JP2022045979A - Hydraulic composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydraulic composition which exhibits good fluidity when an external force such as vibration is applied, and a precast molding method.
A hydraulic composition containing the following component (A), component (B), hydraulic powder, and water, wherein the mortar flow value is 130 mm or less.
(A) Component: Polyacrylic acid having a weight average molecular weight of 200,000 or more and 1,000,000 or less or a salt thereof (B) Component: A group selected from an ethyleneoxy group and a propyleneoxy group having an average number of moles of 1 or more and 100 A copolymer containing the following specific monomer (1b) and a specific monomer (2b) such as methacrylic acid and acrylic acid as a constituent monomer [selection diagram] None

Description

The present invention relates to hydraulic compositions and precast molding methods.

When manufacturing concrete products, a vibrator may be used to fill the formwork with the hydraulic composition. By applying appropriate vibration to the hydraulic composition filled in the mold, the hydraulic composition is filled in every corner of the mold, and the air taken in during transportation and charging is expelled, and the strength and watertightness are increased. It is said that concrete products with excellent properties and durability can be manufactured. Generally, the smaller the fluidity (slump value) of the hydraulic composition, the larger the vibration capacity is required, and the extension of the vibration time causes an increase in manufacturing cost and noise problems. In addition, there is a problem that the surface aesthetics of concrete products are deteriorated due to the generation of water channels due to bleeding. Furthermore, fibers may be blended for the purpose of fire resistance and prevention of peeling / peeling, but it is known that when fibers are added to a hydraulic composition, the fibers tend to reduce the fluidity of the hydraulic composition. Has been done.

Patent Document 1 discloses a dispersant composition for a water-hard composition for centrifugation, which contains the following component (A2), the following component (B2), and water.
(A2) component: A polymer or copolymer containing acrylic acid and / or maleic acid as a constituent monomer, and a compound having an unneutralized carboxyl group (B2) component: a polycarboxylic acid-based dispersant. Dispersant with unneutralized carboxyl group

Patent Document 2 describes an additive for a water-hardening composition containing a water-hardening cement, which is a structural unit (I) derived from a specific unsaturated polyalkylene glycol-based monomer (a) and a specific unsaturated carboxylic acid. A water-hard material dispersant containing a polycarboxylic acid-based copolymer containing a structural unit (II) derived from an acid-based monomer (b), and a strength improver containing polyacrylic acid (salt). Additives for water-hard composition are disclosed.

In Patent Document 3, after kneading the concrete containing the base, one or two or more selected from the component A: a specific polyacrylamide and a specific polyacrylic acid alkali metal salt with respect to the concrete slurry. , B component: alkali metal silicate, C component: specific polyalkylene glycol monoalkyl ether, D component: sodium phosphate, E component: water, an admixture composition containing a specific component. A method for preparing an early-strength concrete is disclosed, which comprises adding a fixed amount to the content.

JP-A-2019-64905 Japanese Unexamined Patent Publication No. 2017-160076 Japanese Unexamined Patent Publication No. 2017-128489

The present invention provides a hydraulic composition that exhibits good fluidity when an external force such as vibration is applied, and a precast molding method.

The present invention relates to a hydraulic composition containing the following component (A), component (B), hydraulic powder, and water and having a mortar flow value of 130 mm or less.
(A) Component: Polyacrylic acid having a weight average molecular weight of 200,000 or more and 1,000,000 or less or a salt thereof (B) Component: Monomer (1b) represented by the following general formula (1b) and the following general formula ( A copolymer containing the monomer (2b) represented by 2b) as a constituent monomer.

[In the ceremony,
R ^1b , R ^2b : may be the same or different, hydrogen atom or methyl group R ^3b : hydrogen atom or -COO (AO) _n X ¹
X ¹ : Hydrogen atom or alkyl group having 1 or more and 4 or less carbon atoms AO: Group selected from ethyleneoxy group and propyleneoxy group n: Average number of moles of AO, 1 or more and 100 or less q: 0 or more 2 The following numbers p: Indicates the number of 0 or 1. ]

[In the ceremony,
R ^4b , R ^5b , R ^6b : may be the same or different and may be a hydrogen atom, a methyl group or (CH ₂ ) _r COM ^2b , where (CH ₂ ) _r COM ^2b is COOM ^1b or another (CH ₂ ). ) _R COM ^2b may form anhydrate, in which case M ^1b , M ^2b of those groups are absent.
M ^1b , M ^2b : may be the same or different, hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium group, alkylammonium group, substituted alkylammonium group, alkyl group, hydroxyalkyl group or Alkali group r: Indicates a number of 0 or more and 2 or less. ]

Further, in the present invention, a water-hard composition containing the component (A), the component (B), a water-hard powder, and water is produced, the water-hard composition is filled in a mold, and vibration molding is performed. Regarding the precast molding method.

