Cement admixture and cement admixture composite

ES 2 396 047 T3

DESCRIPTION

Cement admixture and cement admixture compound.

TECHNICAL FIELD

The present invention relates to a cement additive and a cement additive compound. More particularly, the present invention relates to a cement additive and a cement additive compound capable of exhibiting high water-reducing performance and, furthermore, of providing cement compositions with excellent handling properties.

BACKGROUND TECHNIQUE

Cement admixtures comprising a polycarboxylic acid polymer have been widely used for cement compositions such as cement paste, mortar, and concrete. These are currently essential in the construction of civil engineering and building structures from a cement composition. Said cement additives are used as a water reducing agent. These increase the flowability of cement compositions to thereby reduce the water requirement of cement compositions and are therefore effective in improving the strength and durability of cementitious products. As such water reducing agents, polycarboxylic acid water reducing agents comprising polycarboxylic acid polymers as the main component, which are superior in water reducing performance to naphthalene and other conventional water reducing agents, have already led to good results in many cases as a high-range air-entraining and water-reducing additive.

However, cement admixtures are required to be capable not only of showing water reducing performance in such cement compositions, but also of improving the viscosity of cement compositions to thereby facilitate site work. of its manipulation. Therefore, it is required, in civil engineering construction sites and building structures, that they are not only capable of exhibiting water-reducing performance but also of providing a viscosity at such a level that works at the construction sites will be facilitated. its manipulation. If a cement admixture can show such performance characteristics, it will improve work efficiency in the construction of civil engineering and building structures.

With regard to these requirements, Japanese Patent Application Publication Kokai Hei-09-248438 proposes a dispersant to reduce the viscosity of hydraulic compositions such as cement. However, in construction sites, it is required to make the cement compositions easier to handle, and to have improved basic performances. Therefore, the provision of cement additives that meet these requirements has been requested.

JP-06-279082 describes cement additives which are polymers derived from monomers that are (meth) acrylic monoesters of polyoxyalkylene (PO) n1 (EO) n2 (PO) n3 moieties (PO = propylene oxide, EO = oxide ethylene). JP-09-248438 discloses a polymer in which a random polymerized chain of PO and / or BO (butylene oxide) and EO, or this random polymerized chain and an EO chain are introduced. JP-07-126053 describes a (meth) acrylic ester having a side chain in which there are two polyoxyalkylene blocks, these being a poly (oxyethylene) block and a poly (oxypropylene) block. Similarly, JP-10-194808 describes poly (oxyalkylene) diblock chains.

SUMMARY OF THE INVENTION

It is an object of the present invention, which has been carried out in view of the state of the art mentioned above, to provide a cement additive capable of improving the water-reducing capacity of cement compositions and increasing the strength and durability of cement products. cementation produced from them and capable, in addition, of adjusting the viscosity of said compositions to facilitate work at the sites where they are handled, as well as a cement additive compound.

In the course of research carried out by them in search of cement additives with excellent water-reducing capacity and improvement of workability, the inventors of the present invention first paid attention to the fact that a polycarboxylic acid polymer containing a polyethylene glycol chain can show water-reducing performance characteristics for cement compositions, and found that the viscosity of cement compositions is effectively improved by introducing an alkylene oxide site containing 3 or more carbon atoms in a middle position, which is a specified position of the polyethylene glycol chain and therefore , have come to a conclusion that the problems mentioned above can be solved by using the cement additive. The inventors of the present invention have also discovered that mixing two or more species of the aforementioned cement additives with another or mixing one or two or more species of the aforementioned cement additives with one or two or more species of other cement additives provides mixtures containing cement additives with various characteristics of respective cement additives, thus their capabilities are shown sufficiently and efficiently, and they have finally completed the present invention.

ES 2 396 047 T3 (1)

That is, the present invention relates to a cement additive comprising a polycarboxylic acid polymer, wherein said polycarboxylic acid polymer has a site represented by the following formula (1):

R² R¹

II · —c — c—

H. (CH₂)_x(CO) —or— (C₂H₄O) - (R³O) - (C₂H₄OR)_k—R⁴ (in which R¹ and R² they can be the same or different and each represents a hydrogen atom or a methyl group; R³ it can be the same or different and represents an alkylene group containing from 3 to 18 carbon atoms; x represents a number from 0 to 2; y represents 0 or 1; n and k represent an average molar addition number of an oxyethylene group, where n is a number from 1 to 200 and k is a number from 1 to 200; m represents an average molar addition number of the oxyalkylene group and is a number from 1 to 50; n + m + k is a number from 3 to 200; and R⁴represents a hydrogen atom or a hydrocarbon group containing 1 to 20 carbon atoms).

The present invention also relates to a cement additive composition comprising two or more species of cement additives, wherein at least one of the two or more species of cement additives is the cement additive.

DESCRIPTION OF THE INVENTION

Hereinafter, the present invention is described in detail.

The polycarboxylic acid polymer comprised in the cement additive of the present invention is a polymer comprising two or more carboxylic acids or carboxylate salts in a molecule and in which a specific structure represented by the following formula (1) is introduced in a site (remainder) that constitutes the polymer:

R² R¹

II —c — c— (1)

II

H (CHaVCO) —O— (C₂H₄O) - (R³O) - (C₂H₄OR)_k—R⁴ (in which R¹ and R² they can be the same or different and each represents a hydrogen atom or a methyl group; R³ it can be the same or different and represents an alkylene group containing from 3 to 18 carbon atoms; x represents a number from 0 to 2; y represents 0 or 1; n and k represent an average molar addition number of an oxyethylene group, where n is a number from 1 to 200 and k is a number from 1 to 200; m represents an average molar addition number of the oxyalkylene group and is a number from 1 to 50; n + m + k is a number from 3 to 200; and R⁴represents a hydrogen atom or a hydrocarbon group containing 1 to 20 carbon atoms).

The polyoxyalkylene chain represented by the repeating number of n, myk in the above formula (1) is a form of the so-called ABA block copolymer, and this specific structure is one of the factors for excellent water-reducing ability and a low viscosity. A is composed of oxyethylene with high hydrophilicity and B is composed of a hydrophobic oxyalkylene containing 3 to 18 carbon atoms, in which the hydrophobic part (the part represented as B) exists within the hydrophilic chain (the parts represented as TO). The present invention is characterized by having a hydrophobic part within this hydrophilic chain, thus exerting both water reducing capacity and low viscosity.

In the above-mentioned formula (1), n ​​and k can be the same or different and each represents a number from 1 to 200. If they exceed 200, the viscosity increases and the workability may deteriorate in some cases. Preferably they are 1 to 60, and more preferably they are 1 to 20. m represents a number from 1 to 50, and if it exceeds 50, the water reducing ability may deteriorate or the hydrophobicity may increase in some cases to result in incompatibility with mixing water to be added to the cement and lower workability. The range of m is preferably 1 to 20, more preferably 1 to 5, and even more preferably 1 to 3. n + m + k, which is a sum of n, m and k, is a number from 3 to 200. When n + m + k exceeds 200, the viscosity becomes high, and the workability may become bad. This is preferably a number from 5 to 120, more preferably a number from 5 to 100, and even more preferably a number from 5 to 50. R³ it can be the same or different and each represents an alkylene group containing 3 to 18 carbon atoms, and preferably represents a 2-methylethylene group (generally propylene oxide is a precursor) containing 3 carbon atoms. R⁴ represents a hydrogen atom or a hydrocarbon group containing 1 to 20 carbon atoms, and preferably represents a methyl group.

ES 2 396 047 T3 (2)

The polycarboxylic acid polymer essentially comprised in the present invention can be obtained by polymerizing, for example, one or two or more monomer species having a carboxylic acid or a carboxylate salt and a polymerizable double bond in one molecule and one or two or more monomer species represented by the following formula (2):

R² R¹II c = c

H (CH ^ / CO) —O ~ (C₂H₄O) - (R³O) - (C₂H₄OR)_k~ R⁴ (in which R¹ and R² they can be the same or different and each represents a hydrogen atom or a methyl group; R³ it can be the same or different and represents an alkylene group containing from 3 to 18 carbon atoms; x represents a number from 0 to 2; y represents 0 or 1; n and k represent an average molar addition number of an oxyethylene group, where n is a number from 1 to 200 and k is a number from 1 to 200; m represents an average molar addition number of the oxyalkylene group and is a number from 1 to 50; n + m + k is a number from 3 to 200; and R⁴represents a hydrogen atom or a hydrocarbon group containing 1 to 20 carbon atoms). In the case where a carboxylate salt is used, for example, an alkali metal salt, an alkaline earth metal salt or an ammonium salt can be used, and the above polycarboxylic acid polymer can be obtained by polymerizing these carboxylate salts or forming a salt after polymerizing carboxylic acid monomers.

The monomer represented by the above-mentioned formula (2) can be obtained by adding ethylene oxide in an appropriate amount to give the recommended repeating number to an unsaturated alcohol or an unsaturated carboxylic acid; adding alkylene oxide containing 3 to 18 carbon atoms in an appropriate amount to give the recommended repeating number; and adding ethylene oxide in an appropriate amount to give the recommended repeating number. Furthermore, the monomer can also be obtained by esterification of an alcohol, which is obtained by adding ethylene oxide in an appropriate amount to give the recommended repeating number to an alcohol or a phenol comprising a hydrocarbon group containing 1 to 20 atoms. of carbon, adding alkylene oxide of 3 to 18 carbon atoms in an appropriate amount to give the recommended repeating number, and adding ethylene oxide in an appropriate amount to give the recommended repeating number, with an exchange reaction of unsaturated carboxylic acid or alcohol ester with an unsaturated carboxylic acid ester.

The analytical technique of the copolymer in the present invention (side chain; For example, the side chain of (ethylene oxide) - (alkylene oxide containing 3 to 18 carbon atoms) - (ethylene oxide) in the above formula (1) and (2)) can be specified by combining spectrometry of nuclear magnetic resonance (H-NMR and C-NMR, gas chromatography-mass spectrometry (GC-MS), liquid chromatography-mass spectrometry (LC-MS), capillary electrophoresis and various other analyzes.

As the above-mentioned unsaturated alcohols, there can be mentioned vinyl alcohol, allyl alcohol, methallyl alcohol, 3-buten-1-ol, 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-2-buten-1-ol and

2-methyl-3-buten-1-ol. As the above-mentioned unsaturated carboxylic acid, acrylic acid and methacrylic acid can be mentioned, and alkyl esters of these unsaturated carboxylic acids can be used as the above-mentioned unsaturated carboxylic acid ester. As the alkylene oxide containing 3 to 18 carbon atoms, propylene oxide, butylene oxide or unsaturated hydrocarbon epoxy compound can be mentioned, and among them, propylene oxide is preferred. Preferred as the alcohol or phenols comprising a hydrocarbon group containing 1 to 20 carbon atoms, alkyl alcohols such as methanol, ethanol and butanol; alcohols having an aryl group such as benzyl alcohol; phenols such as phenol and para-methylphenol. Among these, alcohols containing 1 to 3 carbon atoms such as methanol, ethanol and butanol are preferred.

Suitable as the monomer having a carboxylic acid or a carboxylate salt and a polymerizable double bond in a molecule, which is copolymerizable with the monomer represented by the above formula (2) is, for example, a monomer represented by the following formula ( 3):

R⁶ R⁵

C = C (3) l₇ I.

R⁷ COOM¹ (in which R⁵, R⁶ and R⁷ They can be the same or different and each represents a hydrogen atom, a methyl group, or a group represented by - (CH2) ZCOOM², and Z is a number from 0 to 2. The group represented by (CH2)_zCOOM² can form an anhydride with -COOM¹ or the other group represented by - (Ch₂)_zCoOM²; M¹ and M²

ES 2 396 047 T3 can be the same or different and each represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group (an organic ammonium group). As such monomers, an unsaturated monocarboxylic acid monomer or an unsaturated dicarboxylic acid monomer can be mentioned.

They are suitable as the metal atom in M¹ and M² in the above formula (3) univalent metal atoms, for example alkali metal atoms such as lithium, sodium and potassium; divalent metal atoms, for example alkaline earth metal atoms such as calcium and magnesium; and trivalent metal atoms such as aluminum and iron. Suitable as the organic amine group (organic ammonium group), alkanolamine groups (alkanolammonium group) such as ethanolamine group (ethanolammonium group), diethanolamine group (diethanolammonium group) and triethanolamine group (triethanolammonium group), and triethylamine group (diethanolammonium group) can be mentioned. triethylammonium). Also, it can be an ammonium group.

As the monomer represented by the formula (3), there can be mentioned acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid or fumaric acid; monovalent metal salts, divalent metal salts, ammonium salts and organic ammonium salts thereof. Among these, methacrylic acid; Monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts (organic ammonium salts) thereof are preferably used from the viewpoint of improved cement dispersibility (dispersibility).

The ratio of the mass of the site represented by the formula (1) to the total mass of the above-mentioned polycarboxylic acid polymer is preferably 10 to 95% by mass. More preferably, it is 50 to 90% by mass, and even more preferably 65 to 85% by mass. In cases where the above-mentioned polycarboxylic acid polymer is obtained by copolymerizing the monomer (a) represented by the above formula (2) and the monomer (b) represented by the above formula (3), (a) is preferably 10 95% by mass relative to 100% by mass of the total mass of monomers (a) and (b). More preferably, it is 50 to 90% by mass, and even more preferably 65 to 85% by mass. The monomeric components that contain the monomer (a) and (b) can also contain another monomer, as a copolymerizable component, the amount of said monomer is from 0 to 50% by mass with respect to 100% by mass of the total mass of (a) and (b). Suitable as other monomer or monomers different from monomer (a) and (b) are, for example, styrene, esters of (meth) acrylic acid, acrylonitrile, acrylamide, (meth) allylsulfonate, 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) acryloxy sulfonate, (methylsulfonic acid (meth) acrylamidoethylsulfonic acid and 2-methylpropanesulfonic acid (meth) acrylamide. These monomers can be used individually or two or more of them can be used in combination.

The above-mentioned polycarboxylic acid polymer can be obtained by polymerizing these monomers. As the polymerization method, known methods such as aqueous solution polymerization, organic solvent polymerization, emulsion polymerization, or bulk polymerization using a polymerization initiator and optionally a chain transfer agent can be used. As the polymerization initiator, known ones can be used. It is also possible to use persulfate salts such as ammonium persulfate, sodium persulfate and potassium persulfate in combination; hydrogen peroxide; azo compounds such as azobis-2-methylpropionamidine hydrochloride and azoisobutyronitrile; peroxides such as benzoyl peroxide, lauroyl peroxide, and cumene hydroperoxide; and else. Furthermore, as a promoter, reducing agents such as sodium hydrogen sulfite, sodium sulfite, Mohr's salt, sodium pyrobisulfite, sodium formaldehyde sulfoxylate, ascorbic acid and erythorbic acid can be used in combination; and amine compounds such as ethylenediamine, sodium ethylenediaminetetraacetate, and glycine. These polymerization initiators and promoters can be used individually or two or more species can be used in combination.

In the above polymerization method, a chain transfer agent can be used as needed. Usable as said chain transfer agent are one or two or more species of those known in the art. Suitable as the above hydrophobic chain transfer agent are thiol compounds having a hydrocarbon group containing not less than 3 carbon atoms or compounds whose solubility in water at 25 ° C is not more than 10%. For example, there may be mentioned thiol chain transfer agents such as butanethiol, octanethiol, decanethiol, dodecanethiol, hexadecanethiol, octadecanethiol, cyclohexyl mercaptan, thiophenol, octyl thioglycolate, octyl 2-mercaptopropionate, octyl 2-mercaptopropionate, octyl 2-mercaptopropionate. -ethylhexyl, 2-mercaptoethyl octanoate, 1,8-dimercapto-3,6-dioxaoctane, decanetrithiol and dodecyl mercaptan; halides such as carbon tetrachloride, carbon tetrabromide, methylene chloride, bromoform, and bromotrichloroethane; and unsaturated hydrocarbon compounds such as α-methylstyrene dimer, α-terpinene, γterpinene, dipentene and terpinolene. These can be used individually or two or more species can be used in combination. Furthermore, as a hydrophobic chain transfer agent, there may be mentioned thiol chain transfer agents such as mercaptoethanol, thioglycerol, thioglycolic acid, mercaptopropionic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid and 2-mercaptoethanesulfonic acid; primary alcohols such as 2-aminopropane-1-ol; secondary alcohols such as isopropanol; phosphorous acid, hypophosphorous acid, and salts thereof (eg, sodium hypophosphite, potassium hypophosphite), sulfurous acid, hydrosulfurous acid, dithionous acid, metabisulfurous acid, and salts thereof (eg, sodium sulfite, sodium hydrogen sulfite, sodium dithionite , sodium metabisulfite, potassium sulfite, potassium hydrogen sulfite, dithionite

ES 2 396 047 T3 potassium, potassium metabisulfite), and lower oxides and salts thereof. These can be used individually or two or more of them can be used in combination.

As for the above chain transfer agent addition method to the reaction vessel, a continuous charging method such as dropping and split charging can be applied. The chain transfer agent can be introduced individually into the reaction vessel, or it can be mixed in advance with the monomer or solvent.

The above polymerization can be carried out batchwise or continuously. As the solvent to be used where necessary in the polymerization step, any of the known ones can be used, and water can be mentioned; alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, and n-heptane; esters such as ethyl acetate; and ketones such as acetone and methyl ethyl ketone. These can be used individually or two or more species can be used in combination. Among them, one or two or more solvents selected from the group consisting of water and lower alcohols containing 1 to 4 carbon atoms are preferably used from the viewpoint of the solubility of the components of the monomer and the polymer product of polycarboxylic acid.

As for the method of adding the monomers, the polymerization initiator, etc., to the reaction vessel in the above-mentioned polymerization method, the method comprising charging the reaction vessel with all the monomers and then adding the reaction vessel to them is suitable. polymerization initiator to carry out (co) polymerization; the method comprising charging the reaction vessel with some of the monomers and then adding the polymerization initiator and residual monomers to carry out the polymerization; and the method comprising charging the reaction vessel with the polymerization solvent and then adding the total amount of the monomers and the polymerization initiator to it.

Among such methods, the method comprising carrying out the polymerization by adding the polymerization initiator and monomers dropwise successively to the reaction vessel is preferred, since the molecular weight distribution of the product polymer can be narrowed (closed) and the Cement dispersibility to increase the flowability of cement compositions can be improved in this way. Furthermore, the (co) polymerization reaction is preferably carried out by keeping the concentration of a solvent in the reaction vessel during the polymerization at not more than 50%, since the preservation stability of the obtained polymer is further improved by improving the the polymerization capacity of monomers. More preferably, it is not more than 40%, still more preferably not more than 30%.

In the above polymerization method, the polymerization temperature and other polymerization conditions are appropriately selected in accordance with the polymerization method, the solvent, the polymerization initiator, and the chain transfer agent employed. Generally, the polymerization temperature is preferably not less than 0 ° C and not more than 150 ° C. More preferably, it is in the range of 40 to 120 ° C, still more preferably 50 to 100 ° C, and especially preferably 60 to 85 ° C.

The polymer obtained by the above polymerization method as such can be used as the main component of cement additives. When necessary, it can be used after further neutralization with an alkaline substance. Inorganic salts such as hydroxides, chlorides and carbonates of monovalent and divalent metals are preferably used as the alkaline substance; ammonia; and organic amines.

Regarding the weight average molecular weight of the polycarboxylic acid polymer of the present invention, the weight average molecular weight (Mw) as determined by gel permeation chromatography (hereinafter referred to as "GPC") and expressed on a polyethylene glycol equivalent basis, it is preferably 3,000 to 100,000. More preferably, it is 5,000 to 80,000, and even more preferably 7,000 to 40,000.

(GPC molecular weight measurement conditions)

Column used: Tosoh TSK SWXL guard column + TSK G4000SWXL + G3000SWXL + G2000SWXL gel

Eluent: Sodium acetate trihydrate (115.6 g) is dissolved in a mixed solvent consisting of 10999 g of water and 6001 g of acetonitrile, and the solution is further adjusted to pH 6.0 with acetic acid and used as the eluent solution . Injection volume: 100 μl of the 0.5% eluent solution

Eluent flow rate: 0.8 ml / min

Column temperature: 40 ° C

Standard samples: Polyethylene glycol, maximum molecular weights (Mp) 272500, 219300, 85000, 46000, 24000, 12600, 4250, 7100, 1470

Calibration curve order: 3rd order

Detector: Waters, Japan 410 differential refractive index detector

ES 2 396 047 T3

Analysis software: Waters, MILLENNIUM from Japan Ver. 3.21

The cement additive of the present invention comprises the polycarboxylic acid polymer obtained by the above-mentioned method, and is preferably in the state of an aqueous solution in view of proper handling. The cement additive of the present invention may also contain other additives. It is permissible to add the additives when the cement additive is mixed with the cement. As said other cement additives, those other known cement additives (ingredients) shown below can be used.

