JP6223750B2 - Additive for hydraulic materials - Google Patents

Description

  The present invention relates to an additive for hydraulic materials. In detail, it is related with the additive for hydraulic materials which can provide the outstanding shrinkage reduction function, and the outstanding fluidity, and a hydraulic material composition.

  The hydraulic material gives a cured product having excellent strength and durability. For this reason, hydraulic materials are widely used as cement compositions such as cement paste, mortar, and concrete. Hydraulic materials are indispensable for constructing civil engineering and building structures.

  The hydraulic material causes the unreacted water remaining inside to dissipate due to the outside air temperature and humidity conditions after being cured. For this reason, there is a problem that drying shrinkage proceeds, cracks occur in the cured product, and strength, durability, and the like are lowered. When the strength and durability of civil engineering and building structures are reduced, serious problems such as reduced safety and increased repair costs arise.

Laws and regulations have been strengthened against such problems. Under the law concerning the promotion of quality assurance of houses established in June 1999, cracks in concrete are also subject to warranty. According to the Building Construction Standard Specification for Reinforced Concrete Structures revised in February 2009 (JASS 5 (Architectural Institute of Japan)), the shrinkage strain at 26 weeks in concrete over a long life (over 100 years) is 8 × 10 ^-4 or less.

  Recently, shrinkage reducing agents have been regarded as important as a method for reducing drying shrinkage in order to suppress cracks in concrete. Simultaneously with the revision of JASS 5, the Architectural Institute standards for shrinkage reducing agents were established.

  As conventional shrinkage reducing agents, alkylene oxide adducts of alcohols having 1 to 4 carbon atoms (see Patent Document 1), co-adducts of ethylene oxide and propylene oxide of 2 to 8 polyhydric alcohols (see Patent Document 2) ), Alkylene oxide adduct of lower alkylamine (see Patent Document 3), polypropylene glycol in oligomer region (see Patent Document 4), low molecular weight alcohols (see Patent Document 5), alkylene oxide adduct of 2-ethylhexanol (see Patent Document 5) Patent Document 6) has been reported.

  However, these shrinkage reducing agents have a problem that the strength decreases when used in concrete. For this reason, in order to maintain intensity | strength, it is necessary to make the ratio of a cement paste part high, and the problem that concrete cost becomes high arises.

  An alkylene oxide adduct of a divalent to octavalent polyhydric alcohol has been reported as a shrinkage reducing agent that can suppress a decrease in strength when used in concrete (see Patent Documents 7 and 8). However, any of these shrinkage reducing agents needs to be combined with other admixtures such as a powder resin and an expansion material, and the problem that the concrete cost increases cannot be solved.

Japanese Patent Publication No. 56-51148 Japanese Patent Publication No. 1-53214 Japanese Patent Publication No. 1-53215 JP 59-152253 A Japanese Patent Publication No. 6-6500 Japanese Patent No. 2825855 Japanese Patent Laid-Open No. 9-301758 JP 2002-68813 A

  The object of the present invention is a combination with other admixtures, is inexpensive, and when combined with a hydraulic material (Z), suppresses a decrease in strength of the cured product, and has an excellent shrinkage reduction function. It is to provide a highly versatile additive for hydraulic materials and a hydraulic material composition that exhibit excellent fluidity.

  Examples of hydraulic materials (Z) include normal, low heat, medium heat, early strength, super early strength, sulfate resistant portland cement, blast furnace cement, silica cement, fly ash cement, eco cement, silica fume cement, etc. It is done.

The additive for hydraulic material of the present invention is
A hydraulic material additive comprising a compound (G) having an oxyalkylene group and a secondary amino group, and a dispersant for hydraulic material (J),
The compound (G) is represented by the following general formula (1):
R ¹ —NH— (X—NH) _m — (Y ¹ O) _n —R ² (1)
(In General Formula (1), R ¹ represents a hydrocarbon group having 1 to 12 carbon atoms, R ² represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and X represents 2 carbon atoms. Represents an alkylene group of ˜4, m is 0 to 10. Y ¹ O represents an oxyalkylene group having 2 to 4 carbon atoms, and n is the average number of added moles of the oxyalkylene group. is there.)
The mass ratio of the compound (G) to the dispersant (J) is in the range of (G) / (J) = 1/1 to 99/1 in terms of solid content.

  In a preferred embodiment, the dispersant (J) is at least one selected from a lignin sulfonate and a polymer having a polyoxyalkylene group and an anionic group.

  In a preferred embodiment, the dispersant (J) is a polymer having a polyoxyalkylene group and an anionic group.

  In preferable embodiment, mass ratio of the said compound (G) and the said dispersing agent (J) is the range of (G) / (J) = 6 / 4-99 / 1 in conversion of solid content. Features.

  In a preferred embodiment, the compound (G) is a compound obtained by reacting 1 mol of ethylene oxide with 1 mol of a monoalkylamine having 1 to 12 carbon atoms.

  The hydraulic material composition of the present invention is a composition comprising a compound (G) having an oxyalkylene group and a secondary amino group, a dispersant (J), and a hydraulic material (Z). The compound (G) is represented by the general formula (1), and the mass ratio of the compound (G) to the dispersant (J) is (G) / (J) = 1 / in terms of solid content. The range is from 1 to 99/1.

  According to the present invention, a combination with other admixtures is not required and is inexpensive, and when combined with a hydraulic material (Z), the strength reduction of the cured product is suppressed and excellent shrinkage reduction is achieved. It is possible to provide a highly versatile additive for hydraulic materials and a hydraulic material composition that exhibit functions and exhibit excellent fluidity.

<< 1. Additive for hydraulic materials >>
The additive for hydraulic materials of the present invention is an additive used for hydraulic materials, and includes the compound (G) and the dispersant (J).

<1. Compound (G)>
The additive for hydraulic materials of the present invention contains a compound (G) having an oxyalkylene group and a secondary amino group. Only one type of compound (G) may be used, or two or more types may be used.

  The compound (G) is represented by the general formula (1).

R ¹ in the general formula (1) may be a hydrocarbon group having 1 to 12 carbon atoms. Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group having 1 to 12 carbon atoms (aliphatic alkyl group or alicyclic alkyl group), a phenyl group having 6 to 12 carbon atoms, an alkylphenyl group, and phenyl. An aromatic group having a benzene ring such as an alkyl group or a naphthyl group is preferred. In R ¹ , as the number of carbon atoms in the hydrocarbon group increases, the hydrophobicity increases and the compatibility decreases. However, if the number of carbon atoms is small, the shrinkage reduction property decreases, so the number of carbon atoms in R ¹ is 1-8 are preferable, 2-8 are more preferable, 2-6 are still more preferable, and 3-5 are especially preferable. The case of 4 carbon atoms is most preferable.

