JP5351506B2 - Additive composition for hydraulic composition - Google Patents

Description

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

  A hydraulic composition using cement, such as concrete, may evaporate with time after hardening, and may crack due to drying shrinkage. In order to suppress this drying shrinkage, a drying shrinkage reducing agent has been studied as a direct method. As an indirect method, it is effective to reduce the unit amount of water. For this reason, high-performance water reducing agents such as β-naphthalenesulfonic acid formalin high condensate salts and polycarboxylic acid-based high-performance water reducing agents are generally used for drying shrinkage. Used in combination with a reducing agent. For example, as a drying shrinkage reducing agent, an alkylene oxide adduct of an alcohol having 1 to 4 carbon atoms (Patent Document 1), a polyalkylene glycol having an average molecular weight of 400 to 10,000 having an effect of preventing cracking, and a polycarboxylic acid having a dispersibility of concrete. An admixture containing an acid polymer as a main component (Patent Document 2) and an admixture containing a polyhydric alcohol alkylene oxide adduct and a polycarboxylic acid polymer (Patent Document 3) have been proposed. As a high-performance water reducing agent, a phosphate ester polymer capable of producing low-viscosity concrete has been proposed (Patent Document 4).

Recently, durability of concrete structures has been increasing, and effective methods of using shrinkage reducing agents and high performance water reducing agents are being studied. When manufacturing concrete in a green plant, the smaller the number of chemicals to be added, the less the manufacturing burden is reduced in terms of the manufacturing process and addition equipment. Therefore, development of an additive having both a drying shrinkage reducing effect and a dispersing effect is demanded. However, the above-mentioned publication does not disclose a technique that is easy to handle as a one-component product and that simultaneously imparts a drying shrinkage reducing effect, high fluidity retention, stable air entrainment, and high compressive strength to concrete.
Japanese Patent Publication No. 56-51148 JP 2002-12461 A JP 2004-2175 A JP 2006-52381 A

  An object of the present invention is to provide a one-component additive composition for a hydraulic composition that has both a drying shrinkage reduction effect and a dispersion effect.

  The present invention relates to a monomer 1 represented by the following general formula (1), a monomer 2 represented by the following general formula (2), and a monomer 3 represented by the following general formula (3). At least one type of phosphate ester polymer obtained by copolymerization at pH 7 or lower (hereinafter referred to as component (A)), a compound represented by the following general formula (4), and the following general formula The present invention relates to a one-component additive composition for a hydraulic composition containing one or more compounds (B) selected from compounds represented by formula (5) [hereinafter referred to as component (B)].

[Wherein R ¹ and R ² are each a hydrogen atom or a methyl group, R ³ is a hydrogen atom or —COO (AO) _n X, AO is an oxyalkylene group or oxystyrene group having 2 to 4 carbon atoms, n is It is the average added mole number of AO, the number of 3-200, X represents a hydrogen atom or a C1-C18 alkyl group. ]

[Wherein, R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents an alkylene group having 2 to 12 carbon atoms, m1 represents a number of 1 to 30, and M represents a hydrogen atom, an alkali metal or an alkaline earth metal. ]

[Wherein R ⁶ and R ⁸ are each a hydrogen atom or a methyl group, R ⁷ and R ⁹ are each an alkylene group having 2 to 12 carbon atoms, m2 and m3 are each a number from 1 to 30, and M is hydrogen. Represents an atom, an alkali metal or an alkaline earth metal. ]

[Wherein, R ¹² and R ¹³ are each a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, A ¹ and A ² are each an alkylene group having 2 to 8 carbon atoms, and m5 is A ¹ O The number of 1 to 30 and m6, m7 and m8 are the average number of added moles of A ² O, respectively, and the sum of m6, m7 and m8 is 6 to 30. ]

  Moreover, this invention relates to the manufacturing method of the hydraulic composition which mixes the additive composition for hydraulic compositions of the said invention, hydraulic powder, and water.

  According to this invention, it is providing the additive composition for hydraulic compositions which has the drying shrinkage reduction effect and the dispersion effect. Since the composition of the present invention is a one-pack type product, it is excellent in handleability in a raw plant.

<(A) component>
Component (A) of the present invention is a phosphate ester polymer obtained by copolymerizing monomer 1 and a mixed monomer including monomer 2 and monomer 3 at a pH of 7 or less. .

[Monomer 1]
For monomer 1, R ³ in general formula (1) is preferably a hydrogen atom, and AO is preferably an oxyalkylene group having 2 to 4 carbon atoms, and more preferably contains an ethyleneoxy group (hereinafter referred to as EO group). The EO group is preferably 70 mol% or more, more preferably 80 mol% or more, further 90 mol% or more, and even more preferably all AO are EO groups. X is preferably a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, more preferably 1 to 12, further 1 to 4, and further 1 or 2, and more preferably a methyl group. Specific examples include ω-methoxypolyoxyalkylene methacrylate and ω-methoxypolyoxyalkylene acrylate, and ω-methoxypolyoxyalkylene methacrylate is more preferable. Here, n in the formula (1) is 3 to 200, preferably 4 to 120, from the viewpoint of the dispersibility of the polymer in the hydraulic composition and the effect of imparting viscosity. In addition, AO is different among n repeating units on average, and random addition, block addition, or a mixture thereof may be included. AO can contain a propyleneoxy group etc. besides EO group.

[Monomer 2]
Examples of the monomer 2 include phosphoric acid mono (2-hydroxyethyl) methacrylic acid ester, phosphoric acid mono (2-hydroxyethyl) acrylic acid ester, polyalkylene glycol mono (meth) acrylate acid phosphoric acid ester, and the like. Of these, mono (2-hydroxyethyl) methacrylic acid phosphate is preferable from the viewpoint of ease of production and product quality stability.

[Monomer 3]
Examples of the monomer 3 include phosphoric acid di-[(2-hydroxyethyl) methacrylic acid] ester, phosphoric acid di-[(2-hydroxyethyl) acrylic acid] ester, and the like. Among these, di-[(2-hydroxyethyl) methacrylic acid] ester phosphate is preferable from the viewpoint of ease of production and quality stability of the product.

  Either monomer 2 or monomer 3 may be an alkali metal salt, alkaline earth metal salt, ammonium salt, alkylammonium salt or the like of these compounds.

  As for m1 of the monomer 2, and m2 and m3 of the monomer 3, 1-20 are respectively preferable, 1-10 are still more preferable, and 1-5 are more preferable.

  As the monomer 2 and the monomer 3, a mixed monomer containing these can be used. That is, a commercially available product containing a monoester form and a diester form can be used. For example, Phosmer M, Phosmer PE, Phosmer P (Unichemical), JAMP514, JAMP514P, JMP100 (all are Johoku Chemical), Light Ester P -1M, light acrylate P-1A (all Kyoeisha Chemical), MR200 (Daihachi Chemical), Kayamar (Nippon Kayaku), Ethyleneglycol methacrylate phosphate (Aldrich Reagent), etc. are available.

Moreover, the mixed monomer containing the monomer 2 and the monomer 3 is, for example, an organic hydroxy compound represented by the general formula (6), phosphoric anhydride (P ₂ O ₅ ), and water in a predetermined charging ratio. Can be produced as a reaction product.

[Wherein, R ¹⁰ represents a hydrogen atom or a methyl group, R ¹¹ represents an alkylene group having 2 to 12 carbon atoms, and m4 represents a number of 1 to 30. ]

  1-20 are preferable, as for m4 in General formula (6), 1-10 are still more preferable, and 1-5 are more preferable.

  The monomer 2 and the monomer 3 are phosphoric acid ester products of monomers having an unsaturated bond and a hydroxyl group, and the above-mentioned commercially available products and reaction products include a monoester (monomer 2) and It has been confirmed that a compound other than the diester (monomer 3) is contained. These other compounds are considered to be a mixture of polymerizable and non-polymerizable compounds. In the present invention, such a mixture can be used as it is.

