JP5422233B2 - Additive composition for hydraulic composition - Google Patents

Description

  The present invention relates to an additive composition for hydraulic compositions.

  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 alcohol having 1 to 4 carbon atoms (Patent Documents 1 and 2) or a polyalkylene glycol having an average molecular weight of 400 to 10000 having an effect of preventing cracking and dispersibility of concrete. Admixtures containing a polycarboxylic acid polymer as a main component (Patent Document 3) and admixtures containing a polyhydric alcohol alkylene oxide adduct and a polycarboxylic acid polymer (Patent Document 4) have been proposed. Further, as a high-performance water reducing agent, a phosphate ester polymer capable of producing low-viscosity concrete has been proposed (Patent Document 5).

Japanese Patent Publication No. 56-51148 JP 2001-294466 A JP 2002-12461 A JP 2004-2175 A JP 2006-52381 A

  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 a plurality of effects such as a drying shrinkage reduction effect and a dispersion effect is demanded. Further, for such purposes, it is advantageous to make a one-component product using an admixture (for example, shrinkage reducing agent) having good compatibility with the high-performance water reducing agent.

  The problem of the present invention is that it has excellent compatibility with high performance (AE) water reducing agent, has no problem of odor, imparts a drying shrinkage reducing effect to a hydraulic composition such as concrete, and the fluidity of the hydraulic composition An object of the present invention is to provide an additive composition for a hydraulic composition that can simultaneously provide a plurality of excellent physical properties with respect to freeze-thaw resistance and air entrainment, and a method for producing the same.

The present invention is an additive composition for a hydraulic composition containing a mixture of compounds represented by the following general formula (1),
The average value of n determined from the hydroxyl value of the mixture is 3 to 12,
The content of the compound having n of 3 or less in the mixture determined by gas chromatography is 0 to 15 area%, and
The content of the compound having n of 11 or more in the mixture determined by gas chromatography is 0 to 20 area%.
The present invention relates to an additive composition for hydraulic compositions.
R ¹ —O— (AO) _n —R ² (1)
(In the formula, R ¹ and R ² are each a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, A is an alkylene group having 2 to 8 carbon atoms, n is the number of added moles, and 0 (However, the case where R ¹ and R ² are simultaneously hydrogen atoms and the case where they are simultaneously alkyl groups is excluded.)

  The present invention also relates to a method for producing the hydraulic composition additive composition of the present invention, wherein carbon is added to a mixture containing 90 to 99% by weight of a compound in which n is 3 in the general formula (1). It is related with the manufacturing method of the additive composition for hydraulic compositions which has the process of adding the alkylene oxide of several 2-8.

  The present invention also relates to a method for producing the additive composition for hydraulic composition according to the present invention, the step of adding an alkylene oxide having 2 to 8 carbon atoms to an alcohol having 1 to 22 carbon atoms, and the step And a step of reducing the compound in which n in the general formula (1) in the reaction product obtained by the step of 3 is 3 or less, relates to a method for producing an additive composition for a hydraulic composition.

  According to the present invention, it is excellent in compatibility with a high performance (AE) water reducing agent, has no problem of odor, imparts a drying shrinkage reducing effect to a hydraulic composition such as concrete, and the fluidity of the hydraulic composition. An additive for a hydraulic composition capable of simultaneously imparting a plurality of excellent physical properties with respect to freeze-thaw resistance and air entrainment, and a method for producing the same are provided.

[Component (A)]
The component (A) is a mixture of compounds represented by the following general formula (1), the average value of n determined from the hydroxyl value of the mixture is 3 to 12, and n is 3 or less in the mixture The total of the compounds is from 0 to 15% by area, and in the mixture, the total of the compounds having n of 11 or more is from 0 to 20% by area.
R ¹ —O— (AO) _n —R ² (1)
(In the formula, R ¹ and R ² are each a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, A is an alkylene group having 2 to 8 carbon atoms, n is the number of added moles, and 0 (However, the case where R ¹ and R ² are simultaneously hydrogen atoms and the case where they are simultaneously alkyl groups is excluded.)

In the general formula (1), R ¹ and R ² are each a hydrocarbon group having 1 to 22 carbon atoms, and the number of carbon atoms is preferably 1 from the viewpoint of compatibility with a high performance (AE) water reducing agent. To 18, more preferably 2 to 12, still more preferably 2 to 6, and still more preferably 3 to 4. Examples of the hydrocarbon group include an alkyl group and an alkenyl group, and an alkyl group is preferable. One of R ¹ and R ² is preferably a hydrogen atom, and the other is preferably a hydrocarbon group having 1 to 22 carbon atoms.

  Moreover, in General formula (1), A is a C2-C8 alkylene group, From a compatible viewpoint with a high performance (AE) water reducing agent, carbon number becomes like this. Preferably it is 2-6, More preferably 2 to 4, more preferably 2 to 3, still more preferably 2.

  The average value of n obtained from the hydroxyl value in the component (A) is 3 to 12, and preferably 3 to 10, and more preferably from the viewpoints of the effect of reducing drying shrinkage and the compatibility between freeze-thaw resistance and air entrainment. 4-6.

As for the component (A), the average value of n by hydroxyl value, the molecular weight determined from the hydroxyl value of the mixture (average molecular weight), the molecular weight of the portion excluding the molecular weight of R ¹ and R ² moieties, alkylene The value obtained by dividing by the molecular weight of the oxide. Moreover, the hydroxyl value of (A) component can be measured by a well-known method, for example, can be measured by the method of the below-mentioned Example.

  Further, the component (A) has a content of a compound having n of 3 or less determined by gas chromatography in an amount of 0 to 15% by area, and preferably 0 to 0 from the viewpoint of odor, freeze-thaw resistance, and air entrainment. It is 10 area%, More preferably, it is 0-7 area%, More preferably, it is 0-3 area%. Further, the component (A) is preferably 0 to 1% by area, more preferably 0% by area, from the same viewpoint of the content of the compound having n of 2 or less determined by gas chromatography.

  In the present invention, the area% of the content of the compound in the component (A) obtained by gas chromatography (hereinafter sometimes referred to as GC) is the baseline of the gas chromatography chart and the peak of each compound. The ratio of the enclosed area to the total area of the chart is expressed as a percentage (hereinafter, the area% obtained in this way may be simply referred to as area%). The GC conditions are those described in the examples described later.

  In addition, in the component (A), the sum of the compounds in which n in the general formula (1) is 11 or more is 0 to 20 area%, and preferably 0 to 15 area% from the viewpoint of maintaining the effect of reducing drying shrinkage, More preferably, it is 0-10 area%, More preferably, it is 0-5 area%. By subtracting the total area (total area%) of compounds having n of 1 to 10 from the total area (100 area%) of the GC chart obtained under the GC conditions of the present invention, n in the mixture is 11 or more. The area% of the compound can be determined.

  In addition, from the viewpoint of coexistence of freeze-thaw resistance, air entrainment, and drying shrinkage reduction effect, the total of the compounds having n of 4 to 8 in the general formula (1) in the component (A) is preferably 50 to 99. Area%, preferably 55 to 99 area%, more preferably 80 to 99 area%, still more preferably 90 to 99 area%.

  Furthermore, from the viewpoint that freeze-thaw resistance, air entrainment, and drying shrinkage reduction effects are well-balanced and a more excellent drying shrinkage reduction effect is obtained, n in the general formula (1) is 4 in the component (A). It is preferable to contain the compound. Moreover, when (A) component contains the compound whose n in General formula (1) is 4, the content becomes like this. Preferably it is 2-95 area%, More preferably, it is 30-90 area%, More preferably, it is 50 It can be selected from a range of ˜85 area%, more preferably 70-80 area%. At that time, the content of the compound in which n in the general formula (1) is 5 to 8 is preferably an amount such that n in the general formula (1) is within the total preferable range of the compounds in the range of 4 to 8. . In addition, the content of the compound in which n in the general formula (1) is 4 is 3 to 95%, more preferably 15 to 85% in the total area% of the compound in which n in the general formula (1) is 4 to 8. It may be 25 to 80%.

  Moreover, when (A) component contains the compound whose n in General formula (1) is 5, the content becomes like this. Preferably it is 2-95 area%, More preferably, it is 15-90 area%, More preferably, it is 25 It can be selected from a range of ˜80 area%. At that time, the content of the compound having n of 4, 6 to 8 in the general formula (1) is such that the total range of the compounds having n of 4 to 8 in the above general formula (1) is within a suitable range. Is preferred.

  Moreover, when (A) component contains the compound whose n in General formula (1) is 6, the content becomes like this. Preferably it is 5-95 area%, More preferably, it is 10-90 area%, More preferably, it is 15 It can be selected from a range of ˜80 area%. At that time, the content of the compound in which n in the general formula (1) is 4, 5, 7, or 8 is in a preferable range of the total of the compounds in which n in the general formula (1) is 4 to 8. Is preferred.

  Moreover, when (A) component contains the compound whose n in General formula (1) is 7, the content becomes like this. Preferably it is 5-95 area%, More preferably, it is 10-90 area%, More preferably, it is 15 It can be selected from a range of ˜80 area%. At that time, the content of the compound in which n in the general formula (1) is 4 to 6 and 8 is such that the total range of the compounds in which n in the general formula (1) is 4 to 8 is within the preferable range. Is preferred.

