JP2007277575A - Polycarboxylic acid copolymer, its manufacturing method, and its use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polycarboxylic acid copolymer making water-reducing property and operability of a cement composition etc. excellent, and, when fluidity and water-reducing property are the same, making its handling easier, its manufacturing method, and a cement additive and a cement composition containing it, and further a polycarboxylic acid copolymer and a cement additive capable of using favorably in an ultrahigh strength concrete for its ability to improve the strength and durability of its cured products, and a manufacturing method of the polycarboxylic acid copolymer having high water-reducing performance and capable of improving operability in cemnent construction by reducing the viscosity of the cement composition etc. <P>SOLUTION: This polycarboxylic acid copolymer is formed by copolymerization of a polyalkylene glycol unsaturated monomer (A2) having an oxyalkylene group bonded to a polyhydric alcohol residue, and a monomer component containing an unsaturated monocarboxylic acid monomer (B'). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a polycarboxylic acid copolymer, a method for producing a polycarboxylic acid copolymer, a cement additive, and a cement composition. More specifically, a polycarboxylic acid copolymer that can be suitably used as a water reducing agent for ultra-high strength, a method for producing a polycarboxylic acid copolymer, and a cement additive comprising the polycarboxylic acid copolymer And a cement composition.

Polycarboxylic acid-based copolymers are widely used as components of cement additives such as cement compositions such as cement paste, mortar and concrete, and are indispensable for building civil engineering and building structures from cement compositions. It is impossible. A cement additive containing such a polycarboxylic acid copolymer is used as a water reducing agent, and improves the strength and durability of the cured product by reducing the cement composition by increasing the fluidity of the cement composition. Will have the effect of Such a water reducing agent has a high performance as a high-performance AE water reducing agent because it exhibits higher water reducing performance than conventional water reducing agents such as naphthalene.

By the way, high strength and durability are required for the foundations of civil engineering and building structures, and so-called ultra-high-strength concrete that exhibits high performance among concrete is used. As such a water reducing agent for ultra high strength concrete, an ultra high strength water reducing agent having high water reducing performance is used so that the amount of water in the concrete is sufficiently reduced to exhibit high performance. . For example, a copolymer of methacrylic acid and methacrylic acid polyethylene oxide ester is used as the ultrahigh strength water reducing agent. However, when ultrahigh strength concrete is produced using this ultrahigh strength water reducing agent, the viscosity is reduced. There is a need for a super-high-strength water reducing agent that can improve workability because it becomes high concrete.

An alkenyl ether and a maleic anhydride having an oxyalkylene group having 2 to 40 carbon atoms and a terminal structure in which the alkenyl group having 4 to 5 carbon atoms and the specific group having 1 to 24 carbon atoms are essential Is used as a water reducing agent (see, for example, Patent Document 1). However, there is room for devising the structure and properties of the copolymer in order to be suitably applied to the use as a water reducing agent for ultra high strength.

A specific polyamine monomer as compound A, a specific unsaturated carboxylic acid monomer as compound B, and a specific polyalkylene glycol monomer as compound C, compound A: compound B: compound C = 10-40 wt%: 10-40 wt%: 50-80 wt% copolymerized with a water-soluble amphoteric copolymer as a main component. It is disclosed that it can be used as an agent and has excellent on-site workability (for example, see Patent Document 2).

However, in all examples in this publication, compound A, compound B and compound C are copolymerized to obtain a water-soluble amphoteric copolymer, but when high strength concrete is prepared, its viscosity is high. There was a problem in workability due to poor scoop work.
JP-A-7-215746 JP 2000-191356 A

The present invention has been made in view of the above-mentioned present situation, and is excellent in water reduction and workability of cement compositions, etc., and can be handled more easily when fluidity and water reduction are the same. An object of the present invention is to provide an acid copolymer, a method for producing the acid copolymer, a cement additive and a cement composition comprising the acid copolymer. Moreover, since the cured product can be excellent in strength and durability, it is intended to provide a polycarboxylic acid copolymer and a cement additive that can be suitably used for ultra-high-strength concrete. To do. Also provided is a production method for obtaining a polycarboxylic acid copolymer that has high water reduction performance, lowers the viscosity of a cement composition, etc., and has excellent workability during cement construction. It is also the purpose.

As a result of diligent research on a polycarboxylic acid copolymer that can be used as a water reducing agent for ultrahigh strength, the present inventors have found that a polyalkyleneimine unsaturated monomer (A1) and an unsaturated carboxylic acid system Paying attention to polycarboxylic acid copolymer obtained by copolymerizing monomer component which has monomer (B) as essential, if such copolymer has the same fluidity and water-reducing property, it will be handled more It was conceived that an easy-to-use cement composition can be provided and can be suitably used for ultra-high strength concrete and the like. In addition, the polyalkyleneimine unsaturated monomer (A1) may have an oxyalkylene group, or a polyalkylene glycol unsaturated monomer (A3) other than the monomer having an oxyalkylene group. It has also been found that polycarboxylic acid copolymers obtained by copolymerizing essential monomer components can be suitably used for ultra-high-strength concrete and the like.

In addition, polyalkylene glycol unsaturated monomer (A2) and unsaturated monocarboxylic acid monomer (B ′) having a structure in which an oxyalkylene group is bonded to a polyhydric alcohol residue, or a polyhydric alcohol residue. A monomer component comprising a polyalkylene glycol unsaturated monomer (A2 ′) and an unsaturated carboxylic acid monomer (B) having a structure in which an oxyalkylene group is bonded to a group and having a terminal hydroxyl group The monomer component containing the copolymerized polycarboxylic acid copolymer exhibits the same effect as described above, and together with these monomers, the polyalkylene glycol unsaturated monomer (A2 In addition, polycarboxylic acid copolymers obtained by copolymerizing monomer components that are also essential polyalkylene glycol unsaturated monomers (A3) other than) are preferably used for ultra-high-strength concrete. It has also been found that can Rukoto.

Furthermore, in the method for producing a polycarboxylic acid copolymer by copolymerizing a monomer mixture containing a monomer (A) having an oxyalkylene group and an unsaturated carboxylic acid monomer (B), By introducing a hydrophobic group into a part of the copolymer using a functional chain transfer agent, the resulting cement additive containing the polycarboxylic acid copolymer has high water reducing performance and has a cement composition. It has been found that the workability during construction of cement compositions and the like can be improved by reducing the viscosity of the materials.

And a cement additive containing these polycarboxylic acid-based copolymers, a cement additive having a calcium transport value of 10 to 900 mPa · s and / or a cement operating coefficient of 0.05 to 1.0, pH 12 It has been found that a cement composition using a cement additive that has been refined after adjusting to ˜12.5 and that satisfies a specific analytical value can be handled more easily when the flowability and water reduction are the same. The present invention has been reached.

That is, the present invention is a polycarboxylic acid copolymer obtained by copolymerizing a monomer component containing a polyalkyleneimine unsaturated monomer (A1) and an unsaturated carboxylic acid monomer (B). .
The present invention also includes a single monomer comprising a polyalkylene glycol unsaturated monomer (A2) and an unsaturated monocarboxylic acid monomer (B ′) having a structure in which an oxyalkylene group is bonded to a polyhydric alcohol residue. It is also a polycarboxylic acid copolymer obtained by copolymerizing body components.
The present invention also includes a polyalkylene glycol-based unsaturated monomer (A2 ′) and an unsaturated carboxylic acid-based monomer having a structure in which an oxyalkylene group is bonded to a polyhydric alcohol residue and having a terminal hydroxyl group ( It is also a polycarboxylic acid copolymer obtained by copolymerizing a monomer component containing B).

The present invention is also obtained by copolymerizing a monomer component containing a monomer (A) having an oxyalkylene group and an unsaturated carboxylic acid monomer (B) using a hydrophobic chain transfer agent. It is also a method for producing a polycarboxylic acid copolymer.
The present invention is also a polycarboxylic acid copolymer obtained by the above-described method for producing a polycarboxylic acid copolymer.
The present invention is also a cement additive comprising the polycarboxylic acid copolymer.

The present invention is also a cement additive having a calcium transport value of 10 to 900 mPa · s and / or a cement operating coefficient of 0.05 to 1.0.

In the present invention, when purified after adjusting to pH 12 to 12.5, the amount of nitrogen by elemental analysis is 0.1 to 20% by weight, and morpholine and 4- (2-hydroxyethyl) are obtained by pyrolysis GC-MASS. Morpholine and 1-4 dioxane are detected, the GPC peak has no shoulder, the weight average molecular weight (Mw) is 5000 to 300,000, and the absorption peak intensity present at 1640 to 1660 cm ⁻¹ is 1710 in IR measurement. It is 20% or less of the absorption peak intensity existing at ˜1630 cm ⁻¹ , signals are detected at chemical shift positions of 60 to 61 ppm and 69 to 68 ppm by ¹³ C-NMR, and the amount of NMR-PEG is 10 to 99% by weight. Yes, a cement additive with a TCAV of 3 to 900 mg KOH / g.

The present invention is also a cement composition comprising at least water, cement and a cement additive, wherein the cement additive is also a cement composition using the cement additive.
The present invention is described in detail below.

The polycarboxylic acid copolymer of the present invention is obtained by copolymerizing monomer components including (1) a polyalkyleneimine unsaturated monomer (A1) and an unsaturated carboxylic acid monomer (B). Or (2) a polyalkylene glycol-based unsaturated monomer (A2) having a structure in which an oxyalkylene group is bonded to a polyhydric alcohol residue (hereinafter simply referred to as a polyalkylene glycol-based unsaturated monomer) Body (A2)) and a monomer component containing unsaturated monocarboxylic acid monomer (B ′), or (3) a polyhydric alcohol residue. A polyalkylene glycol unsaturated monomer (A2 ′) having a structure in which an oxyalkylene group is bonded and having a terminal hydroxyl group (hereinafter, also simply referred to as a polyalkylene glycol unsaturated monomer (A2 ′)), and Unsaturated carvone Systems monomer a monomer component containing (B) are those copolymerized composed form. In such a polycarboxylic acid copolymer, the monomer (A1) and the monomer (A2) or the monomer (A2 ′) may be used in combination. That is, the polyalkyleneimine unsaturated monomer (A1) and / or the polyalkylene glycol unsaturated monomer (A2) or (A2 ′) and the unsaturated carboxylic acid monomer (B) are essential. The monomer component to be copolymerized is formed. These monomers may be used alone or in combination of two or more. In the present specification, the polyalkylene glycol unsaturated monomer (A2) includes a polyalkylene glycol unsaturated monomer (A2 ′) having a hydroxyl group at the end, and an unsaturated carboxylic acid. The monomer (B) includes an unsaturated monocarboxylic acid monomer (B ′). The polyalkylene glycol unsaturated monomer (A2) is a polyalkylene glycol unsaturated monomer (A2) or a polyalkylene glycol unsaturated monomer (A2) It means the polyalkylene glycol unsaturated monomer (A2 ′) whose terminal is a hydroxyl group, and the unsaturated carboxylic acid monomer (B) is the above (1), (2) or (3) The unsaturated carboxylic acid monomer (B) or the unsaturated monocarboxylic acid monomer (B ′) is meant in accordance with the respective forms.

In a preferred embodiment of the present invention, the polyalkyleneimine unsaturated monomer (A1) has an oxyalkylene group. In the polycarboxylic acid copolymer in the form of the above (1), (2) and (3), the weight ratio of these monomers is the monomer (A1) and / or the monomer (A2). Is preferably 1 to 99% by weight, and the monomer (B) is preferably 99 to 1% by weight. When the weight ratio of these monomers is out of the above range, the function of the repeating unit formed by each monomer cannot be effectively exhibited as described later, and the effects of the present invention are sufficiently obtained. It cannot be expressed. More preferably, the monomer (A1) and / or the monomer (A2) is 20 to 95% by weight, and the monomer (B) is 80 to 5% by weight. The weight ratio of the monomers (A1) and / or (A2) and (B) is 100% by weight of the total weight of the monomers (A1) and / or (A2) and (B). % By weight.

In the present invention, it is preferable that the monomer component further contains a polyalkylene glycol unsaturated monomer (A3) other than the monomer having the oxyalkylene group. The monomer having an oxyalkylene group is a polyalkyleneimine unsaturated monomer (A1) having an oxyalkylene group in the form (1), and in the forms (2) and (3). And a polyalkylene glycol unsaturated monomer (A2) having a structure in which an oxyalkylene group is bonded to a polyhydric alcohol residue. By including such a polyalkylene glycol unsaturated monomer (A3), the effects of the present invention can be exhibited more. In this case, the monomer (A1) and / or (A2) is 1 to 98% by weight, the monomer (B) is 1 to 98% by weight, and the monomer (A3) is 1 to 98% by weight. Preferably there is. More preferably, the monomer (A1) and / or (A2) is 1 to 80% by weight, the monomer (B) is 1 to 50% by weight, and the monomer (A3) is 30 to 98% by weight. More preferably, the monomer (A1) and / or (A2) is 1 to 50% by weight, the monomer (B) is 1 to 40% by weight, and the monomer (A3) is 30 to 98% by weight. is there. Particularly preferably, the monomer (A1) and / or (A2) is 1 to 35% by weight, the monomer (B) is 1 to 30% by weight, and the monomer (A3) is 25 to 98% by weight. . More preferably, the monomer (A1) and / or (A2) is 1 to 20% by weight, the monomer (B) is 1 to 30% by weight, and the monomer (A3) is 25 to 95% by weight. is there. The weight ratio of the monomer (A1) and / or (A2) or (A2 ′), (B) and (A3) is the same as that of the monomer (A1) and / or (A2), (B) and It is weight% when the total weight of (A3) is 100% by weight. In the present invention, as described later, other monomers other than the above-mentioned monomers can be used. However, when other monomers are used, the monomer (A1) and / or ( It is preferable that the sum of A2), (B) and (A3) is the main component in the monomer component.

In the polycarboxylic acid copolymer of the present invention, the repeating unit formed by the polyalkyleneimine unsaturated monomer (A1) and / or the polyalkylene glycol unsaturated monomer (A2) is an unsaturated carboxylic acid. Combined with the functions of the repeating units formed by the monomer (B) and the polyalkylene glycol unsaturated monomer (A3), it exhibits the function of making the cement composition, etc. excellent in water reduction and workability. Therefore, the repeating unit formed by the unsaturated carboxylic acid monomer (B) exhibits the function of adsorbing the polycarboxylic acid copolymer to the cement particles, and the polyalkylene glycol unsaturated The function in which the repeating unit formed by the monomer (A3) improves the dispersibility of the cement composition or the like due to the hydrophilicity and steric repulsion of the oxyalkylene group It is considered to be possible to achieve. The repeating unit formed by the polyalkyleneimine unsaturated monomer (A1) has many nitrogen atoms in one molecule, and the polyalkylene glycol unsaturated monomer (A2). The repeating unit formed by the above has a large number of oxygen atoms in one molecule, but these are also monomer units having a branched structure, and the above functions are effectively exhibited due to this. It is thought that it will be. By exhibiting these functions, it is possible to provide a cement composition that is excellent in water reduction and workability of the cement composition and that is easier to handle when the fluidity and water reduction are the same. Moreover, the strength and durability of the cured product can be made excellent. Therefore, the cement additive containing the polycarboxylic acid copolymer of the present invention is suitable as a water reducing agent for ultra high strength which can be suitably used not only for ordinary strength concrete and high strength concrete but also for ultra high strength concrete. Will be used. Ultra-high-strength concrete is generally called as such in the field of cement composition, that is, the cured product is equivalent to the conventional one even if the water / cement ratio is smaller than that of conventional concrete. Or concrete having a higher strength, for example, the water / cement ratio is 25% by weight or less, further 20% by weight or less, especially 18% by weight or less, particularly 14% by weight or less, especially about 12% by weight. However, it becomes a concrete having workability that does not hinder normal use, and the cured product thereof is 60 N / mm ² or more, further 80 N / mm ² or more, further 100 N / mm ² or more, particularly 120 N / mm ² or more. , in particular 160 N / mm ² or more, and particularly will exhibit 200 N / mm ² or more compression strength.

Next, the monomer which comprises the monomer component which will form the polycarboxylic acid type copolymer of this invention is demonstrated below.
The polyalkyleneimine unsaturated monomer (A1) in the present invention may be a polyalkyleneimine having a polymerizable unsaturated group. For example, the polyalkyleneimine has an amino group or an imino group. It can be obtained by reacting an unsaturated compound having a functional group that reacts with. In the present invention, the polyalkyleneimine unsaturated monomer (A1) preferably has an oxyalkylene group, but such a polyalkyleneimine unsaturated monomer (A1) has an unsaturated group. And a polyalkyleneimine having an oxyalkylene group, for example, a compound in which an alkylene oxide is added to a nitrogen atom of an amino group or imino group of the polyalkyleneimine, a hydroxyl group, an amino group or an imino group of the compound. It can be obtained by reacting an unsaturated compound having a functional group that reacts with. The nitrogen atom of the amino group or imino group to which alkylene oxide is added has an active hydrogen atom.

In order to obtain the polyalkyleneimine unsaturated monomer (A1) having the above oxyalkylene group, as a method for introducing an unsaturated group into a compound obtained by adding an alkylene oxide to the polyalkyleneimine, an alkylene oxide is added to the polyalkyleneimine. A method of introducing an unsaturated group by transesterifying a hydroxyl group of an added compound with an unsaturated compound such as (meth) acrylic acid or (meth) acrylic acid alkyl ester, or a compound in which an alkylene oxide is added to a polyalkyleneimine A method of introducing an unsaturated group by amidating an amino group with an unsaturated compound such as (meth) acrylic acid or (meth) acrylic acid alkyl ester, a hydroxyl group of a compound obtained by adding an alkylene oxide to a polyalkyleneimine (meth) Glycidyl acrylate and (meth) allyl glycidyl A method in which an epoxy compound is reacted to introduce an unsaturated group such as ether is preferred.

As said polyalkylene imine, 1 type (s) or 2 or more types of C2-C8 alkylene imines, such as ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, 1,1-dimethylethyleneimine Homopolymers and copolymers of these alkyleneimines obtained by polymerizing the above by a conventional method are preferred. These may be used alone or in combination of two or more. Such a polyalkyleneimine forms a polyalkyleneimine chain of the polyalkyleneimine unsaturated monomer (A1). The polyalkyleneimine chain has a linear structure and a branched structure. Either a structure or a three-dimensionally crosslinked structure may be used. Furthermore, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and the like may be used. Such a polyalkyleneimine usually has a primary amino group having an active hydrogen atom or a secondary amino group (imino group) in addition to a tertiary amino group in the structure.

Examples of the unsaturated compound include unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid, and citraconic acid; unsaturated carboxylic acid anhydrides such as (meth) acrylic anhydride and maleic anhydride; ) Unsaturated carboxylic acid halides such as acrylic acid chlorides; such as (meth) acrylic acid alkyl esters having 1 to 30 carbon atoms, maleic acid monoesters having 1 to 30 carbon atoms, maleic acid diesters having 1 to 30 carbon atoms, etc. Saturated carboxylic acid esters; epoxy compounds such as glycidyl (meth) acrylate and (meth) allyl glycidyl ether are suitable. These may be used alone or in combination of two or more.