According to the present invention, there is provided a hydraulic composition that exhibits good fluidity when an external force such as vibration is applied, and a precast molding method.

[Hydraulic composition]
<Ingredient (A)>
The component (A) is polyacrylic acid or a salt thereof having a weight average molecular weight of 200,000 or more and 1,000,000 or less.
Examples of the polyacrylic acid or a salt thereof include polyacrylic acid, sodium polyacrylate, potassium polyacrylate and the like, and preferably sodium polyacrylate and potassium polyacrylate.

The component (A) of the present invention may be a monomer other than acrylic acid and may be a copolymer containing a monomer copolymerizable with acrylic acid as long as the effect of the present invention is not hindered. Examples of monomers other than acrylic acid that can be copolymerized with acrylic acid include vinyl-based monomers, acrylic-based monomers, styrene-based monomers, and more specifically, maleic acid, methacrylic acid, and methyl acrylate. , Ethyl acrylate, methyl methacrylate, styrene and the like.

The polyacrylic acid or a salt thereof, which is the component (A) of the present invention, contains 0 mol% or more and 5 mol of a monomer other than acrylic acid, which is copolymerizable with acrylic acid, among all the constituent monomers. It may be a polymer or a copolymer containing% or less, further 3 mol% or less, and further 1 mol% or less.

The weight average molecular weight of the component (A) is 200,000 or more, preferably 250,000 or more, from the viewpoint of adsorptivity to hydraulic powder, viscosity increase of the hydraulic composition, and fluidity after vibration. It is more preferably 300,000 or more, and 1,000,000 or less, preferably 800,000 or less, more preferably 600,000 or less, still more preferably 500,000 or less. This weight average molecular weight was measured by gel permeation chromatography (GPC) under the following conditions.
* GPC conditions Equipment: GPC (HLC-8320GPC) manufactured by Tosoh Corporation Column: TsKgelα-M + TsKgelα-M (manufactured by Tosoh Corporation)
Eluent: 60 mmol / L phosphoric acid, 50 mmol / L LiBr-DMF
Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Detection: RI
Sample size: 1 mg / mL
Standard material: Polystyrene conversion (monodisperse polystyrene with known molecular weight, molecular weight: 590, 3,600, 30,000, 96,400, 929,000, 8,420,000)

<Ingredient (B)>
The component (B) is a copolymer containing the monomer (1b) represented by the general formula (1b) and the monomer (2b) represented by the general formula (2b) as constituent monomers. ..
In the general formula (1b), R ^1b is preferably a hydrogen atom.
In the general formula (1b), R ^2b is preferably a methyl group.
In the general formula (1b), R ^3b is preferably a hydrogen atom.
In the general formula (1b), X ¹ is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.
In the general formula (1b), the AO is preferably an ethyleneoxy group. The AO preferably contains an ethyleneoxy group.
In the general formula (1b), n is the average number of moles of substance added of AO, and is 1 or more, preferably 5 or more, more preferably 10 or more, still more preferably 20 from the viewpoint of viscosity and dispersibility of the hydraulic composition. The number is 100 or less, preferably 80 or less, more preferably 60 or less, still more preferably 50 or less, still more preferably 40 or less.
In the general formula (1b), q1 is preferably 0.
In the general formula (1b), p1 is preferably 1.

In the general formula (2b), R ^4b is preferably a hydrogen atom.
In the general formula (2b), R ^5b is preferably a methyl group.
In the general formula (2b), R ^6b is preferably a hydrogen atom.
For (CH ₂ ) _r COMM ^2b , anhydrate may be formed with COOM ^1b or other (CH ₂ ) _r COMM ^2b , in which case M ^1b and M ^2b of those groups are absent.
M ^1b and M ^2b may be the same or different, hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium group, alkylammonium group, substituted alkylammonium group, alkyl group, hydroxyalkyl group or It is an alkenyl group.
The alkyl group, hydroxyalkyl group, and alkenyl group of M ^1b and M ^2b each preferably have 1 or more carbon atoms and 4 or less carbon atoms.
M ^1b and M ^2b may be the same or different, preferably a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), an ammonium group, or an alkylammonium group, and a hydrogen atom, an alkali metal, or an alkaline soil. Similar metals (1/2 atom) or ammonium groups are more preferred, hydrogen atoms, alkali metals or alkaline earth metals (1/2 atoms) are even more preferred, and hydrogen atoms or alkali metals are even more preferred.
The r of (CH ₂ ) _r COMM ^2b in the general formula (2b) is preferably 1.

The component (B) has a total amount of the monomer (1b) and the monomer (2b) in the constituent monomer of 90% by mass or more, preferably 92% by mass or more, more preferably 95% by mass or more. And it is 100% by mass or less. This total amount may be 100% by mass.

