WO2021085376A1 - Additive for hydraulic materials - Google Patents

Abstract

The present invention provides an additive for hydraulic materials that, when used in a hydraulic material composition, can bring about a satisfactory expression of both adherence by the paste fraction to the aggregate and dispersibility for the hydraulic material composition. The present invention is an additive for hydraulic materials that contains a nitrogenous compound (A), the additive for hydraulic materials being characterized in that the nitrogenous compound (A) has a nitrogen atom content of at least 6.8 mass% relative to 100 mass% for the nitrogenous compound (A); the additive for hydraulic materials additionally contains a compound (B) that has at least one selected from the group consisting of a carboxyl group, sulfonic acid group, phosphoric acid group, groups that are salts of the same, and a phosphate ester group; and the additive for hydraulic materials is used for sprayed concrete applications.

Description

Additives for hydraulic materials

The present invention relates to additives for hydraulic materials. More specifically, the present invention relates to additives for hydraulic materials useful for applications such as sprayed mortar and concrete.

In civil engineering and construction work such as primary lining of tunnels, protection and reinforcement of rock slopes and slopes, and repair and reinforcement of concrete structures, the spraying method of spraying concrete (mortar) on the construction surface is widely used. .. Among the spraying methods, for example, in the wet method, materials other than the quick-setting admixture (hydraulic material, aggregate, water, additives for hydraulic material, etc.) are mixed, and then compressed air or a pump is used to reach the nozzle (discharge port). It is pumped, mixed with the quick-setting admixture sent by another pump just before the nozzle, and sprayed onto the construction surface. In the spraying method, dust generated during construction has become a problem in the working environment, and techniques for reducing dust have been conventionally developed. For example, Patent Document 1 discloses a dust reducing agent composed of a poly (meth) acrylate quaternized product. Patent Documents 2 and 3 disclose spraying materials containing cement concrete containing a quaternary ammonium salt compound.
Patent Document 4 discloses a concrete spraying method in which a cationic polymer in an aqueous solution having a cement weight ratio of 0.02% to 0.5% is dissolved in water and mixed with concrete at the time of spraying. Patent Document 5 describes a water-soluble polymer compound obtained by polymerizing an acrylic monomer represented by a predetermined structure or another acrylic monomer represented by a predetermined structure and another copolymerizable therewith. A dust reducing agent for sprayed acrylic, which is made of a water-soluble polymer compound obtained by copolymerizing with a monomer, is disclosed.

Japanese Unexamined Patent Publication No. 2003-292359 Japanese Unexamined Patent Publication No. 2011-46574 Japanese Unexamined Patent Publication No. 2011-84440 JP-A-59-109663 Japanese Unexamined Patent Publication No. 62-17507

As described above, various additives for hydraulic materials used in the spraying method such as a dust reducing agent are disclosed. In the spraying method, in addition to reducing dust, in order to reduce the loss (rebound amount) due to rebound when sprayed on the construction surface, the paste content in mortar, concrete, etc. has high adhesiveness to the aggregate. Is required. However, the additive for hydraulic material used in the conventional spraying method is sufficient in terms of both the adhesiveness of the paste to the aggregate and the dispersibility of the hydraulic material composition when used in the hydraulic material composition. It wasn't.

The present invention has been made in view of the above situation, and when used in a hydraulic material composition, both the adhesiveness of the paste to the aggregate and the dispersibility of the hydraulic material composition are sufficiently exhibited. It is an object of the present invention to provide an additive for a hydraulic material which can be used.

The present inventor has examined various additives for water-hard materials used in the spraying method, and found that a nitrogen-containing compound having a specific nitrogen atom content, a carboxyl group, a sulfonic acid group, a phosphoric acid group, and these. By using a compound having at least one selected from the group consisting of a salt group and a phosphate ester group in combination, the water-hard material composition is imparted with dispersibility, and the paste component adheres to the aggregate. The present invention has been reached by finding that the above-mentioned problems can be solved brilliantly.

That is, the present invention is an additive for a water-hard material containing a nitrogen-containing compound (A), wherein the nitrogen-containing compound (A) has a nitrogen atom content ratio of 100% by mass of the nitrogen-containing compound (A). The compound having at least 8% by mass and having at least one selected from the group consisting of a carboxyl group, a sulfonic acid group, a phosphoric acid group, a salt group thereof, and a phosphoric acid ester group. (B) is an additive for a water-hard material used for sprayed concrete applications.

The compound (B) is derived from at least one selected from the group consisting of an unsaturated carboxylic acid-based monomer (B1), a sulfonic acid-based monomer (B2) and a phosphoric acid-based monomer (B3). It is preferably a polymer having a structural unit.

The unsaturated carboxylic acid-based monomer (B1) includes (meth) acrylic acid, crotonic acid, isocrotonic acid, citraconic acid, 3-methylcrotonic acid, 2-methyl-2-pentenoic acid, α-hydroxyacrylic acid, and the like. And these monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts; maleic acid, itaconic acid, crotonic acid, citraconic acid, fumaric acid, and these monovalent metal salts, divalent metal salts, Ammonium salts and organic amine salts, their anhydrides, half-esters of these unsaturated dicarboxylic acids with alcohols with 1-22 carbon atoms or glycols with 2-4 carbon atoms, these unsaturated dicarboxylic acids and 1-carbon atoms. It is preferably at least one selected from the group consisting of halfamides with 22 amines.

The compound (B) is preferably a polymer having a structural unit (b1) derived from an unsaturated carboxylic acid-based monomer (B1).

The compound (B) preferably further has a structural unit (c) derived from the (poly) alkylene glycol-based monomer (C).

The compound (B) is a group consisting of a polyalkylaryl sulfonate compound, a melamine formalin resin sulfonate compound, an aromatic amino sulfonate compound, a lignin sulfonate compound, and a polystyrene sulfonate compound. It is preferably at least one selected from the above.

The compound (B) preferably has a weight average molecular weight of 10 to 5 million.

The nitrogen-containing compound (A) is a structural unit having an alkylene group and an amino group and / or a structural unit derived from a nitrogen atom-containing monomer (A1) having a nitrogen atom content of 6.8% by mass or more (A1). It is preferably a polymer having a1).

The nitrogen atom-containing monomer (A1) has the following formulas (3) to (6);

(In formulas (3) to (6), R ² to R ⁴ represent the same or different alkyl groups having a hydrogen atom or 1 to 5 carbon atoms, and X represents a direct bond or a divalent linking group. In formulas (3) and (4), R ⁵ and R ⁶ represent hydrogen atoms or hydrocarbon groups having 1 to 12 carbon atoms, which are the same or different. In formulas (5) and (6), R ⁷ ~ R ⁹ represents the same or different hydrocarbon groups having 1 to 12 carbon atoms ^{. Y −} represents an anion.) A monomer represented by any of the above; a nitrogen-containing heterocyclic group-containing simple substance. Quantum; preferably at least one selected from the group consisting of N-vinylformamide.

The nitrogen-containing compound (A) has at least one selected from the group consisting of a structural unit having an alkylene group and an amino group, a structural unit derived from an allylamine-based monomer, and a structural unit derived from a dialkylamine. It is preferably a polymer.

The nitrogen-containing compound (A) is selected from the group consisting of polyethyleneimine, a polymer having a structural unit derived from an allylamine-based monomer, and a polymer having a structural unit derived from a reaction product of an epoxy compound and an amine compound. It is preferable that it is at least one kind.

