JP2010070396A - Hydraulic composition for ultrahigh strength concrete - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydraulic composition for ultrahigh strength concrete extending a slump value range in which a centrifugally molded and hardened product having good finish and good hardening strength is obtained, when a hardened concrete product is produced by centrifugal molding from ready-mixed ultrahigh strength concrete. <P>SOLUTION: The hydraulic composition for ultrahigh strength concrete includes cement, an inorganic powder, a specific dispersant composition and water, and has a W/P ratio of 10-25 wt.% and a slump value of 0-5 cm. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a hydraulic composition for ultra-high strength concrete and a method for producing a centrifugally molded ultra-high-strength concrete cured body.

  Concrete products, civil engineering, and building structures include products that are compacted with an internal or external vibrator while injecting concrete into the mold, and products obtained by centrifugal compaction such as piles, poles, and fume tubes. Among these, in the manufacture of centrifugal molded products, for example, hollow centrifugal molded products represented by piles, concrete is driven into a cylindrical mold, and then the mold is rotated by a centrifugal molding machine and centrifugal force is used. Manufactured by compacting concrete.

  The production of concrete products by centrifugal molding is said to be suitable as a method for producing high-strength products because excess water in the concrete is squeezed out and the water / hydraulic powder ratio is small. Nowadays, from the viewpoint of increasing the durability of a building, increasing the number of layers, and shortening the construction period, there is a further demand for higher strength of centrifugal molded products such as piles used for ground maintenance. For this reason, it is desirable that the concrete in the fresh state to be put into the formwork also has a smaller water / hydraulic powder ratio. However, if the water / hydraulic powder ratio is reduced, workability such as slump value and viscosity is improved. It is difficult to keep the physical properties that affect In general, regarding the slump value of concrete for centrifugal molding, the slump value cannot be set so large from the viewpoint of centrifugal compaction necessary to finish the inner wall surface of the centrifugal molded body smoothly. It is said that the slump value cannot be made too small from the viewpoint of suppressing the filling property deterioration such as generation.

  Patent Document 1 describes a polycarboxylic acid-based cement dispersant that gives a cement composition having a specific penetration resistance index and slump retention index, and can be used in combination with an antifoaming agent and other surfactants. It is described that the concrete using the agent can be cured after being compacted by centrifugal force.

  Patent Document 2 describes a strength improver for cement containing glycerin or a glycerin derivative and a specific polycarboxylic acid copolymer, and describes that it can be used for a centrifugal molded product.

  Further, Patent Document 3 discloses that a concrete composition for centrifugal molding containing cement, a high-strength material, and a specific water-soluble copolymer as an admixture is tightened by a normal centrifugal force even in combination with a high-strength material. It is described that it is hard and shows sufficient strength.

In Patent Document 4, the daily steam curing strength test value is 100 N / mm ² or more (requirement 1), the initial slump value of the hydraulic composition is 0 to 2 cm (requirement 2), and the water / powder weight ratio is A hydraulic composition satisfying 10 to 22% (Requirement 3) and having a powder weight of 450 to 1000 kg / m ³ (Requirement 4) is suitable for producing an ultra-high strength centrifugal molded cured body. Are listed.

Further, Patent Document 5 uses a flocculant and an anionic surfactant or a nonionic surfactant to inject predetermined bubbles into the concrete inner surface during centrifugal molding, thereby reducing the amount of clogging during centrifugal molding. It describes what you can do.
JP 2004-331489 A JP 2006-282414 A JP 2001-253750 A JP 2006-36629 A JP 63-60141 A

  In centrifugally formed concrete, it is generally considered that when the water / hydraulic powder ratio is low, the filling property is improved as the slump value is increased. For the purpose of simply increasing the slump value, it can be achieved, for example, by increasing the amount of cementitious dispersant added. However, even if the slump value of a system having a low water / hydraulic powder ratio is adjusted by a conventionally known method, it is difficult to satisfy the finish and the hardening strength of the concrete product by centrifugal molding. In other words, the range of slump values that can provide satisfactory finish and hardening strength as a concrete product is actually limited to a narrow range in centrifugal molded concrete having a low water / hydraulic powder ratio. The technique of the above-mentioned patent document is not proposed from the viewpoint of expanding the range of the slump value in which good quality can be obtained in the production of a hardened concrete by centrifugal molding. For example, in Patent Document 4, a centrifugally molded cured body having a high filling property is manufactured by molding a hydraulic composition having a fresh state in a zero slump region with a relatively small centrifugal force at the initial stage of centrifugal molding. However, from the viewpoint of improving workability when filling fresh concrete into a mold, it is desirable that the slump value in the fresh state can be increased.

  The object of the present invention is to produce a hardened body (concrete product) with good finish and hardened strength, especially when producing a hardened concrete from ultrahigh strength concrete by centrifugal molding. It is providing the manufacturing method of the ultra-high-strength concrete hardened | cured material which centrifugally molds the hydraulic composition for water and this composition.

  The present invention is a hydraulic composition for ultra-high-strength concrete containing cement, an inorganic powder, a dispersant composition, and water, having a W / P of 10 to 25% by weight and a slump value of 0 to 5 cm, It is related with the hydraulic composition for super-high-strength concrete whose dispersing agent composition is a dispersing agent composition in any one of the following dispersing agent composition (1) and dispersing agent composition (2).

Dispersant composition (1): one or more compounds (1-1) selected from the following compounds (A) to (D) and one or more compounds (1-1) selected from the following compounds (E) to (G) ( 1-2) in the ratio of 4-25 in the weight ratio of compound (1-2) / compound (1-1).
Dispersant composition (2): one or more compounds (2-1) selected from the following compounds (A) to (C) and one or more compounds (2-2) selected from the following compounds (D) And a dispersant composition containing the compound (2-2) / compound (2-1) in a weight ratio of 0.25 to 4 (excluding the compound (1-2)).

[Compound (A)]
Selected from the monomer (a1) represented by the following general formula (a1-1), the monomer represented by the following general formula (a2-1) and the monomer represented by the following general formula (a2-2) Copolymer containing the monomer (a2) or a salt thereof as a constituent unit

[Where,
R ^1a , R ^2a : hydrogen atom or —CH ₃
R ^3a : hydrogen atom or —COO (A ¹ O) _n1 X ¹
A ¹ : alkylene group having 2 to 4 carbon atoms
X ¹ : a hydrogen atom or an alkyl group having 1 to 18 carbon atoms
m1: Number from 0 to 2
n1: A number from 2 to 300 is shown. ]

[Where,
R ^4a , R ^5a , R ^6a, which may be the same or different, are a hydrogen atom, —CH ₃ or (CH ₂ ) _r COOM ² , and (CH ₂ ) _r COOM ² is COOM ¹ or other (CH ₂ ) _r COOM ² and anhydride may be formed, in which case M ¹ and M ² of those groups are not present.
M ¹ and M ^{2 are each a} hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), an ammonium group, an alkylammonium group, or a substituted alkylammonium group r: a number of 0 to 2. ]

[Where,
R ^7a : hydrogen atom or —CH ₃
Z ^{1 represents a} hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), an ammonium group, an alkyl ammonium group or a substituted alkyl ammonium group. ]

[Compound (B)]
Copolymer of alkenyl ether (b1) represented by the following general formula (b1-1) and maleic acid and / or maleic anhydride (b2) or a salt thereof R ^1b —O (A ² O) _n2 —R ^2b (B1-1)
[Wherein, R ^1b is an alkenyl group having 2 to 4 carbon atoms, A ² O is an oxyalkylene group having 2 to 4 carbon atoms, an average added mole number n2 is a number from 5 to 200, and R ^2b is a number from 1 to 3 carbon atoms. Represents an alkyl group or a hydrogen atom. ]

[Compound (C)]
The monomer (c1) represented by the following general formula (c1-1), the monomer (c2) represented by the following general formula (c2-1), and the single unit represented by the following general formula (c3-1) A phosphate ester copolymer obtained by copolymerizing the monomer (c3) at a pH of 7 or less, or a salt thereof;

