JP2015067521A - Cement additive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cement additive a part of which is restrained from creeping in an intermediate layer of a layered compound such as cement and clay so that even a small amount of the cement additive exhibits satisfactory water-reducing performance and further excellent drying shrinkage reducing performance.SOLUTION: The cement additive contains a polyalkylene glycol compound which is obtained by bonding an organic residue, that exhibits adsorption capacity to at least one of metals, metal compounds and metal ions, to at least two terminals of a straight-chain or branched-chain polyalkylene glycol chain. The organic residue has: at least one functional group selected from the group consisting of a carbonyl group, a hydroxyl group, an amino group, a thiol group, a phosphate group, a phosphite group and a silane group; no vinyl monomer-derived carbon-carbon bond; and 700 or lower molecular weight.

Description

The present invention relates to a cement additive. More specifically, the present invention relates to a cement additive or a drying shrinkage reducing agent used in a cement composition such as cement paste, mortar, and concrete.

Polycarboxylic acid-based water reducing agents having polyalkylene glycols in the side chains of polycarboxylic acids such as poly (meth) acrylic acid (hereinafter referred to as “polycal-based water reducing agents”) are now highly cemented due to their excellent cement dispersion performance. It is an indispensable additive for high durability concrete. The polycal water reducing agent is electrically adsorbed on the cement surface having a positive charge by the polycarboxylic acid of the main chain, and disperses the cement particles by steric repulsion by the polyethylene glycol of the side chain. In high-strength concrete or ultra-high-strength concrete, the viscosity of the concrete becomes extremely high because the water-cement ratio is extremely low, 30% or 20% or less. For this reason, it is difficult for the shovel to be reworked, and sometimes pumping at the percussion site cannot be carried out smoothly. Therefore, Patent Document 1 proposes a polycarbonate-type water reducing agent that lowers the viscosity of concrete, but there is a problem that the amount of addition is sometimes large and uneconomical.

Moreover, as a problem of the polycal-based water reducing agent, Non-Patent Document 1 discloses that a flow value is lowered when an aggregate mixed with clay such as montmorillonite is used. On the other hand, Non-Patent Document 2 discloses that 3CaO.Al ₂ O ₃ (hereinafter also referred to as C ₃ A), which is a component of cement, is an unstable layered compound in the early stage of hydration, 2CaO.Al ₂ O _3. 8H ₂ O (hereinafter also referred to as C ₂ AH ₈ ) and 4CaO · Al ₂ O ₃ · 13H ₂ O (hereinafter also referred to as C ₄ AH ₁₃ ) are produced, and a part of the water reducing agent is intercalated between the layers. To lose the ability to disperse cement particles.

In Non-Patent Document 3, clay may be mixed into concrete from fine aggregates and coarse aggregates of materials, and in this case, a water reducing agent is intercalated between layers of clay, which is a layered compound. It is disclosed that the amount added is extremely large in order to exhibit water reduction performance.

In addition, after the concrete has hardened, unreacted water remaining in the interior is dissipated due to outside air temperature and humidity conditions. For this reason, there is a problem that drying shrinkage proceeds, cracks occur in the cured product, and strength and durability are lowered. When the strength and durability of civil engineering and building structures decrease, serious problems such as reduced safety and increased repair costs arise. Examples of the drying shrinkage reducing agent for reducing the drying shrinkage of such hardened concrete products include alkylene oxide adducts of alcohols having 1 to 4 carbon atoms (see Patent Document 2), ethylene oxides of 2 to 8 valent polyhydric alcohols. And propylene oxide co-adducts (see Patent Document 3), lower alkylamine alkylene oxide adducts (see Patent Document 4), oligomer-region polypropylene glycol (see Patent Document 5), low molecular alcohols (Patent Document 6) 2), an alkylene oxide adduct of 2-ethylhexanol (see Patent Document 7) has been reported.

Patent Document 8 discloses the application of a compound comprising at least one phosphonic acid aminoalkylene group and at least one polyoxyalkylene chain as a cement fluidizing agent. Patent Document 9 discloses polyalkylene. A curing accelerator composition comprising a water-soluble dispersant having at least one polyalkylene glycol structural unit having a functional group at one terminal of glycol is disclosed, and Patent Document 10 discloses a non-polymer function that adsorbs to cement. Disclosed is an oligomeric dispersant comprising component A, a water-soluble nonionic polymer component C that provides dispersibility, and optionally a non-polymer component B disposed between component A and component C to bind them together Has been. Patent Document 11 discloses a block polymer containing a polyalkylene glycol structural unit and a polyglyoxylate structural unit.

JP 2004-43280 A 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 National Patent Publication No. 8-505082 Special table 2013-520390 gazette Special table 2003-504294 gazette JP-A-10-53648

Three outside of A. Jeknavorian, “Interaction of Superplasticizers with Clais-Bearing Aggregates”, Supermarkets, Germany ACI International Conference on Superplasticizers and Other Chemical Admixtures in Concrete, 2003, p143-159 Two outside of J. Plank, “Materials Letters”, 2006, Vol. 60, p 3614-3617 One outside S. Ng, “Cement and Concrete Research”, 2012, Vol. 42, p847-854 One outside J. Plank "Cement and Concrete Research", 2007, Vol. 37, p 537-542

As described above, compounds having various structures as polyalkylene glycol chain-containing compounds have been disclosed. However, a part of the structure of the water reducing agent, such as cement or clay, which causes a large amount of water reducing agent to be added. The problem of intercalation into the layered compound has not been solved.
Further, conventional drying shrinkage reducing agents have insufficient drying shrinkage reduction performance, and there is room for improvement.

The present invention has been made in view of the above situation, and by suppressing the entry of a part of the cement additive between the layers of the layered compound such as cement and clay, it exhibits sufficient water reducing performance even in a small amount, Furthermore, it aims at providing the cement additive excellent also in the drying shrinkage reduction performance.

The present inventor has studied various cement additives excellent in cement dispersibility (water reduction) and adsorbed to at least one of a metal, a metal compound, and a metal ion on at least two ends of a polyalkylene glycol chain. It was conceived that a compound having an organic residue having a specific functional group was used as a cement additive. When such a compound is used as a cement additive, the organic residue at the terminal of the polyalkylene glycol chain is a metal atom or metal in the cement composition such as a metal atom or metal ion on the surface of a layered compound such as cement or clay. As a result of being adsorbed to ions, this prevents the polyalkylene glycol chain from entering between layers of a layered compound such as cement or clay due to steric hindrance or a decrease in the degree of freedom of movement of the polyalkylene glycol chain. Has been found to exhibit a sufficient water reduction performance even in a small amount.
Furthermore, when the present inventor uses such a compound as a cement additive, the organic residue at the end is adsorbed to the cement, so that the polyalkylene glycol chain is prevented from entering between layers of the layered compound, and the cement particles Since the water retention effect is provided in the vicinity of the surface, it has also been found that excellent drying shrinkage reduction performance can be exhibited with the addition amount of a small amount of cement additive. The invention has been reached.

That is, the present invention relates to a polyalkylene glycol compound in which an organic residue capable of adsorbing at least one of a metal, a metal compound, and a metal ion is bonded to at least two ends of a linear or branched polyalkylene glycol chain. And the organic residue has at least one functional group selected from the group consisting of a carbonyl group, a hydroxyl group, an amino group, a thiol group, a phosphoric acid group, a phosphorous acid group, and a silane group, and vinyl It is a cement additive having a molecular weight of 700 or less and having no carbon-carbon bond derived from a monomer.
The present invention is described in detail below.
A combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

≪Cement additive≫
A compound in which an organic residue is bonded to at least two ends of a linear or branched polyalkylene glycol chain according to the present invention (hereinafter also referred to as an organic residue-containing polyalkylene glycol compound) includes a polyalkylene glycol chain, Other structural sites may be included as long as they have at least 3 structural sites with at least two terminal organic residues of the polyalkylene glycol chain. Moreover, when two or more of these structural sites are included, they may be the same or different.

