JP6433291B2 - Processed aggregate and cement composition - Google Patents

Description

  The present invention relates to a treated aggregate and a cement composition.

  Cement compositions such as mortar and concrete generally include cement, aggregate, and water, and preferably further include a cement admixture to increase fluidity and reduce water.

  Recently, there has been an increasing demand for cement compositions to improve the strength performance of cured products in addition to the improvement of water reduction performance. For example, depending on the use of the cement composition, early strength development is desired, and various studies have been made (for example, Patent Document 1).

  On the other hand, depending on the use of the cement composition, it is required to improve the strength of the cured product of the cement composition over a long period of time (for example, a level of 4 weeks).

JP 2011-84459 A

  The subject of this invention is providing the process aggregate which can improve the intensity | strength of the hardened | cured material of a cement composition over a long period of time. Moreover, it is providing the cement composition containing such a process aggregate.

The treated aggregate of the present invention is
It can be obtained by adding a polymer for cement admixture to the aggregate and stirring it, followed by heat treatment.

（一般式（１）中、Ｒ^１は、炭素数１〜３０のアルキル基、炭素数１〜３０のアリール基、または炭素数１〜３０のアラルキル基を表し、Ｒ^２は、ハロゲン基、ヒドロキシ基、アミノ基、炭素数１〜３０のアルコキシ基、炭素数１〜３０のチオアルコキシ基、フェノキシ基、アシロキシ基、またはアミノキシ基を表し、ｍは０〜２の整数であり、Ｒ^１が２個以上の場合はそれらは全て同一でも良いし少なくとも１個が異なっていても良く、Ｒ^２が２個以上の場合はそれらは全て同一でも良いし少なくとも１個が異なっていても良い。） In a preferred embodiment, the cement admixture polymer has a silyl group represented by the general formula (1).

(In General Formula (1), R ¹ represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 1 to 30 carbon atoms, or an aralkyl group having 1 to 30 carbon atoms, and R ² represents a halogen group, hydroxy group A group, an amino group, an alkoxy group having 1 to 30 carbon atoms, a thioalkoxy group having 1 to 30 carbon atoms, a phenoxy group, an acyloxy group, or an aminoxy group, m is an integer of 0 to 2, and R ¹ is 2 When there are two or more, they may all be the same or at least one may be different, and when R ² is two or more, they may all be the same or at least one may be different.)

  The cement composition of the present invention includes the treated aggregate of the present invention.

  ADVANTAGE OF THE INVENTION According to this invention, the process aggregate which can improve the intensity | strength of the hardened | cured material of a cement composition over a long term can be provided. Moreover, the cement composition containing such a process aggregate can be provided.

  In the present specification, the expression “(meth) acryl” means “acryl and / or methacryl”, and the expression “(meth) acrylate” means “acrylate and / or methacrylate”. Means “allyl and / or methallyl”, and “(meth) acrolein” means “acrolein and / or methacrole”. It means "rain". Further, in the present specification, the expression “acid (salt)” means “acid and / or salt thereof”.

≪Processed aggregate≫
The treated aggregate of the present invention can be obtained by adding a polymer for cement admixture to the aggregate and stirring the mixture, followed by heat treatment. That is, in the present invention, a method for producing a treated aggregate or a method for treating an aggregate is performed by adding a cement admixture polymer to the aggregate and stirring the mixture.

  Any appropriate aggregate such as fine aggregate (sand, etc.) or coarse aggregate (crushed stone, etc.) can be adopted as the aggregate. Examples of such aggregates include gravel, crushed stone, granulated slag, and recycled aggregate. Examples of such aggregates include refractory aggregates such as siliceous, clay, zircon, high alumina, silicon carbide, graphite, chromic, chromic, and magnesia.

  The amount of the cement admixture polymer added to the aggregate is preferably 0.01 parts by weight to 2.0 parts by weight and more preferably 0.03 parts by weight to 1.5 parts by weight with respect to 100 parts by weight of the aggregate. Parts by weight, more preferably 0.04 parts by weight to 1.0 parts by weight, and particularly preferably 0.05 parts by weight to 0.5 parts by weight. By adjusting the amount of the cement admixture polymer added to the aggregate within the above range, a treated aggregate capable of further improving the strength of the cured product of the cement composition over a long period of time can be provided.

  When the cement admixture polymer is added to the aggregate, water may coexist. For example, an aqueous solution of a polymer for cement admixture may be added to the aggregate. Any appropriate amount of water can be adopted as long as the effects of the present invention are not impaired.

  The agitation conditions when the cement admixture polymer is added to the aggregate and the agitation is such that the cement admixture polymer can be uniformly dispersed on the surface of the aggregate will not impair the effects of the present invention. Any suitable condition can be employed in the range. The stirring time is preferably 1 minute to 60 minutes, more preferably 3 minutes to 45 minutes, still more preferably 4 minutes to 30 minutes, and particularly preferably 5 minutes to 15 minutes. The stirring speed is preferably 10 rpm to 400 rpm, more preferably 30 rpm to 300 rpm, still more preferably 50 rpm to 200 rpm, and particularly preferably 70 rpm to 150 rpm. As a stirring apparatus, arbitrary appropriate mortar mixers etc. are mentioned, for example.

  The heat treatment is performed after the cement admixture polymer is added to the aggregate and stirred.

  As temperature of heat processing, Preferably it is 50 to 400 degreeC, More preferably, it is 70 to 300 degreeC, More preferably, it is 90 to 200 degreeC, Most preferably, it is 110 to 180 degreeC. By adjusting the temperature of the heat treatment within the above range, a treated aggregate that can further improve the strength of the cured product of the cement composition over a long period of time can be provided.

  The time for the heat treatment is preferably 1 minute to 200 minutes, more preferably 5 minutes to 170 minutes, still more preferably 15 minutes to 150 minutes, and particularly preferably 30 minutes to 130 minutes. By adjusting the heat treatment time within the above range, a treated aggregate that can further improve the strength of the cured product of the cement composition over a long period of time can be provided.

The polymer for cement admixture preferably has a silyl group represented by the general formula (1).

In General Formula (1), R ¹ represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 1 to 30 carbon atoms, or an aralkyl group having 1 to 30 carbon atoms.

In General Formula (1), R ² represents a halogen group, a hydroxy group, an amino group, an alkoxy group having 1 to 30 carbon atoms, a thioalkoxy group having 1 to 30 carbon atoms, a phenoxy group, an acyloxy group, or an aminoxy group. .

In general formula (1), R ² is preferably an alkoxy group having 1 to 30 carbon atoms, more preferably an alkoxy group having 1 to 10 carbon atoms, and further preferably having 1 to 4 carbon atoms. An alkoxy group, particularly preferably an alkoxy group having 1 carbon atom (methoxy group).