[Wherein, R ^1c and R ^2c are each independently a hydrogen atom or a methyl group, R ^3c is a hydrogen atom, or — (CO) _p O (A ³ O) _n3 X ² , and A ³ O has 2 to 4 carbon atoms. Oxyalkylene group or oxystyrene group, p is the number of 0 or 1, n3 is the average added mole number of A ³ O, the number is ^{3 to} 200, X ² is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms Represents. ]

[Wherein, R ^4c is a hydrogen atom or a methyl group, R ^5c is an alkylene group having 2 to 12 carbon atoms, m2 is a number of 1 to 30, and M ³ is a hydrogen atom, an alkali metal or an alkaline earth metal ( 1/2 atom). ]

[Wherein R ^6c and R ^8c are each independently a hydrogen atom or a methyl group, R ^7c and R ^9c are each independently an alkylene group having 2 to 12 carbon atoms, m3 and m4 are each independently 1 to 30 , M ⁴ represents a hydrogen atom, an alkali metal or an alkaline earth metal (1/2 atom). ]

[Compound (D)]
A copolymer of an alkenyl ether (d1) represented by the following general formula (d1-1) and acrylic acid (d2) or a salt thereof, and a molar ratio (d2) of structural units in the copolymer or a salt thereof / (D1) is a copolymer of 95/5 to 50/50 or a salt thereof R ^1d —O (AO) _n4 —R ^2d (d1-1)
[Wherein, R ^1d is an alkenyl group having 2 to 4 carbon atoms, AO is an oxyalkylene group having 2 to 4 carbon atoms, an average added mole number n4 is a number having 20 to 120, and R ^2d is an alkyl having 1 to 3 carbon atoms. A group or a hydrogen atom is shown. ]

[Compound (E)]
Dialkylsulfosuccinate,

[Compound (F)]
It has an aliphatic hydrocarbon group having 8 or less carbon atoms or an aromatic hydrocarbon group having 18 or less carbon atoms and one or more polar groups selected from a carboxyl group, a sulfonic acid group, a sulfuric acid group and a phosphoric acid group. And an anionic compound [excluding those belonging to the compound (1-1) or the compound (E)], wherein the counter ion of the polar group is a counter ion selected from a hydrogen ion, an alkali metal ion and an alkaline earth metal ion.

[Compound (G)]
A nonionic compound having an alkyl group having 1 to 8 carbon atoms and an oxyalkylene group having an average addition mole number of less than 10, and having a HLB of Davis of 5 to 9.

  The present invention also relates to a method for producing a centrifugally formed ultrahigh-strength concrete cured body, which is obtained by centrifugally molding the hydraulic composition for ultrahigh-strength concrete according to the present invention.

  According to the present invention, when producing a hardened concrete from ultrahigh strength concrete, particularly by centrifugal molding, ultrahigh strength concrete capable of widening the slump value range that can provide a hardened body (concrete product) with good finish and hardening strength. Provided are a hydraulic composition for use and a method for producing a hardened ultra-high-strength concrete by centrifugally molding the composition.

  The present invention relates to a hydraulic composition for ultra-high-strength concrete containing cement, inorganic powder, a specific dispersant composition, and water, having a W / P of 10 to 25% by weight and a slump value of 0 to 5 cm.

  In the present invention, W / P is a so-called water / hydraulic powder ratio, and is a weight percentage (% by weight) of water (W) and hydraulic powder (P) in ultra-high strength concrete, that is, (W / P) × 100. Of the inorganic powders used in the preparation of the hydraulic composition for ultra-high-strength concrete, powders corresponding to hydraulic powders, for example, admixtures such as silica fume, blast furnace slag, fly ash, fine limestone powder, etc. Is also included in the weight of P. Here, the hydraulic powder is a powder having a property of being cured by reacting with water, and a single substance does not have curability, but when two or more kinds are combined, hydration is caused by interaction through water. It is a powder that forms and hardens.

〔cement〕
Examples of the cement used in the present invention include ordinary Portland cement, early-strength Portland cement, ultra-early strong Portland cement, and eco-cement (for example, JIS R5214).

[Inorganic powder]
In the present invention, inorganic powder means hydraulic powder and non-hydraulic powder other than cement. Examples of the inorganic powder used in the present invention include hydraulic powders other than cement such as blast furnace slag, fly ash and silica fume, and non-hydraulic powders such as fine limestone powder. Of these, silica fume is preferable. Silica fume cement or blast furnace cement in which these inorganic powders are mixed with cement may be used as the cement and inorganic powder.

(Dispersant composition)
The dispersant composition used in the present invention is any one of the dispersant composition (1) and the dispersant composition (2).
Dispersant composition (1): one or more compounds (1-1) selected from the compounds (A) to (D) and one or more compounds (1-1) selected from the compounds (E) to (G) ( 1-2) in the ratio of 4-25 in the weight ratio of compound (1-2) / compound (1-1).
Dispersant composition (2): one or more compounds (2-1) selected from the above compounds (A) to (C) and one or more compounds (2-2) selected from the above compounds (D) And a dispersant composition containing the compound (2-2) / compound (2-1) in a weight ratio of 0.25 to 4 (excluding the compound (1-2)).

[Composition of Dispersant Composition (1), etc.]
The dispersant composition (1) includes one or more compounds (1-1) selected from the compounds (A) to (D) and one or more compounds selected from the compounds (E) to (G). (1-2) is contained at a ratio of 4 to 25 in a weight ratio of compound (1-2) / compound (1-1). When the weight ratio is within this range, water reduction and workability are excellent. The weight ratio of compound (1-2) / compound (1-1) is preferably 10 to 25, more preferably 15 to 25, from the viewpoint of workability.

  The dispersant composition used in the present invention preferably contains 10 to 60% by weight, further 15 to 40% by weight, and further 20 to 30% by weight of the compound (1-1).

  In addition, the dispersant composition used in the present invention may contain the compound (1-2) in a total amount of 0.5 to 15% by weight, further 0.5 to 10% by weight, and further 1 to 10% by weight. preferable.

  In the dispersant composition (1) used in the present invention, the total of the compound (1-1) and the compound (1-2) is 80 to 100% by weight, more preferably 90 to 100% by weight in the effective component, Further, it is preferably 95 to 100% by weight.

[Composition of Dispersant Composition (2), etc.]
The dispersant composition (2) is composed of at least one compound (2-1) selected from the above compounds (A) to (C) and at least one compound (2-2) selected from the above compound (D). ) At a ratio of 0.25 to 4 in a weight ratio of compound (2-2) / compound (2-1). The weight ratio of compound (2-2) / compound (2-1) is preferably 0.4 to 2.5, more preferably 0.6 to 1.5 from the viewpoint of workability. The dispersant composition (2) is distinguished from the dispersant composition (1) in that it does not contain the compound (1-2). Moreover, after satisfy | filling the weight ratio of the compound (2-2) / compound (2-1) in a dispersing agent composition (2), what contains a compound (1-2) is a dispersing agent composition (1 ).

  Moreover, when the dispersing agent composition (2) used for this invention contains a compound (A), the content is 5 to 60 weight%, Furthermore, 10 to 40 weight%, Furthermore, 10 to 30 weight% is further. preferable.

  Moreover, when the dispersing agent composition (2) used for this invention contains a compound (B), the content is 5 to 60 weight%, Furthermore, 10 to 40 weight%, Furthermore, it is 10 to 30 weight%. preferable.

  Moreover, when the dispersing agent composition (2) used for this invention contains a compound (C), the content is 5 to 60 weight%, Furthermore, 10 to 40 weight%, Furthermore, it is 10 to 30 weight%. preferable.

  Moreover, it is preferable that the dispersing agent composition (2) used for this invention contains 10-60 weight% of compounds (D), Furthermore, 20-60 weight%, Furthermore, 40-60 weight% is contained.

  Further, the dispersant composition (2) used in the present invention comprises 10 to 60% by weight, further 10 to 40% by weight, and more preferably 10% by weight of the compound (A), the compound (B) and the compound (C). It is preferable to contain -30 wt%.

  In the dispersant composition (2) used in the present invention, the total of the compounds (A) to (C) [compound (2-1)] and the compound (D) [compound (2-2)] is 80 to 100% by weight of the effective component, more preferably 90 to 100% by weight, and still more preferably 95 to 100% by weight.

  Hereinafter, the compounds (A) to (G) will be described.