The alkylene oxide added to the polyalkyleneimine is ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, trimethylethylene oxide, tetramethylene oxide, tetramethylethylene oxide, butadiene monooxide, octylene. In addition to alkylene oxides having 2 to 8 carbon atoms such as oxides, aliphatic epoxides such as dipentane ethylene oxide and dihexane ethylene oxide; alicyclic epoxides such as trimethylene oxide, tetramethylene oxide, tetrahydrofuran, tetrahydropyran and octylene oxide; styrene Oxides and aromatic epoxides such as 1,1-diphenylethylene oxide are preferred. These may be used alone or in combination of two or more.

As an example of a reaction formula for obtaining the polyalkyleneimine unsaturated monomer (A1) having the above oxyalkylene group, after synthesizing polyethyleneimine with an initiator and ethyleneimine, a nitrogen atom having an active hydrogen atom possessed by polyethyleneimine A reaction formula in which ethylene oxide is added to form a polyethyleneimine ethylene oxide adduct and then a transesterification reaction is carried out with methacrylic acid is shown below. There is also a method in which polyethyleneimine is synthesized and then ethylene oxide is added to a nitrogen atom having an active hydrogen atom of polyethyleneimine to form a polyethyleneimine ethylene oxide adduct, and then glycidyl methacrylate is reacted.

In the above reaction formula, R ^a represents an initiator, EO represents ethylene oxide, - (EO) n-H is that the ethylene oxide n number to nitrogen atom having active hydrogen atoms in the polyethyleneimine is added MAA represents methacrylic acid. The symbol “...” In the chemical formula represents that the polymer chain continues in the same manner.

In the polyalkyleneimine unsaturated monomer (A1) and the polyalkyleneimine unsaturated monomer (A1) having an oxyalkylene group, the polyalkyleneimine chain has a polyalkyleneimine chain. It is preferably formed mainly of ethyleneimine. In this case, “mainly” means that when the polyalkyleneimine chain is formed of two or more kinds of alkyleneimines, it occupies most of the total number of moles of alkyleneimines. In the present invention, the alkyleneimine that forms the polyalkyleneimine chain is mostly ethyleneimine, so that the hydrophilicity of the polycarboxylic acid copolymer is improved and the effects are sufficiently exerted. Therefore, by using ethyleneimine as an alkyleneimine that forms a polyalkyleneimine chain to such an extent that the above-described effects are sufficiently exerted, it can be said to be the “main body” because it “occupies most” as described above. It will be.

In the alkyleneimine forming the polyalkyleneimine chain, when the “dominance” is represented by mol% of ethyleneimine in 100 mol% of all alkyleneimines, 50 to 100 mol% is preferable. If it is less than 50 mol%, the hydrophilicity of the polyalkyleneimine chain may be lowered. More preferably, it is 60 mol% or more, still more preferably 70 mol% or more, particularly preferably 80 mol% or more, and most preferably 90 mol% or more.

In the polyalkyleneimine unsaturated monomer (A1) and the polyalkyleneimine unsaturated monomer (A1) having an oxyalkylene group, the average number of polymerizations of alkyleneimine per polyalkyleneimine chain is 2 or more is preferable, and 300 or less is preferable. If it is less than 2, the function of the polyalkyleneimine unsaturated monomer (A1) may not be sufficiently exerted, and if it exceeds 300, the polyalkyleneimine unsaturated monomer (A1) has a polymerizability. May decrease. Particularly preferably, it is 3 or more. More preferably, it is 200 or less, More preferably, it is 100 or less, Especially preferably, it is 75 or less, Most preferably, it is 50 or less. In this case, the average polymerization number of diethylenetriamine is 2, and the average polymerization number of triethylenetetramine is 3.

The polyalkylene glycol unsaturated monomer (A2) in the present invention is an unsaturated monomer having a structure in which an oxyalkylene group is bonded to a polyhydric alcohol residue. The polyalkylene glycol unsaturated monomer (A2 ′) is an unsaturated monomer having a terminal hydroxyl group among the polyalkylene glycol unsaturated monomers (A2).
The polyhydric alcohol residue means a group having a structure in which active hydrogen is removed from a hydroxyl group of the polyhydric alcohol, but is not particularly limited to a group formed by reaction with the polyhydric alcohol. The alkylene oxide added to the hydroxyl group of the polyhydric alcohol is the same as described above.

Examples of the method for producing the polyalkylene glycol unsaturated monomer (A2) include (1) a method of introducing an unsaturated group into a compound obtained by adding an alkylene oxide to a polyhydric alcohol, and (2) an unsaturated alcohol. Examples thereof include a method in which 1 mol or more of glycidol is added to 1 mol of unsaturated alcohol polyalkylene glycol adduct to generate 2 or more hydroxyl groups in one molecule, and then alkylene oxide is added.

In the above method (1), as a method for introducing an unsaturated group, a hydroxyl group of a compound obtained by adding an alkylene oxide to a polyhydric alcohol has a (meth) acrylic group such as (meth) acrylic acid or methyl (meth) acrylate. A method of introducing an unsaturated group by esterification or transesterification with an unsaturated compound such as an acid alkyl ester, a glycidyl (meth) acrylate or (meth) allyl having a hydroxyl group of a compound obtained by adding an alkylene oxide to a polyhydric alcohol A method of introducing an unsaturated group by reacting an epoxy compound having 2 to 5 carbon atoms such as glycidyl ether, or an etherification with an alkenyl halide having 2 to 5 carbon atoms such as (meth) allyl chloride. A method of introducing a group and the like are preferable. As unsaturated compounds for introducing unsaturated groups, unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid and citraconic acid; unsaturated compounds such as (meth) acrylic anhydride and maleic anhydride Carboxylic anhydride; unsaturated carboxylic acid halide such as (meth) acrylic acid chloride; (meth) acrylic acid alkyl ester having 1 to 30 carbon atoms, maleic acid monoester having 1 to 30 carbon atoms, 1 to 30 carbon atoms Suitable are unsaturated carboxylic acid esters such as maleic acid diesters; epoxy compounds such as glycidyl (meth) acrylate and (meth) allyl glycidyl ether. These may be used alone or in combination of two or more. In particular, the alkenyl compound-based unsaturated group is preferably an unsaturated group having 4 or more carbon atoms, more preferably an unsaturated group having 5 or more carbon atoms. Moreover, a methallyl group and an isoprenyl group (3-methyl-3-butenyl group) are more preferable than an allyl group. Furthermore, a (meth) acryloyl group is also preferable.

The polyhydric alcohol is not particularly limited as long as it is a compound containing an average of 3 or more hydroxyl groups in one molecule. A preferred form is a compound in which the polyhydric alcohol residue is composed of three elements of carbon, hydrogen and oxygen.

The number of hydroxyl groups of the polyhydric alcohol is preferably 3 or more, and preferably 300 or less. If the number is less than 3, the function of the polyalkylene glycol unsaturated monomer (A2) may not be sufficiently exhibited. If the number exceeds 300, the polymerizability of the polyalkylene glycol unsaturated monomer (A2) decreases. There is a risk. The number is more preferably 4 or more, still more preferably 5 or more, and particularly preferably 6 or more. Further, it is more preferably 100 or less, still more preferably 50 or less, and particularly preferably 25 or less.

As the polyhydric alcohol, polyglycidol, glycerin, polyglycerin, trimethylolethane, trimethylolpropane, 1,3,5-pentatriol, erythritol, pentaerythritol, dipentaerythritol, sorbitol, sorbitan, sorbitol glycerin condensate, Adonitol, arabitol, xylitol, mannitol and the like are preferable. Moreover, as sugars, saccharides of hexoses such as glucose, fructose, mannose, indoses, sorbose, growth, talose, tagatose, galactose, allose, psicose, altrose; arabinose, ribulose, ribose, xylose, xylulose, lyxose, etc. Saccharides of pentoses; saccharides of tetroses such as treose, erythrulose, erythrose; other saccharides such as rhamnose, cellobiose, maltose, isomaltose, trehalose, sucrose, raffinose, gentianose, melezitose; these sugar alcohols, sugar acids ( Saccharides; glucose, sugar alcohols; glucites, sugar acids; gluconic acids) and the like are also suitable. Furthermore, derivatives such as partially etherified products and partially esterified products of these exemplified compounds are also suitable. These can use 1 type (s) or 2 or more types.
Such a compound forms a polyhydric alcohol residue of the polyalkylene glycol unsaturated monomer (A2). Moreover, as an unsaturated compound, the thing similar to what was mentioned above etc. can be used 1 type, or 2 or more types.

In the method (2), examples of the unsaturated alcohol include vinyl alcohol, (meth) allyl alcohol, 3-buten-1-ol, isoprene alcohol (3-methyl-3-buten-1-ol), and 3-methyl. 2-Butene-1, 2-methyl-3-buten-2-ol, 2-methyl-2-buten-1-ol, 2-methyl-3-buten-1-ol, and the like are preferable. As the unsaturated alcohol polyalkylene glycol adduct, a compound having a structure in which a polyalkylene glycol chain is added to such an unsaturated alcohol can be used.

In the polyalkyleneimine unsaturated monomer (A1) and polyalkylene glycol unsaturated monomer (A2) having the oxyalkylene group, the group formed by one oxyalkylene group or the oxyalkylene group is 2 It has a group formed by adding one or more. In a group formed by adding two or more oxyalkylene groups, it is formed by one or more oxyalkylene groups, and when formed by two or more oxyalkylene groups, 2 One or more oxyalkylene groups may be added in any form such as random addition, block addition, and alternate addition. In addition, when two or more groups formed with the said oxyalkylene group exist in one molecule, these may be the same and may differ. A group formed by adding two or more oxyalkylene groups is also referred to as a polyalkylene glycol chain.

The group formed by the oxyalkylene group is preferably mainly composed of an oxyethylene group. In this case, the “main body” means that, as described above, when two or more oxyethylene groups are present in the monomer, the majority of the total number of oxyalkylene groups is present. means. As a result, the hydrophilicity of the polycarboxylic acid-based copolymer is improved, and the function and effect are sufficiently exhibited.

In the above oxyalkylene group, when the “occupying the majority” is expressed in terms of mol% of oxyethylene groups in 100 mol% of all oxyalkylene groups, 50 to 100 mol% is preferable. If it is less than 50 mol%, the hydrophilicity of the group formed from the oxyalkylene group may be lowered. More preferably, it is 60 mol% or more, still more preferably 70 mol% or more, particularly preferably 80 mol% or more, and most preferably 90 mol% or more.

In the polyalkyleneimine unsaturated monomer (A1) and polyalkylene glycol unsaturated monomer (A2) having the oxyalkylene group, the average addition mole number of the oxyalkylene group is 0 to 300. It is preferable. If it exceeds 300, the polymerizability of these monomers may decrease. More preferably, it is 0.3 or more, still more preferably 0.5 or more, particularly preferably 1 or more, and most preferably 2 or more. Further, it is more preferably 270 or less, further preferably 250 or less, particularly preferably 220 or less, and most preferably 200 or less. If the average added mole number of the oxyalkylene group in the polyalkyleneimine unsaturated monomer (A1) or the polyalkylene glycol unsaturated monomer (A2) is out of this range, the fluidity of the cement composition or the like There is a possibility that the function and effect of the polycarboxylic acid-based copolymer having excellent water resistance will not be sufficiently exhibited. The average number of moles added refers to addition in 1 mole of the group formed by the oxyalkylene group of the polyalkyleneimine unsaturated monomer (A1) and the polyalkylene glycol unsaturated monomer (A2). The average value of the number of moles of the oxyalkylene group or the polyalkyleneimine unsaturated monomer (A1) to form 1 mole of a nitrogen atom having an active hydrogen atom that the polyalkyleneimine has The average value of the number of moles of the oxyalkylene group being added or the hydroxyl group of the polyalkylene glycol-based unsaturated monomer (A2) that forms the polyhydric alcohol is 1 mole. Means the average number of moles of oxyalkylene group. The polyalkyleneimine unsaturated monomer (A1) and polyalkylene glycol unsaturated monomer (A2) having an average addition mole number of 0 have no oxyalkylene group.

In the polyalkylene glycol unsaturated monomer (A2), when the monomer component used in the production of the polycarboxylic acid polymer includes the unsaturated monocarboxylic acid monomer (B ′), It is preferable that at least one terminal of the oxyalkylene group having a structure bonded to an alcohol residue is a hydroxyl group. More preferably, all of the terminals of the oxyalkylene group are hydroxyl groups. If at least one terminal of the oxyalkylene group is an alkyl group, the water-reducing property of the cement additive containing a polycarboxylic acid copolymer may be lowered. The polyalkylene glycol unsaturated monomer (A2 ′) is one in which all of the oxyalkylene groups have hydroxyl groups.

The weight average molecular weight of the polyalkyleneimine unsaturated monomer (A1), the polyalkyleneimine unsaturated monomer (A1) having an oxyalkylene group, and the polyalkylene glycol unsaturated monomer (A2) 500 or more, and preferably 500,000 or less. More preferably, it is 1000 or more, More preferably, it is 5000 or more, More preferably, it is 8000 or more, Most preferably, it is 10,000. More preferably, it is 300000 or less, More preferably, it is 200000 or less, More preferably, it is 100000 or less, Most preferably, it is 80000 or less.

The unsaturated carboxylic acid monomer (B) in the present invention may be any monomer having a polymerizable unsaturated group and a group capable of forming a carbanion. (B ′) and unsaturated dicarboxylic acid monomers are preferred.
The unsaturated monocarboxylic acid monomer (B ′) may be any monomer having one unsaturated group and one group capable of forming a carbanion in the molecule. It is a compound represented by the following general formula (1).

In the general formula (1), R represents a hydrogen atom or a methyl group. M represents a hydrogen atom, a metal atom, an ammonium group or an organic amine group.
As a metal atom in M of the general formula (1), a monovalent metal atom such as an alkali metal atom such as lithium, sodium or potassium; a divalent metal atom such as an alkaline earth metal atom such as calcium or magnesium; Trivalent metal atoms such as aluminum and iron are preferred. Moreover, as an organic amine group, alkanolamine groups, such as an ethanolamine group, a diethanolamine group, and a triethanolamine group, a triethylamine group, etc. are suitable. Further, it may be an ammonium group. As such an unsaturated monocarboxylic acid-based monomer, acrylic acid, methacrylic acid, crotonic acid and the like; monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts and the like thereof are preferable. Among these, it is preferable to use methacrylic acid; its monovalent metal salt, divalent metal salt, ammonium salt, organic amine salt, etc. from the viewpoint of improving the cement dispersion performance, and unsaturated carboxylic acid monomer (B ).

The unsaturated dicarboxylic acid monomer may be any monomer having one unsaturated group and two groups capable of forming a carbanion in the molecule, but maleic acid, itaconic acid, citraconic acid , Fumaric acid and the like, monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts thereof, or anhydrides thereof are suitable.
In addition to these, the unsaturated carboxylic acid monomer (B) is a half ester of an unsaturated dicarboxylic acid monomer and an alcohol having 1 to 22 carbon atoms, an unsaturated dicarboxylic acid and carbon number. Preferred are half amides of 1 to 22 amines, half esters of unsaturated dicarboxylic acid monomers and glycols having 2 to 4 carbon atoms, half amides of maleamic acid and glycols having 2 to 4 carbon atoms, and the like. .

The polyalkylene glycol unsaturated monomer (A3) other than the oxyalkylene group-containing monomer in the present invention has a polymerizable unsaturated group and a polyalkylene glycol chain. In the form obtained by copolymerizing the monomer component containing the saturated monomer (A1) and the unsaturated carboxylic acid monomer (B), the polyalkyleneimine unsaturated monomer having the oxyalkylene group ( A different monomer from A1), and a polyalkylene glycol unsaturated monomer (A2) and an unsaturated monocarboxylic acid monomer (A2) having a structure in which an oxyalkylene group is bonded to a polyhydric alcohol residue ( In the form obtained by copolymerizing the monomer component containing B), it is a monomer different from the polyalkylene glycol monomer (A2), Copolymerization of monomer components including polyalkylene glycol unsaturated monomer (A2 ') and unsaturated carboxylic acid monomer (B) having a structure in which a xyalkylene group is bonded and having a terminal hydroxyl group In such a form, any monomer different from the polyalkylene glycol monomer (A2) may be used, and polyalkylene glycol ester monomers and unsaturated alcohol polyalkylene glycol adducts are suitable. The polyalkylene glycol ester monomer may be any monomer having a structure in which an unsaturated group and a polyalkylene glycol chain are bonded via an ester bond. An unsaturated carboxylic acid polyalkylene glycol ester monomer may be used. Compounds are preferred, among which (alkoxy) polyalkylene glycol mono (meth) acrylates are preferred.

The unsaturated alcohol polyalkylene glycol adduct may be a compound having a structure in which a polyalkylene glycol chain is added to an alcohol having an unsaturated group, such as a vinyl alcohol alkylene oxide adduct or a (meth) allyl alcohol alkylene oxide addition. 3-buten-1-ol alkylene oxide adduct, isoprene alcohol (3-methyl-3-buten-1-ol) alkylene oxide adduct, 3-methyl-2-buten-1-ol alkylene oxide adduct, 2-methyl-3-buten-2-ol alkylene oxide adduct, 2-methyl-2-buten-1-ol alkylene oxide adduct, 2-methyl-3-buten-1-ol alkylene oxide adduct, etc. are preferable. It is. Further, such an unsaturated alcohol polyalkylene glycol adduct is preferably a compound represented by the following general formula (2).

In the general formula (2), R ¹ , R ² and R ³ are the same or different and each represents a hydrogen atom or a methyl group. R ⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. R ^X is the same or different and represents an alkylene group having 2 to 18 carbon atoms. m represents the average added mole number of the oxyalkylene group represented by R ^X O, and is a number of 1 to 300. X represents that in the case of a divalent alkylene group having 1 to 5 carbon atoms or a vinyl group, the carbon atom and oxygen atom bonded to X are directly bonded to each other.

When two or more oxyalkylene groups represented by — (R ^X O) — in the general formula (2) are present in the same unsaturated alcohol polyalkylene glycol adduct, — (R ^X O) — The represented oxyalkylene group may be in any addition form such as random addition, block addition, and alternate addition.

The oxyalkylene group represented by-(R ^X O)-is an alkylene oxide adduct having 2 to 18 carbon atoms, and the structure of such an alkylene oxide adduct is ethylene oxide, propylene oxide, butylene oxide, It is a structure formed by one or more of alkylene oxides such as isobutylene oxide, 1-butene oxide and 2-butene oxide. Among such alkylene oxide adducts, ethylene oxide, propylene oxide, and butylene oxide adducts are preferable.

