JP5610244B2 - Novel polycarboxylic acid polymer - Google Patents

Description

  The present invention relates to a novel polycarboxylic acid polymer. More specifically, a polycarboxylic acid system comprising a structural unit derived from an unsaturated alcohol alkylene oxide adduct having a hydrophobic group at a terminal and a structural unit derived from an unsaturated carboxylic acid carboxylic acid It relates to a polymer.

  Conventionally, a polymer composed of an unsaturated alcohol alkylene oxide adduct monomer and an unsaturated carboxylic acid monomer collects various particles and has excellent dispersibility in water. Therefore, they are widely used as surfactants and various solid powder dispersants.

The technology of the above-described polymer is disclosed in various applications.
For example, Patent Document 1 discloses an aqueous slurry dispersant of a water-soluble copolymer obtained from an unsaturated carboxylic acid component unit (I) and an unsaturated alcohol component unit (II), a cement admixture, a scale inhibitor, It has been proposed to be used for detergent builders, waste paper deinking agents, cotton scouring detergents, coal dispersants, and the like.
In Patent Document 2, a copolymer of an α, β-unsaturated carboxylic acid or an anhydride thereof and an alkenyl ether having an oxyalkylene group having 2 to 18 carbon atoms is suitable as a dispersant for gypsum (flowing). The results show that the water is reduced.
In addition, it is obtained by copolymerization of an unsaturated carboxylic acid monomer having an oxyalkylene group having 2 to 18 carbon atoms and / or an unsaturated acid anhydride monomer and an unsaturated alcohol monomer, Detergent builder comprising an amino group-containing polymer in which an amino group is partially introduced (Patent Document 3), ethylenically unsaturated monocarboxylic acid, polyalkylene glycol (meth) acrylate and ethylenically unsaturated dicarboxylic acid Techniques such as a dispersant for inorganic pigment containing a salt of coalescence (Patent Document 4) are disclosed.

  In the above Patent Documents 1 to 4, although an addition of two or more alkylene oxides (for example, ethylene oxide and propylene oxide) in the unsaturated alcohol alkylene oxide adduct has been proposed, an actual test example is ethylene oxide. Only the results of using a single-added alcohol are used, and when two or more types of alkylene oxide are used, the order or site of addition is not studied.

The present invention has been made to further improve the performance as a dispersant under the background of such conventional technology.
In addition, for example, in applications to hydraulic compositions, not only high water reduction performance is required for the purpose of ensuring workability, but also improvement of cure retardance is emphasized because it is a factory product. . In particular, the retarding property is often affected by the type of acid group contained in the polymer, or is often influenced by the amount of the dispersant added, that is, the water reducing property of the dispersant. From the viewpoint of improving the production efficiency of the product, machine formability is also regarded as important, and it is desirable that the mold has excellent peelability from the mold and the pressing surface, and that there is no corner chipping. Furthermore, it is important that the amount of air in the composition can be adjusted, or that the appearance of the molded body (for example, a gypsum product (reinforced board, ceramic plaster, etc.)) is not damaged by coloring or the like depending on the application. It is said.
For this reason, it has been awaited for the advent of a dispersant that can fully study these and satisfy various performances, as well as an additive for various hydraulic composition applications.

  As a result of intensive studies, the present inventors have found that in a polycarboxylic acid polymer comprising a reactive alcohol derivative having a polymerizable binding site and a dibasic acid derivative, one end of the polyalkylene oxide chain of the reactive alcohol derivative. Part is polyalkylene oxide addition having 3 or 4 carbon atoms, that is, the proportion of the alkylene oxide having 3 or 4 carbon atoms at the terminal portion is 0.1 to 30 mol% with respect to the total molar amount of the alkylene oxide chain The polycarboxylic acid-based polymer, which is characterized by being contained in, exhibits excellent dispersion performance in an aqueous dispersion of solid powder, and when added to a hydraulic composition, has water reduction performance and low cure retardation I found out that it works.

  That is, the present invention relates to a polycarboxylic acid polymer 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 chain contains a polyalkylene oxide chain mainly composed of ethylene oxide, and the terminal portion of the polyalkylene oxide chain is 0.1 to 30 mol% based on the total molar amount of the alkylene oxide of the graft chain. It is related with the polycarboxylic acid type | system | group polymer characterized by having C3 or C4 alkylene oxide in the ratio.

  The present invention also relates to a polycarboxylic acid polymer, wherein a part or all of the structural unit derived from the unsaturated carboxylic acid compound is a structural unit derived from fumaric acid and / or a derivative thereof.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４はそれぞれ独立して水素原子又は炭素原子数１乃至２２の炭化水素基を表し、Ｘは―（ＣＨ_２）ｂＯ―を表し、ＡＯは炭素原子数２乃至４のアルキレンオキサイド基を表す。ａはアルキレンオキサイドの平均付加モル数で１乃至２００の数を表し、ｂは１乃至２０の整数を表す。）

（式中、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８はそれぞれ独立して水素原子又は炭素原子数１乃至２２の炭化水素基、−ＣＯＯＨ、−ＣＯＯＭ、−ＣＯＯＹを表すか、あるいはＲ^５とＲ^６、若しくはＲ^７とＲ^８は一緒になって酸無水物を形成する。Ｍはアルカリ金属、アルカリ土類金属、アンモニウム、アルカノールアミンを表し、Ｙは炭素原子数１乃至２２の炭化水素基または−（ＡＯ）ｃ−Ｒ^９を表し、ＡＯは炭素原子数２乃至４のアルキレンオキサイド基を表し、ｃはアルキレンオキサイドの平均付加モル数で１乃至２００の数を表し、Ｒ^９は水素原子又は炭素原子数１乃至２２の炭化水素基を表す。）
さらに本発明は、前記ポリカルボン酸系重合体が、前記構成単位（Ｉ）及び構成単位（ＩＩ）に加え、更に下記の式（ＩＩＩ）で表される構成単位（ＩＩＩ）を含みて構成されることを特徴とする、ポリカルボン酸系重合体に関する。

（式中、Ｚは二塩基酸とポリアルキレンポリアミンを縮合させたポリアミドポリアミン及び／又は該ポリアミドポリアミンの活性イミノ基、アミノ基、アミド残基１当量に対して炭素原子数２乃至４のアルキレンオキサイドを０．１乃至１０モル付加させたポリアミドポリアミン変性物が、アミド結合を介して主鎖の炭素原子と結合する基を表す。） In the present invention, the polycarboxylic acid polymer includes a structural unit (I) represented by the following formula (I) and a structural unit (II) represented by the formula (II). The terminal portion of the polyalkylene oxide chain in (I) is characterized by having an alkylene oxide having 3 or 4 carbon atoms in a proportion of 0.1 to 30 mol% with respect to the total molar amount of the alkylene oxide chain. And a polycarboxylic acid polymer.