<Compound (A)>
The compound (A) is represented by the monomer (a1) represented by the following general formula (a1-1), the monomer represented by the general formula (a2-1), and the general formula (a2-2). A copolymer or a salt thereof containing a monomer (a2) selected from the monomers described above as a structural unit. Compound (A) is a preferred copolymer from the viewpoint of workability (range of slump value that can be molded). As the compound (A), an admixture containing the compound (A), for example, one available as a dispersant for a hydraulic composition can be used.

The n1 alkylene glycols A ¹ O in the formula (a1-1) may be the same or different, and when they are different, random addition or block addition may be used.

  From the viewpoint of polymerization efficiency and cement dispersibility of the polyalkylene glycol, the added mole number n1 needs to be 2 to 300, preferably 2 to 150, and more preferably 2 to 130.

Specific examples of the monomer (a1) include a (half) esterified product of a polyalkylene glycol with one-terminal lower alkyl group blocked such as methoxypolyethylene glycol, methoxypolypropylene glycol, and ethoxypolyethylenepolypropylene glycol, and (meth) acrylic acid or maleic acid. And (meth) acrylic acid, maleic acid, ethylene oxide and propylene oxide adducts to (meth) allyl alcohol are preferably used, R ^3a in general formula (a1-1) is preferably a hydrogen atom, and m1 is 0. preferable. The alkylene oxide (A ¹ O group in the formula (a1-1)) is preferably an oxyethylene group. More preferred are alkoxy, and still more preferred is an esterified product of methoxypolyethylene glycol and (meth) acrylic acid. X ¹ in the general formula (a1-1) is preferably a methyl group.

  As the monomer represented by the formula (a2-1), unsaturated monocarboxylic acid monomers such as (meth) acrylic acid and crotonic acid, and unsaturated dicarboxylic acid monomers such as maleic acid, itaconic acid and fumaric acid Monomers or salts thereof such as alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts and the like can be mentioned, and (meth) acrylic acid or alkali metal salts thereof are preferable.

  Examples of the monomer represented by the formula (a2-2) include (meth) allylsulfonic acid or a salt thereof such as an alkali metal salt, an alkaline earth metal salt, an ammonium salt, and an amine salt.

  As the monomer (a2), it is more preferable to use only the monomer substantially represented by the formula (a2-1) from the viewpoint of controlling the molecular weight of the copolymer.

  The total amount of the monomer (a1) and the monomer (a2) in the monomer mixture constituting the compound (A) is 50% by weight or more, further 80% by weight or more, and substantially 100% by weight. Is preferred. Examples of the copolymerizable monomer other than the monomer (a1) and the monomer (a2) include acrylonitrile, (meth) acrylic acid alkyl ester, (meth) acrylamide, and styrene sulfonic acid.

  In the compound (A), the molar ratio of the monomer (a1) to the monomer (a2) is (a1) / (a2) = 5/95 to 50/50, more preferably 10/90 to 40/60. It is preferable that

  Compound (A) can be produced by a known method. For example, there is a solution polymerization method disclosed in JP-A No. 11-157877. In the presence of a polymerization initiator such as ammonium persulfate or hydrogen peroxide in water or a lower alcohol having 1 to 4 carbon atoms, if necessary, sodium sulfite or What is necessary is just to add mercaptoethanol etc. and to make it react at 50-100 degreeC for 0.5 to 10 hours.

  The compound (A) preferably has a weight average molecular weight (gel permeation chromatography method / standard substance sodium polystyrene sulfonate conversion / water system) in the range of 10,000 to 10,000, more preferably 10,000 to 80,000.

  In addition, when using the dispersing agent for hydraulic compositions containing a compound (A), this dispersing agent becomes a compound (A), Preferably it is 1 to 50 weight%, More preferably, it is 10 to 40 weight%, More preferably Contains 20-30% by weight. Further, the content of the compound (A) in the dispersant composition according to the present invention is preferably 10 to 45% by weight, more preferably 10 to 40% by weight, more preferably 20 to 30% by weight. It is preferable to use the dispersant. In general, the balance of the dispersant is water, an antifoaming agent, and other components.

<Compound (B)>
The compound (B) is a copolymer of alkenyl ether (b1) represented by the general formula (b1-1) and maleic acid and / or maleic anhydride (b2) or a salt thereof. The compound (B) is a preferred copolymer from the viewpoint of workability (range of slump values that can be molded, and filling properties into a mold).

In the general formula (b1-1) of the alkenyl ether (b1) constituting the compound (B), the alkenyl group having 2 to 4 carbon atoms represented by R ^1b is preferably a vinyl group, allyl group, methallyl group, etc. However, among them, an allyl group is preferable in terms of reactivity. A ² O is an oxyalkylene group having 2 to 4 carbon atoms, preferably an oxyethylene group or an oxypropylene group, and more preferably an oxyethylene group. Among the alkylene oxides for forming the A ² O group, the addition form of ethylene oxide (hereinafter referred to as EO) and / or propylene oxide (hereinafter referred to as PO) may be any of single, random, block or alternating. Preferably, EO is added alone. R ^2b is preferably an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. A methyl group is particularly preferable.

  The average added mole number n2 of alkylene oxide is in the range of 5 to 200, preferably 2 to 90, more preferably 10 to 60, and more preferably 20 to 50. Within this range, the hydraulic composition is hardly affected by physical stirring force and temperature, and stable fluidity can be obtained.

  In the compound (B) of the present invention, the molar ratio of the monomer (b1) represented by the general formula (b1-1) to maleic acid and / or maleic anhydride (b2) is (b1) / (B2) = 30/70 to 70/30, more preferably 30/70 to 50/50.

  Examples of the method for producing the compound (B) include methods described in JP-A-2-163108 and JP-A-5-345647. Examples of the salt include alkali metal salts, alkaline earth metal salts, ammonium salts, and alkyl ammonium salts.

  Moreover, the preferable weight average molecular weight of a compound (B) is 3000-300,000, Furthermore, 5000-100,000 from the point of fluidity | liquidity provision. The measuring method of this weight average molecular weight is the same as that of a compound (D).

  Examples of commercially available compounds (B) include Marialim EKM, Marialim AKM (manufactured by NOF Corporation) and Super 200 (manufactured by Denki Kagaku).

  Two or more kinds of compounds (B) can be used in combination, and in that case, it is preferable to use those in which n2 of alkenyl ethers of the general formula (b1-1) used in each production differ by 10 or more. The weight ratio in the case of using two types of copolymers using alkenyl ethers having different n2 of 10 or more is preferably in the range of 20/80 to 80/20. Three or more types of copolymers can be used in combination, and in this case, it is preferable that n2 of all alkenyl ethers differ from each other by 10 or more.

<Compound (C)>
Compound (C) is phosphoric acid obtained by copolymerizing the monomer (c1) with a mixed monomer containing the monomer (c2) and the monomer (c3) at a pH of 7 or less. An ester polymer or a salt thereof. Compound (C) is a known compound described in JP-A-2006-52381. The compound (C) is a preferred copolymer from the viewpoint of workability (range of slump value that can be molded and filling property to a mold).

i) Monomer (c1)
In the monomer (c1), R ^1c in the general formula (c1-1) is preferably a hydrogen atom, and A ³ O is preferably an oxyalkylene group having 2 to 4 carbon atoms, and is referred to as an oxyethylene group (hereinafter referred to as EO group). ) Group is more preferably 70 mol% or more, more preferably 80 mol% or more, further 90 mol% or more, and even more preferably all A ³ O is an EO group. X ² is preferably a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, further 1 to 12, more preferably 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, n3 in the general formula (c1-1) is 3 to 200, preferably 4 to 120, in terms of dispersibility of the polymer in the hydraulic composition and the effect of imparting low viscosity. Further, in the average n3 repeating units in which A ³ O is different, it may include a random addition or block addition or mixture of these. A ³ O can contain an oxypropylene group and the like in addition to the EO group.

ii) Monomer (c2)
As the monomer (c2), 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 can be mentioned. It is done. Of these, mono (2-hydroxyethyl) methacrylic acid phosphate is preferable from the viewpoint of ease of production and product quality stability.

iii) 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.

  From the viewpoint of dispersibility of the hydraulic composition, m2 of the monomer (c2) and m3 and m4 of the monomer (c3) are each preferably 1 to 20, more preferably 1 to 10, and 1 to 5 More preferred.