(a) water soluble macromolecular substances; unsaturated carboxylic acid polymers such as polyacrylic acid (sodium salt), polymethacrylic acid (sodium salt), polymaleic acid (sodium salt) and sodium salt of the acrylic acid-maleic acid copolymer; polyoxyethylene or polyoxypropylene polymers or copolymers thereof, such as polyethylene glycol and polypropylene glycol; nonionic cellulose ethers such as methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose and hydroxypropyl cellulose; polysaccharides produced by microbial fermentation, such as yeast glucans, xanthan gum, p-1,3-glucans (which can be straight chain or branched; for example, curdlan, paramyl, pachyman, scleroglycan, laminaran); polyacrylamide; polyvinyl alcohol; starch; starch phosphate; sodium alginate; jelly; amino-containing acrylic acid copolymers and quaternization products derived therefrom;

(b) Polymeric emulsions; copolymers of various vinyl monomers such as alkyl (meth) acrylates;

(c) Retardants; oxycarboxylic acids (or salts thereof) and inorganic or organic salts, such as gluconic acid, glucoheptonic acid, arabonic acid, malic acid and citric acid, and sodium, potassium, calcium, magnesium, ammonium and triethanolamine salts thereof; saccharides, for example monosaccharides, disaccharides, trisaccharides and oligosaccharides, such as glucose, fructose, galactose, sucrose, xylose, apiose, ribose and isomerized saccharide, oligosaccharides such as dextrin, polysaccharides such as dextran, molasses and mixtures containing them; sugar alcohols such as sorbitol; magnesium fluorosilicate; phosphoric acid and salts thereof or borate esters; aminocarboxylic acids and salts thereof; alkali soluble proteins; humic acid; tannic acid; phenols; polyhydric alcohols such as glycerol; phosphoric acids and derivatives thereof, such as (aminotri) methylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphoric acid, (ethylenediaminetetra) methylenephosphonic acid, (diethylenetriaminepenta) methylenephosphonic acid and alkali metal salts and alkaline earth metal salts thereof ;

(d) High-strength short-term or accelerating agents; soluble calcium salts such as calcium chloride, calcium nitrite, calcium nitrate, calcium bromide, and calcium iodide; chlorides such as iron chloride and magnesium chloride; sulfate salts; potassium hydroxide; sodium hydroxide; carbonate salts; thiosulfate salts; formic acid and formate salts such as calcium formate; alkanolamines; alumina cement; calcium aluminosilicate;

(e) Mineral oil defoaming agents; kerosene, liquid paraffin;

(f) Fat or oil defoaming agents; animal / vegetable oils, sesame oil, castor oil, alkylene oxide adducts derived therefrom;

(g) Fatty acid defoaming agents; oleic acid, stearic acid, alkylene oxide adducts derived from these;

(h) Fatty acid ester antifoaming agents; glycerin monoricinolate, alkenylsuccinic acid derivatives, sorbitol monolaurate, sorbitol trioleate, natural waxes;

(i) Oxyalkylene antifoaming agents; polyoxyalkylenes such as (poly) oxyethylene (poly) oxypropylene adducts; (Poly) oxyalkyl ethers such as diethylene glycol heptyl ether, polyoxyethylene oleyl ether, polyoxypropylene butyl ether, polyoxyethylene-polyoxypropylene 2-ethylhexyl ether, and oxyethylene-oxypropylene adducts of higher alcohols containing 12 to 14 carbon atoms; (poly) oxyalkylene (alkyl) aryl ethers such as polyoxypropylene phenyl ether and polyoxyethylene monophenyl ether; Acetylenic ethers derived from acetylenic alcohol by addition polymerization of an alkylene oxide, such as 2,4,7,9-tetramethyl-5-decino-4,7-diol, 2,5-dimethyl-3-hexyne-2 , 5-diol and 3-methyl-1-butyn-3ol; (poly) oxyalkylene fatty acid esters such as diethylene glycol oleate, diethylene glycol laurate, and ethylene glycol distearate; (poly) oxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan trioleate; (poly) oxyalkylene alkyl (aryl) ether sulfate ester salts such as sodium polyoxypropylene methyl ether sulfate and sodium polyoxyethylene endodecylphenolic ether sulfate; (poly) oxyalkylene alkyl phosphate esters such as (poly) oxyethylene stearyl phosphate; (poly) oxyalkylene alkylamines such as polyoxyethylene laurylamine; polyoxyalkyleneamides;

(j) Alcohol defoaming agents; octyl alcohol, hexadecyl alcohol, acetylenic alcohol, glycols;

(k) Amide defoaming agents; acrylate polyamines;

ES 2 396 047 T3 (l) Phosphate ester defoaming agents; tributyl phosphate, sodium octyl phosphate;

(m) Metallic soap antifoam agents; aluminum stearate, calcium oleate;

(n) Silicone antifoaming agents; dimethylsilicone oils, silicone pastes, silicone emulsions, organic modified polysiloxanes (polyorganosiloxanes such as dimethylpolysiloxane), fluorosilicone oils;

(o) AE (Air Introducer) Agents; resin soaps, saturated or unsaturated fatty acids, sodium hydroxystearate, lauryl sulfate, ABS (alkylbenzene sulfonates), LAS (linear alkylbenzene sulfonates), alkanesulfonates, polyoxyethylene (alkyl) phenyl esters, alkyl (phenyl) ether sulfates, and polyoxyethylene salts the same, polyoxyethylene alkyl (phenyl) ether phosphates and salts thereof, proteinaceous materials, alkenylsulfosuccinic acids, α-olefin sulfonates;

(p) Other surfactants; polyalkylene oxide derivatives produced by adding not less than 10 moles of an alkylene oxide, such as ethylene oxide and / or propylene oxide to a monohydric aliphatic alcohol containing 6 to 30 carbon atoms, such as octadecyl alcohol or stearyl alcohol, a monohydric alicyclic alcohol containing 6 to 30 carbon atoms, such as abiethyl alcohol, a monomercaptan containing 6 to 30 carbon atoms, such as dodecyl mercaptan, an alkylphenol containing 6 to 30 carbon atoms, such as nonylphenol, an amine containing 6 to 30 carbon atoms, such as dodecylamine, or a carboxylic acid containing 6 to 30 carbon atoms, such as lauric acid or stearic acid; alkyldinphenyl ether sulfonate salts containing two sulfo-containing phenyl groups, which may have an alkyl or alkoxy group as a substituent, linked together via an ether bond; various anionic surfactants, various cationic surfactants such as alkylamine acetates and alkyltrimethylammonium chlorides; various nonionic surfactants; various amphoteric substances;

(q) Waterproofing agents; (salts of) fatty acids, fatty acid esters, fats and oils, silicones, paraffins, asphalts, waxes;

(r) Corrosion inhibitors; nitrite salts, phosphate salts, zinc oxide;

(s) Cracking inhibitors; polyoxyalkyl ethers; alkanediols such as 2-methyl-2,4-pentanediol;

(t) Expansive additives; ettringite materials, coals.

As other known cement additives (ingredients), cement wetting agents, thickening agents, segregation inhibitors, flocculants, agents for reducing setting shrinkage, agents for increasing strength, self-leveling agents, corrosion inhibitors, color difference, antifungal agents, blast furnace slag, fly ash, embers ash, clinker ash, shell ash, silica fume, silica dust or gypsum. These known cement additives (ingredients) can be used individually or two or more of them can be used in combination.

Furthermore, the cement additive of the present invention can be used in combination with any of those cement dispersants that are in general use and are well known in the art. Like the above cement dispersants, the following are suitable.

Ligninsulfonates; polyol derivatives; Naphthalenesulfonic acid-formalin condensates; melaminosulfonic acid-formalin condensates; salts of polystyrenesulfonic acid; aminosulfonic acid compounds such as aminoarylsulfonic acid-phenol-formaldehyde condensates as described in Japanese patent application Kokai Publication Hei-01-113419; cement dispersants comprising, as component (a), a copolymer of a polyalkylene glycol mono (meth) acrylate compound and a (meth) acrylic acid compound and / or a salt of said copolymer, as component (b), a copolymer of a polyalkylene glycol mono (meth) aryl ether compound and maleic anhydride and / or a hydrolyzate of said copolymer and / or a salt thereof and, as component (c), a copolymer of a polyalkylene glycol mono (meth) allyl ether compound and a maleic acid ester of a polyalkylene glycol compound, and / or a salt thereof, as described in Japanese Patent Application Kokai Publication Hei-07 -267705; concrete admixtures comprising, as component A, a copolymer of a polyalkylene glycol (meth) acrylate and (meth) acrylic acid (or a salt thereof), as component B, a specific polyethylene glycol-polypropylene glycol compound and, as component C , a specific surfactant, as described in Japanese Patent No. 2508113; copolymers of polyethylene (propylene) glycol (meth) acrylate or polyethylene (propylene) glycol mono (meth) allyl ether, (meth) allylsulfonic acid (or a salt thereof) and (meth) acrylic acid (or a salt thereof ), as described in Japanese Patent Application Kokai Publication Sho-62216950;

copolymers of polyethylene (propylene) glycol (meth) acrylate, (meth) allylsulfonic acid (or a salt thereof) and (meth) acrylic acid (or a salt thereof), as described in Kokai Publication of application for Japanese Patent Hei-01-226757; copolymers of polyethylene (propylene) glycol (meth) acrylate, (meth) allylsulfonic acid (or a salt thereof) or p- (meth) allyloxybenzenesulfonic acid (or a salt thereof) and (meth) acrylic acid (or a salt thereof), as described in Japanese Patent Kokoku Publication Hei-05-36377; ether copolymers

ES 2 396 047 T3 mono (meth) allyl polyethylene glycol and maleic acid (or a salt thereof), as described in Japanese patent application Kokai Publication Hei-04-149056; copolymers of polyethylene glycol (meth) acrylate, (meth) allylsulfonic acid (or a salt thereof), (meth) acrylic acid (or a salt thereof), and alkanediol mono (meth) acrylate, a mono (meth) acrylate of polyalkylene glycol and an α, β-unsaturated monomer having an amide group within the molecule, as described in Japanese Patent Application Kokai Publication Hei-05-170501; copolymers of polyethylene glycol mono (meth) allyl ether, polyethylene glycol mono (meth) acrylate, an alkyl (meth) acrylate, (meth) acrylic acid (or a salt thereof) and (meth) allylsulfonic acid (or a salt thereof). same) or p (meth) allyloxybenzenesulfonic acid (or a salt thereof), as described in Japanese patent application Kokai Publication H06-191918; copolymers of an alkoxypolyalkylene glycol monoallyl ether and maleic anhydride, or hydrolysates thereof, or salts thereof, as described in Japanese Patent Application Kokai Publication Hei-05-43288; copolymers of polyethylene glycol monoallyl ether, maleic acid, and a monomer copolymerizable with these monomers, or salts thereof, or esters thereof, as described in Japanese Patent Kokoku Publication Sho-58-38380;

copolymers of a polyalkylene glycol mono (meth) acrylate monomer, a (meth) acrylic acid monomer, and a monomer copolymerizable with these monomers, as described in Japanese Patent Kokoku Publication Sho-59-18338; copolymers of a (meth) acrylic acid ester having a sulfonic acid group and a monomer copolymerizable with these as necessary, or salts thereof, as described in Japanese Patent Application Kokai Publication Sho-62-119147 ; esterification reaction product of a copolymer of an alkoxypolyalkylene glycol monoallyl ether and maleic anhydride and an alkenyl terminated polyoxyalkylene derivative, as described in Japanese Patent Application Kokai Publication Hei-06271347; esterification reaction product of a copolymer of an alkoxypolyalkylene glycol monoallyl ether and maleic anhydride and a hydroxy terminated polyoxyalkylene derivative, as described in Japanese patent application Kokai Publication Hei-06-298555; copolymers of alkenyl ether monomer obtained by adding an ethylene oxide to a specific unsaturated alcohol, such as 3-methyl-3-buten-1-ol, an unsaturated carboxylic acid monomer and a monomer copolymerizable with these, or salts of the same as described in Japanese Patent Application Kokai Publication Sho-62-68806 or polycarboxylic acids (or salts thereof). These cement dispersants can be used individually or two or more of them can be used in combination.

The present invention also relates to a cement additive composition comprising two or more species of cement additives, wherein at least one of the two or more species of cement additives is the cement additive of the present invention.

The aforementioned cement additive compound comes to have various properties characteristic of mixed cement additives; therefore, the addition to cement compositions leads to the improvement of the water-reducing capacity of cement compositions and to a greater resistance and durability of hardened products obtained from them and provides, in addition, a level of viscosity that facilitates the works in the locations of its manipulation. Such a cement admixture compound can be formed into a mixture by mixing (blending) the cement admixture prior to addition to cement compositions. Alternatively, the cement additive can be added separately to cement compositions and thus formed into a mixture in the cement compositions.

The above-mentioned cement additive compound may be in the form of a mixture in which the above-mentioned cement additive of the present invention and another cement additive are mixed. Examples thereof include (I) a mixture comprising two or more species of the cement additive of the present invention, and (II) a mixture comprising one or two or more species of the cement additive of the present invention and a or two or more different cement additive species of the present invention.

In the embodiment of (I) or (II) mentioned above, in the case where two or more species of the cement additives of the present invention are contained, two or more species of polycarboxylic acid polymers having the site represented by the above-mentioned formula (1) with different alkylene oxide chain length or different copolymer compositions.

Furthermore, as the method for separating the polymer from polycarboxylic acid, processes of cloud point separation, gel permeation chromatography (GPC) preparation, liquid chromatography (LC) preparation, capillary electrophoresis, and dialysis are exemplified, and the polycarboxylic acid polymer can be separated by suitably combining these methods.

In the embodiment of (II), the mixing ratio (in terms of solid matter) of the cement additive of the present invention is preferably 0.1% by mass as a lower limit relative to 100% by mass of the solid matter. of the complete polymers in the cement admixture. More preferably, the lower limit value is 1% by mass, even more preferably 5% by mass, and especially preferably 10% by mass. On the other hand, the upper limit value is preferably 99.9% by mass, more preferably 70% by mass, even more preferably 60% by mass, and especially preferably 50% by mass.

ES 2 396 047 T3

In the above-mentioned embodiment (II), the cement additive different from the cement additive of the present invention in the cement additive composition preferably comprises a polymer, which is composed of monomeric components containing an unsaturated polyalkylene glycol monomer.

Preferably it comprises a polymer having a site represented by the following formula (4):

<img file="ES2396047T3_D0001.tif" />

(in which R⁸, R⁹ and R¹⁰ they can be the same or different and each represents a hydrogen atom or a methyl group; R¹¹ represents a hydrogen atom or a hydrocarbon group containing from 1 to 30 carbon atoms; R^to it can be the same or different and represents an alkylene group containing from 2 to 18 carbon atoms; p represents an average molar addition number of the oxyalkylene group and is a number from 1 to 300; X represents a divalent alkylene group containing 1 to 5 carbon atoms, one -CO- bond, one -R bond^b-CO-, or a direct bond; and R^b represents a divalent alkylene group containing 1 to 5 carbon atoms). In the case where X represents a direct bond, a carbon atom and an oxygen atom bonded to X are bonded differently to each other. In addition, an embodiment is also preferred in which a polymer having a nitrogen atom or a polymer containing a branched structure and an oxyalkylene group is comprised.

That is, the cement additive in the cement additive compound of the present invention preferably comprises at least one polymer species selected from the group consisting of a polymer containing a site represented by the following formula (4), a polymer which it has a nitrogen atom, and a polymer that contains a branched structure and an oxyalkylene group. These polymers and raw materials to produce them can be used individually or two or more of them can be used in combination.

The above-mentioned polymer composed of monomer components containing essentially the unsaturated polyalkylene glycol monomer can be any polymer obtained by polymerizing monomer components comprising the unsaturated polyalkylene glycol monomer. And said unsaturated polyalkylene glycol monomer is preferably a monomer represented by the following formula (5):

R⁸ R⁹¹ IC = C (5)

R¹⁰ X— OCR^toO) p — R¹¹ (in which R⁸, R⁹ and R¹⁰ they can be the same or different and each represents a hydrogen atom or a methyl group; R¹¹ represents a hydrogen atom or a hydrocarbon group containing from 1 to 30 carbon atoms; R^to they can be the same or different and each represents an alkylene group containing from 2 to 18 carbon atoms, and p represents the average molar addition number of the oxyalkylene group and is a number from 1 to 300; X represents an alkylene group containing 1 to 5 carbon atoms, one -CO- bond, one -R bond^b-CO-, or a direct bond, in the case where X represents a direct bond, the carbon atom and oxygen atom bonded to X are directly bonded to each other; R^b represents a divalent alkylene group containing 1 to 5 carbon atoms). Furthermore, it is preferable that the polymer contains an unsaturated carboxylic acid monomer as the monomer component, and may optionally contain another copolymerizable monomer.

Furthermore, R⁸, R⁹, R¹⁰, R¹¹, R^to, R^b, p and X in formula (5) are the same as those mentioned above in formula (4).

The content ratio of the unsaturated polyalkylene glycol monomer and the unsaturated carboxylic acid monomer in the above-mentioned monomer components is preferably not less than 0.1 and not more than 2 based on (unsaturated polyalkylene glycol monomer) / (monomer of unsaturated carboxylic acid) (molar ratio). More preferably, it is not less than 0.3 and not more than 1.2 ...

The weight average molecular weight of the polymer composed of monomeric components containing essentially the unsaturated polyalkylene glycol monomer is preferably not less than 1000 as determined by GPC and is expressed on the basis of polyethylene glycol equivalents. This is more preferably not less than 3000, still more preferably not less than 5000, and especially preferably not less than 7000. On the other hand, it is preferably not more than 500000. It is more preferably not more than 30,000, still more preferably not more than 100,000, and especially preferably not more than 80,000.

ES 2 396 047 T3 weight average molecular is less than 1000, or when it is more than 500000, the dispersibility can be reduced.

The above-mentioned unsaturated carboxylic monomer is preferably a monomer having a carboxylic acid or carboxylate salt and a polymerizable double bond in a molecule as described above. In addition to these, unsaturated dicarboxylic acid semiamides with an amine containing 1 to 22 carbon atoms are also suitable as unsaturated carboxylic acid monomer half ester of unsaturated dicarboxylic acid monomer with an alcohol containing 1 to 22 carbon atoms. , half ester of unsaturated dicarboxylic acid monomer with a glycol containing 2 to 4 carbon atoms, and maleamic acid semiamide with glycol containing 2 to 4 carbon atoms, and else.

The above-mentioned unsaturated polyalkylene glycol monomer is preferably the monomer represented by formula (5) as described above, and for example, an unsaturated alcohol-polyalkylene glycol adduct and a polyalkylene glycol ester monomer are preferred. The unsaturated alcohol polyalkylene glycol adduct can be a compound having a structure such that a polyalkylene glycol chain is added to an alcohol having an unsaturated group. The polyalkylene glycol ester monomer can be any of those monomers having a structure in which an unsaturated group is linked to a polyalkylene glycol chain by an ester bond, an unsaturated carboxylic acid polyalkylene glycol ester compound is suitable, in particular ester (alkoxy) polyalkylene glycol mono (meth) acrylic.

In cases where two or more species of the oxyalkylene group represented by - (R^toO) - in the above formula (5), the oxyalkylene groups represented by - (R^toO) can be in any mode of addition, namely random addition, block addition, or alternate addition.

The oxyalkylene group or groups represented by - (R^toO) -, as mentioned above, are an alkylene oxide adduct containing 2 to 18 carbon atoms. Said alkylene oxide adduct has a structure formed by one or two or more alkylene oxides such as ethylene oxide, propylene 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. Even more preferably, it consists mainly of ethylene oxides. That is, this is preferably a group consisting mainly of an oxyethylene group or groups. In this case, "primarily" means that the oxyethylene group accounts for a majority over the number of all oxyalkylene groups present. When the oxyethylene group represents "a majority", in the above sense, of the above oxyalkylene groups, the proportion thereof as expressed in terms of mole% (mole percent) with respect to 100 mole% of all oxyalkylene groups it is preferably 50 to 100% by mole. If it is less than 50% by mole, the hydrophilicity of the oxyalkylene groups can possibly be reduced. More preferably it is not less than 60% by mole, even more preferably not less than 70% by mole, especially preferably not less than 80% by mole, and most preferably not less than 90% by mole.

The average molar addition number p of the oxyalkylene group represented by R^toOr above is a number from 1 to 300. When p exceeds 300, the polymerization ability of the monomer can be reduced. A preferred range of p is not less than 2 and, in - (R^toO) p-, the average molar addition number of the oxyethylene group (s) is preferably not less than 2. When p is less than 2 or the average molar addition number of the oxyethylene group (s) is less than 2, no levels can be obtained. sufficient hydrophilicity and steric hindrance to disperse cement particles, therefore it may be impossible to obtain excellent flowability. To obtain excellent flowability, a preferred range of p is not less than 3 but not more than 280. More preferably, p is not less than 5, still more preferably not less than 10, especially preferably not less than 20. For on the other hand, p is more preferably not more than 250, especially preferably not more than 150. As for the average molar addition number of the oxyethylene group (s), it is preferably not less than 3 but not more than 280. More preferably this is not less than 10, even more preferably not less than 20. On the other hand, it is more preferably not more than 250, still more preferably not more than 200, especially preferably not more than 150. The number "average molar addition" means the average value for the molar number of the oxyalkylene group in question added in each mole of the group formed by the oxyalkylene group or groups. For preparing low-viscosity concrete, as for the range of p, it is preferably not less than 3 but not more than 100, more preferably not less than 4 but not more than 50, still more preferably not less than 4 but not more than 30, most preferably not less than 5 but not more than 25.

It is possible to use, as the monomer represented by the formula (5), a combination of two or more monomeric species that differ in the average molar addition number p of the oxyalkylene group (s). As a suitable combination, for example, a combination of two monomeric species that differ in the average molar addition p number by no more than 10 (preferably a difference p not greater than 5), a combination of two monomeric species that differ in the number average molar addition p not more than 10 (preferably a difference in p not less than 20), or a combination of not less than three monomeric species that differ in p by not less than 10 (preferably a difference in m not less than 20) from each other. Furthermore, as for the range of p for combined use, it is possible to combine a monomer having an average molar addition number p in the range of 40 to 300 with a monomer having the range of 1 to 40 (the

ES 2 396 047 T3 difference in p not less than 10, preferably not less than 20), or combining a monomer having an average molar addition number p in the range of 20 to 300 with a monomer having the range of 1 to 20 (the difference in m being not less than 10, preferably not less than 20).

In the case where the monomer represented by the formula (5) is a polyalkylene glycol ester monomer, as for the oxyalkylene group represented by - (R^toO) p-, it is preferred that the ethylene oxide site is added to the ester bond site with (meth) acrylic acid (R⁸R⁹C = CR¹⁰-COOH) from the point of view of improving the productivity of esterification with (meth) acrylic acid.