M is the average number of moles of the oxyalkylene group represented by R ^{X O} is the number of 1 to 300. When m exceeds 300, the polymerizability of the monomer is lowered. The preferred range of m is 2 or more, and the average added mole number of the oxyalkylene group in — (R ^X O) m— is preferably 2 or more. If m is less than 2 or the average added mole number of the oxyalkylene group is less than 2, there is a possibility that sufficient hydrophilicity and steric hindrance to disperse the cement particles may not be obtained. There is a possibility that fluidity cannot be obtained. The range of m is preferably 3 or more, and more preferably 280 or less. More preferably, it is 5 or more, more preferably 10 or more, and particularly preferably 20 or more. More preferably, it is 250 or less, and particularly preferably 150 or less. Moreover, as an average addition mole number of an oxyalkylene group, Preferably it is 3 or more, and 280 or less is preferable. More preferably, it is 10 or more, More preferably, it is 20 or more. More preferably, it is 250 or less, More preferably, it is 200 or less, Most preferably, it is 150 or less. The average added mole number means an average value of the number of moles of the organic group added in one mole of the monomer. In addition, as this monomer, it can use combining 2 or more types of monomers from which the average addition mole number m of an oxyalkylene group differs. As a suitable combination, for example, a combination of two types of monomers (A3) having a difference in m of 10 or more (preferably a difference in m of 20 or more), or a difference in the average added mole number m of each is 10 or more ( Preferably, a combination of three or more types of monomers (A3) having a difference of m of 20 or more is used. Furthermore, the range of m to be combined is a combination of a monomer (A3) having an average added mole number m in the range of 40 to 300 and a monomer (A3) in the range of 1 to 40 (provided that the difference in m is 10 or more, preferably 20 or more), a combination of a monomer (A3) having an average added mole number m in the range of 20 to 300 and a monomer (A3) in the range of 1 to 20 (provided that the difference in m is 10 or more, preferably 20 or more).

When R ⁴ has more than 20 carbon atoms, the hydrophobicity of the polycarboxylic acid copolymer becomes too strong, so that good dispersibility cannot be obtained. A preferred form of R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms or hydrogen from the viewpoint of dispersibility. More preferably, it is a hydrocarbon group having 10 or less carbon atoms, more preferably 3 or less carbon atoms, and particularly preferably 2 or less carbon atoms. In addition, in order to achieve excellent material separation prevention performance and an appropriate amount of air entrained in the cement composition, it is preferably a hydrocarbon group having 5 or more carbon atoms. The hydrocarbon group is preferably 20 or less. More preferably, it is a C5-C10 hydrocarbon group. Of the hydrocarbon groups, a saturated alkyl group and an unsaturated alkyl group are preferred. These alkyl groups may be linear or branched.

The unsaturated alcohol polyalkylene glycol adduct may be any of those mentioned above, but polyethylene glycol monovinyl ether, polyethylene glycol monoallyl ether, polyethylene glycol mono (2-methyl-2-propenyl) ether, polyethylene glycol mono ( 2-butenyl) ether, polyethylene glycol mono (3-methyl-3-butenyl) ether, polyethylene glycol mono (3-methyl-2-butenyl) ether, polyethylene glycol mono (2-methyl-3-butenyl) ether, polyethylene glycol Mono (2-methyl-2-butenyl) ether, polyethylene glycol mono (1,1-dimethyl-2-propenyl) ether, polyethylene polypropylene glycol mono (3-methyl) -3-butenyl) ether, methoxy polyethylene glycol mono (3-methyl-3-butenyl) ether, ethoxy polyethylene glycol mono (3-methyl-3-butenyl) ether, 1-propoxy polyethylene glycol mono (3-methyl-3- Butenyl) ether, cyclohexyloxypolyethylene glycol mono (3-methyl-3-butenyl) ether, 1-octyloxypolyethylene glycol mono (3-methyl-3-butenyl) ether, nonylalkoxypolyethylene glycol mono (3-methyl-3-butenyl) ) Ether, lauryl alkoxy polyethylene glycol mono (3-methyl-3-butenyl) ether, stearyl alkoxy polyethylene glycol mono (3-methyl-3-butenyl) ether, pheno Si polyethylene glycol mono (3-methyl-3-butenyl) ether, naphthoxy polyethylene glycol mono (3-methyl-3-butenyl) ether, methoxy polyethylene glycol monoallyl ether, ethoxy polyethylene glycol monoallyl ether, phenoxy polyethylene glycol monoallyl Ether, methoxypolyethylene glycol mono (2-methyl-2-propenyl) ether, ethoxypolyethylene glycol mono (2-methyl-2-propenyl) ether, phenoxypolyethylene glycol mono (2-methyl-2-propenyl) ether and the like are suitable. is there.

The (alkoxy) polyalkylene glycol mono (meth) acrylic acid ester is preferably a compound represented by the following general formula (3).

In the general formula (3), R ⁵ represents a hydrogen atom or a methyl group. R ^X is the same or different and represents an alkylene group having 2 to 18 carbon atoms. R ⁶ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. p represents the average addition mole number of the oxyalkylene group represented by R ^X O, and is a number of 2 to 300.
The general formula of ^{(3) - (R X O} ) - as the oxyalkylene group represented by, R X ^O is the average number of moles of the oxyalkylene group represented by p, the same as in the general formula (2) It is. Moreover, it is preferable from the point of the improvement of the productivity of esterification with (meth) acrylic acid that the ethylene oxide part has added to the ester bond part with (meth) acrylic acid.

P which is an average addition mole number of the oxyalkylene group represented by the above R ^X O is a number of 2 to 300. When p exceeds 300, the polymerizability of the monomer is lowered. The preferred range of p is 2 or more, and the average added mole number of the oxyalkylene group in — (R ^X O) p— is preferably 2 or more. When p is less than 2 or the average added mole number of the oxyalkylene group is less than 2, there is a possibility that sufficient hydrophilicity and steric hindrance to disperse cement particles or the like may not be obtained. There is a possibility that fluidity cannot be obtained. The range of p is preferably 3 or more, and more preferably 280 or less. More preferably, it is 5 or more, More preferably, it is 10 or more, Most preferably, it is 20 or more. Further, it is more preferably 250 or less, further preferably 200 or less, and particularly preferably 150 or less. Moreover, as an average addition mole number of an oxyalkylene group, 5 or more are preferable and 250 or less are preferable. More preferably, it is 10 or more, More preferably, it is 20 or more. Further, it is more preferably 200 or less, and still more preferably 150 or less. The average added mole number means an average value of the number of moles of the organic group added in one mole of the monomer. As the monomer, two or more monomers having different average addition mole numbers p of oxyalkylene groups can be used in combination. Suitable combinations include, for example, a combination of two types of monomers (A3) having a difference in p of 10 or more (preferably a difference in p of 20 or more), or a difference in average added mole number p of 10 or more ( Preferably, a combination of three or more types of monomers (A3) having a difference of p of 20 or more is used. Further, the range of p to be combined is a combination of a monomer (A3) having an average added mole number p in the range of 40 to 300 and a monomer (A3) in the range of 2 to 40 (provided that the difference in p is 10 or more, preferably 20 or more), a combination of a monomer (A3) having an average added mole number p in the range of 20 to 300 and a monomer (A3) in the range of 2 to 20 (provided that the difference in p is 10 or more, preferably 20 or more).

When R ⁶ has more than 30 carbon atoms, the hydrophobicity of the polycarboxylic acid copolymer becomes too strong, so that good dispersibility cannot be obtained. A preferred form of R ⁶ is a hydrocarbon group having 1 to 20 carbon atoms or hydrogen from the viewpoint of dispersibility. More preferably, it is a hydrocarbon group having 10 or less carbon atoms, more preferably 3 or less carbon atoms, and particularly preferably 2 or less carbon atoms. In addition, in order to achieve excellent material separation prevention performance and an appropriate amount of air entrained in the cement composition, it is preferably a hydrocarbon group having 5 or more carbon atoms. The hydrocarbon group is preferably 20 or less. More preferably, it is a C5-C10 hydrocarbon group. Of the hydrocarbon groups, a saturated alkyl group and an unsaturated alkyl group are preferred. These alkyl groups may be linear or branched.

The above (alkoxy) polyalkylene glycol mono (meth) acrylic acid ester may be any of those described above, but methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol. , 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, octanol, 2-ethyl-1-hexanol, nonyl alcohol, lauryl alcohol, cetyl alcohol, stearyl alcohol, etc. 30 aliphatic alcohols, C3-C30 alicyclic alcohols such as cyclohexanol, (meth) allyl alcohol, 3-buten-1-ol, 3-methyl-3-buten-1-ol, etc. Charcoal in any of unsaturated alcohols having 3 to 30 carbon atoms And alkoxy polyalkylene glycols the number 2 to 18 alkylene oxide groups and 1 to 300 mols, the ester of (meth) acrylic acid are preferred.

As the esterified product, the following (alkoxy) polyethylene glycol (poly) (alkylene glycol having 2 to 4 carbon atoms) (meth) acrylic acid esters and the like are preferable.
Methoxy polyethylene glycol mono (meth) acrylate, methoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, methoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, methoxy {polyethylene glycol (poly) propylene glycol (Poly) butylene glycol} mono (meth) acrylate, ethoxypolyethylene glycol mono (meth) acrylate, ethoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, ethoxy {polyethylene glycol (poly) butylene glycol} mono (meta ) Acrylate, ethoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (Meth) acrylate, propoxy polyethylene glycol mono (meth) acrylate, propoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, propoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, propoxy {polyethylene glycol ( Poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate.

Butoxy polyethylene glycol mono (meth) acrylate, butoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, butoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, butoxy {polyethylene glycol (poly) propylene glycol (Poly) butylene glycol} mono (meth) acrylate, pentoxypolyethylene glycol mono (meth) acrylate, pentoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, pentoxy {polyethylene glycol (poly) butylene glycol} mono ( Meth) acrylate, pentoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol } Mono (meth) acrylate, hexoxypolyethylene glycol mono (meth) acrylate, hexoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, hexoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, hexoxy {Polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate.

Heptoxy polyethylene glycol mono (meth) acrylate, heptoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, heptoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, heptoxy {polyethylene glycol (poly) propylene Glycol (poly) butylene glycol} mono (meth) acrylate, octoxypolyethylene glycol mono (meth) acrylate, octoxy {polyethyleneglycol (poly) propyleneglycol} mono (meth) acrylate, octoxy {polyethyleneglycol (poly) butyleneglycol} mono (Meth) acrylate, octoxy {polyethylene glycol (poly) propylene glycol (poly) butylene Recall} mono (meth) acrylate, nonanoxy polyethylene glycol mono (meth) acrylate, nonanoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, nonanoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, Nonanoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate.

Decanoxy polyethylene glycol mono (meth) acrylate, decananoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, decanoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, decanoxy {polyethylene glycol (poly) Propylene glycol (poly) butylene glycol} mono (meth) acrylate, undecanoxy polyethylene glycol mono (meth) acrylate, undecananoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, undecanoxy {polyethylene glycol (poly) butylene glycol } Mono (meth) acrylate, undecanoxy {polyethylene glycol (poly) propylene glycol (Poly) butylene glycol} mono (meth) acrylate, dodecanoxy polyethylene glycol mono (meth) acrylate, dodecananoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, dodecanoxy {polyethylene glycol (poly) butylene glycol} Mono (meth) acrylate, dodecanoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate.

Tridecanoxy polyethylene glycol mono (meth) acrylate, tridecananoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, tridecanoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, tridecanoxy {polyethylene glycol (poly) Propylene glycol (poly) butylene glycol} mono (meth) acrylate, tetradecanoxy polyethylene glycol mono (meth) acrylate, tetradecananoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, tetradecanoxy {polyethylene glycol ( Poly) butylene glycol} mono (meth) acrylate, tetradecanoxy {polyethylene glycol Poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate, pentadecanoxy polyethylene glycol mono (meth) acrylate, pentadecananoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, pentadecanoxy {polyethylene Glycol (poly) butylene glycol} mono (meth) acrylate, pentadecanoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate.

Hexadecanoxy polyethylene glycol mono (meth) acrylate, hexadecananoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, hexadecanoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, hexadecanoxy {polyethylene Glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate, heptadecanoxy polyethylene glycol mono (meth) acrylate, heptadecanoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, heptadecanoxy {Polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, heptadecanoxy {polyethylene group Cole (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate, octadecanoxy polyethylene glycol mono (meth) acrylate, octadecananoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, octadecanoxy {Polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, octadecanoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate.

Nonadecanoxy polyethylene glycol mono (meth) acrylate, nonadecanoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, nonadecanoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, nonadecanoxy {polyethylene glycol (poly) ) Propylene glycol (poly) butylene glycol} mono (meth) acrylate, cyclopentoxypolyethylene glycol mono (meth) acrylate, cyclopentoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, cyclopentoxy {polyethylene glycol (Poly) butylene glycol} mono (meth) acrylate, cyclopentoxy {polyethylene glycol ( B) propylene glycol (poly) butylene glycol} mono (meth) acrylate, cyclohexoxypolyethylene glycol mono (meth) acrylate, cyclohexoxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, cyclohexoxy {polyethylene glycol (poly) ) Butylene glycol} mono (meth) acrylate, cyclohexoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate.

Examples of the (alkoxy) polyalkylene glycol mono (meth) acrylic acid ester include phenoxy polyethylene glycol mono (meth) acrylate, phenoxy {polyethylene glycol (poly) propylene, in addition to the compound represented by the general formula (2). Glycol} mono (meth) acrylate, phenoxy {polyethylene glycol (poly) butylene glycol} mono (meth) acrylate, phenoxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate, (meth) allyloxy Polyethylene glycol mono (meth) acrylate, (meth) allyloxy {polyethylene glycol (poly) propylene glycol} mono (meth) acrylate, (meth) allyloxy { Triethylene glycol (poly) butylene glycol} mono (meth) acrylate, (meth) allyloxy {polyethylene glycol (poly) propylene glycol (poly) butylene glycol} mono (meth) acrylate and the like.

Examples of the polyalkylene glycol ester monomer include (alkoxy) polyalkylene glycol mono (meth) acrylic acid ester, (alkoxy) polyalkylene glycol monomaleic acid ester, and (alkoxy) polyalkylene glycol dimaleic acid. Esters are preferred. As such a monomer, the following are suitable.

Half of an alkyl polyalkylene glycol obtained by adding 1 to 300 moles of oxyalkylene having 2 to 4 carbon atoms to an alcohol having 1 to 22 carbon atoms or an amine having 1 to 22 carbon atoms and the above unsaturated dicarboxylic acid monomer Esters, diesters; half esters and diesters of the above unsaturated dicarboxylic acid monomers and polyalkylene glycols having an average addition mole number of 2 to 300 carbon atoms of glycols having 2 to 4 carbon atoms; triethylene glycol di (meth) acrylates, ( (Poly) ethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, (poly) ethylene glycol (poly) propylene glycol di (meth) acrylate and other (poly) alkylene glycol di (meth) acrylates; triethylene glycol Zimarate, polyethylene Glycol dimaleate and the like (poly) alkylene glycol dimaleate and the like.

The monomer component for forming the polycarboxylic acid-based copolymer of the present invention may further include other units other than the monomers (A1), (A2), (B) and (A3) as necessary. A monomer (C) may be included. As the other monomer (C), the following are preferable. These may be used alone or in combination of two or more.

Styrenes such as styrene, bromostyrene, chlorostyrene, and methylstyrene; dienes such as 1,3-butadiene, isoprene, and isobutylene; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (Meth) acrylate esters such as pentyl (meth) acrylate, hexyl (meth) acrylate, decyl (meth) acrylate, and lauryl (meth) acrylate; α-olefins such as hexene, heptene, decene; methyl Alkyl vinyl ethers such as vinyl ether, ethyl vinyl ether and butyl vinyl ether; vinyl esters such as vinyl acetate; allyl esters such as allyl acetate;

Diesters of unsaturated dicarboxylic acid monomers and alcohols having 1 to 22 carbon atoms, diamides of unsaturated dicarboxylic acids and amines having 1 to 22 carbon atoms, unsaturated dicarboxylic acid monomers and carbon Diesters with glycols of 2-4.

Bifunctional (meth) acrylates such as hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate; vinyl sulfonate, (meth) allyl sulfonate, 2- (meth) acrylate Roxyethyl 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-methylpropanesulfonic acid ( Data) acrylamide, unsaturated sulfonic acids such as styrenesulfonic acid, and their monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts.

Unsaturated amides such as (meth) acrylamide, (meth) acrylic alkylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide; allyls such as allyl alcohol; dimethylaminoethyl (meth) acrylate Unsaturated amino compounds such as methoxypolyethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, methoxypolyethylene glycol mono (meth) allyl ether, and vinyl ethers or allyl ethers such as polyethylene glycol mono (meth) allyl ether.

(Meth) acrylate compounds such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethylethyl (meth) acrylate, methoxypropyl (meth) acrylate, etc. .

Next, the copolymerization method of the monomer component is demonstrated below about the manufacturing method of the polycarboxylic acid-type copolymer of this invention.
As said copolymerization method, it can carry out by well-known polymerization methods, such as solution polymerization and block polymerization, for example using a monomer component and a polymerization initiator. As the polymerization initiator, known ones can be used. Persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate; hydrogen peroxide; azobis-2-methylpropionamidine hydrochloride, azoisobutyronitrile Suitable are azo compounds such as benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide and the like. In addition, as a promoter, reducing agents such as sodium bisulfite, sodium sulfite, molle salt, sodium pyrobisulfite, formaldehyde sodium sulfoxylate, ascorbic acid; and amine compounds such as ethylenediamine, sodium ethylenediaminetetraacetate and glycine are used in combination. You can also These polymerization initiators and accelerators may be used alone or in combination of two or more.

In the copolymerization method, a chain transfer agent can also be used as necessary. As such a chain transfer agent, one or more known ones can be used, but a hydrophobic chain transfer agent is preferably used.

In the above copolymerization method, the monomer component has a monomer (A) having an oxyalkylene group, that is, a polyalkyleneimine unsaturated monomer (A1) having an oxyalkylene group, a polyalkylene glycol unsaturated monomer. When 1 type or 2 types or more of a body (A2) and (A3) are included, it is preferable to use a hydrophobic chain transfer agent. More preferably, the monomer (A) having an oxyalkylene group is a polyalkylene glycol ester monomer and / or an unsaturated alcohol polyalkylene glycol adduct. When a hydrophobic chain transfer agent is used, a hydrophobic group derived from the hydrophobic chain transfer agent is introduced into the copolymer. Thus, a polycarboxylic acid obtained by copolymerizing a monomer component containing a monomer (A) having an oxyalkylene group and an unsaturated carboxylic acid monomer (B) using a hydrophobic chain transfer agent. The method for producing an acid copolymer is also one aspect of the present invention.
In addition, the polycarboxylic acid-type copolymer obtained by the manufacturing method of such a polycarboxylic acid-type copolymer can also exhibit the effect of this invention, and is one of this invention.

The hydrophobic chain transfer agent is preferably a thiol compound having a hydrocarbon group having 3 or more carbon atoms or a compound having a solubility in water of 25 ° C. of 10% or less. The chain transfer agent, butanethiol, octane described above Thiol, decanethiol, dodecanethiol, hexadecanethiol, octadecanethiol, cyclohexyl mercaptan, thiophenol, octyl thioglycolate, octyl 2-mercaptopropionate, octyl 3-mercaptopropionate, 2-ethylhexyl ester mercaptopropionate, octanoic acid 2 -Thiol chain transfer agents such as mercaptoethyl ester, 1,8-dimercapto-3,6-dioxaoctane, decanetrithiol, dodecyl mercaptan; carbon tetrachloride, carbon tetrabromide, methylene chloride, bromoform, Halides mode trichloroethane; alpha-methylstyrene dimer, alpha-terpinene, .gamma.-terpinene, dipentene, unsaturated hydrocarbon compounds such as terpinolene and the like. These may be used alone or in combination of two or more. Among these, it is preferable to include a thiol chain transfer agent having a hydrocarbon group having 3 or more carbon atoms.