  As the monomer (c2) and the monomer (c3), a mixed monomer containing them 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.

  The phosphate ester polymer which is the compound (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, from the viewpoint of the expression of the dispersion effect of the hydraulic composition and the viscosity reduction effect. More preferably, it is 15,000 or more, and preferably 150,000 or less, more preferably 130,000, from the viewpoints of suppression of high molecular weight and gelation by crosslinking, and the effect of dispersion and viscosity reduction of the hydraulic composition. Or less, more preferably 120,000 or less, still more preferably 110,000 or less, and still more preferably 100,000 or less. Therefore, from the viewpoints of 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, It is 00～100,000. 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.

  Mw / Mn of the phosphoric acid ester-based polymer according to the present invention as described above is a viewpoint for ensuring the ease of production of a practical hydraulic composition, dispersibility, viscosity reduction effect, and versatility with respect to materials and temperature. From the viewpoint of achieving both the dispersibility of the hydraulic composition and the viscosity reducing effect, it is 2.6 or less, preferably 2.4 or less, more preferably 2.2 or less, and even more preferably. Is 2.0 or less, more preferably 1.8 or less, and from the viewpoint of combining the two points, preferably 1.0 to 2.4, more preferably 1.0 to 2.2, and still more preferably. It is 1.0-2.0, 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 gel permeation chromatography (GPC) method described in JP-A-2006-52381. In addition, Mw / Mn of the phosphate ester type polymer in the present invention is calculated based on the peak of the polymer.

  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 there are densely adsorbing groups in the molecule. It is thought to form a structure. 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 fill a substance to be adsorbed such as cement particles, which is presumed to be effective in achieving both the dispersibility of the hydraulic composition and the effect of reducing the viscosity.

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

In addition, since the double bond derived from a monomer has disappeared in the phosphate ester polymer according to the present invention by ¹ H-NMR under the following conditions, the monomer (c1), the monomer ( It is presumed to have structural units derived from c2) and the monomer (c3), respectively.
iv) ¹ H-NMR conditions A polymer dissolved in water, 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 the double bond can be determined 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 includes, as its structural units, structural units derived from the monomer (c1), structural units derived from the monomer (c2), and monomers. (C3) The structural unit derived from is included. These structural units are incorporated into the polymer by the addition polymerization of the ethylenically unsaturated bond of the monomer (c1), the monomer (c2), and the monomer (c3). It is a structural unit derived from a monomer. The ratio of these structural units in the polymer depends on the charging ratio. When the monomers used for copolymerization are only the monomers (c1) to (c3), the molar ratio of each structural unit is the monomer. This is considered to be almost the same as the charged molar ratio.

v) Method for Producing Phosphate Ester Polymer Compound (C) can be produced by a known method, for example, the method described in JP-A-2006-52381.

  In the present invention, the compound (C) can be used in two or more, and more preferably three or more. The criterion for selecting a plurality of compounds (C) depends on the composition, constituent materials, performance, etc. of the hydraulic composition. For example, the ratio of the monomer (c1) represented by the general formula (c1-1) is a single amount. A combination comprising 1 to 55 mol% of the copolymer (c1a) in the total amount of the body and a copolymer (c1b) in which the proportion of the monomer (c1) is more than 55 mol% in the total amount of the monomers is desirable. . Furthermore, when a third copolymer is selected in addition to (c1a) and (c1b), that is, when three types of copolymers are used in total, (c1b) should be two types. Preferably, one of (c1b) (second copolymer) is a copolymer in which the proportion of monomer (c1) is more than 55 mol% and not more than 65 mol% in the total amount of monomers, It is preferable that the other (third copolymer) of c1b) is a copolymer in which the proportion of the monomer (c1) exceeds 65 mol% in the total amount of the monomers.

<Compound (D)>
In the general formula (d1-1) of the alkenyl ether (d1) constituting the compound (D) of the present invention, the alkenyl group having 2 to 4 carbon atoms represented by R ^1d is preferably a vinyl group, an allyl group, Although it is a methallyl group etc., an allyl group is especially preferable in terms of reactivity. In addition, when R ^1d in the general formula (d1-1) has 2 to 4 carbon atoms, the effect of the present invention can be sufficiently obtained, and foam entrainment property is also appropriate. R ^2d is preferably an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl, ethyl, and propyl group. A methyl group is particularly preferable.

  The average added mole number n4 of the alkylene oxide is in the range of 20 to 120, preferably 30 to 120, and the alkylene oxide is preferably EO. Within this range, the hydraulic composition is hardly affected by physical stirring force and temperature, and stable fluidity can be obtained.

  The compound (D) of the present invention is a copolymer of the monomer (d1) represented by the general formula (d1-1) and acrylic acid (d2) or a salt thereof, and their molar ratio, The molar ratio of the structural units in the copolymer or salt thereof is (d2) / (d1) = 95/5 to 50/50, preferably 90/10 to 70/30. Examples of the method for producing the compound (D) include methods described in JP-A No. 2002-121056. Examples of the salt include alkali metal salts, alkaline earth metal salts, ammonium salts, and alkyl ammonium salts.

  Moreover, the preferable weight average molecular weight of a compound (D) is 10,000-100,000, Furthermore, 20000-70000 from the point of the water reduction of a hydraulic composition. This weight average molecular weight is measured by a gel permeation chromatography (GPC) method.

  Two or more types of compounds (D) can be used in combination, and in that case, it is preferable to use those in which n4 of the alkenyl ethers of the general formula (d1-1) used in each production is different by 10 or more. The weight ratio when two kinds of copolymers using alkenyl ethers having different n4 of 10 or more are used in combination is preferably in the range of 20/80 to 80/20. In addition, it is also possible to use 3 or more types of copolymers together. In that case, it is preferable that n4 of all the alkenyl ethers differ from each other by 10 or more.

<Compound (E)>
Examples of the dialkylsulfosuccinate include dialkylsulfosuccinate having an alkyl group having 4 to 12 carbon atoms. The dispersibility of the hydraulic composition is improved, and the viscosity of the concrete is lowered, so that the moldability is good. From the viewpoint of expanding the range of the slump value from which the body is obtained, dioctyl sulfosuccinate and di-2-ethylhexyl sulfosuccinate are preferred. The salt is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt.

<Compound (F)>
The compound (F) has an aliphatic hydrocarbon group having 8 or less carbon atoms, preferably 4 to 8 carbon atoms or an aromatic hydrocarbon group having 18 or less carbon atoms, preferably 12 to 18 carbon atoms. A hydrocarbon group is preferred. The aromatic hydrocarbon group may have an aliphatic hydrocarbon group as long as the total carbon number is 18 or less. The compound (F) has one or more polar groups selected from a carboxyl group, a sulfonic acid group, a sulfuric acid group, and a phosphoric acid group, and a sulfonic acid group and a sulfuric acid group are preferable. The counter ion of the polar group is a counter ion selected from a hydrogen ion, an alkali metal ion and an alkaline earth metal ion, preferably an alkali metal ion, and more preferably a sodium ion and a potassium ion. As the compound (F), alkyl (carbon number 4 to 8) sulfonate, alkyl (carbon number 4 to 8) sulfate ester, polyoxyethylene (EO average addition mole number 1 to 10) alkyl (carbon number 4 to 8) Ether sulfate ester salt, alkyl (carbon number 6 to 8) benzene sulfonate, alkyl (carbon number 6 to 8) naphthalene sulfonate, alkenyl succinate and the like, preferably polyoxyethylene (EO average) Addition mole number 1-4) alkyl (carbon number 6-8) ether sulfate ester, alkenyl (carbon number 6-8) succinate, octylbenzenesulfonate, octylnaphthalenesulfonate. The salt is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt.

<Compound (G)>
Compound (G) has an alkyl group having 1 to 8 carbon atoms, preferably 4 to 8 carbon atoms, and an oxyalkylene group having an average addition mole number of less than 10 and preferably 1 to 4 carbon atoms (2 to 4 carbon atoms). These are selected so that the Davis HLB is 5-9, preferably 7-9. The compound (G) is preferably a polyoxyethylene (EO average addition mole number 1 to 9) alkyl (carbon number 1 to 8) ether, more preferably a polyoxyethylene (EO average addition mole number 1 to 4) alkyl ( C4-8) ether.