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

^{(Wherein, R 5, R 6, R} 7, R 8 are each independently hydrogen atom or a hydrocarbon group having a carbon number of 1 to 22, -COOH, -COOM, or represents -COOY, or an ^{R 5} R ⁶ , or R ⁷ and R ⁸ together form an acid anhydride, M represents an alkali metal, alkaline earth metal, ammonium, alkanolamine, and Y represents a hydrocarbon group having 1 to 22 carbon atoms. Or-(AO) c-R ⁹ , AO represents an alkylene oxide group having 2 to 4 carbon atoms, c represents an average added mole number of alkylene oxide and represents a number of 1 to 200, and R ⁹ represents a hydrogen atom. Or a hydrocarbon group having 1 to 22 carbon atoms.)
Furthermore, the present invention is configured such that the polycarboxylic acid polymer includes a structural unit (III) represented by the following formula (III) in addition to the structural unit (I) and the structural unit (II). The present invention relates to a polycarboxylic acid polymer.

(In the formula, Z is a polyamide polyamine obtained by condensing a dibasic acid and a polyalkylene polyamine and / or an alkylene oxide having 2 to 4 carbon atoms with respect to 1 equivalent of an active imino group, amino group or amide residue of the polyamide polyamine. Represents a group bonded to the carbon atom of the main chain through an amide bond.

  The present invention also relates to a polycarboxylic acid polymer 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 chain contains a polyalkylene oxide chain mainly composed of ethylene oxide, and the terminal portion of the polyalkylene oxide chain is 0.1 to 30 mol% based on the total molar amount of the alkylene oxide of the graft chain. A part or all of the structural unit derived from the unsaturated carboxylic acid compound is a structural unit derived from fumaric acid and / or a derivative thereof. The present invention relates to a polycarboxylic acid polymer.

  In addition to the above polycarboxylic acid polymer, the present invention provides a polyamide polyamine obtained by condensing a dibasic acid and a polyalkylene polyamine and / or an active imino group, amino group, and amide residue of 1 equivalent of the polyamide polyamine. The present invention relates to a polycarboxylic acid-based polymer composition comprising a modified polyamide polyamine obtained by adding 0.1 to 10 moles of an alkylene oxide having 2 to 4 carbon atoms.

  And this invention relates to the dispersing agent for hydraulic compositions, the additive for gypsum, the additive for concrete exterior boards, and the water reducing agent for lightweight concrete containing the said polycarboxylic acid type polymer or a polycarboxylic acid type polymer composition. .

According to the present invention, it has excellent dispersion performance with respect to aqueous dispersions of various solid powders, further improves curing retardancy and moldability, is excellent in air amount adjustment ability, and the appearance of the obtained cured body It is possible to provide a polycarboxylic acid-based polymer that can be made excellent.
Therefore, according to the present invention, a dispersant for a hydraulic composition, an additive for gypsum, an additive for a concrete exterior plate, and a water reducing agent for lightweight concrete can be provided.

The present invention relates to a polycarboxylic acid polymer 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 to be bonded includes a polyalkylene oxide chain mainly composed of ethylene oxide, and the terminal portion of the polyalkylene oxide chain is 0.1 to 30 mol% based on the total molar amount of the alkylene oxide of the graft chain. The present invention relates to a polycarboxylic acid polymer characterized by having an alkylene oxide having 3 or 4 carbon atoms in a proportion. More specifically, the polycarboxylic acid polymer is composed of the structural unit (I) and the structural unit (II) shown above, and the polycarboxylic acid polymer is further composed of the structural units (I) and (II). ), Polyamidopolyamine and / or
Or it is comprised including the said structural unit (III) derived from a polyamide polyamine modified material. The polycarboxylic acid 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 the main chain skeleton.
Further, the polycarboxylic acid polymer of the present invention may further include a polyamide polyamine and / or a polyamide polyamine-modified product, and may be in the form of a composition.
The present invention is described in detail below.

（式中、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４はそれぞれ独立して水素原子又は炭素原子数１乃至２２の炭化水素基を表し、Ｘは―（ＣＨ_２）ｂＯ―を表し、ＡＯは炭素原子数２乃至４のアルキレンオキサイド基を表す。ａはアルキレンオキサイドの平均付加モル数で１乃至２００の数を表し、ｂは１乃至２０の整数を表す。） [Structural Unit (I) and Structural Unit (II)]
The structural unit (I) constituting the polycarboxylic acid polymer of the present invention is represented by the following formula.

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

The polyalkylene oxide chain-(AO) a- is preferably mainly composed of ethylene oxide, and its average added mole number is preferably 30 or more, more preferably 50 or more in view of improving the dispersion performance. .
In the structural unit (I), the terminal part of the polyalkylene oxide chain (bonding position with R ⁴ ) is propylene oxide having 3 carbon atoms or 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 desirably, 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%. This is preferable in that the dispersibility is remarkably improved.
Further, R ⁴ is preferably 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 structural unit (I) is, for example, a structural unit derived from the following compound; polyalkylene glycol monoallyl ether, polyalkylene glycol monoalkenyl ether, methoxypolyalkylene glycol monoallyl ether, methoxypolyalkylene glycol monoalkenyl ether, etc. Alkenyl ethers formed from the (alkoxy) polyalkylene glycol 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 preferred compounds are 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, allyl alcohol , An alkylene oxide adduct of an unsaturated alcohol such as oleyl alcohol.
The structural unit (I) may be a structural unit derived from one or a combination of these compounds.

