JP2010030874A - Additive composition for hydraulic composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a one-pack additive composition for a hydraulic composition giving excellent flowability and viscosity reducing effect to the hydraulic composition having water/hydraulic powder ratio of <20 wt.% in a unhardened fresh state and giving excellent shrinkage reducing effect and strength to the hardened body. <P>SOLUTION: The one-pack additive composition for the hydraulic composition comprises a specific copolymer (A) and a compound (B) selected from specific glycol ether-based and specific glycerin derivative-based compound and has the water/hydraulic powder ratio of <20 wt.%. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a one-component additive composition for a hydraulic composition and a method for producing the hydraulic composition.

  In recent years, since the tendency to attach importance to the life cycle cost of a concrete structure has increased, methods for increasing the strength of the concrete structure and suppressing cracks have been studied.

In order to improve the life cycle cost, it has been studied to reduce the unit water amount using a high-performance water reducing agent or to use a drying shrinkage reducing agent. Therefore, high-performance water reducing agents such as β-naphthalenesulfonic acid formalin high condensate salts and polycarboxylic acid-based high-performance water reducing agents are generally used in combination with drying shrinkage reducing agents. Examples of the drying shrinkage reducing agent include alkylene oxide adducts of alcohols having 1 to 4 carbon atoms (Patent Documents 1 and 2), and admixtures mainly composed of polyalkylene glycol having an average molecular weight of 400 to 10,000 and a polycarboxylic acid polymer. (Patent Document 3) has been proposed. As a high-performance water reducing agent, a phosphate ester polymer that can produce low-viscosity concrete in a high-strength region has been proposed (Patent Document 4).
Japanese Patent Publication No. 56-51148 JP 2001-294466 A JP 2002-12461 A JP 2007-182364 A

  However, in the above-mentioned patent documents, the water / hydraulic powder ratio is extremely small, for example, it is highly effective for a hydraulic composition in an ultrahigh strength region where the water / hydraulic powder ratio is less than 20% by weight. There is no mention of obtaining an easy-to-handle additive as a one-component product. Specifically, it gives excellent fluidity, shrinkage reduction effect, and viscosity reduction effect to hydraulic compositions in the ultra-high strength region. There is no disclosure of an additive in a one-component dosage form and a technique for obtaining the additive.

  The object of the present invention is to provide excellent fluidity and viscosity reducing effects in an uncured fresh state with respect to a hydraulic composition such as concrete in an ultrahigh strength region having a water / hydraulic powder ratio of less than 20% by weight. An object of the present invention is to provide an additive composition for a hydraulic composition that can be imparted, can impart an excellent shrinkage reduction effect while maintaining strength in a cured product, and can be used in a one-pack type dosage form.

  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 a water / hydraulic powder ratio containing at least one compound (B) [hereinafter referred to as component (B)] selected from the compounds represented by formula (B2): The present invention relates to a one-component additive composition for hydraulic compositions of less than 20% by 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 ¹ O) _n1 R ^2a (A1)
(In the formula, R ^1a is an alkenyl group having 2 to 4 carbon atoms, A ¹ O is an oxyalkylene group having 2 or 3 carbon atoms, n1 is an average added mole number of A ¹ 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 from 0 to 2, A ² O is an oxyalkylene group having 2 or 3 carbon atoms, and n2 is an average addition of A ² O. Number of moles, 100 to 300, X ¹ 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 ³ O is an oxyalkylene group having 2 or 3 carbon atoms, and n3 is an average addition of A ³ O. Number of moles, a number of 2 to 90, and X ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

(In the formula, R ^1b and R ^2b are each a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, A ⁴ O and A ⁵ O are each an oxyalkylene group having 2 to 8 carbon atoms, m1 is an average number of moles added of a ⁴ O, 1 to 30 number of, m2, m3 and m4 is an average molar number of addition of each a ⁵ O, m2, m3 and total number of m4 is to be 6 to 30 .)

  The present invention also provides a one-component additive composition for a hydraulic composition of the present invention, a hydraulic powder, and water so that the water / hydraulic powder ratio is less than 20% by weight. To a method for producing a hydraulic composition having a water / hydraulic powder ratio of less than 20% by weight.

