are ordinary Portland cement, Belite cement, medium heat cement, early strong cement, super early strong cement, sulfate resistant cement, etc., and blast furnace slag, fly ash, silica fume, stone powder (calcium carbonate powder), etc. May be added. In addition, the hydraulic composition finally obtained by adding sand, sand and gravel as aggregates to these powders is generally called mortar, concrete, etc., respectively. The dispersant of the present invention is not only in the field of ready-mixed concrete and concrete vibration products, but also for self-leveling, for refractories, for plaster, for gypsum slurry, for lightweight or heavy concrete, for AE, for repair, for prepacked, for trayy, It is useful in any field of various concrete such as grout, ground improvement, and cold.

  The hydraulic composition has a water / hydraulic powder ratio [weight percentage (% by weight) of water and hydraulic powder in the slurry, usually abbreviated as W / P. Abbreviated as / C. It can be 65% by weight or less, further 10 to 60% by weight, further 12 to 57% by weight, further 15 to 55% by weight, especially 20 to 55% by weight. In particular, the effect of the dispersant of the present invention is remarkably exhibited even when the unit water content is as low as 40% by weight or less.

  Further, the hydraulic composition containing the dispersant of the present invention is excellent in viscosity reduction and stable in fluid retention, so that the filling property to the mold is remarkable under vibration and is hardened. The voids and bubbles generated on the concrete surface are reduced, which is effective in improving the surface aesthetics. In the present invention, there is provided a method for producing a concrete product in which a hydraulic composition containing the dispersant of the present invention is filled in a mold and molded, and then appropriately cured, followed by demolding. From the viewpoint of sufficiently filling the mold with the hydraulic composition, it is preferable to perform compaction with a vibrator after filling the mold. As for the fluidity of the hydraulic composition (green concrete) used in this method, the slump value (JIS A 1101) is preferably 1 cm to 23 cm, and the slump flow value (JIS A 1150) is preferably 30 cm to 75 cm.

Polymer A Production Example 1
A glass reaction vessel with a stirrer (four-necked flask) was charged with 246.4 g of water, purged with nitrogen while stirring, and heated to 56 ° C. in a nitrogen atmosphere. The mixture of 148.8 g of ω-methoxypolyethyleneglycol methacrylate (10 moles added of ethylene oxide), 39.2 g of methacrylic acid and 2.32 g of 3-mercaptopropionic acid and 43.3 g of 5% aqueous solution of ammonium persulfate took 1.5 hours each. And dripped. Thereafter, aging was performed at the same temperature (56 ° C.) for 3 hours. After completion of the aging, the mixture was neutralized with 48% sodium hydroxide to pH = 6 to obtain a polymer A-1 having a weight average molecular weight of 47,000. Similarly, polymers A-2 and A-7 were produced.

Polymer A Production Example 2
A glass reaction vessel with a stirrer (four-necked flask) was charged with 281.4 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. ω-methoxypolyethylene glycol methacrylate (added mole number of ethylene oxide 120) 336.5g, methacrylic acid 22.2g and 2-mercaptoethanol 1.89g dissolved in water 238.2g and ammonium persulfate 3.68g dissolved in water 45g Each was dropped over 1.5 hours. Subsequently, 1.47 g of ammonium persulfate dissolved in 15 g of water was added dropwise over 30 minutes, and then aging was performed at the same temperature (80 ° C.) for 1 hour. After completion of ripening, neutralization was performed with 18.7 g of 48% sodium hydroxide to obtain a polymer A-3 having a weight average molecular weight of 76000. Similarly, Polymer A-4 was produced.

Polymer A Production Example 3
A glass reaction vessel with a stirrer (four-necked flask) was charged with 1053.1 g of water, purged with nitrogen while stirring, and heated to 78 ° C. in a nitrogen atmosphere. 884.5 g of ω-methoxypolyethylene glycol methacrylate (additional mole number of ethylene oxide 120), 28.1 g of methacrylic acid, 98.5 g of methyl acrylate and 5.11 g of 2-mercaptoethanol dissolved in 526.5 g of water and 11.18 g of ammonium persulfate in water The two dissolved in 63.4 g were added dropwise over 1.5 hours. Subsequently, a solution obtained by dissolving 3.73 g of ammonium persulfate in 21.1 g of water was dropped over 30 minutes, and then aging was performed at the same temperature (78 ° C.) for 1 hour. After completion of aging, the mixture was neutralized with 69.4 g of 20% sodium hydroxide to obtain a polymer A-5 having a weight average molecular weight of 81,000.

