JP4896499B2 - Manufacturing method of concrete products - Google Patents

Description

  The present invention relates to a method for producing a concrete product.

In the manufacture of a concrete product manufactured using a hard-pressed concrete with a very small amount of cement paste, plasticity is required at the time of molding, and it is necessary that it has no fluidity at the time of demolding immediately after molding. General-purpose concrete admixtures such as naphthalene, melamine, and polycarboxylic acid known as concrete admixtures cannot be used. For this reason, it is produced with strong vibrations, but bean plates, soot, corner chips, etc. are likely to occur on the concrete surface, and the noise generated from the vibrator significantly deteriorates the environment, so improvement is desired. For example, Patent Document 1 proposes a manufacturing method that is effective for surface aesthetics even if the vibration output is reduced. On the other hand, a phosphate ester polymer has been proposed as a dispersant for cement (Patent Document 2).
Japanese Patent Laid-Open No. 2001-220195 JP 2000-327386 A

However, in so-called zero slump concrete (also referred to as super hard concrete), when the cement amount per unit amount (unit cement amount) in the cement blend is reduced, for example, 250 kg / m ³ or less, the moldability is lowered.

The object of the present invention is to produce a concrete product excellent in surface aesthetics and dimensional stability even in the case of using cemented concrete with a cement amount of 250 kg / m ³ or less in the production of a concrete product using a mold. It is to provide a method for producing a concrete product.

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). A zero slump concrete composition containing a phosphoric ester polymer (A) [hereinafter referred to as the component (A)] obtained by copolymerization of the above and having a unit cement amount of 250 kg / m ³ or less, The present invention relates to a method for producing a concrete product which is demolded after being filled into a frame. In the present invention, zero slump means a slump defined by JIS A 1101 of less than 1 cm.

[Wherein R ¹ and R ² are each a hydrogen atom or a methyl group, R ³ is a hydrogen atom or — (CH ₂ ) q (CO) pO (AO) rR ⁴ , and AO is an oxyalkylene having 2 to 4 carbon atoms. Group or oxystyrene group, p is a number of 0 or 1, q is a number of 0 to 2, r is an average added mole number of AO, a number of 3 to 300, R ⁴ is a hydrogen atom or a carbon number of 1 to 18 Represents an alkyl group. ]

[Wherein R ¹¹ is a hydrogen atom or a methyl group, R ¹² is an alkylene group having 2 to 12 carbon atoms, m1 is a number of 1 to 30, M ³ and M ⁴ are a hydrogen atom, an alkali metal or an alkaline earth metal, respectively. Represents. ]

[Wherein R ¹³ and R ¹⁵ are each a hydrogen atom or a methyl group, R ¹⁴ and R ¹⁶ are each an alkylene group having 2 to 12 carbon atoms, m2 and m3 are each a number of 1 to 30 and M ⁵ is Represents a hydrogen atom, an alkali metal or an alkaline earth metal. ]

According to the present invention, since the filling property of the zero slump concrete composition with a unit cement amount of 250 kg / m ³ or less into the formwork is good under the pressure vibration, the dimensional stability and the surface appearance are excellent. Concrete products can be manufactured.

  The present invention provides a method for producing a concrete product that can reduce the amount of unit cement of a super hard kneaded hydraulic composition (zero slump). In the present invention, a concrete product is produced by compacting a super hard kneaded (zero slump) hydraulic composition containing the component (A) under pressure and vibration, removing the mold, and then curing.

The surface aesthetics and dimensional stability to which the filling property after molding contributes are preferably as the amount of the fine particle component cement is larger, and generally the unit cement amount is preferably 250 kg / m ³ or more (National Concrete Block Association, (Published in January 1982, Guidelines for Manufacturing Concrete Blocks, p. 21, Article 30). However, in the present invention, by blending the component (A), a concrete product excellent in surface aesthetics and dimensional stability can be obtained even under the condition of a unit cement amount of 250 kg / m ³ or less.

<(A) component>
The component (A) is represented by the monomer 1 represented by the general formula (1), the monomer 2 represented by the general formula (2), and the general formula (3). It is a phosphoric ester polymer obtained by copolymerizing the monomer 3.