  According to the present invention, a hydraulic composition such as concrete in an ultra-high strength region having a water / hydraulic powder ratio of less than 20% by weight has sufficient fluidity and viscosity reducing effects in an uncured fresh state. An additive composition for a hydraulic composition that can be applied, can provide an excellent shrinkage reduction effect while maintaining strength, and can be used in a one-pack type dosage form is provided.

<(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)>
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 ¹ O) _n1 R ^2a (A1)
(In the formula, R ^1a is an alkenyl group having 2 to 4 carbon atoms, A ¹ O is an oxyalkylene group having 2 or 3 carbon atoms, n1 is an average added mole number of A ¹ 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 from 0 to 2, A ² O is an oxyalkylene group having 2 or 3 carbon atoms, and n2 is an average addition of A ² O. Number of moles, 100 to 300, X ¹ 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 ³ O is an oxyalkylene group having 2 or 3 carbon atoms, and n3 is an average addition of A ³ O. Number of moles, a number of 2 to 90, and X ² 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 ¹ O is an oxyethylene group or an oxypropylene group, and may be both of these groups. The additional 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. Among them, a methyl group is preferable.

  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.

Further, the alkenyl ether derivatives, if the scope of the general formula (A1), for example, the A ¹ O is one of the only ones or oxypropylene groups alone oxyethylene group, or two or more may be used.

  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.

  As an example of the compound (1), Marialim EKM, Marialim AKM (manufactured by Nippon Oil & Fats Co., Ltd.) and Super 200 (Electrochemical Co., Ltd.) can be mentioned.

[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 more than 90 and less than 100 can 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 In addition, an adduct of ethylene oxide (hereinafter referred to as EO) and / or propylene oxide (hereinafter referred to as PO) to (meth) acrylic acid is 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 100 to 200 is more preferable.

  As the monomer represented by the general formula (A3), those mentioned in the compound (1) can be used. Preferred monomers are the same as those shown for the compound (1).

  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, and still more 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, more preferably in the range of 20,000 to 100,000, and still more preferably in the range of 30,000 to 85,000 from the viewpoint of imparting stable initial fluidity of the fresh concrete. 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 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 (iii) 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. Further, a monomer having n3 of more than 90 and less than 100 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 Alternatively, an EO and / or PO adduct to (meth) acrylic acid is preferably used. The additional form may be single, random, block, or alternating. More preferred is an esterified product of methoxypolyethylene glycol and (meth) acrylic acid. In particular, when the water / hydraulic powder ratio is 15% by weight or less, an esterified product of methoxypolyethylene glycol having an EO average addition mole number of 2 to 90 and acrylic acid is more preferable from the viewpoint of initial dispersibility and viscosity. .

  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. Preferred monomers are the same as those shown for the compounds (1) and (2).

  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% by weight or more, more preferably 80 to 100% by weight, and still more 100% by weight.

  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 following general formula (B2).

In the general formula (B1), R ^1b and R ^2b are each a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and in the case of a hydrocarbon group, preferably 1 to 22 carbon atoms, more preferably 1 carbon atom. -18, more preferably 1-12, and still more preferably a C 1-4 hydrocarbon group. (A) A C1-C4 hydrocarbon group is preferable from a mixed viewpoint with a component. Examples of the hydrocarbon group include an alkyl group and an alkenyl group, and an alkyl group is preferable. One of R ^1b and R ^2b is preferably a hydrogen atom, and the other is preferably a hydrocarbon group having 1 to 30 carbon atoms.

In General Formula (B1) and General Formula (B2), A ⁴ O and A ⁵ O are each an oxyalkylene group having 2 to 8 carbon atoms, preferably 2 to 6 carbon atoms, more preferably 2 or 2 carbon atoms. 3, and more preferably an oxyalkylene group having 2 carbon atoms.

Moreover, the general formula (B1) m1 in an average addition mole number of oxyalkylene groups A ⁴ O, 1 to 30, preferably 1 to 20, more preferably 1 to 12, more preferably 1 to 8, more More preferably, it is a number of 1-4.

