JP6486129B2 - Functional hydraulic inorganic particles and hydraulic particles containing the same - Google Patents

Description

The present invention relates to functional hydraulic inorganic particles and hydraulic particles containing the same.

In addition to the narrowly defined hydraulic particles that cause a hydration reaction in the presence of water, the hydraulic particles do not hydrate with water alone, but in the presence of a small amount of substance called a stimulant. There are latent hydraulic particles that cause

In general, hydraulic particles are used in combination with a dispersant, water, and fine aggregates, coarse aggregates, and the like, if necessary, to obtain hydraulic compositions such as cement paste, mortar, and concrete. For example, to produce fresh (raw) concrete, in a mixer, in a narrow sense, hydraulic particles such as cement, dispersant, water, fine aggregate and coarse aggregate, and if necessary silica fume, blast furnace A method is employed in which fine powders such as slag and fly ash are added and then mixed for a certain period of time and kneaded until the dispersing agent disperses the paste and the fluidity becomes constant, that is, until the fluidity becomes stable. The time until the fluidity is stabilized after adding water (with a dispersant) to the hydraulic particles is referred to as the kneading time or the time until the kneading, but before the fluidity is stabilized. Usually takes a certain amount of time. As the dispersant, for example, Patent Documents 1 and 2 disclose powdered polycarboxylic acid-based dispersants.

In recent years, ultra-high-strength concrete having a low water / cement ratio has been proposed. Cement containing silica fume is used for such ultra-high-strength concrete, and it has good workability even when the water / cement ratio is low, and it has excellent medium- to long-term strength and structural strength. It has the feature of being. For example, Patent Document 3 discloses a predetermined polycarboxylic acid polymer that can be suitably applied to silica fume cement and the like.

JP-A-11-310444 JP 2000-026145 A International Publication No. 2014/010572 Pamphlet

As described above, the kneading time usually requires a certain time. In particular, the ultra high strength concrete having a low water / hydraulic particle mass ratio tends to increase the time until the fluidity is stabilized, that is, the kneading time. As a result, since the manufacturing time of the hydraulic composition also becomes long, it has a problem from the viewpoint of productivity. However, at present, no technology that can sufficiently solve such problems has been found.

For example, the use of a powdered polycarboxylic acid dispersant as in Patent Documents 1 and 2 does not contribute to shortening the kneading time and the production time of the hydraulic composition (Comparative Test Examples 4 to 6 described later). reference). Further, the polycarboxylic acid polymer of Patent Document 3 is extremely excellent in dispersibility and the like, but there is room for contrivance for significantly reducing the kneading time for obtaining the hydraulic composition and increasing the productivity. was there.

The present invention has been made in view of the above-described situation, functional hydraulic inorganic particles that can significantly reduce the kneading time and can provide a hydraulic composition with excellent fluidity with high productivity, and It aims at providing the hydraulic particle containing this.

As a result of various investigations on the production technique of the hydraulic composition, the present inventor used the hydraulic hydraulic inorganic particles that include the hydraulic inorganic particles and satisfy the predetermined conditions for the production of the hydraulic composition. It has been found that the kneading time until stabilization is significantly shortened and a hydraulic composition exhibiting high fluidity can be provided with good productivity. Even if the water ratio is low, if such functional hydraulic inorganic particles are used, a hydraulic composition exhibiting high fluidity can be easily obtained in a short time, and thus the productivity is extremely excellent. It will be. Then, the inventors have arrived at the present invention by conceiving that the above problems can be solved brilliantly.

That is, the present invention is a functional hydraulic inorganic particle that includes hydraulic inorganic particles and satisfies the following conditions (I) and (II).
(I) Paste prepared in the same manner after heating the functional hydraulic inorganic particles at 550 ° C. at a flow value (P0) of the paste having an amount of water of 15 parts by mass with respect to 100 parts by mass of the functional hydraulic inorganic particles. The ratio (P0 / P1) to the flow value (P1) is 1.5 or more.
(II) After adding 15 parts by mass of water to 100 parts by mass of the functional hydraulic inorganic particles, the time until the paste composed of the functional hydraulic inorganic particles and water becomes uniform is within 180 seconds. .
The present invention is also hydraulic particles containing the functional hydraulic inorganic particles.
The present invention is described in detail below. In addition, the form which combined each preferable form of this invention described below 2 or 3 or more is also a preferable form of this invention.

In the present specification, the “kneading time” means the time until the fluidity is stabilized after adding water to the inorganic particles. "The fluidity is stabilized" means that the softness of the paste containing hydraulic inorganic particles and water becomes uniform. Specifically, the kneading time is confirmed visually and, more precisely, in the same manner as in the condition (II). The kneading time is sometimes referred to as the time until kneading.

[Functional hydraulic inorganic particles]
It can be said that the functional hydraulic inorganic particles of the present invention are those obtained by imparting functionality (fluidity and kneading ease) to the hydraulic inorganic particles, and include the hydraulic inorganic particles.
In this specification, “hydraulic” means a hydrating reaction in the presence of water and a “hydraulic” in a narrow sense that hardens as a solid. It also means “latent hydraulic” in which a hydration reaction takes place in the presence of a small amount of a substance, which hardens as a solid.

Examples of the hydraulic inorganic particles include narrowly defined hydraulic inorganic particles such as cement and alumina; latent hydraulic inorganic particles such as slag; and the like, and are composed of one or more of these. Also good. Among these, cement and blast furnace slag are preferable, and this makes it possible to further shorten the kneading time and to fully exhibit the effects of the present invention. More preferably, it is cement, and such a form in which the hydraulic inorganic particles are cement is one of the preferred forms of the present invention.

Specific examples of the cement include Portland cement (ordinary, early strength, ultra-early strength, low heat, moderate heat, sulfate resistant and low alkali type), various mixed cements (blast furnace cement, silica cement, fly ash cement). , White Portland cement, alumina cement, super fast cement (1 clinker fast cement, 2 clinker fast cement, magnesium phosphate cement), grout cement, oil well cement, low heat cement (low heat blast furnace cement, fly ash mixing) Low exothermic type blast furnace cement, cement with high belite content), ultra-high strength cement, cement-based solidified material, eco-cement (cement produced from one or more of municipal waste incineration ash and sewage sludge incineration ash) .

The functional hydraulic inorganic particles may further contain pozzolanic active inorganic particles in addition to the hydraulic inorganic particles. The pozzolanic active inorganic particles mean inorganic particles having pozzolanic activity, and examples thereof include silica fume, fly ash, cinder ash, husk ash, volcanic ash, and the like, and one or more of these can be used. . Of these, silica fume and fly ash are preferable.

The hydraulic inorganic particles and pozzolanic active inorganic particles preferably have an average particle size in the range of 0.001 to 100 μm, for example. Preferably it is 0.01-100 micrometers, More preferably, it is the range of 0.05-75 micrometers.
In addition, it is preferable that the hydraulic inorganic particles and the pozzolanic active inorganic particles are not yet hydrated (cured), that is, unhydrated.

(Particle size measurement method)
In the present specification, the particle size of the particles can be measured using a commercially available particle size distribution measuring device. As an example, the sample can be ultrasonically dispersed with ethanol using a laser diffraction / scattering particle size distribution analyzer LA-910 manufactured by HORIBA, and then measured under the conditions of a relative refractive index of 1.10.

The functional hydraulic inorganic particles satisfy the condition (I).
That is, the flow value (P0) of the paste whose amount of water is 15 parts by mass with respect to 100 parts by mass of the functional hydraulic inorganic particles, and after heating the functional hydraulic inorganic particles at 550 ° C., The ratio (P0 / P1) with the flow value (P1) is 1.5 or more. That P0 / P1 is in this range means that the functional hydraulic inorganic particles give very high fluidity to the hydraulic composition. Usually, when heated at a high temperature of 550 ° C., when an organic substance (for example, an organic dispersant) is contained, the organic substance is separated from the hydraulic inorganic particles. The flow value of the paste containing can be said to be the physical property value not derived from the organic substance, that is, the original physical property value of the hydraulic inorganic particles constituting the functional hydraulic inorganic particles. Moreover, it can be said that the paste whose amount of water is 15 mass parts with respect to 100 mass parts of functional hydraulic inorganic particles is a paste with a very small water ratio in consideration of the water ratio of a normal hydraulic composition. P0 / P1 is preferably 1.8 or more, more preferably 2.0 or more, and still more preferably 2.2 or more. The upper limit is not particularly limited, but is preferably 50 or less from the viewpoint of handleability.

Here, P0 is a paste in which the amount of water is 15 parts by mass with respect to 100 parts by mass of the functional hydraulic inorganic particles (obtained by kneading after adding 15 parts by mass of water to 100 parts by mass of the functional hydraulic inorganic particles. The paste was measured according to the flow value measuring method described in the examples described later.
P1 is a flow value measured in the same manner as P0, except that the functional hydraulic inorganic particles were heated at 550 ° C. for 3 hours and then the heated functional hydraulic inorganic particles were used.

The functional hydraulic inorganic particles also satisfy the condition (II).
That is, after adding 15 parts by mass of water to 100 parts by mass of the functional hydraulic inorganic particles, the time until the paste composed of the functional hydraulic inorganic particles and water becomes uniform is within 180 seconds. It is. This time corresponds to the kneading time, but this time being within 180 seconds means that the functional hydraulic inorganic particles flow in a short time even for a hydraulic composition having a very small water ratio. It means that sex can be imparted. In general, a paste with a very small water ratio of 15 parts by mass of water with respect to 100 parts by mass of the hydraulic inorganic particles cannot be easily kneaded, so that the kneading time is considerably long. The above time is preferably within 150 seconds, more preferably within 110 seconds, still more preferably within 100 seconds, and particularly preferably within 90 seconds.

Here, the “time until the paste composed of the functional hydraulic inorganic particles and water becomes uniform” in the condition (II) can be determined by visual observation, but more accurately, it is described in the examples described later. It can obtain | require by the measuring method of kneading | mixing time.

For example, the functional hydraulic inorganic particles preferably have an average particle size in the range of 0.01 to 100 μm. By being in such a range, the kneading time can be further shortened, and it becomes possible to give a uniform fluidity to the obtained hydraulic composition. More preferably, it is 0.05-75 micrometers, More preferably, it is the range of 0.1-50 micrometers.

The functional hydraulic inorganic particles of the present invention contain hydraulic inorganic particles and satisfy the above-mentioned conditions (I) and (II), so that the kneading time can be remarkably shortened and the fluidity is improved. It becomes possible to exhibit the effect of the present invention that an excellent hydraulic composition can be provided with high productivity. Therefore, the form is not particularly limited as long as it includes the hydraulic inorganic particles and satisfies the above conditions (I) and (II). For example, the surface of the hydraulic inorganic particles It is preferable that a part or the whole is coated with an organic dispersant. That is, the functional hydraulic inorganic particles preferably include hydraulic inorganic particles and an organic dispersant.
Here, when the functional hydraulic inorganic particles further include pozzolanic active inorganic particles in addition to the hydraulic inorganic particles, the pozzolanic activity is as long as the functional hydraulic inorganic particles satisfy the above-described conditions (I) and (II). The inorganic particles may be partially or wholly coated with an organic dispersant, or may be uncoated, but are preferably coated. is there.

In particular, the functional hydraulic inorganic particles of the present invention have a cement (also referred to as a coated cement) in which a part or all of the surface is coated with an organic dispersant, and a part or all of the surface is coated with an organic dispersant. Further, it is preferable to contain silica fume, fly ash and / or slag. Usually, since pozzolanic active inorganic particles such as silica fume and fly ash have a small particle diameter, when the pozzolanic active inorganic particles are used as they are (that is, without being subjected to a coating treatment) for producing a hydraulic composition, they are kneaded. Time is long and productivity is not enough. However, if particles obtained by coating a part or all of the surface of these pozzolanic active inorganic particles with an organic dispersant and then mixed with the coated cement are used, the kneading time is remarkably reduced when mixed with water. Silica fume cement, fly ash cement and blast furnace slag cement which are shortened and have high fluidity can be easily provided.

The form in which a part or all of the surface of the hydraulic inorganic particles is coated with an organic dispersant means that the organic dispersant is adsorbed or adhered to the surface of the inorganic particles. Since the organic dispersant has carbon atoms, if the organic dispersant is present in the inorganic particles and the carbon content (carbon concentration) on the surface (or the vicinity of the surface) is improved, the surface of the inorganic particles is organic. It is presumed that the system dispersant is adsorbed or adhered, that is, part or all of the surface of the inorganic particles is coated with the organic dispersant.
In addition, it can be confirmed that the organic dispersant is adsorbed or adhered to the particle surface by, for example, measuring the carbon content (carbon concentration) on the particle surface using X-ray photoelectron spectroscopy or the like. it can.

X-ray photoelectron spectroscopy is an analysis method in which a solid surface is excited with soft X-rays under high vacuum and photoelectrons emitted from the surface are measured (hereinafter referred to as XPS analysis method or XPS). This analysis provides information on the oxidation state and concentration of elements present in the vicinity of a few nanometers near the surface, and the relative concentration of C (carbon) relative to Si (silicon) and Ca (calcium) on the surface can be identified. It is done.

(XPS analysis method)
The relative surface concentration of C relative to Si and Ca in the functional hydraulic inorganic particles is calculated from the XPS chart where the vertical axis indicates the number of counts per second and the horizontal axis indicates the binding energy, and the C _1s peak area is _expressed as the C _1s sensitivity coefficient. in value obtained by dividing the value of the peak area was divided by the sensitivity coefficient of the Si _2p of Si _2p, in total of the value of the peak area was divided by the sensitivity coefficient of the Ca _2p of Ca _2p, a value obtained by dividing, It is represented by the following mathematical formula (1).

The peak areas of C _1s , Si _2p and Ca _2p can be measured and calculated by the following procedure.
Measuring apparatus: PHI Quantera SXM manufactured by ULVAC-PKI is used, the X-ray source is AlKα, the beam diameter is 100 μm, and the beam output is 25 W-15 kV.
Sample preparation method: Particle powder as a measurement sample is filled in a φ3 washer manufactured by SUS, and then fixed with finger pressure using a spatula. It is set on a sample table with a SUS jig. Never use carbon-type jigs such as carbon tape.
Depth direction analysis method: Ar ⁺ ions (2 kV-25 mA) are used to perform edging at a rate of 8 nm / min in terms of SiO ₂ to perform depth direction analysis.
In the measurement of Si _2p , Ca _2p , and C _1s , the path energy is set to 280 eV and the energy step is set to 0.5 eV.
The peak area of Si _2p is calculated by accumulating 14 peaks around 100 eV and removing the background by the Shirley method.
The peak area of Ca _2p is calculated by integrating the peak around 345 to 350 eV 14 times, and then removing the background by the Shirley method.
The peak area of C _1s is calculated by accumulating 14 peaks around 285 eV and removing the background by the Shirley method.
The sensitivity coefficient is a value unique to the measuring apparatus, and the sensitivity coefficients of Si _2p , Ca _2p , and C _1s of the apparatus are 119.676, 597.269, and 87.799, respectively. Therefore, the “relative surface concentration” referred to in the present specification is a value obtained using a measurement device “PHI Quantera SXM” manufactured by ULVAC-PKI.

