JP2009155173A - Admixing agent for hydraulic composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an admixing agent for a hydraulic composition which can afford good initial fluidity (kneadability), viscosity-reducing effects and fluidity-retaining ability to the hydraulic composition. <P>SOLUTION: This admixing agent for a hydraulic composition contains a specific alkenylether-based copolymer [compound (1)] and two kinds of specific polycarboxylic acid-based copolymers [compound (2), (3)] different in alkylene oxide addition molar numbers, at specific ratios. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an admixture for a hydraulic composition.

  Among the admixtures for hydraulic compositions, there is one called a high-performance water reducing agent having a large fluidity-imparting effect. Typical examples thereof include naphthalene sulfonic acid formaldehyde condensate salt (naphthalene type), melamine sulfonic acid formaldehyde condensate salt (melamine type), polycarboxylic acid type having a polyoxyalkylene chain, and the like.

  In recent years, concrete, which is a typical hydraulic composition, has become more durable. For example, the amount of water used in concrete has been reduced to increase its strength. Are also expected to increase. In order to reduce the amount of water, it is mainstream to use a polycarboxylic acid-based water reducing agent that is excellent in water reduction and fluid retention.

  Properties required for hydraulic compositions such as concrete have many physical properties required for construction problems in the state of fresh concrete (green concrete) before curing, excellent fluidity, and stable fluidity. That it has a good setting time. In order to satisfy these required characteristics, various polycarboxylic acid-based admixtures have been proposed in the past, and further, a plurality of copolymers including polycarboxylic acid-based polymers have been proposed to be used in combination.

For example, Patent Document 1 describes a cement dispersant in which a specific polycarboxylic acid copolymer and two specific allyl ether copolymers are combined at a predetermined ratio. Patent Document 2 discloses a copolymer of a specific alkenyl ether and maleic acid or a salt thereof (I), a specific monomer (a) such as a (meth) acrylic acid ester of methoxypolyethylene glycol ( A dispersant for a hydraulic composition containing a copolymer (b) obtained by polymerizing a monomer mixture containing a specific monomer (b) such as (meth) acrylic acid is described. . Patent Document 3 describes a cement admixture containing two types of copolymers having different ratios of unsaturated carboxylic acid monomers and different addition mole numbers of oxyalkylene groups as essential components. ing.
JP 7-267705 A JP 2002-187755 A JP 11-335150 A

  In recent years, the amount of building materials produced by secondary concrete products has increased. Further, the building members are required to have higher strength. For this reason, various obstacles such as an increase in concrete viscosity, a decrease in kneadability, and an unstable flow retention behavior have occurred due to an increase in cement amount or a change in cement type. As a result, the productivity is reduced due to a decrease in workability. This is particularly true for products that use moderately hot cement, which has been increasing in recent years.

  The object of the present invention is to provide good initial fluidity (kneading property), viscosity reduction effect, fluidity retention for hydraulic compositions using hydraulic powders that are belite cements such as moderately heated cement. It is providing the admixture for hydraulic compositions which can provide.

The present invention contains the following compounds (1) to (3), the proportion of compound (1) in the total of compounds (1) to (3) is 30 to 90% by weight, and the proportion of compound (2) is 5 It is related with the admixture for hydraulic compositions whose -30 weight% and the ratio of a compound (3) are 5-60 weight%.
<Compound (1)>
Copolymer or salt thereof of alkenyl ether derivative represented by the following general formula (A) and maleic acid R ¹ (AO) _n1 R ² (A)
(In the formula, R ¹ is an alkenyl group having 2 to 4 carbon atoms, AO is an oxyalkylene group having 2 to 3 carbon atoms, n1 is an average added mole number of AO, 2 to 90, and R ² is carbon number. 1 to 3 alkyl groups)
<Compound (2)>
A monomer (b) represented by the following general formula (B) and one or more monomers (c) selected from the compounds represented by the following general formulas (C1) and (C2): c) / (b) = a copolymer obtained by copolymerization at a molar ratio of 70/30 to 95/5.

