WO2019065314A1

WO2019065314A1 - Hydraulic composition for centrifugal molding

Info

Publication number: WO2019065314A1
Application number: PCT/JP2018/034237
Authority: WO
Inventors: 島田恒平; 岡内伸曉; 佐川桂一郎; 吉浪雄亮
Original assignee: 花王株式会社
Priority date: 2017-09-28
Filing date: 2018-09-14
Publication date: 2019-04-04
Also published as: JP2019064905A; JP6873955B2

Abstract

The present invention pertains to a hydraulic composition for centrifugal molding, the hydraulic composition containing, for example: (A1) a cationic polymer having a weight average molecular weight of 1,500-300,000 and having a quaternization degree of 5-100%; (B) a polycarboxylic acid-based dispersant; a hydraulic powder; an aggregate; and water. The present invention also pertains to a hydraulic composition for centrifugal molding, the hydraulic composition containing: (A2) a compound which is a polymer or copolymer having acrylic acid and/or maleic acid as constituent monomers and has an unneutralized carboxyl group; (B2) a polycarboxylic acid-based dispersant having an unneutralized carboxyl group; a hydraulic powder; an aggregate; and water. The present invention also pertains to a hydraulic composition for centrifugal molding, the hydraulic composition containing: (A3) a polymer or copolymer having acrylic acid and/or maleic acid as constituent monomers; (B1) a polycarboxylic acid-based dispersant; (C) a Brønsted acid; a hydraulic powder; an aggregate; and water.

Description

Hydraulic composition for centrifugal molding

The present invention relates to a dispersant composition for a hydraulic composition for centrifugal molding and a method for producing the same, a hydraulic composition for centrifugal molding, and a method for producing a cured hydraulic composition.

BACKGROUND ART Centrifugal molding is known as a method for producing hollow cylindrical concrete molded articles such as pipes, piles, poles and the like. This centrifugal forming method is a method in which the concrete material that has been kneaded is put into the mold, and the concrete is pressed against the inner surface of the mold by the centrifugal force generated by rotating the mold at high speed.
In hydraulic compositions for centrifugal molding, naphthalene type dispersants are often used as dispersants from the viewpoint of moldability of centrifugal molded products, but the need for high strength and anti-seismic reinforcement is increasing regardless of inside and outside the country In the area where a high-hardness cured product is required, as disclosed in No. 606, pp. 29-34 of the Architectural Institute of Japan Architectural Institute of Japan, published by The Architectural Institute of Japan, published in August 2006. In the area where the unit water content of concrete is small, an area where kneading is difficult due to the naphthalene type dispersing agent appears, and actual operation is difficult. Therefore, although the use of highly water-reducible polycarboxylic acid-based dispersants is in progress, the use of polycarboxylic acid-based dispersants causes a problem in the formability of centrifugal molded products.

If the formability of the centrifugally formed product is not good, a predetermined strength can not be obtained, and more labor is required for the digging process at the time of placing, and a large amount of processing for the sludge discharged as a result of the centrifugal forming. It will be expensive. When a polycarboxylic acid-based dispersant is used, the unit water content of the hydraulic composition needs to be in a specific range in order to maintain the formability of the centrifugally molded product, and the control range is narrow, and the surface of the material Since the required addition amount of the dispersant fluctuates due to water fluctuation, temperature change, etc., management is difficult, and it is difficult to manufacture a centrifugally-formed product having good moldability. Therefore, a hydraulic composition for centrifugal molding which exhibits excellent moldability in a wide range of compounding conditions such as the amount of water of the hydraulic composition and the additive amount of the dispersant is desired.

In addition, a dispersant composition containing a polycarboxylic acid-based dispersant does not separate from other additives in order to reduce equipment investment such as storage and measurement of additives in the production of a hydraulic composition. It is desirable to make a single liquefaction in a uniform state.

Japanese Patent Application Laid-Open No. 61-122147 discloses a medium-speed rotation of a concrete having a water-cement ratio of 35% or less and containing 35% or less of a centrifugal force at a water-cement ratio of 35% or less. There is disclosed a method of producing concrete characterized by compacting with

SUMMARY OF THE INVENTION According to the present invention, it is possible to maintain monoliquefaction in a uniform state without separating, and to obtain a cured product having excellent moldability when added to a hydraulic composition for centrifugal molding. For example, a dispersant composition for a hydraulic composition for centrifugal molding having a wide range of conditions such as water amount, a method for producing the same, and a hydraulic composition for centrifugal molding using a polycarboxylic acid-based dispersant, a curable composition having excellent moldability Provided are a hydraulic composition for centrifugal molding and a method for producing a cured hydraulic composition, wherein the compounding conditions under which a body is obtained, for example, the range of conditions such as the amount of water, the addition amount of a dispersant, etc. are wide.

The present invention is a cationic polymer (hereinafter referred to as component (A1)) having a weight average molecular weight of 1,500 to 300,000 and a quaternization ratio of 5 to 100%. (B1) A hydraulic composition for centrifugal molding comprising a polycarboxylic acid-based dispersant (hereinafter referred to as component (B1)), a hydraulic powder, an aggregate and water. Hereinafter, in the present invention, the hydraulic composition for centrifugal molding is referred to as a first hydraulic composition for centrifugal molding.

Moreover, this invention relates to the manufacturing method of the hydraulic composition hardening body containing the following processes.
Step 1: A step of mixing the component (A1), the component (B1), the hydraulic powder, the aggregate and water to obtain a hydraulic composition.
Step 2: A step of filling the hydraulic composition obtained in Step 1 into a mold.
Step 3: A step of clamping the hydraulic composition filled in the mold obtained in Step 2 by centrifugal force.
Step 4: A step of setting the clamped hydraulic composition obtained in step 3 in a mold.
Hereinafter, in the present invention, the method for producing the cured hydraulic composition is referred to as a first method for producing a cured hydraulic composition.

The present invention also relates to a dispersant composition for a hydraulic composition for centrifugal molding, which comprises the following component (A2), the following component (B2), and water.
Component (A2): a polymer or copolymer having acrylic acid and / or maleic acid as constituent monomers, wherein the carboxyl group is not neutralized (B2) component: polycarboxylic acid-based dispersant A dispersant in which carboxyl groups are not neutralized Hereinafter, in the present invention, the above-mentioned dispersant composition for a hydraulic composition for centrifugal molding is used as a first dispersant composition for a hydraulic composition for centrifugal molding.

The present invention also relates to a method for producing a dispersant composition for a hydraulic composition for centrifugal molding, wherein the component (A2), the component (B2) and the water are mixed. Hereinafter, in the present invention, the method for producing the dispersant composition for a hydraulic composition for centrifugal molding is referred to as a first method for producing a dispersant composition for a hydraulic composition for centrifugal molding.

The present invention also relates to a hydraulic composition for centrifugal molding, which comprises the component (A2), the component (B2), a hydraulic powder, an aggregate and water. Hereinafter, in the present invention, the hydraulic composition for centrifugal molding is referred to as a second hydraulic composition for centrifugal molding.

Moreover, this invention relates to the manufacturing method of the hydraulic composition hardening body containing the following processes.
Step 1 ′: a step of mixing the component (A2), the component (B2), the hydraulic powder, the aggregate and water to obtain a hydraulic composition.
Step 2 ': A step of filling the hydraulic composition obtained in Step 1' into a mold.
Step 3 ': A step of clamping the hydraulic composition filled in the mold obtained in Step 2' by centrifugal force.
Step 4 ': a step of setting the clamped hydraulic composition obtained in step 3' in a mold.
Hereinafter, in the present invention, the method for producing the cured hydraulic composition is referred to as a second method for producing a cured hydraulic composition.

Further, the present invention is a dispersant composition for a hydraulic composition for centrifugal molding, which comprises the following component (A3), the following component (B1), the following component (C), and water, and has a pH of 5 or less at 20 ° C. About.
Component (A3): Polymer or copolymer having acrylic acid and / or maleic acid as constituent monomers Component (B1): Polycarboxylic acid dispersant (C) Component: Bronsted acid Hereinafter, in the present invention, The dispersant composition for a hydraulic composition for centrifugal molding is used as a second dispersant composition for a hydraulic composition for centrifugal molding.

Further, according to the present invention, there is provided a dispersant composition for a hydraulic composition for centrifugal molding, wherein the component (A3), the component (B1), the component (C) and water are mixed so as to have a pH of 5 or less. It relates to the manufacturing method. Hereinafter, in the present invention, the method for producing the dispersant composition for a hydraulic composition for centrifugal molding is referred to as a second method for producing a dispersant composition for a hydraulic composition for centrifugal molding.

The present invention also relates to a hydraulic composition for centrifugal molding, which comprises the component (A3), the component (B1), the component (C), a hydraulic powder, an aggregate and water. Hereinafter, in the present invention, the hydraulic composition for centrifugal molding is referred to as a third hydraulic composition for centrifugal molding.

Moreover, this invention relates to the manufacturing method of the hydraulic composition hardening body containing the following processes.
Step 1 ′ ′-1: step of mixing the following (A3) component, the following (B1) component, the following (C) component, and water so that the pH is 5 or less to obtain a dispersant composition (A3) component : Polymer or copolymer having acrylic acid and / or maleic acid as constituent monomers (B1) component: polycarboxylic acid type dispersant (C) component: Bronsted acid step 1 ′ ′-2: step 1 ′ ′ A step of mixing the dispersant composition obtained in 1), hydraulic powder, aggregate and water to obtain a hydraulic composition.
Step 2 ": a step of filling the hydraulic composition obtained in Step 1" -2 into a mold.
Step 3 ′ ′: a step of clamping the hydraulic composition filled in the mold obtained in Step 2 ′ ′ by centrifugal force.
Step 4 ": setting the clamped hydraulic composition obtained in Step 3" in a mold.
Hereinafter, in the present invention, the method for producing the cured hydraulic composition is referred to as a third method for producing the cured hydraulic composition.

According to the present invention, in the hydraulic composition for centrifugal molding using a polycarboxylic acid-based dispersant, the compounding conditions under which a cured product having excellent moldability is obtained, for example, a wide range of conditions such as the amount of water and the amount of dispersant added A hydraulic composition for centrifugal molding and a method for producing a cured hydraulic composition are provided. Further, according to the present invention, in the hydraulic composition for centrifugal molding using a polycarboxylic acid-based dispersant, the formability of the cured product is excellent in a wide range of mixing conditions of the water content of the hydraulic composition and the dispersant addition amount. There is provided a hydraulic composition for centrifugal molding, and a method for producing a cured hydraulic composition. These findings can be applied to, for example, the first hydraulic composition for centrifugal molding of the present invention and the method for producing a first cured composition of the hydraulic composition.

According to the present invention, it is possible to maintain monoliquefaction in a uniform state without separating, and under the compounding conditions such that when added to a hydraulic composition for centrifugal molding, a cured product having excellent moldability can be obtained. For example, a dispersant composition for a hydraulic composition for centrifugal molding having a wide range of conditions such as water amount, a method for producing the same, and a hydraulic composition for centrifugal molding using a polycarboxylic acid-based dispersant, a cured product having excellent moldability The present invention provides a hydraulic composition for centrifugal molding and a method for producing a cured hydraulic composition, wherein the compounding conditions, such as the amount of water, are wide. Further, according to the present invention, it is possible to maintain monoliquefaction in a uniform state without separating, and when added to a hydraulic composition for centrifugal molding, curing is performed in a wide range of the water content of the hydraulic composition. In a dispersant composition for a hydraulic composition for centrifugal molding having excellent formability of a body, a method for producing the same, and a hydraulic composition for centrifugal molding using a polycarboxylic acid-based dispersant, a wide range of water content of the hydraulic composition The hydraulic composition for centrifugal molding which is excellent in the moldability of a hardening object, and the manufacturing method of a hydraulic composition hardening object are provided. These findings include, for example, the first dispersant composition for a hydraulic composition for centrifugal molding according to the present invention and a method for producing the same, the second dispersant composition for a hydraulic composition for centrifugal molding and a method for producing the same, It can apply to the manufacturing method of the hydraulic composition for centrifugal molding, the 2nd manufacturing method of the 2nd hydraulic composition hardening object, the 3rd hydraulic composition for centrifugal molding, and the 3rd hydraulic composition hardening object.

Modes for carrying out the invention (first hydraulic composition for centrifugal molding)
The present inventors have added the cationic polymer which is the component (A1) when kneading using the polycarboxylic acid-based dispersant which is the component (B1) in the first hydraulic composition for centrifugal molding. It has been found that the moldability of the centrifugally molded article is improved. The reason for such an effect to appear is not necessarily clear, but is presumed as follows. In the use of the component (B1) alone, depending on the amount of addition and the amount of water, the inorganic powder may be dispersed excessively and sludge may be generated by capillary flow generated at the time of centrifugal molding, and the components (A1) and (B1) may be used in combination. In addition, since the inorganic powder contained in the hydraulic composition can be effectively agglomerated and the hydraulic powder particles can be organized by crosslinking (the thixotropy is increased), thereby suppressing the generation of capillary flow. It is considered that the outflow of sludge from the centrifugally molded body is suppressed. Further, the present inventors can obtain an improvement effect of strength (hereinafter also referred to as 7-day strength) 7 days after kneading of the hardened body of the hydraulic composition as a secondary effect of the improvement of the moldability of the centrifugally molded body. I found out. The 7-day strength is an index indicating the strength of the cured product. The reason why the 7-day strength improvement effect is obtained is not always clear, but the inorganic early strengthening agent and hydration products discharged in large amounts as sludge from the centrifugally molded body suppress the outflow of sludge from the centrifugally molded body Thus, it is considered that the strength was improved by 7 days by being effectively held in the centrifugal molding.

The present invention contains (A1) component, (B1) component, hydraulic powder, aggregate and water. A first hydraulic composition is provided. Hereinafter, the first hydraulic composition of the present invention will be described.

<(A1) component>
The component (A1) is a cationic polymer having a weight average molecular weight of 1,500 to 300,000 and a quaternization ratio of 5% to 100%. The component (A1) is a polymer compound having a monomer unit containing a cationic group.

As component (A1), polyamidepolyamine / epichlorohydrin condensate, dimethylamine / ammonia / epichlorohydrin condensate, dimethylamine / trimethylamine / epichlorohydrin condensate, cationized cellulose, cationized starch, cationized guar gum, cationized tara gum , Cationized locust bean gum, cationized fenugreek gum, cationized xanthan gum, polymer of diallyl dialkyl quaternary ammonium salt, diallyl dialkyl quaternary ammonium salt / acrylamide copolymer, diallyl dialkyl quaternary ammonium salt / acrylamide / acrylic acid copolymer Polymer, vinyl imidazolium trichloride / vinyl pyrrolidone copolymer, hydroxyethyl cellulose / dimethyldiallyl ammonium chloride co-polymer Combined, polymer of quaternized dimethylaminoethyl methacrylate, polymer of quaternized dimethylaminoethyl acrylate, vinylpyrrolidone / quaternized dimethylaminoethyl methacrylate copolymer, quaternary to which polyoxyalkylene group may be added Polyethylenimine, vinylpyrrolidone / alkylaminoacrylate copolymer, vinylpyrrolidone / alkylaminoacrylate / vinylcaprolactam copolymer, vinylpyrrolidone / methacrylamidopropyl trimethyl ammonium chloride copolymer, alkylacrylamide / acrylate / alkylaminoalkylacrylamide / And polyethylene glycol methacrylate copolymer, adipic acid / dimethylaminohydroxypropyl ethylene triamine copolymer, which may be used alone or in combination. Or more can be used species. Examples of the anion which is a counter ion of these cationic polymers include halide ions such as chloride ion and alkyl sulfate ions such as ethyl sulfate ion, preferably chloride ion or ethyl sulfate ion.

As component (A1), from the viewpoint of centrifugal formability, the weight of polyamidepolyamine / epichlorohydrin condensate, dimethylamine / ammonia / epichlorohydrin condensate, dimethylamine / trimethylamine / epichlorohydrin condensate, diallyl dialkyl quaternary ammonium salt At least one member selected from a combination, a quaternized polyethyleneimine to which a polyoxyalkylene group may be added, and a polymer of a quaternized dimethylaminoethyl methacrylate is preferred, and polyamidepolyamine / epichlorohydrin condensate, dimethylamine / Ammonia / epichlorohydrin condensate, polymer of diallyldialkyl quaternary ammonium salt, quaternized polyethylenimine to which polyoxyalkylene group may be added, and polymer of quaternized dimethylaminoethyl methacrylate And more preferably selected from polyamide polyamine / epichlorohydrin condensates, polymers of diallyldialkyl quaternary ammonium salts, quaternized polyethyleneimines to which polyoxyalkylene groups may be added, and quaternization One or more selected from polymers of dimethylaminoethyl methacrylate are more preferable.

The quaternization rate of the component (A1) is 5% or more, preferably 7% or more, more preferably 9% or more, and 100% or less from the viewpoint of centrifugal formability. In the present invention, the "quaternization ratio" means the ratio (%) of the molar equivalent number of quaternary ammonium groups to the molar equivalent number of all amino groups contained in the cationic polymer. The quaternization ratio is determined by using the cation equivalent (hereinafter referred to as Q4) (meq / g) determined at pH 4 and the cation equivalent (hereinafter referred to as Q10) (meq / g) determined at pH 10 in the following measurement method. It is obtained by the following formula.
[Calculation of quaternization rate]
The quaternization rate is calculated according to the following equation.
Quaternization ratio (%) = Q10 (meq / g) × 100 / Q4 (meq / g)

[Measurement of cation equivalent]
The cation equivalent Q4 and Q10 are measured and calculated at the two points of pH 4 and 10 by the following method. 100 g of a measurement sample is placed in a 200 mL conical beaker, and while stirring with a magnetic stirrer (500 rpm), a 0.5 wt% aqueous sulfuric acid solution is gradually added to adjust the pH. Then add 2-3 drops of toluidine blue indicator (TB indicator) and titrate with N / 400 polyvinyl potassium sulfate (N / 400 PVSK) reagent. The titration rate is 2 mL / min, and the end point is when the measurement sample turns from blue to reddish purple and the reddish purple is retained for 30 seconds.
[Blank test]
The same operation as measurement of cation equivalent is performed except that 100 g of ion exchanged water is used instead of the measurement sample.
[Method of calculation]
Cation equivalent value (meq / g) = (1/2)
× (titer of sample-titre of blank test) × (titer of N / 400 PVSK)

From the viewpoint of centrifugal moldability, the total amount of the monomer having an amino group and the monomer having a quaternary ammonium group in the constituent monomers is preferably 90% by mass or more, and the component (A1) is more preferably Is 92 mass% or more, more preferably 95 mass% or more, and preferably 100 mass% or less. This total amount may be 100% by mass.

The weight average molecular weight of the component (A1) is 1,500 or more, preferably 2,000 or more, more preferably 2,500 or more from the viewpoint of centrifugal formability, and 300,000 or less from the viewpoint of centrifugal formability. Preferably it is 250,000 or less, More preferably, it is 200,000 or less.

The weight average molecular weight of the component (A1) can be measured using gel permeation chromatography (GPC) under the following conditions.
[GPC conditions]
Column: α-M (made by Tosoh Corporation) Two connected eluent: 0.15 mol / L Na sulfate, 1% aqueous acetic acid flow rate: 1.0 mL / min
Temperature: 40 ° C
Detector: RI
Molecular weight standard: pullulan

<(B1) component>
The component (B1) is a polycarboxylic acid dispersant. As the component (B1), a copolymer containing a monomer (B11) represented by the following general formula (B11) and a monomer (B12) represented by the following general formula (B12) as a constituent monomer [ Hereinafter, the copolymer (B1) is mentioned.