  Moreover, when (A) component contains the compound whose n in General formula (1) is 8, the content becomes like this. Preferably it is 5-95 area%, More preferably, it is 10-90 area%, More preferably, it is 15 It can be selected from a range of ˜80 area%. At that time, the content of the compound in which n in the general formula (1) is 4 to 7 is preferably an amount such that n in the above general formula (1) is within the total preferable range of the compounds in the range of 4 to 8. .

  The alkylene oxide adduct such as component (A) can usually be obtained as a reaction product obtained by adding alkylene oxide to a compound having active hydrogen such as alcohol, but the mixture obtained by a general production method is: The distribution of the added mole number corresponding to the component (A) of the present invention is not obtained. For example, when an ethylene oxide adduct having an average addition mole number of about 4 to 5 is obtained, 4 to 5 mol of ethylene oxide is reacted with 1 mol of a monohydric alcohol in the presence of an alkali catalyst. The total number of compounds in which the number of added moles in the mixture) is 3 or less (n in the general formula (1) is 3 or less) exceeds 15 area%.

[Additive composition for hydraulic composition]
The additive composition for a hydraulic composition of the present invention preferably comprises the component (A) in an amount of 3 to 100% by weight, more preferably 10 to 100% by weight, still more preferably 50 to 100% by weight, and still more preferably. Contains 80 to 100% by weight. Ingredients other than the component (A) in the additive composition for hydraulic compositions include water from the viewpoints of safety and workability.

  Depending on the type of component (A), a composition that does not correspond to a dangerous substance (dangerous substance specified in the Fire Service Act) can be obtained by using a liquid composition mixed with water. The content of the component (A) in the liquid composition may be appropriately determined depending on the type of compound to be selected, but is preferably 40 to 98% by weight, more preferably from the viewpoint of exclusion from dangerous substances and high concentration. 50 to 95% by weight, more preferably 80 to 93% by weight.

  Other components of the additive composition for hydraulic composition of the present invention include water reducing agents, high performance water reducing agents, high performance AE water reducing agents (hereinafter, high performance water reducing agents and high performance AE water reducing agents are collectively It is preferable to contain (AE). The component (A) of the present invention is excellent in compatibility with components known as water reducing agents for hydraulic compositions and high performance (AE) water reducing agents. A lignin sulfonate is mentioned as a water reducing agent. Moreover, as a high performance (AE) water reducing agent, a melamine type formaldehyde condensate, a naphthalene type formaldehyde condensate, the following (B) component, and the following (C) component are mentioned. Especially, it is preferable to contain (B) component and / or (C) component. Furthermore, it is preferable to contain (C) component as a high performance (AE) water reducing agent.

  When the B component and the C component are contained in the high performance (AE) water reducing agent, the weight ratio of the (B) component and the (C) component is (B) :( C) = 1: 100 to 70: 100, preferably 10: 100 to 60: 100, more preferably 20: 100 to 50: 100, more preferably 30: 100 to 45: 100.

<(B) component>
The component (B) is at least one copolymer selected from the group consisting of the following compounds (1), (2) and (3). The additive composition for hydraulic composition of the present invention further comprises component (B) from the viewpoint of synergistically enhancing the effect of reducing drying shrinkage indirectly (reduction in unit water amount) and directly (addition of shrinkage reducing agent). It is preferable to use together.

<Compound (1)>
A copolymer of an alkenyl ether derivative represented by the following general formula (B1) and a monomer represented by the following general formula (B3) or a salt thereof R ^1b (A ¹ O) _n1 R ^2b (B1)
(In the formula, R ^1b is an alkenyl group having 2 to 4 carbon atoms, B ¹ O is an oxyalkylene group having 2 or 3 carbon atoms, n1 is an average added mole number of A ¹ O, a number of 2 to 200, R ^2b represents an alkyl group having 1 to 3 carbon atoms.)

[Wherein, R ^{5b to} R ^7b are each independently a hydrogen atom, a methyl group, or (CH ₂ ) _p2 COOM ² , M ¹ and M ² are each independently a hydrogen atom or a cation, and p 2 is 0 to 2 Represents the number of ]

<Compound (2)>
A monomer (i) represented by the following general formula (B2), one or more monomers (ii) selected from the compounds represented by the above general formula (B3) and the following general formula (B4); As a constituent unit, and a molar ratio thereof is (ii) / (i) = 70/30 to 95/5.

Wherein R ^3b and R ^4b are each independently a hydrogen atom or a methyl group, p1 is a number from 0 to 2, A ² O is an oxyalkylene group having 2 or 3 carbon atoms, and n2 is an average addition of A ² O. Number of moles, 100 to 300, X ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

(In the formula, R ^8b represents a hydrogen atom or a methyl group, and Y represents a hydrogen atom or a cation.)

<Compound (3)>
A monomer (iii) represented by the following general formula (B5), and one or more monomers (ii) selected from the compounds represented by the general formula (B3) and the general formula (B4); As a constituent unit, and a molar ratio thereof is (ii) / (iii) = 60/40 to 90/10.

(Wherein R ^9b and R ^10b are each independently a hydrogen atom or a methyl group, p3 is a number from 0 to 2, A ³ O is an oxyalkylene group having 2 or 3 carbon atoms, and n3 is an average addition of A ³ O. Number of moles, a number of 2 to 90, and X ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

[Compound (1)]
In the general formula (B1) 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 ^1b is preferably a vinyl group, an allyl group, a methallyl group, or the like. However, an allyl group is more general and more preferable. A ¹ O is an oxyethylene group or an oxypropylene group, and may be both of these groups. The additional form may be single, random, block, or alternating. An oxyethylene group is preferred. R ^2b is an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. Among them, a methyl group is preferable.

  The average number of added moles n1 of alkylene oxide is in the range of 2 to 200, preferably 2 to 90, more preferably 10 to 70, and more preferably 10 to 50, from the viewpoint of imparting fluidity and low viscosity to fresh concrete. preferable.

Further, the alkenyl ether derivatives, if the scope of the general formulas (B1), for example, the A ¹ O is one of the only ones or oxypropylene groups alone oxyethylene group, or two or more may be used.

  Monomers represented by formula (B3) 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-, and trialkylammonium salts optionally having a hydroxyl group are preferred, and acrylics are more preferred. Acid, methacrylic acid and alkali metal salts thereof.

  The compound (1) of the present invention is a copolymer of the monomer represented by the general formula (B1) and the monomer represented by the general formula (B-3), preferably in a molar ratio of Monomer of formula (B1) / monomer of general formula (B3) = a copolymer of 25/75 to 50/50 or a salt thereof. When the monomer of the general formula (B3) is maleic acid, an anhydride may be used. 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.

  As an example of the compound (1), Marialim EKM, Marialim AKM (manufactured by Nippon Oil & Fats Co., Ltd.) and Super 200 (Electrochemical Co., Ltd.) can be mentioned.

[Compound (2)]
The compound (2) of the present invention includes a monomer (i) represented by the general formula (B2) obtained by adding 100 to 300 moles of an average number of moles of an alkylene oxide having 2 or 3 carbon atoms, and the general formula (B3) and / or (B4), preferably the monomer (ii) represented by the general formula (B3) at a molar ratio of (ii) / (i) = 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 monomer (i) 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 (i) from which n2 differs, the average value of n2 of all the monomers (i) is in the range of 100-300. Adjust the composition to be. For example, when two types of monomers (i) 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 more than 90 and less than 100 can be used in combination as long as the effects of the present invention are not impaired.

  As the monomer (i) represented by the general formula (B2), an esterified product of a polyalkylene glycol with one-end alkyl group blocked such as methoxypolyethylene glycol, methoxypolypropylene glycol, ethoxypolyethylenepolypropyleneglycol and (meth) acrylic acid In addition, an adduct of ethylene oxide (hereinafter referred to as EO) and / or propylene oxide (hereinafter referred to as PO) to (meth) acrylic acid is 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 100 to 200 is more preferable.

  As the monomer represented by the general formula (B3), those mentioned in the compound (1) can be used. Preferred monomers are the same as those shown for the compound (1).

  Examples of the monomer represented by the general formula (B4) include allyl sulfonic acid, methallyl sulfonic acid, or an alkali metal salt, alkaline earth metal salt, ammonium salt, or mono- or di-substituted in which a hydroxyl group may be substituted. Trialkylammonium salts are used.

  Preferably, the compound (2) is a monomer (i) represented by the general formula (B2) and one or more monomers (ii) represented by the general formulas (B3) and (B4). And a monomer mixture containing 50% by weight or more, more preferably 80 to 100% by weight, and still more 100% by weight.