When the relative surface concentration of C with respect to Si and Ca on the surface of the functional hydraulic inorganic particles is measured by XPS, the relative surface concentration of C with respect to Si and Ca on the particle surface (depth 0 nm) is 0.00. The relative surface concentration of C having an average depth of 1 to 2 nm from the particle surface is preferably 0.15 to 50. Thereby, kneading | mixing time can be shortened more and it becomes possible to give the hydraulic composition excellent in fluidity | liquidity with sufficient productivity. The lower limit of the relative surface concentration of C with respect to Si and Ca on the particle surface (depth 0 nm) is more preferably 0.4 or more, still more preferably 0.5 or more, and particularly preferably 0.8 or more. The upper limit is more preferably 30 or less, still more preferably 10 or less, particularly preferably 5 or less, and most preferably 3 or less. The lower limit of the relative surface concentration of C having an average depth of 1 to 2 nm from the particle surface is more preferably 0.18 or more, further preferably 0.20 or more, particularly preferably 0.25 or more, and more preferably 0. .3 or more. The upper limit is more preferably 30 or less, still more preferably 10 or less, particularly preferably 5.0 or less, and most preferably 3.0 or less.

The above-mentioned “relative surface concentration of C having an average depth of 1 to 2 nm from the particle surface” means the relative surface concentration of C at a depth of 1 nm from the surface and the relative surface of C at a depth of 2 nm from the surface. Mean value with concentration. The carbon content ratio on the particle surface (depth 0 nm) may have an effect due to surface contamination, but the effect is reduced at a depth of 1 nm or more from the surface, so an organic dispersant is present on the particle surface. It is possible to more accurately confirm that it is adsorbed or adhered.

As a method for confirming the presence of the organic dispersant in the inorganic particles, a solvent such as water or alcohol was added to the particles partially or wholly covered with the organic dispersant and stirred for a predetermined time. Thereafter, the supernatant can be separated by centrifugation or the like, and the supernatant can be dried and analyzed by NMR or the like.

The functional hydraulic inorganic particles also have a relative surface concentration of carbon (C) with respect to silicon (Si) and calcium (Ca) per unit amount of organic dispersant on the particle surface (depth 0 nm) is 0.6. 10 to 10 is preferable. Thereby, the kneading time can be remarkably shortened, and the effect of the present invention that a hydraulic composition excellent in fluidity can be provided with high productivity can be more sufficiently exhibited. More preferably, it is 0.65-10, More preferably, it is 0.7-8, Especially preferably, it is 0.75-7, More preferably, it is 0.75-6, Most preferably, it is 0.8-5. Furthermore, the relative surface concentration of carbon (C) having an average depth of 1 to 2 nm from the particle surface per unit amount of the organic dispersant obtained by the same method is preferably 0.1 to 5. It is. Thereby, it becomes possible to fully exhibit the effect of this invention. More preferably, it is 0.12-4, More preferably, it is 0.14-3, Most preferably, it is 0.15-2.5.

Here, “the relative surface concentration of carbon (C) with respect to silicon (Si) and calcium (Ca) per unit amount of organic dispersant” is a value obtained by the following method.
1. First, the amount of the organic dispersant present in the functional hydraulic inorganic particles is determined. This “amount of the organic dispersant present in the functional hydraulic inorganic particles” means an ignition loss rate at 150 ° C. (this is calculated by heating the functional hydraulic inorganic particles in an electric furnace). (P)) and the ignition loss rate at 450 ° C. (this is defined as (q)) (= p−q). The ignition loss rate at each temperature here means the mass residual rate (mass%) after heating at each temperature.
2. Next, after measuring XPS of the functional hydraulic inorganic particles to determine the value of the relative surface concentration of carbon (C) with respect to silicon (Si) and calcium (Ca) (this is referred to as (x)) The functional hydraulic inorganic particles were heated in an electric furnace, and the XPS of the inorganic particles after heating at 550 ° C. for 3 hours was measured to determine the relative carbon (C) to silicon (Si) and calcium (Ca). The surface concentration value (this is set as (y)) is obtained, and the difference (= xy) is calculated.
3. Divide the relative surface concentration difference (xy) determined in 2 above by the amount (pq) of the organic dispersant present in the functional hydraulic inorganic particles determined in 1 above. Thus, the value obtained by “(xy) / (pq)” is expressed as “relative surface concentration of carbon (C) relative to silicon (Si) and calcium (Ca) per unit amount of organic dispersant ( z) ".

Particularly in the present invention, when the relative surface concentration of carbon (C) with respect to silicon (Si) and calcium (Ca) per unit amount of organic dispersant on the particle surface is measured by XPS, the relative surface of carbon (C) It is preferable that the concentration is 0.6 to 10 and the average surface concentration of carbon (C) having an average depth of 1 to 2 nm from the particle surface is 0.1 to 5. As a result, the kneading time can be remarkably shortened, and the operational effect of the present invention that can provide a hydraulic composition excellent in fluidity with high productivity can be further exhibited.

The organic dispersant is not particularly limited, and one or more of the commonly used dispersants for hydraulic inorganic particles (also referred to as water reducing agents) can be used. For example, the following compounds are exemplified.
Lignin sulfonate, naphthalene sulfonic acid formalin condensate, melamine sulfonic acid formalin condensate, polystyrene sulfonate, amino sulfonate (for example, aminoaryl sulfonic acid-phenol-formaldehyde condensate, etc., JP-A-1-113419) A sulfonic acid salt such as a polymer; a polymer having a polyoxyalkylene group and an anionic group (for example, ethylene oxide or the like added to a specific unsaturated alcohol such as 3-methyl-3-buten-1-ol) Copolymer or salt thereof obtained using a monomer component containing an alkenyl ether monomer and an unsaturated carboxylic acid monomer (Japanese Patent Laid-Open Nos. 62-68808 and 10-236858, JP, 2001-220417, A)); (meth) acrylic acid Copolymers using ethylene (propylene) glycol ester or polyethylene (propylene) glycol mono (meth) allyl ether, (meth) allylsulfonic acid (salt) and (meth) acrylic acid (salt) (Japanese Patent Laid-Open No. 62-216950) A copolymer obtained by using polyethylene (propylene) glycol ester of (meth) acrylic acid, (meth) allylsulfonic acid (salt) and (meth) acrylic acid (salt) (Japanese Patent Laid-Open No. 1-2226757) A copolymer of polyethylene glycol mono (meth) allyl ether and maleic acid (salt) (see JP-A-4-149056); polyethylene glycol mono (meth) allyl ether, polyethylene glycol mono (meth) Acrylate, (meth) acrylic acid alkyl ester, (meth A copolymer obtained by using acrylic acid (salt) and (meth) allylsulfonic acid (salt) or p- (meth) allyloxybenzenesulfonic acid (salt) (see JP-A-6-191918); A copolymer of an alkoxypolyalkylene glycol monoallyl ether and maleic anhydride, a hydrolyzate thereof or a salt thereof (see JP-A-5-43288);

A copolymer obtained from a monomer component containing a (alkoxy) polyalkylene glycol mono (meth) acrylic acid ester monomer and a (meth) acrylic acid monomer (see Japanese Patent Publication No. 59-18338); (Meth) acrylic acid ester having a sulfonic acid group and, if necessary, a copolymer or a salt thereof using a monomer copolymerizable therewith (see Japanese Patent Publication No. 62-119147); alkoxy polyalkylene glycol mono An esterification reaction product of a copolymer of allyl ether and maleic anhydride and a polyoxyalkylene derivative having a hydroxyl group at the terminal (see JP-A-6-298555); a polyalkylene glycol monoester monomer; (Meth) acrylic acid monomer, unsaturated dicarboxylic acid monomer and / or (meth) allylsulfonic acid monomer Copolymers obtained by use (see JP-A-7-223852); styrene sulfonic acid, sulfoalkyl (meth) acrylate, 2-acrylamido-2-methylpropanesulfonic acid and / or hydroxyalkyl (meth) acrylate monophosphoric acid A copolymer obtained by using an ester, an (alkoxy) polyalkylene glycol mono (meth) acrylate, and an unsaturated carboxylic acid monomer or a salt thereof (see JP-A-11-79811); (alkoxy) A copolymer obtained by using a polyalkylene glycol monovinyl ether monomer, an unsaturated carboxylic acid monomer and (hydroxy) alkyl (meth) acrylate (see JP 2004-307590 A); (alkoxy) poly Alkylene glycol mono (meth) acrylate, Copolymer obtained by using acid monoester monomer and phosphoric acid diester monomer or a salt thereof (see JP 2006-52381 A); unsaturated (poly) alkylene glycol ether monomer And a copolymer of an unsaturated monocarboxylic acid monomer (see JP 2002-121055 A and JP 2002-121056 A);

The organic dispersant is particularly preferably a sulfonic acid-based dispersant (also referred to as a sulfonic acid group-containing compound); a phosphoric acid-based dispersant (also referred to as a phosphoric acid group-containing compound); a polycarboxylic acid-based dispersant; These 1 type (s) or 2 or more types can be used. More preferably, it is preferable to use at least a polycarboxylic acid-based dispersant from the viewpoint of excellent dispersibility and excellent adsorptivity to the surface of hydraulic inorganic particles and pozzolanic active inorganic particles.
Below, the preferable form of a sulfonic acid type dispersing agent, a phosphoric acid type dispersing agent, and a polycarboxylic acid type dispersing agent is demonstrated. In addition, the compound which has at least 2 or more types in a molecule | numerator among a sulfonic acid group, a phosphoric acid group, and a carboxylic acid group is also contained in the preferable organic type dispersing agent of this invention.

In the present specification, the sulfonic acid group includes a sulfonic acid group, and the phosphoric acid group includes a phosphate group. Although the salt which comprises these bases is not specifically limited, For example, an alkali metal salt, alkaline-earth metal salt, ammonium salt, organic ammonium salt etc. are mentioned.

-Sulfonic acid-based dispersant (sulfonic acid group-containing compound)-
The sulfonic acid group-containing compound is a compound having a sulfonic acid group in the molecule, and one or more compounds that are generally used in hydraulic inorganic particles as a sulfonic acid-based dispersant can be used. Among these, a compound having an aromatic group in the molecule is preferable.
Specifically, for example, polyalkylaryl sulfonates such as naphthalene sulfonic acid formaldehyde condensate, methyl naphthalene sulfonic acid formaldehyde condensate, anthracene sulfonic acid formaldehyde condensate; melamine formalin resin sulfonic acid such as melamine sulfonic acid formaldehyde condensate Salts; aromatic amino sulfonates such as aminoaryl sulfonic acid-phenol-formaldehyde condensates; lignin sulfonates such as lignin sulfonates and modified lignin sulfonates; polystyrene sulfonates;

The sulfonic acid group-containing compound is more preferably a condensate (which may be a salt) having a naphthalene structure. Among these, a condensate of a naphthalene sulfonic acid compound represented by the following general formula (1) and an aldehyde compound is particularly preferable from the viewpoint of dispersibility, fluidity retention, strength development, and the like. Note that a mixture of two or more condensates having different degrees of condensation may be used.

In general formula (1), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. M ¹ represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group, an alkyl ammonium group or a substituted alkyl ammonium group.

Examples of the naphthalene sulfonic acid compound represented by the general formula (1) include naphthalene, methyl naphthalene, isopropyl naphthalene, and the like, and one or more can be used.

As said aldehyde compound, if it is a compound which has an aldehyde group (-C (= O) H), it will not specifically limit, 1 type (s) or 2 or more types can be used. For example, formaldehyde, glyoxylic acid, benzaldehyde or a derivative thereof can be used. Examples of the benzaldehyde derivative include benzaldehyde salts in addition to acid derivatives such as benzaldehyde carboxylic acid, benzaldehyde sulfonic acid, benzaldehyde disulfonic acid, benzaldehyde phosphonic acid, and the salts include alkali metal salts, alkaline earth metal salts, ammonium salts. And organic ammonium salts. Of these, formaldehyde is preferable.

The salt of the condensate is not particularly limited, and examples thereof include alkali metal salts, alkaline earth metal salts, ammonium salts, and organic ammonium salts. Among these, alkali metal salts are preferable, and sodium salts are preferable among them.

In the condensation, a sulfonated product of a bisphenol compound may be added in addition to the naphthalene sulfonic acid compound and the aldehyde compound. That is, the condensate may include a condensate (may be a salt) of a sulfonated bisphenol compound and an aldehyde compound.

The bisphenol compound may be a compound having two hydroxyphenyl groups in one molecule of the compound. For example, a compound having a structure in which two hydroxyphenyl groups are bonded via any divalent group is suitable. The divalent group is not particularly limited. For example, —CH ₂ —, —C (Me) ₂ —, —C (Me) (Et) —, —C (Ph) ₂ —, —O—, —S ( ═O) ₂ — and the like (Me represents a methyl group, Et represents an ethyl group, and Ph represents a phenyl group). The hydroxyphenyl group may have a substituent such as an alkyl group or an aryl group.

Specific examples of the bisphenol compound include bis (hydroxyphenyl) propane, bis (hydroxyphenyl) butane, dihydroxydiphenylmethane, dihydroxydiphenyl ether, and dihydroxydiphenylsulfone.
The sulfonation of the bisphenol compound is not particularly limited, and may be performed by a normal method in the presence of a normal sulfonating agent (for example, sulfuric acid, chlorosulfonic acid, sulfur trioxide, etc.).

The condensation reaction is not particularly limited, and ordinary means may be used.
In the condensation reaction of the naphthalene sulfonic acid compound and the aldehyde compound, it is preferable that the ratio thereof (naphthalene sulfonic acid compound / aldehyde compound; mol%) is 10 to 90/90 to 10. More preferably, it is 10-50 / 50-90. Furthermore, when the sulfonated product of the bisphenol compound is added to perform the condensation reaction, the naphthalenesulfonic acid compound is 50 to 99 mol% in the total amount of 100 mol% of the naphthalenesulfonic acid compound and the sulfonated product of the bisphenol compound. It is preferable to do. More preferably, it is 30-90 mol%.