Wherein R ³ and R ⁴ are a hydrogen atom or a methyl group, m1 is a number from 0 to 2, AO is a oxyalkylene group having 2 to 3 carbon atoms, n2 is a number from 100 to 300, and X is a hydrogen atom or Represents an alkyl group having 1 to 3 carbon atoms.)

(Wherein R ^{5 to} R ⁷ are each a hydrogen atom, a methyl group, or (CH ₂ ) _m2 COOM ² , R ⁸ is a hydrogen atom or a methyl group, and M ¹ , M ² , and Y are a hydrogen atom or a positive atom, respectively. Ion, m2 represents the number of 0-2.)
<Compound (3)>
A monomer (d) represented by the following general formula (D), and one or more monomers (c) selected from the compounds represented by the general formulas (C1) and (C2), c) / (d) = a copolymer obtained by copolymerization at a molar ratio of 60/40 to 90/10.

(Wherein R ⁹ and R ¹⁰ are each a hydrogen atom or a methyl group, m3 is a number from 0 to 2, AO is an oxyalkylene group having 2 to 3 carbon atoms, n3 is a number from 2 to 90, and X is a hydrogen atom. Or represents a C1-C3 alkyl group.)

In addition, the present invention is obtained by mixing the following compounds (1) to (3), the ratio of the compound (1) in the total of the compounds (1) to (3) is 30 to 90% by weight, the compound (2 ) Is 5 to 30% by weight, and the proportion of compound (3) is 5 to 60% by weight.
<Compound (1)>
Copolymer or salt thereof of alkenyl ether derivative represented by the following general formula (A) and maleic acid R ¹ (AO) _n1 R ² (A)
(In the formula, R ¹ is an alkenyl group having 2 to 4 carbon atoms, AO is an oxyalkylene group having 2 to 3 carbon atoms, n1 is an average added mole number of AO, 2 to 90, and R ² is carbon number. 1 to 3 alkyl groups)
<Compound (2)>
A monomer (b) represented by the following general formula (B) and one or more monomers (c) selected from the compounds represented by the following general formulas (C1) and (C2): c) / (b) = a copolymer obtained by copolymerization at a molar ratio of 70/30 to 95/5.

(Wherein R ³ and R ⁴ are a hydrogen atom or a methyl group, m1 is a number of 0 to 2, AO is an oxyalkylene group having 2 to 3 carbon atoms, and n2 is an average added mole number of AO; 300 number, X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

(Wherein R ^{5 to} R ⁷ are each a hydrogen atom, a methyl group, or (CH ₂ ) _m2 COOM ² , R ⁸ is a hydrogen atom or a methyl group, and M ¹ , M ² , and Y are a hydrogen atom or a positive atom, respectively. Ion, m2 represents the number of 0-2.)
<Compound (3)>
A monomer (d) represented by the following general formula (D), and one or more monomers (c) selected from the compounds represented by the general formulas (C1) and (C2), c) / (d) = a copolymer obtained by copolymerization at a molar ratio of 60/40 to 90/10.

(In the formula, R ⁹ and R ¹⁰ are each a hydrogen atom or a methyl group, m3 is a number of 0 to 2, AO is an oxyalkylene group having 2 to 3 carbon atoms, and n3 is an average added mole number of AO. The number of -90, X represents a hydrogen atom or a C1-C3 alkyl group.)

  The present invention also relates to a hydraulic composition containing the admixture for hydraulic composition of the present invention and a hydraulic powder.

  ADVANTAGE OF THE INVENTION According to this invention, the admixture for hydraulic compositions which can provide favorable initial fluidity | liquidity (kneading property), a viscosity reduction effect, and fluidity retention with respect to a hydraulic composition is provided. The admixture for a hydraulic composition of the present invention is the above-described hydraulic composition using various hydraulic powders, for example, ordinary Portland cement, medium heat Portland cement, low heat Portland cement, early strength Portland cement and the like. In particular, belite-based cement (cement having a lot of belite components), medium-heated Portland cement, and low-heat Portland cement greatly improve the effect.

