JP2019001919A - Liquid rheology modifier - Google Patents

Abstract

To provide a liquid rheology modifier capable of exhibiting good storage stability irrespective of temperature conditions such as a high temperature and improving characteristics of a dispersion composition such as imparting good flowability and dispersibility to a dispersion composition containing water and powder such as a cement composition and to provide an application thereof.SOLUTION: There are provided a liquid rheology modifier which comprises an (A) component: a water soluble thickener, a (B) component: a dispersant and a (C) component: at least one selected from a polycarboxylic acid-based copolymer obtained by copolymerization of 5 to 90 mass% of a monomer (I), 5 to 90 mass% of a monomer (II), a monomer (III) and 0 to 50 mass% of a monomer (IV) and a salt thereof, where a content ratio (solid content) of each component to 100 mass% of the liquid rheology modifier is the (A) component: the (B) component: the (C) component is 0.1 to 10 mass%: 0.5 to 50 mass%: 0.1 to 10 mass%; and an application thereof.SELECTED DRAWING: None

Description

  The present invention relates to a liquid rheology modifier.

  Increasing the workability of the cement composition is demanded in connection with environmental factors such as a reduction in the number of workers during construction of the cement composition and an improvement in work efficiency. In particular, for a member that is difficult to use a vibrator (for example, an overcrowded reinforcement member or a synthetic structural member that is mostly closed), a self-filling cement composition having high fluidity is used to achieve the above-mentioned purpose. Useful.

  In the development of self-filling cement compositions in recent years, it is required to provide not only high fluidity but also appropriate material separation resistance and good pumpability. A liquid rheology modifier that combines a thickener aimed at imparting appropriate material separation resistance and a dispersant for hydraulic composition aimed at imparting long-term high fluidity (such as a high-performance AE water reducing agent) Since the above properties can be imparted to lower quality cement compositions, they have been utilized in recent years.

  Patent Document 1 discloses that a powdered rheology modifier containing an anionic aromatic compound, a cationic surfactant, and silica fume can adjust liquid rheological properties such as viscosity in a slurry composed of water and powder. Has been. Patent Document 2 discloses a high-flowing mortar in which aggregate separation is suppressed by adding a predetermined amount of a cellulose ether having a predetermined aqueous solution viscosity and a microbial fermentation thickening polysaccharide to a base material having a predetermined cement / aggregate ratio. It is disclosed that the composition can be made. Patent Document 3 discloses that an additive for a cement composition containing a polycarboxylic acid copolymer, a water-soluble cellulose ether, and an antifoaming agent can suppress bleeding, improve workability, and improve material separation resistance. Is disclosed. Patent Document 4 describes that a concrete composition using an admixture containing a thickener and a dispersant composed of hydroxypropyl highly substituted hydroxypropylmethylcellulose has reduced bleeding and good workability. Yes. Patent Document 5 contains a predetermined amount of aggregate, cement, water, a high-performance AE water reducing agent mainly composed of a polycarboxylic acid-based compound, and a thickener mainly composed of a water-soluble cellulose ether. The underwater inseparable concrete thus disclosed is disclosed to have high flow and high strength.

JP 2007-321064 A JP 2003-313069 A International Publication No. 2003/024884 JP 2014-101243 A JP 2001-261419 A

  However, with the powdery rheology modifier of Patent Document 1, the desired effect may not be obtained unless the blending of the modifier and the hydraulic composition is adjusted according to the water cement ratio. In order to satisfy the demand associated with the reduction in quality of concrete, it is required that it can be easily applied to a wide range of water-cement ratios. However, the modifier of Patent Document 1 has a problem that it involves complicated work. It was.

  Although the high fluidity mortar composition of patent document 2 can maintain fluidity | liquidity for a long time by addition of microbial fermentation polysaccharide, there existed a problem that setting time was significantly delayed and workability was deteriorated.

  The additive for cement composition of Patent Document 3 has poor compatibility between the water-soluble cellulose ether and the polycarboxylic acid copolymer in a high temperature environment of about 40 ° C. and may be separated into a solid and liquid. It was difficult to use the additive in summer. When the water-soluble cellulose ether is increased, the compatibility may be further deteriorated, and there is a limit to imparting high viscosity to the cement composition.

  The admixture of Patent Document 4 has poor cement fluidity sustainability, and there is a risk that the flowability may drop rapidly over time after the admixture has been added. This is expected to have a great influence on the pumpability when placing the cement composition.

  The water-soluble cellulose ether of Patent Document 5 has very low solubility, and the solubility is easily affected by the amount of a dispersant used in combination such as an AE water reducing agent and the salt contained in the dispersion during dispersion. In particular, many of the AE water reducing agents used for suppressing bleeding and improving the concrete condition contain a large amount of lignin sulfonate and sodium gluconate, and such AE water reducing agent and water-soluble cellulose ether alone. It is difficult to mix.

  In view of the above problems, the present invention can exhibit good storage stability regardless of high temperature isothermal conditions, and can provide a dispersion composition containing water and powder such as a cement composition at various blending ratios. An object of the present invention is to provide a liquid rheology modifier capable of improving the properties of the dispersion composition, such as imparting good fluidity and dispersibility, and use thereof.

  As a result of intensive studies to achieve the above object, the present inventors have found that a water-soluble thickener, a dispersant, and a polycarboxylic acid copolymer having a predetermined structure or a salt thereof each having a predetermined content The composition contained in the above has good storage stability regardless of temperature conditions even if the mixing ratio of water-soluble thickener and dispersant is arbitrarily set, and is fluid for cement compositions with a wide range of water cement ratios. Has been found to contribute to the improvement of workability and the suppression of bleeding.

  That is, the present invention provides the following [1] to [11].

（式中、Ｒ¹は、炭素原子数２〜５のアルケニル基を表す。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。ｎ１は、オキシアルキレン基の平均付加モル数であり、１〜１００の数を表す。Ｒ²は、水素原子又は炭素原子数１〜３０の炭化水素基を表す。）

（式中、Ｒ³、Ｒ⁴及びＲ⁵は、それぞれ独立に、水素原子又は炭素原子数１〜３のアルキル基を表す。ｍは、０〜２の数を表す。Ａ²Ｏ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。ｎ２は、オキシアルキレン基の平均付加モル数であり、１〜１００の数を表す。Ｘは、水素原子又は炭素原子数１〜３０の炭化水素基を表す。）
〔２〕前記単量体（ＩＩ）が、前記一般式（２）中のｎ２が１である単量体（ＩＩａ）及び前記一般式（２）中のｎ２が２〜１００である単量体（ＩＩｂ）を含む、〔１〕に記載の液状レオロジー改質剤。
〔３〕前記単量体（ＩＩａ）の前記単量体（ＩＩｂ）に対する含量比（ＩＩａ）／（ＩＩｂ）が１／９９〜９９／１である、〔２〕に記載の液状レオロジー改質剤。
〔４〕前記ポリカルボン酸系共重合体及びその塩の重量平均分子量が、ポリエチレングリコール換算で５，０００〜６０，０００である、〔１〕〜〔３〕のいずれか１項に記載の液状レオロジー改質剤。
〔５〕前記（Ａ）成分が、水溶性セルロース系増粘剤である、〔１〕〜〔４〕のいずれか１項に記載の液状レオロジー改質剤。
〔６〕水溶性セルロース系増粘剤が、アルキルセルロース、ヒドロキシアルキルセルロース、ヒドロキシアルキルアルキルセルロース、カルボキシメチルセルロース及びそれらの塩から選ばれる少なくとも１種を含む、〔５〕に記載の液状レオロジー改質剤。
〔７〕水溶性セルロース系増粘剤は、その構成単糖１単位当たりの置換度が０．５〜２．５である、〔５〕又は〔６〕に記載の液状レオロジー改質剤。
〔８〕〔１〕〜〔７〕のいずれか１項に記載の剤を含有する分散組成物。
〔９〕〔１〕〜〔７〕のいずれか１項に記載の剤を含有するセメント組成物。
〔１０〕〔１〕〜〔７〕のいずれか１項に記載の剤を含有する石膏組成物。
〔１１〕〔１〕〜〔７〕のいずれか一項に記載の剤を含有する染料組成物。 [1] Component (A): Water-soluble thickener,
Component (B): lignin sulfonic acid dispersant, oxycarboxylic acid dispersant, naphthalene sulfonic acid dispersant, aminosulfonic acid dispersant, and polycarboxylic acid dispersant (however, (C) component polycarboxylic acid At least one dispersing agent selected from (excluding copolymers and salts thereof), and component (C): monomer (I) represented by the following general formula (1) 5 to 90% by mass, the following general formula Monomer (II) represented by (2) 5 to 90% by mass, unsaturated monocarboxylic acid monomer (III) 1 to 50% by mass, and monomers (I) to (III) 1 or 2 or more monomers selected from the group consisting of, or other monomers (IV) copolymerizable with these polymers, and a polycarboxylic acid copolymer obtained by copolymerization of 0 to 50% by mass; Including at least one selected from the salts thereof,
The content ratio (solid content) of each component with respect to 100% by mass of the liquid rheology modifier is (A) component: (B) component: (C) component = 0.1-10% by mass: 0.5-50% by mass. : 0.1 to 10% by mass
Liquid rheology modifier.