As for the R¹¹ Above, if the number of carbon atoms exceeds 30, the hydrophobicity of the cement admixture compound of the present invention becomes excessively strong, so that a good dispersibility cannot be obtained. From the point of view of dispersibility, a preferred embodiment of R¹¹ is a hydrocarbon group containing 1 to 20 carbon atoms or a hydrogen, more preferably a hydrocarbon group containing no more than 10 carbon atoms, even more preferably no more than 5 carbon atoms, still more preferably no more than 3 carbon atoms, and especially preferably not more than 2 carbon atoms. Among the hydrocarbon groups, saturated alkyl groups and unsaturated alkyl groups are preferred. These alkyl groups can be straight chain or branched. To achieve excellent ability to prevent segregation and make the amount of air introduced into cement compositions suitable, hydrocarbon groups containing not less than 5 carbon atoms are preferred, and hydrocarbon groups containing not more than 20 carbon atoms are preferred. carbon. More preferred are hydrocarbon groups containing 5 to 10 carbon atoms. Among the hydrocarbon groups, saturated alkyl groups and unsaturated alkyl groups are preferred. These alkyl groups can be straight chain or branched.

Suitable as the above-mentioned unsaturated alcohol-polyalkylene glycol adduct, for example, vinyl alcohol-alkylene oxide adducts, (meth) allyl alcohol-alkylene oxide adducts, 3-buten-1-ol-alkylene oxide adducts, adducts of isoprene alcohol (3-methyl-3-buten-1-ol) -alkylene oxide, adducts of

3-methyl-2-buten-1-ol-alkylene oxide, 2-methyl-3-buten-2-ol-alkylene oxide adducts, 2-methyl-2-buten-1-ol-alkylene oxide adducts and 2-methyl-3-buten-1-ol-alkylene oxide adducts.

Suitable as the above-mentioned unsaturated alcohol-polyalkylene glycol adduct are also polyethylene glycol monovinyl ether, methoxypolyethylene glycol monovinyl ether, polyethylene glycol mono (meth) allyl ether, methoxypolyethylene glycol mono (me) allyl ether, mono (2-methyl-2- polyethylene glycol propenyl), polyethylene glycol mono (2-butenyl) ether, polyethylene glycol mono (3-methyl-3-butenyl) ether, polyethylene glycol mono (3-methyl-2-butenyl) ether, Polyethylene glycol mono (2-methyl-3-butenyl) ether, polyethylene glycol mono (2-methyl-2-butenyl) ether, polyethylene glycol mono (1,1-dimethyl-3-propenyl) ether, mono (3-methyl -3-butenyl) from polyethylene-polypropylene glycol, mono (3-methyl-3-butenyl) ether from methoxypolyethylene glycol, mono (3-methyl-3-butenyl) ether from ethoxypolyethylene glycol, mono (3-methyl-3-butenyl) ether from 1-propoxypolyethylene glycol, cyclohexyloxypolyethylene glycol mono (3-methyl-3-butenyl) ether, 1-octyloxypolyethylene glycol mono (3-methyl-3-butenyl) ether, nonylalkoxypolyethylene glycol mono (3-methyl-3-butenyl) ether, lauryl alkoxypolyethylene glycol mono (3-methyl-3-butenyl) ether, mono (3-methyl) ether -3-Butenyl) stearylalkoxypolyethylene glycol, mono (3-methyl-3-butenyl) ether of phenoxypolyethylene glycol, mono (3-methyl-3-butenyl) ether of naphthoxypolyethylene glycol, monoalyl ether of methoxypolyethylene glycol, monoallyl ether of methoxypolyethylene glycol, monoallyl ethoxycol ether, ethylene glycol monoallyl ether Phenoxypolyethylene glycol monoallyl ether, methoxypolyethylene glycol mono (2-methyl-2-propenyl) ether, ethoxypolyethylene glycol mono (2-methyl-2-propenyl) ether or phenoxypolyethylene glycol mono (2-methyl-2-propenyl) ether.

Suitable as the above-mentioned polyalkylene glycol (alkoxy) mono (meth) acrylate are esterification products of (meth) acrylic acid with alkoxypolyalkylene glycols, especially preferably alkoxypolyalkylene glycols which consist mainly of an ethylene oxide group or groups, obtained by adding 1 to 300 moles of an alkylene oxide group or groups containing 2 to 18 carbon atoms to any of aliphatic alcohols containing 1 to 30 carbon atoms such as methanol, ethanol, 1-propanol, 2 -propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, octanol, 2-ethyl-1-hexanol, nonyl alcohol, luaryl alcohol , cetyl alcohol and stearyl alcohol; alicyclic alcohols containing 3 to 30 carbon atoms such as cyclohexanol; and unsaturated alcohols containing 3 to 30 carbon atoms such as (meth) allyl alcohol, 3-buten-1-ol and 3-methyl-3-buten-1-ol.

Suitable as said esterification products are those (alkoxy) polyethylene glycol (poly) (alkylene glycol containing 2 to 4 carbon atoms) (meth) acrylates given below:

Methoxypolyethylene 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} mono (me) acrylate ( poly) propylene glycol- (poly) butylene glycol}, ethoxypolyethylene glycol mono (meth) acrylate, ethoxy mono (me) acrylate {polyethylene glycol- (poly) propylene glycol}, ethoxy mono (meth) acrylate {polyethylene glycol- (poly) butylene glycol} ethoxy mono (meth) acrylate {polyethylene glycol- (poly) propylene glycol- (poly) butylene glycol}, propoxypolyethylene glycol mono (meth) acrylate, propoxy mono (meth) acrylate {polyethylene glycol- (poly) propylene glycol}, mono (meth) acrylate propoxy {polyethylene glycol- (poly) butylene glycol}, propoxy mono (meth) acrylate {polyethylene glycol- (poly) propylene glycol (poly) butylene glycol},

ES 2 396 047 T3 Butoxypolyethylene glycol mono (meth) acrylate, butoxy {polyethylene glycol- (poly) propylene glycol} mono (meth) acrylate, butoxy {polyethylene glycol- (poly) butylene glycol} mono (me) acrylate, mono (meth) acrylate from butoxy {polyethylene glycol (poly) propylene glycol- (poly) butylene glycol}, pentoxypolyethylene glycol mono (me) acrylate, pentoxy [polyethylene glycol- (poly) propylene glycol} mono (me) acrylate {polyethylene glycol- poly) butylene glycol}, pentoxy mono (meth) acrylate {polyethylene glycol- (poly) propylene glycol- (poly) butylene glycol}, hexoxypolyethylene glycol mono (me) acrylate, hexoxy mono (meth) acrylate {polyethylene glycol- (poly) propylene glycol}, mono (meth) acrylate from hexoxy {polyethylene glycol- (poly) butylene glycol}, hexoxy mono (meth) acrylate {polyethylene glycol- (poly) propylene glycol (poly) butylene glycol}, heptoxypolyethylene glycol mono (meth) acrylate, heptoxy mono (meth) acrylate {polyethylene glycol- poly) propylene glycol}, Heptoxy mono (meth) acrylate {polyethylene glycol- (poly) butylene glycol}, heptoxy mono (meth) acrylate {polyethylene glycol (poly) propylene glycol- (poly) butylene glycol}, octoxypolyethylene glycol mono (meth) acrylate, mono (meth) acrylate octoxy {polyethylene glycol- (poly) propylene glycol}, octoxy mono (meth) acrylate {polyethylene glycol- (poly) butylene glycol}, octoxy mono (meth) acrylate {polyethylene glycol- (poly) propylene glycol- (poly) butylene glycol}, mono (meth ) nonanoxypolyethylene glycol acrylate, nonanoxy mono (meth) acrylate {polyethylene glycol- (poly) propylene glycol}, nonanoxy mono (me) acrylate {polyethylene glycol- (poly) butylene glycol}, nonanoxy mono (meth) acrylate {polyethylene glycol- (poly) propylene glycol (poly) butylene glycol }, decanoxypolyethylene glycol mono (me) acrylate, decanoxy mono (meth) acrylate {polyethylene glycol- (poly) propylene glycol}, decanoxy mono (me) acrylate {polyethylene glycol- (poly) butylene glycol}, Decanoxy mono (meth) acrylate {polyethylene glycol (poly) propylene glycol- (poly) butylene glycol}, undecanoxypolyethylene glycol mono (me) acrylate, undecanoxy mono (meth) acrylate {polyethylene glycol- (poly) propylene glycol}, mono (meth) acrylate undecanoxy {polyethylene glycol (poly) butylene glycol}, undecanoxy mono (meth) acrylate {polyethylene glycol- (poly) propylene glycol- (poly) butylene glycol}, dodecanoxypolyethylene glycol mono (meth) acrylate, dodecanoxy mono (meth) acrylate (poly) acrylate (polyethylene glycol) propylene glycol}, dodecanoxy mono (meth) acrylate {polyethylene glycol- (poly) butylene glycol}, dodecanoxy mono (meth) acrylate {polyethylene glycol- (poly) propylene glycol- (poly) butylene glycol}, tridecanoxypolyethylene glycol mono (me) acrylate, mono (meth) acrylate tridecanoxy {polyethylene glycol (poly) propylene glycol}, tridecanoxy mono (meth) acrylate {polyethylene glycol- (poly) butylene glycol}, tridecanoxy mono (meth) acrylate {polyethylene glycol- (poly) propylene glycol- (poly) butylene glycol}, tetradecanoxypolyethylene glycol mono (meth) acrylate, tetradecanoxy mono (meth) acrylate {polyethylene glycol- (poly) propylene glycol}, tetradecanoxy mono (meth) acrylate {polyethylene glycol- (poly) butylene glycol}, tetradecanoxy mono (meth) acrylate {polyethylene glycol- (poly) propylene glycol} (poly) propylene glycol- (poly) butylene glycol}, pentadecanoxy polyethylene glycol mono (meth) acrylate, pentadecanoxy mono (meth) acrylate {polyethylene glycol- (poly) propylene glycol}, pentadecanoxy mono (me) acrylate {polyethylene glycol glycol- {polyethylene glycol glycol} , Pentadecanoxy mono (meth) acrylate {polyethylene glycol- (poly) propylene glycol- (poly) butylene glycol}, hexadecanoxypolyethylene glycol mono (meth) acrylate, hexadecanoxy mono (meth) acrylate {polyethylene glycol (poly) propylene glycol), mono (poly) propylene glycol}, mono (meth) acrylate hexadecanoxy {polyethylene glycol- (poly) butylene glycol}, hexadecanoxy mono (meth) acrylate {polyethylene glycol- (poly) propylene glycol- (poly) butylene glycol}, heptadecanoxypolyethylene glycol mono (me) acrylate, Heptadecanoxy mono (meth) acrylate {polyethylene glycol- (poly) propylene glycol}, heptadecanoxy mono (meth) acrylate {polyethylene glycol- (poly) butylene glycol}, heptadecanoxy mono (meth) acrylate {polyethylene glycol- (poly) propylene glycol- (poly) propylene glycol) butylene glycol}, octadecanoxy polyethylene glycol mono (meth) acrylate, octadecanoxy mono (meth) acrylate {polyethylene glycol- (poly) propylene glycol}, octadecanoxy mono (meth) acrylate {polyethylene glycol- (poly) butylene glycol}, Octadecanoxy mono (meth) acrylate {polyethylene glycol- (poly) propylene glycol- (poly) butylene glycol}, nonadecanoxypolyethylene glycol mono (meth) acrylate, nonadecanoxy mono (meth) acrylate {polyethylene glycol (poly) propylene glycol}, methyl mono (methyl) acrylate nonadecanoxy {polyethylene glycol- (poly) butylene glycol}, nonadecanoxy mono (meth) acrylate {polyethylene glycol- (poly) propylene glycol- (poly) butylene glycol}, cyclopentoxypolyethylene glycol mono (meth) acrylate, cyclopentoxy mono (meth) acrylate {polyethylene glycol- (poly) propylene glycol}, cyclopentoxy mono (me) acrylate {polyethylene glycol- (poly) butylene glycol}, cyclopentoxy mono (meth) acrylate {polyethylene glycol- (poly) propylene glycol- (poly) butylene glycol}, cyclohexoxypolyethylene glycol mono (meth) acrylate, cyclohexoxy mono (meth) acrylate {polyethylene glycol- (poly) propylene glycol}, cyclohexoxy mono (meth) acrylate {polyethylene glycol- (poly) butylene glycol}, cyclohexoxy mono (meth) acrylate {polyethylene glycol- (poly) propylene glycol (poly) butylene glycol}.

As the above-mentioned (alkoxy) polyalkylene glycol mono (me) acrylate, not only the compounds described above, but also phenoxypolyethylene glycol mono (meth) acrylate, phenoxy {polyethylene glycol- (poly) propylene glycol} mono (me) acrylate are suitable. , phenoxy mono (meth) acrylate {polyethylene glycol (poly) butylene glycol}, phenoxy mono (me) acrylate {polyethylene glycol- (poly) propylene glycol- (poly) butylene glycol}, (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 {polyethylene glycol} (poly) propylene glycol- (poly) butylene glycol}.

ES 2 396 047 T3

Suitable as the above unsaturated polyalkylene glycol monomer are not only those described above, but also (alkoxy) polyalkylene glycol monomaleate or (alkoxy) polyalkylene glycol dimaleate. As such monomers, the following are suitable.

Semisters and diesters derived from alkyl (poly) alkylene glycols obtained by adding 1 to 500 moles of an oxyalkylene containing 2 to 18 carbon atoms to an alcohol containing 1 to 30 carbon atoms or an amine containing 1 at 30 carbon atoms and the above-mentioned unsaturated dicarboxylic acid monomers; half esters and diesters derived from the above-mentioned unsaturated dicarboxylic acid monomers and polyalkylene glycols having an average number of moles of a glycol or glycols containing from 2 to 18 carbon atoms as added from 2 to 500; maleamic acid semiamides with polyalkylene glycols having an average number of moles of a glycol or glycols containing from 2 to 18 carbon atoms as added from 2 to 500; (poly) alkylene glycol di (meth) acrylates such as triethylene glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate and (poly) ethylene glycol di (meth) acrylate- (poly) propylene glycol; (poly) alkylene glycol dimaleates such as triethylene glycol dimaleate and polyethylene glycol dimaleate.

As for the copolymerizable monomer or monomers, which may be the monomer component of the polymer composed of monomer components containing an unsaturated polyalkylene glycol monomer, the following compounds can be used.

(Meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate , decyl (meth) acrylate and lauryl (meth) acrylate; bifunctional (meth) acrylate such as hexanediol di (meth) acrylate; (meth) acrylic acid compounds such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethylethyl (meth) acrylate, and methoxypropyl (meth) acrylate .

Hemisters and diesters derived from unsaturated dicarboxylic acid as mentioned above and alcohols containing 1 to 30 'carbon atoms; hemiamides and diamides derived from the above-mentioned unsaturated dicarboxylic acid monomer and an amine containing 1 to 30 carbon atoms; half esters derived from the above-mentioned unsaturated dicarboxylic acid monomer and glycol containing from 2 to 18 carbon atoms; semiamide derived from maleamic acid and glycol containing 2 to 18 carbon atoms; multifunctional (meth) acrylate such as hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate and trimethylolpropane di (meth) acrylate; unsaturated sulfonic acids and monovalent metal salt, divalent metal salt, ammonium salt and organic ammonium salt thereof, for example vinyl sulfonate, (meth) allylsulfonate, 2- (meth) acryloxyethylsulfonate, 3- (meth) acryloxypropylsulfonate, 3- (meth) acryloxy-2-hydroxypropylsulfonate, 3- (meth) acryloxy-2-hydroxypropyl sulfophenyl ether, 3- (meth) acryloxy-2-hydroxypropyloxysulfobenzoate, 4 (meth) acryloxybutyl sulfonate, (meth) acrylamidomethylsulfonate, (meth) acrylamidoethylsulfonate, 2-methylpropanesulfonic acid (meth) acrylamide, and styrene sulfonic acid; amides derived from unsaturated monocarboxylic acid and amines containing 1 to 30 carbon atoms, for example methyl (meth) acrylamide; vinyl aromatic compounds such as styrene, α-methylstyrene, bromostyrene, chlorostyrene, vinyltoluene, and p-methylstyrene; α-olefins such as hexene, heptene, and decene; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, and butyl vinyl ether; allyl esters such as allyl acetate; allyls such as allyl alcohol;

alkanediol mono (meth) acrylates such as 1,4-butanediol mono (meth) acrylates, 1,5-pentanediol mono (meth) acrylate and 1,6-hexanediol mono (meth) acrylate; dienes such as butadiene, isoprene, isobutyrene, 2-methyl-1,3-butadiene, and 2-chloro-1,3-butadiene; unsaturated amides such as (meth) acrylamide, (meth) acrylalkylamide, N-methylol (meth) acrylamide and N, N-dimethyl (meth) acrylamide; unsaturated cyano compounds such as (meth) acrylonitrile and α-chloroacrylonitrile; unsaturated esters such as vinyl acetate and vinyl propionate; unsaturated amines such as aminoethyl (meth) acrylate, methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dibutylaminoethyl (meth) acrylate and vinylpyridine; aromatic divinyl compounds such as divinylbenzene; cyanurates such as triallyl cyanurate; and siloxane derivatives such as polydimethylsiloxanepropylaminomaleamidic acid, polydimethylsiloxaneaminopropyleneaminomaleamidic acid, polydimethylsiloxane-bis (propylaminomaleamidic acid), polydimethylsiloxane-bis (dipropyleneaminomaleamidic acid, 1-dimethylsiloxyl-3-acrylene-propylene-1-dimethylsiloxane-3-acryloxane-propyl) -methylsiloxyl acid ), polydimethylsiloxane-bis (1-propyl-3-acrylate) and polydimethylsiloxane-bis (1-propyl-3-methacrylate).

As the other copolymerizable monomer mentioned above, the following ethylene monomers containing a multi-branched polyoxyalkylene group (1) to (3) can be used: (1) a macromer obtained by adding glycidyl methacrylate to a multi-branched polymer obtained by adding alkylene oxide a polyalkyleneimine; (2) a multi-branched polymer (meth) acrylic ester macromer obtained by adding alkylene oxide to polyalkyleneimine; and (3) a multi-branched polymer maleic acid ester macromer obtained by adding alkylene oxide to polyalkyleneimine. As the aforementioned multi-branched polymer, those obtained by adding alkylene oxide to polyamidopolyimine and a polyhydric alcohol can also be used.

As the above-mentioned polyalkyleneimine, there may be mentioned, for example, a homopolymer and a copolymer obtained by polymerization, in the conventional manner, of one or two or more alkyleneimines containing 2 to 8 carbon atoms, such as ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine and

ES 2 396 047 T3

1,1-dimethylethyleneimine. Said polyalkyleneimine may have any of the straight chain structure, branched chain structure and cross-linked structure in a three-dimensional way. In addition, ethylenediamine, diethylenetriamine, triethylenetetraamine, or tetraethylenepentaamine can also be used. Said polyalkyleneimines generally have, in their structure, not only a tertiary amino group but also primary and secondary amino (imino) groups having an active hydrogen atom, respectively.

The weight average molecular weight of the polyalkyleneimine is preferably 100 to 100,000. More preferably, it is 300 to 50,000, and even more preferably 600 to 10,000.

They are suitable for use as the above alkylene oxide alkylene oxide containing 2 to 8 carbon atoms such as ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, 2-oxide -butene, trimethylethylene oxide, tetramethylene oxide, tetramethylethylene oxide, butadiene monoxide and octylene oxide and, furthermore, aliphatic epoxides such as dipentaneethylene oxide and dihexanoethylene oxide; alicyclic epoxides such as trimethylene oxide, tetramethylene oxide, tetrahydrofuran, tetrahydropyran, and octylene oxide; and aromatic epoxides such as styrene oxide or 1,1-diphenylethylene oxide. Among them, ethylene oxide, propylene oxide and butylene oxide are preferred. More preferably, it consists mainly of ethylene oxides.

The average molar addition number of the oxyalkylene group in the alkylene oxide adduct mentioned above is preferably not less than 0.5 and not more than 300. More preferably, it is not less than 1, still more preferably not less than 1 , 5, especially preferably not less than 2, and most preferably 3. On the other hand, it is more preferably not more than 200, even more preferably not more than 150, especially preferably not more than 100, and most preferably not more than 50. When the average molar addition number of the group oxyalkylene in the aforementioned alkylene oxide adduct is out of range, the hydrophobicity of the polymer to be produced may not become sufficient.

As a preferable embodiment of the polymer comprising the unsaturated polyalkylene glycol monomer of the present invention, there may be mentioned: (i) a polycarboxylic acid polymer having the site represented by the above formula (1) as mentioned above; (ii) a polymer obtained by copolymerizing monomeric components containing an unsaturated mono (polyoxyalkylene) monomer (A), an unsaturated carboxylic acid monomer (B), an unsaturated poly (polyoxyalkylene) monomer (C), and an acid-derived monomer unsaturated carboxylic (D); and (iii) a polymer obtained by polymerizing monomeric components comprising from 20 to 90% by mole of an alkyl (meth) acrylate monomer, from 5 to 60% by mole of an unsaturated polyalkylene glycol monomer and from 5 to 70% in moles of an unsaturated carboxylic acid monomer. Two or more of these embodiments can be used in combination.

Hereinafter, the above-mentioned embodiment (ii) will be described.

In the above-mentioned embodiment (ii), the content ratios of the respective monomers of the monomer components are preferably 20 to 99% by mass of the unsaturated monomer of mono (polyoxyalkylene) (A), 0.1 to 50 % by mass of the unsaturated carboxylic acid monomer (B), 0.1 to 60% by mass of the unsaturated poly (polyoxyalkylene) monomer (C), and 0.1 to 30% by mass of the carboxylic acid derived monomer unsaturated (D). The content ratios of the monomers mentioned above are the values ​​in the case where it is determined that the total amount of monomeric components to be copolymerized is 100% by mass.

The content ratio of the above-mentioned mono (polyoxyalkylene) unsaturated monomer (A) is preferably not less than 20% by mass, more preferably not less than 25% by mass, still more preferably not less than 35% by mass, and especially preferably not less than 45% by mass. Furthermore, it is preferably not more than 99% by mass, more preferably not more than 90% by mass, still more preferably not more than 80% by mass, and especially preferably not more than 70% by mass.