The hydrophobic chain transfer agent may be used in combination with one or two hydrophilic chain transfer agents as necessary. As such a hydrophilic chain transfer agent, known ones can be used, such as mercaptoethanol, thioglycerol, thioglycolic acid, mercaptopropionic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, Thiol chain transfer agents such as 2-mercaptoethanesulfonic acid; primary alcohols such as 2-aminopropan-1-ol; secondary alcohols such as isopropanol; phosphorous acid, hypophosphorous acid and salts thereof (hypophosphorous acid) Sodium sulfate, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionite, metabisulfite and its salts (sodium sulfite, sodium bisulfite, sodium dithionite, sodium metabisulfite, potassium sulfite, sulfurous acid) Potassium hydrogen, potassium dithionite, potassium metabisulfite Lower oxides and salts of) is preferable.

As a method for adding the chain transfer agent to the reaction vessel, a continuous charging method such as dropping or divided charging can be applied. In addition, a chain transfer agent may be introduced alone into the reaction vessel. The monomer (A) having an oxyalkylene group constituting the monomer component, the unsaturated carboxylic acid monomer (B), a solvent, etc. It may be confused with.

The copolymerization method can be carried out either batchwise or continuously. In the copolymerization, a known solvent can be used as necessary. Water: alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol; benzene, toluene, xylene, cyclohexane, n- Aromatic or aliphatic hydrocarbons such as heptane; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone are suitable. These may be used alone or in combination of two or more. Among these, from the viewpoint of the solubility of the monomer component and the resulting polycarboxylic acid copolymer, one or more solvents selected from the group consisting of water and lower alcohols having 1 to 4 carbon atoms. Is preferably used.

In the above copolymerization method, monomer components, polymerization initiators, etc. can be added to the reaction vessel by charging all of the monomer components into the reaction vessel and adding the polymerization initiator into the reaction vessel. Polymerization method: Charge a part of the monomer components into the reaction vessel, add the polymerization initiator and the remaining monomer components into the reaction vessel, and carry out the copolymerization. Charge the reaction vessel with the polymerization solvent. A method of adding the whole amount of the monomer and the polymerization initiator is preferable. Among these methods, the molecular weight distribution of the resulting copolymer can be narrowed (sharpened), and the cement dispersibility, which is an effect of increasing the fluidity of the cement composition, can be improved. It is preferable to perform copolymerization by a method in which an initiator and a monomer are successively dropped into a reaction vessel.

In the above copolymerization method, the copolymerization conditions such as the copolymerization temperature are appropriately determined depending on the copolymerization method used, the solvent, the polymerization initiator, and the chain transfer agent, but the copolymerization temperature is usually 0 ° C. or higher. It is preferable that it is 150 degrees C or less. More preferably, it is 40 degreeC or more, More preferably, it is 50 degreeC or more, Most preferably, it is 60 degreeC or more. More preferably, it is 120 degrees C or less, More preferably, it is 100 degrees C or less, Most preferably, it is 85 degrees C or less.
The copolymer obtained by the above copolymerization method is used as it is as a main component of the cement additive, but may be further neutralized with an alkaline substance as necessary. As the alkaline substance, it is preferable to use inorganic salts such as hydroxides, chlorides and carbonates of monovalent metals and divalent metals; ammonia; organic amines and the like.

In the said copolymerization method, it is preferable to copolymerize a monomer component by making the neutralization rate of the said unsaturated carboxylic acid-type monomer (B) 0-60 mol%. The neutralization rate of the unsaturated carboxylic acid monomer (B) is the unsaturated carboxylic acid forming a salt when the total number of moles of the unsaturated carboxylic acid monomer (B) is 100 mol%. It is represented by mol% of the system monomer (B). When the neutralization rate of the unsaturated carboxylic acid monomer (B) exceeds 60 mol%, the polymerization rate in the copolymerization process does not increase, the molecular weight of the resulting copolymer decreases, or the production efficiency decreases. There is a risk. More preferably, it is 50 mol% or less, More preferably, it is 40 mol% or less, More preferably, it is 30 mol% or less, Especially preferably, it is 20 mol% or less, Most preferably, it is 10 mol% or less.

As a method for carrying out the copolymerization at a neutralization rate of the unsaturated carboxylic acid monomer (B) of 0 to 60 mol%, all of the unsaturated carboxylic acid monomer (B) which is an acid type, that is, all In the unsaturated carboxylic acid monomer (B), a method in which M in the general formula (1) is a hydrogen atom is subjected to copolymerization without neutralization, or unsaturated carboxylic acid monomer Preferred is a method of subjecting the body (B) to a salt form such as a sodium salt or an ammonium salt using an alkaline substance by subjecting it to a copolymerization with a neutralization rate of 0 to 60 mol%. It is.

The polycarboxylic acid copolymer of the present invention is obtained by copolymerizing monomer components as described above. The molecular weight of such a copolymer is determined by gel permeation chromatography (hereinafter referred to as “GPC”). The weight average molecular weight (Mw) in terms of polyethylene glycol is preferably 500 or more and more preferably 500000 or less. If it is less than 500, the water reducing performance of the polycarboxylic acid copolymer may be lowered, and if it exceeds 500,000, the water reducing performance and slump loss preventing ability of the polycarboxylic acid copolymer may be lowered. More preferably, it is 5000 or more, and most preferably 8000 or more. Moreover, More preferably, it is 300000 or less, Most preferably, it is 100000 or less. In the present specification, the weight average molecular weight of the copolymer is a value measured under the following GPC measurement conditions.

When analyzing cement additives, including the copolymer of the present invention, (1) a method of performing analysis without any treatment (2) low molecular weight materials such as residual monomers, water-insoluble such as antifoaming agents There is a method in which analysis is performed after removing a sex substance. As a method for purifying the polymer, the following method is suitable.

Polymer purification conditions Polymer purification conditions 1
1. NaOH 30% by weight aq. To adjust the pH to 12-12.5.
2. The cement additive (polymer aqueous solution) is concentrated with an evaporator and then dried in a vacuum dryer at 50 ° C.
3. The obtained product is Soxhlet extracted with a solvent (diethyl ether, petroleum ether, etc.) and separated into soluble and insoluble components.
4). The insoluble matter is made into a solution of about 40 to 50% by weight, and low molecular weight components such as residual monomers are removed by dialysis or ultrafiltration. The molecular weight cut off is properly used depending on the molecular weight of the residual monomer of GPC. (1000, 3500, 8000, 15000)

Polymer purification conditions 2
1. NaOH 30% by weight aq. To adjust the pH to 12-12.5.
2. The cement additive (polymer aqueous solution) is concentrated with an evaporator and then dried in a vacuum dryer at 50 ° C.
3. The obtained product is Soxhlet extracted with a solvent (diethyl ether, petroleum ether, etc.) and separated into soluble and insoluble components.
4). The cement additive is ultrafiltered through an ultrafiltration membrane (fraction molecular weight 6000).
Depending on the molecular weight of the residual monomer of GPC, the molecular weight cut off is properly used (13000).
The circulation rate of the polymer solution is adjusted so that the ultrafiltration membrane outlet pressure and the ultrafiltration membrane inlet pressure are 0.01 MPa or more.
Filtrate concentration: 0.1 to 10% by weight Adjustment end point: Confirm that residual monomer could be removed by NMR, liquid chromatography or the like.
Ultrafiltration device Funakoshi: FILTRATION SYSTEM PS-24001
Pencil type module (Asahi Kasei Kogyo Co., Ltd.)
Model: AIP-0013
Material: Hollow fiber membrane: Polyacrylonitrile (PAN)
Housing: Polysulfone
Adhesive: Epoxy resin Specifications: Membrane inner diameter (mm): 0.8mm
Number of membranes used (pieces): 100
Effective membrane area (cm ² ): 170
Nominal molecular weight cut-off: 6000
Operating conditions: Maximum operating pressure (kPa): 100
Usable temperature (° C): 50
Usable pH range: 2 to 10
Module dimensions (mm): 20φ x 130L

The polycarboxylic acid copolymer of the present invention is obtained by copolymerizing monomers as described above. The TCAV (total carboxylic acid acid) based on the solid content of such a copolymer or cement additive is used. (Valence) is preferably 3 mgKOH / g or more, and preferably 900 mgKOH / g or less. If it is less than 3 mgKOH / g, the adsorption of the polycarboxylic acid-based copolymer to the cement will be delayed, and it may take time to develop water-reducing performance, or the water-reducing performance may be reduced. If it exceeds 900 mgKOH / g Further, since the adsorption of the polycarboxylic acid copolymer to the cement becomes too fast, the cement particles may be aggregated to reduce the water reduction performance and the slump loss prevention ability. More preferably, it is 5 mgKOH / g or more, More preferably, it is 10 mgKOH / g or more, More preferably, it is 15 mgKOH / g or more, Most preferably, it is 20 mgKOH / g or more, Most preferably, it is 25 mgKOH / g or more. Further, it is more preferably 500 mgKOH / g or less, further preferably 400 mgKOH / g or less, still more preferably 300 mgKOH / g or less, particularly preferably 200 mgKOH / g or less, and most preferably 150 mgKOH / g or less. In the present specification, TCAV is a value measured under the following TCAV (total carboxylic acid value) measurement conditions.

Further, the amount of NMR-PEG of the polycarboxylic acid copolymer of the present invention is preferably 10% by weight or more, and preferably 99% by weight. If the amount is less than 10% by weight, the amount of the dispersing group for dispersing the cement particles is small, so that the aggregation of the cement particles may occur, and the water reduction performance and the ease of handling may be reduced. Adsorption of the carboxylic acid-based copolymer to the cement is delayed, and there is a possibility that it takes time to develop water reduction performance or the water reduction performance is lowered. More preferably, it is 50 weight% or more, More preferably, it is 60 weight% or more, More preferably, it is 65 weight% or more, Most preferably, it is 70 weight% or more. Further, it is more preferably 98% by weight or less, still more preferably 97% by weight or less, still more preferably 95% by weight or less, particularly preferably 93% by weight or less, and most preferably 93% by weight or less. In the present specification, the NMR-PEG amount is a value measured by the following NMR-PEG amount measuring method.

Of the polycarboxylic acid copolymer of the present invention, a form obtained by copolymerizing a monomer component containing a polyalkyleneimine unsaturated monomer (A1) and an unsaturated carboxylic acid monomer (B). The nitrogen content is preferably 0.001% by weight or more, and more preferably 20.0% by weight or less. If it is less than 0.001% by weight, the weight% of the polyalkyleneimine unsaturated monomer becomes small, and the cement composition to be used may be difficult to handle. If it exceeds 20% by weight, Since the amount of amine in the polycarboxylic acid-based copolymer increases, it strongly interacts with the carbonyl group in the copolymer, and the water reduction performance may be reduced. More preferably 0.01% by weight or more, still more preferably 0.05% by weight or more, still more preferably 0.1% by weight or more, particularly preferably 0.5% by weight or more, and most preferably 1.0% by weight or more. It is. More preferably, it is 15.0% by weight or less, more preferably 10.0% by weight or less, still more preferably 8.0% by weight or less, particularly preferably 5.0% by weight or less, and most preferably 3.0% by weight. % Or less.

GPC molecular weight measurement conditions in the present invention, ¹ H-NMR (400 MHz, 200 MHz) measurement conditions, ¹³ C-NMR measurement conditions, IR measurement conditions, pyrolysis GC-MASS measurement conditions, solid content measurement conditions, NMR-PEG amount The measurement conditions are shown below.

GPC molecular weight measurement conditions Column used: TSK guardcolumn SWXL + TSKge1 G4000SWXL + G3000SWXL + G2000SWXL manufactured by Tosoh Corporation
Eluent: An eluent prepared by dissolving 115.6 g of sodium acetate trihydrate in a mixed solvent of 10999 g of water and 6001 g of acetonitrile and adjusting the pH to 6.0 with a 30% aqueous sodium hydroxide solution is used.
Driving amount: 100 μL
Sample concentration: 0.5% by weight
Eluent flow rate: 0.8mL / sec
Column temperature: 35 ° C
Standard substance: polyethylene glycol, weight average molecular weight (Mw) 272500, 219300, 85000, 46000, 24000, 12600, 4250, 7100, 1470.
Detector: Japan Waters, Ltd. Differential refraction detector analysis software: Japan Waters, Inc. MILLENNIUM Ver. 2.18

^<1 H-NMR measurement conditions (400 MHz)>
Model: Unity plus (400MHz) manufactured by varian
Probe: 4-nucleus auto-switchable probe Observation nucleus: Hydrogen nucleus (resonance frequency 400.0)
Measurement conditions: 90 degree pulse 22.5 μsec (45 degree pulse irradiation)
Waiting time 3.0 sec
Integration times 16 times

^<1 H-NMR measurement conditions (200 MHz)>
Model: geminin2000 (200MHz) manufactured by varian
Probe: CH switchable probe Observation nucleus: Hydrogen nucleus (resonance frequency 199.9)
Measurement conditions: 90 degree pulse 10 μsec (45 degree pulse irradiation)
Wait time 1.25 seconds
Integration times 16 times

< ^13C -NMR measurement conditions>
Model: Unity plus (400MHz) manufactured by varian
Probe: 4-nucleus auto-switchable probe Observation nucleus: Carbon nucleus (resonance frequency 100.6)
Measurement conditions: 90 degree pulse 15.1 μsec (1/3 of 90 degree pulse is irradiated)
¹ H pulse output 38 dB
Wait time 0.939 sec
Integration times 25000 times

<IR measurement conditions>
Model: FT-IR manufactured by BIO-RAD
Measurement method: germanium plate thin film formation method 1 drop (about 0.03 mL) of a 5% copolymer aqueous solution is dropped onto a germanium plate.
Water is removed with a vacuum dryer (a vacuum pump may be connected to the desiccator) (25 ° C., 0.001 MPa or less, 10 minutes or more).

<TCAV (total carboxylic acid value) measurement conditions>
Model: Hiranuma Sangyo Co., Ltd. Automatic Titrator COM-550
0.1 mol / L Sodium hydroxide Wako Pure Chemical Industries, Ltd. Volumetric analysis reagent fn (factor)
0.1 mol / L Hydrochloric acid manufactured by Wako Pure Chemical Industries, Ltd.
Solvent: ion-exchanged water / acetonitrile = 50/50% by volume
(1) In a 100 mL beaker, 1 g (0.2 to 0.5 g in terms of solid content) of the cement additive is accurately weighed (W g) (up to 4 digits after the decimal point).
(2) Dilute with 50 mL of solvent.
(3) After adding 5 mL of the hydrochloric acid aqueous solution and confirming that the pH is 3 or less (preferably 2.5 or less), potentiometric titration is performed with the sodium hydroxide aqueous solution.
(4) The amount of sodium hydroxide (V mL) required from the first inflection point to the second inflection point is determined.
fn: 0.1 mol / L Hydroxylation factor NV (% by weight): solid content concentration of cement additive TCAV = (V × 0.1 × fn × 56.11) / (W × NV) mgKOH / g

<Pyrolysis GC-MASS measurement conditions>
Pyrolysis gas chromatography mass spectrometry model: N-5000 quadrupole column manufactured by Hitachi, Ltd .: DB-1 manufactured by GLscience (0.25 mm × 30 m × 0.25 μm)
Curie Point Pyrolyzer Measurement Method 590 ° C
Temperature rising program: 50 ° C. (Hold 5 min) − (5 ° C./min)−150° C .− (10 ° C./min)−250° C. (Hold 5 min)

<Measurement conditions of solid content>
About 0.5 g of cement additive is accurately weighed in an aluminum cup. After heating in a dryer at 130 ° C. for 1 hour under a nitrogen stream, the aluminum cup is taken out, cooled in a desiccator for 10 minutes, and the weight is measured. The solid content is calculated from the weight of the cement additive weighed and the weight remaining after heating.

<Method for measuring NMR-PEG amount>
The weight% of the 3.3 to 4.2 ppm peak (peak appearing at the same position as -OCH ₂ CH _2- of methoxypolyethylene glycol methacrylate) observed by ¹ H-NMR (200 MHz) is determined.
Outline of measurement: From the weight ratio of the polymer and the internal standard substance (trioxane) and the NMR integral ratio, the weight% of the 3.3 to 4.2 ppm peak contained in the polymer is determined using a calibration curve.
Polymer adjustment: The residual monomer is removed by dialysis or the like, and dried with a vacuum dryer until the water content becomes 0.1 wt% or less. Purify so that no other peak appears at 4.9-5.2 ppm by NMR.
Trioxane: Wako Pure Chemical Industries, Ltd. First grade Water content is adjusted to 0.05% by weight or less.
Moisture measuring method: Karl Fischer method calibration substance: Polymer A or methoxypolyethylene glycol methacrylate -OCH 2 _CH 2 in the total weight _- previously obtained the weight ratio of.
Polymer A: “Shin Nakamura Chemical Co., Ltd., M-90G / sodium methacrylate = 70/30 wt%, Mw 20000 to 30000”. The initiator, chain transfer agent, residual monomer, raw material purity, etc. are accurately determined, and the weight ratio of —OCH ₂ CH ₂ — in the total weight is determined.
Weight: Weigh accurately to 0.1 mg.

The polycarboxylic acid copolymer of the present invention can be suitably used as a main component of a cement additive. A cement additive comprising the polycarboxylic acid copolymer of the present invention is also one aspect of the present invention.

A cement additive having a calcium transport value of 10 to 900 mPa · s and / or a cement operating coefficient of 0.05 to 1.0 can provide an easy-to-handle cement composition when the fluidity and water reduction are the same. Such a cement additive is also one aspect of the present invention.

The method for measuring the calcium transport value and the cement operating coefficient in this specification will be described below.
<Method of measuring cement operating coefficient>
Reagents / equipment conditions Ordinary Portland cement (JIS R 5210): manufactured by Taiheiyo Cement Co., Ltd., defoaming agent using Lot cement having a viscosity μ (e) of 5000 to 6000 mPa · s shown below: oxyalkylene-based antifoaming agent Nonyloxypolypropylene glycol polyethylene glycol (average added mole number of propylene oxide 20, average added mole number of ethylene oxide 3)
Standard sand for cement strength test using 0.5% by weight based on the solid additive equivalent of cement additive: JIS R 5201
Mortar mixer: Hobart N-50 5L capacity
Rotation 1: Auto rotation 139rpm, Revolution 61rpm
Rotation 2: Autorotation 285rpm, Revolution 125rpm
Spatula: made of stainless steel See FIG. 2 New Death Cup (300 mL) manufactured by Terraoka Co., Ltd.): Refer to FIG. 3 Repass rotational viscometer: TV-20 viscometer / spindle TA / 10 rpm (manufactured by Toki Sangyo)
Addition amount of cement additive: All addition amount in terms of solid content.

Air volume measuring method: About 450 mL of mortar is put into a 500 mL measuring cylinder, and the volume and weight are measured. The amount of air is calculated from the density of the cement, sand, and ion exchange water used.