[Monomer 1]
In monomer 1, R ¹ and R ² in general formula (1) are each a hydrogen atom or a methyl group. R ³ is a hydrogen atom or — (CH ₂ ) _q (CO) _p O (AO) _r R ⁴ , preferably a hydrogen atom. R ⁴ is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, preferably 1 to 12, more preferably 1 to 4, and further preferably 1 or 2, and particularly preferably a methyl group. When p is 0, AO forms an ether bond with (CH ₂ ) _q, and when p is 1, it forms an ester bond. q is 0 to 2, preferably 0 or 1, and more preferably 0. AO is an oxyalkylene group having 2 to 4 carbon atoms or an oxystyrene group, and AO is preferably an oxyalkylene group having 2 to 4 carbon atoms, more preferably an ethyleneoxy group (hereinafter referred to as EO group), and an EO group. Is 70 mol% or more, more preferably 80 mol% or more, and further preferably 90 mol% or more, and in particular, all AO is preferably an EO group. r is the average added mole number of AO, is a number of 3 to 300, and is 3 to 300, preferably 4 to 120, more preferably from the viewpoint of imparting plasticity to the hydraulic composition of the polymer. It is 4 to 80, more preferably 4 to 50, particularly preferably 4 to 30. Moreover, AO is different in an average of r repeating units, and random addition, block addition, or a mixture thereof may be included. For example, AO can contain a propyleneoxy group etc. besides EO group.

  Monomer 1 includes a half-terminated alkyl-capped polyalkylene glycol such as methoxypolyethylene glycol, methoxypolypropylene glycol, methoxypolybutylene glycol, methoxypolystyrene glycol, ethoxypolyethylenepolypropyleneglycol, (meth) acrylic acid, maleic acid (half ) Esterified products, etherified products with (meth) allyl alcohol, and (meth) acrylic acid, maleic acid, and (meth) allyl alcohol adducts having 2 to 4 carbon atoms are preferably used. In addition, (meth) acrylic acid means acrylic acid and / or methacrylic acid, and (meth) allyl means allyl and / or methallyl (the same applies hereinafter).

  More preferred is an esterified product of alkoxy, particularly methoxypolyethylene glycol and (meth) acrylic acid. Specific examples include ω-methoxypolyoxyalkylene methacrylate and ω-methoxypolyoxyalkylene acrylate, and ω-methoxypolyoxyalkylene methacrylate is more preferable.

  The monomer 1 used for the production of the component (A) can be obtained, for example, by esterification of an alkoxypolyalkylene glycol and (meth) acrylic acid. The esterified product is an unreacted (meth) acrylic acid monomer in terms of acid type from the viewpoint of necessary addition amount and plasticity suitable for molding when used in the super hard kneaded concrete composition used in the present invention. It is preferably 5% by weight or less, more preferably 3% by weight or less, further preferably 1.5% by weight or less, and further preferably 1% by weight or less. Examples of a method for reducing the amount of (meth) acrylic acid remaining during the production of the monomer 1 include topping, steaming, and solvent extraction.

[Monomer 2]
In the monomer (2), R ¹¹ is a hydrogen atom or a methyl group, and R ¹² is an alkylene group having 2 to 12 carbon atoms. m1 is a number from 1 to 30, and M ³ and M ⁴ are each a hydrogen atom, an alkali metal, or an alkaline earth metal. 1-20 are preferable, as for m1 in General formula (2), 1-10 are more preferable, and 1-5 are especially preferable.

  Specific examples include phosphoric acid monoesters of organic hydroxy compounds. Specific examples include polyalkylene glycol mono (meth) acrylate acid phosphates. For example, phosphoric acid mono-[(2-hydroxyethyl) methacrylic acid] ester, phosphoric acid mono-[(2-hydroxyethyl) acrylic acid ester] and the like can be mentioned. Among these, phosphoric acid mono-[(2-hydroxyethyl) methacrylic acid] ester is preferable from the viewpoint of ease of production and product quality stability. Further, alkali metal salts, alkaline earth metal salts, ammonium salts, alkylammonium salts and the like of these compounds may be used.

[Monomer 3]
In the monomer 3, in the general formula (3), R ¹³ and R ¹⁵ are each a hydrogen atom or a methyl group, and R ¹⁴ and R ¹⁶ are each an alkylene group having 2 to 12 carbon atoms. m2, m3 is a number of each 1 to 30, M ⁵ represents a hydrogen atom, an alkali metal or alkaline earth metal. M2 and m3 in the general formula (3) are each preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5.

