JP2016138013A - Dispersant for hydraulic composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dispersant for hydraulic composition reducing unit water content for enhancing workability and durability of concrete, suppressing propagation of organism during storage for suppressing reduction of workability, suppressing reduction of various properties such as slump retention property and entrainment air amount stability and excellent in dispersibility.SOLUTION: There is provided a dispersant for hydraulic composition containing (A) component: a copolymer containing at least two or more kinds of structure units selected from a constitutional unit derived from a monomer represented by the formula (1) (I) and a constitutional unit derived from two monomers of (meth)acrylester (II) and an unsaturated compound having carboxylic acid ester at a terminal and (B) component:an antiseptic and/or an antifungal agent.SELECTED DRAWING: None

Description

  The present invention relates to a dispersant for a hydraulic composition.

  In order to improve the workability and durability of concrete, it is effective to reduce the amount of unit water in the concrete. However, it is known that when the unit water amount is reduced, the fluidity of concrete is lowered and the workability is impaired. Therefore, in order to ensure efficient workability of the concrete even when the unit water amount is reduced, various dispersants having a function of dispersing cement particles are used.

  Examples of the dispersant for the hydraulic composition include a copolymer having a specific unsaturated polyalkylene glycol monomer and a specific unsaturated carboxylic acid monomer, such as polyethylene glycol monoallyl ether and (meth). Copolymers of acrylic acid monomers (Patent Document 1), copolymers containing polyalkylene glycol mono (meth) acrylate monomers (Patent Document 2), and ethylenic unsaturation having an oxyalkylene group Examples thereof include a copolymer having a unit derived from a monomer and a unit derived from an ethylenically unsaturated mono- or dicarboxylic acid ester monomer (Patent Document 3). As a cement admixture using a plurality of dispersants for hydraulic compositions, for example, Patent Document 4 discloses an unsaturated (poly) alkylene glycol ether monomer and an unsaturated monocarboxylic acid monomer, respectively. And a polymer having a specific amount of each of the structural units derived from the above, and a polymer having an oxyalkylene group or a polyoxyalkylene group and a carboxyl group.

  Examples of the storage method of the raw material for the dispersant for the hydraulic composition include a method of storing the alkoxypolyalkylene glycol in a container substituted with an inert gas or added with a radical scavenger (Patent Document 5), poly A method of storing an alkylene glycol monomer as an aqueous solution (Patent Documents 6 and 7), A method of storing a polymer material for cement additive containing alkoxy (poly) alkylene glycol in a container at a temperature below the freezing point (Patent) Reference 8) can be mentioned. Patent Documents 5 to 8 also illustrate methods for producing a copolymer of a specific unsaturated polyalkylene glycol monomer and a specific unsaturated carboxylic acid monomer respectively stored by these methods. It is described that various performances of the dispersant can be improved by suppressing the generation of impurities such as gels produced in the raw material.

JP 56-81320 A JP 58-74552 A JP-A-10-81549 International Publication No. 2002/096823 JP 2000-154049 A JP 2002-173593 A JP 2006-117946 A JP 2002-234762 A

  Although Patent Documents 5 to 8 describe a raw material storage method, they do not describe a storage method after production of the dispersant for a hydraulic composition. When the dispersant for hydraulic compositions is stored, organisms such as molds and fungi grow and cause various performances of the dispersant for hydraulic compositions (for example, slump retention, entrained air volume stability). Such a problem is remarkable when the dispersant contains moisture.

  In view of the above, the present invention aims to solve the above-mentioned problems, and to provide a dispersant for a hydraulic composition that suppresses the propagation of living organisms during storage, suppresses various performance degradations, and has excellent dispersibility. .

（式中、Ｒ¹、Ｒ²およびＲ³は、それぞれ独立に、水素原子または炭素原子数１〜３のアルキル基を表す。ｐは、０〜２の整数を表し、ｑは０〜１の整数を表す。Ａ¹Ｏは、同一若しくは異なって、炭素原子数２〜１８のオキシアルキレン基を表す。ｎは、１〜３００の整数を表す。Ｒ⁴は、水素原子または炭素原子数１〜３０の炭化水素基を表す。）

（式中、Ｒ⁵、Ｒ⁶、およびＲ⁷は、それぞれ独立に、水素原子、−ＣＨ₃または−（ＣＨ₂）_rＣＯＯＭ²を表し、−ＣＨ₃または−（ＣＨ₂）_rＣＯＯＭ²は互いに他の−ＣＯＯＭ¹または−（ＣＨ₂）_rＣＯＯＭ²と無水物を形成していてもよい。無水物を形成している場合、それらの基のＭ¹、Ｍ²は存在しない。Ｍ¹およびＭ²は同一若しくは異なって、水素原子、アルカリ金属、アルカリ土類金属、アンモニウム基、アルキルアンモニウム基または置換アルキルアンモニウム基を表す。ｒは０〜２の整数を表す。）

（式中、Ｒ⁸、Ｒ⁹およびＲ¹⁰は、それぞれ独立に、水素原子または炭素原子数１〜３のアルキル基を表す。Ｒ¹¹は炭素原子数１〜４のヘテロ原子を含んでよい炭化水素基を表す。ｓは、０〜２の整数を表す）
（Ｂ）成分：防腐および／または防カビ剤
〔２〕（Ｂ）成分が、少なくともチアゾリン系化合物を含有する、〔１〕に記載の分散剤。
〔３〕（Ｂ）成分を（Ａ）成分の重量に対して５０ｐｐｍ〜５０００ｐｐｍ含有する、〔１〕又は〔２〕に記載の分散剤。
〔４〕水硬性組成物用分散剤が、（Ｓ）成分：スルホン酸系分散剤および／または（Ｇ）成分：遅延剤をさらに含有する、〔１〕〜〔３〕のいずれか一項に記載の分散剤。 That is, the present invention includes the following [1] to [4].
[1] A dispersant for a hydraulic composition containing the following components (A) and (B).
Component (A): a structural unit (I) derived from a monomer represented by the following general formula (1), a structural unit (II) derived from a monomer represented by the following general formula (2), and Copolymer containing at least two or more structural units selected from the group consisting of structural units (III) derived from monomers represented by the following general formula (3)

(Wherein R ¹ , R ² and R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, p represents an integer of 0 to 2, and q represents 0 to 1) A ¹ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms, n is an integer of 1 to 300, R ⁴ is a hydrogen atom or 1 to 1 carbon atoms. Represents 30 hydrocarbon groups.)

(Wherein R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom, —CH ₃ or — (CH ₂ ) _r COOM ² , —CH ₃ or — (CH ₂ ) _r COOM ² is together other -COOM ¹ or _{-. (CH 2) r COOM} 2 and may form an anhydride when forming the anhydride, M ¹ of those groups, M ² is absent .M ¹ And M ² are the same or different and each represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkylammonium group or a substituted alkylammonium group, and r represents an integer of 0 to 2.)

(In the formula, R ⁸ , R ⁹ and R ¹⁰ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ¹¹ is a carbon atom which may contain a hetero atom having 1 to 4 carbon atoms. Represents a hydrogen group, and s represents an integer of 0 to 2.
Component (B): Antiseptic and / or antifungal agent [2] The dispersant according to [1], wherein the component (B) contains at least a thiazoline compound.
[3] The dispersant according to [1] or [2], wherein the component (B) is contained in an amount of 50 ppm to 5000 ppm based on the weight of the component (A).
[4] The dispersant for a hydraulic composition further contains (S) component: sulfonic acid-based dispersant and / or (G) component: retarder, according to any one of [1] to [3] The dispersant described.

