JP2002234761A - Cement admixture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cement admixture which is suitable for a super high- strength concrete by improving water reducing performance and workability of cement composition, etc., and also improving strength and durability of the cured matter. SOLUTION: In the cement admixture containing a polycarboxylic acid based copolymer, the polycarboxylic acid based copolymer is obtained by copolymerizing a monomer mixture containing (poly)amine based monomer (A), an unsaturated carboxylic acid based monomer (B) and an unsaturated monomer (C) containing polyalkylene glycol chain and the (poly)amine based monomer (A) is obtained by introducing an unsaturated bond to a (poly)amine based compound by an unsaturated compound having an epoxy group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a cement admixture. More specifically, it relates to a cement admixture that can be suitably used for ultra-high strength concrete.

[0002]

2. Description of the Related Art Cement admixtures containing polycarboxylic acid copolymers are widely used as water reducing agents for cement compositions such as cement paste, mortar, concrete, and the like. It is indispensable for building things. In such a cement admixture, it is possible to reduce the water content of the cement composition by increasing the fluidity of the cement composition, and to have the effect of improving the strength and durability of the cured product. High performance AE to exhibit higher water reducing performance than naphthalene based water reducing agent
It has many achievements as a water reducing agent.

[0003] By the way, so-called ultra-high-strength concrete, which exhibits high performance among concretes, requires high strength and durability in the base portion of civil engineering and building structures and the like, and is used. As such a water reducing agent for ultra-high-strength concrete, a water reducing agent for ultra-high-strength water having a high water reducing performance so that the amount of water in the concrete is sufficiently reduced and high performance is exhibited is used. . As the ultra-high strength water reducing agent, for example, a copolymer of methacrylic acid and methacrylic acid polyethylene oxide ester and the like are used. Because it becomes high concrete,
There is a need for a cement admixture that can be used as an ultra-high strength water reducing agent that can improve workability.

Japanese Patent Application Laid-Open No. 2000-191356 discloses that
A specific polyamine monomer as compound A;
A specific unsaturated carboxylic acid-based monomer and a specific polyalkylene glycol-based monomer as compound C, compound A: compound B: compound C = 10 to 40% by weight: 10
４０40% by weight: a cement dispersant mainly composed of a water-soluble amphoteric copolymer copolymerized at a ratio of 50５０80% by weight, which can be used as a dispersant for ultra-high-strength concrete, It is disclosed that the workability is excellent.

[0005] However, in all the examples in this publication, the compound A, the compound B and the compound C are copolymerized to obtain a water-soluble amphoteric copolymer. , The polymerization rate is extremely reduced. Therefore, the molecular weight of the water-soluble amphoteric copolymer is reduced, and the production efficiency is reduced. When such a water-soluble amphoteric copolymer is used for the production of ultra-high-strength concrete, the water-soluble amphoteric copolymer cannot exhibit a sufficient effect in ultra-high-strength concrete requiring high performance. And the performance and quality of the ultra-high-strength concrete will be reduced. Due to this,
Since the strength and durability of hardened products such as civil engineering and building structures may be reduced and problems such as reduced safety and increased repair costs may occur, high performance and quality can be used for ultra-high strength concrete. There is room for studying cement admixtures that can exert the effect.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned circumstances, and is intended to improve the water-reduction and workability of a cement composition and the like, and to further improve the strength and durability of the cured product. Therefore, an object of the present invention is to provide a cement admixture that can be suitably used for ultra-high-strength concrete since it is possible to obtain a cement admixture.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on cement admixtures that can be used for ultra-high-strength concrete, and as a result, have found that unsaturated carboxylic acid monomers (B) and polyalkylene glycols can be used. Polycarboxylic acid obtained by copolymerizing a monomer mixture in which a specific (poly) amine-based monomer (A) is also essential in addition to the fact that an unsaturated monomer having a chain (C) is essential. Attention was first paid to a cement admixture containing a system copolymer, and it was conceived that this could be suitably used for ultra-high strength concrete and the like. When a specific polyamine-based monomer (A ') is also essential, and the copolymerization ratio of the monomer forming the polycarboxylic acid-based copolymer is within a specific range, it is preferably used for ultra-high-strength concrete or the like. It has been found that the present invention has been achieved.

The present invention relates to a cement admixture containing a polycarboxylic acid copolymer, wherein the polycarboxylic acid copolymer comprises a (poly) amine monomer (A) and an unsaturated carboxylic acid copolymer. It is obtained by copolymerizing a monomer mixture containing a monomer (B) and an unsaturated monomer (C) having a polyalkylene glycol chain, and the (poly) amine monomer (A) is (poly) A) A cement admixture which is a monomer in which an unsaturated bond is introduced by an unsaturated compound having an epoxy group into an amine compound. Hereinafter, the present invention will be described in detail.

[0009] The cement admixture of the present invention contains a polycarboxylic acid copolymer. The polycarboxylic acid-based copolymer contains an (poly) amine-based monomer (A), an unsaturated carboxylic acid-based monomer (B), and an unsaturated monomer (C) having a polyalkylene glycol chain. It is obtained by copolymerizing a monomer mixture. The (poly) amine monomer (A)
A monomer in which an unsaturated bond is introduced into a (poly) amine compound by an unsaturated compound having an epoxy group. That is, an unsaturated compound having an epoxy group is ring-opened to an amine or a polyamine such as a (poly) amine-based compound to undergo an addition reaction, thereby producing a monomer having an unsaturated bond introduced into the (poly) amine-based compound. There is no particular limitation as long as it is present, but among the unsaturated compounds having an epoxy group, it is preferable to use an unsaturated compound having a glycidyl group. In the present invention, the (poly) amine monomer (A)
Preferably has an oxyalkylene group. The unsaturated carboxylic acid monomer (B) is not particularly limited as long as it has an unsaturated bond and a group capable of forming a carbanion. The unsaturated monomer (C) having a polyalkylene glycol chain is not particularly limited as long as it is a monomer having an unsaturated bond and a polyalkylene glycol chain. These monomers may be used alone or in combination of two or more.

The weight ratio of these monomers in the monomer mixture is, for example, 5 to 40% by weight of (poly) amine monomer (A), unsaturated carboxylic acid monomer (B) It is preferable to contain 5 to 40% by weight and 20 to 90% by weight of the polyalkylene glycol-based monomer (C).
The weight ratio of the monomers (A), (B) and (C) is calculated by adding the total weight of the monomers (A), (B) and (C) to 1
It is the weight% when it is set to 00 weight%. Further, in the present invention, other monomers other than the above-mentioned monomers can be used, but when other monomers are used, the monomers (A), (B) and (C) It is preferable that the total be the main component in the monomer mixture, for example,
When the monomer mixture is 100% by weight, the total of the monomers (A), (B) and (C) is 50 to 100% by weight.
It is preferable that More preferably, 7
0 to 100% by weight, more preferably 90 to 10% by weight.
0% by weight.

In the polycarboxylic acid copolymer of the present invention, the repeating unit formed by the (poly) amine monomer (A) contains an unsaturated carboxylic acid monomer (B) or a polyalkylene glycol monomer. In combination with the function of the repeating unit formed by the monomer (C), the function of improving the water reducing property and workability of the cement composition and the like is exhibited, and the unsaturated carboxylic acid monomer (B ) Will exhibit the function of adsorbing the polycarboxylic acid-based copolymer to the cement particles, and the repeating unit formed by the polyalkylene glycol-based monomer (C) will have an oxyalkylene group. It is considered that the function of improving the dispersibility of the cement composition and the like is exhibited by the hydrophilicity and the steric repulsion. Further, the repeating unit formed by the (poly) amine-based monomer (A) has a nitrogen atom, and it is considered that the above function is exhibited due to this. By exerting these functions, it is possible to improve the water reducing property and workability of the cement composition and the like, and also to improve the strength and durability of the cured product. Therefore, the cement admixture containing the polycarboxylic acid copolymer of the present invention is suitably used as a super-high-strength water reducing agent that can be suitably used for ultra-high-strength concrete. In addition, ultra-high-strength concrete is what is generally referred to in the field of cement composition, that is, even if the content of water is smaller than that of conventional concrete, its hardened product is equivalent to the conventional one. Or concrete with higher strength, for example, a water / cement ratio of 2
Even if it is 5% or less, especially about 18%, it becomes concrete having workability which does not hinder normal use, and the cured product thereof has a compressive strength of 100 N / mm ² or more.