The weight average molecular weight (Mw) of the sulfonic acid group-containing compound is determined based on the binding property (adsorbability) to the hydraulic inorganic particles and pozzolanic active inorganic particles, the aggregating action of these inorganic particles, and the flow of the obtained hydraulic composition. In view of retention and the like, it is preferable that the weight average molecular weight (Mw) is 3000 to 500,000. More preferably, it is 5000-300,000, More preferably, it is 7000-200,000, Most preferably, it is 8000-100,000.
The weight average molecular weight of the sulfonic acid group-containing compound can be measured, for example, by gel permeation chromatography (also referred to as GPC) using polystyrene sulfonic acid as a standard substance under the following measurement condition (1).

(GPC measurement conditions (1))
Apparatus: Waters Alliance (2695), manufactured by Waters
Analysis software: Waters, Empor professional + GPC option column: Tosoh, TSK guard column SWXL + TSKgel G4000SWXL + G2000SWXL
Detector: Multiwavelength visible ultraviolet (PDA) detector (Waters 2996)
Eluent: 30 mM CH3COONa / CH3CN = 6/4
Standard material for creating calibration curve: polystyrene sulfonic acid [peak top molecular weight (Mp) 976000, 356000, 77900, 15650, 4600] manufactured by Soka Scientific Co., Ltd.
Calibration curve: Created by a cubic equation based on the Mp value and elution time of the polystyrene sulfonic acid. Flow rate: 0.7 mL / min
Column temperature: 40 ° C
Measurement time: 45 minutes Sample solution injection amount: 100 μL (eluent preparation solution with sample concentration of 0.5 mass%)

-Phosphate-based dispersant (phosphate group-containing compound)-
A phosphoric acid group containing compound is a compound which has a phosphoric acid group in a molecule | numerator, and can use 1 type, or 2 or more types of compounds generally used for the hydraulic inorganic particle as a phosphoric acid type dispersing agent. Among these, a phosphoric acid polymer and a phosphoric acid condensate containing polyalkylene glycol are preferable from the viewpoint of better dispersion performance.

The weight average molecular weight (Mw) of the phosphoric acid group-containing compound containing the polyalkylene glycol is determined based on the binding property (adsorbability) to the hydraulic inorganic particles and the pozzolanic active inorganic particles, the aggregating action of these inorganic particles, and the water obtained. Considering the fluidity retention of the hard composition, the weight average molecular weight (Mw) is preferably 3000 to 500,000. More preferably, it is 5000-300,000, More preferably, it is 7000-200,000, Most preferably, it is 8000-100,000.
The weight average molecular weight can be measured, for example, by GPC using polyethylene glycol as a standard substance under the following measurement condition (2).

(GPC measurement conditions (2))
Apparatus: Waters Alliance (2695), manufactured by Waters
Analysis software: Waters, Empor professional + GPC option column: Tosoh, TSK guard column SWXL + TSKgel G4000SWXL + G3000SWXL + G2000SWXL
Detector: differential refractometer (RI) detector (Waters 2414, manufactured by Waters)
Eluent: 115.6 g of sodium acetate trihydrate dissolved in a mixed solvent of 10999 g of water and 6001 g of acetonitrile, and further adjusted to pH 6.0 with acetic acid, a standard substance for preparing a solution calibration curve: polyethylene glycol [peak top molecular weight (Mp 300000, 200000, 107000, 50000, 27700, 11840, 6450, 1470]
Calibration curve: Created by cubic equation based on Mp value and elution time of polyethylene glycol Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Measurement time: 45 minutes Sample solution injection amount: 100 μL (eluent preparation solution with sample concentration of 0.5 mass%)

(I) Phosphoric acid-based polymer The phosphoric acid-based polymer may be a polymer containing a phosphoric acid group. For example, a (poly) alkylene glycol monomer represented by the following general formula (2): The polymer is preferably a polymer obtained by polymerizing a monomer component containing a phosphoric acid monomer represented by the following general formula (3).

In the general formula (2), R ² , R ³ and R ⁴ are the same or different and each represents a hydrogen atom, a methyl group or —COO (A ¹ O) _n —R ⁵ . A ¹ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. n represents the average addition mole number of the oxyalkylene group represented by A ¹ O, and is the same or different and is a number of 1 to 300. R ⁵ is the same or different and represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.

In general formula (3), R ⁶ represents a hydrogen atom or a methyl group. A ² O (also expressed as “OA ² ”) is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. m represents the average addition mole number of the oxyalkylene group represented by A ² O, and is a number of 1 to 300. M ² and M ³ are the same or different and each represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group, an alkyl ammonium group, or a substituted alkyl ammonium group. Either M ² or M ³ may represent CH ₂ ═C (R ⁶ ) —CO— (OA ² ) _m —.

In the general formula (2), R ² , R ³ and R ⁴ are the same or different and represent a hydrogen atom, a methyl group or —COO (A ¹ O) _n —R ⁵ , but at least R ⁴ is hydrogen. Preferably it represents an atom. As R ² and R ³ , R ² is preferably a hydrogen atom and R ³ is preferably a methyl group.

A ¹ O represents an oxyalkylene group having 2 to 18 carbon atoms (the oxyalkylene group also includes an oxystyrene group), and this carbon number is preferably 2 to 8, more preferably 2 to 4, and even more. Preferred is 2, that is, an oxyethylene group. In particular, the oxyethylene group is preferably 70 mol%, more preferably 80 mol% or more, still more preferably 90 mol% or more, particularly preferably 100 mol%, based on 100 mol% of the total number of oxyalkylene groups. (A ¹ O) The (poly) alkylene glycol chain represented by _n is a (poly) ethylene glycol chain.
When two or more kinds of oxyalkylene groups are present, the addition form may be any addition form such as random addition, block addition, and alternate addition.

n represents the average addition mole number of the oxyalkylene group represented by A ¹ O, and is a number of 1 to 300, preferably 3 to 200, more preferably 4 to 120. By being in such a range, the polymerization reactivity of the (poly) alkylene glycol monomer and the hydrophilicity of the resulting polymer become more sufficient, so the effects of the present invention are more fully exhibited. It becomes possible.

R ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.
When R ⁵ represents a hydrocarbon group, the number of carbon atoms (number of carbon atoms) is preferably 1 to 12, more preferably 1 to 4, and particularly preferably 1 from the viewpoint of further improving the hydrophilicity of the resulting polymer. ~ 2. As the hydrocarbon group, for example, an alkyl group (straight chain, branched chain or cyclic), a phenyl group, an alkyl-substituted phenyl group, an alkenyl group, an alkynyl group, an aryl group, and the like are preferable. Chain or cyclic) is preferred, and a methyl group is more preferred.

As the (poly) alkylene glycol monomer represented by the general formula (2), for example, an unsaturated carboxylic acid (poly) alkylene glycol ester compound is preferable. (Meth) acrylate and (hydroxy) polyalkylene glycol mono (meth) acrylate are particularly preferred.

As the (alkoxy) (poly) alkylene glycol mono (meth) acrylate, for example, alkoxy (poly) alkylene glycols obtained by adding 2 to 300 moles of an alkylene oxide group having 2 to 18 carbon atoms to alcohols are suitable. More preferably, it is an esterified product of alkoxy (poly) alkylene glycols mainly composed of ethylene oxide and (meth) acrylic acid.

Examples of the alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, and 2-hexanol. C1-C30 aliphatic alcohols such as 3-hexanol, octanol, 2-ethyl-1-hexanol, nonyl alcohol, lauryl alcohol, cetyl alcohol and stearyl alcohol; C3-C30 fats such as cyclohexanol Cyclic alcohols; (meth) allyl alcohol, 3-buten-1-ol, C3-C30 unsaturated alcohols such as 3-methyl-3-buten-1-ol; and the like.

Specific examples of the esterified product include (alkoxy) (poly) ethylene glycol (poly) (alkylene glycol having 2 to 4 carbon atoms) (meth) acrylic acid esters, (hydroxy) (poly) ethylene glycol ( Poly) (C2-C4 alkylene glycol) (meth) acrylic acid esters and the like are suitable.

Hydroxy polyethylene glycol mono (meth) acrylate, methoxy polyethylene glycol mono (meth) acrylate, hydroxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, methoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, Hydroxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, methoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, hydroxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meta) ) Acrylate, Methoxy {Polyethylene glycol (poly) propylene glycol (poly) butylene glycol } Mono (meth) acrylate, ethoxy polyethylene glycol mono (meth) acrylate, ethoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, ethoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, ethoxy { Polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate, propoxypolyethyleneglycol mono (meth) acrylate, propoxy {polyethyleneglycol (poly) propyleneglycol} mono (meth) acrylate, propoxy {polyethyleneglycol (poly ) Butylene glycol} mono (meth) acrylate, propoxy {polyethylene glycol (poly) propylene glycol (Poly) butylene glycol} mono (meth) acrylate, butoxypolyethylene glycol mono (meth) acrylate, butoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, butoxy {polyethylene glycol (poly) butylene glycol} mono (Meth) acrylate, butoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate, and the like.

In the above general formula (3), A ² O represents an oxyalkylene group having 2 to 18 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8, still more preferably 2 to 4, Particularly preferred is 2, that is, an oxyethylene group. In particular, the oxyethylene group is preferably 70 mol%, more preferably 80 mol% or more, still more preferably 90 mol% or more, particularly preferably 100 mol%, based on 100 mol% of the total number of oxyalkylene groups. (A ² O) The (poly) alkylene glycol chain represented by _n is a (poly) ethylene glycol chain.
When two or more kinds of oxyalkylene groups are present, the addition form may be any addition form such as random addition, block addition, and alternate addition.

m represents the average addition mole number of the oxyalkylene group represented by A ² O, and is a number of 1 to 300, preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 10, Especially preferably, it is 1-5.

Examples of the phosphoric acid monomer represented by the general formula (3) include mono (2-hydroxyethyl) phosphate (meth) acrylate and di-{(2-hydroxyethyl) phosphate (meth) phosphate. Acrylic acid} ester, (poly) alkylene glial mono (meth) acrylate acid phosphate, and the like are preferable. Among these, phosphoric acid mono (2-hydroxyethyl) methacrylic acid ester and phosphoric acid di-{(2-hydroxyethyl) methacrylic acid} ester are particularly preferable from the viewpoint of ease of production and quality stability.

The monomer component is also a monomer copolymerizable with a (poly) alkylene glycol monomer and / or a phosphate monomer, and other monomers (also referred to as other monomers). 1 type or 2 types or more may be included. When other monomers are included, the content is preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less, particularly preferably in 100 mol% of the total amount of monomer components. Is 0 mol%.

Although it does not specifically limit as said other monomer, For example, the unsaturated alcohol polyalkylene glycol adduct illustrated by international publication 2014/010572 [0023]-[0027]; In addition to the unsaturated carboxylic acid monomers exemplified in [0033] and [0036], various diesters exemplified in the publications [0041] to [0042]; diamides; half amides; (poly) Alkylene glycol di (meth) acrylates; polyfunctional (meth) acrylates; (poly) alkylene glycol dimaleates; unsaturated sulfonic acids and salts thereof; amides such as methyl (meth) acrylamide; vinyl aromatics; alkanes Diol mono (meth) acrylates; dienes; unsaturated amides; unsaturated cyanides; Le acids; unsaturated amines; divinyl aromatics; cyanurates; siloxane derivative; and the like.

In the polymerization reaction of the (poly) alkylene glycol monomer and the phosphoric acid monomer, the ratio ((poly) alkylene glycol monomer / phosphoric acid monomer; mol%) is 5 It is preferable to set it to -95 / 95-5. More preferably, it is 10-90 / 90-10. Here, it is calculated that the phosphoric acid monomer is an acid type compound.

The polymerization method of the monomer component containing the (poly) alkylene glycol monomer and the phosphoric acid monomer is not particularly limited, and ordinary polymerization means may be used. For example, a method described in JP 2006-52381 A can be mentioned.

(Ii) Phosphoric acid-based condensate The phosphoric acid-based condensate is preferably, for example, a condensate of a phosphate ester and an aldehyde compound. The phosphoric acid ester is not particularly limited as long as it is an esterified product of phosphoric acid (may be a salt) and a hydroxyl group-containing compound, and one kind or two or more kinds can be used. In addition, any of phosphoric acid monoester, phosphoric acid diester, and phosphoric acid triester may be sufficient.

The phosphoric acid may be a compound having a phosphoric acid group, and examples thereof include compounds having a structure in which —PO ₃ H ₂ or —OPO ₃ H ₂ or the like is bonded to a hydrocarbon skeleton in addition to phosphoric acid. . The hydrocarbon skeleton here is not particularly limited, and an alkyl chain (for example, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms), an aromatic ring (for example, an aromatic ring having 6 to 10 carbon atoms), a heterocycle And a ring (for example, a 5- to 10-membered heterocyclic ring). The heterocyclic ring preferably has 1 to 5 heteroatoms (preferably O, N, S and / or P), more preferably 1 to 3 and still more preferably 1 to 2. Specific examples include phenylphosphonic acid and the like.
In addition, when phosphates are salts, an alkali metal salt, alkaline-earth metal salt, ammonium salt, organic ammonium salt etc. are mentioned, for example.

The hydroxyl group-containing compound preferably has an aromatic ring. Examples thereof include phenol, phenoxy alcohol, phenoxy (poly) alkylene glycol, naphthol, naphthoxy alcohol, naphthoxy (poly) alkylene glycol and the like. The alcohol constituting phenoxy alcohol or naphthoxy alcohol is preferably, for example, an alcohol having 1 to 10 carbon atoms, and the (poly) alkylene glycol chain constituting phenoxy (poly) alkylene glycol or naphthoxy (poly) alkylene glycol is: (Poly) ethylene glycol is preferable, and the average chain length of the (poly) alkylene glycol chain is preferably 1 to 300.
Specific examples of the esterified product of the phosphoric acid and the hydroxyl group-containing compound include, for example, phenoxyethanol phosphate obtained by esterifying phenoxyethanol with phosphoric acid.

As said aldehyde compound, if it is a compound which has an aldehyde group (-C (= O) H), it will not specifically limit, 1 type (s) or 2 or more types can be used. For example, formaldehyde, glyoxylic acid, benzaldehyde or a derivative thereof can be used. Examples of the benzaldehyde derivative include benzaldehyde salts in addition to acid derivatives such as benzaldehyde carboxylic acid, benzaldehyde sulfonic acid, benzaldehyde disulfonic acid, benzaldehyde phosphonic acid, and the salts include alkali metal salts, alkaline earth metal salts, ammonium salts. And organic ammonium salts.

In the above condensation, in addition to the phosphate ester and the aldehyde compound, one or more aromatic compounds and / or heterocyclic compounds having a (poly) alkylene glycol chain may be added. Thereby, dispersibility and dispersion retention can be more imparted or improved.
The aromatic compound and / or heterocyclic compound having a (poly) alkylene glycol chain has, for example, a structure in which a (poly) alkylene glycol chain is bonded to a compound containing an aromatic ring and / or a compound containing a heterocyclic ring. It is preferable.
The compound containing an aromatic ring preferably contains an aromatic ring having 6 to 10 carbon atoms.
The compound containing a heterocyclic ring preferably contains a 5- to 10-membered heterocyclic ring, and preferably has 1 to 5 heteroatoms, more preferably 1 to 3, further preferably 1 to 2 It is. The hetero atom is preferably O, N, S and / or P.