Moreover, m2, m3 and m4 in the general formula (B2) are the average added mole numbers of the oxyalkylene group A ⁵ O, respectively, and the total (m2 + m3 + m4) of m2, m3 and m4 is 6 to 30, preferably 6 to 22, more preferably 6 to 18, more preferably 6 to 14, and still more preferably 6 to 12.

When A ⁵ O in the general formula (B2) is an oxyalkylene group having 3 carbon atoms, the sum of m2, m3 and m4 are preferably 6-9. If it is 6 or more, a sufficient drying shrinkage reducing effect can be obtained, and if it is 9 or less, a sufficiently high concentration with the component (A) can be achieved.

Also, when A ⁵ O in the general formula (B2) is an oxyalkylene group having 2 carbon atoms, the sum of m2, m3 and m4 are preferably 9-12. If it is 9 or more, a sufficient drying shrinkage reducing effect is obtained, and if it is 12 or less, the viscosity when the concentration is increased with the component (A) becomes appropriate.

<One-pack type additive composition for hydraulic composition>
In the one-component additive composition for the 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, and uniform stabilization of the product In view of the above, it is preferably 50% by weight or less. 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 the workability of fresh concrete, the component (A) preferably contains the compound (3). Of these, the compound (3) alone and the combined use of the compound (3) and the compound (2) are preferable. When the compound (3) is used in combination with the compound (1) or the compound (2), the compound (3) in the component (A) is 50% by weight or more, further 50 to 95% by weight, and further 70 to 90% by weight. It is preferable that Moreover, compound (2) is 1 to 40 weight% in (A) component from a viewpoint of coexistence of the quickness of fresh concrete, the quick strength of fresh concrete, and low viscosity, Furthermore, 5 to 30 weight%, Furthermore, 10 to 20% by weight is preferable.

  In the one-component additive composition for the hydraulic composition of the present invention, the content of the component (B) is preferably 5% by weight or more from the viewpoint of shrinkage reduction effect, and from the viewpoint of uniform stabilization of the product. It is preferably 95% by weight or less. Accordingly, it is preferably 5 to 95% by weight, more preferably 5 to 50% by weight, still more preferably 5 to 35% by weight, and still more preferably 10 to 20% by weight.

  In the one-component additive composition for a hydraulic composition of the present invention, the weight ratio (A) / (B) of the total amount of the component (A) and the total amount of the component (B) is 30/70 to 99 /. 1, more preferably 40/60 to 95/5, still more preferably 40/60 to 90/10, and still more preferably 55/45 to 70/30.

  In the one-component additive composition for a hydraulic composition of the present invention, the total content of the component (A) and the component (B) is preferably 10 to 100% by weight, more preferably 10 to 10% by weight. 80% by weight, more preferably 15 to 60% by weight, and still more preferably 20 to 50% by weight.

  The additive composition for a hydraulic composition of the present invention is a one-component liquid composition, and the balance is, for example, water. The one-component additive composition for a hydraulic composition of the present invention is easy to handle because the component (A) has good compatibility with the component (B), and an aqueous solution containing these components does not cause an extreme increase in viscosity. A one-component composition is obtained. The one-component additive composition for the hydraulic composition of the present invention can be obtained as a transparent composition, and further, it is transparent and uniform for 3 months or more by standing at 5 to 40 ° C. Can be maintained.

  From the viewpoint of further improving the viscosity reduction effect and the strength of the cured product, the one-component additive composition for a hydraulic composition of the present invention further comprises a monomer C1 represented by the following general formula (C1): The phosphate ester copolymer obtained by copolymerizing the monomer C2 represented by the following general formula (C2) and the monomer C3 represented by the following general formula (C3) at a pH of 7 or less It is preferable to contain 1 or more types of (C) [it is hereafter called (C) component].

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

(In the formula, R ^4c is a hydrogen atom or a methyl group, OR ^5c is an oxyalkylene group having 2 to 12 carbon atoms, m5 is an average number of added moles of OR ^5c, a number of 1 to 30, and M ³ is a hydrogen atom or Represents a cation.)

(Wherein R ^6c and R ^8c are each a hydrogen atom or a methyl group, OR ^7c and OR ^9c are each an oxyalkylene group having 2 to 12 carbon atoms, and m6 and m7 are average additions of OR ^7c and OR ^9c respectively. The number of moles is independently a number of 1 to 30, and M ⁴ represents a hydrogen atom or a cation.)