The method for copolymerizing a monomer mixture in the present invention will be described below. As the above-mentioned copolymerization method, for example, a known polymerization method such as solution polymerization or bulk polymerization can be performed using a monomer mixture and a polymerization initiator. Known polymerization initiators can be used and are not particularly limited. Examples thereof include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; hydrogen peroxide; azobis-2-methylpropionamidine hydrochloride ,
Azo compounds such as azoisobutyronitrile; peroxides such as benzoyl peroxide, lauroyl peroxide and cumene hydroperoxide; Also,
As the accelerator, for example, a reducing agent such as sodium bisulfite, sodium sulfite, Mohr's salt, sodium pyrobisulfite, formaldehyde sodium sulfoxylate, ascorbic acid; and an amine compound such as ethylenediamine, sodium ethylenediaminetetraacetate, and glycine are used in combination. You can also. These polymerization initiators and accelerators may be used alone or in combination of two or more.

In the above copolymerization method, a chain transfer agent can be used if necessary. As such a chain transfer agent, known ones can be used and are not particularly limited.
For example, mercaptopropionic acid, mercaptopropionic acid 2-ethylhexyl ester, octanoic acid 2-mercaptoethyl ester, 1,8-dimercapto-3,6
-Dioxaoctane, decanetrithiol, dodecylmercaptan, hexadecanethiol, decanethiol,
Examples include carbon tetrachloride, carbon tetrabromide, α-methylstyrene dimer, terpinolene, α-terpinene, γ-terpinene, dipentene, 2-aminopropan-1-ol, and the like. These may be used alone or in combination of two or more.

The above copolymerization method can be carried out either batchwise or continuously. In addition, in the copolymerization, as the solvent used as necessary, a known solvent can be used and is not particularly limited. Examples thereof include water; alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol;
Benzene, toluene, xylene, cyclohexane, n-
Aromatic or aliphatic hydrocarbons such as heptane; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone. These may be used alone,
Two or more kinds may be used in combination. Among them, one or two or more solvents selected from the group consisting of water and lower alcohols having 1 to 4 carbon atoms from the viewpoint of the solubility of the monomer mixture and the obtained polycarboxylic acid copolymer. It is preferable to use

In the above copolymerization method, the method of adding the monomer mixture and the polymerization initiator to the reaction vessel is not particularly limited. For example, all of the monomer mixture is charged into the reaction vessel and the polymerization initiator is added. A method of performing copolymerization by adding the mixture into a reaction vessel; charging a part of the monomer mixture into the reaction vessel, and performing the copolymerization by adding the polymerization initiator and the remaining monomer mixture to the reaction vessel. And a method in which a polymerization solvent is charged into a reaction vessel and the total amount of the monomer and the polymerization initiator is added. Among such methods, the molecular weight distribution of the obtained copolymer can be narrowed (sharpened), and the cement dispersibility, which is an effect of increasing the fluidity of the cement composition or the like, can be improved. The copolymerization is preferably performed by a method in which an initiator and a monomer are sequentially dropped into a reaction vessel.

In the above copolymerization method, the copolymerization conditions such as the copolymerization temperature are appropriately determined depending on the copolymerization method used, the solvent, the polymerization initiator and the chain transfer agent, and are not particularly limited. Is usually preferably 0 to 150 ° C. More preferably, 40 to 120 ° C
The temperature is more preferably from 50 to 100 ° C, and particularly preferably from 60 to 85 ° C. The copolymer obtained by the above-mentioned copolymerization method is used as it is as a component of the cement admixture, but it may be further neutralized with an alkaline substance if necessary. The alkaline substance is not particularly limited. For example, it is preferable to use inorganic salts such as hydroxides, chlorides, and carbonates of monovalent metals and divalent metals; ammonia; and organic amines.

In the above-mentioned copolymerization method, it is preferable to carry out the copolymerization of the monomer mixture with the neutralization rate of the unsaturated carboxylic acid monomer (B) being 0 to 60 mol%. The neutralization rate of the unsaturated carboxylic acid-based monomer (B) is determined based on the total number of moles of the unsaturated carboxylic acid-based monomer (B) being 100 mol%. System monomer (B)
In mol%. When the degree of neutralization of the unsaturated carboxylic acid monomer (B) exceeds 60 mol%, the degree of polymerization in the copolymerization step does not increase, resulting in a decrease in the pure content and molecular weight of the obtained copolymer and an increase in production efficiency. It may decrease. More preferably, it is 0 to 50 mol%, further preferably, it is 0 to 40 mol%, further preferably, it is 0 to 30 mol%, further preferably,
0 to 20 mol%, particularly preferably 0 to 10 m
ol%, and most preferably 0 to 5 mol%.

As a method of carrying out the copolymerization by setting the neutralization rate of the unsaturated carboxylic acid monomer (B) to 0 to 60 mol%, for example, the unsaturated carboxylic acid monomer (B ) By neutralizing the unsaturated carboxylic acid monomer (B) into a salt such as a sodium salt or an ammonium salt using an alkaline substance. A method in which the neutralization rate is set to 0 to 60 mol% and then subjected to copolymerization.

The polycarboxylic acid-based copolymer is obtained by copolymerizing a monomer mixture as described above, but the molecular weight of such a copolymer is not particularly limited. For example, gel permeation chromatography Graphy (hereinafter, “GP
C)), the weight average molecular weight (Mw) in terms of polyethylene glycol is preferably 500 to 500,000. If it is less than 500, the water reducing performance of the polycarboxylic acid-based copolymer may be reduced,
If it exceeds 000, the water reducing performance and slump loss preventing ability of the polycarboxylic acid copolymer may be reduced. More preferably, it is in the range of 5,000 to 300,000, and most preferably in the range of 8,000 to 100,000. In the present specification, the weight average molecular weight of the copolymer is a value measured under the following GPC measurement conditions.

[0020]GPC molecular weight measurement conditions  Column used: Tosoh TSKguardcolumn
 SWXL + TSKge1 G4000SWXL + G3
000SWXL + G2000SWXL Eluent: 100999 g of water, 6001 g of acetonitrile
Dissolve 115.6 g of sodium acetate trihydrate in a mixed solvent of
And then pH 6.0 with 30% aqueous sodium hydroxide solution.
Use the eluent adjusted to. Eluent flow rate: 0.8 ml / sec Column temperature: 35 ° C. Standard substance: polyethylene glycol, weight average molecular weight
(Mw) 272500, 219300, 85000, 4
6000, 24000, 12600, 4250, 710
0, 1470. Detector: Differential refraction detector made by Waters Japan Analysis software: MILLENNI made by Waters Japan
UM Ver. 2.18

The present invention also relates to a cement admixture containing a polycarboxylic acid copolymer, wherein the polycarboxylic acid copolymer comprises 5 to 40% by weight of a polyamine monomer (A '), The polyamine is obtained by copolymerizing a monomer mixture containing 1 to 40% by weight of a saturated carboxylic acid monomer (B) and 10 to 94% by weight of an unsaturated monomer having a polyalkylene glycol chain (C). The system monomer (A ′) is composed of 1.0 mol of a polyalkylene polyamine and a dibasic acid and / or
Or an unsaturated bond obtained by reacting 0.5 to 1.0 mol of an ester of a dibasic acid and an alcohol having 1 to 4 carbon atoms, and 0.01 to 0.5 mol of an unsaturated compound having an epoxy group. Also, it is a cement admixture which is a polyamine-based compound obtained by adding 0 to 300 moles of an alkylene oxide having 2 to 18 carbon atoms to 1 mole of the total of amino groups and imino groups of the polyamine having the following formula.

The cement admixture of the present invention comprises a polycarboxylic acid-based copolymer, wherein the polycarboxylic acid-based copolymer comprises 5 to 40% by weight of a polyamine-based monomer (A ') and an unsaturated carboxylic acid. -Based monomer (B) 1 to 40% by weight and unsaturated monomer (C) 10 having a polyalkylene glycol chain
It is obtained by copolymerizing a monomer mixture containing up to 94% by weight. These monomers may be used alone or in combination of two or more. When the weight ratio of these monomers is out of the above range, the function of the repeating unit formed by each monomer cannot be effectively exerted as described below, and the effect of the present invention is not sufficiently achieved. It cannot be expressed. In addition, the said monomer (A '),
The weight ratio of (B) and (C) is based on monomer (A '),
It is the weight% when the total weight of (B) and (C) is 100 weight%. Further, in the present invention, as will be described later, other monomers other than the above-mentioned monomers can be used, but when other monomers are used, the monomers (A ′) and ) And (C) are preferably the main components in the monomer mixture. For example, when the monomer mixture is 100% by weight, the monomers (A ′) and (B) And (C) are preferably 50 to 100% by weight. More preferably,
70 to 100% by weight, and more preferably 90 to 1% by weight.
00% by weight.