  The dispersant for a hydraulic composition according to the present invention is less likely to accumulate organisms such as molds and fungi even after storage, and is also prevented from being decomposed and contaminated, thereby suppressing reduction in various performances as a dispersant for a hydraulic composition. ing.

  Embodiments of the present invention will be described below. These embodiments are examples of preferred embodiments of the present invention, and the present invention is not limited to these embodiments.

  The dispersant for a hydraulic composition of the present invention contains a component (A) and a component (B).

<(A) component>
(A) A component is a copolymer (A). The copolymer (A) is composed of a structural unit (I) derived from a monomer represented by the following general formula (1), a structural unit derived from a monomer represented by the following general formula (2) (II ), And a copolymer containing at least two or more structural units selected from the group consisting of the structural unit (III) derived from the monomer represented by the following general formula (3).

(Structural unit (I))
The structural unit (I) is a structural unit derived from the monomer represented by the general formula (1).

R ¹ , R ² and R ³ in the general formula (1) each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. R ³ is preferably a hydrogen atom. The alkyl group having 1 to 3 carbon atoms may have a substituent (however, the number of carbon atoms of the substituent is not included in the number of carbon atoms of the alkyl group). R ¹ is preferably a hydrogen atom. R ² is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.

  P in general formula (1) represents the integer of 0-2.

  Q in General formula (1) represents the integer of 0-1.

A ¹ O in the general formula (1) is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. Examples of the oxyalkylene group (alkylene glycol unit) include an oxyethylene group (ethylene glycol unit), an oxypropylene group (propylene glycol unit), and an oxybutylene group (butylene glycol unit). Groups are preferred.

The above “same or different” means that when A ¹ O is contained in the general formula (1) (when n is 2 or more), each A ¹ O may be the same oxyalkylene group. It means that they may be different (two or more) oxyalkylene groups. As a mode when in the general formula ⁽¹⁾ A 1 O is contained more, include aspects oxyethylene groups, two or more oxyalkylene groups selected from the group consisting of oxypropylene groups and oxybutylene groups coexist The oxyethylene group and the oxypropylene group are mixed, or the oxyethylene group and the oxybutylene group are preferably mixed, and the oxyethylene group and the oxypropylene group are more mixed. preferable. In an embodiment in which different oxyalkylene groups are mixed, the addition of two or more oxyalkylene groups may be a block addition or a random addition.

  N in General formula (1) is the average addition mole number of an oxyalkylene group, and represents the integer of 1-300. n is preferably 1 to 100, more preferably 5 to 100, still more preferably 5 to 50, and even more preferably 7 to 45. The average number of moles added means the average value of the number of moles of oxyalkylene groups added to 1 mole of monomer.

R ⁴ in the general formula (1) represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. R ⁴ is preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and preferably a hydrogen or methyl group. Most preferred. If it is this range, since a carbon atom number does not become large too much, the dispersibility of the dispersing agent for hydraulic compositions is exhibited favorably.

  As a manufacturing method of the monomer represented by the general formula (1), for example, 1 to 80 alkylene oxides are added to unsaturated alcohols such as allyl alcohol, methallyl alcohol, and 3-methyl-3-buten-1-ol. The method of adding in moles is mentioned. Monomers that can be produced by this method include (poly) ethylene glycol allyl ether, (poly) ethylene glycol methallyl ether, (poly) ethylene glycol 3-methyl-3-butenyl ether, (poly) ethylene (poly) Propylene glycol allyl ether, (poly) ethylene (poly) propylene glycol methallyl ether, (poly) ethylene (poly) propylene glycol 3-methyl-3-butenyl ether, (poly) ethylene (poly) butylene glycol allyl ether, (poly ) Ethylene (poly) butylene glycol methallyl ether, (poly) ethylene (poly) butylene glycol 3-methyl-3-butenyl ether, methoxy (poly) ethylene glycol allyl ether, methoxy (poly) ethylene glycol meta Ether, methoxy (poly) ethylene glycol 3-methyl-3-butenyl ether, methoxy (poly) ethylene (poly) propylene glycol allyl ether, methoxy (poly) ethylene (poly) propylene glycol methallyl ether, methoxy (poly) ethylene ( Poly) propylene glycol 3-methyl-3-butenyl ether, methoxy (poly) ethylene (poly) butylene glycol allyl ether, methoxy (poly) ethylene (poly) butylene glycol methallyl ether, methoxy (poly) ethylene (poly) butylene glycol An example is 3-methyl-3-butenyl ether. Among these, from the balance of hydrophilicity and hydrophobicity, (poly) ethylene glycol (meth) allyl ether, (poly) ethylene glycol (poly) propylene glycol (meth) allyl ether, (poly) ethylene (poly) propylene glycol (Meth) allyl ether, (poly) ethylene glycol 3-methyl-3-butenyl ether, and (poly) ethylene (poly) propylene glycol 3-methyl-3-butenyl ether are preferred.

  In the present specification, “(poly)” means a case where a plurality of constituent elements or raw materials described subsequently are bonded and / or a case where only one is present. Reference to “(meth) allyl” means methallyl and / or allyl, reference to “(meth) acrylate” means methacrylate and / or acrylate, and reference to “(meth) acrylic acid” means methacrylic acid and / or Or it means acrylic acid.

  Another method for producing the monomer represented by the general formula (1) is (meth) acrylate (hereinafter, “(meth) acrylate” means “acrylate or methacrylate”). Saturated monocarboxylic acid, (poly) ethylene glycol, (poly) ethylene (poly) propylene glycol, (poly) ethylene (poly) butylene glycol, methoxy (poly) ethylene glycol, methoxy (poly) ethylene (poly) propylene glycol, The method of esterifying (poly) alkylene glycol, such as methoxy (poly) ethylene (poly) butylene glycol, is mentioned. Monomers that can be produced by this method include (poly) ethylene glycol (meth) acrylate, (poly) ethylene (poly) propylene glycol (meth) acrylate, (poly) ethylene (poly) butylene glycol (meth) acrylate, (Poly) alkylene glycols (meta) such as methoxy (poly) ethylene glycol (meth) acrylate, methoxy (poly) ethylene (poly) propylene glycol (meth) acrylate, methoxy (poly) ethylene (poly) butylene glycol (meth) acrylate, etc. ) Acrylate is exemplified. Among these, (poly) alkylene glycol (meth) acrylate and methoxy (poly) ethylene glycol (meth) acrylate are preferable, and methoxy (poly) ethylene glycol (meth) acrylate is more preferable.

  The copolymer (A) may contain one type of structural unit (I), or may contain two or more types of structural units (I) derived from different monomers.

(Structural unit (II))
The structural unit (II) is a structural unit derived from the monomer represented by the general formula (2).

R ⁵ , R ⁶ and R ⁷ in the general formula (2) each independently represent a hydrogen atom, —CH ₃ or — (CH ₂ ) _r COOM ² , and —CH ₃ or (CH ₂ ) _r COOM ² May form an anhydride with other —COOM ¹ or — (CH ₂ ) _r COOM ² with each other, and when forming an anhydride, M ¹ and M ² of those groups are not present. R ⁵ is preferably a hydrogen atom. R ⁶ is preferably a hydrogen atom, a methyl group, or (CH ₂ ) _r COOM ² . R ⁷ is preferably a hydrogen atom.

In general formula (2), M ¹ and M ² are the same or different and are a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkylammonium group, or a substituted alkylammonium group. M ¹ and M ² are each preferably a hydrogen atom, an alkali metal, or an alkaline earth metal.