The compound containing an aromatic ring and the compound containing a heterocyclic ring may have one or more substituents. No particular limitation is imposed on the substituent, for ^{_{example, -OH, -OR 7, -COOH,}} -SO 3 H, -PO 3 H 2, -OPO 3 H 2, -NH 2, -N (H) R 7, -NR ⁷ R ^8, in the alkyl group and the like (wherein 1 to 10 carbon atoms, ^{R 7} and ^{R 8} are the same or different, represent a hydrocarbon group, the carbon number from 1 to 4 are preferred. ). The alkyl group having 1 to 10 carbon atoms may further have a phenyl group or a hydroxyphenyl group.

Examples of the compound containing an aromatic ring and a compound containing a heterocyclic ring include phenol, cresol, resorcinol, nonylphenol, methoxyphenol, naphthol, methylnaphthol, butylnaphthol, bisphenol A, aniline, methylaniline, hydroxyaniline, methoxyaniline, Examples include furfuryl alcohol.

The (poly) alkylene glycol chain is preferably composed of, for example, an oxyalkylene group having 2 to 18 carbon atoms. 2-12 are preferable, as for carbon number of an oxyalkylene group, More preferably, it is 2-8, More preferably, it is 2-4, Most preferably, it is 2 or 3, ie, an oxyethylene group and an oxypropylene group.
When two or more oxyalkylene groups are present in the (poly) alkylene glycol chain, the addition form may be any addition form such as random addition, block addition, and alternate addition.

The average chain length of the (poly) alkylene glycol chain is preferably 1 to 300 mol. That is, it is preferable that the average added mole number of the oxyalkylene group is 1 to 300. The lower limit is more preferably 2 or more, further preferably 4 or more, particularly preferably 5 or more, and most preferably 10 or more, and the upper limit is more preferably 280 or less, still more preferably 200 or less.

In the condensation reaction between the phosphate ester and the aldehyde compound, the ratio (phosphate ester / aldehyde compound; mol%) is preferably 10/1 to 1-10. Furthermore, when an aromatic compound and / or heterocyclic compound having a (poly) alkylene glycol chain is added to carry out the condensation reaction, the aromatic compound and / or heterocyclic ring is used with respect to 100 mol% of the aldehyde compound. It is preferable that the total amount of the formula compound and the phosphate ester be 1-1000 mol%. More preferably, it is 10-800 mol%.

The condensation reaction is not particularly limited, and ordinary means may be used. For example, the method described in Japanese translations of PCT publication No. 2008-51080 is mentioned.

The phosphoric acid polymer obtained by the above polymerization or the phosphoric acid condensate obtained by the above condensation can be used as a surface coating agent for hydraulic inorganic particles or pozzolanic active inorganic particles as it is. The polymer may be used after neutralizing with an alkaline substance. As the alkaline substance, inorganic salts such as hydroxides or carbonates of monovalent metals or divalent metals; ammonia; organic amines are suitable. Further, after the reaction is completed, the concentration can be adjusted if necessary.

-Polycarboxylic acid dispersant-
The polycarboxylic acid-based dispersant is preferably a dispersant containing a polymer having a carboxyl group and / or a structure portion thereof (polycarboxylic acid-based polymer), and among them, from the viewpoint of being superior in dispersion performance, Those containing polyalkylene glycol are preferred. More preferably, the organic dispersant includes a polycarboxylic acid polymer containing polyalkylene glycol. Such a polycarboxylic acid polymer is particularly highly adsorbable on the surface of the inorganic particles, and can exhibit sufficient dispersibility after surface coating.

The polyalkylene glycol is preferably formed of one or more of 2 to 18 carbon oxyalkylene groups. When two or more types of oxyalkylene groups are present, the addition form may be any addition form such as random addition, block addition, and alternate addition. As carbon number of the said oxyalkylene group, 2-8 are preferable, More preferably, it is 2-4. More preferably, it is 2, that is, the polyalkylene glycol is preferably polyethylene glycol.

Specific examples of the oxyalkylene group having 2 to 18 carbon atoms include oxyethylene group, oxypropylene, oxybutylene group, oxyisobutylene group, oxybutene group (1-butene oxide, 2-butene oxide, etc.) and the like. Of these, an oxyethylene group and an oxypropylene group are preferable. More preferably, the main component is an oxyethylene group.
An oxyethylene group is mainly composed of ethylene oxide when the polyalkylene glycol is formed of two or more oxyalkylene groups in the number of moles of all alkylene oxides forming the oxyalkylene group. Means that. Thereby, the balance between the hydrophilicity and the hydrophobicity of the polycarboxylic acid polymer becomes better, and the effect exhibited by the polymer is more fully exhibited. Specifically, the oxyethylene group is preferably 50 to 100 mol% in 100 mol% of all oxyalkylene groups constituting the polyalkylene glycol. More preferably, it is 60-100 mol%, More preferably, it is 70-100 mol%, Especially preferably, it is 80-100 mol%, Most preferably, it is 90-100 mol%.

In the polyalkylene glycol, the average number of repeating alkylene glycol (oxyalkylene group) (average number of added moles) is preferably, for example, 2 to 300. More preferably, it is a number of 5 to 300. More preferably, it is 10-150, Most preferably, it is 20-100, More preferably, it is 23-75, Most preferably, it is 25-75.

The polycarboxylic acid dispersant and the polyalkylene glycol in the polycarboxylic acid polymer may be present alone but are preferably included as part of the polymer structure. Specifically, the organic dispersant preferably includes a polycarboxylic acid polymer having a polyalkylene glycol chain.

Examples of the polycarboxylic acid polymer containing the polyalkylene glycol include a structural unit (A) derived from an unsaturated polyalkylene glycol monomer (a) and an unsaturated carboxylic acid monomer (b). A polymer having the derived structural unit (B) is preferred. Such a polymer is superior in the adsorptivity to the hydraulic inorganic particles and the pozzolanic active inorganic particles and the particle dispersibility after the adsorption (that is, after the surface coating), so that the kneading time for obtaining the hydraulic composition is further increased. The fluidity of the obtained hydraulic composition can be further improved. More preferably, it is a polymer obtained by polymerizing a monomer component containing an unsaturated polyalkylene glycol monomer (a) and an unsaturated carboxylic acid monomer (b). Each monomer contained in the monomer component can be used alone or in combination of two or more.
In addition, each structural unit means the structure where the polymerizable double bond (carbon-carbon double bond) which each monomer has became a single bond.
Hereinafter, the unsaturated polyalkylene glycol monomer (a) is also referred to as “monomer (a)”, the unsaturated carboxylic acid monomer (b) is also referred to as “monomer (b)”, A polymer having the structural unit (A) derived from the monomer (a) and the structural unit (B) derived from the monomer (b) is also referred to as “copolymer (I)”.

<Unsaturated polyalkylene glycol monomer (a)>
The unsaturated polyalkylene glycol monomer (a) may be any monomer having a polymerizable unsaturated group and a polyalkylene glycol chain.
The polyalkylene glycol chain is preferably composed of, for example, one or more oxyalkylene groups having 2 to 18 carbon atoms. When two or more types of oxyalkylene groups are present, the addition form may be any addition form such as random addition, block addition, and alternate addition. As carbon number of the said oxyalkylene group, 2-8 are preferable, More preferably, it is 2-4. More preferably, it is 2, that is, the polyalkylene glycol chain is preferably a polyethylene glycol chain.
Specific examples and preferred embodiments of the oxyalkylene group having 2 to 18 carbon atoms are as described above.

In the polyalkylene glycol chain, the average number of repeating alkylene glycols (oxyalkylene groups) (average number of added moles) is preferably, for example, 2 to 300. More preferably, it is a number of 5 to 300. By being in such a range, since the polymerization reactivity of the monomer (a) and the hydrophilicity of the copolymer (I) become more sufficient, the effects of the present invention can be fully exhibited. Is possible. The average added mole number is more preferably 10 to 150, particularly preferably 20 to 100, more preferably 23 to 75, and most preferably 25 to 75.

The unsaturated polyalkylene glycol monomer (a) is particularly preferably represented by the following general formula (4). Thus, the polycarboxylic acid polymer is composed of the structural unit (A) derived from the unsaturated polyalkylene glycol monomer (a) represented by the following general formula (4), and the unsaturated carboxylic acid monomer. The form which is a polymer having the structural unit (B) derived from the body (b) is one of the preferred forms of the present invention. As such a polymer, a polymer obtained by polymerizing a monomer component containing the monomer (a) and the monomer (b) represented by the following general formula (4) is more preferable.

In the formula, R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom or a methyl group. p represents an integer of 0 to 2. q represents 0 or 1; A ³ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. r is the average addition mole number of the oxyalkylene group represented by A ³ O, and is a number of 2 to 300. R ⁹ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.

In the general formula (4), the polyalkylene glycol chain represented by — (A ³ O) _r — is as described above.
In the general formula (4), R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom or a methyl group, and p is 0, 1 or 2. Therefore, the alkenyl group represented by “C (R ⁷ ) H═C (R ⁸ ) — (CH ₂ ) _p —” corresponds to an alkenyl group having 2 to 6 carbon atoms. Preferably, it is 3-5.
Examples of the alkenyl group represented by the above “C (R ⁷ ) H═C (R ⁸ ) — (CH ₂ ) _p —” include a vinyl group, an allyl group, a methallyl group, a 3-butenyl group, and 3-methyl. And a -3-butenyl group. Among these, a vinyl group, an allyl group, a methallyl group, and a 3-methyl-3-butenyl group are preferable.
As R ⁷ and R ⁸ , it is preferable that R ⁷ is a hydrogen atom and R ⁸ is a methyl group, and such a form is one of the preferred embodiments of the present invention.

In the general formula (4), ^{R 9} is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. When R ⁹ represents a hydrocarbon group, the number of carbon atoms (the number of carbon atoms) is preferably 1 to 12, more preferably 1 to 8, from the viewpoint of further improving the hydrophilicity of the copolymer (I). More preferably, it is 1-4, particularly preferably 1-3, and most preferably 1-2.
As the hydrocarbon group, for example, an alkyl group (straight chain, branched chain or cyclic), a phenyl group, an alkyl-substituted phenyl group, an alkenyl group, an alkynyl group, an aryl group and the like are preferable. Among these, an alkyl group (straight chain, branched chain or cyclic) is more preferable. Especially, a C1-C12 linear or branched alkyl group and a C3-C12 alicyclic alkyl group are preferable, More preferably, a C1-C4 linear or branched alkyl group is preferable. A alicyclic alkyl group having 3 to 4 carbon atoms, more preferably a linear or branched alkyl group having 1 to 3 carbon atoms, and an alicyclic alkyl group having 3 carbon atoms.

R ⁹ is particularly preferably a hydrogen atom, a linear or branched alkyl group having 1 to 3 carbon atoms, or an alicyclic alkyl group having 3 carbon atoms, and more preferably a hydrogen atom, a methyl group or ethyl. A group, most preferably a hydrogen atom.

In the general formula (4), q represents 0 or 1, but when q = 0, the monomer (a) is a monomer having an ether structure (also referred to as an ether monomer). Become. When q = 1, the monomer (a) is a monomer having an ester structure (also referred to as an ester monomer). Among these, it is preferable that q = 0, that is, the monomer (a) is an ether-based monomer, which can further enhance the dispersion performance.

When the monomer (a) is an ether monomer, a specific example of the monomer includes an unsaturated polyalkylene glycol ether monomer. Specifically, an unsaturated alcohol polyalkylene glycol adduct, that is, a compound having a structure in which a polyalkylene glycol chain is added to an alcohol having an unsaturated group (referred to as an unsaturated alcohol) is preferable. Such a compound can be obtained, for example, by adding an alkylene glycol (also referred to as alkylene oxide) to an unsaturated alcohol.

The unsaturated polyalkylene glycol ether monomer is particularly preferably the following general formula (5):

(Wherein R ⁷ and R ⁸ are the same or different and represent a hydrogen atom or a methyl group. A ³ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. The average addition mole number of the oxyalkylene group represented by ³ O and a number of 2 to 300. X represents a divalent alkylene group having 1 to 2 carbon atoms or a direct bond R ⁹ is , Represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.)

In the general formula (5), R ⁷ , R ⁸ , A ³ O, r, and R ⁹ are the same as the symbols in the general formula (4).
In the general formula (5), X represents a divalent alkylene group having 1 to 2 carbon atoms or a direct bond. When X represents a direct bond, the carbon atom and the oxygen atom bonded to X in the general formula (5) are directly bonded. Among these, X is preferably a C 1-2 divalent alkylene group. That is, a methylene group or an ethylene group is preferable.

Examples of the unsaturated alcohol polyalkylene glycol adduct represented by the general formula (5) include polyethylene glycol allyl ether, polyethylene glycol methallyl ether, (poly) ethylene glycol 3-methyl-3-butenyl ether, (poly ) Ethylene glycol tetraethylene glycol monovinyl ether, (poly) ethylene (poly) propylene glycol allyl ether, (poly) ethylene (poly) propylene glycol methallyl ether, (poly) ethylene (poly) propylene glycol 3-methyl-3-butenyl Ether, (poly) ethylene (poly) propylene glycol tetraethylene glycol monovinyl ether, (poly) ethylene (poly) butylene glycol allyl ether, (poly) ethylene (poly Butylene glycol methallyl ether, (poly) ethylene (poly) butylene glycol 3-methyl-3-butenyl ether, (poly) ethylene (poly) butylene glycol tetraethylene glycol monovinyl ether, methoxypolyethylene glycol allyl ether, methoxypolyethylene glycol methallyl ether , Methoxy (poly) ethylene glycol 3-methyl-3-butenyl ether, methoxy (poly) ethylene glycol tetraethylene glycol monovinyl ether, methoxy (poly) ethylene (poly) propylene glycol allyl ether, methoxy (poly) ethylene (poly) Propylene glycol methallyl ether, methoxy (poly) ethylene (poly) propylene glycol 3-methyl-3-butenyl ether, Xyl (poly) ethylene (poly) propylene glycol tetraethylene glycol monovinyl ether, methoxy (poly) ethylene (poly) butylene glycol allyl ether, methoxy (poly) ethylene (poly) butylene glycol methallyl ether, methoxy (poly) ethylene (poly) Butylene glycol 3-methyl-3-butenyl ether, methoxy (poly) ethylene (poly) butylene glycol tetraethylene glycol monovinyl ether, and the like are suitable. In the present invention, it is particularly preferable to use one or more of these as the monomer (a) giving the structural unit (A).