The content ratio of the above-mentioned unsaturated carboxylic acid monomer (B) is preferably not less than 0.1% by mass, more preferably not less than 1% by mass, still more preferably not less than 3% by mass, so especially preferably not less than 5% by mass, and most preferably not less than 10% by mass. Furthermore, it is preferably not more than 50% by mass, more preferably not more than 40% by mass, still more preferably not more than 35% by mass, and especially preferably not more than 30% by mass.

The content ratio of the above-mentioned poly (polyoxyalkylene) unsaturated monomer (C) is preferably not less than 0.1% by mass, more preferably not less than 3% by mass, still more preferably not less than 5% by mass, and especially preferably not less than 10% by mass. Furthermore, it is preferably not more than 60% by mass, more preferably not more than 50% by mass, still more preferably not more than 40% by mass, and especially preferably not more than 30% by mass.

ES 2 396 047 T3

The content ratio of the above-mentioned unsaturated carboxylic acid derived monomer (D) is preferably not less than 0.1% by mass, more preferably not less than 2% by mass, and even more preferably not less than 3% by mass, and especially preferably not less than 5% by mass. Furthermore, it is preferably not more than 30% by mass, more preferably not more than 25% by mass, still more preferably not more than 20% by mass, and especially preferably not more than 15% by mass.

In addition to the above-mentioned monomers (A) to (D), a copolymerizable monomer (E) can be used in combination with the monomers (A) to (D). In the case where monomer (E) is used, the ratio is preferably as follows: total monomers (A) to (D) / monomer (E) = 100 to 60/40 to 0 (% mass).

More preferably, total monomers (A) to (D) / monomer (E) = 100 to 65/35 to 0 (% by mass), even more preferably total monomers (A) to (D) / monomer (E) = 100 to 75/25 to 0 (% by mass), and especially preferably the total of monomers (A) to (D) / monomer (E) = 100 to 85 / 15 to 0 (% by mass).

The mono (polyoxyalkylene) unsaturated monomer (A) is preferably similar to the above-mentioned unsaturated polyalkylene glycol monomer. The unsaturated carboxylic acid monomer (B) is preferably similar to the above-mentioned unsaturated carboxylic acid monomer. The unsaturated carboxylic acid derived monomer (D) is preferably a compound derived from an unsaturated carboxylic acid from the other copolymerizable monomers mentioned above. As the above-mentioned monomer (E), the other copolymerizable monomers mentioned above are preferable, except for the monomer (D).

As the unsaturated monomer of poly (polyoxyalkylene) (C), any monomer can be used without any particular limitation, as long as it contains one unsaturated group and two or more polyoxyalkylene groups in one molecule. Preferable examples thereof may include a polyalkyleneimine monomer containing a polymerizable unsaturated group and a polyoxyalkylene group, and a monomer having a structure resulting from the attachment of an oxyalkylene group to the residue of a polyhydric alcohol. In addition, the ethylene monomers containing a polybranched polyoxyalkylene group (1) to (3) described above can be employed as other copolymerizable monomers.

The above-mentioned polyalkyleneimine monomer containing an unsaturated group and a polyoxyalkylene group can be obtained by reacting a compound, which is obtained by adding alkylene oxide to a nitrogen atom of an amino group or an imino group of polyalkyleneimine, with a compound unsaturated containing a functional group reactive with a hydroxyl, amino or imino group. The nitrogen atom of the amino group or imino group to which alkylene oxide is added has an active hydrogen atom.

In the case where the polyalkyleneimine monomer containing an unsaturated group and a polyoxyalkylene group is obtained, suitable for introducing an unsaturated group or groups into the aforementioned compound resulting from the addition of an alkylene oxide to a polyalkyleneimine, for example , the method of introducing the unsaturated group which comprises subjecting the hydroxyl group or groups of the compound resulting from the addition of an alkylene oxide to a polyalkyleneimine for transesterification with an unsaturated compound such as (meth) acrylic acid or (meth) acid alkyl ester acrylic; the method of introducing the unsaturated group which comprises amidating the amino group of the compound resulting from the addition of an alkylene oxide to a polyalkyleneimine with an unsaturated compound such as (meth) acrylic acid or an alkyl ester of (meth) acrylic acid; and the method of introducing the unsaturated group which comprises reacting the hydroxyl group or groups of the compound resulting from the addition of an alkylene oxide to a polyalkyleneimine with an epoxy compound such as glycidyl (meth) acrylate or (meth) allylglycidyl ether.

The polyalkyleneimine mentioned above is preferably the same as mentioned below, and the alkylene oxide to be added to the polyalkyleneimine is preferably the same as mentioned below.

As the above unsaturated compound, for example, unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid and citraconic acid; unsaturated carboxylic acid anhydrides such as (meth) acrylic anhydride and maleic anhydride; unsaturated carboxylic acid halides such as (meth) acrylic chloride; unsaturated carboxylic acid esters such as alkyl (meth) acrylates having an alkyl group containing 1 to 30 carbon atoms, a maleic acid monoester having an alkyl group containing 1 to 30 carbon atoms, and a diester maleic acid having an alkyl group containing 1 to 30 carbon atoms; and epoxy compounds such as glycidyl (meth) acrylate and (meth) allylglycidyl ether.

The following shows, as an example of the reaction formula to obtain the polyalkyleneimine monomer having an unsaturated group and a polyoxyalkylene group mentioned above, the reaction formula according to which polyethyleneimine is synthesized from ethyleneimine using an initiator , A polyethyleneimine-ethylene oxide adduct is then produced by adding ethylene oxide to nitrogen atoms bearing active hydrogen atoms of the polyethyleneimine and carrying out transesterification with is carried out. Also available is the method that comprises synthesizing polyethyleneimine, then doing

ES 2 396 047 T3 that the ethylene oxide is added to nitrogen atoms bearing an active hydrogen atom or atoms of the polyethyleneimine and then reacting the resulting polyethyleneimine-ethylene oxide adduct with glyclidyl methacrylate.

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<td>OR</td><td></td><td>or CL</td><td></td>

In the above reaction formula, Ra represents an initiator, EO represents ethylene oxide, - (EO) rH indicates that the group is a result of the addition of r ethylene oxide molecules to nitrogen atoms bearing an atom or atoms active hydrogen of polyethyleneimine, and MAA represents methacrylic acid. The symbol in the chemical formula means that the polymer chain continues in the same way.

ES 2 396 047 T3

The aforementioned polyalkyleneimine monomer having an unsaturated group and a polyoxyalkylene group has a polyalkyleneimine chain. Preferably, said polyalkyleneimine chain consists mainly of ethyleneimine.

As for the above-mentioned polyalkyleneimine monomer containing an unsaturated group and a polyoxyalkylene group, the average polymerization number of the alkyleneimine in each polyalkyleneimine chain is preferably, for example, 2 to 300. When it is less than 2, the Functions of the polyalkyleneimine monomer may not be fully realized, when it exceeds 300, the polymerization ability of the polyalkyleneimine monomer may possibly be reduced. More preferably it is 2 to 100, even more preferably 3 to 100, still more preferably 5 to 100, especially preferably 5 to 75, and most preferably 5 to 50. In this case, the number average polymerization number of diethylenetriamine is considered as 2 and the average polymerization number of triethylenetetraamine is considered as 3.

The aforementioned polyalkyleneimine monomer containing an unsaturated group and a polyoxyalkylene group has a group or groups formed by an oxyalkylene group or a group or groups resulting from the addition of two or more oxyalkylene groups. The group or groups resulting from the addition of two or more oxyalkylene groups are composed of one or two or more species of oxyalkylene group and, when they are composed of two or more species of oxyalkylene group, the two or more species of oxyalkylene group may be in any mode of addition, for example in a random, block or alternate mode of addition. In cases where a plurality of groups formed by the aforementioned oxyalkylene group (s) occur in one and the same molecule, these may be the same or different. Preferably, said groups formed by the above-mentioned oxyalkylene group or groups are mainly formed by an oxyethylene group or groups.

The average molar addition number of the oxyethylene group (s) in the above-mentioned polyalkyleneimine monomer having an unsaturated group and a polyoxyalkylene group is preferably, for example, 0 to 300. When it exceeds 300, the polymerization capacity of the unsaturated monomer polyalkyleneimine can possibly be reduced. More preferably this is from 0.3 to 270, still more preferably from 0.5 to 250, especially preferably from 1 to 220, and most preferably from 2 to 200. When the average molar addition number of the oxyalkylene group in the unsaturated polyalkyleneimine monomer is outside said range, the functional effects of the polycarboxylic acid copolymer to improve the flowability of a cement composition cannot be sufficiently realized. Furthermore, the polyalkyleneimine monomer with the above average molar addition number of 0 does not contain an oxyalkylene group.

The weight average molecular weight of the polyalkyleneimine monomer having an unsaturated group and a polyoxyalkylene group is preferably, for example, 1000 to 500000. More preferably it is 3000 to 300000, still more preferably 8000 to 200000, still more preferably 10,000 to 100,000, and especially preferably 15,000 to 80,000.

The above-mentioned monomer having a structure resulting from the attachment of an oxyalkylene group to the residue of a polyhydric alcohol can be produced, for example, by reacting a compound resulting from the addition of an alkylene oxide to the hydroxyl group or groups of an alcohol. polyhydric with an unsaturated compound containing a functional group reactive with the hydroxyl group of said compound.

The above-mentioned polyhydric alcohol residue means a group having a structure such that an active hydrogen atom or atoms are removed from a hydroxyl group or groups of a polyhydric alcohol but it is not particularly limited to groups formed during the reaction with the polyhydric alcohol. . As for the alkylene oxide (s) to be added to the hydroxyl group (s) of the polyhydric alcohol, the same as those mentioned hereinbefore may be mentioned.

As the production method of the monomer having a structure resulting from the attachment of an oxyalkylene group to the residue of a polyhydric alcohol, there may be mentioned, for example, (1) the method comprising introducing a compound obtained by adding an oxide or alkylene oxides in a polyhydric alcohol, and (2) the method comprising subjecting not less than 1 mole of glycidol to the addition reaction to each mole of an unsaturated alcohol-polyalkylene glycol adduct of an unsaturated alcohol to generate two or more hydroxyl groups in each molecule, followed by the addition of an alkylene oxide or oxides.

In the above method (1), the introduction of the unsaturated group is carried out, preferably, for example, by the method that comprises esterifying or transesterifying the hydroxyl group or groups of the compound resulting from the addition of an alkylene oxide or oxides to the residue of a polyhydric alcohol with an unsaturated compound such as (meth) acrylic acid or an alkyl ester of (meth) acrylic acid such as methyl (meth) acrylate for introduction of the unsaturated group; the method comprising reacting the hydroxyl group or groups of the compound resulting from the addition of an alkylene oxide or oxides to a polyhydric alcohol with an epoxy compound containing 2 to 5 carbon atoms, such as (meth) acrylate of glycidyl or (meth) allylglycidyl ether, for the introduction of the unsaturated group; or the method comprising esterifying with an alkenyl halide containing 2 to 5 carbon atoms, such as (meth) allyl chloride for the introduction of the unsaturated group. As the unsaturated group or groups of alkenyl compounds, an unsaturated group containing not less than 4 carbon atoms is preferable, more preferably an unsaturated group containing not less than 5 carbon atoms. And they are

ES 2 396 047 T3 preferable methallyl group and isoprenyl (3-methyl-3-butenyl) group to allyl group. Furthermore, the (meth) acryloyl group is also preferable.

The above-mentioned polyhydric alcohol is not particularly restricted but can be any of those compounds having, on average, three or more hydroxyl groups in each molecule. A preferred form is the compound whose polyhydric alcohol residue is made up of three elements, namely carbon, hydrogen and oxygen.

The above polyhydric alcohol preferably contains three or more hydroxyl groups but not more than 300 hydroxyl groups. When the number of said hydroxyl groups is less than 3, the monomer having a structure resulting from the attachment of an oxyalkylene group to the residue of a polyhydric alcohol may not be able to perform its functions to a satisfactory degree. When this exceeds 300, the polymerization ability of the monomer having a structure resulting from the attachment of an oxyalkylene group to the residue of a polyhydric alcohol can possibly be reduced. The number of said hydroxyl groups is more preferably not less than 4, even more preferably not less than 5, and most preferably not less than 6. On the other hand, it is more preferably not more than 100, even more preferably not more than 50, and most preferably not more than 25.

They are suitable for use as polyhydric alcohol polyglycidol, glycerin, polyglycerin, trimethylolethane, trimethylolpropane, 1,3,5-pentatriol, erythritol, pentaerythritol, dipentaerythritol, sorbitol, sorbitan, sorbitol glycerin condensates, adonitol, arabitol or arabitolitol, arabitolitol, arabitol or arabitolitol.

Also suitable for use are saccharides, for example hexose saccharides such as glucose, fructose, mannose, indose, sorbose, gulose, talose, tagatose, galactose, allose, psychose and atrose; pentose saccharides such as arabinose, ribulose, ribose, xylose, xylulose, and lixose; tetrose saccharides such as treose, erythrulose, and erythrose; other saccharides such as rhamnose, cellobiose, maltose, isomalt, trehalose, sucrose, raffinose, gentianose, and melecytose; sugar alcohols and sugar acids derived from them (saccharide: glucose; sugar alcohol: glucitol; sugar acid: gluconic acid). Furthermore, partially etherified or partially esterified derivatives of the compounds specifically mentioned above are also suitable.

Next, the above-mentioned embodiment (iii) will be described.

In the aforementioned embodiment (iii), the monomer is obtained by polymerizing monomeric compounds containing 20 to 90 mole% of an alkyl (meth) acrylate monomer, 5 to 60 mole% of an unsaturated polyalkylene glycol monomer and 5 to 70% by mole of an unsaturated carboxylic acid monomer.

In monomeric components, the ratio of an alkyl (meth) acrylate monomer is 20 to 90% by mole. If the ratio of the alkyl (meth) acrylate monomer is less than 20% by mole, the viscosity of the cement composition may not be lowered sufficiently. The preferable range is 20 to 70% by mole. More preferably, it is 20 to 60% by mole, and even more preferably 22 to 55% by mole. The ratio of an unsaturated polyalkylene glycol monomer is 5 to 60% by mole, but is preferably 10 to 50% by mole. More preferably, it is 15 to 40% by mole. The ratio of an unsaturated carboxylic acid monomer is 5 to 70% by mole, but is preferably 19 to 65% by mole. More preferably, it is 30 to 60% by mole. In addition, in the case where the fourth component is contained in addition to the above-mentioned alkyl (meth) acrylate monomer, the unsaturated polyalkylene glycol monomer, and the unsaturated carboxylic acid monomer, the ratio thereof is preferably in a range of 0 to 30% in moles. These “mole% (percent)” values ​​are those calculated on the basis of 100 mole% of the total alkyl (meth) acrylate monomer, unsaturated polyalkylene glycol monomer, unsaturated carboxylic acid monomer, and fourth component .

The weight average molecular weight of the polymer in the aforementioned embodiment (iii) is preferably not more than 20000. When it exceeds 20000, the slump-holding ability of the cement compositions may not be sufficiently improved, and cement compositions cannot be provided. easy to manipulate. This is preferably 4000 to 18000, more preferably 5000 to 14000, and even more preferably 6000 to 12000.

The unsaturated carboxylic monomer is the same as the above-mentioned unsaturated carboxylic monomer, and the alkyl (meth) acrylate is preferably the alkyl (meth) acrylate in the above-mentioned other copolymerizable monomer.

As the unsaturated monomer of polyalkylene glycol, those mentioned above are preferably used, and those having a polyalkylene glycol chain length of not more than 25 moles are preferable. Accordingly, the function of improving the dispersibility of a cement composition due to the hydrophilicity of the oxyalkylene group and the steric repulsive polyalkylene glycol can be sufficiently performed.

In such a case, the average molar addition number p of oxyalkylene groups represented by R^toOr earlier in the formula mentioned above (5) is a number of 25 or less. A preferred range of p is not less than 2 and the average molar addition number of the oxyethylene group (s) in - (R^toO) p- is preferably not less than 2. When p is less than the above molar number, sufficient levels of steric hindrance may not be obtained

ES 2 396 047 T3 for dispersing cement particles. When the average molar addition number of the oxyethylene group (s) is less than the above molar number, sufficient levels of hydrophilicity may not be obtained to disperse cement particles. The upper limit of the average molar addition number of the oxyethylene group (s) is preferably not more than 24, more preferably not more than 20, and even more preferably not more than

fifteen. The range of p, and the range of the average molar addition number of the oxyethylene group (s) in - (R^toO) pes, preferably 2 to 25. More preferably, they are 2 to 24, and even more preferably 6 to 20.

It is possible to use, as the unsaturated polyalkylene glycol monomer, a combination of two or more monomeric species that differ in the average molar addition number p of the oxyalkylene group (s). As a suitable combination, for example, a combination of two monomeric species that differ in the average molar addition p number by no more than 5 (preferably a difference in p of no more than 3), a combination of two monomeric species that differ in the average molar addition number p by not less than 5 (preferably a difference in p not less than 10), or a combination of not less than three monomeric species that differ by p not less than 5 from each other. Furthermore, regarding the range of p for combined use, it is possible to combine a monomer having an average molar addition number p in the range of 20 to 25 with a monomer having the range of 1 to 20 (the difference in p being not less than 10, and preferably not less than 20).

The polymer composed of monomeric components containing an unsaturated polyalkylene glycol monomer in the present invention can be obtained by the same methods as the polycarboxylic acid polymer polymerization methods to be used for the cement additive of the present invention, and preferably, The methods may include steps of (i) changing the molar ratio of the monomeric components at least once in a reaction vessel during the reaction and / or (ii) carrying out the polymerization using a mixture containing a water soluble polymer and water as the solvent.

Method (i) preferably involves a step of changing the A / C molar ratio at least once during the polymerization of an unsaturated polyoxyalkylene monomer (A), an unsaturated carboxylic acid monomer (B), and another unsaturated monomer (C ), wherein the molar numbers of the respective monomers (A), (B), and (C) charged from the initial phase to that point are represented as A, B, and C, respectively. Furthermore, the above method preferably involves a step of changing at least one of the A / C1 and A / C2 molar ratios at least once during polymerization, wherein C1 and C2 respectively represent the molar numbers of a monomer of (meth) acrylic acid ester and an ethylene monomer containing a multi-branched polyoxyalkylene group, which are preferable as the (C) monomer, charged from the initial phase to that time. In this case, the C1 / C2 molar ratio can be changed or not changed during polymerization if both the (meth) acrylic acid ester monomer and the ethylene monomer containing a multi-branched polyoxyalkylene group are used as the monomer (C) . Furthermore, the B / C molar ratio may or may not be changed during polymerization.

In method (i), the molar ratio of monomer (A) and monomer (B) is preferably kept constant during polymerization. In this case, the A / B molar ratio is constant during polymerization, and at least one of the A / C1 and A / C2 molar ratios is changed, preferably, at least once during polymerization.

The aforementioned change in the molar ratio can be accomplished by increasing the molar ratio, reducing the molar ratio, or combining the increasing and decreasing of the ratios and changing the degrees of alteration. The molar ratio can be changed in stages or continuously. As a method of changing the molar ratio during polymerization in such a manner, a method of adding dropwise one or all of the monomer (A), monomer (B) and monomer (C) to a container of polymerization and change the monomer titration rate stepwise or continuously. Preferably, the titration rate of the other unsaturated monomer (C) is changed. Accordingly, the A / C molar ratio is changed at least once during polymerization to give a copolymer.

By the way, since the A / C molar ratio can be changed at least once during the polymerization, for example, the molar ratio can be changed by carrying out the polymerization of the monomer (A) and the monomer (B) and the polymerization of the monomer. (A), monomer (B), and monomer (C). In this case, there is the polymerization period to produce a copolymer of monomer (A) and monomer (B) and the polymerization period to produce a copolymer of monomer (A), monomer (B), and monomer (C). ). In the case where the monomer (C) is added dropwise, after the polymerization of the monomer (A) and the monomer (B) is carried out, the polymerization of the monomer (A), the monomer (B ) and the monomer (C) is carried out by adding the monomer (C) dropwise to change the A / C molar ratio at least once during the polymerization.

As the above-mentioned acrylic acid ester monomer (C1), the exemplified (meth) acrylic acid esters as the other copolymerizable monomers mentioned above are preferable. As the above-mentioned multi-branched polyoxyalkylene group-containing ethylene monomer (C2), the ethylene monomers containing a multi-branched polyoxyalkylene group exemplified as the other copolymerizable monomers mentioned above are preferable. With respect to the use ratio of the monomers, the use ratio of the (meth) acrylic acid ester monomer (C1) is preferably not less than 0.1% by mole and not more than 100% by mole in the case in which it is determined that the relationship of use of the

ES 2 396 047 T3 unsaturated carboxylic acid monomer (B) is 100 mol%. More preferably, it is not less than 1% by mole, and not less than 60% by mole. Even more preferably, it is not less than 3% by mole, and not less than 30% by mole.

Furthermore, the ratio of ethylene monomer containing a multi-branched polyoxyalkylene group (C2) is preferably not less than 0.01% by mole and not more than 10% by mole. More preferably, it is not less than 0.05% by mole, and not more than 5% by mole. Even more preferably, it is not less than 0.1% by mole, and not less than 3% by mole.

In the above-mentioned methods for changing the molar ratio, at least two different copolymers with different A / B / C molar ratio of the respective monomer units are contained. From the viewpoint that the cement additive using the copolymers has various characteristics of the respective copolymers, and the sufficient effects of the present invention are shown, it is preferable to form a mixture of three or more different types of copolymers with different ratio. molar A / B / C by changing the molar ratio of the respective monomer components during polymerization.

Furthermore, it is preferable to form a copolymer mixture containing at least three types of copolymers among the copolymers obtained by polymerization of monomeric components containing three or more types of monomers, the monomer (A), the monomer (B) and the monomer ( C), and copolymers obtained by polymerization of monomeric components that contain two types of monomers, monomer (A) and monomer (B). That is, it is preferable to form a copolymer mixture containing three or more types of copolymers with different A / B / C molar ratio, or a copolymer mixture containing two or more types of copolymers with different A / B molar ratio. / C and one or more types of copolymers obtained using two types of monomers, monomer (A) and monomer (B).