<Compound (1)>
In the general formula (A) of the alkenyl ether derivative constituting the compound (1) of the present invention, the alkenyl group having 2 to 4 carbon atoms represented by R ¹ is preferably a vinyl group, an allyl group, a methallyl group, or the like. However, an allyl group is more general and more preferable. AO is an oxyethylene group and / or an oxypropylene group, and the addition form may be single, random, block, or alternating. An oxyethylene group is preferred. R ² is an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. A methyl group is preferred.

  The average added mole number n1 of alkylene oxide is in the range of 2 to 90, and is preferably 10 to 70, more preferably 10 to 50, from the viewpoint of imparting fluidity and imparting low viscosity to fresh concrete.

  The compound (1) of the present invention is a copolymer of the monomer represented by the general formula (A) and maleic acid, preferably the molar ratio of the monomer of the general formula (A) / maleic acid = It is a copolymer or its salt which is 25 / 75-50 / 50. Maleic acid may be an anhydride. Examples of the method for producing the compound (1) include methods described in JP-A-2-163108 and JP-A-5-345647.

  Moreover, the preferable weight average molecular weight of a compound (1) is 3000-300,000, Furthermore, 5000-100,000 from a viewpoint of the stable fluidity | liquidity provision of fresh concrete.

  Examples of the compound (1) include Marialim EKM, Marialim AKM (manufactured by NOF Corporation) and Super 200 (manufactured by Electrochemical Co., Ltd.).

<Compound (2)>
The compound (2) of the present invention includes a monomer (b) represented by the general formula (B) obtained by adding 100 to 300 moles of an average number of moles of an alkylene oxide having 2 to 3 carbon atoms, and the general formula (C1) and / or (C2), preferably the monomer (c) represented by the general formula (C1), in a molar ratio of (c) / (b) = 70/30 to 95/5 Obtained by polymerization. From the viewpoint of imparting stable initial fluidity of fresh concrete, the average added mole number n2 of alkylene oxide in the monomer (b) is in the range of 100 to 300, preferably 100 to 250, more preferably 100 to 200, 100-150 is still more preferable. In addition, in the monomer for obtaining a compound (2), when using several monomer (b) from which n2 differs, the average value of n2 of all the monomers (b) is in the range of 100-300. Adjust the composition to be. For example, when two types of monomers (b) are used, one is n2 = 100 to 290, the other is n2 ′ = 100 to 300, preferably n2 ≠ n2 ′ and n2 ′ ≧ n2 + 10, and n2 ′ It is more preferable that ≧ n2 + 30, and it is even more preferable that n2 ′ ≧ n2 + 50. Furthermore, a monomer having n2 of less than 100 may be used in combination as long as the effects of the present invention are not impaired.

  As the monomer (b) represented by the general formula (B), an esterified product of a polyalkylene glycol having a one-end alkyl group blocked such as methoxypolyethylene glycol, methoxypolypropylene glycol or ethoxypolyethylenepolypropyleneglycol and (meth) acrylic acid Also, EO and PO adducts to (meth) acrylic acid are preferably used. The additional form may be single, random, block, or alternating. More preferably, it is an esterified product of methoxypolyethylene glycol and (meth) acrylic acid, and an esterified product of methoxypolyethylene glycol and methacrylic acid having an average added mole number of ethylene oxide of 100 to 200 is more preferable.

  Examples of the monomer represented by the general formula (C1) include unsaturated monocarboxylic acid monomers such as acrylic acid, methacrylic acid, and crotonic acid, maleic anhydride, maleic acid, itaconic anhydride, itaconic acid, and fumaric acid. Unsaturated dicarboxylic acid monomers such as these, or alkali metal salts, alkaline earth metal salts, ammonium salts, mono-, di-, or trialkylammonium salts in which a hydroxyl group may be substituted are preferred, and acrylics are more preferred. Acid, methacrylic acid and alkali metal salts thereof.

  Examples of the monomer represented by the general formula (C2) include allyl sulfonic acid, methallyl sulfonic acid, or an alkali metal salt, an alkaline earth metal salt, an ammonium salt, or a mono or di group in which a hydroxyl group may be substituted. Trialkylammonium salts are used.