  In general formula (2), r represents an integer of 0-2. r is preferably 0 or 1, and more preferably 0.

  Examples of the monomer represented by the general formula (2) include unsaturated monocarboxylic acid monomers and unsaturated dicarboxylic acid monomers. Examples of the unsaturated monocarboxylic acid monomer include acrylic acid, methacrylic acid, crotonic acid, and the like, and monovalent metal salts, ammonium salts, and organic amine salts thereof. Examples of the unsaturated dicarboxylic acid include maleic acid, itaconic acid, citraconic acid, fumaric acid and the like, and monovalent metal salts, ammonium salts and organic amine salts thereof, and anhydrides thereof. As the monomer (II), acrylic acid, methacrylic acid, and maleic acid are preferable.

  The copolymer (A) may contain one type of structural unit (II), or may contain two or more types of structural units (II) derived from different monomers.

(Structural unit (III))
The structural unit (III) is a structural unit derived from the monomer represented by the general formula (3).

In General Formula (3), R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms are the same as those in R ¹ , R ² and R ³ . R ⁸ is preferably a hydrogen atom. R ⁹ is preferably a hydrogen atom. R ⁴ is preferably a hydrogen atom.

In the general formula (3), R ¹¹ represents a hydrocarbon group that may contain a hetero atom having 1 to 4 carbon atoms. The number of carbon atoms is preferably 1 to 3, more preferably 2 to 3, and still more preferably 3. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a phosphorus atom, and a silicon atom, and an oxygen atom is preferable. Examples of the hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a 2-hydroxyethyl group, and a 2-hydroxypropyl group. Groups, 4-hydroxybutyl groups, and glyceryl groups. The number of hetero atoms contained in R ¹¹ may be one or two or more. When two or more heteroatoms are included, each heteroatom may be the same or different from each other.

R ¹¹ is preferably a hydrocarbon group having 1 to 4 carbon atoms containing a hetero atom, and more preferably a hydrocarbon group having 1 to 4 carbon atoms containing an oxygen atom. Examples of the group include a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 4-hydroxybutyl group, and a glyceryl group, and among these, a 2-hydroxypropyl group is preferable.

  In general formula (3), s represents the integer of 0-2. s is preferably 0.

  As a monomer represented by General formula (3), the monoester body of unsaturated monocarboxylic acid is mentioned, for example. Examples of unsaturated monocarboxylic acid monoesters include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate. And glyceryl (meth) acrylate. Of these, 2-hydroxypropyl (meth) acrylate is preferred.

  The copolymer (A) may contain one type of structural unit (III), or may contain two or more types of structural units (III) derived from different monomers.

(Structural unit (IV))
The copolymer (A) may contain a structural unit (IV) separately from the structural units (I) to (III). The structural unit (IV) is a structural unit derived from a monomer copolymerizable with the monomers represented by the general formulas (1) to (3). The monomers copolymerizable with the monomers represented by the general formulas (1) to (3) are structurally distinguished from the monomers represented by the general formulas (1) to (3). Although the monomer which comprises structural unit (IV) is not specifically limited, For example, the following each monomer can be mentioned, It is possible to use 1 type, or 2 or more types of these.

で示されるジアリルビスフェノール類、例えば４，４’−ジヒドロキシジフェニルプロパン、４，４’−ジヒドロキシジフェニルメタン、４，４’−ジヒドロキシジフェニルスルホンの３および３’位アリル置換物； Formula (IV-1):

Diallyl bisphenols, such as 4,4′-dihydroxydiphenylpropane, 4,4′-dihydroxydiphenylmethane, and 3 and 3 ′ allyl substitutes of 4,4′-dihydroxydiphenylsulfone;

で示されるモノアリルビスフェノール類、例えば４，４’−ジヒドロキシジフェニルプロパン、４，４’−ジヒドロキシジフェニルメタン、４，４’−ジヒドロキシジフェニルスルホンの３位アリル置換物； General formula (IV-2):

Monoallyl bisphenols represented by the formula: for example, 4,4'-dihydroxydiphenylpropane, 4,4'-dihydroxydiphenylmethane, 3-position allyl substitute of 4,4'-dihydroxydiphenylsulfone;

で示されるアリルフェノール； General formula (IV-3):

An allylphenol;

Half esters and diesters of unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid and alcohols having 1 to 30 carbon atoms;
Half amides and diamides of the above unsaturated dicarboxylic acids and amines having 1 to 30 carbon atoms;

  Half esters and diesters of an alkyl (poly) alkylene glycol obtained by adding 1 to 500 moles of an alkylene oxide having 2 to 18 carbon atoms to the alcohol or amine and the unsaturated dicarboxylic acid;

  Half esters and diesters of the above unsaturated dicarboxylic acids and glycols having 2 to 18 carbon atoms or polyalkylene glycols having 2 to 500 addition moles of these glycols;

  Half amides of maleamic acid and glycols having 2 to 18 carbon atoms or polyalkylene glycols having 2 to 500 addition moles of these glycols;

  Esters of an alkoxy (poly) alkylene glycol obtained by adding 1 to 500 moles of an alkylene oxide having 2 to 18 carbon atoms to an alcohol having 1 to 30 carbon atoms and an unsaturated monocarboxylic acid such as (meth) acrylic acid;

  Of alkylene oxides having 2 to 18 carbon atoms to unsaturated monocarboxylic acids such as (meth) acrylic acid, such as (poly) ethylene glycol monomethacrylate, (poly) propylene glycol monomethacrylate, (poly) butylene glycol monomethacrylate 1-500 mol adducts (however, the monomers represented by the general formulas (1) to (3) are excluded);

  (Poly) alkylene glycols such as triethylene glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, (poly) ethylene glycol (poly) propylene glycol di (meth) acrylate, etc. Di (meth) acrylates;

  Polyfunctional (meth) acrylates such as hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate;

  (Poly) alkylene glycol dimaleates such as triethylene glycol dimaleate and polyethylene glycol dimaleate;

  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) acryloxybutylsulfonate, (meth) acrylamidomethylsulfonic acid, (meth) acrylamidoethylsulfonic acid, 2- Unsaturated sulfonic acids such as methylpropanesulfonic acid (meth) acrylamide and styrenesulfonic acid, and monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts thereof;

  Amides of unsaturated monocarboxylic acids such as methyl (meth) acrylamide and amines having 1 to 30 carbon atoms;

  Vinyl aromatics such as styrene, α-methylstyrene, vinyltoluene, p-methylstyrene;

  Alkanediol mono (meth) acrylates such as 1,5-pentanediol mono (meth) acrylate and 1,6-hexanediol mono (meth) acrylate (excluding the monomer represented by the general formula (3)) .);

  Dienes such as butadiene, isoprene, 2-methyl-1,3-butadiene, 2-chloro-1,3-butadiene;

  Unsaturated amides such as (meth) acrylamide, (meth) acrylic alkylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide;

  Unsaturated cyanides such as (meth) acrylonitrile, α-chloroacrylonitrile;

  Unsaturated esters such as vinyl acetate and vinyl propionate;

  Unsaturation such as aminoethyl (meth) acrylate, methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, vinylpyridine, etc. Amines (excluding the monomer represented by the general formula (3));

  Divinyl aromatics such as divinylbenzene; cyanurates such as triallyl cyanurate;

  Allyls such as (meth) allyl alcohol and glycidyl (meth) allyl ether;

  Vinyl ethers or allyl ethers such as methoxypolyethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, methoxypolyethylene glycol mono (meth) allyl ether, polyethylene glycol mono (meth) allyl ether, etc. (however, those represented by the general formula (1)) Excluding the mass.); And

  Polydimethylsiloxanepropylaminomaleamic acid, polydimethylsiloxaneaminopropylaminomaleamic acid, polydimethylsiloxane-bis- (propylaminomaleamic acid), polydimethylsiloxane-bis- (dipropylaminomaleamic acid), polydimethyl Siloxane- (1-propyl-3-acrylate), polydimethylsiloxane- (1-propyl-3-methacrylate), polydimethylsiloxane-bis- (1-propyl-3-acrylate), polydimethylsiloxane-bis- (1 Siloxane derivatives such as -propyl-3-methacrylate (excluding the monomer represented by the general formula (3)).