In the above-mentioned method (ii), the water-soluble polymer is preferably a water-soluble polymer having a branched structure and / or a polycarboxylic acid polymer. That is, the polymerization of the monomeric components is preferably carried out using any of the following (1) to (3) as the solvent: (1) a mixture of the water-soluble polymer having a branched structure and water; (2) a mixture of the polycarboxylic acid polymer and water; and (3) a mixture of the water soluble polymer having a branched structure, the polycarboxylic acid polymer, and water.

As described, in method (ii), in the case in which the solvent to be used for the polymerization contains essential water, a mixture containing a water-soluble polymer and water is used as the solvent for the polymerization. and as the water soluble polymer to be used as the solvent, those which do not have any polymerizable unsaturated double bonds and therefore are not taken up in the polymer are preferable. For example, water-soluble polymers other than so-called macromonomers are preferably used.

The polycarboxylic acid polymer can be used in the form of a cement additive, or the polycarboxylic acid monomer can be the water-soluble polymer having the branched structure.

The concentration of the water-soluble polymer to be used as the solvent in the above-mentioned polymerization is preferably not less than 1% by mass and not more than 80% by mass in the total 100% by mass of the water-soluble polymer and water for sufficiently show the effect of the water-soluble polymer as a solubility enhancing agent. More preferably it is not less than 3% by mass and not more than 60% by mass, and even more preferably not less than 5% by mass and not more than 40% by mass.

The amount of the water-soluble polymer to be used as the solvent for the polymer to be synthesized is preferably 1 to 500% by mass in the case where the amount of the polymer to be synthesized is assumed to be 100% by mass. More preferably it is 1 to 300% by mass, still more preferably 1 to 80% by mass, especially preferably 5 to 60% by mass, and most preferably 10 to 40% by mass.

Furthermore, the amount of the water-soluble polymer to be used as a solvent for the monomeric components to be used for the polymerization is preferably not less than 2% by mass in the case where the total amount of all of the components is assumed monomeric to be used for the polymerization is 100% by mass, and more preferably the amount exceeding 10% by mass.

With respect to the above-mentioned water-soluble polymer to be used as a solvent, the water-soluble polymer having a branched structure may be one or two or more polymer species having a structure in which the polymer-forming chains are branched and at the same time least one polymer species selected from the group consisting of alkylene oxide added to polyalkyleneimine (a polyalkyleneimine-alkylene oxide adduct), alkylene oxide added to a polyhydric alcohol (a polyhydric alcohol-alkylene oxide adduct), another alkylene oxide having a branched structure (alkylene oxide having a different branched structure from the polyalkyleneimine-alkylene oxide adduct and an adduct of polyhydric alcohol-alkylene oxide), and polyamidopolyamine having a branched structure is preferably used.

Furthermore, as a polycarboxylic acid polymer to be used as a solvent, it is preferably water soluble and preferably contains 10 or more average molar addition number of the polyoxyalkylene groups. By

Accordingly, the polymer can sufficiently show the effect as a solubility enhancing agent. More preferably it is not less than 25 and not more than 200, even more preferably it is not less than 25 and not more than 100.

Regarding the water solubility of the water-soluble polymer to be used as the solvent, it is preferable to specify the water solubility by HLB (Hydrophilic-Lipophilic Equilibrium). It is preferable that the polycarboxylic acid polymer to be used as a solvent has 19 or more HLB, and it is preferable that another water-soluble polymer has an HLB of 15 or more.

The above-mentioned method (ii) can be suitably applied for the case where the water solubility of the monomeric components to be used for polymerization is low and / or the case where the hydrophobicity of the polymer to be produced is high, and the Gel formation during polymerization can be efficiently suppressed. In such a case, the polymer to be used as a solvent functions effectively as a solubility enhancing agent. Also in this case, the degrees of water solubility and hydrophobicity are preferably specified on the basis of HLB and the average HLB value of the monomeric and / or HLB components of the polymer to be produced is preferably less than 19.5 .

If the HLB of the monomer components and the polymer to be produced is less than 19.5, method (ii) can effectively suppress gel formation in said polymerization system, whereas a conventional production method possibly produces a lot of gel. . The HLB is more preferably not more than 19, more preferably not more than 18.5. In a conventional production method, if the HLB of the monomer components and the polymer to be produced is 18.5 to 19, a large amount of gel is produced. If this is not more than 18.5, there is a high possibility that the polymerization will become difficult. For example, monomeric components are brought together in the polymerization system, so that it becomes impossible to carry out the polymerization uniformly: the polymer to be produced has too high a molecular weight to be insoluble in water; and the polymerization of only monomeric components with high hydrophilicity is promoted and the copolymerization is not sufficiently promoted.

Method (ii) can also preferably be applied if the pH of the polymerization system, ie the pH of the polymerization solution is not less than 1.5 and not more than 7. The pH is more preferably not more than 5. If the pH exceeds this range, the solubility in water of the polymer to be produced increases; therefore, even in the case where the pH is high and the HLB of the monomer components and the polymer to be produced is low, the gel formation probably becomes difficult and the method (ii) cannot sufficiently show the effect advantageous in some cases. However, if the pH is too high, the polymerization ratio of the acidic monomers among the monomer components probably decreases. Accordingly, to effectively show the effect of method (ii), the pH is preferably controlled to be in the range mentioned above.

The above-mentioned HLB is preferably calculated according to Griffin's HLB and is calculated from the following equation:

HLB = (molecular weight of a hydrophilic group) / (molecular weight of the whole body) x 100/5 = (% by mass of the hydrophilic group) ^

In the Griffn HLB mentioned above, for example, an alkyl group is a hydrophobic group and CH2CH2O is a hydrophilic group and the calculation should be performed using 44 as the molecular weight. By the way, in the case of a propylene oxide chain (CH (CH₃) CH2O), one methyl group is considered a hydrophobic group and the others are considered hydrophilic groups (this is not determined according to the Griffin HLB).

Regarding the polycarboxylic acid polymer to be used as solvents in method (ii), the HLB is applied to the side chain (except for carboxylic acid). However, an ester part (COO) is not included.

For example, the calculation can be carried out as follows.

In the case of methyl methacrylate (MMA), the side chain is a methyl group and the HLB value is 0. In the case of methoxypolyethylene glycol monomethacrylate (the average molar addition number of ethylene oxide: 10), the chain side is methoxypolyethylene glycol (methoxy PEG) and the HLB is as follows.

HLB = (44x10) / (15 + 44x10) x 100/5 = 19.34

In the case where the composition of the monomeric components is MMA / methoxypolyethylene glycol monomethacrylate (60/40 molar ratio), the HLB is as follows.

HLB = (44x10x40) / {15x60 + (15 + 44x10) x40} x100 / 5 = 18.4

By the way, side chain means the part represented by "(side chain)" when a monomer is represented by "X- (side chain)" (X represents, for example, C = C-COO, C = CCC or C = DC).

In the above-mentioned method (ii), as a way of existence of the water-soluble polymer and the polymerization method, the polymerization can be carried out by filling a reaction vessel with a polymer at

ES 2 396 047 T3 using as solvent or monomeric components or polymerization can be carried out by adding them dropwise to the reaction vessel. For example, the following methods (1) to (3) are preferable: (1) a reaction vessel is filled with water and the water-soluble polymer, and the monomeric components are added dropwise to carry out polymerization. ; (2) a reaction vessel is filled with water, and the monomer components and the water-soluble polymer are added dropwise thereto to carry out polymerization; and (3) a reaction vessel is filled with water, the water-soluble polymer, and the monomer components to carry out polymerization.

In the reaction vessel in which the water-soluble polymer is obtained by polymerization, the monomeric components can be added freshly, preferably the monomeric components can be added dropwise recently, to carry out the polymerization. In such case, it is preferable to use a water-soluble polymer as a solvent other than a polycarboxylic acid polymer, and it is more preferable to use a water-soluble polymer having a branched structure as a solvent. Furthermore, it is preferable to carry out the polymerization in such a way that gel formation due to the function of the polymer as a solvent is sufficiently suppressed.

In the above-mentioned method (ii), gel formation can be suppressed. The amount of the gel is preferably in a range of not more than 5% by mass, more preferably not more than 0.1% by mass, in the case where it is assumed that the total amount of the monomeric components to be polymerized it is 100% by mass. Accordingly, the quality of the cement admixture compound of the present invention can be improved. The mass of the gel can be calculated by measuring the total mass of the gel remaining on a sieve when the polymerization reaction solution is filtered through a standardized sieve (mesh size 1 mm) according to JIS Z 8801 and the gel in state containing water that adheres to the reaction vessel, stirring paddles, thermometer.

As for the above-mentioned water-soluble polymer having a branched structure, it is preferable to use at least one polymer selected from the group consisting of a polyalkyleneimine-alkylene oxide adduct, a polyhydric alcohol-alkylene oxide adduct, alkylene oxide having a branched structure different from these, and polyamidopolyamine having a branched structure as described above.

The polyalkyleneimine-alkylene oxide adduct can be any polyalkyleneimine that contains an oxyalkylene group, and is preferably the compound resulting from the addition of an alkylene oxide to the nitrogen atom or atoms of the amino and / or imino group or groups of a polyalkyleneimine. , which is described in the above-mentioned poly (polyoxyalkylene) unsaturated monomer (C).

The polyhydric alcohol-alkylene oxide adduct can be any compound that has a structure that results from the attachment of an oxyalkylene group to the residue of a polyhydric alcohol, and is preferably the compound resulting from the addition of an alkylene oxide to the hydroxyl group or groups of a polyhydric alcohol, which is described in the above-mentioned poly (polyoxyalkylene) unsaturated monomer (C).

As the above-mentioned alkylene oxide having a branched structure different from these, a certain compound obtained by reacting alkylene oxide can be mentioned. The dendrimer compound is a compound having a branched structure comprising a plurality of straight chain sites extending radially from the center of the molecule. For example, mention may be made of a compound having a dendrimeric structure composed of a central branch part comprising at least one branch point and straight chain parts radially extending therefrom, and then at least three straight chain parts. in each individual molecule or a compound that has its cross-linked structure. The number of the straight chain parts in the dendrimer compound is preferably 3 to 500, and more preferably 10 to 200.

As a method for producing the aforementioned dendrimer compound, a method comprising using a compound containing at least one active hydrogen in a molecule as the starting substance and carrying out the reaction by adding a chain extending agent can be mentioned. If necessary, a branching agent can be added, and in such a case, the starting substance, the branching agent and the chain extending agent can be added successively or simultaneously to carry out the reaction.

As the above-mentioned starting substance, for example, in the case where the reaction is carried out by adding only the chain extending agent without using the branching agent, a compound containing three or more functional groups is preferred. reactive with the chain extender in a molecule. Furthermore, in the case where the branching is promoted using the branching agent, the starting substance is preferably a compound containing one or more functional groups reactive with the branching agent or the chain extending agent in a molecule. As such a starting substance, there may be mentioned, for example, a polysaccharide such as sorbitol; a polycarboxylic acid such as citric acid; a polyamine such as ethylenediamine and diethylenetriamine.

The chain extension agent mentioned above can be any compound capable of

ES 2 396 047 T3 develop molecular chains while leaving one or more active hydrogen atoms at the end through the continuous addition reaction to the active hydrogen atoms. Alkylene oxide is preferably used and the above-mentioned compounds can be used. The aforementioned branching agent can be any compound capable of being modified into a molecular form that recently has two or more active hydrogen atoms by reaction with an active hydrogen atom, and the agent can be a reactive compound or used for branching by reaction. with the end of mainly a linear molecular chain and which becomes a part of the molecular chain. As such a branching agent, for example, glycidol capable of adding two hydroxyl groups by a molecule addition by a ring-opening reaction of an epoxy group is preferably used.

In the compounds resulting from the addition of an alkylene oxide, the average molar addition number of the alkylene oxide is preferably not less than 10 and not more than 300. When it exceeds 300, the polymerization capacity of the monomer that provides these compounds can decrease. More preferably, it is not less than 15, and even more preferably not less than 20. On the other hand, it is more preferably not more than 270, even more preferably not more than 250, especially preferably not more than 220, and most preferably not more than 200.

The polyamidopolyamine having a branched structure can be any compound that has two or more amino groups and two or more amide bonds in each molecule, and it is preferably a polyamidopolyamine compound that results from the addition of 0 to 8 moles of an alkylene oxide or oxides containing from 2 to 4 carbon atoms to each molecule of the total amino and imino groups of the polyamidopolyamine obtained by reacting 1.0 mole of a polyalkylenepolyamine (hereinafter referred to as "compound (d1)") with 0.8 to 0.95 moles of a dibasic acid and / or an ester of a dibasic acid with an alcohol which contains 1 to 4 carbon atoms (hereinafter referred to as "compound (d2)"). In this case, the product obtained by condensation polymerization of compound (d1) and compound (d2) is converted into a polyamidopolyamine having a constant range of chain length formed by condensation polymerization in a molar ratio of compound (d1 ) / composite (d2) from 5/4 to 20/19 on average. And the addition of 0 to 8 moles of an alkylene oxide or oxides containing 2 to 4 carbon atoms to 1 mole of the sum of the amino and imino groups of this polyamidopolyamine is to provide the polyamidopolyamine compound.

Suitable as alkylene oxide (s) containing 2 to 4 carbon atoms are one or two or more species of ethylene oxide, propylene oxide and butylene oxide.

The above compound (d1) can be any compound having a plurality of alkylene groups and a plurality of amino and / or imino groups in each molecule. Suitable for use are one or two or more species of diethylenetriamine, triethylenetetraamine, tetraethylenepentaamine, pentaethylenehexaamine, dipropylenetriamine, tripropylenetriamine, and tetrapropylenepentaamine. Among these, diethylenetriamine and triethylenetetraamine are preferably used in view of their easy availability and cost of production.

Suitable for use as compound (d2) above (a dibasic acid and / or an ester of a dibasic acid with an alcohol containing 1 to 4 carbon atoms) one or two or more species of malonic acid, succinic acid , fumaric acid, maleic acid, glutamic acid, adipic acid, pimelic acid, phthalic acid, azelaic acid and sebacic acid, and esters of these with an alcohol containing 1 to 4 carbon atoms. Among these, adipic acid is preferably used in view of its easy availability and cost of production.

Suitable as the alcohol containing 1 to 4 carbon atoms and serving to form the above compound (d2) one or two or more species of methanol, ethanol, propanol and butanol, including isomers thereof.

Polyamidopolyamine is obtained by reacting compound (d1) with compound (d2), with or without the use of an additional compound or compounds other than these compounds. To obtain the above-mentioned polyamidopolyamine, it is essential to subject compound (d1) and compound (d2) to condensation polymerization, and in that case, for example, condensation polymerization techniques can be used. In this reaction method, the respective compounds may be reacted all at once or they may be reacted stepwise or successively.

As the polycarboxylic acid polymer to be used as a solvent, a polymer obtained by polymerization of monomeric components containing an unsaturated polyalkylene glycol monomer, an unsaturated carboxylic acid monomer and, if necessary, other unsaturated monomers are preferably used.

As the molar ratio of monomer components in the above-mentioned polycarboxylic acid polymer used as solvent, the molar ratio of (the polyalkylene glycol unsaturated monomer / the unsaturated carboxylic monomer / the other unsaturated monomer) is preferably 3 to 60/20 a of 95/0 to 50. This is more preferably 5 to 50/30 to 90/0 to 20.

The weight average molecular weight of the water soluble polymer having a branched structure and / or the polycarboxylic acid polymer is preferably 5,000 to 100,000, more preferably 10,000 to 40,000, and even more preferably 15,000 to 20,000.

ES 2 396 047 T3

As for the polymer having a nitrogen atom, which may be contained in the cement additive compound of the present invention, an alkylene oxide adduct of polyethyleneimine, polyethyleneimine, polyamidopolyamine, polyvinylpyrrolidone), a vinylpyrrolidone copolymer, are suitable, polyacrylamide, a polyacrylamide copolymer, a copolymer of a monomer having a nitrogen atom, and a copolymerizable monomer. In addition, as the polymer having a nitrogen atom, it is also possible to use the polymer having a nitrogen atom described in the above-mentioned water-soluble polymer in the above-mentioned method (ii).

Suitable as the alkylene oxide in the aforementioned polyethyleneimine alkylene oxide adduct, the same ones mentioned above, and the average molar addition number of the oxyalkylene group is preferably not less than 1 and not more than 100. More preferably , is not more than 50, even more preferably not more than 20, and most preferably not more than 10. The weight average molecular weight of the above-mentioned polymer having a nitrogen atom is preferably not less than 1,000 and not more than 1,000,000. More preferably, it is not less than 5,000 and not more than 100,000, even more preferably not less than 10,000 and not more than 50,000.

As the polymer having a branched structure and an oxyalkylene group, which may be contained in the cement additive compound of the present invention, The alkylene oxide added to a polyhydric alcohol (the polyhydric alcohol-alkylene oxide adduct) and the alkylene oxide having a branched structure (the alkylene oxide having a different branched structure from the polyalkyleneimine-oxide adduct) are preferably used. alkylene and polyhydric alcohol-alkylene oxide adducts). Furthermore, it is also possible to use those different of polymers having nitrogen atoms among the water-soluble polymers in the above-mentioned method (ii).

The cement additive and the cement additive compound of the present invention can be added to cement compositions such as cement paste, mortar, concrete and used in the same way as known cement additives. And these can be suitably used in ultra-high-strength concrete as well.

Suitable as the above cement composition are ones in general use containing cement, water, fine aggregate and coarse aggregate. These can be added with fine powders, such as fly ash, blast furnace slag, silica fume, and limestone. The expression "ultra-high resistance concrete" means the one generally called in the field of cement compositions, specifically that type of concrete which, in terms of resistance of its cementitious products, is comparable to or greater than that of cement species. conventional concrete even when the water / cement ratio is reduced compared to conventional levels. For example, even when the water / cement ratio is not more than 25% by mass, furthermore not more than 20% by mass, in particular not more than 18% by mass, particularly not more than 14% by mass, especially about 12% by mass, this type of concrete shows that level of workability in which no problem will arise in ordinary use, and the cementitious products show a compressive strength of not less than 60 N / mm², furthermore not less than 80 N / mm², even more not less than 100 N / mm², in particular not less than 120 N / mm², particularly not less than 160 N / mm², especially not less than 200 N / mm².

They are suitable as the ordinary old cement, high initial strength, ultra-high initial strength, moderate heat, white Portland cement; and mixed Portland cement species such as high alumina cement, calcium alumina cement, fly ash Portland cement, fly ash slag Portland cement or silica cement. As the amount of formulation and the unit moisture content of such cement per 1 m of concrete is, for example, to produce high-strength, high-durability concrete, the unit moisture content is preferably 100 to 185 kg / m3 and the water / cement ratio is preferably 10 to 70%. More preferably, the unit moisture content is 120 to 175 kg / m³, and the water / cement ratio is 20 to 65%.

As for the ratio of the addition amount of the cement additive and the cement additive compound of the present invention to the cement composition, it is preferred that the polycarboxylic acid polymer, which is contained in the present invention, assumes no less than 0.01% by mass but more than 10% by mass with respect to the total mass of the cement taken as 100% by mass. If this is less than 0.01% by mass, poor performance characteristics may occur. If this exceeds 10% by mass, the savings will be bad. More preferably it is not less than 0.05% by mass but more than 8% by mass, still more preferably not less than 0.1% by mass but more than 5% by mass. Said mass percent values ​​are small values ​​for solid matter.

The following combinations (1) to (6) of different constituents of cement and water in the above-mentioned cement composition can be mentioned as particularly preferred embodiments:

(1) Combination of &lt;1&gt; the cement additive of the present invention and &lt;2&gt; an oxyalkylene antifoam agent as two essential constituents. The mixing mass ratio of the oxyalkylene antifoaming agent &lt;2&gt; is preferably 0.01 to 20% by mass with respect to the cement additive &lt;1&gt;.

ES 2 396 047 T3 (2) Combination of &lt;1&gt; the cement additive of the present invention, &lt;2&gt; the oxyalkylene antifoaming agent, and &lt;3&gt; an AE (air introduction) agent as three essential constituents. Polyoxyalkylenes, polyoxyalkylene alkyl ethers, polyoxyalkylene acetylene ethers, polyoxyalkylene alkylamines are usable as the antifoaming agents. Among them, polyoxyalkylene alkylamines are especially preferable. As the mixing mass ratio of the cement additive &lt;1&gt; and the antifoaming agent &lt;2&gt;, the mixing mass ratio of the antifoaming agent &lt;2&gt; is preferably 0.01 to 20% by mass with respect to the cement additive &lt;1&gt;. Meanwhile, the mixing mass ratio of agent AE &lt;3&gt; is preferably 0.001 to 2% by mass with respect to cement.

(3) Combination of &lt;1&gt; the cement additive of the present invention and &lt;2&gt; a material segregation reducing agent as two essential constituents. Various thickening agents such as nonionic cellulose ethers, and compounds containing, as partial structures, a hydrophobic constituent comprising a hydrocarbon chain containing 4 to 30 carbon atoms and a polyoxyalkylene chain that results from the addition of 2 to 300 moles, on average, of an alkylene oxide or oxides containing 2 to 18 carbon atoms, among others. The mixing mass ratio between cement additive &lt;1&gt; and material segregation reducing agent &lt;2&gt; is preferably 10/90 to 99.99 / 0.01, and more preferably 50/50 at 99.9 / 0.1. Cement compositions containing this combination are suitable for use as high-flow concrete, self-filling concrete, and self-leveling compositions.

(4) Combination of &lt;1&gt; the cement additive of the present invention and &lt;2&gt; a retardant as two essential constituents. Usable as retardants with oxycarboxylic acids such as gluconic acid (salts) and citric acid (salts), saccharides such as glucose, sugar alcohols such as sorbitol, and phosphonic acids such as (aminotri) methylene phosphonic acid, among others. Oxycarboxylic acids are particularly preferred. The mixing mass ratio between cement additive &lt;1&gt; and retardant &lt;2&gt; is preferably 10/90 to 99.9 / 0.1, and more preferably 20/80 to 99/1.