[Monomer C1]
Regarding the monomer C1, R ^3c in the general formula (C1) is preferably a hydrogen atom, and AO is preferably an oxyalkylene group having 2 to 4 carbon atoms, and more preferably includes an oxyethylene group (hereinafter referred to as an EO group). Preferably, the EO group is 70 mol% or more, more preferably 80 mol% or more, further 90 mol% or more, and even more preferably all of the AO are EO groups. X ³ is preferably a hydrogen atom or an alkyl group having 1 to 18, more preferably 1 to 12, further 1 to 4, and further 1 or 2 carbon atoms, 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 formula (C1) is 3 to 200, preferably 4 to 120, in terms of dispersibility of the polymer in the hydraulic composition and the effect of imparting 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 an oxypropylene group in addition to the EO group.

[Monomer C2]
Examples of the monomer C2 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 C3]
Examples of the monomer C3 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.

  Any of the monomer C2 and the monomer C3 may be an alkali metal salt, alkaline earth metal salt, ammonium salt, alkylammonium salt or the like of these compounds.

  As for m5 of monomer C2 and m6 and m7 of monomer C3, 1-20 are respectively preferable, 1-10 are still more preferable, and 1-5 are more preferable.

  As the monomer C2 and the monomer C3, 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 (above, Unichemical), JAMP514, JAMP514P, JMP100 (above, Johoku Chemical), Wright Ester P-1M, light acrylate P-1A (Kyoeisha Chemical), MR200 (Daihachi Chemical), Kayamar (Nippon Kayaku), Ethyleneglycol methacrylate phosphate (Aldrich reagent), etc. can be obtained.

Moreover, the mixed monomer containing the monomer C2 and the monomer C3 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 ^10c represents a hydrogen atom or a methyl group, OR ^11c represents an oxyalkylene group having 2 to 12 carbon atoms, and m8 represents a number of 1 to 30.)

  1-20 are preferable, as for m8 in general formula (C4), 1-10 are still more preferable, and 1-5 are more preferable.

  The monomer C2 and the monomer C3 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 C2) and It has been confirmed that a compound other than the diester (monomer C3) 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 C2) and a diester (monomer C3). 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, the phosphate ester (Y) obtained by making the organic hydroxy compound represented by the said general formula (C4) and a phosphorylating agent react can be used as the monomer C2 and the monomer C3. 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 C1 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)]. It will contain all the water present in it.

  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 of 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 expression of the dispersion effect and 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 is the degree of dispersion. The closer the value is to 1, the closer the molecular weight distribution is to the monodispersion, and the farther from 1 (the larger) the wider the molecular weight distribution.

  The phosphate ester polymer of the present invention having the Mw / Mn value as described above 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.

  Mw / Mn of the phosphoric ester polymer of the present invention as described above is 1.0 or more 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 a dispersibility and a 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 even more preferably 1 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. Is 1.0 to 1.8.

Mw and Mn of the phosphate ester polymer of the present invention 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 C3 which is a diester, 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.

  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, the phosphate ester polymer of the present invention is derived from monomers C1, C2, and C3, respectively, because the double bond derived from the monomer has disappeared by ¹ H-NMR under the following conditions. It is suggested to have a structural unit.
[ ¹ H-NMR conditions]
The polymer dissolved in water which was vacuum dried and dissolved in heavy methanol at a concentration of 3-4 wt.%, Measured by ¹ H-NMR. 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 phosphate ester-based polymer having the Mw / Mn value as described above has, as its constituent units, constituent units derived from monomer C1, constituent units derived from monomer C2, and constituents derived from monomer C3. 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 the monomers C1, C2, and C3 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 the monomers C1 to C3, the molar ratio of each structural unit is the charged molar ratio of the monomers. It is thought that it is almost the same.

<< Production Method of Phosphate Ester Polymer >>
The phosphate ester polymer of the present invention is manufactured by a phosphate ester polymer manufacturing method in which the monomer C1, the monomer C2, and the monomer C3 are copolymerized at a pH of 7 or less. Can do. Moreover, it is preferable to use the mixed monomer containing the monomer C2 and the monomer C3.