  X in the general formula (1) may be an alkylene group having 2 to 4 carbon atoms. X may be only one type of alkylene group or two or more types of alkylene groups. X is preferably a propylene group or an ethylene group, and more preferably an ethylene group.

  In the general formula (1), m may be 0 to 10. m is preferably 0 to 5, more preferably 0 to 2, and still more preferably 0 or 1.

Y ¹ O in the general formula (1) may be an oxyalkylene group having 2 to 4 carbon atoms. Y ¹ O may be one kind of oxyalkylene group or two or more kinds of oxyalkylene groups. When Y ¹ O is two or more oxyalkylene groups, (Y ¹ O) _n may be a random array or a block array. Y ¹ O is preferably an oxypropylene group or an oxyethylene group, and more preferably an oxyethylene group.

In the general formula (1), n represent an average addition number of moles of ^{Y 1} O, n may be any 1-50. n is preferably 1 to 20, more preferably 1 to 10, still more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1.

R ² in the general formula (1) may be a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. When R ² is a hydrocarbon group, R ² is an alkyl group having 1 to 12 carbon atoms (aliphatic alkyl group or alicyclic alkyl group), a phenyl group having 6 to 12 carbon atoms, an alkylphenyl group, Aromatic groups having a benzene ring such as a phenylalkyl group and a naphthyl group are preferred. In R ² , since the hydrophobicity increases and the compatibility decreases as the number of carbon atoms in the hydrocarbon group increases, the number of carbon atoms in the case of the hydrocarbon group is preferably 1 to 8, and 1 to 6 is preferably More preferably, 1-4 is still more preferable. Most preferably, R ² is a hydrogen atom.

  The content ratio of the compound (G) in the hydraulic material additive of the present invention is preferably 0.1 to 10% by mass, more preferably 0.1 to 10% by mass in terms of solid content with respect to the hydraulic material (Z). It is 0.2-8 mass%, More preferably, it is 0.3-5 mass%, Most preferably, it is 0.5-3 mass%. When the content ratio of the compound (G) in the hydraulic material additive of the present invention is out of the above range, the shrinkage reducing function is obtained when the hydraulic material additive of the present invention is combined with the hydraulic material (Z). In addition, the fluidity may not be sufficiently exhibited, and the strength of the hardened concrete may be reduced.

  Examples of the compound (G) include a compound obtained by reacting 1 mol of ethylene oxide with 1 mol of a monoalkylamine having 1 to 12 carbon atoms, specifically, N-methylethanolamine, N-ethylethanolamine. N-propylethanolamine, Nn-butylethanolamine, N-sec-butylethanolamine, N-tert-butylethanolamine, N-pentylethanolamine, N-hexylethanolamine, N-heptylethanolamine, N -Octylethanolamine, N-2-ethylhexylethanolamine, N-nonylethanolamine, N-decylethanolamine, N-laurylethanolamine and the like.

  Among these, when combined with the hydraulic material (Z), N-ethylethanolamine, N-ethylamine, N-ethylethanolamine and N- Propylethanolamine, Nn-butylethanolamine, N-sec-butylethanolamine, N-tert-butylethanolamine, N-pentylethanolamine, N-hexylethanolamine are preferred, N-propylethanolamine, N- n-Butylethanolamine, N-sec-butylethanolamine, and N-tert-butylethanolamine are more preferable, and Nn-butylethanolamine is particularly preferable.

<2. Dispersant (J)>
The additive for hydraulic materials of the present invention contains a dispersant (J). Only 1 type may be sufficient as a dispersing agent (J), and 2 or more types may be sufficient as it.

  The dispersant (J) is preferably at least one selected from lignin sulfonate and a polymer having a polyoxyalkylene group and an anionic group.

  Any appropriate lignin sulfonate can be adopted as the lignin sulfonate. Examples of such lignin sulfonates include monovalent metal salts, divalent metal salts, ammonium salts, and organic ammonium salts of lignin sulfonic acid.

As the polymer having a polyoxyalkylene group and an anionic group, any suitable polymer having a polyoxyalkylene group and an anionic group can be adopted. General formula (2):

(In the formula, R ³ represents a hydrogen atom or a methyl group. R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. Y ² O represents an oxyalkylene group having 2 to 18 carbon atoms. P is 0, 1 or 2. q is 0 or 1. r represents the average number of added moles of the oxyalkylene group represented by Y ² O and is a number of 2 to 300. A structural unit (A) derived from an unsaturated polyalkylene glycol monomer (a) represented by:
The following general formulas (3-1) to (3-3):

(In the formula, R ⁵ and R ⁶ are the same or different and each represents a hydrogen atom, a methyl group, or a —COOM ² group. R ⁷ represents a hydrogen atom or a methyl group. M ¹ and M ² are the same or Differently, it represents a hydrogen atom, a metal atom, an ammonium group or an organic ammonium group, wherein R ⁵ and R ⁶ do not simultaneously represent a —COOM ² group, and when R ⁶ represents a —COOM ² group, R ⁶ and the —COOM ¹ group may form an acid anhydride group.)

(In the formula, R ⁸ represents a hydrogen atom or a methyl group. M ³ represents a hydrogen atom, a metal atom, an ammonium group, or an organic ammonium group.)

(In the formula, R ⁹ represents a hydrogen atom or a methyl group. Y ³ represents an alkylene group having 2 to 12 carbon atoms. S represents a number of 1 to 30. M ⁴ and M ⁵ are the same or different. And represents a hydrogen atom, a metal atom, an ammonium group, or an organic ammonium group.)
A polyanionic copolymer containing the structural unit (B) derived from the monomer (b) having at least one anionic group selected from among the above is preferable.

  The polyanionic copolymer may further contain a structural unit (C) derived from another monomer (c) described later. In addition, each structural unit in the polyanionic copolymer may be one kind or two or more kinds.

  Examples of the monomer (b-1) represented by the general formula (3-1) include unsaturated monocarboxylic monomers such as (meth) acrylic acid and crotonic acid; maleic acid and itaconic acid , Unsaturated dicarboxylic acid monomers such as fumaric acid or salts thereof (for example, alkali metal salts, alkaline earth metal salts, ammonium salts, alkylammonium salts, etc.), etc., preferably (meth) Acrylic acid or an alkali metal salt thereof.

  As the monomer (b-2) represented by the general formula (3-2), for example, (meth) allylsulfonic acid or a salt thereof (for example, alkali metal salt, alkaline earth metal salt, ammonium salt) , Alkyl ammonium salts, etc.).

  Examples of the monomer (b-3) represented by the general formula (3-3) include mono (2-hydroxyethyl) methacrylic acid phosphate and mono (2-hydroxyethyl) acrylic acid phosphate. And polyalkylene glycol mono (meth) acrylate acid phosphates. Of these, mono (2-hydroxyethyl) methacrylic acid ester is preferred from the viewpoint of ease of production and product quality stability. Further, alkali metal salts, alkaline earth metal salts, ammonium salts, alkylammonium salts and the like of these compounds may be used.