（式中、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８はそれぞれ独立して水素原子又は炭素原子数１乃至２２の炭化水素基、−ＣＯＯＨ、−ＣＯＯＭ、−ＣＯＯＹを表すか、あるいはＲ^５とＲ^６、若しくはＲ^７とＲ^８は一緒になって酸無水物を形成する。Ｍはアルカリ金属、アルカリ土類金属、アンモニウム、アルカノールアミンを表し、Ｙは炭素原子数１乃至２２の炭化水素基または−（ＡＯ）ｃ−Ｒ^９を表し、ＡＯは炭素原子数２乃至４のアルキレンオキサイド基を表し、ｃはアルキレンオキサイドの平均付加モル数で１乃至２００の数を表し、Ｒ^９は水素原子又は炭素原子数１乃至２２の炭化水素基を表す。） The structural unit (II) constituting the polycarboxylic acid polymer of the present invention is represented by the following formula.

^{(Wherein, R 5, R 6, R} 7, R 8 are each independently hydrogen atom or a hydrocarbon group having a carbon number of 1 to 22, -COOH, -COOM, or represents -COOY, or an ^{R 5} R ⁶ , or R ⁷ and R ⁸ together form an acid anhydride, M represents an alkali metal, alkaline earth metal, ammonium, alkanolamine, and Y represents a hydrocarbon group having 1 to 22 carbon atoms. Or-(AO) c-R ⁹ , AO represents an alkylene oxide group having 2 to 4 carbon atoms, c represents an average added mole number of alkylene oxide and represents a number of 1 to 200, and R ⁹ represents a hydrogen atom. Or a hydrocarbon group having 1 to 22 carbon atoms.)

Specifically, the structural unit (II) is a structural unit derived from acrylic acid, methacrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, and the like. The acid is contained in a considerable proportion, for example, 10% by mass or more based on the total mass of the polymer.
When the structural unit (II) contains an acid (—COOH) and / or an acid salt (—COOM), these may be in an acid form or a neutralized form, but may be partially neutralized or completely neutralized. The form is preferred as the product form.

In addition, when the structural unit (II) contains an acid derivative (—COOY), Y is specifically a partial ester or a total ester having 1 to 22 carbon atoms, a partial ester or a total ester of a polyalkylene oxide adduct, Examples include (alkoxy) polyalkylene glycol partial esters or total esters. More specifically, (alkoxy) polyalkylene glycol mono (meth) acrylates such as methoxypolyethylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate, methoxypolyethylene glycol monomaleate, methoxypolyethylene glycol dimaleate, polyethylene (Alkoxy) polyalkylene glycol malates such as glycol monomalate and polyethylene glycol dimaleate, (alkoxy) such as methoxypolyethylene glycol monofumarate, methoxypolyethylene glycol difumarate, polyethylene glycol monofumarate, polyethylene glycol difumarate Examples include polyalkylene glycol fumarate. Alkylene oxides can be added individually or in a mixed manner. When two or more types of alkylene oxide are used, either block addition or random addition may be used. Specific examples of the fumaric acid derivative include methoxypolyethylene glycol difumarate.
When the structural unit (II) contains a structural unit derived from fumaric acid and / or a fumaric acid derivative, it is preferably 10 to 100% by weight, more preferably 20%, based on the total weight of all the structural units (II). It is desirable that it is contained in a proportion of from 100 to 100% by mass, particularly preferably from 30 to 100% by mass, most preferably from 50 to 100% by mass.
The polycarboxylic acid-based polymer of the present invention is most preferably a polyalkylene oxide chain in which propylene oxide or butylene oxide is bonded to the end of an ethylene oxide chain having an average addition mole number of 50 or more. The propylene oxide or butylene oxide is contained in a proportion of 0.1 to 20 mol% with respect to the total number of moles of the alkylene oxide chain) and the structural unit (I) derived from the unsaturated alcohol alkylene oxide compound, It is desirable to comprise a structural unit (II) containing a structural unit derived from an acid in a considerable proportion (10% by mass or more based on the total mass of the polymer).

（式中、Ｚは二塩基酸とポリアルキレンポリアミンを縮合させたポリアミドポリアミン及び／又は該ポリアミドポリアミンの活性イミノ基、アミノ基、アミド残基１当量に対して炭素原子数２乃至４のアルキレンオキサイドを０．１乃至１０モル付加させたポリアミドポリアミン変性物がアミド結合を介して主鎖の炭素原子と結合する基を表す。） [Structural unit (III)]
Further, the polycarboxylic acid polymer of the present invention comprises a structural unit (III) derived from a polyamide polyamine and / or a modified polyamide polyamine in addition to the above structural units (I) and (II).
The structural unit (III) is represented by the following formula.

(In the formula, Z is a polyamide polyamine obtained by condensing a dibasic acid and a polyalkylene polyamine and / or an alkylene oxide having 2 to 4 carbon atoms with respect to 1 equivalent of an active imino group, amino group or amide residue of the polyamide polyamine. Represents a group in which 0.1 to 10 mol of a modified polyamide polyamine is bonded to the carbon atom of the main chain via an amide bond.)

  In the structural unit (III), the dibasic acid constituting Z is an aliphatic saturated dibasic acid having 2 to 10 carbon atoms, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, Pimelic acid, suberic acid, azelaic acid, sebacic acid, and the like. Examples of polyalkylene polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, or ethylene units and nitrogen atoms. Examples thereof include a mixture of high-molecular polyethylene polyamines, which is a mixture containing a large amount.

The structural unit (III) is a polyamide polyamine which is a condensate of these dibasic acid and polyalkylene polyamine and / or the number of carbon atoms with respect to 1 equivalent of the active imino group, amino group and amide residue of the polyamide polyamine. A polyamide polyamine modified product obtained by adding 2 to 4 alkylene oxides in an amount of 0.1 to 10 mol is a structural unit formed by bonding maleic anhydride, maleic acid, fumaric acid and an amide bond through an amide bond.
Since some of these polyamide polyamines or polyalkylene oxide-modified polyamide polyamines have a property of being basic in an aqueous solution, they may act as a neutralizing agent for the polycarboxylic acid polymer.