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

  The preferable thing of the monomers C1-C3 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 C1 and the monomers C2 and C3 is such that the monomer C1 / (monomer C2 + monomer C3) = 5/95 to 95/5. Furthermore, 10/90 to 90/10 are preferable. The molar ratio of monomer C1, monomer C2 and monomer C3 is as follows: monomer C1 / monomer C2 / monomer C3 = 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 C2 and the monomer C3, a 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 C3 can be 1-60 mol% in the all monomers used for reaction, Furthermore, it can be 1-30 mol%.
Moreover, the molar ratio of the monomer C2 and the monomer C3 can be set to monomer C2 / monomer C3 = 99/1 to 4/96, and further 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 the monomers C1 to C3. Is preferably used. Further, the upper limit of the amount of 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 C1 to C3. Preferably it can be 15 mol% or less. For more details,
(1) In the case where n of the monomer C1 is 3 to 30,
(1-1) When the molar ratio of the monomer C2 and the monomer C3 in the monomers C1 to C3 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 C2 and the monomer C3 in the monomers C1 to C3 is less than 50 mol%, the chain transfer agent is 4 to 4 to the monomers C1 to C3. It is preferable to use 60 mol%, more preferably 5 to 30 mol%,
(2) When n of monomer C1 is more than 30, it is preferable that the chain transfer agent is used in an amount of 6 to 50 mol%, more preferably 8 to 40 mol%, based on monomers C1 to C3.

  In the production method for obtaining the component (C) of the present invention, the reaction rate of the monomers C2 and 3 is 60% or more, further 70% or more, further 80% or more, further 90% or more, and further 95% or more. It is preferable to carry out to a target, and the usage-amount of a chain transfer agent can be selected from this viewpoint. Here, the reaction rate of the monomers C2 and C3 is calculated by the following equation.

In addition, the ratio (mol%) of the monomer C2 and the monomer C3 in the phosphorus-containing compound in the reaction system at the start and end of the reaction should be calculated based on the ¹ H-NMR measurement result. Can do.

  In the production of the phosphate ester polymer according to the present invention, in addition to the monomers C1 to C3, 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. The total proportion of monomers C1 to C3 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 achieve 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 the production method of the present invention, the reaction temperature of the monomers C1 to C3 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 in terms of gauge pressure). 0.1 atm), more preferably 101.3 to 106.4 kPa (1-1.05 atm).

  In the production method for obtaining the component (C) of the present invention, the monomer solution containing the monomer C2 and / or monomer C3 prepared with an appropriate solvent is preferably used in a predetermined amount of chain transfer agent. Is copolymerized with other monomers at pH 7 or lower. Moreover, you may use the other monomer, polymerization initiator, etc. which can be copolymerized.

  In the production method for obtaining the component (C) of the present invention, the monomer C1, the monomer C2, and the monomer C3 are reacted at a pH of 7 or less. 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. 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, 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 containing monomers C1 to C3. Acid, 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 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]
The production method for obtaining the component (C) of the present invention 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 the monomer C2 and / or the monomer C3 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 a monomer C1, monomer C2, monomer C3, chain transfer agent mixed and dissolved in water, and a 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 C2 and / or the monomer C3 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 C1, C2, C3 and other copolymerizable monomers in the reaction system is preferably 5 to 80% by weight, more preferably 10 to 65% by weight, still 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 C1 is 50 mol% or less in the total amount of monomers from the viewpoint of kneading speed.

  When the dispersant for hydraulic composition contains the component (C), the total content of the component (A) and the component (C) is 5 in the one-component additive composition for hydraulic composition of the present invention. -50% by weight, more preferably 10-40% by weight. In that case, the weight ratio (A) / (C) of the component (A) and the component (C) is preferably 75/25 to 97/3 in terms of effective component. In this weight ratio, the upper limit value occupied by the component (C) is preferably (A) / (C) = 75/25, more preferably 77/23, and still more preferably 80/21. On the other hand, the lower limit value occupied by the component (C) is preferably (A) / (C) = 97/3, more preferably 95/5, and still more preferably 91/9.