The nitrogen-containing compound (A) preferably has a weight average molecular weight of 10 to 5 million.

In the additive for hydraulic materials, the ratio of the nitrogen-containing compound (A) to 100% by mass of the compound (B) is preferably 0.1 to 200% by mass.

The present invention is also a hydraulic material composition containing the above additive for a hydraulic material and a hydraulic material.

The present invention is also a method in which the additive for a hydraulic material is sprayed onto a construction surface together with the hydraulic material.

The additive for a hydraulic material of the present invention has the above-mentioned structure, and can improve the adhesiveness of the paste to the aggregate while imparting dispersibility to the hydraulic material composition. It can be suitably used for concrete and the like.

Hereinafter, preferred embodiments of the present invention will be specifically described, but the present invention is not limited to the following description, and can be appropriately modified and applied without changing the gist of the present invention. A form in which two or three or more of the individual preferred forms of the present invention described below are combined also falls under the preferred form of the present invention.

The additive for a water-hard material of the present invention comprises at least one selected from the group consisting of the nitrogen-containing compound (A), a carboxyl group, a sulfonic acid group, a phosphoric acid group, a group of salts thereof, and a phosphoric acid ester group. The compound (B) having the compound (B) (hereinafter, also referred to as the compound (B)) is included. The anionic (acidic) group in the compound (B) and the cationic (basic) nitrogen-containing compound (A) interact electrostatically to weakly agglomerate the cement particles and adhere to the hydraulic material composition. It is presumed that sex can be imparted. Further, since the compound (B) having an anionic group contributes to the dispersibility of the cement particles, the hydraulic material composition has excellent dispersibility. Further, since the nitrogen-containing compound (A) can suppress an increase in the plastic viscosity of the hydraulic material composition while imparting adhesiveness to the hydraulic material composition, the hydraulic material composition is sprayed. The influence on the pumping property (hydraulic material composition can pass through the pipe) can be sufficiently suppressed.

<Nitrogen-containing compound (A)>
The nitrogen-containing compound (A) has a nitrogen atom content of 6.8% by mass or more with respect to 100% by mass of the nitrogen-containing compound (A). It is preferably 7 to 70% by mass, more preferably 8 to 50% by mass, and further preferably 8.5 to 35% by mass. If the content ratio of nitrogen atoms is in the above preferable range, the adhesiveness of the hydraulic material composition can be further improved.
The content ratio of nitrogen atoms in the nitrogen-containing compound (A) can be calculated from the composition formula of the compound, but it can also be measured by elemental analysis when the composition formula is unknown.

The weight average molecular weight of the nitrogen-containing compound (A) is preferably 10 to 5 million, preferably 10 to 1 million.
Thereby, the adhesiveness of the hydraulic material composition can be further improved.
It is more preferably 3,000 to 800,000, further preferably 5,000 to 700,000, even more preferably 10,000 to 600,000, even more preferably 50,000 to 500,000, and particularly preferably 100,000 to 40,000. It is ten thousand.
Further, from the viewpoint of cost performance, it is also preferable that the weight average molecular weight is 50 to 5 million. It is more preferably 50,000 to 3 million, still more preferably 100,000 to 3 million, particularly preferably 200,000 to 2 million, and most preferably 300,000 to 1 million.
The weight average molecular weight of the nitrogen-containing compound (A) is a value measured by the following method.
<Molecular weight measurement method>
The weight average molecular weight and the number average molecular weight in the present invention can be measured by gel permeation chromatography (GPC) by a known method using pullulan as a standard substance. In the present invention, the following conditions are adopted as the measurement conditions for GPC.
Measuring device; Column used by Shimadzu Corporation; SHODEX OHpak SB-807HQ (2 pcs) + SB-806M / HQ (2 pcs) manufactured by Showa Denko KK
Eluent: Prepared to 0.5 mol% -sodium nitrate, 0.5 mol% -acetic acid Standard substance; Pullulan P-82 (manufactured by Wako Pure Chemical Industries, Ltd.)
Detector; Differential refractometer (manufactured by Shimadzu Corporation)
Flow velocity; 0.4 ml / min.

The nitrogen-containing compound (A) is not particularly limited as long as the content ratio of nitrogen atoms satisfies the above range. For example, polyalkyleneimine and its derivatives; the content ratio of nitrogen atoms is 6.8% by mass or more. A polymer (α1) having a structural unit (a1) derived from the nitrogen atom-containing monomer (A1) (hereinafter, also referred to as a polymer (α1)), and a structure derived from a reaction product of an epoxy compound and an amine compound. A polymer having a unit and the like can be mentioned.

The polyalkyleneimine may have a structural unit having an alkylene group and an amino group, and may have the following formulas (1) and / or (2);

(In the formula, R ¹ represents the same or different alkylene group having 2 to 6 carbon atoms.) It may have a structural unit represented by the same or different.
Specific examples of the alkylene group include an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, and an n-hexylene group.
The alkylene group preferably has 2 to 4 carbon atoms, more preferably 2 to 3 carbon atoms, and most preferably 2 carbon atoms.

Examples of the polyalkyleneimine include polyethyleneimine, polypropyleneimine, polybutyleneimine and the like, such as ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine and 1,1-dimethylethyleneimine. It can be obtained by polymerizing one or more of alkyleneimines having 2 to 6 carbon atoms by a commonly used method.

The polyalkyleneimine derivative is not particularly limited as long as the content ratio of nitrogen atoms and the weight average molecular weight satisfy the above ranges, and for example, a compound obtained by quaternizing the amino group of polyalkyleneimine or polyalkyleneimine has. Examples thereof include compounds in which a substituent is introduced into an amino group or an alkylene group.
The quaternizing agent used for quaternization of the amino group is not particularly limited, but is not particularly limited, but is an alkyl halide such as methyl chloride, ethyl chloride, methyl bromide, methyl iodide; dimethyl sulfate, diethyl sulfate, di-n sulfate. -General alkylating agents such as alkyl sulfates such as propyl can be mentioned.
Examples of the substituent include a hydroxyl group, an alkoxy group, a carboxyl group, an acyl group, a sulfonic acid group, a phosphoric acid group, an ether group, a thioether group, a carbonyl group, an ester group and the like.

The nitrogen atom-containing monomer (A1) is not particularly limited as long as the nitrogen atom content is 6.8% by mass or more with respect to 100% by mass of the nitrogen-containing compound (A). (A1) The content ratio of nitrogen atoms to 100% by mass is preferably 6.8% by mass or more. Specific examples of the nitrogen atom-containing monomer (A1) include the following formulas (3) to (6);

(In formulas (3) to (6), R ² to R ⁴ represent the same or different alkyl groups having a hydrogen atom or 1 to 5 carbon atoms, and X represents a direct bond or a divalent linking group. In formulas (3) and (4), R ⁵ and R ⁶ represent hydrogen atoms or hydrocarbon groups having 1 to 12 carbon atoms, which are the same or different. In formulas (5) and (6), R ⁷ ~ R ⁹ represents the same or different hydrocarbon groups having 1 to 12 carbon atoms; Y ⁻ represents an anion.) A monomer represented by any of the following; imidazole group, pyrazole group, imidazoline. Examples thereof include a nitrogen-containing heterocyclic group-containing monomer such as a group, a triazole group, a tetrazole group, a pyridazine group, a pyrimidine group, a pyrazine group, a purine group, a benzotriazole group and a pteridine group; N-vinylformamide and the like.