  Preferably, the compound (2) is a monomer (b) represented by the general formula (B) and one or more monomers (c) represented by the general formulas (C1) and (C2). And a monomer mixture containing 50% by weight or more, more preferably 80 to 100% by weight or more, and even more preferably 100% by weight.

  The monomer (b) of the general formula (B) constituting the compound (2) and the monomer (c) of the general formula (C1) and / or the general formula (C2) are (c) / (b) = (C) / (b), preferably 75/25 to 95/5, more preferably copolymerized at a molar ratio of 70/30 to 95/5, from the viewpoint of imparting stable initial fluidity of fresh concrete. Is copolymerized at a molar ratio of 80/20 to 95/5, more preferably 85/15 to 95/5.

  The weight average molecular weight of the compound (2) is preferably in the range of 5,000 to 500,000 from the viewpoint of imparting stable initial fluidity of fresh concrete, and in the range of 20,000 to 100,000, and more preferably in the range of 30,000 to 85,000, imparting initial fluidity of fresh concrete. Excellent effect. The weight average molecular weight is determined by gel permeation chromatography (in terms of standard substance sodium polystyrene sulfonate).

  Compound (2) can be produced by a known method. Examples thereof include solution polymerization methods described in JP-A-7-223852, JP-A-4-209737, and JP-A-58-74552. In water and lower alcohols having 1 to 4 carbon atoms, ammonium persulfate, In the presence of a polymerization initiator such as hydrogen oxide, sodium bisulfite, mercaptoethanol or the like may be added if necessary and reacted at 50 to 100 ° C. for 0.5 to 10 hours.

  Other copolymerizable monomers can be used in combination as a raw material for the compound (2). Specifically, acrylonitrile, alkyl (meth) acrylate (C1-12) ester, (meth) acrylamide, styrene, styrene sulfonic acid Etc.

<Compound (3)>
The compound (3) copolymer (b) of the present invention comprises a monomer (d) represented by the above general formula (D) in which an alkylene oxide having 2 to 3 carbon atoms is added in an average addition mole number of 2 to 90 moles. ) And the monomer (c) represented by the general formula (C1) and / or (C2), preferably the general formula (C1), (c) / (d) = 60/40 to 90 / It is obtained by copolymerization at a molar ratio of 10. From the viewpoint of imparting stable fluidity and fluidity retention of fresh concrete, the average added mole number n3 of alkylene oxide in the monomer (b) is in the range of 2 to 90, preferably 5 to 70, and 5 to 50. Is more preferable, and 5 to 40 is even more preferable. In the monomer mixture for obtaining the compound (3), when a plurality of monomers (d) having different n3 are used, the average value of n3 of all the monomers (d) is in the range of 2 to 90. The composition is adjusted to For example, when two types of monomers (d) are used, one is n3 = 2 to 87, the other is n3 ′ = 2 to 90, preferably n3 ≠ n3 ′ and n3 ′ ≧ n3 + 3, and n3 ′ ≧ n3 + 5 is more preferable, and n3 ′ ≧ n3 + 10 is still more preferable. Furthermore, a monomer having n3 exceeding 90 can be used in combination as long as the effects of the present invention are not impaired.

  As the monomer (d) represented by the general formula (D), an esterified product of a polyalkylene glycol having a single-end alkyl group blocked such as methoxypolyethylene glycol, methoxypolypropylene glycol or ethoxypolyethylenepolypropyleneglycol and (meth) acrylic acid Also, EO and PO adducts to (meth) acrylic acid are preferably used. The additional form may be single, random, block, or alternating. More preferably, it is an esterified product of methoxypolyethylene glycol and (meth) acrylic acid, and an esterified product of methoxypolyethylene glycol and methacrylic acid having an EO average addition mole number of 2 to 90 is still more preferable.

  As the monomer represented by the general formula (C1) and the monomer represented by the general formula (C2), those mentioned in the compound (2) can be used.

  Preferably, the compound (3) is a monomer (d) represented by the general formula (D) and one or more monomers (c) represented by the general formulas (C1) and (C2). And a monomer mixture containing 50 wt% or more, further 80 to 100 wt% or more, and further 100 wt%.