The contents of monomer 2 and monomer 3 in the mixture can be calculated based on the ³¹ P-NMR measurement results.
< ³¹ P-NMR measurement conditions>
・ Inverse-gated-decoupling method
・ Measurement range: 6459.9Hz
・ Pulse delay time 30sec
Observation data point 10336
・ Pulse width (5.833μsec) 35 ° pulse ・ Solvent CD ₃ OH (deuterated methanol) (measurement concentration 30% by weight)
・ Number of integration 128

  From the signal of the obtained chart, it is possible to determine the relative quantitative ratio from the area ratio of the signal assigned to each compound as in the following example.

For example, when the organic hydroxy compound is a phosphorous oxide of “2-hydroxyethyl methacrylate”, it can be assigned as follows.
・ 1.8ppm to 2.6ppm: phosphoric acid ・ 0.5ppm to 1.1ppm: Monomer 2 (monoester)
-0.5 ppm to 0.1 ppm: monomer 3 (diester form)
-1.0 ppm to -0.6 ppm: Triester form -11.1 ppm to -10.9 ppm, -12.4 ppm to -12.1 ppm: Pyrophosphate monoester --12.0 ppm to -11.8 ppm: Pyrophosphate diester -11.2 ppm to -11.1ppm: pyrophosphoric acid, other peaks: unknown

  In the present invention, the phosphoric acid content in the mixed monomer was quantified to determine the ratio of monomer 2 and monomer 3 in the mixed monomer. Specifically, the calculation is performed as follows.

  The absolute amount (% by weight) of the phosphoric acid content in the sample is determined by gas chromatography. Since the relative molar ratio of phosphoric acid, mono-isomer and di-isomer in the sample can be obtained from the results of P-NMR, the absolute amounts of mono-isomer and di-isomer were calculated based on the absolute amount of phosphoric acid.

[Phosphoric acid content]
The conditions for gas chromatography are as follows.
Sample: Methylation with diazomethane Example) Methylation by adding 1 to 1.5 cc of diazomethane in diethyl ether to 0.1 g of sample Column: Ultra ALLOY, 15 m × 0.25 mm (inner diameter) × 0.15 μmdf
Carrier gas: He, split ratio 50: 1
Column temperature: 40 ° C. (5 min) (hold) → 10 ° C./min (temperature rise) → 15 min after reaching 300 ° C. Hold inlet temperature: 300 ° C.
Detector temperature: 300 ° C
Under the above conditions, a phosphate-derived peak is detected around 9 minutes, and the phosphate content in the unknown sample can be calculated by a calibration curve method.

  As described above, industrially, phosphate ester monomers are usually available as a mixture containing a monoester (monomer 2) and a diester (monomer 3). Among these, since diesters are likely to have a high molecular weight (gelation) by crosslinking, such a mixture is restricted in production in fields using the properties, for example, thickeners, adhesives, coatings, etc. Can be used suitably without receiving much. On the other hand, in admixtures for hydraulic compositions (dispersants, water reducing agents, etc.), polymers containing phosphate groups are preferable because of their excellent adsorptive power to hydraulic substances, but dispersibility and viscosity are reduced by increasing the molecular weight. The effect is lowered, which is not preferable from the viewpoint of handleability. However, it is industrially disadvantageous to separate the monoester form and the diester form from the mixture of phosphate esters as raw materials from the application and economical properties of the hydraulic composition.

  From the viewpoint of fluidity and viscosity reduction, it is better to use a mixture of phosphate esters containing a large amount of monoester, but even if it contains a large amount of diester, By controlling the polymerization molar ratio, fluidity and viscosity reduction can be adjusted.

Moreover, the phosphate ester (Y) obtained by making the organic hydroxy compound represented by the said General formula (6) and a phosphorylating agent react can be used as the monomers 2 and 3. That is, in the present invention, a phosphate ester copolymer obtained by copolymerizing the following (X) and (Y) at a pH of 7 or less can be used as the copolymer of the component (A).
(X) Monomer 1 represented by the general formula (1).
(Y) Phosphate ester obtained by reacting the organic hydroxy compound represented by the general formula (6) with a phosphorylating agent.

  This phosphate ester (Y) is obtained by phosphorylating the organic hydroxy compound represented by the general formula (6) with a phosphorylating agent.

  Examples of the phosphorylating agent include orthophosphoric acid, phosphorus pentoxide (anhydrous phosphoric acid), polyphosphoric acid, phosphorus oxychloride and the like, and orthophosphoric acid and phosphorus pentoxide are preferable. These may be used alone or in combination of two or more. Further, the phosphorylating agent (Z) described later is also preferable. In this invention, the quantity of the phosphorylating agent at the time of making an organic hydroxy compound and a phosphorylating agent react can be determined timely according to the target phosphate ester composition.

  The phosphoric acid ester (Y) has an organic hydroxy compound and a phosphorylating agent in a ratio defined by the following formula (I) of 2.0 to 4.0, further 2.5 to 3.5, and more preferably 2. What was obtained by making it react on the conditions of 8-3.2 is preferable.

In the present invention, in the formula (I), the phosphorylating agent is treated as P ₂ O ₅ .n (H ₂ O) for convenience.

Further, the phosphorylating agent includes phosphorous pentoxide (Z-1) and at least one selected from the group consisting of water, phosphoric acid and polyphosphoric acid (Z-2) [hereinafter, phosphorylating agent (Z) In this case, too, the formula (I) includes phosphorus pentoxide (Z-1) and at least one selected from the group consisting of water, phosphoric acid and polyphosphoric acid (Z-2). For the sake of convenience, the phosphorylating agent (Z) is treated as P ₂ O ₅ .n (H ₂ O).

The number of moles of the phosphorylating agent defined by the formula (I) is the amount of P ₂ O ₅ unit derived from the phosphorylating agent introduced into the reaction system as a raw material, especially the phosphorylating agent (Z) ( Mol). The number of moles of water indicates the amount (mole) of water (H ₂ O) derived from the phosphorylating agent (Z) introduced into the reaction system as a raw material. That is, the reaction system includes water when polyphosphoric acid is represented as (P ₂ O ₅ .xH ₂ O) and orthophosphoric acid is represented as [1/2 (P ₂ O ₅ .3H ₂ O)]. It will contain all the water present in it.

  Moreover, 20-100 degreeC is preferable and the temperature at the time of adding a phosphorylating agent to an organic hydroxy compound has still more preferable 40-90 degreeC. The time required for adding the phosphorylating agent to the reaction system (the time from the start of addition to the end of addition) is preferably from 0.1 hour to 20 hours, and more preferably from 0.5 hour to 10 hours.

  The temperature of the reaction system after adding the phosphorylating agent is preferably 20 to 100 ° C, more preferably 40 to 90 ° C. The copolymerization can be carried out based on a method for producing a phosphate ester polymer described later.

  After completion of the phosphorylation reaction, the resulting phosphoric acid condensate (an organic compound or a phosphoric acid having a pyrophosphate bond) may be reduced by hydrolysis, or even without hydrolysis, the phosphoric acid of the present invention. It is suitable as a monomer for producing an ester polymer.

  The phosphate ester polymer of the component (A) of the present invention preferably has a weight average molecular weight (Mw) of 10,000 to 150,000. Moreover, it is preferable that Mw / Mn is 1.0-2.6. Here, Mn is the number average molecular weight. Mw is preferably 10,000 or more, more preferably 12,000 or more, still more preferably 13,000 or more, still more preferably 14,000 or more, and even more preferably 15 from the viewpoint of expression of the dispersion effect and viscosity reduction effect. 15,000 or less, preferably 150,000 or less, more preferably 130,000 or less, and still more preferably 120,000 from the viewpoints of high molecular weight by crosslinking, suppression of gelation, and performance in terms of dispersion effect and viscosity reduction effect. Or less, more preferably 110,000 or less, still more preferably 100,000 or less. Therefore, from the viewpoints of the both, preferably 12,000 to 130,000, more preferably 13,000 to 120,000, More preferably, 14,000 to 110,000, still more preferably 15,000 to 100,000. A. It is preferable to have Mw in this range and Mw / Mn is 1.0 to 2.6. Here, the value of Mw / Mn is the degree of dispersion. The closer the value is to 1, the closer the molecular weight distribution is to the monodispersion, and the farther from 1 (the larger) the wider the molecular weight distribution.

