JP6433222B2 - Additive for hydraulic composition - Google Patents

Description

  The present invention relates to an additive for hydraulic compositions. Specifically, water containing a cellulose-based thickener for a hydraulic composition obtained by anion-modifying a cellulose-based raw material and defibrating the resulting anion-modified cellulose, and a dispersant for a hydraulic composition The present invention relates to an additive for a hard composition.

  High-fluidity concrete (concrete that can be self-filled without using a vibrator) is applied to all structures such as RC, PC, and SRC structures. It is used for densely packed reinforcement members that make it difficult to use a vibrator, synthetic structural members that are mostly closed.

  High fluidity concrete is required to have high fluidity and moderate material separation resistance. High fluidity is exhibited by the use of a dispersant for hydraulic composition (such as a high-performance AE water reducing agent), and moderate material separation resistance is exhibited by the addition of a thickener.

  Patent Document 1 describes highly fluid concrete (cement composition) using a thickener mainly composed of water-soluble cellulose ether. Patent Document 2 describes highly fluid concrete (cement composition) using hydrophobized modified hydroxyethyl cellulose as a thickener. Patent Document 3 describes the use of microfibrillated cellulose as a cement additive.

JP 2001-261419 A JP 09-183644 A International Publication No. 2011/039423

  However, the hydraulic composition manufactured using the cement additive described in each patent document improves the material separation resistance and workability immediately after the manufacturing, but maintains the fluidity after a certain period of time. There was a problem regarding the workability and workability. That is, after a certain period of time, there is a problem that the viscosity of the hydraulic composition is excessively increased, or the fluidity is drastically lowered and the workability is greatly lowered.

  Therefore, the present invention imparts appropriate material separation resistance to the hydraulic composition, and has appropriate material separation resistance even after a predetermined time has elapsed after producing the hydraulic composition, and the hydraulic composition. An object of the present invention is to provide an additive for a hydraulic composition that can maintain the fluidity of the product for a long time.

（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。）
［２］アニオン変性セルロースナノファイバーが、アニオン変性セルロースナノファイバーの絶乾重量に対して、カルボキシル基の量が０．６ｍｍｏｌ／ｇ〜２．０ｍｍｏｌ／ｇである酸化セルロースナノファイバーである［１］に記載の水硬性組成物用添加剤。
［３］アニオン変性セルロースナノファイバーが、アニオン変性セルロースナノファイバーのグルコース単位当たりのカルボキシメチル置換度が０．０１〜０．５０であるカルボキシメチル化セルロースナノファイバーである［１］に記載の水硬性組成物用添加剤。
［４］前記Ｂ成分が２種類以上の異なる共重合体を含んでなる、［１］〜［３］のいずれか１項に記載の水硬性組成物用添加剤。
［５］中流動性コンクリート、高流動性コンクリート、および水中不分離性コンクリートのいずれかに用いられる［１］〜［４］のいずれか１項に記載の水硬性組成物用添加剤。
［６］グラウトまたは注入グラウトに用いられる［１］〜［４］のいずれか１項に記載の水硬性組成物用添加剤。
［７］［１］〜［４］のいずれか１項に記載の水硬性組成物用添加剤を含有する水硬性組成物。 The present invention provides the following [1] to [7].
[1] An additive for a hydraulic composition containing the following component A and component B:
<A component>
Anion-modified cellulose nanofiber.
<B component>
The structural unit (I) derived from the monomer represented by the following general formula (1), the structural unit (II) derived from the monomer represented by the following general formula (2), and the following general formula (3) The copolymer containing at least 2 or more types of structural units chosen from the group which consists of structural unit (III) derived from the monomer represented by this.

(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.)
[2] The anion-modified cellulose nanofiber is an oxidized cellulose nanofiber having an amount of carboxyl groups of 0.6 mmol / g to 2.0 mmol / g based on the absolute dry weight of the anion-modified cellulose nanofiber [1] The additive for hydraulic compositions described in 1.
[3] The hydraulic property according to [1], wherein the anion-modified cellulose nanofiber is a carboxymethylated cellulose nanofiber having an carboxymethyl substitution degree of 0.01 to 0.50 per glucose unit of the anion-modified cellulose nanofiber. Additive for composition.
[4] The additive for a hydraulic composition according to any one of [1] to [3], wherein the component B comprises two or more different copolymers.
[5] The additive for a hydraulic composition according to any one of [1] to [4], which is used for any of medium fluidity concrete, high fluidity concrete, and underwater non-separable concrete.
[6] The additive for a hydraulic composition according to any one of [1] to [4], which is used for grout or injection grout.
[7] A hydraulic composition containing the additive for hydraulic composition according to any one of [1] to [4].

  ADVANTAGE OF THE INVENTION According to this invention, the additive for hydraulic compositions which can provide moderate material separation resistance to a hydraulic composition is provided. The hydraulic composition prepared using the additive for hydraulic composition of the present invention has an appropriate material separation resistance even after a predetermined time has elapsed after preparation, and can maintain a long fluidity retention. It is.