The polycarboxylic acid copolymer of the present invention is also formed of a polyamine monomer (A '), an unsaturated carboxylic monomer (B) and a polyalkylene glycol monomer (C). Repeating units represented by (poly) amine-based monomer (A), unsaturated carboxylic acid-based monomer (B) and polyalkylene glycol-based monomer (C) in the above-described polycarboxylic acid-based copolymer, respectively. The same function as the repeating unit formed by the above is obtained, but a monomer having a specific structure having a plurality of nitrogen atoms is used as the polyamine monomer (A '). By setting the copolymerization ratio of the monomers forming the polymer to a specific range, these functions can be more sufficiently exhibited. Therefore, the cement admixture containing the polycarboxylic acid copolymer of the present invention is more preferably used as a water reducing agent for ultra-high strength which can be suitably used for ultra-high strength concrete.

The monomers constituting the monomer mixture which forms the polycarboxylic acid copolymer in the present invention will be described below. In the present invention, the polyamine-based monomer (A ′) is a polyalkylene polyamine (hereinafter, also referred to as compound (a1)) (1.0 mol) and a dibasic acid and / or a dibasic acid with 1 to 1 carbon atoms. Ester with alcohol [4] [hereinafter also referred to as compound (a2)] 0.5
To 1.0 mol, and an unsaturated compound having an epoxy group [hereinafter, also referred to as compound (a3)] 0.01 to 0.5.
It is a polyamine-based compound obtained by adding 0 to 300 moles of an alkylene oxide having 2 to 18 carbon atoms to 1 mole of a total of amino groups and imino groups of a polyamine having an unsaturated bond obtained by reacting moles.

The compound (a1) is not particularly limited as long as it has a plurality of alkylene groups and a plurality of amino groups or imino groups in one molecule. One, two or more of min, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, and the like. Preferably, it is used.

The compound (a2) is not particularly restricted but includes, for example, malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, phthalic acid,
One or two or more of azelaic acid, sebacic acid and esters of these with an alcohol having 1 to 4 carbon atoms may be mentioned. Among them, from the viewpoint of availability and production cost, adipic acid may be used. preferable. The alcohol having 1 to 4 carbon atoms forming the compound (a2) is not particularly limited, and examples thereof include one or more of methanol, ethanol, propanol, butanol and isomers thereof.

The compound (a3) is not particularly limited as long as it has an unsaturated bond and an epoxy group in one molecule, and among the compounds having an epoxy group, a compound having a glycidyl group is preferable. For example, 1 such as glycidyl (meth) acrylate, allyl glycidyl ether, etc.
Species or two or more species. Among them, it is preferable to use glycidyl (meth) acrylate from the viewpoint of availability and production cost.

The compound (a1), the compound (a2) and the compound (a3) are reacted to obtain a polyamine having an unsaturated bond. Compounds other than these compounds may be used additionally. It is not necessary. In order to obtain a polyamine having an unsaturated bond, it is essential to carry out a polycondensation reaction between an amino group derived from the compound (a1) and a carboxyl group derived from the compound (a2). Can be used. Compound (a)
It is essential that the epoxy group derived from the compound (a3) opens and undergoes an addition reaction with the amino group derived from 1),
A known addition reaction method can be used. For example, first, a polycondensation reaction between the compound (a1) and the compound (a2) is performed to obtain a polyamide polyamine, and then an addition reaction is performed between the polyamide polyamine and the compound (a3) to introduce an unsaturated bond. From the beginning, the compound (a1), the compound (a2), and the compound (a3) are simultaneously subjected to a polycondensation reaction or a batch reaction method in which an addition reaction is performed.
In these reaction methods, each compound may be subjected to the reaction collectively, or may be subjected to the reaction stepwise or sequentially. According to these reaction methods and the like, a polycondensation reaction, that is, an amidation reaction is performed to form a polyamide chain, and an addition reaction, that is, a polyamine having an unsaturated bond is produced by ring-opening and addition reaction of an unsaturated compound having an epoxy group. Is formed.

Compound (a1), compound (a2) and compound (a) which form the polyamine having an unsaturated bond
As the ratio of the number of moles of 3), 0.5 to 1.0 mole of compound (a2) and 1.0 mole of compound (a1), and
Compound (a3) is 0.01 to 0.5 mol. As a result, the product of the condensation polymerization of the compound (a1) and the compound (a2) is such that the molar ratio is, on average, compound (a1) / compound (a2) = 2/1 to 1/1. A polyamine having a certain range of chain length is formed by the condensation polymerization reaction, and the polycarboxylic acid copolymer exhibits high water reduction and dispersion stability due to such a structure. When the chain length of the polyamine is shorter than this, that is, 0.5 mol of the compound (a2) is added to 1.0 mol of the compound (a1).
If the amount is less than the mole, the dispersion stability of the polycarboxylic acid-based copolymer will decrease. If the chain length of the polyamine is longer than this, that is, if the compound (a2) exceeds 1.0 mol with respect to 1.0 mol of the compound (a1), the water-reducing property of the polycarboxylic acid copolymer decreases. become. The compound (a2) is preferably 0.6 to 0.98 mol, more preferably 0.8 to 0.95 mol, based on 1.0 mol of the compound (a1).

As the ratio of the number of moles, the compound (a
1) The number of moles of the compound (a3) is 0.1 to 1.0 mole.
If the amount is less than 01 mol, the proportion of the polyamine-based monomer (A ') incorporated in the polycarboxylic acid-based copolymer decreases, and the repeating unit formed from the polyamine-based monomer (A') exhibits Function will be reduced. Also,
If it exceeds 0.5 mol, the structure of the polycarboxylic acid-based copolymer becomes too three-dimensional, and the effect of the present invention cannot be sufficiently exerted. As the number of moles of the compound (a3), 1.0 mole of the compound (a1)
It is preferable that the amount be 0.02 to 0.3 mol. More preferably, the amount is 0.05 to 0.2 mol.

A polyamine compound is obtained by adding 0 to 300 mol of an alkylene oxide having 2 to 18 carbon atoms to 1 mol of the total of the amino group and imino group of the polyamine having an unsaturated bond. .
The alkylene oxide having 2 to 18 carbon atoms to be added to the amino group or imino group of the polyamine having an unsaturated bond is not particularly limited, and examples thereof include one or more of ethylene oxide, propylene oxide, and butylene oxide.

In order to obtain the above-mentioned polyamine-based compound, an alkylene oxide having 2 to 18 carbon atoms may or may not be added to either or both of the amino group and the imino group of the polyamine having an unsaturated bond. May be
It is preferable to add them. In this case, the carbon number is 2 to 18.
Is added to a nitrogen atom of an amino group or imino group having an active hydrogen atom. Carbon number 2
When the number of added moles of the alkylene oxide is more than 300 moles, the number of nitrogen atoms in the polycarboxylic acid-based copolymer is reduced due to an increase in the molecular weight of the polyamine-based compound. The effect cannot be fully exhibited. The preferred number of moles of the alkylene oxide having 2 to 18 carbon atoms is 0.2 to 100 moles based on 1 mole of the total of the amino group and imino group of the polyamine having an unsaturated bond. More preferably, it is 0.5 to 50 mol, and still more preferably 1 to 20 mol.

The above polyamine-based compound is converted to a compound (a
An example of a reaction formula obtained from 1), a compound (a2) and a compound (a3) by a two-stage reaction of a condensation polymerization reaction and an addition reaction is shown below.

[0034]

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In the above reaction formula, EO represents ethylene oxide, -EO-H represents that ethylene oxide is added to a nitrogen atom having an active hydrogen atom in a polyamine having an unsaturated bond, and q represents diethylenetriamine. , R represents the number of moles of adipic acid, and s represents the number of moles of a repeating unit formed from adipic acid and diethylenetriamine.

The unsaturated carboxylic acid monomer (B) in the present invention is not particularly limited as long as it has an unsaturated bond and a group capable of forming a carbanion. Examples thereof include carboxylic acid monomers and unsaturated dicarboxylic acid monomers. The unsaturated monocarboxylic acid-based monomer is not particularly limited as long as the monomer has one unsaturated bond and one group capable of forming a carbanion in the molecule. For example, the following general formula ( The compound represented by 1) is preferred.

[0037]

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In the general formula (1), R represents a hydrogen atom or a methyl group. M represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group. M in the above general formula (1)
The metal atom in is not particularly limited, for example, a monovalent metal atom such as an alkali metal atom such as lithium, sodium and potassium; a divalent metal atom such as an alkaline earth metal atom such as calcium and magnesium; aluminum;
Examples include trivalent metal atoms such as iron. The organic amine group is not particularly limited, and examples thereof include an alkanolamine group such as an ethanolamine group, a diethanolamine group, and a triethanolamine group, and a triethylamine group. Further, it may be an ammonium group. Examples of such unsaturated monocarboxylic acid-based monomers include crotonic acid such as acrylic acid and methacrylic acid; monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts thereof. Among them, methacrylic acid; a monovalent metal salt, a divalent metal salt, an ammonium salt, an organic amine salt and the like are preferably used from the viewpoint of improving the cement dispersing performance, and the unsaturated carboxylic acid monomer (B ).