  The monomer (d) of the general formula (D) constituting the compound (3) and the monomer (c) of the general formula (C1) and / or the general formula (C2) are (c) / (d) From the viewpoint of imparting stable fluidity retention of fresh concrete which is copolymerized at a molar ratio of 60/40 to 90/10, (c) / (d), preferably 65/35 to 90/10, more preferably Is copolymerized in a molar ratio of 65/35 to 85/15, more preferably 65/35 to 80/20.

  The weight average molecular weight of the compound (3) is preferably in the range of 5,000 to 500,000 from the viewpoint of the fluidity of fresh concrete, and in the range of 20,000 to 100,000 and further in the range of 30,000 to 85,000 is more excellent due to the fluidity of fresh concrete. The weight average molecular weight is determined by gel permeation chromatography (in terms of standard substance sodium polystyrene sulfonate).

  Compound (3) can be produced by a known method. Examples thereof include solution polymerization methods described in JP-A-7-223852, JP-A-4-209737, and JP-A-58-74552. In water and lower alcohols having 1 to 4 carbon atoms, ammonium persulfate, In the presence of a polymerization initiator such as hydrogen oxide, sodium bisulfite, mercaptoethanol or the like may be added if necessary and reacted at 50 to 100 ° C. for 0.5 to 10 hours.

  As a raw material for the compound (3), other copolymerizable monomers can be used in combination. Specifically, acrylonitrile, alkyl (meth) acrylate (1 to 12 carbon atoms) ester, (meth) acrylamide, styrene, styrene sulfonic acid Etc.

<Admixture for hydraulic composition>
In the admixture for hydraulic composition of the present invention, the ratio of the compound (1) in the total of the compounds (1) to (3) is 30 to 90% by weight, the ratio of the compound (2) is 5 to 30% by weight, the compound The proportion of (3) is 5 to 60% by weight (the total of the three is 100% by weight). In such a ratio, the ratio of the compound (1) is preferably 40 to 90% by weight, more preferably 50 to 80% by weight, and still more preferably 60 to 80% by weight. Moreover, in this ratio, the ratio of the compound (2) is preferably 10 to 30% by weight, more preferably 10 to 25% by weight, and still more preferably 10 to 20% by weight. Moreover, in this ratio, the ratio of the compound (3) is preferably 10 to 50% by weight, more preferably 10 to 40% by weight, and still more preferably 10 to 30% by weight. The admixture for hydraulic composition of the present invention can be obtained by mixing the compounds (1) to (3) in the above proportions. Good.

  The compound (1) of the present invention affects the concrete viscosity, the compound (2) affects the initial fluidity of fresh concrete, and the compound (3) affects the increase in viscosity and the viscosity retention behavior of fresh concrete. The tendency is strong. However, when the compounds (1) to (3) are combined at a predetermined ratio as in the present invention, a remarkable effect that exceeds the effect predicted from the advantages of each compound can be obtained.

  The admixture for hydraulic composition of the present invention preferably contains the compounds (1) to (3) in a total amount of 80 to 100% by weight, more preferably 90 to 100% by weight, based on the total amount of effective components.

  The admixture for hydraulic composition of the present invention can be obtained by mixing the compounds (1) to (3), but the compounds (1) to (3) of the present invention are Both may be added after blending in advance or separately, or may be used after first diluted with kneaded water.

  Moreover, the admixture for hydraulic compositions of the present invention can be obtained, for example, by mixing an aqueous solution containing the compound (1), an aqueous solution containing the compound (2), and an aqueous solution containing the compound (3). From the viewpoint of workability, a one-component liquid is preferable.

  The admixture for hydraulic composition of the present invention is 0.05 to 0.4 parts by weight, more preferably 0.1 to 0.3 parts by weight, based on 100 parts by weight of the hydraulic powder, as the solid content concentration of the compound (1). In a ratio of 0.1 part by weight, and in a solid content concentration of the compound (2) of 0.01 to 0.15 parts by weight, and further in a ratio of 0.02 to 0.1 part by weight, and the solids concentration of the compound (3) 0.01 to 0.3 parts by weight, and more preferably 0.02 to 0.2 parts by weight from the viewpoint of imparting good initial fluidity, viscosity reducing effect and fluidity retention of fresh concrete. preferable.

