WO2008032799A1

WO2008032799A1 - Novel polycarboxylic acid polymer

Info

Publication number: WO2008032799A1
Application number: PCT/JP2007/067876
Authority: WO
Inventors: Haruyoshi Miyauchi; Katsutoshi Satou
Original assignee: Toho Chemical Industry Co., Ltd.
Priority date: 2006-09-13
Filing date: 2007-09-13
Publication date: 2008-03-20
Also published as: JP5424084B2; JP5594542B2; JPWO2008032799A1; JP2012132017A; JP5610244B2; JP2013216917A

Abstract

[PROBLEMS] To provide a polycarboxylic acid polymer having high dispersing ability in various solid-powder systems. [MEANS FOR SOLVING PROBLEMS] The polycarboxylic acid polymer is one formed from a reactive alcohol derivative having a polymerizable bonding site and a dibasic acid derivative, and is characterized in that the reactive alcohol derivative has a polyalkylene oxide chain having an end part formed by C3 or C4 polyalkylene oxide addition, the content of the C3 or C4 alkylene oxide in the end parts being 0.1-30 mol% based on all alkylene oxide chains.

Description

Specification

Novel polycarboxylic acid polymers

Technical field

[0001] The present invention relates to a novel polycarboxylic acid-based polymer. More specifically, the polycarboxylic acid system is characterized by comprising a constituent unit derived from an unsaturated alcohol alkylene oxide adduct having a hydrophobic group at the end and a constituent unit derived from an unsaturated carboxylic acid carboxylic acid. It relates to a polymer.

Background art

Conventionally, a polymer composed of an unsaturated alcohol alkylene oxide adduct monomer and an unsaturated carboxylic acid monomer collects various particles and has an excellent dispersibility in water. It is widely used as a surfactant and dispersant for various solid powder systems.

[0003] The above-mentioned polymers are for use in various applications!

For example, Patent Document 1 discloses an aqueous slurry dispersant of a water-soluble copolymer obtained from the unsaturated carboxylic acid-based component unit (I) and the unsaturated alcohol-based component unit (II), a cement admixture, a scale inhibitor, It has been proposed for use in detergent builders, waste paper recycling deinking agents, cotton scouring cleaners, coal dispersants, etc.

Further, in Patent Document 2, a copolymer of an α, β-unsaturated carboxylic acid or an anhydride thereof and an alkenyl ether having an C 2 to C 18 oxyalkylene group is suitable as a dispersant for gypsum. It is shown that the results of fluidization and water reduction are shown.

In addition, it is obtained by the copolymerization of an unsaturated carboxylic acid monomer having 2 to 18 carbon atoms and an oxyalkylene group and / or an unsaturated acid anhydride monomer and an unsaturated alcohol monomer. And an acid group-containing polymer in which an amino group is introduced into a part thereof (Patent Document 3), an ethylenically unsaturated monocarboxylic acid, a polyalkylene glycol (meth) atalylate and an ethylenic non Technologies such as dispersants for inorganic pigments containing a salt of a copolymer of a saturated dicarboxylic acid (Patent Document 4) have been disclosed!

In the above Patent Documents 1 to 4, unsaturated alcohol alkylene oxide adducts Although a mixed addition of two or more alkylene oxides (eg, ethylene oxide and propylene oxide) has been proposed in Japan, the actual test examples were limited to the results using alcohols of a single addition of ethylene oxide, If the above alkylene oxide is used, the order or site to be added is / is studied! //! Patent document 1: JP-A-62-68806

Patent Document 2: Japanese Patent Application Laid-Open No. 11 314953

Patent Document 3: Japanese Patent Application Laid-Open No. 2003-192722

Patent Document 4: Japanese Patent Application Laid-Open No. 2005 46781

Disclosure of the invention

Problem that invention tries to solve

[0005] The present invention has been made to further improve the performance as a dispersant under such conventional technical background.

In addition, for example, in applications to hydraulic compositions, since the product is a factory product that is only required to have high water reduction performance for the purpose of securing workability, improvement of the curing delay property is also emphasized. In particular, the curing retardancy is often influenced by the type of acid group contained in the polymer, or depending on the amount of dispersing agent added, ie, the water loss of the dispersing agent. Further, from the viewpoint of improving the production efficiency of the product, mechanical formability is also regarded as important, and it is desirable that the releasability from the formwork and the pressing surface be excellent and that there is no corner chipping of the molded body. Furthermore, it is important that the amount of air in the above composition can be adjusted, or that the appearance of the molded product (for example, plaster products (reinforced board, plaster for porcelain etc., etc.) is not impaired by coloring etc. depending on the application. It is considered as a sex store.

For this reason, it is hoped that the appearance of dispersants capable of sufficiently examining these and satisfying various performances and further additives for various hydraulic composition applications is expected.

Means to solve the problem

[0006] As a result of intensive investigations by the present inventors, it has been found that a polycarboxylic acid-based polymer composed of a reactive alcohol derivative having a polymerizable binding site and a dibasic acid-based derivative! Part of the terminal part of the polyalkylene oxide chain of Or 4 polyalkylene oxide addition, that is, containing at a terminal portion an alkylene oxide having 3 or 4 carbon atoms at a ratio of 0.1 to 30 mol% with respect to the total molar amount of the alkylene oxide chain. It has been found that the polycarboxylic acid-based polymer exhibits excellent dispersion performance in an aqueous dispersion of solid powder, and also exhibits water reduction performance and low curing delay when added to a hydraulic composition.

That is, the present invention relates to a polycarboxylic acid-based polymer including a constituent unit derived from an unsaturated alcohol alkylene oxide compound and a constituent unit derived from an unsaturated carboxylic acid compound. The graft chain bonded to the main chain skeleton of the polymer contains a polyalkylene oxide chain mainly composed of ethylene oxide, and the terminal part of the polyalkylene oxide chain is the total molar amount of the alkylene oxide of the graft chain. The present invention relates to a polycarboxylic acid-based polymer characterized in that it has an alkylene oxide having 3 or 4 carbon atoms in a proportion of 0.1 to 30 mol%.

The present invention is also directed to a polycarboxylic acid-based polymer, characterized in that it is a structural unit derived from a part or all of a structural unit derived from the unsaturated carboxylic acid-based compound and a nucleic acid and / or a derivative thereof. Regarding coalescence.

In the present invention, the polycarboxylic acid-based polymer is constituted by including a constituent unit (I) represented by the following formula (I) and a constituent unit (II) represented by the formula (II): The terminal part of the polyalkylene oxide chain in the constituent unit (I) has an alkylene oxide having 3 or 4 carbon atoms in an amount of 0.1 to 30 mol% based on the total molar amount of the alkylene oxide chain. The present invention relates to a polycarboxylic acid-based polymer characterized in having a proportion.