Polymer B Production Example 1
A glass reaction vessel (four-necked flask) with a stirrer was charged with 218 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. ω-methoxypolyethyleneglycol monomethacrylate (addition mole number of ethylene oxide 23, methacrylic acid content; 0% by weight: NK ester M230G manufactured by Shin-Nakamura Chemical Co., Ltd.), mono (2-hydroxyethyl) methacrylic acid phosphate and phosphoric acid A mixture of 32.3 g of a di-[(2-hydroxyethyl) methacrylic acid] ester (Phosmer M: Unichemical Co., Ltd.) and 1.1 g of 3-mercaptopropionic acid in 55 g of water and ammonium persulfate. Two of 3.8 g dissolved in 43 g of water were added dropwise over 1.5 hours. After aging for 1 hour, 1.9 g of ammonium persulfate dissolved in 22 g of water was added dropwise over 30 minutes, and then aging was performed at the same temperature (80 ° C.) for 1.5 hours. After completion of the aging, the polymer was neutralized with 40.1 g of a 20% aqueous sodium hydroxide solution to obtain a polymer B-1 having a weight average molecular weight of 51000 and Mw / Mn = 1.50. (PH during polymerization: 0.9, reaction rate 100%) Polymers B-2, B-3, and B-5 were similarly produced.

Polymer B Production Example 2
A glass reaction vessel (four-necked flask) equipped with a stirrer was charged with 471 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 290 g of ω-methoxypolyethylene glycol monomethacrylate (average added mole number of ethylene oxide 9) (effective content 84.4%, moisture 10%, methacrylic acid content; 0.9% by weight based on ω-methoxypolyethylene glycol monomethacrylate) ) And phosphoric acid ester (A) 93.8 g and 3-mercaptopropionic acid 11.3 g and ammonium persulfate. Two of the 8.2 g dissolved in 46 g of water were added dropwise over 1.5 hours. After aging for 1 hour, a solution prepared by dissolving 3.3 g of ammonium persulfate in 19 g of water was dropped over 30 minutes, and then aging was performed at the same temperature (80 ° C.) for 1.5 hours. After completion of aging, the mixture was neutralized with 58.2 g of a 32% aqueous sodium hydroxide solution to obtain a copolymer B-4 having a weight average molecular weight of 25000 and Mw / Mn = 1.66. (Monomer polymerization pH: 1.2, reaction rate 99%)

The phosphoric acid ester (A) is obtained by the following production method. Charge 200g 2-hydroxyethyl methacrylate and 36.0g 85% phosphoric acid (H ₃ PO ₄ ) into the reaction vessel and add 89.1g phosphorous pentoxide (anhydrous phosphoric acid) (P ₂ O ₅ ) to a temperature of 60 ° C. Gradually added while cooling so as not to exceed. After completion, the reaction temperature was set to 80 ° C., the reaction was performed for 6 hours, and after cooling, a phosphoric acid ester (A) was obtained.

Polymer B Production Example 3
In a glass reaction vessel (four-necked flask) with a stirrer, 180 g of water and ω-methoxypolyethylene glycol monomethacrylate (addition mole number of ethylene oxide 23, methacrylic acid content; 0% by weight: NK ester M230G manufactured by Shin-Nakamura Chemical Co., Ltd.) After 94 g and 8.8 g of sodium methallyl sulfonate were charged and dissolved, a mixture of mono (2-hydroxyethyl) methacrylic acid phosphate and di-[(2-hydroxyethyl) methacrylic acid] phosphate (Etylene glycol) Add 32.1 g of methacrylate phosphate (Aldrich reagent), add 30% sodium hydroxide solution to adjust the pH to 8.5, replace with nitrogen while stirring, and then raise the temperature to 60 ° C in a nitrogen atmosphere. did. Ammonium persulfate. What melt | dissolved 1.8g in water 43.2g was dripped over 1.0 hour. Thereafter, aging was performed at the same temperature (60 ° C.) for 3.0 hours to obtain a polymer B-6 having a weight average molecular weight of 47000 and Mw / Mn = 1.85. (Monomer polymerization pH: 8.5, reaction rate 100%)

  The monomer molar ratios of the above production examples are summarized in Tables 4 and 5.