(In the formula, R ¹ represents an alkenyl group having 2 to 5 carbon atoms. A ¹ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. N1 represents an oxyalkylene group. (The average number of moles added represents a number of 1 to 100. R ² represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.)

(Wherein, R ^3, R ⁴ and R ⁵ are each independently, .m represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, the .A ² O representing the number of 0 to 2, the same Or, differently, it represents an oxyalkylene group having 2 to 18 carbon atoms, n2 is an average added mole number of the oxyalkylene group, and represents a number of 1 to 100. X is a hydrogen atom or 1 to 1 carbon atoms. Represents 30 hydrocarbon groups.)
[2] The monomer (II) is a monomer (IIa) in which n2 in the general formula (2) is 1, and a monomer in which n2 in the general formula (2) is 2 to 100 The liquid rheology modifier according to [1], comprising (IIb).
[3] The liquid rheology modifier according to [2], wherein the content ratio (IIa) / (IIb) of the monomer (IIa) to the monomer (IIb) is 1/99 to 99/1. .
[4] The liquid according to any one of [1] to [3], wherein the polycarboxylic acid copolymer and a salt thereof have a weight average molecular weight of 5,000 to 60,000 in terms of polyethylene glycol. Rheology modifier.
[5] The liquid rheology modifier according to any one of [1] to [4], wherein the component (A) is a water-soluble cellulose thickener.
[6] The liquid rheology modifier according to [5], wherein the water-soluble cellulose thickener contains at least one selected from alkyl cellulose, hydroxyalkyl cellulose, hydroxyalkylalkyl cellulose, carboxymethyl cellulose, and salts thereof. .
[7] The liquid rheology modifier according to [5] or [6], wherein the water-soluble cellulose thickener has a substitution degree of 0.5 to 2.5 per unit monosaccharide.
[8] A dispersion composition containing the agent according to any one of [1] to [7].
[9] A cement composition containing the agent according to any one of [1] to [7].
[10] A gypsum composition containing the agent according to any one of [1] to [7].
[11] A dye composition containing the agent according to any one of [1] to [7].

  The liquid rheology modifier of the present invention can exhibit good storage stability regardless of temperature conditions, and contains water and powder such as cement composition, dye composition, gypsum composition, etc. in various blending ratios. Thus, good fluidity can be imparted to various dispersion compositions, and the properties of the dispersion composition can be improved. The cement composition containing the liquid rheology modifier of the present invention has good fluidity retention and moderate viscosity, can exhibit good workability and pumpability, and is suitably used in various applications. obtain.

FIG. 1 is a graph showing the correlation (W / C = 55%) between the addition rate of the liquid rheology modifier and the slump flow immediately after kneading for Examples 2 and 3 and Comparative Example 4. FIG. 2 is a graph showing the correlation between the addition rate of the liquid rheology modifier and the slump flow immediately after kneading (W / C = 45%) for Examples 2 and 3 and Comparative Example 4.

  Hereinafter, modes for carrying out the present invention will be described. However, the present invention is not limited to the following embodiments and exemplifications, and can be arbitrarily modified and implemented without departing from the scope of the claims of the present invention and its equivalent scope.

[1. Liquid rheology modifier]
The liquid rheology modifier of this invention contains (A) component, (B) component, and (C) component at least.

<(A) component: Water-soluble thickener>
(A) A component is a water-soluble thickener. The component (A), together with the components (B) and (C), can preferably impart an appropriate viscosity to a dispersion obtained by dispersing powder in water such as a cement composition. This can also provide any material separation resistance and liquid rheological properties. As the component (A), it is preferable that the composition obtained by blending with the components (B) and (C) has good compatibility, and can maintain viscosity and fluidity even after storage for a long time.

  The water-soluble thickener is not particularly limited as long as it is water-soluble and can increase the viscosity of the aqueous solution after dissolution compared to that before dissolution. For example, the water-soluble thickener containing a hydroxy group is increased. Examples thereof include a thickener, a water-soluble polyvinyl alcohol-based thickener, and a water-soluble polysaccharide derivative-based thickener. Since it is easy to adjust the water solubility and the degree of increasing the viscosity, it is preferably a polysaccharide derivative thickener, more preferably a water soluble cellulose thickener. Examples of the water-soluble cellulose thickener include alkyl celluloses such as methyl cellulose, ethyl cellulose, and carboxymethyl cellulose; hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose; hydroxyalkyls such as hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl ethyl cellulose. Examples thereof include alkyl cellulose and salts thereof. Examples of the water-soluble polyvinyl alcohol thickener include polyvinyl alcohol and salts thereof. The water-soluble cellulose thickener is preferably at least one selected from alkyl cellulose, hydroxyalkyl cellulose, hydroxyalkylalkyl cellulose, carboxymethyl cellulose and salts thereof, hydroxyalkyl cellulose, hydroxyalkylalkyl cellulose, carboxymethyl cellulose and the like At least one selected from these salts is more preferred, and hydroxymethylcellulose and hydroxypropylmethylcellulose are more preferred.

(Degree of substitution)
In the water-soluble cellulose thickener, a hydrogen atom of at least one hydroxyl group in the constituent monosaccharide is usually substituted with a substituent. The substituent may be any group other than a hydrogen atom, for example, an alkyl group having 1 to 5 carbon atoms such as a methyl group or an ethyl group, or a group having a hydroxyl group (such as a hydroxyethyl group or a hydroxypropyl group). A hydroxyalkyl group having 1 to 5 carbon atoms). The water-soluble cellulose-based thickener may have one or more types of substituents as long as appropriate solubility in kneaded water and liquid rheology can be obtained. The degree of substitution (etherification degree) per unit monosaccharide constituting the water-soluble cellulose-based thickener is preferably 0.5 or more, more preferably 1.0 or more, and 2.5 or less, and further 2.0 or less. preferable.

(Polysaccharide)
The raw material of the water-soluble cellulose thickener is usually a polysaccharide. The polysaccharide is not particularly limited, and examples thereof include cellulose; starch; rhizome polysaccharides such as konjac mannan and trooaoi sticky substances; sap polysaccharides such as gum arabic, tragacanth, and karaya; Seed polysaccharides such as gums; seaweed polysaccharides such as agar, carrageenan and algin; animal polysaccharides such as chitin, chitosan heparin and chondroitin sulfate; and microbial polysaccharides such as dextran and xanthan gum.

(Molecular weight of water-soluble thickener)
For the weight average molecular weight of the water-soluble thickener, for example, from the viewpoint of obtaining solubility in water and pumpability in a cement composition, the lower limit is preferably 100,000 or more, more preferably 200,000 or more. Preferably, 500,000 or more is more preferable, and the upper limit is preferably 5,000,000 or less, more preferably 2,000,000 or less, and further preferably 1,000,000 or less.

The weight average molecular weight can be measured by a known method in which polyethylene glycol conversion is performed by gel permeation chromatography (GPC). The following conditions can be given as GPC measurement conditions. The weight average molecular weight described in the present specification is a value measured under these conditions.
Measuring device: manufactured by Tosoh Column used: Shodex Column OH-pak SB-806HQ, SB-804HQ, SB-802.5HQ
Eluent: 0.05 mM sodium nitrate / acetonitrile 8/2 (v / v)
Reference material: Polyethylene glycol (Tosoh, GL Science)
Detector: differential refractometer (manufactured by Tosoh)
Calibration curve: Polyethylene glycol standard

(Viscosity of water-soluble thickener)
The B type viscosity at 20 ° C. of a 1% by weight aqueous dispersion of a water-soluble thickener is preferably 10 mPa · s or more, more preferably 50 mPa · s or more, and even more preferably 100 mPa · s, The upper limit is preferably 100,000 mPa · s or less, more preferably 50,000 mPa · s or less, and even more preferably 10,000 mPa · s or less. When the viscosity is less than 10 mPa · s, there is a possibility that the viscosity of the liquid rheology modifier is not appropriate, and there is a possibility that appropriate water retention and material separation resistance may not be given to the cement composition. On the other hand, when it exceeds 100,000 mPa · s, the water-soluble thickener has poor solubility in water and tends to form an aggregate.