  By using the additive for a hydraulic composition of the present invention, a suitable material separation resistance equal to or higher than a thickener for a hydraulic composition such as hydroxyethyl ether conventionally used It can be given to the composition.

  For this reason, the additive for hydraulic compositions of the present invention can be suitably used for various hydraulic compositions, in particular, concrete such as medium fluidity concrete, high fluidity concrete, and underwater non-separable concrete. Moreover, it can use suitably as an additive of the fluid liquid (for example, grout, injection grout) inject | poured in order to fill a cavity, a space | gap, a clearance gap, etc.

<Additive for hydraulic composition>
The hydraulic composition additive of the present invention contains an A component as a cellulose thickener and a B component as a dispersant. The A component and the B component will be sequentially described below.

<A component>
The component A is anion-modified cellulose nanofiber (anion-modified CNF).

  Anion-modified CNF is usually a fine fiber. The fiber width of the anion-modified CNF is usually about 4 nm to about 500 nm. The aspect ratio of anion-modified CNF is usually 100 or more.

  Examples of the method for producing an anion-modified CNF include a method in which a cellulose-based material is anion-modified and the resulting anion-modified cellulose-based material is defibrated.

  The anion-modified CNF may contain other components, but it is preferable that there are few components such as chlorine that corrodes the metal.

(Cellulosic material)
The cellulosic material is not particularly limited. For example, plants (eg, wood, bamboo, hemp, jute, kenaf, agricultural waste, cloth, pulp (eg, softwood unbleached kraft pulp (NUKP), softwood bleached kraft pulp (NBKP), hardwood unbleached kraft pulp (LUKP)) ), Hardwood bleached kraft pulp (LBKP), softwood unbleached sulfite pulp (NUSP), softwood bleached sulfite pulp (NBSP) thermomechanical pulp (TMP), recycled pulp, waste paper, etc.), animals (for example, ascidians), algae , Microorganisms (for example, acetic acid bacteria (Acetobacter)), microbial products, etc. The pulp may be beaten pulp or unbeaten pulp.The cellulosic material is preferably derived from plants or microorganisms. Cellulosic material, more preferably plant-derived cellulosic material . Cellulosic material may be paraphrased as cellulose fibers.

(Anion modified)
Anionic modification of a cellulosic material means introduction of an anionic group into the cellulosic material. Examples of the anionic group include a carboxymethyl group, a carboxyl group, a carboxylate group, and an aldehyde group.

(Anion modification: Carboxymethylation)
The introduction of carboxymethyl group (carboxymethylation) into the cellulosic material can be carried out using a known method and is not particularly limited. It is preferable that the degree of carboxymethyl group substitution per anhydroglucose unit of the obtained anion-modified cellulose-based raw material is 0.01 to 0.50. The degree of carboxymethyl group substitution per glucose unit in the anion-modified cellulose-based raw material can be measured, for example, according to the method described in the examples in the subsequent stage.

  The following method can be mentioned as an example of carboxymethylation. It is not limited to the following manufacturing method, You may introduce a carboxymethyl group by a conventionally well-known method, Using the commercial item of the cellulose raw material (carboxymethylated cellulose raw material) into which the carboxymethyl group was introduce | transduced Also good.

  First, mercerization processing is performed. The mercerization treatment is usually performed by mixing the bottoming raw material, the solvent and the mercerizing agent. The bottoming material includes a cellulosic material.

  The solvent is preferably water and / or a lower alcohol, and more preferably water. Examples of the lower alcohol include methanol, ethanol, N-propyl alcohol, isopropyl alcohol, N-butanol, isobutanol, tertiary butanol and the like alone or in a mixed medium of two or more. When the solvent contains a lower alcohol, the mixing ratio is preferably 60 to 95% by weight. It is preferable that the usage-amount of a solvent is 3-20 weight times of a cellulose raw material.

  Examples of mercerizing agents include alkali metal hydroxides, with sodium hydroxide and potassium hydroxide being preferred. The mercerizing agent is preferably used in an amount of 0.5 to 20 moles per anhydroglucose residue of the starting material.

  The reaction temperature of mercerization is usually 0 to 70 ° C, preferably 10 to 60 ° C. The reaction time of mercerization is usually 15 minutes to 8 hours, preferably 30 minutes to 7 hours. The reaction may be carried out with stirring.

  After the mercerization treatment, an etherification reaction is performed. The etherification reaction is performed by adding a carboxymethylating agent to the reaction system. Examples of the carboxymethylating agent include monochloroacetic acid and sodium monochloroacetate. The addition amount of the carboxymethylating agent is preferably 0.05 to 10.0 times mol per glucose residue of the cellulosic material. The reaction temperature of the etherification reaction is usually 30 to 90 ° C, preferably 40 to 80 ° C. The reaction time is usually 30 minutes to 10 hours, preferably 1 hour to 4 hours.

(Anion modification: carboxylation)
Introduction of an anionic group such as a carboxyl group into a cellulose-based raw material (carboxylation (oxidation)) can be performed using a known method, and is not particularly limited. The amount of carboxyl groups relative to the absolute dry weight of the obtained anion-modified cellulose nanofiber is usually 0.6 mmol / g to 2.0 mmol / g, preferably 1.0 mmol / g to 1.8 mmol / g. It is preferable to adjust the oxidation conditions.