  The one-component additive composition for a hydraulic composition of the present invention has a component (A) (effective amount) of 0.01 with respect to the hydraulic powder from the viewpoint of fluidity and one-component retention. It is preferably used at a ratio of 10 to 10% by weight, more preferably 0.1 to 5% by weight, more preferably 0.1 to 2.5% by weight.

  In addition, the one-component additive composition for a hydraulic composition of the present invention has a component (B) (effective component) with respect to the hydraulic powder from the viewpoint of shrinkage reduction effect and retention of one component. It is preferably used in a proportion of 0.01 to 1% by weight, more preferably 0.05 to 0.7% by weight, more preferably 0.1 to 0.5% by weight.

The amount of component (B) (effective component) added per 1 m ³ of concrete may be appropriately adjusted depending on the water / hydraulic powder ratio and the type and amount of aggregate used, but preferably 0.5 to 10 kg. / M ³ , more preferably 1 to 8 kg / m ³ , more preferably 1.5 to 6 kg / m ³ .

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

  In addition, when the one-component additive composition for the hydraulic composition of the present invention contains the component (C), the component (C) (effective component) is from the viewpoint of maintaining the one-component property and fluidity. It is preferably used in a proportion of 0.01 to 3.0% by weight, more preferably 0.05 to 1.5% by weight, and more preferably 0.1 to 0.5% with respect to the hydraulic powder. % By weight.

  The one-component additive composition for the hydraulic composition of the present invention is composed of (A) component (effective component) and (B) with respect to the hydraulic powder from the viewpoint of retention of one component and fluidity. It is preferable to use it in a proportion of 0.1 to 10.0% by weight in total of component (effective component) and component (C) (effective component) [(A) + (B) + (C)]. Preferably it is 0.2 to 5.0 weight%, More preferably, it is 0.2 to 2.5 weight%.

  The one-component 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.

  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 one-pack type additive composition for a hydraulic composition 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, natural product systems such as β-1,3-glucan, xanthan gum, synthetic systems such as polyacrylic acid amide, polyethylene glycol, EO adduct of oleyl alcohol or a reaction product of this with vinylcyclohexene diepoxide Polymer emulsions such as alkyl (meth) acrylates.

  In addition, the one-component additive composition for hydraulic compositions of the present invention is not only for ready-mixed concrete and concrete vibration products, but also for self-leveling, for refractories, for plaster, for gypsum slurry, for lightweight or heavy concrete. It is useful in any field of various concrete such as for AE, repair, prepacked, trayy, ground improvement, grout, and cold. However, the target hydraulic composition is a hydraulic composition having a water / hydraulic powder ratio of less than 20% by weight.

<Method for producing hydraulic composition>
The present invention includes a hydraulic composition having a water / hydraulic powder ratio of less than 20% by weight, comprising the one-component additive composition for the hydraulic composition of the present invention, a hydraulic powder, and water. A method for producing the composition is provided. In the production method of the present invention, the one-component additive composition for the hydraulic composition of the present invention, the hydraulic powder, and water so that the water / hydraulic powder ratio is less than 20% by weight. The mixing method, mixing apparatus, etc. can employ known means. Moreover, the usage-amount of hydraulic powder, water, and the additive composition of this invention can be suitably selected in the above-mentioned range preferably according to the use of a hydraulic composition, a composition, etc.

  The hydraulic composition produced by the present invention is a 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. It is less than 20% by weight, further 12 to 19% by weight, further 12 to 17% by weight, further 12 to 16% by weight, and further 12 to 15% by weight.

  In the present invention, a hydraulic composition containing a one-component additive composition for the hydraulic composition of the present invention, a hydraulic powder, and water and having a water / hydraulic powder ratio of less than 20% by weight. Things can be provided.

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 .

