JP6751579B2 - Additives for hydraulic compositions - Google Patents

Description

The present invention relates to additives for hydraulic compositions.

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, but as a structure that can make the most effective use of its self-filling property, It is used for overcrowded reinforcement members, which are difficult to use with exciters, and synthetic structural members that are mostly closed.
High-fluidity concrete contains cement, fine aggregate, coarse aggregate, water, and various additives.
Patent Document 1 describes concrete (cement composition) containing a thickener containing cellulose ether as a main component. Further, Patent Document 2 describes concrete (cement composition) in which hydrophobized modified hydroxyethyl cellulose is blended as a thickener. Further, Patent Document 3 describes the use of microfibrillated cellulose as a cement additive.

Japanese Unexamined Patent Publication No. 2001-261419 Japanese Unexamined Patent Publication No. 09-183644 International Publication 2011/039423

High-fluidity concrete is required to have high fluidity and appropriate material separation resistance. However, in recent years, fly ash and the like have been reused for cement due to the improvement of environmental awareness, and the coarseness of fine aggregate has been further deteriorated, so that the concrete condition has deteriorated significantly. Against this background, it is conceivable to add a dispersant for hydraulic composition (high-performance AE water reducing agent, etc.) in order to give high fluidity to highly fluid concrete for the purpose of improving the condition of concrete. It is conceivable to add a thickener to give appropriate material separation resistance.
However, the water-soluble cellulosic thickeners described in the patent documents have very low solubility, and the solubility is easily affected by the amount of the dispersant mixed and the salt contained in the dispersant. In particular, many AE water reducing agents used for suppressing bleeding and improving concrete conditions contain a large amount of lignin sulfonate, and both such AE water reducing agent and water-soluble cellulose-based thickener are used together. Difficult to mix.
Therefore, an object of the present invention is to provide an additive for a hydraulic composition, which imparts appropriate fluidity and material separation resistance to the hydraulic composition in a small amount and has good compatibility of the contained components. To do.

As a result of diligent studies by the present inventors in order to solve the above problems, the above-mentioned additives for a water-hard composition containing a water-soluble thickener and a specific copolymer in a specific weight ratio are used. We found that the problem could be solved. That is, the present invention provides the following [1] to [6].

（式中、
Ｒ^１、Ｒ^２、及びＲ^３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。
ｐは、０〜２の整数を表す。
ｑは、０又は１を表す。
Ａ^１Ｏ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、オキシアルキレン基の平均付加モル数であり、１〜３００の数を表す。
Ｒ^４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、
Ｒ^５、Ｒ^６、及びＲ^７は、それぞれ独立に、水素原子、−ＣＨ_３、又は（ＣＨ_２）_ｒＣＯＯＭ^２を表し、−（ＣＨ_２）_ｒＣＯＯＭ^２は、−ＣＯＯＭ^１又は他の−（ＣＨ_２）_ｒＣＯＯＭ^２と無水物を形成していてもよく、その場合、それらの基のＭ^１及びＭ^２は存在しない。
Ｍ^１及びＭ^２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、又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。）
［２］ 水溶性増粘剤（Ａ）が、ヒドロキシプロピルメチルセルロースである、［１］に記載の水硬性組成物用添加剤。
［３］ 共重合体（Ｂ）が、さらに下記一般式（３）で表される単量体に由来する構成単位を含む、［１］又は［２］に記載の水硬性組成物用添加剤。

（式中、
Ｒ^８、Ｒ^９及びＲ^１０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。
Ｒ^１１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。
ただし、一般式（３）で表される単量体には、一般式（１）で表される単量体は含まれない。）
［４］ 水溶性増粘剤（Ａ）を２種以上含む、［１］〜［３］のいずれか１つに記載の水硬性組成物用添加剤。
［５］ 共重合体（Ｂ）を２種以上含む、［１］〜［４］のいずれか１つに記載の水硬性組成物用添加剤。
［６］ ［１］〜［５］のいずれか１つに記載の水硬性組成物用添加剤を含む、水硬性組成物。 [1] Water-soluble thickener (A) and
A copolymer (B) containing a structural unit derived from a monomer represented by the following general formula (1) and a structural unit derived from a monomer represented by the following general formula (2).
Including
Additive for hydraulic composition in which the weight ratio ((A) / (B)) of the water-soluble thickener (A) to the copolymer (B) is 0.01 / 99.99 to 25/75. ..

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

(In the formula,
R ⁵ , R ⁶ and R ⁷ independently represent a hydrogen atom, -CH ₃ , or (CH ₂ ) _r COM ² , and-(CH ₂ ) _r COM ² is -COOM ¹ or other-. (CH ₂ ) _r COM ² may form an anhydride, in which case M ¹ and M ² of those groups are absent.
M ¹ and M ² represent the same or different hydrogen atoms, alkali metals, alkaline earth metals, ammonium groups, alkylammonium groups, or substituted alkylammonium groups.
r represents an integer from 0 to 2. )
[2] The additive for a hydraulic composition according to [1], wherein the water-soluble thickener (A) is hydroxypropylmethyl cellulose.
[3] The additive for a hydraulic composition according to [1] or [2], wherein the copolymer (B) further contains a structural unit derived from a monomer represented by the following general formula (3). ..

(In the formula,
R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
R ¹¹ represents a hydrocarbon group which may contain a heteroatom having 1 to 4 carbon atoms.
s represents an integer from 0 to 2.
However, the monomer represented by the general formula (3) does not include the monomer represented by the general formula (1). )
[4] The additive for a hydraulic composition according to any one of [1] to [3], which contains two or more kinds of water-soluble thickeners (A).
[5] The additive for a hydraulic composition according to any one of [1] to [4], which contains two or more kinds of copolymers (B).
[6] A hydraulic composition containing the additive for a hydraulic composition according to any one of [1] to [5].

According to the present invention, it is possible to provide an additive for a hydraulic composition, which imparts appropriate fluidity and material separation resistance to the hydraulic composition in a small amount and has good compatibility of the contained components. ..

The additive for a hydraulic composition of the present invention contains a water-soluble thickener (A) and a copolymer (B). Hereinafter, the water-soluble thickener (A) and the copolymer (B) will be described. In addition, in this specification, an agent includes a composition.
<Water-soluble thickener>
The water-soluble thickener (A) according to the present invention is not particularly limited as long as it is water-soluble and can increase the viscosity of the aqueous solution after dissolution as compared with that before dissolution, but is usually water-soluble thickener. The agent (A) is a polymer compound. The water-soluble thickener (A) is preferably a polysaccharide derivative, more preferably a plurality of hydroxy groups contained in the polysaccharide, because it is easy to adjust the degree of water solubility and the degree of increasing the viscosity. Overall, a polysaccharide derivative substituted with an alkyloxy group having 1 to 5 carbon atoms having a hydroxy group and an alkyloxy group having 1 to 5 carbon atoms; or a plurality of hydroxy groups or a plurality of hydroxy groups contained in the polysaccharide. A hydrophobic substituent having a plurality of hydroxy group hydrogen atoms contained in an alkylated derivative of a polysaccharide or a hydroxyalkylated derivative partially or wholly having a hydrocarbon chain having 8 to 40 carbon atoms as a partial structure. , An ionic hydrophilic substituent having at least one group selected from the group consisting of a sulfo group and a sulfonato salt group as a partial structure, and a polysaccharide derivative substituted with, more preferably hydroxypropylmethyl cellulose. .. In the present specification, the group of sulfonate _salts, ^-SO 3 - means a group represented by · ^{M +.} Here, M ⁺ represents a cation. Hereinafter, a polysaccharide derivative preferable as the hydrophobic substituent (P), the ionic hydrophilic substituent (Q), and the water-soluble thickener (A) of the present invention is used. , Called a polysaccharide derivative (A').