  As an example of oxidation, a method in which cellulose is oxidized in water using an oxidizing agent in the presence of a compound selected from the group consisting of an N-oxyl compound and a bromide such as sodium bromide, iodide, or a mixture thereof. Is mentioned. By this oxidation reaction, the primary hydroxyl group at the C6 position of the glucopyranose ring on the surface of the cellulose-based raw material is selectively oxidized to obtain a carboxylated cellulose-based fiber having an aldehyde group, a carboxyl group and / or a carboxylate group on the surface. be able to. The concentration of cellulose during the reaction is not particularly limited, but is preferably 5% by weight or less.

  An N-oxyl compound refers to a compound capable of generating a nitroxyl radical. As the N-oxyl compound, any compound can be used as long as it promotes the target oxidation reaction. Examples of N-oxyl compounds include 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), and 4-hydroxy TEMPO derivatives such as the catalyst described in JP-A-2009-173909. Is preferred.

  The amount of the N-oxyl compound used is not particularly limited as long as it is a catalytic amount that can oxidize cellulose as a raw material. For example, it is preferably 0.01 to 10 mmol, more preferably 0.01 to 1 mmol, and still more preferably 0.05 to 0.5 mmol with respect to 1 g of absolutely dry cellulose. Moreover, it is good in it being about 0.1-4 mmol / L with respect to the reaction system.

  Bromide is a compound containing bromine, examples of which include alkali metal bromides that can dissociate and ionize in water. Further, an iodide is a compound containing iodine, and examples thereof include alkali metal iodide. The amount of bromide or iodide used can be selected as long as the oxidation reaction can be promoted. The total amount of bromide and iodide is, for example, preferably 0.1 mmol to 100 mmol, more preferably 0.1 mmol to 10 mmol, and more preferably 0.5 mmol to 5 mmol with respect to 1 g of absolutely dry cellulose. More preferably.

  As the oxidizing agent, known ones can be used. For example, halogen; halogen acids such as hypohalous acid, halous acid and perhalogen acid; salts of halogen acids; halogen oxides; . Of these, sodium hypochlorite is preferable because it is inexpensive and has a low environmental impact. The amount of the oxidizing agent used is, for example, preferably 0.5 mmol to 500 mmol, more preferably 0.5 mmol to 50 mmol, still more preferably 1 mmol to 25 mmol, and more preferably 3 mmol to 3 mmol to 1 g of absolutely dry cellulose. 10 mmol is most preferred. For example, it is preferable that it is 1-40 mol with respect to 1 mol of N-oxyl compounds.

  The cellulose oxidation step allows the reaction to proceed efficiently even under relatively mild conditions. Therefore, the reaction temperature is preferably 4 to 40 ° C, and may be room temperature of about 15 to 30 ° C. As the reaction proceeds, a carboxyl group is generated in the cellulose, so that the pH of the reaction solution is reduced. In order to advance the oxidation reaction efficiently, an alkaline solution such as an aqueous sodium hydroxide solution is added to maintain the pH of the reaction solution preferably at about 8 to 12, more preferably about 10 to 11. The reaction medium is preferably water because it is easy to handle and hardly causes side reactions.

  The reaction time in the oxidation reaction can be appropriately set according to the progress of the oxidation, and is usually about 0.5 to 6 hours, for example, about 0.5 to 4 hours.

  The oxidation reaction may be performed in two stages. For example, oxidized cellulose obtained by filtration after completion of the first stage reaction may be oxidized again under the same or different reaction conditions. Thereby, reaction inhibition by the salt produced as a by-product in the first-stage reaction can be suppressed, and the cellulosic material can be oxidized efficiently. After the reaction, filtration, washing and the like may be performed to obtain the target product.

  It is preferable that the amount of carboxyl groups is 0.6 mmol / g to 2.0 mmol / g, preferably 1.0 mmol / g to 1.8 mmol / g based on the absolute dry weight of the anion-modified cellulose nanofiber. The amount of anionic groups such as carboxyl groups, carboxylate groups, and aldehyde groups in anion-modified cellulose nanofibers can be adjusted by controlling the amount of the oxidizing agent added and the reaction time. The amount of the carboxyl group of the anion-modified cellulose nanofiber can be measured, for example, according to the method described in the examples in the subsequent stage.

(Defibration processing)
There are no particular limitations on the defibrating treatment conditions of the anion-modified cellulose-based material. The device for defibration (defibration and dispersion) is not particularly limited, and examples thereof include high-speed rotation type, colloid mill type, high-pressure type, roll mill type, and ultrasonic type devices. Or they can be used in combination. It is preferable to use at least a high-pressure apparatus such as a high-pressure or ultrahigh-pressure homogenizer. In the defibrating treatment, it is preferable to apply a strong shearing force to the aqueous dispersion of the anion-modified cellulose raw material using these apparatuses. The apparatus for defibration is preferably a homogenizer such as a high-pressure or ultra-high pressure homogenizer (for example, a wet homogenizer), and applies a pressure to the aqueous dispersion and a high-pressure or ultra-high pressure homogenizer capable of applying a strong shearing force. It is preferable that Thereby, defibration can be advanced efficiently.