When the monomer (a) is an ether monomer such as the unsaturated polyalkylene glycol ether monomer, the monomer (a) can be produced by various methods. It is preferable to obtain by any one of the following production methods 1) to 3).
1) When R ⁹ in the general formula (4) is a hydrogen atom, for example, a predetermined mole addition of an alkylene oxide having 2 to 18 carbon atoms is added to an unsaturated alcohol in the presence of an alkali catalyst and / or an acid catalyst. To obtain the monomer (a).
The unsaturated alcohol is preferably, for example, one or more alcohols having an alkenyl group having 2 to 6 carbon atoms such as allyl alcohol, methallyl alcohol, and 3-methyl-3-buten-1-ol. It is.
Examples of the alkali catalyst include potassium hydroxide and sodium hydroxide, and examples of the acid catalyst include boron trifluoride and tin tetrachloride.

2) When R ⁹ in the general formula (4) is an alkyl group having 1 to 18 carbon atoms, the compound obtained by the above production method 1) obtained by adding a predetermined mole of an alkylene oxide to an unsaturated alcohol, A method of obtaining the monomer (a) by reacting an alkyl halide having 1 to 18 carbon atoms such as methyl chloride in the presence of an alkali catalyst.

3) When R ⁹ in the general formula (4) is an alkyl group having 1 to 18 carbon atoms, contrary to the production method 2), the alcohol having 1 to 18 carbon atoms is substituted with an alcohol having 2 to 18 carbon atoms. A method of obtaining a monomer (a) by further reacting a alkenyl halide having 2 to 6 carbon atoms with a compound obtained by adding a predetermined mole of an alkylene oxide in the presence of an alkali catalyst.
In addition, as for C1-C18 alcohol, C1-C18 alcohols, such as methanol and ethanol, etc. are mentioned.
Examples of the alkenyl halide having 2 to 6 carbon atoms include allyl chloride and methallyl chloride.

When the monomer (a) is an ester monomer, specific examples of the monomer include unsaturated polyalkylene glycol ester monomers, that is, unsaturated groups and polyalkylene glycol chains are esters. Examples thereof include compounds having a structure bonded through a bond. Among such compounds, unsaturated carboxylic acid polyalkylene glycol ester compounds are preferable, and (alkoxy) polyalkylene glycol mono (meth) acrylate and (hydroxy) polyalkylene glycol mono (meth) acrylate are more preferable.

As the (alkoxy) polyalkylene glycol mono (meth) acrylate, for example, alkoxypolyalkylene glycols obtained by adding 2 to 300 moles of an alkylene oxide group having 2 to 18 carbon atoms to alcohols are suitable. More preferably, it is an esterified product of an alkoxy polyalkylene glycol mainly composed of ethylene oxide and (meth) acrylic acid.

Examples of the alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, and 2-hexanol. C1-C30 aliphatic alcohols such as 3-hexanol, octanol, 2-ethyl-1-hexanol, nonyl alcohol, lauryl alcohol, cetyl alcohol and stearyl alcohol; C3-C30 fats such as cyclohexanol Cyclic alcohols; (meth) allyl alcohol, 3-buten-1-ol, C3-C30 unsaturated alcohols such as 3-methyl-3-buten-1-ol; and the like.

Specific examples of the esterified product include the following (alkoxy) polyethylene glycol (poly) (alkylene glycol having 2 to 4 carbon atoms) (meth) acrylic acid esters, (hydroxy) polyethylene glycol (poly) (2 carbon atoms). ~ 4 alkylene glycol) (meth) acrylic acid esters and the like are preferred.

Hydroxy polyethylene glycol mono (meth) acrylate, methoxy polyethylene glycol mono (meth) acrylate, hydroxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, methoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, Hydroxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, methoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, hydroxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meta) ) Acrylate, Methoxy {Polyethylene glycol (poly) propylene glycol (poly) butylene glycol } Mono (meth) acrylate, ethoxy polyethylene glycol mono (meth) acrylate, ethoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, ethoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, ethoxy { Polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate, propoxypolyethyleneglycol mono (meth) acrylate, propoxy {polyethyleneglycol (poly) propyleneglycol} mono (meth) acrylate, propoxy {polyethyleneglycol (poly ) Butylene glycol} mono (meth) acrylate, propoxy {polyethylene glycol (poly) propylene glycol (Poly) butylene glycol} mono (meth) acrylate, butoxypolyethylene glycol mono (meth) acrylate, butoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, butoxy {polyethylene glycol (poly) butylene glycol} mono (Meth) acrylate, butoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate, and the like.

<Unsaturated carboxylic acid monomer (b)>
The unsaturated carboxylic acid monomer (b) is not particularly limited as long as it is a monomer having a polymerizable unsaturated group and a carboxyl group which is an adsorbing group and / or a structural portion of a salt thereof. An unsaturated monocarboxylic acid monomer (b-1) such as a (meth) acrylic acid monomer is preferred. Specifically, one or more of acrylic acid, methacrylic acid, crotonic acid, and these monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts can be used. Among these, (meth) acrylic acid and / or a salt thereof is preferable from the viewpoint of copolymerization.

Examples of the monovalent metal atom that constitutes the monovalent metal salt include lithium, sodium, and potassium. Examples of the divalent metal atom that constitutes the divalent metal salt include calcium and magnesium. . Examples of the organic amine group constituting the organic amine salt include alkanolamine groups such as monoethanolamine group, diethanolamine group and triethanolamine group; alkylamine groups such as monoethylamine group, diethylamine group and triethylamine group; ethylenediamine And polyamine groups such as a triethylenediamine group. When the monomer (b) is a salt, it is preferably an ammonium salt or a monovalent metal salt. A monovalent metal salt is more preferable, an ammonium salt, a sodium salt or a potassium salt is more preferable, and a sodium salt is particularly preferable.

In the copolymer (I), the structural ratio ((A) / (B)) of the structural unit (A) derived from the monomer (a) and the structural body (B) derived from the monomer (b) Is preferably 55 to 95/5 to 45 (mass ratio). More preferably, it is 70-90 / 10-30, and it becomes possible to exhibit the effect of this invention more fully by this. Thus, the structural ratio of the structural unit (A) derived from the unsaturated polyalkylene glycol monomer (a) and the structural unit (B) derived from the unsaturated carboxylic acid monomer (b) ((A) / The form in which (B)) is 70 to 90/10 to 30 (mass ratio) is one of the preferred forms of the present invention. More preferably, it is 75-85 / 15-25, Most preferably, it is 79-85 / 15-21, Most preferably, it is 80-85 / 15-20.
In particular, when one or more unsaturated monocarboxylic acid monomers (b-1) are used as the monomer (b), the structural unit (A) and the unsaturated monocarboxylic acid are used. The structural ratio ((A) / (B-1)) to the structural unit (B-1) derived from the acid monomer (b-1) is 70 to 95/5 to 30 (mass ratio). This makes it possible to exhibit the effects of the present invention more fully. More preferably, it is 75-90 / 10-25, More preferably, it is 79-85 / 15-21, Especially preferably, it is 80-85 / 15-20.

In this specification, when calculating the proportion of the structural unit (B) derived from the unsaturated carboxylic acid monomer (b), the structural unit (B) is a completely neutralized monomer (salt). It shall be calculated as a structural unit derived from. When calculating the ratio of the unsaturated carboxylic acid monomer (b), it is assumed that the monomer (b) is a completely neutralized monomer (salt). For example, when using acrylic acid as the monomer (b) and completely neutralizing with sodium hydroxide in the polymerization reaction, it is assumed that sodium acrylate is used as the monomer (b). Calculate. In the case where maleic acid is used as the monomer (b) and complete neutralization with sodium hydroxide in the polymerization reaction, disodium maleate is used as the monomer (b). ).

The unsaturated carboxylic acid monomer (b) also includes maleic acid, fumaric acid, itaconic acid, and unsaturated dicarboxylic acids such as monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts. It may be a system monomer (b-2), and one or more of these can be used. The salt is as described above. Among these unsaturated dicarboxylic acid monomers (b-2), maleic acid and / or a salt thereof is preferable from the viewpoint of copolymerization.

The copolymer (I) also includes a monomer (a), an unsaturated monocarboxylic acid monomer (b-1), and an unsaturated dicarboxylic acid monomer (b-2). A copolymer obtained by polymerizing the components is also suitable. That is, the copolymer is preferably a copolymer containing the structural unit (A), the structural unit (B-1), and the structural unit (B-2) derived from the unsaturated dicarboxylic acid monomer (b-2). . In this case, the constituent ratio of the constituent units ((A) / (B-1) / (B-2)) is preferably 55 to 85/10 to 30/5 to 15 (mass ratio). Thus, the unsaturated carboxylic acid monomer (b) is an unsaturated monocarboxylic acid monomer (b-1) and an unsaturated dicarboxylic acid monomer (b-2), and is unsaturated. The structural unit (A) derived from the polyalkylene glycol monomer (a), the structural unit (B-1) derived from the unsaturated monocarboxylic acid monomer (b-1), and the unsaturated dicarboxylic acid based single The structural ratio ((A) / (B-1) / (B-2)) to the structural unit (B-2) derived from the monomer (b-2) is 55 to 85/10 to 30/5 to 15 ( The mass ratio) is also one of the preferred embodiments of the present invention. More preferably, it is 60-85 / 10-25-25 / 5, More preferably, it is 65-80 / 15-25 / 5-10.

<Other monomers>
The monomer component may also be one or two unsaturated monoacrylate monomers (c) as monomers copolymerizable with the monomer (a) and the monomer (b). It may contain more than seeds. That is, the copolymer (I) may further contain a structural unit (C) derived from the unsaturated monocarboxylic acid ester monomer (c). By further including the structural unit (C) derived from the unsaturated monoacrylate monomer (c), fluidity can be expected to be maintained for a certain period of time.

As the unsaturated monoacrylate monomer (c), for example, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like are preferable. Among these, methyl acrylate, ethyl acrylate and / or butyl acrylate are more preferable, and butyl acrylate is still more preferable.

When the copolymer (I) further contains a structural unit (C) derived from the unsaturated monocarboxylic acid ester monomer (c), the structural unit (A), the structural unit (B), and the structural unit ( The component ratio ((A) / (B) / (C)) with C) is preferably 55 to 84/10 to 30/1 to 15 (mass ratio). Thus, the copolymer further contains a structural unit (C) derived from an unsaturated monocarboxylic acid ester monomer (c), and a structural unit derived from an unsaturated polyalkylene glycol monomer (a) (A ), The structural unit (B) derived from the unsaturated carboxylic acid monomer (b) and the structural unit (C) derived from the unsaturated monocarboxylic acid ester monomer (c) ((A ) / (B) / (C)) is also from 55 to 84/10 to 30/1 to 15 (mass ratio), which is also a preferred embodiment of the present invention. More preferably, it is 70-83 / 15-25 / 2-10.

The copolymer (I) may also contain structural units derived from one or more of other copolymerizable monomers. Such a structural unit is preferably 30% by mass or less in 100% by mass of all the structural units constituting the copolymer (I). More preferably, it is 20 mass% or less, More preferably, it is 10 mass% or less.

Examples of the other copolymerizable monomers include various diesters; diamides; half amides; (poly) alkylene glycols exemplified in International Publication No. 2014/010572 [0041] to [0042]. Di (meth) acrylates; polyfunctional (meth) acrylates; (poly) alkylene glycol dimaleates; unsaturated sulfonic acids and salts thereof; amides such as methyl (meth) acrylamide; vinyl aromatics; alkanediol mono (Meth) acrylates; dienes; unsaturated amides; unsaturated cyanides; unsaturated esters; unsaturated amines; divinyl aromatics; cyanurates;

The copolymerization reaction can be performed using a polymerization initiator, and can be performed by a method such as polymerization in a solvent or bulk polymerization. The amount of each monomer used in the copolymerization reaction is such that the proportion of each structural unit in the polymer is in the above-described range, taking into account the reaction rate during the copolymerization reaction of each monomer, It is preferable to set appropriately.

The polymerization in the solvent can be carried out batchwise or continuously. The solvent used in this case is water; lower alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol; benzene, toluene, xylene, cyclohexane, Aromatic or aliphatic hydrocarbons such as n-hexane; ester compounds such as ethyl acetate; ketone compounds such as acetone and methyl ethyl ketone are preferred. These may be used alone or in combination of two or more. From the solubility of the raw material monomer and the resulting copolymer (I), and convenience during use of the copolymer (I), it is selected from the group consisting of water and lower alcohols having 1 to 4 carbon atoms. It is preferable to use at least one selected from the above. In that case, methyl alcohol, ethyl alcohol, isopropyl alcohol and the like are particularly effective among the lower alcohols having 1 to 4 carbon atoms.

In the case of carrying out the aqueous solution polymerization, as a radical polymerization initiator, a water-soluble polymerization initiator, for example, a persulfate such as ammonium persulfate, sodium persulfate, potassium persulfate; hydrogen peroxide; 2,2'-azobis- Azoamidine compounds such as 2-methylpropionamidine hydrochloride, cyclic azoamidine compounds such as 2,2′-azobis-2- (2-imidazolin-2-yl) propane hydrochloride, and azonitriles such as 2-carbamoylazoisobutyronitrile Water-soluble azo initiators such as compounds are used. In this case, alkali metal sulfites such as sodium hydrogen sulfite, metabisulphite, sodium hypophosphite, Fe (B) salts such as molle salt, hydroxymethanesulfine Acid sodium dihydrate, hydroxylamine hydrochloride, thiourea, L-ascorbic acid (salt), erythorbium It can also be used in combination accelerator acid (salt) and the like.

For polymerization using lower alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, ester compounds or ketone compounds as solvents, peroxides such as benzoyl peroxide and lauroyl peroxide; hydroperoxides such as cumene hydroperoxide; azobis An azo compound such as isobutyronitrile is used as a polymerization initiator. In this case, an accelerator such as an amine compound can be used in combination. Furthermore, when a water-lower alcohol mixed solvent is used, it can be appropriately selected from the above-mentioned various polymerization initiators or combinations of polymerization initiators and accelerators. The polymerization temperature is appropriately determined depending on the solvent to be used and the polymerization initiator, but is usually 0 to 120 ° C.