  The dispersant composition (1) or (2) used in 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. Strengthening agent or accelerator; foaming agent; resin acid (salt), fatty acid ester, oil and fat, silicone, paraffin, asphalt, wax, etc. waterproofing agent; fluidizing agent; dimethylpolysiloxane, polyalkylene glycol fatty acid ester, mineral oil Antifoaming agents such as oils and fats, oxyalkylenes, alcohols and amides; antifoaming agents; high-performance water reducing agents such as melamine sulfonic acid formalin condensates and aminosulfonic acids; nitrites, phosphates, zinc oxide Rust preventives such as: celluloses such as methylcellulose and hydroxyethylcellulose, β-1,3-glucan, xanthan gum, etc. Water-soluble polymers such as natural products, polyacrylic acid amides, polyethylene glycol, EO adducts of oleyl alcohol or synthetic products such as a reaction product of this with vinylcyclohexene diepoxide; polymers such as alkyl (meth) acrylates An emulsion is mentioned. These components may be mix | blended with the dispersing agent for hydraulic compositions in the case of mix | blending a compound (A). Moreover, the hydraulic composition of this invention can also contain these other additives (materials).

<Hydraulic composition for ultra high strength concrete>
The hydraulic composition for ultra-high-strength concrete of the present invention is a hydraulic composition (fresh hydraulic composition) that becomes ultra-high-strength concrete when cured. In the hydraulic composition for ultrahigh strength concrete of the present invention, W / P is 10 to 25% by weight, preferably 14 to 25% by weight, and more preferably 14 to 20% by weight.

  In the hydraulic composition for ultra high strength concrete of the present invention, the dispersant composition (1) is 0.1 to 5 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the hydraulic powder. Further, it is preferably used at a ratio of 0.2 to 1 part by weight.

  Moreover, in the hydraulic composition for ultra high strength concrete of the present invention, the dispersant composition (2) is 0.1 to 5 parts by weight, more preferably 0.1 to 1 part by weight with respect to 100 parts by weight of the hydraulic powder. Further, it is preferably used at a ratio of 0.2 to 1 part by weight.

  Moreover, when using a dispersing agent composition (1), in the hydraulic composition for super-high-strength concrete of this invention, a compound (A)-a compound (D) are respectively 100 weight part of hydraulic powder. It is preferably used in a proportion of 0.05 to 5.0 parts by weight, further 0.1 to 2.0 parts by weight, and further 0.2 to 1.0 parts by weight.

  Moreover, when using a dispersing agent composition (1), in the hydraulic composition for super-high-strength concrete of this invention, a compound (A) -compound (D) are a total with respect to 100 weight part of hydraulic powder. 0.05 to 5.0 parts by weight, preferably 0.1 to 2.0 parts by weight, and more preferably 0.1 to 1.0 parts by weight.

  Moreover, when using a dispersing agent composition (2), in the hydraulic composition for super-high-strength concrete of this invention, a compound (A)-a compound (C) are respectively 100 weight part of hydraulic powder. It is preferably used in a proportion of 0.05 to 5.0 parts by weight, further 0.1 to 2.0 parts by weight, and further 0.2 to 1.0 parts by weight.

  Moreover, when using a dispersing agent composition (2), in the hydraulic composition for super-high-strength concrete of this invention, a compound (A) -compound (C) is 100 weight part of hydraulic powder in total. 0.05 to 5.0 parts by weight, preferably 0.1 to 2.0 parts by weight, and more preferably 0.1 to 1.0 parts by weight.

  It is preferable that the hydraulic composition for ultrahigh strength concrete of the present invention contains aggregates such as fine aggregate and coarse aggregate. As fine aggregates used in the present invention, mountain sand, land sand, river sand and crushed sand are preferred, and as coarse aggregate, mountain gravel, land gravel, river gravel and crushed stone are preferred. Depending on the application, lightweight aggregates may be used. The terms fine aggregate, coarse aggregate, and lightweight aggregate are based on the “Concrete Overview” (issued on June 10, 1998, published by Technical Shoin).

  Moreover, it is preferable that the hydraulic composition for ultra-high-strength concrete of this invention contains a fine aggregate and a coarse aggregate, and it is more preferable that S / a is 20-33 volume%. It is preferable that it is 25-33 volume%. S / a is related to the surface properties of the hardened concrete. In the hydraulic composition for ultrahigh strength concrete of the present invention, if S / a is within the above range, the inner surface smoothness and the end surface state are good, , Compressive strength is also maintained. In the present invention, S / a is the volume percentage (volume%) of the fine aggregate (S) in the aggregate used for the ultra-high-strength concrete, that is, the fine bone relative to the total with the coarse aggregate (G). It is a material (S) ratio, and is calculated by [S / (S + G)] × 100.

  In the present invention, by using a specific dispersant composition, the fluidity in a fresh state is improved with respect to the hydraulic composition for ultra-high strength concrete having a low W / P, and at the same time, the cured body after centrifugal molding. Can improve the finish and curing strength.

  The centrifugal molding hydraulic composition with a low W / P can be expected to improve the cured hardness of the molded product. Conventionally, if a high slump value is imparted, the finish after molding is impaired, and a workable product is used. It was difficult. However, in the present invention, by using a specific dispersant composition, even if the slump value in the fresh state of the hydraulic composition for centrifugal molding having a low W / P is increased, the finish of the product after centrifugal molding is good. Therefore, the effect of improving the hardening strength inherent to the centrifugal molding hydraulic composition having a low water / hydraulic powder ratio can be sufficiently exhibited. The fact that the slump value can be increased even by several centimeters is extremely significant in the centrifugal molding hydraulic composition with reduced W / P.

  In the hydraulic composition for ultrahigh strength concrete of the present invention, the fine aggregate is preferably used in a proportion of 30 to 150 parts by weight, more preferably 50 to 100 parts by weight, with respect to 100 parts by weight of the hydraulic powder. .

  In the hydraulic composition for ultrahigh strength concrete of the present invention, the coarse aggregate is preferably used in a proportion of 130 to 200 parts by weight, more preferably 150 to 170 parts by weight with respect to 100 parts by weight of the hydraulic powder. .

  The hydraulic composition for ultra-high-strength concrete of the present invention has a slump value of 0 to 5 cm from the viewpoint of ease of compaction by centrifugal force, and particularly immediately after the start of centrifugal compaction as a condition for centrifugal molding of the hydraulic composition. In the case of adopting conditions such as centrifugal molding at an acceleration of 0.1 to 1.5 G for 1 to 5 minutes, the slump value is preferably 1 to 3 cm, and more preferably 1 to 2 cm. The slump value is a slump value in a fresh state after kneading, and in the dispersant composition (1), the types and addition amounts of the compounds (A) to (D) and the compounds (E) to (G) are adjusted. In addition, in the dispersant composition (2), it can be adjusted by adjusting the type and amount of the compound (D), and further the compounds (A) to (C).

[Method for producing centrifugally molded concrete cured body and centrifugally molded ultrahigh strength concrete cured body]
The present invention relates to a method for producing a centrifugally formed ultrahigh strength concrete cured body, in which the ultrahigh strength concrete cured body is produced by centrifugally molding the hydraulic composition for ultrahigh strength concrete of the present invention. As a condition for centrifugal molding at that time, it is preferable to have a step (first stage) of centrifugal molding at an acceleration of 0.1 to 1.5 G for 1 to 5 minutes immediately after the start of centrifugal compaction. Normally, centrifugal compaction is performed immediately after filling the kneaded hydraulic composition for ultra high strength concrete into a mold. Further, the acceleration may vary during centrifugal molding, but it is preferable to maintain a constant acceleration.