  In general formula (1), m is an integer of 0-2.

  In general formula (1), m is preferably 0 to 1, and more preferably 0.

In general formula (1), when two or more R ^{1 s} , they may all be the same or at least one may be different.

In general formula (1), when R ² is 2 or more, they may all be the same or at least one may be different.

Specifically, the silyl group represented by the general formula (1) is preferably —Si (OCH ₃ ) ₃ group, —Si (OC ₂ H ₅ ) ₃ group, —Si (OC ₃ H ₇ ). _{3 group, -Si (O-isoC 3 H} 7) 3 _{group, -Si (OC 4 H 9)} 3 _{group, -Si (O-isoC 4 H} 9) 3 _{group, -Si (O-secC 4 H} 9) ₃ groups, —Si (CH ₃ ) (OCH ₃ ) ₂ groups, —Si (CH ₃ ) (OC ₂ H ₅ ) ₂ groups, —Si (CH ₃ ) (OC ₃ H ₇ ) ₂ groups, —Si (CH ₃ ) (O-isoC ₃ H ₇ ) ₂ groups, -Si (CH ₃ ) (OC ₄ H ₉ ) ₂ groups, -Si (CH ₃ ) (O-isoC ₄ H ₉ ) ₂ groups, -Si (CH ₃ ) (O-secC ₄ H ₉ ) ₂ groups.

  One preferable example of the polymer for cement admixture is a homopolymer having a silyl group represented by the general formula (1). When the polymer for cement admixture has such a configuration, a treated aggregate that can further improve the strength of the cured product of the cement composition over a long period of time can be provided.

  One preferred example of the polymer for cement admixture is a homopolymer having a silyl group represented by the general formula (1), and preferably has a silyl group represented by the general formula (1) at the end of the side chain. It is a homopolymer, more preferably a homopolymer having an alkyl group having a silyl group at the terminal represented by the general formula (1) in the side chain, and particularly preferably a structure represented by the general formula (2) A homopolymer having the unit (II) as a repeating unit.

  In the general formula (2), the explanation of the general formula (1) is used as it is for the silyl group portion.

In General Formula (2), R ³ , R ⁴ , and R ⁵ represent a hydrogen atom or a methyl group.

In general formula (2), R ³ is preferably a hydrogen atom. In general formula (2), R ⁴ is preferably a hydrogen atom. In general formula (2), R ⁵ is preferably a methyl group.

  In general formula (2), X represents an alkylene group having 1 to 30 carbon atoms.

  In general formula (2), X is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and still more preferably an alkylene group having 1 to 6 carbon atoms. And particularly preferably an alkylene group having 1 to 4 carbon atoms.

In the structural unit (II) represented by the general formula (2), particularly preferably m = 0, R ² is OCH ₃ , R ³ is a hydrogen atom, R ⁴ is a hydrogen atom, R ⁵ is a methyl group, X Is —CH ₂ CH ₂ CH ₂ —. When the structural unit (II) represented by the general formula (2) has such a structure, a treated aggregate that can further improve the strength of the cured product of the cement composition over a long period of time can be provided.

  When the polymer for cement admixture is a homopolymer having a silyl group represented by the general formula (1), the mass average molecular weight (Mw) of the polymer for cement admixture is preferably 1000 to 100,000. Preferably it is 2000-50000, More preferably, it is 3000-40000, Most preferably, it is 5000-30000. By adjusting the mass average molecular weight (Mw) of the polymer for cement admixture within the above range, a treated aggregate that can further improve the strength of the cured product of the cement composition over a long period of time can be provided.

  When the polymer for cement admixture is a homopolymer having a silyl group represented by the general formula (1), the molecular weight distribution (Mw / Mn) of the polymer for cement admixture is preferably 1.0 to 5. It is 0, More preferably, it is 1.2-4.5, More preferably, it is 1.4-4.0, Most preferably, it is 1.6-3.5. By adjusting the molecular weight distribution (Mw / Mn) of the polymer for cement admixture within the above range, a treated aggregate that can further improve the strength of the cured product of the cement composition over a long period of time can be provided.

  When the polymer for cement admixture is a homopolymer having a silyl group represented by the general formula (1), the polymer for cement admixture can be obtained by any appropriate method as long as the effects of the present invention are not impaired. Can be manufactured. When the polymer for cement admixture is a homopolymer having a silyl group represented by the general formula (1), the polymer for cement admixture preferably has a silyl group represented by the general formula (1) Monomer polymerization of monomers can be carried out in the presence of a polymerization initiator.

  The monomer having a silyl group represented by the general formula (1) is preferably represented by the general formula (3).

  In the general formula (3), the explanation of the general formula (1) is used as it is for the silyl group portion.

In General Formula (3), R ³ , R ⁴ , and R ⁵ represent a hydrogen atom or a methyl group.

In general formula (3), R ³ is preferably a hydrogen atom. In general formula (3), R ⁴ is preferably a hydrogen atom. In general formula (2), R ⁵ is preferably a methyl group.

  In general formula (3), X represents an alkylene group having 1 to 30 carbon atoms.

  In general formula (3), X is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and still more preferably an alkylene group having 1 to 6 carbon atoms. And particularly preferably an alkylene group having 1 to 4 carbon atoms.

In the monomer represented by the general formula (3), it is particularly preferable that m = 0, R ² is OCH ₃ , R ³ is a hydrogen atom, R ⁴ is a hydrogen atom, R ⁵ is a methyl group, and X is − CH ₂ CH ₂ CH ₂ - is. When the monomer represented by the general formula (3) has such a structure, a treated aggregate that can further improve the strength of the cured product of the cement composition over a long period of time can be provided.

  The monomer having a silyl group represented by the general formula (1) can be synthesized by any appropriate method. Moreover, a commercial item may be used for the monomer which has a silyl group represented by General formula (1).

  Another preferred example of the polymer for cement admixture is a copolymer containing the structural unit (I) derived from the silyl group-containing oil-soluble monomer (a) and the structural unit (II) derived from the acid group-containing monomer (b). It is a coalescence. When the polymer for cement admixture has such a configuration, a treated aggregate that can further improve the strength of the cured product of the cement composition over a long period of time can be provided.

  As the silyl group-containing oil-soluble monomer (a), any appropriate monomer can be adopted as long as it has a silyl group and exhibits oil solubility, as long as the effects of the present invention are not impaired.

  In addition, as a monomer which shows oil solubility, the monomer which does not have a carboxyl group (-COOH) or its salt (-COOM) (M is a metal atom, an ammonium group, or an organic ammonium group) is mentioned, for example.

  In the silyl group-containing oil-soluble monomer (a), the silyl group is preferably represented by the general formula (1).

  Examples of the silyl group-containing oil-soluble monomer (a) include silyl group-containing vinyl monomers listed in paragraph 0011 of JP-A-8-91900.