The organic residue bonded to the end of the polyalkylene glycol chain means an organic residue directly bonded to the end of the polyalkylene glycol chain. Here, the term “end of polyalkylene glycol chain” means that the end of polyalkylene glycol chain having an unmodified end (form in which the end is a hydroxyl group) and the end of polyalkylene glycol chain were modified as described later. Things are included. The structure in which an organic residue is bonded to the end of the polyalkylene glycol chain has a structure in which a hydroxyl group at the end of the polyalkylene glycol chain or a reactive functional group is introduced into the end of the polyalkylene glycol chain, and a modified end, It can be formed by reacting with a compound that provides a residue. The reactive functional group is not particularly limited, and examples thereof include an amino group, a carboxyl group, and an epoxy group. An epoxy group is preferable.

The organic residue is bonded to at least two ends of the polyalkylene glycol chain. When the polyalkylene glycol chain is linear, the organic residue is bonded to both ends of the polyalkylene glycol chain. In the case where the polyalkylene glycol chain is branched, it means that an organic residue is bonded to at least two ends of the main chain end and the branched chain end.

The organic residue is characterized by exhibiting an adsorption ability for at least one of a metal, a metal compound, and a metal ion. Thereby, the organic residue-containing polyalkylene glycol compound of the present invention can be adsorbed to at least one of a metal, a metal compound and a metal ion contained in the cement composition.

In the form in which at least two terminal organic residues of the polyalkylene glycol chain are adsorbed to at least two of the metal, the metal compound and the metal ion in the cement composition, at least two terminal organic residues of the polyalkylene glycol chain are used. The residue is adsorbed on the same metal particle, the same metal compound particle or the same metal ion, and is not adsorbed on the same metal particle, the same metal compound particle or the same metal ion. There is a form to adsorb.
Here, the same particle means particles of the same lump contained in the cement composition, and even if the same lump is formed of a single component, it includes a plurality of components. You may go out. That is, the form in which at least two terminal organic residues of the polyalkylene glycol chain are adsorbed to the same metal particle is a single metal block composed of a single or a plurality of metals, and the polyalkylene glycol chain Means that both at least two terminal organic residues are adsorbed to the one mass, and at least two terminal organic residues of the polyalkylene glycol chain are both adsorbed to the same type of metal. Does not mean that
The same applies to the form in which the organic residues at at least two terminals of the polyalkylene glycol chain are adsorbed on the same metal compound particle.
Cement particles contained in the cement composition are tricalcium aluminate (C ₃ A: 3CaO · Al ₂ O ₃ ), tetracalcium iron aluminate (C ₄ AF: 4CaO · Al ₂ O ₃ · Fe ₂ O ₃ ). , dicalcium silicate _{(C 2 S: 2CaO · SiO} 2) and tricalcium silicate _{(C 3 S: 3CaO · SiO} 2) be a metal compound such as is obtained by set a mosaic non-Patent Document 4, etc. Is known by. Therefore, when at least two terminal organic residues of the polyalkylene glycol chain adsorb to one cement particle, they adsorb to at least two of the metal compounds constituting the mosaic of the cement particle. It will be.

In the case where the organic residues at least two terminals of the polyalkylene glycol chain do not adsorb to the same metal particle, the same metal compound particle or the same metal ion, but adsorb to different particles, the polyalkylene glycol chain Can enter between layers of layered compounds such as cement and clay due to steric hindrance by metal particles, metal compound particles or metal ions adsorbed on at least two terminal organic residues, or reduced freedom of movement of polyalkylene glycol chains It is thought to be suppressed.
On the other hand, when at least two terminal organic residues of the polyalkylene glycol chain adsorb to the same metal particle, the same metal compound particle, or the same metal ion, the organic group of at least two terminals of the polyalkylene glycol chain Residues are fixed to one particle or ion, the polyalkylene glycol chain forms a loop structure, and the polyalkylene glycol chain having the loop structure is placed between layers of a layered compound such as cement or clay due to a reduction in freedom of movement. It is thought that entering is suppressed more.
The loop structure is a structure in which at least two terminal organic residues of the polyalkylene glycol chain are adsorbed on the same particle, so that the polyalkylene glycol chain connecting between the two ends forms a ring.

Among the above metal compounds, there are those of layered compounds having a multilayer structure, and when organic residues at at least two terminals of the polyalkylene glycol chain are adsorbed on the same particles of the layered metal compound, At least two terminal organic residues of the polyalkylene glycol chain may be adsorbed on the same layer of metal compound particles, or may be adsorbed across two different layers. In any case, since the polyalkylene glycol chain of the organic residue-containing polyalkylene glycol compound forms a loop structure on the surface of the metal compound particle, the polyalkylene glycol chain is reduced due to a decrease in freedom of movement. It is considered that the penetration of the layered compound such as cement or clay is further suppressed.

When at least two terminal organic residues of the polyalkylene glycol chain are adsorbed to the metal, metal compound and metal ion contained in the cement, the polyalkylene glycol chain is suppressed from entering between layers of the layered compound, Since a water retention effect is provided near the surface of the cement particles, an excellent drying shrinkage reduction performance can be exhibited with a small amount of cement additive.

The organic residue has at least one functional group selected from the group consisting of a carbonyl group, a hydroxyl group, an amino group, a thiol group, a phosphoric acid group, a phosphorous acid group, and a silane group, and a vinyl monomer It is a group having no carbon-carbon bond derived from the body.
The functional group has an electron donating group having a lone electron pair, and forms a coordination bond with at least one of a metal, a metal compound, and a metal ion, thereby forming at least one of the metal, the metal compound, and the metal ion. Can be adsorbed.

The organic residue preferably has a plurality of functional groups exhibiting adsorption ability for at least one of a metal, a metal compound, and a metal ion. The functional group is more preferably an electron donating group.
When one organic residue has a plurality of electron donating groups, the organic residue can be coordinated to at least one of a metal, a metal compound, and a metal ion through a plurality of coordination sites. That is, the organic residue can bind to at least one of a metal, a metal compound, and a metal ion more strongly due to a chelate effect, and thus is more excellent in the cement dispersion performance deterioration suppressing effect and the drying shrinkage reducing performance of the cement additive. It will be a thing.

The number of functional groups per organic residue is preferably 1-12. More preferably, it is 2-12. When the number of functional groups of the organic residue is 2 to 12, the organic residue and at least one of a metal, a metal compound, and a metal ion can be bonded more strongly. More preferably, it is 3-12.

The organic residue is a group having a molecular weight of 700 or less. If the molecular weight of the organic residue is 700 or less, even if the amount of the cement additive used is small, the effects of the present application such as the suppression of lowering of the cement dispersion performance and the reduction of drying shrinkage can be efficiently exhibited. The molecular weight of the organic residue is preferably 500 or less, more preferably 300 or less, and still more preferably 200 or less. The molecular weight of the organic residue is preferably 40 or more, more preferably 60 or more, still more preferably 80 or more, and particularly preferably 100 or more.

The organic residue of the organic residue-containing polyalkylene glycol compound of the present invention preferably has any of a carbonyl group, a hydroxyl group, an amino group, a phosphoric acid group, or a silane group among the functional groups. More preferably, it has any of a carbonyl group, a hydroxyl group, an amino group, or a phosphate group.

The organic residue having the carbonyl group is not particularly limited as long as it has a carbonyl group, and includes an organic residue having a functional group containing a carbonyl group in the structure such as a carboxyl group, an aldehyde group, an ester group, an amide group, or the like. . The functional group having a carbonyl group is preferably a carboxyl group or an amide group.