<Hydrophobic substituent>
The hydrophobic substituent (P) has 8 or more carbon atoms, preferably 12 or more, more preferably 16 or more, and from the viewpoint of obtaining good material separation resistance and rheology (appropriate fluidity) in poorly compounded concrete. Alkyl glyceryl ether group having a linear or branched alkyl group having 40 or less carbon atoms, preferably 36 or less, more preferably 24 or less; 8 or more carbon atoms, preferably 12 or more, more preferably 16 or more. , And an alkenylglyceryl ether group having a linear or branched alkenyl group having 40 or less carbon atoms, preferably 36 or less, more preferably 24 or less; the hydroxy group may be substituted, and the oxycarbonyl group may be substituted. A linear or branched chain having 8 or more carbon atoms, preferably 12 or more, more preferably 16 or more, and 40 or less carbon atoms, preferably 36 or less, more preferably 24 or less, which may be inserted. Alkyl group; The hydroxy group may be substituted or the oxycarbonyl group may be inserted, the number of carbon atoms is 8 or more, preferably 12 or more, more preferably 16 or more, and the number of carbon atoms is 40 or less, preferably 40 or less. Is 36 or less, more preferably 24 or less, a linear or branched alkenyl group; or a hydroxy group may be substituted or an oxycarbonyl group may be inserted, with 8 or more carbon atoms, preferably. A linear or branched acyl group having 12 or more, more preferably 16 or more, and 40 or less carbon atoms, preferably 36 or less, more preferably 24 or less. From the viewpoint of ease of production and good pumping property in poorly blended concrete, an alkyl glyceryl ether group, a long-chain alkyl group, a 2-hydroxy long-chain alkyl group is preferable, and an alkyl glyceryl ether group is more preferable. .. In the present specification, the long chain means that the number of carbon atoms is 8 or more. Further, the long chain usually has 40 or less carbon atoms. In the present specification, the alkyl glyceryl ether group means a group having the structure of the remaining portion excluding one hydroxy group of the monoalkyl glyceryl ether, that is, 2-hydroxy-3-alkoxypropyl group, 2-. It is an alkoxy-1- (hydroxymethyl) ethyl group. The alkenyl glyceryl ether group means a group having the structure of the remaining portion excluding one hydroxy group of the monoalkenyl glyceryl ether, that is, 2-hydroxy-3-alkenyloxypropyl group and 2-alkenyloxy. It is a -1- (hydroxymethyl) ethyl group. When a hydroxyalkyl group (eg, hydroxyethyl group, hydroxypropyl group) is bonded to the polysaccharide molecule, these hydrophobic substituents (P) are substituted with the hydrogen atom of the hydroxy group of the bonded hydroxyalkyl group. You may be doing it.

<Ionic hydrophilic substituent>
The ionic hydrophilic substituent (Q) is preferably a substituent having at least one group selected from the group consisting of a sulfo group and a sulfonato salt group as a partial structure from the viewpoint of salt resistance in the water-hard composition. Is. Specifically, from the viewpoint of salt resistance in the water-hard composition, for example, a sulfoalkyl group having 1 to 5 carbon atoms or a salt group thereof, which may be substituted with a hydroxy group, can be mentioned. More specifically, as the ionic hydrophilic substituent (Q), for example, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfo-2-hydroxypropyl group, and 2-sulfo-1- (hydroxymethyl). ) Ethyl groups and groups in which the sulfo group contained in these groups is a salt can be mentioned. The polysaccharide derivative (A') may have a plurality of ionic hydrophilic substituents (Q). When a plurality of ionic hydrophilic substituents (Q) have a plurality of sulfo groups, all of them may be in the form of a sulfonato salt group, or only a part thereof may be in the form of a sulfonato salt group. Good. Examples of the cation in the sulfonato salt group include alkali metal ions such as sodium and potassium, alkaline earth metal ions such as calcium and magnesium, organic cations such as amines, and ammonium ions.

<Degree of replacement>
The degree of substitution of the hydrophobic substituent (P) and the ionic hydrophilic substituent (Q) of the polysaccharide derivative (A') is determined from the viewpoint of obtaining appropriate solubility in kneading water and rheology (appropriate fluidity). The degree of substitution by the hydrophobic substituent (P) is preferably 0.0001 or more, more preferably 0.0005 or more, more preferably 1 or less, and even more preferably 0.01 or less per unit of the constituent polysaccharide residue. The degree of substitution by the ionic hydrophilic substituent (Q) is preferably 0.001 or more, more preferably 0.01 or more, more preferably 2 or less, and even more preferably 1 or less per unit of the constituent monosaccharide residue.

<Polysaccharide>
Examples of the polysaccharide used as a raw material for the polysaccharide derivative (A') include cellulose; starch; rhizome polysaccharides such as konjak mannan and trolley aoi adhesive; sap polysaccharides such as arabic gum, tragacant gum and karaya gum; , Seed polysaccharides such as tamarind gum; seaweed polysaccharides such as agar, carrageenan and argin; animal polysaccharides such as chitin, chitosanheparin and chondroitin sulfate; microbial polysaccharides such as dextran and xanthan gum. Examples of the alkylated derivative of the polysaccharide include an alkylated derivative of cellulose, and specific examples thereof include methyl cellulose and ethyl cellulose. Examples of the hydroxyalkylated derivative of the polysaccharide include hydroxyalkylated derivatives of cellulose, and specific examples thereof include hydroxyethyl cellulose and hydroxypropyl cellulose. In particular, cellulose and its derivatives are preferable because they have excellent compatibility with the B component of the present invention, which will be described in detail later. In the present specification, the water-soluble thickener (A) produced from cellulose or a derivative thereof as a raw material is referred to as a cellulosic thickener. Further, a substituent (eg, an alkyl group such as a methyl group and an ethyl group, a hydroxyalkyl group such as a hydroxyethyl group and a hydroxypropyl group, an alkyleneoxy group) is introduced into these polysaccharides to obtain a polysaccharide derivative (A'). In this case, the plurality of substituents contained in the polysaccharide derivative (A') may be a single type of substituent or a plurality of types of substituents. The degree of substitution per constituent monosaccharide residue of the polysaccharide derivative (A') is preferably 0.1 or more, more preferably 0.5 or more, and preferably 5 or less, more preferably 3. It is as follows. When the substituent is an alkyleneoxy group, the degree of substitution, that is, the number of moles added per constituent monosaccharide residue is preferably 0.1 or more, more preferably 0.5 or more, and It is preferably 10 or less, and more preferably 5 or less.