[Formula 1]

R ¹ X-(AO) a-R ⁴

I I

-C-C-(I)

I I

R ² R ³

(Wherein, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, X represents one (CH 2) bO—, AO represents Represents an alkylene oxide group having 2 to 4 carbon atoms, a represents an average addition mole number of alkylene oxide, represents a number of 1 to 200, and b represents an integer of 1 to 20). [Formula 2]

R ⁵ R ⁶

-c-c-(II)

I I

R ⁷ R ⁸

(Wherein, R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, —COOH, —COOM, —COOY, or R ⁵ And R ⁶ or R ⁷ and R ⁸ together form an acid anhydride, M represents an alkali metal, an alkaline earth metal, an amine, an alkanolamine, and Y represents a C 1-22 carbon atom. or a hydrocarbon group - (AO) c- represents R ^9, AO represents an alkylene oxide group having 2 to 4 carbon atoms, c is a number from 1 to 200 in average molar number of addition of alkylene oxide, R ⁹ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms.)

[0010] Further, according to the present invention, the polycarboxylic acid-based polymer comprises the structural unit (I) and the structural unit

The present invention relates to a polycarboxylic acid-based polymer characterized in that it is constituted by further comprising a constituent unit (III) represented by the following formula (III) in addition to (II).

[Chemical 3]

H H

— C C— (III)

I I COOH Z

(Wherein, Z is a polyamidepolyamine obtained by condensing a dibasic acid with a polyalkylenepolyamine and / or an active imino group, an amino group or an amide residue of the polyamidepolyamine, an alkylene oxide having 2 to 4 carbon atoms per equivalent) The modified polyamide polyamine obtained by adding 0.1 to 10 mol of represents a group bonded to a carbon atom of the main chain via an amide bond.)

In addition to the polycarboxylic acid-based polymer described above, the present invention provides a polyamidepolyamine obtained by condensing a dibasic acid and a polyalkylenepolyamine and / or an active imino group, an amino group, and an amide residue of the polyamidepolyamine. The present invention relates to a polycarboxylic acid-based polymer composition comprising a polyamidepolyamine modified product obtained by adding 0.1 to 10 moles of an alkylene oxide having 2 to 4 carbon atoms per equivalent.

In the present invention, the above-mentioned polycarboxylic acid polymer or polycarboxylic acid polymer composition The present invention relates to a dispersant for hydraulic composition, an additive for gypsum, an additive for concrete exterior plate, and a water-reducing agent for lightweight concrete. Effect of the invention

According to the present invention, the resin composition has excellent dispersion performance with respect to aqueous dispersions of various solid powders, further improves the curing delaying property and the moldability, is excellent in the air amount adjusting ability, and has the obtained curing. It is possible to provide a polycarboxylic acid-based polymer that can make the appearance of the body excellent.

Therefore, according to the present invention, a dispersant for hydraulic composition, an additive for gypsum, an additive for concrete exterior plate, and a water reducing agent for lightweight concrete can be provided.

BEST MODE FOR CARRYING OUT THE INVENTION

The present invention is directed to a polymer based on a polybasic acid comprising a structural unit derived from an unsaturated alcohol alkylene oxide compound and a structural unit derived from an unsaturated carboxylic acid compound, The graft chain bonded to the main chain skeleton of the polymer contains a polyalkylene oxide chain mainly composed of ethylene oxide, and the terminal part of the poly (alkylene oxide) chain is the total molar amount of the alkylene oxide of the graft chain. The present invention relates to a polycarboxylic acid-based polymer having an alkylene oxide of 3 to 4 carbon atoms in a ratio of 0.1 to 30 mol%. More specifically, the polycarboxylic acid-based polymer is composed of the structural unit (I) and the structural unit (II) shown above, and the polycarboxylic acid-based polymer further comprises the structural unit (I) and (C) And the above-mentioned structural unit (III) derived from a modified polyamidepolyamine and / or polyamidepolyamine. The polycarboxylic acid-based polymer thus configured has a comb polymer structure in which a graft chain such as a polyalkylene oxide chain or a polyamide polyamine chain is bonded to a main chain skeleton.

The polycarboxylic acid polymer of the present invention may further contain a polyamidepolyamine and / or a modified polyamidepolyamine and may be in the form of a composition.

The present invention will be described in detail below.

[Constituent Unit (I) and Constituent Unit (II)]

Structural unit (I) which comprises the polycarboxylic acid type polymer of this invention is represented by a following formula. [4]

R ¹ X-(AO) a-R ⁴

I I

1 c 1 c 1 (I)

I I

R ² R ³

(Wherein, R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, X represents one (CH 2) bO 2, and AO represents carbon And an alkylene oxide group having 2 to 4 atoms, wherein a represents an average addition mole number of alkylene oxide and represents a number of 1 to 200, and b represents an integer of 1 to 20.

The above polyalkylene oxide chain one (AO) a is preferably mainly ethylene oxide, and the average addition mole number is preferably 30 or more, more preferably 50 or more to improve the dispersion performance. Desirable in terms of

In the structural unit (I), the terminal part of the polyalkylene oxide chain (the bonding position with R ⁴ ) is a propylene oxide having 3 carbon atoms or a butylene oxide having 4 carbon atoms in the total number of moles of the alkylene oxide chain. The content is in the range of 0.1 to 30 mol%. More preferably, it is in the range of 0.1 to 20 mol%, more preferably in the range of 0.1 to 10 mol% or 12 to 20 mol%, and most preferably in the range of 0.5 to 5 mol% or 15 to 20 mol% It is preferable in that the dispersibility is significantly improved.

Furthermore, it is desirable that R ^{4 be} selected from a hydrogen atom, a methyl group, an ethyl group, a butyl group, an isobutyl group, a propyl group or an isopropyl group.

The above structural unit (I) is a structural unit derived from, for example, the following compounds: polyalkylene glycol monochloro nore no tene, poly anolechi lene gluco nor mono mono norole kin norere tenole

And alkenyl ethers formed from (alkoxy) polyalkylene glycols such as methoxypolyanolexylene glyconololemono alino lea tenore and methoxy poly anolexylene glyco-nole mono alkenyl ether and alkenyl ether having 3 to 8 carbon atoms And unsaturated aliphatic ethers which are unsaturated aliphatic alcohol alkylene oxide adducts. Among these, specific examples of the most preferable compounds are: 3-methyl-3-butene-1-ol, 3-methyl-ol-2-butene, 2-methyl-1-butene, 2-methyl-3-butene 2-nonole, aryl alcohol, oleyl alcohol, etc. It is an alkylene oxide adduct of alcohol Yes

The constituent unit (I) is derived from one or more of these compounds.

It may be a unit.

R

Structural unit (II) constituting the polycarboxylic acid polymer of the present invention is represented by the following formula.

[Chem. 5]

6

8

(Wherein, R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, COOH, —COOM, or —COOY, or R ⁵ R ⁶ or R ⁷ and R ⁸ together form an acid anhydride M represents an alkali metal, an alkaline earth metal, an ammonium, an alkanolamine, Y represents a carbon number of 1 to 22 carbon atoms or hydrogen group - represents the (AO) c- R ^9, AO represents an alkylene oxide group having 2 to 4 carbon atoms, c is a number from 1 to 200 in average molar number of addition of alkylene oxide, R ⁹ Represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms.