  When centrifugally forming the hydraulic composition for ultrahigh-strength concrete of the present invention to obtain a centrifugally-molded ultrahigh-strength concrete hardened body, it is preferable to perform centrifugal molding at a low acceleration for a certain time after the start of centrifugal compaction. Specifically, the centrifugal molded ultra-high-strength concrete hardened body of the present invention has an acceleration (hereinafter also referred to as initial acceleration) for 1 to 5 minutes after the start of centrifugal compaction as a centrifugal molding condition of the hydraulic composition. ) Is 0.1 to 1.5 G, that is, the condition that the centrifugal molding is performed at an acceleration of 0.1 to 1.5 G for 1 to 5 minutes immediately after the start of centrifugal compaction, and preferably maintained at a constant acceleration. It is preferable to carry out at The initial acceleration is preferably 0.2 to 1.0 G, more preferably 0.3 to 0.8 G, and still more preferably 0.4 to 0.7 G. Depending on the centrifugal compaction device, the time to reach the set acceleration from 0G is usually within 15 seconds. In the present invention, the time for holding the acceleration includes the time from 0G (start) until reaching the set acceleration.

  When the initial acceleration is in the above range, the centrifugal compaction property in the mold is good, especially when forming a hollow centrifuge tube such as a pile, the hydraulic composition becomes more uniform along the circular tube wall, The inner wall surface can be formed smoothly.

  For example, in the case of 0.5G, the time for performing the centrifugal treatment while maintaining a low acceleration, preferably at a constant acceleration, is preferably 4 to 8 minutes, more preferably 5 to 7 minutes, and in the case of 1G 2 to 7 minutes are preferable, and 4 to 6 minutes are more preferable.

  Further, from the viewpoint of centrifugal compaction, acceleration during centrifugal molding is preferably performed in multiple stages. For example, after centrifugation by the initial acceleration in the first stage, the first stage is preferably 2 to 10G, preferably as the second stage. 2 to 6 minutes after the step, more preferably 3 to 8G for 2 to 6 minutes, still more preferably 4 to 6G for 3 to 5 minutes, as the third step, preferably 10 to 20G after the second step 1 to 5 minutes, more preferably 12-18G for 1-4 minutes, more preferably 13-17G for 2-3 minutes, as the fourth stage, preferably 20-35G for 1-6 minutes after the third stage, more preferably Preferably has 4 steps of 1 to 5 minutes at 22 to 30G, more preferably 1 to 4 minutes at 23 to 28G.

When the hydraulic composition for ultrahigh-strength concrete of the present invention is subjected to centrifugal molding under the above-described conditions, a smooth centrifugal concrete cured body with little variation in the thickness of the inner wall surface can be obtained particularly for a hollow centrifuge tube such as a pile. . Furthermore, in the manufacturing method of the present invention, after the centrifugal molding, it is preferable to steam curing, high strength, for example, compressive strength of the concrete (24 hours later) is 100 N / mm ² or more, further 140 N / mm ² or more ultra-high Preferable steam curing conditions for obtaining a hardened centrifugal molded concrete body are the following (I) to (III).
(I) Prelude: 20 ° C., 1-4 hours (II) Temperature rise: 10-30 ° C./hour (III) Retention: 60-90 ° C., 4-12 hours

After these (I) to (III), it is preferable to further perform the following (IV).
(IV) Temperature drop: 10 to 20 ° C./hour up to 40 ° C. or less

More preferable steam curing conditions are the following (I ′) to (IV ′).
(I ′) Prelude: 20 ° C., 2-4 hours (II ′) Temperature rise: 15-25 ° C./hour (III ′) Retention: 60-90 ° C., 6-10 hours (IV ′) Temperature drop: 40 ° C. or less Up to 10-20 ° C / hour

Moreover, when it is desired to increase the strength after 14 days, the following steam curing conditions (I ″) to (IV ″) are preferable.
(I ″) Prelude: 20 ° C., 3-4 hours (II ″) Temperature rise: 10-20 ° C./hour (III ″) Hold: 60-70 ° C., 4-6 hours (IV ″) Temperature drop : Up to 40 ° C., 10 to 20 ° C./hour

Centrifugal ultra-high strength concrete hardened body manufactured according to the present invention can obtain compressive strength (24 hours) of 100 N / mm ² or more, and further 120 N / mm ² or more, and requires pile and other high strengths. It is suitable as a centrifugal molded product. Moreover, the inner wall surface is smooth and excellent in quality. In addition, this compressive strength is a strength 24 hours after water comes into contact with a hydraulic powder such as cement (24 hours after water contact). In addition, a smooth inner wall surface means that in a tubular product such as a pile, the doughnut-like thickness (thickness in a cross section orthogonal to the longitudinal direction) has a small fluctuation width (thickness difference). A preferred runout width (thickness difference) is 10 mm or less, more preferably 5 mm or less.

《Concrete material》
Concrete was produced according to the formulation shown in Table 1 using the following concrete materials.
W: tap water HC: early strong Portland cement [Pacific Cement Co., Ltd.], density = 3.14 (g / cm ³ )
SF: Silica fume [Kao Corporation], density = 2.25 (g / cm ³ ), specific surface area = 20000 (cm ² / g)
S: fine aggregate, river sand from Minjiang, Fujian, China, surface dry density = 2.65 (g / cm ³ ), FM = 2.90
G: Coarse aggregate, crushed stone from Ako, Hyogo Prefecture, surface dry density = 2.63 (g / cm ³ ), water absorption = 0.65
W / P: [W / (HC + SF)] × 100 (%, weight ratio)
S / a: [S / (S + G)] × 100 (%, volume ratio)

<< Dispersant composition >>
The components used in the dispersant composition are shown below. Using the dispersant composition containing these components, concrete was produced by the following method, and the initial slump value, the smoothness of the inner wall surface, the end face state, and the compressive strength were evaluated for each blending and centrifugal molding condition. In addition, the addition amount of the dispersant composition was appropriately adjusted so that concrete having an initial slump value of 0 to 5 cm was obtained.

[Compound (A)]
A1: Copolymer produced by Synthesis Example A1 below (Synthesis Example A1)
A glass reaction vessel (four-necked flask) with a stirrer was charged with 333 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 300 g of ω-methoxypolyethyleneglycol monomethacrylate (EO added average number of moles 23: NK ester M230G manufactured by Shin-Nakamura Chemical), 69.7 g of methacrylic acid (reagent: Wako Pure Chemical Industries, Ltd.), and 6.3 g of mercaptopropionic acid Two solutions, a mixed solution in which 200 g of water was dissolved in 200 g of water and a solution in which 12.3 g of ammonium persulfate was dissolved in 45 g of water, were dropped into the above reaction vessel over 1.5 hours, respectively. Thereafter, aging was performed for 1 hour, and a solution obtained by dissolving 4.9 g of ammonium persulfate in 15 g of water was added dropwise over 30 minutes, followed by aging for 1.5 hours. The temperature of the reaction system during this series was kept at 80 ° C. After completion of the aging, the mixture was cooled to 40 ° C. or lower, and then neutralized with 50.2 g of a 48% sodium hydroxide aqueous solution to obtain an aqueous solution of a copolymer having a weight average molecular weight of 43,000. Thereafter, the solid content concentration was adjusted to 20% by weight using ion-exchanged water.

[Compound (B)]
B1: Copolymer produced by Synthesis Example B1 below (Synthesis Example B1)
A glass reaction vessel with a stirrer (four-necked flask) was charged with 225 g of water and 300 g of polyoxyethylene (average number of moles of EO added 30) allyl ether, and purged with nitrogen while stirring, up to 80 ° C. in a nitrogen atmosphere. The temperature rose. A mixed solution of maleic acid (reagent: Wako Pure Chemical Industries, Ltd. purity: 99%) 47.4 g and mercaptopropionic acid 3.7 g in water 137 g, and ammonium persulfate 7.1 g in water 90 g The two were dropped into the reaction vessel over 2.5 hours from separate dripping ports. Thereafter, the mixture was aged for 2 hours, and a solution obtained by dissolving 2.8 g of ammonium persulfate in 45 g of water was added dropwise over 60 minutes, followed by aging for 2 hours. The temperature of the reaction system during this series was kept at 80 ° C. After completion of the aging, the mixture was cooled to 40 ° C. or lower, and then neutralized with 26.6 g of a 48% aqueous sodium hydroxide solution to obtain an aqueous solution of a copolymer having a weight average molecular weight of 31,000. Thereafter, the solid content concentration was adjusted to 20% by weight using ion-exchanged water.