  Specific examples include phosphoric acid diesters of organic hydroxy compounds. Specific examples include polyalkylene glycol di (meth) acrylate acid phosphoric acid diester. Examples 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. Further, alkali metal salts, alkaline earth metal salts, ammonium salts, alkylammonium salts and the like of these compounds may be used.

  Monomers 2 and 3 can be used as a mixed monomer including monomer 2 and monomer 3. Further, as the monomer 2 and the monomer 3, a phosphate ester obtained by reacting the organic hydroxy compound represented by the general formula (4) with a phosphorylating agent may be used.

  The mixed monomer including the monomer 2 and the monomer 3 is obtained as a reaction product by reacting, for example, an organic hydroxy compound represented by the general formula (4) and a phosphorylating agent at a predetermined charge ratio. It can also be manufactured.

[Wherein, R ²⁰ represents a hydrogen atom or a methyl group, R ²¹ 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 (4), 1-10 are more preferable, and 1-5 are especially preferable.

  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. The amount of the phosphorylating agent in the reaction of the organic hydroxy compound and the phosphorylating agent can be appropriately determined according to the target phosphate ester composition.

  Examples of mixed monomers including monomer 2 and monomer 3 include mono-[(2-hydroxyethyl) methacrylic acid] phosphate and di-[(2-hydroxyethyl) methacrylic acid] phosphate. When the mixture is produced, it can be synthesized by a known technique (for example, JP-A-57-180618).

  As the mixed monomer including the monomer 2 and the monomer 3, a commercial product including a monoester and a diester can be used. For example, Phosmer M, Phosmer PE, Phosmer P (Unichemical) , JAMP514, JAMP514P, JMP100 (all Johoku Chemical), light ester P-1M, light acrylate P-1A (all Kyoeisha Chemical), MR200 (Daihachi Chemical), Kayamar (Nippon Kayaku), Ethyleneglycol methacrylate phosphate (Aldrich) Reagent).

  It has been confirmed that the above-mentioned commercial products and reaction products contain compounds other than the monoester (monomer 2) and diester (monomer 3). These other compounds are considered to be a mixture of polymerizable and non-polymerizable compounds, but in the present invention, such a mixture (mixed monomer) can be used as it is.

  The component (A) according to the present invention is a phosphate ester polymer obtained by copolymerizing the monomer 1, the monomer 2, and the monomer 3. It is also preferable to use a mixed monomer containing monomer 2 and monomer 3.

  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, and further 5 -96 / 3-80 / 1-60 (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 manufacture of (A) component, it is preferable that the ratio of the monomer 3 shall be 1-60 mol% and also 1-30 mol% in all the monomers used for reaction.

  The molar ratio of monomer 2 to monomer 3 is preferably monomer 2 / monomer 3 = 99/1 to 4/96, more preferably 99/1 to 5/95.

  From the viewpoint of suppressing gelation, the monomer solution containing monomer 2 and / or monomer 3 is preferably used for the reaction at a pH of 7 or less.

Hereinafter, more preferable production conditions will be described from the viewpoints of suppression of gelation, adjustment of a suitable molecular weight, and performance design of the component (A). From such a viewpoint, at the time of copolymerization, 4 mol% or more, further 6 mol% or more, particularly 8 mol% or more of the chain transfer agent is used with respect to the total number of moles of the monomers 1, 2 and 3. It is preferable. The upper limit of the amount of chain transfer agent used is preferably 100 mol% or less, more preferably 60 mol% or less, still more preferably 30 mol% or less, based on the total number of moles of monomers 1, 2 and 3. Most preferably, it can be 15 mol% or less. More specifically, (1) when r of monomer 1 is 3 to 30,
(1-1) When the total molar ratio of the monomers 1, 2 and 3 of the monomer 2 and the monomer 3 is 50 mol% or more, the chain transfer agent is the monomers 1, 2 and 3 It is preferable to use 6 to 100 mol%, particularly 8 to 60 mol%, based on the total of
(1-2) When the molar ratio in the sum of monomers 1, 2 and 3 of monomer 2 and monomer 3 is less than 50 mol%, the chain transfer agent is monomer 1, 2 and It is preferable to use 4 to 60 mol%, particularly 5 to 30 mol%, based on the total of 3.
(2) When r of monomer 1 used for component (A) is more than 30, the chain transfer agent is used in an amount of 6 to 50 mol%, particularly 8 to 40 mol%, based on monomers 1 to 3. Is preferred.