  Component (A) may be one type of water-soluble thickener or a combination of two or more types of water-soluble thickeners.

  The dosage form of the water-soluble thickener is not particularly limited, and any of solid forms such as powders and particles and liquid forms such as solutions, slurries, and dispersions may be used. When the water-soluble thickener is powder, glyoxal or the like may be added in advance and then added to the components (B) and (C). As a result, mamako can be prevented. An antifoaming agent such as tributyl phosphate or a polyalkylene glycol derivative may be used in combination with the component (A). (A) When a component contains the component which has air entrainment property, for example, hydroxypropyl methylcellulose, combined use of the said antifoamer is preferable.

<Component (B): Dispersant>
(B) A component is a dispersing agent. The liquid rheology modifier of the present invention has a high degree of freedom in selecting a dispersant as the component (B) by including the components (A) to (C) in a specific content ratio. Thereby, the liquid rheology modifier of this invention can be used suitably with respect to the cement composition of a wide water cement ratio, and the mixing | blending control of the liquid rheology modifier according to the performance of an aggregate is easy.

  Although a dispersing agent is not specifically limited, For example, AE water reducing agent (For example, a lignin sulfonic acid type dispersing agent, an oxycarboxylic acid type dispersing agent), a naphthalene sulfonic acid type dispersing agent, an aminosulfonic acid type dispersing agent, and mentioned later (C And polycarboxylic acid-based dispersants other than the component).

  Component (B) may be one type of dispersant or a combination of two or more types of dispersants.

<(C) component: polycarboxylic acid copolymer and salt thereof>
Component (C) is at least one compound selected from polycarboxylic acid copolymers and salts thereof described below. The component (C) exhibits good affinity with both the components (A) and (B) because the polycarboxylic acid copolymer used in the present invention has an appropriate number. Since it has a carboxylic acid group and an appropriate number of hydroxyl groups, lignin sulfonic acid, oxycarboxylic acid, naphthalene sulfonic acid, aminosulfonic acid contained in component (B) and water-soluble thickening contained in component (A) It is presumed that this is because of the excellent affinity with both hydroxyl groups contained in the agent.

(Polycarboxylic acid copolymer)
The polycarboxylic acid copolymer is a copolymer obtained by copolymerization of the monomers (I) to (III) or (I) to (IV). The blending ratio of the monomer (I) when obtaining the copolymer is 5 to 90% by mass, preferably 8 to 80% by mass, and more preferably 10 to 70% by mass. The blending ratio of the monomer (II) is 5 to 90% by mass, preferably 10 to 70% by mass, and more preferably 15 to 50% by mass. The compounding ratio of the monomer (III) is 1 to 50% by mass, preferably 2 to 40% by mass, and more preferably 3 to 25% by mass. The compounding ratio of the monomer (IV) is 0 to 50% by mass, preferably 0 to 30% by mass. Therefore, the blending ratio is 5 to 90% by mass of monomer (I), 5 to 90% by mass of monomer (II), 1 to 50% by mass of monomer (III), and monomer (IV), respectively. A combination of 0 to 50% by weight is preferable, monomer (I) 8 to 80% by weight, monomer (II) 10 to 70% by weight, monomer (III) 2 to 40% by weight, and monomer (IV) A combination of 0 to 50 or 0 to 30% by mass is more preferable, monomer (I) 10 to 70% by mass, monomer (II) 15 to 50% by mass, monomer (III) 3 to 3% A combination of 25% by mass and monomer (IV) 0 to 50 or 0 to 30% by mass is more preferable. The blending ratio of each of the above monomers is the blending ratio of the monomer (I) + the blending ratio of the monomer (II) + the blending ratio of the monomer (III) + the monomer (IV) = 100% by mass. It is a blending rate when it is said.

（式中、Ｒ¹は、炭素原子数２〜５のアルケニル基を表す。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。ｎ１は、オキシアルキレン基の平均付加モル数であり、１〜１００の数を表す。Ｒ²は、水素原子又は炭素原子数１〜３０の炭化水素基を表す。） (Monomer (I) represented by general formula (1))
Monomer (I) is represented by the following general formula (1).

(In the formula, R ¹ represents an alkenyl group having 2 to 5 carbon atoms. A ¹ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. N1 represents an oxyalkylene group. (The average number of moles added represents a number of 1 to 100. R ² represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.)

R ¹ in the general formula (1) represents an alkenyl group having 2 to 5 carbon atoms. The number of carbon atoms of the alkenyl group is preferably 3-5. Specific examples of R ¹ include, but are not limited to, an allyl group, a methallyl group, a residue of 3-methyl-3-buten-1-ol, and the like.

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 include oxyethylene group (ethylene glycol unit), oxypropylene group (propylene glycol unit), oxybutylene group (butylene glycol unit), oxyethylene group (ethylene glycol unit), oxypropylene Groups (propylene glycol units) are preferred.

The above “same or different” means that when A ¹ O is contained in the general formula (1) (when n1 is 2 or more), each A ¹ O may be the same oxyalkylene group. Meaning that it may be different (two or more) oxyalkylene groups. In the case where a plurality of A ¹ O are contained in the general formula (1), the oxyethylene group (ethylene glycol unit), the oxypropylene group (propylene glycol unit), and the oxybutylene group (butylene glycol unit) are used. A mode in which two or more selected oxyalkylene groups are mixed is mentioned, a mode in which oxyethylene groups (ethylene glycol units) and oxypropylene groups (propylene glycol) are mixed, or oxyethylene groups (ethylene glycol units) and oxybutylene. It is preferably an embodiment in which a group (butylene glycol unit) is mixed, and more preferably an embodiment in which an oxyethylene group (ethylene glycol unit) and an oxypropylene group (propylene glycol unit) are mixed. 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.

  N1 in General formula (1) is the average addition mole number of an oxyalkylene group, and represents the number of 1-100. n1 is preferably 1 to 50, more preferably 5 to 50, and still more preferably 8 to 50. The average number of moles added means the average number of moles of alkylene glycol units added to 1 mole of monomer.

R ² in the general formula (1) represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. When the number of carbon atoms increases, the cement dispersibility of the liquid rheology modifier may not be sufficiently exhibited. Therefore, R ² is preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom or the number of carbon atoms A hydrocarbon group of 1 to 5 is more preferable, and a hydrogen atom or a methyl group is more preferable.

  As a manufacturing method of monomer (I), the method of adding 1-100 mol of alkylene oxides to unsaturated alcohols, such as allyl alcohol, methallyl alcohol, 3-methyl-3-buten-1-ol, is mentioned, for example. It is done.

  As the monomer (I), for example, (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 methallyl 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 3-methyl-3-butenyl ether is mentioned. As the monomer (I), one or more of these can be used. From the balance of hydrophilicity and hydrophobicity, an ethylene oxide adduct of 3-methyl-3-buten-1-ol is used. Or (poly) ethylene glycol (meth) allyl ether is preferable. Also in the specific example of the monomer (I), the average added mole number of the oxyalkylene group (alkylene glycol unit) is preferably 1 to 70, more preferably 5 to 70, and still more preferably 8 to 70. In the present specification, “(poly)” means that one or two or more constituent elements or raw materials described immediately after that are bonded, and “(meth) allyl” means “allyl or Means "methallyl".

  The monomer (I) may be a single monomer represented by the general formula (1) or a combination of two or more.

  Although the manufacturing method in particular of monomer (I) is not restrict | limited, For example, 1-100 mol of alkylene oxide is added to unsaturated alcohol, such as allyl alcohol, methallyl alcohol, and 3-methyl-3-buten-1-ol. The method of doing is mentioned.

(Monomer (II) represented by general formula (2))
Monomer (II) is represented by the following general formula (2).

(Wherein, R ^3, R ⁴ and R ^5, .m representing each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, the .A ² O representing the number of 0 to 2, identical or Differently, it represents an oxyalkylene group having 2 to 18 carbon atoms, n2 is an average added mole number of the oxyalkylene group, and represents a number of 1 to 100. X is a hydrogen atom or 1 to 30 carbon atoms. Represents a hydrocarbon group of

R < ³ >, R < ⁴ > and R < ⁵ > in General formula (2) represent a hydrogen atom or a C1-C3 alkyl group each independently.