^{R 2} to R ⁴ in the above formulas (3) to (6) represent a hydrogen atom or a methyl group, but R ² and R ³ are preferably hydrogen atoms. In the above formulas (3) to (5), R ⁴ is preferably a hydrogen atom or a methyl group, more preferably a methyl group, and in the above formula (6), R ⁴ is preferably a hydrogen atom.

The ^{hydrocarbon groups in R 5} to R ⁹ may have a chain structure or a ring structure, but a chain structure is preferable. When the hydrocarbon group has a chain structure, it may be linear or have a branch.
The hydrocarbon group is preferably an alkyl group, an alkenyl group or an aryl group, more preferably an alkyl group or an alkenyl group, and even more preferably an alkyl group.
The number of carbon atoms of the hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, particularly preferably 1 to 5, and most preferably 1 to 2.
In the above formula (3) and (4), at least one of ^{R 5} and ^{R 6} are preferably a hydrocarbon group having 1 to 12 carbon atoms, ^{R 5} and both carbons 1 of ^{R 6} More preferably, it is a hydrocarbon group of ~ 12. That is, among the primary to tertiary amino groups, a tertiary amino group is preferable.

^{Y −} in the above formulas (4) to (6) is not particularly limited, but is, for example, hydroxide ion; halide ion such as chlorine ion, bromine ion, iodine ion; dimethyl sulfate ion, diethyl ion sulfate, disulfate sulfate. Alkyl sulfate ions such as -n-propyl ion; ions of organic acids such as acetate ion and the like can be mentioned.
^{Y −} in the above formula (4) is preferably an ion of an organic acid.
^{Y −} in the above formula (5) or (6) is preferably a hydroxide ion; a halide ion or an alkyl sulfate ion.

The divalent linking group in the above formulas (3) to (6) is not particularly limited, but for example, an alkylene group having 1 to 12 carbon atoms such as a methylene group, an ethylene group and a propylene group, the following formula (7);

(In the formula, h is 0 or 1. i represents an integer of 0 to 12.), The following formula (8);

(In the formula, j represents an integer of 0 to 4) and the following formula (9);

(In the formula, k represents an integer of 1 to 10).
In the above formula (7), h is preferably 1, i is preferably 1 to 6, and more preferably 1 to 4.
J in the above formula (8) is preferably 1 to 4, more preferably 1 to 2.
K in the above formula (9) is preferably 1 to 8, and more preferably 1 to 5.

As X in the above formulas (3) to (5), an alkylene group having 1 to 12 carbon atoms and a structure represented by the above formula (7) or (9) are preferable.
The X in the above formula (6) is preferably an alkylene group having 1 to 12 carbon atoms or a structure in which h is 1 in the above formula (7).
The number of carbon atoms of the alkylene group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 or 2. When X is a methylene group, R ² and R ³ are hydrogen atoms, and R ⁴ is a hydrogen atom or a methyl group, the monomer represented by any of the above formulas (3) to (6) is , It becomes an allylamine-based monomer having a (meth) allyl group and an amino group.
On the other hand, when X is a structure in which h is 1 in the above formula (7), R ² and R ³ are hydrogen atoms, and R ⁴ is a hydrogen atom or a methyl group, the above formulas (3) to (6). ) Is an amino group-containing (meth) acrylate-based monomer having a (meth) acrylate group and an amino group. The form in which the nitrogen atom-containing monomer (A1) is an allylamine-based monomer and / or an amino group-containing (meth) acrylate-based monomer is one of the preferred embodiments of the present invention.

Specifically, as the monomer represented by any of the above formulas (3) to (6), N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N, N-dialkylamino group-containing (meth) acrylates such as N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, and monomers obtained by adding a quaternizing agent to the above monomers or these. Neutralized with acids such as hydrochloric acid and acetic acid; acrylamide and derivatives thereof; N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) With N, N-dialkylamino group-containing (meth) acrylamides such as acrylamide, N, N-diethylaminopropyl (meth) acrylamide, monomers added with a quaternizing agent to the above monomers, or acids such as hydrochloric acid and acetic acid thereof. Neutralized products; monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, monoethylaminopropyl (meth) acrylate, 2- (tert-butylamino) (meth) acrylate. ) Monoalkylamino group-containing (meth) acrylates such as ethyl and neutralized products of these with acids such as hydrochloric acid and acetic acid; monomethylaminoethyl (meth) acrylamide, monoethylaminoethyl (meth) acrylamide, monomethylaminopropyl (meth) ) Monoalkylamino group-containing (meth) acrylamides such as acrylamide and monoethylaminopropyl (meth) acrylamide and neutralized products of these with acids such as hydrochloric acid and acetic acid; Meta) Esters of acrylic acid and alkanolamine and neutralized products of these with acids such as hydrochloric acid and acetic acid; N, N-diallylalkylamine, diallyldimethylammonium chloride and the like, to which a quaternizing agent is added. The monomer or its neutralized product with an acid such as hydrochloric acid or acetic acid; 1-allyloxy-3-dibutylamino-2-ol, 1-allyloxy-3-diethanolamino-2-ol, etc. having 2 to 8 carbon atoms. An addition reaction product of an unsaturated monomer having a cyclic ether-containing group and an amine compound having 1 to 24 carbon atoms, a monomer having a quaternizing agent added thereto, or a neutralized product thereof with an acid such as hydrochloric acid or acetic acid. Etc; Vinyl amine , Allylamine, N-methylvinylamine, 1-propene-2-amine, a monomer to which a quaternizing agent is added, or a neutralized product thereof with an acid such as hydrochloric acid or acetic acid.

The amine compound having 1 to 24 carbon atoms is not particularly limited as long as it can react with the cyclic ether structure of an unsaturated monomer having an amino group and having a cyclic ether-containing group having 2 to 8 carbon atoms. The amine compound having 1 to 24 carbon atoms preferably has 1 to 20 carbon atoms, and more preferably 1 to 16 carbon atoms. Examples of the amine compound having 1 to 24 carbon atoms include primary amines and secondary amines. For example, (mono, di) alkylamines having 1 to 24 carbon atoms and (mono, di) having 1 to 24 carbon atoms. ) Alkanolamines, alkylalkanolamines having 1 to 24 carbon atoms and the like can be mentioned.
Examples of (mono, di) alkylamines having 1 to 24 carbon atoms include methylamine, ethylamine, propylamine, butylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, pentylamine, dipentylamine, hexylamine, and dihexylamine. Heptylamine, diheptylamine, octylamine, dioctylamine, dodecylamine, didodecylamine and the like are preferable.
As the (mono, di) alkanolamine having 1 to 24 carbon atoms, methanolamine, ethanolamine, propanolamine, butanolamine, dimethanolamine, diethanolamine, dipropanolamine, dibutanolamine, hexanolamine and the like are preferable.
As the alkylalkanolamine having 1 to 24 carbon atoms, methylethanolamine or the like is preferable.