The unsaturated dicarboxylic acid monomer is not particularly limited as long as it has one unsaturated bond and two groups capable of forming a carbanion in the molecule. Acid, itaconic acid, citraconic acid,
Examples include fumaric acid and the like, monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts, and the like, and anhydrides thereof. As the unsaturated carboxylic acid monomer (B), in addition to these, a half ester of an unsaturated dicarboxylic acid monomer and an alcohol having 1 to 22 carbon atoms,
Half amide of unsaturated dicarboxylic acids and amine having 1 to 22 carbon atoms, unsaturated dicarboxylic acid monomer and 2 to 2 carbon atoms
And a half amide of maleamic acid and a glycol having 2 to 4 carbon atoms.

The unsaturated monomer (C) having a polyalkylene glycol chain in the present invention is not particularly limited as long as it is a monomer having an unsaturated bond and a polyalkylene glycol chain. System monomers and unsaturated alcohol polyalkylene glycol adducts. The polyalkylene glycol ester-based monomer is not particularly limited as long as it has a structure in which an unsaturated bond and a polyalkylene glycol chain are bonded via an ester bond. Examples thereof include polyalkylene glycol ester compounds, and among them, (alkoxy) polyalkylene glycol mono (meth) acrylate is preferable.

The unsaturated alcohol polyalkylene glycol adduct is not particularly limited as long as it has a structure in which a polyalkylene glycol chain is added to an alcohol having an unsaturated bond, and examples thereof include vinyl alcohol alkylene oxide adducts, (Meth) allyl alcohol alkylene oxide adduct, 3-buten-1-ol alkylene oxide adduct, isoprene alcohol (3-methyl-3-buten-1-ol) alkylene oxide adduct, 3-methyl-2-butene- And 1-ol alkylene oxide adducts. As such an unsaturated alcohol polyalkylene glycol adduct, for example, a compound represented by the following general formula (2) is preferable.

[0042]

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In the above general formula (2), R¹ , R^Two And R^Three 
Represents the same or different and represents a hydrogen atom or a methyl group.
You. R^Four Is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
Represents R^X Are the same or different and have 2 to 18 carbon atoms
Represents an alkylene group. m is R ^X Oxya represented by O
Represents the average number of added moles of the alkylene group, and is a number from 1 to 300.
is there. X is a divalent alkylene group having 1 to 5 carbon atoms or
In the case of a nyl group, the carbon atom and oxygen atom
This indicates that the person is directly connected.

[0044] The general formula of ^{(2) - (R X O} ) -
When two or more oxyalkylene groups represented by the formula (1) are present in the same unsaturated alcohol polyalkylene glycol adduct, the oxyalkylene groups represented by-(R ^X O)- Any addition form such as addition may be used.

The oxyalkylene group represented by-(R ^X O)-is an alkylene oxide adduct having 2 to 18 carbon atoms. The structure of such an alkylene oxide adduct is, for example, ethylene oxide or propylene. The structure is formed by one or more alkylene oxides such as oxide, butylene oxide, isobutylene oxide, 1-butene oxide, and 2-butene oxide.
Among such alkylene oxide adducts, ethylene oxide, propylene oxide and butylene oxide adducts are preferred.

M, which is the average number of moles of the oxyalkylene group represented by R ^X O, is a number from 1 to 300.
If m exceeds 300, the polymerizability of the monomer may be reduced. m is preferably 2 or more,
Further, - in (R ^X O) in m-, and the average molar number of addition of oxyethylene group is preferably 2 or more.
When m is less than 2 or the average number of moles of added oxyethylene groups is less than 2, hydrophilicity sufficient to disperse cement particles and the like may be insufficient, and steric hindrance may not be obtained. Fluidity may not be obtained. The range of m is more preferably 10 to
250, more preferably 20 to 150.
The average number of moles of oxyethylene groups added is more preferably 10 to 250, and still more preferably,
20 to 150. The average number of moles added means an average value of the number of moles of the organic group added in one mole of the monomer.

The (alkoxy) polyalkylene glycol mono (meth) acrylate is preferably, for example, a compound represented by the following general formula (3).

[0048]

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In the general formula (3), R ⁵ represents a hydrogen atom or a methyl group. R ^X is the same or different and represents an alkylene group having 2 to 18 carbon atoms. R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. m represents an average number of moles of the oxyalkylene group represented by R ^X O, and 1
~ 300. In the general formula (3),-(R
M, which is the average number of moles of the oxyalkylene group represented by ^X O)-and the oxyalkylene group represented by R ^X O, is the same as in the general formula (2). In addition, it is preferable that an ethylene oxide moiety is added to an ester bond with (meth) acrylic acid from the viewpoint of improving productivity of esterification with (meth) acrylic acid.

When the number of carbon atoms in R ⁶ exceeds 30, the hydrophobicity of the polycarboxylic acid copolymer becomes too strong, so that good dispersibility may not be obtained.
R ⁶ is preferably a hydrocarbon group having 1 to 20 carbon atoms or hydrogen in view of dispersibility. More preferably, it has 1 to 10 carbon atoms, still more preferably 1 to 3 carbon atoms,
Particularly preferred is a hydrocarbon group having 1 to 2 carbon atoms. In order to exhibit excellent material separation prevention performance and to moderate the amount of air entrained in the cement composition, it is preferable to use a hydrocarbon group having 5 to 20 carbon atoms. More preferably, it is a hydrocarbon group having 5 to 10 carbon atoms. Among the hydrocarbon groups, a saturated alkyl group and an unsaturated alkyl group are preferred. These alkyl groups may be linear or branched.

The (alkoxy) polyalkylene glycol mono (meth) acrylate is not particularly limited as long as it is as described above.
Ethanol, 1-propanol, 2-propanol, 1
-Butanol, 2-butanol, 1-pentanol, 2
Having 1 to 30 carbon atoms such as -pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, octanol, 2-ethyl-1-hexanol, nonyl alcohol, lauryl alcohol, cetyl alcohol, and stearyl alcohol; Aliphatic alcohols, alicyclic alcohols having 3 to 30 carbon atoms such as cyclohexanol, (meth) allyl alcohol, 3-butene-
Alkoxypoly obtained by adding 1 to 300 moles of an alkylene oxide group having 2 to 18 carbon atoms to any of unsaturated alcohols having 3 to 30 carbon atoms such as 1-ol and 3-methyl-3-buten-1-ol. Alkylene glycols,
An esterified product with (meth) acrylic acid is exemplified.

Examples of the esterified product include the following (alkoxy) polyethylene glycol (poly)
(Alkylene glycols having 2 to 4 carbon atoms) (meth) acrylates and the like. Methoxy polyethylene glycol mono (meth) acrylate, methoxy {polyethylene glycol (poly) propylene glycol}
Mono (meth) acrylate, methoxy ｛polyethylene glycol (poly) butylene glycol｝ mono (meth) acrylate, methoxy ｛polyethylene glycol (poly) propylene glycol (poly) butylene glycol｝ mono (meth) acrylate, ethoxy polyethylene glycol mono (meth) acrylate Acrylate, ethoxy ト polyethylene glycol (poly) propylene glycol｝ mono (meth) acrylate, ethoxy ｛polyethylene glycol (poly) butylene glycol｝ mono (meth) acrylate, ethoxy ｛polyethylene glycol (poly)
Propylene glycol (poly) butylene glycol mono (meth) acrylate, propoxy polyethylene glycol mono (meth) acrylate, propoxy polyethylene glycol (poly) propylene glycol mono (meth) acrylate, propoxy polyethylene glycol (poly) butylene glycol mono (Meth) acrylate, propoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate.

Butoxy polyethylene glycol mono (meth) acrylate, butoxy ｛polyethylene glycol (poly) propylene glycol｝ mono (meth) acrylate, butoxy ｛polyethylene glycol (poly) butylene glycol｝ mono (meth) acrylate, butoxy ｛polyethylene glycol (poly) ) Propylene glycol (poly) butylene glycol｝ mono (meth) acrylate, pentoxy polyethylene glycol mono (meth)
Acrylate, pentoxy ｛polyethylene glycol (poly) propylene glycol｝ mono (meth) acrylate, pentoxy ｛polyethylene glycol (poly) butylene glycol｝ mono (meth) acrylate, pentoxy ｛polyethylene glycol (poly) propylene glycol (poly) butylene glycol｝ mono (Meth) acrylate, hexoxy polyethylene glycol mono (meth) acrylate, hexoxy ｛polyethylene glycol (poly) propylene glycol プ ロ ピ レ ン mono (meth) acrylate, hexoxy ｛polyethylene glycol (poly)
Butylene glycol mono (meth) acrylate, hexoxy polyethylene glycol (poly) propylene glycol (poly) butylene glycol mono (meth) acrylate.