  The monomer (i) of the general formula (B2) constituting the compound (2) and the monomer (ii) of the general formula (B3) and / or the general formula (B4) are represented by (ii) / (i) = Copolymerized at a molar ratio of 70/30 to 95/5, and (ii) / (i), preferably 75/25 to 95/5, more preferably 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, more preferably in the range of 20,000 to 100,000, and still more preferably in the range of 30,000 to 85,000 from the viewpoint of imparting stable initial fluidity of the fresh concrete. 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) of the present invention includes a monomer (iii) represented by the general formula (B5) obtained by adding 2 to 90 moles of an average number of moles of an alkylene oxide having 2 or 3 carbon atoms, and the general formula (B3) and / or (B4), preferably the monomer (ii) represented by the general formula (B3), at a molar ratio of (ii) / (iii) = 60/40 to 90/10 Obtained by polymerization. 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 (iii) 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 (iii) having different n3 are used, the average value of n3 of all the monomers (iii) is in the range of 2 to 90. The composition is adjusted to For example, when two types of monomers (iii) are used, it is preferable that one is n3 = 2 to 87, the other is n3 ′ = 2 to 90, n3 ≠ n3 ′ and n3 ′ ≧ n3 + 3, and n3 ′ ≧ n3 + 5 is more preferable, and n3 ′ ≧ n3 + 10 is still more preferable. Further, a monomer having n3 of more than 90 and less than 100 can be used in combination as long as the effects of the present invention are not impaired.

  As the monomer (iii) represented by the general formula (B5), 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 Alternatively, an EO and / or PO adduct to (meth) acrylic acid is preferably used. The additional form may be single, random, block, or alternating. More preferred is an esterified product of methoxypolyethylene glycol and (meth) acrylic acid. In particular, when the water / hydraulic powder ratio is 15% by weight or less, an esterified product of methoxypolyethylene glycol having an EO average addition mole number of 2 to 90 and acrylic acid is more preferable from the viewpoint of initial dispersibility and viscosity. .

  As the monomer represented by the general formula (B3) and the monomer represented by the general formula (B4), those exemplified in the compounds (1) and (2) can be used. Preferred monomers are the same as those shown for the compounds (1) and (2).

  Preferably, the compound (3) is a monomer (iii) represented by the general formula (B5) and one or more monomers (ii) represented by the general formulas (B3) and (B4). And a monomer mixture containing 50% by weight or more, more preferably 80 to 100% by weight, and still more 100% by weight.

  The monomer (iii) of the general formula (B5) constituting the compound (3) and the monomer (ii) of the general formula (B3) and / or the general formula (B4) are represented by (ii) / (iii) = Copolymerized at a molar ratio of 60/40 to 90/10, and (ii) / (iii), preferably 65/35 to 90/10, more preferably from the viewpoint of imparting stable fluidity retention of fresh concrete 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.

<(C) component>
Component (C) is a monomer C1 represented by the following general formula (C1), a monomer C2 represented by the following general formula (C2), and a single monomer represented by the following general formula (C3) It is 1 or more types of the phosphate ester type | system | group copolymer obtained by copolymerizing the body C3 at pH 7 or less. The additive composition for hydraulic composition of the present invention preferably further uses component (C) from the viewpoint of further improving the viscosity reducing effect and the strength of the cured product.

[Wherein, R ^1c and R ^2c are each a hydrogen atom or a methyl group, R ^3c is a hydrogen atom or —COO (AO) _n X ³ , AO is an oxyalkylene group or oxystyrene group having 2 to 4 carbon atoms, n Is an average added mole number of AO, a number of ^{3 to} 200, and X ³ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. ]

(In the formula, R ^4c is a hydrogen atom or a methyl group, OR ^5c is an oxyalkylene group having 2 to 12 carbon atoms, m5 is an average number of added moles of OR ^5c, a number of 1 to 30, and M ³ is a hydrogen atom or Represents a cation.)

(Wherein R ^6c and R ^8c are each a hydrogen atom or a methyl group, OR ^7c and OR ^9c are each an oxyalkylene group having 2 to 12 carbon atoms, and m6 and m7 are average additions of OR ^7c and OR ^9c respectively. The number of moles is independently a number of 1 to 30, and M ⁴ represents a hydrogen atom or a cation.)

[Monomer C1]
Regarding the monomer C1, R ^3c in the general formula (C1) is preferably a hydrogen atom, and AO is preferably an oxyalkylene group having 2 to 4 carbon atoms, and more preferably includes an oxyethylene group (hereinafter referred to as an EO group). Preferably, the EO group is 70 mol% or more, more preferably 80 mol% or more, further 90 mol% or more, and even more preferably all of AO are EO groups. X ³ is preferably a hydrogen atom or an alkyl group having 1 to 18, more preferably 1 to 12, further 1 to 4, and further 1 or 2 carbon atoms, 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 (C1) is 3 to 200, preferably 4 to 120, in terms of 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 an oxypropylene group in addition to the EO group.

[Monomer C2]
Examples of the monomer C2 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 C3]
Examples of the monomer C3 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.

  Any of the monomer C2 and the monomer C3 may be an alkali metal salt, alkaline earth metal salt, ammonium salt, alkylammonium salt or the like of these compounds.

  As for m5 of monomer C2 and m6 and m7 of monomer C3, 1-20 are respectively preferable, 1-10 are still more preferable, and 1-5 are more preferable.

  As the monomer C2 and the monomer C3, 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 (above, Unichemical), JAMP514, JAMP514P, JMP100 (above, Johoku Chemical), Wright Ester P-1M, light acrylate P-1A (Kyoeisha Chemical), MR200 (Daihachi Chemical), Kayamar (Nippon Kayaku), Ethyleneglycol methacrylate phosphate (Aldrich reagent), etc. can be obtained.

  The phosphate ester polymer of component (C) 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 described in JP-A-2006-52381. In addition, Mw / Mn of the phosphate ester type polymer in the present invention is calculated based on the peak of the polymer.

  The phosphate ester polymer satisfying Mw / Mn as described above has an appropriate branched structure by suppressing cross-linking by the monomer C3 which is a diester, and has a structure in which adsorbing groups are densely 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, the phosphate ester polymer of the present invention is derived from monomers C1, C2, and C3, respectively, because the double bond derived from the monomer has disappeared by ¹ H-NMR under the following conditions. 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 phosphate ester-based polymer having the Mw / Mn value as described above has, as its constituent units, constituent units derived from monomer C1, constituent units derived from monomer C2, and constituents derived from monomer C3. 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 the monomers C1, C2, and C3 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 the monomers C1 to C3, the molar ratio of each structural unit is the charged molar ratio of the monomers. It is thought that it is almost the same.

[Method for producing phosphate ester polymer]
The phosphate ester polymer of the present invention can be produced by a known method. For example, a method described in JP 2006-52381 A can be mentioned. That is, the phosphate ester polymer of the present invention is produced by a phosphate ester polymer production method in which the monomer C1, the monomer C2, and the monomer C3 are copolymerized at a pH of 7 or less. can do. Moreover, it is preferable to use the mixed monomer containing the monomer C2 and the monomer C3.

  The phosphate ester polymer according to the present invention includes a monomer C1 having an oxyalkylene group represented by the general formula (C1) and a single monomer represented by the general formula (C2) having a phosphate group. It is a polymer obtained by copolymerizing the body C2 and the monomer C3 represented by the general formula (C3).

  The preferable thing of the monomers C1-C3 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 C1 and the monomers C2 and C3 is such that the monomer C1 / (monomer C2 + monomer C3) = 5/95 to 95/5. Furthermore, 10/90 to 90/10 are preferable. The molar ratio of monomer C1, monomer C2 and monomer C3 is as follows: monomer C1 / monomer C2 / monomer C3 = 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 C2 and the monomer C3, a 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 C3 can be 1-60 mol% in the all monomers used for reaction, Furthermore, it can be 1-30 mol%.
Moreover, the molar ratio of the monomer C2 and the monomer C3 can be set to monomer C2 / monomer C3 = 99/1 to 4/96, and further 99/1 to 5/95.

  The total amount of the monomers C1, C2, C3 and other copolymerizable monomers in the reaction system is preferably 5 to 80% by weight, more preferably 10 to 65% by weight, still more preferably 20 to 50% by weight. preferable.

  In the present invention, the component (C) is preferably a copolymer in which the proportion of the monomer C1 is 50 mol% or less in the total amount of monomers from the viewpoint of kneading speed.

  The component (B) and the component (C) can be added to the hydraulic composition separately from the component (A). Moreover, you may use together (B) component and / or (C) component with the additive for hydraulic compositions of this invention containing (A) component as a high performance water reducing agent containing these.

  Moreover, the said (B) component and (C) component can be mix | blended in the additive composition for hydraulic compositions of this invention. Therefore, from the component (A) and the component (B), a one-component additive composition for a hydraulic composition containing the component (A) and the component (B) (hereinafter, the hydraulic composition of the present invention). 1-component additive composition).

  In the one-component additive composition for a hydraulic composition of the present invention, the content of the component (A) is preferably 5% by weight or more from the viewpoint of shrinkage reduction effect and the amount added during use. From the viewpoint of uniform stabilization, it is preferably 95% by weight or less. Accordingly, it is preferably 5 to 95% by weight, more preferably 10 to 70% by weight, still more preferably 20 to 60% by weight, and still more preferably 30 to 50% by weight.

  In the one-component additive composition for a hydraulic composition of the present invention, the total content of the component (B) is preferably 2% by weight or more from the viewpoint of lowering the mortar viscosity, and the product is uniform. From the viewpoint of stabilization, 50% by weight or less is preferable. Therefore, 2 to 50% by weight is preferable, further preferably 3 to 40% by weight, and more preferably 4 to 35% by weight.