[Compound (C)]
C1: Copolymer produced by Synthesis Example C1 below (Synthesis Example C1)
A glass reaction vessel (four-necked flask) equipped with a stirrer was charged with 395 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 261 g of ω-methoxypolyethylene glycol monomethacrylate (EO added mole number 23: NK ester M230G manufactured by Shin-Nakamura Chemical), Phosmer M [mixture of 2-hydroxyethyl methacrylate monophosphate and 2-hydroxyethyl methacrylate diphosphate, Uni Chemical Co., Ltd.] Two solutions, 67.3 g and 4.3 g of mercaptopropionic acid dissolved in 141 g of water and a solution of 8.0 g of ammonium persulfate dissolved in 45 g of water, Dropped into the reaction vessel over 5 hours. Thereafter, the mixture was aged for 1 hour, and a solution prepared by dissolving 1.8 g of ammonium persulfate in 10 g of water was added dropwise over 30 minutes, followed by aging for 1.5 hours. The temperature of the reaction system during this series was kept at 80 ° C. After completion of the aging, the mixture was cooled to 40 ° C. or lower and then neutralized with 66 g of a 30% aqueous sodium hydroxide solution to obtain a copolymer aqueous solution having a weight average molecular weight of 37,000. Thereafter, the solid content concentration was adjusted to 20% by weight using ion-exchanged water.

[Compound (D)]
D1: Copolymer produced by Synthesis Example D1 (Synthesis Example D1)
A glass reaction vessel with a stirrer (four-necked flask) was charged with 406 g of a 65% aqueous solution of polyoxyethylene (average number of moles of EO added 100) allyl ether, and the temperature was raised to 65 ° C. 20.1 g of a 2% aqueous hydrogen peroxide solution was added dropwise thereto. After dropping, 38.4 g of acrylic acid was dropped over 3.0 hours, and at the same time 1.26 g of 3-mercaptopropionic acid (Sigma Aldrich Japan Co., Ltd., reagent), 0.52 g of L-ascorbic acid, ion-exchanged water 33 A monomer mixed solution in which 0.8 g was dissolved was dropped over 3.5 hours. After completion of the dropwise addition, the reaction was terminated by maintaining 65 ° C. for 1 hour. Then, it neutralized with 20% sodium hydroxide aqueous solution, and obtained the aqueous solution of the copolymer of the weight average molecular weight 60000. Then, it adjusted to 20 weight% of solid content using ion-exchange water.

[Compound (E)]
E1: Sodium di-2-ethylhexyl sulfosuccinate

[Compound (F)]
F1: Sodium octylnaphthalene sulfonate F2: Polyoxyethylene (EO average addition mole number 2) -2-ethylhexyl ether sulfate sodium salt F3: Alkenyl (carbon number 8) dipotassium succinate

[Compound (G)]
G1: Polyoxyethylene (EO average addition mole number 2) -2-ethylhexyl ether (HLB5.8)
G2: polyoxyethylene (EO average addition mole number 3) octyl ether (HLB6.1)
G3: polyoxyethylene (EO average addition mole number 2) octylamine (HLB5.8)

[Comparative compound]
Comparative compound 1: Coconut amine acetate Comparative compound 2: Lauryltrimethylammonium chloride Comparative compound 3: Lauryldimethylsulfobetaine

<Production conditions for fresh concrete>
The kneading amount was 40 liters, and the production was as follows.
All the concrete materials other than the dispersant composition and the kneading water are put into a 60 liter forced biaxial mixer, kneaded for 30 seconds, then the mixed solution of the dispersant composition and the kneading water is put in, mixed for an arbitrary time, and then discharged. To do. The kneading time was determined by confirming that the concrete was sufficiently kneaded by visual judgment.

<< Centrifugal molding conditions >>
15 kg of fresh concrete was put into a cylindrical centrifugal mold for manufacturing a pile (φ20 cm × height 30 cm), and centrifugal molding was performed under the conditions shown in Table 2 below. That is, acceleration was applied in four stages: initial speed (first stage), second speed (second stage), third speed (third stage), and fourth speed (fourth stage).

《Steam curing conditions》
The steam curing conditions were as follows (referred to as curing conditions 1).
(I) Prelude: 20 ° C., 3 hours (II) Temperature rise: 20 ° C./hour (III) Retention: 80 ° C., 8 hours (IV) Temperature drop: Up to 20 ° C., 10 ° C./hour

<Measurement of slump value>
The initial slump value of fresh concrete (immediately after kneading) was measured according to JIS A 1101.

<Smoothness of inner wall surface>
Measure the thickness (mm) of the upper and lower parts of the hardened concrete body 24 hours after the contact of water with the hydraulic powder such as cement (from the start of water contact), at 4 diagonal points, 4 each Variations in thickness at a total of 8 locations are indicated by numerical values (mm). The smaller the numerical value (mm), the better the smoothness of the inner wall surface.

<End face condition>
The state of the exposed surfaces at both ends of the hardened concrete body after 24 hours from the contact of water with the hydraulic powder such as cement (from the start of water contact) was evaluated by the following criteria.
Pass: No jumper is generated and both end faces are smooth and uniform. Fail: Jumper is generated

<Measurement of compressive strength>
The compressive strength of the hardened concrete concrete 24 hours after the water contacted the hydraulic powder such as cement (from the start of water contact) was measured using a hydraulic compression tester (manufactured by Tokyo Henki Co., Ltd .: CME II- 500, TK-15).

《Paste evaluation》
In order to confirm the performance of the dispersant composition, the dispersant composition with respect to the cement paste was evaluated. The paste was evaluated by a flow test of a cement paste prepared according to “JIS R5201 Cement Physical Test Method”. At that time, the paste formulation was kneading water / early strong Portland cement = 160 g / 800 g, and the kneading speed of the kneader was low (140 rpm). Tables 3 to 9 also show the results of this paste evaluation.

  The paste evaluation is an index indicating the basic characteristics of the paste when various dispersants are used, and is not an evaluation associated with the concrete evaluation. However, since the basic characteristics do not change, it can be said that in this example, the larger the difference (elongation rate) between the initial flow and the tapping flow, the better the moldability.

The outline of a specific apparatus etc. is as follows.
・ Kneader Main body Motorized to give rotation and reversal motion in the opposite direction to the paddle, rotation: 140 ± 5 rpm, revolution: 62 ± 5 rpm,
Kneading bowl made of stainless steel 5 liters ・ Apparatus used for the flow test Flow table Table diameter: 300 ± 1 mm, table drop: 10.0 ± 0.5 mm
Cone top inner diameter: 70.0 ± 0.5mm
Cone bottom inner diameter: 100.0 ± 0.5mm
Cone height: 60.0 ± 0.5mm
-Flow value measurement Cement paste prepared with a kneader is inserted to half the depth of the cone and butted 15 times over the entire surface with a pestle to compensate for the deficiency and smooth the surface. Immediately after removing the cone correctly upward, two points perpendicular to the direction in which the paste spreads most are measured, and the average value is expressed in mm (initial flow). Immediately after the measurement, 15 drop motions (tapping) are given in 15 seconds, and the spread is measured in the same manner as described above (tapping flow). The difference between the initial flow value and the tapping flow value is “elongation (mm)”, and the percentage of “elongation (mm)” with respect to the initial flow value [(tapping flow value−initial flow value) / initial flow value × 100] is “elongation”. (%) ". The kneading time was adjusted so that the initial flow was 150 ± 5 mm.

Example 1 and Comparative Example 1
A dispersant composition was prepared using Compound (A) to Compound (D) as Compound (1-1) and sodium di-2-ethylhexylsulfosuccinate as Compound (1-2). The above test was conducted according to the concrete composition and production conditions. The compound (1-2) was used so that the weight ratio to the compound (1-1) was the ratio in the table. The results are shown in Tables 3-6.

  In Tables 3 to 6, “◯” in compound (1-1) means that the corresponding component was blended (the same applies hereinafter).

Example 2
A dispersant composition is prepared using the compound (A) to the compound (C) as the compound (2-1) and the compound (D) as the compound (2-2). The above test was conducted. The results are shown in Table 7.

Example 3 and Comparative Example 3
A dispersant composition was prepared using the compound (A) to compound (D) as the compound (1-1) and the compound (E) to compound (G) or a comparative compound as the compound (1-2). Said test was done by the concrete mix and production conditions of 8-9. The results are shown in Tables 8-9.