[Composition ratio of each structural unit]
In the polycarboxylic acid polymer composed of the structural unit (I) and the structural unit (II) described above, the structural ratio thereof is structural unit (I): structural unit (II) = 95 to 60% by mass: 5 to 40% by mass. %, Preferably structural unit (I): structural unit (II) = 90 to 70% by mass: 10 to 30% by mass, more preferably structural unit (I): structural unit (II) = 90 to 80% by mass: 10 It is desirable to be in the range of 20 to 20% by mass. In the polycarboxylic acid polymer composed of the structural unit (I) to the structural unit (III), the structural unit (I): the structural unit (II): the structural unit (III) = 90 to 50% by mass: 8 to 40 mass%: 2 to 10 mass%, preferably in the range of structural unit (I): structural unit (II): structural unit (III) = 90 to 60 mass%: 8 to 30 mass%: 2 to 7 mass It is desirable. (However, the total 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 structural units (IV) that may be contained]
In the above-mentioned polycarboxylic acid polymer, the structural unit (IV) can be contained in addition to these structural units (I) to (III).
Examples of the compound from which the other structural unit (IV) that can be contained includes (meth) acrylic acid (salt), (meth) acrylic acid polyalkylene glycol monoalkyl ether, (meth) allylsulfonic acid (salt), styrene Kinds of sulfonic acids (salts), alkyl (meth) acrylates, styrene, (meth) acrylamides, and the like, as long as they are compounds capable of forming a polymer with the structural units (I) to (III). It is not limited.
For example, incorporating a structural unit derived from an alkali hydrolyzable compound in order to improve dispersibility when adding the polycarboxylic acid polymer to a hydraulic composition or the like is described in Japanese Patent No. 3780465 and the like. It is one of the means that can be easily conceived by the combination.
The structural ratio of the structural unit (IV) is a range of the polycarboxylic acid polymer or the like (structural units (I) to (III)): structural unit (IV) = 100 to 70% by mass: 0 to 30% by mass. However, it is preferably in the range of 100% by mass.

[Polyamide polyamine and / or modified polyamide polyamine]
The polycarboxylic acid polymer composition of the present invention is a polyamide polyamine obtained by condensing a dibasic acid and a polyalkylene polyamine and / or an active imino group, an amino group of the polyamide polyamine, in addition to the polycarboxylic acid polymer. Polyamide polyamine modified products in which 0.1 to 10 moles of alkylene oxide having 2 to 4 carbon atoms are added per equivalent of amide residue can be contained Polyamide polyamine and / or polyamide polyamine modified product content ratio Is preferably in the range of the above polycarboxylic acid polymer: polyamide polyamine and / or polyamide polyamine modified product = 98 to 90% by mass: 2 to 10% by mass.

  The polyalkylene polyamines constituting the polyamide polyamine include ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, hexaethylene heptamine, or a high molecular polyethylene which is a mixture containing a large amount of ethylene units and nitrogen atoms. A mixture of polyamines, polymers of cyclic imines such as polyethyleneimine, polypropyleneimine, poly-3-methylpropylimine, poly-2-ethylpropylimine, polymers of unsaturated amines such as polyvinylamine and polyallylamine, etc. Can be mentioned. Furthermore, polyalkylene polyamines are cyclic imines such as ethyleneimine, propyleneimine, 3-methylpropylimine, 2-ethylpropylimine, unsaturated amides such as N-vinylacetamide, N-vinylformamide, N-vinylphthalimide, and unsaturated. It may be a copolymer of an imide and an unsaturated compound copolymerizable therewith. Examples of unsaturated compounds copolymerizable with cyclic imines, unsaturated amides, unsaturated imides, etc. include dimethylacrylamide, styrene, methyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid, styrene sulfonic acid and their salts, Cyclic sulfide compounds such as ethylene sulfide and propylene sulfide, cyclic ethers such as oxetane, mono- or bisalkyloxetane, mono- or bisalkylchloromethyloxetane, tetrahydrofuran, mono- or bisalkyltetrafluorofuran, 1,2-dioxofuran, trioxy Examples thereof include cyclic formals such as sofuran and N-substituted alkylimines such as N-methylethyleneimine.

Examples of the dibasic acid constituting the polyamide polyamine include fatty acids having 2 to 10 carbon atoms in total such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. Group saturated dibasic acids.
Derivatives thereof can also be used as dibasic acids, for example, dibasic acid anhydrides (eg, anhydrides of the above dibasic acids), dibasic acid esters (eg, monomethyl esters, monoethyl esters, monobutyl esters of the above dibasic acids) , Monopropyl ester, dimethyl ester, diethyl ester, dibutyl ester, dipropyl ester, etc.), or dibasic acid dihalides (dichloride, dibromide, diiodide, etc. of the dibasic acid).

The modified polyamidopolyamine is an alkylene oxide having 2 to 4 carbon atoms to the equivalent of 1 equivalent of the active imino group, amino group and amide residue of the polyamidopolyamine.
1 to 10 mol of added compound is shown. That is, examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and the like. These can be used alone or in combination. When two or more alkylene oxides are used, they are polymerized in a block shape. Alternatively, it may be polymerized randomly.

[Methods for producing each structural unit and polycarboxylic acid polymer]
In obtaining the polycarboxylic acid polymer of the present invention, the production method of 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 a by-product. It needs to be manufactured with attention paid to reducing the diol content. In addition, the polyalkylene oxide adduct of alcohol having a polymerization active group can be used as a raw material for polymerization regardless of the presence or absence of a purification process after production.
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 batch type methods. There are many cases.

  The structural unit (III) is produced by condensing a dibasic acid and a polyamide polyamine in accordance with a usual amidation method, and further forming an amide group with maleic acid, fumaric acid, and maleic anhydride, and if necessary, alkylene oxide A method of adding a polybasic acid, a polycondensate of a dibasic acid and a polyamide polyamine, or a method of forming an alkylene oxide-modified polyamide polyamine added with an alkylene oxide and grafting it to a polycarboxylic acid polymer, after forming a polyamide polyamine Examples thereof include a method of adding alkylene oxide to an aqueous polymer solution grafted to a polymer.