  The applied pressure is usually 50 MPa or more, preferably 100 MPa or more, more preferably 140 MPa or more. The solid content concentration of the anion-modified cellulose-based raw material of the aqueous dispersion is preferably 0.1 to 10% (w / v).

  Prior to the defibrating process with a high-pressure or ultra-high-pressure homogenizer, an anion-modified cellulose-based material may be pretreated as necessary. Examples of the preliminary treatment include a mixing treatment, a stirring treatment, an emulsification treatment, a dispersion treatment, and a viscosity reducing treatment. The mixing process, the stirring process, the emulsifying process, and the dispersing process may be performed using a known mixing, stirring, emulsifying, and dispersing apparatus such as a high-speed shear mixer. Examples of the viscosity reducing treatment include a treatment of hydrolyzing an anion-modified cellulose-based raw material under alkaline conditions. The alkaline condition is usually set to pH 8 or higher. Hydrolysis may be carried out using a reagent such as aqueous hydrogen peroxide or 1M aqueous sodium hydroxide. The reaction temperature can be 20-90 ° C. The reaction time can be 0.5 hours to 4 hours.

  The B-type viscosity of the anion-modified cellulose nanofiber is preferably 10 mPa · S to 100,000 mPa · S. The average fiber diameter of the anion-modified cellulose nanofiber is preferably 2 nm to 50 nm, more preferably 4 nm to 20 nm. The aspect ratio (average fiber length / average fiber diameter) of the anion-modified cellulose nanofiber is preferably 50 to 2000. The B-type viscosity, average fiber diameter, and average fiber length can be measured and calculated under the conditions described in Examples below.

<B component>
Component B is composed of the structural unit (I) derived from the monomer represented by the general formula (1), the structural unit (II) derived from the monomer represented by the following general formula (2), and the following general It is a copolymer containing at least 2 or more types of structural units selected from the group consisting of structural units (III) derived from the monomer represented by formula (3). The copolymer should just have 2 or more types chosen from structural unit (I)-(III), and may have all 3 types.

(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. In general formula (1), when q is 0, an alkylene group having p carbon atoms and A ¹ O are bonded via an oxygen atom.

  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. Within this range, the number of carbon atoms does not become too large, so that the cement dispersibility of the cement admixture is exhibited well.

  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 between hydrophilicity and hydrophobicity, (poly) ethylene glycol (meth) allyl ether, (poly) ethylene (poly) propylene glycol (meth) allyl ether, (poly) ethylene glycol 3-methyl-3 -Butenyl ether, (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. “(Meth) allyl” means methallyl and / or allyl, “(meth) acrylate” means methacrylate and / or acrylate, “(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 as component B 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 these groups are not present. R ⁵ is preferably a hydrogen atom. R ⁶ is preferably a hydrogen atom or —CH ₃ . R ⁷ is preferably a hydrogen atom.

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

  In general formula (2), r represents an integer of 0-2. r is 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 as the component B 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 ¹⁰ 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 2-hydroxyethyl group, 2-hydroxypropyl group, 4-hydroxybutyl group, and glyceryl group, among which 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.

  The copolymer as component B 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 constituting the component B may contain the 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 it does not specifically limit as a monomer which comprises structural unit (IV), 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 as component B may contain one type of structural unit (IV), or may contain two or more types of structural units (IV) derived from different monomers.

(Copolymers B-1 to B-4)
Below, the example of the copolymer which B component may contain is shown. In the following copolymers B-1 to B-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 B-1)
Copolymer B-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 B-2)
Copolymer B-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 B-3)
Copolymer B-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 B-4)
Copolymer B-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 B-1 to B-4)
One of the copolymers B-1 to B-4 may be used as the B component, or two or more may be used as the B component, but it is preferable to use two or more types in combination as the B component. . The two preferred combinations and the content ratio thereof are, for example, as follows: Copolymer B-1 / Copolymer B-2 = 1 to 99% by weight / 1 to 99% by weight, more preferably 10 to 90%. % By weight / 10-90% by weight, more preferably 20-80% by weight / 20-80% by weight; copolymer B-1 / copolymer B-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 B-1 / Copolymer B-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 the content ratios thereof are, for example, as follows: Copolymer B-1 / Copolymer B-2 / Copolymer B-3 = 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, still more preferably 20 to 80% by weight / 20 to 80% by weight / 1 to 70% by weight; Polymer B-1 / Copolymer B-2 / Copolymer B-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 B-2 / copolymer B-3 / copolymer B-4 = 1-99 wt% / 1-99 wt% / 1-99 wt%, more preferably 10-90 wt% / 1-8 Wt% / 10 to 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 B-1 / Copolymer B-2 / Copolymer B-3 / Copolymer B-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, more preferably 20-80 wt% / 20-80 wt% / 1-70 wt% / 20-80 wt%.