The organic residue preferably has at least two functional groups selected from the group consisting of a carbonyl group, a hydroxyl group, an amino group, a thiol group, a phosphoric acid group, a phosphorous acid group, and a silane group. Since such an organic residue can bind to at least one of a metal, a metal compound, and a metal ion more strongly due to a chelate effect, the cement additive is more excellent in suppressing the cement dispersion performance and reducing the drying shrinkage. It will be a thing.

The organic residue is not limited as long as it exhibits an adsorbing ability to at least one of a metal, a metal compound, and a metal ion, but the organic residue preferably has a catechol structure. The organic residue preferably has a pyrrolidone structure. Furthermore, the organic residue preferably has a gluconic acid structure.

It can be confirmed by the following method that the organic residue exhibits an adsorbing ability with respect to at least one of a metal, a metal compound, and a metal ion.
The organic residue-containing polyalkylene glycol compound adsorbed to the metal or the like is filtered off after the organic residue-containing polyalkylene glycol compound and the metal, metal compound or metal ion are dispersed in the solution and then filtered. Is done. Therefore, by conducting quantitative analysis of the total amount of organic carbon in the filtrate and quantifying the organic residue-containing polyalkylene glycol compound that is not adsorbed with the metals etc. contained in the filtrate, The proportion of the organic residue-containing polyalkylene glycol compound adsorbed with the metal or the like with respect to the glycol compound can be determined, and the adsorption ability can be confirmed.

The compound in which an organic residue is bonded to at least two ends of the linear or branched polyalkylene glycol chain of the present invention will be described in detail below on at least two ends of the linear or branched polyalkylene glycol chain. It can be obtained by combining compounds that give organic residues.

The organic residue is a residue formed by bonding a compound that gives an organic residue to the end of a polyalkylene glycol chain, and the compound that gives the organic residue is not particularly a vinyl monomer. Although it does not restrict | limit, Specifically, the following compounds are mentioned.
Amines such as ethylenediamine, diethylenetriamine, triaminotriethylamine, triethylenetetramine, N, N, N ′, N′-tetrakis (2-pyridylmethyl) ethylenediamine; ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, tetra Ethylenepentamine heptaacetic acid, glycol ether diamine tetraacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediamine-N-monoacetic acid, ethylenediamine-N, N'-diacetic acid, ethylenediamine-N, N'-dipropionic acid, N- ( 2-hydroxyethyl) -ethylenediamine-N, N ′, N′-triacetic acid, N, N′-bis (2-hydroxybenzyl) -ethylenediamine-N, N′-diacetic acid, ethylenediamine-N, N, N ′ , N'- Tetrapropionic acid, o,
o′-bis (2-aminophenyl) ethylene glycol-N, N,
N ′, N′-tetraacetic acid, o, o-bis (2-aminoethyl) ethylene glycol-N, N, N ′, N′-tetraacetic acid, glycine, N, N-bis (2-hydroxyethyl) glycine , Trans-1,2-cyclohexanediamine-N, N, N ′, N′-tetraacetic acid, 1,3-diamino-2-hydroxypropane-N, N, N ′, N′-tetraacetic acid, diethylenetriamine-N , N, N ′, N ″, N ″ -pentaacetic acid, 1,6-hexamethylenediamine-N, N, N ′, N′-tetraacetic acid, iminodiacetic acid, N- (2-hydroxyethyl) iminodi Acetic acid, 1,2-diaminopropane-N, N, N ′, N′-tetraacetic acid, triethylenetetramine-N, N, N ′, N ″, N ′ ″, N ′ ″-hexaacetic acid, Aminocarboxylic acids such as glutamic acid, aspartic acid and aminosuccinic acid; triethanolamine Hydroxy amines;

Tartaric acid, citric acid, 2,5-dihydroxy-tetrahydrofuran-2,3,4,5-tetracarboxylic acid, 5-hydroxy-cyclohexane-1,2,3,4-tetracarboxylic acid, 6-hydroxy-tetrahydrofuran-2 , 3,4,5-tetracarboxylic acid, 1,4-dihydroxy-butane-1,1 ′, 4,4′-tetracarboxylic acid, 1,3-dihydroxy-propane-1,1 ′, 3,3 ′ -Hydroxycarboxylic acids such as tetracarboxylic acid, 2- (4-hydroxyphenyl) -propane-1,1 ', 3,3'-tetracarboxylic acid; hydroxyaminocarboxylic acids such as bicine; oxalic acid, maleic acid, succinic acid Acid, 3-butene-1,2,3-tricarboxylic acid, benzene-1,2,4-tricarboxylic acid, 1,2,3,4,5,6-cyclohexanehexacarboxylic acid, etc. Rubonic acids; polyols such as gluconic acid, glucosamic acid, glucoheptonic acid lactone, gluconic acid lactone; tyrone, salicylic acid, sulfosalicylic acid, pyrogallol carboxylic acid, alizarin S, alizarin complexone, kojic acid, 3- (3,4 -Dihydroxyphenyl) -phenols such as L-alanine, 3-hydroxytyramine, DL-adrenaline; imidazoles such as histidine; pyrrolidones such as N-hydroxyethylpyrrolidone; ethylenediamine-N, N, N ′, N′— Aminophosphoric acids such as tetrakis (methylenephosphonic acid) and nitrilotris (methylenephosphonic acid); phosphates; phosphites; phosphonates; phosphinates; 2,3-dimercaptopropanol, unthiol, thioglycolic acid, β- Thiols such as lucaptopropionic acid, dimercaptosuccinic acid, aminoethyl mercaptan, thiooxalic acid, cysteamine; sulfurs such as sodium diethyldithiocarbamate, thiourea, thiocarbazide, thiosemicarbazide; monoalkoxysilane, dialkoxysilane, trialkoxysilane , Silanes such as acyloxysilane and triacyloxysilane;
o-phenanthroline; acetylacetone; eriochrome black T, 1- (2-hydroxy-4-sulfo-1-naphthylazo) -2-hydroxy-3-naphthoic acid, hydroxynaphthol blue, chalcone, eriochrome blue black B O, o'-dihydroxyazos such as Eriochrome Blue SE and Eriochrome Red B; 1-pyridylazo-2-naphthol, 4- (2-pyridylazo) -resorcin, 2- (2-pyridylazo) -p -Cresol, 1- (2-thiazolylazo) -2-naphthol, 4- (2-thiazolylazo) -resorcin, 2- (2-thiazolylazo) -p-cresol, trin, neotrin, 3- (4-sulfophenylazo) -4,5-dihydroxynaphthalene-2,7-disulfonic acid sodium Salts, hydroxy azo such as naphthyl azo relaxin;

Cresolephthalein complexone, thymolphthalein complexone, xylenol orange, methylthymol blue, pyrocatechol violet, pyrogallol red, brompyrogallol red, chromazurol S, eriochrome cyanine R, glycine thymol blue, glycine resole red, etc. Phthalein and triphenylmethanes; murexide; ginsone; thiourea; dithizone; glyoxal bis (2-hydroxyanil); N-benzoyl-N-phenylhydroxylamine; galocyanine; hematoxylin; ferron; calcein, calcein blue, fluoxin , Fluorescent metal indicators such as Anisidine Blue, Stilbene Fluoro Blue S, Morin; Variamin Blue B Base, Bind Shedra In introducing the organic residue at the terminal of the polyalkylene glycol such as redox indicator such as Sgreen / leuco base, 3,3′-dimethylnaphthidine, cacothelin, diphenylcarbazide, diphenylcarbazone, etc. Species or two or more can be used. Among these derivatives of the above compounds, polyalkylene glycol, modified polyalkylene glycol, which will be described later, a compound having a functional group capable of reacting with polyalkylene glycol having an organic residue bonded to one end can be used. .