[In the formula,
R ^11b , R ^12b : identical or different, hydrogen atom or methyl group R ^13b : hydrogen atom or — (CO) _q1 O (AO) _{n1 ′} X ¹
X ¹ : an alkyl group having 1 to 4 carbon atoms AO: a group selected from an ethyleneoxy group and a propyleneoxy group n1 ′: an average added mole number of AO, and a number of 1 to 300 and a number p1: 0 to 2 Number q 1: 0 Indicates the number of 1 or 1. ]

[In the formula,
R ^14b , R ^15b and R ^16b : may be the same or different, and are a hydrogen atom, a methyl group or (CH ₂ ) _r1 COOM ² ; (CH ₂ ) _r1 COOM ² is COOM ¹ or other (CH ₂₎ Anhydrous may be formed with _r1 COOM ² , in which case M ¹ and M ² of those groups are absent.
M ¹ and M ² may be the same or different, and 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 r 1: 0 to 2 Indicates ]

In general formula (B11), R ^11b is preferably a hydrogen atom.
In general formula (B11), R ^12b is preferably a methyl group.
In general formula (B11), R ^13b is preferably a hydrogen atom.
In general formula (B11), X ¹ is preferably a methyl group.
In the general formula (B11), AO is preferably an ethyleneoxy group. Preferably, AO contains an ethyleneoxy group.

In general formula (B11), n1 'is an average added mole number of AO, and is a number of 1 or more and 300 or less. n1 ′ is preferably 10 or more, more preferably 20 or more, and preferably 250 or less, more preferably 200 or less, from the viewpoint of centrifugal moldability and / or strength development of the cured product after centrifugal molding .

In general formula (B11), p1 is preferably 0.
In the general formula (B11), q1 is preferably 1. The copolymer (B1) of the component (B1) comprises a monomer (B11) in which q1 is 1 in the general formula (B11) and a monomer (B12) represented by the general formula (B12). It contains the copolymer which contains as a monomer.

In general formula (B12), R ^14b is preferably a hydrogen atom.
In general formula (B12), R ^15b is preferably a methyl group or a hydrogen atom.
In the general formula (B12), R ^16b is preferably a hydrogen atom.
The _(CH _²⁾ r1 COOM 2, may form a ^{COOM 1} or another _(CH _²⁾ r1 COOM ₂ and anhydride, in which case, ^M 1, ^{M 2} in these groups are not present.
With regard to the copolymer (B1), in the general formula (B12), M ¹ and M ² may be the same or different, and each is preferably a hydrogen atom.
As r 1 of (CH ₂ ) _r1 COOM ^{2 in} the general formula (B12), 1 is preferable.

In the copolymer (B1), the total amount of the monomer (B11) and the monomer (B12) in the constituent monomers is 90% by mass from the viewpoint of centrifugal moldability and / or strength development of the cured product The content is preferably 92% by mass or more, more preferably 95% by mass or more and 100% by mass or less. This total amount may be 100% by mass.

In the copolymer (B1), the ratio of the monomer (B12) to the total of the monomer (B11) and the monomer (B12) is from the viewpoint of centrifugal moldability and / or strength of the cured product after centrifugal molding Preferably, it is 10 mol% or more, more preferably 20 mol% or more, and preferably 99 mol% or less, more preferably 95 mol% or less.

The weight average molecular weight of the copolymer (B1) is preferably 10,000 or more, more preferably 15,000 or more, and preferably 100,000 or less, more preferably 70,000 or less, still more preferably 50,000. It is below. The weight average molecular weight is measured by gel permeation chromatography (GPC) under the following conditions.
* GPC conditions Device: GPC (HLC-8320GPC) made by Tosoh Corp. Column: G4000PWXL + G2500PWXL (made by Tosoh Corp.)
Eluent: 0.2 M phosphate buffer / CH ₃ CN = 9/1
Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Detection: RI
Sample size: 0.2 mg / mL
Standard substance: converted to polyethylene glycol (monodispersed polyethylene glycol: molecular weight 87, 500, 250,000, 145,000, 46,000, 24,000)

<Hydraulic powder>
The hydraulic powder used in the first hydraulic composition for centrifugal molding of the present invention refers to a powder having physical properties to be cured by hydration reaction, and examples thereof include cement, gypsum and the like. Preferred are cements such as ordinary Portland cement, belite cement, medium heat cement, early strength cement, ultra early strength cement, sulfuric acid resistant cement and the like, and blast furnace slag, fly ash, silica fume, stone powder (calcium carbonate powder), etc. In addition, blast furnace slag cement, fly ash cement, silica fume cement, etc. may be added. A hydraulic composition finally obtained by adding sand, sand and gravel as an aggregate to these powders is generally called mortar, concrete or the like.

<Aggregate>
The first hydraulic hydraulic composition for centrifugal molding of the present invention contains an aggregate. The aggregate includes an aggregate selected from fine aggregate and coarse aggregate. As fine aggregate, those specified by No. 2311 in JIS A 0203-2014 can be mentioned. Fine aggregate includes river sand, land sand, mountain sand, sea sand, lime sand, silica sand and crushed sand thereof, blast furnace slag fine aggregate, ferro nickel slag fine aggregate, lightweight fine aggregate (artificial and natural) and regeneration Fine aggregate etc. are mentioned. Further, as the coarse aggregate, those defined by No. 2312 in JIS A 0203-2014 can be mentioned. For example, as coarse aggregate, river gravel, land gravel, mountain gravel, sea gravel, lime gravel, these crushed stones, blast furnace slag coarse aggregate, ferro nickel slag coarse aggregate, lightweight coarse aggregate (artificial and natural) and regeneration Coarse aggregate etc. are mentioned. Fine aggregate and coarse aggregate may be used as a mixture of different types, or a single type may be used.

<Composition of hydraulic composition etc>
In the first hydraulic composition for centrifugal molding of the present invention, the content of the component (A1) is preferably 0.01 parts by mass or more, relative to 100 parts by mass of the hydraulic powder, from the viewpoint of centrifugal moldability. More preferably 0.015 parts by mass or more, further preferably 0.02 parts by mass or more, and from the viewpoint of centrifugal formability, preferably 1 part by mass or less, more preferably 0.90 parts by mass or less, still more preferably 0 The content is not more than 80 parts by mass, more preferably not more than 0.60 parts by mass, still more preferably not more than 0.40 parts by mass.

In the first hydraulic composition for centrifugal molding of the present invention, the content of the component (B1) is based on 100 parts by mass of the hydraulic powder from the viewpoint of centrifugal moldability and / or the strength of the cured product after centrifugal molding. , Preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.10 parts by mass or more, still more preferably 0.20 parts by mass, and centrifugal formability and / or centrifugation From the viewpoint of the strength of the cured product after molding, it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 6 parts by mass or less, still more preferably 4 parts by mass or less, still more preferably 2 parts by mass It is not more than part, more preferably not more than 1.5 parts by mass.

In the first hydraulic composition for centrifugal molding of the present invention, the total content of the components (A1) and (B1) is hydraulic in terms of centrifugal moldability and / or strength of a cured product after centrifugal molding. To 100 parts by mass of the powder, preferably 0.02 parts by mass or more, more preferably 0.05 parts by mass or more, further preferably 0.10 parts by mass or more, still more preferably 0.20 parts by mass or more Or 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 6 parts by mass or less, still more preferably 4 parts by mass from the viewpoint of centrifugal moldability and / or strength of the cured product after centrifugal molding The content is more preferably 2 parts by mass or less.

In the first hydraulic composition for centrifugal molding of the present invention, the mass ratio (B1) / (A1) of the content of the component (A1) to the content of the component (B1) is centrifugal moldability and / or centrifugal molding From the viewpoint of the strength of the cured product later, preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.10 or more, still more preferably 0.50 or more, and centrifugal formability and / or Or from the viewpoint of the strength of the cured product after centrifugal molding, preferably 100 or less, more preferably 90 or less, still more preferably 80 or less, still more preferably 60 or less, still more preferably 40 or less, still more preferably 30 It is below.

The first hydraulic composition for centrifugal molding of the present invention has a water / hydraulic powder ratio (hereinafter sometimes referred to as W / P), but from the viewpoint of centrifugal moldability and strength, 10% by mass or more 12 mass% or more is more preferable, 14 mass% or more is more preferable, and 30 mass% or less is preferable, 25 mass% or less is more preferable, 24 mass% or less is more preferable, 23 mass% or less is further more Preferably, 22 mass% or less is still more preferable.
In the present invention, the water / hydraulic powder ratio is a mass percentage (mass%) of water and hydraulic powder in the hydraulic composition, and is calculated by water / hydraulic powder × 100. The water / hydraulic powder ratio is calculated on the basis of the amount of powder having physical properties to be hardened by hydration reaction. When the powder having physical properties that hardens by hydration reaction contains a high strength admixture, the amount of high strength admixture is also included in the amount of hydraulic powder. The same applies to other quantitative relationships of hydraulic compositions with respect to hydraulic powders.

When the first hydraulic composition for centrifugal molding of the present invention is concrete, the amount of use of the coarse aggregate reduces the expression of strength of the hydraulic composition and the amount of hydraulic powder such as cement to reduce the amount of formwork. The bulk volume is preferably 50% or more, more preferably 55% or more, still more preferably 60% or more, and preferably 100% or less, more preferably 90%, from the viewpoint of improving the packing property to etc. The following content is more preferably 80% or less. Bulk volume is the proportion of the volume of coarse aggregate (including voids) in 1 m ^{3 of} concrete.
When the first hydraulic composition for centrifugal molding of the present invention is concrete, the amount of fine aggregate used is preferably 500 kg / m ³ or more, more preferably from the viewpoint of improving the filling property to a mold or the like. Is 600 kg / m ³ or more, more preferably 700 kg / m ³ or more, and preferably 1000 kg / m ³ or less, more preferably 900 kg / m ³ or less.
When the first hydraulic composition for centrifugal molding of the present invention is a mortar, the amount of fine aggregate used is preferably 800 kg / m ³ or more, more preferably 900 kg / m ³ or more, still more preferably 1000 kg / m ³ or more And preferably 2000 kg / m ³ or less, more preferably 1800 kg / m ³ or less, and still more preferably 1700 kg / m ³ or less.

As the first hydraulic composition for centrifugal molding of the present invention, concrete etc. may be mentioned. Above all, concrete using cement is preferable. The first hydraulic composition for centrifugal molding of the present invention is for self-leveling, for refractories, for plaster, for light weight or heavy concrete, for AE, for repair, for prepacked, for trauma, for ground improvement, for grout, It is useful in any field such as cold and cold use.

The first hydraulic composition for centrifugal molding of the present invention can also contain glycerin and a early strengthening agent such as N-methyldiethanolamine and a chelating agent such as ethylenediaminetetraacetic acid sodium salt. The content of the chelating agent is preferably 0.1 parts by mass or less based on 100 parts by mass in total of the hydraulic powder and the high-strength admixture containing silica, from the viewpoint of strength development after steam curing.

The first hydraulic composition for centrifugal molding of the present invention is a conventional cement dispersant, a water-soluble polymer compound, an air entrainer, a cement wetting agent, an expansive agent, a waterproofing agent, a retarder, a quick-setting agent, and a foaming agent. Components such as foaming agents, waterproofing agents, fluidizing agents, thickening agents, flocculants, drying shrinkage reducing agents, strength promoters, curing accelerators, preservatives, antifoaming agents [(A1) component, (B1) component And the like can be included.

[First Method of Manufacturing Hydraulic Composition for Centrifugal Molding]
The present invention provides a first method for producing a hydraulic composition for centrifugal molding, which comprises mixing the (A1) component, the (B1) component, the hydraulic powder, the aggregate and water. According to this production method, a first hydraulic composition for centrifugal molding of the present invention comprising the component (A1), the component (B1), the hydraulic powder, the aggregate, and water is produced. Hereinafter, the manufacturing method of the 1st hydraulic composition of this invention is demonstrated.

Specific examples and preferred embodiments of the components (A1) and (B1) used in the first method for producing a hydraulic composition for centrifugal molding according to the present invention are the first hydraulic composition for a centrifugal molding according to the present invention. Same as stated.
In addition, specific examples and preferred embodiments of the hydraulic powder and aggregate used in the first method for producing a hydraulic composition for centrifugal molding according to the present invention are described in the first hydraulic composition for centrifugal molding according to the present invention It is the same as the one. The hydraulic powder is used such that W / P is in the range described in the first hydraulic composition for centrifugal molding of the present invention. The amount of aggregate used is also the same as that described in the first hydraulic composition for centrifugal molding of the present invention.
The matters described in the first hydraulic composition for centrifugal molding of the present invention can be appropriately applied to the first method for producing a hydraulic composition for centrifugal molding of the present invention.

In the first method for producing a hydraulic composition for centrifugal molding of the present invention, the component (A1) is preferably 0.01 parts by mass or more, relative to 100 parts by mass of the hydraulic powder, from the viewpoint of centrifugal formability, More preferably 0.015 parts by mass or more, further preferably 0.02 parts by mass or more, and from the viewpoint of centrifugal formability, preferably 1 part by mass or less, more preferably 0.90 parts by mass or less, still more preferably 0 .80 parts by mass or less, more preferably 0.60 parts by mass or less, still more preferably 0.40 parts by mass or less. It is preferable to mix (A1) component so that it may become content of (A1) component in the hydraulic composition for 1st centrifugation of this invention.

In the first method for producing a hydraulic composition for centrifugal molding of the present invention, the component (B1) is added to 100 parts by mass of the hydraulic powder from the viewpoint of centrifugal moldability and / or strength of the cured product after centrifugal molding. , Preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.10 parts by mass or more, still more preferably 0.20 parts by mass, and centrifugal formability and / or centrifugation From the viewpoint of the strength of the cured product after molding, it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 6 parts by mass or less, still more preferably 4 parts by mass or less, still more preferably 2 parts by mass The mixing is carried out in part or less, more preferably 1.5 parts by mass or less. It is preferable to mix the (B1) component so that it may become content of the (B1) component in the hydraulic composition for 1st centrifugation of this invention.

In the first method for producing a hydraulic composition for centrifugal molding of the present invention, the total of the components (A1) and (B1) is a hydraulic powder from the viewpoint of centrifugal moldability and / or strength of a cured product after centrifugal molding. To 100 parts by mass of the body, preferably 0.02 parts by mass or more, more preferably 0.05 parts by mass or more, further preferably 0.10 parts by mass or more, still more preferably 0.20 parts by mass or more, and From the viewpoint of centrifugal moldability and / or strength of the cured product after centrifugal molding, it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 6 parts by mass or less, still more preferably 4 parts by mass or less Still more preferably, it mixes so that it may be 2 mass parts or less. It is preferable to mix the (A1) component and the (B1) component so that the total content of the (A1) component and the (B1) component in the first hydraulic composition for centrifugal molding of the present invention is obtained.

In the first method for producing a hydraulic composition for centrifugal molding according to the present invention, the components (A1) and (B1) may be components (A1), from the viewpoint of centrifugal moldability and / or strength of the cured product after centrifugal molding. The mass ratio (B1) / (A1) of the component and the component (B1) is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.10 or more, still more preferably 0.50 or more, and Or 100 or less, more preferably 90 or less, still more preferably 80 or less, still more preferably 60 or less, still more preferably 40 or less from the viewpoint of centrifugal moldability and / or strength of the cured product after centrifugal molding Even more preferably, it mixes so that it may be 30 or less.

In the first method for producing a hydraulic composition for centrifugal molding according to the present invention, the components (A1) and (B1) and water are mixed in advance and mixed with the hydraulic powder from the viewpoint of productivity. preferable.

Mixing of the component (A1), the component (B1), the hydraulic powder, the aggregate, the water, and the component used as needed is performed using a mixer such as a mortar mixer or a forced twin-screw mixer. be able to. The mixing time is preferably 1 minute or more, more preferably 2 minutes or more, and preferably 5 minutes or less, more preferably 3 minutes or less. In the preparation of the hydraulic composition, the materials and agents described in the first hydraulic composition for centrifugal molding of the present invention and their amounts can be used.

The obtained hydraulic composition is further filled with the hydraulic composition in a mold, cured and cured. As a formwork, the formwork of a building, the formwork for concrete products, etc. are mentioned. As a method for filling the mold, a method of directly feeding from a mixer, a method of pumping the hydraulic composition by a pump and introducing it into the mold, and the like can be mentioned.

During curing of the hydraulic composition, heat curing may be performed to accelerate the curing, and curing may be accelerated. Here, heat curing can accelerate the curing by holding the hydraulic composition at a temperature of 40 ° C. or more and 90 ° C. or less.

[Method of producing cured product of first hydraulic composition]
The present invention provides a method for producing a cured product of a first hydraulic composition, comprising the following steps.
Step 1: A step of mixing the (A1) component, the (B1) component, the hydraulic powder, the aggregate and water to obtain a hydraulic composition.
Step 2: A step of filling the hydraulic composition obtained in Step 1 into a mold.
Step 3: A step of clamping the hydraulic composition filled in the mold obtained in Step 2 by centrifugal force.
Step 4: A step of setting the clamped hydraulic composition obtained in step 3 in a mold.
Hereinafter, the manufacturing method of the 1st hydraulic composition hardening body of this invention is demonstrated.

The specific example and the preferable aspect of (A1) component and (B1) component used for the manufacturing method of the hardened | cured material of the 1st hydraulic composition of this invention respectively are 1st hydraulic composition for centrifugal molding of this invention It is the same as described in.
In addition, specific examples and preferable embodiments of the hydraulic powder and aggregate used in the method for producing a cured product of the first hydraulic composition of the present invention are described in the first hydraulic composition for centrifugal molding of the present invention. It is the same as The hydraulic powder is used such that W / P is in the range described in the first hydraulic composition for centrifugal molding of the present invention. The amount of aggregate used is also the same as that described in the first hydraulic composition for centrifugal molding of the present invention.
The matters described in the first hydraulic forming composition for centrifugal molding and the first method for producing a hydraulic composition for centrifugal forming of the present invention are suitable for the method for producing a cured product of the first hydraulic composition of the present invention. It can apply.

The process for producing a cured product of the first hydraulic composition of the present invention preferably includes the following step 5 in addition to steps 1 to 4.
Step 5: Steam curing the hydraulic composition condensed in step 4 in a mold.

The process for producing a cured product of the first hydraulic composition of the present invention can include the following step 6 in addition to steps 1 to 5.
Step 6: After step 5, the hydraulic composition is cooled and removed from the mold.

The process for producing a cured product of the first hydraulic composition of the present invention can include the following step 7 in addition to steps 1 to 6.
Step 7: A step of curing the cured product of the hydraulic composition obtained in Step 6 at normal temperature and pressure.

In step 1, from the viewpoint of centrifugal formability, the component (A1) is preferably 0.01 parts by mass or more, more preferably 0.015 parts by mass or more, still more preferably 100 parts by mass of hydraulic powder. 0.02 parts by mass or more, and preferably 1 part by mass or less, more preferably 0.90 parts by mass or less, still more preferably 0.80 parts by mass or less, still more preferably 0.60 parts by mass from the viewpoint of centrifugal formability The mixing is carried out in parts by mass or less, more preferably 0.40 parts by mass or less. It is preferable to mix (A1) component so that it may become content of (A1) component in the hydraulic composition for 1st centrifugation of this invention.

In step 1, from the viewpoint of centrifugal moldability and / or strength of the cured product after centrifugal molding, the component (B1) is preferably 0.01 parts by mass or more, relative to 100 parts by mass of the hydraulic powder. The amount is preferably 0.05 parts by mass or more, more preferably 0.10 parts by mass or more, still more preferably 0.20 parts by mass or more, and in view of centrifugal formability and / or cured body strength after centrifugal form. The amount is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 6 parts by mass or less, still more preferably 4 parts by mass or less, still more preferably 2 parts by mass or less, still more preferably 1.5 parts by mass Mix in parts or less. It is preferable to mix the (B1) component so that it may become content of the (B1) component in the hydraulic composition for 1st centrifugation of this invention.