  The admixture for hydraulic composition 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. Strong 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 series, polyalkylene glycol fatty acid ester series Anti-foaming agents such as mineral oils, fats and oils, oxyalkylenes, alcohols, amides, etc .; antifoaming agents; fly ash; melamine sulfonic acid formalin condensates, aminosulfonic acids, polymaleic acid, etc. Agent: Silica fume; Anticorrosive agent such as nitrite, phosphate, zinc oxide; Methyl cellulose, Hydroxyethyl cell Cellulose series such as loose, natural products such as β-1,3-glucan, xanthan gum, synthetic system such as polyacrylic acid amide, polyethylene glycol, EO adduct of oleyl alcohol, or a reaction product of this with vinylcyclohexene diepoxide And water-soluble polymers such as alkyl emulsions such as alkyl (meth) acrylates.

  The hydraulic powder used in the hydraulic composition that is the target of the admixture for the hydraulic composition of the present invention is a powder having physical properties that is cured by a hydration reaction, such as cement and gypsum. Can be mentioned. Preferred are ordinary portland cement, moderately hot portland cement cement, low heat portland cement, early strong portland cement cement, super early strong portland cement cement, sulfate resistant portland cement cement, etc., and blast furnace slag, fly ash, silica fume. , Stone powder (calcium carbonate powder) or the like may be added. In addition, the hydraulic composition finally obtained by adding sand, sand and gravel as aggregates to these powders is generally called mortar and concrete, respectively. The admixture for hydraulic composition of the present invention is not only for ready-mixed concrete and concrete vibration products, but also for self-leveling, for refractories, for plaster, for gypsum slurry, for lightweight or heavy concrete, for AE, for repair, and pre-packed. It is useful in any field of various concrete, such as for use in the field, for use in tromy, for grout, for ground improvement, and for cold use. The admixture for a hydraulic composition of the present invention has a greater improvement in the effect of belite cement (a medium-heated Portland cement, a cement having a large amount of belite components such as low-heat Portland cement) and a medium-heated Portland cement. The admixture for hydraulic composition of the present invention is suitably used for belite cement and further moderately heated Portland cement.

  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 10 to 60% by weight, further 12 to 57% by weight, further 15 to 55% by weight, and further 20 to 55% by weight. Especially, the effect of the admixture for hydraulic compositions of the present invention is remarkably exhibited even in a high powder blend of 40% by weight or less. Belite cement has a large variation in gypsum hemihydrate conversion rate, but in the present invention, by setting the compounding ratio of compounds (1) to (3) within a specific range, pseudo-condensation with hemihydrate gypsum is performed. Therefore, it is presumed that good initial fluidity, viscosity reduction effect and fluidity retention of fresh concrete can be obtained.

<Example 1 and Comparative Example 1>
The admixture obtained by using the compound (1) shown in Table 2, the compound (2) shown in Table 3, and the compound (3) shown in Table 4 as shown in Table 5 was subjected to a mortar test of the composition shown in Table 1. It was. The results are shown in Table 5. The evaluation was performed by the following methods for kneading, viscosity, and fluidity retention of the mortar.

[Mortar test]
(1) Mortar combination

The materials used in Table 1 are as follows.
W: ion-exchanged water C: medium heat Portland cement (1: 1 (weight ratio) mixture of medium heat portland cement manufactured by Taiheiyo Cement Co., Ltd. and medium heat portland cement manufactured by Sumitomo Osaka Cement Co., Ltd.)
S: River sand from Yodogawa, Gifu Prefecture (3.5mm passing product)

(2) Preparation of mortar
In a DALTON universal mixing stirrer (5DM-03-R type, manufactured by Sanei Seisakusho Co., Ltd.), about 1/2 amount of S shown in Table 1 is added, then C is added, and the remaining S is added. After 25 seconds, the mixture of admixture and water mixed in advance (20% by weight aqueous solution of admixture) is added over 5 seconds, kneaded at low speed for 3 minutes, and allowed to stand for 5 minutes. And mortar was prepared by kneading at low speed for 30 seconds. The compounds (1) to (3) constituting the admixture were all used as an aqueous solution having an effective concentration of 20% by weight, and the admixture was used as an aqueous solution having an effective content of 20% by weight.