The organic residue has a structure derived from aminocarboxylic acids, phenols, polyols, pyrrolidones or polycarboxylic acids, that is, aminocarboxylic acids, phenols, polyols, pyrrolidones or polycarboxylic acids are polyalkylenes. It preferably has a residue formed by binding to the end of a glycol chain. More preferably, it has a structure derived from aminocarboxylic acids or phenols.
Among residues derived from aminocarboxylic acids or phenols, aspartic acid, 3- (3,4-dihydroxyphenyl) -L-alanine, 3-hydroxytyramine or DL-adrenaline is bonded to the polyalkylene glycol chain end. More preferably, it is a residue formed by binding aspartic acid or 3-hydroxytyramine to the polyalkylene glycol chain end.
In the case where 3-hydroxytyramine is used as the compound that gives the organic residue, among the total cement additive when 1% by mass of the cement additive of the present invention is added to 100% by mass of the metal, metal Since the ratio (adsorption rate) of what is adsorbed to the metal compound or metal ion is as high as 96%, the cement dispersibility is excellent.

The method for bonding the compound that gives an organic residue to the terminal of the polyalkylene glycol chain is not particularly limited, and a commonly used method can be employed. For example, when the compound giving an organic residue has a carboxyl group (for example, aminocarboxylic acids, hydroxycarboxylic acids, polycarboxylic acids), the organic residue is introduced by an esterification reaction with a hydroxyl group at a polyalkylene glycol terminal. be able to.
In addition, a modified polyalkylene glycol in which a reactive functional group such as an amino group, a carboxyl group, or an epoxy group is introduced at the terminal of the polyalkylene glycol, and a carboxyl group, a hydroxyl group, an amino group, or the like of a compound that gives an organic residue or a derivative thereof Can be introduced with an amide bond, an ester bond, a covalent bond, or the like. As for these, for example, an epoxy group such as polyethylene glycol diglycidyl ether and an amino group such as aspartic acid and 3-hydroxytyramine are reacted to bond them. In addition, if necessary, the hydroxyl group at the other end of the polyalkylene glycol having an organic residue bonded to one end obtained by adding alkylene oxide to the hydroxyl group, amino group, etc. of the compound giving an organic residue. A polyalkylene glycol in which an organic residue is bonded to both ends of the present invention by introducing an amino group, a carboxyl group, an epoxy group, or the like, and further reacting these functional groups with a compound that newly gives the organic residue. You can also get

It is also useful to introduce a phosphonate group by reacting a compound having a phosphonate group at the polyalkylene glycol terminal. In this case, it is preferable to introduce a phosphonate group at two terminals of the polyalkylene glycol, and such a compound is represented by the following formula (1). This compound can be obtained, for example, by a Mannich reaction between α, ω-diaminopolyalkylene glycol, formaldehyde and phosphorous acid.
R ¹ R ² NCH ₂ CH ₂ (OA) _n CH ₂ CH ₂ R ³ R ⁴ (1)
(In the formula, A, identical or ^{different, .R 1, R 2, R} 3 and ^{R 4} representing an alkylene group having 2 to 18 carbon atoms, _-CH 2 -PO independently _{(OM q) 2} or -R ⁵ , wherein at least one of R ¹ and R ² is —CH ₂ —PO (OM _q ) ₂ , and at least one of R ³ and R ⁴ is —CH ₂ —PO (OM) ₂ . R ⁵ represents a hydrogen atom or an unsaturated or saturated hydrocarbon residue, and M is the same or different and each represents a hydrogen atom, an alkali metal, an alkaline earth metal, an amine, and / or an organic amine residue. Is 1 when M is any of a hydrogen atom, an alkali metal, an alkaline earth metal, an amine and / or an organic amine residue, and is 1/2 when M is an alkaline earth metal.)

A in the above formula (1) is preferably an ethylene group and / or a propylene group, and more preferably an ethylene group.
R ⁵ in the above formula (1) is preferably an alkyl group having 1 to 15 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.

When the silane group is introduced by reacting a compound having a silane group at the terminal of the polyalkylene glycol, among the compounds having a silane group, an alkoxysilane having 1 to 10 carbon atoms is preferable, and trialkoxysilane is more preferable. Among them, a compound having a -Si _{(OMe) 3} and / or -Si _(OCH 2 _{CH 3)} 3 is particularly preferred. Examples of the synthesis of such a compound include a reaction of 3- (trialkoxysilyl) propyl isocyanate with polyalkylene glycol or polyalkylene glycol diamine. In the reaction of an isocyanate group with an amine or hydroxy group, a urea or urethane bond is formed, respectively.

When the polyalkylene glycol chain is branched, it has two main chain ends and a branched chain end, so that there are three or more ends. Therefore, it is only necessary that at least two of these ends are modified with an organic residue by introducing an organic residue by reacting the compound that gives the organic residue with at least two ends. The modification rate by the organic residue of the branched polyalkylene glycol chain of the present invention is preferably 20% or more, more preferably 40% or more, more preferably several hundred% of all terminals of the branched polyalkylene glycol chain. Preferably it is 60% or more, particularly preferably 80% or more, and most preferably 100%. If the modification rate of the branched polyalkylene glycol chain of the present invention by an organic residue is 20% or more, cement or clay can be dispersed with a smaller amount of cement additive added, and further exhibits a reduction in drying shrinkage. can do.

The structure of the polyalkylene glycol chain of the organic residue-containing polyalkylene glycol compound of the present invention may be linear or branched. Moreover, you may have 2 or more types of polyalkylene oxide.
The polyalkylene glycol chain of the organic residue-containing polyalkylene glycol compound of the present invention is preferably a polymer chain (polyalkylene oxide) composed of an oxyalkylene group having 2 to 18 carbon atoms. More preferably, carbon number of an oxyalkylene group is the range of 2-8, More preferably, it is the range of 2-4.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, trimethylethylene oxide, tetramethylene oxide, tetramethylethylene oxide, butadiene monooxide, and octylene oxide. It is done. In addition, aliphatic epoxides such as dipentane ethylene oxide and dihexane ethylene oxide; alicyclic epoxides such as trimethylene oxide, tetramethylene oxide, tetrahydrofuran, tetrahydropyran, and octylene oxide; aromatics such as styrene oxide and 1,1-diphenylethylene oxide Epoxides and the like can also be used.

The polyalkylene glycol chain preferably contains an oxyethylene group as an essential component in the oxyalkylene group from the viewpoint of a balance between hydrophilicity and hydrophobicity. The oxyethylene group in 100 mol% of the total alkylene oxide is more preferably 60 mol% or more, further preferably 80 mol% or more, and particularly preferably 90 mol% or more.

The average added mole number of the oxyalkylene group is preferably in the range of 1 to 1000, more preferably 5 or more, further preferably 10 or more, particularly preferably 20 or more, more preferably 800 or less, still more preferably. Is 600 or less, particularly preferably 400 or less.

When the polyalkylene glycol chain is branched, for example, a branched polyalkylene glycol is synthesized by a method in which an alkylene oxide is sequentially added to a polyhydric alcohol such as trimethylolpropane, glycerin, polyglycerin, or polyglycidol. be able to.

When the polyalkylene glycol chain is composed of two or more alkylene oxides, two or more alkylene oxides may be added in any form such as random addition, block addition, and alternate addition.

The organic residue-containing polyalkylene glycol compound of the present invention preferably has a weight average molecular weight of 100,000 or less. More preferably, the weight average molecular weight is 80000 or less, more preferably 60000 or less, particularly preferably 40000 or less, still more preferably 20000 or less, and most preferably 10,000 or less. The weight average molecular weight is preferably 200 or more.
A weight average molecular weight can be measured by the method as described in an Example.