  Only one type of silyl group-containing oil-soluble monomer (a) may be used, or two or more types may be used.

  The silyl group-containing oil-soluble monomer (a) is preferably represented by the general formula (3).

In the monomer represented by the general formula (3), it is particularly preferable that m = 0, R ² is OCH ₃ , R ³ is a hydrogen atom, R ⁴ is a hydrogen atom, R ⁵ is a methyl group, and X is − CH ₂ CH ₂ CH ₂ - is. When the monomer represented by the general formula (2) has such a structure, a treated aggregate that can further improve the strength of the cured product of the cement composition over a long period of time can be provided.

  Examples of the structural unit (I) derived from the silyl group-containing oil-soluble monomer (a) include structural units derived from a silyl group-containing vinyl monomer listed in paragraph 0011 of JP-A-8-91900. It is done. Among these structural units, the structural unit (I) is preferably a structural unit represented by the general formula (2).

  As the acid group-containing monomer (b), any appropriate monomer can be adopted as long as it is a monomer having an acid group as long as the effects of the present invention are not impaired. The acid group may be in the form of a salt.

The acid group-containing monomer (b) is preferably represented by the general formula (4).

In General Formula (4), R ^{6 to} R ⁸ are the same or different and each represents a hydrogen atom, a methyl group, or a — (CH ₂ ) _z COOM group. The — (CH ₂ ) _z COOM group may form an anhydride with the —COOX group or other — (CH ₂ ) _z COOM groups. z is an integer of 0-2.

  M represents a hydrogen atom, a monovalent metal atom, a divalent metal atom, an ammonium group, or an organic ammonium group.

  X represents a hydrogen atom, a monovalent metal atom, a divalent metal atom, an ammonium group, or an organic ammonium group.

  Examples of the acid group-containing monomer (b) represented by the general formula (4) include monocarboxylic acid monomers such as (meth) acrylic acid and crotonic acid or salts thereof; maleic acid, itaconic acid, fumaric acid Dicarboxylic acid monomers such as acids or salts thereof; anhydrides of dicarboxylic acid monomers such as maleic acid, itaconic acid, fumaric acid or salts thereof; and the like. Examples of the salt herein include alkali metal salts, alkaline earth metal salts, ammonium salts, organic ammonium salts, and organic amine salts. Examples of the alkali metal salt include lithium salt, sodium salt, potassium salt and the like. Examples of alkaline earth metal salts include calcium salts and magnesium salts. Examples of the organic ammonium salt include methyl ammonium salt, ethyl ammonium salt, dimethyl ammonium salt, diethyl ammonium salt, trimethyl ammonium salt, and triethyl ammonium salt. Examples of organic amine salts include alkanolamine salts such as ethanolamine salts, diethanolamine salts, and triethanolamine salts.

  The acid group-containing monomer (b) represented by the general formula (4) is preferably (meth) acrylic acid, maleic acid, maleic anhydride, in that the effects of the present invention can be further exhibited. Acrylic acid and methacrylic acid are preferred.

  The unsaturated carboxylic acid monomer (b) represented by the general formula (4) may be one kind or two or more kinds.

  The structural unit (II) derived from the acid group-containing monomer (b) is preferably a structural unit represented by the general formula (5).

In General Formula (5), R ^{6 to} R ⁸ are the same or different and each represents a hydrogen atom, a methyl group, or a — (CH ₂ ) _z COOM group. The — (CH ₂ ) _z COOM group may form an anhydride with the —COOX group or other — (CH ₂ ) _z COOM groups. z is an integer of 0-2.

  M represents a hydrogen atom, a monovalent metal atom, a divalent metal atom, an ammonium group, or an organic ammonium group.

  X represents a hydrogen atom, a monovalent metal atom, a divalent metal atom, an ammonium group, or an organic ammonium group.

  The cement when the polymer for cement admixture is a copolymer containing the structural unit (I) derived from the silyl group-containing oil-soluble monomer (a) and the structural unit (II) derived from the acid group-containing monomer (b). The total content of the structural unit (I) and the structural unit (II) in the admixture polymer is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, More preferably, it is 80 mass%-100 mass%, More preferably, it is 90 mass%-100 mass%, Most preferably, it is 95 mass%-100 mass%, Most preferably, it is 98 mass%-100 mass% is there. The cement when the polymer for cement admixture is a copolymer containing the structural unit (I) derived from the silyl group-containing oil-soluble monomer (a) and the structural unit (II) derived from the acid group-containing monomer (b). By adjusting the total content ratio of the structural unit (I) and the structural unit (II) in the admixture polymer within the above range, a treated aggregate that can further improve the strength of the cured product of the cement composition over a long period of time. Can be provided.

  The cement when the polymer for cement admixture is a copolymer containing the structural unit (I) derived from the silyl group-containing oil-soluble monomer (a) and the structural unit (II) derived from the acid group-containing monomer (b). The total content of the structural unit (I) and the structural unit (II) in the admixture polymer can be known, for example, by various structural analyzes (for example, NMR) of the polymer. In addition, without performing the above various structural analyses, the cement admixture polymer is a structural unit derived from the silyl group-containing oil-soluble monomer (a) (I) and the structural unit derived from the acid group-containing monomer (b) ( II) and a content ratio of the structural unit derived from the various monomers calculated based on the amount of the various monomers used when producing the cement admixture polymer. The total content of the structural unit (I) and the structural unit (II) in the cement admixture polymer may be calculated. That is, when the polymer for cement admixture is a copolymer containing the structural unit (I) derived from the silyl group-containing oil-soluble monomer (a) and the structural unit (II) derived from the acid group-containing monomer (b), The total mass content of the silyl group-containing oil-soluble monomer (a) and the acid group-containing monomer (b) in all the monomer components used in producing the cement admixture polymer is expressed as follows. In the polymer for cement admixture, the copolymer containing the structural unit (I) derived from the silyl group-containing oil-soluble monomer (a) and the structural unit (II) derived from the acid group-containing monomer (b). The total content of the structural unit (I) and the structural unit (II) may be handled.

  The cement when the polymer for cement admixture is a copolymer containing the structural unit (I) derived from the silyl group-containing oil-soluble monomer (a) and the structural unit (II) derived from the acid group-containing monomer (b). The content ratio of the structural unit (I) in the admixture polymer is preferably 5% by mass to 95% by mass, more preferably 10% by mass to 90% by mass, and further preferably 15% by mass to 85%. % By mass, more preferably 20% by mass to 80% by mass, and particularly preferably 25% by mass to 75% by mass. The cement when the polymer for cement admixture is a copolymer containing the structural unit (I) derived from the silyl group-containing oil-soluble monomer (a) and the structural unit (II) derived from the acid group-containing monomer (b). By adjusting the total content of the structural units (I) in the admixture polymer within the above range, it is possible to provide a treated aggregate that can further improve the strength of the cured product of the cement composition over a long period of time. .