In step 1, the total of the components (A1) and (B1) is preferably 0 parts by weight with respect to 100 parts by mass of the hydraulic powder, from the viewpoint of centrifugal moldability and / or strength of the cured product after centrifugal molding. .02 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.10 parts by mass or more, still more preferably 0.20 parts by mass or more, and centrifugal formability and / or curing after centrifugal form From the viewpoint of body strength, preferably 10 parts by mass or less, more preferably 8 parts by mass or less, further preferably 6 parts by mass or less, still more preferably 4 parts by mass or less, still more preferably 2 parts by mass or less Mix as you like. It is preferable to mix the (A1) component and the (B1) component so that the total content of the (A1) component and the (B1) component in the first hydraulic composition for centrifugal molding of the present invention is obtained.

In step 1, from the viewpoint of centrifugal moldability and / or strength of the cured product after centrifugal molding, the mass ratio of the (A1) component to the (B1) component is the (A1) component and the (B1) component (B1) / ( A1) is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.10 or more, still more preferably 0.50 or more, and centrifugal formability and / or a cured product after centrifugal form From the viewpoint of strength, mixing is preferably performed so as to be preferably 100 or less, more preferably 90 or less, still more preferably 80 or less, still more preferably 60 or less, still more preferably 40 or less, still more preferably 30 or less. .

In the step 1, the method of adding and mixing the mixture containing water, the component (A1) and the component (B1) to the mixture containing the aggregate and the hydraulic powder, even when producing the hydraulic composition, It is preferable in that it can be easily mixed uniformly.

As a specific method of step 1, the hydraulic powder and the aggregate are mixed, and a mixture containing water, the (A1) component and the (B1) component is added so as to obtain the mixing amount as described above. And kneading to prepare a hydraulic composition.

In the step 1, the (A1) component and the (B1) component can be separately added to water, hydraulic powder and aggregate and mixed.

In step 1, in view of centrifugal formability and strength, W / P is preferably 10% by mass or more, more preferably 12% by mass or more, still more preferably 14% by mass or more, and preferably 30% by mass or less The hydraulic composition is prepared, more preferably 25% by mass or less, still more preferably 24% by mass or less, still more preferably 23% by mass or less, and still more preferably 22% by mass or less.

The method for filling the hydraulic composition obtained in step 1 into the mold in step 2 is a method in which the hydraulic composition after kneading is discharged from the kneading means and manually poured into the mold in a smooth manner. It can be mentioned.

In step 3, the hydraulic composition filled in the mold is subjected to centrifugal force to clamp the mold, and at this time, it is preferable to change the centrifugal force at least once. In step 3, the hydraulic composition can be clamped with a stepwise change of centrifugal force. That is, in step 3, the hydraulic composition can be clamped at least once by changing the centrifugal force and clamping, and further applying the stepwise changing, further increasing centrifugal force. .

In step 3, it is preferable to clamp the hydraulic composition filled in the mold with a centrifugal force of 0.5 G or more. The centrifugal force of centrifugal molding is preferably 0.5 G or more, and preferably 30 G or less, more preferably 25 G or less. From the aspect of energy cost reduction and formability, it is preferable to keep the centrifugal force in a range of 15 G or more, 30 G or less, and further 25 G or less (also referred to as high centrifugal force) for 1 minute or more.

Compaction with a centrifugal force is performed, for example, with a centrifugal force of 0.5 G to 30 G, preferably 5 minutes or more, more preferably 7 minutes or more, still more preferably 9 minutes or more, and preferably 40 minutes or less. From the viewpoint of compacting the compact smoothly, compaction by holding a high centrifugal force, for example, a centrifugal force of 20 G or more is preferably 1 minute or more, more preferably 3 minutes or more, still more preferably 5 minutes or more, and preferably Do less than 15 minutes. That is, in step 3, the hydraulic composition is preferably applied for a centrifugal force of 0.5 G to 30 G, preferably 5 minutes or more, more preferably 7 minutes or more, still more preferably 9 minutes or more, and preferably 40 minutes or less You can clamp things. In step 3, compaction by holding a centrifugal force of 20 G or more can be carried out preferably for 1 minute or more, more preferably 3 minutes or more, still more preferably 5 minutes or more, and preferably 15 minutes or less.

Compaction by centrifugal force can be performed in stages, and from the viewpoint of formability, a method of increasing centrifugal force G stepwise is preferable. It can carry out until it becomes a desired centrifugal force under the following step conditions. For example, in the case of five stages, in step 3, (1) the initial speed of the first stage is 0.5 G or more and less than 2 G, and the centrifugal force is more than 0 minutes for 15 minutes or less; More than 0 minutes with less than 5 G of centrifugal force and less than 15 minutes with (3) third step, 3 steps of 5 G or more and less than 10 G with centrifugal force of 0 5 minutes with less than 0 G The hydraulic composition has a centrifugal force of 10 G or more and less than 20 G for more than 0 minutes and 15 minutes or less, and a fifth speed that is the fifth step of (5) is 20 G or more and 30 G or less for more than 0 minutes and 15 minutes or less It is preferable to perform mold clamping.

In step 4, the hydraulic composition obtained in step 3 is coagulated. Specifically, air curing for 3 to 4 hours after kneading is performed.

In step 5, the cured hydraulic composition placed in the mold obtained in step 4 is steam cured. In the step 5, steam curing is preferably performed at 40 ° C. or more and 90 ° C. or less, and more preferably, steam curing is performed at 60 ° C. or more and 90 ° C. or less.
Furthermore, in the step 5, it is preferable to carry out steam curing after pre-curing. For example, before curing the ambient temperature of the mold filled with the hydraulic composition (hereinafter sometimes referred to as ambient temperature) to room temperature, preferably 10 ° C. or more and 40 ° C. or less, and standing for 1 hour or more and 4 hours or less After curing, steam curing can be performed at an ambient temperature of 40.degree. C. to 90.degree. C., and further 60.degree. C. to 90.degree.
Pre-curing was carried out as "pre-loading" in Examples and Comparative Examples described later.
The pre-curing is preferably one hour or more from the viewpoint of suppressing a decrease in strength due to cracking of the cured product.
Moreover, when the manufacturing method of the hardened | cured material of this invention includes the process 6, the process 5 and the process 6 can be continuously performed under a series of temperature control.
The steam curing is carried out by maintaining the water vapor around the mold filled with the hydraulic composition for a certain period of time at a predetermined temperature. After applying steam, (1) temperature rise period to reach a predetermined temperature, (2) period to hold for a fixed time at a predetermined temperature, and (3) temperature decrease for a fixed time after held at a predetermined temperature The period may be a period of steam curing.

As a specific steam curing condition in the method for producing a cured product according to the present invention, the ambient temperature of the mold is raised to 60 ° C. to 85 ° C. at a temperature rising rate of 10 ° C. to 30 ° C. per hour as Step 5 And hold the elevated temperature for 2 hours or more and 8 hours or less, then, as step 6, cool the ambient temperature to room temperature, for example 20 ° C. at a temperature drop rate of 5 ° C. or more and 20 ° C. or less per hour; Unmold.
The temperature raising rate is preferably 20 ° C. or less per hour from the viewpoint of suppressing the strength decrease due to the crack of the cured product.
As one example of preferable conditions, a mold filled with a hydraulic composition is allowed to stand (precure) at ambient temperature, for example, 10 ° C. or more and 30 ° C. or less for 3 hours, and is raised by 20 ° C. per hour The ambient temperature is raised to 70 ° C. or more and 90 ° C. or less at a heating rate, and the raised temperature of 70 ° C. or more and 90 ° C. or less is held for 2 hours or more and 6 hours or less, and then at a temperature lowering rate of 10 ° C. per hour. The method may be such that the ambient temperature is cooled to room temperature, for example 20 ° C. (Step 5), left at that temperature for 20 hours to 30 hours, and then the shaped body is removed (Step 6).
In addition, it is also possible to carry out autoclave curing at about 180 ° C.

In step 7, the cured product of the hydraulic composition obtained in step 6 is cured at normal temperature and pressure. Specifically, it is stored at 20 ° C. under atmospheric pressure.

The method for producing a cured product of the first hydraulic composition of the present invention includes steps 1 to 6, and the time from the start of preparation of the hydraulic composition to the removal of the mold in step 6 is 8 hours or more The manufacturing method which is 30 hours or less is mentioned. Here, the start of preparation of a hydraulic composition is a point when hydraulic powder and water contact first.

Method for Producing Hardened Body of First Hydraulic Composition of the Present Invention The cured body of the hydraulic composition obtained by the method for producing a hardened body can be used as a centrifugally formed concrete product, and specifically, piles, poles, A fume pipe etc. are mentioned. The cured product of the hydraulic composition obtained by the method for producing a cured product of the present invention is excellent in initial strength, and can reduce waste generated at the production site of the product with a small amount of generation of slag during production. Moreover, since it is excellent in compaction, the inner surface and end face unevenness of the product are small, the surface appearance is excellent, and the inner surface of the product is smoothed, thereby improving obstacles to the cutting machine during pile driving and Nakabori method. .

[First Dispersing Agent Composition for Centrifugal Molding Hydraulic Composition]
In the first dispersing agent composition for a hydraulic composition for centrifugal molding according to the present invention, the present inventors, as a component (A2), a polymer or copolymer containing acrylic acid and / or maleic acid as constituent monomers It is a polymer, It is a polycarboxylic-acid-type dispersing agent which is a compound in which a carboxyl group is not neutralized, and a component (B2), Comprising: The dispersing agent composition which contains a compound in which a carboxyl group is not neutralized is It has been found that monoliquefaction can be maintained in a uniform state without layering.
The reason for such an effect to appear is not necessarily clear, but is presumed as follows. When the mixing entropy of the two polymers in the common solvent is small and the mixing enthalpy takes a positive value, the mixing Gibbs free energy becomes positive, causing phase separation. By mixing the carboxyl groups in an unneutralized state, the interaction with water molecules can be reduced, and the increase in mixing entropy can be increased. As a result, the mixed Gibbs free energy change takes on a positive value. It is considered that monoliquefaction is maintained in a uniform state without separation.

The present invention provides a first dispersant composition for a hydraulic composition for centrifugal molding, which comprises the component (A2), the component (B2) and water. Hereinafter, the first dispersant composition for a hydraulic composition for centrifugal molding of the present invention will be described.

<(A2) component>
The component (A2) is a polymer or copolymer containing acrylic acid and / or maleic acid as constituent monomers, and is a compound in which the carboxyl group is not neutralized.
The compound whose carboxyl group is not neutralized among (A2) components means that the carboxyl group which the polymer or copolymer which makes acrylic acid and / or maleic acid a structural monomer has is not a salt.

The component (A2) may be a polymer of acrylic acid or maleic acid, or a copolymer of acrylic acid and maleic acid. The component (A2) is preferably a copolymer of acrylic acid and maleic acid from the viewpoint of centrifugal moldability and / or strength development of a cured product.

When the component (A2) is a copolymer containing a monomer of acrylic acid (hereinafter referred to as (A21)) and a monomer of maleic acid (hereinafter referred to as (A22)) as a constituent monomer, In the copolymer of component (A2), the molar ratio (A21) / (A22) of the monomer (A21) to the monomer (A22) is preferably 5/95 or more, more preferably from the viewpoint of centrifugal formability. Preferably it is 10/90 or more, more preferably 20/80 or more, still more preferably 30/70 or more, still more preferably 40/60 or more, still more preferably 50/50 or more, and preferably 95/5 or less More preferably, it is 90/10 or less, more preferably 80/20 or less, still more preferably 70/30 or less.

When the component (A2) is a copolymer containing the monomer (A21) and the monomer (A22) as a constituent monomer, the component (A2) is a monomer in the constituent monomer ( The total amount of A21) and the monomer (A22) is 90% by mass or more, preferably 92% by mass or more, more preferably 95% by mass or more, and 100% by mass or less. This total amount may be 100% by mass.

The weight average molecular weight of the component (A2) is preferably 1,000 or more, more preferably 2,000 or more, and preferably 100,000 or less, more preferably 75,000, from the viewpoint of centrifugal moldability and product viscosity. The following is more preferably 50,000 or less, and still more preferably 10,000 or less. The weight average molecular weight is measured by gel permeation chromatography (GPC) under the following conditions.
* GPC conditions Device: GPC (HLC-8320GPC) made by Tosoh Corp. Column: G4000PWXL + G2500PWXL (made by Tosoh Corp.)
Eluent: 0.2 M phosphate buffer / CH ₃ CN = 9/1
Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Detection: RI
Sample size: 0.2 mg / mL
Standard substance: converted to polyethylene glycol (monodispersed polyethylene glycol: molecular weight 87, 500, 250,000, 145,000, 46,000, 24,000)

<(B2) component>
The component (B2) is a polycarboxylic acid dispersant and is a compound in which the carboxyl group is not neutralized.
The compound whose carboxyl group is not neutralized among (B2) components means that the carboxyl group which a polycarboxylic acid type dispersing agent has is not a salt.

As the component (B2), a copolymer containing a monomer (B21) represented by the following general formula (B21) and a monomer (B22) represented by the following general formula (B22) as a constituent monomer [ Hereinafter, the copolymer (B2) is mentioned.

[In the formula,
R ^{21 b} and R ^{22 b} : identical or different, hydrogen atom or methyl group R ^{23 b} : hydrogen atom or — (CO) _q2 O (AO) _{n2 ′} X ²
X ² : alkyl group having 1 to 4 carbon atoms AO: group selected from ethyleneoxy group and propyleneoxy group n2 ′: average addition mole number of AO, the number of 1 to 300 and the number p2: 0 to 2 Number q2: Indicates the number of 0 or 1. ]

[In the formula,
R ^24b , R ^25b and R ^26b, which may be the same or different, are a hydrogen atom, a methyl group or (CH ₂ ) _r ₂ COOH, and (CH ₂ ) _r ₂ COOH is COOH or other (CH ₂ ) _r ₂ COOH And an anhydride may be formed.
r2: 0 or more and 2 or less. ]

In general formula (B21), R ^21b is preferably a hydrogen atom.
In general formula (B21), R ^22b is preferably a methyl group.
In general formula (B21), R ^23b is preferably a hydrogen atom.
In general formula (B21), X ² is preferably a methyl group.
In the general formula (B21), AO is preferably an ethyleneoxy group. Preferably, AO contains an ethyleneoxy group.

In general formula (B21), n2 'is an average added mole number of AO, and is a number of 1 or more and 300 or less. n2 ′ is a number of preferably 10 or more, more preferably 20 or more, and preferably 250 or less, more preferably 200 or less from the viewpoint of centrifugal moldability and / or strength development of the cured product after centrifugal molding .

In the general formula (B21), p2 is preferably 0.
In the general formula (B21), q2 is preferably 1. The copolymer (B2) of the component (B2) comprises a monomer (B21) in which q2 is 1 in the general formula (B21) and a monomer (B22) represented by the general formula (B22). It contains the copolymer which contains as a monomer.

In general formula (B22), R ^24b is preferably a hydrogen atom.
In the general formula (B22), R ^25b is preferably a methyl group or a hydrogen atom.
In the general formula (B22), R ^26b is preferably a hydrogen atom.
As _r ₂ of (CH ₂ ) _r ₂ COOH in the general formula (B22), 1 is preferable.

In the copolymer (B2), the total amount of the monomer (B21) and the monomer (B22) in the constituent monomers is 90% by mass from the viewpoint of centrifugal moldability and / or strength development of the cured product The content is preferably 92% by mass or more, more preferably 95% by mass or more and 100% by mass or less. This total amount may be 100% by mass.

In the copolymer (B2), the ratio of the monomer (B22) to the total of the monomer (B21) and the monomer (B22) is from the viewpoint of centrifugal moldability and / or strength of the cured product after centrifugal molding Preferably, it is 10 mol% or more, more preferably 20 mol% or more, and preferably 99 mol% or less, more preferably 95 mol% or less.

The weight average molecular weight of the copolymer (B2) is preferably 10,000 or more, more preferably 15,000 or more, and preferably 100,000 or less, more preferably 70,000 or less, still more preferably 50,000. It is below. The weight average molecular weight is measured by gel permeation chromatography (GPC) under the conditions described in the component (B1).

<Composition of Dispersant Composition>
In the first dispersant composition for a hydraulic composition for centrifugal molding of the present invention, the content of the component (A2) is preferably 0.5% by mass or more, from the viewpoint of one-component stability and centrifugal formation. Preferably, it is 1% by mass or more, more preferably 2% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less, still more preferably 15% by mass or less More preferably, it is 5% by mass or less.

In the first dispersing agent composition for a hydraulic composition for centrifugal molding of the present invention, a compound or compounds in which a carboxyl group is not neutralized in a polymer or copolymer containing acrylic acid and / or maleic acid as constituent monomers (( The content of the component (A2) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more from the viewpoint of one-component stability. It is particularly preferable that the content is 100% by mass.

In the first dispersant composition for a hydraulic composition for centrifugal molding of the present invention, the content of the component (B2) is preferably 1% by mass or more, more preferably from the viewpoint of one-component stability and centrifugal formation. 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, still more preferably 30% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, more preferably Is 40 mass% or less.

In the first dispersing agent composition for a hydraulic composition for centrifugal molding of the present invention, the content of the dispersing agent (component (B2) component) in which the carboxyl group is not neutralized in the polycarboxylic acid based dispersing agent is stable in one solution. From the viewpoint of the properties, it is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, and particularly preferably 100% by mass.

In the first dispersant composition for a hydraulic composition for centrifugal molding of the present invention, the total content of the (A2) component and the (B2) component is preferably 1. from the viewpoint of one-component stability and centrifugal formation. 5% by mass or more, more preferably 6% by mass or more, further preferably 12% by mass or more, still more preferably 20% by mass or more, still more preferably 30% by mass or more, and preferably 100% by mass or less, more preferably Is at most 85 mass%, more preferably at most 70 mass%, still more preferably at most 60 mass%, even more preferably at most 50 mass%.

In the first dispersant composition for a hydraulic composition for centrifugal molding of the present invention, the mass ratio (B2) / (A2) of the content of the component (A2) to the content of the component (B2) is a centrifugal moldability And / or from the viewpoint of the strength of the cured product after centrifugal molding, preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.10 or more, still more preferably 1 or more, and centrifugal formability and And / or from the viewpoint of the strength of the cured product after centrifugal molding, preferably 100 or less, more preferably 90 or less, still more preferably 80 or less, still more preferably 60 or less, still more preferably 40 or less, still more preferably It is 30 or less, more preferably 15 or less.

The first dispersant composition for a hydraulic composition for centrifugal molding of the present invention is a liquid composition containing water. In the first dispersant composition for a hydraulic composition for centrifugal molding according to the present invention, the content of water is preferably more than 0% by mass, more preferably 15% by mass or more, still more preferably 30% by mass or more, Preferably it is 98.5 mass% or less, More preferably, it is 94 mass% or less, More preferably, it is 88 mass% or less, More preferably, it is 70 mass% or less, More preferably, it is 60 mass% or less.

The first dispersant composition for a hydraulic composition for centrifugal molding according to the present invention is a conventional cement dispersant, a water-soluble polymer compound, an air entrainer, a cement wetting agent, an expansive agent, a waterproof agent, a retarder, and a quick setting. Components such as thickeners, thickeners, flocculants, drying shrinkage reducing agents, strength enhancers, curing accelerators, preservatives, antifoaming agents [(A2) components, (A3) components, (B1) components, (B2) Can be contained except what falls under components.

[First Method for Producing Dispersant Composition for Hydraulic Composition for Centrifugal Molding]
The present invention provides a first method for producing a dispersant composition for a hydraulic composition for centrifugal molding, which comprises mixing the (A2) component, the (B2) component and water. According to this manufacturing method, the first dispersant composition for a hydraulic composition for centrifugal molding of the present invention containing the (A2) component, the (B2) component, and water is manufactured. Hereinafter, the manufacturing method of the 1st dispersing agent composition for hydraulic compositions for centrifugal molding of this invention is demonstrated.

The specific example and the preferable aspect of (A2) component and (B2) component used for the manufacturing method of the dispersing agent composition for the 1st hydraulic molding compositions of this invention each are 1st centrifugal molding of this invention It is the same as that described for the dispersant composition for hydraulic composition. The matters described in the first dispersant composition for a hydraulic composition for centrifugal molding of the present invention can be appropriately applied to the method for producing the first dispersant composition for a hydraulic composition for centrifugal molding of the present invention. .

In the first method for producing a dispersant composition for a hydraulic composition for centrifugal molding of the present invention, the component (A2) is preferably contained in the mixed material, preferably 0.5 mass, from the viewpoint of one-component stability and centrifugal formation. %, More preferably 1% by mass, further preferably 2% by mass and preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less, still more preferably 15% by mass % Or less, more preferably 5% by mass or less. It is preferable to mix the (A2) component so that it will become content of the (A2) component in the hydraulic composition dispersing agent composition for 1st of this invention.

In the first method for producing a dispersant composition for a hydraulic composition for centrifugal molding of the present invention, the component (B2) is preferably contained in the mixed material in an amount of 1% by mass or more from the viewpoint of one-component stability and centrifugal formation. More preferably 5% by mass or more, still more preferably 10% by mass or more, still more preferably 20% by mass or more, still more preferably 30% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass Hereinafter, more preferably 40 mass% or less is mixed. It is preferable to mix the (B2) component so that it becomes content of the (B2) component in the hydraulic composition dispersing agent composition for 1st of this invention.

In the first method for producing a dispersant composition for a hydraulic composition for centrifugal molding according to the present invention, the (A2) component and the (B2) component, the (A2) component, from the viewpoint of one-component stability and centrifugal formation. The total of components (B2) and (B2) in the mixed material is preferably 1.5% by mass or more, more preferably 6% by mass or more, still more preferably 12% by mass or more, still more preferably 20% by mass or more, further more preferably Is 30% by mass or more, preferably 100% by mass or less, more preferably 85% by mass or less, still more preferably 70% by mass or less, still more preferably 60% by mass or less, still more preferably 50% by mass or less Mix as you like.
It is preferable to mix the (A2) component and the (B2) component so that the total content of the (A2) component and the (B2) component in the first hydraulic composition dispersant composition for centrifugal molding of the present invention is obtained.

In the first method for producing a dispersant composition for a hydraulic composition for centrifugal molding according to the present invention, the (A2) component and the (B2) component are combined from the viewpoint of the centrifugal moldability and / or the strength of the cured product after centrifugal molding. The mass ratio (B2) / (A2) of the component (A2) to the component (B2) is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.10 or more, still more preferably 1 From the viewpoint of centrifugal moldability and / or strength of the cured product after centrifugal molding, preferably 100 or less, more preferably 90 or less, still more preferably 80 or less, still more preferably 60 or less, still more preferably Is mixed so as to be 40 or less, more preferably 30 or less, still more preferably 15 or less.

In the first method for producing a dispersant composition for a hydraulic composition for centrifugal molding according to the present invention, water is preferably contained in an amount of more than 0% by mass, more preferably 15% by mass or more, still more preferably 30% by mass. % And preferably 98.5% by mass or less, more preferably 94% by mass or less, still more preferably 88% by mass or less, still more preferably 70% by mass or less, still more preferably 60% by mass or less Mix in

[Second hydraulic composition for centrifugal molding]
The present inventors have developed a centrifugal molded body by adding the component (A2) when kneading using the polycarboxylic acid-based dispersant which is the component (B2) in the second hydraulic composition for centrifugal molding. It has been found that the formability of is improved.
The reason for such an effect to appear is not necessarily clear, but is presumed as follows. In the use of the component (B2) alone, the inorganic powder is excessively dispersed depending on the amount of addition and the amount of water, and the sludge is generated due to capillary flow generated at the time of centrifugal molding, and the components (A2) and (B2) are used in combination. Since the inorganic powder contained in the hydraulic composition can be effectively agglomerated and the hydraulic powder particles can be organized by crosslinking (increase in thixotropy), the generation of capillary flow is suppressed. It is considered that the outflow of sludge from the centrifugally molded body is suppressed. Further, the present inventors can obtain an improvement effect of strength (hereinafter also referred to as 7-day strength) 7 days after kneading of the hardened body of the hydraulic composition as a secondary effect of the improvement of the moldability of the centrifugally molded body. I found out. The 7-day strength is an index indicating the strength of the cured product. The reason why the 7-day strength improvement effect is obtained is not always clear, but the inorganic early strengthening agent and hydration products discharged in large amounts as sludge from the centrifugally molded body suppress the outflow of sludge from the centrifugally molded body Thus, it is considered that the strength was improved by 7 days by being effectively held in the centrifugal molding.

The present invention provides a second hydraulic composition for centrifugal molding, which comprises the component (A2), the component (B2), a hydraulic powder, an aggregate and water. Hereinafter, the second hydraulic composition of the present invention will be described.

Specific examples and preferred embodiments of the components (A2) and (B2) used in the second hydraulic composition for centrifugal molding according to the present invention are the dispersant composition for the first hydraulic composition for centrifugal molding according to the present invention. It is the same as the one mentioned in the article. Further, specific examples and preferable embodiments of the hydraulic powder and aggregate used for the second hydraulic composition for centrifugal molding of the present invention are the same as those described for the first hydraulic composition for centrifugal molding of the present invention, respectively. It is the same. The items described in the first dispersing agent composition for a hydraulic composition for centrifugal molding and the method for producing the same of the present invention can be appropriately applied to the second hydraulic composition for a centrifugal molding of the present invention.

<Composition of hydraulic composition etc>
In the second hydraulic forming composition for centrifugal molding of the present invention, the content of the component (A2) is preferably 0.01 parts by mass or more, relative to 100 parts by mass of the hydraulic powder, from the viewpoint of centrifugal formability. More preferably 0.015 parts by mass or more, further preferably 0.02 parts by mass or more, and from the viewpoint of centrifugal formability, preferably 1 part by mass or less, more preferably 0.90 parts by mass or less, still more preferably 0 The content is not more than 80 parts by mass, more preferably not more than 0.60 parts by mass, still more preferably not more than 0.40 parts by mass.

In the second hydraulic forming composition for centrifugal molding of the present invention, a compound or compounds in which a carboxyl group is not neutralized in a polymer or copolymer containing acrylic acid and / or maleic acid as constituent monomers ((A2) component) The content of is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, from the viewpoint of one-component stability. % Is particularly preferred.

In the second hydraulic forming composition for centrifugal molding of the present invention, the content of the component (B2) is based on 100 parts by mass of the hydraulic powder from the viewpoint of the centrifugal moldability and / or the cured product strength after centrifugal forming. , Preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.10 parts by mass or more, still more preferably 0.20 parts by mass, and centrifugal formability and / or centrifugation From the viewpoint of the cured body strength after molding, it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 6 parts by mass or less, still more preferably 4 parts by mass or less, still more preferably 2 parts by mass or less Still more preferably, it is 1 part by mass or less.

In the second hydraulic forming composition for centrifugal molding of the present invention, the content of the dispersant (component (B2)) in which the carboxyl group is not neutralized in the polycarboxylic acid-based dispersant is from the viewpoint of one-component stability. The content is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, and particularly preferably 100% by mass.

In the second hydraulic forming composition for centrifugal molding of the present invention, the total content of the (A2) component and the (B2) component is the (A2) component from the viewpoint of the centrifugal moldability and / or the cured product strength after centrifugal molding. The total of components (B2) and (B2) is preferably 0.02 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.10 parts by mass or more, per 100 parts by mass of hydraulic powder. The amount is more preferably 0.20 parts by mass or more, and preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 6 parts by mass from the viewpoint of centrifugal moldability and / or strength of the cured product after centrifugal molding. The content is at most parts by mass, more preferably at most 4 parts by mass, still more preferably at most 2 parts by mass.

In the second hydraulic forming composition for centrifugal molding of the present invention, the mass ratio (B2) / (A2) of the content of the component (A2) to the content of the component (B2) is centrifugal moldability and / or centrifugal molding From the viewpoint of cured body strength later, preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.10 or more, still more preferably 1 or more, and after centrifugal formability and / or centrifugal molding From the viewpoint of the cured product strength, preferably 100 or less, more preferably 90 or less, still more preferably 80 or less, still more preferably 60 or less, still more preferably 40 or less, still more preferably 30 or less, further more Preferably it is 15 or less.

The second hydraulic forming composition for centrifugal molding according to the present invention has a water / hydraulic powder ratio (hereinafter sometimes referred to as W / P), but 10% by mass or more from the viewpoint of centrifugal formability and strength. 12 mass% or more is more preferable, 14 mass% or more is more preferable, and 30 mass% or less is preferable, 25 mass% or less is more preferable, 24 mass% or less is more preferable, 23 mass% or less is further more Preferably, 22 mass% or less is still more preferable.

In the second hydraulic forming composition for centrifugal molding of the present invention, the use amount of the coarse aggregate and the use amount of the fine aggregate are the same as those described in the first hydraulic composition for centrifugal forming of the present invention .

Concrete etc. are mentioned as a hydraulic composition for centrifugal molding. Above all, concrete using cement is preferable. The hydraulic composition of the present invention can be used for self leveling, for refractories, for plaster, for light weight or heavy concrete, for AE, for repair, for prepacked, for toremy, for ground improvement, for grout, for chilling, etc. Is also useful in the field of

The second hydraulic composition for centrifugal molding of the present invention can also contain glycerin and a early strengthening agent such as N-methyldiethanolamine and a chelating agent such as ethylenediaminetetraacetic acid sodium salt. The content of the chelating agent is preferably 0.1 parts by mass or less based on 100 parts by mass in total of the hydraulic powder and the high-strength admixture containing silica, from the viewpoint of strength development after steam curing.

The second hydraulic forming composition for centrifugal molding of the present invention is a conventional cement dispersant, a water-soluble polymer compound, an air entrainer, a cement wetting agent, an expansive agent, a waterproofing agent, a retarder, a quick-setting agent, a foaming agent. Components such as foaming agents, waterproofing agents, fluidizing agents, thickeners, flocculants, drying shrinkage reducing agents, strength promoters, curing accelerators, preservatives, antifoaming agents [(A2) components, (A3) components , (B1) component, except for those corresponding to the (B2) component can be contained.

[Second method for producing hydraulic composition for centrifugal molding]
The present invention provides a second method for producing a hydraulic composition for centrifugal molding, which comprises mixing the (A2) component, the (B2) component, the hydraulic powder, the aggregate and water. According to this production method, a second hydraulic composition for centrifugal molding of the present invention comprising the component (A2), the component (B2), the hydraulic powder, the aggregate, and water is produced. Hereinafter, the manufacturing method of the 2nd hydraulic composition of this invention is demonstrated.

Specific examples and preferred embodiments of the components (A2) and (B2) used in the second method for producing a hydraulic composition for centrifugal molding according to the present invention are respectively for the first hydraulic composition for centrifugal molding according to the present invention The same as described for the dispersant composition.
In addition, specific examples and preferable embodiments of the hydraulic powder and aggregate used in the second method for producing a hydraulic composition for centrifugal molding according to the present invention are the same as described in the first hydraulic composition for centrifugal molding according to the present invention Is the same as The hydraulic powder is used such that W / P is in the range described in the second hydraulic composition for centrifugal molding of the present invention. The amount of aggregate used is also the same as that described in the first hydraulic composition for centrifugal molding of the present invention.
The matters described in the first dispersing agent composition for a hydraulic composition for centrifugal molding of the present invention and the method for producing the same, and the second hydraulic composition for a centrifugal molding, are the second hydraulic composition for a centrifugal molding of the present invention It can apply suitably to the manufacturing method of.

In the second method for producing a hydraulic composition for centrifugal molding of the present invention, the component (A2) is preferably 0.01 parts by mass or more, relative to 100 parts by mass of the hydraulic powder, from the viewpoint of centrifugal formability, More preferably 0.015 parts by mass or more, further preferably 0.02 parts by mass or more, and from the viewpoint of centrifugal formability, preferably 1 part by mass or less, more preferably 0.90 parts by mass or less, still more preferably 0 .80 parts by mass or less, more preferably 0.60 parts by mass or less, still more preferably 0.40 parts by mass or less. It is preferable to mix (A2) component so that it may become content of (A2) component in the hydraulic composition for 2nd centrifugation of this invention.

In the second method for producing a hydraulic composition for centrifugal molding of the present invention, the component (B2) is added to 100 parts by mass of the hydraulic powder from the viewpoint of centrifugal moldability and / or strength of the cured product after centrifugal molding. , Preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.10 parts by mass or more, still more preferably 0.20 parts by mass, and centrifugal formability and / or centrifugation From the viewpoint of the strength of the cured product after molding, it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 6 parts by mass or less, still more preferably 4 parts by mass or less, still more preferably 2 parts by mass The mixing is carried out in parts by weight or less, more preferably in parts by weight or less. It is preferable to mix the (B2) component so that it will become content of the (B2) component in the hydraulic composition for 2nd centrifugation of this invention.

In the second method for producing a hydraulic composition for centrifugal molding of the present invention, the total of the components (A2) and (B2) is a hydraulic powder from the viewpoint of centrifugal moldability and / or strength of a cured product after centrifugal molding. To 100 parts by mass of the body, preferably 0.02 parts by mass or more, more preferably 0.05 parts by mass or more, further preferably 0.10 parts by mass or more, still more preferably 0.20 parts by mass or more, and From the viewpoint of centrifugal moldability and / or strength of the cured product after centrifugal molding, it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 6 parts by mass or less, still more preferably 4 parts by mass or less Still more preferably, it mixes so that it may be 2 mass parts or less. It is preferable to mix the (A2) component and the (B2) component so as to be the total content of the (A2) component and the (B2) component in the second hydraulic composition for centrifugal molding of the present invention.

In the second method for producing a hydraulic composition for centrifugal molding of the present invention, the (A2) component and the (B2) component can be combined with the (A2) component from the viewpoint of centrifugal moldability and / or strength of the cured product after centrifugal molding. The mass ratio (B2) / (A2) of the component (B2) is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.10 or more, still more preferably 1 or more, and centrifugation From the viewpoint of moldability and / or strength of the cured product after centrifugal molding, it is preferably 100 or less, more preferably 90 or less, still more preferably 80 or less, still more preferably 60 or less, still more preferably 40 or less, more preferably More preferably, it mixes so that it is 30 or less, More preferably, it is 15 or less.

In the second method for producing a hydraulic composition of the present invention, it is preferable to previously mix the components (A2) and (B2) and water with the hydraulic powder from the viewpoint of productivity. In the second method for producing a hydraulic composition of the present invention, the addition of the components (A2) and (B2) is carried out using the first dispersant composition for a hydraulic composition for centrifugal molding of the present invention Preferably, the first dispersant composition for a hydraulic composition for centrifugal molding of the present invention and water are mixed in advance and mixed with a hydraulic powder.

Mixing of the component (A2), the component (B2), the hydraulic powder, the aggregate, the water, and the component used as necessary is carried out using a mixer such as a mortar mixer or a forced twin-screw mixer. It can be carried out. The mixing time is preferably 1 minute or more, more preferably 2 minutes or more, and preferably 5 minutes or less, more preferably 3 minutes or less. In the preparation of the hydraulic composition, the materials and agents described in the second hydraulic composition for centrifugal molding of the present invention and their amounts can be used.

[Method for Producing Second Hardened Composition of Hydraulic Composition]
This invention provides the manufacturing method of the hardening body of the 2nd hydraulic composition containing the following processes.
Step 1 ': A step of mixing the (A2) component, the (B2) component, the hydraulic powder, the aggregate and water to obtain a hydraulic composition.
Step 2 ': A step of filling the hydraulic composition obtained in Step 1' into a mold.
Step 3 ': A step of clamping the hydraulic composition filled in the mold obtained in Step 2' by centrifugal force.
Step 4 ': a step of setting the clamped hydraulic composition obtained in step 3' in a mold.
Hereinafter, the manufacturing method of the 2nd hydraulic composition hardening body of this invention is demonstrated.

The specific example and the preferable aspect of (A2) component and (B2) component used for the manufacturing method of the hardened | cured material of the 2nd hydraulic composition of this invention respectively are 1st hydraulic composition for centrifugal molding of this invention It is the same as described in the dispersant composition.
In addition, specific examples and preferred embodiments of the hydraulic powder and aggregate used in the method for producing a cured product of the second hydraulic composition of the present invention are described in the first hydraulic composition for centrifugal molding of the present invention. It is the same as The hydraulic powder is used such that W / P is in the range described in the second hydraulic composition for centrifugal molding of the present invention. The amount of aggregate used is also the same as that described in the first hydraulic composition for centrifugal molding of the present invention.
The first dispersant composition for a hydraulic composition for centrifugal molding according to the present invention and a method for producing the same, the second hydraulic composition for a centrifugal molding, and the items described in the second method for producing a hydraulic composition for a centrifugal molding It can apply suitably to the manufacturing method of the hardening body of the 2nd hydraulic composition of this invention.

The process for producing a cured product of the second hydraulic composition of the present invention preferably includes the following step 5 'in addition to steps 1' to 4 '.
Step 5 ': Steam curing the hydraulic composition condensed in step 4' in a mold.

The process for producing a cured product of the second hydraulic composition of the present invention can include the following step 6 ′ in addition to steps 1 ′ to 5 ′.
Step 6 ': A step of cooling the hydraulic composition after the step 5' and removing it from the mold.

The method for producing a cured product of the second hydraulic composition of the present invention can include the following step 7 ′ in addition to steps 1 ′ to 6 ′.
Step 7 ': a step of curing the cured product of the hydraulic composition obtained in Step 6' at normal temperature and pressure.

In step 1 ′, the component (A2) is preferably 0.01 parts by mass or more, more preferably 0.015 parts by mass or more, and further preferably 100 parts by mass of the hydraulic powder from the viewpoint of centrifugal formability. Is preferably at most 1 part by mass, more preferably at most 0.90 parts by mass, still more preferably at most 0.80 parts by mass, still more preferably at most 1 part by mass, from the viewpoint of centrifugal formability. 60 parts by mass or less, more preferably 0.40 parts by mass or less. It is preferable to mix (A2) component so that it may become content of (A2) component in the hydraulic composition for 2nd centrifugation of this invention.

In step 1 ′, the component (B2) is preferably 0.01 parts by mass or more, relative to 100 parts by mass of the hydraulic powder, from the viewpoint of centrifugal moldability and / or strength of the cured product after centrifugal molding. More preferably 0.05 parts by mass or more, still more preferably 0.10 parts by mass or more, still more preferably 0.20 parts by mass or more, and in view of centrifugal formability and / or strength of cured body after centrifugal form Or less, preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 6 parts by mass or less, still more preferably 4 parts by mass or less, still more preferably 2 parts by mass or less, still more preferably 1 part by mass Mix below. It is preferable to mix the (B2) component so that it will become content of the (B2) component in the hydraulic composition for 2nd centrifugation of this invention.

In step 1 ′, the total of the components (A2) and (B2) is preferably 100 parts by mass of the hydraulic powder from the viewpoint of centrifugal moldability and / or strength of the cured product after centrifugal molding. 0.02 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.10 parts by mass or more, still more preferably 0.20 parts by mass, and centrifugal formability and / or after centrifugal form From the viewpoint of cured body strength, preferably 10 parts by mass or less, more preferably 8 parts by mass or less, further preferably 6 parts by mass or less, still more preferably 4 parts by mass or less, still more preferably 2 parts by mass or less Mix to become It is preferable to mix the (A2) component and the (B2) component so as to be the total content of the (A2) component and the (B2) component in the second hydraulic composition for centrifugal molding of the present invention.

In step 1 ′, the mass ratio of the (A2) component to the (B2) component, the (A2) component and the (B2) component, from the viewpoint of centrifugal moldability and / or the strength of the cured product after centrifugal molding, (B2) / (A2) is preferably 0.01 or more, more preferably 0.05 or more, still more preferably 0.10 or more, still more preferably 1 or more, and centrifugal formability and / or cured body strength after centrifugal form From the viewpoint of point of view, preferably 100 or less, more preferably 90 or less, still more preferably 80 or less, still more preferably 60 or less, still more preferably 40 or less, still more preferably 30 or less, still more preferably 15 or less Mix to be

In Step 1 ′, the method of adding and mixing the mixture containing water, the component (A2) and the component (B2) to the mixture containing the aggregate and the hydraulic powder is a method of mixing even when producing a hydraulic composition It is preferable in that it can be easily mixed uniformly. The addition of the components (A2) and (B2) is preferably performed using the first dispersant composition for a hydraulic composition for centrifugal molding of the present invention, and the first hydraulic composition for a centrifugal molding of the present invention A method of adding and mixing a mixture containing a dispersant composition for a composition and water to a mixture containing an aggregate and a hydraulic powder enables easy and uniform mixing even when producing a hydraulic composition. It is preferable in point.

As a specific method of the step 1 ′, a hydraulic powder and an aggregate are mixed, and a mixture containing water, the (A2) component and the (B2) component is mixed as described above. The process of adding and knead | mixing and preparing a hydraulic composition is mentioned.

In step 1 ', the components (A2) and (B2) can be separately added to water, hydraulic powder, aggregate and mixed.

In step 1 ′, W / P is preferably 10% by mass or more, more preferably 12% by mass or more, still more preferably 14% by mass or more, and preferably 30% by mass or less from the viewpoint of centrifugal formability and strength. The hydraulic composition is prepared, more preferably 25% by mass or less, still more preferably 24% by mass or less, still more preferably 23% by mass or less, and still more preferably 22% by mass or less.

Specific examples and preferable embodiments of the steps 2 'to 7' are the same as the embodiments described in the steps 2 to 7, respectively, in the method for producing a cured product of the first hydraulic composition of the present invention.

The production method of the present invention comprises steps 1 ′ to 6 ′, and the time taken from preparation of the hydraulic composition to removal from the mold in step 6 ′ is 8 hours or more and 30 hours or less. The manufacturing method of the hardening body of a composition is mentioned. Here, the start of preparation of a hydraulic composition is a point when hydraulic powder and water contact first.

The cured product of the hydraulic composition obtained by the method for producing a cured product of the second hydraulic composition of the present invention can be used as a centrifugally formed concrete product, and specifically, piles, poles, fume tubes and the like are mentioned. Be The cured product of the hydraulic composition obtained by the method for producing a cured product of the present invention is excellent in initial strength, and can reduce waste generated at the production site of the product with a small amount of generation of slag during production. Moreover, since it is excellent in compaction, the inner surface and end face unevenness of the product are small, the surface appearance is excellent, and the inner surface of the product is smoothed, thereby improving obstacles to the cutting machine during pile driving and Nakabori method. .

[Second Dispersing Agent Composition for Centrifugal Molding Hydraulic Composition]
In the second dispersant composition for a hydraulic composition for centrifugal molding according to the present invention, the present inventors have found that a polymer or copolymer comprising acrylic acid and / or maleic acid as component (A3) as constituent monomers Among the polycarboxylic acid-based dispersants which are combined and component (B1), compounds in which each carboxyl group is neutralized (that is, a compound in which the carboxy group is a salt) or unneutralized compounds (that is, the carboxy group is not a salt) Whichever the compound is contained, the component (C) is contained, and if the pH at 20 ° C. is 5 or less, the dispersant composition maintains one liquefaction in a uniform state without separation. I found that I could do it.
The reason for such an effect to appear is not necessarily clear, but is presumed as follows. When the mixing entropy of the two polymers in the common solvent is small and the mixing enthalpy takes a positive value, the mixing Gibbs free energy becomes positive, causing phase separation. By containing the component (C) and setting the pH at 20 ° C. in the dispersant composition to 5 or less, the carboxyl group approaches an unneutralized state, and the interaction with water molecules is reduced, Since the mixing entropy can be increased, it is considered that, as a result, the mixed Gibbs free energy change takes a positive value, and monoliquefaction is maintained in a uniform state without separation.

The present invention comprises a second dispersant composition for a hydraulic composition for centrifugal molding, which comprises the component (A3), the component (B1), the component (C), and water and has a pH of 5 or less at 20 ° C. provide. Hereinafter, the second dispersant composition for a hydraulic composition for centrifugal molding of the present invention will be described.

<(A3) component>
The component (A3) is a polymer or copolymer having acrylic acid and / or maleic acid as constituent monomers. The component (A3) may be either a compound in which the carboxyl group in the component (A3) is neutralized or an unneutralized compound. The compound in which the carboxyl group in component (A) is not neutralized means that the carboxyl group in the polymer or copolymer having acrylic acid and / or maleic acid as constituent monomers is not a salt. Further, the compound in which the carboxyl group in the component (A) is neutralized means that the carboxyl group contained in the polymer or copolymer having acrylic acid and / or maleic acid as a constituent monomer is a salt.

The component (A3) may be a polymer of acrylic acid or maleic acid, or a copolymer of acrylic acid and maleic acid. The component (A3) is preferably a copolymer of acrylic acid and maleic acid from the viewpoint of centrifugal moldability and / or strength development of a cured product.

When the component (A3) is a copolymer containing a monomer of acrylic acid (hereinafter referred to as (A31)) and a monomer of maleic acid (hereinafter referred to as (A32)) as a constituent monomer, In the copolymer of the component (A3), the molar ratio (A31) / (A32) of the monomer (A31) to the monomer (A32) is preferably 5/95 or more, more preferably from the viewpoint of centrifugal formability. Preferably it is 10/90 or more, more preferably 20/80 or more, still more preferably 30/70 or more, still more preferably 40/60 or more, still more preferably 50/50 or more, and preferably 95/5 or less More preferably, it is 90/10 or less, more preferably 80/20 or less, still more preferably 70/30 or less.

When the component (A3) is a copolymer containing the monomer (A31) and the monomer (A32) as a constituent monomer, the component (A3) is a monomer in the constituent monomer ( The total amount of A31) and the monomer (A32) is 90% by mass or more, preferably 92% by mass or more, more preferably 95% by mass or more, and 100% by mass or less. This total amount may be 100% by mass.

The weight average molecular weight of the component (A3) is preferably 1,000 or more, more preferably 2,000 or more, and preferably 100,000 or less, more preferably 75,000, from the viewpoint of centrifugal moldability and product viscosity. The following is more preferably 50,000 or less, and still more preferably 10,000 or less. The weight average molecular weight is measured by gel permeation chromatography (GPC) under the conditions described in the component (A2).

<(B1) component>
The component (B1) is a polycarboxylic acid dispersant. The component (B1) may be either a compound in which the carboxyl group in the component (B1) is neutralized or an unneutralized compound. The compound in which the carboxyl group in the component (B1) is not neutralized means that the carboxyl group of the polycarboxylic acid dispersant is not a salt. The compound in which the carboxyl group in the component (B1) is neutralized means that the carboxyl group contained in the polycarboxylic acid dispersant is a salt.
Specific examples and preferred embodiments of the component (B1) are the same as the embodiments described in the component (B1) of the first hydraulic composition of the present invention.

<(C) component>
The component (C) is a Bronsted acid. However, the components (A2), (A3), (B1) and (B2) are excluded from the component (C). A Bronsted acid is an acid that has a proton and can release or dissociate the proton in a liquid composition containing water, and is different from an acid that does not have a proton such as a Lewis acid. The component (C) includes lactic acid, acetic acid, citric acid, maleic acid, fumaric acid, pyruvic acid, benzoic acid, hydrochloric acid, gluconic acid, tartaric acid, adipic acid, sulfuric acid, phosphoric acid, oxalic acid and nitric acid, One or more of these may be used.

The component (C) is preferably at least one selected from carboxylic acids (organic acids having at least one carboxy group) from the viewpoint of easiness of pH adjustment and safety, and lactic acid, acetic acid, citric acid, maleic acid, One or more selected from fumaric acid, pyruvic acid, benzoic acid, gluconic acid, tartaric acid, adipic acid, and oxalic acid is more preferable, and one or more selected from lactic acid, acetic acid, citric acid, and gluconic acid is more preferable. From the viewpoint of economy, component (C) is preferably one or more selected from hydrochloric acid, sulfuric acid, phosphoric acid and nitric acid, more preferably one or more selected from hydrochloric acid, sulfuric acid and phosphoric acid, hydrochloric acid and One or more selected from sulfuric acid is more preferable.

<Composition of Dispersant Composition>
In the second dispersant composition for a hydraulic composition for centrifugal molding of the present invention, the content of the component (A3) is preferably 0.5% by mass or more, from the viewpoint of one-component stability and centrifugal formation. It is preferably 1% by mass or more, more preferably 2% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, still more preferably 5% by mass or less .

In the second dispersant composition for a hydraulic composition for centrifugal molding of the present invention, the content of the component (B1) is preferably 1% by mass or more, more preferably from the viewpoint of one-component stability and centrifugal formation. It is 5% by mass or more, more preferably 10% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 45% by mass or less, still more preferably 40% by mass or less.

In the second dispersant composition for a hydraulic composition for centrifugal molding of the present invention, the total content of the (A3) component and the (B1) component is preferably 1. from the viewpoint of one-component stability and centrifugal formation. The content is 5% by mass or more, more preferably 6% by mass or more, further preferably 12% by mass or more, and preferably 80% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less.

In the second dispersant composition for a hydraulic composition for centrifugal molding of the present invention, the mass ratio (B1) / (A3) of the content of the component (A3) to the content of the component (B1) is a centrifugal moldability And / or from the viewpoint of the strength of the cured body after centrifugal molding, preferably 0.1 or more, more preferably 1 or more, still more preferably 10 or more, and the aspect of cured body strength after centrifugal molding and / or centrifugal molding From the point of view, preferably 100 or less, more preferably 90 or less, still more preferably 80 or less, still more preferably 70 or less, still more preferably 60 or less, still more preferably 50 or less, still more preferably 40 or less More preferably, it is 30 or less.

In the second dispersant composition for a hydraulic composition for centrifugal molding of the present invention, the content of the component (C) is preferably 0.1% by mass or more from the viewpoint of strength and safety of the hydraulic composition. More preferably, it is 0.5% by mass or more, more preferably 1% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less.

The second dispersant composition for a hydraulic composition for centrifugal molding of the present invention is a liquid composition containing water. In the second dispersant composition for a hydraulic composition for centrifugal molding of the present invention, the content of water is preferably more than 0% by mass, more preferably 15% by mass or more, still more preferably 30% by mass or more, Preferably it is 98.5 mass% or less, More preferably, it is 94 mass% or less, More preferably, it is 88 mass% or less, More preferably, it is 70 mass% or less, More preferably, it is 60 mass% or less.

In the second dispersant composition for a hydraulic composition for centrifugal molding of the present invention, the pH at 20 ° C. is 5 or less, preferably 4.8 or less, more preferably 4. from the viewpoint of storage stability and safety. It is 6 or less, and preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more. The pH is a value measured at 20 ° C. in accordance with item 8.3 of JIS K 3362; 2008.

The second dispersant composition for a hydraulic composition for centrifugal molding according to the present invention is a conventional cement dispersant, a water-soluble polymer compound, an air entrainer, a cement wetting agent, an expansive agent, a waterproof agent, a retarder, and a quick setting. Components such as thickeners, thickeners, flocculants, drying shrinkage reducing agents, strength enhancers, curing accelerators, preservatives, antifoaming agents [(A2) components, (A3) components, (B1) components, (B2) Can be contained except what falls under components.

[Method of producing second dispersant composition for hydraulic composition for centrifugal molding]
This invention manufactures the 2nd dispersant composition for hydraulic compositions for centrifugal molding which mixes (A3) component, (B1) component, (C) component, and water so that pH may become 5 or less. Provide a way. According to this production method, the second dispersant composition for a hydraulic composition for centrifugal molding of the present invention, which comprises the component (A3), the component (B1), the component (C) and water, is produced. Hereinafter, the manufacturing method of the 2nd dispersant composition for hydraulic composition for centrifugal molding of this invention is demonstrated.

The specific example and the preferable aspect of (A3) component and (B1) component used for the manufacturing method of the dispersing agent composition for the hydraulic composition for 2nd centrifugation of this invention respectively are 2nd centrifugal molding of this invention It is the same as that described for the dispersant composition for hydraulic composition. The matters described in the second dispersant composition for a hydraulic composition for centrifugal molding of the present invention can be appropriately applied to the method for producing the second dispersant composition for a hydraulic composition for centrifugal molding of the present invention. .

In the second method for producing a dispersant composition for a hydraulic composition for centrifugal molding of the present invention, the component (A3) is preferably contained in the mixed material, preferably 0.5 mass, from the viewpoint of one-component stability and centrifugal formation. %, More preferably 1% by mass, further preferably 2% by mass and preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, still more preferably 5% by mass Mix up to%. It is preferable to mix (A3) component so that it may become content of (A3) component in the hydraulic composition dispersant composition for 2nd centrifugation of this invention.

In the second method for producing a dispersant composition for a hydraulic composition for centrifugal molding of the present invention, the component (B1) is preferably contained in the mixed material in an amount of 1% by mass or more from the viewpoint of one-component stability and centrifugal formation. , More preferably 5% by mass or more, further preferably 10% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 45% by mass or less, still more preferably 40% by mass or less Mix. It is preferable to mix the (B1) component so that it may become content of the (B1) component in the hydraulic composition dispersant composition for 2nd centrifugation of this invention.

In the second method for producing a dispersant composition for a hydraulic composition for centrifugal molding according to the present invention, the (A3) component and the (B1) component, the (A3) component, from the viewpoint of one-component stability and centrifugal formation. The total of components (B1) and (B1) in the mixed material is preferably 1.5% by mass or more, more preferably 6% by mass or more, still more preferably 12% by mass or more, and preferably 100% by mass or less, more preferably It mixes so that it may be 80 mass% or less, more preferably 60 mass% or less, and still more preferably 50 mass% or less.
It is preferable to mix the (A3) component and the (B1) component such that the total content of the (A3) component and the (B1) component in the second hydraulic composition dispersant for centrifugal molding of the present invention is obtained.

In the second method for producing a dispersant composition for a hydraulic composition for centrifugal molding of the present invention, the (A3) component and the (B1) component are combined from the viewpoint of the centrifugal moldability and / or the strength of the cured product after centrifugal molding. The mass ratio (B1) / (A3) of the (A3) component to the (B1) component is preferably 0.1 or more, more preferably 1 or more, still more preferably 10 or more, and centrifugal formability and / or centrifugation From the viewpoint of the strength of the cured product after molding, it is preferably 100 or less, more preferably 90 or less, still more preferably 80 or less, still more preferably 70 or less, still more preferably 60 or less, more preferably 50 or less, It mixes so that it may become still more preferably 40 or less, still more preferably 30 or less.

In the second method for producing a dispersant composition for a hydraulic composition for centrifugal molding of the present invention, from the viewpoint of strength and safety of the hydraulic composition, the component (C) is preferably contained in the mixed material, preferably 0.1. More preferably, it is 0.5% by mass or more, more preferably 1% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less Mix. It is preferable to mix (C) component so that it may become content of (C) component in the hydraulic composition dispersant composition for 2nd centrifugation of this invention.

In the second method for producing a dispersant composition for a hydraulic composition for centrifugal molding according to the present invention, water is preferably contained in an amount of more than 0% by mass, more preferably 15% by mass or more, still more preferably 30% by mass. % And preferably 98.5% by mass or less, more preferably 94% by mass or less, still more preferably 88% by mass or less, still more preferably 70% by mass or less, still more preferably 60% by mass or less Mix in

In the second method for producing a dispersant composition for a hydraulic composition for centrifugal molding of the present invention, the pH is 5 or less, preferably 4.8 or less, more preferably 4. from the viewpoint of storage stability and safety. It mixes so that it may become 6 or less, and preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more. The pH is a value measured in accordance with item 8.3 of JIS K 3362; 2008.

[Third hydraulic forming composition for centrifugal molding]
The present inventors have found that the third hydraulic composition for centrifugal molding containing the (A3) component, the (B1) component, and the (C) component improves the moldability of the centrifugal molded body.
The reason for such an effect to appear is not necessarily clear, but is presumed as follows. In the use of the component (B1) alone, depending on the amount of addition and the amount of water, the inorganic powder may be dispersed excessively and sludge may be generated by capillary flow generated at the time of centrifugal molding, and the components (A3) and (B1) may be used in combination. Since the inorganic powder contained in the hydraulic composition can be effectively agglomerated and the hydraulic powder particles can be organized by crosslinking (increase in thixotropy), the generation of capillary flow is suppressed. It is considered that the outflow of sludge from the centrifugally molded body is suppressed. Further, the present inventors can obtain an improvement effect of strength (hereinafter also referred to as 7-day strength) 7 days after kneading of the hardened body of the hydraulic composition as a secondary effect of the improvement of the moldability of the centrifugally molded body. I found out. The 7-day strength is an index indicating the strength of the cured product. The reason why the 7-day strength improvement effect is obtained is not always clear, but the inorganic early strengthening agent and hydration products discharged in large amounts as sludge from the centrifugally molded body suppress the outflow of sludge from the centrifugally molded body Thus, it is considered that the strength was improved by 7 days by being effectively held in the centrifugal molding.

The present invention provides a third hydraulic composition for centrifugal molding, which comprises (A3) component, (B1) component, (C) component, hydraulic powder, aggregate and water. Hereinafter, the third hydraulic composition of the present invention will be described.

Specific examples and preferred embodiments of the component (A3) and the component (B1) used in the third hydraulic composition for centrifugal molding of the present invention are the dispersant composition for the second hydraulic composition for centrifugal molding of the present invention. It is the same as the one mentioned in the article. Further, specific examples and preferable embodiments of the hydraulic powder and aggregate used for the third hydraulic composition for centrifugal molding of the present invention are the same as those described for the first hydraulic composition for centrifugal molding of the present invention, respectively. It is the same. The matters described in the second dispersant composition for a hydraulic composition for centrifugal molding and the method for producing the same according to the present invention can be appropriately applied to the third hydraulic composition for a centrifugal molding of the present invention.

<Composition of hydraulic composition etc>
In the third hydraulic composition for centrifugal molding of the present invention, the content of the component (A3) is preferably 0.01 parts by mass or more, relative to 100 parts by mass of the hydraulic powder, from the viewpoint of centrifugal moldability. More preferably 0.015 parts by mass or more, still more preferably 0.02 parts by mass or more, and from the viewpoint of centrifugal formability, preferably 1 part by mass or less, more preferably 0.75 parts by mass or less, still more preferably 0 It is not more than 50 parts by mass, more preferably not more than 0.25 parts by mass, still more preferably not more than 0.10 parts by mass.

In the third hydraulic composition for centrifugal molding of the present invention, the content of the component (B1) is based on 100 parts by mass of the hydraulic powder from the viewpoint of centrifugal moldability and / or the strength of the cured product after centrifugal molding. , Preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.10 parts by mass or more, still more preferably 0.20 parts by mass, and centrifugal formability and / or centrifugation From the viewpoint of the cured body strength after molding, it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 6 parts by mass or less, still more preferably 4 parts by mass or less, still more preferably 2 parts by mass or less Still more preferably, it is 1 part by mass or less.

In the third hydraulic composition for centrifugal molding of the present invention, the total content of the components (A3) and (B1) is the component (A3) from the viewpoint of centrifugal moldability and / or strength of the cured product after centrifugal molding. The total of components (B1) and (B1) is preferably 0.02 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.10 parts by mass or more, per 100 parts by mass of hydraulic powder. The amount is more preferably 0.20 parts by mass or more, and preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 6 parts by mass from the viewpoint of centrifugal moldability and / or strength of the cured product after centrifugal molding. It is the mass part or less, more preferably 4 parts by mass or less, still more preferably 2 parts by mass or less, still more preferably 1 part by mass or less.

In the third hydraulic composition for centrifugal molding of the present invention, the mass ratio (B1) / (A3) of the content of the component (A3) to the content of the component (B1) is centrifugal moldability and / or centrifugal molding Preferably, it is 0.1 or more, more preferably 1 or more, still more preferably 10 or more, and from the viewpoint of centrifugal formability and / or cured body strength after centrifugal molding, from the viewpoint of subsequent cured body strength. Is 100 or less, more preferably 90 or less, still more preferably 80 or less, still more preferably 70 or less, still more preferably 60 or less, still more preferably 50 or less, still more preferably 40 or less, still more preferably 30 or less It is.

In the third hydraulic composition for centrifugal molding of the present invention, the content of the component (C) is preferably 0.1 parts by mass with respect to 100 parts by mass of the hydraulic powder from the viewpoint of strength development of the hydraulic composition. 001 parts by mass or more, more preferably 0.01 parts by mass or more, further preferably 0.05 parts by mass or more, and preferably 1 part by mass or less, more preferably 0.75 parts by mass or less, still more preferably 0.50 parts by mass It is at most 10 parts by mass, more preferably at most 0.10 parts by mass.

The third hydraulic composition for centrifugal molding according to the present invention has a water / hydraulic powder ratio (hereinafter sometimes referred to as W / P), but 10% by mass or more from the viewpoint of centrifugal moldability and strength. 12 mass% or more is more preferable, 14 mass% or more is more preferable, 16 mass% or more is still more preferable, and 30 mass% or less is preferable, 28 mass% or less is more preferable, 26 mass% or less 25 mass% or less is still more preferable, 24 mass% or less is still more preferable, 22 mass% or less is still more preferable.

In the third hydraulic forming composition for centrifugal molding of the present invention, the use amount of the coarse aggregate and the use amount of the fine aggregate are the same as those described in the first hydraulic composition for centrifugal forming of the present invention .

The third hydraulic composition for centrifugal molding of the present invention can also contain glycerin and a early strengthening agent such as N-methyldiethanolamine and a chelating agent such as ethylenediaminetetraacetic acid sodium salt. The content of the chelating agent is preferably 0.1 parts by mass or less based on 100 parts by mass in total of the hydraulic powder and the high-strength admixture containing silica, from the viewpoint of strength development after steam curing.

The third hydraulic composition for centrifugal molding of the present invention is a conventional cement dispersant, a water-soluble polymer compound, an air entrainer, a cement wetting agent, an expansive agent, a waterproofing agent, a retarder, a quick-setting agent and a foaming agent. Components such as foaming agents, waterproofing agents, fluidizing agents, thickeners, flocculants, drying shrinkage reducing agents, strength promoters, curing accelerators, preservatives, antifoaming agents [(A2) components, (A3) components , (B1) component, except for those corresponding to the (B2) component can be contained.

[Third Method of Manufacturing Hydraulic Composition for Centrifugal Molding]
The present invention provides a method for producing a third hydraulic composition for centrifugal molding, which comprises mixing the components (A3), (B1), (C), hydraulic powder, aggregate and water. According to this production method, a third hydraulic composition for centrifugal molding of the present invention, which comprises the component (A3), the component (B1), the component (C), the hydraulic powder, the aggregate, and water, is produced. Hereinafter, the manufacturing method of the 3rd hydraulic composition of this invention is demonstrated.

Specific examples and preferred embodiments of the (A3) component, the (B1) component and the (C) component to be used in the third method for producing a hydraulic composition for centrifugal molding of the present invention are the second centrifugal molding of the present invention It is the same as that described for the dispersant composition for hydraulic composition.
In addition, specific examples and preferable embodiments of the hydraulic powder and aggregate used in the third method for producing a hydraulic composition for centrifugal molding according to the present invention are the same as described in the first hydraulic composition for centrifugal molding according to the present invention Is the same as The hydraulic powder is used such that W / P is in the range described in the third hydraulic composition for centrifugal molding of the present invention. The amount of aggregate used is also the same as that described in the first hydraulic composition for centrifugal molding of the present invention.
The second embodiment of the dispersant composition for a hydraulic composition for centrifugal molding according to the present invention, the method for producing the same, and the third hydraulic composition for a centrifugal molding, the third embodiment of the hydraulic composition for a centrifugal molding according to the present invention It can apply suitably to the manufacturing method of.

In the third method for producing a hydraulic composition for centrifugal molding of the present invention, the component (A3) is preferably 0.01 parts by mass or more, relative to 100 parts by mass of the hydraulic powder, from the viewpoint of centrifugal formability, More preferably 0.015 parts by mass or more, still more preferably 0.02 parts by mass or more, and from the viewpoint of centrifugal formability, preferably 1 part by mass or less, more preferably 0.75 parts by mass or less, still more preferably 0 .50 parts by mass or less, more preferably 0.25 parts by mass or less, still more preferably 0.10 parts by mass or less. It is preferable to mix (A3) component so that it may become content of (A3) component in the hydraulic composition for 3rd centrifugation of this invention.

In the third method for producing a hydraulic composition for centrifugal molding of the present invention, the component (B1) is added to 100 parts by mass of the hydraulic powder from the viewpoint of centrifugal moldability and / or the strength of the cured product after centrifugal molding. , Preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.10 parts by mass or more, still more preferably 0.20 parts by mass, and centrifugal formability and / or centrifugation From the viewpoint of the strength of the cured product after molding, it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 6 parts by mass or less, still more preferably 4 parts by mass or less, still more preferably 2 parts by mass The mixing is carried out in parts by weight or less, more preferably in parts by weight or less. It is preferable to mix the (B1) component so that it may become content of the (B1) component in the 3rd hydraulic composition for centrifugal molding of this invention.

In the third method for producing a hydraulic composition for centrifugal molding of the present invention, the total of the components (A3) and (B1) is a hydraulic powder from the viewpoint of centrifugal moldability and / or strength of a cured product after centrifugal molding. To 100 parts by mass of the body, preferably 0.02 parts by mass or more, more preferably 0.05 parts by mass or more, further preferably 0.10 parts by mass or more, still more preferably 0.20 parts by mass or more, and From the viewpoint of centrifugal moldability and / or strength of the cured product after centrifugal molding, it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 6 parts by mass or less, still more preferably 4 parts by mass or less Still more preferably, it mixes so that it may be 2 mass parts or less, still more preferably 1 mass part or less. It is preferable to mix the (A3) component and the (B1) component so as to be the total content of the (A3) component and the (B1) component in the third hydraulic composition for centrifugal molding of the present invention.

In the third method for producing a hydraulic composition for centrifugal molding of the present invention, the (A3) component and the (B1) component can be combined with the (A3) component from the viewpoint of centrifugal moldability and / or strength of the cured product after centrifugal molding. The mass ratio (B1) / (A3) of the component and (B1) component is preferably 0.1 or more, more preferably 1 or more, still more preferably 10 or more, and centrifugal formability and / or a cured product after centrifugal form From the viewpoint of strength, it is preferably 100 or less, more preferably 90 or less, still more preferably 80 or less, still more preferably 70 or less, still more preferably 60 or less, still more preferably 50 or less, still more preferably 40 Hereinafter, the mixing is more preferably to 30 or less.

In the third method for producing a hydraulic composition for centrifugal molding of the present invention, the component (C) is preferably contained in an amount of preferably 100 parts by mass with respect to 100 parts by mass of the hydraulic powder from the viewpoint of strength development of the hydraulic composition. 001 parts by mass or more, more preferably 0.01 parts by mass or more, further preferably 0.05 parts by mass or more, and preferably 1 part by mass or less, more preferably 0.75 parts by mass or less, still more preferably 0.50 parts by mass The mixing is carried out in parts by mass or less, more preferably 0.10 parts by mass or less. It is preferable to mix (C) component so that it may become content of (C) component in the 3rd hydraulic composition for centrifugal molding of this invention.

In the third method for producing a hydraulic composition of the present invention, from the viewpoint of productivity, the components (A3) and (B1), the component (C), and water are mixed in advance and mixed with the hydraulic powder. Is preferred. In the third method for producing a hydraulic composition of the present invention, the addition of the (A3) component, the (B1) component and the (C) component is the second dispersant composition for a hydraulic composition for centrifugal molding of the present invention. It is preferable to add using a substance, and it is more preferable to mix beforehand the dispersing agent composition for hydraulic compositions for centrifugal molding of this invention, and water, and to mix with hydraulic powder.

Mixing of (A3) component, (B1) component, (C) component, hydraulic powder, aggregate, water, and components used as needed is a mortar mixer, forced twin screw mixer Can be performed using a mixer such as The mixing time is preferably 1 minute or more, more preferably 2 minutes or more, and preferably 5 minutes or less, more preferably 3 minutes or less. In the preparation of the hydraulic composition, the materials and agents described in the second hydraulic composition for centrifugal molding of the present invention and their amounts can be used.

[Method for Producing Third Cured Product of Hydraulic Composition]
This invention provides the manufacturing method of the hardened | cured material of the 3rd hydraulic composition containing the following processes.
Step 1 ′ ′-1: a step of obtaining a dispersant composition by mixing the following component (A3), the following component (B1), the following component (C), and water so that the pH is 5 or less 2: A step of mixing the dispersant composition obtained in step 1 ′ ′-1, the hydraulic powder, the aggregate, and water to obtain a hydraulic composition.
Step 2 ": a step of filling the hydraulic composition obtained in Step 1" -2 into a mold.
Step 3 ′ ′: a step of clamping the hydraulic composition filled in the mold obtained in Step 2 ′ ′ by centrifugal force.
Step 4 ": setting the clamped hydraulic composition obtained in Step 3" in a mold.
Hereinafter, the manufacturing method of the 3rd hydraulic composition hardening body of this invention is demonstrated. Also, step 1 ′ ′-1 and step 1 ′ ′ − 2 are combined to form step 1 ′ ′.

Specific examples and preferred embodiments of the components (A3), (B1) and (C) used in the method for producing a cured product of the third hydraulic composition of the present invention are the second centrifugal of the present invention, respectively. It is the same as that described for the dispersant composition for a hydraulic composition for molding.
In addition, specific examples and preferred embodiments of the hydraulic powder and aggregate used in the method for producing a cured product of the third hydraulic composition of the present invention are described in the first hydraulic composition for centrifugal molding of the present invention. It is the same as The hydraulic powder is used such that W / P is in the range described in the third hydraulic composition for centrifugal molding of the present invention. The amount of aggregate used is also the same as that described in the first hydraulic composition for centrifugal molding of the present invention.
The second embodiment of the dispersant composition for a hydraulic composition for centrifugal molding according to the present invention, the method for producing the same, the third hydraulic composition for centrifugal molding, and the method described in the third method for producing a hydraulic composition for centrifugal molding It can apply suitably to the manufacturing method of the hardening body of the 3rd hydraulic composition of this invention.

The process for producing a cured product of the third hydraulic composition of the present invention preferably includes the following step 5 "in addition to steps 1" to 4 ".
Step 5 ": Steam curing the hydraulic composition condensed in Step 4" in a mold.

The process for producing a cured product of the third hydraulic composition of the present invention can include the following step 6 ′ ′ in addition to steps 1 ′ ′ to 5 ′ ′.
Step 6 ": After step 5", a step of cooling the hydraulic composition and removing it from the formwork.

The method for producing a cured product of the third hydraulic composition of the present invention can include the following step 7 ′ ′ in addition to steps 1 ′ ′ to 6 ′ ′.
Step 7 ′ ′: a step of curing the cured product of the hydraulic composition obtained in Step 6 ′ ′ at normal temperature and pressure.

The specific example and the preferred embodiment of the method for obtaining the dispersant composition of step 1 ′ ′-1 are the same as the method for producing the second dispersant composition for a hydraulic composition for centrifugal molding of the present invention.

In step 1 ′ ′-2, the component (A3) is preferably 0.01 parts by mass or more, more preferably 0.015 parts by mass or more, with respect to 100 parts by mass of the hydraulic powder, from the viewpoint of centrifugal formability. The amount is more preferably 0.02 parts by mass or more, and preferably 1 part by mass or less, more preferably 0.75 parts by mass or less, still more preferably 0.50 parts by mass or less, from the viewpoint of centrifugal formability. 0.25 parts by mass or less, more preferably 0.10 parts by mass or less The component (A3) is mixed so as to be the content of the component (A3) in the third hydraulic composition for centrifugal molding of the present invention It is preferable to do.

In step 1 ′ ′-2, the component (B1) is preferably 0.01 parts by mass with respect to 100 parts by mass of the hydraulic powder from the viewpoint of centrifugal moldability and / or strength of the cured product after centrifugal molding Or more, more preferably 0.05 parts by mass or more, still more preferably 0.10 parts by mass or more, still more preferably 0.20 parts by mass or more, and the viewpoint of centrifugal formability and / or cured body strength after centrifugal form From the viewpoint of, preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 6 parts by mass or less, still more preferably 4 parts by mass or less, still more preferably 2 parts by mass or less, still more preferably 1 It is preferable to mix the (B1) component so as to be the content of the (B1) component in the third hydraulic composition for centrifugal molding of the present invention.

In step 1 ′ ′-2, the total amount of the components (A3) and (B1) is 100 parts by mass of the hydraulic powder from the viewpoint of centrifugal moldability and / or strength of the cured product after centrifugal molding, Preferably it is 0.02 parts by mass or more, more preferably 0.05 parts by mass or more, still more preferably 0.10 parts by mass or more, still more preferably 0.20 parts by mass and centrifugal formability and / or centrifugal molding From the viewpoint of the strength of the cured product, it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 6 parts by mass or less, still more preferably 4 parts by mass or less, still more preferably 2 parts by mass The mixture is more preferably 1 part by mass or less The total content of the components (A3) and (B1) in the third hydraulic composition for centrifugal molding of the present invention (A3) Ingredients and (B1) It is preferred to mix the minute.

In step 1 ′ ′-2, the mass ratio of the (A3) component to the (B1) component, the (A3) component and the (B1) component, from the viewpoint of centrifugal moldability and / or the strength of the cured product after centrifugal molding (B3) ) / (A1) is preferably 0.1 or more, more preferably 1 or more, further preferably 10 or more, and preferably 100 from the viewpoint of centrifugal moldability and / or strength of the cured product after centrifugal molding. Or less, more preferably 90 or less, still more preferably 80 or less, still more preferably 70 or less, still more preferably 60 or less, still more preferably 50 or less, still more preferably 40 or less, still more preferably 30 or less Mix as you like.

In step 1 ′ ′-2, from the viewpoint of strength development of the hydraulic composition, the amount of the component (C) is preferably 0.001 parts by mass or more, more preferably 0. 01 parts by mass or more, more preferably 0.05 parts by mass or more, and preferably 1 part by mass or less, more preferably 0.75 parts by mass or less, still more preferably 0.50 parts by mass or less, still more preferably 0. The component (C) is preferably mixed so that the content of the component (C) in the third hydraulic composition for centrifugal molding of the present invention is achieved.

In step 1 ′ ′ − 2, W / P is preferably 10% by mass or more, more preferably 12% by mass or more, still more preferably 14% by mass or more, still more preferably 16% by mass from the viewpoint of centrifugal formability and strength. %, And preferably 30% by mass or less, more preferably 28% by mass or less, further preferably 26% by mass or less, still more preferably 25% by mass or less, still more preferably 24% by mass or less, still more preferably 22 mass% or less hydraulic composition is prepared.

In step 1 ′ ′-2, a mixture containing the dispersant composition obtained in step 1 ′ ′-1 (the second dispersant composition for a hydraulic composition for centrifugal molding of the present invention) and water is used as an aggregate and an aggregate. The method of adding to and mixing with the mixture containing the hydraulic powder is preferable in that it can be uniformly mixed easily even when producing the hydraulic composition.

Specific examples and preferable embodiments of the steps 2 ′ ′ to 7 ′ ′ are respectively the same as the embodiments described in the steps 2 to 7 in the method for producing a cured product of the first hydraulic composition of the present invention.

The production method of the present invention comprises steps 1 ′ ′ to 6 ′ ′, and the time taken from preparation of the hydraulic composition to removal from the mold in step 6 ′ ′ is 8 hours or more and 30 hours or less. A method for producing a cured product of the composition may be mentioned, wherein the start of preparation of the hydraulic composition is when the hydraulic powder and water first come in contact with each other.

The cured product of the hydraulic composition obtained by the method for producing a cured product of the third hydraulic composition of the present invention can be used as a centrifugally formed concrete product, and specifically, piles, poles, fume tubes, etc. are mentioned. Be The cured product of the hydraulic composition obtained by the method for producing a cured product of the present invention is excellent in initial strength, and can reduce waste generated at the production site of the product with a small amount of generation of slag during production. Moreover, since it is excellent in compaction, the inner surface and end face unevenness of the product are small, the surface appearance is excellent, and the inner surface of the product is smoothed, thereby improving obstacles to the cutting machine during pile driving and Nakabori method. .

Example The following were used as the (A1) component, the (A1 ′) component (the comparison component of the (A1) component), and the (B1) component shown in Tables 1 and 2.

(A1) Component (a1-1): Polymethacroyloxyethyl dimethylethyl ammonium sulfate ethyl salt, weight average molecular weight 120,000, quaternization ratio 99%
(A1-2): Polyamide polyamine / epichlorohydrin condensate, weight average molecular weight 20,000, EPA-03, manufactured by Yokkaichi Gosei Co., Ltd., quaternization rate 10%
(A1-3): dimethylamine / ammonia / epichlorohydrin condensate, weight average molecular weight 15,000, PDA-2, manufactured by Yokkaichi Gosei Co., Ltd., quaternization rate 84%
(A1-4): dimethylamine / ammonia / epichlorohydrin condensate, weight average molecular weight 20,000, PDA-3, manufactured by Yokkaichi Gosei Co., Ltd., quaternization rate 80%
(A1-5): diallyldimethyl ammonium chloride polymer, weight average molecular weight 30,000, PAS-H-5L, manufactured by Nitto Bo Medical Co., Ltd., 100% quaternization ratio
(A1-6): diallyldimethyl ammonium chloride polymer, weight average molecular weight 200,000, PAS-H-10L, manufactured by Nitto Bo Medical Co., Ltd., 100% quaternization rate
(A1-7): diallyl methyl ethyl ammonium ethyl sulfate polymer, weight average molecular weight 37,000, PAS-24, manufactured by Nitto Bo Medical Co., Ltd., 100% quaternization ratio
(A1-8): Chloride of quaternized polyethyleneimine to which polyoxyethylene (hereinafter referred to as EO) is added, weight average molecular weight 7,300, synthetic product by ordinary method, quaternization ratio 99%
(A1-9): Chloride of quaternized polyethyleneimine to which EO is added, weight average molecular weight 2,500, synthetic product by ordinary method, quaternization ratio 99%

(A1 ') component (comparative component of (A1) component)
(A1′-1): chloride of quaternized polyethyleneimine to which EO is added, weight average molecular weight 3,000, PAE-01, manufactured by Yokkaichi Gosei Co., Ltd., quaternization ratio 2%
(A1′-2): dimethylamine / trimethylamine / epichlorohydrin condensate, weight average molecular weight 1,000, PDT-2, manufactured by Yokkaichi Gosei Co., Ltd., quaternization rate 95%
(A1′-3): stearyltrimethyl ammonium chloride, quaternization ratio 99%, weight average molecular weight 348

The quaternization ratio of the components (A1) and (A1 ′) is the cation equivalent (hereinafter referred to as Q4) (meq / g) determined at pH 4 in the following measurement method and the cation equivalent determined at pH 10 (below , Q10) (meq / g) using the following formula.
[Calculation of quaternization rate]
The quaternization rate was calculated according to the following equation.
Quaternization ratio (%) = Q10 (meq / g) × 100 / Q4 (meq / g)

[Measurement of cation equivalent]
The cation equivalent Q4 (meq / g) and Q10 were measured and calculated at the two points of pH 4 and 10 according to the following method.
100 g of a measurement sample is placed in a 200 mL conical beaker, and while stirring with a magnetic stirrer (500 rpm), a 0.5 wt% aqueous sulfuric acid solution is gradually added to adjust the pH. Then add 2-3 drops of toluidine blue indicator (TB indicator) and titrate with N / 400 polyvinyl potassium sulfate (N / 400 PVSK) reagent. The titration rate is 2 mL / min, and the end point is when the measurement sample turns from blue to reddish purple and the reddish purple is retained for 30 seconds.
[Blank test]
The same operation as measurement of cation equivalent is performed except that 100 g of ion exchanged water is used instead of the measurement sample.
[Method of calculation]
Cation equivalent value (meq / g) = (1/2)
× (titer of sample-titre of blank test) × (titer of N / 400 PVSK)

(B1) Component (b1-1): methacrylic acid / methoxypolyethylene glycol (23) monomethacrylate polymer (the number in parentheses is the average added mole number, the same shall apply hereinafter) (molar ratio 73/27), monomer (B12) / Monomer (B11) = 73/27 (molar ratio), weight average molecular weight 50,000
(B1-2): methacrylic acid / methoxy polyethylene glycol (46) monomethacrylate / acrylic acid (molar ratio 45/26/29), monomer (B12) / monomer (B11) = 74/26 (molar ratio) ), Weight average molecular weight 35,000

(B1 ') component (comparative component of (B1) component)
(B1′-1): Formaldehyde condensate of naphthalene sulfonic acid: weight average molecular weight 15,000, manufactured by Kao Corporation, Mayty HS

Example 1x and Comparative Example 1x
(1) Mortar formulation The mortar formulation is shown below. W / P is the ratio (mass%) of water / hydraulic powder.

* Compounding mortar (P): 400 g (1: 1 mixture of ordinary portland cement manufactured by Pacific Cement Co., Ltd. and ordinary portland cement manufactured by Sumitomo Osaka Cement Co., Ltd., specific gravity 3.16)
Tap water (W): 120 g (including the component (A1), the component (A1 ′), the component (B1), and the antifoaming agent)
W / P: 30% by mass
Sand: 700 g (manufactured by Kyoto Prefecture Joyo, surface dry specific gravity 2.50 g / cm ³ )
Antifoaming agent: Foam Rex 797, manufactured by Nikka Chemical Co., Ltd., 0.01% by mass added to cement Note that component (A1), component (A1 ′), component (B1), and component in tap water Since the amount of the foaming agent was a trace amount to the mortar composition, the W / P was calculated by adding it to the amount of tap water.

(2) Preparation of mortar A composition containing the component (A1), the component (A1 ′), the component (B1), the antifoaming agent, and water was prepared so as to be the addition amounts in Table 1. The composition was added to water (W) of the mortar compounding material, and was prepared along with other mortar compounding materials. The mortar was prepared by kneading (60 rpm, 60 seconds, then 120 rpm, 120 seconds) of the compounding components using a mortar mixer defined in JIS R 5201.

(3) Evaluation of mortar fluidity The mortar immediately after kneading was filled in a flow cone (upper diameter 70 mm × lower diameter 100 mm × height 60 mm) described in JIS R 5201, and mortar flow was measured. The results are shown in Table 1.

(4) Evaluation of Sludge Resistance The mortar flow measured as in (3) is compared with the mortar flow measured by adding only the component (B1) of Comparative Example 1x-1, and an index of sludge inhibition by the concrete test Sludge resistance was evaluated by calculating the mortar flow inhibition rate (%) derived from the following formula that is suggested to be. The results are shown in Table 1. The mortar resistance which is excellent in sludge resistance and is excellent in the moldability in the case of centrifugal forming can be obtained, so that a mortar flow control rate is large.

Mortar flow suppression rate (%) = {(mortar flow of comparative example 1x-1)-(mortar flow of each example, comparative example)} * 100 / (mortar flow of comparative example 1x-1)

In Table 1, the addition amount of (A1) component and (B1) component is an addition amount (mass part) with respect to 100 mass parts of hydraulic powder, and is an addition amount of solid content (active ingredient). When the component (A1 ′) is used instead of the component (A1), the component (A1 ′) is described in the column of the component (A1) for convenience, and the mass ratio (B1) / (A1) is (A1) ) Is a value calculated by replacing the component with the component (A1 ′).

In contrast to Comparative Example 1x-1, which is a hydraulic composition containing only the polycarboxylic acid-based dispersant of component (B1) in Table 1, a hydraulic composition containing components (A1) and (B1) is used. In Examples 1x-1 to 1x-12, it is suggested that the mortar flow inhibition rate which is an index of the sludge resistance is high, and it is suggested that the hydraulic powder particles are effectively aggregated, and the sludge resistance is excellent. I understand. On the other hand, in Comparative Examples 1x-2 to 1x-5 using the component (A1 ') instead of the component (A1), it is understood that the mortar flow inhibition rate as an index of the sludge resistance is low and the sludge resistance performance is inferior. .

Example 2x and Comparative Example 2x
(1) Concrete mix The concrete mix is shown below. W / P is the ratio (mass%) of water / hydraulic powder, and the amount (P) of hydraulic powder is the total of early strength cement (P ₁ ) and inorganic early strengthening agent (P ₂ ) Amount.

* Concrete blended early strength cement (P ₁ ): 12.6 kg (Pacific Cement Co., Ltd., specific gravity 3.16)
Inorganic early strengthening agent (P ₂ ): 1.00 kg (amorphous silica / anhydrite = 80/20% by mass of a mixture, specific gravity 2.45)
Tap water (W): the amount described in Tables 2 and 3 (including (A1) component, (A1 ') component, (B1) component, and (B1') component)
W / P: Sand described in Tables 2 and 3. 18.88 kg (Koga barras crushed sand, manufactured by Koka Shiga Prefecture, density 2.58 g / cm ³ )
Gravel: 28.35 kg (Crushed stone, manufactured by Ieshima, Hyogo Prefecture, density 2.61 g / cm ³ )
In addition, since the quantity of those components of the (A1) ingredient, the (A1 ') ingredient, the (B1) ingredient, and the (B1') ingredient in tap water is a trace amount to mortar composition, The W / P was calculated.

(2) Preparation of concrete A composition containing the components (A1), (A1 ′), (B1), (B1 ′) and water is prepared so that the addition amounts in Tables 2 and 3 are obtained. The composition was added to water (W) of a concrete compounding material, and was prepared by stirring. Concrete is charged into a forced twin-screw mixer (manufactured by KYC) in the order of gravel, about half amount of sand, a mixture of early strength cement and inorganic early strengthening agent, and the remaining sand, and the air is kneaded for 30 seconds, and The above prepared water was quickly added and mixed for 240 seconds to obtain concrete.

(3) Evaluation of Slump The slump was measured based on JIS A 1101 and JIS A 1150 for the concrete immediately after kneading. The results are shown in Tables 2 and 3.

(4) Evaluation of centrifugally-formed concrete The concrete 10 minutes after kneading is put into a centrifugally-formed frame (inner diameter 20 cm, outer diameter 25 cm, height 40 cm), initial speed is 1 G for 2 minutes, 2 speed is 3 G for 2 minutes The centrifugation was performed under the conditions of 3G for 7 minutes, 2G for 4G, 3 minutes for 15G, and 3G for 25G for 5 minutes. Then, after pre-curing for 4 hours at 20 ° C., the temperature was raised to 70 ° C. at a rate of 20 ° C./hour, and steam curing was performed for 4 hours at 70 ° C. Then, natural cooling to 20 ° C. and mold removal were followed in the air for curing for 7 days in total for 7 days to obtain a cylindrical concrete cured body (inner diameter 12 cm, outer diameter 20 cm, height 30 cm). In addition, the 7-day compressive strength (7-day strength) of the obtained centrifugally molded article was measured based on JIS A 1108. The results are shown in Tables 2 and 3.

Measure the thickness (mm) of the upper end face of the hardened tubular concrete at four points on the diagonal and the thickness (mm) at the lower end face at four points on the diagonal, for a total of eight points. Deviations were calculated, and the results are shown in Tables 2 and 3. The smaller the standard deviation, the smaller the variation in the thickness of the cylindrical cured product, and the better the centrifugal formability. The upper limit value at which the formability can be judged to be good by visual observation is 1.5 (mm), and in Tables 2 and 3, symbols are shown based on the following criteria in accordance with the standard deviation of thickness (mm) .
Evaluation standard ○: Standard deviation of thickness (mm) of 8 places of cylindrical cured body is less than 1.5 ×: Standard deviation of thickness (mm) of 8 places of cylindrical cured body is 1.5 or more

In Tables 2 and 3, the addition amounts of the (A1) component and the (B1) component are addition amounts (parts by mass) with respect to 100 parts by mass of the hydraulic powder, and are addition amounts of solid contents (active parts). When the component (A1 ′) is used instead of the component (A1), the component (A1 ′) is described in the column of the component (A1) for convenience, and the mass ratio (B1) / (A1) is (A1) ) Is a value calculated by replacing the component with the component (A1 ′). Moreover, when using (B1 ') component instead of (B1) component, (B1') component was described in the column of (B1) component for convenience. Further, Comparative Example 2x-2 and Example 2x-2 are described in both of Table 2 and Table 3 for convenience.

Relative to Comparative Examples 2x-1 to 2x-2, which are hydraulic compositions containing only the polycarboxylic acid-based dispersant of the component (B1) in Table 2, water containing the components (A1) and (B1) It can be seen that Examples 2x-1 to 2x-4, which are hard compositions, have excellent moldability over a wide range of water content of the hydraulic composition. In addition, in Comparative Example 2x-3, which is a hydraulic composition containing only a naphthalene-based dispersant as a comparative component in place of the component (B1), adjustment of fresh concrete is performed under the same conditions as Comparative Example 2x-2. It could not be carried out, and it was not possible to evaluate the formability and the 7-day strength.
Further, in Table 3, relative to Comparative Examples 2x-2 and 2x-4 to 2x-5 which are hydraulic compositions containing only the polycarboxylic acid-based dispersant of the component (B1), the component (A1) and the component (B1) It can be seen that Examples 2x-2, 2x-5 to 2x-11, which are hydraulic compositions containing the components, have excellent moldability over a wide range of dispersant additions of the hydraulic composition.
Furthermore, in Table 3, as a comparative component of the component (A1), a hydraulic composition containing a component (A1 ′) which is a comparative component satisfying the molecular weight and not satisfying the quaternization ratio, Comparative Example 2x-7, In Comparative Example 2x-8, which is a hydraulic composition containing a component (A1 ′) that is a comparative component that does not satisfy the molecular weight and satisfies only the quaternization rate, the improvement of the centrifugal formability that is the effect of the present invention It turns out that the effect can not be confirmed.

The components (A2), (A2 ') (the comparative component of the component (A2)), the components (B2) and (B2') (the comparative component of the component (B2)) shown in Tables 4 to 6 are as follows. The thing was used.

(A2) Component (a2-1): Polymer of Poise 530 (acrylic acid polymer, manufactured by Kao Corporation, weight average molecular weight 5,000, neutralization of carboxyl group in the polymer, ie, a compound which is a salt) The compound (a2-2) which made the carboxyl group in the unneutralized (namely, a carboxyl group is not a salt): poise 520 (acrylic acid-maleic acid copolymer, acrylic acid / maleic acid = 70/30 (molar ratio) ), Kao Co., Ltd. product, weight average molecular weight 5,000, the carboxyl group in the polymer is neutralized, ie, the compound which is a salt is not neutralized (ie, the carboxyl group is not a salt) in the polymer of the polymer Compound made into)

(A2 ') component (comparative component of (A2) component)
(A2′-1): a compound in which the carboxyl group in the polymer is a sodium salt by neutralizing the compound of (a2-1) with a 48% aqueous sodium hydroxide solution (reagent: manufactured by Wako Pure Chemical Industries, Ltd.)

(B2) Component (b2-1): methacrylic acid / methoxypolyethylene glycol (23) monomethacrylate polymer (the average number of added moles in parentheses, the same applies hereinafter) (molar ratio 73/27), monomer (B22) / Monomer (B21) = 73/27 (molar ratio), weight average molecular weight 50,000, compound in which the carboxyl group in the polymer is not neutralized, ie, not a salt

(B2 ') component (comparative component of (B2) component)
(B2'-1): a compound in which the carboxyl group in the polymer is a sodium salt by neutralizing the compound of (b2-1) with a 48% aqueous sodium hydroxide solution (reagent: Wako Pure Chemical Industries, Ltd.) (B2'-2): naphthalene sulfonic acid-formaldehyde condensate: weight average molecular weight 15,000, manufactured by Kao Corporation, Mighty HS

Example 1y and Comparative Example 1y
(1) Preparation of Dispersant Composition A dispersant composition containing each component was prepared such that the addition amount described in Table 4 was obtained. The preparation method is as follows: after preparation as a 40% aqueous solution in which the components (A2) or (A2 ') and the components (B2) or (B2') are described in Table 4, then the ratio in Table 4 will be water Was added, No. The mixture was prepared by using a magnetic stirrer at 100 ° C. and 20 ° C. in an 8 m steel screw tube.

(2) Appearance evaluation About the appearance of the prepared dispersing agent composition, after leaving still and preserve | saving at 20 degreeC for 3 months, it observed visually and determined with the following evaluation criteria. The results are shown in Table 4.
Uniform: Maintaining uniform transparency.
Separation: It is confirmed that two layers are separated.

In Table 4, when using (A2 ') component instead of (A2) component, (A2') component was described in the column of (A2) component for convenience. Moreover, when using (B2 ') component instead of (B2) component, (B2') component was described in the column of (B2) component for convenience. Moreover, the addition amount of (A2) component, (A2 ') component, (B2) component, and (B2') component is an addition amount of solid content (active component).

In Table 4, in the case of Comparative Examples 1y-1 to 1y-3 using either (a2'-1) or (b2'-1), in which the carboxyl group is a neutralized compound, that is, the carboxyl group is a salt compound. It was confirmed that the adjusted dispersant composition was separated into two layers after storage. On the other hand, in the case of Example 1y-1 in which both unneutralized (a2-1) and (b2-1) were mixed, it was found that uniform liquefaction can be maintained even after the above storage.

Example 2 y and Comparative Example 2 y
(1) Mortar formulation The mortar formulation is shown below. W / P is the ratio (mass%) of water / hydraulic powder.

* Blended mortar mortar (P): 400 g (1: 1 mixture of Pacific Portland Ltd. ordinary portland cement and Sumitomo Osaka Cement Inc. ordinary portland cement, specific gravity 3.16)
Tap water (W): 120 g (including the (A2) component, the (B2) component, and the antifoaming agent)
W / P: 30% by mass
Sand: 700 g (manufactured by Kyoto Prefecture Joyo, surface dry specific gravity 2.50 g / cm ³ )
Antifoaming agent: Foam Rex 797, manufactured by Nikka Chemical Co., Ltd., 0.01% by mass added to cement Note that the components (A2), (B2) and taping agent in tap water are Since the amount of the component is very small relative to the mortar composition, W / P was calculated by being included in the amount of tap water.

(2) Preparation of mortar A composition containing the component (A2), the component (B2), the antifoaming agent and water was prepared so as to be the addition amounts in Table 5. The composition was added to water (W) of the mortar compounding material, and was prepared along with other mortar compounding materials. The mortar was prepared by kneading (60 rpm, 60 seconds, then 120 rpm, 120 seconds) of the compounding components using a mortar mixer defined in JIS R 5201.

(3) Evaluation of mortar fluidity The mortar immediately after kneading was filled in a flow cone (upper diameter 70 mm × lower diameter 100 mm × height 60 mm) described in JIS R 5201, and mortar flow was measured. The results are shown in Table 5.

(4) Evaluation of Sludge Resistance The mortar flow measured according to (3) is compared with the mortar flow measured by adding only the component (B2) of Comparative Example 2y-1, and a concrete test is an indicator of sludge inhibitory property Sludge resistance was evaluated by calculating the mortar flow inhibition rate (%) derived from the following formula that is suggested to be. The results are shown in Table 5. The mortar resistance which is excellent in sludge resistance and is excellent in the moldability in the case of centrifugal forming can be obtained, so that a mortar flow control rate is large.

Mortar flow suppression rate (%) = {(mortar flow of comparative example 2 y-1)-(mortar flow of each example)} x 100 / (mortar flow of comparative example 2 y-1)

In Table 5, the addition amount of (A2) component and (B2) component is an addition amount (mass part) with respect to 100 mass parts of hydraulic powder, and is an addition amount of solid content (active ingredient).

In contrast to Comparative Example 2y-1, which is a hydraulic composition containing only the polycarboxylic acid-based dispersant as the component (B2) in Table 5, it is a hydraulic composition containing the components (A2) and (B2). In Examples 2 y-1 to 2 y-4, it is suggested that the mortar flow suppression rate which is an index of the sludge resistance is high, it is suggested that the hydraulic powder particles are effectively aggregated, and the sludge resistance is excellent. I understand.

Example 3 y and Comparative Example 3 y
(1) Concrete mix The concrete mix is shown below. W / P is the ratio of water / hydraulic powder (% by mass), and the amount of hydraulic powder is the total of early-strength cement (P ₁ ) and high-strength admixture (P ₂ ) .

* Concrete blended early strength cement (P ₁ ): 12.6 kg (Pacific Cement Co., Ltd., specific gravity 3.16)
High strength admixture (P ₂ ): 1.00 kg (amorphous silica / anhydrite = 80/20% by weight mixture, specific gravity 2.45)
Tap water (W): the amount described in Table 6 (including the (A2) component, the (B2) component, and the (B2 ') component)
W / P: Sand described in Table 6: 18.88 kg (Koga barras crushed sand, manufactured by Koka Shiga Prefecture, density 2.58 g / cm ³ )
Gravel: 28.35 kg (Crushed stone, manufactured by Ieshima, Hyogo Prefecture, density 2.61 g / cm ³ )
In addition, since the quantity of those ingredients is trace amount with respect to concrete composition, the quantity of tap water is included in the quantity of tap water, and (A2) ingredient, (B2) ingredient, and (B2 ') ingredient in tap water are included in W / P Was calculated.

(2) Preparation of concrete A composition containing the (A2) component, the (B2) component, the (B2 ') component, and water is prepared so that the addition amounts in Table 6 are obtained, and the water (W) of the concrete composition material is prepared The composition was added to the solution and stirred to prepare. Concrete is charged into a forced twin-screw mixer (manufactured by KYC) in the order of gravel, about half amount of sand, a mixture of early strength cement and inorganic early strengthening agent, and the remaining sand, and the air is kneaded for 30 seconds, and The above prepared water was quickly added and mixed for 240 seconds to obtain concrete.

(3) Evaluation of Slump The slump was measured based on JIS A 1101 and JIS A 1150 for the concrete immediately after kneading. The results are shown in Table 6.

(4) Evaluation of centrifugally-formed concrete Compressive strength at 7 days of age of the cylindrical concrete cured body obtained by the same method as the evaluation of (4) centrifugally-formed concrete in <Example 2x and Comparative Example 2x> ( 7 days strength) was measured, the thickness of eight places of the cured product was measured, the standard deviation was calculated, and the moldability was evaluated based on the same standard. The results are shown in Table 6.