Measurement method: 1080 g of ordinary Portland cement adjusted to 25 ° C. and 1350 g of standard sand for cement strength test are put in a mortar mixer, stirred for 10 seconds at rotation 1, and then a predetermined amount of cement additive and antifoaming agent are added. 270 g (25 ° C.) of ion-exchanged water was added, and the mixture was further stirred for 3 minutes at rotation 1 and subsequently stirred for 2 minutes at rotation 2 to obtain mixture C.

All of the mixture C was placed in a plastic cylindrical container (capacity 1.2 L, lower diameter 90 mm, upper diameter 110 mm, height 140 mm), and after mixing for 1 minute 20 seconds, 5 minutes to the right using a spatula for 5 seconds. Twist to the left 5 times. A mini slump cone placed on a stainless steel plate (a hollow container having an upper inner diameter of 50 mm, a lower inner diameter of 100 mm, and a height of 150 mm) is filled with one third of the mixture C, and pokes with a glass rod 25 times so as to finish the spiral. In addition, squeeze 25 times with a glass rod as much as 1/3. Similarly, pack the remaining third. At a time 10 minutes after the start of kneading, the mini slump cone was lifted vertically, and the “maximum length” and “vertical length” of the mixture C spread on the stainless steel plate were measured. Let an average value be a flow value (mm).

Under the condition that the air amount is adjusted to 2.0-4.0% by volume, the amount of cement additive added to normal Portland cement is changed (solid content conversion), and the graph of the relationship between the amount added and the flow value is written. The amount of cement additive required to make the value 200 mm is determined. (The addition amount at this time is defined as the standard addition amount.) When the flow value is within the range of 200 ± 25 mm, the addition amount is 2 points or more, or when the flow value is within the range of 200 ± 50 mm, the addition amount is 3 points or more. The flow value must be measured. When the air amount is out of the range of 2.0 to 4.0% by volume, the defoamer amount is changed from 0.5% by weight, and both the flow value and the air amount are within the specified range. And determine the amount of cement additive.

Next, 600 g of ordinary Portland cement adjusted to 25 ° C. was put in a mortar mixer, stirred for 10 seconds at rotation 1, and then 150 g of ion-exchanged water added with the cement additive and antifoaming agent of the standard addition amount obtained earlier. (25 ° C.) is added, and after kneading for 50 seconds, the kneading is temporarily stopped, and the cement paste adhered to the mortar mixer wall is scraped off for 30 seconds. And it knead | mixes for 3 minutes and 40 seconds with rotation 1, and the mixture D is obtained.

All of the mixture D is put into a New Death Cup (300 mL) manufactured by Terraoka Co., Ltd. and stirred 30 times to the right and 30 times to the left with a spatula for 60 seconds to uniformly disperse the cement paste.
Viscosity measurement is started at a time after a total of 10 minutes from the start of mechanical mixing of the mixture D with a helipath rotary viscometer (adjusting the spindle position to a 175 mL scale position = 3.8 cm from the bottom). The viscosity 2 minutes after the start of viscosity measurement is defined as viscosity μ (d).

(Excluding the cement additive and antifoaming agent) In the same manner as in the mixture D, 600 g of ordinary Portland cement and 240 g of ion-exchanged water are put into a mortar mixer and stirred to obtain a mixture E. The viscosity is measured in the same manner as the mixture D, and the viscosity after 2 minutes from the start of the viscosity measurement is measured. The measurement is performed twice, and the average value of the two times is taken as the viscosity μ (e).
Viscosity μ (d) / viscosity μ (e) is defined as a cement operating coefficient.

<Measurement method of calcium transport value>
Reagent / equipment conditions Calcium carbonate: SS # 80 manufactured by Nippon Flour & Chemical Co.
Calcium hydroxide: Wako Pure Chemical Industries, Ltd. Toyoura Gossa: Toyoura Soseki Mining Co., Ltd. mortar mixer: Hobart N-50, capacity 5L
Rotation 1: Auto rotation 139rpm, Revolution 61rpm
Rotation 2: Autorotation 285rpm, Revolution 125rpm
Spatula: Stainless steel See Fig. 2 PACK-ACE (600 mL) manufactured by Terraoka
Homomixer: 1000 rpm See FIG. 4 B-type viscometer: 6 rpm, rotor no. 2. Start rotating 30 seconds after setting the rotor.
Addition amount of cement additive: All addition amount in terms of solid content.

Measurement method 300 g of calcium carbonate, 0.3 g of calcium hydroxide and 250 g of Toyoura cinnabar are adjusted to 25 ° C. and stirred in rotation 1 for 30 seconds, and then ion-exchanged water to which a predetermined amount of cement additive is added. Add 75 g (25 ° C.) and stir for an additional 5 minutes at rotation 2 to obtain mixture A.

All of the mixture A was placed in a plastic cylindrical container (capacity 1.2 L, lower diameter 90 mm, upper diameter 110 mm, height 140 mm), and 30 seconds and 58 minutes after the addition of ion-exchanged water, using a spatula for 30 seconds to the right And 15 times to the left.

“Maximum length” of the mixture spread on the stainless steel plate by filling the mixture A in a hollow cylindrical vessel with a diameter of 55 mm and a height of 50 mm placed on a stainless steel plate, and lifting the cylindrical container vertically one hour after the addition of ion-exchange water. And “the length in the vertical direction” and the average value of these two values is taken as the flow value (mm).

The amount of cement additive added to calcium carbonate (in terms of solid content) is changed, and the amount of cement additive required to make the flow value 160 mm is obtained (this amount added is defined as the standard calcium addition amount).

Subsequently, 300 g of calcium carbonate adjusted to 25 ° C. and 75 g of ion-exchanged water (25 ° C.) to which a cement additive having a standard amount of calcium was added were added to Terraoka PACK-ACE (600 mL) (upper diameter 87 mm, lower diameter). In a plastic cylindrical container 80 mm high and 120 mm high), stirred 90 times to the right and 90 times to the left in 3 minutes using a stainless steel rod (width 9 mm, thickness 2 mm), and further stirred for 9 minutes with a homomixer. Get.

The temperature of the mixture B is adjusted to 25 ° C. in a constant temperature water bath immediately before being transferred to a 100 mL screw tube (a glass container having a diameter of 35 mm and a height of 100 mm), and immediately before being transferred to the 100 mL screw tube, 3 using a stainless rod (width 9 mm, thickness 2 mm) Stir 180 times to the right and 180 times to the left for a minute to fully disperse the precipitated calcium carbonate. Put the mixture B up to a height of 80 mm in a 100 mL screw tube, measure the viscosity of the mixture B with a B-type viscometer 60 minutes after the start of stirring with a homomixer, and the indicated value 180 seconds after the start of rotation is the calcium transfer value. And

In the said cement additive, a calcium transport value is 10-900 mPa * s and / or a cement operation coefficient is 0.05-1.0.
A cement composition using a cement additive having a cement operating coefficient exceeding 1.0 is poor in workability and difficult to handle. In addition, a cement composition using a cement additive having a cement operating coefficient lower than 0.05 is easy to separate the cement paste and the aggregate (sand / stone), has a lot of breathing water, and is difficult to handle. Preferably it is 0.05 or more, More preferably, it is 0.1 or more, More preferably, it is 0.2 or more. Further, it is preferably 0.95 or less, more preferably 0.90 or less, still more preferably 0.85 or less, and particularly preferably 0.80 or less.

A cement composition using a cement additive having a calcium transport value exceeding 900 mPa · s has a high viscosity and is difficult to handle. In addition, the cement composition using a cement additive having a calcium transport value lower than 10 mPa · s has a low viscosity of the cement composition, the cement paste and the aggregate (sand / stone) are easily separated, and there is a lot of breathing water. It becomes difficult. The pressure is preferably 10 Pa · s or more and 850 mPa · s or less. Particularly preferred is 50 Pa · s or more, and most preferred is 100 Pa · s or more. Further, it is more preferably 800 mPa · s or less, further preferably 750 mPa · s or less, particularly preferably 700 mPa · s or less, and most preferably 650 mPa · s or less.

When purified after adjustment to pH 12 to 12.5, the amount of nitrogen by elemental analysis is 0.1 to 20% by weight, and morpholine, 4- (2-hydroxyethyl) morpholine, and 1 by pyrolysis GC-MASS -4 dioxane is detected, the GPC peak has no shoulder, the weight average molecular weight (Mw) is 5000 to 300000, and the absorption peak intensity existing in 1640 to 1660 cm ^-1 is 1710 to 1630 cm ^-1 in IR measurement It is 20% or less of the existing absorption peak intensity, signals are detected at chemical shift positions of 60 to 61 ppm and 69 to 68 ppm by ¹³ C-NMR, the amount of NMR-PEG is 10 to 99% by weight, and TCAV is 3 A cement additive of ~ 900 mgKOH / g is also easier to handle when the fluidity and water reduction are the same. Such cement additives are also one aspect of the present invention.

By combining the nitrogen content, pyrolysis GC-MASS, IR, and ¹³ C-NMR measurement results, the polyalkyleneimine unsaturated monomer (A1) having the oxyalkylene group is contained in the cement additive. Is shown. That is, the cement additive whose analytical values satisfy the above range contains the polyalkyleneimine unsaturated monomer (A1) having the oxyalkylene group. In addition, if the peak of GPC is one, that is, if there is no shoulder in the peak, the polyalkyleneimine unsaturated monomer (A1) having an oxyalkylene group is copolymerized, and simply by mixing Not shown. The IR measurement shows that there is no amide bond, and the polyalkyleneimine unsaturated monomer (A1) having an oxyalkylene group is not copolymerized with a polyamide monomer, acrylic amide or the like. ) Is copolymerized.

The above-mentioned cement additive is purified by the following method, and the analytical value is in the above range.
(Cement additive purification method)
1. NaOH 30% by weight aq. To adjust the pH to 12-12.5.
2. The cement additive (polymer aqueous solution) is concentrated with an evaporator and then dried in a vacuum dryer at 50 ° C.
3. The obtained product is Soxhlet extracted with a solvent (diethyl ether, petroleum ether, etc.) and separated into soluble and insoluble components.
4). The insoluble matter is made into a solution of about 40 to 50% by weight, and low molecular weight components such as residual monomers are removed by dialysis or ultrafiltration. The molecular weight cut off is properly used depending on the molecular weight of the residual monomer of GPC. (1000, 3500, 8000, 15000)

The measurement conditions for the pyrolysis GC-MASS, GPC, IR, ¹³ C-NMR, TCAV, and NMR-PEG amount in the present invention are the same as those for the polycarboxylic acid polymer described above.

In the cement additive of the present invention, if the amount of nitrogen by elemental analysis when purified by the above method is less than 0.1% by weight, the cement composition using this cement additive may be difficult to handle. If it exceeds 20% by weight, the water reducing performance may be deteriorated. Preferably, it is 0.5 weight% or more, More preferably, it is 1.0 weight% or more. Further, it is preferably 15% by weight or less, more preferably 10% by weight or less, still more preferably 8% by weight or less, and particularly preferably 3% by weight or less. The amount of nitrogen is the weight ratio of nitrogen atoms to the solid content of 100% by weight of the cement additive.

When morpholine, 4- (2-hydroxyethyl) morpholine, and 1-4 dioxane are detected by the pyrolysis GC-MASS, a cement composition using this cement additive becomes easy to handle.

In the cement additive, it is necessary that the GPC peak has no shoulder. “The peak has no shoulder” means that there are only two inflection points from the peak start point to the peak end in the GPC chart as shown in FIG. Further, when the weight average molecular weight (Mw) is 5000 or less, the water reduction performance may be lowered, and when it exceeds 300,000, the water reduction performance and slump loss prevention ability may be lowered. Preferably, it is 8000 or more, and most preferably 10,000 or more. Further, it is preferably 300,000 or less, and most preferably 500,000 or less. The weight average molecular weight is a value measured under the GPC measurement conditions.

In the cement additive, it is necessary that the absorption peak intensity existing at 1640 to 1660 cm ⁻¹ in IR measurement is 20% or less of the absorption peak intensity existing at 1710 to 1630 cm ⁻¹ . This means that amide bonds are hardly present in the copolymer. Preferably, 15% or less of the absorption peak intensity absorption peak intensity existing in 1640～1660Cm ^-1 is present in 1710~1630cm ^-1. More preferably, it is 10% or less, More preferably, it is 5% or less, Most preferably, it is 3% or less.

In the ¹³ C-NMR, when signals are detected at chemical shift positions of 60 to 61 ppm and 69 to 68 ppm, the cement composition using the cement additive becomes easy to handle.

When the NMR-PEG amount is less than 10% by weight, the amount of the dispersing group for dispersing the cement particles is small, so that the aggregation of the cement particles occurs, the water reduction performance and the ease of handling are reduced, and exceed 99% by weight. And when it exceeds 99 weight%, time will be required for expression of water reduction performance, or water reduction performance will fall. Preferably it is 50 weight% or more, More preferably, it is 60 weight% or more, More preferably, it is 65 weight% or more, Most preferably, it is 70 weight% or more. Further, it is preferably 98% by weight or less, more preferably 97% by weight or less, further preferably 95% by weight or less, particularly preferably 93% by weight or less, and most preferably 93% by weight or less.

If the TCAV is less than 3 mgKOH / g, it takes time to develop water-reducing performance, or the water-reducing performance decreases. If it exceeds 900 mgKOH / g, cement particles aggregate to reduce water-reducing performance and slump loss prevention ability. There is a fear. Preferably it is 5 mgKOH / g or more, More preferably, it is 10 mgKOH / g or more, More preferably, it is 15 mgKOH / g or more, Most preferably, it is 20 mgKOH / g or more, Most preferably, it is 25 mgKOH / g or more. Further, it is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, further preferably 300 mgKOH / g or less, particularly preferably 200 mgKOH / g or less, and most preferably 150 mgKOH / g or less.

Cement additive whose calcium transfer value is 10 to 900 mPa · s and / or cement operating coefficient is 0.05 to 0.9, and analytical value when purified after adjustment to pH 12 to 12.5 or higher is in the above range. One preferred form of the cement additive is a monomer component containing the above-mentioned (1) polyalkyleneimine unsaturated monomer (A1) and unsaturated carboxylic acid monomer (B). A polymer comprising a polycarboxylic acid copolymer obtained by polymerization, (2) a monomer comprising a polyalkylene glycol unsaturated monomer (A2) and an unsaturated monocarboxylic acid monomer (B ′) Comprising a polycarboxylic acid copolymer obtained by copolymerizing a monomer component, (3) a polyalkylene glycol unsaturated monomer (A2 ′) and an unsaturated carboxylic acid monomer (B ) Monomer component containing (4) a monomer component containing a monomer (A) having an oxyalkylene group and an unsaturated carboxylic acid monomer (B). A polycarboxylic acid copolymer obtained by copolymerization using a hydrophobic chain transfer agent. Also in this case, the preferred form of the polycarboxylic acid copolymer is the same as described above. That is, in the form (1), the polyalkyleneimine unsaturated monomer (A1) preferably has an oxyalkylene group, and in the forms (1), (2) and (3), The monomer component preferably contains a polyalkylene glycol unsaturated monomer (A3) other than the monomer having the oxyalkylene group. Moreover, you may combine suitably the form of (1), (2), (3) and (4).

The cement additive of the present invention will be described below.
The cement additive can be used in addition to a cement composition such as cement paste, mortar, and concrete.
As the cement composition, those usually used including cement, water, fine aggregate, coarse aggregate and the like are suitable. Moreover, what added fine powders, such as fly ash, blast furnace slag, a silica fume, a liquid silica fume, and a limestone, may be used. Such a cement composition comprising at least water, cement, and a cement additive, wherein the cement additive uses the cement additive, is also one aspect of the present invention.

As the cement, portland cement such as normal, early strength, super early strength, moderate heat, white, etc .; mixed portland cement such as alumina cement, fly ash cement, blast furnace cement, silica fume cement, high flow cement and the like are suitable. As the blending amount and unit water amount per 1 m ³ of concrete of the cement, in order to produce highly durable and high strength concrete, the unit water amount is 80 to 185 kg / m ³ , and the water / cement ratio is 10 to 70%. It is preferable to do. More preferably, the unit water amount is 100 to 175 kg / m ³ and the water / cement ratio is 10 to 65%. Moreover, gravel, crushed stone, granulated slag, recycled aggregate, fireproof aggregate, etc. can be used as the aggregate.

The method for adding the cement additive to the cement composition is not particularly limited. The addition amount of the cement additive to the cement composition may be 0.01 to 10% by weight with respect to 100% by weight of the total amount of the cement of the present invention. preferable. If the amount is less than 0.01% by weight, the performance may be insufficient. If the amount exceeds 10% by weight, the economy is inferior. In addition, the said weight% is a value of solid content conversion.

Since the cement composition has high fluidity, it is effective for precast concrete, centrifugal molding concrete, vibration compaction concrete, steam-cured concrete, shotcrete, etc. in addition to ultra-high-strength concrete. Furthermore, medium-fluidity concrete (concrete with a slump value of 22 to 25 cm), high fluidity concrete (concrete with a slump value of 25 cm or more and a slump flow value of 50 to 70 cm), self-filling concrete, self It is also effective for mortar and concrete that require high fluidity such as leveling materials.

The cement additive can be used in combination with a commonly used known cement dispersant. Known cement dispersants that can be used are not particularly limited, and various sulfonic acid dispersants having a sulfonic acid group in the molecule, and various polycarboxylic acid types having a polyoxyalkylene chain and a carboxyl group in the molecule. A dispersing agent is mentioned. Examples of the sulfonic acid dispersant include lignin sulfonate; polyol derivative; naphthalene sulfonic acid formalin condensate; melamine sulfonic acid formalin condensate; polystyrene sulfonate; aminoaryl sulfonic acid-phenol-formaldehyde condensate and the like. A sulfonic acid type | system | group etc. are mentioned. Examples of the polycarboxylic acid-based dispersing agent include aminosulfonic acid-based dispersants such as aminoarylsulfonic acid-phenol-formaldehyde condensates as described in JP-A-1-113419; described in JP-A-7-267705. As a component (a), a polyalkylene glycol mono (meth) acrylic acid ester compound and a (meth) acrylic acid compound copolymer and / or a salt thereof, and as a component (b) a polyalkylene glycol mono Copolymer of (meth) allyl ether compound and maleic anhydride and / or its hydrolyzate and / or salt thereof, and (c) component, polyalkylene glycol mono (meth) allyl ether compound and , Copolymers of polyalkylene glycol compounds with maleic acid esters and / or As a component A as described in Japanese Patent No. 2508113, a copolymer of polyalkylene glycol ester of (meth) acrylic acid and (meth) acrylic acid (salt), as component B, A specific polyethylene glycol polypropylene glycol compound, a concrete additive comprising a specific surfactant as component C; polyethylene (propylene) glycol ester of (meth) acrylic acid or polyethylene as described in JP-A-62-216950 A copolymer comprising (propylene) glycol mono (meth) allyl ether, (meth) allylsulfonic acid (salt), and (meth) acrylic acid (salt).