<Molecular weight of water-soluble thickener>
The weight average molecular weight of the water-soluble thickener (A) is preferably 100,000 or more from the viewpoint of obtaining good solubility in water and good pumping property in a hydraulic composition (eg, concrete). 200,000 or more is more preferable, 500,000 or more is further preferable, 5,000,000 or less is preferable, 2,000,000 or less is more preferable, and 1,000,000 or less is further preferable.

<Manufacturing of polysaccharide derivatives>
<Introduction of substituent>
The polysaccharide derivative (A') can be produced by a known method using the above-mentioned polysaccharide as a raw material, and a commercially available product can be used as the polysaccharide derivative.
When the polysaccharide derivative (A') has a hydrophobic substituent (P) and an ionic hydrophilic substituent (Q), the hydrophobic substituent (P) and the ionic hydrophilic substituent on the polysaccharide derivative (A') The order of introduction of the groups (Q) is not particularly limited, and the hydrophobic substituent (P) may be introduced first, and then the ionic hydrophilic substituent (Q) may be introduced, or the ionic hydrophilic substituent (Q) may be introduced. The substituent (Q) may be introduced first and then the hydrophobic substituent (P), or the hydrophobic substituent (P) and the ionic hydrophilic substituent (Q) may be introduced at the same time. You may go. For example, the polysaccharide derivative (A') partially hydrophilizes the hydrogen atoms of a plurality of hydroxy groups possessed by the polysaccharide or the alkylated derivative of the polysaccharide or the hydroxyalkylated derivative (introduction of the hydrophobic substituent (P)). Alternatively, it can be obtained by hydrophilizing (introducing an ionic hydrophilic substituent (Q)) and then hydrophilizing or hydrophilizing some or all of the remaining hydroxy groups, or hydrophilization and hydrophilization. Obtained by doing it at the same time.

<Example of introduction of substituent>
The introduction of the hydrophobic substituent (P) and the ionic hydrophilic substituent (Q) can be carried out, for example, as follows. That is, a polysaccharide or an alkylated derivative of a polysaccharide or a hydroxyalkylated derivative, an alkyl glycidyl ether having an alkyl group having 8 to 40 carbon atoms in the presence of an alkali; an alkenyl group having 8 to 40 carbon atoms. Alkenyl glycidyl ether having 8 to 40 carbon atoms, linear or branched saturated hydrocarbon epoxide: 8 to 40 carbon atoms, straight or branched unsaturated hydrocarbon epoxide; carbon atoms Halides of linear or branched saturated hydrocarbons of 8-40; halides of linear or branched unsaturated hydrocarbons with 8-40 carbon atoms; linear or branched with 8-40 carbon atoms Chain saturated hydrocarbon halohydrin; linear or branched unsaturated hydrocarbon halohydrin having 8 to 40 carbon atoms; linear or branched saturated hydrocarbon acyl halide having 8 to 40 carbon atoms; Acyl halides of straight or branched unsaturated hydrocarbons with 8 to 40 carbon atoms; esters with 8 to 40 carbon atoms; or carboxylics with 8 to 40 carbon atoms A hydrophobic substituent (P) is introduced by reacting with an acid anhydride, and the obtained intermediate reaction product is further subjected to vinyl sulfonic acid; a carbon atom in which a hydroxyl group may be substituted in the presence of an alkali. It can be carried out by reacting with haloalkanesulfonic acids of numbers 1 to 5; or salts thereof to introduce an ionic hydrophilic substituent (Q).

<Content of water-soluble thickener (A)>
The content ratio of the water-soluble thickener (A) in the additive for the water-hard composition of the present invention is not particularly limited, but the water-soluble thickener (A) is based on 100 parts by weight of the additive for the water-hard composition. The amount is preferably 0.1 parts by weight or more, more preferably 0.3 parts by weight or more, further preferably 0.5 parts by weight or more, preferably 4.0 parts by weight or less, and more preferably 3.0 parts by weight or less. More preferably, it is 2.0 parts by weight or less. The blending ratio of the water-soluble thickener (A) to the additive for the hydraulic composition is not particularly limited, but the weight ratio is preferably 0.1 / 100 or more, more preferably 0.3 /. It is 100 or more, more preferably 0.5 / 100 or more, preferably 4.0 / 100 or less, more preferably 3.0 / 100 or less, still more preferably 2.0 / 100 or less. is there. Usually, by blending in such a range, the above-mentioned preferable content ratio, more preferable content ratio, and further preferable content ratio can be realized.

The additive for a hydraulic composition of the present invention may contain only one kind of water-soluble thickener (A) or two or more kinds.

<Copolymer (B)>
(Polymer)
The copolymer (B) contained in the additive for a water-hard composition of the present invention is represented by a structural unit derived from a monomer represented by the following general formula (1) and the following general formula (2). It is a copolymer (B) containing a structural unit derived from a monomer.

(Polymer (I) represented by the general formula (1))
First, a monomer represented by the general formula (1) (also referred to as a monomer (I)) will be described.

(In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. P represents an integer of 0 to 2. Q is 0 or 1. A ¹ O is the same or different and represents an oxyalkylene group having 2 to 18 carbon atoms. N is the average number of moles of the oxyalkylene group added and represents a number of 1 to 300. R ⁴ Represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.)

R ¹ , R ² and R ³ in the general formula (1) independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and preferably each independently represent a hydrogen atom or a methyl group. ..

P in the general formula (1) represents an integer of 0 to 2, preferably 0 or 1.

Q in the general formula (1) represents 0 or 1.
Preferably, p represents 0 and q represents 1, or p represents 1 or 2 and q represents 0.

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

The above "same or different" means that when a plurality of A ¹ Os are contained in the general formula (1) (when n is 2 or more), even if each A ¹ O is the same oxyalkylene group. It means that it may be different (two or more kinds) oxyalkylene groups. When a plurality of A ¹ O are contained in the general formula (1), an embodiment comprises a group consisting of an oxyethylene group (ethylene glycol unit), an oxypropylene group (propylene glycol unit) and an oxybutylene group (butylene glycol unit). Examples include a mode in which two or more selected oxyalkylene groups are mixed, and a mode in which an oxyethylene group (ethylene glycol unit) and an oxypropylene group (propylene glycol unit) are mixed, or an oxyethylene group (ethylene glycol unit) and oxy. It is preferable that the butylene group (butylene glycol unit) is mixed, and it is more preferable that the oxyethylene group (ethylene glycol unit) and the oxypropylene group (propylene glycol unit) are mixed. In the embodiment in which different oxyalkylene groups are mixed, the addition of two or more kinds of oxyalkylene groups may be a block-like addition or a random-type addition.

N in the general formula (1) is the average number of moles of oxyalkylene groups added, and represents a number of 1 to 300. n is 300 or less, preferably 100 or less, more preferably 50 or less, and even more preferably 45 or less. n is 1 or more, preferably 5 or more, and more preferably 7 or more. n is preferably 1 to 100, more preferably 5 to 100, further preferably 5 to 50, and most preferably 7 to 45. The average number of moles added means the average value of the number of moles of the alkylene glycol unit added to one mole of the monomer.

R ⁴ in the general formula (1) represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. Since the number of carbon atoms of the hydrocarbon group represented by R ⁴ is not too large, the additive for the water-hard composition can sufficiently disperse the water-hard material (eg, cement), so that R ² is a hydrogen atom or It is preferably 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 most preferably a hydrogen or methyl group.