  The phosphate ester polymer of the present invention having the Mw / Mn value as described above is a polymer having a branched structure based on a diester structure, but has a great feature that the molecular weight distribution is very narrow. Such a phosphoric ester polymer of the present invention can be suitably produced by a production method described later.

  Mw / Mn of the phosphoric ester polymer of the present invention as described above is 1.0 or more from the viewpoint of ensuring practical production ease, dispersibility, viscosity reduction effect, and versatility with respect to materials and temperature. From the viewpoint of achieving both a dispersibility and a viscosity reducing effect, it is 2.6 or less, preferably 2.4 or less, more preferably 2.2 or less, still more preferably 2.0 or less, and even more preferably 1 From the viewpoint of combining the above two points, it is preferably 1.0 to 2.4, more preferably 1.0 to 2.2, still more preferably 1.0 to 2.0, and still more preferably. Is 1.0 to 1.8.

Mw and Mn of the phosphate ester polymer of the present invention are those measured by gel permeation chromatography (GPC) method under the following conditions. In addition, Mw / Mn of the phosphate ester type polymer in the present invention is calculated based on the peak of the polymer. [GPC conditions]
Column: G4000PWXL + G2500PWXL (Tosoh)
Eluent: 0.2M phosphate buffer / CH ₃ CN = 9/1
Flow rate: 1.0mL / min
Column temperature: 40 ° C
Detection: RI
Sample size: 0.2mg / mL
Reference material: Polyethylene glycol equivalent

  The phosphate ester polymer satisfying Mw / Mn as described above has an appropriate branched structure by suppressing cross-linking by the monomer 3 which is a diester, and has a structure in which adsorbing groups are closely present in the molecule. It is thought to form. Further, since the degree of dispersion Mw / Mn is controlled within a predetermined range, it approaches a system in which molecules of the same size are monodispersed, so that it is considered possible to increase the amount of adsorption on the adsorption target substance (for example, cement particles). Satisfying both of these conditions makes it possible to densely pack the substance to be adsorbed, such as cement particles, and is estimated to be effective in achieving both a dispersibility and a viscosity reducing effect.

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

In addition, since the double bond derived from a monomer has disappeared by ¹ H-NMR under the following conditions, the phosphate ester-based polymer of the present invention is derived from monomers 1, 2, and 3, respectively. It is suggested to have a structural unit.
[ ¹ H-NMR conditions]
A polymer dissolved in water and dried under reduced pressure is dissolved in deuterated methanol at a concentration of 3 to 4% by weight, and ¹ H-NMR is measured. The residual rate of double bonds is measured by an integrated value of 5.5 to 6.2 ppm. In addition, the measurement of ¹ H-NMR uses “Mercury 400 NMR” manufactured by Varian, the number of data points is 42052, the measurement range is 6410.3 Hz, the pulse width is 4.5 μs, the pulse waiting time is 10 s, and the measurement temperature is 25.0 ° C. Performed under conditions.

  That is, the phosphoric acid ester-based polymer having the Mw / Mn value as described above has, as its constituent units, constituent units derived from monomer 1, constituent units derived from monomer 2, and constituents derived from monomer 3. Includes units. These structural units are structural units derived from the respective monomers incorporated into the polymer by cleavage of the ethylenically unsaturated bonds of monomers 1, 2, and 3 and addition polymerization. The ratio of these structural units in the polymer depends on the charging ratio, and when the monomers used for copolymerization are only monomers 1 to 3, the molar ratio of each structural unit is the monomer charging molar ratio. It is thought that it is almost the same.

<< Production Method of Phosphate Ester Polymer >>
The phosphate ester polymer of the present invention is produced by a phosphate ester polymer production method in which the monomer 1, the monomer 2 and the monomer 3 are copolymerized at a pH of 7 or less. Can do. Moreover, it is preferable to use a mixed monomer containing monomer 2 and monomer 3.

  The present inventors have found that a polymer derived from a specific phosphate ester is useful for reducing the viscosity of a hydraulic composition which is one of the problems of the present invention. However, it has been found that the prior art does not provide sufficient disclosure for the problem of industrializing such polymers.

  As described above, it was difficult to use a phosphate ester monomer that was industrially obtained as a mixture for the use of a hydraulic composition, but a monomer containing monomer 2 and / or monomer 3 A raw material containing a diester body by copolymerizing the monomer 1, the monomer 2 and the monomer 3 which are phosphate ester monomers, using the body solution for the reaction in a specific pH range The generation of cross-linking (high molecular weight, gelation) can be suppressed even with the use of, and the excellent performance as a dispersant for a hydraulic composition of a phosphate ester polymer can be maintained. Then, it becomes a very advantageous manufacturing method.

  The phosphate ester polymer according to the present invention includes a monomer 1 having an oxyalkylene group represented by the general formula (1) and a single monomer represented by the general formula (2) having a phosphate group. It is a polymer obtained by copolymerizing the body 2 and the monomer 3 represented by the general formula (3).

  The preferable thing of the monomers 1-3 is as above-mentioned, respectively, and the above-mentioned commercial item and reaction product can also be used.

  In the copolymerization of the monomers, the molar ratio between the monomer 1 and the monomers 2 and 3 is as follows: monomer 1 / (monomer 2 + monomer 3) = 5/95 to 95/5 Furthermore, 10/90 to 90/10 are preferable. The molar ratio of monomer 1, monomer 2 and monomer 3 is as follows: monomer 1 / monomer 2 / monomer 3 = 5 to 95/3 to 90/1 to 80 / 5 to 96/3 to 80/1 to 60 (however, the total is 100) is preferable. In addition, about the monomer 2 and the monomer 3, the molar ratio and mol% shall be calculated based on an acid type compound (hereinafter the same).

Moreover, in this invention, the ratio of the monomer 3 in all the monomers used for reaction can be 1-60 mol%, Furthermore, it can be 1-30 mol%.
Further, the molar ratio of the monomer 2 and the monomer 3 can be set to monomer 2 / monomer 3 = 99/1 to 4/96, and more preferably 99/1 to 5/95.
Since the monomer raw material containing the monomer 3 in such a range is generally expected to be gelled, it is usually used as a raw material for producing a polymer for a dispersant for a hydraulic composition. Not. However, in the present invention, by using the monomer solution containing monomer 2 and / or monomer 3 at a pH of 7 or less for the reaction, gelation is suppressed and suitable as a dispersant for a hydraulic composition. Such a phosphoric acid ester polymer can be produced at an industrially practical level.

Hereinafter, more preferable production conditions will be described from the viewpoints of gelation suppression, adjustment of a suitable molecular weight, and performance design of a dispersant for hydraulic composition. From this point of view, in the present invention, in the copolymerization, the chain transfer agent is 4 mol% or more, further 6 mol% or more, and further 8 mol% or more based on the total number of moles of monomers 1 to 3. Is preferably used. Further, the upper limit of the amount of the chain transfer agent used is preferably 100 mol% or less, more preferably 60 mol% or less, still more preferably 30 mol% or less, and still more preferably relative to the total number of moles of monomers 1 to 3. Preferably it can be 15 mol% or less. For more details,
(1) When n of monomer 1 is 3 to 30,
(1-1) When the molar ratio of the monomer 2 and the monomer 3 in the monomers 1 to 3 is 50 mol% or more, the chain transfer agent is 6 to It is preferable to use 100 mol%, more preferably 8 to 60 mol%,
(1-2) When the molar ratio of the monomer 2 and the monomer 3 in the monomers 1 to 3 is less than 50 mol%, the chain transfer agent is 4 to 4 with respect to the monomers 1 to 3. It is preferable to use 60 mol%, more preferably 5 to 30 mol%,
(2) When n of monomer 1 exceeds 30, the chain transfer agent is preferably used in an amount of 6 to 50 mol%, more preferably 8 to 40 mol%, based on monomers 1 to 3.