The finally obtained polycarboxylic acid polymer of the present invention has a weight average molecular weight (gel permeation chromatography method (hereinafter referred to as “GPC method”), converted to polyethylene glycol) in the range of 10,000 to 500,000. Is more preferable, and a weight average molecular weight in the range of 10,000 to 100,000 is desirable in order to exhibit excellent dispersion performance. In addition, the molecular weight can be controlled by adjusting the type and / or amount of radical polymerization initiator used in aqueous solution polymerization, but the molecular weight distribution can also be controlled by using a chain transfer agent together. It is.
In the present invention, the “polycarboxylic acid polymer” may be composed only of a polymer, but generally includes unreacted components and side reaction products generated in each polymerization step, alkylene oxide addition step and the like. Ingredients are also included.

[Uses of polycarboxylic acid polymers]
The polycarboxylic acid polymer and polymer composition of the present invention are aqueous dispersions of various solid powders by adjusting the neutralization rate of acid groups and adjusting the content of polyamide polyamine according to various applications. The performance can be widely exhibited as a dispersing agent. In addition, the polycarboxylic acid polymer of the present invention can be used as it is (without adding anything) as the above-mentioned dispersant, and a known and publicly used additive is appropriately adopted depending on various uses. It can also be used in the form of a combined admixture.

Specific examples of uses of the polycarboxylic acid polymer of the present invention include inorganic dispersants, pigment dispersants, hair styling agents, cosmetic base materials / additives, paints, pigment coatings using inorganic compound dispersion techniques. Additives, yield improvers, drainage improvers, excavation soil treatment agents, viscosity modifiers, ceramic binders, agricultural chemical additives, hydraulic composition additives, and so on. It is also suitable for repair agents, sludge treatment agents, ore granulation aids, and the like. It is also suitably used for pitch dispersants, paper strength enhancers, pigment coating binders, papermaking dispersants, deinking agents, detergent additives, powder detergent builders, and liquid detergent builders.
In addition, by utilizing the surfactant activity of the polycarboxylic acid polymer of the present invention, an antistatic agent, a film / fiber lubricant, a water retention agent, a fiber treatment agent, a dyeing improver, a fiber softener, a surfactant, It can also be used for emulsifiers, demulsifiers, bubble regulators, scale inhibitors, etc., and can be suitably used for a wide range of applications.

As an example of the above-mentioned application, additives for hydraulic compositions are described in detail. For example, additives for various concrete products, additives for grout, additives for concrete repair materials, additives for gypsum board, hydraulic self-leveling It can be used as an additive for cement and an additive for cement gypsum composite material.
And when using the polycarboxylic acid-type polymer of this invention as an additive for gypsum board, a well-known additive can be added and it can be set as the dispersing agent composition for gypsum. Examples of the additive include foaming agents such as alkyl sulfates, alkyl ether sulfates, and alkyl sulfonates, and foam stabilizers, antifoaming agents, water repellents, and adhesives. These may be used individually by 1 type, or may use 2 or more types together.
The additive for gypsum board may be used by adding 0.01 to 5% by mass (mass ratio of additive solid content) to the raw material gypsum. There are various methods for adding the additive for gypsum board, but a method of preparing a gypsum slurry by diluting and adding to water before kneading with gypsum is common. Examples of gypsum include anhydrous gypsum, hemihydrate gypsum, and dihydrate gypsum.
In addition, the additives used together with the additive for gypsum board include general-purpose water reducing agents, foaming agents, antifoaming agents, foam stabilizers, curing regulators, and the like, and glass fibers, carbon fibers, waste paper, A gypsum board is also produced together with virgin pulp or the like, or pearlite, foamed steel or the like which is a lightweight aggregate.

The polycarboxylic acid-based polymer and polymer composition of the present invention are particularly suitable among the above-mentioned applications. Dispersant for hydraulic composition, additive for gypsum, additive for concrete exterior board, water reducing agent for lightweight concrete It can be done.
Moreover, according to various uses, it can also use in the form of the admixture which employ | adopted and combined the publicly known and used additive suitably.

As a result of repeated studies on many polymers, the present inventors have found that a structural unit composed of an unsaturated alcohol alkylene oxide adduct in which a specific alkylene oxide is added at a specific position and ratio, and a structural unit composed of an unsaturated carboxylic acid. And a polycarboxylic acid polymer containing the polycarboxylic acid polymer and a polyamide polyamine and / or a polyalkylene oxide-modified polyamine as a constituent unit. It came to find out that it had the better dispersibility than.
It has not yet been elucidated how the above-mentioned excellent effects can be obtained, but in the unsaturated alcohol alkylene oxide adduct, two kinds of alkylene oxide to be added, ethylene oxide and propylene oxide or butylene oxide, were used. A certain amount of propylene oxide or butylene oxide is arranged 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 polymer structure. Therefore, when applied to an aqueous dispersion of various solid powders, it is considered that the collection and dispersibility of the powder particles are improved.
Furthermore, the use of fumaric acid and / or fumaric acid derivatives in the unsaturated carboxylic acid causes a change in the arrangement state of the acid groups in the polymer, thereby improving the dispersion performance of various solid powder aqueous dispersions. I think it led to an effect. However, there are various mechanisms other than the above. For example, the use of a fumaric acid compound can reduce unreacted monomers due to an increase in the polymerization rate of the polycarboxylic acid polymer, and control the molecular weight of the polymer. Together with the ease of use, we believe that the synergistic effect of these has led to an improvement in dispersion performance.

Next, based on an Example, this invention is demonstrated in detail. The present invention is obtained by the manufacturing method described above and is not limited to this example.
In addition, unless otherwise indicated,% and part described below represent mass% and mass part.