Among the monomers represented by any of the above formulas (3) to (6), preferably, N, N-diallylmethylamine and a monomer obtained by adding a quaternizing agent to the monomer, or hydrochloric acid or acetic acid thereof. A monomer having a structural unit derived from a dialkylamine such as an N, N-dialkylamino group or a neutralized product of an acid (dialkylamine-containing monomer), that is, an N, N-dialkylamino group-containing (meth). Acrylates and their neutralized products with acids such as hydrochloric acid and acetic acid, monomers with a quaternizing agent added to them, N, N-dialkylamino group-containing (meth) acrylamides and their acids such as hydrochloric acid and acetic acid. A monomer obtained by adding a quaternizing agent to these, more preferably N, N-diallylmethylamine, a monomer having a quaternizing agent added thereto, or an acid such as hydrochloric acid or acetic acid thereof. These are neutralized products of N, N-dialkylamino group-containing (meth) acrylates, neutralized products of these with acids such as hydrochloric acid and acetic acid, and monomers to which a quaternizing agent is added.
The quaternizing agent is not particularly limited, but is an alkyl halide such as methyl chloride, ethyl chloride, methyl bromide, methyl iodide; dimethyl sulfate, diethyl sulfate, di-n-propyl sulfate and the like. Examples thereof include general alkylating agents such as alkyl sulfate.

Examples of the nitrogen-containing heterocyclic group-containing monomer include vinyl imidazole, vinyl pyrazole, vinyl imidazoline, vinyl triazole, vinyl tetrazole, vinyl pyridazine, vinyl pyrimidine group, vinyl pyrazine, vinyl purine, vinyl benzotriazole, vinyl pteridine and the like. Can be mentioned.

The N-vinylformamide and acrylonitrile are copolymerized and then hydrolyzed to obtain a polyamidine-based polymer, which can be used as the nitrogen-containing compound (A).

The polymer (α1) having the structural unit (a1) derived from the nitrogen atom-containing monomer (A1) is not particularly limited as long as the content ratio of the nitrogen atom and the weight average molecular weight satisfy the above ranges. Even if it is a homopolymer of the nitrogen atom-containing monomer (A1), it is a copolymer of two or more kinds of nitrogen atom-containing monomer (A1) and other than the nitrogen atom-containing monomer (A1). It may be a copolymer with the monomer (E).

The other monomer (E) is not particularly limited, but is a carboxyl group-containing simple substance such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, 2-methyleneglutaric acid, and salts thereof. Quantities: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, α- Hydroxyl-containing alkyl (meth) acrylates such as hydroxymethylethyl (meth) acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic Alkyl (meth) acrylates which are esters of alkyl groups having 1 to 18 carbon atoms of (meth) acrylic acid such as lauryl acid;

Vinyl esters such as vinyl acetate; Alkens such as ethylene and propylene; Aromatic vinyl monomers such as styrene; Maleimide derivatives such as maleimide, phenylmaleimide and cyclohexylmaleimide; nitrile group-containing vinyl such as (meth) acrylonitrile System monomers; monomers having a sulfonic acid group such as 3-allyloxy-2-hydroxypropanesulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, styrenesulfonic acid, vinylsulfonic acid and salts thereof; Monomers having a phosphonic acid group such as vinyl phosphonic acid and (meth) allyl phosphonic acid; aldehyde group-containing vinyl monomers such as (meth) achlorine; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and butyl vinyl ether Other functional group-containing monomers such as vinyl chloride, vinylidene chloride, allyl alcohol; polyalkylene glycol (meth) acrylate, monoalkoxypolyalkylene glycol (meth) acrylate, vinyl alcohol, (meth) allyl alcohol, isoprenol, etc. Examples thereof include polyalkylene glycol chain-containing monomers such as monomers having a structure in which 1 to 300 mol of alkylene oxide is added to unsaturated alcohol. As for these other monomers, only one kind may be used alone, or two or more kinds may be used in combination.

Examples of the polymer having a structural unit derived from the dialkylamine include a polymer having a structural unit derived from a dialkylamine-containing monomer and a reaction product of an epoxy compound and an amine compound. As the polymer having a structural unit derived from dialkylamine, a reaction product of an epoxy compound and an amine compound is preferable. The epoxy compound used as a raw material for the reaction product of the epoxy compound and the amine compound is preferably epichlorohydrin, and the epihalohydrin is not particularly limited, but for example, epichlorohydrin, epibromohydrin, 2-methylepichlorohydrin. , 2-Methyl epibromohydrin, 2-ethyl epichlorohydrin and the like. Epichlorohydrin is preferred.

The amine compound used as a raw material for the reaction product of the epoxy compound and the amine compound is preferably an alkyl group-containing amine compound, more preferably a dialkylamine having an alkyl group having 1 to 3 carbon atoms, and particularly preferably carbon. It is a dialkylamine having an alkyl group of several 1-2, most preferably a dimethylamine.

The ratio of the structural unit (a1) in the polymer (α1) is not particularly limited as long as the content ratio of nitrogen atoms is 6.8% by mass or more with respect to 100% by mass of the polymer (α1), but the total structural unit. It is preferably 50 to 100% by mass with respect to 100% by mass. It is more preferably 60 to 100% by mass, further preferably 70 to 100% by mass, and particularly preferably 80 to 100% by mass.

As for the ratio of the structural unit (e) derived from the other monomer (E) in the polymer (α1), the content ratio of the nitrogen atom is 6.8% by mass or more with respect to 100% by mass of the polymer (α1). The range is not particularly limited, but it is preferably 0 to 50% by mass with respect to 100% by mass of all structural units. It is more preferably 0 to 40% by mass, further preferably 0 to 30% by mass, and particularly preferably 0 to 20% by mass.

The method for producing the polymer having the structural unit derived from the nitrogen atom-containing monomer (A1) is not particularly limited, but the monomer component containing the nitrogen atom-containing monomer (A1) is polymerized by a commonly used method. Can be obtained by

The nitrogen-containing compound (A) has a polymer having a structural unit having an alkylene group and an amino group, an allylamine-based monomer, and / or a structural unit derived from an amino group-containing (meth) acrylate-based monomer. A polymer having a structural unit derived from a reaction product of an epoxy compound such as epihalohydrin and an amine compound is preferable. More preferably, it is polyalkyleneimine, polydiallyldimethylammonium chloride, polyepichlorohydrindimethylamine (poly-2hydroxypropyldimethylammonium chloride), and even more preferably polyethyleneimine. The embodiment in which the nitrogen-containing compound (A) is polyethyleneimine is one of the preferred embodiments of the present invention.
The above-mentioned amine compound is preferably the above-mentioned alkyl group-containing amine compound.

<Compound (B)>
The compound (B) is a compound having at least one selected from the group consisting of a carboxyl group, a sulfonic acid group, a phosphoric acid group, a group of salts thereof, and a phosphoric acid ester group. Among the above functional groups, a carboxyl group and a group of this salt are preferable.
Examples of the salt include monovalent metal salts such as alkali metals such as sodium and potassium; divalent metal salts such as alkaline earth metals such as magnesium and calcium; ammonium salts; organic amine salts and the like.

The compound (B) has a weight having a structural unit derived from a monomer having at least one selected from the group consisting of a carboxyl group, a sulfonic acid group, a phosphoric acid group, a group of salts thereof, and a phosphoric acid ester group. It is preferably coalesced. That is, the compound (B) is at least one selected from the group consisting of an unsaturated carboxylic acid-based monomer (B1), a sulfonic acid-based monomer (B2), and a phosphoric acid-based monomer (B3). It is preferably a polymer having a structural unit of origin.