  From the viewpoint of workability of fresh concrete, the component (B) preferably contains the compound (3). Of these, the compound (3) alone and the combined use of the compound (3) and the compound (2) are preferable. When the compound (3) is used in combination with the compound (1) or the compound (2), the compound (3) in the component (B) is 50% by weight or more, further 50 to 95% by weight, and further 70 to 90% by weight. It is preferable that Moreover, compound (2) is 1 to 40 weight% in (B) component from a viewpoint of coexistence of the quick-strength of fresh concrete, the early strength of fresh concrete, and low viscosity, Furthermore, 5 to 30 weight%, Furthermore, 10 to 20% by weight is preferable.

  In the one-component additive composition for a hydraulic composition of the present invention, the weight ratio (B) / (A) of the total amount of the component (A) to the total amount of the component (B) is 5/95 to 50 / It is preferably 50, more preferably 7/93 to 45/50, still more preferably 10/90 to 40/60, and still more preferably 20/80 to 35/65.

  In the one-component additive composition for a hydraulic composition of the present invention, the total content of the component (A) and the component (B) is preferably 10 to 100% by weight, more preferably 10 to 10% by weight. 80% by weight, more preferably 20 to 70% by weight, still more preferably 30 to 60% by weight.

  The one-component additive composition for the hydraulic composition of the present invention is a liquid composition, and the balance is, for example, water. In the one-component additive composition for hydraulic compositions of the present invention, the component (B) is compatible with the component (A), and an aqueous solution containing these components does not cause an extreme increase in viscosity, so that it is easy to handle. A one-component composition is obtained. The one-component additive composition for the hydraulic composition of the present invention can be obtained as a transparent composition, and further, it is transparent and uniform for 3 months or more by standing at 5 to 40 ° C. Can be maintained.

  Moreover, the one-pack type additive composition for hydraulic compositions of this invention can contain (C) component further. In the one-component additive composition for the hydraulic composition of the present invention, the total content of the component (C) is preferably 3 to 30% by weight, and 5 to 25% by weight from the viewpoint of ensuring good workability. Is more preferable. In the case of containing the component (C), in the one-component additive composition for the hydraulic composition of the present invention, the total content of the component (B) and the component (C) is 3 to 30% by weight in terms of an effective component. Further, 5 to 25% by weight is preferable. In that case, the weight ratio of the component (B) to the component (C) is preferably (B) :( C) = 1: 100 to 70: 100, more preferably 10: 100 to 60: 100, in terms of effective component. More preferably, it is 20: 100-50: 100, More preferably, it is 30: 100-45: 100.

  The additive for a hydraulic composition of the present invention, for example, a one-component additive composition for a hydraulic composition, has a (A ) The component (effective component) is preferably used in a proportion of 0.01 to 2% by weight, more preferably 0.1 to 1.0% by weight, more preferably 0.2 to 0.5% by weight. is there.

  Moreover, the additive for hydraulic compositions of the present invention, for example, the one-component additive composition for hydraulic compositions, is based on the hydraulic powder from the viewpoint of fluidity and one-component retention. B) Component (effective part) is preferably used in a proportion of 0.01 to 5% by weight, more preferably 0.1 to 2.5% by weight, more preferably 0.1 to 1.0% by weight. It is.

The amount of (A) component (effective component) added per 1 m ³ of concrete may be appropriately adjusted depending on the water / hydraulic powder ratio and the type and amount of aggregate used, but preferably 0.5 to 10 kg. / M ³ , more preferably 1 to 8 kg / m ³ , more preferably 1.5 to 6 kg / m ³ .

  The additive for a hydraulic composition of the present invention, for example, a one-component additive composition for a hydraulic composition, is based on (A) the hydraulic powder from the viewpoint of maintaining the one-component property and fluidity. It is preferably used in a proportion of 0.1 to 10% by weight, more preferably 0.2 to 5% by weight, more preferably 0.8% by weight in total of the component (effective part) and the component (B) (effective part). 2 to 3% by weight.

  Moreover, when the additive for hydraulic compositions of the present invention, for example, the one-component additive composition for hydraulic compositions contains the component (C), the component (C) (effective component) is a one-component. From the viewpoint of retention and fluidity, it is preferably used in a proportion of 0.01 to 3.0% by weight, more preferably 0.05 to 1.5% by weight, and more preferably to the hydraulic powder. Preferably it is 0.1 to 0.5 weight%.

  The additive for a hydraulic composition of the present invention, for example, a one-component additive composition for a hydraulic composition, is based on (A) the hydraulic powder from the viewpoint of maintaining the one-component property and fluidity. The ratio of 0.1 to 10.0% by weight in the sum of (component (effective)), (B) component (effective) and (C) component (effective) [(A) + (B) + (C)] It is preferably used in an amount of 0.2 to 5.0% by weight, more preferably 0.2 to 2.5% by weight.

  The additive for hydraulic compositions of the present invention, for example, a one-component additive composition for hydraulic compositions, can be applied to various inorganic hydraulic powders that exhibit curability by hydration reaction, including various cements. Can be used.

  Examples of the cement include ordinary Portland cement, moderately-heated 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 mixed with cement (for example, SFPC made by Taiheiyo Cement, SFC, SFCS made by Ube Mitsubishi Cement, etc.) and blast furnace cement (Type A, Type B, Type C) may be used.

  The additive for hydraulic compositions of the present invention, for example, the one-pack type additive composition for hydraulic compositions, 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, natural product systems such as β-1,3-glucan, xanthan gum, synthetic systems such as polyacrylic acid amide, polyethylene glycol, EO adduct of oleyl alcohol or a reaction product of this with vinylcyclohexene diepoxide Polymer emulsions such as alkyl (meth) acrylates.

  Further, the additive for hydraulic compositions of the present invention, for example, a one-component additive composition for hydraulic compositions, is used in the field of ready-mixed concrete, concrete vibration products, for self-leveling, for refractories, for plasters, It is useful in any field of various concrete such as gypsum slurry, lightweight or heavy concrete, AE, repair, pre-packed, trayy, ground improvement, grout, and cold.

<Method for producing additive composition for hydraulic composition>
The additive composition for hydraulic compositions of the present invention comprises a step of adding an alkylene oxide having 2 to 8 carbon atoms to a mixture containing 90 to 99% by weight of a compound wherein n is 3 in the general formula (1). It can be obtained from a method for producing an additive composition for hydraulic composition (hereinafter referred to as production method 1).

  In the production method 1, a mixture containing 90 to 99% by weight of the compound in which n is 3 in the general formula (1) can be obtained by separation and purification by distillation after adding an alkylene oxide having 2 to 8 carbon atoms. . It is preferable to add 1 to 4 moles, and further 1 to 2 moles of an alkylene oxide having 2 to 8 carbon atoms per mole of a mixture containing 90 to 99% by weight of the compound in which n is 3 in the general formula (1). .

As an example of the production method 1, a mixture containing a compound in which R ¹ in the general formula (1) is an alkyl group having 4 carbon atoms, A is an ethylene group, n is 3, and R ² is a hydrogen atom is added to a mixture having 2 carbon atoms. A case where EO is added will be described.

  A predetermined amount of butanol and a predetermined amount of KOH are charged into a reaction vessel equipped with a stirrer, and after the inside of the vessel is sufficiently substituted with nitrogen, the temperature is raised under a predetermined pressure. When the target temperature is reached, EO is gradually charged, and a predetermined amount of EO (3 mol with respect to butanol) is charged under a predetermined pressure while increasing the pressure. Thereafter, an aging reaction is carried out at a predetermined temperature until the pressure drop ceases. After cooling to a predetermined temperature and neutralizing, it is withdrawn from the reaction vessel. Analyze the pH of the 5% aqueous solution of this reaction product and the EO adduct distribution by GC (content of compound having an addition mole number n, hereinafter sometimes referred to as EO distribution), and confirm the numerical value. Furthermore, a hydroxyl value is measured and the average value of n is confirmed. A Hertzian flask equipped with a rectifying column is charged with a predetermined amount of a reaction neutralized product, butanol (a compound with n = 0), and then an EO 1 molar adduct (n = 1) under predetermined conditions such as reflux ratio, degree of vacuum, and temperature. Compound) and then the EO2 molar adduct (compound where n is 2) are removed, and then the EO3 molar adduct (compound where n is 3) are distilled off. The distribution analysis of the EO3 molar adduct is conducted by GC. If the content of the compound is 90 to 99% by weight, the compound is used as it is; otherwise, the content of the compound is 90 to 99% by weight. Repeat the removal of the low addition mole product until.

  Next, a predetermined amount of the mixture and a predetermined amount of KOH flakes are charged into a reaction vessel equipped with a stirrer, and after the inside of the vessel is replaced with nitrogen, the temperature is raised under a predetermined pressure. When the target temperature is reached, EO is gradually charged, and a predetermined amount of EO is charged under a predetermined pressure while increasing the pressure. Thereafter, an aging reaction is carried out at a predetermined temperature until the pressure drop ceases. After cooling to a predetermined temperature and neutralizing, it is withdrawn from the reaction vessel. The pH of a 5% aqueous solution of this reaction product is analyzed for EO distribution by GC, and the numerical value is confirmed. Furthermore, a hydroxyl value is measured and the average value of n is confirmed.