  In the production method for obtaining the component (A) of the present invention, the reaction rate of the monomers 2 and 3 is 60% or more, further 70% or more, further 80% or more, further 90% or more, and further 95% or more. It is preferable to carry out to a target, and the usage-amount of a chain transfer agent can be selected from this viewpoint. Here, the reaction rate of the monomers 2 and 3 is calculated by the following equation.

The ratio (mol%) of monomer 2 and monomer 3 in the phosphorus-containing compound in the reaction system at the start and end of the reaction should be calculated based on the above ¹ H-NMR measurement results. Can do.

  In the production of the phosphate ester polymer according to the present invention, in addition to the monomers 1 to 3, other monomers capable of copolymerization can be used. Examples of other copolymerizable monomers include allyl sulfonic acid, methallyl sulfonic acid, any of these alkali metal salts, alkaline earth metal salts, ammonium salts, and amine salts. In addition, acrylic monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and the like, and any one or more of alkali metal salts, alkalis Anhydrous compounds such as earth metal salts, ammonium salts, amine salts, methyl esters, ethyl esters and maleic anhydride may also be used. Furthermore, (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, 2- (meth) acrylamide-2-metasulfonic acid, 2- (meth) acrylamide-2-ethanesulfonic acid, Examples include 2- (meth) acrylamide-2-propanesulfonic acid, styrene, styrenesulfonic acid and the like. The total proportion of monomers 1 to 3 in all monomers is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, and even more preferably 75 to 100 mol%, and further the phosphate ester type of the present invention. From the viewpoint of achieving the performance as the dispersant described in the polymer, it is more than 95 mol% to 100 mol%, more preferably 97 to 100 mol%, and even more preferably 100 mol%.

  In the production method of the present invention, the reaction temperature of the monomers 1 to 3 is preferably 40 to 100 ° C., more preferably 60 to 90 ° C., and the reaction pressure is 101.3 to 111.5 kPa (1 to 1 in terms of gauge pressure). 0.1 atm), more preferably 101.3 to 106.4 kPa (1-1.05 atm).

  In the production method for obtaining the component (A) of the present invention, a monomer solution containing the monomer 2 and / or monomer 3 prepared with an appropriate solvent is preferably used in a predetermined amount of chain transfer agent. Is copolymerized with other monomers at pH 7 or lower. Moreover, you may use the other monomer, polymerization initiator, etc. which can be copolymerized.

  In the production method for obtaining the component (A) of the present invention, the monomer 1, the monomer 2 and the monomer 3 are reacted at a pH of 7 or less. In the present invention, the pH at 20 ° C. of the reaction solution collected during the reaction (from the start of the reaction to the end of the reaction) is defined as the pH during the reaction. Usually, the reaction may be started under conditions that clearly show that the pH during the reaction is 7 or less (monomer ratio, solvent, other components, etc.).

  When the reaction system is non-aqueous, it can be measured by adding an amount of water capable of measuring pH to the reaction system.

In the case of the monomers 1 to 3 that are the subject of the present invention, if the reaction is carried out under the conditions exemplified in the following (1) and (2), the pH during the reaction is usually adjusted under consideration of other conditions. It is considered to be 7 or less. Further, the pH may temporarily exceed 7 in the initial stage of the reaction as long as it does not affect the entire reaction, such as no gel is formed.
(1) A monomer solution having a pH of 7 or less containing all of monomers 1 to 3 is used for the copolymerization reaction of monomers 1 to 3.
(2) The copolymerization reaction of monomers 1 to 3 is started at pH 7 or less. That is, the reaction is started after the reaction system containing the monomers 1 to 3 is brought to pH 7 or lower.

In particular,
(I) The pH of the monomer solution containing the monomers 1 to 3 is adjusted to 7 or less to initiate the copolymerization reaction. (Ii) A monomer solution containing the monomers 1 to 3 (pH is arbitrary but is preferably 7 or less) is dropped into the reaction system.
(Iii) A monomer solution containing monomer 1 (pH is arbitrary but preferably 7 or less) and a monomer solution containing monomer 2 (pH is arbitrary but 7 or less are preferred). ) And a monomer solution containing the monomer 3 (pH is arbitrary but is preferably 7 or less) are separately added dropwise to the reaction system.
(Iv) Reaction is performed by appropriately combining the above. For example, a part of a monomer solution containing the monomers 1 to 3 (pH is arbitrary but preferably 7 or less) is charged into the reaction system, and the remaining monomer solution is dropped into the reaction system. .

  In the above (iii) and (iv), it is necessary to control the dropping conditions of the monomer solution to be dropped so as not to deviate from the set monomer molar ratio. Moreover, in said (ii)-(iv), other reaction conditions are considered so that pH of the reaction system containing the dripped monomers 1-3 may be 7 or less, Preferably it is 4 or less.

  The pH of the reaction system can be adjusted with an inorganic acid (phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, etc.), NaOH, KOH, triethanolamine, or the like, if necessary.

  As described above, in the production method for obtaining the component (A) of the present invention, in order to make the pH of the reaction system during the reaction 7 or less, among the monomer solutions used for the reaction, the monomer 2, The pH of the monomer solution containing at least one of the monomers 3 is preferably 7 or less. The monomer solution having a pH of 7 or lower contains at least one of monomer 2 and monomer 3, and contains monomer 1, and further contains a chain transfer agent and other monomers. It may be. Here, the monomer solution containing the monomer 2 and / or the monomer 3 is preferably a water-containing system (that is, the solvent contains water) for pH measurement. May be measured by adding the required amount of water. From the viewpoint of uniformity of the monomer solution, prevention of gelation, and suppression of performance degradation, the pH is 7 or less, preferably 0.1 to 6, and more preferably 0.2 to 4.5. Monomer 1 is also preferably used as a monomer solution having a pH of 7 or less. This pH is at 20 ° C.

  The pH of the reaction system (polymerization system) before the reaction in which the monomer is finally charged is 20 ° C. from the viewpoint of stability when controlling the molecular weight of the polymer and ease of pH control during the reaction. It is preferably 6 or less, more preferably 5 or less, still more preferably 4 or less, and even more preferably 2 or less. Preferably, the pH of the monomer solution containing monomer 2 and / or monomer 3 (pH of the reaction system at the start of the reaction), the pH of the reaction system during the reaction, and the pH of the reaction system at the end of the reaction are Both are 7 or less.

  In addition, when these monomers 1 to 3 are not used in a water-containing state (that is, dropped as a liquid component as they are), the pH of the polymerization system is inevitably 7 or less, and such a method is also suitable. The pH of the final polymerization system before neutralization is preferably 6 or less, further 5 or less, further 4 or less, and further 2 or less.

[Chain transfer agent]
The chain transfer agent has a function of causing a chain transfer reaction in radical polymerization (a reaction in which a growing polymer radical reacts with another molecule to move a radical active site). It is a substance to be added.

  Examples of chain transfer agents include thiol chain transfer agents and halogenated hydrocarbon chain transfer agents, and thiol chain transfer agents are preferred.

As the thiol-based chain transfer agent, those having a —SH group are preferable, and further a general formula HS—R—Eg (wherein R represents a hydrocarbon-derived group having 1 to 4 carbon atoms, E is —OH, —COOM, —COOR ′ or SO ₃ M group, M represents a hydrogen atom, monovalent metal, divalent metal, ammonium group or organic amine group, and R ′ represents an alkyl having 1 to 10 carbon atoms. In which g represents an integer of 1 to 2, for example, mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, Octyl thioglycolate, octyl 3-mercaptopropionate, and the like. From the viewpoint of the chain transfer effect in the copolymerization reaction including monomers 1 to 3, mercaptopropionic acid, Mercaptoethanol are preferable, more preferably mercaptopropionic acid. These 1 type (s) or 2 or more types can be used.

  Examples of the halogenated hydrocarbon chain transfer agent include carbon tetrachloride and carbon tetrabromide.

  Examples of other chain transfer agents include α-methylstyrene dimer, terpinolene, α-terpinene, γ-terpinene, dipentene, 2-aminopropan-1-ol and the like. A chain transfer agent can use 1 type (s) or 2 or more types.