The metal adsorbed by the organic residues at at least two terminals of the polyalkylene glycol chain of the organic residue-containing polyalkylene glycol compound is not particularly limited. For example, typical elements and groups 8, 9 and 10 of the periodic table are included. And metals classified as group 11 and group 11 transition elements. Preferably, an alkali metal, an alkaline earth metal, a metal element of Group 8, 10, 11, 12, 12, 13, or the like of the periodic table can be used, and more preferably, an alkali metal, an alkaline earth, or the like. Base metals such as metal, zinc, aluminum and iron.

The metal compound to which the organic residue is adsorbed is not particularly limited, and examples thereof include CaCO ₃ , SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , and CaSO ₄ . Moreover, cement and clay are mentioned. The cement is iron aluminate tetracalcium C ₄ AF (4CaO · Al ₂ O ₃ · Fe ₂ O ₃ ), tricalcium aluminate C ₃ A (3CaO · Al ₂ O ₃ ), dicalcium silicate C ₂ S (2CaO). - including _SiO 2), the tricalcium silicate _{C 3 S (3CaO · SiO 2} ) as a main component. Clay includes clay minerals having a layered structure and clay minerals having no layered structure such as imogolite and allophane. In this specification, any clay is included. Examples of clay minerals having a layered structure include swellable minerals such as smectite, vermiculite, montmorillonite, bentonite, illite, hectorite, halloysite, mica and brittle mica; kaolin mineral (kaolinite), serpentine, pyrophyllite, talc, chlorite Non-swelling minerals such as light can be mentioned. Among these, the cement additive of the present invention is more preferably used for cement, more preferably used for clay made of clay mineral having a layered structure, and together with cement in the presence of clay made of clay mineral having a layered structure. More preferably, montmorillonite is more preferable as the clay.

The montmorillonite is a kind of silicate mineral represented by the following formula (2), and includes an alumosilicate layer and a metal ion layer (where metal ions are hydrated and not hydrated). Viscosity mineral (clay) having a multilayer structure.
M _X (Mg, Al, Fe) ₂ (OH) ₂ [Si ₄ O ₁₀ ] · nH ₂ O (2)
(In the formula, M represents Na, K, Mg or Ca. _X is 1 when M is Na or K, and is 1/2 when M is Mg or Ca.)

Although the metal ion which the said organic residue adsorb | sucks is not restrict | limited in particular, For example, the ion of the metal classified into a typical element and the transition element of the 8th group, the 9th group, the 10th group, and the 11th group of a periodic table is mentioned. Preferred examples include ions of alkali metals, alkaline earth metals, and metal elements of Group 8, Group 10, Group 11, Group 12, Group 13 and Group 14 of the periodic table, and more preferably, alkali metal, alkali Ions of base metals such as earth metals, zinc, aluminum and iron.

The metal ion may be a metal ion present on the surface of clay or the like contained in the cement composition. For example, when there is a layer of montmorillonite metal ions on the surface of montmorillonite contained in the cement composition, Na ⁺ , K ⁺ , Ca ²⁺ , and Mg ²⁺ may exist.

≪Cement composition≫
The present invention is also a cement composition containing the cement additive of the present invention and cement as essential components. In the cement composition, at least two organic residues of a compound in which an organic residue is bonded to at least two ends of a linear or branched polyalkylene glycol chain in a cement additive are a metal, a metal compound, and a metal. A form that adsorbs to at least two of the ions is preferred.
As described above, the cement additive of the present invention is one in which the polyalkylene glycol chain of the organic residue-containing polyalkylene glycol compound is suppressed from entering between layers of a layered compound such as cement or clay. The cement composition can exhibit sufficient water reduction performance and drying shrinkage reduction performance only by containing a small amount of cement additive.

The metal particles, metal compound particles, and metal ions are contained in cement or clay contained in the cement composition and are not particularly limited, but specific examples thereof include the above-described organic residue-containing polyalkylene glycol compounds. It is the same as the metal, metal compound, and metal ion whose organic residue has an adsorption ability.

Although it does not specifically limit as said cement, For example, Portland cement (ordinary, early strength, very early strength, moderate heat, sulfate resistance, and each low alkali type), various mixed cements (blast furnace cement, silica cement, fly ash cement) ), White Portland cement, alumina cement, super fast cement (1 clinker fast cement, 2 clinker fast cement, magnesium phosphate cement), grout cement, oil well cement, low heat cement (low heat blast furnace cement, fly ash) Mixed low heat generation type blast furnace cement, cement with high belite content), ultra-high strength cement, cement-based solidified material, eco-cement (cement manufactured from one or more of municipal waste incineration ash and sewage sludge incineration ash) In addition, blast furnace slag, fly ash , Cinder ash, clinker ash, husk ash, silica fume, silica powder, may be added fine powders or gypsum limestone powder.

The cement composition of the present invention may contain clay such as montmorillonite, which is a layered compound. Even when the cement composition contains clay, the organic residue-containing polyalkylene glycol compound of the present invention is a clay. By adsorbing on the surface, the penetration of the polyalkylene glycol chain between the clay layers is suppressed.
As described above, the organic residue-containing polyalkylene glycol compound of the present invention is characterized in that the polyalkylene glycol chain can be inhibited from intercalating between the layers of the layered compound, and is used in a cement composition containing a large amount of the layered compound. More effective. That is, it is one of the preferred embodiments of the cement composition of the present invention that the cement composition of the present invention contains clay such as montmorillonite which is a layered compound.

The cement composition of the present invention may be a hydraulic composition using a hydraulic material other than cement. The cement additive (or organic residue-containing polyalkylene glycol compound) of the present invention is also effective for a hydraulic composition using a hydraulic material other than cement, specifically, for the cement additive of the present invention. The hydraulic composition etc. which require a compound and a gypsum are mentioned. Moreover, the cement composition of the present invention may further contain water, and by containing water, hydraulic properties are exhibited and hardened. The cement composition of the present invention may contain fine aggregate (sand, etc.), coarse aggregate (crushed stone, etc.) and the like as necessary. Specific examples of such a cement composition include cement paste, mortar, concrete, plaster and the like.

As the above aggregate, in addition to gravel, crushed stone, granulated slag, recycled aggregate, etc., siliceous, clay, zircon, high alumina, silicon carbide, graphite, chrome, chromic, magnesia, etc. The refractory aggregate can be used. In the cement composition containing the compound of the present invention, the unit water amount per 1 m ³ , the amount of cement used and the water / cement ratio are not particularly limited, and the unit water amount is 100 to 185 kg / m ³ , the amount of cement used is 250 to 800 kg / m ³ , water / cement ratio = 10 to 70% by weight, preferably unit water amount 120 to 175 kg / m ³ , used cement amount 270 to 800 kg / m ³ , water / cement ratio = 20 to 65% is recommended, poor blending It can be used in a wide range of to rich blends, and is effective for both high-strength concrete with a large amount of unit cement and poor blend concrete with a unit cement amount of 300 kg / m ³ or less.

In the cement composition containing the organic residue-containing polyalkylene glycol compound of the present invention, the blending ratio of the above compound is not particularly limited, but when used for mortar, concrete, etc. using hydraulic cement, the cement weight 0.01 to 3.0%, preferably 0.02 to 2.0%, more preferably 0.05 to 1.0%. By this addition, various preferable effects such as reduction in unit water amount, increase in strength, and improvement in durability are brought about. If the blending ratio is less than 0.01%, the performance is insufficient, and conversely, even if a large amount exceeding 3.0% is used, the effect is practically peaked and disadvantageous in terms of economy. If the blending ratio is 0.01 to 3.0%, such a problem can be sufficiently suppressed.