Heptoxy polyethylene glycol mono (meth) acrylate, heptoxy ｛polyethylene glycol (poly) propylene glycol｝ (meth) acrylate, heptoxy ｛polyethylene glycol (poly) butylene glycol｝ (meth) acrylate,
Heptoxy polyethylene glycol (poly) propylene glycol (poly) butylene glycol mono (meth) acrylate, octoxy polyethylene glycol mono (meth) acrylate, octoxy polyethylene glycol (poly) propylene glycol mono (meth) acrylate, octoxy polyethylene Glycol (poly) butylene glycol mono (meth) acrylate, octoxy polyethylene glycol (poly) propylene glycol (poly) butylene glycol mono (meth) acrylate, nonanoxy polyethylene glycol mono (meth) acrylate, nonanoxy polyethylene glycol (poly ) Propylene glycol (mono (meth) acrylate, nonoxy) polyethylene glycol (poly) butylene Recall} mono (meth) acrylate, Nonanokishi {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate.

Decanoxy polyethylene glycol mono (meth) acrylate, decananoloxy polyethylene glycol (poly) propylene glycol mono (meth)
Acrylate, decanoxy, polyethylene glycol (poly) butylene glycol, mono (meth) acrylate, decanoloxy, polyethylene glycol (poly) propylene glycol (poly) butylene glycol, mono (meth) acrylate, undecanoxy polyethylene glycol mono (meth) acrylate, Undecanoloxy polyethylene glycol (poly) propylene glycol mono (meth) acrylate, undecanoloxy polyethylene glycol (poly) butylene glycol mono (meth) acrylate, undecanoloxy polyethylene glycol (poly) propylene glycol (poly) butylene glycol mono (meth) ) Acrylate, dodecanooxypolyethylene glycol mono (meth) acrylate, dodecanoloxy Ethylene glycol (poly)
Propylene glycol mono (meth) acrylate, dodecanoxy polyethylene glycol (poly) butylene glycol mono (meth) acrylate, dodecanoxy polyethylene glycol (poly) propylene glycol (poly) butylene glycol mono (meth) acrylate.

Tridecanoloxypolyethylene glycol mono (meth) acrylate, tridecanoloxy ｛polyethylene glycol (poly) propylene glycol｝ mono (meth) acrylate, tridecanoloxy ｛polyethylene glycol (poly) butylene glycol｝ mono (meth)
Acrylate, tridecanoloxy ｛polyethylene glycol (poly) propylene glycol (poly) butylene glycol｝ mono (meth) acrylate, tetradecanoloxypolyethylene glycol mono (meth) acrylate, tetradecanoloxy ｛polyethylene glycol (poly) propylene glycol｝ mono ( (Meth) acrylate, tetradecanoloxy ｛polyethylene glycol (poly) butylene glycol｝ mono (meth) acrylate, tetradecanoloxy ｛polyethylene glycol (poly) propylene glycol (poly) butylene glycol｝ mono (meth) acrylate, pentadecanoloxypolyethylene glycol mono (meta) ) Acrylate, pentadecanoxy ｛polyethylene glycol (poly) propylene glycol｝ mono (meth) acrylic Over DOO, Pentadekanokishi {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, Pentadekanokishi {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate.

Hexadecanoloxy polyethylene glycol mono (meth) acrylate, hexadecanoloxy ナ ノ polyethylene glycol (poly) propylene glycol｝ mono (meth) acrylate, hexadecanoxy ｛polyethylene glycol (poly) butylene glycol｝ mono (meth) acrylate, Hexadecanoloxy ｛polyethylene glycol (poly) propylene glycol (poly) butylene glycol｝ mono (meth) acrylate, heptadecanoloxy polyethylene glycol mono (meth) acrylate, heptadecanoxy ｛polyethylene glycol (poly) propylene glycol｝ mono (meth) Acrylate, heptadecanoloxy ｛polyethylene glycol (poly) butylene glycol｝ mono (meth) acrylate,
Heptadecanoloxy ｛polyethylene glycol (poly) propylene glycol (poly) butylene glycol｝ mono (meth) acrylate, octadecanoxy polyethylene glycol mono (meth) acrylate, octadecanoxy （polyethylene glycol (poly) propylene glycol｝ mono (meth) Acrylates, octadecanoxy, polyethylene glycol (poly) butylene glycol, mono (meth) acrylate, and octadecanoxy, polyethylene glycol (poly) propylene glycol (poly) butylene glycol, mono (meth) acrylate.

Nonadecanoxy polyethylene glycol mono (meth) acrylate, nonadecananoloxy polyethylene glycol (poly) propylene glycol mono (meth) acrylate, nonadecanoxy polyethylene glycol (poly) butylene glycol mono (meth)
Acrylate, nonadecanoxy ｛polyethylene glycol (poly) propylene glycol (poly) butylene glycol｝ mono (meth) acrylate, cyclopentoxypolyethylene glycol mono (meth) acrylate, cyclopentoxy ｛polyethylene glycol (poly) propylene glycol｝ mono (meth) Acrylate, cyclopentoxy ｛polyethylene glycol (poly) butylene glycol｝ mono (meth) acrylate, cyclopentoxy ｛polyethylene glycol (poly) propylene glycol (poly) butylene glycol｝ mono (meth) acrylate, cyclohexoxy polyethylene glycol mono (meth) acrylate ) Acrylate, cyclohexoxy ｛polyethylene glycol (poly) propylene glycol｝ mono (meth) acrylate , Cyclohexoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, cyclohexoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate.

Examples of the (alkoxy) polyalkylene glycol mono (meth) acrylate include, in addition to the compound represented by the general formula (2), phenoxypolyethylene glycol mono (meth) acrylate, phenoxydiethylene Glycol (poly) propylene glycol mono (meth) acrylate, phenoxy polyethylene glycol (poly) butylene glycol mono (meth) acrylate, phenoxy polyethylene glycol (poly) propylene glycol (poly) butylene glycol mono (meth) acrylate,
(Meth) allyloxypolyethylene glycol mono (meth) acrylate, (meth) allyloxy ｛polyethylene glycol (poly) propylene glycol｝ mono (meth) acrylate, (meth) allyloxy ｛polyethylene glycol (poly) butylene glycol｝ mono (meth) acrylate And (meth) allyloxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate.

Examples of the polyalkylene glycol ester-based monomer include the following in addition to (alkoxy) polyalkylene glycol mono (meth) acrylate.

(Polyethylene) such as triethylene glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, (poly) ethylene glycol (poly) propylene glycol di (meth) acrylate, etc. ) Alkylene glycol di (meth) acrylates; alkoxy (poly) alkylene glycol monomaleates; alkoxy (poly) alkylene glycol dimaleates such as triethylene glycol dimaleate and polyethylene glycol dimaleate; Alcohols and amines with 1 to 22 carbon atoms to 2 to 4 carbon atoms
Half-esters and diesters of alkyl polyalkylene glycols to which 1 to 300 moles of oxyalkylenes have been added and the unsaturated dicarboxylic acid monomers; Half esters, diesters and the like with polyalkylene glycol having an average number of moles of 2 to 300.

The monomer mixture forming the polycarboxylic acid copolymer in the present invention may further contain, if necessary, other monomers (D) other than the above-mentioned essential monomers. . The other monomer (D) is not particularly limited, and includes, for example, the following. These may be used alone or in combination of two or more.

Styrenes such as styrene, bromostyrene, chlorostyrene and methylstyrene; dienes such as 1,3-butadiene, isoprene and isobutylene; (meth)
Methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate,
(Meth) acrylic esters such as hexyl (meth) acrylate, decyl (meth) acrylate, and lauryl (meth) acrylate; α-olefins such as hexene, heptene, and decene; methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether Alkyl vinyl ethers such as vinyl acetate; vinyl esters such as vinyl acetate; allyl esters such as allyl acetate.

Diesters of the above unsaturated dicarboxylic acid monomers and alcohols having 1 to 22 carbon atoms, diamides of the above unsaturated dicarboxylic acids and amines having 1 to 22 carbon atoms,
A diester of the unsaturated dicarboxylic acid-based monomer and a glycol having 2 to 4 carbon atoms.