  The cement when the polymer for cement admixture is a copolymer containing the structural unit (I) derived from the silyl group-containing oil-soluble monomer (a) and the structural unit (II) derived from the acid group-containing monomer (b). The content ratio of the structural unit (II) in the admixture polymer is preferably 5% by mass to 95% by mass, more preferably 10% by mass to 90% by mass, and further preferably 15% by mass to 85%. % By mass, more preferably 20% by mass to 80% by mass, and particularly preferably 25% by mass to 75% by mass. The cement when the polymer for cement admixture is a copolymer containing the structural unit (I) derived from the silyl group-containing oil-soluble monomer (a) and the structural unit (II) derived from the acid group-containing monomer (b). By adjusting the total content of the structural units (II) in the admixture polymer within the above range, it is possible to provide a treated aggregate that can further improve the strength of the cured product of the cement composition over a long period of time. .

  The cement when the polymer for cement admixture is a copolymer containing the structural unit (I) derived from the silyl group-containing oil-soluble monomer (a) and the structural unit (II) derived from the acid group-containing monomer (b). The content ratio of the structural unit (I) or the structural unit (II) in the admixture polymer can be known, for example, by various structural analyzes (for example, NMR) of the polymer. In addition, without performing the above various structural analyses, the cement admixture polymer is a structural unit derived from the silyl group-containing oil-soluble monomer (a) (I) and the structural unit derived from the acid group-containing monomer (b) ( II) and a content ratio of the structural unit derived from the various monomers calculated based on the amount of the various monomers used when producing the cement admixture polymer. The content ratio of the structural unit (I) or the structural unit (II) in the cement admixture polymer may be calculated. That is, when the polymer for cement admixture is a copolymer containing the structural unit (I) derived from the silyl group-containing oil-soluble monomer (a) and the structural unit (II) derived from the acid group-containing monomer (b), The content ratio of the mass of the silyl group-containing oil-soluble monomer (a) in all the monomer components used for producing the cement admixture polymer is expressed as the structural unit (I) in the polymer for cement admixture of the present invention. The content ratio of the mass of the acid group-containing monomer (b) may be treated as the content ratio of the structural unit (II) in the cement admixture polymer.

  The cement when the polymer for cement admixture is a copolymer containing the structural unit (I) derived from the silyl group-containing oil-soluble monomer (a) and the structural unit (II) derived from the acid group-containing monomer (b). In addition to the structural unit (I) and the structural unit (II), the admixture polymer may contain a structural unit (III) derived from another monomer (c). The structural unit (III) derived from the other monomer (c) may be only one kind or two or more kinds.

  The other monomer (c) is a monomer copolymerizable with the silyl group-containing oil-soluble monomer (a) and the acid group-containing monomer (b).

  Examples of the other monomer (c) include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; non-polymers such as methyl (meth) acrylate and glycidyl (meth) acrylate. Esters of saturated monocarboxylic acids and alcohols having 1 to 30 carbon atoms; (anhydrous) half esters of unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid and alcohols having 1 to 30 carbon atoms; (Anhydrous) Diesters of unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid and alcohols having 1 to 30 carbon atoms; half amides of the above unsaturated dicarboxylic acids and amines having 1 to 30 carbon atoms A diamide of the above unsaturated dicarboxylic acid and an amine having 1 to 30 carbon atoms; Half esters of an alkyl (poly) alkylene glycol obtained by adding 1 to 500 moles of an alkylene oxide having 2 to 18 carbon atoms to coal or amine and the unsaturated dicarboxylic acid; 2 to 18 carbon atoms added to the alcohol or amine Diesters of alkyl (poly) alkylene glycols having 1 to 500 moles of alkylene oxide added thereto and the above unsaturated dicarboxylic acids; the above unsaturated dicarboxylic acids and glycols having 2 to 18 carbon atoms or the number of moles of these glycols added Half-esters with 2-500 polyalkylene glycols; diesters of unsaturated dicarboxylic acids with 2-18 carbon atoms or polyalkylene glycols with 2 to 500 addition moles of these glycols; 2-18 carbon atoms Chole or half amides of these glycols with polyalkylene glycols having an addition mole number of 2 to 500; (poly) alkylene glycols such as (poly) ethylene glycol di (meth) acrylate and (poly) propylene glycol di (meth) acrylate Di (meth) acrylates; polyfunctional (meth) acrylates such as hexanediol di (meth) acrylate and trimethylolpropane tri (meth) acrylate; (poly) alkylene glycol dimaleates such as polyethylene glycol dimaleate; vinyl sulfonate Unsaturated sulfonic acids (salts) such as (meth) allyl sulfonate and styrene sulfonic acid; Amides of unsaturated monocarboxylic acids such as methyl (meth) acrylamide and amines having 1 to 30 carbon atoms; Styrene, α -Methyl Vinyl aromatics such as tylene and vinyltoluene; alkanediol mono (meth) acrylates such as 1,4-butanediol mono (meth) acrylate; dienes such as butadiene and isoprene; (meth) acrylic (alkyl) amide; Unsaturated amides such as N-methylol (meth) acrylamide and N, N-dimethyl (meth) acrylamide; unsaturated cyanates such as (meth) acrylonitrile; unsaturated esters such as vinyl acetate; amino (meth) acrylate Unsaturated amines such as ethyl, dimethylaminoethyl (meth) acrylate and vinylpyridine; divinyl aromatics such as divinylbenzene; allyls such as (meth) allyl alcohol and glycidyl (meth) allyl ether; (methoxy) polyethylene Vinyl ether such as glycol monovinyl ether Kind; and the like. Examples of the salt herein include alkali metal salts, alkaline earth metal salts, ammonium salts, organic ammonium salts, and organic amine salts. Examples of the alkali metal salt include lithium salt, sodium salt, potassium salt and the like. Examples of alkaline earth metal salts include calcium salts and magnesium salts. Examples of the organic ammonium salt include methyl ammonium salt, ethyl ammonium salt, dimethyl ammonium salt, diethyl ammonium salt, trimethyl ammonium salt, and triethyl ammonium salt. Examples of organic amine salts include alkanolamine salts such as ethanolamine salts, diethanolamine salts, and triethanolamine salts.