  In the monomer (b-3) represented by the general formula (3-3), s is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 5.

  In the polyanionic copolymer, the proportion of the structural units (A) and (B) is preferably 1% by mass or more with respect to 100% by mass of all the structural units. When the structural unit (A) and the structural unit (B) are 1% by mass or more, the cement dispersion performance can be more sufficiently exhibited. The content ratio of the structural unit (A) in the total amount of the structural units (A) and (B) of 100% by mass is preferably 50 to 97% by mass, more preferably 65 to 97% by mass, and still more preferably 70%. It is -96 mass%, Most preferably, it is 75-96 mass%. Moreover, as a content rate of the structural unit (B) which occupies in the total amount 100 mass% of structural unit (A) and (B), Preferably it is 3-50 mass%, More preferably, it is 3-35 mass%, More preferably, Is 4 to 30% by mass, particularly preferably 4 to 25% by mass.

  Here, in the present specification, when calculating the proportion of the structural unit (B) derived from the monomer (b) having the anionic group, the structural unit (B) is a completely neutralized single monomer. It is calculated as a structural unit derived from a body (salt). For example, when acrylic acid is used as the monomer (b) and neutralized with sodium hydroxide in the polymerization reaction, sodium acrylate is used as the monomer (b). ).

  Among the polyanionic copolymers, the monomer (b) having an anionic group is an unsaturated carboxylic acid monomer (b-1) represented by the general formula (3-1). A polycarboxylic acid copolymer is preferred. When such a polycarboxylic acid copolymer is used, the carboxyl group derived from the unsaturated carboxylic acid monomer (b-1) has an action of adsorbing to the cement particles, and the unsaturated polyalkylene glycol single monomer Since the polyalkylene glycol chain derived from the monomer (a) acts as a dispersing group for dispersing the cement particles, higher dispersion performance can be exhibited.

Polycarboxylic acid copolymer Next, the monomer components constituting the polycarboxylic acid copolymer will be further described. In addition, each monomer can use 1 type (s) or 2 or more types, respectively.
(Unsaturated polyalkylene glycol monomer (a))
The monomer (a) is a monomer represented by the above general formula (2), and the structural unit (A) derived from the monomer (a) is a monomer (a). Means a structure in which the unsaturated double bond (carbon-carbon double bond) portion of the is a single bond.

In the general formula ^{(2), Y} 2 O represents an oxyalkylene group having 2 to 18 carbon atoms. Among these, an oxyalkylene group having 2 to 8 carbon atoms is preferable, and examples thereof include an oxyethylene group, an oxypropylene group, an oxybutylene group, and an oxystyrene group. An oxyalkylene group having 2 to 4 carbon atoms is more preferable, and an oxyethylene group is particularly preferable. The polyalkylene glycol chain represented by (Y ² O) _r may be formed by two or more oxyalkylene groups. In this case, two or more oxyalkylene groups are randomly added, Any addition form such as block addition or alternate addition may be used.

In the said General formula (2), it is suitable that the ratio of the oxyethylene group which occupies in 100 mol% of all oxyalkylene groups is 50 mol% or more. Thereby, sufficient dispersibility can be exhibited. More preferably 70 mol% or more, still more preferably 80 mol% or more, particularly preferably 90 mol% or more, most preferably 100 mol%, that is, a polyalkylene represented by (Y ² O) _r only by an oxyethylene group A glycol chain is formed. In addition, as the combination having two or more oxyalkylene groups, (oxyethylene group, oxypropylene group), (oxyethylene group, oxybutylene group), (oxyethylene group, oxystyrene group) are preferable. . Among these, (oxyethylene group, oxypropylene group) is more preferable.

  The average addition mole number (average chain length of the polyalkylene glycol chain) r of the oxyalkylene group is a number of 2 to 300. From the viewpoint of improving the dispersion performance by the polycarboxylic acid copolymer, the lower limit of r is preferably not less than a specific value in the following order. That is, 5 or more and 10 or more are preferable. On the other hand, when r exceeds 300, the copolymerizability may not be sufficient, and the dispersibility retention performance may not be sufficiently exhibited. Therefore, it is preferable that the upper limit value of r is not more than a specific value in the following order. That is, 250 or less, 200 or less, and 160 or less are preferable. As a suitable range of r, 5-250, 5-200, 10-160 is mentioned. A plurality of monomers (a) having different r values may be used. The average chain length of polyalkylene glycol chain (average number of added moles of oxyalkylene group) is a polycarboxylic acid-based copolymer having a polycarboxylic acid-based copolymer derived from the unsaturated polyalkylene glycol monomer (a). It means the average value of the number of moles of oxyalkylene group added to 1 mole of alkylene glycol chain.

In the general formula (2), R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, and the hydrophobicity increases as the number of carbon atoms of the hydrocarbon group increases, and the dispersibility is sufficient. Therefore, the number of carbon atoms of the hydrocarbon group is preferably 1-20. More preferably, it is 1-12, More preferably, it is 1-10, Most preferably, it is 1-6, Most preferably, it is 1-4. As the hydrocarbon group, for example, an alkyl group (straight chain, branched chain or cyclic), a phenyl group, an alkyl-substituted phenyl group, an alkenyl group, an alkynyl group, an aryl and the like are preferable. Of these, an alkyl group (straight chain, branched chain or cyclic) is preferable. R ⁴ is particularly preferably a hydrogen atom, a methyl group or an ethyl group.

  In the general formula (2), q is 0 or 1, but when q represents 0, the monomer (a) represented by the general formula (2) is a monomer having an ether structure. (Ether type monomer), and when q represents 1, it is a monomer having an ester structure (ester type monomer).

  When the monomer (a) represented by the general formula (2) is an ether monomer, specific examples of the monomer include an unsaturated alcohol polyalkylene glycol adduct, that is, an unsaturated group. Examples thereof include compounds having a structure in which a polyalkylene glycol chain is added to an alcohol having an unsaturated alcohol. Such a compound can be obtained, for example, by adding an alkylene oxide to an unsaturated alcohol.

  The unsaturated alcohol is not particularly limited as long as it has a group having an unsaturated bond and a hydroxyl group, but preferably has a group having a double bond and a hydroxyl group, and has a group having a double bond and a hydroxyl group. It is more preferable to have one each.

  As the unsaturated alcohol, for example, methallyl alcohol, allyl alcohol, 3-methyl-3-buten-1-ol and the like are preferable.