Examples of the monomer (I) in which q is 0 include (poly) ethylene glycol allyl ether, (poly) ethylene glycol metalyl ether, (poly) ethylene glycol 3-methyl-3-butenyl ether, and (poly). Ethylene (poly) propylene glycol allyl ether, (poly) ethylene (poly) propylene glycol metalyl ether, (poly) ethylene (poly) propylene glycol 3-methyl-3-butenyl ether, (poly) ethylene (poly) butylene glycol allyl Ether, (poly) ethylene (poly) butylene glycol metallic ether, (poly) ethylene (poly) butylene glycol 3-methyl-3-butenyl ether, methoxy (poly) ethylene glycol allyl ether, methoxy (poly) ethylene glycol metallic ether , Methoxy (poly) ethylene glycol 3-methyl-3-butenyl ether, methoxy (poly) ethylene (poly) propylene glycol allyl ether, methoxy (poly) ethylene (poly) propylene glycol metallic 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 metallic ether, methoxy (poly) ethylene (poly) butylene glycol 3 −Methyl-3-butenyl ether can be mentioned. Among these, since the hydrophilicity and hydrophobicity balance of the copolymer (B) can be made excellent, the (poly) polyethylene glycol (meth) allyl ether is used as the monomer (I) in which q is 0. Alternatively, (poly) ethylene (poly) propylene glycol allyl ether is preferable. In addition, in this specification, "(poly)" means that one or more components or raw materials described immediately after that are bonded. In addition, in this specification, "(meth) allyl" means "allyl or methallyl".

Examples of the monomer (I) in which q is 1 include (poly) alkylene glycol (meth) acrylate (eg, (poly) ethylene glycol (meth) acrylate, (poly) ethylene (poly) propylene glycol (meth). Acrylate, (poly) ethylene (poly) butylene glycol (meth) acrylate,), alkoxy (poly) alkylene glycol (meth) acrylate (eg, methoxy (poly) ethylene glycol (meth) acrylate, methoxy (poly) ethylene (poly) Examples thereof include propylene glycol (meth) acrylate and methoxy (poly) ethylene (poly) butylene glycol (meth) acrylate. Among these, as the monomer (I) in which q is 1, (poly) alkylene glycol (meth) acrylate or methoxy (poly) ethylene glycol (meth) acrylate is preferable, and methoxy (poly) ethylene glycol (meth) acrylate is preferable. ) Acrylate is more preferable. In addition, in this specification, "(meth) acrylate" means "acrylate or methacrylate".

The monomer (I) can be produced by a known method.
As a method for producing the monomer (I) in which q is 0, for example, 1 to 300 mol of alkylene oxide is added to an unsaturated alcohol such as allyl alcohol, metallic alcohol, 3-methyl-3-butene-1-ol. There is a method of adding.

Examples of the method for producing the monomer (I) in which q is 1 include unsaturated monocarboxylic acids such as (meth) acrylate, (poly) ethylene glycol, and (poly) ethylene (poly) propylene glycol. Esterification of (poly) alkylene glycols such as (poly) ethylene (poly) butylene glycol, methoxy (poly) ethylene glycol, methoxy (poly) ethylene (poly) propylene glycol, and methoxy (poly) ethylene (poly) butylene glycol. There is a way to do it.

In the above example of the production method, the average number of moles of (poly) alkylene glycol added is preferably 1 to 300, more preferably 5 to 100, still more preferably 5 to 50, and most preferably. It is 7 to 45.

The copolymer (B) may contain only one type of structural unit derived from the monomer (I) represented by the general formula (1), or may contain two or more types.

(Polymer (II) represented by the general formula (2))
Next, the monomer represented by the general formula (2) (hereinafter, also referred to as monomer (II)) will be described.

^(Wherein, R 5, ^{R 6,} and ^{R 7} each independently represent a hydrogen atom, -CH _3, or _- represents a ^{_{(CH 2) r COOM 2,}} - (CH 2) r COOM 2 may COOM ¹ Alternatively, it may form an anhydride with other − (CH ₂ ) _r COMM ² , in which case M ¹ and M ² of their groups are absent; M ¹ and M ² are the same or different, Represents a hydrogen atom, alkali metal, alkaline earth metal, ammonium group, alkylammonium group, or substituted alkylammonium group. R represents an integer from 0 to 2.)

Examples of the monomer (II) include unsaturated monocarboxylic acid-based monomers and unsaturated dicarboxylic acid-based monomers. Examples of unsaturated monocarboxylic acid-based monomers include acrylic acid, methacrylic acid, and crotonic acid, and salts thereof (eg, monovalent metal salt, ammonium salt, and organic amine salt). Examples of unsaturated dicarboxylic acid-based monomers include maleic acid, itaconic acid, citraconic acid, and fumaric acid, salts thereof (eg, monovalent metal salt, ammonium salt, and organic amine salt), and their salts. Anhydrous is mentioned.
The copolymer (B) may contain only one type of structural unit derived from the monomer (II) represented by the general formula (2), or may contain two or more types.

(Polymer (III) represented by the general formula (3))
The copolymer (B) contained in the additive for a hydraulic composition of the present invention is further derived from a monomer represented by the following general formula (3) (hereinafter, also referred to as a monomer (III)). It may include a structural unit to be used.

(In the formula, R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ¹¹ may contain a hetero atom having 1 to 4 carbon atoms. Representing a hydrocarbon group. S represents an integer of 0 to 2. However, the monomer represented by the general formula (3) does not include the monomer represented by the general formula (1). .)

Preferably, R ⁸ , R ⁹ and R ¹⁰ are independently hydrogen atoms or methyl groups, and more preferably R ⁸ , R ⁹ and R ¹⁰ are hydrogen atoms, or R ⁹ is a methyl group. And R ⁸ and R ¹⁰ are hydrogen atoms.

Examples of the hydrocarbon group represented by R ¹¹ which may contain a hetero atom having 1 to 4 carbon atoms include an alkyl group having 1 to 4 carbon atoms and a monohydroxyalkyl group having 1 to 4 carbon atoms. More specifically, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a glyceryl group, a 2-hydroxyethyl group, a 2-hydroxypropyl group, and a 4-hydroxybutyl group can be mentioned.
The hydrocarbon group represented by R ¹¹ which may contain a heteroatom having 1 to 4 carbon atoms is preferably a monohydroxyalkyl group having 1 to 4 carbon atoms, and more preferably a hydroxypropyl group. More preferably, it is a 2-hydroxypropyl group.

Examples of the monomer (III) include monoesters of unsaturated monocarboxylic acids. Examples of monoesters of unsaturated monocarboxylic acids include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth). Examples thereof include acrylate and glyceryl (meth) acrylate. The monomer (III) is preferably a monohydroxyalkyl ester having 1 to 4 carbon atoms of the (meth) acrylate, and more preferably a hydroxypropyl (meth) acrylate.
The copolymer (B) may contain only one type of structural unit derived from the monomer (III) represented by the general formula (3), or may contain two or more types.