In the component (B), the ratio of the monomer (2b) in the total of the monomer (1b) and the monomer (2b) is preferably 2% by mass or more from the viewpoint of dispersibility of the water-hard composition. , More preferably 4% by mass or more, further preferably 5% by mass or more, still more preferably 10% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 25% by mass or less. Even more preferably, it is 20% by mass or less.

The weight average molecular weight of the component (B) is preferably 10,000 or more, more preferably 20,000 or more, still more preferably 30,000 or more, still more preferably 35, from the viewpoint of dispersibility of the hydraulic composition. It is 000 or more, preferably 100,000 or less, more preferably 70,000 or less, still more preferably 50,000 or less, still more preferably 40,000 or less.

The number average molecular weight of the component (B) is preferably 15,000 or more, more preferably 25,000 or more, still more preferably 35,000 or more, and preferably 80, from the viewpoint of dispersibility of the hydraulic composition. It is 000 or less, more preferably 50,000 or less.

In the component (B), the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably 1.0 or more, more preferably 1. It is 1 or more, more preferably 1.2 or more, and preferably 7.0 or less, more preferably 4.5 or less, still more preferably 2.0 or less.

The weight average molecular weight and the number average molecular weight of the component (B) are measured by the gel permeation chromatography (GPC) method under the following conditions, respectively.
* GPC conditions Equipment: GPC (HLC-8320GPC) manufactured by Tosoh Corporation Column: G4000PWXL + G2500PWXL (manufactured by Tosoh Corporation)
Eluent: 0.2M 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: Polyethylene glycol equivalent (monodisperse polyethylene glycol with known molecular weight, molecular weight 87,500, 250,000, 145,000, 46,000, 24,000)

The water-hardening composition of the present invention has, as optional components, an antifoaming agent, an antiseptic, a water-hardening composition early-strength component, a curing accelerator, a curing retarder, an AE agent, a waterproofing agent, a shrinkage reducing agent, and a rust preventive agent. It can contain a crack reducing agent, a pH adjusting agent, and other surfactants (excluding the components (A) to (B)).

The hydraulic powder used in the hydraulic composition of the present invention is a powder that hardens when mixed with water, and is, for example, ordinary Portland cement, early-strength Portland cement, ultra-early-strength Portland cement, and sulfuric acid-resistant. Examples thereof include salt Portland cement, low heat Portland cement, white Portland cement, and eco-cement (for example, JIS R5214, etc.). Among these, cement selected from early-strength Portland cement, ordinary Portland cement, sulfuric acid-resistant Portland cement and white Portland cement is preferable and early-strength from the viewpoint of shortening the time required to reach the required strength of the hydraulic composition. Cement selected from Portland cement and ordinary Portland cement is more preferable.

Further, the hydraulic powder may contain blast furnace slag, fly ash, silica fume, anhydrous gypsum and the like, and may also contain non-hydraulic limestone fine powder and the like. As the water-hard powder, blast furnace cement, fly ash cement, silica fume cement or the like in which cement is mixed with blast furnace slag, fly ash, silica fume or the like may be used.
Examples of the hydraulic powder include cement or a mixed powder of cement and bentonite.

In the water-hard composition of the present invention, the component (A) is adsorbed to the water-hard powder with respect to 100 parts by mass of the water-hard powder, the viscosity of the water-hard composition is increased, and the fluidity after vibration is applied. From the viewpoint of, preferably 0.005 part by mass or more, more preferably 0.01 part by mass or more, further preferably 0.02 part by mass or more, and preferably 1.0 part by mass or less, more preferably 0.5 part by mass. It is contained in an amount of parts by mass or less, more preferably 0.2 parts by mass or less, still more preferably 01 parts by mass or less, still more preferably 0.5 parts by mass or less.

In the water-hard composition of the present invention, the component (B) is preferably 0.01 part by mass or more, more preferably 0, from the viewpoint of dispersibility of the water-hard composition with respect to 100 parts by mass of the water-hard powder. 0.02 parts by mass or more, more preferably 0.03 parts by mass or more, still more preferably 0.05 parts by mass or more, still more preferably 0.07 parts by mass or more, still more preferably 0.09 parts by mass or more, more. More preferably 0.11 part by mass or more, still more preferably 0.13 part by mass or more, and preferably 2.0 part by mass or less, more preferably 1.0 part by mass or less, still more preferably 0.5 part by mass. Hereinafter, it is more preferably contained in an amount of 0.3 parts by mass or less.

In the hydraulic composition of the present invention, the mass ratio (B) / (A) of the content of the component (A) to the content of the component (B) is the thickening, dispersibility, and addition of the hydraulic composition. From the viewpoint of fluidity after shaking, it is preferably 0.01 or more, more preferably 0.1 or more, still more preferably 1 or more, still more preferably 2 or more, still more preferably 3 or more, still more preferably 4 or more. , More preferably 5 or more, and preferably 50 or less, more preferably 20 or less, still more preferably 16 or less, even more preferably 12 or less, still more preferably 10 or less.