  When the monomer (a) represented by the general formula (2) is an ester monomer, specific examples of the monomer include a polyalkylene glycol ester monomer, that is, an unsaturated group and Examples thereof include compounds having a structure in which a polyalkylene glycol chain is bonded via an ester bond. For example, unsaturated carboxylic acid polyalkylene glycol ester compounds are suitable. Among these, (alkoxy) polyalkylene glycol mono (meth) acrylate is preferable, and methoxypolyethylene glycol mono (meth) acrylate is particularly preferable.

(Unsaturated carboxylic acid monomer (b-1))
The monomer (b-1) is a monomer containing an unsaturated double bond (carbon-carbon double bond) and a carboxyl group and / or a carboxylate. In addition, with the structural unit (B-1) derived from the unsaturated carboxylic acid monomer (b-1), the unsaturated double bond portion of the monomer (b-1) is a single bond. Means structure. Here, including a carboxyl group and / or a carboxylate salt means that a group represented by -COOM (M represents a hydrogen atom, a metal atom, an ammonium group, or an organic ammonium group) is 1 per molecule. It means having one or more. Examples of the metal atom include alkali metals such as sodium and potassium; alkaline earth metals such as magnesium and calcium; aluminum and iron. Examples of organic amines that form organic ammonium groups include alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; alkylamines such as monoethylamine, diethylamine, and triethylamine; polyamines such as ethylenediamine and triethylenediamine. Among these, the carboxylate is preferably an ammonium salt, a sodium salt, or a potassium salt, and more preferably a sodium salt.

  As the unsaturated carboxylic acid monomer (b-1), an unsaturated monocarboxylic acid monomer containing an unsaturated double bond and one carboxyl group or carboxylate in one molecule, An unsaturated dicarboxylic acid-based monomer containing an unsaturated double bond and two carboxyl groups or carboxylates in the molecule is preferred.

  Specific examples of the unsaturated monocarboxylic acid monomer include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-hydroxyacrylic acid, α-hydroxymethylacrylic acid and derivatives thereof, These salts are mentioned.

  Specific examples of the unsaturated dicarboxylic acid-based monomer include unsaturated dicarboxylic acids such as maleic acid, itaconic acid, citraconic acid, fumaric acid, and mesaconic acid, salts thereof, and anhydrides thereof. Can be mentioned. Among these, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid and salts thereof are preferable from the viewpoint of polymerizability. Of these, acrylic acid, methacrylic acid, and salts thereof are more preferable. That is, the carboxylic acid monomer (b-1) preferably includes (meth) acrylic acid or a salt thereof. By including a structure derived from (meth) acrylic acid or a salt thereof, the resulting polycarboxylic acid copolymer can exhibit further superior dispersibility in a smaller amount. Acrylic acid and methacrylic acid are collectively referred to as “(meth) acrylic acid”.

(Other monomer (c))
The polyanionic copolymer may contain a structural unit (C) derived from the monomer (c) other than the essential monomer components (a) and (b). Such a monomer (c) may be any monomer that can be copolymerized with the monomer (a) and / or (b), and includes, for example, one or more of the following compounds. Can be used.

  Hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; unsaturated monocarboxylic acids such as methyl (meth) acrylate and glycidyl (meth) acrylate and alcohols having 1 to 30 carbon atoms Esters of (anhydrous) half esters and diesters of unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid with alcohols having 1 to 30 carbon atoms; the above unsaturated dicarboxylic acids and 1 to carbon atoms 30 half-amides and diamides with amines; half esters of alkyl (poly) alkylene glycols obtained by adding 1 to 500 moles of alkylene oxides having 2 to 18 carbon atoms to the alcohols or amines and the unsaturated dicarboxylic acids, Diesters; the above unsaturated dicarls Half esters and diesters of acids and glycols having 2 to 18 carbon atoms or polyalkylene glycols having 2 to 500 moles of addition of these glycols; maleamic acid and glycols having 2 to 18 carbon atoms or of these glycols Half amides with polyalkylene glycols having an addition mole number of 2 to 500; (poly) alkylene glycol di (meth) acrylates such as (poly) ethylene glycol di (meth) acrylate and (poly) propylene glycol di (meth) acrylate Polyfunctional (meth) acrylates such as hexanediol di (meth) acrylate and trimethylolpropane tri (meth) acrylate;

  (Poly) alkylene glycol dimaleates such as polyethylene glycol dimaleate; Unsaturated sulfonic acids (salts) such as vinyl sulfonate, (meth) allyl sulfonate, 2-methylpropane sulfonic acid (meth) acrylamide, styrene sulfonic acid; methyl Amides of unsaturated monocarboxylic acids such as (meth) acrylamide and amines having 1 to 30 carbon atoms; vinyl aromatics such as styrene, α-methylstyrene and vinyltoluene; 1,4-butanediol mono (meta ) Alkanediol mono (meth) acrylates such as acrylates; Dienes such as butadiene and isoprene; and (meth) acrylic (alkyl) amides, N-methylol (meth) acrylamides, N, N-dimethyl (meth) acrylamides and the like Saturated amides; (meth) acryloni Unsaturated cyanides such as ril; Unsaturated esters such as vinyl acetate; Unsaturated amines such as aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate and vinylpyridine; Divinyl aromatics such as divinylbenzene And allyls such as (meth) allyl alcohol and glycidyl (meth) allyl ether.

  Next, a method for obtaining the polycarboxylic acid copolymer will be described. As a method for obtaining the polycarboxylic acid-based copolymer, a monomer containing monomer (a) and monomer (b) and, if necessary, monomer (c) is used by using a polymerization initiator. The monomer component may be copolymerized, but the type and amount of the monomer contained in the monomer component are set so that the structural unit constituting the polycarboxylic acid copolymer falls within the range described above. It is preferable to set appropriately. That is, it is preferable to appropriately set the type and amount of the monomer contained in the monomer component so that the proportion of the structural units constituting the polycarboxylic acid copolymer is in the preferred range described above. . Therefore, the content of each of the monomers (a) and (b) is 1% by mass or more with respect to 100% by mass of all monomer components used to obtain the polycarboxylic acid copolymer. Is preferred. Moreover, as a content rate of the monomer (a) in the total amount 100 mass% of the monomers (a) and (b), preferably 50 to 97 mass%, more preferably 65 to 97 mass%, More preferably, it is 70-96 mass%, Most preferably, it is 75-96 mass%. Further, the content ratio of the monomer (b) in the total amount of the monomers (a) and (b) of 100% by mass is preferably 3 to 50% by mass, more preferably 3 to 35% by mass, More preferably, it is 4-30 mass%, Most preferably, it is 4-25 mass%.

  The total ratio (mass%) of the monomers (a) and (b) is preferably 70 to 100 mass% with respect to 100 mass% of all monomer components. That is, it is preferable that the content rate of another monomer (c) is 0-30 mass% with respect to 100 mass% of all the monomer components. The total ratio of the monomers (a) and (b) in 100% by mass of all monomer components is more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass. %. In order to obtain a highly dispersible polycarboxylic acid copolymer in high yield, the proportion of the monomer (a) is 50 mol% or less with respect to 100 mol% of all monomer components. Is preferred. More preferably, it is 48 mol% or less.