  The copolymer (A) may contain one type of structural unit (IV), or may contain two or more types of structural units (IV) derived from different monomers.

(Copolymers A-1 to A-4)
Below, the example of the copolymer which A component can contain is shown. In the following copolymers A-1 to A-4, each of the structural units (I) to (IV) may be one kind, or at least one structural unit may be a combination of two or more kinds. Good.

(Copolymer A-1)
Copolymer A-1 has a structural unit (I) and a structural unit (II). The content ratio of each structural unit is preferably structural unit (I) / structural unit (II) = 1 mol% to 99 mol% / 1 mol% to 99 mol%, more preferably 10 mol% to 90 mol%. It is mol% / 10 mol%-90 mol%, More preferably, it is 20 mol%-80 mol% / 20 mol%-80 mol%.

(Copolymer A-2)
Copolymer A-2 has a structural unit (I) and a structural unit (III). The content ratio of each structural unit is preferably structural unit (I) / structural unit (III) = 1 mol% to 99 mol% / 1 mol% to 99 mol%, more preferably 10 mol% to 90 mol. The mol% / 10 mol% to 99 mol%, and more preferably 10 mol% to 80 mol% / 20 mol% to 99 mol%.

(Copolymer A-3)
Copolymer A-3 has a structural unit (II) and a structural unit (III). The content ratio of each structural unit is preferably structural unit (II) / structural unit (III) = 1 mol% to 99 mol% / 1 mol% to 99 mol%, more preferably 1 mol% to 90 mol%. It is mol% / 10 mol% -99 mol%, More preferably, it is 1 mol% -80 mol% / 20 mol% -99 mol%.

(Copolymer A-4)
Copolymer A-4 has a structural unit (I), a structural unit (II), and a structural unit (III). The content ratio of each structural unit is preferably structural unit (I) / structural unit (II) / structural unit (III) = 1 mol% to 99 mol% / 1 mol% to 99 mol% / 1 mol% to 99. Mol%, more preferably 10 mol% to 90 mol% / 1 mol% to 90 mol% / 10 mol% to 90 mol%, still more preferably 15 mol% to 90 mol% / 1 mol%. -80 mol% / 20 mol%-90 mol%.

(Optimum combination of copolymers A-1 to A-4)
One of the copolymers A-1 to A-4 may be used as the A component, or two or more may be used as the A component, but it is preferable to use two or more types in combination as the A component. . The two preferred combinations and the content ratio thereof are, for example, as follows: Copolymer A-1 / Copolymer A-2 = 1 to 99 wt% / 1 to 99 wt%, more preferably 10 to 90 % By weight / 10-90% by weight, more preferably 20-80% by weight / 20-80% by weight; Copolymer A-1 / Copolymer A-3 = 1-99% by weight / 1-99% by weight, More preferably, it is 1-99 weight% / 1-90 weight%, More preferably, it is 1-99 weight% / 1-80 weight%; Copolymer A-1 / Copolymer A-4 = 1-99 weight% / 1 to 99% by weight, more preferably 10 to 90% by weight / 10 to 90% by weight, still more preferably 20 to 80% by weight / 20 to 80% by weight. The three preferred combinations and their content ratios are, for example, as follows: Copolymer A-1 / Copolymer A-2 / Copolymer A-3 = 1 to 99 wt% / 1 to 99 wt% / 1 to 99% by weight, more preferably 10 to 90% by weight / 10 to 90% by weight / 1 to 80% by weight, still more preferably 20 to 80% by weight / 20 to 80% by weight / 1 to 70% by weight; Polymer A-1 / Copolymer A-2 / Copolymer A-4 = 1-99 wt% / 1-99 wt% / 1-99 wt%, more preferably 10-90 wt% / 10-90 % By weight / 10-90% by weight, more preferably 20-80% by weight / 20-80% by weight / 20-80% by weight; Copolymer A-2 / Copolymer A-3 / Copolymer A-4 = 1 to 99 wt% / 1 to 99 wt% / 1 to 99 wt%, more preferably 10 to 90 wt% / 1 to 80 wt% % / 10-90 wt%, more preferably 20 to 80 wt% / 1 to 70 wt% / 20 to 80 wt%. The four preferred combinations and their content ratios are, for example, as follows: Copolymer A-1 / Copolymer A-2 / Copolymer A-3 / Copolymer A-4 = 1 to 99 wt. % / 1 to 99% by weight / 1 to 99% by weight / 1 to 99% by weight, more preferably 10 to 90% by weight / 10 to 90% by weight / 1 to 80% by weight / 10 to 90% by weight, still more preferably 20-80 wt% / 20-80 wt% / 1-70 wt% / 20-80 wt%.

<Method for producing copolymer>
The copolymer (A) can be produced by copolymerizing each predetermined monomer by a known method. Examples of the method include polymerization methods such as polymerization in a solvent and bulk polymerization.

(Reaction solvent)
Examples of the solvent used in the polymerization in the solvent include water; lower alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol; aromatic hydrocarbons such as benzene, toluene and xylene; fats such as cyclohexane and n-hexane. Group hydrocarbons; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone. From the viewpoint of solubility of the raw material monomer and the resulting copolymer, it is preferable to use one or more selected from the group consisting of water and lower alcohols, and among these, water is more preferable.

  When copolymerization is performed in a solvent, each monomer and a polymerization initiator may be continuously dropped into each reaction vessel, or a mixture of each monomer and a polymerization initiator are dropped continuously into each reaction vessel. Also good. Alternatively, a solvent may be charged into the reaction vessel, and a mixture of the monomer and the solvent and a polymerization initiator solution may be continuously dropped into the reaction vessel, or a part or all of the monomer may be charged into the reaction vessel and polymerized. The initiator may be continuously dropped.

(Initiator)
The polymerization initiator that can be used for copolymerization is not particularly limited. Examples of the polymerization initiator that can be used for copolymerization in an aqueous solvent include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; and water-solubility such as t-butyl hydroperoxide and hydrogen peroxide. A peroxide is mentioned. Under the present circumstances, you may use together accelerators, such as L-ascorbic acid, sodium hydrogensulfite, and a Mole salt. Examples of the polymerization initiator that can be used for the copolymerization in a solvent such as a lower alcohol, aromatic hydrocarbon, aliphatic hydrocarbon, ester or ketone include, for example, benzoyl peroxide and lauryl peroxide. Oxides; hydroperoxides such as cumene peroxide; aromatic azo compounds such as azobisisobutyronitrile. At this time, an accelerator such as an amine compound may be used in combination. What is necessary is just to select suitably the polymerization initiator which can be used when copolymerizing in a water-lower alcohol mixed solvent from the combination of the above-mentioned polymerization initiator or a polymerization initiator, and an accelerator. The polymerization temperature varies depending on the polymerization conditions such as the solvent used and the type of polymerization initiator, but is usually 50 to 120 ° C.