(Other building blocks)
The copolymer (B) may contain a structural unit derived from the monomer (IV) other than the above-mentioned monomers (I) to (III). The copolymer (B) may contain only one type or two or more types as a constituent unit derived from the monomer (IV). Examples of the monomer (IV) include the following monomers. In the following examples, the monomers contained in the monomers (I) to (III) are excluded from the monomer (IV).
General formula (IV-1):

3 and 3'-position allyl substitutions of diallyl bisphenols represented by, for example, 4,4'-dihydroxydiphenylpropane, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylsulfone;

General formula (IV-2):

Three-position allyl substitutions of monoallyl bisphenols represented by, for example, 4,4'-dihydroxydiphenylpropane, 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenylsulfone;

General formula (IV-3):

で示されるアリルフェノール；

Allylphenol indicated by;

Half-esters and diesters of unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, and citraconic acid and alcohols having 1 to 30 carbon atoms;
Half-amides and diamides of the unsaturated dicarboxylic acids and amines having 1 to 30 carbon atoms;
Half-esters and diesters of alkyl (poly) alkylene glycols obtained by adding 1 to 500 mol of an alkylene oxide having 2 to 18 carbon atoms to the alcohol or amine and the unsaturated dicarboxylic acids.
Half-esters and diesters of the unsaturated dicarboxylic acids and glycols having 2 to 18 carbon atoms or polyalkylene glycols having 2 to 500 additional moles of these glycols;
Half-amides of maleamic acid and glycols with 2 to 18 carbon atoms or polyalkylene glycols with 2 to 500 moles of these glycols;
Esters of alkoxy (poly) alkylene glycol obtained by adding 1 to 500 mol of alkylene oxide having 2 to 18 carbon atoms to alcohol having 1 to 30 carbon atoms and unsaturated monocarboxylic acids such as (meth) acrylic acid; Alkoxy 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, and (poly) butylene glycol monomethacrylate. 1-500 mol additives;

(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 Di (meth) acrylates;
Polyfunctional (meth) acrylates such as hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and trimethylolpropane di (meth) acrylate;
(Poly) alkylene glycol dimalates such as triethylene glycol dimalate and polyethylene glycol dimalate;
Vinyl Sulfonate, (Meta) Allyl Sulfonate, 2- (Meta) Acryloxyethyl Sulfonate, 3- (Meta) Acryloxypropyl Sulfonate, 3- (Meta) Acryloxy-2-Hydroxypropyl Sulfonate, 3- (Meta) Acryloxy-2 -Hydroxypropyl sulfophenyl ether, 3- (meth) acryloxy-2-hydroxypropyloxysulfobenzoate, 4- (meth) acryloxybutyl sulfonate, (meth) acrylamide methyl sulfonic acid, (meth) acrylamide ethyl sulfonic acid, 2- Unsaturated sulfonic acids such as methylpropanesulfonic acid (meth) acrylamide and styrenesulfonic acid, and their monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts;
Amides of unsaturated monocarboxylic acids such as methyl (meth) acrylamide and amines with 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, and 1,6-hexanediol mono (meth) acrylate;
Dienes such as butadiene, isoprene, 2-methyl-1,3-butadiene, 2-chlor-1,3-butadiene;

Unsaturated amides such as (meth) acrylamide, (meth) acrylic alkylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide;
(Meta) Unsaturated cyanes such as acrylonitrile and α-chloroacrylonitrile;
Unsaturated esters such as vinyl acetate and vinyl propionate;
Unsaturation of (meth) aminoethyl 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
Polydimethylsiloxane propylaminomale amidoic acid, polydimethylsiloxane aminopropylene aminomale amidoic acid, polydimethylsiloxane-bis- (propylaminomale amidoic acid), polydimethylsiloxane-bis- (dipropylene aminomale amidoic acid), polydimethyl Siloxane- (1-propyl-3-acrylate), polydimethylsiloxane- (1-propyl-3-methacrylate), polydimethylsiloxane-bis- (1-propyl-3-acrylate), polydimethylsiloxane-bis- (1) A siloxane derivative such as −propyl-3-methacrylate).

<Example of copolymer B>
Examples of the copolymer (B) include the following copolymers B-1 and B-2. The copolymer (B) is preferably the copolymer B-1 or the copolymer B-2 shown below. The copolymer (B) may contain only one type or two or more types of the copolymer (B) as a structural unit derived from the monomers represented by the general formulas (1) to (3). ..

(Copolymer B-1)
The copolymer B-1 contains a structural unit derived from the monomer (I) represented by the general formula (1) and a structural unit derived from the monomer (II) represented by the general formula (2). Including. Preferably, in the copolymer B-1, the structural unit derived from the monomer (I) / the structural unit derived from the monomer (II) is 1/99 to 99/1 in a molar ratio, which is preferable. Is 10/90 to 90/10.

(Copolymer B-2)
The copolymer B-2 is represented by the monomer (I) represented by the general formula (1), the monomer (II) represented by the general formula (2), and the general formula (3). Contains monomer (III). Preferably, in the copolymer B-3, in a molar ratio, a structural unit derived from the monomer (I) / (a structural unit derived from the monomer (II) + a configuration derived from the monomer (III)). The unit) is 1/99 to 99/1, more preferably 10/90 to 90/10.

<Method for producing copolymer (B)>
The copolymer (B) in the present invention 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; and fats such as cyclohexane and n-hexane. Cyclic or aliphatic 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 obtained copolymer, 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 copolymerization is carried out in a solvent, each monomer and the polymerization initiator may be continuously added dropwise to the reaction vessel, or a mixture of the monomers and the polymerization initiator may be continuously added dropwise to the reaction vessel. You may. Further, the solvent may be charged into the reaction vessel, and the mixture of the monomer and the solvent and the polymerization initiator solution may be continuously added dropwise to the reaction vessel, or a part or all of the monomer may be charged into the reaction vessel. The polymerization initiator may be continuously added dropwise.

(Initiator)
The polymerization initiator that can be used for copolymerization is not particularly limited, but when copolymerization is carried out in an aqueous solvent, for example, persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; t-butyl Examples thereof include water-soluble organic peroxides such as hydroperoxide. At this time, an accelerator such as sodium bisulfite or molle salt may be used in combination. Further, when performing copolymerization in a solvent such as a lower alcohol, an aromatic hydrocarbon, an alicyclic or aliphatic hydrocarbon, an ester or a ketone, for example, a peroxide such as a benzoyl peroxide or a lauryl peroxide is used. Hydrocarbons such as cumene peroxide; aromatic azo compounds such as azobisisobutyronitrile can be used as the polymerization initiator. At this time, an accelerator such as an amine compound may be used in combination. Further, when copolymerization is carried out in a water-lower alcohol mixed solvent, for example, the above-mentioned polymerization initiator or combination of the polymerization initiator and the accelerator can be appropriately selected and used. The polymerization temperature varies depending on the polymerization conditions such as the solvent used and the type of the polymerization initiator, but is usually in the range of 50 to 120 ° C.