A copolymer comprising polyethylene (propylene) glycol ester of (meth) acrylic acid, (meth) allylsulfonic acid (salt), and (meth) acrylic acid (salt) as described in JP-A-1-226757; As described in JP-B-5-36377, (meth) acrylic acid polyethylene (propylene) glycol ester, (meth) allylsulfonic acid (salt) or p- (meth) allyloxybenzenesulfonic acid (salt), and Copolymer comprising (meth) acrylic acid (salt); copolymer of polyethylene glycol mono (meth) allyl ether and maleic acid (salt) as described in JP-A-4-149056; JP-A-5-170501 (Meth) acrylic acid polyethylene glycol ester, (meth) allylsulfonic acid ( ), (Meth) acrylic acid (salt), alkanediol mono (meth) acrylate, polyalkylene glycol mono (meth) acrylate, and α, β-unsaturated monomer having an amide group in the molecule Polymerization; as described in JP-A-6-191918, polyethylene glycol mono (meth) allyl ether, polyethylene glycol mono (meth) acrylate, (meth) acrylic acid alkyl ester, (meth) acrylic acid (salt), and ( Copolymer comprising meth) allylsulfonic acid (salt) or p- (meth) allyloxybenzenesulfonic acid (salt); alkoxypolyalkylene glycol monoallyl ether and maleic anhydride as described in JP-A-5-43288 Copolymer or its hydrolyzate or its salt; Polyethylene glycol monoallyl ether as described in 58-38380 JP, maleic acid, and copolymers composed of these monomers copolymerizable with monomer, or a salt thereof, or an ester thereof.

As described in JP-B-59-18338, polyalkylene glycol mono (meth) acrylic acid ester monomer, (meth) acrylic acid monomer, and a monomer copolymerizable with these monomers A copolymer comprising a polymer; a copolymer comprising a (meth) acrylic acid ester having a sulfonic acid group and a monomer copolymerizable therewith as described in JP-A-62-1119147, or Salt thereof; as described in JP-A-6-271347, an esterification reaction product of a copolymer of an alkoxy polyalkylene glycol monoallyl ether and maleic anhydride and a polyoxyalkylene derivative having an alkenyl group at the terminal; Copolymer of alkoxypolyalkylene glycol monoallyl ether and maleic anhydride as described in Kaihei 6-298555 , Esterification reaction product with a polyoxyalkylene derivative having a hydroxyl group at the terminal; as described in JP-A-62-68806, ethylene oxide or the like is added to a specific unsaturated alcohol such as 3-methyl-3-buten-1-ol. Added alkenyl ether monomers, unsaturated carboxylic acid monomers, copolymers consisting of monomers copolymerizable with these monomers, or polycarboxylic acids (salts) such as salts thereof ). These cement dispersants may be used alone or in combination of two or more. Among the cement dispersants that can be used in combination, it is particularly preferable to use various polycarboxylic acid-based dispersants having a polyoxyalkylene chain and a carboxyl group in the molecule, and specific examples of the polycarboxylic acid-based dispersants. Include the copolymers shown in Table 1.

When the above cement dispersant is used in combination, it is not uniquely determined depending on the type of cement dispersant used, blending, test conditions, etc., but the proportion of the blended weight of the cement additive and the cement dispersant Is preferably 5 to 95:95 to 5. More preferably, it is 10-90: 90-10.
Moreover, the said cement additive can also be used in combination with another cement additive. As the other cement additives, other known cement additives (materials) as shown below are suitable.

(1) Water-soluble polymer substances: polyacrylic acid (sodium), polymethacrylic acid (sodium), polymaleic acid (sodium), unsaturated carboxylic acid polymer such as sodium salt of acrylic acid / maleic acid copolymer; polyethylene Polyoxyethylene or polyoxypropylene polymers such as glycol and polypropylene glycol or copolymers thereof; Nonionic cellulose ethers such as methyl cellulose, ethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, carboxyethyl cellulose, hydroxypropyl cellulose; yeast glucan Or xanthan gum, β-1,3 glucans (both linear and branched), and examples include curdlan, paramylon, pachyman, Polysaccharides produced by microbial fermentation such as cleroglucan, laminaran, etc .; polyacrylamide; polyvinyl alcohol; starch; starch phosphate ester; sodium alginate; gelatin; copolymer of acrylic acid having an amino group in its molecule and its quaternary Compounds and the like.

(2) Polymer emulsion: Copolymers of various vinyl monomers such as alkyl (meth) acrylate.
(3) retarder: oxycarboxylic such as gluconic acid, glucoheptonic acid, arabonic acid, malic acid or citric acid, and inorganic salts or organic salts thereof such as sodium, potassium, calcium, magnesium, ammonium, triethanolamine, etc. Acids and salts thereof; monosaccharides such as glucose, fructose, galactose, saccharose, xylose, apiose, ribose and isomerized sugar; oligosaccharides such as disaccharides and trisaccharides; oligosaccharides such as dextrin; Sugars, sugars such as molasses containing them; sugar alcohols such as sorbitol; magnesium silicate; phosphoric acid and its salts or boric acid esters; aminocarboxylic acids and their salts; alkali-soluble proteins; humic acids; Phenol; polyhydric alcohol such as glycerine; aminotri ( Tylene phosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) and their alkali metal salts, alkaline earth metal salts and other phosphonic acids and their derivatives etc.

(4) Early strengthening agents / accelerators: soluble calcium salts such as calcium chloride, calcium nitrite, calcium nitrate, calcium bromide and calcium iodide; chlorides such as iron chloride and magnesium chloride; sulfates; potassium hydroxide; Sodium hydroxide; carbonate; thiosulfate; formate such as formic acid and calcium formate; alkanolamine; alumina cement; calcium aluminate silicate.
(5) Mineral oil-based antifoaming agent: cocoon oil, liquid paraffin, etc.
(6) Fat and oil-based antifoaming agents: animal and vegetable oils, sesame oil, castor oil, alkylene oxide adducts thereof and the like.
(7) Fatty acid-based antifoaming agent: oleic acid, stearic acid, and these alkylene oxide adducts.
(8) Fatty acid ester antifoaming agent: glycerin monoricinoleate, alkenyl succinic acid derivative, sorbitol monolaurate, sorbitol trioleate, natural wax and the like.

(9) Oxyalkylene antifoaming agents: polyoxyalkylenes such as (poly) oxyethylene (poly) oxypropylene adducts; diethylene glycol heptyl ether, polyoxyethylene oleyl ether, polyoxypropylene butyl ether, polyoxyethylene polyoxypropylene (Poly) oxyalkyl ethers such as 2-ethylhexyl ether and oxyethyleneoxypropylene adducts to higher alcohols having 12 to 14 carbon atoms; (poly) oxyalkylenes such as polyoxypropylene phenyl ether and polyoxyethylene nonylphenyl ether (Alkyl) aryl ethers; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,5-dimethyl-3-hexyne-2,5-diol, 3-methyl-1- Spotted Acetylene ethers obtained by addition polymerization of alkylene oxide to acetylene alcohol such as -3-ol; (poly) oxyalkylene fatty acid esters such as diethylene glycol oleate, diethylene glycol laurate, ethylene glycol distearate; polyoxyethylene sorbitan (Poly) oxyalkylene sorbitan fatty acid esters such as monolaurate and polyoxyethylene sorbitan trioleate; (poly) oxyalkylene alkyl (aryl) such as sodium polyoxypropylene methyl ether sulfate and sodium polyoxyethylene dodecylphenol ether sulfate ) Ether sulfate esters; (Poly) oxy such as (poly) oxyethylene stearyl phosphate Ruki alkylene alkyl phosphate esters; polyoxyethylene such as polyoxyethylene lauryl amine (poly) oxyalkylene alkyl amines; polyoxyalkylene amide.

(10) Alcohol-based antifoaming agent: octyl alcohol, hexadecyl alcohol, acetylene alcohol, glycols and the like.
(11) Amide antifoaming agent: acrylate polyamine and the like.
(12) Phosphate ester antifoaming agent: tributyl phosphate, sodium octyl phosphate, etc.
(13) Metal soap type antifoaming agent: aluminum stearate, calcium oleate, etc.
(14) Silicone antifoaming agent: dimethyl silicone oil, silicone paste, silicone emulsion, organically modified polysiloxane (polyorganosiloxane such as dimethylpolysiloxane), fluorosilicone oil and the like.

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

(16) Other surfactants: aliphatic monohydric alcohols having 6 to 30 carbon atoms in the molecule such as octadecyl alcohol and stearyl alcohol, and those having 6 to 30 carbon atoms in the molecule such as abiethyl alcohol Intramolecular such as alicyclic monohydric alcohol, dodecyl mercaptan, etc. Intramolecular such as monovalent mercaptan having 6-30 carbon atoms in the molecule, such as nonylphenol, alkylphenol having 6-30 carbon atoms in the molecule, dodecylamine, etc. 10 mol or more of an alkylene oxide such as ethylene oxide or propylene oxide was added to a carboxylic acid having 6 to 30 carbon atoms in the molecule such as an amine having 6 to 30 carbon atoms, lauric acid or stearic acid. Polyalkylene oxide derivatives; having an alkyl group or alkoxyl group as a substituent Alkyl diphenyl ether sulfonates in which two phenyl groups having a sulfone group are ether-bonded; various anionic surfactants; various cationic surfactants such as alkylamine acetate and alkyltrimethylammonium chloride; various nonions Surfactants; various amphoteric surfactants.

(17) Waterproofing agent: fatty acid (salt), fatty acid ester, fats and oils, silicon, paraffin, asphalt, wax and the like.
(18) Rust inhibitor: nitrite, phosphate, zinc oxide and the like.
(19) Crack reducing agent: polyoxyalkyl ethers; alkanediols such as 2-methyl-2,4-pentanediol.
(20) Expansion material: Ettlingite, coal, etc.

Other known cement additives (materials) include cement wetting agents, thickeners, separation reducing agents, flocculants, drying shrinkage reducing agents, strength enhancers, self-leveling agents, rust preventives, colorants, and antifungal agents. Agents, blast furnace slag, fly ash, cinder ash, clinker ash, husk ash, silica fume, silica powder, gypsum and the like. These known cement additives (materials) may be used alone or in combination of two or more.

In the cement composition, the following (1) to (7) may be mentioned as particularly preferred embodiments for components other than cement and water.
(1) A combination comprising essentially two components (i) the cement additive of the present invention and (ii) an oxyalkylene antifoaming agent. The blending weight ratio of the oxyalkylene antifoaming agent (ii) is preferably in the range of 0.001 to 10% by weight with respect to the cement additive (i).
(2) A combination comprising essentially three components: (i) the cement additive of the present invention, (ii) a polycarboxylic acid dispersant, and (iii) an oxyalkylene antifoaming agent. The blending weight ratio of the cement additive (i) and the copolymer (ii) is preferably in the range of 5/95 to 95/5, and more preferably in the range of 10/90 to 90/10. The blending weight ratio of the oxyalkylene antifoaming agent (iii) is 0.001 to 10% by weight based on the total amount of the cement additive (i) and the polycarboxylic acid dispersant (ii). A range is preferred.
(3) A combination comprising essentially two components: (i) the cement additive of the present invention, and (ii) a sulfonic acid-based dispersant having a sulfonic acid group in the molecule. Examples of the sulfonic acid dispersant include lignin sulfonate, naphthalene sulfonic acid formalin condensate, melamine sulfonic acid formalin condensate, polystyrene sulfonate, aminoaryl sulfonic acid-phenol-formaldehyde condensate and the like. An agent or the like can be used. The blending weight ratio between the cement additive (i) and the sulfonic acid-based dispersant having a sulfonic acid group in the molecule (ii) is preferably 5/95 to 95/5, and 10/90 to 90. / 10 is more preferable.

(4) A combination which essentially comprises two components (i) the cement additive of the present invention and (ii) lignin sulfonate. The blending weight ratio of the cement additive (i) and the lignin sulfonate salt (ii) is preferably 5/95 to 95/5, more preferably 10/90 to 90/10.
(5) A combination comprising essentially two components (i) the cement additive of the present invention and (ii) a material separation reducing agent. As the material separation reducing agent, various thickeners such as nonionic cellulose ethers can be used. The blending weight ratio of the cement additive (i) and the material separation reducing agent (ii) is preferably 10/90 to 99.99 / 0.01, and 50/50 to 99.9 / 0. 1 is more preferable. The cement composition of this combination is suitable as high fluidity concrete, self-filling concrete and self-leveling material.
(6) A combination comprising two components, i.e., the cement additive of the present invention and (ii) a retarder. As the retarder, oxycarboxylic acids such as gluconic acid (salt) and citric acid (salt), sugars such as glucose, sugar alcohols such as sorbitol, phosphonic acids such as aminotri (methylenephosphonic acid), and the like can be used. . The blending weight ratio of the cement additive (i) and the retarder (ii) is preferably in the range of 50/50 to 99.9 / 0.1, and in the range of 70/30 to 99/1. More preferred.
(7) A combination comprising essentially two components (i) the cement additive of the present invention and (ii) an accelerator. As the accelerator, soluble calcium salts such as calcium chloride, calcium nitrite and calcium nitrate, chlorides such as iron chloride and magnesium chloride, formates such as thiosulfate, formic acid and calcium formate, and the like can be used. The blending weight ratio of the cement additive (i) and the accelerator (ii) is preferably in the range of 10/90 to 99.9 / 0.1, and in the range of 20/80 to 99/1. More preferred.

The above-mentioned cement additive may be used in combination with the above-described known cement dispersant and cement additive (material), in addition to those that improve the dispersibility of the cement composition, foam suppression, and the like.
As a method of adding the cement additive or the cement dispersant to the cement composition, it is preferable to mix these cement additives or the cement dispersant to obtain a cement additive, which is easily mixed into the cement composition. .

The cement composition to which the above cement additive is added has excellent fluidity and fluidity retention, and therefore has excellent water reduction and workability, and also has excellent strength and durability of the cured product. . Therefore, the cement additive containing the polycarboxylic acid copolymer of the present invention can be suitably used for ultra-high strength concrete, and can exhibit a sufficient effect as a water reducing agent for ultra-high strength. .

For the composition, materials used and mixing method of the above ultra-high-strength concrete, Summary of the Annual Meeting of the Architectural Institute of Japan (Kanto) (2001-9.) P. 197-200, Outline of the 56th Annual Conference of the Japan Society of Civil Engineers, V-137 ("A Device for Strength Development of Ultra-High Strength Concrete") (2001) p. Examples of preferred embodiments of the present invention are as follows.

Table 2 will be described below.
W / C (% by weight) is the weight% of water relative to cement, and s / a (volume%) is the volume% of fine aggregate with respect to the total aggregate (fine aggregate + coarse aggregate). . W is a unit water amount, C is a unit cement amount, S is a unit fine aggregate amount, and G is a unit coarse aggregate amount. a is the absolute volume of the whole aggregate (fine aggregate + coarse aggregate), and s is the absolute volume of the fine aggregate.

(Materials used)
Cement: manufactured by Ube Mitsubishi Cement Co., Ltd., silica fume cement (density = 3.08 g / cm ³ , brain; specific surface area = 5600 cm ² / g)
Fine aggregate: land sand of Oigawa (surface dry density = 2.57 g / cm ³ , water absorption = 2.15%, FM = 2.76)
Coarse aggregate: Ome crushed stone (surface dry density = 2.65 g / cm ³ , actual volume ratio = 0.59, FM = 6.74, MS = 20 mm)

(Kneading method)
Using a 55 liter forced biaxial mixer, 30 liters per batch are kneaded in the following procedure.
Cement and fine aggregate are kneaded for 10 seconds, and then water added with cement additive is mixed and further kneaded for the “mortar mixing time (seconds)” specified in Table 2. Then, coarse aggregate is mixed and kneaded for 90 seconds to prepare ultra high strength concrete.

Table 3 will be described below.
W / B (wt%) is the weight% of water relative to the binder (cement + silica fume), and s / a (volume%) is the fine aggregate relative to the total aggregate (fine aggregate + coarse aggregate). The volume percentage of aggregate. W is a unit water amount, B is a unit binder amount, that is, a combination of cement and silica fume fine powder (B = C + SF), C is a unit cement amount, and SF and unit are silica fume. The amount of fine powder, S is the unit fine aggregate amount, and G is the unit coarse aggregate amount. a is the absolute volume of the whole aggregate (fine aggregate + coarse aggregate), and s is the absolute volume of the fine aggregate.

(Materials used)
Cement: Low heat Portland cement (density = 3.22 g / cm ³ , brain specific surface area = 3280 cm ² / g)
Fine aggregate: land sand of Oigawa (surface dry density = 2.57 g / cm ³ , water absorption = 2.15%, FM = 2.76)
Coarse aggregate: Ome crushed stone (surface dry density = 2.65 g / cm ³ , actual volume ratio = 0.59, FM = 6.74, MS = 20 mm)

(Kneading method)
Using a 55 liter forced biaxial mixer, 30 liters per batch are kneaded in the following procedure.
Cement, silica fume fine powder, and fine aggregate are kneaded for 60 seconds, mixed with water to which a cement additive is added, and after confirming that the mortar is uniformly mixed, knead for another 30 seconds. Then, coarse aggregate is mixed and kneaded for 90 seconds to prepare ultra high strength concrete.

Since the polycarboxylic acid copolymer of the present invention has the above-described structure, it is excellent in water reduction and workability of a cement composition, etc. by using it as a component of a cement additive, and its cured product. Therefore, it can be suitably applied to cement paste, mortar, concrete, etc., particularly ultra high strength concrete.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “%” means “% by weight”.

Example 1
Polyethyleneimine ethylene oxide adduct (compound obtained by adding ethylene oxide with an average addition mole number of 3 to active hydrogen of polyethyleneimine of Mw 600) in a glass reactor equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux cooling device 500 The reaction apparatus was purged with nitrogen under stirring and cooled to 20 ° C. or lower under a nitrogen atmosphere. The reaction system was kept at 20 ° C. or lower, and 44.3 parts of glycidyl methacrylate was added over 1 hour. After completion of the addition, stirring was continued at 20 ° C. or lower for 1 hour to obtain a polyethyleneimine / ethylene oxide adduct monomer (polyethyleneimine EO adduct macromer).

Example 2
Polyethyleneimine ethylene oxide adduct (compound obtained by adding ethylene oxide with an average addition mole number of 3 to active hydrogen of polyethyleneimine of Mw 600) in a glass reactor equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux cooling device 500 The reaction apparatus was purged with nitrogen under stirring and cooled to 20 ° C. or lower under a nitrogen atmosphere. While keeping the inside of the reaction system at 20 ° C. or less, 51.2 parts of methacrylic anhydride was added in 1 hour. After completion of the addition, stirring was continued at 20 ° C. or lower for 1 hour to obtain a polyethyleneimine / ethylene oxide adduct monomer (polyethyleneimine EO adduct macromer).

Example 3
A glass reactor equipped with a thermometer, a stirrer, a dripping device, a nitrogen introducing tube and a reflux cooling device was charged with 984.3 parts of water, and the inside of the reactor was purged with nitrogen under stirring, and heated to 80 ° C. in a nitrogen atmosphere. did. 625.5 parts of methoxypolyethyleneglycol monomethacrylate (average addition mole number of ethylene oxide 25), 166.0 parts of methacrylic acid, 208.5 parts of polyethyleneimine EO adduct macromer synthesized in Example 1, 250.0 parts of water and chain A monomer aqueous solution mixed with 15.7 parts of 3-mercaptopropionic acid as a transfer agent and 200.0 parts of a 10.4% aqueous ammonium persulfate solution were added dropwise over 2 hours. After completion of the dropwise addition, 50.0 parts of a 10.4% ammonium persulfate aqueous solution was further added dropwise over 0.5 hours. Subsequently, the temperature was maintained at 80 ° C. for 2 hours to complete the polymerization reaction, and a polycarboxylic acid copolymer aqueous solution having a weight average molecular weight of 17400 was obtained.