  The polycarboxylic acid copolymer can be produced by a known method. For example, the solution polymerization method described in JP-A-58-74552 and JP-A-2001-220417 is exemplified, and polymerization of ammonium persulfate, hydrogen peroxide, etc. is started in water or a lower alcohol having 1 to 4 carbon atoms. In the presence of the agent, a reducing agent such as L-ascorbic acid and a chain transfer agent such as mercaptopropionic acid may be added as necessary and reacted at 30 to 100 ° C. for 0.5 to 10 hours.

  The polycarboxylic acid copolymer can be used as it is as a main component of the dispersant, but it is preferable to adjust the pH to 5 or more from the viewpoint of handleability. The copolymerization reaction is preferably performed at a pH of less than 5, and it is preferable to adjust the pH to 5 or more after the copolymerization. The pH can be adjusted using, for example, an alkaline substance such as an inorganic salt such as a monovalent metal or divalent metal hydroxide or carbonate; ammonia; an organic amine; Further, after the reaction is completed, the concentration can be adjusted if necessary. The polycarboxylic acid copolymer may be used as a main component of the dispersant as it is in the form of an aqueous solution, or it may be neutralized with a divalent metal hydroxide such as calcium or magnesium. It may be used after being made into a valent metal salt and dried, or supported on an inorganic powder such as silica fine powder and dried.

  As the mass average molecular weight (Mw) of the polycarboxylic acid copolymer, it is preferable that the mass average molecular weight (Mw) is 500,000 or less in consideration of its handleability and the retention of the cement composition. . More preferably, it is 300,000 or less, More preferably, it is 200,000 or less, Most preferably, it is 100,000 or less. Moreover, it is preferable that Mw is 3000 or more from the viewpoint that adsorbing to cement particles to some extent tends to exhibit performance, and that the adsorption power increases as Mw increases. More preferably, it is 5000 or more, More preferably, it is 7000 or more, Especially preferably, it is 10,000 or more, Most preferably, it is 20,000 or more. In addition, the mass mean molecular weight of the said polycarboxylic acid type-copolymer can be calculated | required by the gel permeation chromatography (GPC) analysis method mentioned later.

  The dispersant (J) may contain any other appropriate water reducing agent. Examples of such water reducing agents include polyol derivatives, oxycarboxylic acids such as gluconic acid, and monovalent metal salts, divalent metal salts, ammonium salts, organic ammonium salts, naphthalene sulfonic acid formalin condensates, and the like.

  When the dispersant (J) contains lignin sulfonate, the content ratio of the lignin sulfonate in the hydraulic material additive of the present invention is calculated in terms of solid content with respect to the hydraulic material (Z). Preferably it is 0.01-0.8 mass%, More preferably, it is 0.02-0.6 mass%, More preferably, it is 0.05-0.5 mass%, Most preferably, it is 0.1 It is -0.3 mass%. When the content of lignin sulfonate in the hydraulic material additive of the present invention is out of the above range, the hydraulic material additive of the present invention is combined with the hydraulic material (Z). Since it affects the dispersibility of (Z), the shrinkage reduction function and fluidity may not be sufficiently exhibited, and further, the strength of the hardened concrete may be reduced.

  When the dispersant (J) contains a polymer having a polyoxyalkylene group and an anionic group, the inclusion of the polymer having the polyoxyalkylene group and the anionic group in the hydraulic material additive of the present invention The ratio is preferably 0.01 to 1% by mass, more preferably 0.01 to 0.8% by mass, and still more preferably 0.00% in terms of solid content with respect to the hydraulic material (Z). It is 02-0.5 mass%, Most preferably, it is 0.03-0.5 mass%. When the content of the polymer having a polyoxyalkylene group and an anionic group in the additive for hydraulic material of the present invention is out of the above range, the additive for hydraulic material of the present invention is converted into a hydraulic material (Z). When combined with the above, since it affects the dispersibility of the hydraulic material (Z), there is a possibility that the shrinkage reduction function and fluidity may not be sufficiently exhibited, and further the strength of the hardened concrete may be reduced. .

<3. Antifoaming agent (D)>
The hydraulic material additive of the present invention preferably contains an antifoaming agent (D). Only one type of antifoaming agent (D) may be used, or two or more types may be used.

  Any appropriate antifoaming agent can be adopted as the antifoaming agent (D). Examples of the antifoaming agent (D) include mineral oil-based antifoaming agents, fat-based antifoaming agents, fatty acid-based antifoaming agents, fatty acid ester-based antifoaming agents, oxyalkylene-based antifoaming agents, alcohol-based antifoaming agents, and amides. Examples thereof include system defoamers, phosphate ester defoamers, metal soap defoamers, and silicone defoamers. Of these, oxyalkylene antifoaming agents are preferred.

  Examples of the mineral oil-based antifoaming agent include cocoon oil and liquid paraffin. Examples of the oil-based antifoaming agent include animal and vegetable oils, sesame oil, castor oil, and alkylene oxide adducts thereof. Examples of the fatty acid-based antifoaming agent include oleic acid, stearic acid, and alkylene oxide adducts thereof. Examples of the fatty acid ester-based antifoaming agent include glycerin monoricinoleate, alkenyl succinic acid derivative, sorbitol monolaurate, sorbitol trioleate, natural wax and the like. Examples of the alcohol-based antifoaming agent include octyl alcohol, 2-ethylhexyl alcohol, hexadecyl alcohol, acetylene alcohol, glycols and the like. Examples of the amide antifoaming agent include acrylate polyamine. Examples of the phosphoric acid ester antifoaming agent include tributyl phosphate, sodium octyl phosphate and the like. Examples of the metal soap antifoaming agent include aluminum stearate and calcium oleate. Examples of the silicone antifoaming agent include dimethyl silicone oil, silicone paste, silicone emulsion, organically modified polysiloxane (polyorganosiloxane such as dimethylpolysiloxane), fluorosilicone oil, and the like.