<Method for producing copolymer>
The copolymer as the component B 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 copolymerization is carried out in an aqueous solvent when obtaining a copolymer, the pH during polymerization usually becomes strongly acidic due to the influence of a monomer having an unsaturated bond, but this may be adjusted to an appropriate pH. . 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, phosphoric acid is preferable 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. In addition, these may be subjected to polymerization by adding a part of an alkaline substance before polymerization, and then the pH of the copolymer may be further adjusted.

(Molecular weight)
The weight average molecular weight of the copolymer as the component B 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 further 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.

  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

<Content ratio of component A and component B>
The content ratio of component A and component B in the hydraulic composition additive is preferably A component / B component = (0.01 wt% to 20 wt%) / (80 wt% to 99.99 wt%). More preferably, A component / B component = (0.02 wt% to 15 wt%) / (75 wt% to 99.98 wt%).

<Contained form of component A and component B>
In the additive for hydraulic compositions of the present invention, there is no limitation on the content of the A and B components. For example, the A and B components may be included as they are, or each of the A and B components or both may be formulated as a solution dissolved in a solvent, a dispersed dispersion, or a suspended suspension. It may be.

<Usage method of additive for hydraulic composition>
The additive 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. The time when the dispersant for hydraulic composition is added to other components constituting the hydraulic composition or to hydraulic materials other than the hydraulic composition may be during use of the hydraulic composition. In addition, the additive for hydraulic composition of the present invention in a powdered form is mixed in advance with components other than water constituting the hydraulic composition, such as cement powder and dry mortar, It can also be used as a premix product to which water is added for floor finishing, grout and the like.

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

<Hydraulic composition using additive for hydraulic composition>
The hydraulic composition of this invention should just contain the additive 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 (for example, normal, early strength, very early strength, moderate heat, sulfate-resistant and their respective low alkali types), various mixed cements (for example, blast furnace cement, silica cement, fly ash cement), white Portland cement , Alumina cement, super fast cement (eg 1 clinker fast cement, 2 clinker fast cement, magnesium phosphate cement), grout cement, oil well cement, low exothermic cement (eg low exothermic blast furnace cement, fly ash mixing) Low exothermic type blast furnace cement, cement with high belite content, ultra-high strength cement, cement-based solidified material, eco-cement (for example, cement manufactured using one or more of municipal waste incineration ash and sewage sludge incineration ash) Is mentioned. Components other than cement such as blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, limestone powder, and other cement may be added to the cement.

  The hydraulic composition may contain 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 limitation in particular about the mixture ratio of the additive for hydraulic compositions in a hydraulic composition. For example, when the cement composition is mortar or concrete, the additive amount (blending amount) of the present invention is preferably 0.01 to 5.0% by weight based on the total weight of the cement. Preferably it is 0.02 to 2.0 weight%, More preferably, it is 0.05 to 1.0 weight%. By using this added amount, the obtained cement composition has various preferable effects such as a reduction in unit water amount, an increase in strength, and an improvement in durability. When the blending ratio is 0.01% by weight or more, the resulting 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 of the present invention 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. It is. Furthermore, medium fluidity concrete (concrete with a slump value of 22-25 cm), high fluidity concrete (concrete with a slump value of 25 cm or more and slump flow value of 50-70 cm), underwater non-separable concrete, self-filling It is also useful as mortar or concrete, which requires high fluidity, such as porous concrete and self-leveling material.

  The additive for hydraulic composition of the present invention can be used as it is as a dispersant for cement. Furthermore, other dispersants for hydraulic compositions, water-soluble polymers, polymer emulsions, air entrainers, cement wetting agents, swelling agents, waterproofing agents, retarders, thickeners, flocculants, drying shrinkage reducing agents, strength You may use together well-known concrete additives, such as an enhancer, an effect promoter, an antifoamer, AE agent, and other surfactant. Another dispersing agent may be used independently and may use 2 or more types. Known additives for concrete include, for example, carboxyl groups and / or their salt-containing compounds (CA agents) and sulfonic acid groups and / or their salt-containing compounds (SA agents).

  Examples of the CA agent include sodium polyacrylate and sodium gluconate, but are not limited thereto. Among these compounds, one kind or two or more kinds can be used.

  Examples of the SA agent include sodium lignin sulfonate and naphthalene sulfonic acid, but are not limited thereto. Among these compounds, one kind or two or more kinds can be used.

  When the additive for hydraulic composition of the present invention and the additive of the above (CA agent) and / or (SA agent) are used in combination, the ratio is not particularly limited. For example, when the two components are used in combination, the hydraulic composition additive of the present invention / (CA agent) or (SA agent) = 0.1 wt% to 99.9 wt% / 0.1 wt. % To 99.9% by weight is preferable. For example, when the three components are used in combination, the hydraulic composition additive of the present invention / (CA agent) / (SA agent) = 0.1 wt% to 99.9 wt% / 0.1 wt. % To 99.9 wt% / 0.1 wt% to 99.9 wt% is preferable.