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

The above “same or different” means that when A ² O is contained in the general formula (2) (when n2 is 2 or more), each A ² O may be the same oxyalkylene group. Meaning that it may be different (two or more) oxyalkylene groups. In the case where a plurality of A ² O are contained in the general formula (2), the embodiment is selected from the group consisting of an oxyethylene group (ethylene glycol), an oxypropylene group (propylene glycol), and an oxybutylene group (butylene glycol unit). A mode in which two or more oxyalkylene groups are mixed is mentioned, a mode in which oxyethylene groups (ethylene glycol units) and oxypropylene groups (propylene glycol units) are mixed, or oxyethylene groups (ethylene glycol units) and oxybutylene groups (Butylene glycol unit) is preferably mixed, and an oxyethylene group (ethylene glycol unit) and oxypropylene group (propylene glycol unit) are more 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.

  N2 in General formula (2) is the average addition mole number of an oxyalkylene group, and represents the number of 1-100. n2 is preferably 1 to 50. The average number of moles added means the average number of moles of alkylene glycol units added to 1 mole of monomer.

  Monomer (II) may be one type of monomer represented by the general formula (2) or a combination of two or more types. Monomer (II) preferably includes a combination of two types of monomers (IIa) and (IIb) having different average addition mole numbers of oxyalkylene groups, and more preferably the combination. Thereby, the cement composition can exhibit excellent and fluidity even after a long time has elapsed after the addition of the liquid rheology modifier. The added mole number n2a of the monomer (IIa) is 1, and the average added mole number n2b of the monomer (IIb) is preferably 2 to 100, more preferably 5 to 50.

  When the monomer (II) is the monomer (IIa) and (IIb), the mass ratio (the total is 100 mass%) is (IIa) / (IIb) is (1 to 99) / (99-1) is preferred, (20-80) / (80-20) is more preferred, and (40-70) / (60-30) is even more preferred.

  X in the general formula (2) represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. If the number of carbon atoms is increased, the cement dispersibility of the liquid rheology modifier may not be sufficiently exhibited. Therefore, X is preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom or the number of carbon atoms is 1 The hydrocarbon group of ˜5 is more preferable, and a hydrogen atom or a methyl group is more preferable.

  Examples of the monomer (II) include an unsaturated monocarboxylic acid such as (meth) acrylate (hereinafter, “(meth) acrylate” means “acrylate or methacrylate”), and (poly) ethylene glycol. , (Poly) ethylene (poly) propylene glycol, (poly) ethylene (poly) butylene glycol, methoxy (poly) ethylene glycol, methoxy (poly) ethylene (poly) propylene glycol, methoxy (poly) ethylene (poly) butylene glycol, etc. Of (poly) alkylene glycols. Specifically, for example, (poly) ethylene glycol (meth) acrylate, (poly) ethylene (poly) propylene glycol (meth) acrylate, (poly) ethylene (poly) butylene glycol (meth) acrylate, methoxy (poly) ethylene Such as glycol (meth) acrylate, methoxy (poly) ethylene (poly) propylene glycol (meth) acrylate, methoxy (poly) ethylene (poly) butylene glycol (meth) acrylate, (poly) propylene glycol (meth) acrylate, ) Alkylene glycol (meth) acrylate. As the monomer (II), one or a combination of two or more of these can be used, but (poly) alkylene glycol (meth) acrylate is preferably used, and (poly) ethylene glycol (meth) It is more preferable to use acrylate, methoxy (poly) ethylene glycol (meth) acrylate, (poly) propylene glycol (meth) acrylate (for example, hydroxypropyl acrylate). The average number of added moles of (poly) alkylene glycol is preferably 1-50. When monomer (IIa) is (poly) alkylene glycol (meth) acrylate, the number of added moles of the oxyalkylene group is 1, and when monomer (IIb) is (poly) alkylene glycol, When the monomer (IIb) is methoxy (poly) ethylene glycol (meth) acrylate, the number of added moles of the oxyalkylene group is preferably 2 to 100, and more preferably 5 to 50.

(Unsaturated monocarboxylic acid monomer (III))
Examples of the unsaturated monocarboxylic acid monomer (III) include carboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, and salts thereof (for example, monovalent metal salts, divalent metal salts, ammonium salts, Organic amine salt). Monomer (III) may be one of these or a combination of two or more thereof, and among them, it is preferable to contain acrylic acid or a salt thereof, methacrylic acid or a salt thereof. When acrylic acid or its salt and methacrylic acid or its salt are used in combination, the mass ratio of acrylic acid or its salt (III-1) to methacrylic acid or its salt (III-2) (total of 100% by mass) [(III-1) / (III-2)] is preferably (1 to 50%) / (99% to 50%). Monomer (III) may be one type of the compound group as described above, or may be a combination of two or more types.

(Monomer (IV) other than (I) to (III))
The monomer (IV) is not particularly limited as long as it is a monomer copolymerizable with one or more monomers selected from the group consisting of monomers (I), (II) and (III). . The monomer (IV) does not include the monomer (I), the monomer (II), and the monomer (III).

  Examples of the monomer (IV) include the following monomers. In addition, monomers (I) to (III) are not included in the following examples of monomers. Monomer (IV) may be one type or a combination of two or more types.

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及び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 ester of (poly) oxyalkylene alkyl ether or (poly) oxyalkylene alkylamine 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 amides, diesters, diamides;
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 (poly) alkylene alkyl ethers 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 unsaturated monocarboxylic acids such as (meth) acrylic acid;
(Poly) ethylene glycol monomethacrylate, (poly) propylene glycol monomethacrylate, (poly) in which 1 to 500 mol of alkylene oxide having 2 to 18 carbon atoms is added to unsaturated monocarboxylic acids such as (meth) acrylic acid Butylene glycol monomethacrylate, etc .;

(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 1,4-butanediol mono (meth) acrylate, 1,5-pentanediol mono (meth) acrylate, 1,6-hexanediol mono (meth) acrylate;
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;
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; 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).

  In obtaining a polycarboxylic acid copolymer and a salt thereof, if necessary, a monomer other than monomer (I), monomer (II), monomer (III) and monomer (IV) The body may be used.

(Polycarboxylic acid copolymer salt)
Examples of the salt of the polycarboxylic acid copolymer include monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts of the above copolymer.

(Production method)
The polycarboxylic acid copolymer and the salt thereof can be produced by copolymerizing each predetermined monomer simultaneously or sequentially by a known method. Examples of the method include polymerization methods such as polymerization in a solvent and bulk polymerization.

  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 or the copolymer to be obtained, it is preferable to use one or more selected from the group consisting of water and lower alcohols, and it is more preferable to use water among them.

  When performing a polymerization reaction 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.

  The polymerization initiator that can be used for the polymerization reaction is not particularly limited. Examples of the polymerization initiator that can be used for the polymerization reaction in an aqueous solvent include persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; water-soluble organic peroxides such as t-butyl hydroperoxide; Examples include peroxides such as hydrogen oxide. In this case, an accelerator such as sodium hydrogen sulfite and a mol salt can be used in combination. When copolymerization is performed in a solvent such as a lower alcohol, aromatic hydrocarbon, alicyclic or aliphatic hydrocarbon, ester or ketone, for example, a peroxide such as benzoyl peroxide or lauryl peroxide. Hydroperoxides such as cumene peroxide; aromatic azo compounds such as azobisisobutyronitrile can be used as the polymerization initiator. Under the present circumstances, promoters, such as an amine compound, and reducing agents, such as ascorbic acid, can also be used together. What is necessary is just to select suitably the polymerization initiator which can be used when performing a polymerization reaction 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 30 to 120 ° C.

  In the polymerization reaction, the molecular weight may be adjusted using a chain transfer agent as necessary. Examples of the chain transfer agent include known compounds such as mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, octyl thioglycolate, or 2-mercaptoethanesulfonic acid. Thiol compounds; phosphorous acid, hypophosphorous acid, or salts thereof (for example, sodium hypophosphite, potassium hypophosphite), sulfurous acid, hydrogen sulfite, dithionite, metabisulfite, and salts thereof (For example, sodium sulfite, potassium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium dithionite, potassium dithionite, sodium metabisulfite, potassium metabisulfite) and lower oxides thereof and salts thereof . A chain transfer agent may be used individually by 1 type, and may use 2 or more types together. Furthermore, in order to adjust the molecular weight of the polycarboxylic acid copolymer and its salt, in addition to the monomers (I) to (IV), monomers having higher chain transfer properties (V ) Is also effective. Examples of the monomer (V) having a high chain transfer property include (meth) allylsulfonic acid (salt) monomers. The blending ratio of the monomer (V) is usually 20% by mass or less and preferably 10% by mass or less in the polycarboxylic acid copolymer or a salt thereof. The blending ratio of the monomer (V) is as follows: the blending ratio of the monomer (I) + the blending ratio of the monomer (II) + the blending ratio of the monomer (III) + the monomer (IV). The blending ratio when the blending ratio is 100% by mass.