(Chain transfer agent)
In the copolymerization, the molecular weight can be adjusted using a chain transfer agent as necessary. Examples of the chain transfer agent used include mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, octyl thioglycolate, and 2-mercaptoethanesulfonic acid. Known thiol compounds; phosphorous acid, hypophosphorous acid, and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionite, metabisulfite, and the like Lower oxides of salts (sodium sulfite, potassium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium dithionite, potassium dithionite, sodium metabisulfite, potassium metabisulfite, etc.) and salts thereof; It is done. These may be used alone or in combination of two or more. In order to adjust the molecular weight of the copolymer, a monomer having high chain transferability other than the monomer represented by the general formulas (1) to (3) and the monomer constituting the structural unit (VI) (V) may be used. Examples of the monomer (V) having a high chain transfer property include (meth) allylsulfonic acid (salt) monomers. The blending ratio of the monomer (V) in the copolymer is usually 20% by weight or less, and preferably 10% by weight or less. The above-mentioned blending ratio is the blending ratio of the monomer represented by the general formula (1) + the blending ratio derived from the monomer represented by the general formula (2) + general when the copolymer is produced. The blending ratio of the monomer represented by the formula (3) + the blending ratio of the monomer constituting the structural unit (IV) = 100 wt%.

(Neutralization)
When the copolymer (A) is copolymerized in an aqueous solvent, the pH at the time of polymerization usually becomes strongly acidic due to the influence of the monomer having an unsaturated bond, but this is adjusted to an appropriate pH. May be. If it is necessary to adjust the pH during polymerization, the pH should be adjusted using an acidic substance such as phosphoric acid, sulfuric acid, nitric acid, alkylphosphoric acid, alkylsulfuric acid, alkylsulfonic acid, and (alkyl) benzenesulfonic acid. Good. Among these acidic substances, it is preferable to use phosphoric acid because it has a pH buffering action. However, in order to eliminate the instability of the ester bond of the ester monomer, it is preferable to perform the polymerization at pH 2-7. Moreover, although there is no limitation in particular in the alkaline substance which can be used for adjustment of pH, alkaline substances, such as NaOH and Ca (OH) _2, are common. The pH adjustment may be performed on the monomer before polymerization or may be performed on the copolymer solution after polymerization. These may be polymerized by adding a part of an alkaline substance before polymerization, and then further pH adjustment (for example, pH 3-7 adjustment) may be performed on the copolymer.

(concentration)
Although there is no limitation in solid content concentration in (A) component, it is preferable that it is 5 weight% or more, and it is more preferable that it is 15 weight% or more. The upper limit is preferably 70% by weight or less, and more preferably 65% by weight or less. Therefore, the solid content concentration in the component (A) is preferably 5% by weight to 70% by weight and preferably 15% by weight to 65% by weight with respect to the total weight of the dispersant for hydraulic composition. preferable.

  The copolymer (A) may be liquid. An aqueous solvent is illustrated as a solvent in the case of a liquid. Examples of the aqueous solvent include water, alcohols having 1 to 6 carbon atoms (such as ethyl alcohol, methyl alcohol, ethylene glycol and diethylene glycol), and ketones having 1 to 6 carbon atoms (such as methyl isobutyl ketone and acetone). You may use individually or in mixture. As the aqueous solvent, water is preferred.

  (A) A component contains the monomer represented by either of General formula (1)-(3) which is a raw material of a copolymer (A), and one or more chosen from this monomer. May be.

  When obtaining the copolymer (A), treatments such as removal of the reaction solvent, concentration, and purification may be performed as necessary. These processing methods may be conventionally known methods.

(Molecular weight)
The weight average molecular weight (Mw) of the copolymer (A) is preferably 5,000 or more, more preferably 6,000 or more, and further preferably 6,500 or more. Thereby, when the additive for hydraulic composition is added, the dispersibility of the hydraulic composition is sufficiently exhibited, and a water reduction rate higher than that of the AE water reducing agent such as lignin sulfonic acid type or oxycarboxylic acid type can be obtained. , Fluidity or workability can be improved. The upper limit of the weight average molecular weight is preferably 60,000 or less, more preferably 50,000 or less, and still more preferably 30,000 or less. Thereby, the aggregation effect | action of the particle | grains in a hydraulic composition is suppressed, and workability | operativity can be made favorable. The weight average molecular weight is preferably 5,000 to 60,000, more preferably 6,000 to 50,000, and more preferably 6,500 to 30,000.

  The molecular weight distribution (Mw / Mn) of the copolymer is preferably 1.0 or more, and more preferably 1.20 or more. The upper limit is preferably 3.0 or less, and more preferably 2.50 or less. The molecular weight distribution is preferably in the range of 1.2 to 3.0.

  In addition, the weight average molecular weight in this invention can be measured by the well-known method converted into polyethyleneglycol by gel permeation chromatography (GPC).

Although there is no limitation in particular as measurement conditions of GPC, the following conditions can be mentioned as an example. The weight average molecular weight in the latter examples is a value measured under these conditions.
Measuring device; column used by Tosoh; Shodex Column OH-pak SB-806HQ, SB-804HQ, SB-802.5HQ
Eluent: 0.05 mM sodium nitrate / acetonitrile 8/2 (v / v)
Standard material: Polyethylene glycol (Tosoh, GL Science)
Detector: differential refractometer (manufactured by Tosoh)
Calibration curve; polyethylene glycol standard

<(B) component>
The component (B) is an antiseptic and / or antifungal agent (B).

  In this specification, antiseptic means the effect | action which suppresses the proliferation of microorganisms and prevents corruption. The action may or may not be a bactericidal action. Anti-fungal means the action of preventing the formation of fungi and / or their hyphae on the surface of an object. As the component (B), any one of a drug having only antiseptic action, a drug having only antifungal action, and a drug having both antiseptic action and antifungal action can be used.

The antiseptic and / or antifungal agent is not particularly limited as long as it has a preservative action and / or antifungal action. Examples include the following compounds:
Formaldehyde, methylenebisthiocyanate, 1,2-benzisothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, N-butylbenzisothiazolin-3-one, 5-chloro-2-methyl-4-isothiazoline Organic nitrogen sulfur compounds such as -3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one;
2,2-dibromo-2-nitroethanol, 2,2-dibromo-3-nitrilopropionamide, 1,2-bis (bromoacetoxy) ethane, 1,4-bis (bromoacetoxy) -2-butene, 1, Organic bromine compounds such as 2-bis (bromoacetoxy) -propane and bis (tribromomethyl) sulfone;
Organic sulfur compounds such as 4,5-dichloro-1,2-dithiol-3-one; and 2-chloro-3-nitrilopropionamide, 2-bromo-3-nitrilopropionamide, 2,2-dichloro-3 -Compounds of halocyanoacetamide type compounds such as nitrilopropionamide and 2,2-dibromo-3-nitrilopropionamide.

  Of these, organic nitrogen sulfur compounds are preferred, thiazoline compounds are more preferred, 1,2-benzisothiazoline-3-one, 2-methyl-4-isothiazoline-3-one, N-butylbenzisothiazoline-3-one Is more preferable, and even more preferably, 1,2-benzisothiazolin-3-one is contained.

