JP5311891B2 - Additive composition for hydraulic composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an additive composition for a hydraulic composition, with which kneadability and curing property, that cause trouble in cost aspect, can be simultaneously satisfied while securing good fresh physical properties in a hydraulic composition in which the ratio of water to a hydraulic powder is &lt;20 wt.%. <P>SOLUTION: The additive composition for a hydraulic composition contains a predetermined copolymer (A) and a compound (B) selected from predetermined glycol ether-based compounds and predetermined glycerol derivative-based compounds, and is suitably used in a hydraulic composition in which the ratio of water to a hydraulic powder is &lt;20 wt.%. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to an additive composition for a hydraulic composition and a hydraulic composition.

  Among the admixtures for hydraulic compositions, there is one called a high-performance water reducing agent having a large fluidity-imparting effect. Typical examples include naphthalene sulfonic acid formaldehyde condensate salt (naphthalene type), melamine sulfonic acid formaldehyde condensate salt (melamine type), polycarboxylic acid type having a polyoxyalkylene chain, and the like.

  A high-strength hydraulic composition (hereinafter referred to as high-strength concrete) has a smaller water / hydraulic powder ratio (hereinafter referred to as water / cement ratio) than a normal-strength (general strength) concrete. It is prepared by mixing. Such high-strength concrete compositions generally have problems such as long time required for kneading, large change in fluidity over time (fluidity increases and decreases with time), and high concrete viscosity. Furthermore, since the unit amount of the hydraulic powder during blending is larger than that of ordinary concrete, the amount of the high-performance water reducing agent for obtaining a predetermined fluidity is inevitably increased. As a result, the hydration of the hydraulic powder is delayed, and the cured physical properties such as condensation are greatly affected. When these high-strength hydraulic compositions are used practically, among these problems, the cost impact is particularly significant. The increase in the mixing time related to productivity and the cured material properties that are rate-limiting in the construction process. There are two points.

  The problem of kneading time and viscosity increase has not been sufficiently solved even with a polycarboxylic acid-based water reducing agent, and an additive having a higher concrete viscosity reducing effect is desired. In addition, an early strengthening agent has been proposed for improving the cured properties, but it is not sufficient.

From such a background, Patent Document 1 discloses the viscosity of high-strength concrete containing a vinyl copolymer containing a high-chain-length oxyalkylene group, a short-chain-length oxyalkylene group and a specific monomer as essential components. An admixture excellent in reduction and suppression of setting delay is disclosed. Patent Document 2 proposes a dispersant for a hydraulic composition containing a specific phosphate ester polymer. Patent Document 3 discloses a cement strength improver containing glycerin or a glycerin derivative and a specific polycarboxylic acid copolymer.
JP-A-11-157897 Japanese Patent Laid-Open No. 2007-182364 JP-A-2006-282414

  An object of the present invention is to simultaneously satisfy the kneading property and the cured material property that hinder the cost while ensuring good fresh properties in a hydraulic composition such as concrete in a high-strength region. It is to provide an additive composition that can impart such an effect to a hydraulic composition having a hydraulic powder ratio of less than 20% by weight.

  The present invention relates to at least one copolymer (A) selected from the group consisting of the following compounds (1), (2) and (3) [hereinafter referred to as component (A)], and the following general formula (B1). And one or more compounds (B) selected from the compounds represented by the following general formula (B2) [hereinafter referred to as component (B)], and the water / hydraulic powder ratio is It is related with the additive composition for hydraulic compositions used with the hydraulic composition of less than 20 weight%.

<Compound (1)>
A copolymer of an alkenyl ether derivative represented by the following general formula (A1) and a monomer represented by the following general formula (A3) or a salt thereof R ^1a (A ² O) _n1 R ^2a (A1)
(In the formula, R ^1a is an alkenyl group having 2 to 4 carbon atoms, A ² O is an oxyalkylene group having 2 or 3 carbon atoms, n1 is an average added mole number of A ² O, a number of 2 to 200, R ^2a represents an alkyl group having 1 to 3 carbon atoms.)

[Wherein, R ^{5a to} R ^7a are each independently a hydrogen atom, a methyl group, or (CH ₂ ) _p2 COOM ² , M ¹ and M ² are each independently a hydrogen atom or a cation, and p2 is 0 to 2 Represents the number of ]

<Compound (2)>
A monomer (i) represented by the following general formula (A2), one or more monomers (ii) selected from the compounds represented by the above general formula (A3) and the following general formula (A4); As a constituent unit, and a molar ratio thereof is (ii) / (i) = 70/30 to 95/5.

Wherein R ^3a and R ^4a are each independently a hydrogen atom or a methyl group, p1 is a number of 0 to 2, A ³ O is an oxyalkylene group having 2 or 3 carbon atoms, and n2 is an average addition of A ³ O. Number of moles, 100 to 300, X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

(In the formula, R ^8a represents a hydrogen atom or a methyl group, and Y represents a hydrogen atom or a cation.)

<Compound (3)>
Monomer (iii) represented by the following general formula (A5) and one or more monomers (ii) selected from the compounds represented by the general formula (A3) and the general formula (A4) As a constituent unit, and a molar ratio thereof is (ii) / (iii) = 60/40 to 90/10.

Wherein R ^9a and R ^10a are each independently a hydrogen atom or a methyl group, p3 is a number from 0 to 2, A ⁴ O is an oxyalkylene group having 2 or 3 carbon atoms, and n3 is an average addition of A ⁴ O. Number of moles, a number of 2 to 90, and X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

(In the formula, R ^1b is a hydrogen atom, a methyl group or an ethyl group, and Z is —OH or —O—CH ₂ CH ₂ —OH.)

(In the formula, A ¹ O represents an oxyalkylene group having 2 to 4 carbon atoms, m1, m2, and m3 each represent the number of added moles of A ¹ O, and the average value of the total of m1, m2, and m3 is 0.5. ~ 2.5.)

  Moreover, this invention relates to the hydraulic composition containing the additive composition for hydraulic compositions of the said invention, hydraulic powder, an aggregate, and water.

  According to the present invention, for a hydraulic composition having a water / hydraulic powder ratio of less than 20% by weight, a cured hydraulic composition having excellent productivity while maintaining good fresh physical properties, such as high-strength concrete. An additive composition for a hydraulic composition is obtained. When the additive composition of the present invention is used, in a hydraulic composition having a water / hydraulic powder ratio of less than 20% by weight, ultrahigh-strength concrete can be obtained in a short kneading time, and it has excellent early strength, so that it is demolded. The time can be shortened, that is, the construction period can be shortened. Ultimately, these effects lead to a reduction in construction costs.

<(A) component>
The component (A) is at least one copolymer selected from the group consisting of the following compounds (1), (2) and (3).
<Compound (1)>
Copolymer or salt thereof of an alkenyl ether derivative represented by the following general formula (A1) and a monomer represented by the following general formula (A3) R ^1a (A ² O) _n1 R ^2a (A1)
(In the formula, R ^1a is an alkenyl group having 2 to 4 carbon atoms, A ² O is an oxyalkylene group having 2 or 3 carbon atoms, n1 is an average added mole number of A ² O, a number of 2 to 200, R ^2a represents an alkyl group having 1 to 3 carbon atoms.)