The unsaturated carboxylic acid-based monomer (B1) is not particularly limited as long as it has a carboxyl group and / or a salt group thereof and an ethylenically unsaturated hydrocarbon group (unsaturated group), but is unsaturated. Examples thereof include monocarboxylic acid-based monomers and unsaturated dicarboxylic acid-based monomers.

The unsaturated monocarboxylic acid-based monomer may be a monomer having one unsaturated group and one group capable of forming a carboanion in the molecule, and may be, for example, (meth) acrylic acid or crotonic acid. , Isocrotonic acid, tigric acid, 3-methylcrotonic acid, 2-methyl-2-pentenoic acid, α-hydroxyacrylic acid, etc .; these monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts; A half ester of a saturated dicarboxylic acid-based monomer and an alcohol having 1 to 22 carbon atoms or a glycol having 2 to 4 carbon atoms; a half amide of an unsaturated dicarboxylic acid-based monomer and an amine having 1 to 22 carbon atoms, etc. Can be mentioned.

The unsaturated dicarboxylic acid-based monomer may be a monomer having one unsaturated group and two groups capable of forming a carboanion in the molecule, and may be maleic acid, itaconic acid, mesaconic acid, or citracon. Examples thereof include acids, fumaric acids and the like, their monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts and the like, and their anhydrides.
As the unsaturated carboxylic acid-based monomer (B1), (meth) acrylic acid (salt), maleic acid (salt) or maleic anhydride is preferable. More preferably, it is (meth) acrylic acid (salt), and particularly preferably methacrylic acid (salt).

The sulfonic acid-based monomer (B2) is not particularly limited as long as it has a sulfonic acid group and / or a salt group thereof, but is -SO ₃ Z as a sulfonic acid group and / or a salt group thereof. (Z represents a hydrogen atom, a monovalent metal atom, a divalent metal atom, an ammonium group or an organic amine group.) It is preferable that one molecule has one or more groups.

Examples of the sulfonic acid-based monomer (B2) include vinyl sulfonic acid, (meth) allyl sulfonic acid, metallicyloxybenzene sulfonic acid, isoprene sulfonic acid, 2-methylpropane sulfonic acid (meth) acrylamide, and styrene sulfonic acid. , 2-Hydroxy-3-allyloxysulfonic acid, sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate, sulfobutyl (meth) acrylate and other unsaturated sulfonic acid-based monomers (B2-1), sulfonic acid groups Monolignol, naphthalene sulfonic acid, methyl naphthalene sulfonic acid, anthracene sulfonic acid, alkylaryl sulfonic acid, melamine sulfonic acid, aminoaryl sulfonic acid, and monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts thereof. , And one or more of these can be used.

The phosphoric acid-based monomer (B3) is not particularly limited as long as it has a phosphoric acid (salt) group and / or a phosphoric acid ester group, but the following formula (10);
-OPO ₃ M ₂ (10)
(In the formula, M represents a hydrocarbon group which may have a hydrogen atom, a monovalent metal atom, a divalent metal atom, a trivalent metal atom, an organic amine group, or a substituent, which may be the same or different. It is preferable that one molecule has one or two or more groups represented by (.). The hydrocarbon group which may have a substituent is not particularly limited, and examples thereof include groups derived from aromatic alcohols and quinones described later.
As the M, a hydrogen atom, a monovalent metal atom or a divalent metal atom is preferable, a monovalent metal atom is more preferable, and sodium is further preferable.

The phosphoric acid-based monomer (B3) preferably further has an aromatic group and / or a heterocyclic aromatic group in the structure.
The aromatic group may be a group having an aromatic ring derived from an aromatic compound such as benzene, naphthalene, anthracene, tetracene, or pentacene (a group obtained by extracting a hydrogen atom from an aromatic compound) and having a substituent. You may be doing it.
The heterocyclic aromatic group is a group having a heterocyclic aromatic ring derived from a heterocyclic aromatic compound such as furan, thiophene, pyrrol, pyrazole, imidazole, pyridine, pyridazine, pyrimidine, and pyrazine (heterocyclic aromatic group). It may have a substituent (a group obtained by extracting a hydrogen atom from a compound).
As the phosphoric acid-based monomer (B3), a phosphoric acid-based monomer (B3-1) having an aromatic ring group derived from an aromatic compound is preferable, and one having an aryl group is more preferable.

The phosphoric acid-based monomer (B3-1) has the following formula (11);

(In the formula, M represents a hydrocarbon group which may have a hydrogen atom, a monovalent metal atom, a divalent metal atom, a trivalent metal atom, an organic amine group, or a substituent, which may be the same or different. Q ¹ represents a direct bond or a divalent linking group. R ¹⁰ represents a hydrogen atom or a substituent other than a phosphate base and a phosphate ester group). Is more preferable.
The ^Q 1 -OPO ₃ M _2, bonding site and the number of ^{R 10} is not particularly limited, but it may have a plurality.

The above Q ¹ is not particularly limited as long as it is a divalent linking group, but it is preferably a divalent hydrocarbon group that may have a hetero atom. More preferably, it is a (poly) oxyalkylene group. Specific examples and preferable examples of the oxyalkylene group include those similar to the oxyalkylene group having 2 to 18 carbon atoms in the formula (13) described later, and the oxyethylene group is most preferable. The average number of moles of the (poly) oxyalkylene group added is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 2, and most preferably 1.

Examples ^{of the substituent of R 10} include an alkyl group having 1 to 10 carbon atoms, an aliphatic hydrocarbon group such as an alkenyl group, an alkoxy group, a hydroxyl group, an acyl group, an ether group, an amide group, an ester group, a ketone group and a carboxyl group. , A carboxyl group salt, a sulfonic acid group, a sulfonic acid group salt, a (poly) alkylene glycol chain-containing group and the like.

Specifically, as the phosphoric acid-based monomer (B3-1), for example, phenoxyethanol, phenoxydiglycol, (methoxyphenoxy) ethanol, methylphenoxyethanol, bis (β-hydroxyethyl) hydroquinone ether, nonylphenol, phenol, cresol. , Resolsinol, catechol, hydroquinone, naphthol, and aromatic alcohols such as furfuryl alcohol and phosphor oxides of quinones.
Specifically, the phosphor oxides include phenoxyethanol phosphate, phenoxydiglycol phosphate, (methoxyphenoxy) ethanol phosphate, methylphenoxyethanol phosphate, bis (β-hydroxyethyl) hydroquinone ether phosphate, and bis (β-hydroxyethyl) hydroquinone ether diphosphate. , And nonylphenol phosphate and the like.
Of these, phenoxyethanol phosphate, phenoxydiglycol phosphate, and bis (β-hydroxyethyl) hydroquinone ether diphosphate are preferable, and phenoxyethanol phosphate is more preferable.
For phosphorylation of the aromatic alcohols and quinones, it is preferable to use a phosphoric acid compound such as phosphoric acid (salt) or polyphosphoric acid (salt).