[Polymerization initiator]
In the production method for obtaining the component (A) of the present invention, it is preferable to use a polymerization initiator, and the polymerization initiator is used in an amount of 5 mol% or more, further 7 to It is preferable to use 50 mol%, and further 10-30 mol%.

  As an aqueous polymerization initiator, persulfuric acid ammonium salt or alkali metal salt or hydrogen peroxide, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis (2-methylpropionamide) Water-soluble azo compounds such as dihydrate are used. In addition, an accelerator such as sodium bisulfite and an amine compound can be used in combination with the polymerization initiator.

[solvent]
The production method for obtaining the component (A) of the present invention can be carried out by a solution polymerization method, and as the solvent used in that case, water or water and methyl alcohol, ethyl alcohol, isopropyl alcohol Examples of the solvent include hydrous solvents containing acetone, methyl ethyl ketone, and the like. In view of handling and reaction equipment, water is preferred. In particular, when an aqueous solvent is used, a monomer solution containing monomer 2 and / or monomer 3 is used for the reaction at a pH of 7 or less, further 0.1 to 6, and further 0.2 to 4. Performing the polymerization reaction is preferable from the viewpoint of uniformity (handleability) of the monomer mixture, monomer reaction rate, and crosslinking by hydrolysis of the pyro compound of the phosphoric acid compound.

  An example of the manufacturing method for obtaining (A) component of this invention is shown. A predetermined amount of water is charged into a reaction vessel, the atmosphere is replaced with an inert gas such as nitrogen, and the temperature is raised. Prepare monomer 1, monomer 2, monomer 3, chain transfer agent mixed and dissolved in water, and polymerization initiator dissolved in water, and take 0.5 to 5 hours. Drip into the reaction vessel. At that time, each monomer, chain transfer agent and polymerization initiator may be dropped separately, or a mixed solution of monomers can be charged in a reaction vessel in advance and only the polymerization initiator can be dropped. is there. That is, the chain transfer agent, the polymerization initiator, and other additives may be added as an additive solution separately from the monomer solution, or may be added to the monomer solution after being added. From the viewpoint of stability, it is preferable to supply the reaction system as an additive solution separately from the monomer solution. In any case, the pH of the solution containing the monomer 2 and / or the monomer 3 is preferably 7 or less. Further, the copolymerization reaction is carried out with an acid agent or the like while maintaining the pH at 7 or less, and preferably aging is carried out for a predetermined time. The polymerization initiator may be added dropwise at the same time as the monomer, or may be added in portions, but it is preferable to add in portions in terms of reducing unreacted monomers. For example, in the total amount of the polymerization initiator to be finally used, 1/2 to 2/3 polymerization initiator is added simultaneously with the monomer, and the remainder is aged for 1 to 2 hours after the completion of the monomer dropping, It is preferable to add. If necessary, it is further neutralized with an alkali agent (such as sodium hydroxide) after completion of ripening to obtain the phosphate ester polymer according to the present invention.

  The total amount of the monomers 1, 2, 3 and other copolymerizable monomers in the reaction system is preferably 5 to 80% by weight, more preferably 10 to 65% by weight, even more preferably 20 to 50% by weight. preferable.

  In this invention, (A) component can use 2 or more types, and also 3 or more types. The standard for selecting a plurality of components (A) depends on the composition, constituent materials, performance, etc. of the hydraulic composition. For example, the ratio of the monomer 1 represented by the general formula (1) is in the total amount of monomers. A combination containing 1 to 55 mol% of the copolymer (A1) and the copolymer (A2) in which the proportion of the monomer 1 is more than 55 mol% in the total amount of the monomers is desirable. Furthermore, when a third copolymer is selected in addition to (A1) and (A2), that is, when three types of copolymers are used in total, (A2) should be two types. Preferably, one of the (A2) (second copolymer) is a copolymer in which the proportion of the monomer 1 is more than 55 mol% and not more than 65 mol% in the total amount of the monomers, (A2) The other (third copolymer) is preferably a copolymer in which the proportion of monomer 1 is more than 65 mol% in the total amount of monomers.

<(B) component>
The component (B) is one or more compounds selected from the compound represented by the general formula (4) and the compound represented by the following general formula (5).

In General formula (4), R < ¹² > and R < ¹³ > are respectively a hydrogen atom or a C1-C30 hydrocarbon group, Preferably it is C1-C22, More preferably, it is C1-C18, More preferably It is 1-12, More preferably, it is a C1-C4 hydrocarbon group. At least one of R ¹² and R ¹³ is preferably a hydrocarbon group. (A) A C1-C4 hydrocarbon group is preferable from a mixed viewpoint with a component. Examples of the hydrocarbon group include an alkyl group and an alkenyl group, and an alkyl group is preferable. Specific examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, and an n-butyl group. R ¹² is preferably a hydrocarbon group having 1 to 4 carbon atoms, and R ¹³ is preferably a hydrogen atom.

In General Formula (4) and General Formula (5), A ¹ and A ² are alkylene groups having 2 to 8 carbon atoms, preferably 2 to 6 carbon atoms, more preferably 2 to 3 carbon atoms, and still more preferably. Is an alkylene group having 2 carbon atoms.

Further, m5 in formula (4) is the average addition mole number of oxyalkylene groups A ¹ O, 1 to 30, preferably 1 to 20, more preferably 1 to 12, more preferably 1 to 8, more More preferably, it is a number of 1-4.

Further, m6, m7 and m8 in the general formula (5) are the average added mole numbers of the oxyalkylene group A ² O, respectively, and 6 to 30, preferably 6 to 6 in total (m6 + m7 + m8) of m6, m7 and m8. 22, more preferably 6 to 18, more preferably 6 to 14, and still more preferably 6 to 12.

When A ² in the general formula (5) is an alkylene group having 3 carbon atoms, the total of m6, m7 and m8 is preferably 6-9. If it is 6 or more, a sufficient drying shrinkage reducing effect can be obtained, and if it is 9 or less, a sufficiently high concentration with the component (A) can be achieved.

Further, when A ² in the general formula (5) is an alkylene group having 2 carbon atoms, m6, m7 and total m8 is preferably 9-12. If it is 9 or more, a sufficient drying shrinkage reduction effect is obtained, and if it is 12 or less, the viscosity when the concentration is increased with the component (A) becomes appropriate.

<Additive composition for hydraulic composition>
In the additive composition for a hydraulic composition of the present invention, the content of the component (A) is preferably 3 to 30% by weight, more preferably 4 to 25% by weight, more preferably 5 as the concentration of the effective component. -20% by weight, more preferably 7-15% by weight. 3% by weight or more is preferable from the viewpoint of the amount added during use, and 30% by weight or less is preferable from the viewpoint of product stability.

  In the additive composition for a hydraulic composition of the present invention, the content of the component (B) is preferably 5 to 70% by weight, more preferably 10 to 65% by weight, more preferably 20 as the effective component concentration. -60% by weight, more preferably 30-55% by weight. 5% by weight or more is preferable from the viewpoint of the amount added during use, and 70% by weight or less is preferable from the viewpoint of product stability.

  Moreover, in the additive composition for hydraulic compositions of this invention, the total amount of (A) component and the weight ratio of (B) component are (A) :( B) = 5: 95-50: 50 in conversion of an effective part. It is preferably 7:93 to 45:55, more preferably 10:90 to 40:60, and still more preferably 12:88 to 35:65.

  Moreover, in the additive composition for hydraulic compositions of this invention, it is preferable that the total content of (A) component and (B) component is 8-95 weight% in conversion of an effective component, More preferably, 20- It is 90% by weight, more preferably 30 to 70% by weight, and still more preferably 40 to 60% by weight. The additive composition for hydraulic composition of the present invention is a one-component liquid composition, and the balance is, for example, water. The additive composition for hydraulic compositions of the present invention is a one-component type that is easy to handle because the component (A) is compatible with the component (B) and the aqueous solution containing these components does not cause an extreme increase in viscosity. It becomes a composition. The additive composition for a hydraulic composition of the present invention can be obtained as a transparent composition, and is further stored at 5 to 40 ° C. for 3 months or more at any temperature. Can be maintained.