(Chain transfer agent)
Further, in the copolymerization, the molecular weight may be adjusted by using a chain transfer agent, if necessary. Chain transfer agents used include, for example, mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thioapple acid, octyl thioglycolate, and 2-mercaptoethanesulfonic acid. Known thiol compounds; sodium bisulfite, hypophosphite, and salts thereof (sodium bisulfite, potassium hypophosphate, etc.), sulfite, hydrogen sulfite, dithionic acid, metabisulfite, and their salts. Lower oxides of salts (sodium bisulfite, potassium sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, sodium bisulfite, potassium bisulfite, sodium metabisulfite, potassium metabisulfite, etc.) and salts thereof; etc. Be done. These may be used alone or in combination of two or more. Further, in order to adjust the molecular weight of the copolymer (B), as a monomer for obtaining the copolymer (B), in addition to the above-mentioned monomers (I) to (IV), further chain transfer is possible. Higher monomers (V) may be used. Examples of the monomer (V) having high chain transferability include (meth) allylsulfonic acid (salt) -based monomers. The blending ratio of the monomer (V) is usually 20% by weight or less, preferably 10% by weight or less in the copolymer (B). The above compounding ratio is the compounding ratio of the monomer (I) + the compounding ratio of the monomer (II) + the compounding ratio of the monomer (III) + the compounding ratio of the monomer (IV) = 100% by weight. It is the compounding ratio when.

(Neutralization)
When copolymerizing in an aqueous solvent when obtaining a copolymer, the pH at the time of polymerization is usually 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, adjust the pH using an acidic substance such as phosphoric acid, sulfuric acid, nitric acid, alkylphosphate, alkylsulfuric acid, alkylsulfonic acid, or (alkyl) benzenesulfonic acid. Can be done. Among these acidic substances, it is preferable to use phosphoric acid because it has a pH buffering action. However, in order to eliminate the instability of the ester bond of the ester-based monomer, it is preferable to carry out the polymerization at pH 2 to 7. The alkaline substance that can be used for adjusting the pH is not particularly limited, but alkaline substances such as NaOH and Ca (OH) ₂ are generally used. The pH adjustment may be performed on a solution containing a monomer before polymerization, or may be performed on a solution containing a copolymer after polymerization. Further, these may be polymerized by adding a part of alkaline substances before the polymerization, and then the pH of the solution containing the copolymer may be adjusted.

(Molecular weight)
The weight average molecular weight of the copolymer (B) is preferably 5,000 or more, more preferably 6,000 or more, and even more preferably 6,500 or more. As a result, the dispersibility of the hydraulic material of the additive for 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, and the fluidity and / Alternatively, the workability is improved, and the desired effect as a cement additive (cement dispersant) can be sufficiently exhibited. 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. As a result, the agglutination action of cement particles is suppressed, and workability can be improved. The weight average molecular weight is preferably 5,000 to 60,000.
The molecular weight distribution (Mw / Mn) of the copolymer (B) 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 1.0 to 3.0, more preferably in the range of 1.2 to 3.0.

The weight average molecular weight in the present invention can be measured by a known method of converting to polyethylene glycol by gel permeation chromatography (GPC).
The measurement conditions for GPC are not particularly limited, but the following conditions can be mentioned as examples. The weight average molecular weight in the latter example is a value measured under this condition.
Measuring device: Made by Tosoh Columns used: Shodex Volume OH-pak SB-806HQ, SB-804HQ, SB-802.5HQ
Eluent: 0.05 mM sodium nitrate / acetonitrile 8/2 (v / v)
Standard substance: Polyethylene glycol (manufactured by Tosoh, manufactured by GL Science)
Detector: Differential refractometer (manufactured by Tosoh)
Calibration curve: Polyethylene glycol standard

<Contents of component A and component B>
The contents of the component (A) and the component (B) in the additive for the hydraulic composition of the present invention are not particularly limited. When the additive for the hydraulic composition is in the form of an aqueous solution described later, the content of the component (A) in the additive for the hydraulic composition is preferably relative to the additive for the hydraulic composition. It is 0.1% by weight to 1.5% by weight. The content of the component (B) in the additive for the hydraulic composition is preferably 4.5% by weight to 20% by weight with respect to the additive for the hydraulic composition.

<Weight ratio of component A to component B>
The weight ratio ((A) / (B)) of the water-soluble thickener (A) to the copolymer (B) in the additive for a hydraulic composition of the present invention is 0.01 / 99.99 to 25 /. It is 75, preferably 0.02 / 99.98 or more, more preferably 1/99 or more, further preferably 5/95 or more, preferably 20/80 or less, and more preferably. , 15/85 or less. The weight ratio ((A) / (B)) is preferably 0.01 / 99.99 to 20/80, and more preferably 1/99 to 20/80.

<Containing form of component A and component B>
In the additive for a water-hard composition of the present invention, the content forms of the components (A) and (B) are not limited, and the components (A) and (B) may be contained as they are, or the components (A) and (B) may be contained as they are. B) Each or both of the components may be blended as a solution in which a solvent is dissolved, a dispersion in which the components are dispersed, or a suspension in which the components are suspended.

The additive for a hydraulic composition of the present invention can be in the form of an aqueous solution containing the components (A) and (B) in which the components (A) and (B) are dissolved in water.

<Usage form and usage of additives for hydraulic composition>
The additive for a hydraulic composition of the present invention is usually preferably used in the form of an aqueous solution, but it can also be used in the form of a dried powder. The time when the additive for the hydraulic composition is contained in the hydraulic composition is not particularly limited, and may be, for example, when the hydraulic composition is used. Further, the additive for the hydraulic composition of the present invention in a powdered form is mixed in advance with the components other than water constituting the cement composition such as cement powder and dry mortar, and plastered and floored. It can also be used as a premix product to be used by adding water for finishing, grouting and the like.

The additive for hydraulic composition of the present invention can be added to a hydraulic material such as cement and used as a hydraulic composition (eg, cement composition) such as cement paste, mortar, concrete, plaster, grout and the like. it can. The additive for a hydraulic composition of the present invention can impart material separation resistance and appropriate fluidity to the hydraulic composition, and can adjust the initial fluidity of the hydraulic composition. Therefore, the additive for hydraulic composition of the present invention can be particularly preferably used for medium-fluidity concrete, high-fluidity concrete, and inseparable underwater concrete, and fills cavities, voids, gaps, and the like. Therefore, it can be suitably used as an additive for a fluid liquid (grout, injection grout) to be injected, or as an additive for improving the state of concrete even in ordinary concrete.

<Hydraulic composition containing additives for hydraulic composition>
The hydraulic composition of the present invention (eg, cement composition) may contain an additive for the hydraulic composition, and the hydraulic material to be combined is not particularly limited. Examples of the hydraulic material include cement, gypsum (hemihydrate gypsum, dihydrate gypsum, etc.), and dolomite. The most common hydraulic material is cement.

The cement is not particularly limited. For example, Portoland cement (normal, early-strength, ultra-fast-strength, moderate heat, sulfate-resistant and each low-alkali form), various mixed cements (blast furnace cement, silica cement, fly ash cement), white Portorand cement, alumina cement, Ultra-fast-hardening cement (1 clinker fast-hardening cement, 2 clinker fast-hardening cement, magnesium phosphate cement), grout cement, oil well cement, low heat-generating cement (low-heat-generating blast furnace cement, fly ash mixed low-heat-generating blast furnace cement, belite High-content cement), ultra-high-strength cement, cement-based solidifying material, eco-cement (cement manufactured from one or more of municipal waste incineration ash and sewage sludge incineration ash) and the like. Fine powder such as blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, limestone powder, gypsum and the like may be added to the cement.