  The cement when the polymer for cement admixture is a copolymer containing the structural unit (I) derived from the silyl group-containing oil-soluble monomer (a) and the structural unit (II) derived from the acid group-containing monomer (b). The content ratio of the structural unit (III) in the admixture polymer can be known by, for example, various structural analyzes (for example, NMR) of the polymer. In addition, without performing the above various structural analyses, the cement admixture polymer is a structural unit derived from the silyl group-containing oil-soluble monomer (a) (I) and the structural unit derived from the acid group-containing monomer (b) ( II) and a content ratio of the structural unit derived from the various monomers calculated based on the amount of the various monomers used when producing the cement admixture polymer. The content ratio of the structural unit (III) in the cement admixture polymer may be calculated. That is, when the polymer for cement admixture is a copolymer containing the structural unit (I) derived from the silyl group-containing oil-soluble monomer (a) and the structural unit (II) derived from the acid group-containing monomer (b), The content ratio of the mass of the other monomer (c) in the total monomer component used when the polymer for cement admixture is produced is the content ratio of the structural unit (III) in the polymer for cement admixture. Can be treated as.

  The cement when the polymer for cement admixture is a copolymer containing the structural unit (I) derived from the silyl group-containing oil-soluble monomer (a) and the structural unit (II) derived from the acid group-containing monomer (b). The mass average molecular weight (Mw) of the polymer for admixture is preferably 1000 to 100,000, more preferably 2000 to 50000, further preferably 3000 to 40000, and particularly preferably 5000 to 30000. The cement when the polymer for cement admixture is a copolymer containing the structural unit (I) derived from the silyl group-containing oil-soluble monomer (a) and the structural unit (II) derived from the acid group-containing monomer (b). By adjusting the mass average molecular weight (Mw) of the polymer for admixture within the above range, a treated aggregate capable of further improving the strength of the cured product of the cement composition over a long period of time can be provided.

  The cement when the polymer for cement admixture is a copolymer containing the structural unit (I) derived from the silyl group-containing oil-soluble monomer (a) and the structural unit (II) derived from the acid group-containing monomer (b). The molecular weight distribution (Mw / Mn) of the admixture polymer is preferably 1.0 to 5.0, more preferably 1.2 to 4.5, and still more preferably 1.4 to 4.0. Yes, particularly preferably 1.6 to 3.5. The cement when the polymer for cement admixture is a copolymer containing the structural unit (I) derived from the silyl group-containing oil-soluble monomer (a) and the structural unit (II) derived from the acid group-containing monomer (b). By adjusting the molecular weight distribution (Mw / Mn) of the polymer for admixture within the above range, a treated aggregate that can further improve the strength of the cured product of the cement composition over a long period of time can be provided.

  The cement when the polymer for cement admixture is a copolymer containing the structural unit (I) derived from the silyl group-containing oil-soluble monomer (a) and the structural unit (II) derived from the acid group-containing monomer (b). The admixture polymer can be produced by any appropriate method as long as the effects of the present invention are not impaired. The cement when the polymer for cement admixture is a copolymer containing the structural unit (I) derived from the silyl group-containing oil-soluble monomer (a) and the structural unit (II) derived from the acid group-containing monomer (b). The admixture polymer can be preferably produced by polymerizing (copolymerizing) the monomer component containing the silyl group-containing oil-soluble monomer (a) and the acid group-containing monomer (b) in the presence of a polymerization initiator.

  The silyl group-containing oil-soluble monomer (a) can be synthesized by any appropriate method. Moreover, you may use a commercial item for a silyl group containing oil-soluble monomer (a).

  The polymerization to obtain the cement admixture polymer can be performed by any suitable method. Examples thereof include solution polymerization and bulk polymerization. Examples of the solution polymerization method include a batch method and a continuous method. Solvents that can be used for solution polymerization include water; alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, and n-hexane; esters such as ethyl acetate. Compounds; ketone compounds such as acetone and methyl ethyl ketone; cyclic ether compounds such as tetrahydrofuran and dioxane; and the like.

  When performing polymerization to obtain a polymer for cement admixture, a water-soluble polymerization initiator, for example, a persulfate such as ammonium persulfate, sodium persulfate, potassium persulfate; hydrogen peroxide; 2 2,2′-azobis (N- (2-carboxyethyl) -2-methylpropionamidine) hydrate, 2,2′-azobis-2-methylpropionamidine hydrochloride, etc., 2,2′-azobis Water-soluble azo initiators such as cyclic azoamidine compounds such as 2- (2-imidazolin-2-yl) propane hydrochloride, and azonitrile compounds such as 2-carbamoylazoisobutyronitrile may be used. These polymerization initiators include alkali metal sulfites such as sodium hydrogen sulfite, metabisulfites, sodium hypophosphite, Fe (II) salts such as molle salts, sodium hydroxymethanesulfinate dihydrate, hydroxylamine hydrochloride Accelerators such as salt, thiourea, L-ascorbic acid (salt), and erythorbic acid (salt) can also be used in combination. Among these combined forms, a combination of an ammonium persulfate and an accelerator such as L-ascorbic acid (salt) is preferable. Each of these polymerization initiators and accelerators may be only one kind or two or more kinds.

  When performing solution polymerization using a lower alcohol, aromatic hydrocarbon, aliphatic hydrocarbon, ester compound, or ketone compound as a solvent, or when performing bulk polymerization, benzoyl peroxide, lauroyl peroxide may be used as a polymerization initiator. Peroxides such as oxide and sodium peroxide; hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide; azo compounds such as azobisisobutyronitrile; When such a polymerization initiator is used, an accelerator such as an amine compound can be used in combination. Furthermore, when a water-lower alcohol mixed solvent is used, it can be appropriately selected from the above-mentioned various polymerization initiators or combinations of polymerization initiators and accelerators.

  The reaction temperature in the polymerization for obtaining the cement admixture polymer is appropriately determined depending on the polymerization method, solvent, polymerization initiator, and chain transfer agent used. The reaction temperature is preferably 0 ° C. or higher, more preferably 30 ° C. or higher, further preferably 50 ° C. or higher, preferably 150 ° C. or lower, more preferably 120 ° C. or lower. More preferably, it is 100 ° C. or lower.

  Any appropriate method can be adopted as a method for charging the monomer into the reaction vessel. As such a charging method, for example, a method in which the entire amount is initially charged into the reaction vessel, a method in which the entire amount is divided or continuously charged into the reaction vessel, a part is initially charged in the reaction vessel, and the rest is put in the reaction vessel. The method of dividing | segmenting or carrying out continuously etc. is mentioned. Further, the charging rate of the monomer per unit time may be changed continuously or stepwise by changing the charging rate of the monomer into the reaction vessel continuously or stepwise during the reaction. The polymerization initiator may be charged into the reaction vessel from the beginning, may be dropped into the reaction vessel, or these may be combined according to the purpose.

  A chain transfer agent may be used in the polymerization for obtaining a cement admixture polymer. Only one type of chain transfer agent may be used, or two or more types may be used.