Specifically, the above structural unit (II) is a structural unit derived from acrylic acid, methacrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid and the like, and exhibits the best performance. For this purpose, fumaric acid is contained in a considerable proportion, for example, 10% by mass or more based on the total mass of the polymer.

When the above structural unit (単位) contains! /, 酸 acid (COOH) and / or acid salt (COOM), they may be in the form of acid or in the form of neutralized, but partially neutralized or completely neutralized The mixed form is preferred as the product form!

When an acid derivative (one COOY) is contained in the above-mentioned constituent unit (II), Y is specifically a partial ester or a whole ester having 1 to 22 carbon atoms, or a part of a polyalkylene oxide adduct. Esters or whole esters, partial esters or whole esters of (alkoxy) polyalkylene glycols and the like can be mentioned. More specifically, (alkoxy) polyalkylene glycol mono (meth) atalylates such as methoxypoly ethylene glycol mono (meth) atalylate, polyethylene glycol mono (meth) atalylate, etc .; (Anolekoxy) polyanolequile glycol malates such as N-glyco monole monomaleate, methoxy polyethylene glycolo di-state maleate, polyethylene glycolone mono-maleate, polyethylene glycolo mono-lemenalate, methoxypolyethylene glycol monofumarate, methoxypolyethylene monoglycolate Examples include (alkoxy) polyalkylene glycol fumarates such as fumarate, polyethylene glycol monolemono fumarate, polyethylene glycol difumarate and the like. The alkylene oxide can be added singly or in combination, and when two or more alkylene oxides are used, the block addition power P or random addition may be used. As a specific example of the fumaric acid derivative, methoxypolyethylene glycol difumarate can be mentioned.

When the above structural unit (II) contains a fumaric acid and / or a structural unit derived from a fumaric acid derivative, it is preferably 10 to 100% by mass, more preferably 10% to 100% by mass in the total mass of all the structural units (II). It is desirable to include 20 to 100% by mass, particularly preferably 30 to 100% by mass, and most preferably 50 to 100% by mass.

The polycarboxylic acid-based polymer of the present invention is most preferably a polyalkylene oxide chain obtained by bonding propylene oxide or butylene oxide to the end of an ethylene oxide chain having an average addition mole number of 50 or more. Component units (I) derived from an unsaturated alcohol alkylene oxide compound having a propylene oxide or butylene oxide ratio of 0.1 to 20 mol% with respect to the total number of moles of the alkylene oxide chain, and fumar Structural unit (II) force containing an acid-derived structural unit in a substantial proportion (10% by mass or more with respect to the total mass of the polymer), force that is desirable S, desired.

[Constituent unit (III)]

The polycarboxylic acid-based polymer of the present invention comprises structural units (III) derived from polyamide polyamines and / or polyamide polyamine modified products in addition to the above structural units (I) and (II).

Structural unit (III) is represented by the following formula.

[Chemical 6] HH

— C c— (III)

I I COOH Z

(Wherein, z is a polyamidepolyamine obtained by condensing a dibasic acid with a polyalkylenepolyamine and / or an active imino group, an amino group or an amide residue of the polyamidepolyamine, an alkylene oxide having 2 to 4 carbon atoms per equivalent) Represents a group in which 0.1 to 10 moles of the polyamide polyamine modified product is attached to a carbon atom of the main chain via an amide bond.

In the above structural unit (III), the above dibasic acid constituting Z has a total of 2 to 2 carbon atoms.

10 aliphatic saturated dibasic acids, such as oxalic acid, malonic acid, succinic acid, daltalic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and the like, and examples of polyalkylene polyamines include ethylene diamine, diethylene acid Triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, or a mixture of high molecular weight polyethylenepolyamine which is a mixture containing a large number of ethylene units and nitrogen atoms, and the like can be mentioned. .

The above structural unit (III) is a polyamide which is a condensation product of the dibasic acid and a polyalkylenepolyamine, a polyamine and / or (or, the active polyamide, an active amino group of an polyamine, an amino group, an amide, 0.1 to 10 moles of an alkylene oxide having 2 to 4 carbon atoms is added per 1 equivalent of the remaining group with respect to the polyamidepolyamine modified product force Maleic anhydride, maleic acid, fumanoleic acid and the like via an amide bond Component unit.

Since some of these polyamidepolyamines or polyalkyleneoxide-modified polyamidepolyamines have the property of exhibiting basicity in aqueous solution, they sometimes act as neutralizing agents for polycarboxylic acid polymers.

[Percentage of Composition of Each Constituent Unit]

In the polycarboxylic acid-based polymer which is the constituent unit (I) and constituent unit (II) described above, their constituent ratio is constituent unit (I): constituent unit (II) = 95 to 60% by mass 5 to 40% by mass, preferably structural unit (I): structural unit (11) = 90 to 70% by mass: 10 to 30% by mass, more preferably structural unit (I): structural unit (II) = 90 to 80 mass%: It is desirable to be in the range of 10 to 20 mass%. In addition, a polycarbolide consisting of the structural unit (I) to the structural unit (III) In the acid polymer, constituent unit (I): constituent unit (II): constituent unit (III) = 90 to 50% by mass: 8 to 40% by mass: 2 to 10% by mass, preferably a constituent unit (I ): Structural unit (II): Structural unit (III) = 90 to 60% by mass: 8 to 30% by mass: It is desirable to be in the range of 2 to 7% by mass! (However, the total of each of the structural unit (I) and the structural unit (II), or the structural unit (I) to the structural unit (III) is 100% by mass.)

[Other Constituent Units (IV)]

In the above-described polycarboxylic acid-based polymer, the constituent unit (IV) can be contained S in addition to the constituent units (I) to (III).

Examples of the compound from which the above-mentioned constituent unit (IV) can be derived include (meth) acrylic acid (salt), (meth) acrylic acid polyalkylene glycol monoalkyl ether, (meth) aryl sulfonic acid (salt), styrene It is a compound such as sulfonic acid (salt), alkyl (meth) acrylate, styrene, (meth) acrylamide and the like if it is a compound capable of forming a polymer with the above structural units (I) to (III). It is not particularly limited.

For example, when a polycarboxylic acid polymer is added to a hydraulic composition or the like, incorporating a structural unit derived from an alkali hydrolyzable compound in order to improve the dispersibility is disclosed in Japanese Patent No. 3780465, etc. It is one of the means that can be easily conceived in combination of The constituent ratio of the structural unit (IV) is in the range of 100 to 70% by mass: structural unit (IV) = 100 to 70% by mass (structural units (I) to (III)) (provided that a sum total 100 mass ^_0/0) is preferably in the range of.