[Wherein, R ^{5a to} R ^7a are each independently a hydrogen atom, a methyl group, or (CH ₂ ) _p2 COOM ² , M ¹ and M ² are each independently a hydrogen atom or a cation, and p2 is 0 to 2 Represents the number of ]

<Compound (2)>
A monomer (i) represented by the following general formula (A2), one or more monomers (ii) selected from the compounds represented by the above general formula (A3) and the following general formula (A4); As a constituent unit, and a molar ratio thereof is (ii) / (i) = 70/30 to 95/5.

Wherein R ^3a and R ^4a are each independently a hydrogen atom or a methyl group, p1 is a number of 0 to 2, A ³ O is an oxyalkylene group having 2 or 3 carbon atoms, and n2 is an average addition of A ³ O. Number of moles, 100 to 300, X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

(In the formula, R ^8a represents a hydrogen atom or a methyl group, and Y represents a hydrogen atom or a cation.)

<Compound (3)>
Monomer (iii) represented by the following general formula (A5) and one or more monomers (ii) selected from the compounds represented by the general formula (A3) and the general formula (A4) As a constituent unit, and a molar ratio thereof is (ii) / (iii) = 60/40 to 90/10.

Wherein R ^9a and R ^10a are each independently a hydrogen atom or a methyl group, p3 is a number from 0 to 2, A ⁴ O is an oxyalkylene group having 2 or 3 carbon atoms, and n3 is an average addition of A ⁴ O. Number of moles, a number of 2 to 90, and X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

[Compound (1)]
In the general formula (A1) of the alkenyl ether derivative constituting the compound (1) of the present invention, the alkenyl group having 2 to 4 carbon atoms represented by R ^1a is preferably a vinyl group, an allyl group, a methallyl group, or the like. However, an allyl group is more general and more preferable. A ² O is an oxyethylene group and / or an oxypropylene group, and the addition form may be single, random, block or alternating. An oxyethylene group is preferred. R ^2a is an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. From the viewpoint of dispersibility of concrete, a methyl group is preferred.

  The average number of added moles n1 of alkylene oxide is in the range of 2 to 200, preferably 2 to 90, more preferably 10 to 70, and more preferably 10 to 50, from the viewpoint of imparting fluidity and low viscosity to fresh concrete. preferable.

  Examples of the monomer represented by the general formula (A3) include unsaturated monocarboxylic acid monomers such as acrylic acid, methacrylic acid, and crotonic acid, maleic anhydride, maleic acid, itaconic anhydride, itaconic acid, and fumaric acid. Unsaturated dicarboxylic acid monomers such as these, or alkali metal salts, alkaline earth metal salts, ammonium salts, mono-, di-, and trialkylammonium salts optionally having a hydroxyl group are preferred, and acrylics are more preferred. Acid, methacrylic acid and alkali metal salts thereof.

  The compound (1) of the present invention is a copolymer of the monomer represented by the general formula (A1) and the monomer represented by the general formula (A-3), preferably in a molar ratio of Monomer of formula (A1) / monomer of general formula (A3) = a copolymer of 25/75 to 50/50 or a salt thereof. When the monomer of the general formula (A3) is maleic acid, an anhydride may be used. Examples of the method for producing the compound (1) include methods described in JP-A-2-163108 and JP-A-5-345647.

  Moreover, the preferable weight average molecular weight of a compound (1) is 3000-300,000, Furthermore, 5000-100,000 from a viewpoint of the stable fluidity | liquidity provision of fresh concrete.

  Examples of the compound (1) include Marialim EKM, Marialim AKM (manufactured by NOF Corporation) and Super 200 (manufactured by Electrochemical Co., Ltd.).

[Compound (2)]
The compound (2) of the present invention comprises a monomer (i) represented by the general formula (A2) obtained by adding 100 to 300 moles of an alkylene oxide having 2 or 3 carbon atoms in an average addition mole number, and the general formula (A3) and / or (A4), preferably the monomer (ii) represented by the general formula (A3), at a molar ratio of (ii) / (i) = 70/30 to 95/5 Obtained by polymerization. From the viewpoint of imparting stable initial fluidity of fresh concrete, the average added mole number n2 of alkylene oxide in monomer (i) is in the range of 100 to 300, preferably 100 to 250, more preferably 100 to 200, 100-150 is still more preferable. In addition, in the monomer for obtaining a compound (2), when using several monomer (i) from which n2 differs, the average value of n2 of all the monomers (i) is in the range of 100-300. Adjust the composition to be. For example, when two types of monomers (i) are used, one is n2 = 100 to 290, the other is n2 ′ = 100 to 300, preferably n2 ≠ n2 ′ and n2 ′ ≧ n2 + 10, and n2 ′ It is more preferable that ≧ n2 + 30, and it is even more preferable that n2 ′ ≧ n2 + 50. Furthermore, a monomer having n2 of less than 100 may be used in combination as long as the effects of the present invention are not impaired.

  As the monomer (i) represented by the general formula (A2), an esterified product of a polyalkylene glycol having a single-end alkyl group blocked such as methoxypolyethylene glycol, methoxypolypropylene glycol, ethoxypolyethylenepolypropyleneglycol and (meth) acrylic acid Also, EO and PO adducts to (meth) acrylic acid are preferably used. The additional form may be single, random, block, or alternating. More preferably, it is an esterified product of methoxypolyethylene glycol and (meth) acrylic acid, and an esterified product of methoxypolyethylene glycol and methacrylic acid having an average added mole number of ethylene oxide of 100 to 200 is more preferable.

  As the monomer represented by the monomer represented by the general formula (A3), those exemplified in the compound (1) can be used.

  Examples of the monomer represented by the general formula (A4) include allyl sulfonic acid, methallyl sulfonic acid, or an alkali metal salt, alkaline earth metal salt, ammonium salt, or mono or di group in which a hydroxyl group may be substituted. Trialkylammonium salts are used.

  Preferably, the compound (2) is a monomer (i) represented by the general formula (A2) and one or more monomers (ii) represented by the general formulas (A3) and (A4). And a monomer mixture containing 50% by weight or more, more preferably 80 to 100% by weight or more, and even more preferably 100% by weight.

  The monomer (i) of the general formula (A2) constituting the compound (2) and the monomer (ii) of the general formula (A3) and / or the general formula (A4) are (ii) / (i) = Copolymerized at a molar ratio of 70/30 to 95/5, and (ii) / (i), preferably 75/25 to 95/5, more preferably from the viewpoint of imparting stable initial fluidity of fresh concrete Is copolymerized at a molar ratio of 80/20 to 95/5, more preferably 85/15 to 95/5.

  The weight average molecular weight of the compound (2) is preferably in the range of 5,000 to 500,000 from the viewpoint of imparting stable initial fluidity of fresh concrete, and in the range of 20,000 to 100,000, and more preferably in the range of 30,000 to 85,000, imparting initial fluidity of fresh concrete. Excellent effect. The weight average molecular weight is determined by gel permeation chromatography (in terms of standard substance sodium polystyrene sulfonate).

  Compound (2) can be produced by a known method. Examples thereof include solution polymerization methods described in JP-A-7-223852, JP-A-4-209737, and JP-A-58-74552. In water and lower alcohols having 1 to 4 carbon atoms, ammonium persulfate, In the presence of a polymerization initiator such as hydrogen oxide, sodium bisulfite, mercaptoethanol or the like may be added if necessary and reacted at 50 to 100 ° C. for 0.5 to 10 hours.

  Other copolymerizable monomers can be used in combination as a raw material for the compound (2). Specifically, acrylonitrile, alkyl (meth) acrylate (C1-12) ester, (meth) acrylamide, styrene, styrene sulfonic acid Etc.