<A component>
<Production example: A1>
5 g (absolutely dried) of bleached softwood unbeaten pulp (Nippon Paper Industries Co., Ltd.) was added to 500 ml of an aqueous solution in which 78 mg (0.5 mmol) of TEMPO (Sigma Aldrich) and 754 mg (7.4 mmol) of sodium bromide were dissolved. Was stirred until evenly dispersed. After adding 16 ml of a 2M aqueous sodium hypochlorite solution to the reaction system, the pH was adjusted to 10.3 with a 0.5N aqueous hydrochloric acid solution to initiate an oxidation reaction (oxidation treatment). During the reaction, the pH in the system was lowered, but a 0.5N aqueous sodium hydroxide solution was successively added to adjust the pH to 10. After reacting for 2 hours, the mixture was filtered through a glass filter and washed thoroughly with water to obtain oxidized cellulose having a carboxyl group amount of 1.60 mmol / g.

  Next, 1% (w / v) of hydrogen peroxide was added to the 5% (w / v) slurry of oxidized cellulose with respect to the oxidized cellulose, and the pH was adjusted to 12 with 1M sodium hydroxide. After this slurry was treated at 80 ° C. for 2 hours, it was filtered through a glass filter and thoroughly washed with water (low viscosity treatment: hydrolysis with alkali).

  When the low-viscosity 2% (w / v) oxidized cellulose slurry was treated five times with an ultra-high pressure homogenizer (20 ° C., 140 MPa), a transparent gel-like anion-modified cellulose nanofiber dispersion (1% (w / v) A B-type viscosity (60 rpm, 20 ° C.): 356 mPa · s) of the cellulose nanofiber dispersion of v) was obtained. The obtained anion-modified cellulose nanofibers had an average fiber diameter of 6 nm and an aspect ratio of 100 or more.

<Measurement method of each physical property>
(Amount of carboxyl group of oxidized cellulose)
Prepare 60 ml of 0.5% by mass slurry of oxidized cellulose, add 0.1 M hydrochloric acid aqueous solution to pH 2.5, then add 0.05 N aqueous sodium hydroxide solution dropwise until the pH reaches 11. Was calculated from the amount (a) of sodium hydroxide consumed in the neutralization step of the weak acid where the change in electrical conductivity was gradual, using the following equation.

[formula]
Amount of carboxyl group [mmol / g pulp] = a [ml] × 0.05 / weight of oxidized cellulose [g]

(Measuring method of average fiber diameter and aspect ratio)
For the average fiber diameter and average fiber length of the anion-modified cellulose nanofiber dispersion, an atomic force microscope (AFM) is used when the diameter is 20 nm or less, and a field emission scanning electron microscope (FE-SEM) is used when the diameter is 20 nm or more. 200 randomly selected fibers were analyzed. The aspect ratio was calculated using the following formula.

[formula]
Aspect ratio = average fiber length / average fiber diameter

<Production Example A2>
To a stirrer capable of mixing pulp, add 200 g of pulp (LBKP, Nippon Paper Industries Co., Ltd.) by dry weight and 264 g of sodium hydroxide by dry weight, and add water so that the pulp solid concentration is 15% by weight. added. Then, after stirring for 30 minutes at 30 ° C., the temperature was raised to 70 ° C., and 351 g of sodium monochloroacetate (in terms of active ingredient) was added. After reacting for 1 hour, the reaction product was taken out, neutralized and washed to obtain anion-modified cellulose having a carboxymethyl substitution degree of 0.15 per glucose unit. Thereafter, the anion-modified pulp was adjusted to a solid concentration of 1% (w / v) and treated three times with a high-pressure homogenizer at 20 ° C. and a pressure of 150 MPa to obtain an anion-modified cellulose nanofiber dispersion. The obtained anion-modified cellulose nanofibers had an average fiber diameter of 8 nm, an aspect ratio of 100 or more, and a B-type viscosity of 9000 mPa · s.

<Measurement method of each physical property>
(Measurement method of carboxymethyl substitution degree per glucose unit)
About 2.0 g of anion-modified cellulose nanofiber (absolutely dry) was precisely weighed and put into a 300 mL conical stoppered Erlenmeyer flask. Methanol nitrate, that is, 100 mL of methanol with 1000 mL of special grade concentrated nitric acid added, was shaken for 3 hours to convert the carboxymethyl cellulose salt (CM cellulose) into H-CM cellulose. 1.5-2.0 g of the absolutely dry H-CM-modified cellulose was precisely weighed and placed in a 300 mL conical stoppered Erlenmeyer flask. H-CM cellulose was wetted with 15 mL of 80% methanol, 100 mL of 0.1N NaOH was added, and the mixture was shaken at room temperature for 3 hours. As an indicator, using phenolphthalein was back titrated excess NaOH with 0.1N-H ₂ SO _4. The degree of carboxymethyl substitution (DS) was calculated by the following formula:

A = [(100 × F ′ − (0.1N—H ₂ SO ₄ amount) (mL) × F) × 0.1] / (absolute dry mass of H-CCM cellulose (g))
DS = 0.162 × A / (1-0.058 × A)
A: 1N-NaOH amount required for neutralizing 1 g of H-CM cellulose (mL)
F ′: Factor of 0.1N—H ₂ SO ₄ F: Factor of 0.1N—NaOH