The hydraulic composition of the present invention preferably contains fibers such as synthetic fibers from the viewpoint of preventing explosion when the cured body is exposed to a flame or the like and heated. Examples of the fiber include synthetic fibers having a length of 6 to 50 mm in which the volume decreases or decomposes and volatilizes by being softened or melted at 100 ° C. and a diameter of 5 to 500 μm. When the cured body is heated, the fiber contained in the cured body is reduced in volume or decomposed and volatilized, so that distortion due to expansion of the cured body can be alleviated and explosion of the cured body can be prevented. Synthetic fibers include polyacetal fibers, nylon fibers, aramid fibers, polyester fibers, acrylic fibers, vinylon fibers, polypropylene fibers, synthetic fibers such as polyethylene fibers, and regenerated fibers such as rayon fibers. Of these, polyacetal fibers are preferred. From the viewpoint of obtaining high-strength concrete of 80 N / mm ² or more, the fiber is 0.01 to 5.0% by volume, more preferably 0.05 to 3.5% by volume, and still more preferably 0.1% to the hydraulic composition. It is preferable to use ~ 3.5% by volume.

  The timing of mixing the fibers may be determined appropriately in consideration of the fresh properties of the concrete produced for each compounding, but from the viewpoint of obtaining high fluidity efficiently, it was kneaded before adding the coarse aggregate. It is preferable to put into mortar.

  The hydraulic composition of the present invention preferably contains an expansion material from the viewpoint of suppressing self-shrinkage while maintaining the drying shrinkage and the strength after curing of the hydraulic composition. As the inflatable material, those defined in JIS A 6202 can be used. Specifically, the expansion material chosen from the expansion material which has calcium sulfoaluminate as a main component, and the expansion material which has quicklime as a main component is mentioned. The expansion material is preferably used in an amount of 1 to 30 parts by weight, further 3 to 20 parts by weight, and further 5 to 15 parts by weight with respect to 100 parts by weight of the hydraulic powder (for example, cement). In the production of the hydraulic composition, the expansion material is preferably added together with the hydraulic powder (for example, cement).

<Additive for hydraulic composition>
(1) Component (A) The components shown in Table 1 below were used as the component (A). The following A-1, A-2 and A-3 were produced according to the method described in the production example of JP-A-7-223852.

(2) Component (B) The component shown in Table 2 below was used as the component (B). For convenience, comparative compounds other than the component (B) are also shown in Table 2.

(3) Component (C) As the component (C), the copolymer C-1 obtained in the following Production Example C-1 was used. Table 3 shows an outline of C-1.

[Production Example] (Production of Copolymer C-1)
A glass reaction vessel (four-necked flask) equipped with a stirrer was charged with 423 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 407 g of ω-methoxypolyethylene glycol monomethacrylate (average added mole number of EO 23) (effective content 60.8%, moisture 35%), mono (2-hydroxyethyl) methacrylate and di-[(2 -Hydroxyethyl) methacrylic acid] ester mixture 65.0 g of phosphoric acid ester (C ') and 4.1 g of 3-mercaptopropionic acid and 7.6 g of ammonium persulfate dissolved in 30.4 g of water The two were added over 1.5 hours each. 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 (C ′) used in the production example of 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, phosphoric acid ester (C ′) was obtained.

<Preparation and evaluation of concrete>
Under the blending conditions shown in Table 4, 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 65 ± 10 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. The antifoaming agent is blended in an amount of 0.2% by weight in advance in the additive composition when the component (B) is a compound of the general formula (B1) or when the general formulas (B1) and (B2) are mixed. In the case of the compound of B2) or the comparative compounds (B-5, B-6), 0.006% by weight was blended. In addition, about this concrete, according to the test method shown below, the measurement of the slump value, the air amount, the compressive strength (age age 1 day), and the shrinkage | contraction amount (age age 26 weeks) was performed with the following method, respectively. The composition (effective component concentration) of the additive composition for a hydraulic composition is as shown in Table 5 (the balance is water), and was used by adding it to the kneading water so as to have the addition amount shown in Table 6. The evaluation results are shown in Table 6.
-Slump value: Measured according to JIS-A1101.
-Air amount: Measured according to JIS-A1128.
-Compressive strength: It measured based on JIS-A1108.
-Shrinkage: Measured according to JIS-A1229.