Bifunctional (meth) acrylates such as hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate and trimethylolpropane di (meth) acrylate; vinyl sulfonate, (meth) allyl sulfonate, 2- ( (Meth) acryloxyethylsulfonate, 3- (meth) acryloxypropylsulfonate, 3- (meth) acryloxy-2
-Hydroxypropylsulfonate, 3- (meth) acryloxy-2-hydroxypropylsulfophenyl ether, 3- (meth) acryloxy-2-hydroxypropyloxysulfobenzoate, 4- (meth) acryloxybutylsulfonate, (meth) acrylamidomethyl Unsaturated sulfonic acids such as sulfonic acid, (meth) acrylamidoethylsulfonic acid, 2-methylpropanesulfonic acid (meth) acrylamide, styrenesulfonic acid, etc., and their monovalent metal salts, divalent metal salts, ammonium salts and organic compounds Amine salts.

Unsaturated amides such as (meth) acrylamide, (meth) acrylalkylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide; allyls such as allyl alcohol; dimethylaminoethyl ( Unsaturated amino compounds such as meth) acrylates; vinyl ethers or allyl ethers such as methoxypolyethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, methoxypolyethylene glycol mono (meth) allyl ether, and polyethylene glycol mono (meth) allyl ether.

The method for copolymerizing the monomer mixture in the present invention is the same as the above-described copolymerization method for the polycarboxylic acid copolymer. Further, the molecular weight of the polycarboxylic acid-based copolymer in the present invention is the same as the molecular weight of the above-described polycarboxylic acid-based copolymer.

The cement admixture of the present invention contains the above polycarboxylic acid copolymer. The cement admixture means an agent that can be mixed with the cement composition or the like, that is, an agent containing a cement additive or the like. The cement admixture containing the polycarboxylic acid-based copolymer as a main component is one of preferred embodiments of the present invention.

The above-mentioned polycarboxylic acid copolymer can be suitably used as a main component of a cement additive constituting a cement admixture, and such a cement additive will be described below. The above cement additive can be used in addition to a cement composition such as a cement paste, mortar, concrete and the like. The cement composition is not particularly limited, for example, cement,
Commonly used materials including water, fine aggregate, coarse aggregate and the like can be mentioned. Further, fine powders such as fly ash, blast furnace slag, silica fume, limestone and the like may be added.

The cement is not particularly restricted but includes, for example, portland cements of ordinary, fast, ultrafast, moderate heat and white color; mixed portland cements such as alumina cement, fly ash cement, blast furnace cement, silica cement and the like. Is mentioned. The amount of cement and the unit water amount per m ³ of concrete are not particularly limited. For example, in order to produce high-durability and high-strength concrete, the unit water amount is 80 to 185 kg / m ³ ,
It is preferable to set the water / cement ratio to 10 to 70%.
More preferably, the unit water amount is 100 to 175 kg / m ³ ,
Water / cement ratio = 10-65%.

The method and amount of the cement additive to be added to the cement composition are not particularly limited.
The amount of addition is preferably such that the polycarboxylic acid copolymer for cement additive in the present invention is 0.01 to 10% by weight based on 100% by weight of the total amount of cement. If the amount is less than 0.01% by weight, the performance may be insufficient. If the amount is more than 10% by weight, the economical efficiency is deteriorated. In addition, the said weight% is a value of solid content conversion.

The above cement additive can be used in combination with a commonly used cement dispersant. The cement dispersant is not particularly limited, and examples thereof include the following. Lignin sulfonic acid salt; polyol derivative; naphthalene sulfonic acid formalin condensate; melamine sulfonic acid formalin condensate; polystyrene sulfonic acid salt; Aminosulfonic acid type; JP-A-7-267705
As described in Japanese Patent Application Publication No. JP-A-2002-209, as a component (a), a copolymer of a polyalkylene glycol mono (meth) acrylate compound and a (meth) acrylic compound and / or a salt thereof, and as a component (b), A copolymer of a polyalkylene glycol mono (meth) allyl ether compound and maleic anhydride and / or a hydrolyzate thereof; and /
Or, a cement dispersant comprising a salt thereof, a copolymer of a polyalkylene glycol mono (meth) allyl ether-based compound and a maleic acid ester of a polyalkylene glycol-based compound, and / or a salt thereof as a component (c). ;
As described in Japanese Patent No. 2508113, a copolymer of a polyalkylene glycol ester of (meth) acrylic acid and (meth) acrylic acid (salt) is used as an A component, and a specific polyethylene glycol polypropylene glycol-based is used as a B component. Concrete admixture comprising a specific surfactant as a compound and a C component;
No. 50, polyethylene (propylene) glycol ester of (meth) acrylic acid or polyethylene (propylene) glycol mono (meth) allyl ether, (meth) allylsulfonic acid (salt), and
Copolymer of (meth) acrylic acid (salt).

As described in JP-A-1-226575, polyethylene (propylene) glycol ester of (meth) acrylic acid, (meth) allylsulfonic acid (salt),
And a copolymer consisting of (meth) acrylic acid (salt); as described in JP-B-5-36377, polyethylene (propylene) glycol ester of (meth) acrylic acid, (meth) allylsulfonic acid (salt) or p- (meth) allyloxybenzenesulfonic acid (salt), and
Copolymer of (meth) acrylic acid (salt);
Copolymers of polyethylene glycol mono (meth) allyl ether and maleic acid (salt) as described in JP-A-149056; polyethylene glycol esters of (meth) acrylic acid as described in JP-A-5-170501, (Meth) allylsulfonic acid (salt), (meth) acrylic acid (salt), alkanediol mono (meth) acrylate, polyalkylene glycol mono (meth) acrylate, and α, β-unsaturated having an amide group in the molecule Copolymers composed of monomers; polyethylene glycol mono (meth) allyl ether, polyethylene glycol mono (meth) acrylate, alkyl (meth) acrylate, (meth) acrylic acid as described in JP-A-6-191918 (Salt), and (meth) allylsulfonic acid (salt) or Copolymer of p- (meth) allyloxybenzenesulfonic acid (salt); JP-A-5-432
No. 88, a copolymer of an alkoxypolyalkylene glycol monoallyl ether and maleic anhydride, or a hydrolyzate thereof, or a salt thereof; a polyethylene glycol monomer as described in JP-B-58-38380. Copolymers consisting of allyl ether, maleic acid, and monomers copolymerizable with these monomers, or salts or esters thereof.

As described in JP-B-59-18338, polyalkylene glycol mono (meth) acrylate monomers, (meth) acrylate monomers, and
Copolymers composed of monomers copolymerizable with these monomers; (meth) acrylic acid esters having a sulfonic acid group as described in JP-A-62-119147, and copolymerizable therewith if necessary. Copolymer consisting of various monomers or a salt thereof; a copolymer of alkoxypolyalkylene glycol monoallyl ether and maleic anhydride as described in JP-A-6-271347, and having an alkenyl group at a terminal Esterification reaction product with a polyoxyalkylene derivative; a copolymer of an alkoxypolyalkylene glycol monoallyl ether and maleic anhydride as described in JP-A-6-298555, and a polyoxyalkylene derivative having a hydroxyl group at a terminal. Esterification product of 3-methyl-3-butene-1- as described in JP-A-62-68806. Alkenyl ether-based monomer, unsaturated carboxylic acid-based monomer obtained by adding ethylene oxide or the like to a specific unsaturated alcohol such as alcohol, and a copolymer comprising a monomer copolymerizable with these monomers. Coalescing, or
Polycarboxylic acids (salts) such as salts thereof. These cement dispersants may be used alone or in combination of two or more.

When the above cement dispersant is used in combination,
Although it cannot be unambiguously determined depending on the type of cement dispersant used, the composition and the test conditions, the proportion of the compounding weight of the cement additive and the cement dispersant is 5 to 9%.
5: 95-5 is preferred. More preferably,
10-90: 90-10. Further, the above-mentioned cement additive can be used in combination with other cement additives. The other cement additives are not particularly limited, and include, for example, other known cement additives (materials) as shown below.

(1) Water-soluble polymer substance: Polymerization of unsaturated carboxylic acid such as polyacrylic acid (sodium), polymethacrylic acid (sodium), polymaleic acid (sodium), and sodium salt of acrylic acid / maleic acid copolymer object;
Polyoxyethylene or polyoxypropylene polymers such as polyethylene glycol and polypropylene glycol or copolymers thereof; methylcellulose,
Nonionic cellulose ethers such as ethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, carboxyethylcellulose, and hydroxypropylcellulose; yeast glucan, xanthan gum, β-1,3 glucans (either linear or branched) Polysaccharides produced by microbial fermentation such as curdlan, paramylon, bakiman, scleroglucan, laminaran, etc.); polyacrylamide; polyvinyl alcohol; starch; starch phosphate; sodium alginate; gelatin; Acrylic acid copolymer having an amino group therein and a quaternary compound thereof.