<Production example: A3>
5 g of bleached softwood unbeaten pulp (Nippon Paper) (absolutely dried) was added to 500 ml of an aqueous solution in which 78 mg (0.5 mmol) of TEMPO (Sigma Aldrich) and 754 mg (7.4 mmol) of sodium bromide were dissolved. Stir until evenly dispersed. After adding 18 ml of 2M aqueous sodium hypochlorite solution to the reaction system, the pH was adjusted to 10.3 with 0.5N aqueous hydrochloric acid solution to start the oxidation reaction (oxidation treatment). During the reaction, the pH in the system was lowered, but a 0.5N aqueous sodium hydroxide solution was successively added to adjust the pH to 10. After reacting for 2 hours, the mixture was filtered through a glass filter and washed thoroughly with water to obtain oxidized cellulose having a carboxyl group amount of 1.7 mmol / g.

  Subsequently, when the oxidized cellulose slurry obtained above was adjusted to 1% (w / v) with water and treated five times with an ultrahigh pressure homogenizer (20 ° C., 140 MPa), a transparent gel-like anion-modified cellulose nanofiber was obtained. A dispersion (B type viscosity (60 rpm, 20 ° C.): 1400 mPa · s) of a 1% (w / v) cellulose nanofiber dispersion was obtained. The obtained anion-modified cellulose nanofibers had an average fiber diameter of 4 nm and an aspect ratio of 100 or more.

<Production example: A4>
The anion-modified cellulose nanofiber dispersion obtained in the same manner as in Production Example A3 except that the amount of sodium hypochlorite aqueous solution added was 11 ml, and the B-type viscosity of the obtained anion-modified cellulose nanofiber dispersion was 5400 mPa · s. The average fiber diameter was 7 nm and the aspect ratio was 100 or more.

<B component>
<Production Example B1-1>
501 parts of water and ethylene oxide adduct of 3-methyl-3-buten-1-ol (average number of moles of ethylene oxide added) in a glass reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen inlet tube and a dropping device 30 pieces) 500 parts (21 mol%) were 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 100 parts (79 mol%) of acrylic acid and 501 parts of water were mixed, and a mixed solution of 12 parts of ammonium persulfate and 188 parts of water were continuously added to a reaction vessel maintained at 80 ° C. for 1 hour each. It was dripped. Furthermore, the aqueous solution of the copolymer was obtained by making it react for 1 hour in the state hold | maintained at 100 degreeC. The copolymer in the liquid was a copolymer (B1-1) (weight average molecular weight 20,200, Mw / Mn 1.7).

<Production Example B1-2>
100 parts of water was charged into a glass reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen introduction tube and a dropping device, the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 75 ° C. under a nitrogen atmosphere. Thereafter, 90 parts (30 mol%) of methoxypolyethylene glycol methacrylate (average number of added moles of ethylene oxide 18), 20 parts (70 mol%) of methacrylic acid, 21 parts of water, and 0.9 part of 3-mercaptopropionic acid A mixture of monomer aqueous solution mixed with 1 part of sodium persulfate and 29 parts of water was continuously added dropwise to a reaction vessel maintained at 75 ° C. for 2 hours each. Furthermore, the aqueous solution of a copolymer was obtained by making it react for 1 hour in the state hold | maintained at 75 degreeC. The copolymer in the liquid was a copolymer (B1-2) (weight average molecular weight 26,000, Mw / Mn 2.0).

<Production Example B2-1>
501 parts of water and ethylene oxide adduct of 3-methyl-3-buten-1-ol (average number of moles of ethylene oxide added) in a glass reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen inlet tube and a dropping device 30 pieces) 500 parts (26 mol%) were 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 135 parts (74 mol%) of 2-hydroxypropyl acrylate and 501 parts of water were mixed, and a mixed liquid of 12 parts of ammonium persulfate and 188 parts of water were each maintained at 80 ° C. for 1 hour. It was dripped continuously into the container. Furthermore, the aqueous solution of the copolymer was obtained by making it react for 1 hour in the state hold | maintained at 100 degreeC. The copolymer in the liquid was a copolymer (B2-1) (weight average molecular weight 22,200, Mw / Mn 1.7).

<Production Example B3-1>
A glass reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen introduction tube, and a dropping device was charged with 501 parts of water, 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 obtained by mixing 130 parts (63 mol%) of acrylic acid, 135 parts (37 mol%) of 2-hydroxypropyl acrylate and 501 parts of water, and a mixed solution of 12 parts of ammonium persulfate and 188 parts of water, respectively. In 1 hour, it was continuously added dropwise to a reaction vessel maintained at 80 ° C. Furthermore, the aqueous solution of the copolymer was obtained by making it react for 1 hour in the state hold | maintained at 100 degreeC. The copolymer in the liquid was a copolymer (B3-1) (weight average molecular weight 12,200, Mw / Mn1.4).