  The additive composition for hydraulic compositions of the present invention preferably contains a polycarboxylic acid copolymer (C) [hereinafter referred to as component (C)].

  As the component (C), the monomer (a) represented by the following general formula (7), the monomer represented by the following general formula (8-1), and the following general formula (8-2) are represented. Examples thereof include a polycarboxylic acid copolymer containing a monomer (b) selected from monomers as a structural unit.

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

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

[Where,
R ^7c : hydrogen atom or methyl group
Z: A hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkylammonium group or a substituted alkylammonium group. ]

The n1 alkylene glycols A ³ O in the formula (7) may be the same or different. If they are different, random addition or block addition may be used.

  Considering the polymerization efficiency of the polyalkylene glycol, the added mole number n1 is 300 or less, preferably 150 or less, more preferably 130 or less. From the viewpoint of cement dispersibility, 2 to 300 mol is preferable.

From the viewpoint of the properties of the cement dispersibility and the hydraulic composition, the average value n1 _AV of n1 in the general formula (7) is preferably 5 to 200, more preferably 7 to 150, more preferably 9 to 130, 9 to 120 is more preferred.

Specific examples of the monomer (a) include (half) esterified products of polyalkylene glycols with one-terminal lower alkyl group blocked such as methoxypolyethylene glycol, methoxypolypropylene glycol, ethoxypolyethylenepolypropylene glycol, (meth) acrylic acid and maleic acid. And ether compounds with (meth) allyl alcohol, and (meth) acrylic acid, maleic acid, ethylene oxide and propylene oxide adducts to (meth) allyl alcohol are preferably used, and R ^3c in the general formula (1) Is preferably a hydrogen atom, preferably p = 1 and m = 0. The alkylene oxide (A ³ O group in the formula (7)) is preferably an oxyethylene group. More preferred are alkoxy, and still more preferred is an esterified product of methoxypolyethylene glycol and (meth) acrylic acid.

  As monomers represented by the formula (8-1), unsaturated monocarboxylic acid monomers such as (meth) acrylic acid and crotonic acid, and unsaturated dicarboxylic acid monomers such as maleic acid, itaconic acid and fumaric acid Monomers or salts thereof such as alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts and the like can be mentioned, and (meth) acrylic acid or alkali metal salts thereof are preferable.

  Examples of the monomer represented by the formula (8-2) include (meth) allylsulfonic acid or a salt thereof such as an alkali metal salt, an alkaline earth metal salt, an ammonium salt, and an amine salt.

  As the monomer (b), it is more preferable to use only the monomer represented by the formula (8-1) from the viewpoint of controlling the molecular weight of the copolymer.

  The total amount of the monomer (a) and the monomer (b) in the monomer mixture constituting the component (C) is preferably 50% by weight or more, more preferably 80% by weight or more, and even more preferably 100% by weight. . Examples of copolymerizable monomers other than the monomer (a) and the monomer (b) include acrylonitrile, (meth) acrylic acid alkyl ester, (meth) acrylamide, and styrene sulfonic acid.

  (C) component can be manufactured by a well-known method. For example, the solution polymerization method of JP-A-11-157897 can be mentioned. In the presence of a polymerization initiator such as ammonium persulfate or hydrogen peroxide in water or a lower alcohol having 1 to 4 carbon atoms, if necessary, sodium sulfite or What is necessary is just to add mercaptoethanol etc. and to make it react at 50-100 degreeC for 0.5 to 10 hours.

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

  In the additive composition for hydraulic composition of the present invention, the weight ratio of the component (A) to the component (C) is (A) :( C) = 100: 1 to 100: 40 in terms of effective component. preferable. In this weight ratio, the upper limit value occupied by the component (C) is preferably (A) :( C) = 100: 35, further 100: 30, and more preferably 100: 25. On the other hand, the lower limit occupied by the component (C) is preferably (A) :( C) = 100: 3, more preferably 100: 10. Further, the total content of the component (A) and the component (C) is preferably 3 to 30% by weight, more preferably 5 to 25% by weight in terms of the effective component.

  Furthermore, the additive composition for hydraulic composition of the present invention comprises a monomer represented by the general formula (9) and a monomer represented by the general formula (10) from the viewpoint of maintaining fluidity. It is preferable to contain a copolymer obtained by polymerization [hereinafter referred to as component (D)].

[Wherein, R ^{1d to} R ^3d each represents a hydrogen atom or a methyl group, A ⁴ O represents an oxyalkylene group having 2 to 4 carbon atoms, n represents an average number of moles of A ⁴ O added, and 20 Represents a number of ˜50, R ^4d represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, q represents an integer of 0 to 2, and p represents 0 or 1. ]

[Wherein, R ^5d is a hydrocarbon group that may contain a hetero atom having 1 to 4 carbon atoms. ]

  Examples of the monomer represented by the general formula (9) include the same monomers as the monomer (a) of the component (C).

Monomer represented by the formula (10) is an acrylic acid ester monomer, it can be considered as an ester of structure, an alcohol compound represented by acrylic acid and R ^5d -OH, R ^5d Is a hydrocarbon group containing 1 to 4 carbon atoms, preferably 2 to 3 heteroatoms. A hetero atom is an oxygen atom, a nitrogen atom or the like. Specific examples include 2-hydroxyethyl acrylate, methyl acrylate, hydroxybutyl acrylate, methoxyethyl acrylate, and the like. From the viewpoint of maintaining fluidity, 2-hydroxyethyl acrylate is preferable.

  The monomer represented by the general formula (9) is preferably 25 to 95% by weight, more preferably 25 to 25% in the monomer mixture constituting the component (D) from the viewpoint of fluidity and fluidity retention. It is 90% by weight, more preferably 28 to 80% by weight, and still more preferably 35 to 75% by weight.

  The monomer represented by the general formula (10) is preferably 5 to 75% by weight, more preferably 10 to 75% in the monomer mixture constituting the component (D) from the viewpoint of fluidity retention. % By weight, more preferably 20 to 72% by weight, and still more preferably 25 to 65% by weight.

  From the viewpoint of fluidity retention, the total amount of the monomer represented by the general formula (9) and the monomer represented by the general formula (10) is (D) in the monomer mixture constituting the component. Preferably it is 90-100 weight%, More preferably, it is 95-100 weight%, More preferably, it is 98-100 weight%.

  The weight ratio of the monomer represented by the general formula (9) and the monomer represented by the general formula (10) (monomer (9) / monomer (10)) is from the viewpoint of fluidity retention. , Preferably 25/75 to 95/5, more preferably 25/75 to 90/10, more preferably 28/72 to 80/20, more preferably 35/65 to 75/25, still more preferably 45 / 55-65 / 35.

  In addition to the monomer represented by the general formula (9) and the monomer represented by the general formula (10), the component (D) includes a carboxylic acid such as (meth) acrylic acid, maleic acid, and maleic anhydride. An acid monomer can be contained.

  (D) component can be manufactured by the method similar to (C) component.

  The content of the component (D) is preferably 0.5 to 45 parts by weight, more preferably 1 to 25 parts by weight, with respect to 100 parts by weight in total of the components (A) and (B). More preferred is 20 parts by weight. Moreover, 0.5-40 weight part is preferable with respect to a total of 100 weight part of (A) component, (B) component, and (C) component, 1-20 weight part is more preferable, 2.5-15 weight part Part is more preferred.

  The additive composition for hydraulic composition of the present invention is 0.15 to 5.5 weight in total of component (A) (effective component) and component (B) (effective component) with respect to the hydraulic powder. %, Preferably 0.3 to 3.5% by weight, more preferably 0.45 to 2% by weight.

  The additive composition for hydraulic composition of the present invention is preferably used at a ratio of 0.05 to 1% by weight of component (A) (effective component) with respect to the hydraulic powder. Is 0.1 to 0.7% by weight, more preferably 0.15 to 0.5% by weight.

  Moreover, it is preferable that the additive composition for hydraulic composition of the present invention is used in a proportion of 0.1 to 5% by weight of (B) component (effective component) with respect to the hydraulic powder. More preferably, it is 0.2 to 2.5 weight%, More preferably, it is 0.3 to 1.5 weight%.