  The reaction product thus obtained can be used as it is as the component (A) of the present invention, but the composition may be adjusted as necessary.

  Moreover, the additive composition for hydraulic compositions of the present invention comprises a step of adding an alkylene oxide having 2 to 8 carbon atoms to an alcohol having 1 to 22 carbon atoms, and a general reaction product obtained by the step. It can be obtained from a method for producing an additive composition for a hydraulic composition (hereinafter referred to as production method 2), which comprises a step of reducing a compound wherein n in formula (1) is 3 or less.

  In production method 2, a method of adding an alkylene oxide having 2 to 8 carbon atoms to an alcohol having 1 to 22 carbon atoms is a method in which the reaction is performed under the conditions of a predetermined pressure and a predetermined temperature in the presence of an alkali catalyst such as potassium hydroxide. It is done. In that case, when the alcohol is monovalent, the alkylene oxide having 2 to 8 carbon atoms is preferably 1 to 10 mol, more preferably 1 to 5 mol, and still more preferably 2 to 3 mol per mol of the alcohol. Moreover, as a method of reducing the compound in which n in general formula (1) in the reaction product obtained by the process is 3 or less, the reaction product is reduced under reduced pressure (for example, 13.3 to 1.33 kPa). And a method of refluxing at a predetermined temperature for a predetermined time, and it is preferable to carry out by changing the conditions according to the compound to be reduced. For example, the pressure and temperature can be changed in stages, and n can be sequentially distilled off from 0, 1, 2, and 3.

  As an example of production method 2, a case where EO having 2 carbon atoms is added to alcohol having 4 carbon atoms (butanol) will be described.

  A predetermined amount of butanol and a predetermined amount of KOH are charged into a reaction vessel equipped with a stirrer, and after the inside of the vessel is sufficiently substituted with nitrogen, the temperature is raised under a predetermined pressure. When the target temperature is reached, EO is gradually charged, and a predetermined amount of EO (3 mol with respect to butanol) is charged under a predetermined pressure while increasing the pressure. Thereafter, an aging reaction was performed at a predetermined temperature until the pressure drop was subsided. After cooling to a predetermined temperature and neutralizing, it is withdrawn from the reaction vessel. Analyze pH of 5% aqueous solution of this reaction product and EO distribution by GC to confirm the numerical value. Furthermore, a hydroxyl value is measured and the average value of n is confirmed. A Hertzian flask equipped with a rectifying column is charged with a predetermined amount of a reaction neutralized product, butanol (a compound with n = 0), and then an EO 1 molar adduct (n = 1) under predetermined conditions such as reflux ratio, degree of vacuum, and temperature. Compound) and then the EO2 molar adduct (compound where n is 2) and then the EO3 molar adduct (compound where n is 3) are distilled off. Thereafter, the mixture is distilled while changing the reflux ratio, the degree of vacuum, etc. to obtain a mixture containing EO4, 5 mol adduct. The mixture is analyzed for EO distribution by GC to confirm the numerical value. Furthermore, a hydroxyl value is measured and the average value of n is confirmed.

<Method for producing hydraulic composition>
The additive composition for a hydraulic composition of the present invention is used for producing a hydraulic composition containing a 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 [water and hydraulic properties in slurry from the viewpoint of producing concrete that can be constructed with higher strength while maintaining the amount of water necessary for the hydration reaction of cement. The percentage by weight (% by weight) of the powder, usually abbreviated as W / P, but abbreviated as W / C when the powder is cement. ] 10 to 60% by weight, further 15 to 55% by weight, further 20 to 53% by weight, further 30 to 50% by weight, and further 40 to 50% by weight.

In the hydraulic composition of the present invention, the unit amount of the hydraulic powder is preferably 250 to 2000 kg / m ³ , more preferably 270 to 1500 kg / m ³ , still more preferably 300 to 1000 kg / m ³ , particularly preferably. 300 to 400 kg / m ³ .

In the hydraulic composition of the present invention, the unit amount of water is preferably 120 to 190 kg / m ³ , preferably 150 to 185 kg / m ³ , more preferably 160 to 175 kg / m ³ .

The hydraulic composition of the present invention preferably contains fibers such as synthetic fibers from the viewpoint of preventing explosion when the cured body is exposed to a flame or the like and heated. Examples of the fiber include synthetic fibers having a length of 6 to 50 mm in which the volume decreases or decomposes and volatilizes by being softened or melted at 100 ° C. and a diameter of 5 to 500 μm. When the cured body is heated, the fiber contained in the cured body is reduced in volume or decomposed and volatilized, so that distortion due to expansion of the cured body can be alleviated and explosion of the cured body can be prevented. Examples of synthetic fibers include polyacetal fibers, nylon fibers, aramid fibers, polyester fibers, acrylic fibers, vinylon fibers, synthetic fibers such as polypropylene fibers and polyethylene fibers, and regenerated fibers such as rayon fibers. Of these, polyacetal fibers are preferred. From the viewpoint of obtaining high-strength concrete of 80 N / mm ² or more, the fiber is 0.01 to 5.0% by volume, more preferably 0.05 to 3.5% by volume, and still more preferably 0.1% to the hydraulic composition. It is preferable to use ~ 3.5% by volume.

  The timing of mixing the fibers may be determined appropriately in consideration of the fresh properties of the concrete produced for each compounding, but from the viewpoint of obtaining high fluidity efficiently, it was kneaded before adding the coarse aggregate. It is preferable to put into mortar.

  The hydraulic composition of the present invention preferably contains an expansion material from the viewpoint of suppressing self-shrinkage while maintaining the drying shrinkage and the strength after curing of the hydraulic composition. As the inflatable material, those defined in JIS A 6202 can be used. Specifically, the expansion material chosen from the expansion material which has calcium sulfoaluminate as a main component, and the expansion material which has quicklime as a main component is mentioned. The expansion material is preferably used in an amount of 1 to 30 parts by weight, further 3 to 20 parts by weight, and further 5 to 15 parts by weight with respect to 100 parts by weight of the hydraulic powder (for example, cement). In the production of the hydraulic composition, the expansion material is preferably added together with the hydraulic powder (for example, cement).

<Additive composition for hydraulic composition>
(1) Component (A) and Comparative Mixture As the component (A) and the comparative mixture, the mixtures A-1 to A-14 obtained in the following Production Examples A-1 to A-14 were used.

[Production Example A-1] (Production of Mixture A-1)
A stainless steel 6L reaction vessel equipped with a stirrer was charged with 1824.4 g of butanol and 3.4 g of KOH flakes, and after sufficiently replacing the inside of the vessel with nitrogen, the temperature was raised at 0.02 MPa. When the temperature reached 135 ° C., EO was gradually charged, and while increasing the pressure, 2168.5 g of EO was charged at a maximum pressure of 0.4 MPa. Thereafter, an aging reaction was carried out at 135 ° C. until the pressure drop ceased. After cooling to a temperature of 60 ° C. and neutralizing with 3.7 g of acetic acid, it was extracted from the reaction vessel. The 5% aqueous solution of this reaction product had a pH of 6.5. As a result of analyzing the EO distribution by GC, the sum of compounds having n [n in general formula (1), the same applies hereinafter] of 3 or less is 76.5% by area, and the sum of compounds having n of 4 to 10 is The total of the compounds having 23.2 area% and n of 11 or more was 0.3 area% (EO average added mole number 2.3). A glass 5 L Hertz flask equipped with a rectifying column was charged with 3.5 kg of the reaction product, reflux ratio = 5, vacuum degree 13.3 kPa (100 torr), butanol at a temperature of about 58 ° C., n at 1 at a temperature of about 110 ° C. The compound in which n was 2 at a temperature of about 160 ° C. and the compound in which n was 3 at a temperature of about 190 ° C. were removed. Thereafter, the reflux ratio was changed to 2 and the degree of vacuum was changed to 1.33 kPa (10 torr), and distillation was performed leaving 10% of the residue to obtain a mixture A-1. Table 1 shows the results of analyzing the EO distribution of the distilled product (mixture A-1) by GC. In the mixture A-1, the content of the compound having n [n in the general formula (1), the same applies hereinafter] of 3 or less is 1.5 area%, and the content of the compound having n is 4 or 5 is 98.5 area. %, The content of the compound having n of 6 or more was 0 area% (hydroxyl value 216.6 mgKOH / g, EO average added mole number 4.2 by hydroxyl value). Here, the hydroxyl value was obtained by acetylating 1 g of a sample and measuring the number of mg of potassium hydroxide necessary for neutralizing acetic acid bonded to the hydroxyl group (the same applies hereinafter).