(3) Evaluation (3-1) Kneading property The time during which mortar was prepared with a uniform and fluidity was judged visually and used as the kneading time.

(3-2) Viscosity The prepared mortar is packed in a flow cone used for the flow test of JIS R 5201, and then the flow cone is lifted vertically, and then the maximum length of the mortar spread on the table and the length in the direction perpendicular thereto. The average value was taken as the “immediate flow value”. The addition amount of the admixture aqueous solution was determined so that the mortar flow value was 240 to 260 mm. Transfer the entire amount of the prepared mortar to a container (1L stainless steel beaker: 120 mm inner diameter), and stir at 50 rpm using Z-2310 manufactured by EYELA (Tokyo Rika Kikai Co., Ltd., stirring rod: height 50 mm, inner diameter 5 mm × 6 pieces / length 110 mm). The torque value after 30 seconds was evaluated as the viscosity of the mortar.

(3-3) Flow retention The “flow value immediately after” obtained in the evaluation of the viscosity and the flow value are measured again 15 minutes after the measurement of the flow value immediately after that to obtain “the flow value after 15 minutes”. . The fluid retention was evaluated based on the fluid retention obtained by the following equation.
Flow retention (%) = flow value after 15 minutes / flow value immediately after × 100

  In Table 5, the compounding ratio of the compounds (1) to (3) is the weight percent of each compound in the total of the compounds (1) to (3). Further, the amount of admixture added is the weight part of 20% by weight aqueous solution of the admixture with respect to 100 parts by weight of cement (the same applies hereinafter).

<Example 2 and Comparative Example 2>
The admixture of Example 1-14 in Table 2 (1-3 / 2-5 / 3-6 = 60/20/20, weight ratio) (Admixture I) and this composition were 1-3 / 2-5. Using the comparative admixture (admixture II) with / 3-6 = 20/10/70 (weight ratio), the C in the mortar formulation of Table 2 was changed to the cement of Table 6. Evaluation similar to Example 1 etc. was performed. The results are shown in Table 6.

The cements in Table 6 are as follows.
・ Normal Portland cement: 1: 1 (weight ratio) mixture of ordinary Portland cement manufactured by Taiheiyo Cement Co., Ltd. and ordinary Portland cement manufactured by Sumitomo Osaka Cement Co., Ltd. 1: 1 (weight ratio) mixture of medium heat fever Portland cement manufactured by Cement Co., Ltd. Low heat Portland cement: 1: 1 (weight ratio) mixture of low heat Portland cement manufactured by Taiheiyo Cement Co., Ltd. and low heat Portland cement manufactured by Sumitomo Osaka Cement Co., Ltd. Hayashi Portland Cement: A 1: 1 (weight ratio) mixture of Hayashi Portland Cement, Taiheiyo Cement Co., Ltd. and Sumitomo Osaka Cement Co., Ltd.

Claims (4)

The following compounds (1) to (3) are contained, and the ratio of the compound (1) in the total of the compounds (1) to (3) is 30 to 90% by weight, and the ratio of the compound (2) is 5 to 30% by weight. An admixture for hydraulic composition, wherein the proportion of compound (3) is 5 to 60% by weight.
<Compound (1)>
Copolymer or salt thereof of alkenyl ether derivative represented by the following general formula (A) and maleic acid R ¹ (AO) _n1 R ² (A)
(In the formula, R ¹ is an alkenyl group having 2 to 4 carbon atoms, AO is an oxyalkylene group having 2 to 3 carbon atoms, n1 is an average added mole number of AO, 2 to 90, and R ² is carbon number. 1 to 3 alkyl groups)
<Compound (2)>
A monomer (b) represented by the following general formula (B) and one or more monomers (c) selected from the compounds represented by the following general formulas (C1) and (C2): c) / (b) = a copolymer obtained by copolymerization at a molar ratio of 70/30 to 95/5.