  The reaction rate of the monomers 2 and 3 is preferably 60% or more, more preferably 70% or more, more preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more. It can be selected from the viewpoint. Here, the reaction rate of the monomers 2 and 3 is calculated by the following equation.

In addition, the ratio (mol%) of the ethylenically unsaturated bond of the monomer 2 and the monomer 3 in the phosphorus-containing compound in the reaction system at the start and end of the reaction is measured by the following ¹ H-NMR. It can be calculated based on the result.
[ ¹ H-NMR conditions]
The component (A) 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 ratio of ethylenically unsaturated bonds is measured by an integral 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. Perform under conditions.

  In the production of the component (A), in addition to the monomers 1, 2, and 3, other monomers that can be copolymerized 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, 2, and 3 in all monomers is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, particularly preferably 75 to 100 mol%, and more than 95 mol% to 100 Mole%, more preferably 97-100 mol% is preferred.

  In the production of component (A), the monomer is preferably copolymerized in the presence of a predetermined amount of chain transfer agent. Moreover, you may use the other monomer, polymerization initiator, etc. which can be copolymerized.

  The reaction temperature of the monomers 1, 2 and 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 1.1 atm) in gauge pressure. 3-106.4 kPa (1-1.05 atm) is preferred.

  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.

  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 preferably 7 or less, more preferably 0.1 to 6, and further 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.

  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. It is preferable to start the reaction 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 method for producing the component (A), the monomers 1, 2 and 3 are reacted under the conditions exemplified in the following (1) and (2), usually under consideration of other conditions, The pH during the reaction is considered to be 7 or less.
(1) A monomer solution having a pH of 7 or less containing all of the monomers 1, 2 and 3 is used for the copolymerization reaction of the monomers 1, 2 and 3.
(2) The copolymerization reaction of the monomers 1, 2 and 3 is started at pH 7 or less. That is, the reaction is started after the reaction system containing the monomers 1, 2 and 3 is brought to pH 7 or lower.

[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 chain transfer agent, those having a —SH group are preferable, and in particular, the general formula HS—R—Eg (wherein R represents a hydrocarbon-derived group having 1 to 4 carbon atoms, and 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, Examples include octyl thioglycolate, octyl 3-mercaptopropionate, and the like from the viewpoint of chain transfer effect in a copolymerization reaction including monomers 1 to 3. 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]
(A) In the manufacturing method of a component, it is preferable to use a polymerization initiator, and it is 5 mol% or more, especially 7-50 mol with respect to the total number of moles of the monomers 1, 2, and 3 especially. %, Particularly 10 to 30 mol% is preferred.

  Examples of aqueous polymerization initiators include ammonium persulfate salt or alkali metal salt, hydrogen peroxide, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis (2-methylpropionamide) dihydrate, etc. These water-soluble azo compounds can be used. In addition, an accelerator such as sodium bisulfite and an amine compound can be used in combination with the polymerization initiator.

[solvent]
In the production of the component (A), it can be carried out by a solution polymerization method, and the solvent used in that case contains water or water and methyl alcohol, ethyl alcohol, isopropyl alcohol acetone, methyl ethyl ketone or the like. And hydrous solvent solvents. In view of handling and reaction equipment, water is preferred. In particular, when an aqueous solvent is used, the pH of the monomer solution containing the monomer 2 and / or the monomer 3 is preferably 7 or less, more preferably 0.1 to 6, particularly 0.2 to 4. A copolymerization reaction is preferably used for the reaction in terms of uniformity of the monomer mixture (handleability), monomer reaction rate, and suppression of crosslinking by hydrolysis of the pyro compound of the phosphoric acid compound.

  (A) An example of the manufacturing method of a component 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 preferably performed with an acid agent or the like while maintaining the pH at 7 or less, and preferably aging is performed 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. This production example is suitable as a method for producing the component (A) according to the present invention.

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

  The component (A) preferably has a weight average molecular weight (Mw) of 10,000 to 150,000. The component (A) has a Mw of 10,000 or more, preferably 12,000 or more, more preferably 13,000 or more, more preferably 14,000 or more, particularly from the viewpoint of necessary addition amount and imparting plasticity. Preferably it is 15,000 or more, and it is 150,000 or less, preferably 130,000 or less, more preferably from the viewpoints of high molecular weight by crosslinking, suppression of gelation and performance in terms of fluidity expression and separation suppression. 120,000 or less, more preferably 110,000 or less, particularly preferably 100,000 or less, and from the viewpoints of both, preferably 12,000 to 130,000, more preferably 13,000 to 120,000, More preferably, it is 14,000-110,000, Most preferably, it is 15,000-100,000. It is preferable to have Mw in this range and Mw / Mn is 1.0 to 2.6. Here, Mn is a number average molecular weight.