<Evaluation 1>
With respect to the dispersants obtained by using the polymers A and B obtained above as shown in Tables 6 and 7, tests were conducted on the mortars with the formulations shown in Table 2 and the concretes with the formulations shown in Table 3. The results are shown in Tables 6 and 7. Evaluation was performed by the following methods for mortar viscosity, steam curing strength, and flow retention.

[Mortar test]
(1) Mortar combination

The materials used in Table 2 are as follows.
C: Ordinary cement (1: 1 mixture of ordinary Portland cement manufactured by Taiheiyo Cement Co., Ltd. and ordinary Portland cement manufactured by Sumitomo Osaka Cement Co., Ltd.)
W: Ion exchange water S: Mountain sand from Kimitsu, Chiba Prefecture

(2) Preparation of mortar Into a container (1 L stainless beaker: inner diameter 120 mm), about 1/2 amount of S of the composition shown in Table 2 is added, then C is added, and the remaining S is further added as a stirrer. Mixing of dispersant and water premixed after 200 seconds of air kneading using EYELA Z-2310 (Tokyo Rika Instruments, stirring rod: height 50 mm, inner diameter 5 mm × 6 pieces / length 110 mm) The solution was added over 5 seconds, the material between the wall and the stirring bar was scraped off for 30 seconds after the addition, and water was added and kneaded for 3 minutes to prepare a mortar. In addition, an antifoamer was added as needed, and it adjusted so that entrained air amount might be 2% or less.

(3) Evaluation (3-1) Viscosity Using a cone having an upper opening diameter of 70 mm, a lower opening diameter of 100 mm, and a height of 60 mm, the addition amount of the polymer is determined so that the mortar flow value is 190 to 210 mm. The torque applied to the mortar at this time was detected by connecting a recorder to the torque tester shown in FIG. 1, and the mortar was previously determined from the torque-viscosity relational expression created with polyethylene glycol (Mw20,000) shown in FIG. The viscosity was calculated from the torque. At the time of creating the torque-viscosity relational expression of polyethylene glycol, the torque output voltage value (mV) is recorded from the recorder by the monitor output 60W and the output signal DC0-5V. In this evaluation, it is desirable that the mortar viscosity is 4000 mPa · s or less. In addition, 190-210 mm of this mortar flow value is an average value of the maximum value of the mortar flow value and the mortar flow value measured in the direction perpendicular to the length of 1/2 of the line segment that gives the maximum value.

(3-2) Steam Curing Strength The mortar prepared as described above is filled into a 4 cm × 4 cm × 16 cm mold, left at 20 ° C. for 1 hour, and then placed in a steam curing tank preliminarily adjusted to 70 ° C., after 4 hours. After taking out and leaving still at 20 degreeC for 1 hour, it demolded and measured steam hardening intensity | strength according to JISA1108.

[Concrete test]
(1) Concrete mix The concrete mix is as shown in Table 3.

The materials used in Table 3 are as follows.
C: Ordinary Portland cement (1: 1 mixture of ordinary Portland cement manufactured by Taiheiyo Cement Co., Ltd. and ordinary Portland cement manufactured by Sumitomo Osaka Cement Co., Ltd.)
W: Ion-exchange water S: Fine aggregate, mountain sand from Kimitsu, Chiba G: Coarse aggregate, lime crushed stone from Mt. Torigata, Kochi

(2) Preparation of concrete Using a forced biaxial mixer manufactured by IHI as a mixer to be used, concrete was prepared in a concrete volume of 30 liters, stirring time for 10 seconds, and 90 seconds after adding kneaded water. At that time, the addition amount of the copolymer was adjusted so that the slump flow value was 350 to 420 mm. The slump flow value is an average value of the maximum slump flow value and the slump flow value measured in a direction perpendicular to the length of a half of the line segment giving the maximum value. Table 6 shows the amount of copolymer added (effective weight% in cement) necessary to achieve this slump flow at a concrete temperature of 20 ° C. (20 to 22 ° C.). In addition, the slump flow test of concrete is JIS A 1150 (maximum size of coarse aggregate (G) 20 mm, concrete temperature 20-22 ° C., how to pack samples: packed in 3 layers, and each layer with 25 push rods. I followed. The amount of concrete air (JIS A 1128) was adjusted by adding an antifoaming agent and an AE agent so that the amount of entrained air was 3.5 to 5.5% by volume. The addition amount of the copolymer at a concrete temperature of 10 ° C. (10 to 12 ° C.) was the same as that of the concrete test at 20 ° C.