[Production Example A1 (Production of EO-added polyamide polyamine)]
In a reaction vessel equipped with a stirrer equipped with a nitrogen introduction tube, a thermometer, and a water sample tube with a condenser, 199 g of polyalkylene polyamine (product name: Polyate) manufactured by Tosoh Corporation and 68 g of adipic acid
Was stirred while introducing nitrogen, and then the temperature was raised to 160 ° C. The reaction was continued for 8 hours, and the reaction was terminated when the acid value reached 10. The amount of reaction dehydration was 17 g. Next, after adding 245 g of water and cooling to 60 ° C. as an aqueous solution, 89 g of ethylene oxide was added over 4 hours at the same temperature, followed by aging for 1 hour, and 584 g of an aqueous solution of EO-added polyamide polyamine A1 (solid content concentration: 58%) )

[Production Example A2 (Production of polyamide polyamine)]
In a reaction vessel equipped with a stirrer equipped with a nitrogen introduction tube, a thermometer, and a water sample tube with a condenser, 199 g of polyalkylene polyamine (product name: Polyate) manufactured by Tosoh Corporation and 68 g of adipic acid
Was stirred while introducing nitrogen, and then the temperature was raised to 160 ° C. The reaction was continued for 8 hours, and the reaction was terminated when the acid value reached 10. The amount of reaction dehydration was 17 g. Next, 250 g of water was added and cooled to 60 ° C. as an aqueous solution to obtain 500 g of an aqueous solution of polyamide polyamine A2 (solid content concentration: 50%).

[Production Example B1 (Production of polycarboxylic acid polymer)]
In a stainless steel autoclave equipped with a nitrogen introduction tube, a stirrer, and a thermometer, 402 g of 3-methyl-3-buten-1-ol 50EO2PO adduct (block adduct), 286 g of ion-exchanged water, 6.62 g of maleic anhydride, 59.fumaric acid 59. 6 g was charged with stirring. After sufficiently purging with nitrogen 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. Next, 26.7 g of polyamide polyamine A1 aqueous solution and 170 g of ion-exchanged water were added, and the mixture was further stirred for 1 hour. The polymerization solution was cooled to 50 ° C., neutralized with 25.0 g of 48% aqueous sodium hydroxide solution, and 998 g of an aqueous solution of polycarboxylic acid polymer B1 (solid content concentration: 50%, weight average molecular weight: 26,000). Obtained.

[Production Example B2 (Production of polycarboxylic acid polymer)]
In a stainless steel autoclave equipped with a nitrogen introduction tube, a stirrer and a thermometer, 402 g of 3-methyl-3-buten-1-ol 50EO2PO adduct (block adduct), 286 g of ion-exchanged water, 33.1 g of maleic anhydride, 33.fumaric acid 33. 1 g was charged with stirring. After sufficiently purging with nitrogen 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. Next, 26.7 g of polyamide polyamine A1 aqueous solution and 170 g of ion-exchanged water were added, and the mixture was further stirred for 1 hour. The polymerization solution was cooled to 50 ° C., neutralized with 25.0 g of 48% aqueous sodium hydroxide solution, and 998 g of an aqueous solution of polycarboxylic acid polymer B2 (solid content concentration: 50%, weight average molecular weight: 29,000). Obtained.

[Production Example B3 (Production of polycarboxylic acid polymer)]
3-methyl-3-buten-1-ol 50EO5PO adduct 402 g (block adduct), ion-exchanged water 286 in a stainless steel autoclave with a nitrogen introduction tube, a stirrer, and a thermometer
g, maleic anhydride 6.62 g and fumaric acid 59.6 g were charged with stirring. After sufficiently purging with nitrogen 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. Next, 30.4 g of polyamide polyamine A2 aqueous solution and 166 g of ion-exchanged water were added, and the mixture was further stirred for 1 hour. The polymerization solution was cooled to 50 ° C., neutralized with 25.0 g of 48% aqueous sodium hydroxide solution, and 998 g of an aqueous solution of polycarboxylic acid polymer B3 (solid content concentration: 50%, weight average molecular weight: 31,000). Obtained.

[Production Example B4 (Production of polycarboxylic acid polymer)]
In a stainless steel autoclave equipped with a nitrogen introduction tube, a stirrer, and a thermometer, 402 g of 3-methyl-3-buten-1-ol 50EO2PO adduct (block adduct), 286 g of ion-exchanged water, 59.6 g of maleic anhydride, 6. Charge 62 g with stirring. After sufficiently purging with nitrogen 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. Next, 26.7 g of polyamide polyamine A1 aqueous solution and 170 g of ion-exchanged water were added, and the mixture was further stirred for 1 hour. The polymerization solution was cooled to 50 ° C., neutralized with 25.0 g of 48% sodium hydroxide aqueous solution, and 998 g of an aqueous solution of polycarboxylic acid polymer B4 (solid content concentration: 50%, weight average molecular weight: 30,000). Obtained.

[Production Example B5 (Production of polycarboxylic acid polymer)]
Nitrogen inlet tube, stirrer, stainless steel autoclave with thermometer 402 g 3-methyl-3-buten-1-ol 50EO0.5PO adduct (block adduct), 286 g ion-exchanged water, 33.1 g maleic anhydride, fumaric acid 33.1 g was charged with stirring. After sufficiently purging with nitrogen 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. Next, 30.4 g of polyamide polyamine A2 aqueous solution 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., and then 4 g of ethylene oxide is added to the polymerization solution. After aging at the same temperature for 1 hour, the solution is neutralized with 25.0 g of a 48% aqueous sodium hydroxide solution to obtain a polycarboxylic acid polymer. 1,002 g of an aqueous solution of B5 (solid content concentration: 50%, weight average molecular weight: 29,000) was obtained.

[Production Example B6 (Production of polycarboxylic acid polymer)]
In a stainless steel autoclave with a nitrogen inlet tube, a stirrer, and a thermometer, 402 g of 3-methyl-3-buten-1-ol 50EO2PO adduct (block adduct), 286 g of ion-exchanged water, 6.62 fumaric acid, 59. maleic anhydride. 6 g was charged with stirring. After sufficiently purging with nitrogen 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., 25.0 g of 48% sodium hydroxide aqueous solution and 164 g of ion-exchanged water were added, and the mixture was further stirred for 1 hour. 965 g (concentration 50%, weight average molecular weight: 37,000) of an aqueous solution of polycarboxylic acid polymer B6 was obtained.

[Production Example B7 (Production of polycarboxylic acid polymer)]
In a stainless steel autoclave equipped with a nitrogen introduction tube, a stirrer, and a thermometer, 402 g of 3-methyl-3-buten-1-ol 50EO2PO adduct (block adduct), 286 g of ion-exchanged water, 6.62 g of maleic anhydride, 59.fumaric acid 59. 6 g was charged with stirring. After sufficiently purging with nitrogen 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., 25.0 g of 48% aqueous sodium hydroxide solution and 164 g of ion-exchanged water were added, and the mixture was further stirred for 1 hour. 965 g of aqueous solution of polycarboxylic acid polymer B7 (solid content concentration: 50%, weight average molecular weight: 24,000) was obtained.