(A) Mw and Mn of a component are measured by the gel permeation chromatography (GPC) method of the following conditions.
[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

  Further, in the chart pattern showing the molecular weight distribution obtained by the GPC method under the above conditions, the area where the molecular weight is 100,000 or more is 5% or less of the total area of the chart, and the fluidity (required addition amount reduction) More preferable in terms.

<Concrete composition of zero slump>
In the production method of the present invention, a zero slump concrete composition containing the component (A) and having a unit cement amount of 250 kg / m ³ or less is used. Unit cement content of the concrete composition is preferably ^{230~250kg / m 3, 240~250kg / m} 3 and more preferably. Examples of the cement include ordinary portland cement, blast furnace cement, fly ash cement, alumina cement and the like.

Further, increasing the unit water amount not only causes a decrease in dimensional stability but also reduces the surface aesthetics, so the unit water amount of the concrete composition is preferably 120 kg / m ³ or less, 90 to 120 kg / m ³ , Further, 100 to 120 kg / m ³ , particularly 110 to 120 kg / m ³ is preferable.

  The amount of component (A) added to the concrete composition is preferably 0.01 to 1.0 part by weight, more preferably 0.05 to 0.7 part, particularly 0.1 -0.5 part is preferable from the surface of a filling property.

  In the concrete composition used for this invention, a well-known additive (material) can be used together with (A) component. For example, AE agent, AE water reducing agent, fluidizing agent, high performance water reducing agent, retarder, early strengthening agent, accelerator, foaming agent, foaming agent, antifoaming agent, thickener, waterproofing agent, antifoaming agent, etc. Examples include quartz sand, blast furnace slag, fly ash, and silica fume.

Furthermore, the concrete composition used in the present invention preferably contains aggregate in order to obtain a zero slump with a unit cement amount of 250 kg / m ³ or less. Aggregates include fine aggregates and coarse aggregates. Fine aggregates include mountain sand, land sand, river sand, crushed sand, and coarse aggregates include mountain gravel, land gravel, river gravel, crushed stone, and the like. A lightweight aggregate may be used depending on the type of the molded body. The term “aggregate” is based on “Concrete Overview” (published on June 10, 1998, published by Technical Shoin).

In the production method of the present invention, a zero slump concrete composition containing the component (A) is filled into a mold, molded, and then demolded to obtain a concrete block, a concrete plate, a concrete pipe, and porous concrete. Etc. to obtain concrete products. From the viewpoint of productivity, it is preferable to perform mold release immediately after molding without curing, after mold filling is completed, that is, to perform immediate mold release. In the present invention, a zero slump concrete composition having a unit cement amount of 250 kg / m ³ or less is used. Further, when filling the mold, it is preferable to perform a pressurizing operation such as vibration or press molding by a vibration molding machine from the viewpoint of sufficiently filling the concrete composition in the mold without a gap. In the present invention, vibration and pressurization can be filled in the mold at a weaker level than before. In this invention, even if it uses the concrete composition which reduced the unit cement amount, since it is excellent in a moldability, it is advantageous to cost reduction.

Production Example A1
366 g of water was charged into a glass reaction vessel (four-necked flask) equipped with a stirrer, and was purged with nitrogen while stirring, and the temperature was raised to 80 ° C. in a nitrogen atmosphere. 450 g of ω-methoxypolyethyleneglycol monomethacrylate (average added mole number of ethylene oxide 23) (effective part 60.8% by weight, moisture 35% by weight), phosphoric acid mono-[(2-hydroxyethyl) methacrylic acid] ester and phosphorus A mixture of 71.6 g of phosphoric acid ester (A), which is a mixture of acid di-[(2-hydroxyethyl) methacrylic acid] ester and 4.5 g of 3-mercaptopropionic acid, and 8.4 g of ammonium persulfate in water Two of those dissolved in 48 g were added dropwise over 1.5 hours. After aging for 1 hour, 1.8 g of ammonium persulfate dissolved in 10 g of water was added dropwise over 30 minutes, and then aging was carried out at the same temperature (80 ° C.) for 1.5 hours. After completion of aging, the mixture was neutralized with 44.4 g of a 32% aqueous sodium hydroxide solution to obtain a polymer a-1 having a weight average molecular weight of 35,000. (Monomer polymerization pH: 1.0, reaction rate 100%)