[Polyamide polyamine and / or polyamide polyamine modified product]

The polycarboxylic acid polymer composition of the present invention is a polyamidepolyamine obtained by condensing a dibasic acid and a polyalkylenepolyamine in addition to the above polycarboxylic acid polymer, and / or an active imino group of the polyamidepolyamine, amino A polyamide polyamide modified product obtained by adding 0.1 to 10 moles of an alkylene oxide having 2 to 4 carbon atoms to 1 equivalent of an amide residue can be contained.

The content ratio of the polyamidepolyamine and / or the polyamidepolyamine modified product is in the range of the above-mentioned polycarboxylic acid based polymer: polyamidepolyamine and / or polyamidepolyamine modified product = 98 to 90% by mass: 2 to 10% by mass. Is preferred. The polyalkylene polyamines constituting the above polyamide polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, or a large number of ethylene units and nitrogen atoms. Mixtures of high-molecular-weight polyethylene polyamines, which are mixtures including, etc., polymers of cyclic amines such as polyethyleneimine, polypropyleneimine, poly (3-methylpropylimine), poly (2-ethylpropylimine), unsaturated amines such as polyureamin and polyallylamine These include polymers and the like. Furthermore, polyalkylene polyamines include cyclic amines such as ethyleneimine, propyleneimine, 3-methylpropylimine, 2-acetylpropylimine, unsaturated amides such as N-butylacetamide, N-butylformamide, and N-butylphthalimide, and unsaturated imides And a copolymer of an unsaturated compound copolymerizable with Examples of unsaturated compounds copolymerizable with cyclic imides, unsaturated amides, unsaturated imides and the like include, for example, dimethyleacrylamide, styrene, methyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid, styrene sulfonic acid and the like These salts, cyclic sulfide compounds such as ethylene sulfide and propylene sulfide, oxetanes, mono or bis alkyl oxetanes, mono or bis alkyl chloromethyl oxetanes, tetrahydrofuran, cyclic such as mono or bis alkyl tetra fluorofuran Ethers, cyclic formals such as 1,2-dioxofuran, trioxofuran and the like, N-substituted alkyl imines such as N-methylethyleneimine and the like can be mentioned.

Examples of the dibasic acid constituting the above polyamidepolyamine include a oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and the like having a total of 2 to 2 carbon atoms. There are 10 aliphatic saturated dibasic acids.

Derivatives thereof may also be used as dibasic acids, such as dibasic acid anhydrides (eg, anhydrides of the above dibasic acids), dibasic acid esters (eg, monomethyl esters of the above dibasic acids, monoethinole ester). Nore, monobutynore Estenole, monopropynore Estenole, dimethynol ester, jettyl ester, dibutyl ester, dipropyl ester etc., or dibasic acid dihalide (dichloride of the above dibasic acid, dibrominated compound, Iodide etc.) can be mentioned.

Further, the above-mentioned modified polyamidepolyamine means an alkylene oxide having 2 to 4 carbon atoms per 0.1 equivalent of the active imino group, amino group and amide residue of the above polyamidepolyamine. It shows a compound to which 10 moles have been added. That is, as this alkylene oxide,

And ethylene oxide, propylene oxide, butylene oxide, etc., which may be used alone or in combination, and when two or more alkylene oxides are used, they may be polymerized in block form to give random or random Polymerize on!

[Method for Producing Each Constituent Unit and Polycarboxylic Acid-Based Polymer]

In order to obtain the polycarboxylic acid polymer of the present invention, the method for producing the unsaturated alcohol alkylene oxide adduct from which the structural unit (I) is derived and the polymerization method for obtaining the polycarboxylic acid polymer are not particularly limited.

However, in the alkylene oxide addition reaction during the production of the unsaturated alcohol alkylene oxide adduct, the polymerization active group (unsaturated group) does not lose its polymerization activity, does not transfer the position of the polymerization active group, and is by-produced. It needs to be manufactured paying attention to reducing the diol content. The polyalkylene oxide adduct of alcohol having a polymerization active group can be used as a raw material for polymerization after production regardless of the purification process.

In the method for producing a polycarboxylic acid-based polymer, the same polymer can be obtained by any of solvent polymerization, aqueous solution polymerization, continuous type and notch type. Many things to be done ,.

In the method of producing the structural unit (III), the dibasic acid and the polyamidepolyamine are condensed according to a conventional amidation method, and further, an amide group with maleic acid, fumaric acid and maleic anhydride is formed, which is necessary. According to the method, an alkylene oxide is added, a condensation product of a dibasic acid and a polyamide polyamine, or an alkylene oxide-modified polyamide polyamide to which an alkylene oxide is added is formed to be grafted on a polycarboxylic acid polymer. Examples thereof include a method of adding alkylene oxide to an aqueous polymer solution grafted with a polycarboxylic acid polymer after formation.

The polycarboxylic acid-based polymer of the present invention finally obtained has a weight-average molecular weight of 10,000-2000 by gel permeation chromatography (hereinafter referred to as “GPC method”, polyethylene glycol conversion). The range of 500,000 is appropriate, and more preferably, the weight-average molecular weight is in the range of 000 to 100,000. Power is desirable in order to exhibit excellent dispersion performance. Yes. In addition, it is also possible to control molecular weight distribution by using in combination a force chain transfer agent or the like whose molecular weight can be controlled by adjusting the type and / or amount of radical polymerization initiator etc. in aqueous solution polymerization. It is.

In the present invention, the "polycarboxylic acid polymer" may be a polymer only, but in general, unreacted components and by-products generated in each polymerization step, alkylene oxide addition step, etc. The ingredients included are also included.

[Use of Polycarboxylic Acid-Based Polymer]

The polycarboxylic acid-based polymer and polymer composition of the present invention are aqueous dispersions of various solid powders by adjusting the neutralization ratio of the acid group, adjusting the content of the polyamide polyamine, etc. according to various uses. Its performance can be widely exhibited as a dispersant in In addition, the polycarboxylic acid-based polymer of the present invention can be used as the above-mentioned dispersant as it is (without adding anything), and, according to various applications, publicly known and commonly used additives are appropriately adopted. It can also be used in the form of combined admixtures.

Specific examples of applications of the polycarboxylic acid-based polymer of the present invention include inorganic dispersants, pigment dispersants, hair setting agents, cosmetic base materials * additives, and paints, using dispersion techniques of inorganic compounds. Additives for surface coating, retention improver, drainage improver, excavated soil treatment agent, viscosity control agent, ceramic binder, pesticide additive, hydraulic composition additive, etc. It is also suitably used as a flocculant, repair agent, sludge treatment agent, granulating aid for ores, etc. as equipment use. It is also suitably used as a pitch dispersant, a paper strength additive, a binder for pigment coating, a papermaking dispersant, a deinking agent, a detergent additive, a powder detergent builder, a liquid detergent builder, and others of the present invention Antistatic agent, film 'fiber lubricant, water retention agent, fiber treatment agent, dye improver, fiber softener, surfactant, emulsifier, emulsifier, demulsifier, utilizing the surface active action of the polycarboxylic acid polymer It can also be used as a cell regulator, scale inhibitor, etc., and can be suitably used in a wide range of applications.