[Production Example C1 (Production of polycarboxylic acid polymer)]
A stainless steel autoclave equipped with a nitrogen introduction tube, a stirrer and a thermometer was charged with stirring with 402 g of 3-methyl-3-buten-1-ol 2PO50EO adduct (block adduct), 286 g of ion-exchanged water and 66.2 g of maleic anhydride. It is. After sufficiently purging with nitrogen 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., 165 g of ion exchanged water and 25.0 g of 48% aqueous sodium hydroxide solution were added, and the mixture was further stirred for 1 hour. To obtain 966 g of an aqueous solution of the polycarboxylic acid polymer C1 (solid content concentration: 50%, weight average molecular weight: 29,000).

[Production Example C2 (Production of polycarboxylic acid polymer)
A four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introducing tube, and a reflux condenser was charged with 395 g of water, and the inside of the flask was purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. Next, a mixture of 250 g of methoxypolyethylene glycol methacrylate (average number of moles of ethylene oxide added 5 mol), 62.5 g of methacrylic acid, 9.4 g of 10% aqueous solution of thioglycolic acid, and 9.4 g of sodium persulfate 10% solution was 120. After being required and dropped, the mixture was stirred at the same temperature for 4 hours to complete the polymerization reaction. After cooling the reaction liquid to 50 ° C., it was neutralized with 48% caustic soda to pH 7 to obtain 837 g of an aqueous solution of polycarboxylic acid polymer C2 (solid content concentration: 40%, weight average molecular weight: 26,000). Obtained.

[Performance test of polycarboxylic acid polymer]
<Gypsum dispersibility>
Polycarboxylic acid polymers B1 to B7 and C1 and C2 of the above production examples, and as a comparative example 3, melamine sulfonic acid soda formalin condensate (MSFF) is accurately weighed on a solid basis, and water is added to give a total amount of 65 g. The kneaded water was adjusted so that To this was added 100 g of cherry-grilled gypsum Class A (manufactured by Yoshino Gypsum Co., Ltd.) (water gypsum ratio 65%), and kneaded for 20 seconds with a small juicer mixer. A φ50 mm × H50 mm cylindrical hollow cylinder was prepared in the center of a urethane board (35 cm × 35 cm), and the kneaded gypsum slurry was poured until the container was full. Thereafter, the hollow cylinder was pulled up in a direction perpendicular to the urethane board, and the spread of the gypsum slurry was measured. The diameter that was considered to be the maximum spread and the diameter perpendicular to it were measured, and the average value was used as an index of dispersibility.

<Gypsum curing delay>
As in the dispersibility test, polycarboxylic acid polymers B1 to B7, C1 and C2, and melamine sulfonic acid soda formalin condensate (MSFF) are weighed in a required amount based on the solid content, and kneading water is added in total. It adjusted so that it might be 162g. To this was added 250 g of cherry-grilled gypsum class A (Yoshino Gypsum Co., Ltd.) (water gypsum ratio 65%), and kneaded for 10 seconds with a small juicer mixer. After mixing, the finished gypsum slurry is immediately transferred to a paper cup. A digital thermometer is inserted here, and the exothermic temperature associated with the setting of the gypsum is measured in units of 1 minute. Time was used as an index of cure retardation.
The results obtained are shown in Table 2.

From the results of Examples 1 to 7 shown in Table 2, when the polycarboxylic acid polymer of the present invention was added to the gypsum slurry, excellent dispersibility was shown as compared with the comparative example. Moreover, regarding the retarding property, a better result was obtained as compared with the comparative example.
On the other hand, Comparative Example 1 in which no PO group was blocked at the end of the alkylene oxide chain resulted in inferior dispersibility and cure retardance compared to the Examples, and the conventional polycarboxylic acid polymer Although the corresponding comparative example 2 showed the comparatively excellent result in the dispersibility, the result which produced the hardening delay was obtained.
Further, Comparative Example 3 corresponding to a conventional dispersant containing formaldehyde obtained a result that the dispersibility was inferior although the curing was quick.

<Gypsum colorability>
Polycarboxylic acid polymers B1, B6 and B7 of the above-mentioned production examples, (meth) acrylic acid-meth PEG (meth) acrylate polymer (PC) as Comparative Example 4 and sodium naphthalene sulfonate (NSF) as Comparative Example 5 ) Was accurately weighed on a solid basis, water was added, and the kneaded water was adjusted to a total amount of 165 g. To this was added 300 g of cherry-gloss baked gypsum class A (Yoshino Gypsum Co., Ltd.) (water gypsum ratio 55%), and kneaded 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 left at 80 ° C. for 24 hours. The color of the solidified gypsum lump surface after 24 hours was visually confirmed to evaluate the colorability.
The obtained results are shown in Table 3.

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, the case of 0.4% addition is equivalent to the case of no additive. Even when 0.8% was added, there was a slight coloration, but the result was clearly superior in non-coloring properties as compared with Comparative Examples 4 and 5.
Therefore, the polycarboxylic acid-based polymer of the present invention has an accompanying effect of preventing a decline in product value due to coloring when used for producing a gypsum product (reinforced board, ceramic gypsum, etc.) in which the gypsum surface is exposed. Have.

<Extrudability as an additive for concrete exterior panels>
Using the polycarboxylic acid polymers B1, B3, and B5 of the above-mentioned production examples and sodium naphthalene sulfonate (NSF), an extrudability test was conducted as an additive for a concrete exterior board with the composition shown in Table 4 below. .
The kneading mixture for the concrete exterior board uses a Hobart mixer, and the water prepared by adding each polycarboxylic acid polymer or sodium naphthalene sulfonate in advance to cement, silica sand, pulp, methylcellulose, Kneaded 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 results obtained are shown in Table 5.

  As is clear from the results of Examples 11 to 13 shown in Table 5, when the polycarboxylic acid polymer of the present invention is used, the extrusion speed is about as compared with the case where NSF (sodium naphthalene sulfonate) is used. The result was about twice as fast, that is, improved extrudability.