(2) Polymer emulsions: copolymers of various vinyl monomers such as alkyl (meth) acrylate and the like. (3) retarders: gluconic acid, glucoheptonic acid, arabonic acid, malic acid or citric acid, and oxycarboxylic acids such as inorganic salts or organic salts such as sodium, potassium, calcium, magnesium, ammonium, and triethanolamine; Acids and salts thereof; monosaccharides such as glucose, fructose, galactose, saccharose, xylose, apiose, ribose and isomerized sugars; oligosaccharides such as disaccharides and trisaccharides; oligosaccharides such as dextrins; Sugars, sugars such as molasses containing them;
Sugar alcohols such as sorbitol; magnesium silicofluoride;
Phosphoric acid and salts or borates thereof; aminocarboxylic acids and salts thereof; alkali-soluble proteins; humic acids;
Tannic acid; phenol; polyhydric alcohols such as glycerin; aminotri (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and their alkalis Phosphonic acids such as metal salts and alkaline earth metal salts and derivatives thereof;

(4) Early strength agent / promoter: calcium chloride,
Calcium nitrite, calcium nitrate, calcium bromide,
Soluble calcium salts such as 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) Mineral oil-based antifoaming agents: kerosene, liquid paraffin and the like. (6) Oil-based antifoaming agents: animal and vegetable oils, sesame oil, castor oil, alkylene oxide adducts thereof and the like. (7) Fatty acid antifoaming agents: oleic acid, stearic acid, alkylene oxide adducts thereof and the like. (8) Fatty acid ester antifoaming agents: glycerin monoricinoleate, alkenyl succinic acid derivatives, sorbitol monolaurate, sorbitol trioleate, natural wax and the like.

(9) Oxyalkylene-based antifoaming agents: polyoxyalkylenes such as (poly) oxyethylene (poly) oxypropylene adduct; diethylene glycol heptyl ether, polyoxyethylene oleyl ether;
(Poly) oxyalkyl ethers such as polyoxypropylene butyl ether, polyoxyethylene polyoxypropylene 2-ethylhexyl ether, and oxyethylene oxypropylene adducts to higher alcohols having 12 to 14 carbon atoms; polyoxypropylene phenyl ether, polyoxy (Poly) oxyalkylene (alkyl) aryl ethers such as ethylene nonylphenyl ether; 2,4,7,9-tetramethyl-5-decyne-
4,7-diol, 2,5-dimethyl-3-hexyne-
Acetylene ethers obtained by addition-polymerizing an alkylene oxide to acetylene alcohol such as 2,5-diol and 3-methyl-1-butyn-3-ol; diethylene glycol oleate, diethylene glycol laurate, ethylene glycol distearate and the like. (Poly) oxyalkylene fatty acid esters;
(Poly) oxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan trioleate; (poly) oxy such as sodium polyoxypropylene methyl ether sulfate and sodium polyoxyethylene dodecyl phenol ether sulfate Alkylene alkyl (aryl) ether sulfates; (poly)
(Poly) such as oxyethylene stearyl phosphate
Oxyalkylenealkyl phosphates; (poly) oxyalkylenealkylamines such as polyoxyethylene laurylamine; polyoxyalkyleneamides;

(10) Alcohol antifoaming agents: octyl alcohol, hexadecyl alcohol, acetylene alcohol, glycols and the like. (11) Amide-based antifoaming agent: acrylate polyamine and the like. (12) Phosphate ester antifoam: tributyl phosphate,
Sodium octyl phosphate and the like. (13) Metal soap-based antifoaming agents: aluminum stearate, calcium oleate and the like. (14) silicone antifoaming agent: dimethyl silicone oil,
Silicone paste, silicone emulsion, organically modified polysiloxane (polyorganosiloxane such as dimethylpolysiloxane), fluorosilicone oil and the like.

(15) AE agent: resin soap, saturated or unsaturated fatty acid, sodium hydroxystearate, lauryl sulfate, ABS (alkylbenzene sulfonic acid), LAS (linear alkylbenzene sulfonic acid),
Alkane sulfonate, polyoxyethylene alkyl (phenyl) ether, polyoxyethylene alkyl (phenyl) ether sulfate or salt thereof, polyoxyethylene alkyl (phenyl) ether phosphate or salt thereof, protein material, alkenyl sulfosuccinic acid, α- Olefin sulfonates and the like.

(16) Other surfactants: 6 to 3 molecules per molecule such as octadecyl alcohol and stearyl alcohol.
Aliphatic monohydric alcohol having 0 carbon atoms, alicyclic monohydric alcohol having 6 to 30 carbon atoms in a molecule such as abiethyl alcohol, 6 to 30 carbon atoms in a molecule such as dodecyl mercaptan, etc. Monovalent mercaptans having atoms, nonylphenols and the like, alkylphenols having 6 to 30 carbon atoms in the molecule, dodecylamines and the like having 6 to 30 carbon atoms in the molecule, molecules such as lauric acid and stearic acid Polyalkylene oxide derivatives in which an alkylene oxide such as ethylene oxide or propylene oxide is added in an amount of 10 mol or more to a carboxylic acid having 6 to 30 carbon atoms therein; and may have an alkyl group or an alkoxyl group as a substituent. Alkyl diphenyl ether in which two phenyl groups having a sulfone group are ether-bonded Rusuruhon acid salts; various anionic surfactants; alkylamine acetates, various cationic surfactants such as alkyl trimethyl ammonium chloride; and various nonionic surfactants; various amphoteric surfactants.

(17) Waterproofing agent: fatty acid (salt), fatty acid ester, oil and fat, silicon, paraffin, asphalt,
Wax and the like. (18) Rust inhibitors: nitrites, phosphates, zinc oxide and the like. (19) Crack reducing agents: polyoxyalkyl ethers; alkanediols such as 2-methyl-2,4-pentanediol and the like. (20) Expansive materials: ettringite, coal, etc.

Other known cement additives (materials) include cement wetting agents, thickening agents, separation reducing agents, flocculants,
Drying shrinkage reducing agent, strength enhancer, self-leveling agent, rust inhibitor, coloring agent, fungicide, blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, gypsum, etc. Can be. These known cement additives (materials) may be used alone or in combination of two or more.

The above-mentioned cement additives may be used in combination with the above-mentioned known cement dispersants and cement additives (materials) in addition to those which improve the dispersibility, foam control and the like of the cement composition. The method for adding the cement additive or the cement dispersant to the cement composition is not particularly limited,
For example, it is preferable to mix these cement additives and cement dispersants to form a cement admixture to facilitate mixing into the cement composition.

[0086] The cement composition to which the cement admixture of the present invention is added has excellent fluidity and fluidity retention, so that it has excellent water reduction and workability, and the cured product has high strength and durability. It will be excellent. Therefore, the cement admixture of the present invention can be suitably used for ultra-high-strength concrete, and can exert a sufficient effect as a super-high-strength water reducing agent.

[0087]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Unless otherwise specified,% means% by weight.

Production Example 1 (Polyamide polyamine monomer:
AGE-1) Diethylenetriamine 6 was added to a glass reaction vessel equipped with a thermometer, a stirrer, a nitrogen inlet tube, a water separator, and a condenser.
00g was charged and heated to 90 ° C. Next, adipic acid 7
30.9 g was added, adipic acid was dissolved in diethylene triamine, and the temperature in the reaction vessel was increased to 14 under a nitrogen atmosphere.
The temperature was kept at 0 ° C. to 160 ° C., and the generated water was extracted. When the acid value reaches 16, allyl glycidyl ether 9
2.9 g and hydroquinone monomethyl ether
7 g was added, and the mixture was further stirred at 160 ° C. for 2 hours. afterwards,
Water was added to obtain an aqueous solution of a polyamide polyamine monomer having a solid content of 58.3%. Subsequently, the polyamide polyamine monomer aqueous solution 192 obtained above was placed in an autoclave.
6.6 g was charged and the temperature was raised to 50 ° C. Next, 630.5 g of ethylene oxide was added dropwise over 2 hours, and then aged for 2 hours to obtain a polyamide polyamine monomer (A
GE-1, solid content: 68.6%).

Production Example 2 (Polyamide polyamine monomer:
GMA-1) Diethylenetriamine 6 was added to a glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, a water separator, and a condenser.
00g was charged and heated to 90 ° C. Next, adipic acid 7
30.9 g was added, adipic acid was dissolved in diethylene triamine, and the temperature in the reaction vessel was increased to 14 under a nitrogen atmosphere.
The temperature was kept at 0 ° C. to 160 ° C., and the generated water was extracted. The reaction was terminated when the acid value reached 18, and water was added to obtain an aqueous solution of a polyamide polyamine monomer having a solid content of 60.8%. Subsequently, in an autoclave, 246.6 g of the aqueous solution of the polyamide polyamine monomer obtained above and 53.times. Of water.
4 g was charged and the temperature was raised to 50 ° C. Next, 15.0 g of glycidyl methacrylate and 0.23 g of hydroquinone monomethyl ether were charged and reacted for 1 hour. Thereafter, 75.8 g of ethylene oxide was added dropwise over 2 hours, and then aged for 2 hours to obtain a polyamide polyamine monomer (GMA-1, solid content: 61.6%).