[Compound (3)]
The compound (3) of the present invention includes a monomer (iii) represented by the general formula (A5) in which an alkylene oxide having 2 or 3 carbon atoms is added in an average addition mole number of 2 to 90 moles, and the general formula (A3) and / or (A4), preferably the monomer (ii) represented by the general formula (A3), at a molar ratio of (ii) / (iii) = 60/40 to 90/10 Obtained by polymerization. From the viewpoint of imparting stable fluidity and fluidity retention of fresh concrete, the average added mole number n3 of alkylene oxide in the monomer (iii) is in the range of 2 to 90, preferably 5 to 70, and 5 to 50. Is more preferable, and 5 to 40 is even more preferable. In addition, in the monomer mixture for obtaining the compound (3), when a plurality of monomers (iii) having different n3 are used, the average value of n3 of all the monomers (d) is in the range of 2 to 90. The composition is adjusted to For example, when two types of monomers (iii) are used, it is preferable that one is n3 = 2 to 87, the other is n3 ′ = 2 to 90, n3 ≠ n3 ′ and n3 ′ ≧ n3 + 3, and n3 ′ ≧ n3 + 5 is more preferable, and n3 ′ ≧ n3 + 10 is still more preferable. Furthermore, a monomer having n3 exceeding 90 can be used in combination as long as the effects of the present invention are not impaired.

  As the monomer (iii) represented by the general formula (A5), an esterified product of a polyalkylene glycol having a single-end alkyl group blocked such as methoxypolyethylene glycol, methoxypolypropylene glycol, ethoxypolyethylenepolypropyleneglycol and (meth) acrylic acid Also, EO and PO adducts to (meth) acrylic acid are preferably used. The additional form may be single, random, block, or alternating. More preferably, it is an esterified product of methoxypolyethylene glycol and (meth) acrylic acid, and an esterified product of methoxypolyethylene glycol and methacrylic acid having an EO average addition mole number of 2 to 90 is still more preferable. From the viewpoint of achieving both salt resistance in concrete and low viscosity of concrete, the average added mole number of EO is preferably 4 to 80, and more preferably 9 to 40.

  As the monomer represented by the general formula (A3) and the monomer represented by the general formula (A4), those exemplified in the compounds (1) and (2) can be used.

  Preferably, the compound (3) is a monomer (iii) represented by the general formula (A5) and one or more monomers (ii) represented by the general formulas (A3) and (A4). And a monomer mixture containing 50 wt% or more, further 80 to 100 wt% or more, and further 100 wt%.

  The monomer (iii) of the general formula (A5) constituting the compound (3) and the monomer (ii) of the general formula (A3) and / or the general formula (A4) are represented by (ii) / (iii) = Copolymerized at a molar ratio of 60/40 to 90/10, and (ii) / (iii), preferably 65/35 to 90/10, more preferably from the viewpoint of imparting stable fluidity retention of fresh concrete Is copolymerized in a molar ratio of 65/35 to 85/15, more preferably 65/35 to 80/20.

  The weight average molecular weight of the compound (3) is preferably in the range of 5,000 to 500,000 from the viewpoint of the fluidity of fresh concrete, and in the range of 20,000 to 100,000 and further in the range of 30,000 to 85,000 is more excellent due to the fluidity of fresh concrete. The weight average molecular weight is determined by gel permeation chromatography (in terms of standard substance sodium polystyrene sulfonate).

  Compound (3) can be produced by a known method. Examples thereof include solution polymerization methods described in JP-A-7-223852, JP-A-4-209737, and JP-A-58-74552. In water and lower alcohols having 1 to 4 carbon atoms, ammonium persulfate, In the presence of a polymerization initiator such as hydrogen oxide, sodium bisulfite, mercaptoethanol or the like may be added if necessary and reacted at 50 to 100 ° C. for 0.5 to 10 hours.

  As a raw material for the compound (3), other copolymerizable monomers can be used in combination. Specifically, acrylonitrile, alkyl (meth) acrylate (1 to 12 carbon atoms) ester, (meth) acrylamide, styrene, styrene sulfonic acid Etc.

<(B) component>
The component (B) is one or more compounds selected from the compound represented by the general formula (B1) and the compound represented by the general formula (B2).

In General Formula (B1), R ^1b is a hydrogen atom, a methyl group, or an ethyl group, and Z is —OH or —O—CH ₂ CH ₂ —OH. Examples of the compound of the general formula (B1) include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,2-butanediol and the like, and diethylene glycol and 1,2-butanediol are preferable from the viewpoint of improving the surface appearance. .

In the general formula (B2), A ¹ O is an oxyalkylene group having 2 to 4 carbon atoms, preferably an oxyalkylene group having 2 or 3 carbon atoms, and more preferably an oxyalkylene group having 2 carbon atoms.

Moreover, m1, m2 and m3 in the general formula (B2) each represent the number of added moles of A ¹ O, and the average value of the sum of m1, m2 and m3 (m1 + m2 + m3) is 0 from the viewpoint of improving the surface aesthetics. 0.5 to 2.5, preferably 0.5 to 2.0, more preferably 0.5 to 1.5.

  The compound of the general formula (B2) can be obtained as a mixture of glycerin and an alkylene oxide adduct of glycerin (1 mol adduct, 2 mol adduct, 3 mol adduct of glycerin). That is, a mixture of compounds represented by the following general formula (B2 ′) can be used.

(In the formula, A ¹ O is an oxyalkylene group having 2 to 4 carbon atoms, and m 1 ′, m 2 ′ and m 3 ′ are each the added mole number of A ¹ O, and each is an integer of 0 or 1 or more. , M1 ′, m2 ′ and m3 ′ are integers in which the average value of the sum of m1 ′, m2 ′ and m3 ′ in the mixture is 0.5 to 2.5.)

  In that case, the total proportion of alkylene oxide 1 to 3 mol adduct of glycerin in the mixture (a compound in which the sum of m1 ′, m2 ′ and m3 ′ is an integer of 1 to 3) is improved in surface aesthetics and production cost. From the viewpoint, it is preferably 40% by weight or more, more preferably 50 to 100% by weight, and still more preferably 60 to 100% by weight. Moreover, the ratio of the alkylene oxide 1 mol adduct of glycerin in the mixture is preferably 10% by weight or more, more preferably 20 to 100% by weight, further 20 to 60% by weight, and still more preferably 20 to 40% by weight from the same viewpoint. The proportion of the glycerin alkylene oxide 2 mol adduct is 5% by weight or more, more preferably 10 to 30% by weight, and the proportion of the glycerin alkylene oxide 3 mol adduct is 0 to 25% by weight, more preferably 0 to 10% by weight. preferable. Further, from the viewpoint of improving the surface aesthetics, the proportion of glycerin (alkylene oxide 0 mol adduct) in the mixture is preferably 0 to 60% by weight, more preferably 0 to 40% by weight, and still more preferably 0 to 20% by weight. The proportion of the adduct having 4 moles or more of alkylene oxide is preferably 0 to 30% by weight, more preferably 0 to 15% by weight, and still more preferably 0 to 5% by weight. The proportion is preferably 60% by weight or less, more preferably 50% by weight or less, and still more preferably 40% by weight or less.