The phosphoric acid ester (A) used in this production example was prepared by charging 200 g of 2-hydroxyethyl methacrylate and 36.0 g of 85% phosphoric acid (H ₃ PO ₄ ) in a reaction vessel. Obtained by gradually adding 89.1 g of (phosphoric acid) (P ₂ O ₅ ) while cooling so that the temperature does not exceed 60 ° C., setting the reaction temperature to 80 ° C., reacting for 6 hours, and cooling. Is. This phosphate esterified product (A) was also used in some of the following production examples.

Production Example A2
371 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. 500 g of ω-methoxypolyethyleneglycol monomethacrylate (average added mole number of ethylene oxide 23) (effective part 60.8% by weight, moisture 35% by weight), phosphoric acid mono-[(2-hydroxyethyl) methacrylic acid] ester and phosphorus A mixture of 34.1 g of phosphoric acid ester (A), which is a mixture of acid di-[(2-hydroxyethyl) methacrylic acid] ester and 2.8 g of 3-mercaptopropionic acid, and 7.2 g of ammonium persulfate in water Two of those dissolved in 41 g were added dropwise over 1.5 hours. After aging for 1 hour, 1.6 g of ammonium persulfate dissolved in 9 g of water was added dropwise over 30 minutes, and then aging was carried out at the same temperature (80 ° C.) for 1.5 hours. After completion of the aging, the mixture was neutralized with 21.2 g of a 32% aqueous sodium hydroxide solution to obtain a polymer a-2 having a weight average molecular weight of 34,000. (Monomer polymerization pH: 1.1, reaction rate 100%)

Production Example A3
A glass reaction vessel (four-necked flask) with a stirrer was charged with 381 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 520 g of ω-methoxypolyethyleneglycol monomethacrylate (average addition mole number of ethylene oxide 23) (effective part 60.8% by weight, moisture 35% by weight), mono-[(2-hydroxyethyl) methacrylic acid] phosphate and phosphorus A mixture of 28.6 g of phosphoric acid ester (A) which is a mixture of acid di-[(2-hydroxyethyl) methacrylic acid] ester and 2.8 g of 3-mercaptopropionic acid, and 7.2 g of ammonium persulfate in water Two of those dissolved in 41 g were added dropwise over 1.5 hours. After aging for 1 hour, 1.6 g of ammonium persulfate dissolved in 9 g of water was added dropwise over 30 minutes, and then aging was carried out at the same temperature (80 ° C.) for 1.5 hours. After completion of aging, the mixture was neutralized with 17.7 g of a 32% aqueous sodium hydroxide solution to obtain a polymer a-3 having a weight average molecular weight of 36000. (Monomer polymerization pH: 1.1, reaction rate 100%)

Production Example A4
A glass reaction vessel (four-necked flask) equipped with a stirrer was charged with 471 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 290 g of ω-methoxypolyethyleneglycol monomethacrylate (average addition mole number of ethylene oxide 9) (effective content 84.4% by weight, moisture 10% by weight), phosphoric acid mono-[(2-hydroxyethyl) methacrylic acid] ester and phosphorus A mixture of 93.8 g of phosphoric acid ester (A), which is a mixture of acid di-[(2-hydroxyethyl) methacrylic acid] ester and 11.3 g of 3-mercaptopropionic acid, and 8.2 g of ammonium persulfate in water Two of those dissolved in 46 g were added dropwise over 1.5 hours. After aging for 1 hour, a solution prepared by dissolving 3.3 g of ammonium persulfate in 19 g of water was dropped over 30 minutes, and then aging was performed at the same temperature (80 ° C.) for 1.5 hours. After completion of aging, the solution was neutralized with 58.2 g of a 32% aqueous sodium hydroxide solution to obtain a polymer a-4 having a weight average molecular weight of 25,000. (Monomer polymerization pH: 1.0, reaction rate 99%)