When carrying out the polymerization reaction in an aqueous solvent when obtaining the copolymer, the pH during the polymerization reaction is usually strongly acidic due to the influence of the monomer having an unsaturated bond, but it may be adjusted to an appropriate pH. . An acidic substance can be used for adjusting the pH, and examples of the acidic substance include phosphoric acid, sulfuric acid, nitric acid, alkyl phosphoric acid, alkyl sulfuric acid, alkyl sulfonic acid, and (alkyl) benzene sulfonic acid. The acidic substance is preferably phosphoric acid because of its advantages such as having a pH buffering action. In order to eliminate the instability of the ester bond of the ester monomer, the pH of the polymerization reaction is preferably 2 to 7. An alkaline substance may be used for adjusting the pH, and examples thereof include NaOH and Ca (OH) ₂ . The pH adjustment may be performed on the monomer before the polymerization reaction or on the copolymer solution after the polymerization reaction. Moreover, an alkaline substance may be added before the polymerization reaction to perform the polymerization reaction, and then the pH of the copolymer obtained may be adjusted.

(Molecular weight)
The weight average molecular weight of the polycarboxylic acid copolymer and its salt is preferably 5,000 or more. If it is less than 5,000, the liquid rheology modifier may not exhibit the desired effect as a cement dispersant. For example, even when added to a cement composition, there is a risk that a water reduction rate exceeding that of an AE water reducing agent such as a lignin sulfonic acid dispersant or an oxycarboxylic acid dispersant cannot be obtained, and fluidity or workability is not improved. is there. The upper limit of the weight average molecular weight is preferably 50,000 or less. If it exceeds 50,000, the cohesive action is exhibited in the cement composition, which may lead to a decrease in workability. Therefore, the weight average molecular weight is preferably 5,000 to 50,000, and more preferably 8,000 to 40,000.

(Molecular weight distribution)
The molecular weight distribution (Mw / Mn) of the polycarboxylic acid copolymer or salt thereof is preferably 1.2 or more, and more preferably 1.4 or more. The upper limit is preferably 3.0 or less, and more preferably 2.5 or less. Therefore, Mw / Mn is preferably 1.2 to 3.0, and more preferably 1.4 to 2.5.

  Component (C) may be one type selected from polycarboxylic acid copolymers and salts thereof, or a combination of two or more types.

<(D) component: (poly) alkylene glycol alkenyl ether monomer>
The liquid rheology modifier of this invention may contain (D) component. The component (D) is a (poly) alkylene glycol alkenyl ether monomer. When the liquid rheology modifier of the present invention contains the component (D), the obtained liquid rheology modifier improves the state of the cement composition, for example, an appropriate increase in free water, and improves workability. be able to.

  Specific examples and preferred examples of the (poly) alkylene glycol alkenyl ether monomer are the same as the specific examples and preferred examples of the compound represented by the general formula (1) as the monomer (I). The (poly) alkylene glycol alkenyl ether monomer may be the same as or different from the monomer (I).

  Component (D) may be one type of (poly) alkylene glycol alkenyl ether monomer or a combination of two or more types.

  The content ratio of the component (D) in the liquid rheology modifier of the present invention is preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 100% by mass of the component (C). It is 20 mass% or less. When it exceeds 30% by mass, the dispersibility in the cement composition may not be sufficiently exhibited, which is not preferable. Moreover, in order to obtain the workability improvement effect by the component (D), the lower limit is usually 0.1% by mass.

  The component (D) may be blended with other components separately from the component (C), or may be blended with the component (C). For example, there may be a residue of the monomer (I) that has not been copolymerized during the production of the polycarboxylic acid copolymer or salt thereof, and these may be used as the components (C) and (D). May be. When producing the polycarboxylic acid copolymer or its salt, the polymerization reaction is stopped when the monomer (I) used as a raw material remains separately from the polycarboxylic acid copolymer or its salt. By doing so, a composition containing a (poly) alkylene glycol alkenyl ether monomer and a polycarboxylic acid copolymer or a salt thereof can be obtained. The point at which the polymerization reaction is stopped can be determined according to the blending ratio of the monomer (I) to the polycarboxylic acid copolymer or salt thereof. That is, when the residual amount of the (poly) alkylene glycol alkenyl ether monomer relative to the polycarboxylic acid copolymer or salt thereof is preferably 80% by mass or less, more preferably 60% by mass or less. To stop. The polymerization reaction is stopped when the lower limit of the residual amount is usually 1% by mass.

<(E) component: water-soluble polyalkylene glycol in which both terminal groups are hydrogen atoms>
The liquid rheology modifier of this invention may contain (E) component. Component (E) is a water-soluble polyalkylene glycol in which both terminal groups are hydrogen atoms. That both terminal groups are hydrogen atoms means that the terminal of the main chain is a hydrogen atom, that is, the terminal of the main chain is not substituted with a substituent other than a hydrogen atom. Water-soluble means soluble in water.

  Examples of the water-soluble polyalkylene glycol in which both terminal groups are hydrogen atoms include polyethylene glycol, polypropylene glycol, polyethylene polypropylene glycol, polyethylene polybutylene glycol, and the like, and polyethylene glycol is preferable.

  300-2,000 are preferable and, as for the weight average molecular weight of water-soluble polyalkylene glycol whose both terminal groups are hydrogen atoms, 300-1,000 are more preferable.

  The component (E) may be a water-soluble polyalkylene glycol in which one type of both terminal groups is a hydrogen atom, or a combination of two or more types.

  The content ratio of the component (E) in the liquid rheology modifier of the present invention is usually less than 1% by weight with respect to the component (C). Although a minimum is not specifically limited, Usually, it is 0.001 weight% or more with respect to (C) component.

  The component (E) may be blended with other components separately from the component (C), or may be blended with the component (C). For example, in the production of a polycarboxylic acid copolymer or a salt thereof, water-soluble polyalkylene glycol having both terminal groups as hydrogen atoms may be generated as a by-product, and these may be converted into components (C) and (E). May be used as

<Ingredients other than (A) to (E)>
The liquid rheology modifier is a component other than (A) to (E), for example, AE agent, water reducing agent, AE water reducing agent, high performance water reducing agent, high performance AE water reducing water, as long as the desired effect is not impaired. Agent, flow agent, retarder, quick setting agent, dust reducing agent, underwater non-separable admixture, separation reducing agent, pumping aid, antifreeze / anti-cold agent, alkali aggregate reaction inhibitor, neutralization inhibitor, You may contain a shrinkage reducing agent, a heat | fever hydration inhibitor, a foaming agent, a foaming agent, an admixture for immediate desorption, and two or more combinations chosen from these.

(Content ratio of components (A) to (C))
The content ratio (solid content) of each component in the liquid rheology modifier of the present invention may be arbitrarily set, but (A) component: (B) component: (C) component = (0.1-10 mass) %): (0.5-50 mass%): (0.1-10 mass%), preferably (A) component: (B) component: (C) component = (0.5-5 mass%) ): (1.0-30% by mass): (0.5-5% by mass).

  When the content ratio of the component (A) is lower than 0.1% by mass, there is a possibility that the material separation resistance and the bleeding suppressing effect cannot be expressed with respect to the cement composition utilizing this. If it is higher than 10% by mass, the fluidity of the cement composition may not be exhibited, and the viscosity may increase significantly, making it difficult to handle.

  When the content ratio of the component (B) is lower than 0.5% by mass, the predetermined cement dispersibility may not be exhibited. If it is higher than 50% by mass, bleeding may occur in the cement composition using the same.

  When the content ratio of the component (C) is lower than 0.1% by mass, the storage stability is deteriorated due to the separation of the rheology modifier and may not be used as a modifier. When it is higher than 10% by mass, there is a possibility that a certain initial water reduction cannot be secured.

  If the content ratio of the components (A) to (C) of the liquid rheology modifier of the present invention is within the above range, the blending ratio of the components (A) and (B) may be arbitrarily set within this range. Good storage stability can be obtained regardless of temperature conditions. Therefore, the rheology modifier of the present invention has very good storage stability in tanks, transportation lorries and construction sites even under high temperature environments.