<Hardness and bubble entrapment as water reducing agent for lightweight concrete (ALC)>
Using the polycarboxylic acid polymers B1, B3, and B5 of the above-mentioned production examples, (meth) acrylic acid-methPEG (meth) acrylate polymer (PC), and sodium naphthalene sulfonate (NSF), the following Table 6 The mortar slurry was evaluated for curability and bubble entrapment with the formulation shown in FIG.
For the mortar slurry, a mixer equipped with a simple stirring blade was used, and water prepared by adding each polycarboxylic acid polymer, PC or NSF in advance to cement, quartzite, quicklime, gypsum, and aluminum was added. Kneaded for 2 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 the mold could be removed after a predetermined time (90 minutes). Thereafter, the cured mortar cross section was cut with a piano wire, and the embedding property of bubbles was visually evaluated.
The results obtained are shown in Table 7.

From the results of Examples 14 to 16 shown in Table 7, when the polycarboxylic acid-based polymer of the present invention is used, it can be cured and demolded within a predetermined time, and no entrapment of bubbles occurs. Test results were obtained.
That is, since the polycarboxylic acid polymer of the present invention satisfies both the curability and the bubble entrapment property, it was found useful as a water reducing agent for ALC.

On the other hand, in Comparative Example 7 in which a general-purpose polycarboxylic acid-based polymer was blended, demolding within a predetermined time could not be performed due to curing delay, and in Comparative Example 8 in which naphthalene sulfonic acid soda was blended, the curability was Although excellent, the viscosity was increased due to low water reduction, and the result was that coarse bubbles would not escape.

Japanese Patent Laid-Open No. 62-68806 JP 11-314953 A JP 2003-192722 A JP 2005-46781 A

Claims (3)

In a polycarboxylic acid polymer comprising a structural unit derived from an unsaturated alcohol alkylene oxide compound and a structural unit derived from an unsaturated carboxylic acid compound, a graft chain bonded to the main chain skeleton of the polymer Includes a polyalkylene oxide chain mainly composed of ethylene oxide, and the terminal portion of the polyalkylene oxide chain is a carbon atom at a ratio of 0.1 to 30 mol% with respect to the total molar amount of alkylene oxide of the graft chain. Having an alkylene oxide of formula 3 or 4;
In addition to the structural unit (I) represented by the following formula (I) and the structural unit (II) represented by the formula (II), the polycarboxylic acid polymer is further represented by the following formula (III). Comprising the structural unit (III),
The terminal portion of the polyalkylene oxide chain in the structural unit (I) has an alkylene oxide having 3 or 4 carbon atoms in a proportion of 0.1 to 30 mol% with respect to the total molar amount of the alkylene oxide chain. A polycarboxylic acid polymer.

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

^{(Wherein, R 5, R 6, R} 7, R 8 are each independently hydrogen atom or a hydrocarbon group having a carbon number of 1 to 22, -COOH, -COOM, or represents -COOY, or an ^{R 5} R ⁶ , or R ⁷ and R ⁸ together form an acid anhydride, M represents an alkali metal, alkaline earth metal, ammonium, alkanolamine, and Y represents a hydrocarbon group having 1 to 22 carbon atoms. Or-(AO) c-R ⁹ , AO represents an alkylene oxide group having 2 to 4 carbon atoms, c represents an average added mole number of alkylene oxide and represents a number of 1 to 200, and R ⁹ represents a hydrogen atom. Or a hydrocarbon group having 1 to 22 carbon atoms.)

(In the formula, Z is a polyamide polyamine obtained by condensing a dibasic acid and a polyalkylene polyamine and / or an alkylene oxide having 2 to 4 carbon atoms with respect to 1 equivalent of an active imino group, amino group or amide residue of the polyamide polyamine. Represents a group bonded to the carbon atom of the main chain through an amide bond. In addition to the polycarboxylic acid polymer according to claim 1, a polyamide polyamine obtained by condensing a dibasic acid and a polyalkylene polyamine and / or an active imino group of the polyamide polyamine,
A polycarboxylic acid polymer composition comprising a modified polyamide polyamine obtained by adding 0.1 to 10 moles of an alkylene oxide having 2 to 4 carbon atoms to 1 equivalent of an amino group and an amide residue object. A polycarboxylic acid polymer composition comprising a polycarboxylic acid polymer and a polyamide polyamine modified product,
The polycarboxylic acid polymer is configured to include 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 portion of the polyalkylene oxide chain is based on the total molar amount of alkylene oxide of the graft chain. Having an alkylene oxide of 3 or 4 carbon atoms in a proportion of 0.1 to 30 mol%,
The polycarboxylic acid polymer includes a structural unit (I) represented by the following formula (I) and a structural unit (II) represented by the formula (II):
The terminal portion of the polyalkylene oxide chain in the structural unit (I) has an alkylene oxide having 3 or 4 carbon atoms in a proportion of 0.1 to 30 mol% with respect to the total molar amount of the alkylene oxide chain. A polycarboxylic acid polymer,

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

^{(Wherein, R 5, R 6, R} 7, R 8 are each independently hydrogen atom or a hydrocarbon group having a carbon number of 1 to 22, -COOH, -COOM, or represents -COOY, or an ^{R 5} R ⁶ , or R ⁷ and R ⁸ together form an acid anhydride, M represents an alkali metal, alkaline earth metal, ammonium, alkanolamine, and Y represents a hydrocarbon group having 1 to 22 carbon atoms. Or-(AO) c-R ⁹ , AO represents an alkylene oxide group having 2 to 4 carbon atoms, c represents an average added mole number of alkylene oxide and represents a number of 1 to 200, and R ⁹ represents a hydrogen atom. Or a hydrocarbon group having 1 to 22 carbon atoms.)
The polyamide polyamine modified product is a polyamide polyamine obtained by condensing a dibasic acid and a polyalkylene polyamine and / or an alkylene having 2 to 4 carbon atoms with respect to 1 equivalent of an active imino group, amino group or amide residue of the polyamide polyamine. It is a polyamide polyamine modified product added with 0.1 to 10 moles of oxide,
Polycarboxylic acid polymer composition.