The cement additive of the present invention essentially comprises the above-mentioned organic residue-containing polyalkylene glycol compound, and only the organic residue-containing polyalkylene glycol compound can be a cement additive, but further contains an antifoaming agent. Sometimes. By adding an antifoaming agent, the change with time of the entrained air amount can be reduced. If the amount of entrained air is too small, the freeze-thaw cycle resistance will deteriorate, and if the amount of entrained air is too large, the concrete strength will be low, so it is necessary to keep the entrained air at a constant amount. By using it, the amount of entrained air can be maintained stably over time, and concrete with stable quality can be supplied.

The antifoaming agent is not particularly limited as long as it is a commonly used antifoaming agent. For example, mineral oil-based antifoaming agents such as coconut oil and liquid paraffin; fat and oil-based antifoaming agents such as animal and vegetable oils, sesame oil, castor oil, and their alkylene oxide adducts; fatty acids such as oleic acid, stearic acid, and these alkylene oxide adducts Defoaming agents: fatty acid esters such as diethylene glycol monolaurate, glycerin monoricinoleate, alkenyl succinic acid derivatives, sorbitol monolaurate, sorbitol trioleate, polyoxyethylene monolaurate, polyoxyethylene sorbitol monolaurate, natural wax Antifoaming agents; alcohol-based antifoaming agents such as octyl alcohol, hexadecyl alcohol, acetylene alcohol, glycols, and polyoxyalkylene glycol; amide-based antifoaming agents such as polyoxyalkylene amide and acrylate polyamine Agents: Phosphate ester defoamers such as tributyl phosphate and sodium octyl phosphate; Metal soap defoamers such as aluminum stearate and calcium oleate; Silicon oil, silicone paste, silicone emulsion, organic modified polysiloxane, fluoro Examples thereof include silicon-based antifoaming agents such as silicone oil; oxyalkylene-based antifoaming agents such as polyoxyethylene polyoxypropylene adducts, and the like, and one or more of these can be used.

Among the antifoaming agents exemplified above, oxyalkylene antifoaming agents are preferable. This is because when the compound for cement additive of the present invention and the oxyalkylene-based antifoaming agent are used in combination, the amount of antifoaming agent used is small, and the compatibility between the antifoaming agent and the copolymer is excellent. . The oxyalkylene-based antifoaming agent is not particularly limited as long as it is a compound having an oxyalkylene group in the molecule and an effect of reducing bubbles in an aqueous liquid, and among them, it is represented by the following formula (3). Certain oxyalkylene antifoaming agents are preferred.
^{R 1 {-T- (R 2 O} ) t-R 3} n (3)
Wherein R ¹ and R ³ are each independently hydrogen, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 1 to 22 carbon atoms, an alkynyl group having 1 to 22 carbon atoms, a phenyl group or an alkylphenyl group. (The carbon number of the alkyl group in the alkylphenyl group is 1 to 22), and R ² O represents one kind or a mixture of two or more kinds of oxyalkylene groups having 2 to 4 carbon atoms, and two or more kinds. In this case, it may be added in blocks or randomly, and t is the average number of moles of oxyalkylene group added, and represents a number from 0 to 300. When t is 0, R ¹ and R ³ are not simultaneously hydrogen, T represents a group of —O—, —CO ₂ —, —SO ₄ —, —PO ₄ — or —NH—, and n is an integer of 1 or 2 And when R ¹ is hydrogen, n is 1.)

Examples of the oxyalkylene-based antifoaming agent represented by the above formula (3) include polyoxyalkylenes such as (poly) oxyethylene (poly) oxypropylene adducts; diethylene glycol heptyl ether, polyoxyethylene oleyl ether, poly (Poly) oxyalkylene alkyl ethers such as oxypropylene butyl ether, polyoxyethylene polyoxypropylene-2-ethylhexyl ether, oxyethylene oxypropylene adducts to higher 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-3-hexyne Acetylene ethers obtained by addition polymerization of alkylene oxide to acetylene alcohols such as 2,5-diol and 3-methyl-1-butyn-3-ol; diethylene glycol oleate, diethylene glycol laurate, ethylene glycol distearate, etc. (Poly) oxyalkylene fatty acid esters; (Poly) oxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan trioleate; polyoxypropylene methyl ether sodium sulfate, polyoxyethylene dodecylphenol (Poly) oxyalkylene alkyl (aryl) ether sulfate esters such as sodium ether sulfate; (poly) oxyethylenes (Poly) oxyalkylene alkyl phosphates such as allyl phosphate; (poly) oxyalkylene alkyl amines such as polyoxyethylene laurylamine; and the like, and one or more of these can be used. .

When the antifoaming agent is contained, the content thereof is preferably 0.01 to 300% by weight, and 0.5 to 200% by weight, based on 100% by weight of the organic residue-containing polyalkylene glycol compound of the present invention. Is more preferable, and it is further more preferable that it is 1 to 100 weight%.

The cement additive of the present invention (or organic residue-containing polyalkylene glycol compound) is effective for concrete for concrete secondary products, concrete for centrifugal molding, concrete for vibration compaction, steam-cured concrete, shotcrete, etc. Furthermore, it is also effective for mortar and concrete that require high fluidity, such as high fluidity concrete, self-filling concrete, and self-leveling material. The compound of the present invention can be used as a main component of a cement admixture as it is in the form of an aqueous solution, but is dried after neutralizing with a divalent metal hydroxide such as calcium or magnesium to obtain a polyvalent metal salt. Or may be used after being powdered by being supported on an inorganic powder such as silica-based fine powder and drying.

The cement additive (or organic residue-containing polyalkylene glycol compound) of the present invention may be further used in combination with a commonly used cement dispersant. The commonly used cement dispersant that can be used in combination is not particularly limited, and various sulfonic acid-based dispersants having a sulfonic acid group in the molecule, and various polycarboxylic acids having a polyoxyalkylene chain and a carboxyl group in the molecule. System dispersants. As the sulfonic acid-based dispersant, for example,
Examples include lignin sulfonates; polyol derivatives; naphthalene sulfonic acid formalin condensates; melamine sulfonic acid formalin condensates; polystyrene sulfonates; amino sulfonic acid series such as aminoaryl sulfonic acid-phenol-formaldehyde condensates. Examples of the polycarboxylic acid-based dispersant include a polyalkylene glycol mono (meth) acrylate ester having a polyoxyalkylene chain in which an alkylene oxide having 2 to 18 carbon atoms is added in an average addition mole number of 2 to 300. A copolymer obtained by copolymerizing a monomer component containing a monomer and a (meth) acrylic acid monomer as essential components; an alkylene oxide having 2 to 18 carbon atoms in an average addition mole number of 2 to 300 The essential component is a polyalkylene glycol mono (meth) acrylate monomer having an added polyoxyalkylene chain, a (meth) acrylic acid monomer and a (meth) acrylic acid alkyl ester. A copolymer obtained by copolymerizing the monomer components contained in the above; 2 to 300 additions of an alkylene oxide having 2 to 18 carbon atoms in average addition mole number Polyalkylene glycol mono (meth) acrylic acid ester monomer having a reoxyalkylene chain, (meth) acrylic acid monomer and (meth) allylsulfonic acid (salt) (or vinylsulfonic acid (salt), p A copolymer obtained by copolymerizing a monomer component containing three kinds of monomers as essential components with (meth) allyloxybenzenesulfonic acid (salt); Polyalkylene glycol mono (meth) acrylic acid ester monomer, (meth) acrylic acid monomer, and (meth) allylsulfonic acid having a polyoxyalkylene chain with an alkylene oxide added in an average addition mole number of 2 to 300 (Meth) acrylamide and / or 2- (meth) is further added to a copolymer obtained by copolymerizing a monomer component containing three kinds of monomers as essential components with (salt). Copolymer obtained by graft polymerization of chloramido-2-methylpropane sulfonic acid; polyalkylene glycol mono (meth) acrylic acid having a polyoxyalkylene chain obtained by adding 2 to 300 average addition moles of alkylene oxide having 2 to 18 carbon atoms Polyalkylene glycol mono (meth) allyl ether monomer having a polyoxyalkylene chain in which an ester monomer and an alkylene oxide having 2 to 18 carbon atoms are added in an average addition mole number of 2 to 300, and (meth) acrylic acid Copolymerization of monomer components containing four types of monomers as essential components: a series monomer and (meth) allylsulfonic acid (salt) (or p- (meth) allyloxybenzenesulfonic acid (salt)) Copolymer obtained by adding 2 to 300 average addition moles of alkylene oxide having 2 to 18 carbon atoms A copolymer obtained by copolymerizing a monomer component containing a polyalkylene glycol mono (meth) allyl ether monomer having a alkylene chain and a maleic acid monomer as essential components; As an essential component, a polyalkylene glycol mono (meth) allyl ether monomer having a polyoxyalkylene chain obtained by adding 2 to 300 of an average addition mole number of alkylene oxide and a polyalkylene glycol ester monomer of maleic acid A copolymer obtained by copolymerizing a monomer component containing; a polyalkylene glycol mono (meth) allyl ether having a polyoxyalkylene chain in which an alkylene oxide having 2 to 18 carbon atoms is added in an average addition mole number of 2 to 300 Copolymer of maleic monomer and maleic anhydride and polyoxyalkylene derivative having a hydroxyl group at the terminal A polyalkylene glycol mono (3-methyl-3-butenyl) ether monomer having a polyoxyalkylene chain in which an alkylene oxide having 2 to 18 carbon atoms is added in an average addition mole number of 2 to 300; A copolymer obtained by copolymerizing a monomer component containing a (meth) acrylic acid monomer as an essential component; a poly having an average addition mole number of 2 to 18 carbon atoms of an alkylene oxide Copolymer obtained by copolymerizing monomer component containing polyalkylene glycol mono (3-methyl-3-butenyl) ether monomer having oxyalkylene chain and maleic acid monomer as essential components And the like. In addition, a plurality of commonly used cement dispersants can be used in combination.