[Production Example A-2] (Production of Mixture A-2)
In a 0.5 L reaction vessel made of stainless steel with a stirrer, 100 g of a compound with 3 n (mixture A-6) and 0.07 g of KOH flakes separated by rectification in the production process of mixture A-1 in Production Example A-1. After charging and sufficiently replacing the inside of the container with nitrogen, the temperature was raised at 0.02 MPa. When the temperature reached 135 ° C., EO was gradually charged, and while increasing the pressure, 42.7 g of EO was charged at a maximum pressure of 0.4 MPa. Thereafter, an aging reaction was carried out at 135 ° C. until the pressure drop ceased. After cooling to a temperature of 60 ° C. and neutralizing with 0.07 g of acetic acid, the mixture was extracted from the reaction vessel to obtain a mixture A-2. The 5% aqueous solution of this mixture A-2 had pH = 6.2. In the mixture A-2, the content of the compound having n of 3 or less was 13.5 area%, the total of the compounds having n of 4 to 10 was 86.4 area%, and the content of the compound having n of 11 or more was 0.00. It was 1 area% (hydroxyl value 193.5 mgKOH / g, EO average addition mole number 4.9 by hydroxyl value). Table 1 shows the results of EO distribution analysis by GC.

[Production Example A-3] (Production of Mixture A-3)
In a stainless steel 0.5 L reaction vessel equipped with a stirrer, 100 g of a compound of n 3 and 0.07 g of KOH flakes separated by rectification in the production process of the mixture A-1 in Production Example A-1 were charged, and the vessel was filled with nitrogen After sufficiently replacing the temperature, the temperature was raised at 0.02 MPa. When the temperature reached 135 ° C., EO was gradually charged, and while increasing the pressure, 64.1 g of EO was charged at a maximum pressure of 0.4 MPa. Thereafter, an aging reaction was carried out at 135 ° C. until the pressure drop ceased. After cooling to a temperature of 60 ° C. and neutralizing with 0.07 g of acetic acid, the mixture was extracted from the reaction vessel to obtain a mixture A-3. The 5% aqueous solution of this mixture A-3 had pH = 6.2. In the mixture A-3, the content of the compound having n of 3 or less is 6.0 area%, the total of the compounds having n of 4 to 10 is 91.4 area%, and the content of the compound having n of 11 or more is 2. 6 area% (hydroxyl value 168.6 mgKOH / g, EO average addition mole number 5.9 by hydroxyl value). Table 1 shows the results of EO distribution analysis by GC.

[Production Example A-4] (Production of Mixture A-4)
In a stainless steel 0.5 L reaction vessel equipped with a stirrer, 100 g of a compound of n 3 and 0.07 g of KOH flakes separated by rectification in the production process of Mixture A-1 in Production Example A-1 and 0.07 g of KOH flakes were charged, and the vessel was filled with nitrogen. After sufficiently replacing the temperature, the temperature was raised at 0.02 MPa. When the temperature reached 135 ° C., EO was gradually charged, and 106.8 g of EO was charged at a maximum pressure of 0.4 MPa while increasing the pressure. Thereafter, an aging reaction was carried out at 135 ° C. until the pressure drop ceased. After cooling to a temperature of 60 ° C. and neutralizing with 0.07 g of acetic acid, the mixture was extracted from the reaction vessel to obtain a mixture A-4. The 5% aqueous solution of this mixture A-4 had a pH of 6.2. In the mixture A-4, the content of compounds having n of 3 or less was 0.8 area%, the total of compounds having n of 4 to 10 was 83.4 area%, and the content of compounds having n of 11 or more was 15. It was 8 area% (hydroxyl value 135.9 mgKOH / g, EO average addition mole number 7.7 by hydroxyl value). Table 1 shows the results of EO distribution analysis by GC.

[Production Example A-5] (Production of Mixture A-5)
A stainless steel 6L reaction vessel equipped with a stirrer was charged with 1824.4 g of butanol and 3.4 g of KOH flakes, and after sufficiently replacing the inside of the vessel with nitrogen, the temperature was raised at 0.02 MPa. When the temperature reached 135 ° C., EO was gradually charged, and while increasing the pressure, 2168.5 g of EO was charged at a maximum pressure of 0.4 MPa. Thereafter, an aging reaction was carried out at 135 ° C. until the pressure drop ceased. After cooling to a temperature of 60 ° C. and neutralizing with 3.7 g of acetic acid, it was extracted from the reaction vessel. The 5% aqueous solution of this reaction product had a pH of 6.5. As a result of analyzing the EO distribution by GC, the total of compounds with n of 3 or less was 76.5 area%, the total of compounds with n of 4 to 10 was 23.2 area%, and n was 11 or more. The total was 0.3 area% (EO average added mole number 2.3). A glass 5 L Hertz flask equipped with a rectifying column was charged with 3.5 kg of the reaction product, reflux ratio = 5, vacuum degree 13.3 kPa (100 torr), butanol at a temperature of about 58 ° C., n at 1 at a temperature of about 110 ° C. Then, the compound having n = 2 was separated by distillation at a temperature of 160 ° C. to obtain a mixture A-5. In the mixture A-5, the content of the compound having n of 3 or less is 100 area%, the content of the compound in which n is 1 is 0.6 area%, and the content of the compound in which n is 2 is 99.0 area %, And the content of the compound having n of 3 was 0.4 area% (hydroxyl value 345.2 mgKOH / g, EO average added mole number 2.0 by hydroxyl value). Table 1 shows the results of EO distribution analysis by GC.

[Production Example A-6] (Production of Mixture A-6)
A stainless steel 6L reaction vessel equipped with a stirrer was charged with 1824.4 g of butanol and 3.4 g of KOH flakes, and after sufficiently replacing the inside of the vessel with nitrogen, the temperature was raised at 0.02 MPa. When the temperature reached 135 ° C., EO was gradually charged, and while increasing the pressure, 2168.5 g of EO was charged at a maximum pressure of 0.4 MPa. Thereafter, an aging reaction was carried out at 135 ° C. until the pressure drop ceased. After cooling to a temperature of 60 ° C. and neutralizing with 3.7 g of acetic acid, it was extracted from the reaction vessel. The 5% aqueous solution of this reaction product had a pH of 6.5. As a result of analyzing the EO distribution by GC, the total of compounds having n of 3 or less was 76.5%, the total of compounds having n of 4 to 10 was 23.2%, and the total of compounds having n11 or more was 0.00. 3% (EO average added mole number 2.3). A glass 5 L Hertz flask equipped with a rectifying column was charged with 3.5 kg of the reaction product, reflux ratio = 5, vacuum degree 13.3 kPa (100 torr), butanol at a temperature of about 58 ° C., n at 1 at a temperature of about 110 ° C. After removing the compound with n of 2 at a temperature of about 160 ° C., the compound with n of 3 was distilled off at a temperature of about 190 ° C. to obtain a mixture A-6. In the mixture A-6, the content of the compound having n of 3 or less is 99.5 area%, the content of the compound in which n is 2 is 1.5 area%, and the content of the compound in which n is 3 is 98. The content of the compound having 0 area% and n of 4 was 0.5 area% (hydroxyl value 273.9 mgKOH / g, EO average added mole number 3.0 by hydroxyl value). Table 1 shows the results of EO distribution analysis by GC.

[Production Example A-7] (Production of Mixture A-7)
A stainless steel 6L reaction vessel equipped with a stirrer was charged with 1824.4 g of butanol and 3.4 g of KOH flakes, and after sufficiently replacing the inside of the vessel with nitrogen, the temperature was raised at 0.02 MPa. When the temperature reached 135 ° C., EO was gradually charged, and while increasing the pressure, 2168.5 g of EO was charged at a maximum pressure of 0.4 MPa. Thereafter, an aging reaction was carried out at 135 ° C. until the pressure drop ceased. After cooling to a temperature of 60 ° C. and neutralizing with 3.7 g of acetic acid, the mixture was extracted from the reaction vessel to obtain a mixture A-7. The 5% aqueous solution of this mixture A-7 had a pH of 6.5. In the mixture A-7, the content of the compound having n of 3 or less is 76.6 area%, the content of the compound having n of 4 to 10 is 23.1 area%, and the content of the compound having n of 11 or more is 0 3 area% (hydroxyl value 363.2 mgKOH / g, EO average added mole number 1.8 by hydroxyl value). Table 1 shows the results of EO distribution analysis by GC.

[Production Example A-8] (Production of Mixture A-8)
358.8 g of butanol and 0.7 g of KOH flakes were charged in a stainless steel 2 L reaction vessel equipped with a stirrer, and the inside of the vessel was sufficiently replaced with nitrogen, followed by heating at 0.02 MPa. When the temperature reached 135 ° C., EO was gradually charged, and 639.8 g of EO was charged at a maximum pressure of 0.4 MPa while increasing the pressure. Thereafter, an aging reaction was carried out at 135 ° C. until the pressure drop ceased. After cooling to a temperature of 60 ° C. and neutralizing with 0.7 g of acetic acid, the mixture was extracted from the reaction vessel to obtain a mixture A-8. The 5% aqueous solution of this mixture A-8 had a pH = 6.2. In the mixture A-8, the content of the compound having n of 3 or less was 54.7 area%, the content of the compound having n of 4 to 10 was 43.6 area%, and the content of the compound having n of 11 or more was 1 0.7 area% (hydroxyl value 268.1 mgKOH / g, EO average addition mole number 3.1 by hydroxyl value). Table 1 shows the results of EO distribution analysis by GC.