Wherein R ³ and R ⁴ are a hydrogen atom or a methyl group, m1 is a number from 0 to 2, AO is a oxyalkylene group having 2 to 3 carbon atoms, n2 is a number from 100 to 300, and X is a hydrogen atom or Represents an alkyl group having 1 to 3 carbon atoms.)

(Wherein R ^{5 to} R ⁷ are each a hydrogen atom, a methyl group, or (CH ₂ ) _m2 COOM ² , R ⁸ is a hydrogen atom or a methyl group, and M ¹ , M ² , and Y are a hydrogen atom or a positive atom, respectively. Ion, m2 represents the number of 0-2.)
<Compound (3)>
A monomer (d) represented by the following general formula (D), and one or more monomers (c) selected from the compounds represented by the general formulas (C1) and (C2), c) / (d) = a copolymer obtained by copolymerization at a molar ratio of 60/40 to 90/10.

(Wherein R ⁹ and R ¹⁰ are each a hydrogen atom or a methyl group, m3 is a number from 0 to 2, AO is an oxyalkylene group having 2 to 3 carbon atoms, n3 is a number from 2 to 90, and X is a hydrogen atom. Or represents a C1-C3 alkyl group.) It is obtained by mixing the following compounds (1) to (3), the proportion of compound (1) in the total of compounds (1) to (3) is 30 to 90% by weight, and the proportion of compound (2) is 5 to 5%. An admixture for hydraulic composition, comprising 30% by weight and the proportion of compound (3) is 5 to 60% by weight.
<Compound (1)>
Copolymer or salt thereof of alkenyl ether derivative represented by the following general formula (A) and maleic acid R ¹ (AO) _n1 R ² (A)
(In the formula, R ¹ is an alkenyl group having 2 to 4 carbon atoms, AO is an oxyalkylene group having 2 to 3 carbon atoms, n1 is an average added mole number of AO, 2 to 90, and R ² is carbon number. 1 to 3 alkyl groups)
<Compound (2)>
A monomer (b) represented by the following general formula (B) and one or more monomers (c) selected from the compounds represented by the following general formulas (C1) and (C2): c) / (b) = a copolymer obtained by copolymerization at a molar ratio of 70/30 to 95/5.

(Wherein R ³ and R ⁴ are a hydrogen atom or a methyl group, m1 is a number of 0 to 2, AO is an oxyalkylene group having 2 to 3 carbon atoms, and n2 is an average added mole number of AO; 300 number, X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

(Wherein R ^{5 to} R ⁷ are each a hydrogen atom, a methyl group, or (CH ₂ ) _m2 COOM ² , R ⁸ is a hydrogen atom or a methyl group, and M ¹ , M ² , and Y are a hydrogen atom or a positive atom, respectively. Ion, m2 represents the number of 0-2.)
<Compound (3)>
A monomer (d) represented by the following general formula (D), and one or more monomers (c) selected from the compounds represented by the general formulas (C1) and (C2), c) / (d) = a copolymer obtained by copolymerization at a molar ratio of 60/40 to 90/10.

(In the formula, R ⁹ and R ¹⁰ are each a hydrogen atom or a methyl group, m3 is a number of 0 to 2, AO is an oxyalkylene group having 2 to 3 carbon atoms, and n3 is an average added mole number of AO. The number of -90, X represents a hydrogen atom or a C1-C3 alkyl group.)   N1 of the alkenyl ether derivative represented by the general formula (A) in the compound (1) is a number of 10 to 50, n2 of the monomer (b) in the compound (2) is a number of 100 to 200, and the compound The admixture for hydraulic composition according to claim 1 or 2, wherein n3 of the monomer (d) in (3) is a number of 5 to 40.   The hydraulic composition containing the admixture for hydraulic compositions of any one of Claims 1-3, and hydraulic powder.