(5) Combination of &lt;1&gt; the cement additive of the present invention and &lt;2&gt; an accelerator as two essential constituents. Usable as accelerators are soluble calcium salts such as calcium chloride, calcium nitrite, and calcium nitrate, chlorides such as iron chloride and magnesium chloride, thiosulfate salts, formic acid, and formate salts such as calcium formate, among others. The mixing mass ratio between cement additive &lt;1&gt; and accelerator &lt;2&gt; is preferably 0.1 / 99.9 to 90/10, and more preferably 1/99 to 70/30.

(6) Combination of &lt;1&gt; the cement additive of the present invention and &lt;2&gt; a sulfonic acid (type) dispersant containing a sulfonic acid group in the molecule as two essential constituents. Usable as the sulfonic acid dispersants are lignin sulfonates, naphthalenesulfonic acid formaldehyde condensates, melaminosulfonic acid-formalin condensates, polystyrene sulfonic acid salts or aminoarylsulfonic acid-phenol-formaldehyde condensates. The mixing mass ratio between the cement additive &lt;1&gt; and the sulfonic acid dispersant &lt;2&gt; is preferably 5/95 to 95/5, and more preferably 10/90 to 90/10.

In the present invention, when the cement additive compound is used in the cement composition, it is preferable to change the formulation forms (mixing forms) of the polymer according to the required properties and the mixing conditions of the cement composition. . For example, in view of the compressive strength, it is preferable to mix two species of introduced polymers with a backbone of PPG (polypropylene glycol) rather than mixing one species of said polymer. Thus, it becomes possible to improve the compressive strength by 3 to 15% in comparison with the case of mixing one species of the polymer. In addition, the state and the holding capacity of the settlement also become higher. The molar ratio of PO (propylene oxide) in a polymer species is preferably 3 to 20% by mole, especially preferably 8 to 15% by mole. On the other hand, in view of the water reducing ability, it is preferable to mix an introduced polymer species with a PPG backbone. When two species of the polymers are mixed, the amount of addition of the cement admixture compound possibly tends to increase. The molar ratio of PO in a polymer species is preferably 3 to 20 mol%, especially preferably 8 to 15 mol%.

The cement additive and the cement additive compound of the present invention, having the constitution described hereinabove, can be suitably applied to various cement compositions and, furthermore, can provide such a viscosity level as to facilitate work in the locations of its handling, so that the use of the cement additive of the present invention leads to an improvement in the water-reducing capacity of cement compositions and to an increased strength and durability of hardened products obtained therefrom and, further, to a viscosity that facilitates work at cement composition handling sites, thereby improving work efficiency in civil engineering construction and building structures.

BEST WAYS TO CARRY OUT THE INVENTION

ES 2 396 047 T3

The following examples illustrate the present invention more specifically. They are, however, in no way limiting the scope of the invention. In the examples, "part or parts" means "part or parts by mass" and "%" represents "% by mass", unless otherwise specified.

In the following Examples , the weight average molecular weight of the polymer was measured by the following conditions.

&lt;Molecular weight measurement conditions by GPC&gt;

Column used: guard Tosoh TSK SWXL + gel TSK G4000SWXL + G3000SWXL + G2000SWXL

Eluent: sodium acetate trihydrate (115.6 g) is dissolved in a mixed solvent consisting of 10999 g of water and 6001 g of acetonitrile, and the solution is further adjusted to pH 6.0 with acetic acid and used as the solution of the eluent.

Injection volume: 100 μl of the eluent solution with a polymer concentration of 0.5%

Eluent flow rate: 0.8 ml / min

Column temperature: 40 ° C

Standard samples: Polyethylene glycol, maximum molecular weights (Mp) 272500, 219300, 85000, 46000, 24000, 12600, 4250, 7100, 1470

Calibration curve order: 3rd order

Detector: Waters, Japan 410 differential refractive index detector

Analysis software: Waters, MILLENNIUM Ver. 3.21 from Japan

Production example 1 (Production of H- (OC2H4) 1₃- (OC₃H6) 2- (OC2H4) 10-OCH₃)

A reaction apparatus equipped with a thermometer, stirrer, raw material inlet tube, and nitrogen inlet tube was charged with 1100 g of polyethylene glycol monomethyl ether (n = 10) and 0.5 g of potassium hydroxide. The inside of the reaction vessel was purged with nitrogen, and heated to 120 ° C. While maintaining this temperature, 235 g of propylene oxide were added over 3 hours. After the addition, the reaction solution was aged at 120 ° C for 2 hours, and the reaction vessel was again purged with nitrogen and at 120 ° C. Then 1165 g of ethylene oxide were added over 3 hours. After the addition, the reaction solution was further aged at 120 ° C for 1 hour to obtain alkylene glycol monomethyl ether with a hydroxyl value of 48 mg-KOH / g.

Production example 2 (Production of monomer (a))

A reaction vessel equipped with a thermometer, a stirrer, raw material inlet tube and condensed water separation tube was charged with 2203 g of the alkylene glycol monomethyl ether obtained in Production Example 1,450 g of methacrylic acid, 59 g of para-toluenesulfonic acid monohydrate, 0.5 g of phenothiazine and, as azeotropic solvent, 265 g of cyclohexane. While maintaining the temperature at 115 ° C for 20 hours, the esterification was carried out by removing the condensed water. At the 99% esterification efficiency (the alkylene glycol monomethyl ether conversion ratio), 556 g of distilled water and 46 g of 30% sodium hydroxide solution were added. Then, the reaction vessel was heated again to remove cyclohexane by azeotropic boiling, and distilled water was added to obtain an aqueous solution of a mixture of 70% of the ester compound (a-1) having a monomer structure ( a) and 10% unreacted methacrylic acid.

Example A

A reaction vessel equipped with a thermometer, stirrer, dropping device, nitrogen inlet tube, and reflux condenser was charged with 50 g of distilled water, and the contents were heated to 80 ° C. Next, a solution composed of 203 g of a mixture of esterification product (a-1) and methacrylic acid obtained in Production Example 2, 17.6 g of methacrylic acid, 76.6 g of distilled water and 2, 8 g of 3-mercaptopropionic acid was added dropwise over 4 hours, and a solution consisting of 47.9 g of distilled water and 2.1 g of ammonium persulfate was added dropwise over 5 hours to the reaction vessel. The reaction mixture was then aged by keeping the temperature in the vessel at 80 ° C for 1 hour and cooled, and the mixture was neutralized with a 30% aqueous sodium hydroxide solution at pH 7. In addition, water was added thereto distilled to give a cement additive (1) (solid matter concentration 20%) containing a polymer

ES 2 396 047 T3 having 75% of the esterification product derived site (a-1) with a weight average molecular weight of

14000.

Example B

A reaction vessel equipped with a thermometer, stirrer, dropping device, nitrogen inlet tube, and reflux condenser was charged with 50 g of distilled water, and the contents were heated to 80 ° C. Next, a solution composed of 214 g of a mixture of the esterification product (a-1) and methacrylic acid obtained in Production Example 2, 8.6 g of methacrylic acid, 74.8 g of distilled water and 2.4 g of 3-mercaptopropionic acid was added dropwise over 4 hours, and a solution consisting of 47.9 g of distilled water and 2.1 g of ammonium persulfate was added dropwise over 5 hours to the reaction vessel. The reaction mixture was then aged by keeping the temperature in the vessel at 80 ° C for 1 hour and cooled, and the mixture was neutralized with a 30% aqueous sodium hydroxide solution at pH 7. In addition, water was added thereto distilled to give a cement additive (2) (20% solid matter concentration) containing a polymer having 80% of the site derived from the esterification product (a-1) with a weight average molecular weight of 15000.

Example C

A reaction vessel equipped with a thermometer, stirrer, dropping device, nitrogen inlet tube, and reflux condenser was charged with 50 g of distilled water, and the contents were heated to 80 ° C. Next, a solution composed of 214 g of a mixture of the esterification product (a-1) and methacrylic acid obtained in Production Example 2, 8.6 g of methacrylic acid, 74.8 g of distilled water and 1, 3 g of 3-mercaptopropionic acid was added dropwise over 4 hours, and a solution consisting of 47.9 g of distilled water and 2.1 g of ammonium persulfate was added dropwise over 5 hours to the reaction vessel. The reaction mixture was then aged by keeping the temperature in the vessel at 80 ° C for 1 hour and cooled, and the mixture was neutralized with a 30% aqueous sodium hydroxide solution at pH 7. In addition, water was added thereto distilled to give a cement additive (3) (20% solid matter concentration) containing a polymer having 80% of the site derived from the esterification product (a-1) with a weight average molecular weight of 20000.

Comparative Example A

A reaction vessel equipped with a thermometer, stirrer, dropping device, nitrogen inlet tube, and reflux condenser was charged with 333.7 g of distilled water, and the contents were heated to 80 ° C. Next, a solution composed of 375.3 g of methoxypolyethylene glycol monomethacrylate (the average molar addition number of ethylene oxide is 25), 74.7 g of methacrylic acid, 112.5 g of distilled water and 3.8 g of 3-mercaptopropionic acid was added dropwise over 4 hours, and a solution consisting of 94.8 g of distilled water and 5.2 g of ammonium persulfate was added dropwise over 5 hours to the reaction vessel. The reaction mixture was then aged by maintaining the temperature in the vessel at 80 ° C for 1 hour, and then cooled. Next, the mixture was neutralized with a 30% aqueous sodium hydroxide solution at pH 7, more distilled water was added to give a cement additive (comparative 1) (20% solid matter concentration) containing a polymer having a weight average molecular weight of 22000.

Using the cement additives obtained in Examples A to C and Comparative Example A, concrete was prepared using each additive, and the flowability and mixing states were evaluated with a trowel. The results are shown in Table 1.

&lt;Concrete test&gt;

(Concrete formulation)

Regarding the unit quantity of formulation, 172 kg / m were used³ of water, 491 kg / m³ cement (product of Taiheiyo Cement, ordinary Portland cement), 909.8 kg / m³ coarse aggregate (crushed Oume stone), 744.5 kg / m³ fine aggregate (sand from the Ohigawa River).

An antifoam agent MA404 (product of Pozzolith Bussan Co., Ltd.) and an AE agent MA303A (product of Pozzolith Bussan Co., Ltd.) were mixed in amounts of 0.003% and 0.01%, respectively, of the mass of cement.

The mixing amount of the cement additive with respect to the cement mass was calculated as the amount of solid matter of the additive, and is shown in Table 1 in% (% by mass).

In the aforementioned amount, cement, fine aggregates and coarse aggregates were loaded into a 50 L force mixer and conducted for dry mixing for 10 seconds. Subsequently, water formulated with each cement admixture was added, and further mixing was performed for 60 seconds to produce concrete. The obtained concrete was measured to determine the slump flow value and the amount of air (air content) according to the Japanese Industrial Standards (JIS A 1101,1128, and 6204). In the slump test, the time required from a point where a slump cone was measured is dragged to a point where the fluidization of concrete stopped, and was determined as the stop value

ES 2 396 047 T3 flow rate to be shown in table 1.

The condition of the concrete shows the feeling when the concrete was mixed using a trowel and was evaluated based on the values ​​of 5 points from 1 to 5 points. That is, 5 points were scored in the case of the excellent condition that a light touch and a wet but not slimy feel were felt and 1 point was scored in the case of the lower condition that the heavy and sticky touch and a feeling were felt. slimy and rigid, and the higher point means better, easier-to-handle concrete.

Table 1

<td>Cement additive</td><td>Amount of addition (% by mass)</td><td>Settling flow value (mm)</td><td>Flow stop value (sec)</td><td>Amount of air (% by volume)</td><td>Condition of concrete (point)</td>

<td> (1)</td><td> 0,15</td><td> 540</td><td> 11,4</td><td> 4,0</td><td> 4</td>

<td> (2)</td><td> 0,14</td><td> 480</td><td> 10,3</td><td> 4,6</td><td> 5</td>

<td> (3)</td><td> 0,14</td><td> 500</td><td> 10,8</td><td> 4,5</td><td> 5</td>

<td>(Comparative 1)</td><td> 0,13</td><td> 520</td><td> 13,3</td><td> 3,7</td><td> 1</td>

As shown in Table 1, the cement admixture of the present invention had short flow stop values, showing low viscosity and the feeling of mixing by a paddle was good and therefore it was found to be easy to apply. handle and excellent docility in construction.

Production example 3

A reaction apparatus made of glass equipped with a thermometer, stirrer, dropping device and reflux condenser was charged with 754 g of a polyethyleneimine-ethylene oxide adduct (compound obtained by adding 20 moles, on average, of oxide of ethylene to an active hydrogen atom of polyethyleneimine with a molecular weight of 600), 1.27 g of acetic acid and 0.15 g of p-methoxyphenol, and the contents were heated to 90 ° C with stirring. Keeping the temperature in the reaction system at 90 ° C, 12.5 g of glycidyl methacrylate was added over 30 minutes. After the addition was complete, stirring continued at 90 ° C for 1 hour, and then the contents were cooled to 60 ° C, an additional 768 g of water and 14.3 g of acetic acid were added to give a macromeric aqueous solution of polyethyleneimine-ethylene oxide adduct.

Production example 4

A reaction vessel equipped with a thermometer, stirrer, dropping device, nitrogen inlet tube, and reflux condenser was charged with 700 g of distilled water, and the contents were heated to 70 ° C. Next, a solution composed of 832.5 g of methoxypolyethylene glycol monomethacrylate (the average molar addition number of ethylene oxide is 10), 260.5 g of methacrylic acid, 154.1 g of methyl methacrylate, 36.2 g of a 48% aqueous sodium hydroxide solution, 40.2 g of 3-mercaptopropionic acid and 243 g of distilled water were added dropwise over 5 hours. Then, 240 g of a 2.1% aqueous hydrogen peroxide solution was added dropwise over 6 hours, 240 g of a 2.7% L-ascorbic acid aqueous solution was added dropwise over 6 hours . After 4 hours and 5 minutes from the start of the dripping of these solutions, 208 g of the macromeric solution obtained in Production Example 3 was added dropwise at 3.78 g per minute. After completion of the dripping of all the solutions, the temperature was kept at 70 ° C for 1 hour. The reaction mixture was then cooled and then neutralized with a 30% aqueous sodium hydroxide solution to pH 7, whereby a cement additive with a weight average molecular weight of 6000 is obtained as determined by chromatography of gel permeation and expressed based on polyethylene glycol equivalents.

Production example 5

A reaction vessel equipped with a thermometer, stirrer, dropping device, nitrogen inlet tube, and reflux condenser was charged with 995 g of distilled water, and the contents were heated to 70 ° C. Next, a solution composed of 1067 g of methoxypolyethylene glycol monomethacrylate (the average molar addition number of ethylene oxide is 6), 283 g of methacrylic acid, 41.2 g of a 48% aqueous solution of sodium hydroxide, 20 g of 3-Mercaptopropionic acid and 354 g of distilled water were added dropwise over 5 hours, and 240 g of a 6.5% aqueous ammonium persulfate solution were added dropwise over 6 hours to the reaction vessel. After completion of the dripping, the temperature was kept at 70 ° C for 1 hour. The reaction mixture was then cooled and then neutralized with a 30% aqueous sodium hydroxide solution to pH 7, thereby obtaining a cement additive with a weight average molecular weight of 14000 as determined by chromatography of gel permeation and expressed on the basis of polyethylene glycol equivalents.

Production example 6

ES 2 396 047 T3

A reaction apparatus equipped with a thermometer, stirrer, dropping device and reflux condenser was charged with 1200 g of a polyethyleneimine-ethylene oxide adduct (compound obtained by adding 3 moles, on average, of ethylene oxide to a 600 molecular weight polyethyleneimine active hydrogen atom), 0.25 g of methoquinone, 37.5 g of acetic acid, and the contents were heated to 90 ° C under reflux cooling with stirring. After maintaining the temperature at 90 ° C for 30 minutes, 94.7 g of glycidyl methacrylate was added dropwise over 1 hour to the reaction vessel. The contents were then aged at 90 ° C for 1 hour and then cooled to 65 ° C, and 1980 g of distilled water and 157.2 g of methacrylic acid were added. The contents were further cooled to room temperature to give a macromer of the polyethyleneimine-ethylene oxide adduct.

Production example 7

A glass-made reaction apparatus equipped with a thermometer, stirrer, dropping device, and reflux condenser was charged with 344 g of distilled water, and the inside of the reaction apparatus was purged with nitrogen with stirring, and the contents were heated to 70 ° C. Next, a monomeric aqueous solution composed of 1076 g of methoxypolyethylene glycol monomethacrylate (the average molar addition number of ethylene oxide is 4), 190 g of methacrylic acid, 754.6 g of the polyethyleneimine-oxide adduct macromeric solution of ethylene obtained in Production Example 6, 21.7 g of a 48% aqueous sodium hydroxide solution, 44.6 g of 3-mercaptopropionic acid and 287 g of distilled water were added dropwise over 5 hours, and 240 g of a 2.0% aqueous hydrogen peroxide solution and 240 g of an aqueous L-ascorbic acid solution were respectively added dropwise over 6 hours to the reaction vessel. Then, the temperature was further kept at 70 ° C for 1 hour, and then the polymerization reaction was terminated, whereby, a polycarboxylic acid cement additive having a weight average molecular weight of 10000 is obtained.

As shown in Table 2, a concrete test was carried out under the same conditions as described above using the cement admixture alone or in the form of mixtures. Results are shown in table 2.

Table 2

<td rowspan="2">Additive (mixing ratio)</td><td rowspan="2">Amount of addition (% by mass)</td><td colspan="3">Settling flow value (mm)</td><td rowspan="2">Water reduction capacity</td><td rowspan="2">Retention capacity</td><td rowspan="2">Condition of concrete (point)</td>

<td>Immediately after mixing</td><td>30 minutes later</td><td>60 minutes later</td>

<td>A-1</td><td> 0,17</td><td> 590</td><td> 405</td><td> 310</td><td> ©</td><td>Δ</td><td> 4</td>

<td>A-1 / B (30/70)</td><td> 0,275</td><td> 520</td><td> 450</td><td> 410</td><td>OR</td><td>OR</td><td> 4</td>

<td>A-1 / B / C (27/63/19)</td><td> 0,275</td><td> 525</td><td> 450</td><td> 410</td><td>OR</td><td>OR</td><td> 5</td>

<td>B</td><td> 0,5</td><td> 490</td><td> 500</td><td> 510</td><td>X</td><td> ©</td><td> 4</td>

<td>A-1 / D / E / C (27/44/19/10)</td><td> 0,28</td><td> 510</td><td> 470</td><td> 430</td><td>OR</td><td>OR</td><td> 5</td>

In Table 2, "A-1" means the cement additive (2) produced in Example B, "B" means the cement additive produced in Production Example 4, "C" means polyethyleneimine-oxide adduct. ethylene (compound obtained by adding 20 moles, on average, of ethylene oxide to an active hydrogen atom of polyethyleneimine with a molecular weight of 600), "D" means the cement additive produced in Production Example 5, "E" means the polycarboxylic acid cement additive produced in Production Example 7. The mixing ratio of the additives is a mass ratio of the solid matter and the amount of addition means the amount of the solid matters relative to cement on a mass% basis. The evaluation of the condition of the concrete was carried out as described above and the evaluation of the water reduction capacity and the retention capacity was carried out based on the following criteria:

®: Very good

O: Good

Δ: Quite lower

X: Lower

As shown in Table 2, in the cases in which both A-1 and B were used alone, the states of the

ES 2 396 047 T3 concrete were excellent enough. But in the case of A-1 alone, there is still room for improvement in the settlement flow holding capacity, and in the case of B alone, there is still room for improvement in the water-reducing capacity. However, its mixing provided an excellent additive in water reduction capacity and retention capacity without deteriorating the excellent condition of the concrete. Furthermore, the addition of C improved the condition of the concrete. In addition, the addition of C, D, and E to A-1 provided an excellent additive in water reducing ability, holding ability, and condition of the concrete.

Examples 1 to 27, Comparative Examples 1 to 7

With the monomers shown in table 3, the polymers (1) to (21) having the composition relationships in table 4 were obtained. The weight average molecular weights (Mw) of the respective polymers are shown in table 4 By mixing these polymers or adducts shown in Table 3, the cement additive compound of the present invention (Examples 1 to 27) and cement additive compounds for comparison (Comparative Examples 1 to 7) were obtained. The species of the polymers and adducts used and their mixing ratio are shown in Table 5.