  The additive composition for a hydraulic composition of the present invention can be used for various inorganic hydraulic powders that exhibit curability by a hydration reaction, including various cements. The additive composition for hydraulic composition of the present invention may be in the form of powder or liquid. In the case of a liquid form, those using water as a solvent or a dispersion medium (such as an aqueous solution) are preferable from the viewpoint of workability and reduction of environmental load.

  Examples of the cement include ordinary Portland cement, early-strength Portland cement, ultra-early-strength Portland cement, and eco-cement (for example, JIS R5214). As hydraulic powder other than cement, blast furnace slag, fly ash, silica fume and the like may be included, and non-hydraulic limestone fine powder and the like may be included. Silica fume cement or blast furnace cement mixed with cement may be used.

  The additive composition for hydraulic compositions of the present invention can also contain other additives (materials). For example, resin soap, saturated or unsaturated fatty acid, sodium hydroxystearate, lauryl sulfate, alkylbenzene sulfonic acid (salt), alkane sulfonate, polyoxyalkylene alkyl (phenyl) ether, polyoxyalkylene alkyl (phenyl) ether sulfate (salt) ), Polyoxyalkylene alkyl (phenyl) ether phosphates (salts), protein materials, AE agents such as alkenyl succinic acid and α-olefin sulfonate; oxy such as gluconic acid, glucoheptonic acid, alabonic acid, malic acid, citric acid Delayers such as carboxylic acids, dextrins, monosaccharides, oligosaccharides, polysaccharides, etc .; foaming agents; thickeners; silica sand; AE water reducing agents; calcium chloride, calcium nitrite, calcium nitrate , Cal bromide Soluble calcium salts such as um, calcium iodide, chlorides such as iron chloride and magnesium chloride, sulfates, potassium hydroxide, sodium hydroxide, carbonates, thiosulfates, formic acid (salts), alkanolamines, etc. Strongening agent or accelerator; foaming agent; waterproofing agent such as resin acid (salt), fatty acid ester, oil, fat, silicone, paraffin, asphalt, wax; blast furnace slag; fluidizing agent; dimethylpolysiloxane, polyalkylene glycol fatty acid ester Anti-foaming agents such as mineral oils, fats and oils, oxyalkylenes, alcohols and amides; antifoaming agents; fly ash; high-performance water reducing agents such as melamine sulfonic acid formalin condensates and aminosulfonic acids; silica fume Rust preventives such as nitrite, phosphate, zinc oxide; cellulose such as methylcellulose and hydroxyethylcellulose; Water-soluble polymers such as natural products such as β-type, β-1,3-glucan, xanthan gum, synthetic systems such as polyacrylic acid amide or a reaction product of this with vinylcyclohexene diepoxide; alkyl (meth) acrylate And polymer emulsions.

  In addition, the additive composition for hydraulic composition of the present invention is used in the field of ready-mixed concrete, concrete vibration products, for self-leveling, for refractories, for plaster, for gypsum slurry, for lightweight or heavy concrete, for AE, It is useful in any field of various concrete such as repair, prepacked, torme, ground improvement, grout, and cold.

<Method for producing hydraulic composition>
This invention provides the manufacturing method of the hydraulic composition containing the additive composition for hydraulic compositions of the said invention, hydraulic powder, and water. In the production method of the present invention, the additive composition for hydraulic composition of the present invention, the hydraulic powder, and water are mixed, and the mixing method, mixing device, and the like can employ known means. Moreover, the usage-amount of hydraulic powder, water, and the additive composition of this invention can be suitably selected in the above-mentioned range preferably according to the use of a hydraulic composition, a composition, etc.

  The hydraulic composition produced by the present invention is a paste, mortar, concrete or the like containing water and hydraulic powder (cement), but may contain aggregate. Examples of the aggregate include fine aggregate and coarse aggregate. The fine aggregate is preferably mountain sand, land sand, river sand and crushed sand, and the coarse aggregate is preferably mountain gravel, land gravel, river gravel and crushed stone. Depending on the application, lightweight aggregates may be used. The term “aggregate” is based on “Concrete Overview” (published on June 10, 1998, published by Technical Shoin).

  The hydraulic composition has a water / hydraulic powder ratio [weight percentage (% by weight) of water and hydraulic powder in the slurry, usually abbreviated as W / P. Abbreviated as / C. ] 65% by weight or less, further 18 to 60% by weight, further 20 to 55% by weight, further 30 to 52% by weight, and further 30 to 50% by weight.

<Additive composition for hydraulic composition>
(1) Component (A) As the component (A), copolymers A-1 to A-4 obtained in the following Production Examples A-1 to A-4 were used.

[Production Example A-1] (Production of Copolymer A-1)
A glass reaction vessel (four-necked flask) with a stirrer was charged with 423 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. ω-Methoxypolyethyleneglycol monomethacrylate (average added mole number of ethylene oxide 23) 407 g (effective part 60.8%, moisture 35%), mono (2-hydroxyethyl) methacrylate phosphate and di-[( 2-hydroxyethyl) methacrylic acid] ester, a mixture of 65.0 g of phosphoric acid ester (A) and 4.1 g of 3-mercaptopropionic acid and ammonium persulfate. Two of 7.6 g dissolved in 30.4 g of water were added dropwise over 1.5 hours. After aging for 1 hour, 1.7 g of ammonium persulfate dissolved in 6.7 g of water was added dropwise over 30 minutes, and then aging was performed at the same temperature (80 ° C.) for 1.5 hours. After completion of aging, the mixture was neutralized with 63.5 g of a 30% aqueous sodium hydroxide solution to obtain a copolymer A-1.

The phosphoric acid ester (A) used in this example and the following production examples was obtained by the following production method. Charge 200g 2-hydroxyethyl methacrylate and 36.0g 85% phosphoric acid (H ₃ PO ₄ ) into the reaction vessel and add 89.1g phosphorous pentoxide (anhydrous phosphoric acid) (P ₂ O ₅ ) to a temperature of 60 ° C. Gradually added while cooling so as not to exceed. After completion, the reaction temperature was set to 80 ° C., the reaction was performed for 6 hours, and after cooling, a phosphoric acid ester (A) was obtained.

[Production Example A-2] (Production of Copolymer A-2)
446.2 g of water was charged into a glass reaction vessel (four-necked flask) equipped with a stirrer, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. ω-methoxypolyethyleneglycol monomethacrylate (average added mole number of ethylene oxide 9) 259.5 g (effective content 84.4%, moisture 10%), mono (2-hydroxyethyl) methacrylate and di-phosphate A mixture of 83.8 g of phosphoric acid ester (A) which is a mixture of [(2-hydroxyethyl) methacrylic acid] ester and 10.1 g of 3-mercaptopropionic acid and ammonium persulfate. Two of 7.3 g dissolved in 46 g of water were added dropwise over 1.5 hours. After aging for 1 hour, 2.9 g of ammonium persulfate dissolved in 11.8 g of water was added dropwise over 30 minutes, and then aging was performed at the same temperature (80 ° C.) for 1.5 hours. After completion of aging, the mixture was neutralized with 85.4 g of a 30% aqueous sodium hydroxide solution to obtain a copolymer A-2.

[Production Example A-3] (Production of Copolymer A-3)
A glass reaction vessel (four-necked flask) with a stirrer was charged with 430.1 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. ω-methoxypolyethyleneglycol monomethacrylate (average added mole number of ethylene oxide 23) 478.3 g (effective content 60.8%, moisture 35%), mono (2-hydroxyethyl) methacrylate and di-phosphate A mixture of 26.2 g of phosphoric acid ester (A) which is a mixture of [(2-hydroxyethyl) methacrylic acid] ester and 2.6 g of 3-mercaptopropionic acid and 6.6 g of ammonium persulfate into 26.4 g of water. Two of the dissolved ones were added dropwise over 1.5 hours. After aging for 1 hour, 1.5 g of ammonium persulfate dissolved in 5.8 g of water was added dropwise over 30 minutes, and then aging was performed at the same temperature (80 ° C.) for 1.5 hours. After completion of aging, the mixture was neutralized with 31.0 g of a 30% aqueous sodium hydroxide solution to obtain a copolymer A-3.