The bulk polymerization uses a peroxide such as benzoyl peroxide or lauroyl peroxide as a polymerization initiator; a hydroperoxide such as cumene hydroperoxide; an azo compound such as azobisisobutyronitrile, and the like, at a temperature of 50 to 200 ° C. Done in

The method of charging each monomer into the reaction vessel is not particularly limited. The method of initially charging the entire amount into the reaction vessel at once, the method of dividing or continuously charging the entire amount into the reaction vessel, and the initial charging into the reaction vessel. Any method may be used in which the remainder is divided or continuously charged into the reaction vessel. Specific examples of a suitable charging method include the following methods (1) to (4).
(1) A method of continuously charging all of the monomers into the reaction vessel.
(2) A method in which all of the monomer (a) is initially charged into the reaction vessel and all other monomers are continuously charged into the reaction vessel.
(3) A method in which a part of the monomer (a) is initially charged into the reaction vessel, and the remainder of the monomer (a) and all other monomers are continuously charged into the reaction vessel.
(4) A part of the monomer (a) and a part of the other monomer are initially charged into the reaction vessel, and the remainder of the monomer (a) and the rest of the other monomer are respectively added to the reaction vessel. A method of splitting into several times alternately.
Furthermore, by changing the charging rate of each monomer into the reaction vessel during the reaction continuously or stepwise, the charging mass ratio of each monomer per unit time can be changed continuously or stepwise. You may make it synthesize | combine the mixture of the copolymer from which the ratio of each structural unit in a polymer differs in a polymerization reaction. The radical polymerization initiator may be charged into the reaction vessel from the beginning, may be dropped into the reaction vessel, or may be combined according to the purpose.

Further, a chain transfer agent can be used in combination for adjusting the molecular weight of the obtained copolymer (I). Chain transfer agents include mercaptoethanol, thioglycerol, thioglycolic acid, 3-mercaptopropionic acid, thiomalic acid, 2-mercaptoethanesulfonic acid and other thiol chain transfer agents; isopropyl alcohol and other secondary alcohols; phosphorous acid Hypophosphorous acid and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionic acid, metabisulfite and salts thereof (sodium sulfite, sodium hydrogen sulfite, dithione) Commonly used hydrophilic chain transfer agents such as lower oxides of sodium acid, sodium metabisulfite and the like and salts thereof can be used.

The copolymer (I) obtained as described above can be used as it is as a surface coating agent for hydraulic inorganic particles or pozzolanic active inorganic particles, but if necessary, the copolymer (I). May be used after neutralizing with an alkaline substance. As the alkaline substance, inorganic salts such as hydroxides or carbonates of monovalent metals or divalent metals; ammonia; organic amines are suitable. Further, after the reaction is completed, the concentration can be adjusted if necessary.

The weight average molecular weight (Mw) of the polycarboxylic acid-based copolymer is determined based on the binding property (adsorbability) to the hydraulic inorganic particles and the pozzolanic active inorganic particles, the aggregating action of these inorganic particles, and the resulting hydraulic composition. Considering the fluidity retention of the material, it is preferable that the weight average molecular weight (Mw) is 3000 to 500,000. More preferably, it is 5000-300,000, More preferably, it is 7000-200,000, Most preferably, it is 8000-100,000.
The weight average molecular weight of the polymer can be measured, for example, by GPC using polyethylene glycol as a standard substance under the GPC measurement condition (2) described above.

The functional hydraulic inorganic particles of the present invention preferably have a hydration degree of 0.1 or less. Thereby, hydraulic particles having high hydration activity can be obtained without impairing the hydration characteristics of the hydraulic inorganic particles, and the effects of the present invention can be more fully exhibited. More preferably, it is 0.07 or less, More preferably, it is 0.04 or less. The lower limit of the hydration degree is preferably 0. That is, the degree of hydration is preferably 0 to 0.1, more preferably 0 to 0.07, and still more preferably 0 to 0.04.

In the present specification, “degree of hydration” means a value measured by the following method.
The functional hydraulic inorganic particles are heated in an electric furnace, and the ignition loss rate at 450 ° C. (this is defined as (q)) and the ignition loss rate at 550 ° C. (this is defined as (r)) The difference (= q−r) is defined as the degree of hydration.
Here, the ignition loss rate at each temperature means the mass residual rate (mass%) after heating at each temperature.

(Hydraulic inorganic particles)
The present invention is also hydraulic particles containing the functional hydraulic inorganic particles of the present invention described above. Such hydraulic particles include, for example, hydraulic inorganic particles and / or pozzolanic active inorganic particles that do not correspond to the functional hydraulic inorganic particles as necessary together with the functional hydraulic inorganic particles. Is mentioned. In this case, the functional hydraulic inorganic particles are preferably 2% by mass or more with respect to the total amount of the inorganic particles of 100% by mass, in order to more fully express the effect of the functional hydraulic inorganic particles. Preferably it is 5 mass% or more, More preferably, it is 10 mass% or more, Most preferably, it is 20 mass% or more, More preferably, it is 30 mass% or more, Most preferably, it is 100 mass%.

[Method for producing functional hydraulic inorganic particles]
The functional hydraulic inorganic particles of the present invention are obtained by, for example, dispersing hydraulic inorganic particles (and, if necessary, pozzolanic active inorganic particles) in a solvent containing an organic dispersant, and then distilling off the solvent to obtain a powder. It can obtain by the manufacturing method including the process to convert. In addition, the said manufacturing method may further include the other process (for example, washing | cleaning process etc.) employ | adopted by a normal manufacturing means.

In the above production method, first, the hydraulic inorganic particles (and the pozzolanic active inorganic particles as required) are added to the organic dispersant and the solvent and dispersed in the solvent until a slurry is formed (also referred to as a dispersion step). The dispersing means is not particularly limited, and it is preferable to use a commonly used technique such as stirring (kneading). The hydraulic inorganic particles and the pozzolanic active inorganic particles are as described above.

The said solvent should just contain the organic type dispersing agent and the said inorganic particle can disperse | distribute. For example, it is preferable to contain an organic solvent or water. Thus, both the form in which the said solvent contains an organic solvent, and the form in which the said solvent contains water are preferable. Among these, the solvent preferably contains an organic solvent in order to control hydration of the hydraulic inorganic particles and the like.
In addition, when the said solvent contains water and an organic solvent, it is suitable that water is 50 mass% or less with respect to 100 mass% of the total amount of the organic solvent and water in the said solvent. Thereby, it becomes possible to control the hydration of the hydraulic inorganic particles. More preferably, it is 30 mass% or less, More preferably, it is 10 mass% or less, Especially preferably, it is 5 mass% or less, More preferably, it is 1 mass% or less, Most preferably, as a ratio of the water with respect to 100 mass% of the total amount of an organic solvent and water. It is most preferable that water is not substantially included, that is, when an organic solvent is used, water is not substantially included.

Examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, and glycerin; ethers such as tetrahydrofuran, diethyl ether, dioxane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether. Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate; aromatic hydrocarbons such as toluene, xylene and ethylbenzene Use one or more of chloroform, amides such as dimethylformaldehyde, etc. It can be. Preferably, alcohols, ethers, ketones, and esters are used, and alcohols or mixed solvents of alcohols and other organic solvents are more preferable.

In the dispersion step, the amount of the solvent is preferably an amount that contains the organic dispersant and that allows the dispersion of the hydraulic inorganic particles (and the pozzolanic active inorganic particles as required). Specifically, it is preferable to use 5 to 2000 parts by weight of the solvent with respect to 100 parts by weight of the hydraulic inorganic particles and / or the pozzolanic active inorganic particles. More preferably 10 parts by weight or more, still more preferably 14 parts by weight or more, more preferably 300 parts by weight or less, still more preferably 200 parts by weight or less, particularly preferably 100 parts by weight or less, and most preferably 50 parts by weight. It is as follows. If the amount of the solvent is small, the inorganic particles cannot be sufficiently dispersed and the inorganic particles cannot be prevented from agglomerating, so that the kneading time cannot be shortened. If the amount of the solvent is too large, a large amount of energy and time are required for distilling off the solvent, which is not economical.

The amount of the solvent is preferably 500 to 100,000 parts by weight with respect to 100 parts by weight of the organic dispersant in the obtained functional hydraulic inorganic particles. More preferably 1000 parts by weight or more, further preferably 1400 parts by weight or more, particularly preferably 2000 parts by weight or more, most preferably 2300 parts by weight or more, more preferably 50000 parts by weight or less, still more preferably 30000 parts by weight. The amount is particularly preferably 20000 parts by weight or less.

The amount of the organic dispersant used may be appropriately determined in consideration of the physical properties of the hydraulic inorganic particles and the pozzolanic active inorganic particles, the dispersibility of the obtained functional hydraulic inorganic particles, etc. The amount is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the inorganic particles and / or the pozzolanic active inorganic particles. Within this range, the hydraulic inorganic particles and pozzolanic active inorganic particles can be more fully and efficiently coated, and the dispersibility of the resulting functional hydraulic inorganic particles can be more fully exhibited. . More preferably, it is 0.01-5 weight part, More preferably, it is 0.05-4 weight part, Especially preferably, it is 0.05-3 weight part.

In the said manufacturing method, after the said dispersion | distribution process, a solvent is distilled off and pulverization is performed (it is also called a pulverization process). The means for distilling off the solvent is not particularly limited. For example, the solvent may be volatilized by heating or drying, and it is also suitable to distill off the solvent under reduced pressure. The powdering means is not particularly limited, and pulverization may be performed using a raw material pulverizer or the like.
In addition, it is suitable to adjust the particle diameter of the functional hydraulic inorganic particle obtained using a sieve (for example, JIS test sieve etc.) after a powdering process.

(Hydraulic composition)
The functional hydraulic inorganic particles of the present invention can be mixed with water to give a hydraulic composition. Such a hydraulic composition containing the functional hydraulic inorganic particles and water is one of the preferred embodiments of the present invention. Examples of the hydraulic composition include cement paste, mortar, concrete, plaster and the like.

The hydraulic composition may contain aggregates such as fine aggregate (sand, etc.) and coarse aggregate (crushed stone, etc.) as necessary. Specifically, for example, gravel, crushed stone, granulated slag, recycled aggregate, etc., siliceous, clay, zircon, high alumina, silicon carbide, graphite, chrome, chromic, magnesia Fireproof aggregates such as can also be used.

The hydraulic composition may also contain a dispersant as required. The hydraulic composition containing the functional hydraulic inorganic particles of the present invention can exhibit sufficient fluidity even without a separate dispersant, but may further contain a dispersant as necessary. As the dispersant, one or more commonly used ones can be used. Specific examples are as described above.

The hydraulic composition may further contain normal hydraulic inorganic particles and / or pozzolanic active inorganic particles in addition to the functional hydraulic inorganic particles, if necessary. In this case, the functional hydraulic inorganic particles are preferably 2% by mass or more with respect to the total amount of the inorganic particles of 100% by mass, in order to more fully express the effect of the functional hydraulic inorganic particles. Preferably it is 5 mass% or more. More preferably, it is 10 mass% or more, More preferably, it is 30 mass% or more, Especially preferably, it is 50 mass% or more, More preferably, it is 80 mass% or more, Most preferably, it is 100 mass%.

In the hydraulic composition, the unit water amount per 1 m ^3, the total amount of hydraulic particles (referred to as B) (the amount used B), and the water / B ratio (mass ratio) are unit water amount = 100 to 185 kg / m ^3, use B amount = 250~800kg / ^{m 3,} it is preferable that the water / B ratio = 0.1 to 0.7. More preferably, the unit water amount is 120 to 175 kg / m ³ , the used B amount is 270 to 800 kg / m ³ , and the water / B ratio is 0.1 to 0.65, and can be used widely from poor blends to rich blends. However, it is also very effective for high-strength concrete having a unit water amount of 500 kg / m ³ or more and ultrahigh-strength concrete having 900 kg / m ³ or more. Further, in the present invention, a hydraulic composition having a low water / B ratio has an effect that the kneading time is fast and excellent fluidity can be exhibited. It can be confirmed more sufficiently when the / B ratio is 0.5 or less. The water / B ratio is more preferably 0.4 or less, still more preferably 0.35 or less, still more preferably 0.3 or less, particularly preferably 0.25 or less, and most preferably 0.2 or less.

The hydraulic composition is also effective, for example, for ready-mixed concrete, concrete for secondary concrete products (precast concrete), centrifugal molded concrete, vibration compacted concrete, steam-cured concrete, shotcrete, etc. High fluidity of medium fluidity concrete (concrete with slump value of 22-25cm), high fluidity concrete (concrete with slump value of 25cm or more, slump flow value of 50-70cm), self-filling concrete, self-leveling material, etc. It is also effective for required mortar and concrete.

The hydraulic composition may further include one or more of those usually used as a cement additive (material). For example, water-soluble polymeric substances exemplified in International Publication No. 2014/010572 [0066] to [0072]; polymer emulsions; retarders; early strengthening agents / accelerators; mineral oil-based antifoaming agents; Fatty acid defoamer; Fatty acid ester defoamer; Oxyalkylene defoamer; Alcohol defoamer; Amide defoamer; Phosphate ester defoamer; Metal soap defoamer; Silicone Antifoaming agent; AE agent; other surfactants; waterproofing agent; rust preventive agent; crack reducing agent; expansion agent; cement wetting agent; thickener; separation reducing agent; A self-leveling agent; a rust preventive agent; a colorant; an antifungal agent;

[Method for producing hydraulic composition]
The hydraulic composition using the functional hydraulic inorganic particles includes, for example, a step of mixing the functional hydraulic inorganic particles, water, and other components added as necessary. And other steps are not particularly limited. In the present invention, by using the functional hydraulic inorganic particles, a hydraulic composition having high fluidity can be easily obtained in a short time. Therefore, a method for producing such a hydraulic composition includes water It is extremely useful in the technical field where a hard composition is used.
The technique of the present invention can also be applied to inorganic particles that are cured by reaction with water such as gypsum, and is within the scope of the invention.

Since the functional hydraulic inorganic particles of the present invention are configured as described above, the kneading time can be remarkably shortened, and the productivity of the hydraulic composition can be greatly improved. Moreover, since the hydraulic composition using such functional hydraulic inorganic particles is extremely excellent in fluidity, it greatly contributes to the civil engineering / construction field and the like where concrete is handled.

In Test Example 1, the time when the cement and water are added is 0 second (s), and the state of the hydraulic composition until the stirring is stopped is taken every 20 to 60 seconds (s). In Test Example 1, the time when the cement and water were added was set to 0 second (s), and the power consumption of the Hobart mixer was measured over time. In Comparative Test Example 2, the time when the cement and water were added was set to 0 second (s), and the state of the hydraulic composition until the stirring was stopped was photographed over time. In comparative test example 2, it is the graph which measured the power consumption of a Hobart mixer with time, making cement and water injection time into 0 second (s).

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. In addition, the weight average molecular weight of the polymer obtained in the preparation example was measured by the GPC measurement method described above, and the particle size of the particles and the relative surface concentration of C _1s with respect to the surface Si _2p and Ca _2p were determined by the method described above. Measured with Further, in the following production examples and test examples, kneading was performed at a first speed (139 rpm) using a mixer manufactured by Hobert (N-50; hereinafter also referred to as a “Hobert mixer”).
The flow value and kneading time of the cement paste obtained in the test example were measured as follows.