Example 4
Charge 117.2 parts of water to a glass reactor equipped with a thermometer, stirrer, dripping device, nitrogen inlet tube and reflux cooling device, purge the reactor with nitrogen under stirring, and heat to 80 ° C. in a nitrogen atmosphere. did. 69.5 parts of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added 25), 25.2 parts of methacrylic acid, 25.3 parts of the polyethyleneimine EO adduct macromer synthesized in Example 1, 30.0 parts of water and chain A monomer aqueous solution mixed with 2.8 parts of 3-mercaptopropionic acid as a transfer agent and 24.0 parts of a 10.4% aqueous ammonium persulfate solution were added dropwise over 2 hours. After completion of the dropwise addition, 6.0 parts of 10.4% aqueous ammonium persulfate solution was further added dropwise over 0.5 hours. Thereafter, the temperature was maintained at 80 ° C. for 2 hours to complete the polymerization reaction, and a polycarboxylic acid copolymer aqueous solution having a weight average molecular weight of 14,000 was obtained.

Example 5
Into a glass reactor equipped with a thermometer, stirrer, dripping device, nitrogen inlet tube and reflux cooling device, 1458.2 parts of water were charged, the inside of the reactor was purged with nitrogen under stirring, and heated to 80 ° C. in a nitrogen atmosphere. did. Monomer aqueous solution in which 581.7 parts of methoxypolyethylene glycol monoacrylate (average number of added moles of ethylene oxide 23), 149.5 parts of acrylic acid, 203.0 parts of water, and 20.2 parts of 3-mercaptopropionic acid as a chain transfer agent are mixed. Then, an aqueous solution obtained by mixing 198.8 parts of the polyethyleneimine EO adduct macromer synthesized in Example 1 and 198.8 parts of water, and 248.0 parts of a 15% aqueous sodium persulfate solution were added dropwise over 2 hours. After completion of the dropwise addition, 62.0 parts of a 15% aqueous sodium persulfate solution was further added dropwise over 0.5 hours. Thereafter, the temperature was maintained at 80 ° C. for 2 hours to complete the polymerization reaction, and an aqueous polycarboxylic acid copolymer solution having a weight average molecular weight of 11,300 was obtained.

Example 6
A glass reactor equipped with a thermometer, stirrer, dripping device, nitrogen inlet tube and reflux cooling device was charged with 1455.3 parts of water, the inside of the reactor was purged with nitrogen, and heated to 80 ° C. in a nitrogen atmosphere. did. Monomer aqueous solution in which 539 parts of methoxypolyethylene glycol monoacrylate (average added mole number of ethylene oxide 23), 189.2 parts of acrylic acid, 202.9 parts of water, and 20.8 g of 3-mercaptopropionic acid as a chain transfer agent were mixed, Examples An aqueous solution obtained by mixing 201.9 parts of the polyethyleneimine EO adduct macromer synthesized in 1 and 201.9 parts of water and 248 parts of a 15% aqueous sodium persulfate solution were added dropwise over 2 hours. After the completion of dropping, 62 parts of a 15% aqueous sodium persulfate solution was further added dropwise over 0.5 hours. Thereafter, the temperature was maintained at 80 ° C. for 2 hours to complete the polymerization reaction, and a polycarboxylic acid copolymer aqueous solution having a weight average molecular weight of 11,000 was obtained.

Example 7
Charge 117.2 parts of water to a glass reactor equipped with a thermometer, stirrer, dripping device, nitrogen inlet tube and reflux cooling device, purge the reactor with nitrogen under stirring, and heat to 80 ° C. in a nitrogen atmosphere. did. 69.5 parts of methoxy polyethylene glycol monomethacrylate (average number of moles of ethylene oxide added 25), 25.2 parts of methacrylic acid, 25.3 parts of macromer of polyethyleneimine EO adduct synthesized in Example 2, 30 parts of water and chain transfer agent The monomer aqueous solution mixed with 2.8 parts of 3-mercaptopropionic acid and 24.0 parts of 10.4% ammonium persulfate aqueous solution were added dropwise over 2 hours. After completion of the dropwise addition, 6.0 parts of 10.4% aqueous ammonium persulfate solution was further added dropwise over 0.5 hours. Thereafter, the temperature was maintained at 80 ° C. for 2 hours to complete the polymerization reaction, and an aqueous polycarboxylic acid copolymer solution having a weight average molecular weight of 12,000 was obtained.

Example 8
984.3 g of water was charged into a glass reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux cooling device, and the inside of the reaction device was purged with nitrogen under stirring, and heated to 80 ° C. in a nitrogen atmosphere. . 603.9 g of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added 25), 187.6 g of methacrylic acid, 208.5 g of the polyethyleneimine EO adduct macromer synthesized in Example 1, 250 g of water and 18 g of 3-mercaptopropionic acid The mixed monomer aqueous solution and 200 g of 10.4% ammonium persulfate aqueous solution were added dropwise over 2 hours. After completion of the dropwise addition, 50 g of a 10.4% aqueous ammonium persulfate solution was further added dropwise over 30 minutes. Thereafter, the temperature was maintained at 80 ° C. for 2 hours to complete the polymerization reaction, and a polycarboxylic acid copolymer aqueous solution having a weight average molecular weight of 12300 was obtained.

Example 9
A glass reactor equipped with a thermometer, a stirrer, a dripping device, a nitrogen introduction tube and a reflux cooling device was charged with 187.3 g of ion-exchanged water, and the reaction system was heated to 65 ° C. in a nitrogen atmosphere and then oxidized. 3.1 g of a 30% aqueous solution of hydrogen water was added. Thereto, 32.0 g of a mixed solution of 532.0 g of an 80% aqueous solution of IPN-25, 1.2 g of L-ascorbic acid, 2.0 g of 1-octanethiol, 71.6 g of acrylic acid and 36.8 g of ion-exchanged water 3 Dropped over time. After completion of the dropping, the polymerization reaction was completed by aging at 65 ° C. for 1.5 hours. The reaction solution was adjusted to pH = 7 with a 30% aqueous sodium hydroxide solution to obtain an aqueous solution of a polycarboxylic acid copolymer having a weight average molecular weight of 36,300.

Comparative Example 1
99.7 g of water was charged into a glass reaction vessel equipped with a thermometer, a stirrer, a nitrogen introduction tube and a reflux cooling device, and the inside of the reaction device was purged with nitrogen under stirring and heated to 80 ° C. in a nitrogen atmosphere. A monomer aqueous solution consisting of 79 g of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added 25), 21 g of methacrylic acid, 24.7 g of water and 0.66 g of 3-mercaptopropionic acid was added for 4 hours, 1.2 g of ammonium persulfate and 23. An initiator aqueous solution consisting of 8 g was dropped into the reaction vessel over 5 hours. After completion of the dropwise addition of the aqueous initiator solution, the temperature was continuously maintained at 80 ° C. for 1 hour to complete the polymerization reaction. After completion of the reaction, the mixture was neutralized with 30% aqueous sodium hydroxide solution to pH 7.0 to obtain a copolymer having a weight average molecular weight of 24,000.

Method for preparing mortar 800 g of Pacific ordinary Portland cement (trade name, manufactured by Taiheiyo Cement Co., Ltd.) and 400 g of Toyoura cinnabar were kneaded with a mortar mixer (trade name: N-50, manufactured by Tesco Corp.) at low speed for 30 seconds. Next, 180 g of water containing the polycarboxylic acid copolymer produced in the example or the copolymer produced in the comparative example was added to a mixture of cement and sand kneaded and kneaded for 5 minutes at high speed. A mortar was prepared. The polycarboxylic acid copolymer of the example and the copolymer of the comparative example were blended so that the solid content% by weight with respect to the cement weight was the value shown in Table 4. In addition, in preparation of each mortar, the empty kneading and kneading conditions by the mortar mixer were made uniform.

Evaluation Method (1) Mortar Uniform Time Mortar when adding 180 g of water mixed with polycarboxylic acid copolymer or copolymer into a kneaded cement and sand mixture and kneading at high speed for 5 minutes with a mortar mixer. The time (seconds) at which the was in a uniform state was measured visually to obtain a mortar uniform time. The results are shown in Table 4.

(2) Flow value The prepared mortar was packed into a hollow cylindrical container having a diameter of 55 mm and a height of 50 mm placed on a stainless steel plate 6 minutes after water injection. Next, after the hollow cylindrical container was lifted vertically, the diameter of the mortar spread on the stainless steel plate was measured in two longitudinal and lateral directions, and this average value was defined as a flow value (mm). The larger the flow value, the higher the fluidity. The results are shown in Table 4.

(3) The penetration time adjusted mortar was packed in a cement paste container specified in JIS R 5201, allowed to stand for 15 minutes for 75 minutes, and then a Vicat needle device equipped with a standard bar specified in JIS R 5201. The standard bar was dropped from the state in which the tip of the standard bar was in contact with the mortar packed in the cement paste container. The time required for the standard bar to reach the bottom of the cement paste container was defined as the penetration time (seconds). The longer the penetration time, the higher the viscosity of the mortar. The results are shown in Table 4.

When the copolymer of Comparative Example 1 containing no polyethyleneimine EO adduct macromer and the polycarboxylic acid-based copolymer of Example containing a polyethyleneimine EO adduct macromer were compared for mortar penetration time after 15 minutes and 75 minutes, In the copolymer of Comparative Example 1, the penetration time after 75 minutes is 1.65 seconds, whereas in the polycarboxylic acid copolymer of the example, the penetration time is 0.59 to 1.30 seconds. It can be seen that the time is shorter and the viscosity of the mortar is lower than that of the mortar prepared using the copolymer of Comparative Example 1. It can be seen that the polycarboxylic acid copolymer containing the polyethyleneimine EO adduct macromer has an effect of reducing the viscosity of the mortar.

Example 10
300 parts of a sorbitol ethylene oxide adduct (compound in which ethylene oxide is added to the hydroxyl group of sorbitol with an average addition mole number of 10) in a glass reactor equipped with a thermometer, a stirrer, a dropping device, a nitrogen introducing tube / air introducing tube and a reflux cooling device Then, 0.08 part of sodium hydroxide was charged, and the temperature was raised to 90 ° C. in an air atmosphere. While maintaining the reaction system at 90 ° C., 22.9 of glycidyl methacrylate was added in 1 hour. After completion of the addition, stirring was continued at 90 ° C. for 2 hours to obtain a sorbitol / ethylene oxide adduct monomer (sorbitol EO adduct macromer).

Example 11
A glass reactor equipped with a thermometer, stirrer, dripping device, nitrogen inlet tube and reflux cooling device was charged with 82.5 parts of water, and the inside of the reactor was purged with nitrogen under stirring and heated to 80 ° C. in a nitrogen atmosphere. did. 72.3 parts of methoxypolyethylene glycol monomethacrylate (average number of added moles of ethylene oxide 25), 22.5 parts of methacrylic acid, 25.2 parts of sorbitol EO adduct macromer synthesized in Example 10, 64.6 parts of water and chain transfer A monomer aqueous solution in which 2.88 parts of 3-mercaptopropionic acid was mixed as an agent and 22.5 parts of a 4.6% ammonium persulfate aqueous solution were added dropwise over 3 hours. After completion of the dropwise addition, 7.5 parts of a 4.6% aqueous ammonium persulfate solution was further added dropwise over 1 hour. Thereafter, the temperature was maintained at 80 ° C. for 1 hour to complete the polymerization reaction, and a polycarboxylic acid copolymer aqueous solution having a weight average molecular weight of 16,300 was obtained.

Example 12
Triethylenetetramine ethylene oxide adduct (addition of ethylene oxide to triethylenetetramine-NH with an average addition mole number of 10) to a glass reactor equipped with a thermometer, stirrer, dropping device, nitrogen introduction tube / air introduction tube and reflux cooling device The compound was charged in 400 parts and heated to 90 ° C. in an air atmosphere. The reaction system was maintained at 90 ° C., and 30.6 parts of glycidyl methacrylate was added over 1 hour. After completion of the addition, stirring was continued at 90 ° C. for 2 hours to obtain a triethylenetetramine / ethylene oxide adduct monomer (triethylenetetramine EO adduct macromer).

Example 13
A glass reactor equipped with a thermometer, stirrer, dripping device, nitrogen inlet tube and reflux cooling device was charged with 83.6 parts of water, the inside of the reactor was purged with nitrogen, and heated to 80 ° C. in a nitrogen atmosphere. did. 72.3 parts of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added 25), 22.5 parts of methacrylic acid, 25.2 parts of macromer of triethylenetetramine EO adduct synthesized in Example 12, 64.6 parts of water and A monomer aqueous solution mixed with 1.78 parts of 3-mercaptopropionic acid as a chain transfer agent and 22.5 parts of a 4.6% ammonium persulfate aqueous solution were added dropwise over 3 hours. After completion of the dropwise addition, 7.5 parts of a 4.6% aqueous ammonium persulfate solution was further added dropwise over 1 hour. Thereafter, the temperature was maintained at 80 ° C. for 1 hour to complete the polymerization reaction, and a polycarboxylic acid copolymer aqueous solution having a weight average molecular weight of 17,000 was obtained.

Example 14
Poly (n = 10) glycerin ethylene oxide adduct (average number of moles of ethylene oxide added to the hydroxyl group of polyglycerin is 4) in a glass reactor equipped with a thermometer, stirrer, dripping device, nitrogen introduction tube / air introduction tube and reflux cooling device The compound added in step 3) and 0.08 part of sodium hydroxide were charged, and the temperature was raised to 90 ° C. in an air atmosphere. The reaction system was maintained at 90 ° C., and 30.2 parts of glycidyl methacrylate was added over 1 hour. After completion of the addition, stirring was continued at 90 ° C. for 2 hours to obtain a polyglycerin / ethylene oxide adduct monomer (polyglycerin EO adduct macromer).

Example 15
A glass reactor equipped with a thermometer, stirrer, dripping device, nitrogen inlet tube and reflux cooling device was charged with 82.5 parts of water, and the inside of the reactor was purged with nitrogen under stirring and heated to 80 ° C. in a nitrogen atmosphere. did. 72.3 parts of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added 25), 22.5 parts of methacrylic acid, 25.2 parts of the polyglycerol EO adduct macromer synthesized in Example 14, 64.6 parts of water and chain A monomer aqueous solution mixed with 2.88 parts of 3-mercaptopropionic acid as a transfer agent and 22.5 parts of a 4.6% ammonium persulfate aqueous solution were added dropwise over 3 hours. After completion of the dropwise addition, 7.5 parts of a 4.6% aqueous ammonium persulfate solution was further added dropwise over 1 hour. Thereafter, the temperature was maintained at 80 ° C. for 1 hour to complete the polymerization reaction, and a polycarboxylic acid copolymer aqueous solution having a weight average molecular weight of 18900 was obtained.

Example 16
A glass reactor equipped with a thermometer, stirrer, dripping device, nitrogen inlet tube and reflux cooling device was charged with 83.6 parts of water, the inside of the reactor was purged with nitrogen, and heated to 80 ° C. in a nitrogen atmosphere. did. 72.3 parts of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added 100), 22.5 parts of methacrylic acid, 25.2 parts of macromer of triethylenetetramine EO adduct synthesized in Example 12, 64.6 parts of water and A monomer aqueous solution mixed with 1.78 parts of 3-mercaptopropionic acid as a chain transfer agent and 22.5 parts of a 4.6% ammonium persulfate aqueous solution were added dropwise over 3 hours. After completion of the dropwise addition, 7.5 parts of a 4.6% aqueous ammonium persulfate solution was further added dropwise over 1 hour. Thereafter, the temperature was maintained at 80 ° C. for 1 hour to complete the polymerization reaction, and a polycarboxylic acid copolymer aqueous solution having a weight average molecular weight of 47,000 was obtained.

Example 17
Triethylenetetramine ethylene oxide adduct (addition of ethylene oxide to -NH of triethylenetetramine with an average addition mole number of 10) to a glass reactor equipped with a thermometer, stirrer, dropping device, nitrogen introduction tube / air introduction tube and reflux cooling device The compound was charged in 400 parts and heated to 90 ° C. in an air atmosphere. The reaction system was kept at 90 ° C., and 24.6 parts of allyl glycidyl ether was added over 1 hour. After completion of the addition, stirring was continued at 90 ° C. for 2 hours to obtain a triethylenetetramine / ethylene oxide adduct monomer (triethylenetetramine EO adduct macromer (2)).

Example 18
A glass reactor equipped with a thermometer, stirrer, dripping device, nitrogen inlet tube and reflux cooling device was charged with 83.6 parts of water, the inside of the reactor was purged with nitrogen, and heated to 80 ° C. in a nitrogen atmosphere. did. Polyethylene glycol mono (3-methyl-3-butenyl) ether (average number of moles of ethylene oxide added 50) 72.3 parts, acrylic acid 22.5 parts, triethylenetetramine EO adduct macromer (2) synthesized in Example 17 A monomer aqueous solution in which 25.2 parts, 64.6 parts of water and 1.78 parts of 3-mercaptopropionic acid as a chain transfer agent were mixed, and 22.5 parts of a 4.6% aqueous ammonium persulfate solution were added dropwise over 3 hours. After completion of the dropwise addition, 7.5 parts of a 4.6% aqueous ammonium persulfate solution was further added dropwise over 1 hour. Thereafter, the temperature was maintained at 80 ° C. for 1 hour to complete the polymerization reaction, and a polycarboxylic acid copolymer aqueous solution having a weight average molecular weight of 19000 was obtained.

When mortar was prepared using the copolymers of Examples 16 and 18, mortar with fluidity was obtained.
Mortar preparation conditions: 800 g of Pacific ordinary Portland cement (trade name, manufactured by Taiheiyo Cement) and 400 g of Toyoura standard sand were kneaded with a mortar mixer (trade name: N-50, manufactured by Tesco) at low speed for 30 seconds. Next, 180 g of water blended with 1.6 g of the copolymers of Examples 26 and 28 (in terms of solid content) was added to a mixture of cement and sand that had been kneaded, and kneaded at high speed for 5 minutes to prepare a mortar. did.

Measurement of cement operating coefficient According to the above <Method for measuring cement operating coefficient>, standard addition amount, viscosity μ, and cement operating coefficient were determined.
In the determination of the standard addition amount, the addition amount of the agent (copolymer) to the cement and the flow value at that time are shown in Table 5, and these relationships are shown in FIG. Table 6 shows the standard addition amount, flow value, viscosity after 2 minutes, and cement operating coefficient.

In Table 5, the addition amount of the agent (cement additive) is the addition amount in terms of solid content with respect to cement.

In Table 6, the viscosity μ (e) after 2 minutes from the completion of the kneading of the mixture E is 5670 mPa · s.

When the cement operating coefficients of the copolymer of Comparative Example 1 containing no EO adduct macromer and the copolymers of Examples 3, 4, 8, 11, 13, and 15 containing various EO adduct macromers were compared, Comparative Example 1 The copolymer of 2.0 is not less than 2.0, whereas the copolymer of Examples 3, 4, 8, 11, 13, and 15 is very low, 1.0 or less. In addition, the coefficient of cement operation of the copolymer of Example 9 is as low as 0.3 or less.