Example 4
A dispersant composition was prepared using the above compounds (A) to (B) as the compound (1-1) and sodium di-2-ethylhexyl sulfosuccinate as the compound (1-2). The above test was conducted according to the manufacturing conditions. The results are shown in Table 10.

  In all of Examples 4-1 to 4-3, a cured product after centrifugal molding having a good slump value range and a good finish and curing strength is obtained. In Examples 4-1 and 4-2, the initial speed acceleration is 0.7 G, and a centrifugal condition in which the initial acceleration is lower than 2.5 G in Example 4-3 is adopted. When compared with the same slump value, in Examples 4-1 and 4-2, the inner wall surface smoothness is better than that in Example 4-3. This is the same as that in Examples 4-1 and 4-2. Under centrifugal molding conditions 1 and 2, since the initial acceleration is low, it is considered that the paste content can be prevented from being unevenly distributed in the thickness direction of the inner wall surface due to the difference in specific gravity while ensuring the filling property to the end face. . Therefore, when producing the ultra-high-strength concrete hardened body by centrifugally forming the hydraulic composition for ultra-high-strength concrete of the present invention, adopting the predetermined initial acceleration as described above, and further including this It can be seen that it is desirable to load the acceleration in multiple stages.

  From the results of Tables 3 to 10, the hydraulic composition for ultra-high-strength concrete of the present invention has a slump value in the range of 0 to 5 cm, is excellent in centrifugal moldability (inner wall surface smoothness, end face state), and has a compressive strength. It turns out that a high super high-strength concrete hardening body can be manufactured. Therefore, in this invention, the area | region of the slump value from which the super-high-strength concrete hardening body of favorable quality is obtained can be expanded.

Claims (4)

A hydraulic composition for ultra-high-strength concrete containing cement, inorganic powder, a dispersant composition, and water, having a W / P of 10 to 25% by weight and a slump value of 0 to 5 cm. Is a hydraulic composition for ultra high strength concrete, which is a dispersant composition of any one of the following dispersant composition (1) and dispersant composition (2).
Dispersant composition (1): one or more compounds (1-1) selected from the following compounds (A) to (D) and one or more compounds (1-1) selected from the following compounds (E) to (G) ( 1-2) in the ratio of 4-25 in the weight ratio of compound (1-2) / compound (1-1).
Dispersant composition (2): one or more compounds (2-1) selected from the following compounds (A) to (C) and one or more compounds (2-2) selected from the following compounds (D) And a dispersant composition containing the compound (2-2) / compound (2-1) in a weight ratio of 0.25 to 4 (excluding the compound (1-2)).
[Compound (A)]
Selected from the monomer (a1) represented by the following general formula (a1-1), the monomer represented by the following general formula (a2-1) and the monomer represented by the following general formula (a2-2) Copolymer containing the monomer (a2) or a salt thereof as a constituent unit

[Where,
R ^1a , R ^2a : hydrogen atom or —CH ₃
R ^3a : hydrogen atom or —COO (A ¹ O) _n1 X ¹
A ¹ : alkylene group having 2 to 4 carbon atoms
X ¹ : a hydrogen atom or an alkyl group having 1 to 18 carbon atoms
m1: Number from 0 to 2
n1: A number from 2 to 300 is shown. ]

[Where,
R ^4a , R ^5a , R ^6a, which may be the same or different, are a hydrogen atom, —CH ₃ or (CH ₂ ) _r COOM ² , and (CH ₂ ) _r COOM ² is COOM ¹ or other (CH ₂ ) _r COOM ² and anhydride may be formed, in which case M ¹ and M ² of those groups are not present.
M ¹ and M ^{2 are each a} hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), an ammonium group, an alkylammonium group, or a substituted alkylammonium group r: a number of 0 to 2. ]

[Where,
R ^7a : hydrogen atom or —CH ₃
Z ^{1 represents a} hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), an ammonium group, an alkyl ammonium group or a substituted alkyl ammonium group. ]
[Compound (B)]
Copolymer of alkenyl ether (b1) represented by the following general formula (b1-1) and maleic acid and / or maleic anhydride (b2) or a salt thereof R ^1b —O (A ² O) _n2 —R ^2b (B1-1)
[Wherein, R ^1b is an alkenyl group having 2 to 4 carbon atoms, A ² O is an oxyalkylene group having 2 to 4 carbon atoms, an average added mole number n2 is a number from 5 to 200, and R ^2b is a number from 1 to 3 carbon atoms. Represents an alkyl group or a hydrogen atom. ]
[Compound (C)]
The monomer (c1) represented by the following general formula (c1-1), the monomer (c2) represented by the following general formula (c2-1), and the single unit represented by the following general formula (c3-1) A phosphate ester copolymer obtained by copolymerizing the monomer (c3) at a pH of 7 or less, or a salt thereof;

[Wherein, R ^1c and R ^2c are each independently a hydrogen atom or a methyl group, R ^3c is a hydrogen atom, or — (CO) _p O (A ³ O) _n3 X ² , and A ³ O has 2 to 4 carbon atoms. Oxyalkylene group or oxystyrene group, p is the number of 0 or 1, n3 is the average added mole number of A ³ O, the number is ^{3 to} 200, X ² is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms Represents. ]

[Wherein, R ^4c is a hydrogen atom or a methyl group, R ^5c is an alkylene group having 2 to 12 carbon atoms, m2 is a number of 1 to 30, and M ³ is a hydrogen atom, an alkali metal or an alkaline earth metal ( 1/2 atom). ]

[Wherein R ^6c and R ^8c are each independently a hydrogen atom or a methyl group, R ^7c and R ^9c are each independently an alkylene group having 2 to 12 carbon atoms, m3 and m4 are each independently 1 to 30 , M ⁴ represents a hydrogen atom, an alkali metal or an alkaline earth metal (1/2 atom). ]
[Compound (D)]
A copolymer of an alkenyl ether (d1) represented by the following general formula (d1-1) and acrylic acid (d2) or a salt thereof, and a molar ratio (d2) of structural units in the copolymer or a salt thereof / (D1) is a copolymer of 95/5 to 50/50 or a salt thereof R ^1d —O (AO) _n4 —R ^2d (d1-1)
[Wherein, R ^1d is an alkenyl group having 2 to 4 carbon atoms, AO is an oxyalkylene group having 2 to 4 carbon atoms, an average added mole number n4 is a number having 20 to 120, and R ^2d is an alkyl having 1 to 3 carbon atoms. A group or a hydrogen atom is shown. ]
[Compound (E)]
Dialkyl sulfosuccinate [compound (F)]
It has an aliphatic hydrocarbon group having 8 or less carbon atoms or an aromatic hydrocarbon group having 18 or less carbon atoms and one or more polar groups selected from a carboxyl group, a sulfonic acid group, a sulfuric acid group and a phosphoric acid group. And an anionic compound [excluding those belonging to the compound (1-1) or the compound (E)], wherein the counter ion of the polar group is a counter ion selected from a hydrogen ion, an alkali metal ion, and an alkaline earth metal ion.
[Compound (G)]
A nonionic compound having an alkyl group having 1 to 8 carbon atoms and an oxyalkylene group having an average addition mole number of less than 10, and having a HLB of Davis of 5 to 9.   A method for producing a centrifugally formed ultrahigh strength concrete cured body, wherein the hydraulic composition for ultrahigh strength concrete according to claim 1 is subjected to centrifugal molding to produce an ultrahigh strength concrete cured body.   3. Centrifugal ultra-high strength concrete hardening according to claim 2, wherein the centrifugal molding has a step (first stage) of centrifugal molding for 1 to 5 minutes at an acceleration of 0.1 to 1.5 G immediately after the start of centrifugal compaction. Body manufacturing method.   The centrifugal molding further includes a step of performing centrifugal molding for 2 to 6 minutes at an acceleration of 2 to 10 G after the first stage (second stage), and a centrifugal molding for 1 to 5 minutes at an acceleration of 10 to 20 G after the second stage. Centrifugal molded ultra-high strength concrete having four steps: a step (third step), and a step (second step) of centrifugal molding for 1 to 6 minutes at an acceleration of 20 to 35 G after the third step. The method for producing a centrifugally formed ultrahigh strength concrete cured body according to claim 3, wherein the thickness of the inner wall surface of the cured body is small and smooth.