<Additive composition for hydraulic composition>
In the additive composition for a hydraulic composition of the present invention, the total content of the component (A) is preferably 5% by weight or more from the viewpoint of lowering the mortar viscosity as the effective component concentration, and the product is uniform. From the viewpoint of stabilization, 50% by weight or less is preferable. Therefore, 5 to 50 weight% is preferable, More preferably, it is 10 to 40 weight%, More preferably, it is 20 to 35 weight%.

  From the viewpoint of imparting fluidity retention of fresh concrete, the component (A) preferably contains the compound (3). Of these, the compound (3) alone or the combination of the compound (2) and the compound (3) is preferable. In the component (A), the compound (3) is preferably 50% by weight or more, more preferably 50 to 90% by weight, and still more preferably 60 to 80% by weight. In addition, the compound (2) is 1 to 40% by weight, more preferably 10 to 35% in the component (A), from the viewpoint of improving the early strength and kneading property and maintaining low viscosity and fluidity retention. % By weight, more preferably 20-30% by weight.

  In the additive composition for a hydraulic composition of the present invention, the content of the component (B) is preferably 5% by weight or more from the viewpoint of improving demolding strength as the concentration of the effective component, and the product is uniform. From the viewpoint of stabilization, it is preferably 95% by weight or less. Accordingly, it is preferably 5 to 95% by weight, more preferably 10 to 50% by weight, and still more preferably 20 to 30% by weight.

  In the additive composition for hydraulic composition of the present invention, the weight ratio of the total amount of component (A) and the total amount of component (B) is effective from the viewpoint of workability and early strength of the hydraulic composition. In conversion, (A) / (B) is preferably 30/70 to 99/1, more preferably 45/55 to 97/3, still more preferably 50/50 to 90/10.

  Moreover, in the additive composition for hydraulic compositions of the present invention, the total content of the component (A) and the component (B) is from the viewpoint of handleability, such as the measurement of the additive composition for hydraulic compositions. It is preferably 10 to 100% by weight in terms of effective content, more preferably 10 to 60% by weight, more preferably 15 to 40% by weight, and still more preferably 20 to 40% by weight.

  The additive composition for a hydraulic composition of the present invention is composed of (A) component (effective component) and (B) component with respect to the hydraulic powder from the viewpoint of workability and early strength of the hydraulic composition. It is preferably used in a proportion of 0.1 to 10% by weight in total of (effective amount), more preferably 0.2 to 5% by weight, more preferably 0.2 to 3% by weight.

  From the viewpoint of fluidity of the hydraulic composition, the additive composition for hydraulic composition of the present invention has (A) component (effective content) of 0.01 to 10% by weight with respect to the hydraulic powder. It is preferably used in a proportion, more preferably 0.1 to 5% by weight, more preferably 0.1 to 2% by weight.

  Moreover, the additive composition for hydraulic compositions of the present invention has a component (B) (effective content) of 0.01 to 1 with respect to the hydraulic powder from the viewpoint of the early strength of the hydraulic composition. It is preferable to use it in the ratio of weight%, More preferably, it is 0.05-0.7 weight%, More preferably, it is 0.1-0.5 weight%.

  The additive composition of the present invention is an additive composition for a hydraulic composition having a water / hydraulic powder ratio of less than 20% by weight. In such an ultrahigh strength hydraulic composition, the initial flow The mechanism that makes it possible to achieve both compatibility (slump flow value) and fast-curing is in the adsorbability of the component (B) to the cement mineral and the timing at which fluidity is imparted to the concrete by the component (A). For example, by adding ethylene oxide (hereinafter referred to as EO) to glycerin, the affinity with water is increased and the adsorption to cement is delayed. Therefore, since the component (B) acts on the cement mineral when the dispersion effect by the component (A) is sufficiently expressed, the dispersibility is not greatly impaired even if the early strength is expressed. However, if the number of moles of EO added to glycerin is too large, the adsorptive action on cement is weakened, and early strength cannot be obtained. In addition, while general concrete is produced in a short kneading time of about 30 seconds, in a hydraulic composition having a water / hydraulic powder ratio of less than 20% by weight, the kneading time is It will be quite long (for example, 8 minutes as in the examples below). In such kneading for a long time, glycerin not added with EO is adsorbed to the cement too early, so it adsorbs to the cement at the initial stage of kneading, and the form of the cement mineral involved in the early strength changes due to the kneading for a long time. End up. In combination, it is considered that in the hydraulic composition having a water / hydraulic powder ratio of less than 20% by weight, the original fast-acting effect of glycerin is weakened. Therefore, it is considered that the initial fluidity is increased to some extent.

<(C) component>
The additive composition for hydraulic composition of the present invention contains the above component (A) and component (B), and further, as component (C), a single amount represented by the following general formula (C1) Phosphoric acid ester system obtained by copolymerizing the body 1, the monomer 2 represented by the following general formula (C2), and the monomer 3 represented by the following general formula (C3) at a pH of 7 or less A polymer (C) can be contained.

[Wherein, R ^1c and R ^2c are each independently a hydrogen atom or a methyl group, R ^3c is a hydrogen atom or —COO (AO) _n X, AO is a C 2-4 oxyalkylene group or oxystyrene group, p is the number of 0 or 1, n is the average added mole number of AO, 3 to 200, and X represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. ]

(In the formula, R ^4c represents a hydrogen atom or a methyl group, OR ^5c represents an oxyalkylene group having 2 to 12 carbon atoms, m4 represents a number of 1 to 30, and M represents a hydrogen atom or a cation.)

(Wherein R ^6c and R ^8c are each independently a hydrogen atom or a methyl group, OR ^7c and OR ^9c are each independently an oxyalkylene group having 2 to 12 carbon atoms, m5 and m6 are each independently 1 to 1) 30 number, M represents a hydrogen atom or a cation.)

  Component (C) of the present invention is a phosphate ester polymer obtained by copolymerizing monomer 1 and a mixed monomer including monomer 2 and monomer 3 at a pH of 7 or less. May be.

[Monomer 1]
For monomer 1, R ^3c in formula (C1) is preferably a hydrogen atom, AO is preferably an oxyalkylene group having 2 to 4 carbon atoms, and more preferably contains an ethyleneoxy group (hereinafter referred to as EO group). The EO group is preferably 70 mol% or more, more preferably 80 mol% or more, further 90 mol% or more, and even more preferably all EO groups. X is preferably a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, more preferably 1 to 12, further 1 to 4, and further 1 or 2, and more preferably a methyl group. Specific examples include ω-methoxypolyoxyalkylene methacrylate and ω-methoxypolyoxyalkylene acrylate, and ω-methoxypolyoxyalkylene methacrylate is more preferable. Here, n in the general formula (C1) is 3 to 200, preferably 4 to 120, from the viewpoint of the dispersibility of the polymer in the hydraulic composition and the effect of imparting low viscosity. In addition, AO is different among n repeating units on average, and random addition, block addition, or a mixture thereof may be included. AO can contain a propyleneoxy group etc. besides EO group.

[Monomer 2]
Examples of the monomer 2 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.

[Monomer 3]
Examples of the monomer 3 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.

  Either monomer 2 or monomer 3 may be an alkali metal salt, alkaline earth metal salt, ammonium salt, alkylammonium salt or the like of these compounds.

  M4 of monomer 2 and m5 and m6 of monomer 3 are each preferably 1-20, more preferably 1-10, from the viewpoint of the adsorptivity of component (C) to the hydraulic powder. Is more preferable.