  The component (B) may be a single antiseptic and / or antifungal agent component, or a combination of two or more. When the component (B) is a combination of two or more antiseptic and / or antifungal components, it is preferable that the combination contains at least one thiazoline compound. Other components to be combined include, for example, amine compounds (eg, 3-amino-1-propanol, 1,2-diaminopropane, N-ethylaminoethylamine, and 3-ethoxypropylamine), quaternary ammonium salts (eg, , Didecyldimethylammonium chloride, alkyldimethylbenzylammonium chloride and didecylmethylpolyoxyethylammonium propionate), aldehydes (eg, glutaraldehyde, and orthophthalaldehyde), organic bromo compounds (eg, 1,2-bis ( Halogenated acetic acid esters such as bromoacetoxy) ethane, 1,4-bis (bromoacetoxy) -2-butene, 1,2-bis (bromoacetoxy) -propane). Of these, amine compounds are preferable, and 3-amino-1-propanol and 1,2-diaminopropane are more preferable.

  Quaternary ammonium salts include didecyl dimethyl ammonium salts, didecyl diethyl ammonium salts, dicetyl dimethyl ammonium salts, di higher alkyl di lower alkyl ammonium salts such as didodecyl dimethyl ammonium salts, such as didecyl methyl polyoxyethyl ammonium. Di-higher alkyl lower alkyloxyalkylene-containing alkylammonium salts such as salts such as dodecyldimethylbenzylammonium salt, dodecyldiethylbenzylammonium salt, dodecyldimethyl (3,4-dichlorobenzyl) ammonium salt, cetyldimethylbenzylammonium salt, alkyl ( C12-C16) Higher alkyldi-lower alkylbenzylates such as dimethylbenzylammonium salt and octadodecyldimethylbenzylammonium salt Monium salts such as benzyldimethyl {2- [2- (p-1,1,3,3-tetramethylbutylphenoxy) -ethoxy] ethyl} ammonium salt, benzyldimethyl [(p-diisobutylphenoxy) -ethoxyethyl] Benzyldilower alkyloxyalkylene-containing alkylammonium salts such as ammonium salts, for example, higher alkyl such as decyltrimethylammonium salt, cetyltrimethylammonium salt, dodecyltrimethylammonium salt, dodecyltriethylammonium salt, alkyl (C12-C18) dimethylethylammonium salt Tri-lower alkyl ammonium salts such as N-triethyl-N-chloro-N′-benzyl-N′-dodecylglycinamide, cetylpyridinium salts, 2-tridecylpyridinium salts 1-hexadecyl-pyridinium salt, 2-dodecylisoquinolinium salt, 2-octyl-1- (2-hydroxyethyl) imidazolinium salt, 6-dodecyloxybenzylquinolinium salt, benzyldecylpiperidinium salt, etc. N-higher alkyl heterocyclic compounds of

  Combinations of two or more antiseptic and / or antifungal components are described in JP-A No. 2005-314324, JP-A No. 2005-314342, JP-A No. 2005-314343 and JP-A No. 2005-314344. A combination of a thiazoline compound and an amine compound, a combination of a thiazoline compound and a quaternary ammonium salt described in JP-A-11-72111, a methylenebisthiocyanate and a halogenated acetic acid described in JP-A-06-65006 Examples of combinations of esters are exemplified.

  The content of the component (B) is not particularly limited, but is preferably 10 ppm or more, more preferably 50 ppm or more, and further preferably 100 ppm or more with respect to the weight of the component (A). Even more preferably, it is at least 200 ppm. The upper limit is preferably 5000 ppm or less, more preferably 4000 ppm or less, and still more preferably 3000 ppm or less. Therefore, the dispersant for hydraulic composition of the present invention preferably contains the component (B) in the range of 10 ppm to 5000 ppm, and in the range of 50 to 5000 ppm with respect to the weight of the component (A). Is more preferable, it is more preferable to contain in the range of 100 ppm to 4000 ppm, and still more preferable to contain in the range of 200 ppm to 3000 ppm.

  When the component (B) includes a thiazoline compound and an amine compound, the content ratio of the thiazoline compound is preferably 6 to 40% by weight, and more preferably 10 to 33% by weight. The content of the amine compound is preferably 7 to 47% by weight, and more preferably 11 to 36% by weight.

  When the component (B) contains a thiazoline compound and an amine compound, the hydraulic composition dispersant preferably further contains ethylene glycol or propylene glycol. Thereby, (B) component can be stabilized. The content of ethylene glycol or propylene glycol is preferably 1 to 10% by weight based on the thiazoline-based compound and the amine compound.

  It is preferable that (B) component is mixed with the aqueous solution whose (A) component and (B) component contain the (A) density | concentration of 75 weight% or less. More preferably, the component (B) is mixed in an aqueous solution having a concentration of the component (A) of 5 to 70% by weight. As the component (A), one type of each of the copolymers A-1 to A-4 may be used as the A component, or two or more types may be used as the A component.

<(S) component>
The dispersant for hydraulic composition of the present invention may contain (S) component: sulfonic acid-based dispersant. Examples of the component (S) include naphthalene sulfonic acid formaldehyde condensate, melamine sulfonic acid formaldehyde condensate, and lignin sulfonate. (S) A component may be only 1 type and may be a combination of 2 or more types. It is preferable that content of (S) component is 0.01 to 50 weight% with respect to (A) component.

<(G) component>
The dispersant for hydraulic composition of the present invention may contain (G) component: retarder. Thereby, the hydration reaction of a hydraulic composition can be delayed and the time required for coagulation can be extended.

  Examples of the retarder include oxycarboxylic acids such as gluconic acid, gluconate, citric acid and citrate, sugars such as glucose, and sugar alcohols such as sorbitol. (G) Only 1 type may be sufficient as a component and 2 or more types of combinations may be sufficient as it. It is preferable that content of (G) component is 0.01 to 50 weight% with respect to (A) component.

<Optional component>
The dispersant for hydraulic composition of the present invention may contain an optional component other than the components (A), (B), (S) and (G) as long as the effects of the present invention are not hindered. . Optional components include, for example, water-soluble polymers, curing accelerators, thickeners, polymer emulsions, air entrainers, cement wetting agents, swelling agents, waterproofing agents, thickeners, flocculants, drying shrinkage reducing agents, Known concrete additives such as a strength enhancer, an antifoaming agent, an AE agent, and a surfactant can be used. These may be used alone or in combination of two or more.

  Examples of the water-soluble polymer include polyalkylene glycol, specifically, polyethylene glycol, polypropylene glycol, polyethylene polypropylene glycol, polyethylene polybutylene glycol, and the like. The content of the water-soluble polymer is preferably 0.01% by weight to 50% by weight with respect to the component (A).

  Examples of the curing accelerator include soluble calcium salts such as calcium chloride, calcium nitrite and calcium nitrate, chlorides such as iron chloride and magnesium chloride, and formate salts such as thiosulfate, formic acid and calcium formate. The curing accelerator may be one type or a combination of two or more types. It is preferable that content of a hardening accelerator is 0.01 to 50 weight% with respect to (A) component.

  Examples of the thickener include hydroxypropylmethylcellulose, carboxymethylcellulose, known cellulose nanofibers, and known cellulose nanocrystals. One thickener may be used or a combination of two or more thickeners may be used. It is preferable that content of a thickener is 0.01 to 50 weight% with respect to (A) component.

The dispersing agent for hydraulic composition of the present invention has suppressed the propagation of organisms, and the content of bacteria, microorganisms, etc. is small or substantially not contained. Although it is difficult to uniformly determine the number of viable bacteria in the preparation, the culture is carried out at 36 ° C. and a relative humidity of 80%, and stored for 10 days, 20 days, and 30 days, respectively, and then JIS K 0350- The number of viable bacteria of general bacteria measured by the method described in 10-10 is preferably 10 ³ or less in 1 mL of the dispersant for hydraulic composition. General bacteria are the same as defined bacteria described in JIS K 0350-10-10, and form colonies in the medium when cultured at 36 ± 1 ° C. for 24 ± 2 hours using a standard agar medium. All bacteria.