[0035] As an example of the above-mentioned application, when mention is made of additives for hydraulic composition, for example, various additives for concrete products, additives for grout, additives for concrete repair material, additives for gypsum board, water Additive for hard self-felling, additive for cement gypsum composite material It can be used for

When the polycarboxylic acid-based polymer of the present invention is used as an additive for gypsum board, a known additive can be added to form a gypsum dispersant composition. Examples of the additive include foams such as alkyl sulfates, alkyl ether sulfates and alkyl sulfonates, foam stabilizers, antifoams, water repellents, adhesives and the like. These may be used alone or in combination of two or more.

The above-mentioned gypsum board additive may be used by adding 0.1 to 5% by mass (additive solid content mass ratio) to the raw material gypsum. There are various addition methods of the above-mentioned gypsum board additive, but a general method is to prepare a gypsum slurry by diluting and adding to water before mixing with gypsum. Gypsum includes anhydrous gypsum, hemihydrate gypsum, dihydrate gypsum and the like.

In addition, additives used with the above-mentioned gypsum board additives include general-purpose water reducing agents, foam agents, antifoaming agents, foam stabilizers, hardening regulators, etc. Further, glass fibers, carbon fibers, waste paper as reinforcing fibers, etc. It is also practiced to add virgin pulp or the like, or to make a gypsum board together with a lightweight aggregate such as perlite and foamed steel.

The polycarboxylic acid-based polymer and polymer composition of the present invention are a dispersant for hydraulic composition, an additive for gypsum, an additive for concrete exterior plate, which is particularly preferable among the above-mentioned applications, and a lightweight It can be used as a water reducing agent for concrete.

Further, according to various uses, well-known and commonly used additives can be appropriately adopted and used in the form of a combined admixture.

[0037] As a result of extensive research on polymers, the present inventors have found that structural units consisting of unsaturated alcohol alkylene oxide adducts in which specific alkylene oxides are added at specific positions and proportions and unsaturated carboxylic acids And a polycarboxylic acid-based polymer comprising the structural unit comprising the polycarboxylic acid-based polymer, and a polycarboxylic acid-based polymer containing this polycarboxylic acid-based polymer and a polyamidepolyamine and / or a polyalkylene oxide-modified polyamine in the constituent unit, etc. It was found that the compound had better dispersibility than the analog compound of It has not yet been clarified how the above-mentioned excellent effects can be obtained! /,! /, In the above-mentioned unsaturated alcohol alkylene oxide adduct, ethylene oxide and propylene oxide or butylene oxide as an alkylene oxide to be added 2 types , A certain amount of propylene oxide or butylene oxide is disposed at the end of the alkylene oxide chain, and the chain length of the alkylene oxide chain is long, and the polycarboxylic acid polymer has a comb-like polymer structure. It is considered that when applied to aqueous dispersions of various solid powders, the ability to collect and disperse powder particles is improved due to the presence of

Furthermore, by using fumaric acid and / or fumaric acid derivative in the above-mentioned unsaturated carboxylic acid, the change of the arrangement state of the acid group in the polymer occurs, and the dispersion performance of the aqueous dispersion of various solid powders is improved. I think that it led to the effect. However, there are various mechanisms other than the above, for example, the use of a fumaric acid compound reduces the unreacted monomers due to an increase in the polymerization rate of the polycarboxylic acid polymer, and controls the molecular weight of the polymer. In addition to the fact that it has become easier, it is considered that the synergetic effect of these will lead to the improvement of the dispersion performance.

Example

The present invention will be described in more detail based on the following examples. The present invention is obtained by the above production method, and is not limited to this example.

In addition, unless otherwise indicated,% and part described below represent mass% and a mass part.

[Production Example Al (Production of EO Added Polyamide Polyamine)]

In a reaction vessel equipped with a stirrer and equipped with a nitrogen introducing pipe, thermometer, condenser, and a condenser, 199 g of poly (alkylene polyamine) (product name: Poly Sate from Tosoh Co., Ltd.) and 68 g of adipic acid were charged and stirred while introducing nitrogen. Then the temperature was raised to 160 ° C. The reaction was continued for 8 hours, and was terminated when the acid value reached 10. The reaction dehydration amount was 17 g. Next, 245 g of water was added and cooled to 60 ° C. as an aqueous solution, 89 g of ethylene oxide was added over 4 hours at the same temperature, and then aging was performed for 1 hour to obtain 584 g of aqueous solution of EO-added polyamidepolyamine A1 (solid content concentration : 58%).

Production Example A2 (Production of Polyamide Polyamine)

In a reaction vessel equipped with a stirrer and equipped with a nitrogen introducing pipe, thermometer, condenser, and a condenser, 199 g of poly (alkylene polyamine) (product name: Poly Sate from Tosoh Co., Ltd.) and 68 g of adipic acid were charged and stirred while introducing nitrogen. Then the temperature was raised to 160 ° C. reaction Was continued for 8 hours, and the reaction was terminated when the acid value reached 10. The reaction dehydration amount was 17 g. Then, 250 g of water was added and the mixture was cooled to 60 ° C. as an aqueous solution to obtain 500 g (solid content concentration: 50%) of an aqueous solution of polyamidepolyamine A2.

Production Example B1 (Production of Polycarboxylic Acid-Based Polymer)

In a stainless steel autoclave equipped with a nitrogen inlet tube, a stirrer, and a thermometer, 3-methyl-3-butane 1-monole 50 g of a caro product with 50EO 2 PO (block adduct), 286 g of ion exchanged water, 6.62 g of maleic anhydride, fumaric acid 59 Charged with stirring 6 g. After thoroughly performing nitrogen substitution and raising the temperature to 60 ° C., 22.2 g of a 14% aqueous solution of sodium persulfate was charged and reacted for 6 hours while maintaining the same temperature. After completion of the reaction, the temperature was raised to 80 ° C., and stirring was continued for 1 hour. Then, 26.7 g of an aqueous polyamidepolyamine A1 solution and 170 g of ion-exchanged water were added, and the mixture was further stirred for 1 hour. The polymerization solution is cooled to 50 ° C., neutralized with 25. Og of 48% aqueous sodium hydroxide solution, and 998 g of aqueous solution of polycarboxylic acid polymer B1 (solids concentration: 50%, weight average molecular weight: 26,000 Got).