Table 3

<td>Monomer</td><td>Structural formula or explanation</td>

<td>Monomer (1)</td><td>CH2 = C (CH3) COO- (C2H4O)₁3- (CaH6O) 2- (C2H4O)₁0-CH3</td>

<td>Monomer (2)</td><td>CH2 = C (CH3) COO- (C2H4O) 7- (CaH6O) 2- (C2H4O) 6-CH3</td>

<td>Monomer (3)</td><td>CH2 = C (CH3) COO- (C2H40) 4,5- (C3H6O)₁, 5- (C2H4O) 4-CH3</td>

<td>Monomer (4)</td><td>CH2 = C (CH3) CH2CH2-O- (C2H4O) 26- (CsH6O) 4- (C2H4O) 20-H</td>

<td>Monomer (5)</td><td>CH2 = C (CH3) COO- (C2H4O) 26-CH3</td>

<td>Monomer (6)</td><td>CH2 = C (CH3) COO- (C2H4O) 10-CH3</td>

<td>Monomer (7)</td><td>CH2 = C (CH3) COO- (C2H4O) 6-CH3</td>

<td>Monomer (8)</td><td>CH₂= C (CH₃) COO- (C₂H₄OR)₄-CH₃</td>

<td>Monomer (9)</td><td>CH2 = C (CH3) CH2CH2-O- (C2H4O) 50-H</td>

<td>Monomer (10)</td><td>Methacrylic acid</td>

<td>Monomer (11)</td><td>Acrylic acid</td>

<td>Monomer (12)</td><td>Maleic acid</td>

<td>Monomer (13)</td><td>A compound obtained by adding 1.5 moles of glycidyl methacrylate with respect to 1 mole of a polyalkyleneimine-alkylene oxide adduct obtained by adding 3 moles of ethylene oxide (EO) with respect to 1 equivalent of hydrogen atom active (-NH) derived from a polyethyleneimine amino group (Mw = 600)</td>

<td>Adduct (1)</td><td>A polyalkyleneimine-alkylene oxide adduct obtained by adding 3 moles of ethylene oxide with respect to 1 equivalent of active hydrogen atom (-NH) derived from an amino group of polyethyleneimine (Mw = 1800)</td>

<td>Adduct (2)</td><td>A polyalkyleneimine-alkylene oxide adduct obtained by adding 20 moles of ethylene oxide with respect to 1 equivalent of active hydrogen atom (-NH) derived from a polyethyleneimine amino group (Mw = 600)</td>

<td>Adduct (3)</td><td>A polyalkyleneimine-alkylene oxide adduct obtained by adding 10 moles of ethylene oxide, then 6 moles of propylene oxide and 10 more moles of ethylene oxide with respect to 1 equivalent of active hydrogen atom (-NH) derived of an amino group of polyethyleneimine (Mw = 600)</td>

<td>Adduct (4)</td><td>A polyalkyleneimine-alkylene oxide adduct obtained by adding 3 moles of ethylene oxide, then 6 moles of propylene oxide and 80 more moles of ethylene oxide with respect to 1 equivalent of active hydrogen atom (-NH) derived of an amino group of polyethyleneimine (Mw = 600)</td>

ES 2 396 047 T3

Table 4

<td>Polymer</td><td colspan="3">Composition</td><td colspan="3">Ratio (% by weight)</td><td>Molecular weight</td>

<td>Polymer (1)</td><td>Monomer (1)</td><td>Monomer (10)</td><td></td><td> 75,0</td><td> 25,0</td><td></td><td> 14000</td>

<td>Polymer (2)</td><td>Monomer (1)</td><td>Monomer (10)</td><td>Monomer (10)</td><td> 75,0</td><td> 15,0</td><td> 10,0</td><td> 13600</td>

<td>Polymer (3)</td><td>Monomer (1)</td><td>Monomer (10)</td><td></td><td> 90,5</td><td> 9,5</td><td></td><td> 21300</td>

<td>Polymer (4)</td><td>Monomer (1)</td><td>Monomer (10)</td><td></td><td> 90,5</td><td> 9,5</td><td></td><td> 35800</td>

<td>Polymer (5)</td><td>Monomer (1)</td><td>Monomer (10)</td><td></td><td> 92,5</td><td> 7,5</td><td></td><td> 40500</td>

<td>Polymer (6)</td><td>Monomer (2)</td><td>Monomer (10)</td><td></td><td> 87,5</td><td> 12,5</td><td></td><td> 22000</td>

<td>Polymer (7)</td><td>Monomer (2)</td><td>Monomer (10)</td><td></td><td> 87,5</td><td> 12,5</td><td></td><td> 17000</td>

<td>Polymer (8)</td><td>Monomer (3)</td><td>Monomer (10)</td><td></td><td> 85,0</td><td> 15,0</td><td></td><td> 22000</td>

<td>Polymer (9)</td><td>Monomer (3)</td><td>Monomer (10)</td><td></td><td> 85,0</td><td> 15,0</td><td></td><td> 17000</td>

<td>Polymer (10)</td><td>Monomer (4)</td><td>Monomer (11)</td><td></td><td> 85,0</td><td> 15,0</td><td></td><td> 38000</td>

<td>Polymer (11)</td><td>Monomer (4)</td><td>Monomer (11)</td><td></td><td> 92,7</td><td> 7,5</td><td></td><td> 35000</td>

<td>Polymer (12)</td><td>Monomer (4)</td><td>Monomer (12)</td><td></td><td> 87,5</td><td> 12,5</td><td></td><td> 30000</td>

<td>Polymer (13)</td><td>Monomer (5)</td><td>Monomer (10)</td><td></td><td> 80,0</td><td> 20,0</td><td></td><td> 22000</td>

<td>Polymer (14)</td><td>Monomer (5)</td><td>Monomer (10)</td><td></td><td> 87,5</td><td> 12,5</td><td></td><td> 20000</td>

<td>Polymer (15)</td><td>Monomer (5)</td><td>Monomer (10)</td><td></td><td> 90,5</td><td> 9,5</td><td></td><td> 37000</td>

<td>Polymer (16)</td><td>Monomer (6)</td><td>Monomer (10)</td><td></td><td> 75,0</td><td> 25,0</td><td></td><td> 20000</td>

<td>Polymer (17)</td><td>Monomer (7)</td><td>Monomer (10)</td><td></td><td> 75,0</td><td> 25,0</td><td></td><td> 8500</td>

<td>Polymer (18)</td><td>Monomer (8)</td><td>Monomer (10)</td><td>Monomer (13)</td><td> 60,</td><td> 20,0</td><td> 20,0</td><td> 9000</td>

<td>Polymer (19)</td><td>Monomer (9)</td><td>Monomer (eleven)</td><td></td><td> 85,0</td><td> 15,0</td><td></td><td> 38000</td>

<td>Polymer (20)</td><td>Monomer (9)</td><td>Monomer (eleven)</td><td></td><td> 92,7</td><td> 7,5</td><td></td><td> 35000</td>

<td>Polymer (21)</td><td>Monomer (9)</td><td>Monomer (12)</td><td></td><td> 87,5</td><td> 12,5</td><td></td><td> 30000</td>

In Table 4, "% by weight" represents "% by mass".

ES 2 396 047 T3

Table 5

<td rowspan="2"></td><td colspan="4">Polymer and adduct species</td><td colspan="4">Mixing ratio (% by weight)</td>

<td>Polymer A</td><td>Polymer B</td><td>Polymer C</td><td>Adduct</td><td>Polymer A</td><td>Polymer B</td><td>Polymer C</td><td>Adduct</td>

<td>Example 1</td><td>Polymer (1)</td><td>Polymer (3)</td><td></td><td></td><td> 30</td><td> 70</td><td></td><td></td>

<td>Example 2</td><td>Polymer (1)</td><td>Polymer (4)</td><td></td><td></td><td> 30</td><td> 70</td><td></td><td></td>

<td>Example 3</td><td>Polymer (1)</td><td>Polymer (4)</td><td></td><td></td><td> 20</td><td> 80</td><td></td><td></td>

<td>Example 4</td><td>Polymer (1)</td><td>Polymer (5)</td><td></td><td></td><td> 30</td><td> 70</td><td></td><td></td>

<td>Example 5</td><td>Polymer (1)</td><td>Polymer (3)</td><td></td><td>Adduct (2)</td><td> 30</td><td> 60</td><td></td><td> 10</td>

<td>Example 6</td><td>Polymer (1)</td><td>Polymer (3)</td><td></td><td>Adduct (3)</td><td> 30</td><td> 60</td><td></td><td> 10</td>

<td>Example 7</td><td>Polymer (1)</td><td>Polymer (3)</td><td></td><td>Adduct (4)</td><td> 30</td><td> 60</td><td></td><td> 10</td>

<td>Example 8</td><td>Polymer (2)</td><td>Polymer (5)</td><td></td><td></td><td> 30</td><td> 70</td><td></td><td></td>

<td>Example 9</td><td>Polymer (1)</td><td>Polymer (17)</td><td>Polymer (18)</td><td>Adduct (1)</td><td> 23</td><td> 47</td><td> 15</td><td> 15</td>

<td>Example 10</td><td>Polymer (1)</td><td>Polymer (17)</td><td>Polymer (18)</td><td>Adduct (3)</td><td> 23</td><td> 47</td><td> 15</td><td> 15</td>

<td>Example 11</td><td>Polymer (1)</td><td>Polymer (17)</td><td>Polymer (18)</td><td>Adduct (4)</td><td> 23</td><td> 47</td><td> 15</td><td> 15</td>

<td>Example 12</td><td>Polymer (1)</td><td>Polymer (17)</td><td>Polymer (6)</td><td>Adduct (4)</td><td> 23</td><td> 47</td><td> 15</td><td> 15</td>

<td>Example 13</td><td>Polymer (13)</td><td>Polymer (17)</td><td>Polymer (6)</td><td>Adduct (4)</td><td> 23</td><td> 47</td><td> 15</td><td> 15</td>

<td>Example 14</td><td>Polymer (1)</td><td>Polymer (7)</td><td></td><td>Adduct (4)</td><td> 30</td><td> 60</td><td></td><td> 10</td>

<td>Example 15</td><td>Polymer (13)</td><td>Polymer (7)</td><td></td><td>Adduct (4)</td><td> 30</td><td> 60</td><td></td><td> 10</td>

<td>Example 16</td><td>Polymer (1)</td><td>Polymer (17)</td><td></td><td>Adduct (4)</td><td> 10</td><td> 80</td><td></td><td> 10</td>

<td>Example 17</td><td>Polymer (1)</td><td>Polymer (17)</td><td></td><td></td><td> 20</td><td> 80</td><td></td><td></td>

<td>Example 18</td><td>Polymer (1)</td><td>Polymer (7)</td><td></td><td>Adduct (3)</td><td> 30</td><td> 60</td><td></td><td> 10</td>

<td>Example 19</td><td>Polymer (1)</td><td>Polymer (8)</td><td></td><td></td><td> 30</td><td> 70</td><td></td><td></td>

<td>Example 20</td><td>Polymer (1)</td><td>Polymer (9)</td><td></td><td></td><td> 30</td><td> 70</td><td></td><td></td>

<td>Example 21</td><td>Polymer (16)</td><td>Polymer (9)</td><td></td><td></td><td> 30</td><td> 70</td><td></td><td></td>

<td>Example 22</td><td>Polymer (16)</td><td>Polymer (9)</td><td></td><td>Adduct (4)</td><td> 30</td><td> 60</td><td></td><td> 10</td>

<td>Example 23</td><td>Polymer (10)</td><td>Polymer (7)</td><td></td><td></td><td> 20</td><td> 80</td><td></td><td></td>

ES 2 396 047 T3

<td>Example 24</td><td>Polymer (10)</td><td>Polymer (17)</td><td></td><td></td><td> 20</td><td> 80</td><td></td><td></td>

<td>Example 25</td><td>Polymer (eleven)</td><td>Polymer (7)</td><td></td><td></td><td> 30</td><td> 70</td><td></td><td></td>

<td>Example 26</td><td>Polymer (12)</td><td>Polymer (7)</td><td></td><td></td><td> 20</td><td> 80</td><td></td><td></td>

<td>Example 27</td><td>Polymer (12)</td><td>Polymer (17)</td><td></td><td></td><td> 20</td><td> 80</td><td></td><td></td>

<td>Ex Comp. 1</td><td>Polymer (13)</td><td>Polymer (14)</td><td></td><td></td><td> 30</td><td> 70</td><td></td><td></td>

<td>Ex Comp. 2</td><td>Polymer (13)</td><td>Polymer (fifteen)</td><td></td><td></td><td> 40</td><td> 60</td><td></td><td></td>

<td>Ex Comp. 3</td><td>Polymer (16)</td><td>Polymer (17)</td><td>Polymer (18)</td><td>Adduct (1)</td><td> 23</td><td> 47</td><td> 15</td><td> 15</td>

<td>Ex Comp. 4</td><td>Polymer (13)</td><td>Polymer (17)</td><td>Polymer (18)</td><td>Adduct (2)</td><td> 23</td><td> 47</td><td> 15</td><td> 15</td>

<td>Ex Comp. 5</td><td>Polymer (13)</td><td>Polymer (17)</td><td></td><td>Adduct (2)</td><td> 10</td><td> 80</td><td></td><td> 10</td>

<td>Ex Comp. 6</td><td>Polymer (19)</td><td>Polymer (14)</td><td></td><td></td><td> 20</td><td> 80</td><td></td><td></td>

<td>Ex Comp. 7</td><td>Polymer (twenty)</td><td>Polymer (14)</td><td></td><td></td><td> 30</td><td> 70</td><td></td><td></td>

In Table 5, "% by weight" represents "% by mass".

&lt;Concrete test&gt;

With the cement additives shown in Examples 1 to 27 and Comparative Examples 1 to 7, concretes were prepared and the respective properties were evaluated for each concrete. The concrete formulation followed the relationship shown in Table 6 below.

Table 6

<td rowspan="2">W / C (% by mass)</td><td rowspan="2">Fine aggregate ratio (% by volume)</td><td colspan="5">Mixing unit quantity (kg / m³)</td>

<td>Air</td><td>Cement water</td><td>Cement</td><td>Coarse aggregate</td><td>Fine aggregate</td>

<td> 45</td><td> 48,1</td><td> 45</td><td> 172,0</td><td> 382,2</td><td> 909,8</td><td> 835,1</td>

<td> 30</td><td> 42,9</td><td> 45</td><td> 172,2</td><td> 573,3</td><td> 909,8</td><td> 676,6</td>

The descriptions in Table 6 are as follows.

W / C (% by mass): water / cement x 100

Fine aggregate ratio (% by volume):

Amount of fine aggregates / (coarse aggregates + fine aggregates) x 100

Cement: mix three species of ordinary Portland cements, produced by Taiheiyo Cement, Sumitomo Osaka Cement and Ube Mitsubishi Cement

Coarse aggregate: crushed limestone produced in Hachinohe, Aomori prefecture

Fine aggregate: quarry sand produced in Chiba prefecture

With the aforementioned formulation, the concretes were mixed using a forced action mixer (40 rpm rotation: 50 l content). The mixing method was as follows, and 30 liters of

ES 2 396 047 T3 concrete per batch.

W / C 45 (in the case where W / C is 45% by mass): Coarse aggregates, fine aggregates and cement were charged at once, and mixing was done at dry mixing for 10 seconds .

Then, water mixed with the cement additive was added to carry out mixing for 90 seconds to produce a concrete.

W / C 30 (in the case where W / C is 30% by mass): The fine aggregates and the cement were charged at once, and the mixing was carried out at dry mixing for 10 seconds. Then, water mixed with the cement additive was added to carry out mixing for 60 seconds. In addition, the coarse aggregates were loaded into it, and the mixture was mixed for 60 seconds to produce a concrete.

The results in the case that W / C is 45% by mass are shown in Table 7, and the results in the case that W / C is 30% by mass are shown in Table 8, respectively.

ES 2 396 047 T3

Table 7

<td rowspan="14">(W / C = 45%)</td><td rowspan="4">Evaluation elements</td><td colspan="2">* 9 compressive strength</td><td>or</td><td>OR</td><td>OR</td><td>OR</td><td>or</td><td>OR</td><td>OR</td><td>OR</td><td>OR</td><td>OR</td><td>or</td>

<td colspan="2">* 8 status</td><td>or</td><td>OR</td><td>v ~ o</td><td>v ~ o</td><td>v ~ o</td><td>OR</td><td>OR</td><td>OR</td><td>OR</td><td>OR</td><td>or</td>

<td colspan="2">* 7 slump holding capacity</td><td> ©</td><td>OR</td><td>or</td><td> ©</td><td>or</td><td> ©</td><td> ©</td><td>OR</td><td> &lt;</td><td>OR</td><td>or</td>

<td colspan="2">* 6 water reduction capacity</td><td>or</td><td> ©</td><td> ©</td><td> &lt;</td><td>or</td><td>OR</td><td>OR</td><td>OR</td><td>or</td><td>or</td><td>or</td>

<td colspan="2">* 5 compressive strength</td><td>N AND E z</td><td> 48,6</td><td> 49,1</td><td> 49.7</td><td> 48,8</td><td> 48,6</td><td> 50,4</td><td> 51,3</td><td> 50,9</td><td> 46,8</td><td> 49,6</td><td> 50,0</td>

<td colspan="2">Initial air quantity</td><td>% by volume</td><td>CM sf</td><td>CD</td><td>CD sf</td><td>The f</td><td>OR sf</td><td>sf</td><td>CD CO</td><td>IT</td><td>CM sf</td><td>CO sf</td><td>CD sf</td>

<td colspan="2">4 * Slump flow decrease ratio</td><td> £</td><td> -12,8</td><td> -19,8</td><td> -16,5</td><td> -11,3</td><td> -17,1</td><td> -13,6</td><td> -13,4</td><td> -19,5</td><td> -20,2</td><td>IT</td><td> -18,1</td>

<td rowspan="3">Settlement flow value</td><td>60 minutes later</td><td>mm</td><td> 375</td><td> 325</td><td> 355</td><td> 355</td><td> 340</td><td> 350</td><td> 355</td><td> 330</td><td> 335</td><td> 330</td><td> 340</td>

<td>30 minutes later</td><td>mm</td><td> 405</td><td> 355</td><td> 415</td><td> 370</td><td> 375</td><td> 386</td><td> 395</td><td> 360</td><td> 350</td><td> 360</td><td> 370</td>

<td>Initial phase</td><td>mm</td><td> 430</td><td> 405</td><td> 425</td><td> 400</td><td> 410</td><td> 405</td><td> 410</td><td> 410</td><td> 420</td><td> 400</td><td> 415</td>

<td colspan="2">* 3 agent AE</td><td>% in weigh</td><td> 0,01</td><td> 0,01</td><td> 0,01</td><td> 0,01</td><td> 0,01</td><td> 0,01</td><td> 0,01</td><td> 0,01</td><td> 0,001</td><td> 0,001</td><td> 0,001</td>

<td colspan="2">* 2 antifoam agent</td><td>% in weigh</td><td> 0,0071</td><td> 0,007</td><td> 0,005</td><td> 0,005</td><td> 0,005</td><td> 0,007</td><td> 0,007</td><td> 0,005</td><td>OR</td><td>OR</td><td>OR</td>

<td colspan="2">* 1 additive</td><td>% in weigh</td><td> 0,18</td><td> 0,16</td><td> 0,16</td><td> 0,19</td><td> 0,16</td><td> 0,17</td><td> 0,17</td><td> 0,16</td><td> 0,18</td><td> 0,17</td><td> 0,17</td>

<td colspan="3"></td><td>Example 1</td><td>Example 2</td><td>Example 3</td><td>O Q_ E &lt;D UJ</td><td>Example 5</td><td>Example 6</td><td>Example 7</td><td>Example 8</td><td>Example 9</td><td>OR Q_ AND? &lt;D UJ</td><td>Example eleven</td>

ES 2 396 047 T3

<td rowspan="14">(W / C = 45%)</td><td rowspan="4">Evaluation elements</td><td colspan="2">* 9 compressive strength</td><td>or</td><td>or</td><td> ©</td><td> ©</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td>OR</td><td>or</td><td>OR</td>

<td colspan="2">or ~ or $ ° (Λ &lt;D</td><td>or</td><td>&lt;or</td><td>or</td><td>&lt;or</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td>OR</td><td>or</td><td>OR</td>

<td colspan="2">* 7 slump holding capacity</td><td> &lt;</td><td> &lt;</td><td> &lt;</td><td> &lt;</td><td>or</td><td>or</td><td> ©</td><td>or</td><td>or</td><td> ©</td><td>or</td><td>OR</td>

<td colspan="2">* 6 water reduction capacity</td><td> ©</td><td> ©</td><td>or</td><td> ©</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td>OR</td><td>or</td><td> ©</td>

<td colspan="2">* 5 compressive strength</td><td>N AND E z</td><td>co N</td><td>° θ N</td><td>co 'co</td><td>or IT</td><td>co co '</td><td>co r-. '</td><td>rCD</td><td>co'</td><td>O) r-. '</td><td>co r-. '</td><td>O) r-. '</td><td>LO O) '</td>

<td colspan="2">Initial air quantity</td><td>% by volume</td><td></td><td>hsf</td><td>co</td><td>IT</td><td>or what</td><td>it'</td><td>hm</td><td>IT</td><td>CM</td><td></td><td>hm</td><td>CM M^-'</td>

<td colspan="2">4 * Slump flow decrease ratio</td><td> £</td><td>CO o '</td><td>LO or 'CN</td><td>O) or 'CN</td><td>LO or 'CN</td><td>Mad'</td><td>or O) '</td><td>°° M · '</td><td>or O) '</td><td>Mad'</td><td>co</td><td>co co '</td><td>co O) '</td>

<td rowspan="3">Settlement flow value</td><td>60 minutes later</td><td>EE</td><td>LO or co</td><td>or co</td><td>Or youCO</td><td>OR CO CO</td><td>o co co</td><td>or CM co</td><td>Mad</td><td>or co</td><td>o co co</td><td>o LO co</td><td>I co co</td><td>LO CM CO</td>

<td>30 minutes later</td><td>EE</td><td>I co co</td><td>Youco</td><td>OO) CO</td><td>Orco</td><td>I co co</td><td>Mad</td><td>I CO co</td><td>I rco</td><td>or rco</td><td>o co co</td><td>I rco</td><td>LO CO CO</td>

<td>Initial phase</td><td>EE</td><td>I co co</td><td>or O) co</td><td>or with you^-</td><td>IT</td><td>LO O) co</td><td>LO O) co</td><td>LO or</td><td>or CM</td><td>LO or</td><td>or</td><td>or</td><td>IT OR</td>

<td colspan="2">* 3 agent AE</td><td>co &lt;υ ω _ &lt;1&gt; Q.</td><td>ooo '</td><td>ooo '</td><td>or</td><td>or</td><td>or</td><td>or</td><td>ooo '</td><td>ooo '</td><td>CM ooo '</td><td>CM ooo '</td><td>CM ooo '</td><td>co ooo '</td>

<td colspan="2">* 2 antifoam agent</td><td>% in weigh</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td>

<td colspan="2">OR &gt; ^r(or</td><td>co &lt;υ ω Q_</td><td>LO or</td><td>LO or</td><td>ro</td><td>co o</td><td>ro</td><td>ro</td><td>co or</td><td>CO or</td><td>co or</td><td>co or</td><td>ro</td><td>or</td>

<td colspan="3"></td><td>or Q. E ™ &lt;D LlJ</td><td>or Q. E $ 2 &lt;D LlJ</td><td>Example 14</td><td>or Q. E í &lt;D Í_U</td><td>or Q. AXIS &lt;D Í_U</td><td>or Q_ E ^ &lt;D LlJ</td><td>or Q. ΕΪ &lt;D i-Ll</td><td>or Q. E 2 &lt;D LlJ</td><td>Example twenty</td><td>or Q_ E cÑ &lt;D i-Ll</td><td>Example 22</td><td>Example 2. 3</td>