  Examples of the oxyalkylene-based antifoaming agent include polyoxyalkylenes such as (poly) oxyethylene (poly) oxypropylene adducts; diethylene glycol heptyl ether, polyoxyethylene oleyl ether, polyoxypropylene butyl ether, polyoxyethylene polyoxy (Poly) oxyalkylene alkyl ethers such as propylene 2-ethylhexyl ether, higher alcohols having 8 or more carbon atoms and oxyethyleneoxypropylene adducts to secondary alcohols having 12 to 14 carbon atoms; polyoxypropylene phenyl ether, poly (Poly) oxyalkylene (alkyl) aryl ethers such as oxyethylene nonylphenyl ether; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,5-dimethyl Acetylene ethers obtained by addition polymerization of alkylene oxide to acetylene alcohols such as 3-hexyne-2,5-diol and 3-methyl-1-butyn-3-ol; diethylene glycol oleate, diethylene glycol laurate, ethylene glycol distearate (Poly) oxyalkylene fatty acid esters such as acid esters; (poly) oxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan trioleate; polyoxypropylene methyl ether sodium sulfate, poly (Poly) oxyalkylene alkyl (aryl) ether sulfate salts such as sodium oxyethylene dodecyl phenol ether sulfate; Shi ethylene stearyl such as phosphoric acid ester (poly) oxyalkylene alkyl phosphoric acid esters; polyoxyethylene such as polyoxyethylene lauryl amine (poly) oxyalkylene alkyl amines; polyoxyalkylene amides; and the like.

  When the antifoaming agent (D) is contained in the hydraulic material additive of the present invention, the content of the antifoaming agent (D) in the hydraulic material additive of the present invention is the hydraulic material (Z). On the other hand, in terms of solid content, it is preferably 0.000001 to 1% by mass, more preferably 0.000005 to 0.5% by mass, still more preferably 0.00001 to 0.1% by mass, Especially preferably, it is 0.00001-0.05 mass%, Most preferably, it is 0.00005-0.01 mass%.

<4. Other ingredients>
The hydraulic material additive of the present invention may contain other components as necessary as long as the effects of the present invention are exhibited. Other components include, for example, water, water-soluble polymer substances, polymer emulsions, pH adjusters, retarders, early strengthening agents / accelerators, surfactants, waterproofing agents, rust preventives, crack reducing agents, swelling Materials, cement wetting agents, thickeners, separation reducing agents, flocculants, other drying shrinkage reducing agents, strength enhancers, self-leveling agents, coloring agents, fungicides, blast furnace slag, fly ash, cinder ash, clinker ash , Husque ash, silica fume, silica powder, gypsum and the like. Such other components may be only one type or two or more types.

  However, the additive for hydraulic material of the present invention does not require a combination with other admixtures and is inexpensive, and when combined with a hydraulic material (Z), the strength of the concrete cured product is reduced. It is possible to suppress the occurrence of cracks in the hardened concrete by an excellent shrinkage reduction function, and to exert an excellent fluidity. Therefore, other components such as those listed above may be omitted if not necessary except for water.

(Preparation of additives for hydraulic materials)
What is necessary is just to prepare the additive for hydraulic materials of this invention by arbitrary appropriate methods. For example, the compound (G) and the dispersant (J) are used essentially, and if necessary, at least one selected from the antifoaming agent (D) and any other component may be used in any appropriate manner. What is necessary is just to mix by the method. Any appropriate order may be adopted as the order of mixing. Further, the compound (G) and the dispersant (J) may be mixed in advance and then mixed with the hydraulic material (Z), or may be separately added and mixed with the hydraulic material (Z). .

  The mass ratio of the compound (G) and the dispersant (J) may be in the range of (G) / (J) = 1/1 to 99/1 in terms of solid content, preferably 1/1 to 90. / 1, more preferably 1/1 to 80/1.

  When combined with the hydraulic material (Z), the additive for hydraulic material of the present invention has both an excellent shrinkage reducing function and excellent fluidity. The additive for hydraulic material of the present invention contains the compound (G) at a high concentration, the compound (G) has excellent stability over time, is excellent in compatibility without being separated and precipitated, and has a water / cement ratio. The application range is wide, and it is possible to produce concrete having a water / cement ratio (mass ratio) of preferably 60% to 15%. Therefore, it is highly versatile and can be used by being added to a cement composition for various uses.

≪2. Hydraulic material composition >>
The hydraulic material composition of the present invention includes the hydraulic material additive of the present invention and a hydraulic material (Z).

  The hydraulic material (Z) is usually selected from low heat, moderate heat, early strength, super early strength, sulfate resistant portland cement, blast furnace cement, silica cement, fly ash cement, eco cement, silica fume cement, etc. Examples include at least one kind of cement. When the hydraulic material (Z) is cement, the hydraulic material composition of the present invention may be a concrete composition.

  If the said hydraulic material composition is finally the composition containing each structural component of the additive for hydraulic materials of this invention, and a hydraulic material (Z), the preparation process will not be ask | required. That is, a part selected from each constituent component constituting the hydraulic material composition (each constituent component of the hydraulic material additive of the present invention, the hydraulic material (Z), and other components as required) May be prepared by mixing the remaining components in advance, or all of the components constituting the hydraulic material composition may be mixed together.

  The hydraulic material composition preferably includes aggregate and water. Examples of the aggregate include fine aggregate and coarse aggregate. A hydraulic material composition containing cement, fine aggregate, and water but not coarse aggregate is sometimes referred to as “mortar”.

  Examples of the fine aggregate include river sand, mountain sand, sea sand, crushed sand, heavy aggregate, lightweight aggregate, slag aggregate, and recycled aggregate.

  Examples of the coarse aggregate include river gravel, crushed stone, heavy aggregate, lightweight aggregate, slag aggregate, and recycled aggregate.

  Examples of the water include tap water, water other than tap water (river water, lake water, well water, etc.) shown in Appendix 9 of JIS A 5308, and recovered water.

Moreover, the said hydraulic material composition can contain the other well-known hydraulic material additive (material) which is illustrated to the following (1)-(12).
(1) Water-soluble polymer substances: nonionic cellulose ethers such as methylcellulose, ethylcellulose, carboxymethylcellulose; polysaccharides produced by microbial fermentation such as yeast glucan, xanthan gum, β-1.3 glucans; polyethylene glycol, etc. Polyoxyalkylene glycols; polyacrylamide and the like.
(2) Polymer emulsion: Copolymers of various vinyl monomers such as alkyl (meth) acrylate.
(3) Curing retarder: oxycarboxylic acid or salt thereof such as gluconic acid, glucoheptonic acid, alabonic acid, malic acid, citric acid; sugar and sugar alcohol; polyhydric alcohol such as glycerin; aminotri (methylenephosphonic acid) Phosphonic acid and its derivatives.
(4) Early strengthening agents / accelerators: soluble calcium salts such as calcium chloride, calcium nitrite, calcium nitrate, calcium bromide and calcium iodide; chlorides such as iron chloride and magnesium chloride; sulfates; potassium hydroxide; Sodium hydroxide; carbonate; thiosulfate; formate such as formic acid and calcium formate; alkanolamine; alumina cement; calcium aluminate silicate.
(5) AE agent: resin soap, saturated or unsaturated fatty acid, sodium hydroxystearate, lauryl sulfate, ABS (alkylbenzene sulfonic acid), alkane sulfonate, polyoxyethylene alkyl (phenyl) ether, polyoxyethylene alkyl (phenyl) ether Sulfate ester or a salt thereof, polyoxyethylene alkyl (phenyl) ether phosphate ester or a salt thereof, protein material, alkenyl sulfosuccinic acid, α-olefin sulfonate and the like.
(6) Other surfactants: various anionic surfactants; various cationic surfactants such as alkyltrimethylammonium chloride; various nonionic surfactants; various amphoteric surfactants.
(7) Waterproofing agent: fatty acid (salt), fatty acid ester, fats and oils, silicon, paraffin, asphalt, wax and the like.
(8) Rust preventive: nitrite, phosphate, zinc oxide and the like.
(9) Crack reducing agent: polyoxyalkyl ether and the like.
(10) Expansion material: Ettlingite, coal, etc.