When the compound (B) is a polymer having a structural unit derived from a monomer having a phosphoric acid ester group, a (poly) alkylene glycol chain and an aromatic ring group and / or a heterocyclic aromatic group are further added. It is preferable that the compound has a structural unit derived from the polymer (hereinafter, also referred to as (poly) alkylene glycol chain-containing monomer).
Specific examples of the (poly) alkylene glycol chain-containing monomer include the above-mentioned aromatic alcohols; compounds in which an alkylene oxide is added to an aromatic amine such as aniline. Preferably, it is a compound obtained by adding an alkylene oxide to aromatic alcohols such as phenol, cresol, resorcinol, catechol, hydroquinone, naphthol, and furfuryl alcohol.
Among the structural units derived from the above (poly) alkylene glycol chain-containing monomer, the following formula (12);

(In the formula, Q ² represents a direct bond or a divalent linking group. R ¹¹ represents a hydrogen atom or a substituent other than a phosphate base and a phosphate ester group. R ¹² O is the same or represents Differently, it represents an oxyalkylene group having 2 to 18 ^{carbon atoms. R 13} represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. M represents the average number of moles of the oxyalkylene group added, and 1 to 1 to It is preferable that it has a structural unit represented by (a number of 300).

Examples of the divalent linking group for the Q ^2, an oxygen atom, a sulfur atom, a halogen atom, -NH-, such as a divalent hydrocarbon group which may have a hetero atom. Divalent hydrocarbon group which may have a hetero atom is the same as the divalent hydrocarbon group which may have a hetero atom in to Q ¹ the formula (11). Preferably a Q ² oxygen atom, a -NH-, more preferably an oxygen atom.
The hydrocarbon group having 1 to 30 carbon atoms in R ¹³ is the same as the hydrocarbon group having 1 to 30 carbon atoms ^{in R 17 of the formula (13) described later.}
A hydrogen atom is preferable as ^{R 13.}
The preferred form of the oxyalkylene group represented by R ¹² O is the same as that of the oxyalkylene group in AO of the formula (13) described later.
The m is preferably 5 to 280, more preferably 5 to 160, and even more preferably 9 to 120.

As the monomer having the (poly) alkylene glycol chain and the aromatic ring group and / or the heterocyclic aromatic group, for example, 2-phenoxyethanol, phenoxypolyethylene glycol and the like are preferable.

The polymer having a structural unit derived from a monomer having a phosphoric acid ester group may have a structural unit represented by the above formula (11) and a structural unit represented by the formula (12). preferable. In this case, the molar ratio of the structural unit represented by the formula (11) to the structural unit represented by the formula (12) (formula (11) / formula (12)) may be 0.3 to 4. preferable. It is more preferably 0.4 to 3.5, and even more preferably 0.45 to 3.

In the polymer having a structural unit derived from a monomer having a phosphoric acid ester group, the structural units represented by the above formulas (11) and (12) are bonded by a divalent linking group derived from an aldehyde compound. Is preferable. It is a condensate in which structural units derived from a monomer are bonded by a divalent linking group derived from an aldehyde compound.
Examples of the aldehyde compound include formaldehyde; compounds having an alkyl group having 1 to 5 carbon atoms such as acetaldehyde, propionaldehyde, butanal and an aldehyde group: glyoxylic acid, benzaldehyde, paraformaldehyde and the like. Formaldehyde, benzaldehyde and paraformaldehyde are preferable, and formaldehyde is most preferable.

The polymer having a structural unit derived from the phosphoric acid-based monomer (B3) may not have an aromatic group or a heterocyclic aromatic group in the structure, for example, a phosphoric acid (salt). It may have a structural unit derived from an unsaturated phosphate-based monomer (B3-2) having a group and / or a phosphate ester group and an ethylenically unsaturated hydrocarbon group (unsaturated group). As the unsaturated phosphoric acid-based monomer (B3-2), for example, an esterified product of an unsaturated carboxylic acid and a compound having two or more hydroxyl groups in one molecule, and an esterified product of phosphoric acid are preferable. is there. Specifically, an esterified product of a hydroxyl group-containing (meth) acrylate such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 1,4-butanediol mono (meth) acrylate and phosphoric acid; Examples thereof include esterified products of polyalkylene glycol mono (meth) acrylate such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate and phosphoric acid, and one or more of these can be used. ..

Among the unsaturated carboxylic acid-based monomer (B1), the sulfonic acid-based monomer (B2), and the phosphoric acid-based monomer (B3), the unsaturated carboxylic acid-based monomer (B1) is preferable. The compound (B) is preferably a polymer having a structural unit (b1) derived from an unsaturated carboxylic acid-based monomer (B1).

The compound (B) is selected from the group consisting of an unsaturated carboxylic acid-based monomer (B1), an unsaturated sulfonic acid-based monomer (B2-1) and an unsaturated phosphoric acid-based monomer (B3-2). If the structural unit (b) is derived from at least one of the following formulas (13);

(In the formula, R ¹⁴ , R ¹⁵ and R ¹⁶ represent the same or different hydrogen atom or methyl group. R ¹⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. (AO) represents the same or different oxyalkylene group. N represents the average number of moles of oxyalkylene group added, and is a number from 1 to 500. P represents a number from 0 to 4. Represents 0 or 1), preferably having a structural unit (c) derived from the (poly) alkylene glycol-based monomer (C).

In the above formula (13), AO represents an oxyalkylene group "same or different", which may be the same for all n oxyalkylene groups of AO present in the polyalkylene glycol. It means that they can be different.
In the above formula (13), n represents the average number of moles of the oxyalkylene group added, which is a number of 1 to 500, preferably 2 to 300, more preferably 3 to 250, and further preferably 10 to. It is 150, and particularly preferably 20 to 80.
The alkylene group constituting the oxyalkylene group preferably has 2 to 18 carbon atoms. It is more preferably 2 to 10, still more preferably 2 to 8, and particularly preferably 2 to 4.

The (poly) oxyalkylene group represented by (AO) n is an alkylene oxide adduct, and examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, 1-butene oxide, and 2-butene oxide. Examples include styrene oxide. Of these, alkylene oxide having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide and butylene oxide is preferable, and ethylene oxide and propylene oxide are more preferable.

When the (poly) oxyalkylene group is any two or more kinds of alkylene oxide adducts selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide and the like, any of random addition, block addition, alternating addition and the like. It may be in the form of. In order to secure a balance between hydrophilicity and hydrophobicity, it is preferable to have an oxyethylene group as an essential component as the oxyalkylene group in the polyalkylene glycol, and more preferably 50 mol% or more is an oxyethylene group. , 90 mol% or more is more preferably an oxyethylene group.

^{R 14} to R ¹⁶ in the above formula (13) represent a hydrogen atom or a methyl group, which are the same or different. Preferably, R ¹⁴ and R ¹⁵ are hydrogen atoms, and R ¹⁶ is a hydrogen atom or a methyl group. More preferably, R ¹⁴ and R ¹⁵ are hydrogen atoms and R ¹⁶ is a methyl group.

In the above formula (13), p represents a number from 0 to 4, q represents 0 or 1, but when q is 0, p is preferably 1 or 2. In this case, R ¹⁶ is more preferably a methyl group.
When q is 1, p is preferably 0. In this case, R ¹⁶ is more preferably a hydrogen atom or a methyl group.
When p is 0 and q is 0, the AO first bonded to the oxygen atom bonded to the carbon-carbon double bond is preferably an oxyalkylene group having 4 carbon atoms.
The p is preferably 0, and the form in which p is 0 and q is 1 is one of the preferred embodiments of the present invention.