The water-hardening composition of the present invention has a water / water-hardening powder ratio (W / C) of preferably 15% by mass or more, more preferably 20% by mass, from the viewpoint of strength development and moldability of the water-hardening composition. % Or more, more preferably 25% by mass or more, and preferably 100% by mass or less, more preferably 70% by mass or less, still more preferably 50% by mass or less, the water and the water-hard powder are mixed.
Here, the water / water-hard powder ratio (W / C) is a mass percentage (mass%) of water and the water-hard powder in the water-hard composition, and is calculated by water / powder × 100.
The water-hard powder is selected from powder having a physical property of hardening by a hydration reaction such as cement, powder having a pozolan action, powder having latent water-hardness, and stone powder (calcium carbonate powder). When powders are included, in the present invention, those amounts are also included in the amount of the water-hard powder. When the powder having physical properties that are cured by the hydration reaction contains a high-strength admixture, the amount of the high-strength admixture is also included in the amount of the water-hard powder. This also applies to other mass parts related to the mass of the hydraulic powder.

In the hydraulic composition of the present invention, the content of the hydraulic powder is preferably 400 kg or more, more preferably 410 kg or more per 1 m ³ of the hydraulic composition from the viewpoint of workability and economy of the hydraulic composition. It is more preferably 420 kg or more, preferably 500 kg or less, more preferably 480 kg or less, still more preferably 450 kg or less.

The hydraulic composition of the present invention can contain an aggregate. Examples of the aggregate include aggregates selected from fine aggregates and coarse aggregates. Examples of the fine aggregate include those specified by No. 2311 in JIS A0203-2014. Fine aggregates include river sand, land sand, mountain sand, sea sand, lime sand, silica sand and their crushed sand, blast furnace slag fine aggregate, ferronickel slag fine aggregate, lightweight fine aggregate (artificial and natural) and recycled. Examples include fine aggregates. In addition, examples of the coarse aggregate include those specified by No. 2312 in JIS A 0203-2014. For example, coarse aggregates include river gravel, land gravel, mountain gravel, sea gravel, lime gravel, crushed stones of these, blast furnace slag coarse aggregate, ferronickel slag coarse aggregate, lightweight coarse aggregate (artificial and natural) and recycled. Coarse aggregate and the like can be mentioned. As the fine aggregate and the coarse aggregate, different types may be mixed and used, or a single type may be used.

When the hydraulic composition of the present invention is concrete, that is, when the hydraulic composition containing (A) component, (B) component, hydraulic powder, coarse aggregate, fine aggregate and water, coarse bone The bulk volume of the material is preferably 50% from the viewpoint of developing the strength of the hydraulic composition, reducing the amount of the hydraulic powder such as cement used, and improving the filling property into the mold and the like. The above is more preferably 55% or more, further preferably 60% or more, and preferably 100% or less, more preferably 90% or less, still more preferably 80% or less. The bulk volume is the ratio of the volume (including voids) of the coarse aggregate in 1 m ³ of concrete.
Further, when the water-hard composition is concrete, that is, when the water-hard composition contains (A) component, (B) component, water-hard powder, coarse aggregate, fine aggregate and water, the fine aggregate The amount of the material used is preferably 500 kg / m ³ or more, more preferably 600 kg / m ³ or more, still more preferably 700 kg / m ³ or more, and preferably 700 kg / m 3 or more, from the viewpoint of improving the filling property into the mold or the like. It is 1,000 kg / m ³ or less, more preferably 900 kg / m ³ or less.
When the water-hard composition is a mortar, that is, when the water-hard composition contains (A) component, (B) component, water-hard powder, fine aggregate and water, the amount of the fine aggregate used is preferable. Is 800 kg / m ³ or more, more preferably 900 kg / m ³ or more, still more preferably 1,000 kg / m ³ or more, and preferably 2,000 kg / m ³ or less, more preferably 1,800 kg / m ³ . Below, it is more preferably 1,700 kg / m ³ or less.

The hydraulic composition of the present invention may be a mortar. That is, the hydraulic composition of the present invention contains (A) component, (B) component, hydraulic powder, fine aggregate and water.
The hydraulic composition of the present invention is a hydraulic composition containing (A) component, (B) component, hydraulic powder, fine aggregate and water when the hydraulic composition is used as a mortar. From the viewpoint of workability and separation resistance of the hydraulic composition, the mortar flow (fluidity) value is 130 mm or less, preferably 128 mm or less, more preferably 125 mm or less, and preferably 100 mm or more, more preferably. Is 110 mm or more, more preferably 115 mm or more. In the present invention, the mortar flow (fluidity) value of the hydraulic composition refers to the value measured by the measuring method described in "JIS R 5201".