  Other known hydraulic material additives (materials) include cement wetting agents, thickeners, separation reducing agents, flocculants, drying shrinkage reducing agents, strength enhancers, self-leveling agents, colorants, antifungal agents, etc. Can be mentioned. These known hydraulic material additives (materials) may be used alone or in combination of two or more.

  Arbitrary appropriate methods can be employ | adopted about the manufacturing method of the said hydraulic material composition, a conveyance method, a placement method, a curing method, a management method, etc.

  The hydraulic material composition can be used as it is as concrete (fresh concrete) or the like.

  Any appropriate amount of the hydraulic material additive of the present invention in the hydraulic material composition can be used depending on the purpose. For example, it is preferable to set it as 0.5-10.0 mass% in conversion of solid content with respect to hydraulic material (Z). Moreover, when the capacity | capacitance of the hydraulic material (Z) in the said hydraulic material composition exceeds 14 volume%, Preferably it is 0.5-10.0 in conversion of solid content with respect to hydraulic material (Z). It is mass%, More preferably, it is 0.5-6.0 mass%.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. Unless otherwise specified, parts and% in the examples are based on mass.

<GPC molecular weight measurement conditions>
Column used: TSK guard column SWXL + TSKge1 G4000SWXL + G3000SWXL + G2000SWXL manufactured by Tosoh Corporation
Eluent: 115.6 g of sodium acetate trihydrate is dissolved in a mixed solvent of 10999 g of water and 6001 g of acetonitrile, and an eluent solution adjusted to pH 6.0 with a 30% aqueous sodium hydroxide solution is used.

Implanted amount: 100 μL of 0.5% eluent solution
Eluent flow rate: 0.8 mL / min
Column temperature: 40 ° C
Standard substance: polyethylene glycol, mass average molecular weight (Mw) 272500, 219300, 85000, 46000, 24000, 12600, 4250, 7100, 1470.

Calibration curve order: cubic equation Detector: 410 manufactured by Japan Waters Inc. Differential refraction detector Analysis software: manufactured by Japan Waters Inc. MILLENNIUM Ver. 3.21
Evaluation of physical properties of mortar <Kneading of mortar>
A predetermined amount of the additive for hydraulic material and antifoaming agent shown in Table 1 are weighed and diluted with water. When the water / cement ratio (W / C) is 50%, the total mass after dilution is 225 g and W / C is What is adjusted to 202.5 g at 45% is put into a Hobart mortar mixer (model number N-50, manufactured by Hobart). Next, 450 g of ordinary Portland cement manufactured by Taiheiyo Cement Co., Ltd. is put into a mortar mixer at low speed. After the addition, kneading is performed at a low speed for 30 seconds, and then 1350 g of standard sand for cement strength test (as defined in 5.1.3 of JIS R 5201-1997 Annex 2) is added at a low speed for 30 seconds, and 30 times at a high speed rotation Knead for 2 seconds and stop rotating. The mortar is scraped off and allowed to stand for 1 minute 30 seconds, and then kneaded for 1 minute at high speed.

<Measurement of mortar air volume>
The mortar air amount was measured using a 500 ml graduated cylinder in accordance with JIS-A1174 (unit volume mass test method of polymer cement mortar not yet solidified and test method (mass method) based on mass of air amount).

<Measurement of flow value>
The mortar obtained by the above kneading is packed in two layers in a flow cone (described in JIS R 5201-1997), the cone is pulled up, and immediately 15 drops are given for 15 seconds. This was measured, and this was set as a 15-stroke flow value. The flow value was measured according to JIS R 5201-1997.

  The larger the 15-stroke flow value, the better the fluidity.

<Evaluation of shrinkage reduction>
Mortar kneading was carried out as described above. Next, preparation of a mortar specimen (4 × 4 × 16 cm) for evaluation of shrinkage reduction was performed according to JIS-A1129. Silicone grease was applied to the mold in advance to stop the water and make it easy to remove the mold. In addition, gauge plugs were attached to both ends of the specimen. The formwork into which the mortar obtained by kneading was poured was put into a container, sealed, stored at 20 ° C., and subjected to initial curing. One day later, the mold was removed from the mold, and the silicon grease adhering to the specimen was washed with water using a scourer, and then cured in still water at 20 ° C. for 6 days (water curing). In accordance with JIS-A1129, use a dial gauge (manufactured by West Japan Testing Machine Co., Ltd.), wipe the surface water of the specimen cured in still water for 6 days with a paper towel, and then immediately measure the length. Based on. Thereafter, the sample was stored in a constant temperature and humidity chamber set at a temperature of 20 ° C. and a humidity of 60%, and measured in a timely manner. In addition, the mortar which has not added the additive for hydraulic materials was made into the reference mortar. At this time, the length change ratio is a ratio of the shrinkage amount of the additive-added mortar for hydraulic material to the shrinkage amount of the reference mortar, as shown by the following formula, and the smaller the value, the more the shrinkage can be reduced.

Length change ratio = {(Shrinkage of additive mortar for hydraulic material) / (Shrinkage of reference mortar)} × 100
[Production Example 1]: Production of copolymer (1) In a glass reactor equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux cooling device, 14.66 parts by mass of ion-exchanged water, 3- 49.37 parts by mass of an unsaturated polyalkylene glycol ether monomer (IPN50) obtained by adding 50 moles of ethylene oxide to methyl-3-buten-1-ol on average, and the inside of the reaction apparatus was purged with nitrogen under stirring. After heating to 60 ° C., 2.39 parts by mass of a 2% aqueous hydrogen peroxide solution was added, and an aqueous solution consisting of 3.15 parts by mass of acrylic acid and 0.79 parts by mass of ion-exchanged water was added for 3.0 hours, and An aqueous solution composed of 0.13 parts by mass of 3-mercaptopropionic acid, 0.06 parts by mass of L-ascorbic acid and 15.91 parts by mass of ion-exchanged water was added dropwise over 3.5 hours. Thereafter, after maintaining the temperature at 60 ° C. for 1 hour, the polymerization reaction was terminated by cooling, the pH was adjusted to 7.0 with a 48% aqueous sodium hydroxide solution, and the copolymer (1) having a mass average molecular weight of 37700 An aqueous solution of was obtained.