^{R 17} in the above formula (13) represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms. It is preferably a hydrocarbon group or a hydrogen atom having 1 to 20 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and further preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. , Particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and most preferably a hydrocarbon group having 1 to 3 carbon atoms.

Examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group and a 3-pentyl group. , Hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, isooctyl group, 2,3,5-trimethylhexyl group, 4-ethyl-5-methyloctyl group and 2-ethylhexyl group, Linear or branched alkyl groups such as tetradecyl group, octadecyl group, icosyl group; cyclic alkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; phenyl group, benzyl group, phenethyl group, o -, M- or p-tolyl group, 2,3- or 2,4-xylyl group, mesityl group, naphthyl group, anthryl group, phenanthryl group, biphenylyl group, benzhydryl group, trityl group, aryl group such as pyrenyl group, etc. Can be mentioned. Of these, linear, branched or cyclic alkyl groups are preferred.

Specific examples of the (poly) alkylene glycol-based monomer (C) include polyalkylene glycol mono (poly) ethylene glycol mono (meth) acrylate, (poly) propylene glycol mono (meth) acrylate, and the like. Meta) acrylate; alkoxypolyalkylene glycol mono (meth) acrylate such as methoxy (poly) ethylene glycol mono (meth) acrylate, methoxy (poly) propylene glycol mono (meth) acrylate; vinyl alcohol, (meth) allyl alcohol, 3 -Methyl-3-butene-1-ol (isoprenol), 3-methyl-2-butene-1-ol, 2-methyl-3-butene-2-ol, 2-methyl-2-buten-1-ol, It is a compound in which 1 to 500 mol of an alkylene oxide is added to any of 2-methyl-3-butene-1-ol, and more preferably 3-methyl-3-butene-1-ol (isoprenol), (meth). It is a compound obtained by adding 1 to 500 mol of alkylene oxide to allyl alcohol. The "alkylene oxide" in the above example is preferably ethylene oxide or propylene oxide. Of these, a compound obtained by adding 1 to 500 mol of alkylene oxide to 3-methyl-3-butene-1-ol (isoprenol) or (meth) allyl alcohol is preferable.

The ratio of the structural unit (b) of the compound (B) is preferably 1 to 90% by mass with respect to 100% by mass of all the structural units. It is more preferably 3 to 80% by mass, further preferably 5 to 50% by mass, and particularly preferably 7 to 20% by mass.

The ratio of the structural unit (c) of the compound (B) is preferably 10 to 99% by mass with respect to 100% by mass of the total structural units. It is more preferably 20 to 97% by mass, further preferably 50 to 95% by mass, and particularly preferably 80 to 93% by mass.

The compound (B) preferably has a weight average molecular weight of 10 to 1,000,000. It is more preferably 5,000 to 100,000, further preferably 75,000 to 70,000, and particularly preferably 10,000 to 40,000. When the compound (B) is a polymer having a structural unit derived from the phosphoric acid-based monomer (B3), the weight average molecular weight is preferably 3000 to 100,000.
The weight average molecular weight can be measured by the method described in Examples.

When the compound (B) is a compound having a carboxyl group and / or a group of this salt, the structural unit (b1) derived from the unsaturated carboxylic acid-based monomer (B1) and the (poly) alkylene glycol-based single amount. A copolymer having a structural unit (c) derived from the body (C) is preferable.

When the compound (B) is a compound having a sulfonic acid group and / or a salt group thereof, specifically, a naphthalene sulfonic acid formaldehyde condensate, a methylnaphthalene sulfonic acid formaldehyde condensate, an anthracene sulfonic acid formaldehyde condensate, etc. Polyalkylaryl sulfonate-based compounds; Melamine formalin resin sulfonate-based compounds such as melamine sulfonic acid formaldehyde condensate; Aromatic amino sulfonate-based compounds such as aminoaryl sulfonic acid-phenol-formaldehyde condensate; Lignin sulfonate-based compounds such as acid salts and modified lignin sulfonates; polystyrene sulfonate-based compounds and the like can be mentioned.

When the compound (B) is a compound having at least one selected from the group consisting of a phosphate group, a group of this salt and a phosphate ester group, (alkoxy) polyalkylene glycol mono (meth) acrylate, phosphorus Copolymers having a (poly) oxyalkylene group and a phosphate ester group in the molecule, such as an acid monoester monomer and a copolymer obtained from a phosphate diester monomer; (poly) A monomer having an oxyalkylene group and an aromatic ring group and / or a heterocyclic aromatic group, a phosphoric acid (salt) group and / or a phosphate ester group and an aromatic ring group and / or a heterocyclic aromatic group. Polycondensation products composed of a monomer having a group and an aldehyde compound; a polymer having an aromatic triazine structural unit, a polyalkylene glycol structural unit, and a phosphate ester structural unit can be mentioned.

The additive for a water-hard material of the present invention contains the above-mentioned nitrogen-containing compound (A) and compound (B), and the content ratio thereof is not particularly limited, but nitrogen is added to 100% by mass of compound (B). The ratio of the contained compound (A) is preferably 0.1 to 200% by mass. Thereby, the adhesiveness of the hydraulic material composition can be further improved. It is more preferably 0.1 to 100% by mass, further preferably 0.5 to 50% by mass, still more preferably 1 to 20% by mass, and particularly preferably 2 to 10% by mass.
The compound (B) is a compound having a carboxyl group and / or a group of this salt, and / or a compound having at least one selected from the group consisting of a phosphate group, a group of this salt and a phosphate ester group. In some cases, the ratio of the nitrogen-containing compound (A) to 100% by mass of the compound (B) is preferably 0.1 to 180% by mass. It is more preferably 0.3 to 100% by mass, further preferably 0.5 to 40% by mass, still more preferably 1 to 30% by mass, and particularly preferably 2 to 20% by mass.
When the compound (B) is a compound having a sulfonic acid group and / or a group of this salt, the ratio of the nitrogen-containing compound (A) to 100% by mass of the compound (B) is 1 to 100% by mass. Is preferable. It is more preferably 5 to 50% by mass, and even more preferably 10 to 30% by mass.
In addition, compound (B) has (i) a carboxyl group and a group of this salt, (ii) a sulfonic acid group and a group of this salt, (iii) a phosphoric acid group, a group of this salt and a phosphoric acid ester group. When it has two or more groups of i) to (iii), for example, when it has a carboxyl group and a sulfonic acid group, it is classified into the compound having a larger proportion of these groups.

A method for producing a polymer having a structural unit derived from a monomer having at least one selected from the group consisting of a carboxyl group, a sulfonic acid group, a phosphoric acid group, a group of salts thereof, and a phosphoric acid ester group is particularly suitable. Although not limited, it can be obtained by polymerizing a monomer component containing these monomers by a commonly used method.