ES 2 396 047 T3

<td rowspan="14">(W / C = 45%)</td><td rowspan="4">Evaluation elements</td><td colspan="2">* 9 compressive strength</td><td>or</td><td>OR</td><td>OR</td><td>OR</td><td> &lt;</td><td> &lt;</td><td> &lt;</td><td> &lt;</td><td> &lt;</td><td> &lt;</td>

<td colspan="2">* 8 status</td><td>or</td><td>OR</td><td>OR</td><td>OR</td><td>X</td><td>X</td><td>A ~ X</td><td>X</td><td>X</td><td>X</td>

<td colspan="2">* 7 slump holding capacity</td><td> &lt;</td><td>OR</td><td>OR</td><td> &lt;</td><td>X</td><td> &lt;</td><td> &lt;</td><td>X</td><td>X</td><td>X</td>

<td colspan="2">* 6 water reduction capacity</td><td>or</td><td>or</td><td>or</td><td>or</td><td>or</td><td> &lt;</td><td> &lt;</td><td>or</td><td>or</td><td>or</td>

<td colspan="2">* 5 compressive strength</td><td>N AND E z</td><td> 48,2</td><td> 48,6</td><td> 48,2</td><td> 47,7</td><td> 45,9</td><td> 45,9</td><td> 45,0</td><td> 46,4</td><td> 45,5</td><td> 45,9</td>

<td colspan="2">Initial air quantity</td><td>% by volume</td><td>The f</td><td> 4,0</td><td> 3,8</td><td> 4,3</td><td>it'</td><td> 00</td><td> 4,4</td><td> 4,7</td><td> 4,2</td><td> 4,6</td>

<td colspan="2">4 * Slump flow decrease ratio</td><td> £</td><td> -21,5</td><td> -19,3</td><td> -18,5</td><td> -22,2</td><td> -25,6</td><td> -21,0</td><td> -22,6</td><td> -25,6</td><td>CN l CN</td><td> -30,8</td>

<td rowspan="3">Settlement flow value</td><td>60 minutes later</td><td>mm</td><td> 310</td><td> 335</td><td> 330</td><td> 315</td><td> 305</td><td> 320</td><td> 325</td><td> 305</td><td> 295</td><td> 270</td>

<td>30 minutes later</td><td>mm</td><td> 360</td><td> 380</td><td> 365</td><td> 350</td><td> 350</td><td> 365</td><td> 340</td><td> 345</td><td> 320</td><td> 310</td>

<td>Initial phase</td><td>mm</td><td> 395</td><td> 415</td><td> 405</td><td> 405</td><td> 410</td><td> 405</td><td> 420</td><td> 410</td><td> 405</td><td> 390</td>

<td colspan="2">* 3 agent AE</td><td>% in weigh</td><td> 0,004</td><td> £00'0</td><td> 0,004</td><td> £00'0</td><td> 0,002</td><td> 0,002</td><td> 0,001</td><td> 0,001</td><td> 0,002</td><td> 0,002</td>

<td colspan="2">* 2 antifoam agent</td><td>% in weigh</td><td>OR</td><td>OR</td><td>OR</td><td>OR</td><td>OR</td><td>OR</td><td>OR</td><td>OR</td><td>OR</td><td>OR</td>

<td colspan="2">* 1 additive</td><td>% in weigh</td><td> 0,13</td><td> 0,15</td><td> 0,16</td><td> 0,15</td><td> 0,16</td><td> 0,18</td><td> 0,18</td><td> 0,17</td><td> 0,16</td><td> 0,16</td>

<td colspan="3"></td><td>Example 24</td><td>Example 25</td><td>Example 26</td><td>Example 27</td><td>Ex Comp. 1</td><td>Ex Comp. 2</td><td>Ex Comp. 3</td><td>Ex Comp. 4</td><td>Ex Comp. 5</td><td>Ex Comp. 6</td>

ES 2 396 047 T3

<td rowspan="14">(W / C = 45%)</td><td rowspan="4">Evaluation elements</td><td colspan="2">* 9 compressive strength</td><td> &lt;</td>

<td colspan="2">* 8 status</td><td>X</td>

<td colspan="2">* 7 slump holding capacity</td><td>X</td>

<td colspan="2">* 6 water reduction capacity</td><td>or</td>

<td colspan="2">* 5 compressive strength</td><td>N AND E z</td><td> 46,4</td>

<td colspan="2">Initial air quantity</td><td>% by volume</td><td>The f</td>

<td colspan="2">4 * Slump flow decrease ratio</td><td> £</td><td> -34,2</td>

<td rowspan="3">Settlement flow value</td><td>60 minutes later</td><td>mm</td><td> 260</td>

<td>30 minutes later</td><td>mm</td><td> 300</td>

<td>Initial phase</td><td>mm</td><td> 395</td>

<td colspan="2">* 3 agent AE</td><td>% in weigh</td><td> 0,002</td>

<td colspan="2">* 2 antifoam agent</td><td>% in weigh</td><td>OR</td>

<td colspan="2">* 1 additive</td><td>% in weigh</td><td> 0,16</td>

<td colspan="3"></td><td>CL ω or OR</td>

ES 2 396 047 T3

The descriptions in Table 7 are as follows.

"% By weight" represents the ratio by mass of solids to 100% by mass of a cement solid.

Settlement flow value in Table 7 and Table 8 are measured by the following method:

Freshly mixed concrete (pre-mixed concrete) obtained by the above-mentioned method to produce concrete was remixed in 2 cycles with a trowel, and then the slump flow value was measured: the slump flow value was defined as the value of the initial phase. In addition, the concrete was remixed in 2 cycles with a trowel after 30 minutes and 60 minutes from the start of mixing (just before the start of mixing by adding mixing water), and then the slump flow value was measured: the value of Settling flow was defined respectively as the value 30 minutes later and the value 60 minutes later.

* 1 Total amount after mixing of Polymers A, B, C and adducts * 2 The antifoam agent manufactured by NMB Company (trademark: MICROAIR 404) was used * 3 The agent AE manufactured by NMB Company (trademark : MICROAIR 303) * 4 Calculated by the following formula {(Settling flow value after the 60 minute period) - (the initial settling flow value) / the initial settling flow value * 5 Resistance measurement values compression after curing in water for 7 days; measurements were carried out according to JIS A1108 * 6 Evaluated as follows according to the amount of additive used (* 1) ®: not more than 0.16% by mass

O: more than 0.16% by mass and not more than 0.18% by mass

Δ: more than 0.18% by mass and not more than 0.22% by mass

X: greater than 0.22% by mass * 7 Evaluated as follows by the slump flow decrease ratio (* 4) ®: not greater than -15%

Or: greater than -15% and not greater than -20%

Δ: greater than -20% and not greater than -25%

X: greater than -25% * 8 Concrete states

Or: Resistance is small when mixed; a light and smooth concrete

Δ: Intermediate between O and X

X: Resistance is great when mixed; a heavy and viscous concrete * 9 Evaluated as follows by compressive strength (* 5) ®: not less than 52 (N / mm²)

O: not less than 47 (N / mm²)

Δ: less than 47 (N / mm²)

ES 2 396 047 T3

Table 8

<td rowspan="12">(W / C = 30%)</td><td rowspan="3">Evaluation elements</td><td colspan="2">* 7 status</td><td>or</td><td>OR</td><td>V ~ O</td><td>V ~ O</td><td>v ~ o</td><td>OR</td><td>OR</td><td>OR</td><td>OR</td><td>OR</td><td>or</td>

<td colspan="2">* 6 slump holding capacity</td><td> &lt;</td><td> &lt;</td><td>OR</td><td> ©</td><td>or</td><td> ©</td><td> &lt;</td><td>OR</td><td> ©</td><td> ©</td><td> ©</td>

<td colspan="2">* 5 water reduction capacity</td><td> &lt;</td><td>or</td><td> &lt;</td><td> &lt;</td><td>or</td><td> &lt;</td><td>or</td><td> &lt;</td><td> &lt;</td><td> &lt;</td><td>or</td>

<td colspan="2">Initial air quantity</td><td>% by volume</td><td>IT</td><td> 4,6</td><td> 4,8</td><td> 4,8</td><td>it'</td><td>it'</td><td>LO_ M '</td><td>LO_ M '</td><td>LO_ M '</td><td> 4,2</td><td> 4,2</td>

<td colspan="2">4 * Slump flow decrease ratio</td><td> £</td><td> -14,0</td><td> -13,9</td><td>r- ~ CD</td><td> -4,2</td><td> -12,7</td><td> -4,9</td><td> -13,3</td><td>I heard</td><td> £‘£-</td><td>ψ</td><td>OR IT</td>

<td rowspan="3">Settlement flow value</td><td>60 minutes later</td><td>mm</td><td> 520</td><td> 525</td><td> 560</td><td> 575</td><td> 615</td><td>OR 00 IT</td><td> 520</td><td>or what</td><td> 595</td><td>or 00 IT</td><td> 565</td>

<td>30 minutes later</td><td>mm</td><td>OR 00 IT</td><td> 565</td><td>IT 00 LO</td><td> 595</td><td> 575</td><td> 009</td><td> 555</td><td>IT 00 LO</td><td> 640</td><td> 620</td><td> 605</td>

<td>Initial phase</td><td>mm</td><td> 605</td><td> 610</td><td> 009</td><td> 009</td><td> 590</td><td> 610</td><td> 009</td><td> 605</td><td> 615</td><td> 605</td><td> 595</td>

<td colspan="2">* 3 agent AE</td><td>% in weigh</td><td> 0,005</td><td> 0,005</td><td> 0,005</td><td> 0,005</td><td> 0,005</td><td> 0,005</td><td> 0,005</td><td> 0,004</td><td> £00'0</td><td> £00'0</td><td> 0,004</td>

<td colspan="2">* 2 antifoam agent</td><td>% in weigh</td><td>eoo'o</td><td> £00'0</td><td> £00'0</td><td> 0,004</td><td> 0,002</td><td> £00'0</td><td> £00'0</td><td>OR</td><td>OR</td><td>OR</td><td>OR</td>

<td colspan="2">* 1 additive</td><td>% in weigh</td><td> 0,38</td><td> 0,35</td><td> 0,37</td><td> 0,40</td><td> 0,34</td><td> 0,36</td><td> 0,34</td><td> 0,37</td><td> 0,38</td><td> 0,36</td><td> 0,35</td>

<td colspan="3"></td><td>Example 1</td><td>Example 2</td><td>Example 3</td><td>O Q_ E &lt;D UJ</td><td>Example 5</td><td>Example 6</td><td>Example 7</td><td>Example 8</td><td>Example 9</td><td>OR Q_ AND? &lt;D UJ</td><td>Exampleraise</td>

ES 2 396 047 T3

<td rowspan="12">(W / C = 30%)</td><td rowspan="3">Evaluation elements</td><td colspan="2">* 7 status</td><td>OR</td><td>V ~ O</td><td>or</td><td>V ~ O</td><td>OR</td><td>or</td><td>or</td><td>or</td><td>or</td><td>OR</td><td>or</td><td>OR</td>

<td colspan="2">* 6 slump holding capacity</td><td>or</td><td> &lt;</td><td> &lt;</td><td> &lt;</td><td> ©</td><td> ©</td><td>or</td><td>or</td><td>or</td><td>OR</td><td>or</td><td> &lt;</td>

<td colspan="2">* 5 water reduction capacity</td><td>or</td><td>or</td><td> &lt;</td><td> &lt;</td><td>OR</td><td>or</td><td> &lt;</td><td> &lt;</td><td> &lt;</td><td> &lt;</td><td>or</td><td>or</td>

<td colspan="2">Initial air quantity</td><td>% by volume</td><td>The F</td><td>sf</td><td>CD co '</td><td>or yes</td><td>CD_</td><td>co_ sf</td><td>CN lo '</td><td>or what</td><td>CD_ M^-'</td><td>r-</td><td>° θ</td><td>CD_</td>

<td colspan="2">4 * Slump flow decrease ratio</td><td> £</td><td>noo</td><td>ro '</td><td>sf</td><td>IT_</td><td>CD sf</td><td>LO CN</td><td>CN CD</td><td>co 00</td><td>CO 00</td><td>co CD</td><td>CO CD</td><td>CO o '</td>

<td rowspan="3">Settlement flow value</td><td>60 minutes later</td><td>EE</td><td>LO nLO</td><td>or nLO</td><td>or CD Ν '</td><td>OO LO</td><td>LO Ν 'CD</td><td>OR CD LO</td><td>O Ν 'LO</td><td>or CD LO</td><td>LO LO</td><td>or what</td><td>LO LO</td><td>LO CO LO</td>

<td>30 minutes later</td><td>EE</td><td>or CD LO</td><td>LO CD LO</td><td>O Ν 'LO</td><td>CD CN LO</td><td>LO LO CD</td><td>OR S</td><td>LO CD LO</td><td>OR CO LO</td><td>OR CD LO</td><td>LO rLO</td><td>LO CO LO</td><td>O rLO</td>

<td>Initial phase</td><td>EE</td><td>LO CD LO</td><td>LO or CD</td><td>O rLO</td><td>LO CO LO</td><td>IT S</td><td>LO OR CD</td><td>LO CD LO</td><td>OO CD</td><td>LO OR CD</td><td>or CD LO</td><td>IT S</td><td>oo CD</td>

<td colspan="2">* 3 agent AE</td><td>co &lt;υ ω ~ &lt;1&gt; Q.</td><td>CO OO o '</td><td>co ooo '</td><td>ro oo '</td><td>rO O o '</td><td>CO OO o '</td><td>CN OO o '</td><td>CN OO o '</td><td>OO o '</td><td>CN OO o '</td><td>OO o '</td><td>OO o '</td><td>LO OO o '</td>

<td colspan="2">* 2 antifoam agent</td><td>% in weigh</td><td>OR</td><td>or</td><td>or</td><td>or</td><td>OR</td><td>OR</td><td>OR</td><td>OR</td><td>OR</td><td>OR</td><td>OR</td><td>OR</td>

<td colspan="2">OR &gt; ^r(or</td><td>co &lt;υ ω £ crQ_</td><td>CO co o '</td><td>CN co o '</td><td>CD co o '</td><td>rco o '</td><td>CN CO o '</td><td>CO CO o '</td><td>CD CO o '</td><td>rco o '</td><td>rco o '</td><td>rco oo '</td><td>LO CO o '</td><td>CN CO o '</td>

<td colspan="3"></td><td>Example 12</td><td>or Q. E $ 2 &lt;D Lu</td><td>Example 14</td><td>Example fifteen</td><td>OR Q. axis &lt;D Lu</td><td>OR Q_ E ^ &lt;D Lu</td><td>OR Q. ΕΪ &lt;D Lu</td><td>or Q. E 2 &lt;D Lu</td><td>Example twenty</td><td>or Q_ E cÑ &lt;D Lu</td><td>Example 22</td><td>Example 2. 3</td>

ES 2 396 047 T3

<td rowspan="12">(W / C = 30%)</td><td rowspan="3">Evaluation elements</td><td colspan="2">* 7 status</td><td>or</td><td>OR</td><td>OR</td><td>OR</td><td>X</td><td>X</td><td>A ~ X</td><td>X</td><td>X</td><td>X</td>

<td colspan="2">* 6 slump holding capacity</td><td> &lt;</td><td>OR</td><td> &lt;</td><td> &lt;</td><td> &lt;</td><td> &lt;</td><td> ©</td><td>OR</td><td>X</td><td> &lt;</td>

<td colspan="2">* 5 water reduction capacity</td><td>or</td><td>OR</td><td>or</td><td>or</td><td>or</td><td>X</td><td> &lt;</td><td> &lt;</td><td>or</td><td>or</td>

<td colspan="2">Initial air quantity</td><td>% by volume</td><td> 4,3</td><td></td><td> 4,6</td><td>IT</td><td> 4,8</td><td> 4,6</td><td>IT_</td><td> 4,3</td><td> 4,9</td><td> 4,2</td>

<td colspan="2">4 * Slump flow decrease ratio</td><td> £</td><td> -13,1</td><td>CM I heard</td><td> -12,5</td><td> -14,9</td><td> -13,2</td><td> -12,1</td><td>oo '</td><td> -9,0</td><td> -20,5</td><td> -14,0</td>

<td rowspan="3">Settlement flow value</td><td>60 minutes later</td><td>mm</td><td> 530</td><td> 540</td><td> 525</td><td> 515</td><td> 525</td><td> 545</td><td> 665</td><td> 555</td><td> 465</td><td> 520</td>

<td>30 minutes later</td><td>mm</td><td> 560</td><td> 570</td><td> 575</td><td>OR IT</td><td> 575</td><td>IT 00 LO</td><td> 665</td><td> 605</td><td> 520</td><td> 565</td>

<td>Initial phase</td><td>mm</td><td> 610</td><td> 595</td><td> 009</td><td> 605</td><td> 605</td><td> 620</td><td> 615</td><td> 610</td><td>IT 00 LO</td><td> 605</td>

<td colspan="2">* 3 agent AE</td><td>% in weigh</td><td> 0,005</td><td>eoo'o</td><td> £00'0</td><td> £00'0</td><td> £00'0</td><td> £00'0</td><td> £00'0</td><td> £00'0</td><td> £00'0</td><td> £00'0</td>

<td colspan="2">* 2 antifoam agent</td><td>% in weigh</td><td>OR</td><td>OR</td><td>OR</td><td>OR</td><td>OR</td><td>OR</td><td>OR</td><td>OR</td><td>OR</td><td>OR</td>

<td colspan="2">* 1 additive</td><td>% in weigh</td><td> 0,30</td><td> 0,38</td><td> 0,35</td><td> 0,33</td><td> 0,32</td><td> 0,42</td><td> 0,42</td><td> 0,37</td><td> 0,33</td><td> 0,32</td>

<td colspan="3"></td><td>Example 24</td><td>Example 25</td><td>Example 26</td><td>Example 27</td><td>Ex Comp. 1</td><td>Ex. Comp. 2</td><td>Ex Comp. 3</td><td>Ex. Comp. 4</td><td>Ex. Comp. 5</td><td>Ex Comp. 6</td>

ES 2 396 047 T3

<td rowspan="12">(W / C = 30%)</td><td rowspan="3">Evaluation elements</td><td colspan="2">* 7 status</td><td>X</td>

<td colspan="2">* 6 slump holding capacity</td><td>X</td>

<td colspan="2">* 5 water reduction capacity</td><td>or</td>

<td colspan="2">Initial air quantity</td><td>% by volume</td><td> 3,9</td>

<td colspan="2">4 * Slump flow decrease ratio</td><td> £</td><td> -15,8</td>

<td rowspan="3">Settlement flow value</td><td>60 minutes later</td><td>mm</td><td>IT OR IT</td>

<td>30 minutes later</td><td>mm</td><td>OR IT</td>

<td>Initial phase</td><td>mm</td><td> 009</td>

<td colspan="2">* 3 agent AE</td><td>% in weigh</td><td> £00'0</td>

<td colspan="2">* 2 antifoam agent</td><td>% in weigh</td><td>OR</td>

<td colspan="2">* 1 additive</td><td>% in weigh</td><td> 0,32</td>

<td colspan="3"></td><td>CL ω or OR</td>

ES 2 396 047 T3

The descriptions in Table 8 are as follows.

"% By weight" represents the ratio of solids to 100% by mass of a cement solid.

* 1 Total amount after mixing of Polymers A, B, C and adducts * 2 The antifoam agent manufactured by NMB Company (trademark: MICROAIR 404) was used * 3 The agent AE manufactured by NMB Company (trademark : MICROAIR 303) * 4 Calculated by the following formula {(Settling flow value after the 60 minute period) - (the initial settling flow value)} / the initial settling flow value * 5 Evaluated as follows according to the amount of additive used (* 1):

®: not more than 0.30% by mass

O: more than 0.30% by mass and not more than 0.35% by mass

Δ: more than 0.35% by mass and not more than 0.40% by mass

X: greater than 0.40% by mass * 6 Evaluated as follows by the slump flow decrease ratio (* 4) ®: not greater than -5%

Or: greater than -5% and not greater than -10%

Δ: greater than -10% and not greater than -15%

X: greater than -15% * 7 Concrete states

Or: Resistance is small when mixed; a light and smooth concrete

Δ: Intermediate between 0 and X

X: Resistance is great when mixed; a heavy and viscous concrete

As shown in Table 7, in the formulation state of W / C = 45% by mass, it was found that instead of the case where an introduced polymer species is mixed with a backbone of PPG (polypropylene glycol) , the case where two species of the polymers are mixed is superior in the state and the slump retention ability, and it was especially found that the compressive strength improved by 3 to 15%. Additionally, the molar ratio of PO (propylene oxide) in a polymer species is especially preferably 8 to 15% by mole. On the other hand, as shown in table 8, in the formulation state of W / C = 30% by mass, it was found that the water reduction capacity was superior when a kind of introduced polymer was mixed with a skeleton by PPG. When two polymer species are mixed, the amount of addition tends to increase. The molar ratio of PO in a polymer species is preferably 8 to 15% by mole.

Furthermore, Comparative Examples 1 to 7 are the embodiments in which polymers without being introduced with a PPG backbone are used in combination, but it is clear that, compared to the Examples, they have a bad state and are not provided with strength. .

Regarding the correspondence of Examples and Comparative Examples, Examples 1 to 4 correspond to Comparative Examples 1 and 2, Examples 9 to 12 correspond to Comparative Examples 3 and 4, Examples 14 to 22 correspond to Examples Comparative Examples 1, 2 and 5, Examples 23 to 25 correspond to Comparative Example 6, and Examples 26 and 27 correspond to Comparative Example 7, respectively.

The present application claims priority according to 35 USC 119 of Japanese patent application No. 2003128594, filed May 7, 2003, entitled "CEMENT ADMIXTURE", Japanese patent application No. 2003-346161, filed October 3 2003, entitled "CEMENT ADMIXTURE AND CEMENT ADMIXTURE COMPOSITE."