<Manufacturing method>
The manufacturing method of a liquid rheology modifier is not specifically limited, Usually, what is necessary is just to mix (A)-(C) component and arbitrary components. The mixing method is not particularly limited. For example, each component may be added to the solution and mixed, or at least one component is dispersed, mixed, suspended or dissolved in a solvent, and the remaining components are added thereto. You may mix. It is preferable that at least the component (C) and the components (D) and (E) contained as necessary are dispersed, mixed, suspended or dissolved in a solvent.

  The solvent is usually an aqueous solvent. 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). These aqueous solvents may be used individually by 1 type, and may mix and use 2 or more types. As the aqueous solvent, water is preferred.

<Dosage form, form>
The form of the liquid rheology modifier is not particularly limited, and may be a liquid such as a solution, suspension, mixed liquid, or dispersion, or a powder such as a dried or powdered product of these liquids. In addition, the liquid rheology modifier of the present invention is mixed in advance with components other than water constituting the cement composition such as cement powder and dry mortar, and water is added during plastering, floor finishing, grout, etc. It is good also as a premix product used.

<Application>
When the liquid rheology modifier of the present invention is added to a liquid composition containing water and powder, its fluidity can be continuously adjusted. For this reason, the rheology modifier of this invention can be used for a cement composition, a gypsum composition, and a dye composition.
For example, when a liquid rheology modifier is added to the cement composition, it can impart arbitrary material separation resistance and rheology, and appropriately adjust the initial fluidity and fluidity over time of the cement composition. It can be adjusted. Further, it can be suitably used in a summer space or a sealed space where heat is easily generated. Therefore, the liquid rheology modifier of this invention can be utilized as a dispersing agent for cement compositions, and an AE water reducing agent.

  The cement composition targeted by the liquid rheology modifier of the present invention is not particularly limited because the content ratio of the components (A) and (B) can be appropriately adjusted. For example, a cement composition with a water cement ratio of 60% used for an AE water reducing agent and a cement composition with a water cement ratio of 40% for which a high performance AE water reducing agent is used can be targeted. A function can be effectively expressed with respect to a thing.

  When adding the liquid rheology modifier of this invention to a cement composition, you may use together with the other additive for cement compositions. Other additives include, for example, cement dispersants, water-soluble polymers, polymer emulsions, air entrainers, cement wetting agents, swelling agents, waterproofing agents, retarders, thickeners, flocculants, drying shrinkage reducing agents, Strength enhancers, effect accelerators, antifoaming agents, AE agents, other surfactants, known cement composition additives such as CA agents and SA agents described below, and combinations of two or more selected from these Can be mentioned. For example, foaming can be improved by using an antifoaming agent together.

  Examples of the carboxyl group and / or salt-containing compound (CA agent) include, but are not limited to, sodium polyacrylate and sodium gluconate. Examples of the sulfonic acid group and / or salt-containing compound (SA agent) include sodium lignin sulfonate and naphthalene sulfonic acid, but are not limited thereto. When the liquid rheology modifier of the present invention is used in combination with at least one selected from the above-mentioned CA agent and SA agent, the ratio thereof is the liquid rheology modifier of the present invention / CA agent or SA agent = 0.1% by mass. ˜99.9% by mass / 0.1% by mass to 99.9% by mass, and the mass ratio when the three components are used in combination is the rheology modifier / CA agent / SA agent of the present invention = 0.1 mass. % To 99.9% by mass / 0.1% by mass to 99.9% by mass / 0.1% by mass to 99.9% by mass.

[2. Cement composition]
The cement composition of the present invention includes a liquid rheology modifier. 0.001-10 mass% is preferable with respect to 100 mass% of mass of a cement composition, and, as for content of a liquid rheology modifier, 0.01-5 mass% is more preferable. If the addition amount is less than 0.001% by mass, the material separation resistance and bleeding suppression may not be achieved. If the addition amount exceeds 10% by mass, the setting time of the cement composition may be significantly delayed.

  The cement composition usually includes a hydraulic component. Examples of the hydraulic component include cement paste, mortar, concrete, and plaster.

  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 heat cement (low heat blast furnace cement, fly ash mixing) Low exothermic type blast furnace cement, cement with high content of belite), ultra-high strength cement, cement-based solidified material, eco-cement (cement manufactured from one or more of municipal waste incineration ash and sewage sludge incineration ash) It is done. 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.

  As described above, since the liquid rheology modifier can adjust the liquid rheology of the cement composition having a wide range of water cement ratio, the water cement ratio in the cement composition is not particularly limited.

  The cement composition may include an 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

  When the cement composition is mortar or concrete, the addition amount (blending amount) of the component (B) contained in the liquid rheology modifier is preferably 0.01 with respect to the total mass of the cement composition. -5.0 mass%, More preferably, it is 0.02-2.0 mass%, More preferably, it is 0.05-1.0 mass%. By setting this addition amount, various preferable effects such as reduction of unit water amount, increase of strength, and improvement of durability are sufficiently brought to the obtained cement composition. If the blending ratio is less than 0.01% by mass, the resulting cement composition may not be sufficient in terms of performance. On the other hand, even if a large amount exceeding 5.0% by mass is used, the effect is substantially reduced. There is a risk that it will hit a peak and be disadvantageous in terms of economy.

  Therefore, a cement composition containing the rheology modifier of the present invention, and further a cured product of the cement composition constitutes the present invention. For example, the rheology modifier of the present invention can be suitably used for a medium fluidity cement composition, a high fluidity cement composition, an underwater non-separable cement composition, It can be suitably used as an additive for a fluid liquid or paste (grouting, pouring grout) to be injected for filling, or for improving the state of the cement composition even in ordinary cement compositions.

  The liquid rheology modifier of the present invention includes, for example, a ready-mixed cement composition, a cement composition for a secondary product (precast cement composition), a cement composition for centrifugal molding, a cement composition for vibration compaction, and steam curing. It can be effectively used for cement compositions such as cement compositions, underwater cement compositions, spray cement compositions and the like. Furthermore, a medium-fluid cement composition (cement composition with a slump value in the range of 22 to 25 cm), a high fluid cement composition (cement composition with a slump value of 25 cm or more and a slump flow value in the range of 50 to 70 cm, self It can also be suitably used for mortar or concrete, cement composition, gypsum composition and dye composition which require high fluidity such as a filling cement composition and a self-leveling material.

[3. Dispersion composition]
The dispersion composition of the present invention includes a liquid rheology modifier. Thereby, the characteristic of a dispersion composition can be improved. Examples of the dispersion composition include a gypsum composition and a dye composition in addition to the cement composition described above.

[4. Gypsum composition]
The gypsum composition of the present invention includes a liquid rheology modifier. Thereby, the state of a gypsum composition can be improved and workability (workability) can be improved.

  The gypsum composition means a slurry obtained by mixing gypsum and water. The gypsum composition of the present invention includes both a composition before curing and a composition (cured product) after curing. The gypsum is not particularly limited, and examples thereof include hemihydrate gypsum and type 2 anhydrous gypsum which are frequently used for industrial purposes. The content of gypsum and the content of the liquid rheology modifier in the gypsum composition can be appropriately set.

[5. Dye composition]
The gypsum composition of the present invention includes a liquid rheology modifier. Thereby, the state of a dye composition can be improved and workability | operativity can be improved.
The dye composition means a composition in which a dye is dissolved or dispersed in a dispersion medium. Examples of the dye include water-soluble dyes such as acid dyes, reactive dyes, direct dyes, cationic dyes and basic dyes; oil-soluble dyes such as disperse dyes and solvent dyes; organic pigments; and carbon black. The dispersion medium is appropriately selected depending on the dye, and usually an organic solvent or an aqueous solvent is selected. The content of the dye and the content of the liquid rheology modifier in the dye composition can be appropriately set.

  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,% indicates mass%, part indicates mass part, and concentration indicates solid content concentration relative to the total amount.