[Production Example A-9] (Production of Mixture A-9)
A stainless steel 2 L reaction vessel equipped with a stirrer was charged with 295.8 g of butanol and 0.6 g of KOH flakes, and after the inside of the vessel was sufficiently replaced with nitrogen, the temperature was raised at 0.02 MPa. When the temperature reached 135 ° C., EO was gradually charged, and EO703.1 g was charged at a maximum pressure of 0.4 MPa while increasing the pressure. Thereafter, an aging reaction was carried out at 135 ° C. until the pressure drop ceased. After cooling to a temperature of 60 ° C. and neutralizing with 0.6 g of acetic acid, the mixture was extracted from the reaction vessel to obtain a mixture A-9. The 5% aqueous solution of this mixture A-9 had a pH of 6.3. In the mixture A-9, the content of a compound having n of 3 or less is 41.7 area%, the content of a compound having n of 4 to 10 is 54.8 area%, and the content of a compound having n of 11 or more is 3 It was 0.5 area% (hydroxyl value 220.4 mgKOH / g, EO average addition mole number 4.1 by hydroxyl value). Table 1 shows the results of EO distribution analysis by GC.

[Production Example A-10] (Production of Mixture A-10)
218.8 g of butanol and 0.4 g of KOH flakes were charged in a stainless steel 2 L reaction vessel equipped with a stirrer, and after the inside of the vessel was sufficiently replaced with nitrogen, the temperature was raised at 0.02 MPa. When the temperature reached 135 ° C., EO was gradually added, and 780.3 g of EO was charged at a maximum pressure of 0.4 MPa while increasing the pressure. Thereafter, an aging reaction was carried out at 135 ° C. until the pressure drop ceased. After cooling to a temperature of 60 ° C. and neutralizing with 0.4 g of acetic acid, the mixture was extracted from the reaction vessel to obtain a mixture A-10. The 5% aqueous solution of this mixture A-10 had a pH of 6.1. In the mixture A-10, the content of the compound having n of 3 or less is 21.1 area%, the content of the compound having n of 4 to 10 is 67.2 area%, and the content of the compound having n of 11 or more is 11 0.7 area% (hydroxyl value 161.7 mgKOH / g, EO average addition mole number 6.2 by hydroxyl value). Table 1 shows the results of EO distribution analysis by GC.

[Production Example A-11] (Production of Mixture A-11)
A stainless steel 2 L reaction vessel equipped with a stirrer was charged with 173.6 g of butanol and 0.4 g of KOH flakes, and after the inside of the vessel was sufficiently replaced with nitrogen, the temperature was raised at 0.02 MPa. When the temperature reached 135 ° C., EO was gradually charged, and 825.5 g of EO was charged at a maximum pressure of 0.4 MPa while increasing the pressure. Thereafter, an aging reaction was carried out at 135 ° C. until the pressure drop ceased. After cooling to a temperature of 60 ° C. and neutralizing with 0.4 g of acetic acid, the mixture was extracted from the reaction vessel to obtain a mixture A-11. The 5% aqueous solution of this mixture A-11 had pH = 6.6. In the mixture A-11, the content of the compound having n of 3 or less is 10.1 area%, the content of the compound having n of 4 to 10 is 64.6 area%, and the content of the compound having n of 11 or more is 25. It was 3 area% (hydroxyl value 131.0 mgKOH / g, EO average addition mole number 8.0 by hydroxyl value). Table 1 shows the results of EO distribution analysis by GC.

[Production Example A-12] (Production of Mixture A-12)
143.9 g of butanol and 0.5 g of KOH flakes were charged in a stainless steel 2 L reaction vessel equipped with a stirrer, and the temperature inside the vessel was sufficiently replaced with nitrogen, followed by heating at 0.02 MPa. When the temperature reached 135 ° C., EO was gradually added, and 855.0 g of EO was charged at a maximum pressure of 0.4 MPa while increasing the pressure. Thereafter, an aging reaction was carried out at 135 ° C. until the pressure drop ceased. After cooling to a temperature of 60 ° C. and neutralizing with 0.5 g of acetic acid, the mixture was extracted from the reaction vessel to obtain a mixture A-12. The 5% aqueous solution of this mixture A-12 had a pH of 6.3. In the mixture A-12, the content of the compound having n of 3 or less was 6.4 area%, the content of the compound having n of 4 to 10 was 56.6 area%, and the content of the compound having n of 11 or more was 37. It was 0.0 area% (hydroxyl value 110.8 mgKOH / g, EO average addition mole number 9.8 by hydroxyl value). Table 1 shows the results of EO distribution analysis by GC.

[Production Example A-13] (Production of Mixture A-13)
77.5 g of butanol and 0.6 g of KOH flakes were charged into a stainless steel 2 L reaction vessel equipped with a stirrer, and the inside of the vessel was sufficiently replaced with nitrogen, followed by heating at 0.02 MPa. When the temperature reached 135 ° C., EO was gradually charged, and 921.3 g of EO was charged at a maximum pressure of 0.4 MPa while increasing the pressure. Thereafter, an aging reaction was carried out at 135 ° C. until the pressure drop ceased. After cooling to a temperature of 60 ° C. and neutralizing with 0.6 g of acetic acid, the mixture was extracted from the reaction vessel to obtain a mixture A-13. The 5% aqueous solution of this mixture A-13 had a pH of 6.5. In the mixture A-13, the content of the compound having n of 3 or less is 0.6 area%, the content of the compound having n of 4 to 10 is 17.2 area%, and the content of the compound having n of 11 or more is 82 0.2% by area (hydroxyl value 60.5 mgKOH / g, EO average added mole number 19.4 by hydroxyl value). Table 1 shows the results of EO distribution analysis by GC.

[Production Example A-14] (Production of Mixture A-14)
In a stainless steel 0.5 L reaction vessel with a stirrer, 60 g of a compound of n = 3 and 0.05 g of KOH flakes separated by rectification in the production process of mixture A-1 in Production Example A-1 were charged, and the vessel was filled with nitrogen. After sufficiently replacing the temperature, the temperature was raised at 0.02 MPa. When the temperature reached 135 ° C., EO was gradually added, and 89.7 g of EO was charged at a maximum pressure of 0.4 MPa while increasing the pressure. Thereafter, an aging reaction was carried out at 135 ° C. until the pressure drop ceased. After cooling to a temperature of 60 ° C. and neutralizing with 0.05 g of acetic acid, the mixture was extracted from the reaction vessel to obtain a mixture A-4. The 5% aqueous solution of this mixture A-4 had a pH of 6.2. In the mixture A-4, the content of the compound where n is 3 is 0.1 area%, the total of the compounds where n is 4 to 10 is 58.0 area%, and the content of the compound where n is 11 or more is 41.9. It was area% (hydroxyl value 113.1 mgKOH / g, EO average addition mole number 9.6 by hydroxyl value). Table 1 shows the results of EO distribution analysis by GC.

  Regarding the component (A) and the comparative mixture obtained above, Table 1 shows the EO average addition mole number based on the hydroxyl value and the compound distribution (EO distribution) for each addition mole number. The area% of compounds having n of 11 or more was determined by subtracting the total area (total area%) of compounds having n of 1 to 10 from the total area (100 area%) of the GC chart.

In addition, EO distribution of (A) component and a comparison mixture was measured according to the following GC conditions, and area% was computed based on GC chart obtained by this analysis method. Further, the area% value of GC measurement in the present invention is a value when the area of the peak of the solvent used for washing the syringe and the peak on the lower boiling point side thereof is not counted by setting the recorder.
[GC analysis method]
1. Take a drop of sample into a 2 ml lidded sample bottle.
2. Add 1 ml of TMS (trimethylsilyl ether) agent and shake well for about 1 minute.
3. After filtering the liquid with a 1 μ filter, GC analysis is performed under the following conditions.
<GC conditions>
Device (main unit): HP-6890 (manufactured by Hewlett-Packard Company)
Oven: Initial temperature: 40 ° C Initial time: 5 min
Temperature increase rate: up to 150 ° C at 5.0 ° C / min
Temperature increase rate: Up to 350 ° C at 10.0 ° C / min
Maximum temperature: 350 ° C., 12 min Holding column: Capillary column frontier UA-1 15.0 m × 250.0 μm
Injection volume: 1.0 μl

<High performance water reducing agent>
(1) Component (B) As the component (B), copolymers B-1 to B-2 obtained in the following Production Examples B-1 to B-2 were used.

[Production Example B-1] (Production of Copolymer B-1)
A glass reaction vessel (four-necked flask) equipped with a stirrer was charged with 281.4 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. ω-methoxypolyethyleneglycol methacrylate (EO average addition mole number 120) 336.5 g, methacrylic acid 22.2 g, 2-mercaptoethanol 1.89 g dissolved in water 238.2 g and ammonium persulfate 3.68 g in water 45 g The two dissolved ones were added dropwise over 1.5 hours. Subsequently, a solution prepared by dissolving 1.47 g of ammonium persulfate in 15 g of water was added dropwise over 30 minutes, and then aged at the same temperature (80 ° C.) for 1 hour. After completion of the 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 B-2] (Production of Copolymer B-2)
It was produced in accordance with the method described in the production example of JP-A-7-223852.

  The component (B) obtained above is summarized in Table 2.

  In the table, EO is an abbreviation for ethylene oxide, and the numbers in parentheses are the average number of moles added.

(2) Component (C) As the component (C), copolymers C-1 to C-2 obtained in the following Production Examples C-1 to C-2 were used.