<Measurement of flow value>
The prepared paste was packed in a hollow cylindrical container having a diameter of 55 mm and a height of 50 mm placed on a horizontal table, and then the hollow cylindrical container was lifted vertically, and the diameter of the paste spread on the table was adjusted to 2 The direction was measured, and this average value was taken as the flow value.

<Measuring method of kneading time>
The time until the paste is kneaded can be confirmed visually as shown in FIGS. 1 and 3, but the smart power outlet is a mixer manufactured by Hobert (N-50; hereinafter also referred to as a mixer or a Hobart mixer). The kneading time can also be calculated from the change in the effective power consumption of the mixer (sampling rate: measured at 1 time / second), which is in good agreement with visual confirmation.
By the time kneading is finished, the load on the mixer once increases and the effective power consumption increases. Thereafter, as the paste becomes softer, the effective power consumption decreases and settles to a constant value. Observing the effective power consumption of the Hobert mixer over time changes as shown in FIGS. When the maximum and becomes the time to start kneading after 3 seconds after the X _0, active power draw from past maximum peak follows the decay curve. The attenuation curve can be approximated by the following equation:
Y ₀ + Z ₀ × EXP (− (time−X ₀ )) / τ
(In the formula, X ₀ indicates the time when the effective power consumption becomes maximum after 3 seconds from the start of kneading. Y ₀ and Z ₀ indicate constants. Τ is from the point where the effective power consumption becomes maximum. (The relaxation time is indicated. EXP represents an exponential function with e as the base.)
Using the above formulas from the attenuation curves of FIGS. 2 and 4, Y ₀ , Z ₀ , and τ can be changed to draw an approximate curve of actual measurement values. The sum of τ and X ₀ of the obtained approximation curve calculated as the kneading time.

Preparation Example 1 (Preparation of polycarboxylic acid dispersant (1))
A glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube and a reflux condenser was charged with 350 g of ion-exchanged water, and the reactor was purged with nitrogen under stirring, and the temperature was raised to 80 ° C. Next, an aqueous solution prepared by dissolving 315.2 g of methoxypolyethylene glycol methacrylate (addition mole number of ethylene oxide: 23 mol), 83.7 g of methacrylic acid, and 8.5 g of 3-mercaptopropionic acid with 171.4 g of ion-exchanged water for 3 hours. It was dripped over. At the same time, an aqueous solution in which 6.6 g of sodium persulfate was dissolved in 63.5 g of ion-exchanged water was dropped over 4 hours. After completion of the dropping, stirring was continued at 80 ° C. for 1 hour to complete the polymerization reaction, and an aqueous solution of a polycarboxylic acid copolymer having a weight average molecular weight (Mw) of 9500 was obtained. A sodium hydroxide aqueous solution was added to the obtained polycarboxylic acid copolymer aqueous solution, neutralized to pH 7, and then dried under reduced pressure (50 mmHg) at 50 ° C. to prepare a waxy polycarboxylic acid copolymer. . This is referred to as a polycarboxylic acid dispersant (1).

Preparation Example 2 (Preparation of polycarboxylic acid dispersant (2))
In a glass reaction vessel equipped with a thermometer, stirrer, dropping funnel, nitrogen inlet tube and reflux condenser, 209.0 g of ion-exchanged water and 3-methyl-3-buten-1-ol were averaged with ethylene oxide (EO). 444.8 g of unsaturated polyalkylene glycol ether (IPN-50) added with 50 mol was charged, and the reactor was purged with nitrogen under stirring, and the temperature was raised to 60 ° C. Next, an aqueous solution obtained by diluting 85.2 g of acrylic acid with 154.3 g of ion-exchanged water was dropped over 5 hours. At the same time, an aqueous solution in which 0.94 g of L-ascorbic acid and 8.0 g of 3-mercaptopropionic acid were dissolved in 48.9 g of ion-exchanged water, and an aqueous solution in which 4.9 g of ammonium persulfate was dissolved in 44.0 g of ion-exchanged water. It was dripped over 5 hours. After completion of the dropping, stirring was continued at 60 ° C. for 1 hour to complete the polymerization reaction, and an aqueous solution of a polycarboxylic acid copolymer having a weight average molecular weight (Mw) of 10,000 was obtained. A sodium hydroxide aqueous solution was added to the obtained polycarboxylic acid copolymer aqueous solution, neutralized to pH 7, dried at 50 ° C. under reduced pressure (50 mmHg), pulverized, and 70 mesh in the JIS test sieve mesh conversion table. To a powdery polycarboxylic acid-based copolymer passing through This is referred to as a polycarboxylic acid dispersant (2).

Preparation Example 3 (Preparation of phosphate dispersant (1))
In a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser, 200 g of ion-exchanged water was charged, the reaction apparatus was purged with nitrogen, and the temperature was raised to 80 ° C. Next, 65.9 g of methoxypolyethylene glycol methacrylate (addition mole number of ethylene oxide: 23 mol), mono (2-hydroxyethyl) methacrylic acid phosphate and di-[(2-hydroxyethyl) methacrylic acid] ester An aqueous solution prepared by dissolving 40.6 g of a mixture (Light Ester P-1M, manufactured by Kyoeisha Chemical Co., Ltd.) and 1.7 g of 3-mercaptopropionic acid with 97.0 g of ion-exchanged water was added dropwise over 1.5 hours. At the same time, an aqueous solution in which 4.7 g of ammonium persulfate was dissolved in 45 g of ion-exchanged water was added dropwise over 1.5 hours. After completion of the dropping, stirring was continued at 80 ° C. for 1 hour, and then an aqueous solution in which 2.4 g of ammonium persulfate was dissolved in 15 g of ion-exchanged water was dropped over 1 hour. After completion of the dropwise addition, stirring was continued at 80 ° C. for 1.5 hours, and then the polymerization reaction was terminated to obtain a phosphoric acid copolymer aqueous solution having a weight average molecular weight (Mw) of 20000. A sodium hydroxide aqueous solution was added to the obtained phosphoric acid copolymer aqueous solution, neutralized to pH 7, dried under reduced pressure (50 mmHg) at 50 ° C., pulverized, and 70 mesh in the JIS test sieve mesh conversion table was obtained. A powdered phosphoric acid copolymer was prepared. This is referred to as a phosphoric acid dispersant (1).

Preparation Example 4 (Preparation of phosphate dispersant (2))
In a glass reaction vessel equipped with a thermometer, stirrer, dropping funnel, nitrogen inlet tube and reflux condenser, 13.8 g of ion-exchanged water, 250.0 g of polyethylene glycol (added moles of ethylene oxide: 120 mol) monophenyl ether Then, 29.7 g of phenylphosphonic acid and 9.2 g of sulfuric acid were charged, the reactor was purged with nitrogen under stirring, and the temperature was raised to 100 ° C. Next, an aqueous solution obtained by diluting 4.23 g of formaldehyde with 7.86 g of ion-exchanged water was added dropwise over 1 hour. After completion of the dropping, stirring was continued at 100 ° C. for 1 hour to complete the polycondensation reaction, and an aqueous solution of a phosphoric acid-based condensate having a weight average molecular weight (Mw) of 25000 was obtained. Sodium hydroxide aqueous solution is added to the obtained phosphoric acid-based condensate aqueous solution, neutralized to pH 7, dried at 50 ° C. under reduced pressure (50 mmHg), pulverized, and passed through 70 mesh in the JIS test sieve mesh conversion table. To a powdered phosphoric acid condensate. This is referred to as a phosphoric acid dispersant (2).

Production Example 1 (Production of surface-coated inorganic particles (1))
700 g of silica fume cement manufactured by Ube Mitsubishi Cement Co., Ltd. was charged into a Hobart mixer (N-50), and 3.5 g of polycarboxylic acid-based dispersant (1) obtained in Preparation Example 1 (0.5 mass relative to the solid content of cement). %) 108.5 g of the dissolved aqueous solution (105 g of water, water / cement mass ratio = 0.15) was put into the mixer. After the addition, the mixture was stirred at the first speed for 300 seconds, and then the stirring was stopped, and the paste adhering to the container wall surface was scraped off over 30 seconds. After 330 seconds from the introduction of the aqueous solution, the speed was switched to the second speed, stirring was resumed, stirring was continued for 90 seconds, and stirring was stopped. The obtained paste was transferred to a vat and dried under reduced pressure (50 mmHg) at 50 ° C. to completely distill off water (partially remained as bound water). Silica fume cement (surface-coated inorganic particles) whose surface is coated with a polycarboxylic acid dispersant (1) after drying, pulverizing, adjusting the particle size using a sieve corresponding to 70 mesh in the JIS test sieve mesh conversion table (Also referred to as (1)).

Production Example 2 (Production of surface-coated inorganic particles (2))
700 g of silica fume cement manufactured by Ube Mitsubishi Cement Co., Ltd. was charged into a Hobart mixer (N-50), and 4.2 g of polycarboxylic acid-based dispersant (2) obtained in Preparation Example 2 (0.6 mass based on cement solids) %) 109.2 g of the dissolved aqueous solution (105 g of water, water / cement mass ratio = 0.15) was put into the mixer. After the addition, the mixture was stirred at the first speed for 300 seconds, and then the stirring was stopped, and the paste adhering to the container wall surface was scraped off over 30 seconds. After 330 seconds from the introduction of the aqueous solution, the speed was switched to the second speed, stirring was resumed, stirring was continued for 90 seconds, and stirring was stopped. The obtained paste was transferred to a vat and dried under reduced pressure (50 mmHg) at 50 ° C. to completely distill off water (partially remained as bound water). Silica fume cement (surface-coated inorganic particles) whose surface is coated with a polycarboxylic acid dispersant (2) after drying, pulverizing, adjusting the particle size using a sieve corresponding to 70 mesh in the JIS test sieve mesh conversion table (Also referred to as (2)).

Production Example 3 (Production of surface-coated inorganic particles (3))
14 g of sulfonic acid dispersant (Mighty 150, manufactured by Kao Co., Ltd.), which was put into a Hobart mixer (N-50) and 700 g of silica fume cement made by Ube Mitsubishi Cement Co., Ltd., dried and pulverized, was 2 (0.0% by mass) 119 g of the dissolved aqueous solution (105 g of water, water / cement mass ratio = 0.15) was charged into the mixer. After the addition, the mixture was stirred at the first speed for 300 seconds, and then the stirring was stopped, and the paste adhering to the container wall surface was scraped off over 30 seconds. After 330 seconds from the introduction of the aqueous solution, the speed was switched to the second speed, stirring was resumed, stirring was continued for 90 seconds, and stirring was stopped. The obtained paste was transferred to a vat and dried under reduced pressure (50 mmHg) at 50 ° C. to completely distill off water (partially remained as bound water). After drying, pulverization is performed, the particle size is adjusted using a sieve corresponding to 70 mesh in the JIS test sieve mesh conversion table, and the silica fume cement (surface-coated inorganic particles (3) is coated with a sulfonic acid dispersant). Obtained).

Production Example 4 (Production of surface-coated inorganic particles (4))
700 g of silica fume cement made by Ube-Mitsubishi Cement Co., Ltd. is charged into a Hobart mixer (N-50), and 7 g of the phosphoric acid dispersant (1) obtained in Preparation Example 3 is dissolved (1.0% by mass with respect to the solid content of cement). 112 g of the aqueous solution (105 g of water, water / cement mass ratio = 0.15) was put into the mixer. After the addition, the mixture was stirred at the first speed for 300 seconds, and then the stirring was stopped, and the paste adhering to the container wall surface was scraped off over 30 seconds. After 330 seconds from the introduction of the aqueous solution, the speed was switched to the second speed, stirring was resumed, stirring was continued for 90 seconds, and stirring was stopped. The obtained paste was transferred to a vat and dried under reduced pressure (50 mmHg) at 50 ° C. to completely distill off water (partially remained as bound water). After drying, pulverization is performed, the particle size is adjusted using a sieve corresponding to 70 mesh in the JIS test sieve mesh conversion table, and the silica fume cement (surface-coated inorganic particles (surface-coated inorganic particles) whose surface is coated with a phosphoric acid dispersant (1) 4)) was obtained.

Production Example 5 (Production of surface-coated inorganic particles (5))
700 g of silica fume cement manufactured by Ube Mitsubishi Cement Co., Ltd. was charged into a Hobart mixer (N-50), and 3.5 g of phosphoric acid dispersant (2) obtained in Preparation Example 4 (0.5% by mass with respect to the solid content of the cement). ) 108.5 g of the dissolved aqueous solution (105 g of water, water / cement mass ratio = 0.15) was put into the mixer. After the addition, the mixture was stirred at the first speed for 300 seconds, and then the stirring was stopped, and the paste adhering to the container wall surface was scraped off over 30 seconds. After 330 seconds from the introduction of the aqueous solution, the speed was switched to the second speed, stirring was resumed, stirring was continued for 90 seconds, and stirring was stopped. The obtained paste was transferred to a vat and dried under reduced pressure (50 mmHg) at 50 ° C. to completely distill off water (partially remained as bound water). After drying, pulverization is performed, the particle size is adjusted using a sieve corresponding to 70 mesh in the JIS test sieve mesh conversion table, and the surface is coated with a silica fume cement (surface-coated inorganic particles (surface-coated inorganic particles ( 5)) was obtained.

For the surface-coated silica fume cement (surface-coated inorganic particles (1)) obtained in Production Example 1, the relative surface concentration of C _1s with respect to Si _2p and Ca _2p on the particle surface was measured by XPS. Next, the cement product was weighed to the fourth decimal place (about 5 g) using a precision balance in the crucible. A crucible containing a weighed silica fume cement was placed in an electric furnace (ADVANTEC, KM-600), and heated at 150 ° C. in a nitrogen atmosphere (flow rate: 2 L / min) for 2 hours. Two hours later, the crucible is taken out from the electric furnace, allowed to cool to room temperature in a desiccator, and the silica fume cement is weighed to the fourth decimal place with a precision balance and heated from the ratio of the charged amount and the remaining amount. The residual ratio (p) of was measured. Subsequently, the same crucible was put into the electric furnace again and heated at 450 ° C. in a nitrogen atmosphere (flow rate 2 L / min) for 2 hours. After 2 hours, the mixture was allowed to cool in the desiccator, and the residual rate (q) after heating at 450 ° C. was measured. From the difference between the residual rate (p) at 150 ° C. and the residual rate (q) at 450 ° C., the content (= p−q) of the organic dispersant in the silica fume cement was calculated.
Subsequently, the same crucible was put into the electric furnace again and heated at 550 ° C. in a nitrogen atmosphere (flow rate 2 L / min) for 2 hours. About the obtained cement, the relative surface concentration of C _1s with respect to Si _2p and Ca _2p on the particle surface was measured by XPS. From the obtained results, the relative surface concentration of C relative to Si and Ca per unit amount of organic dispersant was calculated. The results are shown in Table 1.

