JP6248261B2 - Cement strength improver - Google Patents

Description

  The present invention relates to a cement strength improver.

  Conventionally, it is a granular material obtained by pulverizing a material containing calcined kaolin, and in particular, a cement containing 5% by weight or more of fine powder having a particle size of 0.075 mm or less with respect to the entire granular material A strength improving material for a cured body is known (Patent Document 1).

JP 2003-306361 A

  In the conventional cement hardening body strength improvement material, there exists a problem that the intensity | strength of a cement composition does not fully improve. An object of the present invention is to provide a cement strength improver that can sufficiently improve the strength of a cement composition.

The feature of the cement strength improver of the present invention is that the fatty acid ester (A), at least one compound (B) selected from the group consisting of a hydrocarbon oil (b1 ) and a polyoxyalkylene compound (b3), and a fatty acid metal salt (c1), fatty acid amide (c2), viewed including the at least one solid particles (C) selected from the group consisting of wax (c3) and hydrophobic silica (c4), fatty acid esters (a), compound Based on the total weight of (B) and solid particles (C), the content of fatty acid ester (A) is 40 to 99% by weight, the content of compound (B) is 0.9 to 50% by weight, solid The gist is that the content of the particles (C) is 0.1 to 15% by weight .

  The cement strength improver of the present invention can sufficiently improve the strength of the cement composition. In particular, the compressive strength of the hardened body of the cement composition is dramatically improved.

  As fatty acid ester (A), the viscosity in 25 degreeC is 1-3000 mPa * s, and ester with a C2-C30 fatty acid and C1-C30 1-8 hydric alcohol is contained.

  The viscosity is measured with a Brookfield viscometer (25 ° C., 60 rpm) in accordance with “9 Viscosity Measurement Method Using a Single Cylindrical Rotational Viscometer” of JIS Z8803: 2011 (hereinafter the same). .

Fatty acids include saturated fatty acids and unsaturated fatty acids.
Saturated fatty acids include C2-C30 saturated fatty acids, and straight chain saturated fatty acids and branched chain saturated fatty acids can be used.

  Examples of the linear saturated fatty acid include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, serotic acid, and melicic acid.

  Examples of the branched chain saturated fatty acid include isobutyric acid, isovaleric acid, pivalic acid, and isostearic acid.

  As unsaturated fatty acid, C3-C30 unsaturated fatty acid is contained and a linear unsaturated fatty acid and a branched unsaturated fatty acid can be used.

  Examples of the linear unsaturated fatty acid include acrylic acid, crotonic acid, heptenoic acid, myristoleic acid, palmitoleic acid, oleic acid and triacontenoic acid.

  Examples of branched chain unsaturated fatty acids include methacrylic acid, isomiristoleic acid and isooleic acid.

  Of these, from the viewpoint of improving cement strength, linear saturated fatty acids and linear unsaturated fatty acids are preferable, and lauric acid, myristic acid, palmitic acid, stearic acid, crotonic acid, heptenoic acid, myristoleic acid, palmitolein are more preferable. Acids, oleic acid, erucic acid, linoleic acid and linolenic acid, particularly preferably myristic acid, palmitic acid, stearic acid, myristoleic acid, palmitoleic acid, oleic acid, erucic acid, linoleic acid and linolenic acid, most preferably palmitic acid , Stearic acid, palmitoleic acid, oleic acid, erucic acid, linoleic acid and linolenic acid.

  These fatty acids may be a single component or may contain a plurality of fatty acids.

  Among monohydric alcohols having 1 to 30 carbon atoms, monohydric alcohols include monools having 1 to 30 carbon atoms, such as methanol, ethanol, propanol, butanol, hexanol, octanol, decanol, undecanol, dodecanol, Examples include tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, icosanol, heicosanol and triacontanol.

  Dihydric alcohols include diols having 2 to 6 carbon atoms, such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, cyclohexanediol, butanediol, pentanediol, hexanediol, trimethylene glycol, catechol, resorcin and hydroquinone. Etc.

  The trihydric alcohol includes a triol having 3 to 5 carbon atoms, and examples thereof include glycerin, trimethylolpropane, trimethylolethane, butanetriol, and pentanetriol.

  The tetrahydric alcohol includes a tetraol having 5 to 6 carbon atoms, and examples thereof include pentaerythritol, diglycerin, sorbitan, and mannitan.

  Examples of the 5- to 8-hydric alcohol include polyols having 5 to 12 carbon atoms, and examples thereof include arabit, tetraglycerin, sorbit (sorbitol), mannitol, and sucrose.

  Among these, from the viewpoint of improving cement strength, a monohydric to tetrahydric alcohol is preferable, and ethylene glycol, propylene glycol, glycerin, trimethylol ethane, trimethylol propane, sorbitan, and a monohydric alcohol having 1 to 12 carbon atoms are more preferable. Particularly preferred are ethylene glycol, glycerin, methanol, ethanol, propanol and butanol, most preferred glycerin.

  The fatty acid ester (A) can be obtained by a known method. For example, a method obtained by partially or completely esterifying a fatty acid and an alcohol with an acid catalyst can be mentioned.

  Preferred examples of the fatty acid ester (A) include methyl laurate, octyldodecyl myristate, butyl stearate, sorbitan sesquioleate, glycerin (mono / di) oleate, rapeseed oil, soybean oil, corn oil and palm oil. . Note that “(mono / di)” means mono and / or di (hereinafter the same).

  These fatty acid esters (A) may be a single compound or may contain a plurality of compounds.

  The fatty acid ester (A) can be easily obtained from the market, and examples thereof include the following products.

<Ester of monohydric alcohol and fatty acid>
Exepearl (registered trademark) series (HO, MC, ML-85, IPM, IPP, OD-M, MS, BS, EH-S, TD-S, M-OL, MY-M, etc.) {Kao Corporation}
Unistar (registered trademark) series (M-182A, MB-816, MB-876, MB-871, MB-881, M-9676, M-2222SL, etc.) {NOF CORPORATION}

<Glycerin fatty acid ester>
RHEODOL (registered trademark) series (MS-50, MS-60, MS-165V, etc.) {Kao Corporation}
NIKKOL (registered trademark) series (MGU, MGM, AMV, ASEV, BV, MGIS, MGOL-70, DGS-80, etc.) {Nikko Chemicals Corporation}
Soybean oil, palm oil, palm oil, linseed oil, cottonseed oil, rapeseed oil, etc. {Nisshin Oillio Group Co., Ltd.}

<Trimethylolpropane fatty acid ester>
Trimethylolpropane tricaprylate, trimethylolpropane trilaurate, trimethylolpropane trioleate, etc. {Sanko Chemical Co., Ltd.}

<Sorbitan fatty acid ester>
Ionette (registered trademark) series (S-80, S-60C, S-80, S-85, etc.) {Sanyo Chemical Industries, Ltd.}

  The content (% by weight) of the fatty acid ester (A) is preferably 40 to 99, more preferably 50 to 90, based on the total weight of the fatty acid ester (A), the compound (B) and the solid particles (C). Especially preferably, it is 60-85.

  The compound (B) can be used without limitation as long as it is at least one selected from the group consisting of hydrocarbon oil (b1), higher alcohol (b2) and polyoxyalkylene compound (b3).

  Examples of the hydrocarbon oil (b1) include hydrocarbon oils having a viscosity at 25 ° C. of 1 to 500 mPa · s and an initial boiling point of 150 to 300 ° C. at normal pressure (approximately 101 kPa), mineral spirits, kerosene, paraffin, etc. Is mentioned.

  The higher alcohol (b2) includes natural alcohols and synthetic alcohols having 8 to 30 carbon atoms.

  Natural alcohols include saturated alcohols (such as capryl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, eicosanol, docosanol, tetracosanol, hexacosanol, octacosanol and myricyl alcohol) and unsaturated alcohols (such as oleyl alcohol). ) And the like.

  Synthetic alcohols include linear, unbranched saturated alcohols synthesized by the Ziegler method, linear primary alcohols or branched primary alcohols synthesized by the oxo method, and mixtures of these alcohols having different carbon numbers, In addition, linear secondary alcohol produced by air oxidation of paraffin and the like can be mentioned.

  Of these higher alcohols, natural alcohols are preferable from the viewpoint of improving cement strength, and cetyl alcohol, stearyl alcohol, oleyl alcohol, octyldodecanol and behenyl alcohol are more preferable.

  As a polyoxyalkylene compound (b3), if it is a compound containing several oxyalkylene group, it can be used without a restriction | limiting, and the compound represented by General formula (1) can illustrate preferably.

R ^1- (OA) n-OR ² (1)

R ¹ is an acyl group having 2 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a reaction residue obtained by removing a hydroxyl group from a 2 to 8 valent alcohol, or 1 to 30 carbon atoms. A reaction residue excluding a hydroxyl group of a partial ester of a ^{2- to} 8-hydric alcohol and a fatty acid having 1 to 30 carbon atoms, R ² is a hydrogen atom, an acyl group having 2 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, or An alkenyl group having 2 to 30 carbon atoms, OA represents an oxyalkylene group having 2 to 4 carbon atoms, and n represents an integer of 2 to 100.

Examples of the acyl group having 2 to 30 carbon atoms include a saturated carboxylic acyl group and an unsaturated carboxylic acyl group.
Examples of saturated carboxylic acid acyl groups include acetyl (ethanoyl), propanoyl, butanoyl, pentanoyl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, undecanoyl, dodecanoyl, tridecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, heptadecanoyl, Examples include decanoyl, nonadecanoyl, icosanoyl, eicosanoyl, heicosanoyl, henecosanoyl, docosanoyl, tricasanoyl, tetracosanoyl, pentacosanoyl, hexacosanoyl, heptacosanoyl, octacosanoyl, nonacosanoyl and triacontanoyl.

  Unsaturated carboxylic acid acyl groups include acryloyl, methacryloyl, crotonoyl, isocrotonoyl, butenoyl, butadienoyl, pentenoyl, hexenoyl, heptenoyl, octenoyl, nonenoyl, decenoyl, undecenoyl, dodecenoyl, tetradecenoyl, oleroyl, oleoyl , Cycloheptanoyl, methylcyclopentanoyl, methylcyclohexanoyl, methylcycloheptanoyl, cyclopentenoyl, 2,4-cyclopentadienoyl, cyclohexenoyl, 2,4-cyclohexadenoyl, cycloheptenoyl Methylcyclopentenoyl, methylcyclohexenoyl, methylcycloheptenoyl and the like.

  Examples of the alkyl group having 1 to 30 carbon atoms include a linear alkyl group and a branched alkyl group.

  Linear alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl , Tricosyl, tetracosyl, heptacosyl, hexaxyl, heptacosyl, octacosyl, nonacosyl and triaconsil.

  Examples of the branched alkyl group include isopropyl, isobutyl, t-butyl, isopentyl, neopentyl, isohexyl, 2-ethylhexyl, isotridecyl, isotetradecyl, isooctadecyl, isotriaconyl, 2-ethylhexyl, 2-propylheptyl, 2-propyl Examples include butyloctyl, 2-hexyldecyl, 2-octyldodecyl, 2-decyltetradecyl, 2-dodecylhexyl, 2-dodecylhexadecyl, 3,5,5-trimethylhexyl, and 3,7,11-trimethyldodecyl. It is done.

  Examples of the alkenyl group having 2 to 30 carbon atoms include straight-chain alkenyl groups and branched-chain alkenyl groups.

  Linear alkenyl groups include vinyl, allyl, propenyl, butenyl, pentenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, icocenyl, hexocenyl, , Tetracosenyl, heptacosenyl, hexaxenyl, heptacosenyl, octacocenyl, nonacosenyl, triaconenyl and the like.

  Examples of the branched alkenyl group include isobutenyl, isopentenyl, neopentenyl, isohexenyl, isotridecenyl, isooctadecenyl and isotriacontenyl.

  The divalent to octavalent alcohol is the same as that obtained by removing the monovalent alcohol from the above 1 to 30 carbon number 1 to 8 alcohol. In addition, the hydroxyl group removed from 2-8 hydric alcohol may be one, and multiple may be sufficient as it.

  As a reaction residue except the hydroxyl group of the partial ester of a C1-C30 2-8 hydric alcohol and a C1-C30 fatty acid, said C1-C30 2-8 hydric alcohol and said above-mentioned There may be one hydroxyl group that is a partial ester with a fatty acid having 1 to 30 carbon atoms and is excluded from a partial ester between a 2 to 8 alcohol having 1 to 30 carbon atoms and a fatty acid having 1 to 30 carbon atoms. However, there may be more than one.

Among R ¹ , from the viewpoint of improving cement strength, the hydroxyl group was removed from an acyl group having 2 to 22 carbon atoms, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, and a 2- to 4-valent alcohol. A reaction residue is preferably a reaction residue obtained by removing a hydroxyl group from a partial ester of a divalent alcohol with a trivalent alcohol and a fatty acid, more preferably an acyl group having 12 to 18 carbon atoms, an alkyl group having 12 to 18 carbon atoms, and a carbon number. 12-18 alkenyl groups, ethylene glycol residues, propylene glycol residues, glycerin residues, trimethylol ethane residues, trimethylol propane residues, ethylene glycol monooleate residues, ethylene glycol monostearate Rate residue, propylene glycol monooleate residue, propylene glycol monostearate residue, glycerin ( Mono / di) oleate residue, glycerin (mono / di) stearate residue, trimethylolethane (mono / di) oleate residue, trimethylolethane (mono / di) stearate residue, trimethylol Propane (mono / di) oleate residue and trimethylolpropane (mono / di) stearate residue, particularly preferably dodecanoyl, octadecanoyl, oleoyl, dodecyl, octadecyl, dedocenyl, octadecenyl, ethylene glycol residue, glycerin Residues, ethylene glycol monooleate residues, ethylene glycol monostearate residues, glycerin (mono / di) oleate residues and glycerin (mono / di) stearate residues, most preferably oleoyl, octadecenyl, Glycerin residue, glycerin (mono / di) Rate residues and glycerin is the residue of (mono / di) stearate.

Among R ² , from the viewpoint of improving cement strength, a hydrogen atom, an acyl group having 2 to 22 carbon atoms, an alkyl group having 1 to 22 carbon atoms, and an alkenyl group having 2 to 22 carbon atoms are preferable, more preferably a hydrogen atom, C3-C18 acyl group, C2-C18 alkyl group and C2-C18 alkenyl group, particularly preferably a hydrogen atom, ethyl, propyl, butyl, dodecanoyl, octadecanoyl, oleoyl, dodecyl, octadecyl , Dedocenyl and octadecenyl, most preferably hydrogen atom, oleoyl, octadecenyl.

  OA represents an oxyalkylene group having 2 to 4 carbon atoms, and includes oxyethylene, oxypropylene, and oxybutylene. Of these, oxyethylene and oxypropylene are preferred, and oxyethylene is more preferred.

  OA may contain two or more oxyalkylene groups. When two or more kinds of oxyalkylene groups are contained, any of block, random and a mixture thereof may be used, but a block of oxyethylene and oxypropylene is preferable.

  From the viewpoint of improving cement strength, n is preferably an integer of 2 to 60, more preferably 3 to 45, and particularly preferably an integer of 4 to 30.

  The polyoxyalkylene compound (b3) can be produced by a known method (Japanese Patent Laid-Open No. 2003-268291, Japanese Patent Laid-Open No. 9-117607, etc. and the above esterification reaction) and the like.

  Examples of the polyoxyalkylene compound (b3) include polyoxyethylene glycol monocetyl ether, polyoxyethylene glycol monostearyl ether, polyoxyethylene glycol monooleyl ether, castor oil ethylene oxide adduct, polyoxyethylene glycol monostearate, polyoxy Ethylene glycol diolate, butoxypolyoxyethylene stearyl ether, glyceryl polyoxyethylene (mono / di / tri) oleate, glycerin (mono / di) oleate polyoxyethylene adduct and glycerin (mono / di) oleate polyoxypropylene adduct Etc. can be preferably exemplified. Note that “(mono / di / tri)” means mono, di and / or tri.

  The polyoxyalkylene compound (b3) can be easily obtained from the market, and examples thereof include the following products.

<Polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether>
Braunon (registered trademark) series (CH-302L, SR-702, EN-1502) {Aoki Yushi Kogyo Co., Ltd.}

<Castor oil ethylene oxide adduct>
BROWNON (registered trademark) BR-404 {Aoki Oil & Fat Co., Ltd.}

<Polyoxyethylene glycol (mono / di) lauric acid ester, polyoxyethylene glycol (mono / di) oleic acid ester, polyoxyethylene glycol (mono / di) stearic acid ester>
Ionette (registered trademark) series (MS-400, MS-1000, MO-200, DL-200, DO-600, DS-400, DS-4000, etc.) {Sanyo Chemical Industries, Ltd.}

<Polyoxypropylene glycol monodecyl ether, polyoxypropylene glycol monoisodecyl ether>
Braunon series (NDB-800, NDB-1400, IDEP-608, IDEP-802, etc.) {Aoki Yushi Kogyo Co., Ltd.}

  The content (% by weight) of the compound (B) is preferably 0.9 to 50, more preferably 5 to 5 based on the total weight of the fatty acid ester (A), the compound (B) and the solid particles (C). 45, particularly preferably 10-38.

  The solid particles (C) are solid at 25 ° C. and are at least one selected from the group consisting of a fatty acid metal salt (c1), a fatty acid amide (c2), a wax (c3), and a hydrophobic silica (c4). It can be used without any restrictions.

  The fatty acid metal salt (c1) is composed of a salt of a residue obtained by removing a hydrogen atom from a fatty acid and a metal atom. In addition, the meaning of both a salt and a complex is contained in a fatty acid metal salt. Moreover, fatty acid metal salt (c1) may be comprised only by 1 type, and 2 or more types of mixtures may be sufficient as it.

Fatty acids include saturated fatty acids and unsaturated fatty acids (same as above).
Metal atoms include alkali metals (such as lithium, sodium and potassium), alkaline earth metals (such as barium, calcium and magnesium), transition metals (zinc, nickel, iron, copper, manganese, cobalt, silver, gold, platinum, Palladium, titanium, zirconium, cadmium, etc.), periodic table group 13 metals (aluminum, etc.), group 14 metals (tin, lead, etc.) or lanthanoid metals (lanthanum, cerium, etc.) are included.

  As such a fatty acid metal salt (c1), the compound represented by General formula (2) can be illustrated preferably.

^{(R 3 -COO) pM (2} )

R ³ represents an alkyl group having 1 to 30 carbon atoms or an alkenyl group having 2 to 30 carbon atoms, M represents a 1 to 3 valent metal atom, and p represents an integer of 1 to 3.

In General formula (2), a C1-C30 alkyl group or a C2-C30 alkenyl group (R < ³ >) is the same as the above.

  Among these, from the viewpoint of improving cement strength, a linear alkyl group and a linear alkenyl group are preferable, more preferably a linear alkyl group, particularly preferably a linear alkyl group having 8 to 24 carbon atoms, most preferably dodecyl and Octadecyl.

  Examples of the 1-3 valent metal atom (M) include the above metal atoms. Among these, from the viewpoint of improving cement strength, a divalent metal atom and a trivalent metal atom are preferable, a zinc atom, a magnesium atom, and an aluminum atom are more preferable, and an aluminum atom is particularly preferable.

  p represents an integer of 1 to 3, preferably an integer of 2 to 3, and more preferably an integer of 3.

  Such a fatty acid metal salt may be a single compound having one kind of p or a plurality of mixtures having different p. Moreover, the mixture from which the kind of alkyl group or alkenyl group differs may be sufficient.

More preferable examples of the fatty acid metal salt (c1) include zinc laurate, zinc behenate, calcium stearate, zinc stearate, aluminum stearate and barium stearate.
Such a fatty acid metal salt (c1) can be easily obtained from the market, and examples thereof include the following products.

  Calcium stearate, Oblate CA-65, Powder base L, Zinc behenate, Aluminum stearate 300, Aluminum stearate 600, Aluminum stearate 900 and barium stearate {NOF CORPORATION}

  The fatty acid amide (c2) includes a fatty acid bisamide of a C 1-6 alkylene diamine and a C 10-22 fatty acid, and a C 10-22 fatty acid monoamide.

  Examples of fatty acid bisamides include ethylene bisstearylamide, ethylene bispalmitylamide, ethylene bismyristylamide, ethylene bislaurylamide, ethylene bisoleylamide, propylene bisstearylamide, propylene bispalmitylamide, propylene bismyristylamide, propylene bislauryl. Amide, propylene bis oleyl amide, butylene bis stearyl amide, butylene bis palmityl amide, butylene bis myristyl amide, butylene bis lauryl amide, butylene bis oleyl amide, methylene bis lauryl amide, methylene bis stearyl amide, hexamethylene bis stearyl amide, ethylene -Bis-12-hydroxystearylamide and hexamethylene-bis-12-hydroxystearyl Amide.

  Examples of fatty acid monoamides include stearyl amide, N-stearyl stearyl amide, and N-methyl stearyl amide.

  Of these, fatty acid bisamide is preferable from the viewpoint of improving cement strength, more preferably ethylene bisstearylamide, ethylene bispalmitylamide, ethylene bislaurylamide, methylene bisstearylamide, and hexamethylene bisstearylamide, particularly preferably ethylene. Bisstearylamide, ethylenebispalmitylamide and ethylenebismyristylamide.

The wax (c3) includes natural wax and synthetic wax.
Natural waxes include plant waxes (carnauba wax, candelilla wax, sugar wax, rice wax, wood wax, bayberry wax, ocully wax, esparto wax, etc.), animal waxes (beeswax, insect wax, whale wax, shellac wax). And lanolin wax), petroleum wax (paraffin wax, microcrystalline wax, etc.), mineral wax (ozokerite wax, ceresin, etc.) and the like are used.

  Synthetic waxes include oxidized natural wax, polyethylene wax, oxidized polyethylene wax, acid-modified polyethylene wax, polypropylene wax, acid-modified polypropylene wax and Fischer-Tropsch wax.

  As the oxidized natural wax, those obtained by oxidizing the above natural wax by air oxidation and / or ozone oxidation (introducing a carboxy group, a hydroxyl group and / or a formyl group) can be used.

  Polyethylene wax is obtained by polymerization of ethylene, obtained by thermal decomposition (lower molecular weight) of polyethylene for general molding, and obtained by separation and purification of low molecular weight polyethylene by-produced when producing polyethylene for general molding. However, any of these methods can be used.

  The weight average molecular weight (Mw-a) of the polyethylene wax is preferably 500 to 10,000, more preferably 600 to 9,000, and particularly preferably 700 to 8,000. The weight average molecular weight (Mw-a) of the polyethylene wax was measured using a static light scattering photometer {for example, a static light scattering photometer SLS-6000 manufactured by Otsuka Electronics Co., Ltd.) as the solvent. The temperature is measured at 160 ° C.

  The melting point (° C.) of the polyethylene wax is preferably 60 to 200, more preferably 70 to 180, and particularly preferably 80 to 170.

  In addition, melting | fusing point is 3 of JISK7121-1987. It is measured according to (2) and 8.6 (1) (the same applies hereinafter). That is, a measurement sample is put into a container (for example, 560-002, manufactured by Seiko Instruments Inc.) of a DSC apparatus (for example, DSC-6200, manufactured by Seiko Instruments Inc.), and nitrogen gas is introduced at 40 mL / min. Heat and melt at a heating rate of 10 ° C per minute up to a temperature of 30 ° C, hold at that temperature for 10 minutes, then cool to a temperature about 100 ° C lower than the melting temperature at a cooling rate of 5 ° C per minute and hold until the device is stable To do. Next, the melting peak observed at the time of heating at a heating rate of 10 ° C. per minute is defined as the melting point.

  As the oxidized polyethylene wax, those obtained by oxidizing the above-mentioned polyethylene wax by air oxidation and / or ozone oxidation (introducing a carboxy group, a hydroxyl group and / or a formyl group) can be used.

  As the acid-modified polyethylene wax, a carboxylic acid-modified polyethylene obtained by grafting an unsaturated double bond-containing carboxylic acid (such as α, β-unsaturated monocarboxylic acid and α, β-unsaturated dicarboxylic acid) to the polyethylene wax described above. Wax etc. can be used.

  Examples of the α, β-unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, isocrotonic acid and 2-ethylacrylic acid. Examples of the α, β-unsaturated dicarboxylic acid include maleic acid, maleic anhydride, malonic acid, succinic acid, itaconic acid and fumaric acid.

  Polypropylene wax can be obtained by polymerization of propylene, obtained by thermal decomposition (lower molecular weight) of polypropylene for general molding, or by separation and purification of low molecular weight polyethylene by-produced when producing polypropylene for general molding. Although there is what is obtained, what was obtained by any method can also be used.

  As a weight average molecular weight (Mw-b) of a polypropylene wax, 1000-50000 are preferable, More preferably, it is 1500-40000, Most preferably, it is 2000-30000. The weight average molecular weight (Mw-b) of the polypropylene wax is measured in the same manner as the weight average molecular weight (Mw-a) of the polyethylene wax.

  The melting point (° C.) of the polypropylene wax is preferably 60 to 200, more preferably 70 to 180, and particularly preferably 80 to 170.

  As the oxidized polypropylene wax, one obtained by oxidizing the above polypropylene wax by air oxidation and / or ozone oxidation (introducing a carboxy group, a hydroxyl group and / or a formyl group) can be used.

  As the acid-modified polypropylene wax, a carboxylic acid-modified polypropylene obtained by grafting an unsaturated double bond-containing carboxylic acid (such as α, β-unsaturated monocarboxylic acid and α, β-unsaturated dicarboxylic acid) to the above-described polypropylene wax. Wax etc. can be used.

  Fischer-Tropsch wax is obtained by distilling the product obtained from the coal-based gas by the age method and hydrogenating this highest-boiling fraction. Is preferred.

  Of these waxes (c3), plant wax, petroleum wax, oxidized natural wax, polyethylene wax, oxidized polyethylene wax and acid-modified polyethylene wax are preferable from the viewpoint of improving cement strength, and more preferably carnauba wax, paraffin wax, microwax. Crystalline wax, oxidized carnauba wax, and polyethylene wax having a weight average molecular weight (Mw-a) of 600 to 9000 and oxides thereof.

  As the hydrophobic silica (c4), silica (ca) {silica means hydrophilic silica. The same applies hereinafter. } Is a hydrophobic silica obtained by hydrophobizing with a lipophilic compound (c-b).

  Silica (ca) includes amorphous synthetic silica (precipitation silica, gel silica, pyrolysis silica, fused silica, etc.).

  Precipitated silica is silica obtained by neutralizing sodium silicate with an acid in an alkaline environment, and filtering and drying the resulting precipitate. Gel silica is a silica obtained by neutralizing sodium silicate with an acid in an acidic environment and filtering and drying the resulting precipitate. Pyrolytic silica is silica obtained by burning a silicon compound such as silicon tetrachloride in an oxyhydrogen flame. The fused silica is silica obtained by melting and spheroidizing silica powder in a flame. Of these, precipitation method silica, gel method silica and pyrolysis method silica are preferable, precipitation method silica and pyrolysis method silica are more preferable, and precipitation method silica is particularly preferable.

  Silica (ca) is readily available from the market. Examples of product series names that can be obtained from the market are shown below.

  As the precipitated silica, Nipsil series {Tosoh Silica Co., Ltd., “Nipsil” is a registered trademark of Tosoh Silica Co., Ltd. } As gel method silica, Carplex series, SYLYSIA series {Fuji Silysia Co., Ltd., "SYLYSIA" is a registered trademark of WK FF Co., Ltd. } As the pyrogenic silica, Aerosil series {Nippon Aerosil Co., Ltd. and Evonik Degussa, "Aerosil" is a registered trademark of Evonik Degussa GmbH. } As the fused silica, Admafine series {Admatex, “Admafine” is a registered trademark of Toyota Motor Corporation. } Etc. are mentioned.

  The lipophilic compound (cb) used for hydrophobizing silica (ca) includes silicone compounds, polydimethylsiloxane, alkyl group-modified polydimethylsiloxane (modified alkyl group having 2 to 6 carbon atoms). ), Alkoxy group-modified polydimethylsiloxane (modified alkoxy group having 2 to 4 carbon atoms), hydroxyl group-modified polydimethylsiloxane, amino group-modified polydimethylsiloxane, polyether-modified polydimethylsiloxane, hydrogen polydimethylsiloxane, phenyl group-modified poly Examples include dimethylsiloxane, silicone resin, and halogen-modified polydimethylsiloxane.

  Of these lipophilic compounds (c-b), polydimethylsiloxane, alkyl group-modified polydimethylsiloxane, hydrogen polydimethylsiloxane and silicone resin are preferable from the viewpoint of improving cement strength, and more preferably polydimethylsiloxane, Genpolydimethylsiloxane and silicone resin.

  A known method (for example, U.S. Pat. No. 3,307,698 and U.S. Pat. No. 3,634,288) can be applied to hydrophobize silica (ca) with a lipophilic compound (c-b).

  When hydrophobizing using the lipophilic compound (c-b), the amount of use (wt%) of the lipophilic compound (c-b) is 2 to 80, based on the weight of silica (c-a). More preferably, it is 5-70, Most preferably, it is 10-50. When it is within this range, the cement strength is further improved.

  Of the silica (ca), hydrophobic silica obtained by hydrophobizing precipitated silica and pyrogenic silica can be easily obtained from the market. Examples of product names are given below.

<Hydrophobic silica obtained by hydrophobizing precipitated silica>
Nipsil SS series, Sipernat D and C series, and SYLOPHOBIC series {Fuji Silysia Chemical Co., Ltd., "SYLOPHOBIC" is a registered trademark of Fuji Silysia Chemical Co., Ltd. }etc.

<Hydrophobic silica obtained by hydrophobizing pyrogenic silica>
Aerosil C series {Nippon Aerosil Co., Ltd. and Evonik Degussa}, Reolosil MT and DM series {Tokuyama Co., Ltd.}

  The methanol wettability (M value) of the hydrophobic silica (c4) is preferably 30 to 90, more preferably 35 to 85, particularly preferably 40 to 80, and most preferably 45 to 75.

  Methanol wettability (M value) is a concept representing the degree of hydrophobicity. The higher the M value, the lower the hydrophilicity, and the uniform measurement sample {hydrophobic silica (c4)} in the water / methanol mixed solution. When dispersing, it is represented by the volume ratio of the minimum amount of methanol and can be determined by the following method.

<Methanol wettability (M value) calculation method>
0.2 g of a measurement sample {hydrophobic silica (c4)} is added to 50 mL of water in a beaker having a capacity of 250 mL, and methanol is then added dropwise from a burette until the entire amount of the measurement sample is uniformly suspended. At this time, the liquid in the beaker is constantly stirred with a magnetic stirrer, and when the total amount of the measurement sample is uniformly suspended in the liquid, the end point is set, and the methanol volume percentage of the liquid in the beaker at the end point is determined as methanol wettability (M value). ).

  Of these solid particles (C), fatty acid amide (c2), wax (c3) and hydrophobic silica (c4) are preferable from the viewpoint of improving cement strength, and it is preferable to contain at least one of these.

  The content (% by weight) of the solid particles (C) is preferably 0.1 to 15, more preferably based on the total weight of the fatty acid ester (A), the compound (B) and the solid particles (C). It is 0.2 to 10, particularly preferably 0.5 to 8.

  In addition to the fatty acid ester (A), the compound (B) and the solid particles (C), the cement strength improver of the present invention includes other components {synthetic resin, natural resin, emulsifier, silicone oil, hydrophilic silica, etc.} And / or known additives {antifoaming agents, dispersants, thickeners, antifungal agents, antiseptics, rust inhibitors, antioxidants, anti-skinning agents, etc .; for example, JP 2000-327946 A and JP-A-2004-305882, etc.}, water or the like may be contained.

  Synthetic resins include polyester, polyvinyl alcohol, poly (meth) acrylic acid, polyurethane and polyurea.

  Polyesters include polylactic acid, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid polybutylene succinate block copolymer, caprolactone butylene succinate copolymer, butylene succinate adipate copolymer, butylene succinate carbonate Examples thereof include copolymers, polyhydroxybutyrate and hydroxybutyrate hydroxysuccinate copolymers.

  The weight average molecular weight (Mw-c) of the polyester is preferably 5,000 to 500,000, more preferably 10,000 to 300,000.

The weight average molecular weight (Mw-c) of the polyester is measured by gel permeation chromatography (GPC) method using (poly) methyl methacrylate having a known molecular weight as a standard substance (column temperature: 40 ° C., eluent: Tetrahydrofuran, flow rate 0.8 ml / min, sample concentration: 0.4 wt% eluent solution.).

  Examples of the polyvinyl alcohol include fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, cation-modified polyvinyl alcohol, anion-modified polyvinyl alcohol, and nonion-modified polyvinyl alcohol.

  These polyvinyl alcohols are known (for example, JP-A-2006-28233, JP-A-10-119423, JP-A-1-206088, JP-A-61-237681, JP-A-63-330779. No. 7, JP-A-7-285265, JP-A-7-9758, and JP-A-8-25795) can be used.

  Among these polyvinyl alcohols, fully saponified polyvinyl alcohol and partially saponified polyvinyl alcohol are preferable, and partially saponified polyvinyl alcohol is more preferable.

  As for the polymerization degree of polyvinyl alcohol, 500-4000 are preferable, More preferably, it is 1000-3000.

  Examples of poly (meth) acrylic acid include (meth) acrylic acid homopolymer, (meth) acrylic acid, alkyl ester having 1 to 22 carbon atoms of (meth) acrylic acid, and alkylene having 1 to 18 carbon atoms Copolymers composed of copolymerized monomers such as (meth) acrylates of oxide (2 to 4 carbon) adducts are included.

  The poly (meth) acrylic acid may further contain a monomer such as (meth) acrylonitrile, styrene (styrene, methylstyrene, hydroxystyrene, divinylbenzene), allyl alcohol, or the like as a structural unit.

  The weight average molecular weight (Mw-d) of poly (meth) acrylic acid is preferably 5,000 to 1,000,000, more preferably 20,000 to 500,000.

  The weight average molecular weight (Mw-d) of poly (meth) acrylic acid is measured by gel permeation chromatography (GPC) using sodium polyacrylate having a known molecular weight as a standard substance (column temperature 40, elution). Liquid: 0.1-MPB disodium hydrogen phosphate aqueous solution: 0.1-MPB sodium dihydrogen phosphate aqueous solution = 1: 1 (molar ratio), flow rate 0.8 ml / min, sample concentration: 0.4 wt% Eluent solution).

  The polyurethane includes a polymer having diisocyanate and a polyol and / or polycarboxylic acid as constituent units.

  Examples of the diisocyanate include diisocyanates having 8 to 16 carbon atoms (such as hexamethylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate and 4,4'-methylenebis (cyclohexyl isocyanate)).

  Examples of the polyol include polyhydric alcohols having 2 to 6 carbon atoms (ethylene glycol, diethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.) and alkylene oxides having 2 to 4 carbon atoms to these polyhydric alcohols. Examples include adducts added at 1 to 50 moles per mole.

  Examples of the polycarboxylic acid include polycarboxylic acids having 4 to 14 carbon atoms (terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid. And dimer acid).

  Polyurea includes a polymer having diisocyanate and polyamine as structural units.

  Examples of the polyamine include C2-C6 polyamines, such as ethylenediamine, hexamethylenediamine, and triethylenetetramine.

  Natural resins include cellulose compounds, starch compounds, chitin and chitosan.

  Examples of the cellulose compound include cellulose, carboxymethylcellulose, carboxyethylcellulose, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, oxidized cellulose, acetylcellulose, aminoacetylcellulose, allylcellulose, cellulose acetate, and acetate cellulose.

  Among these cellulose compounds, cellulose, methyl cellulose, ethyl cellulose, cellulose acetate and cellulose acetate are preferable, and cellulose and cellulose acetate are more preferable.

  Examples of the starch compound include starch, carboxymethyl starch, carboxyethyl starch, methyl starch, ethyl starch, hydroxyethyl starch, oxidized starch, acetyl starch, aminoacetyl starch, allyl starch, acetate starch and acetate starch.

  Of these starch compounds, starch, methyl starch, ethyl starch and esterified starch are preferred, and starch and esterified starch are more preferred.

  As the emulsifier, nonionic, cationic, anionic or amphoteric emulsifiers can be used.

  Examples of nonionic emulsifiers include alkylene oxide adducts of higher alkylamines, alkylene oxide adducts of higher fatty acid amides, and alkylene oxide adducts of acetylene glycol. However, the fatty acid ester (A) and the polyoxyalkylene compound (b3) are not included in the nonionic emulsifier.

  Examples of cationic emulsifiers include higher alkylamine salts, higher alkylamine alkylene oxide adducts, solomin A type cationic emulsifiers, sapamin A type cationic emulsifiers, Arcobel A type cationic emulsifiers, imidazoline type cationic emulsifiers, higher alkyltrimethylammonium salts, higher alkyls. Examples thereof include dimethylbenzylammonium salt, sapamine-type quaternary ammonium salt, pyridinium salt and the like.

  As an anionic emulsifier, fatty acid alkali metal salt, fatty acid ammonium salt, fatty acid amine salt, α-olefin sulfonate, alkylbenzene sulfonic acid and its salt, alkyl sulfate ester salt, alkyl ether sulfate ester salt, N-acyl alkyl taurine salt And alkylsulfosuccinate. However, the fatty acid metal salt (c1) is not included in the anionic emulsifier.

  Examples of amphoteric emulsifiers include higher alkylaminopropionates and higher alkyldimethylbetaines.

  Of these emulsifiers, nonionic emulsifiers and anionic emulsifiers are preferred, more preferably higher alkylamine alkylene oxide adducts, higher fatty acid amide alkylene oxide adducts, fatty acid alkali metal salts, fatty acid ammonium salts, and alkylbenzenesulfonic acids. A salt thereof and an alkylsulfosuccinate, particularly preferably an alkylene oxide adduct of a higher alkylamine, an alkylbenzenesulfonic acid and a salt thereof, and an alkylsulfosuccinate.

  The silicone oil includes known silicone oils and the like, and silicone oils and modified silicone oils used as a hydrophobizing agent can be used.

  When other components are contained, the content (% by weight) is preferably 0.1 to 20, based on the total weight of the fatty acid ester (A), the compound (B) and the solid particles (C), Preferably it is 0.2-15, Most preferably, it is 0.5-10. Within this range, the cement strength may be further improved.

  When other additives are contained, the content (% by weight) is preferably 0.01 to 20, based on the total weight of the fatty acid ester (A), the compound (B) and the solid particles (C), More preferably, it is 0.05-15, Most preferably, it is 0.1-10. Within this range, the cement strength may be further improved.

  When water is contained, the content (% by weight) is preferably 0.1 to 55, more preferably based on the total weight of the fatty acid ester (A), the compound (B) and the solid particles (C). 1-50, particularly preferably 2-40.

  The cement strength improver of the present invention comprises a fatty acid ester (A), a compound (B) and solid particles (C), and other components and / or other additives as necessary, water (hereinafter omitted). If it contains "constituent component"), the production method is not limited, but it is preferable that these constituent components are uniformly mixed.

  When mixing the “component”, the fatty acid metal salt (c1), the fatty acid amide (c2) and / or the wax (c3) of the solid component (C) is more easily mixed. In order to melt and atomize, heat mixing may be performed.

  In the case of mixing by heating, the temperature (° C.) is preferably from 100 to 180, more preferably from 103 to 170, particularly preferably from 105 to 160, and most preferably from 110 to 150.

  In the case of mixing by heating, in order to adjust the particle size and crystal state of the solid particles (C), (1) rapid cooling or (2) slow cooling, or (3) heat treatment (heating temperature and final temperature during cooling) Aging at an intermediate temperature) and then cooling to the final temperature.

  After mixing the “components”, a homogenization treatment may be performed to make the “components” more uniform.

  As the homogenization treatment, it is preferable to carry out the treatment using an emulsifying disperser (disper mill, homogenizer or gorin homogenizer, ultrasonic emulsifier, etc.).

  The volume average particle diameter (μm) of the solid particles (C) contained in the cement strength improver of the present invention is preferably 0.1 to 100, more preferably 0.15 to 20, particularly preferably 0.2 to. 10, most preferably 0.25-5. Within this range, the cement strength is further improved.

  The volume average particle size is determined by using a laser diffraction particle size analyzer in accordance with JIS Z8825-1: 2001 (for example, Microtrac series manufactured by Leeds & Northrup, Partica LA series manufactured by Horiba, Ltd.), and n-hexane {purity 96% by weight or more. } A measurement dispersion was prepared by adding a measurement sample to 1000 parts by weight so that the concentration of the measurement sample was 0.1% by weight. After measuring at a measurement temperature of 25 ± 5 ° C., the refraction of n-hexane 1.3749 as the refractive index, and 50% cumulative volume average particle diameter using the literature value ("A GUIDE FOR ENTING MICROTRAC" RUN INFORMATION "(F3) DATA", created by Leeds & Northrup), Inc.) as the refractive index of the measurement sample (The same applies hereinafter).

  The solid particles (C) may be crushed with a crusher or the like to bring the volume average particle diameter into a preferred range.

  As the crusher, a known crusher or the like can be used. Wet medium type crusher {Bead Mill, Sand Grinder, Colloid Mill, Attritor (manufactured by Nihon Coke Industries Co., Ltd., “Attritor” is a registered trademark of Nihon Coke Industries Co., Ltd.) ), DISPERMAT (manufactured by VMA-GETAMANN GMBH)}, wet jet mill {Nanomizer (manufactured by Yoshida Kikai Co., Ltd., “Nanomizer” is a registered trademark of SG Engineering Co., Ltd.), Starburst (stock) "Starburst" manufactured by Sugino Machine Co., Ltd. is a registered trademark of Sugino Machine Co., Ltd.), Gorin homogenizer (manufactured by APV), etc.}.

  In the cement strength improver of the present invention, the solid particles (C) are emulsified or dispersed in the fatty acid ester (A) and the compound (B) to obtain an emulsified dispersion (ABC), which is then supported on the powder. May be.

  The powder is not limited as long as it is at least one selected from the group consisting of hydrophilic silica, aluminum oxide, titanium oxide, calcium carbonate, magnesium carbonate, carbon black and talc, preferably calcium carbonate and hydrophilic silica, More preferred is hydrophilic silica.

0.5-1000 are preferable, as for the BET specific surface area (m < ² > / g) of powder, More preferably, it is 50-800, Most preferably, it is 100-500. Within this range, the cement strength is further improved.

  The powder has a di-n-butyl phthalate (DBP) oil absorption (ml / 100 g) of preferably 10 to 500, more preferably 50 to 400, and particularly preferably 100 to 300. Within this range, the cement strength is further improved.

  The volume average particle diameter (μm) of the powder is preferably 0.1 to 1000, more preferably 3 to 500, and particularly preferably 5 to 300. Within this range, the cement strength is further improved.

  The content (% by weight) of the emulsified dispersion (ABC) is preferably 1 to 70, more preferably 10 to 65, particularly preferably 20 to 60, based on the total weight of the emulsified dispersion (ABC) and the powder. It is. Within this range, the cement strength is further improved.

  The content (% by weight) of the powder is preferably 30 to 99, more preferably 35 to 90, and particularly preferably 40 to 80, based on the total weight of the emulsified dispersion (ABC) and the powder. Within this range, the cement strength is further improved.

  The cement strength improver of the present invention preferably constitutes a cement composition together with cement, water, filler and the like.

  Examples of the cement include Portland cement (ordinary Portland cement, early-strength Portland cement, super early-strength Portland cement, moderately hot Portland cement, sulfate-resistant Portland cement, etc .; JIS R5210: 2003), blast furnace cement (JIS R5211: 2003), silica Cement (JIS R5212-1997), fly ash cement (JIS R5213-1997), etc. are mentioned. These cements can be used as one kind or a mixture of two or more kinds. Of these, Portland cement is preferable, and class G or class H cement in the API (American Petroleum Institute) standard is more preferable.

  Fillers include aggregates (aggregate river sand, crushed sand, cinnabar sand, meteorite powder, wollastonite, limestone, mica, lightweight aggregate, silica fume, fly ash, slag, pozzolana, etc.), reinforcing materials (asbestos, rock asbestos, Glass fiber, pulp, waste paper, polyamide fiber, vinylon fiber, carbon fiber, etc.), organic particles (polystyrene particles, polyvinylidene chloride particles, polyethylene particles, polypropylene particles, chloroprene rubber latex, styrene butadiene rubber latex, etc.) and inorganic particles (glass) Bead, silica, silica alumina, etc.). These fillers can be used as one kind or a mixture of two or more kinds. Among these, from the viewpoint of the strength of the cement composition, aggregates, organic particles, and inorganic particles are preferable, organic particles, particularly preferably polypropylene particles and styrene butadiene rubber latex, and most preferably polypropylene particles.

  In the cement composition, known additives (AE agent, AE water reducing agent, high performance water reducing agent, retarder, early strengthening agent, accelerator, foaming agent, foaming agent used together with cement as necessary. , Antifoaming agent, quick setting agent, swelling agent, thickener, waterproofing agent, bentonite, etc.), and these may be used alone or in combination. When these additives are included, the amount of these additives is the same as in a normal case.

  The amount of the cement strength improver of the present invention can be appropriately increased or decreased depending on the composition, temperature, concentration, etc. of the cement composition, but is preferably 0.01 to 10% by weight based on the weight of the cement and filler. More preferably, it is 0.05 to 5% by weight, particularly preferably 0.1 to 2% by weight.

The volume average particle diameter of the solid particles (C) used in the examples was measured by the following method.
<Volume average particle diameter of solid particles (C)>
N-Hexane is added to the measurement sample {cement strength improver} so that the concentration of the solid particles (C) is about 0.1% by weight, diluted, and then an ultrasonic disperser (manufactured by Hiel-scher GmbH). , ULTRASONIC PROCESSOR MODELUP400S, and so on.) Was dispersed for 1 minute at an output of 60% to prepare a dispersion. Next, the volume average particle size of the solid particles (C) in the dispersion was measured with a laser diffraction / scattering particle size distribution measuring device (manufactured by Horiba, Ltd., Partica LA-950, the same applies hereinafter).

The methanol wettability (M value) of hydrophobic silica was measured by the following method.
<Pretreatment>
When the measurement sample contains components other than hydrophobic silica, the hydrophobic silica is separated.
In a 70 mL glass container, 5 g of a measurement sample and 30 mL of n-hexane are added and mixed with a spatula, and then centrifuged (10 minutes at 4800 rpm) in a laboratory high-speed centrifuge {manufactured by Sigma Laborentrifgen GmbH, Model 3-16}. Discard the supernatant, add 30 mL of n-hexane, mix with a spatula, and disperse for 1 minute at an output of 60% using an ultrasonic disperser (manufactured by Hiel-scher GmbH, ULTRASONIC PROCESSOR MODELUP400S). Other components are dissolved in n-hexane, and then centrifuged again (at 4800 rpm for 10 minutes). The supernatant is discarded, heated to 80 ° C. to volatilize n-hexane, and the hydrophobic silica is separated. .

<Measurement of M value>
0.2 g of a measurement sample {hydrophobic silica} was added to 50 mL of ion-exchanged water in a 250 mL beaker. Subsequently, while constantly stirring the liquid in the beaker with a magnetic stirrer, methanol (Kanto Chemical Co., Inc., reagent grade, the same applies hereinafter) was gradually added dropwise from the burette to the beaker along the wall. The dropwise addition of methanol was continued until the entire amount of the measurement sample was uniformly suspended in ion-exchanged water. The drop amount (g) of methanol when the entire amount of the measurement sample was uniformly suspended was recorded, and the M value was calculated from the following formula.

M value = (Methanol dropping amount) ÷ {(Methanol dropping amount) +50} × 100

<Example 1>
In a container that can be heated, stirred and cooled, 45 parts of fatty acid ester (a11) {methyl laurate, Exepearl ML-85, Kao Corporation} and fatty acid ester (a12) {Sorbitan monooleate, Ionette S-80, Sanyo Chemical Industries, Ltd.} 5 parts, hydrocarbon oil (b11) {paraffinic neutral oil, Cosmo SP-10, Cosmo Oil Lubricants Co., Ltd.} 36 parts, polyoxyalkylene compound (b301) {polyoxyethylene (polymerization) Degree: 2) glycol monooleyl ether, brownon EN-1502, Aoki Yushi Kogyo Co., Ltd.} 2 parts, wax (c31) {polyethylene oxide wax, Epolen E-10, Eastman Chemical Japan Co., Ltd.} 12 parts, synthesis Resin (1) {Polymethyl methacrylate, tuftic TM) FH-S015, Toyobo Co., Ltd.} and 0.5 parts, followed by stirring and mixing at 0.99 ° C., to obtain a mixed solution was cooled with stirring to 30 ° C.. This mixed solution is transferred to a stainless steel container and homogenized by stirring at 4000 rpm with a homogenizer (High Flex Disperser HG-92G, Taitec Co., Ltd.), and the cement strength improver (1) of the present invention. Got.
The volume average particle diameter of the solid particles (C) in the cement strength improver (1) was 15 μm.

<Example 2>
"Fatty acid ester (a11) 45 parts", "Fatty acid ester (a12) 5 parts", "Hydrocarbon oil (b11) 36 parts", "Polyoxyalkylene compound (b301) 2 parts", "Wax (c31) 12 parts ”And“ synthetic resin (1) 0.5 part ”,“ fatty acid ester (a13) {Sorbitan triolate, Ionette S-85, Sanyo Chemical Industries, Ltd.} 15 parts ”,“ fatty acid ester (a14) {rapeseed oil , Japan Oilio Group Co., Ltd.}, “Higher alcohol (b21) {2-octyldodecanol, Calcoal 200GD, Kao Corporation}, 10 parts”, “Polyoxyalkylene compound (b302) {Polyoxyethylene (degree of polymerization) : 20) glycol dioleate, Ionette DO-1000, Sanyo Chemical Industries, Ltd.} 5 parts ”,“ Polio Sialkylene compound (b303) {polyoxypropylene (degree of polymerization: 40) monobutyl ether, Newpol (registered trademark) LB-1715, Sanyo Chemical Industries, Ltd.} 5 parts "and" fatty acid metal salt (c11) {tristearic acid The cement strength improver (2) of the present invention was obtained in the same manner as in Example 1 except that the content was changed to “aluminum, aluminum stearate 900, NOF Corporation} 5 parts”.
The volume average particle diameter of the solid particles (C) in the cement strength improver (2) was 12 μm.

<Example 3>
"Fatty acid ester (a11) 45 parts", "Fatty acid ester (a12) 5 parts", "Hydrocarbon oil (b11) 36 parts", "Polyoxyalkylene compound (b301) 2 parts", "Wax (c31) 12 parts ”,“ Synthetic resin (1) 0.5 part ”and“ At 150 ° C. ”,“ Fatty acid ester (a15) {2-octyldodecyl myristate, Exepar OD-M, Kao Corporation} 99 parts ” “Oxyalkylene compound (b302) 0.9 part”, “hydrophobic silica (c41) {hydrophobic silica, Nipseal SS-70, Tosoh Silica Co., Ltd.} 0.1 part” and “at 25-30 ° C.” Except that, the cement strength improver (3) of the present invention was obtained in the same manner as in Example 1.
The volume average particle diameter of the solid particles (C) in the cement strength improver (3) was 10 μm, and the M value of the hydrophobic silica (c41) was 65.

<Example 4>
"Fatty acid ester (a11) 45 parts", "Fatty acid ester (a12) 5 parts", "Hydrocarbon oil (b11) 36 parts", "Polyoxyalkylene compound (b301) 2 parts", "Wax (c31) 12 parts ”,“ Synthetic resin (1) 0.5 part ”and“ at 150 ° C. ”,“ Fatty acid ester (a14) 40 parts ”,“ Higher alcohol (b22) {behenyl alcohol, Calcoal 220-80, Kao Corporation} 20 Parts "," polyoxyalkylene compound (b304) {castor oil ethylene oxide adduct, BROWNON BR-404, Aoki Oil & Fat Co., Ltd.} 15 parts "," polyoxyalkylene compound (b305) {polyoxyethylene (degree of polymerization: 9 ) Glycol monostearate ester, Ionette MS-400, Sanyo Chemical Industries, Ltd.} 10 parts "," Fatty acid a (C21) {Ethylenebisoleylamide, Alflow (registered trademark) AD-281F, NOF Corporation} 5 parts "," Hydrophobic silica (c42) {Aerosil RX-200, Nippon Aerosil Co., Ltd.} 10 parts "and Except having changed to "at 25-30 degreeC", it carried out similarly to Example 1, and obtained the cement strength improvement agent (4) of this invention.
The volume average particle diameter of the solid particles (C) in the cement strength improver (4) was 1 μm. The M value of hydrophobic silica (c42) was 70.

<Example 5>
"Fatty acid ester (a11) 45 parts", "Fatty acid ester (a12) 5 parts", "Hydrocarbon oil (b11) 36 parts", "Polyoxyalkylene compound (b301) 2 parts", "Wax (c31) 12 parts "0.5 parts of synthetic resin (1)", "94.8 parts of fatty acid ester (a14)", "polyoxyalkylene compound (b306) {polyoxyethylene (degree of polymerization: 4) glycol dilaurate ester" , Ionette DL-200, Sanyo Chemical Industries, Ltd.} 5 parts ”,“ Fatty acid amide (c21) 0.2 part ”and“ Silicone oil {modified silicone oil, X22-4515, Shin-Etsu Chemical Co., Ltd.} 5 parts ” A cement strength improver (5) of the present invention was obtained in the same manner as in Example 1 except for the change.
The volume average particle diameter of the solid particles (C) in the cement strength improver (5) was 10 μm.

<Example 6>
In a container that can be heated, stirred and cooled, 5 parts of fatty acid ester (a12), hydrocarbon oil (b12) {mineral oil, Cosmo SC22, 20 parts of Cosmo Oil Lubricants Co., Ltd., fatty acid amide (c22) {ethylene bisstearyl Amide, Alflow (registered trademark) H-50S, NOF Corporation} 5 parts, hydrophobic silica (c42) 5 parts and emulsifier {calcium dodecylbenzenesulfonate, Teika Power (registered trademark) BC-2070M, Teika Corporation} While heating 2.5 parts, the temperature was raised to 140 ° C. and stirring was continued for 15 minutes at this temperature to obtain an amide solution.

Subsequently, 65 parts of fatty acid ester (a14) was stirred at 20 to 30 ° C., and an amide solution was added little by little, and stirred for 15 minutes to obtain a mixed solution. The temperature of the mixed solution during and after the amide solution was charged was 25 to 75 ° C. The mixed solution cooled to 25 ° C. was uniformly mixed at 3500 psi (24.1 MPa) using a Gorin homogenizer (manufactured by Manton Gorin) to obtain a cement strength improver (6) of the present invention. The temperature during and after the uniform mixing was 25 to 40 ° C.
The volume average particle diameter of the solid particles (C) in the cement strength improver (6) was 2 μm.

<Example 7>
1 mol part (284 parts) of stearic acid {reagent special grade, Wako Pure Chemical Industries, Ltd.}, potassium hydroxide {reagent special grade, Wako Pure Chemical Industries, Ltd. } After 0.9 parts were uniformly mixed, the temperature was raised to 100 ° C. while replacing with pressurized nitrogen. Then, after dehydrating under reduced pressure (0.013 MPa or less; the same shall apply hereinafter) for 1 hour and raising the temperature to 150 ° C., 2 mol part (88 parts) of ethylene oxide (EO) is reduced to 0.2 MPa or less at this temperature. The solution was added dropwise while keeping, and further stirred at the same temperature for 4 hours. Next, after cooling to 90 ° C. and adding 9.3 parts of ion-exchanged water (2.5% by weight of the total of the raw materials; the same applies hereinafter), an alkali adsorbent (1) {Kyoward (registered trademark) 600 , Kyowa Chemical Industry Co., Ltd.} 18.6 parts (5% by weight of the total amount of raw materials; the same shall apply hereinafter) is added and stirred at the same temperature for 1 hour to convert potassium hydroxide into the alkali adsorbent (1). Adsorbed. Next, at the same temperature, Nutsche, suction bottle and No. 2 Filter paper {Toyo Filter Paper Co., Ltd.} was used to filter out the alkali adsorbent (1). {Additionally, after adding ion-exchanged water and alkali adsorbent (1) and stirring, filter the alkali adsorbent (1). This operation is abbreviated as “alkali adsorption treatment”. }. The obtained filtrate was dehydrated under reduced pressure at 120 ° C. to obtain a polyoxyalkylene compound (b307) [polyoxyethylene (degree of polymerization: 2) glycol stearic acid monoester].

"Fatty acid ester (a11) 45 parts", "Fatty acid ester (a12) 5 parts", "Hydrocarbon oil (b11) 36 parts", "Polyoxyalkylene compound (b301) 2 parts", "Wax (c31) 12 parts "0.5 parts of synthetic resin (1)", 71 parts of fatty acid ester (a11), 5 parts of polyoxyalkylene compound (b302), 20 parts of polyoxyalkylene compound (b307), " A mixed solution was obtained in the same manner as in Example 1 except that the fatty acid metal salt (c11) was changed to 2 parts and the fatty acid amide (c21) was changed to 2 parts. This mixed liquid was mixed with a wet medium type pulverizer {DISPERMAT SL-C-12 (manufactured by VMA-GETAMANN GMMH, the same applies hereinafter) filled with 100 ml of zirconia beads having a particle size of 0.7 mm for 5 minutes at a rotor speed of 1000 rpm. By crushing, the cement strength improver (7) of the present invention was obtained.
The volume average particle diameter of the solid particles (C) in the cement strength improver (7) was 6 μm.

<Example 8>
"Fatty acid ester (a11) 45 parts", "Fatty acid ester (a12) 5 parts", "Hydrocarbon oil (b11) 36 parts", "Polyoxyalkylene compound (b301) 2 parts", "Wax (c31) 12 parts ”And“ 0.5 parts of synthetic resin (1) ”,“ fatty acid ester (a11) 10 parts ”,“ fatty acid ester (a16) {Sorbitan sesquioleate, Rheodor AO-15V, Kao Corporation} 75 parts ”,“ The cement strength of the present invention is the same as in Example 1 except that the polyoxyalkylene compound (b302) is 10 parts, the fatty acid metal salt (c11) is 2 parts, and the fatty acid amide (c22) is 3 parts. An improver (8) was obtained.
The volume average particle diameter of the solid particles (C) in the cement strength improver (8) was 14 μm.

<Example 9>
In a reaction vessel equipped with a dehydrating and cooling device that can be heated, cooled and stirred, polyoxyalkynelene compound (b301) {polyoxyethylene (degree of polymerization: 2) glycol monooleyl ether, Braunon EN-1502, Aoki Yushi Kogyo Co., Ltd. } 1 mole part (268.5 parts), stearic acid {reagent grade 1, Wako Pure Chemical Industries, Ltd.} 284 parts (1 mole part) and paratoluenesulfonic acid {reagent special grade, Wako Pure Chemical Industries, Ltd.} 8. After preparing 6 parts (0.05 mole part) of a uniform mixture to prepare a mixture, the reaction vessel was purged with nitrogen, and then the temperature of the mixture was raised to 130 ° C. while removing the generated water. Reaction was performed for 20 hours to obtain a reaction product. Then, 172 parts of an alkali adsorbent (2) {magnesium oxide, Kyoward 100, Kyowa Chemical Industry Co., Ltd.} was added to the reaction product, and the mixture was stirred at 100 ° C for 1 hour, and then subjected to an alkali removal agent by vacuum filtration Was removed to obtain a polyoxyalkylene compound (b308) {polyoxyethylene (degree of polymerization: 2) stearic acid ester of glycol monooleyl ether}.

"Fatty acid ester (a11) 45 parts", "Fatty acid ester (a12) 5 parts", "Hydrocarbon oil (b11) 36 parts", "Polyoxyalkylene compound (b301) 2 parts", "Wax (c31) 12 parts "0.5 parts of synthetic resin (1)", "fatty acid ester (a17) {corn oil, Nissin Oilio Group 90 parts}", "9.5 parts of polyoxyalkylene compound (b308)", "Wax (c32) {Carnauba wax, refined fine-grained Carnauba S, Toa Kasei Co., Ltd.} 0.5 part" and "Synthetic resin (2) {Polycaprolactone, Plaxel (registered trademark) H1P, Daicel Chemical Industries, Ltd.} 0 Except for the change to “.5 parts”, the cement strength improver (9) of the present invention was obtained in the same manner as in Example 1.
The volume average particle diameter of the solid particles (C) in the cement strength improver (9) was 13 μm.

<Example 10>
Glycerin {reagent special grade, Wako Pure Chemical Industries, Ltd.} 1 mol part (92 parts), potassium hydroxide {reagent special grade, Wako Pure Chemical Industries, Ltd.} After uniformly mixing 0.5 part, the temperature was raised to 100 ° C. while replacing with pressurized nitrogen. Then, after dehydrating under reduced pressure (0.013 MPa or less) for 1 hour and raising the temperature to 150 ° C., at this temperature, 3 mol parts (132 parts) of ethylene oxide (EO) was dropped while maintaining 0.4 MPa or less. Stir for 4 hours at the same temperature. Subsequently, after cooling to 90 ° C. and adding 4.5 parts of ion-exchanged water, “alkali adsorption treatment” was performed. The obtained filtrate was dehydrated under reduced pressure at 120 ° C. to obtain a polyoxyalkylene compound (b309) {glycerin ethylene oxide 3 mol adduct}.

  In a reaction vessel equipped with a dehydration cooling apparatus that can be heated, cooled and stirred, 1 mol part (224 parts) of a polyoxyalkylene compound (b309), oleic acid {reagent grade 1, Wako Pure Chemical Industries, Ltd.} 283 parts ( 1 mol part) and p-toluenesulfonic acid {reagent special grade, Wako Pure Chemical Industries, Ltd.} 8.6 parts (0.05 mol part) are uniformly mixed to prepare a mixed solution, and then the inside of the reaction vessel is purged with nitrogen After that, the temperature of the mixed solution was raised to 130 ° C., and the reaction was carried out for 20 hours while removing generated water to obtain a reaction product. Then, 172 parts of an alkali adsorbent (2) {magnesium oxide, Kyoward 100, Kyowa Chemical Industry Co., Ltd.} was added to the reaction product, and the mixture was stirred at 100 ° C. for 1 hour, and then filtered under reduced pressure. (2) was removed to obtain a polyoxyalkylene compound (b310) {monooleate of glycerin ethylene oxide 3 mol adduct}.

"Fatty acid ester (a11) 45 parts", "Fatty acid ester (a12) 5 parts", "Hydrocarbon oil (b11) 36 parts", "Polyoxyalkylene compound (b301) 2 parts", "Wax (c31) 12 parts "And 0.5 parts of synthetic resin (1)" are replaced with "fatty acid ester (a18) {glycerin monooleate, Excel O-95R, Kao Corporation} 32 parts", "fatty acid ester (a12) 8 parts", ""Hydrocarbon oil (b12) 37 parts", "polyoxyalkylene compound (b302) 5 parts", "polyoxyalkylene compound (b310) 5 parts", "fatty acid metal salt (c12) 5 parts", "hydrophobic silica ( c41) 8 parts "and" synthetic resin (3) {polylactic acid, Terramac (registered trademark) TE-2000, Unitika Ltd.} 1 part ". To obtain a cement strength enhancers (10) of the present invention.
The volume average particle diameter of the solid particles (C) in the cement strength improver (10) was 10 μm.

<Example 11>
"Fatty acid ester (a11) 45 parts", "Fatty acid ester (a12) 5 parts", "Hydrocarbon oil (b11) 36 parts", "Polyoxyalkylene compound (b301) 2 parts", "Wax (c31) 12 parts And “synthetic resin (1) 0.5 part”, “fatty acid ester (a17) 70 parts”, “polyoxyalkylene compound (b310) 15 parts”, “fatty acid metal salt (c12) 5 parts”, “fatty acid” A cement strength improver (11) of the present invention was obtained in the same manner as in Example 1, except that the amide (c22) was changed to 2 parts and the hydrophobic silica (c41) was changed to 8 parts.
The volume average particle diameter of the solid particles (C) in the cement strength improver (11) was 12 μm.

<Example 12>
In a reaction vessel equipped with a dehydrating and cooling device that can be heated, cooled and stirred, 1 mol part (224 parts) of polyoxyalkylene compound (b310), 2 mol parts of oleic acid (565 parts) and paratoluenesulfonic acid {reagent special grade , Wako Pure Chemical Industries, Ltd.} 8.6 parts (0.05 mole part) was uniformly mixed to prepare a mixed solution, and the reaction vessel was purged with nitrogen, and then the temperature of the mixed solution was raised to 130 ° C. The reaction was carried out for 20 hours while warming and removing the produced water. Then, 172 parts of an alkali adsorbent (2) was added to the reaction product, and the mixture was stirred at 100 ° C. for 1 hour, and then the alkali adsorbent (2) was removed by filtration under reduced pressure to obtain a polyoxyalkylene compound (b311). ) {Trioleic acid ester of glycerin ethylene oxide 3 mol adduct} was obtained.

"Fatty acid ester (a11) 45 parts", "Fatty acid ester (a12) 5 parts", "Hydrocarbon oil (b11) 36 parts", "Polyoxyalkylene compound (b301) 2 parts", "Wax (c31) 12 parts "0.5 parts of synthetic resin (1)", "60 parts of fatty acid ester (a17)", "3 parts of polyoxyalkylene compound (b302)", "34 parts of polyoxyalkylene compound (b311)" and " The cement strength improver (12) of the present invention was obtained in the same manner as in Example 1 except that the fatty acid amide (c23) {erucic acid monoamide, Alfro P-10, NOF Corporation} 3 parts "was changed. .
The volume average particle diameter of the solid particles (C) in the cement strength improver (12) was 23 μm.

<Example 13>
In a container capable of heating and stirring, 85 parts of fatty acid ester (a11), 8 parts of hydrocarbon oil (b12) and silica (c-a1) {precipitation silica, Nipsil (registered trademark) VN-3, Tosoh silica Co., Ltd.} 4.9 parts was charged and the lipophilic compound (c-b1) {silicone resin, SR-2400, Toray Dow Corning Co., Ltd.} 2.1 parts at 25 ° C. while stirring at low speed (750 rpm). I put it in. Next, the mixture is heated to 150 ° C. and stirred with a homogenizer (High Flex Disperser HG-92G, Taitec Co., Ltd.) at 4000 rpm for 3 hours to react silica (c-a1) with the lipophilic compound (c-b1). Thus, the hydrophobic silica (c43) was prepared, and the cement strength improver (13) of the present invention containing the hydrophobic silica (c43) was obtained.
The volume average particle diameter of the solid particles (C) in the cement strength improver (13) was 18 μm, and the M value of the hydrophobic silica (c43) was 70.

<Example 14>
"Fatty acid ester (a11) 85 parts", "Hydrocarbon oil (b12) 8 parts", "Silica (c-a1) 4.9 parts" and "Lipophilic compound (c-b1) 2.1 parts""Fatty acid ester (a15) 42 parts", "Polyoxyalkylene compound (b306) 50 parts", "Silica (c-a2) {Precipitated silica, Nipsil KQ, Tosoh Silica Co., Ltd.} 7.6 parts" and " Hydrophobic compound (c-b2) {Polydimethylsiloxane, KF-96-3000CS, Shin-Etsu Chemical Co., Ltd.} 0.4 parts "Hydrophobic silica (c44) in the same manner as in Example 13, except that it was changed to 0.4 parts" A dispersion was obtained. This dispersion was crushed for 5 minutes at a rotor rotation speed of 1000 rpm with a wet medium type pulverizer filled with 100 ml of zirconia beads having a particle size of 0.7 mm to obtain the cement strength improver (14) of the present invention. .
The volume average particle diameter of the solid particles (C) in the cement strength improver (14) was 10 μm, and the M value of the hydrophobic silica (c44) was 40.

<Example 15>
"Fatty acid ester (a11) 85 parts", "Hydrocarbon oil (b12) 8 parts", "Silica (c-a1) 4.9 parts" and "Lipophilic compound (c-b1) 2.1 parts""Fatty acid ester (a19) {soybean oil, Nissin Oilio Group Co., Ltd.} 58 parts", "Fatty acid ester (a12) 5 parts", "Hydrocarbon oil (b12) 25 parts", "Polyoxyalkylene compound (b305)" Hydrophobic silica (c45) in the same manner as in Example 13, except that it was changed to “5 parts”, “4.6 parts of silica (c-a1)” and “2.4 parts of lipophilic compound (c-b1)”. ) Dispersion was obtained. Subsequently, this dispersion, “3 parts of an emulsifier {sodium dioctylsulfosuccinate}”, was added to a stirrable container and stirred at 25 to 30 ° C. for 30 minutes to obtain a dispersion. This dispersion was crushed for 60 minutes at a rotational speed of the rotor of 4000 rpm in a wet medium type pulverizer filled with 100 ml of zirconia beads having a particle diameter of 0.7 mm to obtain the cement strength improver (15) of the present invention. .
The volume average particle diameter of the solid particles (C) in the cement strength improver (15) was 0.2 μm, and the M value of the hydrophobic silica (c45) was 80.

<Example 16>
"Fatty acid ester (a11) 85 parts", "Hydrocarbon oil (b12) 8 parts", "Silica (c-a1) 4.9 parts" and "Lipophilic compound (c-b1) 2.1 parts" Same as Example 13 except for changing to "Fatty acid ester (a11) 49.5 parts", "Silica (c-a1) 0.35 parts" and "Lipophilic compound (c-b2) 0.15 parts" Thus, a dispersion of hydrophobic silica (c46) was obtained. This dispersion was crushed for 120 minutes at a rotor rotational speed of 4000 rpm with a wet medium type pulverizer filled with 100 ml of zirconia beads having a particle diameter of 0.7 mm to obtain a crushed liquid. 50 parts of this crushed liquid and 50 parts of the cement strength improver (12) obtained in Example 12 were uniformly mixed to obtain a cement strength improver (16) of the present invention.
The volume average particle diameter of the solid particles (C) in the cement strength improver (16) was 0.1 μm, and the M value of the hydrophobic silica (c46) was 70.

<Comparative Example 1>
Echizen tile (Ceramica Co., Ltd.) was crushed with a jaw crusher (JCA-100, Makino Co., Ltd.), then crushed with a roll crusher (MRCA-0 Makino Co., Ltd.), and further with a ball mill (LP-M2 Ito Seisakusho Co., Ltd.) A comparative cement strength improver (H1) was obtained by pulverizing and sieving with a 0.075 mm mesh screen to obtain a fine powder having a particle size of 0.075 mm or less (density 2.62 g / cm ³ ).

  Using the cement strength improvers (1) to (16) obtained in the examples and the comparative cement strength improver (H1), a cement composition was prepared by the following method, and the compressive strength was measured. The results are shown in Tables 4-6.

<Adjustment of cement composition>
Among the blending components shown in Tables 1 to 3, a predetermined amount of components other than the water reducing agent and water was air-kneaded for 10 seconds using a mortar mixer {Model: C138A-486, Maruto Seisakusho Co., Ltd.}, then the water reducing agent and Water was added in the blending amounts shown in Tables 1 to 3, and kneaded for 3 minutes to obtain a cement composition for evaluation.
Further, a blank cement composition was obtained in the same manner as above without adding a cement strength improver.

<Evaluation of compressive strength>
Cement compositions (Examples 1 to 16, Comparative Example 1 and blank) were placed in a cylindrical frame having a diameter of 50 mm and a height of 100 mm, sealed with a plastic bag so as not to evaporate water, and molded and cured.
According to “JIS A1108: 2006 (Method of compressive strength test of concrete); corresponding to ISO 1920-4: 2005”, the compressive strength in a sealed state in a room at 20 ° C. was measured after 1 day and after 28 days. .

In Table 1, the following components were used.
Cement: Ordinary Portland cement, Taiheiyo Cement Co., Ltd.
Water reducing agent: Sanyo Reberon (registered trademark) PHL, Sanyo Chemical Industries, Ltd. Thickener: Methylcellulose (90SH-30000), Shin-Etsu Chemical Co., Ltd.

In Table 2, the following components were used.
Cement: Class G cement (OWC), Ube Mitsubishi Materials Corporation Filler: Styrene butadiene latex (A-3255)
Asahi Kasei Chemicals Co., Ltd. Water reducing agent: Sanyo Reberon PHL, Sanyo Chemical Industries, Ltd. Thickener: Methylcellulose (90SH-30000), Shin-Etsu Chemical Co., Ltd.

In Table 3, the following components were used.
Cement: Class G cement (OWC) Ube Mitsubishi Cement Co., Ltd. Filler: Polypropylene particles (Flowbren (registered trademark) Q9A379)
Sumitomo Seika Co., Ltd. Water reducing agent: Sanyo Reberon PHL, Sanyo Chemical Industries, Ltd. Thickener: Methylcellulose (90SH-30000), Shin-Etsu Chemical Co., Ltd.

When the cement strength improvers (1) to (16) of the present invention were used, the compressive strength after curing of the cement composition was higher than when the comparative cement strength improver (H1) was used or compared with the blank. That is, the cement strength improver of the present invention was able to greatly improve the compressive strength of the blank compared to the comparative cement strength improver.

Claims (2)

Fatty acid ester (A);
At least one compound (B) selected from the group consisting of a hydrocarbon oil (b1 ) and a polyoxyalkylene compound (b3);
Fatty acid metal salts (c1), fatty acid amide (c2), it viewed including the at least one solid particles (C) selected from the group consisting of wax (c3) and hydrophobic silica (c4),
Based on the total weight of the fatty acid ester (A), the compound (B) and the solid particles (C), the content of the fatty acid ester (A) is 40 to 99% by weight, and the content of the compound (B) is 0.9. Cement strength improver, characterized in that the content of solid particles (C) is 0.1 to 15% by weight . A cement composition comprising cement, water, a filler, and the cement strength improver according to claim 1 .