<Production Example B4-1>
148 parts of water in a glass reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen introduction tube and a dropping device, and polyethylene glycol polypropylene glycol monoallyl ether (average number of added moles of ethylene oxide: 37, average of propylene oxide 94 parts (5 mol%) of 3 addition moles, random addition of ethylene oxide and propylene oxide) were charged, the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 80 ° C. in a nitrogen atmosphere. Thereafter, 35 parts (40 mol%) of methacrylic acid, 5 parts (7 mol%) of acrylic acid, 63 parts (5 mol%) of methoxypolyethylene glycol methacrylate (average number of moles of ethylene oxide added 25), 60 of hydroxypropyl acrylate Part (43 mol%), a monomer aqueous solution in which 8 parts of 3-mercaptopropionic acid and 165 parts of water were mixed, and a mixture of 3 parts of ammonium persulfate and 47 parts of water were each kept at 80 ° C. for 2 hours. It was dripped continuously into the container. Furthermore, the aqueous solution of the copolymer was obtained by making it react for 1 hour in the state hold | maintained at 100 degreeC. The copolymer in the liquid was a copolymer (B4-1) (weight average molecular weight 11,100, Mw / Mn1.5).

<Comparative Production Example 1>
As a comparative component of component A, NEOVISCO MC RM4000 (hydroxypropylmethylcellulose) manufactured by Sansho Co., Ltd. was used as component (C-1).

<Examples 1-9 and Comparative Examples 1-2>
At ambient temperature (20 ° C.), coarse aggregate, fine aggregate, cement, water and the cement admixture shown in Table 2 were added as shown in Table 1 and mixed for 90 seconds by mechanical kneading with 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 the spread of fresh concrete), air quantity JISA1128, concrete viscosity evaluation) was performed. The viscosity of the concrete was evaluated according to the following criteria by sensory evaluation by five evaluators. The test results are shown in Table 3.

<Viscosity evaluation criteria>
A: Handling is very good when the concrete is cut back with a scoop, and the separation of the concrete from the scoop is very good.
○: Good handling when the concrete is cut back with a scoop, and separation of the concrete from the scoop is good.
X: Handling when the concrete is cut back with a scoop is poor, and the concrete is not separated from the scoop.
Material separation: Separation of concrete components (not usable as concrete material)

<Underwater separation resistance evaluation>
Water is put into a cylinder made of transparent acrylic resin with a diameter of 19 cm and a height of 1 m to a height of 90 cm, and 2 kg of concrete is poured into the stainless steel beaker in 4 portions in 500 g and dropped in water. The water turbidity in the central part of the cylinder was observed and the water separation resistance was evaluated according to the following criteria.
A: There is almost no turbidity.
○: Slightly cloudy.
X: It is very muddy.

[Footnotes in Table 1]
C: 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)
3 types of cement mixed in equal amounts 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)
Additive (solid content conversion) See Tables 2 and 3

[Footnotes in Table 2]
In Table 2, the values in parentheses indicate the solid content weight% (total 100 weight%).

  In Table 3, “addition rate” of the cement admixture indicates a solid content addition rate of the admixture to the cement. SLF indicates a slump flow.

  As is clear from Table 3, the concrete of each example had a higher SLF value after 120 minutes and higher fluid retention than the concrete of Comparative Example 1. Moreover, the concrete of each Example had favorable concrete viscosity compared with the concrete of each comparative example, and was hard to isolate | separate in water. These results show that the hydraulic composition to which the additive of the present invention has been added has excellent fluidity and fluidity retention, has moderate material separation resistance even after a predetermined time, This shows that the workability can be remarkably improved.

Claims (5)

The additive for hydraulic compositions containing the following A component and B component.
<A component>
Anion-modified cellulose nanofiber that is at least one selected from the group consisting of the following (A1) to (A3) :
(A1) Oxidized cellulose nanofibers having an amount of carboxyl groups of 0.6 mmol / g to 2.0 mmol / g based on the absolutely dry weight of the oxidized cellulose nanofibers;
(A2) carboxymethylated cellulose nanofibers having a carboxymethyl substitution degree per glucose unit of carboxymethylated cellulose nanofibers of 0.01 to 0.50; and
(A3) Oxidized cellulose nanofiber or carboxymethylated cellulose nanofiber having a fiber width of 4 nm to 500 nm and an aspect ratio of 100 or more .
<B component>
The structural unit (I) derived from the monomer represented by the following general formula (1), the structural unit (II) derived from the monomer represented by the following general formula (2), and the following general formula (3) The copolymer containing at least 2 or more types of structural units chosen from the group which consists of structural unit (III) derived from the monomer represented by this.

(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.) The additive for hydraulic compositions according to claim 1, wherein the component B comprises two or more different copolymers. The additive for hydraulic compositions according to claim 1 or 2 , which is used for any of medium fluidity concrete, high fluidity concrete and underwater non-separable concrete. The additive for hydraulic compositions according to any one of claims 1 to 3 , which is used for grout or injection grout.   The hydraulic composition containing the additive for hydraulic compositions of any one of Claims 1-4.