  Any appropriate chain transfer agent can be adopted as the chain transfer agent. Examples of such chain transfer agents include thiol chain transfer agents such as mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, and 2-mercaptoethanesulfonic acid; Secondary alcohols such as isopropanol; phosphorous acid, hypophosphorous acid, and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionite, metabisulfite, And lower salts of salts thereof (sodium sulfite, potassium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium dithionite, potassium dithionite, sodium metabisulfite, potassium metabisulfite, etc.) and salts thereof, etc. Is mentioned.

  The produced polymer can be subjected to concentration adjustment as necessary with respect to the solution obtained by the production.

  The produced polymer may be used as it is in the form of a solution, or may be used after being powdered by supporting it on an inorganic powder such as silica-based fine powder and drying it.

≪Cement composition≫
The cement composition of the present invention includes the treated aggregate of the present invention.

  In addition to the treated aggregate of the present invention, the cement composition of the present invention preferably contains cement and water, and more preferably contains cement, water and a cement admixture.

  The cement admixture preferably contains a polymer for cement admixture, more preferably for the cement admixture used to obtain the treated aggregate of the present invention, in that the effect of the present invention can be expressed more effectively. Contains polymer.

  The cement admixture may contain any appropriate other component in addition to the cement admixture polymer as long as the effects of the present invention are not impaired.

  Examples of other components include a cement dispersant. When cement dispersant is used, the blending ratio of polymer for cement admixture and cement dispersant (cement admixture polymer / cement dispersant) is different in the type of cement dispersant used, blending conditions, test conditions, etc. Can set any appropriate blending ratio. Only one cement dispersant may be used, or two or more cement dispersants may be used.

  Examples of the cement dispersant include a sulfonic acid-based dispersant having a sulfonic acid group in the molecule, and a polycarboxylic acid-based dispersant other than the polycarboxylic acid-based copolymer contained in the cement dispersant composition of the present invention. Can be mentioned.

  Examples of the sulfonic acid-based dispersant include polyalkylaryl sulfonate-based sulfonic acid-based dispersants such as naphthalene sulfonic acid formaldehyde condensate, methyl naphthalene sulfonic acid formaldehyde condensate, anthracene sulfonic acid formaldehyde condensate; melamine sulfonic acid Melamine formalin sulfonate-based sulfonic acid dispersants such as formaldehyde condensates; Aromatic amino sulfonate-based sulfonic acid dispersants such as aminoaryl sulfonic acid-phenol-formaldehyde condensates; lignin sulfonates, Examples thereof include lignin sulfonate sulfonic acid dispersants such as modified lignin sulfonate; polystyrene sulfonate sulfonic acid dispersants;

  The cement admixture can contain any appropriate other cement additive (material) as long as the effects of the present invention are not impaired. Examples of such other cement additives (materials) include other cement additives (materials) exemplified in the following (1) to (12). The mixing ratio of the polymer for cement admixture that can be included in the cement admixture and such other cement additives (materials) is arbitrarily appropriate depending on the type and purpose of the other cement additives (materials) to be used. Various mixing ratios can be employed.

(1) Water-soluble polymer substances: nonionic cellulose ethers such as methylcellulose, ethylcellulose, carboxymethylcellulose; polysaccharides produced by microbial fermentation such as yeast glucan, xanthan gum, β-1.3 glucans; polyethylene glycol, etc. Polyoxyalkylene glycols; polyacrylamide and the like.

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

(3) Curing retarder: oxycarboxylic acid or salt thereof such as gluconic acid, glucoheptonic acid, alabonic acid, malic acid, citric acid; sugar and sugar alcohol; polyhydric alcohol such as glycerin; aminotri (methylenephosphonic acid) 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) Oxyalkylene-based antifoaming agent: polyoxyalkylenes such as (poly) oxyethylene (poly) oxypropylene adducts; polyoxyalkylene alkyl ethers such as diethylene glycol heptyl ether; polyoxyalkylene acetylene ethers; ) Oxyalkylene fatty acid esters; polyoxyalkylene sorbitan fatty acid esters; polyoxyalkylene alkyl (aryl) ether sulfate salts; polyoxyalkylene alkyl phosphate esters; polyoxypropylene polyoxyethylene laurylamine (propylene oxide 1-20) Mole additions, ethylene oxide 1-20 mol adducts, etc.), fatty acid-derived amines obtained from cured beef tallow added with alkylene oxide (propylene oxide 1-20 mol) Additionally, polyoxyalkylene alkyl amines ethylene oxide 20 mol adduct) or the like; polyoxyalkylene amide.

(6) Antifoaming agents other than oxyalkylene type: Mineral oil type, fat type, fatty acid type, fatty acid ester type, alcohol type, amide type, phosphate ester type, metal soap type, silicone type and the like.

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

(8) Other surfactants: various anionic surfactants; various cationic surfactants such as alkyltrimethylammonium chloride; various nonionic surfactants; various amphoteric surfactants.

(9) Waterproofing agent: fatty acid (salt), fatty acid ester, fats and oils, silicon, paraffin, asphalt, wax and the like.

(10) Rust inhibitor: nitrite, phosphate, zinc oxide and the like.

(11) Crack reducing agent: polyoxyalkyl ether and the like.

(12) Expansion material: Ettlingite, coal, etc.

  Other known cement additives (materials) include cement wetting agents, thickeners, separation reducing agents, flocculants, drying shrinkage reducing agents, strength enhancers, self-leveling agents, rust preventives, colorants, and antifungal agents. An agent etc. can be mentioned. These known cement additives (materials) may be one kind or two or more kinds.

  Arbitrary appropriate cement can be employ | adopted as a cement contained in the cement composition of this invention. Examples of such cements include Portland cement (ordinary, early strength, ultra-early strength, moderate heat, sulfate resistance and low alkali types thereof), various mixed cements (blast furnace cement, silica cement, fly ash cement), White Portland Cement, Alumina Cement, Super Fast Cement (1 Clinker Fast Cement, 2 Clinker Fast Cement, Magnesium Phosphate Cement), Grout Cement, Oil Well Cement, Low Exothermic Cement (Low Exothermic Blast Furnace Cement, Low Fly Ash Mixing) Exothermic blast furnace cement, belite high-content cement), ultra-high strength cement, cement-based solidified material, eco-cement (cement produced from one or more of municipal waste incineration ash and sewage sludge incineration ash). Furthermore, fine powders and gypsum such as blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica powder, and limestone powder may be added to the cement composition of the present invention. The cement contained in the cement composition of the present invention may be only one type or two or more types.

  In the cement composition of the present invention, any appropriate other materials such as fine aggregate (sand, etc.) and coarse aggregate (crushed stone, etc.) can be used in addition to the treated aggregate of the present invention within a range not impairing the effects of the present invention. The aggregate may be included.

  Examples of such aggregates include gravel, crushed stone, granulated slag, and recycled aggregate. Examples of such aggregates include refractory aggregates such as siliceous, clay, zircon, high alumina, silicon carbide, graphite, chromic, chromic, and magnesia.