When the above commonly used cement dispersant is used in combination, the blending weight ratio between the organic residue-containing polyalkylene glycol compound of the present invention and the commonly used cement dispersant is the type of the commonly used cement dispersant to be used, Although it is not uniquely determined due to the difference in test conditions and the like, it is preferably in the range of 5:95 to 95: 5, more preferably 10:90 to 90:10.

The cement additive containing the organic residue-containing polyalkylene glycol compound of the present invention may be used in combination with other commonly used cement additives (materials) as exemplified in the following (1) to (10). it can. When other commonly used cement additives (materials) are used in combination, the blending weight ratio of the organic residue-containing polyalkylene glycol compound of the present invention to the other commonly used cement additives (materials) is the other used. Although it is not uniquely determined by the difference in the type, blending, and test conditions of a commonly used cement additive (material), it is preferably in the range of 5:95 to 99.9: 0.01.

(1) Water-soluble polymer substances: polyacrylic acid (sodium), polymethacrylic acid (sodium) polymaleic acid (sodium), unsaturated carboxylic acid polymer such as sodium salt of acrylic acid / maleic acid copolymer; polyethylene glycol , Polymers of polyoxyethylene such as polypropylene glycol, polyoxypropylene or copolymers thereof; nonionic cellulose ethers such as methylcellulose, ethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, carboxyethylcellulose, hydroxypropylcellulose; methylcellulose, ethylcellulose , Alkylated derivatives of polysaccharides such as hydroxyethyl cellulose, hydroxypropyl cellulose or hydroxyalkyl Hydrophobic substituents in which part or all of the hydroxyl groups of the derivative have a hydrocarbon chain having 8 to 40 carbon atoms as a partial structure and a sulfonic acid group or a salt thereof as a partial structure. A polysaccharide derivative substituted with a substituent; yeast glucan, xanthan gum, β-1.3 glucan (which may be linear or branched, for example, curdlan, baramilon, bakiman, scleroglucan Polysaccharides produced by microbial fermentation such as polyacrylamide, polyvinyl alcohol, starch, starch phosphate ester, sodium alginate, gelatin, copolymers of acrylic acid having amino groups in the molecule, and quaternary compounds thereof .

(2) Polymer emulsion: Copolymers of various vinyl monomers such as alkyl (meth) acrylate.
(3) retarder: oxycarboxylic such as gluconic acid, glucoheptonic acid, arabonic acid, malic acid or citric acid, and inorganic salts or organic salts thereof such as sodium, potassium, calcium, magnesium, ammonium, triethanolamine, etc. Acid; monosaccharides such as glucose, fructose, galactose, saccharose, xylose, abitose, repose, isomerized sugar, oligosaccharides such as disaccharides and trisaccharides, oligosaccharides such as dextrin, polysaccharides such as dextran, etc. Sugars such as molasses; sugar alcohols such as sorbitol; magnesium silicofluoride; phosphoric acid and its salts or borate esters; aminocarboxylic acids and salts thereof; alkali-soluble proteins; humic acid; tannic acid; Polyhydric alcohols such as glycerin; Phosphonic acid and derivatives thereof such as phonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and alkali metal salts and alkaline earth metal salts thereof etc.

(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
(Alkyl benzene sulfonic acid), LAS (linear alkyl benzene sulfonic acid), alkane sulfonate, polyoxyethylene alkyl (phenyl) ether, polyoxyethylene alkyl (phenyl) ether sulfate or salt thereof, polyoxyethylene alkyl (phenyl) ether phosphorus Acid esters or salts thereof, protein materials, alkenyl sulfosuccinic acid, α-olefin sulfonate and the like.

(6) Other surfactants: aliphatic monohydric alcohols having 6 to 30 carbon atoms in the molecule such as octadecyl alcohol and stearyl alcohol, and those having 6 to 30 carbon atoms in the molecule such as abiethyl alcohol Intramolecular such as alicyclic monohydric alcohol, dodecyl mercaptan, etc. Intramolecular such as monovalent mercaptan having 6-30 carbon atoms in the molecule, such as nonylphenol, alkylphenol having 6-30 carbon atoms in the molecule, dodecylamine, etc. 10 mol or more of an alkylene oxide such as ethylene oxide or propylene oxide was added to a carboxylic acid having 6 to 30 carbon atoms in the molecule such as an amine having 6 to 30 carbon atoms, lauric acid or stearic acid. Polyalkylene oxide derivatives having an alkyl group or an alkoxy group as a substituent Good alkyl diphenyl ether sulfonates in which two phenyl groups having a sulfone group are ether-bonded; various anionic surfactants; various cationic surfactants such as alkylamine acetate and alkyltrimethylammonium chloride; various nonionic interfaces Activators; 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 commonly used cement additives (materials) include, for example, cement wetting agents, thickeners, separation reducing agents, flocculants, drying shrinkage reducing agents, strength enhancing agents, self-leveling agents, rust preventives, and coloring agents. And fungicides.

The cement additive of the present invention has the above-described configuration, and is excellent in the cement dispersion performance lowering suppression effect and drying shrinkage reducing performance. Therefore, the cement dispersant used in cement compositions such as cement paste, mortar, and concrete or dry shrinkage reduction is used. It can be used as an agent.

It is a graph which shows dry shrinkage reduction performance evaluation of the cement composition using the cement additive of this invention.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.
In addition, about the analysis of the obtained compound for cement additives, it carried out as follows.