(A) Component <A-1> Hydroxypropyl methylcellulose (manufactured by Sankisha, NEOVISCO MC)
<A-2> Hydroxyethyl cellulose (manufactured by Sanki Co., Ltd., SANHEC)
<A-3> Carboxymethyl cellulose (manufactured by Nippon Paper Industries Co., Ltd., Sunrose F350HC)

(B) Component <B-1> Mixed dispersant of lignin sulfonate and oxycarboxylate (Floric S, Floric S)
<B-2> Aminosulfonic acid-based dispersant (manufactured by Floric, Floric SF-200S)
<B-3> Polycarboxylic acid-based dispersant (manufactured by Floric, Floric SF-500S)

(C) Component In Examples and Comparative Examples, the following copolymers (C-1) to (C-5) were used as the (C) component and its comparative products.
<Production Example C1>
157 parts of water and ethylene oxide adduct of 3-methyl-3-buten-1-ol (average addition of ethylene oxide) in a glass reaction vessel equipped with a thermometer, a stirring device, a reflux device, a nitrogen introducing tube and a dropping device The reaction vessel was purged with nitrogen under stirring and heated to 80 ° C. under a nitrogen atmosphere. Thereafter, an aqueous monomer solution in which 8 parts of acrylic acid, 63 parts of methoxypolyethylene glycol methacrylate (average number of added moles of ethylene oxide of 13), 30 parts of hydroxyethyl acrylate, 5 parts of ascorbic acid and 165 parts of water were mixed with ammonium persulfate 3 And a mixture of 47 parts of water were continuously dropped into a reaction vessel maintained at 80 ° C. for 2 hours each. Furthermore, the aqueous solution of the copolymer was obtained by making it react for 1 hour in the state hold | maintained at 80 degreeC. The content of polyethylene glycol allyl ether in the copolymer was 25% by mass, and the content of water-soluble polyethylene glycol in which both terminal groups were hydrogen atoms was 0.7% by mass. This solution was adjusted to pH 7 with 30% NaOH aqueous solution. The copolymer in the liquid was a copolymer (C-1) (weight average molecular weight 28,000, Mw / Mn 1.9).

<Production Example C2>
A glass reaction vessel equipped with a thermometer, stirring device, refluxing device, nitrogen introducing tube and dropping device was charged with 124 parts of water and 60 parts of polyethylene glycol monoallyl ether (average number of added moles of ethylene oxide of 35) under stirring. The reaction vessel was heated to 80 ° C. Thereafter, 5 parts of methacrylic acid, 4 parts of acrylic acid, 122 parts of methoxypolyethylene glycol methacrylate (average added mole number of ethylene oxide 13), 8 parts of hydroxypropyl acrylate, 2 parts of 3-mercaptopropionic acid, and 24 parts of water were mixed. The monomer aqueous solution and a mixed solution of 1 part ammonium persulfate and 49 parts water were continuously added dropwise to a reaction vessel maintained at 100 ° C. for 2 hours each. 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 content of polyethylene glycol allyl ether in the copolymer was 20% by mass, and the content of water-soluble polyethylene glycol in which both terminal groups were hydrogen atoms was 0.5% by mass. This solution was adjusted to pH 6 with 31% NaOH aqueous solution. The copolymer in the liquid was a copolymer (C-2) (weight average molecular weight 12,400, Mw / Mn 1.7).

<Production Example C3>
125 parts of water in a glass reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen introducing tube and a dropping device, and polyethylene glycol polypropylene glycol monoallyl ether (average added mole number of ethylene oxide 33, average of propylene oxide (Additional mole number 2, random addition of ethylene oxide and propylene oxide) 30 parts were charged, the reaction vessel was purged with nitrogen under stirring, and the temperature was raised to 80 ° C. under a nitrogen atmosphere. Then, 11 parts of methacrylic acid, 1 part of acrylic acid, 90 parts of methoxypolyethylene glycol methacrylate (average number of added moles of ethylene oxide 25), 100 parts of hydroxypropyl acrylate, 4 parts of 3-mercaptopropionic acid, and 20 parts of water are mixed. The monomer aqueous solution and a mixed solution of 3 parts of ammonium persulfate and 47 parts of water were continuously dropped into a reaction vessel maintained at 100 ° C. for 2 hours each. Furthermore, the aqueous solution of the copolymer was obtained by making it react for 1 hour in the state hold | maintained at 100 degreeC. This solution was adjusted to pH 4 with 31% NaOH aqueous solution. The copolymer in the liquid was a copolymer (C-3) (weight average molecular weight 13,800, Mw / Mn 1.4).

<Production Example C4>
100 parts of water and 30 parts of polyethylene glycol polypropylene glycol monoallyl ether (average number of moles of ethylene oxide added 10) are charged into a glass reaction vessel equipped with a thermometer, a stirring device, a reflux device, a nitrogen introduction tube and a dropping device. The reaction vessel was purged with nitrogen under stirring and heated to 50 ° C. under a nitrogen atmosphere. Thereafter, 15 parts of methacrylic acid, 2 parts of acrylic acid, 78 parts of methoxypolyethylene glycol methacrylate (average number of added moles of ethylene oxide 13), 34 parts of hydroxypropyl acrylate, 2 parts of ascorbic acid, 5 parts of 3-mercaptopropionic acid, An aqueous monomer solution mixed with 18 parts of water and a mixed solution of 1 part of hydrogen peroxide and 49 parts of water were continuously dropped into a reaction vessel maintained at 50 ° C. for 3 hours each. Furthermore, the aqueous solution of the copolymer was obtained by making it react for 1 hour in the state hold | maintained at 50 degreeC. This solution was adjusted to pH 4 with 31% NaOH aqueous solution. The copolymer in the liquid was a copolymer (C-4) (weight average molecular weight 16,200, Mw / Mn 1.5).

<Production Example C5>
A glass reaction vessel equipped with a thermometer, a stirrer, a reflux device, a nitrogen introduction tube and a dropping device was charged with 733 parts of water. Then, 21 parts of methacrylic acid, 30 parts of acrylic acid, 92 parts of methoxypolyethylene glycol methacrylate (average number of added moles of ethylene oxide 25), 70 parts of water, a mixture of 3 parts of ammonium persulfate and 87 parts of water The liquid was continuously dropped into a reaction vessel maintained at 50 ° C. for 2 hours each. Furthermore, the aqueous solution of the copolymer was obtained by making it react for 1 hour in the state hold | maintained at 50 degreeC. The content of the copolymer of the monomer composed of acrylic acid and / or acrylate and the monomer composed of methacrylic acid and / or methacrylate is 2% by mass with respect to the copolymer. Was adjusted to pH 7 with 30% NaOH aqueous solution. The copolymer in the liquid was a copolymer (C-5) (weight average molecular weight 18,300, Mw / Mn 1.6).

<Rheology modifier test (Examples 1-7 and Comparative Examples 1-5)>
Each component was mixed so that it might become the solid content density | concentration of Table 1, and the sample was obtained. Each sample was evaluated for storage stability and viscosity.

<Storage stability>
First, the compatibility of each sample immediately after mixing was evaluated according to the following criteria. Furthermore, the sample was stored at 20 ° C. and 40 ° C. for 1 month, and the storage stability after storage at each temperature was evaluated according to the following criteria. The results are shown in Table 2.

<Evaluation criteria for compatibility and storage stability>
A: Uniformly mixed.
○: Some aggregates are observed.
X: Completely separated and settled.

<Viscosity measurement>
Simultaneously with the storage stability test, the viscosity of each sample was measured. That is, each sample was stored at 40 ° C. for one month, and the viscosity after storage was measured using a B-type viscometer under the conditions of 20 ° C. and 60 rpm. The results are shown in Table 2.

<About Samples of Examples 1-7 and Comparative Examples 1-5>

<Cement composition test (Examples 8 to 21 and Comparative Examples 6 to 13)>
Cement compositions to which the samples of Examples 1 to 7 and Comparative Examples 1 to 4 were added were prepared by the following procedure. At ambient temperature (20 ° C.), coarse aggregate, fine aggregate, cement, and water blended as shown in Table 3 (W / C = 55%) and Table 5 (W / C = 45%), and Table 4 Alternatively, the amount of each listed in Table 6 and each sample were put into a forced biaxial mixer and kneaded for 90 seconds by mechanical kneading with a forced biaxial mixer to obtain a cement composition (each sample was mixed with water). Input). About the obtained cement composition, the slump test, the air content measurement, the viscosity evaluation, and the bleeding evaluation were performed in the following procedures.

<Slump test, air volume measurement and viscosity evaluation>
Immediately after the cement composition is discharged from the forced biaxial mixer, a fresh cement composition test (slump test JIS A 1101 (measured as a slump value, the fall distance from the top of the fresh cement composition as a slump value), Air amount JIS A 1128, cement composition viscosity evaluation). The viscosity of the cement composition was evaluated according to the following criteria by sensory evaluation by five evaluators. The test results are shown in Table 4 (W / C = 55%) and Table 6 (W / C = 45%). Further, under the same test conditions as in Tables 3 and 4, the correlation between the addition rate (% by weight with respect to the weight of the cement composition) and the slump flow immediately after kneading was measured. The results (W / C = 55%) are shown in FIG. Further, under the same test conditions as in Tables 5 and 6, the correlation between the addition rate (% by weight with respect to the weight of the cement composition) and the slump flow immediately after kneading was measured. The results (W / C = 45%) are shown in FIG.