Various components used in Examples and Comparative Examples Table 1 shows the compounds (G), dispersants (J), and antifoaming agents (D) used in Examples 1 to 6 and Comparative Examples 1 to 4.

  Here, in the compound (G), MBM is Nn-butylethanolamine, BMEA is Nt-butylethanolamine, and BAAE is 2-((2- (butylamino) ethyl) amino). Ethanol and MBD are Nn-butyldiethanolamine, and EA is N- (β-aminoethyl) ethanolamine. Moreover, in a dispersing agent (J), a dispersing agent (1) is a lignin sulfonic acid type AE water reducing agent (BASF Japan make, brand name "Pozoris No. 70"). Further, LG299 of the antifoaming agent (D) is an oxyalkylene antifoaming agent (trade name “Adecanol LG299” manufactured by ADEKA).

  From Table 1, in Examples 1 to 6, the mortar 15-stroke flow value is 150 mm or more, and the fluidity is good compared to Comparative Example 1 in which the dispersant (J) is not used. Compared with Comparative Examples 3 and 4, the length change ratio is remarkably small. Therefore, it turns out that the additive for hydraulic materials of this invention shows the outstanding fluidity | liquidity and shrinkage reduction property. In Comparative Example 1, the fluidity of the mortar was small, and a specimen for evaluating shrinkage reduction could not be produced. Moreover, in the comparative example 2 which does not use an antifoamer, since the air quantity of the mortar became 8.5% and the air quantity became very large compared with Examples 1-6, evaluation of flow and shrinkage reduction property Did not.

  According to the present invention, it does not require a combination with other admixture materials, is inexpensive, and, when combined with a hydraulic material, suppresses a decrease in strength of the cured product and exhibits an excellent shrinkage reduction function, Since a highly versatile additive for hydraulic materials that exhibits excellent fluidity can be provided, these are useful as shrinkage reducing agents for hydraulic materials.

Claims (9)

An additive for hydraulic material comprising a compound (G) having an oxyalkylene group and a secondary amino group and a dispersant for hydraulic material (J),
The compound (G) is represented by the following general formula (1):
R ¹ —NH— (X—NH) _m — (Y ¹ O) _n —R ² (1)
(In General Formula (1), R ¹ represents a hydrocarbon group having 1 to 12 carbon atoms, R ² represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and X represents 2 carbon atoms. Represents an alkylene group of ˜4, m is 0 to 10. Y ¹ O represents an oxyalkylene group having 2 to 4 carbon atoms, and n is an average added mole number of the oxyalkylene group, which is 1 to 50. is there.)
Represented by
The dispersant (J) is a polymer having a polyoxyalkylene group and an anionic group,
The weight ratio of the compound (G) and said dispersant (J) are in terms of solid content, a hydraulic material, characterized in that in the range of (G) / (J) = 1 / 1~99 / 1 Additives. An additive for hydraulic material comprising a compound (G) having an oxyalkylene group and a secondary amino group and a dispersant for hydraulic material (J),
The compound (G) is represented by the following general formula (1 '):
      R ¹ -NH- (X-NH) _m -(Y ¹ O) _n -R ²           (1 ’)
(In the general formula (1 '), R ¹ Represents a hydrocarbon group having 1 to 12 carbon atoms, R ² Represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, X represents an alkylene group having 2 to 4 carbon atoms, and m is 0 to 10. Y ¹ O represents an oxyalkylene group having 2 to 4 carbon atoms, and n is an average addition mole number of the oxyalkylene group. )
Represented by
The dispersant (J) is at least one selected from the group consisting of lignin sulfonate and a polymer having a polyoxyalkylene group and an anionic group,
A hydraulic material, wherein the mass ratio of the compound (G) and the dispersant (J) is in the range of (G) / (J) = 1/1 to 99/1 in terms of solid content Additives. Weight ratio of the compound (G) and the dispersing agent (J) is in terms of solid content, claim 1, characterized in that in the range of (G) / (J) = 6 / 4~99 / 1 Or the additive for hydraulic materials of 2 . The additive for hydraulic material according to any one of claims 1 to 3 , wherein the compound (G) is a compound obtained by reacting 1 mol of ethylene oxide with 1 mol of a monoalkylamine having 1 to 12 carbon atoms. The additive for hydraulic material according to any one of claims 1 to 4, further comprising an antifoaming agent (D). A hydraulic material composition comprising a compound (G) having an oxyalkylene group and a secondary amino group, a dispersant (J) and a hydraulic material (Z) ,
The compound (G) is represented by the following general formula (1):
R ¹ —NH— (X—NH) _m — (Y ¹ O) _n —R ² (1)
(In General Formula (1), R ¹ represents a hydrocarbon group having 1 to 12 carbon atoms, R ² represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and X represents 2 carbon atoms. Represents an alkylene group of ˜4, m is 0 to 10. Y ¹ O represents an oxyalkylene group having 2 to 4 carbon atoms, and n is an average added mole number of the oxyalkylene group, which is 1 to 50. is there.)
Represented by
The dispersant (J) is a polymer having a polyoxyalkylene group and an anionic group,
The weight ratio of the compound (G) and said dispersant (J) is a hydraulic material composition, which is a range in terms of a solid content of (G) / (J) = 1 / 1~99 / 1 object. A hydraulic material composition comprising a compound (G) having an oxyalkylene group and a secondary amino group, a dispersant (J) and a hydraulic material (Z),
The compound (G) is represented by the following general formula (1 '):
      R ¹ -NH- (X-NH) _m -(Y ¹ O) _n -R ²           (1 ’)
(In the general formula (1 '), R ¹ Represents a hydrocarbon group having 1 to 12 carbon atoms, R ² Represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, X represents an alkylene group having 2 to 4 carbon atoms, and m is 0 to 10. Y ¹ O represents an oxyalkylene group having 2 to 4 carbon atoms, and n is an average addition mole number of the oxyalkylene group. )
Represented by
The dispersant (J) is at least one selected from the group consisting of lignin sulfonate and a polymer having a polyoxyalkylene group and an anionic group,
The hydraulic property, wherein the mass ratio of the compound (G) and the dispersant (J) is in the range of (G) / (J) = 1/1 to 99/1 in terms of solid content Material composition. Furthermore, the hydraulic material composition of Claim 6 or 7 containing an antifoamer (D). The hydraulic material composition according to claim 8, wherein a content ratio of the antifoaming agent (D) is 0.000001 to 1% by mass in terms of solid content with respect to the hydraulic material (Z).