Production Example B2 (Production of Polycarboxylic Acid-Based Polymer)

In a stainless steel autoclave equipped with a nitrogen introduction tube, a stirrer and a thermometer, 3-methyl-3-buten 1-monole 50 EO 2 PO with a carotene 402 g (block adduct), ion-exchanged water 286 g, maleic anhydride 33. lg, fumaric acid 33 The lg was charged with stirring. After thoroughly performing nitrogen substitution and raising the temperature to 60 ° C., 22.2 g of a 14% aqueous solution of sodium persulfate was charged and reacted for 6 hours while maintaining the same temperature. After completion of the reaction, the temperature was raised to 80 ° C., and stirring was continued for 1 hour. Then, 26.7 g of an aqueous polyamidepolyamine A1 solution and 170 g of ion-exchanged water were added, and the mixture was further stirred for 1 hour. The polymerization solution is cooled to 50 ° C., neutralized with 25. Og of 48% aqueous sodium hydroxide solution, and 998 g of aqueous solution of polycarboxylic acid type polymer B2 (solids concentration: 50%, weight average molecular weight: 29, 000) Got).

Production Example B3 (Production of Polycarboxylic Acid-Based Polymer)

In a stainless steel autoclave equipped with a nitrogen introduction tube, a stirrer and a thermometer, 3-methyl- 3-buteno 1-no-nole 402 g of a caro-product with 50EO 5 PO (block adduct), ion-exchanged water 286 g, maleic anhydride 6.62 g, fumaric acid 59 Charged with stirring 6 g. After performing sufficient nitrogen substitution and raising the temperature to 60 ° C, 22.2 g of a 14% aqueous solution of sodium persulfate is charged, The reaction was carried out for 6 hours while maintaining the temperature. After completion of the reaction, the temperature was raised to 80 ° C., and stirring was continued for 1 hour. Then, 30.4 g of an aqueous solution of polyamide polyamine A2 and 166 g of ion exchanged water were added, and the mixture was further stirred for 1 hour. The polymerization solution is cooled to 50 ° C., neutralized with 25. Og of 48% aqueous sodium hydroxide solution, and 998 g of aqueous solution of polycarboxylic acid polymer B3 (solids concentration: 50%, weight average molecular weight: 31, 000) Got).

Production Example B4 (Production of Polycarboxylic Acid-Based Polymer)

In a stainless steel autoclave equipped with a nitrogen introduction tube, a stirrer and a thermometer, 3-methyl-3-butane 1-monole 50 g of a caro-product with 50EO 2 PO (block adduct), 286 g of ion exchanged water, 59.6 g of maleic anhydride, fumaric acid 6 Charge to 62 g while stirring. After sufficiently performing nitrogen substitution and raising the temperature to 60 ° C., 22.2 g of a 14% aqueous solution of sodium persulfate was charged and reacted for 6 hours while maintaining the same temperature. After completion of the reaction, the temperature was raised to 80 ° C. and stirring was continued for 1 hour. Then, 26.7 g of an aqueous polyamidepolyamine A1 solution and 170 g of ion-exchanged water were added, and the mixture was further stirred for 1 hour. The polymerization solution is cooled to 50 ° C., neutralized with 25. Og of 48% aqueous sodium hydroxide solution, and 998 g of aqueous solution of polycarboxylic acid polymer B4 (solids concentration: 50%, weight average molecular weight: 30,000) Got).

Production Example B5 (Production of Polycarboxylic Acid-Based Polymer)

In a stainless steel autoclave equipped with a nitrogen introduction tube, a stirrer, and a thermometer, 3-methyl-3-buteno-1-one, 50 g of 50EO. 5PO adduct (block adduct), 286 g of ion exchanged water, 33. lg of maleic anhydride, fumaric acid 33. Charge lg with stirring. After sufficient nitrogen exchange and raising the temperature to 60 ° C., 22.2 g of a 14% aqueous solution of sodium persulfate was charged, and reaction was carried out for 6 hours while maintaining the same temperature. After completion of the reaction, the temperature was raised to 80 ° C. Stirring was continued for 1 hour. Next, 30.4 g of an aqueous solution of polyamide polyamine A2 and 166 g of ion exchanged water were added, and the mixture was further stirred for 1 hour. The polymerization solution is cooled to 50 ° C., 4 g of ethylene oxide is then added to the polymerization solution, aged at the same temperature for 1 hour, neutralized with 25. Og of 48% aqueous sodium hydroxide solution, and polycarboxylic acid-based polymer An aqueous solution of united B5 1, 002 g (solids concentration: 50%, weight average molecular weight: 29,000) was obtained.

Production Example B6 (Production of Polycarboxylic Acid-Based Polymer)

3-Methyl-3-bu in a stainless steel autoclave with nitrogen inlet tube, stirrer, thermometer Ten grams of carbon dioxide with 50EO 2 PO (block adduct), 286 g of ion-exchanged water, 6.62 fumaric acid and 59.6 g of maleic anhydride were charged with stirring. After thoroughly performing nitrogen substitution and raising the temperature to 60 ° C., 22.2 g of a 14% aqueous solution of sodium persulfate was charged and reacted for 6 hours while maintaining the same temperature. After completion of the reaction, the temperature was raised to 80 ° C., and stirring was continued for 1 hour. After cooling to 50 ° C., 25.O g of a 48% aqueous sodium hydroxide solution and 164 g of ion exchanged water were added, and the mixture was further stirred for 1 hour. There were obtained 965 g (concentration 50%, weight average molecular weight: 37,000) of an aqueous solution of polycarboxylic acid polymer B6.

Production Example B7 (Production of Polycarboxylic Acid-Based Polymer)

In a stainless steel autoclave equipped with a nitrogen inlet tube, a stirrer, and a thermometer, 3-methyl-3-butane 1-monole 50 g of a caro product with 50EO 2 PO (block adduct), 286 g of ion exchanged water, 6.62 g of maleic anhydride, fumaric acid 59 Charged with stirring 6 g. After thoroughly performing nitrogen substitution and raising the temperature to 60 ° C., 22.2 g of a 14% aqueous solution of sodium persulfate was charged and reacted for 6 hours while maintaining the same temperature. After completion of the reaction, the temperature was raised to 80 ° C., and stirring was continued for 1 hour. The mixture was cooled to 50 ° C., 25.O g of 48% aqueous sodium hydroxide solution and 164 g of deionized water were added, and the mixture was further stirred for 1 hour. There were obtained 965 g (solids concentration: 50%, weight average molecular weight: 24,000) of an aqueous solution of a polycarboxylic acid polymer B7.

Production Example C1 (Production of Polycarboxylic Acid-Based Polymer)

In a stainless steel autoclave equipped with a nitrogen introduction tube, a stirrer, and a thermometer, 402 g (block adduct) of 3-methyl 3-buteno 1 PONOE 2 O caro compound with PO 50 EO, 286 g of ion exchanged water, and 66.2 g of maleic anhydride while stirring I was charged. After sufficient nitrogen substitution and heating up to 60 ° C., 22.2 g of a 14% aqueous solution of sodium persulfate was charged, and the reaction was carried out for 6 hours while maintaining the same temperature. After completion of the reaction, the temperature was raised to 80 ° C., and stirring was continued for 1 hour. After cooling to 50 ° C., 165 g of ion-exchanged water and 25.O g of a 48% aqueous sodium hydroxide solution were added, and the mixture was further stirred for 1 hour. The reaction mixture was neutralized with to obtain 966 g (solids concentration: 50%, weight average molecular weight: 29,000) of an aqueous solution of polycarboxylic acid polymer C1.