Comparative Production Example 1 (polyamide polyamine monomer: H-1) Diethylene triamine 6 was placed in a glass reaction vessel equipped with a thermometer, a stirrer, a nitrogen inlet tube, a water separator, and a condenser.
00g was charged and heated to 90 ° C. Next, adipic acid 7
30.9 g was added, adipic acid was dissolved in diethylene triamine, and the temperature in the reaction vessel was increased to 14 under a nitrogen atmosphere.
The temperature was kept at 0 ° C. to 160 ° C., and the generated water was extracted. When the acid value reached 14, 70.1 g of methacrylic acid and 1.7 g of hydroquinone monomethyl ether were added,
Further, the reaction was carried out at 160 ° C., and produced water was extracted. After the acid value reached 18, water was added and the solid content was 58.3.
% Of an aqueous solution of a polyamide polyamine monomer. Subsequently, 1926.6 g of the polyamide polyamine monomer aqueous solution obtained above was charged into an autoclave, and the autoclave was heated at 50 ° C.
Temperature. Next, 630.5 g of ethylene oxide was added dropwise over 2 hours, and then aged for 2 hours to obtain a polyamide polyamine monomer (H-1, solid content: 68.6).
%).

Example 1 A glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser was charged with 105 g of water, the inside of the reaction vessel was replaced with nitrogen under stirring, and the mixture was stirred under a nitrogen atmosphere. Heated to 90 ° C. Next, 56.29 g of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide 25), 14.95 g of methacrylic acid, and the polyamide polyamine monomer (A-
1) Starting by dissolving 165.5 g of a monomer aqueous solution obtained by mixing 18.76 g, 75.01 g of water and 0.52 g of 3-mercaptopropionic acid as a chain transfer agent, 2.34 g of ammonium persulfate in 27.66 g of water for 2 hours. The agent aqueous solution was dropped into the reaction vessel over 2.5 hours. Then 2
The temperature is maintained at 90 ° C. continuously for a period of time to complete the polymerization reaction,
A cement admixture comprising a copolymer having a weight average molecular weight of 19,100 was obtained.

Example 2 102.2 g of water and a polyamide polyamine monomer (A-2) synthesized in Production Example 2 were placed in a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser.
7.1 g was charged and the inside of the reaction vessel was replaced with nitrogen under stirring.
Heated to 80 ° C. under a nitrogen atmosphere. Next, 99.6 g of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide 25 added), 28.3 g of methacrylic acid, 31.8 g of water, and 3-chain as a chain transfer agent.
A monomer aqueous solution (160.7 g) mixed with mercaptopropionic acid (0.9 g) was treated with ammonium persulfate (1.6) for 4 hours.
g in 28.4 g of water was added dropwise to the reaction vessel over 5 hours. After that, it is 8 for one hour
At 0 ° C., the polymerization reaction was completed and the weight average molecular weight was 2
Thus, a cement admixture comprising a copolymer of No. 0900 was obtained.

Comparative Example 1 105 g of water was charged into a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube and a reflux condenser, and the inside of the reaction vessel was replaced with nitrogen under stirring, and the mixture was stirred under a nitrogen atmosphere. Heated to 90 ° C. Next, 56.29 g of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide 25), 14.95 g of methacrylic acid, and the polyamide polyamine monomer (H
-1) 165.5 g of a monomer aqueous solution obtained by mixing 18.76 g, 75.01 g of water and 0.52 g of 3-mercaptopropionic acid as a chain transfer agent was dissolved for 2 hours, and 2.34 g of ammonium persulfate was dissolved in 27.66 g of water. The initiator aqueous solution was dropped into the reaction vessel over 2.5 hours. afterwards,
The polymerization reaction was completed by maintaining 90 ° C. continuously for 2 hours to obtain a cement admixture comprising a copolymer having a weight average molecular weight of 20,000.

[0094]Mortar adjustment method  Pacific ordinary Portland cement (trade name, Pacific Seme
800g, 400g Toyoura standard sand
30 by Kisa (trade name: N-50, manufactured by Hobart)
Kneaded for seconds. Then, the copolymer synthesized in the examples or
Is kneaded with 180 g of water containing the copolymer synthesized in the comparative example.
Into a mixed cement and sand mixture and
The mortar was prepared by kneading for minutes. Example copolymers and
And the copolymers of Comparative Examples
It was blended so that the amount% became the value shown in Table 1. In addition,
In the preparation of each mortar, mortar mixer
The kneading and kneading conditions were made uniform.

[0095]Evaluation method  (1) Mortar uniform time 180 g of water containing the polymer was mixed with a mortar mixer.
Pour into a mixture of cement and sand that has been kneaded and rotate at high speed
Time when mortar became uniform when kneading for 5 minutes
(Seconds) was visually measured to obtain a mortar uniform time. (2) Flow value Six minutes after pouring the prepared mortar, place it on a stainless steel plate.
Placed in a hollow cylindrical container with a diameter of 55 mm and a height of 50 mm
Stuffed, then lifted this hollow cylindrical container vertically
After that, the diameter of the mortar spread on the stainless steel plate
The average value is measured as the flow value (mm)
did. The higher the flow value, the higher the liquidity
I have.

[0096]

[Table 1]

A glycidyl group was added to the copolymer of Comparative Production Example using a monomer (A) having an unsaturated bond introduced by an amide bond with an unsaturated compound having a carboxyl group in the polyamine compound and the polyamine compound of the present invention. The amount of addition required to obtain the same flow value of the copolymers of Examples 1 and 2 using the monomer (A) having an unsaturated bond introduced by an ether bond depending on the unsaturated compound having In the copolymers of Examples, the addition amount is required to be 0.43% by weight / cement, whereas in the copolymers of Examples 1 and 2 of the present invention, the addition amount is 0.4% by weight.
40% by weight, 0.30% by weight / cement and the same flow value can be obtained with a smaller amount of addition than the copolymer of Comparative Production Example, indicating that the water-reducing property is excellent. Further, when comparing the mortar uniformity time, the copolymer of Comparative Production Example was 110 seconds, while the copolymers of Examples 1 and 2 were 85 and 65 seconds. You can see that there is.

[0098]

Since the cement admixture of the present invention has the above-mentioned constitution, the cement composition and the like have excellent water-reducing properties and workability, and have excellent strength and durability of the cured product. Therefore, it can be suitably applied to cement paste, mortar, concrete, etc., particularly, ultra-high strength concrete.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C04B 103: 30 C04B 103: 30 (72) Inventor Hiromichi Tanaka 5-8 Nishimitabicho, Suita-shi, Osaka No. Nippon Shokubai Co., Ltd. (72) Inventor Ken Hirata 5-8 Nishiburi-cho, Suita-shi, Osaka F-term (reference) 4J001 DA01 DB01 EB04 EB05 EB06 EB07 EB08 EC01 EC77 EC79 FB03 FC03 FD01 FD05 GA13 GB02 GE01 JA20 JC06 4J027 AC02 AC03 AC04 AC06 AD02 BA03 BA04 BA05 BA06 BA07 CB02 CD00

Claims (2)

[Claims] 1. A cement admixture containing a polycarboxylic acid copolymer, wherein the polycarboxylic acid copolymer comprises:
It is obtained by copolymerizing a monomer mixture containing a (poly) amine monomer (A), an unsaturated carboxylic acid monomer (B) and an unsaturated monomer (C) having a polyalkylene glycol chain. The cement admixture, wherein the (poly) amine monomer (A) is a monomer obtained by introducing an unsaturated bond into a (poly) amine compound by an unsaturated compound having an epoxy group. 2. A cement admixture containing a polycarboxylic acid copolymer, wherein the polycarboxylic acid copolymer comprises 5 to 40% by weight of a polyamine monomer (A ') and an unsaturated carboxylic acid. 1 to 40% by weight of the system monomer (B) and 10 to 94 unsaturated monomers (C) having a polyalkylene glycol chain
The polyamine-based monomer (A ') is prepared by copolymerizing a dialkyl acid and / or a diacid and / or carbon number with respect to 1.0 mol of a polyalkylene polyamine. 0.5 to 1.0 mol of an ester with an alcohol of 1 to 4, and 0.01 of an unsaturated compound having an epoxy group.
A polyamine compound obtained by adding 0 to 300 moles of an alkylene oxide having 2 to 18 carbon atoms to a total of 1 mole of amino groups and imino groups of a polyamine having an unsaturated bond obtained by reacting from 0.5 to 0.5 moles. A cement admixture characterized by the fact that: