JP6116283B2 - Improving agent composition for hydraulic material - Google Patents

Description

  The present invention relates to an improver composition for hydraulic materials. More particularly, the present invention relates to a hydraulic material improver composition having an excellent crack suppression function against drying shrinkage cracks of hydraulic materials.

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

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

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

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

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

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

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

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

  The problem of the present invention is that it does not require a combination with other admixtures, is excellent in freeze-thaw resistance, and exhibits excellent crack suppression function without causing a decrease in the strength of the cured product. The object is to provide a material improver composition. Moreover, it is providing the cement composition containing such a modifier composition for hydraulic materials.

The improver composition for hydraulic material of the present invention is:
General formula (1):
^{_{[R 1 -O- (X 1 O}} ) m -] p Y [-O- (X 2 O) n -R 2] q (1)
(In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and X ¹ O and X ² O each independently represent a carbon atom. Represents an oxyalkylene group of formulas 2 to 4, m and n represent the average number of added moles of X ¹ O and X ² O, respectively, m and n are each independently 0 to 500, and m + n = 2 to 500, Y represents a residue of a compound containing a hydroxyl group, and p and q are each independently 0 to 6. However, p and q are not 0 at the same time.
A hydraulic material improver composition comprising a compound (A) represented by formula (B) and a compound (B):
The compound (B) is a crosslinked product having an unsaturated monomer as a monomer unit,
The unsaturated monomer contains at least one selected from anionic monomers and nonionic monomers,
The anionic monomer includes a sulfonic acid (salt) monomer.

  In a preferred embodiment, the compound (A) and the compound (B) are contained in a weight ratio of (A) / (B) = 60/40 to 99/1.

  In a preferred embodiment, the nonionic monomer includes an N-vinyl lactam monomer.

  In preferable embodiment, the water absorption capacity | capacitance after 24 hours with respect to the aqueous solution containing 0.6 weight% of calcium nitrate tetrahydrate and 0.089 weight% of potassium hydroxide of the said compound (B) is 8 g / g or more. is there.

  The cement composition of the present invention includes the improver composition for hydraulic material of the present invention and cement.

  According to the present invention, it does not require a combination with other admixtures, is excellent in freeze-thaw resistance, and exhibits excellent crack suppression function without causing a decrease in the strength of the cured product. Material improver compositions can be provided. Moreover, the cement composition containing such a modifier composition for hydraulic materials can be provided.

It is a figure which shows the form of the ring restraint specimen used for evaluation of the crack resistance in the Example of this invention.

≪≪Modifier composition for hydraulic materials≫≫
The improver composition for hydraulic material of the present invention comprises a compound (A) and a compound (B).

  Only one type of compound (A) may be used, or two or more types may be used. Only one type of compound (B) may be used, or two or more types may be used.

  The addition amount of the improver composition for hydraulic material of the present invention is preferably 0.5 to 20% by weight, more preferably 0, in terms of solid content with respect to the hydraulic material (cement or the like). .5 wt% to 15 wt%, more preferably 1 wt% to 10 wt%. The additive composition of the hydraulic material for the hydraulic material according to the present invention is adjusted to 0.5 to 20% by weight in terms of solid content with respect to the hydraulic material. Can effectively exhibit a crack-inhibiting function and freeze-thaw resistance.

  The hydraulic material improver composition of the present invention contains the compound (A) and the compound (B) in a weight ratio, preferably (A) / (B) = 60/40 to 99/1. To do. When the ratio of (A) / (B) is within the above range, the hydraulic material improver composition of the present invention is capable of suppressing cracks by using the compound (A) and the compound (B) in combination. In addition, the effect of synergistically improving the freeze-thaw resistance can be obtained, and the fresh physical properties of the concrete can be maintained well. The ratio of (A) / (B) is more preferably 70/30 to 98/2, and still more preferably 90/10 to 95/5.

<Compound A>
Compound (A) is represented by general formula (1).
^{_{[R 1 -O- (X 1 O}} ) m -] p Y [-O- (X 2 O) n -R 2] q (1)

In the general formula ^{(1), R 1, R} 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. R ¹ and R ² are preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms, still more preferably, It is a hydrogen atom.

In General Formula (1), X ¹ O and X ² O each independently represent an oxyalkylene group having 2 to 4 carbon atoms. X ¹ O and X ² O may each be one kind of oxyalkylene group or two or more kinds of oxyalkylene groups. When X ¹ O is two or more oxyalkylene groups, (X ¹ O) _m may be a random array or a block array. When X ² O is two or more oxyalkylene groups, (X ² O) _n may be a random array or a block array. X ¹ O and X ² O are preferably an oxypropylene group or an oxyethylene group, and more preferably an oxyethylene group.

In general formula (1), m and n represent the average added mole numbers of X ¹ O and X ² O, respectively, m and n are each 0 to 500, preferably 1 to 100, m + n = 2 to 500, preferably m + n = 5 to 500.

When either X ¹ O or X ² O is an oxypropylene group, m and n are preferably 1 to 20, and more preferably 1 to 10.

When both X ¹ O and X ² O are oxyethylene groups, m and n are preferably 5 to 200, more preferably 10 to 150, and still more preferably 20 to 100.

  By setting m and n within the above ranges, the compound (A) represented by the general formula (1) is used in combination with the compound (B) to synergistically improve the hydraulic material composition of the present invention. It is possible to improve the crack suppressing function and freeze-thaw resistance of objects.

Y represents a residue of a compound containing a hydroxyl group. That is, Y means the Y portion in the hydroxyl group-containing compound represented by Y— (OH) _r (where r is an integer of 1 or more). Examples of the compound containing a hydroxyl group include compounds in which at least one hydrogen atom bonded to a hydrocarbon having 1 to 8 carbon atoms is replaced with a hydroxyl group. Specific examples of the compound containing a hydroxyl group include monohydric alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol and 2-ethylhexanol; ethylene glycol, propylene glycol and the like. Glycols; polymethyl alcohols such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, glycerin, polyglycerin; and the like. Among these, the compound containing a hydroxyl group is preferably a glycol such as ethylene glycol or propylene glycol, and more preferably ethylene glycol.

  p and q are 0-6 independently of each other. However, p and q are not 0 at the same time. The sum of p and q is preferably 2 to 12, and more preferably 2 to 6.

  Specific examples of the compound (A) include, for example, polyethylene glycol monoalkyl ether obtained by adding ethylene oxide to an alcohol having 1 to 4 carbon atoms; trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, sorbitol, glycerin. And a compound obtained by adding ethylene oxide to a polyhydric alcohol such as polyglycerin; polyethylene glycol; Of these, the compound (A) is preferably polyethylene glycol. The weight average molecular weight of such polyethylene glycol is preferably 200 to 20000, more preferably 400 to 10000, and still more preferably 1000 to 6000.

  In the improver composition for hydraulic material of the present invention, the compound (A) represented by the general formula (1) is preferably 0.01% by weight to 10% by weight in terms of solid content with respect to the hydraulic material. % To use. More preferably, it is 0.03 to 5 weight%, More preferably, it is 0.05 to 3 weight%, Especially preferably, it is 0.1 to 2 weight%. When the amount of the compound (A) represented by the general formula (1) is less than 0.01% by weight in terms of solid content with respect to the hydraulic material, there is a possibility that the crack suppressing function cannot be sufficiently exhibited. If it exceeds 10% by weight, the crack suppressing function corresponding to the amount used may not be exhibited, which is uneconomical in terms of cost.

<Compound B>
Compound (B) is a crosslinked product having an unsaturated monomer as a monomer unit, and the unsaturated monomer contains at least one selected from an anionic monomer and a nonionic monomer The anionic monomer includes a sulfonic acid (salt) monomer. The unsaturated monomer contains any appropriate other monomer as long as the effect of the present invention is not impaired, other than at least one selected from anionic monomers and nonionic monomers You may do it. In the unsaturated monomer, the content ratio of at least one selected from an anionic monomer and a nonionic monomer is preferably 1% by weight to 100% by weight, more preferably 3% by weight to 99%. % By weight, more preferably 5% by weight to 98% by weight, and particularly preferably 10% by weight to 95% by weight. In the unsaturated monomer, when the content ratio of at least one selected from an anionic monomer and a nonionic monomer is within the above range, the crack of the improver composition for hydraulic material of the present invention is cracked. The inhibitory function and freeze-thaw resistance can be further improved. As the anionic monomer, only one kind of anionic monomer may be used, or two or more kinds of anionic monomers may be used. As the nonionic monomer, only one kind of nonionic monomer may be used, or two or more kinds of nonionic monomers may be used.

(Anionic monomer)
The anionic monomer includes a sulfonic acid (salt) monomer. Examples of the sulfonic acid (salt) monomer include vinyl sulfonate, (meth) allyl sulfonate, 2- (meth) acryloxyethyl sulfonate, 3- (meth) acryloxypropyl sulfonate, 3- (meth) acryloxy- 2-hydroxypropyl sulfonate, 3- (meth) acryloxy-2-hydroxypropylsulfophenyl ether, 3- (meth) acryloxy-2-hydroxypropyloxysulfobenzoate, 4- (meth) acryloxybutyl sulfonate, (meth) acrylamide Unsaturated sulfonic acids such as methylsulfonic acid, (meth) acrylamide ethylsulfonic acid, 2-methylpropanesulfonic acid (meth) acrylamide, and styrenesulfonic acid, as well as their monovalent metal salts, divalent metal salts, ammonium salts, Oh Such as fine organic ammonium salts. The content ratio of the sulfonic acid (salt) monomer in the anionic monomer is preferably 3% by weight to 95% by weight, more preferably 5% by weight to 90% by weight, and still more preferably. It is 7 to 85% by weight, particularly preferably 10 to 80% by weight. When the content ratio of the sulfonic acid (salt) monomer in the anionic monomer falls within the above range, the crack suppressing function and freeze-thaw resistance of the improver composition for hydraulic material of the present invention are improved. It can be improved further.

  As an anionic monomer, you may contain other anionic monomers other than a sulfonic acid (salt) type monomer. Examples of such other anionic monomers include carboxylic acid (salt) monomers, phosphoric acid (salt) monomers, and boric acid (salt) monomers. Among these, carboxylic acid (salt) monomers are preferable. Examples of the carboxylic acid (salt) monomer include unsaturated monocarboxylic acid monomers such as acrylic acid, methacrylic acid, and crotonic acid; unsaturated dicarboxylic acid monomers such as maleic acid, itaconic acid, and fumaric acid. And anhydrides or salts of these carboxylic acids (for example, alkali metal salts, alkaline earth metal salts, ammonium salts, alkylammonium salts and substituted alkylammonium salts). When a carboxylic acid (salt) monomer is contained in the anionic monomer, the content is preferably 5 wt% to 97 wt%, more preferably 10 wt% to 95 wt%. More preferably 15 to 93% by weight, particularly preferably 20 to 90% by weight. When the content ratio of the carboxylic acid (salt) monomer in the anionic monomer is within the above range, the crack suppressing function and freeze-thaw resistance of the improver composition for hydraulic material of the present invention are improved. This can be further improved.

(Nonionic monomer)
Examples of nonionic monomers include N-vinyl lactam monomers, polyalkylene glycol monomers, amide monomers, and the like.

  When the nonionic monomer contains an N-vinyl lactam monomer, the N-vinyl lactam monomer in all unsaturated monomers (excluding crosslinkable monomers) forming the compound (B) It is preferable that the content ratio of the monomer is a certain level or more as described later. When the nonionic monomer contains a polyalkylene glycol monomer, the polyalkylene glycol monomer in all unsaturated monomers (excluding crosslinkable monomers) forming the compound (B) It is preferable that the content ratio of is not less than a certain value as will be described later. When the nonionic monomer contains an amide monomer, the content ratio of the amide monomer in all unsaturated monomers (excluding crosslinkable monomers) forming the compound (B) is As will be described later, it is preferably a certain value or more. In addition, the total unsaturated monomer here is the concept which does not contain the crosslinkable monomer mentioned later.

  As the N-vinyl lactam monomer, any appropriate N-vinyl lactam monomer can be adopted as long as it does not impair the effects of the present invention as long as it is a monomer having an N-vinyl lactam structure. . Examples of such N-vinyl lactam monomers include N-vinyl-2-pyrrolidone, N-vinyl caprolactam, and N-vinyl imidazoline. As the N-vinyl lactam monomer, only one N-vinyl lactam monomer may be used, or two or more N-vinyl lactam monomers may be used. Among the N-vinyl lactam monomers, N-vinyl-2-pyrrolidone is particularly preferable from the viewpoint of safety of the monomer itself and the obtained cross-linked product.

  The N-vinyl lactam monomer can be produced by any appropriate method. For example, when the N-vinyl lactam monomer is N-vinyl-2-pyrrolidone, a method in which N-hydroxyethylpyrrolidone is subjected to vapor phase dehydration is particularly preferable. As a specific method for vapor-phase dehydration reaction of N-hydroxyethylpyrrolidone, for example, a method reported in Japanese Patent Application Laid-Open No. 8-141402 and Japanese Patent No. 2939433 may be employed. In the above method, it is preferable to use γ-butyrolactone, which is a precursor of N-hydroxyethylpyrrolidone, derived from maleic anhydride. N-vinyl-2-pyrrolidone is N-vinyl-2-pyrrolidone obtained by vinylation of 2-pyrrolidone with acetylene, and ethanolamine is allowed to act on butyrolactone to give 1- (β-oxyethyl) -2-pyrrolidone. The acetic ester intermediate obtained by the reaction of N-vinyl-2-pyrrolidone and N- (2-hydroxyethyl) -2-pyrrolidone obtained as a dehydrated salt with acetic anhydride is deacetated by changing the hydroxyl group to chlorine with thionyl chloride. N-vinyl-2-pyrrolidone obtained as described above may be used.

  The N-vinyl lactam monomer produced by the production method as described above is usually used for polymerization through a purification step.

  When the unsaturated monomer forming the compound (B) contains an N-vinyl lactam monomer, the total unsaturated monomer (excluding the crosslinkable monomer) forming the compound (B) The content ratio of the N-vinyl lactam monomer is preferably 30% by weight or more, more preferably 40% by weight to 90% by weight, and further preferably 60% by weight to 80% by weight. In addition, the total unsaturated monomer here is the concept which does not contain the crosslinkable monomer mentioned later.

  As the polyalkylene glycol monomer, any appropriate polyalkylene glycol monomer may be used as long as it does not impair the effects of the present invention as long as it is a monomer having a polyalkylene glycol chain and a polymerizable group. obtain. Examples of such polyalkylene glycol monomers include methoxypolyethylene glycol mono (meth) acrylate, methoxypolyethylene glycol / polypropylene glycol mono (meth) acrylate, methoxypolyethylene glycol / polybutylene glycol mono (meth) acrylate, ethoxy Examples include polyethylene glycol / polypropylene glycol mono (meth) acrylate, ethoxypolyethylene glycol / polybutylene glycol mono (meth) acrylate, phenoxypolyethylene glycol mono (meth) acrylate, and benzyloxypolyethylene glycol mono (meth) acrylate. As the polyalkylene glycol monomer, only one type of polyalkylene glycol monomer may be used, or two or more types of polyalkylene glycol monomers may be used.

  When all unsaturated monomers forming compound (B) contain polyalkylene glycol monomers, all unsaturated monomers (excluding crosslinkable monomers) forming compound (B) The content ratio of the polyalkylene glycol monomer is preferably 70% by weight or more, more preferably 80% by weight to 100% by weight, and still more preferably 85% by weight to 100% by weight. In addition, the total unsaturated monomer here is the concept which does not contain the crosslinkable monomer mentioned later.

  As the amide monomer, any appropriate amide monomer can be adopted as long as it does not impair the effects of the present invention as long as it has a amide structure. Examples of such amide monomers include (meth) acrylamide, (meth) acrylalkylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide and the like. As the amide monomer, only one amide monomer may be used, or two or more amide monomers may be used. Among the amide monomers, (meth) acrylamide is particularly preferable from the viewpoint of versatility.

  When the unsaturated monomer forming the compound (B) contains an amide monomer, the amide single monomer in all unsaturated monomers (excluding the crosslinkable monomer) forming the compound (B) The content ratio of the monomer is preferably 30% by weight or more, more preferably 40% by weight to 90% by weight, and still more preferably 60% by weight to 80% by weight. In addition, the total unsaturated monomer here is the concept which does not contain the crosslinkable monomer mentioned later.

Nonionic monomers such as N-vinyl lactam monomers, polyalkylene glycol monomers, amide monomers, etc., as unsaturated monomers (excluding crosslinkable monomers) forming the compound (B) A monomer copolymerizable with the monomer (other monomer) can be used. As the other monomer, only one other monomer may be used, or two or more other monomers may be used. Examples of such other monomers include:
1) Unsaturated monocarboxylic acid monomers such as acrylic acid, methacrylic acid, crotonic acid, or partially neutralized or completely neutralized products of these monovalent metals, divalent metals, ammonia and organic amines;
2) Unsaturated dicarboxylic acid monomers such as maleic acid, fumaric acid, itaconic acid, citraconic acid, or partially neutralized or completely neutralized products of these monovalent metals, divalent metals, ammonia and organic amines ;
3) Vinyl sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate, 2-hydroxysulfopropyl (meth) ) Unsaturated sulfonic acids such as acrylate, sulfoethylmaleimide, 3-allyloxy-2-hydroxypropane sulfonic acid, or partially neutralized or completely neutralized by monovalent metal, divalent metal, ammonia or organic amine System monomers;
4) Hydrophobic monomers such as (meth) acrylic acid ester, styrene, 2-methylstyrene, vinyl acetate;
5) 2-hydroxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, allyl alcohol, polyethylene glycol monoallyl ether, polypropylene glycol monoallyl ether, 3-methyl-2-butene- 1-ol (prenol), polyethylene glycol monoprenol ether, polypropylene glycol monoprenol ether, 2-methyl-3-buten-2-ol (isoprene alcohol), polyethylene glycol monoisoprene alcohol ether, polypropylene glycol monomonoisoprene alcohol ether , N-methylol (meth) acrylamide, glycerol mono (meth) acrylate, glycerol monoary Ethers, such as vinyl alcohol, hydroxyl group-containing unsaturated monomer;
6) Cationic monomers such as dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) acrylamide;
7) Nitrile monomers such as (meth) acrylonitrile;
8) Phosphorus-containing monomers such as (meth) acrylamide methanephosphonic acid, (meth) acrylamide methanephosphonic acid methyl ester, 2- (meth) acrylamide-2-methylpropanephosphonic acid;
Etc.

  Among the other monomers, from the viewpoint of copolymerization with nonionic monomers such as N-vinyl lactam monomers, polyalkylene glycol monomers, amide monomers, etc., 1 ) Unsaturated monocarboxylic acid monomers or 3) unsaturated sulfonic acid monomers are preferred, and 3) unsaturated sulfonic acid monomers are particularly preferred.

  The content of other monomers in the total unsaturated monomers (excluding crosslinkable monomers) forming the compound (B) is preferably 0% by weight to 70% by weight, more preferably 5%. % By weight to 40% by weight, more preferably 10% by weight to 30% by weight. In addition, the total unsaturated monomer here is the concept which does not contain the crosslinkable monomer mentioned later.

  As other monomers, when using acidic group-containing monomers such as unsaturated monocarboxylic acid monomers, unsaturated dicarboxylic acid monomers, unsaturated sulfonic acid monomers, or basic When the group-containing monomer is used, any of those in which the acidic group and the basic group are unneutralized, partially neutralized, or completely neutralized can be used without any problem.

  In order to form the compound (B), a crosslinkable monomer copolymerizable with an unsaturated monomer such as an anionic monomer or a nonionic monomer can be used. The crosslinkable monomer here is a crosslinkable monomer having at least two polymerizable double bond groups per molecule. As the crosslinkable monomer, only one type of crosslinkable monomer may be used, or two or more types of crosslinkable monomers may be used. A cross-linked product having a cross-linked structure can be obtained by copolymerizing an appropriate amount of the cross-linkable monomer with an unsaturated monomer such as an anionic monomer or a nonionic monomer.

  Examples of the crosslinkable monomer include N, N′-methylenebis (meth) acrylamide, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, and trimethylolpropane tri (meth). Acrylate, trimethylolpropane di (meth) acrylate, glycerin tri (meth) acrylate, glycerin acrylate methacrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Triallyl cyanurate, triallyl isocyanurate, triallyl phosphate, triallylamine, poly (meth) allyloxyalkane, divinylbenzene, divinyl Toluene, divinyl xylene, divinyl naphthalene, divinyl ether, divinyl ketone, trivinylbenzene, tolylene diisocyanate, hexamethylene diisocyanate, and the like.

  Arbitrary appropriate usage-amounts can be employ | adopted for the usage-amount of a crosslinkable monomer in the range which does not impair the effect of this invention. Preferably, the crosslinkable monomer is used in the range of 0.05 mol% to 1.0 mol% with respect to all unsaturated monomers (excluding the crosslinkable monomer).

  The compound (B) preferably has a water absorption capacity after 24 hours with respect to an aqueous solution containing 0.6% by weight of calcium nitrate tetrahydrate and 0.089% by weight of potassium hydroxide of 8 g / g or more. When the compound (B) has such a water absorption capacity, the improver composition for hydraulic material of the present invention can more effectively express the crack suppressing function and freeze-thaw resistance.

  The compound (B) is preferably in the form of particles, and the average particle size (average particle size) is preferably 10 μm to 1000 μm, more preferably 50 μm to 600 μm. When the average particle size of the compound (B) is in such a small range, the compound (B) is easily dispersed uniformly in the cement composition, and thus the effect of the present invention is easily exhibited.

  Compound (B) may be produced by any appropriate method. The method for producing compound (B) preferably includes a polymerization step. Examples of the polymerization method that can be employed in such a polymerization step include a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, and a precipitation polymerization method. When a solvent is used in such a polymerization method, examples of such a solvent include water; alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, and diethylene glycol; Only 1 type may be used for a solvent and 2 or more types may be used for it. As such a solvent, it is preferable to use water essentially.

  When a solvent is used in the polymerization method, the concentration of the unsaturated monomer (including the crosslinkable monomer) in the polymerization reaction solution is preferably 25% by weight to 80% by weight. When the concentration of the unsaturated monomer (including the crosslinkable monomer) is less than 25% by weight, since a long time is required for drying, the resin may be deteriorated during drying. On the other hand, if the concentration of the unsaturated monomer (including the crosslinkable monomer) exceeds 80% by weight, it is difficult to control the polymerization and the residual monomer may increase.

  In the production of the compound (B), a method of polymerizing an unsaturated monomer (excluding a crosslinkable monomer) in the presence of a crosslinkable monomer may be employed. A method of post-crosslinking treatment after polymerizing (excluding crosslinkable monomers) may be employed. As a method of post-crosslinking treatment after polymerizing unsaturated monomers (excluding crosslinkable monomers), for example, (i) UV after polymerizing unsaturated monomers (excluding crosslinkable monomers) (Ii) a method in which an unsaturated monomer (excluding a crosslinkable monomer) is polymerized and then self-crosslinked by polymerization, (iii) an unsaturated monomer (a crosslinkable monomer is And (iv) a method of self-crosslinking by adding heat after polymerization, and (iv) a radical polymerizable crosslinking agent after polymerizing unsaturated monomers (excluding crosslinkable monomers). And a method of heating and / or light irradiation after containing a radical polymerization initiator. When carrying out the polymerization reaction in the production of the compound (B), any appropriate reaction conditions can be adopted as the reaction conditions such as reaction temperature and pressure within the range not impairing the effects of the present invention. For example, the reaction temperature is preferably 20 ° C. to 150 ° C., and the pressure in the reaction system is preferably normal pressure or increased pressure. Moreover, as an addition method of each preparation component at the time of performing a polymerization reaction in manufacture of a compound (B), arbitrary appropriate addition methods can be employ | adopted in the range which does not impair the effect of this invention. Examples of such an addition method include a batch method and a continuous method. When a polymerization reaction is carried out in the production of the compound (B), as a means for initiating polymerization, for example, a method of adding a polymerization initiator, a method of irradiating UV, a method of applying heat, light in the presence of a photoinitiator The method etc. which irradiate can be employ | adopted.

  Any appropriate polymerization initiator can be adopted as the polymerization initiator as long as it generates radicals by heating or the like. As such a polymerization initiator, a water-soluble polymerization initiator that is uniformly dissolved in water at a concentration of 5% by weight or more at room temperature is particularly preferable. Specifically, for example, peroxides such as hydrogen peroxide and t-butyl hydroperoxide; 2- (carbamoylazo) isobutyronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis (2-methyl-N-phenylprolionamidine) dihydrochloride, 2,2′-azobis [2- (N-allylamidino) propane] dihydrochloride, 2,2′-azobis [ 2- (5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] 2 hydrochloric acid Salts, azo compounds such as 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide]; persulfates such as potassium persulfate, ammonium persulfate and sodium persulfate; Phosphate and hydrogen peroxide, sodium sulfoxylate and t- butyl hydroperoxide, a redox type initiator to generate radicals in combination with an oxidizing agent and a reducing agent such as persulfate and a metal salt; and the like. Only 1 type may be used for a polymerization initiator and it may use 2 or more types together.

  As a usage-amount of a polymerization initiator, arbitrary appropriate usage-amounts can be employ | adopted in the range which does not impair the effect of this invention. The amount used is preferably 0.002% by weight to 15% by weight, more preferably 0.01% by weight to the total unsaturated monomer (including the crosslinkable monomer). 5% by weight. By keeping the amount used within the above range, the hydraulic material improver composition of the present invention can more effectively express the crack suppressing function and freeze-thaw resistance.

  In carrying out the polymerization reaction in the production of the compound (B), a basic pH regulator may be used for the purpose of accelerating the polymerization reaction or preventing hydrolysis of the unsaturated monomer. The basic pH adjuster can be added by any appropriate addition method. As such an addition method, for example, a method of charging in the system from the initial stage of polymerization or a method of sequentially adding during polymerization may be used. Specific examples of the basic pH adjuster include ammonia, aliphatic amines, aromatic amines, sodium hydroxide, potassium hydroxide, and the like. Among these, ammonia is particularly preferable. Only 1 type may be used for a basic pH adjuster and it may use 2 or more types together. When a basic pH adjuster is used, any appropriate amount can be adopted as the amount used within a range not impairing the effects of the present invention. The amount used is such that the solution during polymerization preferably has a pH range of 5 to 10, more preferably 7 to 9.

  When carrying out the polymerization reaction in the production of the compound (B), any appropriate transition metal salt may be used for the purpose of promoting the polymerization reaction and the like within a range not impairing the effects of the present invention. Specific examples of such transition metal salts include carboxylates and chlorides such as copper, iron, cobalt, and nickel. Such transition metal salts may be used alone or in combination of two or more. When such a transition metal salt is used, any appropriate use amount can be adopted as the use amount as long as the effects of the present invention are not impaired. The amount used is preferably 0.1 ppb to 20000 ppb, more preferably 1 ppb to 5000 ppb, based on the total unsaturated monomers (including crosslinkable monomers). By keeping the amount used within the above range, the hydraulic material improver composition of the present invention can more effectively express the crack suppressing function and freeze-thaw resistance.

  In carrying out the polymerization reaction in the production of the compound (B), any appropriate other additive such as a chain transfer agent and a buffer may be used within a range not impairing the effects of the present invention.

  The improver composition for hydraulic material of the present invention may contain any appropriate water reducing agent. Examples of such water reducing agents include amino sulfonic acid series such as lignin sulfonate, naphthalene sulfonic acid formalin condensate, melamine sulfonic acid formalin condensate, polystyrene sulfonate, aminoaryl sulfonic acid-phenol-formaldehyde condensate. A sulfonic acid-based water reducing agent such as a polyol derivative; a polymer having a polyoxyalkylene group and an anionic group (preferably a polymer having a polyoxyalkylene group and a carboxyl group (polycarboxylic acid-based water reducing agent), poly A polymer having an oxyalkylene group and a phosphate group).

  Examples of the polymer having a polyoxyalkylene group and a carboxyl group (polycarboxylic acid-based water reducing agent) include alkylenes for specific unsaturated alcohols such as (meth) allyl alcohol and 3-methyl 3-buten-1-ol. Copolymer obtained from a monomer composition containing an alkenyl ether monomer to which an oxide is added and an unsaturated carboxylic acid monomer such as (meth) acrylic acid or maleic acid, or a salt thereof 236858 and JP-A-2001-220417); obtained from a monomer composition containing (alkoxy) polyalkylene glycol mono (meth) acrylate monomer and (meth) acrylic monomer And the like (see JP-B-59-18338 and JP-A-7-223852).

  Examples of the polymer having a polyoxyalkylene group and a phosphate group include, for example, a single monomer containing a specific monomer having a polyoxyalkylene group, a phosphate monoester monomer, and a phosphate diester monomer. Examples thereof include a copolymer obtained from the monomer composition (see JP-A-2006-052381).

  Among the water reducing agents as described above, lignin sulfonate, naphthalene sulfonic acid formalin condensate, and polycarboxylic acid water reducing agent are preferable.

  The improver composition for hydraulic material of the present invention may contain any other appropriate component for hydraulic material as exemplified in the following (1) to (20).

  (1) Water-soluble polymer material: polyacrylic acid (sodium), polymethacrylic acid (sodium), polymaleic acid (sodium), unsaturated carboxylic acid polymer such as sodium salt of acrylic acid / maleic acid copolymer; methylcellulose Nonionic cellulose ethers such as ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, hydroxypropyl cellulose; alkylated or hydroxyalkylated derivatives of polysaccharides such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose A hydrophobic substituent in which some or all of the hydroxyl atoms have a hydrocarbon chain having 8 to 40 carbon atoms as a partial structure, a sulfonic acid group, or Polysaccharide derivatives substituted with ionic hydrophilic substituents containing these salts as a partial structure; yeast glucan, xanthan gum, β-1,3 glucans (both linear and branched chain, examples) Polysaccharides produced by microbial fermentation such as curdlan, paramylon, pachyman, scleroglucan, laminaran, etc.); polyacrylamide; polyvinyl alcohol; starch; starch phosphate ester; sodium alginate; gelatin; Copolymers of acrylic acid having amino groups and quaternary compounds thereof;

  (2) Polymer emulsion: Copolymers of various vinyl monomers such as alkyl (meth) acrylate.

  (3) retarder: gluconic acid, glucoheptonic acid, arabonic acid, malic acid or citric acid, and oxycarboxylic acids such as sodium, potassium, calcium, magnesium, ammonium, triethanolamine and other inorganic or organic salts Monosaccharides such as glucose, fructose, galactose, saccharose, xylose, apiose, ribose and isomerized sugar, oligosaccharides such as disaccharide and trisaccharide, oligosaccharides such as dextrin, polysaccharides such as dextran, and the like Sugars such as molasses; sugar alcohols such as sorbitol; magnesium silicofluoride; phosphoric acid and its salts or borate esters; aminocarboxylic acids and salts thereof; alkali-soluble proteins; humic acid; tannic acid; Polyhydric alcohols such as glycerin; amino Li (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), and their alkali metal salts, alkaline earth metal salts, etc. Phosphonic acid and its derivatives;

  (4) Early strengthening agents / accelerators: soluble calcium salts such as calcium chloride, calcium nitrite, calcium nitrate, calcium bromide and calcium iodide; chlorides such as iron chloride and magnesium chloride; sulfates; potassium hydroxide; Sodium hydroxide; carbonate; thiosulfate; formate such as formic acid and calcium formate; alkanolamine; alumina cement; calcium aluminate silicate;

  (5) Mineral oil-based antifoaming agent: cocoon oil, liquid paraffin, etc.

  (6) Fat and oil-based antifoaming agents: animal and vegetable oils, sesame oil, castor oil, alkylene oxide adducts thereof and the like.

  (7) Fatty acid-based antifoaming agent: oleic acid, stearic acid, and these alkylene oxide adducts.

  (8) Fatty acid ester antifoaming agent: glycerin monoricinoleate, alkenyl succinic acid derivative, sorbitol monolaurate, sorbitol trioleate, natural wax and the like.

  (9) Oxyalkylene antifoaming agents: polyoxyalkylenes such as (poly) oxyethylene (poly) oxypropylene adducts; diethylene glycol heptyl ether, polyoxyethylene oleyl ether, polyoxypropylene butyl ether, polyoxyethylene polyoxypropylene (Poly) oxyalkyl ethers such as -2-ethylhexyl ether and oxyethylene oxypropylene adducts to higher alcohols having 12 to 14 carbon atoms; (poly) such as polyoxypropylene phenyl ether and polyoxyethylene nonyl phenyl ether Oxyalkylene (alkyl) aryl ethers; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 3-methyl- 1 Acetylene ethers obtained by addition polymerization of alkylene oxide to acetylene alcohol such as butyn-3-ol; (poly) oxyalkylene fatty acid esters such as diethylene glycol oleate, diethylene glycol laurate, ethylene glycol distearate; polyoxyethylene (Poly) oxyalkylene sorbitan fatty acid esters such as sorbitan monolaurate and polyoxyethylene sorbitan trioleate; (poly) oxyalkylene alkyl such as sodium polyoxypropylene methyl ether sulfate and sodium polyoxyethylene dodecylphenol ether sulfate ( Aryl) ether sulfate salts; (Poly) oxypolyethylene stearyl phosphate, etc. (poly) Xylene polyoxyalkylene alkyl phosphoric acid esters; polyoxyethylene such as polyoxyethylene lauryl amine (poly) oxyalkylene alkyl amines; polyoxyalkylene amide; and the like.

  (10) Alcohol-based antifoaming agent: octyl alcohol, hexadecyl alcohol, 2-ethylhexyl alcohol, acetylene alcohol, glycols and the like.

  (11) Amide antifoaming agent: acrylate polyamine and the like.

  (12) Phosphate ester antifoaming agent: tributyl phosphate, sodium octyl phosphate, etc.

  (13) Metal soap type antifoaming agent: aluminum stearate, calcium oleate, etc.

  (14) Silicone antifoaming agent: dimethyl silicone oil, silicone paste, silicone emulsion, organically modified polysiloxane (polyorganosiloxane such as dimethylpolysiloxane), fluorosilicone oil and the like.

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

  (16) Other surfactants: aliphatic monohydric alcohols having 6 to 30 carbon atoms in the molecule such as octadecyl alcohol and stearyl alcohol; 6-30 carbon atoms in the molecule such as abiethyl alcohol Alicyclic monohydric alcohol having; monovalent mercaptan having 6 to 30 carbon atoms in the molecule such as dodecyl mercaptan; alkylphenol having 6 to 30 carbon atoms in the molecule such as nonylphenol; molecule such as dodecylamine Amines having 6 to 30 carbon atoms in them; polyalkylene oxide derivatives (for example, carboxylic acids having 6 to 30 carbon atoms in the molecule such as lauric acid and stearic acid, ethylene oxide, propylene oxide, etc. Alkylene oxide added 10 mol or more); alkyl group or alkoxy Alkyldiphenyl ether sulfonates in which two phenyl groups having a sulfonic acid group may be ether-bonded; various anionic surfactants; various cations such as alkylamine acetate and alkyltrimethylammonium chloride Various surfactants; various nonionic surfactants; various amphoteric surfactants;

  (17) Waterproofing agent: fatty acid (salt), fatty acid ester, oil and fat, silicone, paraffin, asphalt, wax and the like.

  (18) Rust preventive: nitrite, phosphate, zinc oxide and the like.

  (19) Shrinkage reducing agent: polyoxyalkyl ether and the like.

  (20) Expansion material: Ettlingite, lime, etc.

  Other components for hydraulic materials include concrete admixtures, cement wetting agents, thickeners, separation reducing agents, flocculants, strength enhancers, self-leveling agents, colorants, antifungal agents and the like. In addition, only 1 type may be used for another component for hydraulic materials, and 2 or more types may be used together.

  The improving agent composition for hydraulic materials of the present invention may be used in combination with other admixtures as necessary within the range of the effects of the present invention. However, the improver composition for hydraulic materials according to the present invention can suppress the strength reduction of the cured product and can exhibit an excellent crack-inhibiting function without combining with other admixtures, and has excellent freeze-thaw resistance. It can be expressed. Therefore, when considering providing the hydraulic material improver composition of the present invention at low cost, other admixtures are not necessarily used in combination.

  Arbitrary appropriate methods can be employ | adopted about the manufacturing method of the improving agent composition for hydraulic materials of this invention. For example, when the improving agent composition for hydraulic materials of the present invention contains the compound (A) and the compound (B), mixing may be performed by any appropriate mixing method.

  The use form of the improver composition for hydraulic material of the present invention is generally a method of adding to the hydraulic material composition, but the hydraulic material of the present invention is applied to the surface of the cured hydraulic material composition after curing. The improving agent composition may be applied or sprayed.

  The improver composition for hydraulic materials according to the present invention has a wide range of application of the water / cement ratio, and can be produced to concrete having a water / cement ratio (weight ratio) of preferably 60% to 15%.

≪≪Cement composition≫≫
The cement composition of the present invention includes the improver composition for hydraulic material of the present invention and cement. The cement composition of the present invention preferably contains fine aggregate and water in addition to the hydraulic material improver composition of the present invention and cement, and such a cement composition may be referred to as mortar. is there. The cement composition of the present invention preferably further comprises fine aggregate, coarse aggregate and water in addition to the hydraulic material improver composition of the present invention and cement. Such a cement composition May be referred to as concrete.

  Examples of the cement used in the production of the cement composition include normal, low heat, moderately hot, early strength, ultra-early strength, sulfate-resistant, portland cement such as low alkali type thereof, blast furnace cement, silica cement, fly ash cement, etc. Eco-cement (cement produced from one or more of municipal waste incineration ash and sewage sludge incineration ash); silica fume cement; white Portland cement; alumina cement; Cement, magnesium phosphate cement); grout cement; oil well cement; low exothermic cement (low exothermic blast furnace cement, fly ash mixed low exothermic blast furnace cement, high belite-containing cement); ultra high strength cement; cement solidified material And so on. Examples of the powder that can be contained in the cement composition include silica fume, fly ash, cinder ash, clinker ash, husk ash, silica powder, limestone fine powder, blast furnace slag fine powder, expansion material, and other minerals. Examples include fine powder. Examples of the fine aggregate include river sand, mountain sand, sea sand, crushed sand, heavy aggregate, lightweight aggregate, slag aggregate, recycled aggregate, and the like. Examples of the coarse aggregate include river gravel, crushed stone, heavy aggregate, lightweight aggregate, slag aggregate, recycled aggregate, and the like. Examples of water include tap water, water other than tap water (river water, lake water, well water, etc.) shown in Appendix 9 of JIS A 5308, recovered water, and the like.

  Any appropriate additive may be contained in the cement composition. Examples of such additives include curing accelerators, setting retarders, rust preventives, waterproofing agents, preservatives, and the like.

  Any appropriate method can be adopted as a method for producing, transporting, placing, curing, and managing the cement composition.

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

<Evaluation of crack resistance>
300 g of a predetermined amount of the improver composition for hydraulic material weighed and mixed with water, and 600 g of ordinary Portland cement (manufactured by Taiheiyo Cement Co., Ltd.), Hobart type mortar mixer (manufactured by Hobart Co., model number: N-50) The mixture was kneaded at low speed for 3 minutes to obtain a cement paste for preparing an evaluation specimen.
The obtained cement paste (250 g) was poured into a ring restraint test mold (outer frame: polystyrene with PE lid, metal ring: SUS304) to prepare a ring restraint specimen having the shape shown in FIG. Sealing curing was performed for one day.
After sealing curing for 3 days, the cured paste was taken out of the ring restraint test mold and used as a ring restraint specimen. The form of the ring restraint specimen is as shown in FIG.
This specimen was stored in a constant temperature and humidity room at a room temperature of 20 ° C. and a humidity of 60%, and the crack resistance was evaluated. The time from the start of storage until the specimen was cracked was defined as the crack occurrence time. It shows that it is excellent in crack resistance, so that the crack generation time is long.
<Weight average particle size measurement conditions>
The weight average particle diameter (D50) of the crosslinked product was measured according to the measurement method disclosed in European Patent No. 0349240. That is, using a sieve corresponding to a JIS standard sieve (The IIDA TESTING SIEVE, inner diameter 80 mm, JIS Z8801-1 (2000)) having openings of 300 μm, 212 μm, 150 μm, 106 μm, 75 μm, 45 μm, or JIS standard sieve Then, 10 g of the crosslinked product was classified. After classification, the weight of each sieve was measured, and the weight percentage (% by weight) having a particle diameter of less than 150 μm was calculated. The weight average particle diameter (D50) was obtained by plotting the residual percentage R of each particle size on a logarithmic probability paper, and reading the particle diameter corresponding to R = 50% by weight from this graph as the weight average particle diameter (D50). .
In addition, a weight average particle diameter (D50) means the particle diameter of the standard sieve corresponding to 50 weight% of the whole crosslinked material.
<Water absorption magnification (FSC) measurement conditions>
The measurement of FSC (water absorption magnification suspended under no pressure) was performed according to ERT440.2-02.
0.2 g of the cross-linked product was weighed, uniformly put into a non-woven bag (60 × 85 mm), heat sealed, and then adjusted to 25 ± 3 ° C. calcium nitrate tetrahydrate (0.6 wt%) + hydroxylation It was immersed in 500 mL of potassium (0.089 wt%) aqueous solution. After 24 hours, the bag was pulled up and suspended for 10 minutes for draining. Thereafter, the mass W3 [g] of the bag was measured.
The same operation was performed without adding the cross-linked product, and the mass W4 [g] of the bag at that time was measured. FSC (water absorption capacity without pressure) was calculated according to the following formula.
FSC (g / g) = (W3-W4) / (mass of crosslinked product (0.2 g))-1

[Production Example 1]: Synthesis of (M-10) 0.4 g of flaky sodium hydroxide was charged into a stainless steel high-pressure reaction vessel equipped with a thermometer, a stirrer, nitrogen, and an ethylene oxide introduction tube. Nitrogen replacement was sufficiently performed by repeating nitrogen pressurization and evacuation. Next, 57.5 g of methanol was charged, and the temperature of this mixed solution was raised to 90 ° C. The initial pressure was set to 0.15 MPa, and 790 g of ethylene oxide was added over 8 hours. During this period, the reaction temperature was maintained at 125 ± 5 ° C., and the reaction pressure was maintained at 0.78 MPa or less. The reaction temperature was further maintained for 2 hours to complete the addition reaction of ethylene oxide to methanol to obtain M-10 in which 10 mol of ethylene oxide was added to 1 mol of methanol.

[Production Example 2]: Synthesis of (M-25) 75.1 g of M-10 obtained in Production Example 1 was charged into a stainless steel high-pressure reaction vessel equipped with a thermometer, a stirrer, nitrogen, and an ethylene oxide introduction tube. The inside of the reaction vessel was sufficiently replaced with nitrogen by repeating nitrogen pressurization and evacuation. Next, the internal temperature was set to 150 ° C., the initial pressure was set to 0.15 MPa, and 105 g of ethylene oxide was added over 6 hours. During this period, the reaction temperature was maintained at 150 ± 5 ° C., and the reaction pressure was maintained at 0.78 MPa or less. The reaction temperature was further maintained for 1 hour to complete the addition reaction of ethylene oxide to obtain M-25 in which 25 mol of ethylene oxide was added to 1 mol of methanol.

[Production Example 3]: Synthesis of (M-50) 82.3 g of M-25 obtained in Production Example 2 was charged into a stainless steel high-pressure reaction vessel equipped with a thermometer, a stirrer, nitrogen, and an ethylene oxide introduction tube. The inside of the reaction vessel was sufficiently replaced with nitrogen by repeating nitrogen pressurization and evacuation. Next, the internal temperature was set to 150 ° C., the initial pressure was set to 0.15 MPa, and 80 g of ethylene oxide was added over 5 hours. During this period, the reaction temperature was maintained at 150 ± 5 ° C., and the reaction pressure was maintained at 0.78 MPa or less. The reaction temperature was further maintained for 1 hour to complete the addition reaction of ethylene oxide to obtain M-50 in which 50 mol of ethylene oxide was added to 1 mol of methanol.

[Production Example 4]: Synthesis of (Crosslinked product 1) An inner diameter of 85 mm, a cylindrical plastic container (capacity 1000 mL), 94.2 g of N-vinyl-2-pyrrolidone, sodium 2-acrylamido-2-methylpropanesulfonate ( (50% aqueous solution) 130.3 g, 0.965 g of methylenebisacrylamide, and 174.9 g of water were added and mixed well, then immersed in a hot water bath at 60 ° C., and nitrogen gas was blown in at 2 L / min for 20 minutes. Dissolved oxygen was removed. Then, 2.372 g of 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride aqueous solution of 3 mass% with respect to 100 wt% of the total monomers was added and mixed, Static polymerization was carried out. After the polymerization exotherm passed the peak, the warm water bath was heated to 80 ° C. and allowed to stand for 30 minutes. After standing, the obtained gel-like product was cut into a size of about 5 mm with scissors and then dried at 115 ° C. for 2 hours. The obtained dried product is pulverized with a roll mill, classified using a JIS standard sieve having openings of 250 μm and 45 μm, a weight average particle size of 180 μm, and a 24-hour water absorption capacity in a calcium nitrate / potassium hydroxide aqueous solution. The crosslinked product 1 which was 18 g / g was obtained.

[Production Example 5]: Synthesis of (Crosslinked product 2) A reactor equipped with a stirring blade, a reflux condenser, a thermometer, a nitrogen gas inlet tube and a dropping funnel was prepared in a four-necked separable flask having a capacity of 2000 mL. After adding 800 g of cyclohexane and 4.5 g of sucrose fatty acid ester (Daiichi Kogyo Seiyaku Co., Ltd., DK Ester (registered trademark) F-50) as a dispersant to this separable flask, put it in a hot water bath up to 75 ° C. Mixing while raising the temperature, the sucrose fatty acid ester was dissolved. Thereafter, nitrogen gas was blown at 2 L / min for 20 minutes to remove dissolved oxygen in the solution. Separately, a sufficiently mixed monomer aqueous solution (94.9 g of N-vinyl-2-pyrrolidone, 130.3 g of sodium 2-acrylamido-2-methylpropanesulfonate (50% aqueous solution), 0.228 g of methylenebisacrylamide , 174.9 g of water) was put into a 500 ml dropping funnel, nitrogen gas was blown in at 2 L / min for 20 minutes to remove dissolved oxygen in the aqueous solution, and 3% 2,2′-azobis [2- ( 2-Imidazolin-2-yl) propane] dihydrochloride aqueous solution 2.372 g was added and mixed uniformly. This was dropped into cyclohexane heated to 75 ° C. and dispersed. After completion of the dropwise addition, the polymerization reaction was completed by maintaining the liquid temperature in the separable flask at 75 ° C. for 60 minutes. Subsequently, the hot water bath was set to 90 ° C. or higher and azeotropic dehydration was performed to a solid content of 85%, followed by filtration. After completion of filtration, the solution was left to stand for 16 hours in a dryer at 80 ° C. Thereafter, classification is performed using JIS standard sieves having openings of 250 μm and 45 μm, and a cross-linked product 2 having a weight average particle size of 149 μm and a 24-hour absorption in a calcium nitrate / potassium hydroxide aqueous solution of 26 g / g is obtained. It was.

[Production Example 6]: Synthesis of (Crosslinked product 3) An inner diameter of 85 mm, a cylindrical plastic container (capacity: 1000 mL), sodium acrylate 62.6 g, acrylamide 110.4 g, methylenebisacrylamide 0.24 g, water 329.8 g Then, the mixture was sufficiently mixed, and then immersed in a hot water bath at 25 ° C., and nitrogen gas was blown at 2 L / min for 20 minutes to remove dissolved oxygen in the aqueous solution. Thereafter, 3.88 g of a 20% aqueous sodium persulfate solution and 3.88 g of a 2% L-ascorbic acid aqueous solution were added and mixed, followed by standing polymerization. After the polymerization exotherm passed the peak, the warm water bath was heated to 90 ° C. and allowed to stand for 40 minutes. After standing, the obtained gel-like product was cut into a size of about 5 mm with scissors and then dried at 115 ° C. for 2 hours. The obtained dried product is pulverized with a roll mill, classified using a JIS standard sieve having openings of 250 μm and 45 μm, a weight average particle size of 150 μm, and a 24-hour water absorption ratio in a calcium nitrate / potassium hydroxide aqueous solution. The crosslinked product 3 which was 18 g / g was obtained.

[Production Example 7]: Synthesis of (Crosslinked Product 4) In a cylindrical plastic container (capacity 1000 mL) with an inner diameter of 85 mm, 4-sulfoethyl methacrylate sodium salt 43.2 g, methacrylic acid 43 g, sodium methacrylate 140.4 g, After adding 1.84 g of methylenebisacrylamide and 340 g of water and mixing well, it was immersed in a hot water bath at 40 ° C., and nitrogen gas was blown at 2 L / min for 20 minutes to remove dissolved oxygen in the aqueous solution. Thereafter, 2 g of a 10% ammonium persulfate aqueous solution and 1 g of a 1% L-ascorbic acid aqueous solution were added and mixed, followed by standing polymerization. After the polymerization exotherm passed the peak, the warm water bath was heated to 90 ° C. and allowed to stand for 60 minutes. After standing, the obtained gel-like product was cut into a size of about 5 mm with scissors and then dried at 150 ° C. for 3 hours. The obtained dried product is pulverized with a roll mill, classified using a JIS standard sieve having openings of 250 μm and 45 μm, a weight average particle size of 159 μm, and a 24-hour water absorption capacity in a calcium nitrate / potassium hydroxide aqueous solution. The crosslinked product 4 which was 17 g / g was obtained.

[Comparative Production Example 1]: Synthesis of (Comparative Cross-Linked Product 1) In a cylindrical plastic container (capacity 1000 mL) with an inner diameter of 85 mm, 39.8 g of acrylic acid, 379.1 g of 37% sodium acrylate aqueous solution, polyethylene glycol diacrylate ( (Molecular weight 522) 0.55 g and 69.4 g of water were added and mixed well, then immersed in a hot water bath at 60 ° C., and nitrogen gas was blown at 2 L / min for 20 minutes to remove dissolved oxygen in the aqueous solution. Thereafter, 2.37 g of a 3% by weight aqueous sodium persulfate solution was added and mixed, and then subjected to stationary polymerization. After the polymerization exotherm passed the peak, the warm water bath was heated to 80 ° C. and allowed to stand for 30 minutes. The obtained gel was cut into a size of about 5 mm with scissors and then dried at 180 ° C. for 30 minutes. The obtained dried product is pulverized by a roll mill, classified using a JIS standard sieve having openings of 850 μm and 45 μm, a weight average particle size of 429 μm, and a 24-hour water absorption capacity in a calcium nitrate / potassium hydroxide aqueous solution. A comparative cross-linked product 1 of 5 g / g was obtained.

[Example 1]
As shown in Table 1, PEG 6000 (Daiichi Kogyo Seiyaku Co., Ltd.) was used as the compound (A), and the cross-linked product 1 obtained in Production Example 4 was used as the compound (B). Thus, an improving agent composition (1) was produced.
The evaluation results are shown in Table 1.

[Example 2]
As shown in Table 1, PEG1000 (Daiichi Kogyo Seiyaku Co., Ltd.) is used as the compound (A), and the cross-linked product 1 obtained in Production Example 4 is used as the compound (B). Thus, an improver composition (2) was produced.
The evaluation results are shown in Table 1.

Example 3
As shown in Table 1, PEG1000 (Daiichi Kogyo Seiyaku Co., Ltd.) is used as the compound (A), and the cross-linked product 1 obtained in Production Example 4 is used as the compound (B). Thus, an improver composition (3) was produced.
The evaluation results are shown in Table 1.

Example 4
As shown in Table 1, PEG1000 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is used as the compound (A), and the crosslinked product 2 obtained in Production Example 5 is used as the compound (B). Thus, an improving agent composition (4) was produced.
The evaluation results are shown in Table 1.

Example 5
As shown in Table 1, PEG400 (Daiichi Kogyo Seiyaku Co., Ltd.) is used as the compound (A), and the crosslinked product 3 obtained in Production Example 6 is used as the compound (B). Thus, an improving agent composition (5) was produced.
The evaluation results are shown in Table 1.

Example 6
As shown in Table 1, using M-50 obtained in Production Example 3 as the compound (A) and the cross-linked product 1 obtained in Production Example 4 as the compound (B), blended at a weight ratio shown in Table 1. Thus, an improving agent composition (6) was produced.
The evaluation results are shown in Table 1.

Example 7
As shown in Table 1, using M-25 obtained in Production Example 2 as the compound (A) and the cross-linked product 2 obtained in Production Example 5 as the compound (B), blended in the weight ratio shown in Table 1. Thus, an improving agent composition (7) was produced.
The evaluation results are shown in Table 1.

Example 8
As shown in Table 1, using M-10 obtained in Production Example 1 as the compound (A) and the cross-linked product 3 obtained in Production Example 6 as the compound (B), blended at a weight ratio shown in Table 1. Thus, an improving agent composition (8) was produced.
The evaluation results are shown in Table 1.

Example 9
As shown in Table 1, using M-10 obtained in Production Example 1 as the compound (A) and the cross-linked product 4 obtained in Production Example 7 as the compound (B), blended in the weight ratio shown in Table 1. Thus, an improving agent composition (9) was produced.
The evaluation results are shown in Table 1.

[Comparative Example 1]
As shown in Table 1, crack resistance evaluation was performed without using the improver composition of the present invention.
The evaluation results are shown in Table 1.

[Comparative Example 2]
As shown in Table 1, the compound (A) is not used, the cross-linked product 1 obtained in Production Example 4 is used as the compound (B), and blended at a weight ratio shown in Table 1 to improve the composition (C2 ) Was manufactured.
The evaluation results are shown in Table 1.

[Comparative Example 3]
As shown in Table 1, the compound (B) is not used, PEG1000 (Daiichi Kogyo Seiyaku Co., Ltd.) is used as the compound (A), and is blended in the weight ratio shown in Table 1 to improve the composition (C3 ) Was manufactured.
The evaluation results are shown in Table 1.

[Comparative Example 4]

Example 4
As shown in Table 1, PEG1000 (Daiichi Kogyo Seiyaku Co., Ltd.) was used as the compound (A), and the comparative crosslinked product 1 obtained in Comparative Production Example 1 was used as the compound (B). The improver composition (C4) was produced by blending.
The evaluation results are shown in Table 1.

  In Table 1, in Examples 1-9 using the improving agent composition of the present invention, the crack generation time exceeds 60 hours, and it can be seen that excellent crack resistance can be expressed. On the other hand, in Comparative Examples 1-4, the crack generation time is shorter than in the Examples, and it can be seen that it does not reach the improver composition of the present invention.

The hydraulic material improver composition of the present invention can be suitably used as a highly versatile hydraulic material improver composition for cement compositions such as mortar and concrete.

Claims (5)

Of compound (A) and of compound (B) and comprises a to a hydraulic material for modifier composition,
The compound _{(A), HO (CH 2 CH 2 O} ) m - (CH 2 CH 2) -O- (CH 2 CH 2 O) n -H (m is 10 to 150, n is 10 to 150) or CH ₃ O (CH ₂ CH ₂ O) _n H (n is 25 to 200),
The compound (B) is a crosslinked product having an unsaturated monomer as a monomer unit,
The unsaturated monomer contains at least one selected from anionic monomers and nonionic monomers,
The anionic monomer gas sulfonic acid (salt) -based a monomer,
The sulfonic acid (salt) monomer is vinyl sulfonate, (meth) allyl sulfonate, 2- (meth) acryloxyethyl sulfonate, 3- (meth) acryloxypropyl sulfonate, 3- (meth) acryloxy-2- Hydroxypropyl sulfonate, 3- (meth) acryloxy-2-hydroxypropylsulfophenyl ether, 3- (meth) acryloxy-2-hydroxypropyloxysulfobenzoate, 4- (meth) acryloxybutyl sulfonate, (meth) acrylamidomethylsulfone Selected from acids, (meth) acrylamide ethylsulfonic acid, 2-methylpropanesulfonic acid (meth) acrylamide, styrenesulfonic acid, and monovalent metal salts, divalent metal salts, ammonium salts, and organic ammonium salts thereof It is one even without,
The nonionic monomer is at least one selected from an N-vinyl lactam monomer and an amide monomer,
The N-vinyl lactam monomer is at least one selected from N-vinyl-2-pyrrolidone, N-vinyl caprolactam, and N-vinyl imidazoline;
The amide monomer is at least one selected from (meth) acrylamide, (meth) acrylalkylamide, N-methylol (meth) acrylamide, and N, N-dimethyl (meth) acrylamide .
An improving agent composition for hydraulic materials. The improvement agent composition for hydraulic materials according to claim 1, wherein the unsaturated monomer contains an unsaturated monocarboxylic acid monomer as another monomer. The compound (A) and said compound and (B), in a weight ratio, (A) / (B) = 60 / 40~99 in a proportion of / 1, hydraulic material according to claim 1 or 2 Improver composition.   The water absorption capacity after 24 hours with respect to an aqueous solution containing 0.6% by weight of calcium nitrate tetrahydrate and 0.089% by weight of potassium hydroxide of the compound (B) is 8 g / g or more. 4. The improving agent composition for hydraulic material according to any one of 3 to 3.   A cement composition comprising the improver composition for hydraulic material according to any one of claims 1 to 4 and cement.

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