The materials used in the table are as follows.
C: SFPC (registered trademark) (silica fume premix cement, Taiheiyo Cement Co., Ltd.) Density: 3.07 g / cm ³
W: Tap water S: Fine aggregate Mountain sand from Joyo, Kyoto Prefecture Density: 2.55 g / cm ³
G: Coarse aggregate Lime crushed stone from Mt. Torigata, Kochi Density: 2.72 g / cm ³
S / a: [S / (S + G)] × 100 (volume%)

  In the table, for 1 component, if it can be kept at 5 ° C, 20 ° C or 40 ° C for a period of 3 months or more, it can be maintained and cannot be maintained. No one-component.

  In the table, the additive amount of the hydraulic composition additive composition is the weight% of the effective amount relative to the cement weight.

  As described above, in Examples 1 to 9, the shrinkage amount is about 20 to 30% smaller than that in Comparative Example 1, and the shrinkage reduction effect is excellent. Moreover, in Example 6, the better viscosity, shrinkage reduction effect, and strength are obtained by using the component (C) in combination. In Example 7, the compression strength is further increased by using the component (C) in a system in which two types of the component (A) are used in combination. In Examples 8 and 9, the viscosity, shrinkage reduction effect, and strength are maintained at good levels even when the addition amount is reduced. In Example 9, even when the addition amount is reduced by using the component (C) in a system in which two types of the component (A) are used in combination, the compressive strength is further increased.

  Even when the component (A) in Examples 1 to 9 is replaced with the compound (1), an additive composition having a one-component property and exhibiting the same fresh characteristics and cured body characteristics can be obtained.

Claims (4)

One or more copolymers (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) The water / hydraulic powder ratio is less than 20% by weight containing the compound and one or more compounds (B) selected from the compounds represented by the following general formula (B2) [hereinafter referred to as component (B)] A one-component additive composition for a hydraulic composition.
<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 ¹ O) _n1 R ^2a (A1)
(In the formula, R ^1a is an alkenyl group having 2 to 4 carbon atoms, A ¹ O is an oxyalkylene group having 2 or 3 carbon atoms, n1 is an average added mole number of A ¹ 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 from 0 to 2, A ² O is an oxyalkylene group having 2 or 3 carbon atoms, and n2 is an average addition of A ² O. Number of moles, 100 to 300, X ¹ 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 ³ O is an oxyalkylene group having 2 or 3 carbon atoms, and n3 is an average addition of A ³ O. Number of moles, a number of 2 to 90, and X ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

(In the formula, R ^1b and R ^2b are each a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, A ⁴ O and A ⁵ O are each an oxyalkylene group having 2 to 8 carbon atoms, m1 is an average number of moles added of a ⁴ O, 1 to 30 number of, m2, m3 and m4 is an average molar number of addition of each a ⁵ O, m2, m3 and total number of m4 is to be 6 to 30 .) The one-component additive composition for a hydraulic composition according to claim 1, wherein the weight ratio (A) / (B) of the component (A) to the component (B) is 30/70 to 99/1. Furthermore, a monomer C1 represented by the following general formula (C1), a monomer C2 represented by the following general formula (C2), and a monomer C3 represented by the following general formula (C3) , Containing at least one phosphate ester copolymer (C) obtained by copolymerization at a pH of 7 or less (hereinafter referred to as component (C)), and the weight ratio of component (A) to component (C) ( The hydraulic composition according to claim 1 or 2, wherein A) / (C) is 75/25 to 97/3, and the total content of component (A) and component (C) is 5 to 50% by weight. A one-component additive composition.

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

(In the formula, R ^4c is a hydrogen atom or a methyl group, OR ^5c is an oxyalkylene group having 2 to 12 carbon atoms, m5 is an average number of added moles of OR ^5c, a number of 1 to 30, and M ³ is a hydrogen atom or Represents a cation.)

(Wherein R ^6c and R ^8c are each a hydrogen atom or a methyl group, OR ^7c and OR ^9c are each an oxyalkylene group having 2 to 12 carbon atoms, and m6 and m7 are average additions of OR ^7c and OR ^9c respectively. The number of moles is independently a number of 1 to 30, and M ⁴ represents a hydrogen atom or a cation.)   The one-component additive composition for a hydraulic composition according to any one of claims 1 to 3, a hydraulic powder, and water, wherein a water / hydraulic powder ratio is less than 20% by weight. A method for producing a hydraulic composition having a water / hydraulic powder ratio of less than 20% by weight.