The hydraulic composition of the present invention may be concrete. That is, the hydraulic composition of the present invention contains (A) component, (B) component, hydraulic powder, coarse aggregate, fine aggregate and water.
The hydraulic composition of the present invention is the case where the hydraulic composition is made of concrete, that is, water containing (A) component, (B) component, hydraulic powder, coarse aggregate, fine aggregate and water. In the case of a hydraulic composition, the mortar flow (fluidity) value of the mortar obtained by sifting the hydraulic composition through a sieve with a nominal opening of 5 mm is 130 mm or less from the viewpoint of workability and separation resistance of the hydraulic composition. It is preferably 128 mm or less, more preferably 125 mm or less, and preferably 100 mm or more, more preferably 110 mm or more, still more preferably 115 mm or more.
The hydraulic composition of the present invention is the case where the hydraulic composition is made of concrete, that is, water containing (A) component, (B) component, hydraulic powder, coarse aggregate, fine aggregate and water. The slump value in the case of a hydraulic composition is preferably 3 cm or more, more preferably 5 cm or more, still more preferably 8 cm or more, and preferably 12 cm or less from the viewpoint of workability and moldability of the hydraulic composition. .. Slump is one of the physical property values for quantitatively evaluating the consistency and workability of a hydraulic composition. In the present invention, the slump of the hydraulic composition refers to a value measured by the measuring method described in "JIS A 1101".

The water-hardening composition of the present invention preferably contains fibers such as synthetic fibers from the viewpoint of preventing explosion, preventing peeling, preventing peeling, and improving bending strength of the cured product obtained from the water-hard composition. Since the hydraulic composition of the present invention has good fluidity, even when fibers are blended, for example, when the hydraulic composition is filled in the mold, vibration is applied to the hydraulic composition in the mold. The composition can be filled to every corner. The fiber is preferably a fiber whose volume is reduced or decomposed / volatilized by being softened or melted at a high temperature, for example, 100 ° C. The length of the fiber may be 6 mm or more and 50 mm or less. The diameter of the fiber may be 5 μm or more and 1,000 μm or less. Synthetic fibers having such a fiber length and a fiber diameter are preferable. When the cured product is heated, the fibers are reduced in volume or decomposed / volatilized to alleviate the strain caused by the expansion of the cured product due to heating and prevent the cured product from exploding. Examples of the synthetic fiber include polyacetal fiber, nylon fiber, aramid fiber, polyester fiber, acrylic fiber, vinylon fiber, polypropylene fiber, synthetic fiber such as polyethylene fiber, and recycled fiber such as rayon fiber, and polypropylene fiber is preferable. When the hydraulic composition of the present invention contains fibers, the hydraulic composition is 0.01% by volume or more, further 0.05% by volume or more, and further 80N / mm ² based on the hydraulic composition. From the viewpoint of obtaining the above high-strength concrete, it is preferably contained in an amount of 0.1% by volume or more, 5.0% by volume or less, and further preferably 3.5% by volume or less.

The hydraulic composition of the present invention may be a hydraulic composition for vibration molding. In particular, the hydraulic composition of the present invention may be precast concrete. Since the precast molding method uses a strong vibration vibrator such as a table vibrator or a formwork vibrator, it is characteristic in that the vibration during the vibration molding mold is stronger than that in the field casting. To give an example of a preferred composition of precast concrete,
Hydraulic powder, preferably 300 parts by mass or more and 500 parts by mass or less of cement,
140 parts by mass or more and 180 parts by mass or less of water,
Fine aggregate 600 parts by mass or more and 1200 parts by mass or less,
Coarse aggregate 600 parts by mass or more and 1200 parts by mass or less,
Sand aggregate volume ratio (s / a) 30% or more and 60% or less,
(A) Component 0.005 part by mass or more and 0.2 part by mass or less (100 parts by mass of hydraulic powder),
(B) Component 0.01 parts by mass or more and 2.0 parts by mass or less (100 parts by mass of hydraulic powder),
Is.

The cured product obtained from the hydraulic composition of the present invention can be used for structures and concrete products. As structures, for example, main parts such as columns, beams, floor boards, bearing walls of reinforced concrete, steel-framed reinforced concrete buildings, roads, bridges, piers, girders, tunnels, waterways, dams, sewers, breakwaters, retaining walls, etc. Civil engineering structures can be mentioned. Examples of concrete products include vibration molded products such as culverts, gutters and segments, and centrifugal molded products such as poles, piles and hume pipes.

The hydraulic composition of the present invention is preferably compacted by applying vibration during molding. Examples of the vibrator used at the time of molding include a rod-shaped vibrator, a table type vibrator, and a formwork vibrator. The vibration time during molding is preferably 5 seconds or longer, more preferably 15 seconds or longer, further preferably 30 seconds or longer, and preferably 1,000 seconds or shorter, more preferably 800 seconds or shorter, still more preferably 600 seconds or shorter. Is. The vibration acceleration during molding is preferably 0.5 G or more, more preferably 1 G or more, and preferably 15 G or less, more preferably 10 G or less. The vibration acceleration 1G corresponds to the gravitational acceleration. As for the method of applying vibration during molding, it is preferable to gradually increase the vibration from a weak vibration.