<Usage form of dispersant for hydraulic composition>
The dispersant for hydraulic composition of the present invention can be used in the form of an aqueous solution or in the form of powder after drying. Further, the dispersant for the hydraulic composition of the present invention in a powdered form is mixed in advance with a component other than water constituting the cement composition, such as cement powder and dry mortar, and the plasterer, floor It can also be used as a premix product to which water is added during finishing, grouting and the like.

  The dispersant for hydraulic composition of the present invention can be added to a hydraulic material such as cement and used as a hydraulic composition for cement paste, mortar, concrete, plaster and the like.

  The hydraulic composition of this invention should just contain the said dispersing agent for hydraulic compositions, and the hydraulic material to combine is not specifically limited. Examples of the hydraulic material include cement, gypsum (semihydrate gypsum, dihydrate gypsum, etc.), and dolomite. The most common hydraulic material is cement.

  The cement is not particularly limited. For example, Portland cement (ordinary, early strength, very early strength, moderate heat, sulfate-resistant and low alkali type of each), 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, fly ash mixed low exothermic blast furnace cement, belite High-content cement), ultra-high-strength cement, cement-based solidified material, eco-cement (cement produced using at least one of municipal waste incineration ash and sewage sludge incineration ash). Blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, limestone powder and other fine powder, gypsum and the like may be added to the cement.

  Moreover, the hydraulic composition may contain the aggregate. The aggregate may be either a fine aggregate or a coarse aggregate. Examples of aggregates include sand, gravel, crushed stone; granulated slag; recycled aggregate, etc .; siliceous, clay, zircon, high alumina, silicon carbide, graphite, chrome, chromic, magnesia Fireproof aggregates such as

  There is no particular limitation on the blending ratio of the dispersant for hydraulic composition in the hydraulic composition. For example, when the hydraulic composition is mortar or concrete, the addition amount (blending amount) of the copolymer (A) contained in the dispersant for hydraulic composition is such that the total amount of the hydraulic material (cement). It is preferably 0.01 to 5.0% by weight, more preferably 0.02 to 2.0% by weight, and 0.05 to 1.0% by weight based on the weight. Further preferred. As a result, the obtained cement composition has various preferable effects such as reduction in unit water amount, increase in strength, and improvement in durability. When the blending ratio is 0.01% by weight or more, the resulting hydraulic composition (cement composition) can be sufficient in performance. By being 5.0% by weight or less, an effect commensurate with the amount added can be obtained, which is economical.

  The hydraulic composition is effective as, for example, ready-mixed concrete, concrete for concrete secondary products (precast concrete), concrete for centrifugal molding, concrete for vibration compaction, steam-cured concrete, shotcrete, etc. is there. Furthermore, 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-leveling material It is also effective as mortar or concrete that requires high fluidity such as.

  The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto. In the examples, unless otherwise indicated, “%” means “% by weight” and “parts” means “parts by weight”.

<Production Example A1-1>
5,010 kg of water and ethylene oxide adduct of 3-methyl-3-buten-1-ol (average addition of ethylene oxide) in a stainless steel reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen introduction tube and a dropping device Mole number 30) (3 MBO) 5,000 kg (21 mol%) was charged, the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 80 ° C. in a nitrogen atmosphere. Thereafter, an aqueous monomer solution in which 1,000 kg (79 mol%) of acrylic acid (AA) and 5,010 kg of water were mixed, and a stirred mixed solution of 120 kg of ammonium persulfate and 1880 kg of water were maintained at 80 ° C. for 2 hours each. The reaction vessel was continuously added dropwise. Furthermore, it was made to react for 1 hour in the state hold | maintained at 100 degreeC. Thereafter, it is cooled to 80 ° C. in an additional apparatus located at the rear stage of the reaction vessel, neutralized to pH 6 with sodium hydroxide and simultaneously added with water, so that a copolymer having a concentration of 30% (weight average molecular weight Mw20,200, An aqueous solution (A1-1) of Mw / Mn 1.7) was obtained.

<Production Example A1-2>
A stainless steel reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen introduction tube and a dripping device was charged with 7,000 kg of water, the reaction vessel was purged with nitrogen, and the temperature was raised to 75 ° C. under a nitrogen atmosphere. did. Thereafter, methoxy polyethylene glycol methacrylate (MPEG-MA) (average number of moles of ethylene oxide added 18) 6,300 kg (30 mol%), methacrylic acid (MA) 1,400 kg (70 mol%), water 1,470 kg, Then, a monomer aqueous solution in which 56 kg of 3-mercaptopropionic acid was mixed, and a stirred mixture of 70 kg of sodium persulfate and 2,030 kg of water were continuously added dropwise to a reaction vessel maintained at 75 ° C. for 2 hours. Furthermore, it was made to react for 1 hour in the state hold | maintained at 75 degreeC. Thereafter, in an additional apparatus located at the rear stage of the reaction vessel, the mixture is cooled to 65 ° C., neutralized to pH 6 with sodium hydroxide and simultaneously added with water, so that a copolymer having a concentration of 30% (weight average molecular weight Mw 26,000, Mw / Mn 2.0) aqueous solution (A1-2) was obtained.

<Production Example A2-1>
5,010 kg of water, ethylene oxide adduct of 3-methyl-3-buten-1-ol (3MBO) (ethylene oxide) in a stainless steel reaction vessel equipped with a thermometer, a stirring device, a reflux device, a nitrogen introduction tube and a dropping device The average added mole number of 30) 5,000 kg (26 mol%) was charged, the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 80 ° C. under a nitrogen atmosphere. Thereafter, a monomer aqueous solution in which 1,350 kg (74 mol%) of 2-hydroxypropyl acrylate (HPA) and 5,010 kg of water were mixed with a stirred mixture of 120 kg of ammonium persulfate and 1,880 kg of water for 2 hours each. The solution was continuously added dropwise to a reaction vessel maintained at 90 ° C. Furthermore, it was made to react for 1 hour in the state hold | maintained at 100 degreeC. Thereafter, it is cooled to 80 ° C. in an additional apparatus located at the rear stage of the reaction vessel, neutralized to pH 4 with sodium hydroxide and simultaneously added with water, so that a copolymer having a concentration of 30% (weight average molecular weight Mw22,200, An aqueous solution (A2-1) of Mw / Mn 1.7) was obtained.

<Production Example A3-1>
A stainless steel reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen introduction tube and a dropping device was charged with 5,010 kg of water, the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 80 ° C. under a nitrogen atmosphere. . Thereafter, an aqueous monomer solution prepared by mixing 1,300 kg (63 mol%) of acrylic acid (AA), 1,350 kg (37 mol%) of 2-hydroxypropyl acrylate (HPA) and 5,010 kg of water, 120 kg of ammonium persulfate and 1 of water , 880 kg of the stirred mixed solution was continuously dropped into a reaction vessel maintained at 80 ° C. for 4 hours each. Furthermore, it was made to react for 1 hour in the state hold | maintained at 80 degreeC. Thereafter, concentration is carried out with an additional device located at the rear stage of the reaction vessel, and neutralized to pH 4 with sodium hydroxide, so that a copolymer having a concentration of 40% (weight average molecular weight Mw12,200, Mw / Mn1.4) Solution (A3-1) was obtained.