Production Example A5
489 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. 290 g of ω-methoxypolyethyleneglycol monomethacrylate (average addition mole number of ethylene oxide 9) (effective content 84.4% by weight, moisture 10% by weight), phosphoric acid mono-[(2-hydroxyethyl) methacrylic acid] ester and phosphorus A mixture of 53.2 g of phosphoric acid ester (A) which is a mixture of acid di-[(2-hydroxyethyl) methacrylic acid] ester and 9.1 g of 3-mercaptopropionic acid and 7.8 g of ammonium persulfate in water Two of those dissolved in 44 g were added dropwise over 1.5 hours. After aging for 1 hour, a solution prepared by dissolving 3.1 g of ammonium persulfate in 18 g of water was dropped 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 33.0 g of a 32% aqueous sodium hydroxide solution to obtain a polymer a-5 having a weight average molecular weight of 21,000. (Monomer polymerization pH: 1.1, reaction rate 98%)

Production Example A6
A glass reaction vessel (four-necked flask) with a stirrer was charged with 189 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 40 g of ω-methoxypolyethylene glycol monomethacrylate (addition mole number of ethylene oxide 9: NK ester M90G manufactured by Shin-Nakamura Chemical Co., Ltd.), mono-[(2-hydroxyethyl) methacrylic acid] phosphate and di-[(2- Hydroxyethyl) methacrylic acid] ester mixture (Fosmer M: Unichemical Co., Ltd.) 43.8 g and 3-mercaptopropionic acid 1.6 g in water 40 g and ammonium persulfate 5.4 g in water 62 g Two of the dissolved ones were added dropwise over 1.5 hours. After aging for 1 hour, 2.7 g of ammonium persulfate dissolved in 31 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 54.4 g of a 20% aqueous sodium hydroxide solution to obtain a polymer a-6 having a weight average molecular weight of 51,000. (Monomer polymerization pH: 1.1, reaction rate 100%)

Production Example A7
A glass reaction vessel (four-necked flask) with a stirrer was charged with 218 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 55 g of ω-methoxypolyethylene glycol monomethacrylate (addition mole number of ethylene oxide 23: NK ester M230G manufactured by Shin-Nakamura Chemical Co., Ltd.), mono-[(2-hydroxyethyl) methacrylic acid] phosphate and di-[(2- Hydroxyethyl) methacrylic acid] ester mixture (Fosmer M: Unichemical Co., Ltd.) 32.3 g and 3-mercaptopropionic acid 1.1 g dissolved in water 55 g and ammonium persulfate 3.8 g in water 43 g Two of the dissolved ones were added dropwise over 1.5 hours. After aging for 1 hour, 1.9 g of ammonium persulfate dissolved in 22 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 40.1 g of a 20% aqueous sodium hydroxide solution to obtain a polymer a-7 having a weight average molecular weight of 51,000. (Monomer polymerization pH: 1.3, reaction rate 100%)

Production Example B1
A glass reaction vessel with a stirrer (four-necked flask) was charged with 281.4 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. What dissolved 336.5 g of ω-methoxypolyethylene glycol methacrylate (added mole number of ethylene oxide 120), 22.2 g of methacrylic acid and 1.89 g of 2-mercaptoethanol in 238.2 g of water, and dissolved 3.68 g of ammonium persulfate in 45 g of water. The two were added dropwise over 1.5 hours each. Subsequently, 1.47 g of ammonium persulfate dissolved in 15 g of water was added dropwise over 30 minutes, and then aging was performed at the same temperature (80 ° C.) for 1 hour. After completion of aging, the mixture was neutralized with 18.7 g of 48% sodium hydroxide to obtain a copolymer b-1. (Weight average molecular weight 79000)

Production Example B2
A glass reaction vessel with a stirrer (four-necked flask) was charged with 246.4 g of water, purged with nitrogen while stirring, and heated to 56 ° C. in a nitrogen atmosphere. The mixture of 148.8 g of ω-methoxypolyethyleneglycol methacrylate (ethylene oxide addition number 10), 39.2 g of methacrylic acid and 2.32 g of 3-mercaptopropionic acid, and 43.3 g of 5% aqueous solution of ammonium persulfate for 1.5 hours each It was dripped over. Thereafter, aging was performed at the same temperature (56 ° C.) for 3 hours. After completion of aging, the mixture was neutralized with 48% sodium hydroxide to pH = 6 to obtain a copolymer b-2. (Molecular weight 34000)