  As the monomer 2 and the monomer 3, a mixed monomer containing these can be used. That is, a commercially available product containing a monoester form and a diester form can be used. For example, Phosmer M, Phosmer PE, Phosmer P (Unichemical), JAMP514, JAMP514P, JMP100 (all are Johoku Chemical), Light Ester P -1M, light acrylate P-1A (all Kyoeisha Chemical), MR200 (Daihachi Chemical), Kayamar (Nippon Kayaku), Ethyleneglycol methacrylate phosphate (Aldrich Reagent), etc. are available.

Moreover, the mixed monomer containing the monomer 2 and the monomer 3 is, for example, an organic hydroxy compound represented by the general formula (C4), phosphoric anhydride (P ₂ O ₅ ), and water in a predetermined charging ratio. Can be produced as a reaction product.

(Wherein R ^11c represents a hydrogen atom or a methyl group, OR ^12c represents an oxyalkylene group having 2 to 12 carbon atoms, and m7 represents a number of 1 to 30.)

  1-20 are preferable, as for m7 in general formula (C4), 1-10 are still more preferable, and 1-5 are more preferable.

  The monomer 2 and the monomer 3 are phosphoric acid ester products of monomers having an unsaturated bond and a hydroxyl group, and the above-mentioned commercially available products and reaction products include a monoester (monomer 2) and It has been confirmed that a compound other than the diester (monomer 3) is contained. These other compounds are considered to be a mixture of polymerizable and non-polymerizable compounds. In the present invention, such a mixture can be used as it is.

  As described above, industrially, phosphate ester monomers are usually available as a mixture containing a monoester (monomer 2) and a diester (monomer 3). Among these, since diesters are likely to have a high molecular weight (gelation) by crosslinking, such a mixture is restricted in production in fields using the properties, for example, thickeners, adhesives, coatings, etc. Can be used suitably without receiving much. On the other hand, in admixtures for hydraulic compositions (dispersants, water reducing agents, etc.), polymers containing phosphate groups are preferable because of their excellent adsorptive power to hydraulic substances, but dispersibility and viscosity are reduced by increasing the molecular weight. The effect is lowered, which is not preferable from the viewpoint of handleability. However, it is industrially disadvantageous to separate the monoester form and the diester form from the mixture of phosphate esters as raw materials from the application and economical properties of the hydraulic composition.

  From the viewpoint of fluidity and viscosity reduction, it is better to use a mixture of phosphate esters containing a large amount of monoester, but even if it contains a large amount of diester, By controlling the polymerization molar ratio, fluidity and viscosity reduction can be adjusted.

Moreover, as the monomers 2 and 3, phosphate ester (Y) obtained by reacting the organic hydroxy compound represented by the general formula (C4) with a phosphorylating agent can be used. That is, in the present invention, a phosphate ester copolymer obtained by copolymerizing the following (X) and (Y) at pH 7 or less can be used as the copolymer of the component (C).
(X) Monomer 1 represented by the general formula (C1).
(Y) Phosphate ester obtained by reacting the organic hydroxy compound represented by the general formula (C4) with a phosphorylating agent.

  This phosphate ester (Y) is obtained by phosphorylating the organic hydroxy compound represented by the general formula (C4) with a phosphorylating agent.

  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. Further, the phosphorylating agent (Z) described later is also preferable. In this invention, the quantity of the phosphorylating agent at the time of making an organic hydroxy compound and a phosphorylating agent react can be determined timely according to the target phosphate ester composition.

  The 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, further 2.5 to 3.5, and more preferably 2. What was obtained by making it react on the conditions of 8-3.2 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.

Further, the phosphorylating agent includes phosphorous pentoxide (Z-1) and at least one selected from the group consisting of water, phosphoric acid and polyphosphoric acid (Z-2) [hereinafter, phosphorylating agent (Z) In this case, too, the formula (I) includes phosphorus pentoxide (Z-1) and at least one selected from the group consisting of water, phosphoric acid and polyphosphoric acid (Z-2). For the sake of convenience, the phosphorylating agent (Z) is treated as P ₂ O ₅ .n (H ₂ O).

The number of moles of the phosphorylating agent defined by the formula (I) is the amount of P ₂ O ₅ unit derived from the phosphorylating agent introduced into the reaction system as a raw material, especially the phosphorylating agent (Z) ( Mol). 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)]. Contains all the water present within.

  Moreover, 20-100 degreeC is preferable and the temperature at the time of adding a phosphorylating agent to an organic hydroxy compound has still more preferable 40-90 degreeC. 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 from 0.1 hour to 20 hours, and more preferably from 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. The copolymerization can be carried out based on a method for producing a phosphate ester polymer described later.

  After completion of the phosphorylation reaction, the resulting phosphoric acid condensate (an organic compound or a phosphoric acid having a pyrophosphate bond) may be reduced by hydrolysis, or even without hydrolysis, the phosphoric acid of the present invention. It is suitable as a monomer for producing an ester polymer.

  The phosphate ester polymer as the component (C) of the present invention preferably has a weight average molecular weight (Mw) of 10,000 to 150,000. Moreover, it is preferable that Mw / Mn is 1.0-2.6. Here, Mn is the number average molecular weight. Mw is preferably 10,000 or more, more preferably 12,000 or more, still more preferably 13,000 or more, still more preferably 14,000 or more, and even more preferably 15 from the viewpoint of the expression of the dispersion effect and the viscosity reduction effect. 15,000 or less, preferably 150,000 or less, more preferably 130,000 or less, and still more preferably 120,000 from the viewpoints of high molecular weight by crosslinking, suppression of gelation, and performance in terms of dispersion effect and viscosity reduction effect. Or less, more preferably 110,000 or less, still more preferably 100,000 or less. Therefore, from the viewpoints of the both, preferably 12,000 to 130,000, more preferably 13,000 to 120,000, More preferably, 14,000 to 110,000, still more preferably 15,000 to 100,000. A. It is preferable to have Mw in this range and Mw / Mn is 1.0 to 2.6. Here, the value of Mw / Mn represents the degree of dispersion of the molecular weight distribution, and the closer to 1, the closer the molecular weight distribution to monodispersion, and the farther from 1 (larger), the wider the molecular weight distribution.

  The phosphate ester polymer according to the present invention having the above Mw / Mn value is a polymer having a branched structure based on a diester structure, but has a great feature that the molecular weight distribution is very narrow. Such a phosphoric ester polymer of the present invention can be suitably produced by a production method described later.

  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 reducing effect, it is 2.6 or less, preferably 2.4 or less, more preferably 2.2 or less, still more preferably 2.0 or less, and still more 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, still more preferably 1.0 to 2.0, and still more. Preferably it is 1.0-1.8.

Mw and Mn of the phosphate ester polymer according to the present invention are those measured by a 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, and has a structure in which adsorbing groups are closely 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.

  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.

In addition, since the double bond derived from a monomer has disappeared by ¹ H-NMR under the following conditions, the phosphate ester polymer according to the present invention is derived from monomers 1, 2, and 3, respectively. It is estimated that it has a constitutional unit.
[ ¹ H-NMR conditions]
A polymer 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 rate of double bonds is measured by an integrated 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. Performed under conditions.

  That is, the phosphoric acid ester-based polymer having the Mw / Mn value as described above has, as its constituent units, constituent units derived from monomer 1, constituent units derived from monomer 2, and constituents derived from monomer 3. Includes units. These structural units are structural units derived from the respective monomers incorporated into the polymer by cleavage of the ethylenically unsaturated bonds of monomers 1, 2, and 3 and addition polymerization. The ratio of these structural units in the polymer depends on the charging ratio, and when the monomers used for copolymerization are only monomers 1 to 3, the molar ratio of each structural unit is the monomer charging molar ratio. It is thought that it is almost the same.