[Weight average molecular weight measurement conditions]
Device: Waters Alliance (2695)
Analysis software: Waters, Empor professional + GPC option column: Tosoh Co., Ltd., TSKguardcolumnsSWXL + TSKgelG4000SWXL + G3000SWXL + G2000SWXL
Detector: differential refractometer (RI) detector (Waters 2414), multi-wavelength visible ultraviolet (PDA) detector (Waters 2996)
Eluent: A solution prepared by dissolving 115.6 g of sodium acetate trihydrate in a mixed solvent of 10999 g of water and 6001 g of acetonitrile, and further adjusting the pH to 6.0 with acetic acid. Standard material for preparing a calibration curve: polyethylene glycol (peak top molecular weight (Mp 272, 500, 219300, 107000, 50000, 24000, 12600, 7100, 4250, 1470)
Calibration curve: Prepared by a cubic equation based on the Mp value and elution time of polyethylene glycol.
Flow rate: 1 mL / min Column temperature: 40 ° C
Measurement time: 45 minutes Sample injection volume 100 μL

Production Example 1
A 300 mL four-necked flask equipped with a stirring blade, thermometer, condenser, and dropping funnel was charged with 40.4 g of Denacol EX-861 (poly (n = 22) ethylene glycol diglycidyl ether; manufactured by Nagase ChemteX Corporation). The mixture was heated to an internal temperature of 50 ° C. and stirred. Here, 10.0 g of L-aspartic acid, 12.3 g of 48% sodium hydroxide aqueous solution, and 57.2 g of pure water were slowly added dropwise over 0.5 hours while maintaining the internal temperature at 50 ° C. The compound (1) of the present invention was obtained by further stirring for 2.5 hours.

Production Example 2
A 100 mL four-necked flask equipped with a stirring blade, a thermometer, a condenser tube, and a dropping funnel was charged with 10.7 g of Denacol EX-861 (poly (n = 22) ethylene glycol diglycidyl ether; manufactured by Nagase ChemteX Corporation), The mixture was heated to an internal temperature of 50 ° C. and stirred. While maintaining a mixed liquid of 3.5 g of 3-hydroxytyramine hydrochloride and 13.8 g of pure water at an internal temperature of 50 ° C. over 0.5 hours, the mixture was further stirred for 2.5 hours. The compound (2) of this invention was obtained.

Comparative production example 1
Unsaturated alcohol 127 in which 72.26 parts of ion-exchanged water and 50 mol of ethylene oxide were added to 3-methyl-3-buten-1-ol in a glass reaction vessel equipped with a thermometer, stirrer, dropping funnel and reflux condenser .74 parts was charged and the temperature was raised to 65 ° C., and then 0.71 part of a 30% aqueous hydrogen peroxide solution was added thereto, and 46.58 parts of a 40% aqueous acrylic acid solution was added for 3 hours to a 3-mercaptopropionic acid solution. 67 parts were added dropwise over 3 hours and 12.97 parts of an L-ascorbic acid 2.1% aqueous solution over 3.5 hours. Subsequently, the temperature was maintained at 65 ° C. for 60 minutes to complete the polymerization reaction, the temperature was lowered to 50 ° C. or less, and neutralized so that the pH was changed from pH 4 to pH 7 with 76.07 parts of a 12.2% aqueous solution of sodium hydroxide. A comparative compound (2) comprising a polymer aqueous solution having a weight average molecular weight of 29,000 was obtained.

[Preparation of mortar]
225 g of a predetermined amount of the compound of the present invention or comparative compound weighed and diluted with water, 450 g of ordinary Portland cement (manufactured by Taiheiyo Cement), standard sand for cement strength test (JIS R5201-1997, appendix 2, 5. According to JIS R5201-1997, mortar was kneaded using 1350 g of 13.3 g (specified by 1.3: Cement Association) using a Hobart type mortar mixer (manufactured by Hobart, model number: N-50), and the flow value was measured. It shows that the fluidity | liquidity of a mortar is so high that a flow value is large.
Moreover, it adjusted using the antifoamer (polyalkylene glycol derivative) as needed so that the amount of mortar air might be less than +/- 3 volume% with respect to the amount of air of the mortar (reference mortar) which does not add a polymer. . When using montmorillonite clay (bentonite: Kunigel V1 (manufactured by Kunimine Kogyo Co., Ltd.)), it was used by adding to standard sand.

[Measurement of mortar air volume]
The mortar air amount was measured using a 500 ml graduated cylinder according to JIS A1174 (unit volume mass test method of polymer cement mortar not yet solidified and test method based on weight of air amount (weight method)).

The measurement results of the mortar flow value are shown in Table 1.
Polyethylene glycol (Mw1000, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as the comparative compound (1).
The mortar flow value was measured under the following measurement conditions.
Water / cement ratio: 0.5
Cement / fine aggregate ratio: 1/3
Antifoaming agent: Oxyalkylene antifoaming agent

In Table 1 above, the addition amount of the compound represents a ratio with respect to 100% of the cement weight, and the addition amount of the antifoaming agent represents a ratio with respect to the addition amount of 100% of the compound.

In the compounds (1) and (2) of the present invention, the flow value is improved as compared with the case where no compound is added or polyethylene glycol (Mw1000) is added. In the compound (2) of the present invention, although the addition amount is small, the elongation of the flow value is large.

The mortar flow value when montmorillonite was added to the mortar was measured, and the influence of montmorillonite on the mortar flow value was investigated.
The results are shown in Table 2.
The measurement conditions are the same as the measurement of the mortar flow value.

In Table 2 above, the addition amount of the compound represents the ratio with respect to the weight of the cement of 100%, the addition amount of the clay represents the ratio with respect to the weight of the fine aggregate of 100%, and the addition amount of the antifoaming agent is the addition amount of the compound The ratio with respect to 100% is expressed.

In Comparative Compound (2), the flow value is reduced by 21% when clay is added compared to the case where no clay is added, whereas Compound (2) of the present invention has a flow value of 7% as compared with the case where no clay is added. The decline has remained.

Example 4
The drying shrinkage reduction performance was evaluated by the following evaluation method.
In the drying shrinkage reduction performance evaluation, the changes over time in shrinkage strain when the compound (1) of the present invention was added are shown in FIG.
For comparison, the same evaluation was performed when the compound of the present invention was not added.
[Method for evaluating drying shrinkage reduction performance]
The mortar was kneaded according to JIS A1129.
Next, preparation of a mortar specimen (4 × 4 × 16 cm) for evaluation of drying shrinkage reduction was performed according to JIS.
Carried out according to 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 in a container, sealed and stored at 20 ° C., and initial curing was performed. After 2 days, 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 5 days (water curing).
The specimen was measured according to JIS A1129-3 using a dial gauge (manufactured by West Japan Testing Machine Co., Ltd.). After wiping off the water on the surface of the specimen cured for 5 days in still water with a paper towel, the length was measured immediately, and the length at this point was used as a reference. 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.
The addition amount of the compound (1) of the present invention was 1.2% with respect to 100% of the cement weight.
FIG. 1 shows that when the compound of the present invention is added, the drying shrinkage is smaller than when no compound is added, and there is an effect of reducing the drying shrinkage.

Claims (5)

A polyalkylene glycol compound having an organic residue capable of adsorbing to at least one of a metal, a metal compound and a metal ion bonded to at least two ends of a linear or branched polyalkylene glycol chain;
The organic residue has at least one functional group selected from the group consisting of a carbonyl group, a hydroxyl group, an amino group, a thiol group, a phosphoric acid group, a phosphorous acid group, and a silane group, and a vinyl monomer A cement additive having a molecular weight of 700 or less and having no body-derived carbon-carbon bond. The organic residue has at least two functional groups selected from the group consisting of a carbonyl group, a hydroxyl group, an amino group, a thiol group, a phosphoric acid group, a phosphorous acid group, and a silane group. The cement additive according to 1. The cement additive according to claim 1 or 2, wherein the organic residue has a structure derived from aminocarboxylic acids or phenols. The cement additive according to any one of claims 1 to 3, wherein the organic residue has a catechol structure. A cement composition comprising the cement additive according to any one of claims 1 to 4 and cement as essential components.

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