Examples 1-8 and Comparative Examples 1-5
The copolymer obtained above was added to the following concrete composition as shown in Table 1 to produce a concrete composition of zero slump, and a shaped article having the shape of FIG. 1 was produced by a vibration molding machine. The vibration molding machine is “Chiyoda DG-3” (manufactured by Chiyoda Giken Co., Ltd., biaxial unbalanced weight vertical vibration method), with a vibration frequency of 6100vpm, vibration of the vibrator motor output of 3.7kW × 2, frequency 30Hz (maximum The press molding (press pressure 0.34 MPa (3.5 kg / cm ² )) was performed at an acceleration of 2.6 G) for 30 seconds, and the mold was removed immediately after. The obtained molded body was visually observed after 24 hours, and the surface condition and dimensional accuracy were evaluated by the following judgments. For dimensional accuracy, the height of the molded body (L in FIG. 1) was measured with a caliper. The results are also shown in Table 1. The void in the evaluation of the surface state refers to a portion that is not filled with concrete in the mold.

(Concrete mix)
Cement: C = 240 kg (manufactured by Taiheiyo, ordinary Portland cement, density = 3.16 g / cm ³ )
Water: W = 115kg (tap water)
Fine aggregate: S = 964 kg (produced by Kimitsu, Chiba, density = 2.60 g / cm ³ )
Coarse aggregate: G = 1096 kg (crushed stone from Wakayama, density = 2.62 g / cm ³ )
W / C = 47.9%
S / A = 47.0%

(Surface condition)
◎… No corner chipping, no gap ○… No corner chipping, few gaps △… Cut corners and few gaps ×… Cut corners, many gaps (Dimensional accuracy)
◎ ... Error less than 1mm ○ ... Error from 1mm to less than 3mm △ ... Error from 3mm to less than 7mm × ... Error from 7mm or more

(note)
In the table, the addition amount of the copolymer is parts by weight with respect to 100 parts by weight of cement. Comparative product 1 and comparative product 2 are as follows.
Comparative product 1: Table 5 of JP-A-2005-22907, additive of Example 1-8 Comparative product 2: Table 6 of JP-A-2005-22907, additive of Example 1-16

BRIEF DESCRIPTION OF THE DRAWINGS It is the schematic of the concrete molded object manufactured in the Example, (a) is a top view, (b) is a front view.

Claims (4)

Monomer 1 represented by the following general formula (1), monomer 2 represented by the following general formula (2), and monomer 3 represented by the following general formula (3) are copolymerized A zero slump concrete composition containing a phosphoric ester polymer (A) obtained in this manner, having a unit cement amount of 230 to 250 kg / m ³ and a unit water amount of 110 to 120 kg / m ³ , A method for producing a concrete product in which a frame is filled and demolded immediately after molding.

[Wherein R ¹ and R ² are each a hydrogen atom or a methyl group, R ³ is a hydrogen atom or — (CH ₂ ) q (CO) pO (AO) rR ⁴ , AO is an oxyalkylene group having 2 carbon atoms , p is the number of 1 , q is the number of 0 , r is the average added mole number of AO, the number of 4 to 30 , and R ⁴ represents a methyl group . ]

[Wherein R ¹¹ is a hydrogen atom or a methyl group, R ¹² is an alkylene group having 2 to 12 carbon atoms, m1 is a number of 1 to 5 , M ³ and M ⁴ are a hydrogen atom, an alkali metal or an alkaline earth metal, respectively. Represents. ]

[Wherein, R ¹³ and R ¹⁵ are each a hydrogen atom or a methyl group, R ¹⁴ and R ¹⁶ are each an alkylene group having 2 to 12 carbon atoms, m2 and m3 are each a number of 1 to 5 , and M ⁵ is Represents a hydrogen atom, an alkali metal or an alkaline earth metal. ]   The method for producing a concrete product according to claim 1, wherein the concrete composition of zero slump contains 0.1 to 0.5 parts by weight of the phosphate ester polymer (A) with respect to 100 parts by weight of cement. Phosphoric acid ester-based polymer (A), in the presence of a chain transfer agent, according to claim 1 or 2, wherein is obtained by copolymerizing a monomer 1 and monomer 2 and monomer 3 Method of manufacturing concrete products. Phosphoric acid ester-based polymer (A), at pH7 or less, any one of claim 1 to 3 is obtained by copolymerizing a monomer 1 and monomer 2 and monomer 3 The manufacturing method of the concrete product as described.

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