[Method for producing hydraulic composition]
The present invention relates to a method for producing a hydraulic composition in which a component (A), a component (B), a hydraulic powder, and water are mixed. In the method for producing this hydraulic composition, it is preferable that the hydraulic composition is a hydraulic composition for vibration molding and further precast concrete. That is, this manufacturing method may be a manufacturing method of precast concrete. The hydraulic composition according to the present invention, for example, the slump value of precast concrete is preferably 3 cm or more and 12 cm or less.

The embodiments described in the hydraulic composition of the present invention can be appropriately applied to the method for producing a hydraulic composition of the present invention.
The components (A), (B), optional components, preferred embodiments, etc. in the method for producing a hydraulic composition of the present invention are the same as those described in the hydraulic composition of the present invention.
Further, the hydraulic powder, arbitrary aggregate, fiber, preferred embodiment and the like in the method for producing a hydraulic composition of the present invention are the same as those described in the hydraulic composition of the present invention.
In the method for producing a hydraulic composition of the present invention, the mixed amount of the component (A) and the component (B) and the mass ratio (B) / (A) are the components described in the hydraulic composition of the present invention. The content can be replaced with a mixed amount and applied.

In the present invention, a component (A), a component (B), a hydraulic powder, and water are mixed to produce a hydraulic composition, and the hydraulic composition is filled in a mold and vibrated. Regarding the molding method. Further, in the present invention, the component (A), the component (B), the hydraulic powder, and water are mixed to produce a hydraulic composition, and the hydraulic composition is filled in a mold and vibration-molded. , Regarding the precast molding method. In these molding methods, the slump value of the hydraulic composition is preferably 3 cm or more and 12 cm or less. As described above, since the precast molding method uses a strong vibration vibration machine such as a table vibrator or a formwork vibrator, it is characteristic in that the vibration at the time of vibration molding is stronger than that of in-situ casting.

The embodiments described in the hydraulic composition of the present invention can be appropriately applied to the molding method of the present invention and further to the precast molding method.
The molding method of the present invention, further, the component (A), the component (B), an optional component, a preferable embodiment, and the like in the precast molding method are the same as those described in the hydraulic composition of the present invention.
Further, the molding method of the present invention, further, the hydraulic powder, arbitrary aggregate, fiber, preferable embodiment, etc. in the precast molding method are the same as those described in the hydraulic composition of the present invention.
In the molding method of the present invention and further, in the precast molding method, the mixed amount of the component (A) and the component (B) and the mass ratio (B) / (A) are the components described in the hydraulic composition of the present invention. The content can be replaced with a mixed amount and applied.

The following components were used as the component (A), the component (A') (comparative component of the component (A)), and the component (B).

<Ingredient (A)>
A-1: Polyacrylic acid, manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight 250,000
A-2: Polyacrylic acid, manufactured by Toagosei Co., Ltd., weight average molecular weight 800,000
A-3: Polyacrylic acid, manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight 1,000,000
A-4: Sodium polyacrylate, manufactured by Toagosei Co., Ltd., weight average molecular weight 500,000

<(A') component (comparative component of (A) component)>
A'-1: Polyacrylic acid, manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight 25,000
A'-2: Polyacrylic acid, manufactured by Wako Pure Chemical Industries, Ltd., weight average molecular weight 5,000

<Example of synthesis of component (B)>
Production Example B1 (Production of Copolymer B-1)
356 parts of ion-exchanged water was charged in a glass reaction vessel (four-necked flask) equipped with a stirrer, the inside of the reaction vessel was replaced with nitrogen under stirring, and the mixture was heated to 80 ° C. under a nitrogen atmosphere. Next, a monomer aqueous solution in which 327 parts of methacrylic acid (273 mol of methoxypolyethylene glycol) ester, 58 parts of methacrylic acid and 176 parts of ion-exchanged water were mixed, and 2.8 parts of 3-mercaptopropionic acid and 27.7 parts of ion-exchanged water were mixed. A mixed aqueous solution of 3.3 parts of ammonium persulfate and 18.6 parts of ion-exchanged water was added dropwise in 2 hours, and after the completion of the dropping, 1.1 parts of ammonium persulfate and 6.2 parts of ion-exchanged water were further mixed. The aqueous solution was added dropwise over 0.5 hours. After the completion of the dropping, the temperature was maintained at 80 ° C. for 1 hour, and aging was carried out. Then, the reaction solution was neutralized with an aqueous sodium hydroxide solution at a temperature of 80 ° C. or lower to obtain an aqueous solution containing a copolymer (B-1) having a weight average molecular weight of 37,000.

Table 1 shows the component (B) obtained in the above production example.

In Table 1, the mass% of the monomer is the mass% in the total of the monomer (1b) and the monomer (2b).

<Mortar test>
(1) Mortar formulation Table 2 shows the mortar formulation. W / C is the ratio (% by mass) of water / hydraulic powder.

The components used in the mortar formulation in Table 2 are as follows.
-Water (W): Tap water (water temperature 20 ° C.) (including the amount of component (A) or component (A') and component (B) added)
-Cement (C): Ordinary Portland cement, manufactured by Taiheiyo Cement Co., Ltd., density 3.14 g / cm ³
-Fine aggregate (S): mountain sand, density 2.72 g / cm ³

(2) Preparation of mortar A composition containing the component (A) or the component (A'), the component (B), an antifoaming agent and water was prepared so as to be the amount added in Table 3. The composition was added to water (W) of the mortar compounding material and prepared together with other mortar compounding materials. The mortar was prepared by kneading the ingredients (60 rpm, 180 seconds) using a mortar mixer specified in JIS R5201. The mass part of each component in Table 3 is the mass part in terms of effective component with respect to 100 parts by mass of cement.

(3) Evaluation of mortar fluidity The mortar immediately after kneading is filled in a flow cone (upper diameter 70 mm × lower diameter 100 mm × height 60 mm) described in JIS R5201 and mortar flow is performed on a plastic plate of 30 cm × 30 cm. It was measured. The results are shown in Table 3.

(4) Evaluation of mortar vibration fluidity A plastic plate whose mortar flow was measured was placed on a desktop vibrator (Jintai dental technology vibration machine) and vibrated until the mortar flow reached 200 mm under the condition of vibration acceleration of 2 G. did. Then, the mortar flow was measured by vibrating for 10 seconds under the condition of vibration acceleration of 2 G. The value obtained by subtracting the mortar flow after the vibration from the value before the vibration was defined as the spread of the flow after the vibration. The results are shown in Table 3.

In Table 3, the difference between the examples and the comparative examples regarding the spread of the mortar flow without vibration and the spread of the mortar flow after vibration is recognized by those skilled in the art as a significant difference.

<Concrete test>
Coarse aggregate (G), fine aggregate (S) (half amount), cement (C), fine aggregate (in the amount shown in Table 4) in a concrete mixer (manufactured by Kitagawa Iron Works, WHQ-60A). S) Add in the order of (half amount), perform dry kneading for 10 seconds, and knead water (W) containing the component (A) or the component (A') and the component (B) in the amount (part by mass) of Table 5. Was added. Then, the concrete was prepared by kneading the concrete with a concrete mixer for 120 seconds. The mass part of each component in Table 5 is the mass part in terms of effective component with respect to 100 parts by mass of cement.

The components used in the concrete formulation in Table 4 are as follows.
-Water (W): Tap water (water temperature 20 ° C.) (including the amount of component (A) or component (A') and component (B) added)
-Cement (C): Ordinary Portland cement, manufactured by Taiheiyo Cement Co., Ltd., density 3.14 g / cm ³
-Fine aggregate (S): crushed sand, density 2.72 g / cm ³
-Coarse aggregate (G): gravel, density 2.64 g / cm ³

In Table 4, W / C is a mass ratio of the blended amount of water and the blended amount of cement, and is obtained by [water blending amount / cement blending amount] × 100 (mass%).

<Slump test, vibration fluidity test>
After kneading, concrete slump was measured according to JIS A 1101. The slump measurement was performed on a table vibrator (KC-399 manufactured by Kansai Kikai Seisakusho). After the slump measurement, vibration was applied for 15 seconds at a vibration acceleration of 2 G, and the slump throw value after vibration was measured. The slump flow value was calculated as an average value by measuring the diameter at which the spread is considered to be the maximum and the diameter in the orthogonal direction with a caliper. By subtracting the value before vibration from the flow value after vibration, the spread of the flow after vibration was obtained.
Further, the concrete immediately after kneading was passed through a metal net sieve having a nominal opening of 5 mm defined by JIS Z-8801, and the flow value of the obtained mortar was measured using the flow cone described in JIS R5201. The results are shown in Table 5.

<Evaluation of concrete surface aesthetics>
Immediately after kneading into a metal mold (horizontal bottom length: 5 cm, vertical bottom length: 10 cm, height 50 cm) to which a mold release agent (product name: Parat, manufactured by Yamamune Chemical Co., Ltd.) has been applied in advance. Each of the concrete was packed in one layer, compacted with a table vibrator at a vibration acceleration of 10 G for 60 seconds, filled with concrete, and cured in the air (20 ° C.) in a room at 20 ° C. to be hardened. Twenty-four hours after the concrete preparation, the cured specimen was removed from the mold to obtain a specimen. The number of bubble marks (surface bubble marks) having a diameter of 3 mm or more on the surface of the concrete specimen was visually counted and judged according to the following evaluation criteria. The results are shown in Table 5. It should be noted that the smaller the number of bubble marks having a diameter of 3 mm or more, the better the surface aesthetics.
Rank A: There were no holes with a diameter of 3 mm or more in the specimen, or 9 or less.
Rank B: There were 10 or more and 14 or less holes in the specimen with a diameter of 3 mm or more.
Rank C: There were 15 or more and 19 or less holes in the specimen with a diameter of 3 mm or more.
Rank D: There were 20 or more and 29 or less holes in the specimen with a diameter of 3 mm or more.
Rank E: There were 30 or more holes with a diameter of 3 mm or more in the specimen.

In Table 5, the difference between the example and the comparative example regarding the slump without vibration and the slump flow after vibration is recognized by those skilled in the art as a significant difference.

Claims (9)

A hydraulic composition containing the following component (A), component (B), hydraulic powder, and water, wherein the mortar flow value is 130 mm or less.
(A) Component: Polyacrylic acid having a weight average molecular weight of 200,000 or more and 1,000,000 or less or a salt thereof (B) Component: Monomer (1b) represented by the following general formula (1b) and the following general formula ( A copolymer containing the monomer (2b) represented by 2b) as a constituent monomer.

[In the ceremony,
R ^1b , R ^2b : may be the same or different, hydrogen atom or methyl group R ^3b : hydrogen atom or -COO (AO) _n X ¹
X ¹ : Hydrogen atom or alkyl group having 1 or more and 4 or less carbon atoms AO: Group selected from ethyleneoxy group and propyleneoxy group n: Average number of moles of AO, 1 or more and 100 or less q: 0 or more 2 The following numbers p: Indicates the number of 0 or 1. ]

[In the ceremony,
R ^4b , R ^5b , R ^6b : may be the same or different and may be a hydrogen atom, a methyl group or (CH ₂ ) _r COM ^2b , where (CH ₂ ) _r COM ^2b is COOM ^1b or another (CH ₂ ). ) _R COM ^2b may form anhydrate, in which case M ^1b , M ^2b of those groups are absent.
M ^1b , M ^2b : may be the same or different, hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium group, alkylammonium group, substituted alkylammonium group, alkyl group, hydroxyalkyl group or Alkali group r: Indicates a number of 0 or more and 2 or less. ] The hydraulic composition according to claim 1, wherein the content of the hydraulic powder is 400 kg or more and 500 kg or less per 1 m ³ of the hydraulic composition. The water-hard composition according to claim 1 or 2, wherein the mass percentage (water / water-hard powder ratio) of water and the water-hard powder in the water-hard composition is 30% by mass or more and 40% by mass or less. .. The hydraulic composition according to any one of claims 1 to 3, wherein the hydraulic composition has a slump value of 3 cm or more and 12 cm or less. The water according to any one of claims 1 to 4, wherein the mass ratio (B) / (A) of the content of the component (A) to the content of the component (B) is 0.01 or more and 50 or less. Rigid composition. The hydraulic composition according to any one of claims 1 to 5, which is for vibration molding. The hydraulic composition according to any one of claims 1 to 6, which is precast concrete. A precast molding method in which a hydraulic composition containing the following component (A), component (B), hydraulic powder, and water is produced, the hydraulic composition is filled in a mold, and vibration molding is performed.
(A) Component: Polyacrylic acid having a weight average molecular weight of 200,000 or more and 1,000,000 or less or a salt thereof (B) Component: Monomer (1b) represented by the following general formula (1b) and the following general formula ( A copolymer containing the monomer (2b) represented by 2b) as a constituent monomer.

[In the ceremony,
R ^1b , R ^2b : may be the same or different, hydrogen atom or methyl group R ^3b : hydrogen atom or -COO (AO) _n X ¹
X ¹ : Hydrogen atom or alkyl group having 1 or more and 4 or less carbon atoms AO: Group selected from ethyleneoxy group and propyleneoxy group n: Average number of moles of AO, 1 or more and 100 or less q: 0 or more 2 The following numbers p: Indicates the number of 0 or 1. ]

[In the ceremony,
R ^4b , R ^5b , R ^6b : may be the same or different and may be a hydrogen atom, a methyl group or (CH ₂ ) _r COM ^2b , where (CH ₂ ) _r COM ^2b is COOM ^1b or another (CH ₂ ). ) _R COM ^2b may form anhydrate, in which case M ^1b , M ^2b of those groups are absent.
M ^1b , M ^2b : may be the same or different, hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium group, alkylammonium group, substituted alkylammonium group, alkyl group, hydroxyalkyl group or Alkali group r: Indicates a number of 0 or more and 2 or less. ] The precast molding method according to claim 8, wherein the hydraulic composition has a slump value of 3 cm or more and 12 cm or less.