(3) Flow retention ratio The ratio of the initial concrete flow value (concrete flow value immediately after stirring) of the concrete prepared above and the concrete flow value after 15 minutes was defined as the flow retention ratio (%). Here, the fluid retention is calculated by the following equation.
Fluid retention (%) = (A / B) × 100
A: Concrete flow value after 15 minutes (mm) -200 (mm)
B: Concrete flow value immediately after stirring (mm) -200 (mm)
(Because a slump cone with a lower inner diameter of 200 mm is used, A and B are reduced by 200)

  The closer the value of the fluid retention is to 100, the more the fluidity does not change after 15 minutes. In addition, this fluid retention was measured about each of concrete temperature 20 degreeC and 10 degreeC. A smaller difference in flow retention between 20 ° C. and 10 ° C. (shown as an absolute value in the table) means a smaller change in behavior of flow retention due to temperature difference.

The symbols in the table are as follows. In the table, the numbers in parentheses are EO average addition moles. MEPEG-E: ω-methoxypolyethylene glycol monomethacrylate,
MAA: methacrylic acid, AA-Me: methyl acrylate, HEMA-MPE: 2-hydroxyethyl methacrylate monophosphate, HEMA-DPE: 2-hydroxyethyl methacrylate diphosphate, Mw: weight average molecular weight, Mn: number average Molecular weight

It shows that temperature dependency is so small that the difference of a flow retention is small. The difference in fluid retention is 15%
It is suitable that it is below, preferably 10% or below. In addition, since Example 7 contains B-6 as the polymer B, Examples 1 and 8 have a large content of the polymer A, so that the mortar viscosity is increased.

<Evaluation 2>
With respect to the dispersant obtained by using the polymer A and the polymer B obtained above as shown in Table 9, tests were conducted on the concrete having the composition shown in Table 8. The results are shown in Table 9. Evaluation performed the surface aesthetics of concrete with the following method.

(1) Concrete mix

The materials used in Table 8 are as follows.
W: Tap water C: Ordinary Portland cement (specific gravity 3.16)
S: Fine sand, land sand from Kimitsu, Chiba Prefecture (specific gravity 2.61)
G: Coarse aggregate, crushed stone from Yura, Wakayama (specific gravity 2.61)

(2) Preparation of concrete All materials were charged under the blending conditions shown in Table 8 and kneaded with a biaxial mixer for 90 seconds. The concrete slump was adjusted with the dispersant shown in Table 9 so as to be 8 cm to 12 cm. A fatty acid ester antifoaming agent (Formrex 797, manufactured by Nikka Chemical Co., Ltd.) was added to the dispersant in an amount of 0.1%.

(3) Evaluation The prepared concrete is put into a steel mold having a length of 10 cm, a width of 20 cm, and a height of 20 cm, and is vibrated for 20 seconds with a table type vibrator (amplitude 0.15 mm, 3300 vpm). 2 hours after the introduction, the temperature was increased to 18 ° C./hr, the retention was 65 ° C. for 4 hours, and then the steam curing conditions were allowed to cool. After 24 hours, the mold was removed and the specimen surface 10 × 20 × 20 cm = 4000 cm ² The state of voids and bubbles was observed with the naked eye, and the surface aesthetics of the concrete skin surface was evaluated from the average of the four surfaces as follows. The results are shown in Table 9.
○: No bubbles of 3 mm or more Δ: Number of bubbles of 3 mm or more, 1 to 5 × Number of bubbles of 3 mm or more, 6 or more

* The blending ratio of the polymer A indicates (A1) / (A2).
** The blend ratio of the polymer B indicates (B1) / (B2).
***% by weight of concrete as an effective component of the total of polymer A and polymer B