In the cement composition of the present invention, any appropriate value can be set as the unit water amount per 1 m ³ , the amount of cement used, and the water / cement ratio. Such values, preferably, unit water is ^{100kg / m 3 ~185kg / m 3} , the amount of cement used is ^{250kg / m 3 ~800kg / m 3} , water / cement ratio (mass ratio) = is 0.1 to 0.7, more preferably, a unit water amount is ^{120kg / m 3 ~175kg / m 3} , the amount of cement used is ^{270kg / m 3 ~800kg / m 3} , water / cement ratio ( (Mass ratio) = 0.12 to 0.65. As described above, the cement composition of the present invention can be widely used from poor blending to rich blending, and can be used for both high-strength concrete with a large amount of unit cement and poor blended concrete with a unit cement amount of 300 kg / m ³ or less. It is valid.

  When the cement composition of the present invention contains a polymer for cement admixture, any appropriate content ratio may be adopted as the content of the polymer for cement admixture in the cement composition of the present invention depending on the purpose. obtain. As such a content ratio, when used for mortar or concrete using hydraulic cement, the content ratio of the polymer for cement admixture with respect to 100 parts by mass of cement is preferably 0.01 parts by mass to 10 parts by mass. More preferably, it is 0.02 mass part-5 mass parts, More preferably, it is 0.05 mass part-3 mass parts. By setting it as such a content rate, various favorable effects, such as reduction of unit water amount, an increase in intensity | strength, and an improvement in durability, are brought about. When the content ratio is less than 0.01 parts by mass, sufficient performance may not be exhibited. When the content ratio exceeds 10 parts by mass, the effect that can be achieved substantially reaches its peak and also from the economical aspect. May be disadvantageous.

  As a content ratio of the cement admixture in the cement composition of the present invention, any appropriate content ratio can be adopted depending on the purpose. As such a content ratio, the content ratio of the cement admixture with respect to 100 parts by mass of cement is preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.05 parts by mass to 8 parts by mass, More preferably, it is 0.1 mass part-5 mass parts. When the content ratio is less than 0.01 parts by mass, sufficient performance may not be exhibited. When the content ratio exceeds 10 parts by mass, the effect that can be achieved substantially reaches its peak and also from the economical aspect. May be disadvantageous.

  The cement composition of the present invention can be effective for ready-mixed concrete, concrete for concrete secondary products, concrete for centrifugal molding, concrete for vibration compaction, steam-cured concrete, shotcrete, and the like. The cement composition of the present invention includes medium-fluidity concrete (concrete with a slump value of 22 to 25 cm), high-fluidity concrete (concrete with a slump value of 25 cm or more and a slump flow value of 50 to 70 cm), self-filling concrete, self It can also be effective for mortar and concrete that require high fluidity, such as leveling materials.

  The cement composition of the present invention may be prepared by blending the constituent components by any appropriate method. For example, the method etc. which knead | mix a structural component in a mixer are mentioned.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. Unless otherwise specified, the term “part” means mass part, and the term “%” means mass%.

<Measurement of compressive strength>
A kneader for mechanical kneading, a spoon, a flow table, a flow cone, and a stick according to JIS-R5201-1997 were used. At this time, unless otherwise specified, a mortar test was performed in accordance with JIS-R5201-1997.
The sand used for the test was adjusted as follows.
(Sand used in Examples): A polymer solution for cement admixture and ion-exchanged water were mixed and stirred for 5 minutes, and this solution was added to 1350 g of standard sand for cement strength test in accordance with JIS-R5201-1997. Using a Hobart mortar mixer (model number N-50, manufactured by Hobart), the mixture was stirred for 10 minutes to uniformly disperse the cement admixture polymer on the sand surface. Then, the sand which the polymer for cement admixture couple | bonded with the surface was adjusted by heat-processing for 90 minutes at 150 degreeC.
(Sand used in comparative example): Standard sand for cement strength test according to JIS-R5201-1997 was used.
The material and mortar used in the test consisted of 587 g of ordinary portland cement manufactured by Taiheiyo Cement, 264.1 g of ion-exchanged water containing an aqueous solution of a polymer for cement admixture and an antifoaming agent prepared by the method described above, It is. The antifoaming agent was added for the purpose of avoiding the influence of air bubbles on the dispersibility of the mortar composition so that the air amount was 3.0% or less. Specifically, the oxyalkylene-based antifoaming agent was used in an amount so as to be 0.1% with respect to the cement admixture copolymer. When the amount of air in the mortar is larger than 3.0%, the amount of the antifoaming agent is adjusted so that the amount of air becomes 3.0% or less.
The mortar was prepared at room temperature (20 ± 2 ° C.) using a Hobart mortar mixer (model number N-50, manufactured by Hobart) for 4 minutes and 30 seconds. Specifically, a prescribed amount of cement is put in a kneading bowl, attached to a kneader and started at a low speed. 15 seconds after starting the paddle, a specified amount of cement admixture polymer and water containing antifoam is added for 15 seconds. Then, sand is added and mixed at a low speed for 30 seconds, then at a high speed and continuously mixed for 30 seconds. Remove the kneader from the kneader and stop kneading for 120 seconds, then attach the kneader again to the kneader and knead for 60 seconds at high speed (4 minutes 30 minutes after starting at the first low speed) After 10 seconds, stir 10 times each with a spoon. The kneaded mortar is divided into two layers and packed in a flow cone placed on a flow table. Each layer is struck 15 times over the entire surface so that the tip of the stab stick is about half the depth of the layer, and finally, the shortage is compensated, the surface is smoothed, and the start is started at a low speed first. 6 minutes later, after the flow cone was lifted vertically, the diameter of the mortar spread on the table was measured in two directions, and this average value was taken as the flow value.
After kneading, the flow value and the amount of air were measured to prepare a sample for compressive strength test, and the compressive strength after 28 days was measured under the following conditions.
Specimen creation: 50mm x 100mm
Specimen curing (28 days): Temperature 20 ° C., humidity 60%, constant temperature and humidity air curing for 24 hours, then curing the specimen in water for 27 days: Specimen surface polishing (use of specimen polishing finish machine)
Compressive strength measurement: Automatic compressive strength meter (Maekawa Seisakusho)