In addition, the cement composition may contain aggregate. The aggregate may be either a fine aggregate or a coarse aggregate. Aggregates include, for example, sand, gravel, crushed stone; granulated slag; recycled aggregate, etc .; silica stone, clayey, zirconite, high alumina, silicon carbide, graphite, chromium, chromogy, magnesia. And other refractory aggregates.

The blending ratio of the additive for the hydraulic composition in the hydraulic composition (eg, cement composition) is not particularly limited, and for example, the target hydraulic composition (eg, cement composition, concrete). An amount that can realize the rheology (fluidity) of the above may be blended. For example, when the hydraulic composition (cement composition) is mortar or concrete, the addition amount (blending amount) of the additive for the hydraulic composition of the present invention is preferable with respect to the total weight of the cement. Is 0.01 to 5.0% by weight, more preferably 0.02 to 2.0% by weight, still more preferably 0.05 to 1.0% by weight. By setting this addition amount, the obtained cement composition has various preferable substances such as material separation resistance, rheological property, fluidity, reduction of unit water amount, increase of strength, and improvement of durability. The effect is fully brought about. If the above compounding ratio is less than 0.01% by weight, the obtained cement composition may not have sufficient performance, and conversely, even if a large amount exceeding 5.0% by weight is used, the effect is substantially effective. It may reach a plateau and be disadvantageous in terms of economy.

The above cement composition is effective as concrete such as ready mixed concrete, concrete for secondary concrete products (precast concrete), concrete for centrifugal molding, concrete for vibration compaction, steam curing concrete, and sprayed concrete. .. Furthermore, medium-fluidity concrete (concrete with a slump value in the range of 22 to 25 cm), high-fluidity concrete (concrete with a slump value of 25 cm or more and a slump flow value in the range of 50 to 70 cm), self-filling concrete, self-leveling material. It is also effective as mortar or concrete that requires high fluidity such as.

The additive for a hydraulic composition of the present invention can be used as it is as a dispersant for a hydraulic material (eg, cement) or an AE water reducing agent. In particular, since the additive for hydraulic composition of the present invention has less foaming, it is not necessary to use an antifoaming agent in combination. However, the additive for hydraulic composition of the present invention may be used in combination with other optional components such as an antifoaming agent. For example, the additive for hydraulic composition of the present invention is still another dispersant for hydraulic composition, water-soluble polymer, polymer emulsion, air entraining agent, cement wetting agent, swelling agent, waterproofing agent, retarding agent. , Thickeners, flocculants, drying shrinkage reducing agents, strength enhancers, effect promoters, defoaming agents, AE agents, and other known concrete additives such as surfactants may be used in combination. The other additives may be used alone or in combination of two or more. Examples of known additives for concrete include, but are not limited to, the following additives.

A compound containing a carboxyl group and / or a salt thereof (CA agent) (eg, sodium polyacrylate, sodium gluconate). One or more of these compounds may be used.

A compound containing a sulfonic acid group and / or a salt thereof (SA agent) (eg, sodium lignin sulfonate, naphthalene sulfonic acid). One or more of these compounds may be used.

When the additive for a hydraulic composition of the present invention and the above-mentioned (CA agent) and / or (SA agent) additive are used in combination, the ratio is not particularly limited. For example, the weight ratio when the two components are used in combination is the additive for the water-hard composition of the present invention / ((CA agent) or (SA agent)) = 0.1% by weight / 99.9% by weight to 99. It is 9% by weight / 0.1% by weight, and the weight ratio when the three components are used in combination is the additive for the water-hard composition of the present invention / ((CA agent) + (SA agent)) = 0.1% by weight. % / 99.9% by weight to 99.9% by weight / 0.1% by weight.

The present invention will be described in more detail with reference to Examples below, but the present invention is not limited thereto. Unless otherwise specified, parts indicate parts by weight and% indicates% by weight.

<Component A>
In the examples and comparative examples, the following water-soluble thickeners (A-1) to (A-2) were used as the component A.
<A-1> Methyl cellulose (manufactured by Shin-Etsu Chemical, Metrose SM)
<A-2> Hydroxypropyl methylcellulose (manufactured by Shin-Etsu Chemical Co., Ltd., Metrose 60SH)

<B component>
In the examples, the following copolymers (B-1) to (B-3) were used as the B component.
<Manufacturing example B1>
501 parts of water, 3-methyl-3-butene-1-ol ethylene adduct adduct (average number of moles of ethylene oxide adduct) in a glass reaction vessel equipped with a thermometer, agitator, reflux device, nitrogen introduction tube and dropping device. (25 pieces) 400 parts were charged, the inside of the reaction vessel was replaced with nitrogen under stirring, and the temperature was raised to 80 ° C. under a nitrogen atmosphere. Then, an aqueous monomer solution prepared by mixing 80 parts of acrylic acid and 532 parts of water and a mixed solution of 10 parts of ammonium persulfate and 190 parts of water were continuously added dropwise to a reaction vessel kept at 80 ° C. for 1 hour each. Further, an aqueous solution of the copolymer was obtained by reacting for 1 hour while keeping the temperature at 100 ° C. The copolymer in the liquid was a copolymer (B-1) (weight average molecular weight 22,000, Mw / Mn 1.7).

<Manufacturing example B2>
A glass reaction vessel equipped with a thermometer, agitator, a reflux device, a nitrogen introduction tube and a dropping device was charged with 400 parts of water and 600 parts of an ethylene oxide adduct of metallic alcohol (average number of moles of ethylene oxide added: 48). The inside of the reaction vessel was replaced with nitrogen under stirring, and the temperature was raised to 60 ° C. under a nitrogen atmosphere. Then, an aqueous monomer solution prepared by mixing 105 parts of 2-hydroxypropyl acrylate and 391 parts of water and a mixed solution of 12 parts of ammonium persulfate and 188 parts of water were continuously added dropwise to a reaction vessel kept at 80 ° C. for 1 hour each. .. Further, an aqueous solution of the copolymer was obtained by reacting for 1 hour while keeping the temperature at 100 ° C. The copolymer in the liquid was a copolymer (B-2) (weight average molecular weight 25,200, Mw / Mn 1.7).

<Manufacturing example B3>
148 parts of water in a glass reaction vessel equipped with a thermometer, agitator, reflux device, nitrogen introduction tube and dropping device, and polyethylene glycol polypropylene glycol monoallyl ether (average number of moles of ethylene oxide added 37, average of propylene oxide) 94 parts of ethylene oxide and propylene oxide (random addition of ethylene oxide and propylene oxide) were charged with 3 additional moles, the inside of the reaction vessel was replaced with nitrogen under stirring, and the temperature was raised to 80 ° C. under a nitrogen atmosphere. After that, 35 parts of methacrylic acid, 5 parts of acrylic acid, 63 parts of methoxypolyethylene glycol methacrylate (average number of moles of ethylene oxide added 25), 60 parts of 2-hydroxypropyl acrylate, 8 parts of 3-mercaptopropionic acid, 165 parts of water. And a mixed solution of 3 parts of ammonium persulfate and 47 parts of water were continuously added dropwise to a reaction vessel kept at 80 ° C. for 2 hours each. Further, an aqueous solution of the copolymer was obtained by reacting for 1 hour while keeping the temperature at 100 ° C. The copolymer in the liquid was a copolymer (B-3) (weight average molecular weight 11,100, Mw / Mn1.5).