[Production Example A-4] (Production of Copolymer A-4)
359 g of water was charged into a glass reaction vessel with a stirrer (four-necked flask), purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. ω-methoxypolyethyleneglycol monomethacrylate (average addition mole number of ethylene oxide 23) 467.9 g (effective content 60.8%, moisture 35%), mono (2-hydroxyethyl) methacrylate phosphate and di-phosphate A mixture of 31.9 g of phosphoric acid ester (A) which is a mixture of [(2-hydroxyethyl) methacrylic acid] ester and 2.6 g of 3-mercaptopropionic acid and ammonium persulfate. Two of 6.7 g dissolved in 26.9 g of water were added dropwise over 1.5 hours. After aging for 1 hour, 1.5 g of ammonium persulfate dissolved in 6.0 g of water was added dropwise over 30 minutes, and then aging was performed at the same temperature (80 ° C.) for 1.5 hours. After completion of aging, the mixture was neutralized with 35.9 g of a 30% aqueous sodium hydroxide solution to obtain a copolymer A-4.

  Table 1 summarizes the outlines of the copolymers A-1 to A-4 obtained above.

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

(3) Component (C) The components shown in Table 3 below were used as the component (C).

(4) Component (D) The component (D) obtained in the following Production Example D-1 was used.

Production Example D-1
A glass reaction vessel (four-necked flask) with a stirrer was charged with 364.9 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. omega-methoxypolyethyleneglycol monomethacrylate (average added mole number of ethylene oxide 23) 475.3 g (effective portion 60.8%, moisture 35%), hydroxyethyl acrylate 90.6 g and 3-mercaptopropionic acid 3.31 g Two of the monomer solution mixed and dissolved and 4.75 g of ammonium persulfate dissolved in 45 g of water started to be dropped at the same time and dropped over 1.5 hours respectively, then 0.71 g of ammonium persulfate was added to 15 g of water. What was dissolved in was dropped over 0.5 hours. Thereafter, aging was performed at 80 ° C. for 1 hour. After completion of aging, the mixture was neutralized with a 20% aqueous sodium hydroxide solution to obtain a copolymer D-1.

<Preparation and evaluation of concrete>
Under the blending conditions shown in Table 4, cement (C), fine aggregate (S), and coarse aggregate (G) were added using a 100 L forced biaxial mixer, and kneaded for 10 seconds. 1 cm, additive composition, air entrainment agent (main component is polyoxyethylene lauryl ether sulfate) and antifoaming agent (main component is fatty acid ester) so that the target air entrainment amount is 4.5 to 5.5% Kneading water (W) was added and kneaded for 90 seconds. The air entraining agent was added to the kneaded water in an amount of 0.003% by weight based on the cement weight. Further, when the component (B) is a compound of the general formula (4), the antifoaming agent is blended in the additive composition in an amount of 0.1% by weight, and the compound of the general formula (5) or the comparative B-1, In the case of Comparative B-2, 0.03% by weight was blended. In addition, about this concrete, according to the test method shown below, the measurement of the slump value, the amount of air, drying shrinkage, and compressive strength (material age 28 days) was performed with the following method, respectively. The composition (effective component concentration) of the additive composition for a hydraulic composition is as shown in Table 5 (the balance is water), and was used by adding it to the kneading water so as to have the addition amount shown in Table 6. The evaluation results are shown in Table 6.
-Slump value: Measured according to JIS-A1101.
-Air amount: Measured according to JIS-A1128.
-Compressive strength: It measured based on JIS-A1108.
Drying shrinkage: measured in accordance with JIS-A1129-2 (contact gauge method). That is, a specimen of 100 mm × 100 mm × 400 mm was prepared and stored in a constant temperature and humidity chamber at a temperature of 20 ° C. ± 1 ° C. and a humidity of 60%, and the length change rate (× 10 ⁻⁶ ) of material age 91 days It was measured. It shows that drying shrinkage is so small that a rate of length change is small.

Water (W): Tap water Cement (C): Ordinary Portland cement (commercial product density 3.16)
Fine aggregate (S1): Land sand (density 2.62) FM 2.95
Fine aggregate (S2): Crushed sand (density 2.64) FM2.91
Fine aggregate (S3): mountain sand (density 2.61) FM 2.29
Coarse aggregate (G): Gravel (density 2.70) Actual rate 60.1%

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

  Among the above, for example, in Example 1, the flow retention (slump value) is maintained well for 90 minutes, and the air amount is Comparative Example 2 [(A) no component, (B), (C) component combined system ] Is stable for 90 minutes, and the compressive strength is nearly 10% higher. Further, the length change rate is also reduced by about 16% compared to Comparative Example 1.

  Also, in Example 3, the amount of air is stable for 90 minutes and the compressive strength is about 10% or more higher than Comparative Example 3 [(A) no component, (B), (C) combined system).

  Further, from Examples 6, 7, and 8, even when the component (C) is used in an amount of about 25% by weight of the component (A), the change in the amount of air over time is not affected.

  Moreover, even when one type of component (A) is used as in Examples 9 and 10, good physical properties such as fluidity retention and air stability can be obtained. Furthermore, it can be seen that by using a plurality of components (A) as in Examples 1 to 8, good physical properties, shrinkage reduction effect, and strength can be obtained with a smaller addition amount.

  On the other hand, when the (A) component is not used as in Comparative Examples 2 and 3 and the (B) and (C) components are used in combination, an increase in the amount of air over time is recognized, and the amount of air in the concrete is defined in 90 minutes. It will exceed 6% of the value. In addition, as in Comparative Examples 4 and 5, the glycerin and the glycerin ethylene oxide average 3 mol addition product cannot secure the fluidity retention. In addition, the length change rate is large.

Claims (5)

A monomer 1 represented by the following general formula (1), a monomer 2 represented by the following general formula (2), and a monomer 3 represented by the following general formula (3), pH 7 One or more types (A) of a phosphate ester polymer obtained by copolymerization below, and one or more types of compounds (B) selected from diethylene glycol monobutyl ether and a compound represented by the following general formula (5): A one-pack type additive composition for hydraulic compositions.

[Wherein R ¹ and R ² are each a hydrogen atom or a methyl group, R ³ is a hydrogen atom or —COO (AO) _n X, AO is an oxyalkylene group or oxystyrene group having 2 to 4 carbon atoms, n is It is the average added mole number of AO, the number of 3-200, X represents a hydrogen atom or a C1-C18 alkyl group. ]

[Wherein, R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents an alkylene group having 2 to 12 carbon atoms, m1 represents a number of 1 to 30, and M represents a hydrogen atom, an alkali metal or an alkaline earth metal. ]

[Wherein R ⁶ and R ⁸ are each a hydrogen atom or a methyl group, R ⁷ and R ⁹ are each an alkylene group having 2 to 12 carbon atoms, m2 and m3 are each a number from 1 to 30, and M is hydrogen. Represents an atom, an alkali metal or an alkaline earth metal. ]

Wherein, ^{A 2} is an alkylene group having a carbon number of 2 to 8, m 6, m7 and m8 is an average molar number of addition of each A ² O, m6, the sum of m7 and m8 becomes 6 to 30 Is a number. ]   The content of the component (A) is 3 to 30% by weight, the content of the component (B) is 5 to 70% by weight, and the weight ratio of the component (A) to the component (B) is (A) :( B The additive composition for hydraulic compositions according to claim 1, wherein the composition is 5:95 to 50:50.   Furthermore, it contains a polycarboxylic acid copolymer (C) [hereinafter referred to as component (C)], and the weight ratio of component (A) to component (C) is (A) :( C) = 100: 1. The additive composition for hydraulic compositions according to claim 1 or 2, wherein the total content of the component (A) and the component (C) is 3 to 30% by weight.   The additive composition for hydraulic composition according to any one of claims 1 to 3, wherein the component (A) is at least two of the phosphate ester polymers.   The manufacturing method of the hydraulic composition which mixes the additive composition for hydraulic compositions of any one of Claims 1-4, hydraulic powder, and water.