Test example 1
500 g of the silica fume cement (surface-coated inorganic particles (1)) obtained in Production Example 1 was charged into a Hobart mixer (N-50), and 75 g of water was charged into the mixer (water / cement mass ratio = 0.15). After the addition, the mixture was stirred at the first speed for 300 seconds, and then the stirring was stopped, and the paste adhering to the container wall surface was scraped off over 30 seconds. After 330 seconds from the addition of water, stirring was resumed at the second speed and stirring was continued for 90 seconds. Table 2 shows the kneading time calculated from the transition of the power consumption of the mixer using a smart power outlet (FX-5204PS: manufactured by Fujitsu Limited) with the cement and water being charged at 0 seconds. The results of measuring the flow value of the obtained paste are shown in Table 2.

Next, 500 g of the silica fume cement (surface-coated inorganic particles (1)) obtained in Production Example 1 was heated at 550 ° C. for 3 hours in an electric furnace (KM-600 manufactured by ADVANTEC), and then cooled to 20 ° C. Was put into a Hobart mixer (N-50), and 75 g of water was put into the mixer (water / cement mass ratio = 0.15). After the addition, the mixture was stirred at the first speed for 300 seconds, and then the stirring was stopped, and the paste adhering to the container wall surface was scraped off over 30 seconds. After 330 seconds from the addition of water, stirring was resumed at the second speed and stirring was continued for 90 seconds. The flow value of the paste thus obtained was measured. The results are shown in Table 2 in the “Paste flow value after ignition loss” column.

Test Examples 2-5
Kneading time in the same manner as in Test Example 1 except that the silica fume cement (surface-coated inorganic particles (2) to (5)) obtained in Production Examples 2 to 5 was used instead of the surface-coated inorganic particles (1). And the flow value was measured. The results are shown in Table 2.

Comparative Test Example 1
500 g of silica fume cement manufactured by Ube Mitsubishi Cement Co., Ltd. was charged into a Hobart mixer, and 2.5 g (0.5% by mass with respect to the solid content of the cement) of the polycarboxylic acid-based dispersant (1) obtained in Preparation Example 1 was dissolved. 77.5 g of aqueous solution (75 g of water, water / cement mass ratio = 0.15) was put into the mixer. After the addition, a cement paste was prepared in the same manner as in Test Example 1. Table 2 shows the kneading time calculated from the transition of the power consumption of the mixer using a smart power outlet (FX-5204PS: manufactured by Fujitsu Limited) with the cement and water being charged at 0 seconds. In addition, Table 2 shows the result of measuring the flow value of the obtained paste.

Next, 500 g of silica fume cement manufactured by Ube Mitsubishi Cement Co., Ltd. was heated at 550 ° C. for 3 hours in an electric furnace (KM-600 manufactured by ADVANTEC Co., Ltd.), and then the cement cooled to 20 ° C. was put into a Hobart mixer (N-50). 77.5 g (75 g of water, water / cement mass ratio = 0.15) of an aqueous solution prepared by dissolving 2.5 g of polycarboxylic acid dispersant (1) (0.5% by mass with respect to the solid content of cement) Was put into the mixer. After the addition, a cement paste was prepared in the same manner as in Test Example 1. The flow value was measured for this paste. The results are shown in Table 2 in the “Paste flow value after ignition loss” column.

Comparative test example 2
Silica fume cement (500 g) manufactured by Ube Mitsubishi Cement Co., Ltd. was charged into a Hobart mixer, and 3.0 g (0.6% by mass with respect to the solid content of cement) of polycarboxylic acid-based dispersant (2) obtained in Preparation Example 2 was dissolved. 78.0 g of aqueous solution (75 g of water, water / cement mass ratio = 0.15) was put into the mixer. After the addition, a cement paste was prepared in the same manner as in Test Example 1. Table 2 shows the kneading time calculated from the transition of the power consumption of the mixer using a smart power outlet (FX-5204PS: manufactured by Fujitsu Limited) with the cement and water being charged at 0 seconds. In addition, Table 2 shows the result of measuring the flow value of the obtained paste.

Next, 500 g of silica fume cement manufactured by Ube-Mitsubishi Cement Co., Ltd. was heated at 550 ° C. for 3 hours in an electric furnace (ADVANTEC Co., Ltd. KM-600), and the cement cooled to 20 ° C. was put into a Hobart mixer (N-50). And 78.0 g of an aqueous solution in which 3.0 g (0.6% by mass with respect to the solid content of the cement) of the polycarboxylic acid-based dispersant (2) is dissolved (75 g of water, water / cement mass ratio = 0.15). Was put into the mixer. After the addition, a cement paste was prepared in the same manner as in Test Example 1. The flow value was measured for this paste. The results are shown in Table 2 in the “Paste flow value after ignition loss” column.

Comparative test example 3
Silica fume cement (500 g) manufactured by Ube Mitsubishi Cement Co., Ltd. was charged into a Hobart mixer (N-50), and 10 g of polycarboxylic acid-based dispersant (2) obtained in Preparation Example 2 (2.0% by mass with respect to the solid content of cement) 85 g of the dissolved aqueous solution (75 g of water, water / cement mass ratio = 0.15) was put into the mixer. After the addition, a cement paste was prepared in the same manner as in Test Example 1. Table 2 shows the kneading time calculated from the transition of the power consumption of the mixer using a smart power outlet (FX-5204PS: manufactured by Fujitsu Limited) with the cement and water being charged at 0 seconds. The results of measuring the flow value of the obtained paste are shown in Table 2.

Next, 500 g of silica fume cement manufactured by Ube-Mitsubishi Cement Co., Ltd. was heated at 550 ° C. for 3 hours in an electric furnace (ADVANTEC Co., Ltd. KM-600), and the cement cooled to 20 ° C. was put into a Hobart mixer (N-50). Then, 85 g of aqueous solution (75 g of water, water / cement mass ratio = 0.15) in which 10 g of polycarboxylic acid dispersant (2) (2.0% by mass with respect to the solid content of cement) is dissolved is placed in the mixer. I put it in. After the addition, a cement paste was prepared in the same manner as in Test Example 1. The flow value was measured for this paste. The results are shown in Table 2 in the “Paste flow value after ignition loss” column.

Comparative Test Example 4
4.2 g of powdered polycarboxylic acid-based dispersant (2) obtained in Preparation Example 2 (0.6% by mass with respect to cement solids) is mixed with 700 g of silica fume cement manufactured by Ube Mitsubishi Cement Co., Ltd. A premix cement containing a polycarboxylic acid dispersant (2) was obtained. 500 g of this premix cement was put into a Hobart mixer (N-50), and 75 g of water was put into the mixer (water / cement mass ratio = 0.15). After the addition, a cement paste was prepared in the same manner as in Test Example 1. Table 2 shows the kneading time calculated from the transition of power consumption of the mixer using a smart power outlet (FX-5204PS: manufactured by Fujitsu) with 0 seconds for cement and water addition and 0 seconds for cement and water addition. It was described in. The results of measuring the flow value of the obtained paste are shown in Table 2.

Next, 700 g of silica fume cement manufactured by Ube Mitsubishi Cement Co., Ltd. was heated at 550 ° C. for 3 hours in an electric furnace (AD-VANTEC KM-600). This was mixed with 4.2 g of powdery polycarboxylic acid-based dispersant (2) (0.6% by mass based on the solid content of cement) to obtain a premix cement. 500 g of this premix cement was put into a Hobart mixer (N-50), and 75 g of water was put into the mixer (water / cement mass ratio = 0.15). After the addition, a cement paste was prepared in the same manner as in Test Example 1. The flow value was measured for this paste. The results are shown in Table 2 in the “Paste flow value after ignition loss” column.

Comparative Test Example 5
Silica fume cement (500 g) manufactured by Ube Mitsubishi Cement Co., Ltd. was put into a Hobart mixer (N-50), dried and pulverized into 10 g of sulfonic acid-based dispersant (Mighty 150: manufactured by Kao Corporation) (2 per cement solids). 0.0 mass%) dissolved aqueous solution 85 g (75 g of water, water / cement mass ratio = 0.15) was put into the mixer. After the addition, a cement paste was prepared in the same manner as in Test Example 1. Table 2 shows the kneading time calculated from the transition of the power consumption of the mixer using a smart power outlet (FX-5204PS: manufactured by Fujitsu Limited) with the cement and water being charged at 0 seconds. In addition, Table 2 shows the result of measuring the flow value of the obtained paste.

Next, 500 g of silica fume cement manufactured by Ube-Mitsubishi Cement Co., Ltd. was heated at 550 ° C. for 3 hours in an electric furnace (ADVANTEC Co., Ltd. KM-600), and the cement cooled to 20 ° C. was put into a Hobart mixer (N-50). 85 g of an aqueous solution in which 10 g (2.0% by mass with respect to cement solids) of a sulfonic acid dispersant (Mighty 150: manufactured by Kao Corporation), which has been dried and powdered, is dissolved (75 g of water, water / cement) Mass ratio = 0.15) was put into the mixer. After the addition, a cement paste was prepared in the same manner as in Test Example 1. The flow value was measured for this paste. The results are shown in Table 2 in the “Paste flow value after ignition loss” column.

Comparative Test Example 6
14 g of sulfonic acid dispersant (Mighty 150: manufactured by Kao Corporation) powdered by drying was mixed with 700 g of silica fume cement manufactured by Ube Mitsubishi Cement Co., Ltd., and powdered. A premix cement containing a sulfonic acid dispersant was obtained. 500 g of this premix cement was put into a Hobart mixer (N-50), and 75 g of water was put into the mixer (water / cement mass ratio = 0.15). After the addition, a cement paste was prepared in the same manner as in Test Example 1. Table 2 shows the kneading time calculated from the transition of power consumption of the mixer using a smart power outlet (FX-5204PS: manufactured by Fujitsu) with 0 seconds for cement and water addition and 0 seconds for cement and water addition. It was described in. The results of measuring the flow value of the obtained paste are shown in Table 2.

Next, 700 g of silica fume cement manufactured by Ube Mitsubishi Cement Co., Ltd. was heated at 550 ° C. for 3 hours in an electric furnace (AD-VANTEC KM-600). This was mixed with 14 g (2.0% by mass with respect to cement solid content) of a sulfonic acid-based dispersant (Mighty 150, manufactured by Kao Corporation) that was dried and powdered to obtain a premix cement. 500 g of this premix cement was put into a Hobart mixer (N-50), and 75 g of water was put into the mixer (water / cement mass ratio = 0.15). After the addition, a cement paste was prepared in the same manner as in Test Example 1. The flow value was measured for this paste. The results are shown in Table 2 in the “Paste flow value after ignition loss” column.

The surface-coated inorganic particles obtained in Production Examples 1 to 5 satisfy the conditions (I) and (II) of the present invention. That is, it corresponds to the functional hydraulic inorganic particles of the present invention.
On the other hand, since the cements obtained in Comparative Test Examples 1 to 3 and 5 do not satisfy the condition (I), the cement particles used here do not have the ability to impart sufficient fluidity to the hydraulic composition. (Or low). Therefore, it was indispensable to add a dispersant to obtain a paste having fluidity. The cement obtained in Comparative Test Examples 4 and 6 was obtained by previously mixing a powdered dispersant with cement or the like, but the kneading time is long and the productivity is not good. Similar results can be read in Comparative Test Example 5.
As mentioned above, in order to obtain the hydraulic composition which can shorten kneading time remarkably and is excellent in fluidity, it is necessary to contain hydraulic inorganic particles and to satisfy conditions (I) and (II). I understood.

1 and 3 confirmed the following.
In Test Example 1, agglomeration of inorganic particles did not occur immediately after water was added to the surface-coated inorganic particles (1). Since an aggregate of inorganic particles was not constructed, water quickly spread over the inorganic particles and reached an equilibrium state between dispersion and aggregation in a short time (90 seconds) (see FIG. 1). On the other hand, in Comparative Test Example 2, as shown in FIG. 3, immediately after the water containing the dispersant is added, the inorganic particles instantly aggregate and the water containing the dispersant is constrained in the aggregate. It took a long time until it became lumpy and dispersion and aggregation reached equilibrium.

In Test Examples 1 to 5, after the solid surface-coated inorganic particles were obtained in Production Examples 1 to 5, water was added to prepare a paste. In general, since inorganic particles such as cement particles are circulated in a solid state, the time required to obtain the particles (solid surface-coated inorganic particles) in a state of being circulated is not included in the kneading time. . The surface-coated inorganic particles of the present invention have a particularly remarkable effect in that the production time for obtaining a hydraulic composition can be greatly shortened only by using this.

Claims (3)

Including hydraulic inorganic particles and organic dispersant ,
The hydraulic inorganic particles are at least one selected from the group consisting of cement and blast furnace slag,
The hydraulic inorganic particles are partially or entirely coated with an organic dispersant, and the organic dispersant is a group consisting of a sulfonic acid dispersant, a phosphoric acid dispersant, and a polycarboxylic acid dispersant. At least one selected from
And the functional hydraulic inorganic particle characterized by satisfying the following conditions (I) and (II).
(I) Paste prepared in the same manner after heating the functional hydraulic inorganic particles at 550 ° C. at a flow value (P0) of the paste having an amount of water of 15 parts by mass with respect to 100 parts by mass of the functional hydraulic inorganic particles. the ratio of the flow value (P1) of (P0 / P1) is state, and are 1.5 or more,
The flow value of the paste was determined by filling the paste in a hollow cylindrical container having a diameter of 55 mm and a height of 50 mm placed on a horizontal table, and then lifting the hollow cylindrical container vertically and then spreading the paste on the table It is the average value of the values measured for the vertical and horizontal directions.
(II) After adding 15 parts by mass of water to 100 parts by mass of the functional hydraulic inorganic particles, the time until the paste composed of the functional hydraulic inorganic particles and water becomes uniform is within 180 seconds. The
The time until the paste becomes uniform is obtained by observing the effective power consumption of a mixer N-50 manufactured by Hobert that kneads the paste over time to obtain an attenuation curve.
Y ₀ + Z ₀ × EXP (− (time−X ₀ )) / τ
(In the formula, X ₀ indicates the time when the effective power consumption becomes maximum after 3 seconds from the start of kneading. Y ₀ and Z ₀ indicate constants. Τ is from the point where the effective power consumption becomes maximum. Indicates relaxation time, EXP represents an exponential function with e as the base.)
Is the sum of τ and X ₀ of the approximate curve obtained measured values with. The functional hydraulic inorganic particles according to claim 1, wherein the hydraulic inorganic particles are cement. 3. A hydraulic particle comprising the functional hydraulic inorganic particle according to claim 1.