<< Production Method of Phosphate Ester Polymer >>
The phosphate ester polymer according to the present invention is produced by a phosphate ester polymer production method in which the monomer 1, the monomer 2, and the monomer 3 are copolymerized at a pH of 7 or less. be able to. Moreover, it is preferable to use a mixed monomer containing monomer 2 and monomer 3.

  The phosphate ester polymer according to the present invention includes a monomer 1 having an oxyalkylene group represented by the general formula (C1) and a single monomer represented by the general formula (C2) having a phosphoric acid group. It is a polymer obtained by copolymerizing the body 2 and the monomer 3 represented by the general formula (C3).

  The preferable thing of the monomers 1-3 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 between the monomer 1 and the monomers 2 and 3 is as follows: monomer 1 / (monomer 2 + monomer 3) = 5/95 to 95/5 Furthermore, 10/90 to 90/10 are preferable. The molar ratio of monomer 1, monomer 2 and monomer 3 is as follows: monomer 1 / monomer 2 / monomer 3 = 5 to 95/3 to 90/1 to 80 / 5 to 96/3 to 80/1 to 60 (however, the total is 100) is preferable. In addition, about the monomer 2 and the monomer 3, the molar ratio and mol% shall be calculated based on an acid type compound (hereinafter the same).

  Moreover, in this invention, the ratio of the monomer 3 in all the monomers used for reaction can be 1-60 mol%, Furthermore, it can be 1-30 mol%.

  Further, the molar ratio of the monomer 2 and the monomer 3 can be set to monomer 2 / monomer 3 = 99/1 to 4/96, and more preferably 99/1 to 5/95.

Hereinafter, more preferable production conditions will be described from the viewpoint of gelation suppression, adjustment of a suitable molecular weight, and performance design as a dispersant. From this point of view, in the present invention, in the copolymerization, the chain transfer agent is 4 mol% or more, further 6 mol% or more, and further 8 mol% or more based on the total number of moles of monomers 1 to 3. Is preferably used. 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, and still more preferably relative to the total number of moles of monomers 1 to 3. Preferably it can be 15 mol% or less. For more details,
(1) When n of monomer 1 is 3 to 30,
(1-1) When the molar ratio of the monomer 2 and the monomer 3 in the monomers 1 to 3 is 50 mol% or more, the chain transfer agent is 6 to It is preferable to use 100 mol%, more preferably 8 to 60 mol%,
(1-2) When the molar ratio of the monomer 2 and the monomer 3 in the monomers 1 to 3 is less than 50 mol%, the chain transfer agent is 4 to 4 with respect to the monomers 1 to 3. It is preferable to use 60 mol%, more preferably 5 to 30 mol%,
(2) When n of monomer 1 exceeds 30, the chain transfer agent is preferably used in an amount of 6 to 50 mol%, more preferably 8 to 40 mol%, based on monomers 1 to 3.

  In the production method for obtaining the component (C) of the present invention, the reaction rate of the monomers 2 and 3 is 60% or more, further 70% or more, further 80% or more, further 90% or more, and further 95% or more. Preferably, the amount of chain transfer agent used can be selected from this point of view. Here, the reaction rate of the monomers 2 and 3 is calculated by the following equation.

The ratio (mol%) of monomer 2 and monomer 3 in the phosphorus-containing compound in the reaction system at the start and end of the reaction should be calculated based on the above ¹ H-NMR measurement results. Can do.

  In the production of the phosphate ester polymer according to the present invention, in addition to the monomers 1 to 3, other monomers capable of copolymerization 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, carboxylic acid 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 alkali metal salts, alkali 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. The total proportion of monomers 1 to 3 in all monomers is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, and even more preferably 75 to 100 mol%, and further achieves performance as a dispersant. From this viewpoint, it is preferable that the content be more than 95 mol% to 100 mol%, further 97 to 100 mol%, and more preferably 100 mol%.

  In addition, in the manufacturing method for obtaining (C) component of this invention, the reaction temperature of the monomers 1-3 is 40-100 degreeC, Furthermore, 60-90 degreeC is preferable, and reaction pressure is 101.3 in gauge pressure. ˜111.5 kPa (1 to 1.1 atm), more preferably 101.3 to 106.4 kPa (1 to 1.05 atm).

  In addition, a monomer solution containing the above monomer 2 and / or monomer 3 prepared with an appropriate solvent is co-polymerized with other monomers at a pH of 7 or less in the presence of a predetermined amount of chain transfer agent. It is preferable to polymerize. Moreover, you may use the other monomer, polymerization initiator, etc. which can be copolymerized.

  (C) component of this invention is obtained by making the monomer 1, the monomer 2, and the monomer 3 react at pH 7 or less. 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) may be 7 or less. Usually, the reaction may be started 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.

[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.

  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-based chain transfer agent, those having a —SH group are preferable, and further a 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 or 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, mercaptopropion. , 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 for obtaining the component (C) of the present invention, it is preferable to use a polymerization initiator, and the polymerization initiator is used in an amount of 5 mol% or more, further 7 to It is preferable to use 50 mol%, and further 10-30 mol%.

  As an aqueous polymerization initiator, persulfuric acid ammonium salt or alkali metal salt or hydrogen peroxide, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis (2-methylpropionamide) Water-soluble azo compounds such as dihydrate are used. In addition, an accelerator such as sodium bisulfite and an amine compound can be used in combination with the polymerization initiator.

[solvent]
In the production method for obtaining the component (A) of the present invention, it can be carried out by a solution polymerization method. As the solvent used in that case, water or water and methyl alcohol, ethyl alcohol, isopropyl alcohol Examples of the solvent include hydrous solvents containing acetone, methyl ethyl ketone, and the like. In view of handling and reaction equipment, water is preferred. In particular, when an aqueous solvent is used, a monomer solution containing monomer 2 and / or monomer 3 is used for the reaction at a pH of 7 or less, further 0.1 to 6, and further 0.2 to 4. Performing the polymerization reaction is preferable from the viewpoint of uniformity (handleability) of the monomer mixture, monomer reaction rate, and crosslinking by hydrolysis of the pyro compound of the phosphoric acid compound.

  An example of the manufacturing method for obtaining (C) component of this invention 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 2, monomer 3, chain transfer agent mixed and dissolved in water, and polymerization initiator dissolved in water, and take 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 2 and / or the monomer 3 is preferably 7 or less. Further, the copolymerization reaction is carried out with an acid agent or the like while maintaining the pH at 7 or less, and preferably aging is carried out 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.

  The total amount of the monomers 1, 2, 3 and other copolymerizable monomers in the reaction system is preferably 5 to 80% by weight, more preferably 10 to 65% by weight, even more preferably 20 to 50% by weight. preferable.

  In the present invention, the component (C) is preferably a copolymer in which the proportion of the monomer 1 is 50 mol% or less in the total amount of monomers from the viewpoint of kneading speed.

  In the additive composition for hydraulic composition of the present invention, the total content of the component (A) and the component (C) is preferably 5 to 50% by weight, more preferably 10 to 40% by weight. Moreover, it is preferable that the weight ratio of (A) component and (C) component is (A) / (C) = 100/1-100/40 in conversion of an effective part. In this weight ratio, the upper limit value occupied by the component (C) is preferably (A) / (C) = 100/35, more preferably 100/30, and even more preferably 100/25. On the other hand, the lower limit occupied by the component (C) is preferably (A) / (C) = 100/3, more preferably 100/5, and even more preferably 100/10.