Schematic diagram of torque tester and recorder used for measuring mortar viscosity in evaluation of examples Torque-viscosity relational expression with polyethylene glycol (weight average molecular weight 20,000) used for calculation of mortar viscosity in evaluation of Examples

Claims (10)

A polycarboxylic acid polymer A having a carboxylic acid group and an oxyalkylene group and / or an oxystyrene group;
Copolymerizing monomer 1 represented by the following general formula (1), monomer 3 represented by the following general formula (3), and monomer 4 represented by the following general formula (4) A polymer B obtained by
Dispersant for hydraulic composition containing

[In the formula, R ¹ and R ² are each a hydrogen atom or a methyl group, R ³ is a hydrogen atom, or — (CH ₂ ) _q (CO) _p O (AO) _r R ⁴ , and AO has 2 to 4 carbon atoms. An oxyalkylene group or an oxystyrene group, p is a number of 0 or 1, q is a number of 0 to 2, r is an average added mole number of AO, a number of 3 to 300, R ⁴ is a hydrogen atom or a carbon number of 1 Represents an alkyl group of ˜18. ]

[Wherein R ¹¹ is a hydrogen atom or a methyl group, R ¹² is an alkylene group having 2 to 12 carbon atoms, m1 is a number of 1 to 30, M ³ and M ⁴ are a hydrogen atom, an alkali metal or an alkaline earth metal, respectively. Represents. ]

[Wherein R ¹³ and R ¹⁵ are each a hydrogen atom or a methyl group, R ¹⁴ and R ¹⁶ are each an alkylene group having 2 to 12 carbon atoms, m2 and m3 are each a number of 1 to 30 and M ⁵ is Represents a hydrogen atom, an alkali metal or an alkaline earth metal. ] The polymer A is a polymer obtained by copolymerizing the monomer 1 represented by the following general formula (1) and the monomer 2 represented by the following general formula (2). Item 4. A hydraulic composition dispersant according to Item 1.

[In the formula, R ¹ and R ² are each a hydrogen atom or a methyl group, R ³ is a hydrogen atom, or — (CH ₂ ) _q (CO) _p O (AO) _r R ⁴ , and AO has 2 to 4 carbon atoms. An oxyalkylene group or an oxystyrene group, p is a number of 0 or 1, q is a number of 0 to 2, r is an average added mole number of AO, a number of 3 to 300, R ⁴ is a hydrogen atom or a carbon number of 1 Represents an alkyl group of ˜18. ]

Wherein, R ⁵ to R ⁷ are each a hydrogen atom, a methyl group or ^{_{(CH 2) s COOM 2,}} (CH 2) s COOM 2 is COOM ¹ or another (CH _{²⁾ s} COOM ₂ and anhydrous In this case, M ¹ and M ² of those groups are not present. s represents the number of 0-2. M ¹ and M ² each represent a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkyl ammonium group, a substituted alkyl ammonium group, an alkyl group, a hydroxyalkyl group, or an alkenyl group. ]   The dispersant for a hydraulic composition according to claim 1 or 2, wherein the polymer B is obtained by copolymerizing the monomers 1, 3, and 4 at a pH of 7 or less.   The dispersant for a hydraulic composition according to any one of claims 1 to 3, wherein the polymer B is obtained by copolymerizing the monomers 1, 3 and 4 in the presence of a chain transfer agent.   The dispersing agent for hydraulic compositions according to claim 4, wherein the chain transfer agent is used in an amount of 4 mol% or more based on the total number of moles of the monomers 1, 3, and 4.   The dispersing agent for hydraulic compositions according to any one of claims 1 to 5, comprising polymer A and polymer B in a weight ratio of 95/5 to 5/95 (polymer A / polymer B).   The weight average molecular weight (Mw) of the polymer B is 12,000 to 130,000, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 1.0 to 2.6. The dispersant for hydraulic compositions according to any one of claims 1 to 6.   A hydraulic composition containing hydraulic powder, water, and the dispersant for hydraulic composition according to claim 1.   A method for producing a concrete product comprising the hydraulic composition according to claim 8.   A method for producing a concrete product, wherein the hydraulic composition of claim 8 is filled in a mold and molded, and then demolded.

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