<Production Example A4-1>
In a stainless steel reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen introduction tube and a dripping device, 4,440 kg of water and polyethylene glycol polypropylene glycol monoallyl ether (average added mole number of ethylene oxide 37, propylene oxide The average number of moles added, 3, random addition of ethylene oxide and propylene oxide) (PEG-AL) 2,820 kg (5 mol%) was charged, the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 80 ° C. under a nitrogen atmosphere did. Thereafter, 1,050 kg (40 mol%) of methacrylic acid (MA), 150 kg (7 mol%) of acrylic acid (AA), methoxypolyethylene glycol methacrylate (average number of added moles of ethylene oxide 25) (MPEG-MA) 1, 890 kg (5 mol%), hydroxypropyl acrylate (HPA) 1,800 kg (43 mol%), 3-mercaptopropionic acid 240 kg, water 4,950 kg mixed monomer aqueous solution, ammonium persulfate 90 kg and water 1,410 kg stirring The mixed solution was continuously dropped into a reaction vessel maintained at 80 ° C. for 2 hours each. Furthermore, it was made to react for 1 hour in the state hold | maintained at 100 degreeC. Thereafter, it is cooled to 80 ° C. in an additional apparatus located at the rear stage of the reaction vessel, neutralized to pH 4 with sodium hydroxide and simultaneously added with water, so that a copolymer having a concentration of 40% (weight average molecular weight Mw 11,100, Mw / Mn1.5) aqueous solution (A4-1) was obtained.

(Footnote in Table 1)
3MBO: Ethylene oxide adduct of 3-methyl-3-buten-1-ol PEG-AL: polyethylene glycol polypropylene glycol monoallyl ether MPEG-MA: methoxypolyethylene glycol methacrylate AA: acrylic acid MA: methacrylic acid HPA: 2- Hydroxypropyl acrylate

<Production Example B1>
According to Formulation Example 1 of JP-A-2005-314324, 1,2-benzisothiazolin-3-one: 33%; 3-amino-1-propanol: 30%; And / or the fungicide (B1) was obtained.

<Production Example B2>
According to Formulation Example 2 of JP-A-2005-314342, 1,2-benzisothiazolin-3-one: 10%; 1,2-diaminopropane: 40%; propylene glycol: 10%; and distilled water: 40% Was added to obtain an antiseptic and / or antifungal agent (B2).

<Production Example B3>
1,2-Benzisothiazolin-3-one: 100% as antiseptic and / or antifungal agent (B3).

<Examples 1 to 10, Comparative Examples 1 to 5>
(Measurement of viable cell count after culture)
The viable count of general bacteria in the medium to which each combination of components A and B in Table 2 was added was measured by the method described in JIS K 0350-10-10. The culture was performed at 36 ° C. and a relative humidity of 80%, and the culture period was 10 days, 20 days, and 30 days. Component B was added at 500 ppm with respect to component A. Table 2 shows the test results at the initial stage of the A component culture (at the start of the culture) and after each culture period.

(Concrete test)
At ambient temperature (20 ° C.), coarse aggregate, fine aggregate, cement, water and the cement admixture shown in Table 3 were added as shown in Table 3, and kneaded for 90 seconds by mechanical kneading using a forced biaxial mixer. (The cement admixture was added after mixing with water). Thereafter, immediately after the concrete was discharged, a fresh concrete test (slump test JISA1101 (measured as the flow value of fresh concrete spread, flow amount JISA1128)) was performed. The test results are shown in Table 4.

C: 3 parts of the following cements are mixed in equal amounts Normal Portland cement (Mitsubishi Ube, Ltd., specific gravity 3.16)
Ordinary Portland cement (manufactured by Taiheiyo Cement Co., Ltd., specific gravity 3.16)
Normal Portland cement (Made by Tokuyama Co., Ltd., specific gravity 3.16)
W: Tap water S1: Crushed lime sand from Tsukumi, Oita Prefecture (fine aggregate, specific gravity 2.66)
S2: Crushed stone from Shunan, Yamaguchi Prefecture (fine aggregate, specific gravity 2.66)
G1, G2 Crushed stone from Iwakuni, Yamaguchi Prefecture (coarse aggregate, specific gravity 2.73, 2.66)
Cement admixture (solid content conversion): Use samples after 30 days of culture in Table 2

  In Table 4, “addition amount” of the cement admixture indicates the solid content concentration of the component (A) with respect to the cement. SLF indicates a slump flow.

The following were used as the (S) component and the (G) component. (S) component: sodium lignin sulfonate (manufactured by Nippon Paper Industries Co., Ltd., trade name: Sunflow RH)
(G) Component: Sodium gluconate (manufactured by Fuso Chemical Co., Ltd., trade name: C-PARN)

  In Table 5, “addition amount” of the cement admixture indicates the solid content concentration of the component (A) with respect to the cement. SLF indicates a slump flow.

  As is clear from Table 2, the viable cell count of the dispersants of Examples 1 to 10 including the components (A) and (B) is low compared to Comparative Examples 1 to 5 including only the component (A), It was below the initial level even after 30 days. In addition, in the dispersants of Comparative Examples 1 to 5, a rotting odor was confirmed after 20 days, whereas in the dispersing agents of Examples 1 to 10, no rotting odor was confirmed after 30 days. As is clear from Tables 4 and 5, the concrete obtained by adding the dispersants of Examples 1 to 10 including the components (A) and (B) is a comparative example including only the component (A) corresponding to each. As compared with the SLF, the SLF and the flow residual ratio were high, and the fluctuation was small after 60 minutes. Further, the air amount in the comparative example tended to increase after the lapse of time, but the air amount in the example hardly changed. These results show that the dispersing agent for hydraulic compositions of the present invention suppresses the growth of organisms such as molds and fungi, and thus has good performance such as slump retention and fed air stability. ing.

Claims (4)

The dispersing agent for hydraulic compositions containing the following (A) component and (B) component.
Component (A): a structural unit (I) derived from a monomer represented by the following general formula (1), a structural unit (II) derived from a monomer represented by the following general formula (2), and Copolymer containing at least two or more structural units selected from the group consisting of structural units (III) derived from monomers represented by the following general formula (3)

(Wherein R ¹ , R ² and R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, p represents an integer of 0 to 2, and q represents 0 to 1) A ¹ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms, n is an integer of 1 to 300, R ⁴ is a hydrogen atom or 1 to 1 carbon atoms. Represents 30 hydrocarbon groups.)

(Wherein R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom, —CH ₃ or — (CH ₂ ) _r COOM ² , —CH ₃ or — (CH ₂ ) _r COOM ² is together other -COOM ¹ or _{-. (CH 2) r COOM} 2 and may form an anhydride when forming the anhydride, M ¹ of those groups, M ² is absent .M ¹ And M ² are the same or different and each represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkylammonium group or a substituted alkylammonium group, and r represents an integer of 0 to 2.)

(In the formula, R ⁸ , R ⁹ and R ¹⁰ each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ¹¹ is a carbon atom which may contain a hetero atom having 1 to 4 carbon atoms. Represents a hydrogen group, and s represents an integer of 0 to 2.
Component (B): antiseptic and / or antifungal agent   The dispersing agent according to claim 1, wherein the component (B) contains at least a thiazoline-based compound.   The dispersing agent of Claim 1 or 2 which contains 50 ppm-5000 ppm of (B) component with respect to the weight of (A) component.   The dispersant according to any one of claims 1 to 3, wherein the dispersant for the hydraulic composition further contains (S) component: sulfonic acid-based dispersant and / or (G) component: retarder.