In Table 6, the addition amount of (A2) component and (B2) component is an addition amount (mass part) with respect to 100 mass parts of hydraulic powder, and is an addition amount of solid content (active ingredient). Moreover, when using (B2 ') component instead of (B2) component, (B2') component was described in the column of (B2) component for convenience.

Relative to Comparative Examples 3y-1 to 3y-2, which are hydraulic compositions containing only the polycarboxylic acid-based dispersant of component (B2) in Table 6, water containing components (A2) and (B2) It can be seen that Examples 3 y-A 1 to 3 y-A 2, 3 y-B 1 to 3 y-B 2 which are hard compositions have excellent moldability over a wide range of water content of the hydraulic composition. Further, Comparative Example 3y-3, which is a hydraulic composition containing only a naphthalene-based dispersant as a comparative component in place of the component (B2), performs the preparation of fresh concrete under the same conditions as Comparative Example 3y-2. It could not be carried out, and it was not possible to evaluate the formability and the 7-day strength.

As components (A3), (B1) and (B1 ') (comparative components of components (B1)) and (C) shown in Tables 7 to 10, the following were used.

(A3) Component (a3-1): acrylic acid polymer, Poise 530, manufactured by Kao Corporation, weight average molecular weight 5,000, a compound wherein the carboxyl group in the polymer is neutralized, that is, a salt (a3-2) ): Acrylic acid / maleic acid copolymer, poise 520, acrylic acid / maleic acid = 70/30 (molar ratio), manufactured by Kao Corporation, weight average molecular weight 5,000, neutralization of carboxyl groups in the polymer That is, compounds that are salts

(B1) Component (b1-3): acrylic acid / polyethylene glycol (60) isoprenyl ether polymer (the average number of moles added in parentheses, the same applies hereinafter) (molar ratio 75/25), monomer (B12) / Monomer (B11) = 75/25 (molar ratio), weight average molecular weight 40,000, the carboxyl group in the polymer is neutralized, ie, a compound which is a salt (b1-4): methacrylic acid / methoxy polyethylene glycol ( 23) Monomethacrylate polymer (the average addition mole number in parentheses, the same applies hereinafter) (molar ratio 73/27), monomer (B12) / monomer (B11) = 73/27 (molar ratio), weight average Compound (b1-5) having a molecular weight of 50,000 and a carboxyl group in the polymer being neutralized, that is, a salt: methacrylic acid / methoxypolyethylene glycol (120) monomethacrylate Copolymer (average number of moles added in parentheses, the same applies hereinafter) (molar ratio 80/20), monomer (B12) / monomer (B11) = 80/20 (molar ratio), weight average molecular weight 60, 000, a compound in which the carboxyl group in the polymer is neutralized, ie, a salt

(C) Component The compounds shown in Tables 7 to 10 were used.

Example 1z and Comparative Example 1z
(1) Preparation of Dispersant Composition A dispersant composition containing each component was prepared so as to have the amount described in Table 7. After preparing as an aqueous solution which makes (A3) component and (B1) component the ratio of Table 7 according to the preparation method, water is added so that it may become the ratio of Table 4, No. The mixture was prepared by using a magnetic stirrer at 100 ° C. and 20 ° C. in an 8 m steel screw tube. Subsequently, the component (C) was added to the ratio described in Table 7 to adjust the pH at 20 ° C. to the value described in Table 7. The pH was measured in accordance with item 8.3 of JIS K 3362; 2008.

(2) Appearance evaluation About the appearance of the prepared dispersing agent composition, after leaving still and preserve | saving at 20 degreeC for 3 months, it observed visually and determined with the following evaluation criteria. The results are shown in Table 7.
Uniform: Maintaining uniform transparency.
Separation: It is confirmed that two layers are separated.

In Table 7, the addition amount of (A3) component, (B1) component, and (C) component is the addition amount of solid content (active component).

In Table 7, in the components (A3) and (B1), in the case of Comparative Examples 1z-1 to 1z-2 in which the carboxyl group contains a neutralized compound, ie, a salt compound, and the pH is more than 5, the prepared dispersions It was confirmed that the agent composition was separated into two layers after the above storage. On the other hand, in the components (A3) and (B1), even if the carboxyl group contains a neutralized or salt compound, the component (C) is contained to adjust the pH to 5 or less. Example 1z-1 In the case of the dispersant composition of ̃1z-19, it can be seen that uniform stability can be maintained even after the above storage, and one liquefaction can be maintained.

Examples 2z to 4z and Comparative Examples 2z to 4z
(1) Concrete mix The concrete mix is shown below. W / P is the ratio of water / hydraulic powder (% by mass), and the amount of hydraulic powder is the total of early-strength cement (P ₁ ) and high-strength admixture (P ₂ ) .

* Concrete blended early strength cement (P ₁ ): 12.6 kg (Pacific Cement Co., Ltd., specific gravity 3.16)
High strength admixture (P ₂ ): 1.00 kg (amorphous silica / anhydrite = 80/20% by weight mixture, specific gravity 2.45)
Tap water (W): the amount described in Tables 8 to 10 (including the (A3) component, the (B1) component, the (B1 ') component, and the (C) component)
W / P: Sand described in Tables 8 to 10: 18.88 kg (Koga Ballas Crushed Sand, Shiga Prefecture Koka, Density 2.58 g / cm ³ )
Gravel: 28.35 kg (Crushed stone, manufactured by Ieshima, Hyogo Prefecture, density 2.61 g / cm ³ )
The components (A3), (B1), (B1 '), and (C) in tap water are included in the amount of tap water because the amount of these components is very small relative to the concrete composition. Then W / P was calculated.

(2) Preparation of concrete A composition containing the components (A3), (B1), (B1 '), (C) and water is prepared so that the addition amounts in Tables 8 to 10 are obtained, and the concrete The composition was added to water (W) of the compounding material, and was prepared by stirring. Concrete is charged into a forced twin-screw mixer (manufactured by KYC) in the order of gravel, about half amount of sand, a mixture of early strength cement and inorganic early strengthening agent, and the remaining sand, and the air is kneaded for 30 seconds, and The above prepared water was quickly added and mixed for 240 seconds to obtain concrete.

(3) Evaluation of Slump The slump was measured based on JIS A 1101 and JIS A 1150 for the concrete immediately after kneading. The results are shown in Tables 8-10.

(4) Evaluation of centrifugally-formed concrete Compressive strength at 7 days of age of the cylindrical concrete cured body obtained by the same method as the evaluation of (4) centrifugally-formed concrete in <Example 2x and Comparative Example 2x> ( 7 days strength) was measured, the thickness of eight places of the cured product was measured, the standard deviation was calculated, and the moldability was evaluated based on the same standard. The results are shown in Tables 8-10.

In Tables 8 to 10, the addition amounts of the (A3) component, the (B1) component, and the (C) component are the addition amounts (parts by mass) with respect to 100 parts by mass of the hydraulic powder, and the addition amounts of solid contents (active parts) It is. Moreover, when using (B1 ') component instead of (B1) component, (B1') component was described in the column of (B1) component for convenience.

Relative to Comparative Examples 2z-1 to 2z-2, which are hydraulic compositions containing only the polycarboxylic acid-based dispersant of component (B1) in Table 8, water containing components (A3) and (B1) It can be seen that Examples 2z-1 to 2z-2, which are hard compositions, have excellent moldability over a wide range of water content of the hydraulic composition. In addition, in Comparative Example 2z-3, which is a hydraulic composition containing only a naphthalene-based dispersant as a comparative component instead of the component (B1), adjustment of fresh concrete is performed under the same conditions as in Comparative Example 2z-1. It was not possible to evaluate moldability and 7-day strength.

Further, in Comparative Example 3z-1 to 3z-3, which is a hydraulic composition containing only the polycarboxylic acid-based dispersant of the component (B1) in Table 9, the component (A3) and the component (B1) are contained. It can be seen that Examples 3z-1 to 3z-2, which are hydraulic compositions, have excellent moldability over a wide range of water content of hydraulic compositions.

Further, in Table 10, components (A3) and (B1) are contained relative to Comparative Examples 4z-1 to 4z-3, which are hydraulic compositions containing only the polycarboxylic acid-based dispersant as the component (B1). It can be seen that Examples 4z-1 to 4z-2, which are hydraulic compositions, have excellent moldability over a wide range of water content of hydraulic compositions.

Claims

(A1) Cationic polymer (hereinafter referred to as component (A1)) having a weight average molecular weight of 1,500 to 300,000 and a quaternization ratio of 5 to 100%, (B1) poly A hydraulic composition for centrifugal molding, comprising a carboxylic acid-based dispersant (hereinafter referred to as component (B1)), a hydraulic powder, an aggregate and water.
The hydraulic composition for centrifugal molding according to claim 1, wherein the weight average molecular weight of the component (A1) is 2,000 or more and 200,000 or less.
The hydraulic composition for centrifugal molding according to claim 1 or 2, wherein the quaternization ratio of the component (A1) is 7% or more and 100% or less.
The hydraulic composition for centrifugal molding according to any one of claims 1 to 3, wherein a ratio of water / hydraulic powder is 10% by mass or more and 30% by mass or less.
The hydraulic composition for centrifugal molding according to any one of claims 1 to 3, wherein a ratio of water / hydraulic powder is 10% by mass or more and 25% by mass or less.
The hydraulic composition for centrifugal molding according to any one of claims 1 to 5, wherein the content of the component (A1) is 0.01 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass of the hydraulic powder. .
The mass ratio (B1) / (A1) of the content of the component (A1) to the content of the component (B1) is 0.01 or more and 100 or less according to any one of claims 1 to 6. Hydraulic composition.
The manufacturing method of hydraulic composition hardening body containing the following processes.
Step 1: (A1) A cationic polymer (hereinafter referred to as component (A1)) having a weight average molecular weight of 1,500 to 300,000 and a quaternization ratio of 5 to 100% B1) A step of mixing a polycarboxylic acid based dispersant (hereinafter referred to as component (B1)), a hydraulic powder, an aggregate and water to obtain a hydraulic composition.
Step 2: A step of filling the hydraulic composition obtained in Step 1 into a mold.
Step 3: A step of clamping the hydraulic composition filled in the mold obtained in Step 2 by centrifugal force.
Step 4: A step of setting the clamped hydraulic composition obtained in step 3 in a mold.
The method for producing a cured hydraulic composition according to claim 8, wherein a hydraulic composition having a water / hydraulic powder ratio of 10% by mass to 30% by mass is prepared in step 1.
The method for producing a cured hydraulic composition according to claim 8, wherein a hydraulic composition having a water / hydraulic powder ratio of 10% by mass to 25% by mass is prepared in step 1.
The hydraulic composition according to any one of claims 8 to 10, wherein component (A1) is mixed in an amount of 0.01 to 1 part by mass with respect to 100 parts by mass of hydraulic powder in step 1. Method for producing a cured product.
The method for producing a cured hydraulic composition according to any one of claims 8 to 11, comprising the following step 5 after the step 4.
Step 5: Steam curing the set hydraulic composition obtained in Step 4 in a mold.
The manufacturing method of the hydraulic composition hardened body of Claim 12 whose steam curing temperature is 40 to 90 degreeC at the process 5.
The dispersing agent composition for hydraulic compositions for centrifugal moldings containing the following (A2) component, the following (B2) component, and water.
Component (A2): a polymer or copolymer having acrylic acid and / or maleic acid as constituent monomers, wherein the carboxyl group is not neutralized (B2) component: polycarboxylic acid-based dispersant Dispersant with unneutralized carboxyl groups
The dispersant composition for a hydraulic composition for centrifugal molding according to claim 14, wherein the total content of the components (A2) and (B2) is 0.02% by mass or more and 10% by mass or less.
The hydraulic composition for centrifugal molding according to claim 14 or 15, wherein the mass ratio (B2) / (A2) of the content of the component (A2) to the content of the component (B2) is 0.01 or more and 100 or less. Dispersant composition.
The manufacturing method of the dispersing agent composition for hydraulic compositions for centrifugal molding which mixes the following (A2) component, the following (B2) component, and water.
Component (A2): a polymer or copolymer having acrylic acid and / or maleic acid as constituent monomers, wherein the carboxyl group is not neutralized (B2) component: polycarboxylic acid-based dispersant Dispersant with unneutralized carboxyl groups
The hydraulic composition for centrifugal moldings containing the following (A2) component, the following (B2) component, hydraulic powder, an aggregate, and water.
Component (A2): a polymer or copolymer having acrylic acid and / or maleic acid as constituent monomers, wherein the carboxyl group is not neutralized (B2) component: polycarboxylic acid-based dispersant Dispersant with unneutralized carboxyl groups
The hydraulic composition for centrifugal molding according to claim 18, wherein the weight average molecular weight of the component (A2) is 1,000 or more and 100,000 or less.
The hydraulic composition for centrifugal molding according to claim 18, wherein the weight average molecular weight of the component (A2) is 2,000 or more and 50,000 or less.
The hydraulic composition for centrifugal molding according to any one of claims 18 to 20, wherein the content of the component (A2) is 0.01 to 1 part by mass with respect to 100 parts by mass of the hydraulic powder. .
The mass ratio (B2) / (A2) of the content of the component (A2) to the content of the component (B2) is 0.01 or more and 100 or less according to any one of claims 18 to 21. Hydraulic composition for centrifugal molding.
The hydraulic composition for centrifugal molding according to any one of claims 18 to 22, wherein a ratio of water / hydraulic powder is 10% by mass or more and 30% by mass or less.
The hydraulic composition for centrifugal molding according to any one of claims 18 to 22, wherein a ratio of water / hydraulic powder is 10% by mass or more and 25% by mass or less.
The manufacturing method of hydraulic composition hardening body containing the following processes.
Step 1 ′: a step of mixing a component (A2), a component (B2), a hydraulic powder, an aggregate and water to obtain a hydraulic composition.
Component (A2): a polymer or copolymer having acrylic acid and / or maleic acid as constituent monomers, wherein the carboxyl group is not neutralized (B2) component: polycarboxylic acid-based dispersant Step 2 ′: filling the hydraulic composition obtained in Step 1 ′ in a mold frame.
Step 3 ': A step of clamping the hydraulic composition filled in the mold obtained in Step 2' by centrifugal force.
Step 4 ': a step of setting the clamped hydraulic composition obtained in step 3' in a mold.
The method for producing a cured hydraulic composition according to claim 25, wherein a hydraulic composition having a water / hydraulic powder ratio of 10% by mass to 30% by mass is prepared in step 1 '.
The method for producing a cured hydraulic composition according to claim 26, wherein a hydraulic composition having a water / hydraulic powder ratio of 10% by mass to 25% by mass is prepared in step 1 '.
The hydraulic composition according to any one of claims 25 to 27, wherein in step 1 ', the component (A2) is mixed in an amount of 0.01 to 1 part by mass with respect to 100 parts by mass of the hydraulic powder. Method of producing a cured product
The method for producing a cured hydraulic composition according to any one of claims 25 to 28, comprising the following step 5 'after the step 4'.
Step 5 ': Steam curing the set hydraulic composition obtained in Step 4' in a mold.
The method for producing a cured hydraulic composition according to claim 29, wherein in the step 5 ', the steam curing temperature is 40 ° C to 90 ° C.
A dispersant composition for a hydraulic composition for centrifugal molding, containing a component (A3), a component (B1), a component (C) and a water, and having a pH of 5 or less at 20 ° C.
Component (A3): Polymer or copolymer having acrylic acid and / or maleic acid as constituent monomers Component (B1): Polycarboxylic acid dispersant (C) Component: Bronsted acid
The dispersant composition for a hydraulic composition for centrifugal molding according to claim 31, wherein the pH at 20 ° C is 4.8 or less.
The dispersant composition for a hydraulic composition for centrifugal molding according to claim 31 or 32, wherein the component (C) is a carboxylic acid.
The water for centrifugal molding according to any one of claims 31 to 33, wherein the component (C) is at least one selected from lactic acid, acetic acid, citric acid, maleic acid, fumaric acid, pyruvic acid and benzoic acid. Dispersant composition for hard composition.
The dispersant for a hydraulic composition for centrifugal molding according to any one of claims 31 to 34, wherein the total content of the components (A3) and (B1) is 1.5% by mass or more and 100% by mass or less. Composition.
The mass ratio (B1) / (A3) of the content of the component (A3) to the content of the component (B1) is 0.1 or more and 100 or less according to any one of claims 31 to 35. Dispersant composition for hydraulic composition for centrifugal molding.
The manufacturing method of the dispersing agent composition for hydraulic compositions for centrifugal molding which mixes the following (A3) component, the following (B1) component, the following (C) component, and water so that pH may become 5 or less.
Component (A3): Polymer or copolymer having acrylic acid and / or maleic acid as constituent monomers (B1) Component: Polycarboxylic acid dispersant (C) Component: Bronsted acid
The hydraulic composition for centrifugal moldings containing the following (A3) component, the following (B1) component, the following (C) component, hydraulic powder, an aggregate, and water.
Component (A3): Polymer or copolymer having acrylic acid and / or maleic acid as constituent monomers Component (B1): Polycarboxylic acid dispersant (C) Component: Bronsted acid
The hydraulic composition for centrifugal molding according to claim 38, wherein the weight average molecular weight of the component (A3) is 1,000 or more and 100,000 or less.
The hydraulic composition for centrifugal molding according to claim 38, wherein the weight average molecular weight of the component (A3) is 2,000 or more and 50,000 or less.
The hydraulic composition for centrifugal molding according to any one of claims 38 to 40, wherein the content of the component (A3) is 0.01 to 1 part by mass with respect to 100 parts by mass of the hydraulic powder. .
42. The mass ratio (B1) / (A3) of the content of the component (A3) to the content of the component (B1) according to any one of claims 38 to 41, which is 0.1 or more and 100 or less. Hydraulic composition for centrifugal molding.
The hydraulic composition for centrifugal molding according to any one of claims 38 to 42, wherein a ratio of water / hydraulic powder is 10% by mass or more and 30% by mass or less.
The hydraulic composition for centrifugal molding according to any one of claims 38 to 42, wherein a ratio of water / hydraulic powder is 10% by mass or more and 25% by mass or less.
The manufacturing method of hydraulic composition hardening body containing the following processes.
Step 1 ′ ′-1: step of mixing the following (A3) component, the following (B1) component, the following (C) component, and water so that the pH is 5 or less to obtain a dispersant composition (A3) component : Polymer or copolymer having acrylic acid and / or maleic acid as constituent monomers (B1) component: polycarboxylic acid type dispersant (C) component: Bronsted acid step 1 ′ ′-2: step 1 ′ ′ A step of mixing the dispersant composition obtained in 1), hydraulic powder, aggregate and water to obtain a hydraulic composition.
Step 2 ": a step of filling the hydraulic composition obtained in Step 1" -2 into a mold.
Step 3 ′ ′: a step of clamping the hydraulic composition filled in the mold obtained in Step 2 ′ ′ by centrifugal force.
Step 4 ": setting the clamped hydraulic composition obtained in Step 3" in a mold.
The method for producing a cured hydraulic composition according to claim 45, wherein a hydraulic composition having a water / hydraulic powder ratio of 10% by mass to 30% by mass is prepared in step 1 ′ ′-2.
The method for producing a cured hydraulic composition according to claim 45, wherein a hydraulic composition having a water / hydraulic powder ratio of 10% by mass to 25% by mass is prepared in step 1 ′ ′-2.
The component (A) is mixed so as to be 0.01 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass of the hydraulic powder in the step 1 ′ ′-2. The manufacturing method of the hydraulic composition hardening body as described in 4.
The method for producing a cured hydraulic composition according to any one of claims 45 to 48, which has the following step 5 "after the step 4".
Step 5 ": Steam curing the set hydraulic composition obtained in Step 4" in a mold.
50. The method for producing a cured hydraulic composition according to claim 49, wherein the steam curing temperature is 40 ° C. to 90 ° C. in the step 5 ′ ′.