Production Example C2 (Production of Polycarboxylic Acid-Based Polymer)

In a four-necked flask equipped with a thermometer, stirrer, dropping funnel, nitrogen inlet tube, and reflux condenser, 395 g of water is charged and the inside of the flask is purged with nitrogen while being stirred up to 80 ° C. in a nitrogen atmosphere Heated. Then a mixture of 250 g of methoxypolyethylene glycol metatarylate (ethylene oxide average average calo monole number 5 monole), 62.5 g of methanoleic acid, 9.4 g of 10% aqueous solution of glyconoleic acid and 9.4 g of sodium persulfate solution. After dropping for 120 minutes, the mixture was stirred at the same temperature for 4 hours to complete the polymerization reaction. The reaction solution is cooled to 50 ° C. and neutralized with 48% caustic soda until pH 7 to obtain 837 g of an aqueous solution of polycarboxylic acid polymer C2 (solids concentration: 40%, weight average molecular weight: 26,000) I got

[table 1]

Table 1 Formulation examples of preparation examples B 1 to B 7, C 1 and C 2

* 1 Calculated as ethylene oxide added to polyamide A2 in the polymerization step to become polyamide A1.

[Performance test of polycarboxylic acid polymer]

Necessary amounts of polycarboxylic acid polymers B1 to B7 and C1 and C2 of the above Production Example and melamine sodium sulfonate formalin condensate (MSFF) as Comparative Example 3 are weighed based on the solid content, water is added, and the total amount is 65 g. Adjust the mixing water to become To this, add 100 g of Sakura Indoku Gypsum Grade A (manufactured by Yoshino Gypsum Co., Ltd.) (65% water / gypsum ratio), The mixing was done for a second. A φ50 mm × H50 mm cylindrical hollow cylinder was prepared in advance at the center of a urethane board (35 cm × 35 cm), and the mixed gypsum slurry was poured until the container was full. After that, the hollow cylinder was pulled up in the direction perpendicular to the urethane board, and the spread of the gypsum slurry was measured. The maximum diameter of the spread and the diameter perpendicular to it were measured, and the average value was used as an indicator of dispersibility.

Gypsum set retarding property>

In the same manner as in the dispersibility test, polyboric acid polymers B1 to B7, C1 and C2, and melamine sulfonic acid soda formalin condensate (MSFF) are positively weighed on the basis of solid content, and mixing water is added to total. Adjusted to 162 g. To this was added 250 g of Sakura Indoku Gypsum Grade A (manufactured by Yoshino Shikoshi Co., Ltd.) (65% water / gypsum ratio), and mixed for 10 seconds with a small juicer mixer. After mixing, immediately transfer the finished gypsum slurry to a paper cup, insert a digital thermometer into this, measure the heat generation temperature for hardening of the plaster in 1 minute unit, and raise the time to reach the maximum temperature The peak time was taken as an indicator of curing delay.

The results thus obtained are shown in Table 2.

[Table 2]

Table 2 Evaluation results of dispersibility and curing delay

※: Melamine sulfonate sodium formalin condensate (MSFF)

From the results of Examples 1 to 7 shown in Table 2, the polycarboxylic acid polymer of the present invention was treated with gypsum When added to the slurry, superior dispersibility was shown as compared with the comparative example. Also, regarding the curing delaying property, good results were obtained as compared with the comparative example.

On the other hand, Comparative Example 1 in which no PO group is added to the end of the alkylene oxide chain is inferior to both the examples in the dispersion property and the curing delay property, and the conventional polycarboxylic acid polymer Although Comparative Example 2 corresponding to Comparative Example 2 showed relatively excellent results in dispersibility, results were obtained that curing delay was caused.

Furthermore, in Comparative Example 3 corresponding to the conventional dispersant containing formaldehyde, although the curing was fast, the result that the dispersibility was inferior was obtained.

[0055] <Gypsum colorability>

As the polycarboxylic acid-based polymers Bl, B6 and B7 of the above-mentioned Production Examples, and as Comparative Example 4 (meth) acrylic acid-methoPEG (meth) atalylate-based polymer (PC) and Naphthalene sulfonic acid as Comparative Example 5. The required amount of soda (NSF) was weighed on a solid basis, and water was added to adjust kneading water to a total amount of 165 g. To this was added 300 g of Sakura Indoku Gypsum Grade A (manufactured by Yoshino Gypsum Co., Ltd.) (55% water / gypsum ratio), and mixed for 30 seconds with a small juicer mixer.

The finished gypsum slurry was poured into an aluminum cup (diameter 54 mm, depth 23 mm) and allowed to stand at 80 ° C. for 24 hours. The color of the solidified gypsum block surface after 24 hours was visually confirmed to evaluate the colorability.

The obtained results are shown in Table 3.

[Table 3]

Evaluation results of colorability

○ Slightly browned

Δ light brown

X brown

※ 2: (Meth) acrylic acid-Met PEG (Meth) atarylate polymer

※ 3: Sodium naphthalene sulfonate

From the results of Examples 8 to 10 shown in Table 3, when the polycarboxylic acid polymer of the present invention is added to a gypsum slurry and cured, no additive is added in the case of 0.4% addition. Comparative Example 4 and Comparative Example 4 showed the same white color as in the case, although some were slightly colored even with the addition of 0.8%.

The result that clear non-colorability is clearly obtained compared to 5 was obtained.

Therefore, the polycarboxylic acid-based polymer of the present invention can be used to prevent the decline in product value due to coloring when used in the preparation of gypsum products (strengthened board, plaster for pottery, etc.) in which gypsum skin is exposed. It also has an accompanying effect.

Using the polycarboxylic acid-based polymers Bl, B3 and B5 and the sodium naphthalenesulfonate (NSF) of the above-mentioned production example, the extrusion formability test as an additive for a concrete exterior plate with the composition shown in the following Table 4 Did.

Use a Hobart mixer to mix the mixture for concrete exterior plate, add water prepared by adding each polycarboxylic acid polymer or sodium naphthalene sulfonate beforehand to cement, key sand, polypropylene, methylcellulose And mixed for 180 seconds.

Thereafter, a molded plate (width 100 mm, thickness 15 mm) was produced by extrusion, and the extrusion moldability as an extruded plate was evaluated from the extrusion speed at this time.

The obtained results are shown in Table 5. [0059] [Table 4]

Table 4 Material composition of molding plate

Ingredient formulation

Ordinary portland cement · ^{1 1} 100 parts

100 parts of key sand

Waste paper pulp 2. 8 parts

Water 1 12 parts

Additive ' ² (solid content basis) 2 parts

MITONORECE / RELOSE 4 parts

※ 丄: Normal Portland cement (Pacific Cement Co., Ltd.) Density 3. 16 g / cm ³ ※? : Polycarboxylic acid polymers B1, B3 and B5 or

Naphthalene sulfonic acid soda (NSF)

[0060] [Table 5]

Extruded sheet formability

As apparent from the results of Examples 11 to 13 shown in Table 5, when the polycarboxylic acid-based polymer of the present invention is used, compared with the case where NSF (sodium naphthalene sulfonate) is used, the extrusion is performed. The result is that the speed is about 2 times faster, that is, the extrudability is improved.