[Production Example C-1] (Production of Copolymer C-1)
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 number of moles of EO added 23) (effective content 60.8%, moisture 35%), mono (2-hydroxyethyl) methacrylic acid ester and di-[(2 -Hydroxyethyl) methacrylic acid] ester mixture (C ′) 71.6 g and 3-mercaptopropionic acid 4.5 g mixed with ammonium persulfate. Two of 8.4 g dissolved in 48 g of water 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 copolymer C-1 having a weight average molecular weight of 35,000. (Monomer polymerization pH: 1.0, reaction rate 100%)

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

[Production Example C-2] (Production of Copolymer C-2)
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 number of moles of EO added: 23) (effective content: 60.8%, moisture: 35%), mono (2-hydroxyethyl) methacrylate and di-[(2 -Hydroxyethyl) methacrylic acid] phosphoric ester (C ') which is a mixture of ester (same as Production Example C-1) and 22.8 g of 3-mercaptopropionic acid mixed with 2.8 g of ammonium persulfate. Two of 7.2 g dissolved in 41 g of water 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 copolymer C-2 having a weight average molecular weight of 36000. (Monomer polymerization pH: 1.1, reaction rate 100%)

  The components (C) obtained above are summarized in Table 3.

(3) Composition of high performance water reducing agent, etc. The above components (B) and (C) were blended in the ratios shown in Table 4 below to prepare an effective 23% by weight aqueous solution of the high performance water reducing agent and used for concrete evaluation. .

<Preparation and evaluation of concrete>

Water (W): Tap water Cement (C): Ordinary Portland cement (commercially available density: 3.16 g / cm ³ )
Fine aggregate (S1): Mountain sand from Joyo, Kyoto (Density: 2.56 g / m ³ ) (FM: 2.73)
Fine aggregate (S2): Yodogawa coarse sand (density: 2.60 g / cm ³ ) (FM: 2.66)
Coarse aggregate (G): gravel (density: 2.61 g / cm ³ ) (FM: 6.87)
W / C: (W / C) × 100 (% by weight)
S / a: [(S1 + S2) / (S1 + S2 + G)] × 100 (volume%)

  Cement (C), fine aggregate (S), and coarse aggregate (G) were added using a 100 L forced biaxial mixer under the blending conditions shown in Table 5, and kneaded for 10 seconds. Air-entraining agent (main component is polyoxyethylene lauryl ether sulfate) and antifoaming agent (main component is fatty acid ester) and 23% by weight high performance so that the target air volume is 3.0 to 6.0%. Kneading water containing a water reducing agent aqueous solution (the total amount of these additive components and water is W) was added and kneaded for 90 seconds. The air entraining agent was added to the kneading water in an amount of 0.002% by weight based on the cement weight. Moreover, 0.1 weight% of antifoamers were mix | blended in (A) component. This concrete was used as base concrete (Comparative Example 1 in Table 6). Next, by adding the component (A) to the base concrete mixing water (air entraining agent, antifoaming agent, high-performance water reducing agent, (A) the sum of the component and water W), the fluidity of the base concrete, The effects on air entrainment, drying shrinkage, and freeze-thaw resistance were evaluated. These concretes were measured for slump, air content, drying shrinkage, and freeze-thaw resistance according to the following test methods. Moreover, the odor of the component (A) was evaluated according to the test method shown below. The evaluation results are shown in Table 6.

The addition amount of the component (A) was 1.5 kg / m ^{3 as} a unit amount of the concrete blend, and the addition amount of the 23 wt% high-performance water reducing agent aqueous solution was 0.75 wt% with respect to the cement weight.

(1) Fluidity evaluation Slumps were measured in accordance with JIS-A1101 to obtain fluidity evaluation.
(2) Air entrainment evaluation The amount of air was measured according to JIS-A1128.
(3) Drying shrinkage evaluation Drying shrinkage was measured according to JIS-A1129 (contact gauge method). That is, a specimen of 100 mm × 100 mm × 400 mm was prepared and stored in a constant temperature and humidity room at a temperature of 20 ° C. ± 1 ° C. and a humidity of 60%, and the length change rate (× 10 ⁻⁶ ) of the material age 56 days. It was measured. It shows that drying shrinkage is so small that a rate of length change is small. In this evaluation, the length change rate is preferably 680 (× 10 ⁻⁶ ) or less.
(4) Freeze-thaw resistance evaluation Freeze-thaw resistance was measured according to JIS-A1148. That is, a 100 × 100 × 400 mm specimen was prepared and cured in water until age 28, after which the test was started. The test contents were such that the center temperature of the specimen decreased from 5 ° C. to −18 ° C. and increased from −18 ° C. to 5 ° C., and this was repeated 300 times. At this time, the relative kinematic modulus of 60% or more was determined to be “A” having excellent freeze-thaw resistance, and less than 60% was determined to be “B” having inferior freeze-thaw resistance.
(5) Odor evaluation Sensory evaluation was performed by one panelist skilled in odor. That is, 50 ml of the component (A) is put into a 100 ml glass screw tube, capped, the cap of the screw tube is removed, and the smell at the entrance of the screw tube is smelled and evaluated according to the following criteria. In addition, since the high performance water reducing agent of Table 6 does not have a problem of odor, a good product can be obtained if there is no problem in the odor of the component (A) even when it is a one-pack type.
No specific odor: A
Peculiar odor: B
Strong peculiar odor: C

  From the results of Table 6, it can be seen that, when the component (A) of the present invention is used, concrete having a small rate of change in length and excellent freeze-thaw resistance can be produced at the target slump value and air amount. The component (A) of the present invention is also excellent in odor. Therefore, the additive composition for hydraulic composition of the present invention has no problem of odor and can simultaneously impart a plurality of excellent physical properties to concrete. On the other hand, in Comparative Examples 1 to 14 that do not use the component (A) of the present invention, it is impossible to achieve both odor and imparting a plurality of excellent physical properties.

  Moreover, even if the EO average addition mole number is the same in the structure of the component (A), for example, Example 1 using A-1 (EO average addition mole number 4.2) of the product of the present invention and A- When compared with Comparative Example 6 using 9 (EO average added mole number is 4.1), Comparative Example 6 has a large rate of change in length and is inferior in freeze-thaw resistance and odor. It can be seen that the effect of is not obtained. Further, Comparative Example 7 (using A-10 having an EO average addition mole number of 6.2) is equivalent to EO average addition mole number being equivalent to Example 3 (using A-3 having an EO average addition mole number of 5.9). However, the rate of change in length is larger than that of Example 3, and the freeze-thaw resistance is inferior. Further, Comparative Example 8 (using A-11 having an EO average addition mole number of 8.0) has an average addition mole number equivalent to that of Example 4 (using A-4 having an EO average addition mole number of 7.7). Although a compound is used, the length change rate is larger than that in Example 4. In other words, it was revealed by the present invention that the compound having the structure of component (A) has a great difference in the effect due to the EO distribution even when the EO average added mole number is about the same. Therefore, the EO distribution for the component (A) defined in the present invention is technically significant.

  A one-component additive composition for a hydraulic composition containing 36% by weight of component (A), 14% by weight of high-performance water reducing agent, and 50% by weight of water in combination with Examples 1 to 7 in Table 6. Were prepared and stored at 20 ° C. for 3 months, all maintained a transparent and uniform state.

Claims (6)

An additive composition for a hydraulic composition containing a mixture of compounds represented by the following general formula (1),
The average value of n according to the hydroxyl value of the mixture is 3 to 12,
The content of the compound having n of 3 or less in the mixture determined by gas chromatography is 0 to 15 area%, and
The content of the compound having n of 11 or more in the mixture determined by gas chromatography is 0 to 20 area%.
Additive composition for hydraulic composition.
R ¹ —O— (AO) _n —R ² (1)
(In the formula, R ¹ and R ² are each a hydrogen atom or an alkyl group having 2 to 6 carbon atoms, A is an alkylene group having 2 to 4 carbon atoms, and n is the added mole number of AO. (It is an integer of 0 or more, except when R ¹ and R ² are hydrogen atoms at the same time and when they are simultaneously alkyl groups.)   The additive composition for hydraulic compositions according to claim 1, wherein the content of the compound having n of 4 to 8 in the mixture determined by gas chromatography is 50 to 99 area%.   The additive composition for hydraulic compositions according to claim 1 or 2, comprising 3 to 100% by weight of the mixture. R in general formula (1) ¹ And R ² The additive composition for hydraulic compositions according to any one of claims 1 to 3, wherein one of the above is a hydrogen atom and the other is an alkyl group having 4 carbon atoms. It is a manufacturing method of the additive composition for hydraulic compositions in any one of Claims 1-4 , Comprising: The mixture containing 90-99weight% of the compound whose n in General formula (1) is 3 a step of adding an alkylene oxide with carbon number 2-4, the method for producing a hydraulic composition additive composition. A process of claim 1 any one for hydraulic compositions additive composition according to 4, comprising the steps of adding the alkylene oxide from 2 4 carbon atoms in the alcohol having 2 to 6 carbon atoms, The manufacturing method of the additive composition for hydraulic compositions which has the process of reducing the compound whose n in General formula (1) in the reaction product obtained by this process is 3 or less.