[Example 1]
A glass reactor equipped with a thermometer, stirrer, dropping device, nitrogen inlet tube, and reflux condenser was charged with 55.0 parts of methanol, and the reactor was purged with nitrogen under stirring. After raising the temperature, a solution (A) consisting of 72.8 parts of 3-methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) and 35.0 parts of methanol was added dropwise over 4.0 hours. At the same time as the dropwise addition of (A), the azo initiator 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamide] hydrate (VA-057, manufactured by Wako Pure Chemical Industries, Ltd.) 2.8952 And a solution (B) consisting of 37.105 parts of methanol was added dropwise over 5.0 hours. Thereafter, the temperature was maintained at 58 ° C. for 1 hour, followed by cooling to complete the polymerization and obtain a solution containing the cement admixture polymer (1). The weight average molecular weight of the cement admixture polymer (1) was 20000, and the molecular weight distribution (Mw / Mn) was 2.0.
10.26 parts of polymer (1) for cement admixture adjusted to a 10% by mass methanol solution and 1.026 parts of ion-exchanged water were mixed and stirred for 5 minutes. This solution was added to 1350 parts of standard sand for cement strength test according to JIS-R5201-1997, and stirred for 10 minutes using a Hobart type mortar mixer (model No. N-50, manufactured by Hobart). Polymer (1) for use was uniformly dispersed on the sand surface. Then, the sand (1) which the polymer (1) for cement admixtures couple | bonded with the surface was adjusted by heat-processing at 150 degreeC for 90 minute (s).
Evaluation was performed using the obtained sand (1). The results are shown in Table 1.

[Comparative Example 1]
Evaluation was performed in the same manner as in Example 1 by using standard sand for cement strength test according to JIS-R5201-1997 instead of sand (1). The results are shown in Table 1.

[Example 2]
A glass reactor equipped with a thermometer, a stirrer, a dropping device, a nitrogen inlet tube, and a reflux cooling device was charged with 96.25 parts of methanol, and the reactor was purged with nitrogen under stirring, and the temperature was raised to 58 ° C. under a nitrogen atmosphere. After raising the temperature, 99.145 parts of methoxypolyethylene glycol monomethacrylate (NK ester, M-90G, manufactured by Shin-Nakamura Chemical Co., Ltd.), 11.651 parts of methacrylic acid (MAA) and 3-methacryloxypropyltrimethoxysilane ( KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.) 11.526 parts, 0.178 parts of mercaptopropionic acid (MPA) and 61.25 parts of methanol (A) was added dropwise over 4.0 hours, and (A) At the same time as the azo initiator 2,2'-azobis [N- (2-carboxyethyl) -2-methylprop ionamidine] hydrate (VA-057, manufactured by Wako Pure Chemical Industries, Ltd.) and a solution (B) consisting of 3.9176 parts of methanol and 66.082 parts of methanol were added dropwise over 5.0 hours. Thereafter, the temperature was maintained at 58 ° C. for 1 hour, followed by cooling to complete the polymerization, and a solution containing the cement admixture polymer (2) was obtained. The weight average molecular weight of the cement admixture polymer (2) was 20000, and the molecular weight distribution (Mw / Mn) was 2.0.
10.26 parts of cement admixture polymer (2) adjusted to a 10% by mass methanol solution and 1.026 parts of ion-exchanged water were mixed and stirred for 5 minutes. This solution was added to 1350 parts of standard sand for cement strength test according to JIS-R5201-1997, and stirred for 10 minutes using a Hobart type mortar mixer (model No. N-50, manufactured by Hobart). Polymer (2) for use was uniformly dispersed on the sand surface. Then, the sand (2) which the polymer (2) for cement admixtures couple | bonded with the surface was adjusted by heat-processing at 150 degreeC for 90 minute (s).
The results are shown in Tables 2 and 4.

[Comparative Example 2]
Evaluation was performed in the same manner as in Example 2 by using standard sand for cement strength test in accordance with JIS-R5201-1997 instead of sand (2). The results are shown in Table 2.

Example 3
A solution containing the cement admixture polymer (3) was obtained in the same manner as in Example 2 except that the raw material composition shown in Table 2 was used. The polymer for cement admixture (3) had a weight average molecular weight of 20,000 and a molecular weight distribution (Mw / Mn) of 2.0.
10.26 parts of polymer (3) for cement admixture adjusted to a 10% by mass methanol solution and 1.026 parts of ion-exchanged water were mixed and stirred for 5 minutes. This solution was added to 1350 parts of standard sand for cement strength test according to JIS-R5201-1997, and stirred for 10 minutes using a Hobart type mortar mixer (model No. N-50, manufactured by Hobart). Polymer (3) for use was uniformly dispersed on the sand surface. Then, the sand (3) which the polymer (3) for cement admixtures couple | bonded with the surface was adjusted by heat-processing at 150 degreeC for 90 minute (s).
The results are shown in Tables 3 and 4.

[Comparative Example 3]
Evaluation was performed in the same manner as in Example 3 by using standard sand for cement strength test in accordance with JIS-R5201-1997 instead of sand (3). The results are shown in Table 3.

  The treated aggregate of the present invention is suitably used for cement compositions such as cement paste, mortar, and concrete.

Claims (3)

A method for producing a treated aggregate, comprising adding a polymer for cement admixture to the aggregate and stirring the mixture ,
The cement admixture polymer has a structural unit (II) represented by the general formula (2).
Manufacturing method of processed aggregate.

(In General Formula (2), R ¹ represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 1 to 30 carbon atoms, or an aralkyl group having 1 to 30 carbon atoms, and R ² represents a halogen group, hydroxy group A group, an amino group, an alkoxy group having 1 to 30 carbon atoms, a thioalkoxy group having 1 to 30 carbon atoms, a phenoxy group, an acyloxy group, or an aminoxy group, m is an integer of 0 to 2, and R ¹ is 2 When there are two or more, they may all be the same or at least one may be different, and when R ² is two or more, they may all be the same or at least one may be different, R ³ , R ⁴ and R ^{5 each} represents a hydrogen atom or a methyl group, and X represents an alkylene group having 1 to 30 carbon atoms.) A method for treating an aggregate, comprising adding a polymer for a cement admixture to the aggregate and stirring the mixture, followed by heat treatment,
The cement admixture polymer has a structural unit (II) represented by the general formula (2).
Aggregate processing method .

(In General Formula (2), R ¹ represents an alkyl group having 1 to 30 carbon atoms, an aryl group having 1 to 30 carbon atoms, or an aralkyl group having 1 to 30 carbon atoms, and R ² represents a halogen group, hydroxy group A group, an amino group, an alkoxy group having 1 to 30 carbon atoms, a thioalkoxy group having 1 to 30 carbon atoms, a phenoxy group, an acyloxy group, or an aminoxy group, m is an integer of 0 to 2, and R ¹ is 2 When there are two or more, they may all be the same or at least one may be different, and when R ² is two or more, they may all be the same or at least one may be different, R ³ , R ⁴ and R ^{5 each} represents a hydrogen atom or a methyl group, and X represents an alkylene group having 1 to 30 carbon atoms.) The resulting treated aggregate in the production method according to claim 1, formulated cement, water, a manufacturing method of the cement composition.