  Since the component (C) has a branched structure (hyperbranch), it has a compact polymer form. Therefore, the amount of powder such as ultra-high-strength concrete is extremely large, and even in a split acid system where the distance between particles is narrow, it has high mobility and has a strong adsorptive group called a phosphate group. Also, since the adsorption speed is fast, there is an effect of improving the wettability of the cement powder with a small amount. For this reason, it is preferable to use the component (C) from the viewpoint of shortening the kneading time.

  The additive composition for a hydraulic composition of the present invention can be used for various inorganic hydraulic powders that exhibit curability by a hydration reaction, including various cements. The additive composition for hydraulic composition of the present invention may be in the form of powder or liquid. In the case of a liquid form, those using water as a solvent or a dispersion medium (such as an aqueous solution) are preferable from the viewpoint of workability and reduction of environmental load.

  Examples of the cement include ordinary Portland cement, early-strength Portland cement, ultra-early-strength Portland cement, and eco-cement (for example, JIS R5214). As hydraulic powder other than cement, blast furnace slag, fly ash, silica fume and the like may be included, and non-hydraulic limestone fine powder and the like may be included. Silica fume cement or blast furnace cement mixed with cement may be used.

  The additive composition for hydraulic compositions 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. Strongening 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, polyalkylene glycol fatty acid ester Anti-foaming agents such as mineral oils, fats and oils, oxyalkylenes, alcohols and amides; antifoaming agents; fly ash; high-performance water reducing agents such as melamine sulfonic acid formalin condensates and aminosulfonic acids; silica fume Rust preventives such as nitrite, phosphate, zinc oxide; cellulose such as methylcellulose and hydroxyethylcellulose; Water-based systems such as natural products such as β-type, β-1,3-glucan, xanthan gum, synthetic systems such as polyacrylic acid amide, polyethylene glycol, ethylene oxide adduct of oleyl alcohol or a reaction product thereof with vinylcyclohexene diepoxide Polymer emulsions such as alkyl (meth) acrylates.

  In addition, the additive composition for hydraulic composition of the present invention is used in the field of ready-mixed concrete, concrete vibration products, for self-leveling, for refractories, for plaster, for gypsum slurry, for lightweight or heavy concrete, for AE, It is useful in any field of various concrete such as repair, prepacked, torme, ground improvement, grout, and cold.

<Hydraulic composition>
The present invention provides a hydraulic composition having a water / hydraulic powder ratio of less than 20% by weight, comprising the additive composition for hydraulic composition of the present invention, a hydraulic powder, and water. To do.

  The hydraulic composition of the present invention is paste, mortar, concrete or the like containing water and hydraulic powder (cement), but may contain aggregate. Examples of the aggregate include fine aggregate and coarse aggregate. The fine aggregate is preferably mountain sand, land sand, river sand and crushed sand, and the coarse aggregate is preferably mountain gravel, land gravel, river gravel and crushed stone. Depending on the application, lightweight aggregates may be used. The term “aggregate” is based on “Concrete Overview” (published on June 10, 1998, published by Technical Shoin).

  The hydraulic composition has a water / hydraulic powder ratio [water and hydraulic properties in slurry from the viewpoint of producing concrete that can be constructed with higher strength while maintaining the amount of water necessary for the hydration reaction of cement. The percentage by weight (% by weight) of the powder, usually abbreviated as W / P, but abbreviated as W / C when the powder is cement. ] Is less than 20% by weight, more preferably 8 to 19% by weight, further 10 to 17% by weight, and still more preferably 12 to 16% by weight.

In the hydraulic composition of the present invention, the unit amount of the hydraulic powder is preferably 300 to 2000 kg / m ³ , more preferably 500 to 1500 kg / m ³ , and still more preferably 1000 to 1350 kg / m ³ .

In the hydraulic composition of the present invention, the unit amount of water is preferably 120 to 190 kg / m ³ , preferably 150 to 185 kg / m ³ , more preferably 160 to 170 kg / m ³ .

<Components of Additive Composition for Hydraulic Composition>
(1) Component (A) The following components were used as component (A).
A-1 [compound (2)]: monoester of methanol EO (EO average addition mole number 120) adduct and methacrylic acid [general formula (A2)] / methacrylic acid [general formula (A3)] = 10 / 90 (molar ratio) copolymer Na salt (weight average molecular weight 42000)
A-2 [compound (3)]: monoester of methanol EO (EO average addition mole number 23) adduct and methacrylic acid [general formula (A5)] / methacrylic acid [general formula (A3)] = (30 / 70 molar ratio) copolymer Na salt (weight average molecular weight 51000)
A-1 and A-2 were produced according to the method described in the production example of JP-A-7-223852.
A-3 [compound (2) and compound (3)]: A mixture in which the above A-1 and A-2 are mixed at a weight ratio of A-1 / A-2 = 30/70.

(2) Component (B) The following compounds were used as component (B).
B-1: Glycerin EO adduct produced by the following Production Example B (EO average addition mole number 1)
-B-2: Diethylene glycol-B-3: 1,2-butanediol

[Production Example B]
A 2 liter autoclave was charged with 230.3 g and 1.4 g of glycerin and KOH, respectively, and heated to 130 ° C. at a stirring speed of about 600 rpm. Next, dehydration was performed for 30 minutes at 130 ° C. and 1.3 kPa. Thereafter, the temperature was raised to 155 ° C. The above reaction mixture was reacted with 110.1 g of EO (corresponding to 1 mol of EO with respect to 1 mol of glycerin). The reaction conditions at this time were a temperature of 155 ° C. and a pressure of 0.1 to 0.3 MPa (gauge pressure). After completion of the reaction, the temperature was cooled to 80 ° C., and an glycerin EO average 1 mol adduct was obtained. The EO distribution of this adduct was as follows: unreacted glycerin (EO = 0 mol): 36%, EO = 1 mol adduct: 37%, EO = 2 mol adduct: 19%, EO = 3 mol adduct: 6 %, EO = 4 mol or more adduct: 2% (% is based on weight).

(3) Comparative compound of component (B) The following compounds were used as comparative compounds of component (B).
-B'-1: Glycerin-B'-2: Glycerin EO adduct manufactured according to the manufacture example B of said B-1 (EO average addition mole number 5). The EO distribution of this adduct was as follows: unreacted glycerin (EO = 0 mol): 2%, EO = 1 mol adduct: 7%, EO = 2 mol adduct: 15%, EO = 3 mol adduct: 17% EO = 4 mol or more adduct: 59% (% is based on weight).
-B'-3: The glycerol EO adduct manufactured according to the manufacture example B of said B-1 (EO average addition mole number 3). The EO distribution of this adduct was as follows: unreacted glycerin (EO = 0 mol): 3%, EO = 1 mol adduct: 11%, EO = 2 mol adduct: 22%, EO = 3 mol adduct: 26% EO = 4 mol or more adduct: 38% (% is based on weight).