The polycarboxylic acid-based polymers Bl, B3 and B5 of the above-mentioned production example, and (meth) acrylic acid-methoPEG (meth) atalylate polymer (PC) and sodium naphthalenesulfonate (NSF) were used to obtain the following Table 6 The hardenability and air bubble entrapment property of the mortar slurry were evaluated by the composition shown in the above.

For mortar slurry, use a mixer equipped with a simple stirring blade, cement, silica stone, Water prepared by adding each polycarboxylic acid-based polymer, PC or NSF in advance to quick lime, gypsum, and aluminum was added and mixed for 180 seconds.

Thereafter, it was poured into a mold having a width of 600 mm, a length of 600 mm and a height of 600 mm, and it was evaluated whether it was possible to remove the mold after a predetermined time (90 minutes). Thereafter, the hardened mortar cross section was cut with a piano wire, and the bubble entrapment property was visually evaluated.

The obtained results are shown in Table 7.

[Table 6]

Table 6 Lightweight concrete

Ingredient formulation

Normal bolt land cement '40 parts

45 parts of silica stone

10 parts of quicklime

3⁄4 * 5 copies

70 parts of water

Aluminum 0. 06 part

Additive ⁵⁸² (based on solid content) 0.5 parts

※ ェ: Ordinary portland cement (manufactured by Pacific Cement Co., Ltd.) Density 3. 16 g Z cm ³ ※ 2: Polycarboxylic acid polymer Bl, B3 and B5 or

Naphthalene sulfonic acid soda (NSF)

[Table 7]

Table 7-Evaluation results of curability and air bubble entrapment

※ ^ Curable evaluation index

:: Demolding is possible in a predetermined time (90 minutes)

X: Sufficient strength can not be obtained due to delayed curing and can not be demolded

«2: Bubble embracement evaluation index

:: Slurry viscosity lowering air bubbles not included

X: Slurry is high viscosity, coarse bubbles remain

* 3: (Meth) acrylic acid-metho PEG (Meth) atarylated polymer * 4: Naphthalene sulfonic acid

From the results of Examples 14 to 16 shown in Table 7, when the polycarboxylic acid polymer of the present invention is used, it can be cured and removed within a predetermined time, and the inclusion of air bubbles is also possible. The test results were obtained to make V not occur.

That is, it was found that the polycarboxylic acid-based polymer of the present invention is useful as a water reducing agent for ALC because it satisfies both the curability and the bubble entrapment property.

On the other hand, in Comparative Example 7 in which a general-purpose polycarboxylic acid-based polymer is blended, demolding can not be performed within a predetermined time due to curing delay, and in Comparative Example 8 in which sodium naphthalenesulfonate is blended. Although it is excellent in the curability, it has a low water removability, so that the force viscosity becomes large, and the result is that coarse bubbles are not removed.

Claims

The scope of the claims

[1] A polycarboxylic acid-based polymer constituted by including a structural unit derived from an unsaturated alcohol alkylene oxide compound and a structural unit derived from an unsaturated carboxylic acid compound, and the polymer The graft chain bonded to the main chain skeleton contains a polyalkylene oxide chain mainly composed of ethylene oxide, and the terminal part of the polyalkylene oxide chain is 0 based on the total molar amount of the alkylene oxide of the graft chain. · A polycarboxylic acid-based polymer characterized by having an alkylene oxide having 3 or 4 carbon atoms in a proportion of 1 to 30 mol%.

[2] The polycarboxylic acid according to claim 1, wherein a part or all of the constituent units derived from the unsaturated carboxylic acid compound is a constituent unit derived from fumaric acid and / or a derivative thereof. Based polymer.

[3] The polycarboxylic acid-based polymer is composed of a constituent unit (I) represented by the following formula (I) and a constituent unit (II) represented by the formula (II), and the constituent unit (I The alkylene oxide having 3 or 4 carbon atoms at the end of the polyalkylene oxide chain in 0.1 to 30 mol% with respect to the total molar amount of the alkylene oxide chain. The polycarboxylic acid-based polymer according to claim 1 or 2.

[Formula 1]

R ¹ X- (AO) a -R ⁴

I I

-C-C- (I)

I I

R ² R ³

(Wherein, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, X represents one (CH 2) bO—, AO represents And C represents an alkylene oxide group having 2 to 4 carbon atoms, a represents an average addition mole number of alkylene oxide, represents a number of 1 to 200, and b represents an integer of 1 to 20.

[Formula 2]

R ⁵ R ⁶

-C-C- (II)

I I

R ⁷ R ⁸ (Wherein, R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, —COOH, —COOM, —COOY, or R ⁵ And R ⁶ or R ⁷ and R ⁸ together form an acid anhydride, M represents an alkali metal, an alkaline earth metal, an amine, an alkanolamine, and Y represents a C 1-22 carbon atom. or a hydrocarbon group - (AO) c- represents R ^9, AO represents an alkylene oxide group having 2 to 4 carbon atoms, c is a number from 1 to 200 in average molar number of addition of alkylene oxide, R ⁹ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms.)

[4] The polycarboxylic acid-based polymer is configured to further include a constituent unit (III) represented by the following formula (III) in addition to the constituent unit (I) and the constituent unit (II) A polycarboxylic acid-based polymer according to claim 3, characterized in that.

[Chemical 3]

H H

-c c one (III)

I I COOH Z

[5] A polyamide polyamine obtained by condensing a dibasic acid and a polyalkylene polyamine in addition to the polycarboxylic acid polymer according to any one of claims 1 to 4 and / or an active imino group of the polyamide polyamine, A polycarboxylic acid-based polymer is characterized in that it contains a polyamide polyamine modified product in which 0.1 to 10 moles of an alkylene oxide of 2 to 4 carbon atoms is added to an amino group or an amide residue equivalent. Combined composition.

[6] A dispersant for a hydraulic composition, comprising the polycarboxylic acid polymer according to any one of claims 1 to 4 or the polycarboxylic acid polymer composition according to claim 5.

[7] An additive for gypsum, comprising the polycarboxylic acid polymer according to any one of claims 1 to 4 or the polycarboxylic acid polymer composition according to claim 5.

[8] The polycarboxylic acid-based polymer according to any one of claims 1 to 4 or claim 5 The additive for concrete exterior boards containing the polycarboxylic acid type polymer composition of description.

[9] A water reducing agent for lightweight concrete, comprising the polycarboxylic acid polymer according to any one of claims 1 to 4 or the polycarboxylic acid polymer composition according to claim 5.