The specifications of Toyoura Tosago are shown below.
Toyoura cinnamon standard mesh Flue 300 microns Residue 1% or less Standard mesh Flue 106 microns Residue 95% or more Unit volume weight (kg / L) 1.50 or more particle size (standard sieve residue:%) and chemical composition are shown in Table 7 And shown in Table 8.

Calcium transport value According to the above <Method for measuring calcium transport value>, the standard calcium addition amount and the calcium transport value were determined. In the determination of the standard addition amount, the addition amount of the agent (copolymer) to the cement and the flow value at that time are shown in Table 9, and the relationship between them is shown in FIG. The standard addition amount and calcium transport value are shown in Table 10.

In Table 9, the addition amount of the agent (cement additive) is the addition amount in terms of solid content with respect to cement.

Results When the calcium transport value of the copolymer of Comparative Example 1 containing no polyethyleneimine EO adduct macromer and the copolymer of Example 8 containing polyethyleneimine EO adduct macromer was compared, the copolymer of Comparative Example 1 was 1780 mPa. -Although it is s, in the copolymer of Example 8, it is very low with 625 mPa * s.

The “mortar penetration time after 75 minutes” indicating the viscosity of the mortar was compared with the “cement operating coefficient” and “calcium transport value” which are the performance of the cement additive.

Comparing the cement operation coefficient and the calcium transport value of the copolymer of Comparative Example 1 not containing the EO adduct macromer and the copolymer of Example 8 containing the EO adduct macromer, the copolymer of Comparative Example 1 showed cement operation. Whereas the coefficient is 2.0 or more and the calcium transport value is 1780 mPa · s, the copolymer of Example 8 has a cement operating coefficient of 1.0 or less and the calcium transport value is very low as 625 mPa · s. ing. The lower the cement operating coefficient / calcium transport value, the shorter the mortar penetration time after 75 minutes, which is a guideline for easy handling of ready-mixed concrete, and it is possible to obtain ready-to-handle ready-mixed concrete. Moreover, the cement operating coefficient of the copolymer of Example 9 is as very low as 0.4 or less, and ready-to-handle ready-mixed concrete can be obtained.

Unless otherwise indicated, the analytical measurement conditions for the polymer of Example 8 were the same as those described in this specification.
FIG. 7 shows the GPC chart and peak results of the unpurified polymer, and FIG. 8 shows the GPC chart and peak results of the purified polymer (purified product). FIG. 9 shows the H-NMR chart of the unpurified polymer, and FIG. 10 shows the H-NMR chart of the purified product. A C-NMR chart of the unpurified polymer is shown in FIG. 11, and a C-NMR chart of the purified product is shown in FIG. An IR chart of the unpurified polymer is shown in FIG. 13, and an IR chart of the purified product is shown in FIG. The potentiometric titration curve used to measure the TCAV of the crude polymer is shown in FIG. The H-NMR chart used for the measurement of NMR-PEG of the purified product is shown in FIG. FIG. 17 shows an enlarged view of 60 to 80 ppm in FIG.

<Purification conditions>
Polymer purification conditions 2 described herein were followed.
<Elemental analysis>
Unrefined: H8.5 wt%, C50.8 wt%, N1.1 wt%
Refined product: H8.6% by weight, C52.3% by weight, N1.2% by weight
Chisso derived from polyethyleneimine EO adduct macromer has been detected.

<Pyrolysis GC-MASS>
Purified products: methacrylic acid, hydroxyethyl methacrylate, ethoxyethyl methacrylate, polyethylene glycol (n = 2-4), 1,4-dioxane, 9-crown-3-ether, 12-crown-4-ether, morpholine, 4- (2-hydroxyethyl) morpholine, 4- (2-aminoethyl) morpholine and the like were detected.
Since morpholine and its derivatives are detected in the purified product, it can be confirmed that the functional group of ethylene oxide added to polyalkyleneimine is present, so it is confirmed that polyethyleneimine EO adduct macromer is copolymerized it can. From the detection of ethoxyethyl methacrylate and polyethylene glycol (n = 2 to 4), it can be confirmed that polyethylene glycol monomethacrylate is copolymerized.

<GPC>
Unrefined: Mw12300, Mn7900, Mp9300
Refined products: Mw15600, Mn8900, Mp13900
It can be confirmed that the peak of the residual monomer is reduced in the purified product.

<H-NMR>
From FIG. 9 and FIG. 10, a peak of —N—CH— derived from a polyethyleneimine EO adduct macromer can be confirmed.

<C-NMR>
From FIG. 11 and FIG. 12, the peak derived from the carbon atom next to the nitrogen atom derived from the polyethyleneimine EO adduct macromer can be confirmed. No C═O peak derived from the amide group was observed. Peaks were confirmed at 60.4 and 68.4 ppm.

<IR>
Table 12 shows the results of IR analysis. No C═O stretching vibration derived from the amide group was observed.

<TCAV>
Solid content of copolymer: 38.5% by weight, sampling amount: 1.1256 g
Amount of sodium hydroxide required from the first inflection point to the second inflection point: 13.161 mL
Initial pH 2.60, first inflection point pH 3.50, second inflection point pH 9.94
fn: 1.003, TCAV: 65.8 mgKOH / g

<NMR-PEG amount>
Collection weight of refined product: 0.0441 g
Collection weight of trioxane: 0.0455g
NMR integration ratio Trioxane / 3.3-4.2 ppm peak: 0.8781
Heavy water: 1.2413 g
Calibration curve material: Weight ratio of —OCH ₂ CH ₂ — in polymer A used polymer A in the above specification: 55.180% by weight
Created calibration curve [Y] = 0.551 [X] -0.0031
[X]: NMR integration ratio
[Y]: Weight ratio Trioxane / Polymer A
(NMR-PEG amount) = 0.0455 × 0.5518 / 0.0441 / (0.851 × 0.8781-0.0031) × 100 = 76.5% by weight

A mortar test was conducted on the copolymer of Example 8 using the following copolymers A, B, C and D.
Copolymer A: PGM25 / sodium methacrylate = 80/20% by weight, weight average molecular weight 20000
Copolymer B: PGM100 / sodium methacrylate = 90/10% by weight, weight average molecular weight 50000
Copolymer C: IPN50 / sodium maleate = 85/15 wt%, weight average molecular weight 30000
Copolymer D: IPN25 / sodium acrylate = 90/10% by weight, weight average molecular weight 25000
PGM25: Methoxypolyethylene glycol monomethacrylate (average number of added moles of ethylene oxide 25)
PGM100: Methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added 100)
IPN50: Polyethylene glycol mono (3-methyl-3-butenyl) ether (average number of moles of ethylene oxide added 50)
IPN25: Polyethylene glycol mono (3-methyl-3-butenyl) ether (average number of added moles of ethylene oxide 25)

Mortar test Pacific normal Portland cement (trade name, manufactured by Taiheiyo Cement Co., Ltd.) 800 g and Toyoura standard sand 400 g were air-kneaded with a mortar mixer (trade name: N-50, manufactured by Tesco) at low speed for 30 seconds. Next, 240 g of water in which the copolymer of Example 8 and the above copolymer were blended in the proportions shown in Table 13 was added to a mixture of cement and sand that had been kneaded and kneaded at high speed for 5 minutes. Mortar was prepared.
Mortar was packed in a hollow cylinder having a diameter of 55 mm and a height of 55 mm. Next, after lifting the cylinder vertically, the diameter of the mortar spread on the table was measured in two directions, and this average was taken as the flow value. The results are shown in Table 13.

In Table 13, the amount used is the amount of solid content of each copolymer relative to cement.
It was confirmed that a sufficient flow value was obtained even when used in combination with a polycarboxylic acid polymer.

Example 19
A glass reactor equipped with a thermometer, a stirrer, a dripping device, a nitrogen introducing tube and a reflux cooling device was charged with 185.8 g of ion-exchanged water, and the reaction system was heated to 65 ° C. in a nitrogen atmosphere, and then oxidized. 3.1 g of a 30% aqueous solution of hydrogen water was added. Thereto, 530.0 g of an 80% aqueous solution of a polyalkylene glycol monoalkenyl ether monomer (hereinafter referred to as IPN-25) obtained by adding 25 moles of ethylene oxide to 3-methyl-3-buten-1-ol. A mixed solution of 1.2 g of L-ascorbic acid and 3.9 g of 1-octanethiol and a mixed solution of 71.3 g of acrylic acid and 38.7 g of ion-exchanged water were added dropwise over 3 hours. After completion of the dropping, the polymerization reaction was completed by aging at 65 ° C. for 1.5 hours. The reaction solution was adjusted to pH = 7 with a 30% aqueous sodium hydroxide solution to obtain an aqueous solution of a polycarboxylic acid copolymer having a weight average molecular weight of 21,900.

Example 20
A glass reactor equipped with a thermometer, a stirrer, a dripping device, a nitrogen introducing tube and a reflux cooling device was charged with 271.4 g of an 80% aqueous solution of IPN-25 and 218.2 g of ion-exchanged water, and in the reaction system under a nitrogen atmosphere. After raising the temperature to 65 ° C., 2.6 g of a 30% aqueous solution of hydrogen peroxide was added. Then, 271.4 g of 80% aqueous solution of IPN-25, 1.0 g of L-ascorbic acid, 2.6 g of 1-octanethiol, 56.9 g of 2-hydroxyethyl acrylate, 19.8 g of acrylic acid, ion exchange A mixture of 13.3 g of water was added dropwise over 3 hours. After completion of the dropping, the polymerization reaction was completed by aging at 65 ° C. for 1.5 hours. The reaction solution was adjusted to pH = 7 with a 30% aqueous sodium hydroxide solution to obtain an aqueous solution of a polycarboxylic acid copolymer having a weight average molecular weight of 23,600.

Comparative Example 2
A glass reactor equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux cooling device was charged with 185.5 g of ion-exchanged water, and the temperature of the reaction system was raised to 65 ° C. in a nitrogen atmosphere. 3.1 g of a 30% aqueous solution of hydrogen water was added. Thereto, a mixed solution of 529.9 g of 80% aqueous solution of IPN-25, 1.2 g of L-ascorbic acid, 4.0 g of 3-mercaptopropionic acid, 71.3 g of acrylic acid, and 38.7 g of ion-exchanged water was added. It was dripped in 3 hours. After completion of the dropping, the polymerization reaction was completed by aging at 65 ° C. for 1.5 hours. The reaction solution was adjusted to pH = 7 with a 30% aqueous sodium hydroxide solution to obtain an aqueous solution of a polycarboxylic acid copolymer having a weight average molecular weight of 21,500.

Comparative Example 3
A glass reactor equipped with a thermometer, a stirrer, a dripping device, a nitrogen introducing tube and a reflux cooling device was charged with 271.8 g of an 80% aqueous solution of IPN-25 and 218.1 g of ion-exchanged water, and in a reaction system in a nitrogen atmosphere. After raising the temperature to 65 ° C., 2.6 g of a 30% aqueous solution of hydrogen peroxide was added. Then, 271.8 g of 80% aqueous solution of IPN-25, 1.0 g of L-ascorbic acid, 1.9 g of 3-mercaptopropionic acid, 57.0 g of 2-hydroxyethyl acrylate, 19.8 g of acrylic acid, ion A mixture of 13.2 g of exchange water was added dropwise over 3 hours. After completion of the dropping, the polymerization reaction was completed by aging at 65 ° C. for 1.5 hours. The reaction solution was adjusted to pH = 7 with a 30% aqueous sodium hydroxide solution to obtain an aqueous solution of a polycarboxylic acid copolymer having a weight average molecular weight of 23,600.

Evaluation method (1) Mortar adjustment method Taiheiyo Ordinary Portland cement (trade name, manufactured by Taiheiyo Cement Co., Ltd.) 1080 g, cement strength test standard sand (JIS R 5201) 1350 g mortar mixer (trade name: N-50, manufactured by Tesco Corporation) ) And kneaded at low speed for 10 seconds. Next, 324 g of water blended with the polycarboxylic acid copolymer produced in Examples 9 and 19 or Comparative Example 2 was added to a mixture of cement and sand that had been kneaded and kneaded for 5 minutes at a low speed. Was prepared. The polycarboxylic acid-based copolymer of the example and the copolymer of the comparative example were blended so that the solid content weight% (hereinafter referred to as addition amount) with respect to the cement weight was a value shown in Table 14. In addition, in preparation of each mortar, the empty kneading and kneading conditions by the mortar mixer were made uniform.

(Flow measurement method)
The prepared mortar was packed into a mini slump cone (bottom surface = diameter 100 mm, top surface = diameter 50 mm, height = 150 mm) placed on a stainless steel plate 6.5 minutes after the start of emptying. Next, after 10 minutes from the start of kneading, the mini slump cone was lifted vertically, and then the diameter of the mortar spread on the stainless steel plate was measured in two vertical and horizontal directions, and this average value was defined as a flow value (mm).

(Determination method of addition amount)
The flow amount was measured while changing the addition amount, and the addition amount at which the flow value was 190 to 200 mm was determined. The results are shown in Table 14.

(Paste adjustment method)
600 g of Pacific ordinary Portland cement (trade name, manufactured by Taiheiyo Cement Co., Ltd.) was placed in a mortar mixer (trade name: N-50, manufactured by Tesco) and kneaded for 10 seconds at a low speed. Next, 180 g of water blended with the polycarboxylic acid copolymer produced in Examples 9 and 19 or Comparative Example 2 so as to have the determined addition amount shown in Table 14 was added to the empty kneaded cement in 5 seconds. And kneading for 1 minute at low speed. Next, the rotation was stopped, the cement adhering to the wall surface was scraped off for 30 seconds, the kneading was further completed at a low speed, and the kneading was finished after 5 minutes. 400 cc of the prepared paste was put into a disposable beaker having a diameter of 8 cm, and the viscosity was measured with a helipath rotational viscometer (BROOKFIELD DV-II / spindle A91 / 10 rotation). At this time, the position of the pindle was adjusted to a position of 3.5 cm from the bottom. In addition, the measurement was performed in a room controlled at an air temperature of 23 ° C. so that there was no influence of the viscosity measurement position and temperature in the paste. Ten minutes after the start of empty kneading, measurement with a helicopter rotational viscometer was started, and the change in viscosity over time was followed. Table 14 shows the paste viscosity and paste state after 3 minutes.

The copolymer of Comparative Example 2 synthesized with 3-mercaptopropionic acid as a hydrophilic chain transfer agent and the copolymers of Examples 9 and 19 synthesized with 1-octanethiol as a hydrophobic chain transfer agent were used. When the paste viscosity was compared, in Comparative Example 2, Examples 9 and 19 were very low at 1,120-2,880 compared to 8,320 (mPa · s). From this, it can be seen that the copolymer having a hydrophobic group introduced using a hydrophobic chain transfer agent has a considerably lower paste viscosity than Comparative Example 2 having no hydrophobic group introduced. Moreover, it turned out that the state of a paste is also uniform compared with a comparative example, and water floating is not seen.

It is an example for demonstrating the case where a peak does not have a shoulder about the peak of GPC, and the case where a peak has a shoulder. It is a conceptual diagram of the spatula (made of stainless steel) used in the measurement of a cement operation coefficient and a calcium transport value. It is a conceptual diagram of a new death cup (300 mL) made by Terraoka Co., Ltd. used in measurement of a cement operating coefficient and a calcium transport value. It is a conceptual diagram of the screw (four blades) of a homomixer used in the measurement of a calcium transport value. In the examples, the relationship between the addition amount of the agent (copolymer) to the cement and the flow value when using normal Portland cement, which was used when determining the standard addition amount according to the measurement method of the cement operating coefficient, It is a graph to show. In an Example, it is a graph which shows the relationship between the addition amount of the agent (copolymer) with respect to cement, and the flow value used when determining the standard addition amount of calcium according to the measuring method of a calcium transport value. It is the result (GPC chart and peak result of unpurified product) which measured GPC, without refine | purifying the polycarboxylic acid type-copolymer manufactured in Example 8. FIG. It is the result (GPC chart and peak result of a refined product) which refine | purified the polycarboxylic acid type-copolymer manufactured in Example 8, and measured GPC. It is the result (H-NMR chart of unpurified product) which measured H-NMR, without refine | purifying the polycarboxylic acid type-copolymer manufactured in Example 8. FIG. It is the result (H-NMR chart of a refined product) which refine | purified the polycarboxylic acid type-copolymer manufactured in Example 8, and measured H-NMR. It is the result (C-NMR chart of a crude product) which measured C-NMR, without refine | purifying the polycarboxylic acid type-copolymer manufactured in Example 8. FIG. It is the result (C-NMR chart of a refined product) which refine | purified the polycarboxylic acid type-copolymer manufactured in Example 8, and measured C-NMR. It is the result (IR chart of unrefined product) which measured IR, without refine | purifying the polycarboxylic acid-type copolymer manufactured in Example 8. FIG. It is the result (IR chart of a refined product) which refine | purified the polycarboxylic acid type-copolymer manufactured in Example 8, and measured IR. It is a titration curve (potentiometric titration curve of unpurified product) when potentiometric titration was performed according to TCAV measurement conditions without purifying the polycarboxylic acid copolymer produced in Example 8. It is the H-NMR chart of a refined product when the polycarboxylic acid copolymer produced in Example 8 was purified and H-NMR was measured according to the NMR-PEG amount measurement method. It is an enlarged view of 60-80 ppm of FIG.

Claims (9)

Copolymerizes monomer components including polyalkylene glycol unsaturated monomer (A2) and unsaturated monocarboxylic acid monomer (B ′) having a structure in which an oxyalkylene group is bonded to a polyhydric alcohol residue. A polycarboxylic acid copolymer characterized by comprising: A unit comprising a polyalkylene glycol unsaturated monomer (A2 ′) and an unsaturated carboxylic acid monomer (B) having a structure in which an oxyalkylene group is bonded to a polyhydric alcohol residue and having a terminal hydroxyl group. A polycarboxylic acid copolymer obtained by copolymerizing a monomer component. Furthermore, the said monomer component contains polyalkylene glycol type | system | group unsaturated monomer (A3) other than the monomer which has the said oxyalkylene group, The polycarboxylic acid type | system | group of Claim 1 or 2 characterized by the above-mentioned. Copolymer. It is obtained by copolymerizing a monomer component containing a monomer (A) having an oxyalkylene group and an unsaturated carboxylic acid monomer (B) using a hydrophobic chain transfer agent. A method for producing a polycarboxylic acid copolymer. The method for producing a polycarboxylic acid copolymer according to claim 4, wherein the hydrophobic chain transfer agent includes a thiol chain transfer agent having a hydrocarbon group having 3 or more carbon atoms. A polycarboxylic acid copolymer obtained by the method for producing a polycarboxylic acid copolymer according to claim 4 or 5. A cement additive comprising the polycarboxylic acid copolymer according to claim 1, 2, 3 or 6. The cement additive according to claim 7, wherein a calcium transport value is 10 to 900 mPa · s and / or a cement operating coefficient is 0.05 to 1.0. A cement composition comprising at least water, cement, and cement additive,
A cement composition using the cement additive according to claim 7 or 8, as the cement additive.

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