<Viscosity evaluation criteria>
A: Appropriate viscosity is imparted to the cement composition, and bleeding is hardly observed.
○: Viscosity is imparted to the cement composition, but bleeding is observed.
X: Viscosity is not imparted to the cement composition, and large bleeding is also observed.

<Bleeding evaluation>
Evaluation was carried out by the method defined in JIS A 1123. A smaller amount of bleeding indicates that the cement composition has material separation resistance. The results are shown in Tables 4 and 6.

普通ポルトランドセメント（宇部三菱セメント株式会社製、比重３．１６）
普通ポルトランドセメント（太平洋セメント株式会社製、比重３．１６）
普通ポルトランドセメント（株式会社トクヤマ製、比重３．１６）
水道水
Ｓ１：掛川産山砂（細骨材、比重２．５７）
Ｓ２：岩瀬産砕砂（細骨材、比重２．６１）
Ｇ：青梅産砕石（粗骨材、比重２．６５）
サンプル（固形分換算） 表４参照

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)
Tap water S1: Kakegawa mountain sand (fine aggregate, specific gravity 2.57)
S2: Crushed sand from Iwase (fine aggregate, specific gravity 2.61)
G: Ome crushed stone (coarse aggregate, specific gravity 2.65)
Sample (solid content conversion) See Table 4

  In Table 4, “addition rate (% by mass)” indicates the solid addition rate of the liquid rheology modifier with respect to 100% by mass of the cement composition. SL represents the slump value (cm).

普通ポルトランドセメント（宇部三菱セメント株式会社製、比重３．１６）
普通ポルトランドセメント（太平洋セメント株式会社製、比重３．１６）
普通ポルトランドセメント（株式会社トクヤマ製、比重３．１６）
水道水
Ｓ１：掛川産山砂（細骨材、比重２．５７）
Ｓ２：岩瀬産砕砂（細骨材、比重２．６１）
Ｇ：青梅産砕石（粗骨材、比重２．６５）
サンプル（固形分換算） 表６参照

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)
Tap water S1: Kakegawa mountain sand (fine aggregate, specific gravity 2.57)
S2: Crushed sand from Iwase (fine aggregate, specific gravity 2.61)
G: Ome crushed stone (coarse aggregate, specific gravity 2.65)
Sample (solid content conversion) See Table 6

  In Table 6, “addition rate (mass%)” of the sample indicates the solid addition ratio of the sample with respect to 100 mass% of the cement composition. SLF indicates a slump flow value (mm).

  Table 2 shows the following. The samples of Examples 1 to 7 had good compatibility and were very excellent not only in environmental temperature (20 ° C.) but also in storage stability under a high temperature environment. On the other hand, in Comparative Examples 1 to 4 that do not contain the component (C) and Comparative Example 5 that does not contain the component (B) and (C), the viscosity after storage in a high-temperature environment is reduced, and storage stability Some have poor compatibility and poor compatibility. Especially, in the comparative example 4 and the comparative example 5, the high temperature storage property deteriorated by gelatinization. These results show that the liquid rheology modifier of the present invention has good compatibility and storage stability.

  Table 4 and Table 6 show the following. The cement compositions of Examples 8 to 21 had an appropriate viscosity as compared with Comparative Examples 6 to 13, the amount of bleeding was suppressed low, the amount of air was also appropriate, and the concrete state was improved. These results show that the rheology modifier of the present invention containing the components (A) to (C) at a predetermined concentration can maintain storage stability even when added in a large amount, and exhibits dispersibility commensurate with the added amount. This indicates that the component (C) can prevent aggregation of the components (A) and (B). In addition, these results show that the liquid rheology modifier of the present invention can impart fluidity to cement compositions with a wide range of water cement ratios, regardless of the amount of addition, and that It is possible to hold it.

  The following can be understood from FIGS. In a cement composition blending condition of a water cement ratio (W / C = 45%) called a general strength region and a slightly higher water cement ratio (W / C = 55%), Comparative Example 4 has 1.5% by weight. Addition of a liquid rheology modifier in excess of 1 indicated that the increase in slump flow value was not observed or decreased, giving viscosity to the cement composition rather than dispersibility. As described above, the conventional cement additive has a reversal phenomenon in which an increase in the slump flow value is not recognized or decreases with an increase in the addition rate. On the other hand, in Examples 2 and 3, the slump flow value increased as the sample addition rate increased. These results show that the liquid rheology modifier of the present invention can suppress the deterioration of the viscosity accompanying the increase in the addition amount, which has been a problem in the prior art, and can provide dispersibility commensurate with the addition amount. Indicates that there is no limit.

  The liquid rheology modifier of the present invention is excellent in storage stability, and even under high-temperature environments such as summertime, it is possible to omit temperature adjustment measures such as installation of a cooling device that was necessary when storing conventional products, Economic efficiency can be improved. Since the liquid rheology modifier of the present invention can exhibit good fluidity even after storage, it can be used to adjust the liquid rheology of a dispersion composition containing water and powder. Above all, by adding to the cement composition, the workability during construction can be drastically improved, and the aggregate separation resistance can be imparted to the cement composition, increasing its strength, durability and other properties. be able to. Further, the liquid rheology modifier of the present invention can obtain a desired effect even if the content ratio of the components (A) and (B) is changed within a predetermined range, if necessary. It can utilize suitably with respect to the cement composition of this.

Claims (11)

(A) component: water-soluble thickener,
Component (B): lignin sulfonic acid dispersant, oxycarboxylic acid dispersant, naphthalene sulfonic acid dispersant, aminosulfonic acid dispersant, and polycarboxylic acid dispersant (however, (C) component polycarboxylic acid At least one dispersing agent selected from (excluding copolymers and salts thereof), and component (C): monomer (I) represented by the following general formula (1) 5 to 90% by mass, the following general formula Monomer (II) represented by (2) 5 to 90% by mass, unsaturated monocarboxylic acid monomer (III) 1 to 50% by mass, and monomers (I) to (III) 1 or 2 or more monomers selected from the group consisting of, or other monomers (IV) copolymerizable with these polymers, and a polycarboxylic acid copolymer obtained by copolymerization of 0 to 50% by mass; Including at least one selected from the salts thereof,
The content ratio (solid content) of each component with respect to 100% by mass of the liquid rheology modifier is (A) component: (B) component: (C) component = 0.1-10% by mass: 0.5-50% by mass. : 0.1 to 10% by mass
Liquid rheology modifier.

(In the formula, R ¹ represents an alkenyl group having 2 to 5 carbon atoms. A ¹ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. N1 represents an oxyalkylene group. (The average number of moles added represents a number of 1 to 100. R ² represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.)

(Wherein, R ^3, R ⁴ and R ⁵ are each independently, .m represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, the .A ² O representing the number of 0 to 2, the same Or, differently, it represents an oxyalkylene group having 2 to 18 carbon atoms, n2 is an average added mole number of the oxyalkylene group, and represents a number of 1 to 100. X is a hydrogen atom or 1 to 1 carbon atoms. Represents 30 hydrocarbon groups.)   The monomer (II) is a monomer (IIa) in which n2 in the general formula (2) is 1, and a monomer (IIb) in which n2 in the general formula (2) is 2 to 100 The liquid rheology modifier according to claim 1, comprising:   The liquid rheology modifier according to claim 2, wherein the content ratio (IIa) / (IIb) of the monomer (IIa) to the monomer (IIb) is from 1/99 to 99/1.   The liquid rheology modifier according to any one of claims 1 to 3, wherein the polycarboxylic acid copolymer and a salt thereof have a weight average molecular weight of 5,000 to 60,000 in terms of polyethylene glycol.   The liquid rheology modifier according to any one of claims 1 to 4, wherein the component (A) is a water-soluble cellulose-based thickener.   The liquid rheology modifier according to claim 5, wherein the water-soluble cellulose-based thickener contains at least one selected from alkyl cellulose, hydroxyalkyl cellulose, hydroxyalkylalkyl cellulose, carboxymethyl cellulose, and salts thereof.   The liquid rheology modifier according to claim 5 or 6, wherein the water-soluble cellulose thickener has a substitution degree of 0.5 to 2.5 per unit monosaccharide.   The dispersion composition containing the agent of any one of Claims 1-7.   The cement composition containing the agent of any one of Claims 1-7.   The gypsum composition containing the agent of any one of Claims 1-7.   The dye composition containing the agent as described in any one of Claims 1-7.

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