<Comparison example>
In the comparative example, Floric S (manufactured by Floric, main component: lignin sulfonate and oxycarboxylic acid salt) was used as the AE water reducing agent.

<Example 1, Reference Example 2, Examples 2-9 and Comparative Examples 1 and 2>
A component: A-1, A-2 and B component: B-1, B-2, B-3, or AE water reducing agent: Floric S instead of B component are mixed in the combination shown in Table 1. Then, a cement additive (additive for hydraulic composition) was prepared. The obtained cement additive was subjected to the following compatibility test, foaming evaluation, and viscosity measurement.

<Compatibility test>
The compatibility between the water-soluble thickener (component A) and the copolymer (component B) was tested according to the following procedure.
The cement additives of Examples 1, Reference Example 2, Examples 2 to 9 and Comparative Examples 1 and 2 were prepared (kneaded) and then stored at 20 ° C. and 40 ° C. for one month to prepare the cement additives. The degree of separation was evaluated. The evaluation criteria are as follows. The less turbidity, the less separation and the better the compatibility between the components. The results of the compatibility test are shown in Table 3.
⊚: There is almost no turbidity.
◯: There is some turbidity, but there is no problem in use.
Δ: There is turbidity.
×: Very cloudy.

<Evaluation of foaming>
10 ml of the cement additive of Example 1, Reference Example 2, Examples 2 to 6 and Comparative Example 1 to 2 was added to a vial (volume 50 ml) containing a stirrer bar, and a magnetic stirrer (manufactured by Tokyo University of Science and Technology) was added. ) After stirring at 300 rpm for 1 minute, foaming on the liquid surface was visually evaluated. The evaluation results of foaming are shown in Table 2.
⊚: Very little foaming.
◯: There is little foaming.
×: Lots of foaming

<Viscosity measurement>
The viscosities of the cement additives of Examples 1, Reference Example 2, Examples 2-9 and Comparative Examples 1 and 2 were also measured. The viscosity was measured using a B-type viscometer at 20 ° C. and 60 rpm. The results are shown in Table 3.

<Concrete test>
Concrete (cement composition, hydraulic composition) to which the cement additives of Examples 1, Reference Example 2, Examples 2 to 9 and Comparative Examples 1 and 2 were added was prepared by the following procedure, and the obtained concrete was prepared. A slump test, air volume measurement, viscosity evaluation, and bleeding evaluation were performed.
At the ambient temperature (20 ° C.), the coarse aggregate, fine aggregate, cement, and water formulated as shown in Table 4 and the cement additive shown in Table 1 are added to the forced biaxial mixer, and the forced biaxial mixer is used. The mixture was mechanically kneaded for 90 seconds. The cement additive was mixed with water and charged into a forced biaxial mixer. Then, immediately after the concrete was discharged from the forced biaxial mixer, a fresh concrete test (slump test JIS A1101 (measured by measuring the spread of fresh concrete as a flow value), air volume JIS A1128, concrete viscosity evaluation) was performed. The viscosity of concrete was evaluated by a sensory evaluation by five evaluators according to the following criteria. The test results are shown in Table 5.

<Evaluation criteria for viscosity>
◎: The handling when the concrete is cut back with a scoop is very good, and the separation of the concrete from the scoop is very good.
◯: Good handling when cutting back concrete with a shovel, and good separation of concrete from the shovel.
×: The handling when the concrete is cut back with a shovel is poor, and the concrete is not separated from the shovel poorly.

<Bleeding evaluation>
The evaluation was performed by the method specified in JIS A1123. The smaller the bleeding amount, the more the concrete has material separation resistance. The results are shown in Table 5.

C: Equal weight mixture of the following three types of cement Ordinary Portland cement (manufactured by Ube-Mitsubishi Cement Co., Ltd., specific gravity 3.16)
Ordinary Portland cement (manufactured by Taiheiyo Cement Co., Ltd., specific gravity 3.16)
Ordinary Portland cement (manufactured by Tokuyama Corporation, specific gravity 3.16)
W: Tap water S1: Mountain sand from Kakegawa (fine aggregate, specific gravity 2.57)
S2: Crushed sand from Iwase (fine aggregate, specific gravity 2.61)
G: Crushed stone from Ome (coarse aggregate, specific gravity 2.65)
Cement additive (solid content conversion) See Table 5.

In Table 5, the "addition rate" of the cement additive indicates the tangible addition rate of the additive to the cement. In addition, SL indicates a slump, respectively.

As is clear from the results shown in Table 3, the cement additives of Examples 1 to 9 have less turbidity, good compatibility with the water-soluble thickener and the copolymer, less foaming, and the cement additive. There was no problem with the properties of. Further, as is clear from the results shown in Table 5, a predetermined fluidity can be obtained in the concrete using the cement additive of Examples 1 to 9, and the cement additive of Comparative Example 1 or 2 was used. The amount of bleeding could be reduced compared to concrete. As a result of the above, the additive for a hydraulic composition of the present invention has excellent compatibility of the contained components, and imparts rheology (appropriate fluidity) and material separation resistance to the hydraulic composition. Show to get.

Claims (4)

Water-soluble thickener (A) and
A structural unit derived from a monomer represented by the following general formula (1), a structural unit derived from a monomer represented by the following general formula (2), and a simple unit represented by the following general formula (3). A copolymer (B) containing a structural unit derived from a dimer and
Including
The water-soluble thickener (A) contains hydroxypropylmethyl cellulose and contains
Weight ratio copolymer of water-soluble thickener (A) (B) (( A) / (B)) is Ri 0.01 / 99.99 to 25/75 der,
The copolymer (B) contains at least a structural unit derived from hydroxypropyl (meth) acrylate as a structural unit derived from the monomer represented by the general formula (3).
It is an aqueous solution,
Additives for hydraulic compositions.

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

(In the formula,
R ⁵ , R ⁶ and R ⁷ independently represent a hydrogen atom, -CH ₃ , or (CH ₂ ) _r COM ² , and-(CH ₂ ) _r COM ² is -COOM ¹ or other-. (CH ₂ ) _r COM ² may form an anhydride, in which case M ¹ and M ² of those groups are absent.
M ¹ and M ² represent the same or different hydrogen atoms, alkali metals, alkaline earth metals, ammonium groups, alkylammonium groups, or substituted alkylammonium groups.
r represents an integer from 0 to 2. )

(In the formula,
R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
R ¹¹ represents a hydrocarbon group which may contain a heteroatom having 1 to 4 carbon atoms.
s represents an integer from 0 to 2.
However, the monomer represented by the general formula (3) does not include the monomer represented by the general formula (1). ) The additive for a hydraulic composition according to claim 1, which contains two or more kinds of water-soluble thickeners (A). The additive for a hydraulic composition according to claim 1 or 2, which contains two or more kinds of copolymers (B). A hydraulic composition comprising the additive for a hydraulic composition according to any one of claims 1 to 3 .