(4) Component (C) The following components were used as component (C).
C-1: Phosphate ester copolymer produced by the following Production Example C [Production Example C]
A glass reaction vessel (four-necked flask) with a stirrer was charged with 423 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. ω-Methoxypolyethyleneglycol monomethacrylate (average added mole number of ethylene oxide 23) 407 g (effective part 60.8%, moisture 35%), mono (2-hydroxyethyl) methacrylate phosphate and di-[( 2-hydroxyethyl) methacrylic acid] ester, a mixture of 65.0 g of a phosphoric acid ester and 4.1 g of 3-mercaptopropionic acid and ammonium persulfate. Two of 7.6 g dissolved in 30.4 g of water were added dropwise over 1.5 hours. After aging for 1 hour, 1.7 g of ammonium persulfate dissolved in 6.7 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 aging, the mixture was neutralized with 63.5 g of a 30% aqueous sodium hydroxide solution to obtain a copolymer C-1 (weight average molecular weight 34000).

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

<Preparation and evaluation of concrete>
Under the blending conditions shown in Table 1, cement (C) and fine aggregate (S) were added using a 100 L forced biaxial mixer, and kneaded for 30 seconds. Add kneading water (W) containing additive composition and antifoaming agent (main component is fatty acid ester) and knead for 360 seconds so that the target slump is 60 ± 15 cm and the target air entrainment amount is 3.0% or less. After preparing the mortar, the coarse aggregate (G) was charged and then kneaded for 120 seconds to discharge the concrete. In addition, the additive composition used what was mix | blended (A) component and (B) component with the kind and composition of Table 2 so that the weight% with respect to cement might become as Table 2. FIG. About this concrete, according to the test method shown below, the measurement of the slump value, the amount of air, and the compressive strength (age age 7 days) was performed with the following method, respectively. The evaluation results are shown in Table 2.
-Slump value: Measured according to JIS-A1101.
-Air amount: Measured according to JIS-A1128.
-Mortar kneading speed: After adding kneading water, it was visually observed until it became a mortar in which water, cement and sand were uniformly mixed, and measured with a stopwatch.
-Setting time: Measured according to JIS-A1147.
-Compressive strength: It measured based on JIS-A1108. However, the age of two materials of 20 hours strength and 7 days strength was measured. The 20-hour strength is the 20-hour strength of the specimen that was allowed to stand at 20 ° C. after preparation of the concrete, and the 7-day strength was 7 days in the steam curing apparatus at 70 ° C. The strength was set to stand.

Water (W): Waterworks Cement (C): SFPC (registered trademark) (Silica fume premix cement, Taiheiyo Cement Co., Ltd., density 3.07 g / cm ³ )
・ Fine aggregate (S): mountain sand (density 2.55 g / cm ³ )
Coarse aggregate (G): crushed limestone (density 2.72 g / cm ³ )

  In Table 2, the addition amount of the component (A) and the component (B) is% by weight of cement. MS is the mortar kneading speed.

  As shown in Table 2, in Examples 1 to 9 using the component (A) and the component (B) of the present invention, the water / hydraulic powder ratio is good for a hydraulic composition having a water content of less than 20% by weight. It is possible to simultaneously satisfy the shortening of the kneading time and the improvement of the initial hardening strength while ensuring the fresh properties. Especially, compared with the comparative example 1, the shortening of setting time and the improvement of the early age strength of 20 hours are remarkable in Example 1. In Examples 2 and 3, since the amount of component (B) added was larger than that in Example 1, better results were obtained in shortening the setting time and improving the early age strength of 20 hours. Further, as in Example 4, by mixing A-1 (EO addition mole number 120) as the component (A), the kneading time and the setting time are further reduced as compared with Example 2, and Example 5 , 7 and 9, the kneading speed is further improved by mixing C-1 (phosphoric acid copolymer).

  In addition, even when the component (A) in Examples 1 to 9 is replaced with the compound (1), the additive composition for hydraulic composition exhibits the same effects of shortening the setting time and kneading time and improving the strength. You can get things.

Claims (5)

The following compound (2) and one or more copolymers selected from the group consisting of (3) and (A), 1, selected from compounds represented by 2- butanediol and Formula (B2) 1 A hydraulic composition containing at least one kind of compound (B), wherein the copolymer (A) is a combined use of the compound (2) and the compound (3), and the water / hydraulic powder ratio is less than 20% by weight. The additive composition for hydraulic compositions used with a thing.
<Compound (2)>
The monomer (i) represented by the following general formula (A2), the following general formula (A3) and one or more monomers selected from compounds represented by the following general formula (A4) and (ii) As a constituent unit, and a molar ratio thereof is (ii) / (i) = 70/30 to 95/5.

Wherein R ^3a and R ^4a are each independently a hydrogen atom or a methyl group, p1 is a number of 0 to 2, A ³ O is an oxyalkylene group having 2 or 3 carbon atoms, and n2 is an average addition of A ³ O. Number of moles, 100 to 300, X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

[Wherein, R ^{5a to} R ^7a are each independently a hydrogen atom, a methyl group, or (CH ₂ ) _p2 COOM ² , M ¹ and M ² are each independently a hydrogen atom or a cation, and p2 is 0 to 2 Represents the number of ]

(In the formula, R ^8a represents a hydrogen atom or a methyl group, and Y represents a hydrogen atom or a cation.)
<Compound (3)>
Monomer (iii) represented by the following general formula (A5) and one or more monomers (ii) selected from the compounds represented by the general formula (A3) and the general formula (A4) As a constituent unit, and a molar ratio thereof is (ii) / (iii) = 60/40 to 90/10.

Wherein R ^9a and R ^10a are each independently a hydrogen atom or a methyl group, p3 is a number from 0 to 2, A ⁴ O is an oxyalkylene group having 2 or 3 carbon atoms, and n3 is an average addition of A ⁴ O. Number of moles, a number of 2 to 90, and X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

(In the formula, A ¹ O represents an oxyalkylene group having 2 to 4 carbon atoms, m1, m2, and m3 each represent the number of added moles of A ¹ O, and the average value of the total of m1, m2, and m3 is 0.5. ~ 2.5.)   The additive composition for hydraulic composition according to claim 1, wherein a weight ratio of the copolymer (A) to the compound (B) is (A) / (B) = 30/70 to 99/1. Furthermore, the monomer 1 represented by the following general formula (C1), the monomer 2 represented by the following general formula (C2), and the monomer 3 represented by the following general formula (C3) The additive composition for hydraulic compositions according to claim 1 or 2, comprising a phosphate ester polymer (C) obtained by copolymerization at pH 7 or lower.

[Wherein, R ^1c and R ^2c are each independently a hydrogen atom or a methyl group, R ^3c is a hydrogen atom or —COO (AO) _n X, AO is a C 2-4 oxyalkylene group or oxystyrene group, p is the number of 0 or 1, n is the average added mole number of AO, 3 to 200, and X represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. ]

(In the formula, R ^4c represents a hydrogen atom or a methyl group, OR ^5c represents an oxyalkylene group having 2 to 12 carbon atoms, m4 represents a number of 1 to 30, and M represents a hydrogen atom or a cation.)

(Wherein R ^6c and R ^8c are each independently a hydrogen atom or a methyl group, OR ^7c and OR ^9c are each independently an oxyalkylene group having 2 to 12 carbon atoms, m5 and m6 are each independently 1 to 1) 30 number, M represents a hydrogen atom or a cation.)   The addition for hydraulic composition according to claim 3, wherein the weight ratio of the copolymer (A) to the phosphate ester polymer (C) is (A) / (C) = 100/1 to 100/40. Agent composition.   The additive composition for hydraulic compositions according to any one of claims 1 to 4, a hydraulic powder, an aggregate, and water, wherein the water / hydraulic powder ratio is 20% by weight. Less than hydraulic composition.