<Additives for hydraulic materials and hydraulic material compositions>
The additive for a hydraulic material of the present invention contains the above-mentioned nitrogen-containing compound (A) and compound (B), and may contain two or more of the compound (A) and the compound (B), respectively. The content of the compound (A) in the additive for a hydraulic material (when two or more kinds of the compound (A) and the compound (B) are contained, the total content thereof) is not particularly limited, but is a hydraulic material. The solid content (that is, non-volatile content) in the additive is preferably 5 to 90% by mass based on 100% by mass. It is more preferably 20 to 90% by mass, still more preferably 30 to 75% by mass.
In the present specification, the "additive for hydraulic material" refers to an additive added to a hydraulic material composition such as cement paste, mortar, and concrete, and only the above-mentioned nitrogen-containing compound (A) is used. It may be an agent comprising the above-mentioned nitrogen-containing compound (A) and compound (B), and may be an agent containing not only the above-mentioned nitrogen-containing compound (A) and compound (B) but also other additives described later as necessary.
In addition, in the additive for hydraulic material of this invention, the form which does not contain any of the following (1) and (2) is also one of the embodiments of this invention.
(1) Polydimethylammonium chloride (product code 522376, manufactured by SIGMA-ALDRICH) is contained in an amount of 0.01% by mass based on the cement, and a polycarboxylic acid copolymer (3-methyl-3-butene-1-ol) is used as a water reducing agent. It contains unsaturated alcohol: acrylic acid = 87:13 (mass ratio), weight average molecular weight 19000) to which 50 mol of ethylene oxide is added.
(2) Poly-2 hydroxypropyl dimethylammonium chloride (manufactured by Yokkaichi Synthetic Co., Ltd.) is contained in an amount of 0.01% by weight based on cement, and a polycarboxylic acid copolymer (3-methyl-3-butene-1) is used as a water reducing agent. -An unsaturated alcohol in which 50 mol of ethylene oxide is added to all: acrylic acid = 87:13 (mass ratio), weight average molecular weight 19000).

The additive for a hydraulic material of the present invention is preferably used in a hydraulic material composition containing a hydraulic material. That is, a hydraulic material composition containing an additive for a hydraulic material and a hydraulic material is also one of the present inventions. The form in which the hydraulic material composition further contains an aggregate is also one of the preferred embodiments of the present invention.

In the above hydraulic material composition, as the blending ratio of the additive for hydraulic material of the present invention, for example, the total ratio of the nitrogen-containing compound (A) and the compound (B), which are essential components of the present invention, is solid. In terms of minutes, it is preferable to set it to be 0.005 to 10% by mass with respect to 100% by mass of the total amount of the hydraulic material. It is more preferably 0.01 to 5% by mass, and even more preferably 0.02 to 3% by mass. In the present specification, the solid content can be measured as follows.
<Solid content measurement method>
1. 1. Weigh the aluminum dish.
The solid content measurement object is precisely weighed in the aluminum dish precisely weighed in 2.1.
3. 3. The solid content measurement material precisely weighed in 2 is placed in a dryer whose temperature has been adjusted to 130 ° C. under a nitrogen atmosphere for 1.5 hours.
After 4.1 hours, remove from the dryer and allow to cool in a desiccator at room temperature for 15 minutes.
5. After 15 minutes, remove from the desiccator and weigh the aluminum dish + the object to be measured.
The solid content is measured by subtracting the mass of the aluminum plate obtained in 1 from the mass obtained in 6.5 and dividing by the mass of the solid content measurement product obtained in 2.

The water-hardening material is not particularly limited as long as it has water-hardness or latent water-hardness. For example, ordinary Portland cement, early-strength Portland cement, moderate heat Portland cement, low heat Portland cement and other Portland cement and silica are used. Cement, fly ash cement, blast furnace cement, alumina cement, belite high content cement, various mixed cements; components of cement such as tricalcium silicate, dicalcium silicate, tricalcium aluminate, tetracalcium iron aluminate; latent hydraulic hardness Examples thereof include fly ash, silica fume, slag, lime fine powder and the like having the above. These may be used alone or in combination of two or more. Among these, ordinary Portland cement is usually commonly used and can be preferably applied.

In addition to gravel, crushed stone, granulated slag, recycled aggregate, etc., the above-mentioned aggregates include silica stone, clay, zirconite, high alumina, silicon carbide, graphite, chromium, chromog, magnesia, etc. Fire-resistant aggregate and the like.

The additive for a water-hard material of the present invention may be used in combination with other additives other than the additive for a water-hard material of the present invention in the water-hard material composition, and the other additive is highly water-soluble. Molecular substances, retarders, quick-setting agents, fast-strengthening agents / accelerators, mineral oil-based defoamers, oil-based defoamers, fatty acid-based defoamers, fatty acid ester-based defoamers, oxyalkylene-based defoamers, alcohols Defoamers, amide defoamers, phosphate ester defoamers, metal soap defoamers, silicone defoamers, AE agents, surfactants, waterproofing agents, rust preventives, preservatives, cracks Reducer, swelling agent, cement wetting agent, thickener, separation reducing agent, coagulant, drying shrinkage reducing agent, strength enhancer, self-leveling agent, coloring agent, antifoaming agent, blast furnace slag, fly ash, cinder ash, Examples thereof include cement additives (materials) such as clinker ash, husk ash, silica fume, silica powder, colloidal silica, fiber, and plaster.

The quick-setting agent is not particularly limited as long as it is a known quick-setting agent. The quick-setting agent used may be a powder quick-setting agent, a liquid quick-setting agent, or a slurry-type quick-setting agent. Examples of the liquid quick-setting admixture include aluminum sulfate, fluorine, and alkali metals, and those containing these and alkanolamines, and one or more of these can be used. Further, as the liquid quick-setting admixture used in the present invention, a known water-soluble hydration accelerator can be used. Examples of the hydration accelerator include organic hydration accelerators such as formic acid or a salt thereof, acetic acid or a salt thereof, and lactic acid or a salt thereof, water glass, nitrate, nitrite, thiosulfate, and thiocyanate. It is possible to use an inorganic hydration accelerator such as a salt. Examples of the powder quick-setting admixture include those containing calcium aluminates, sulfates, alkali metal aluminates, alkali metal carbonates, and oxycarboxylic acids, and one or two of these. The above can be used.

The defoaming agent is not particularly limited as long as it is a known defoaming agent. For example, mineral oil defoamers such as kerosene and liquid paraffin; oil and fat defoamers such as animal and vegetable oils, sesame oil, castor oil and these alkylene oxide adducts; fatty acids such as oleic acid, stearic acid and these alkylene oxide adducts. Defoamer; fatty acid esters such as diethylene glycol monolaurate, glycerin monolithinolate, alkenyl succinolate derivative, sorbitol monolaurate, sorbitol trioleate, polyoxyethylene monolaurate, polyoxyethylene sorbitol monolaurate, natural wax, etc. Defoaming agents; alcohol-based defoaming agents such as octyl alcohol, hexadecyl alcohol, acetylene alcohol, glycols, polyoxyalkylene glycol; amide-based defoaming agents such as polyoxyalkylene amide and acrylate polyamine; tributyl phosphate, sodium Phosphate defoamers such as octyl phosphate; Metal soap defoamers such as aluminum stearate and calcium oleate; Silicone defoamers such as silicone oil, silicone paste, silicone emulsion, organically modified polysiloxane, fluorosilicone oil, etc. Foaming agents; oxyalkylene-based defoaming agents such as polyoxyethylene polyoxypropylene adducts; and the like, and one or more of these can be used. Among the above-exemplified defoaming agents, the oxyalkylene-based defoaming agent is most preferable. When the copolymer for cement admixture of the present invention is used in combination with an oxyalkylene defoaming agent, the amount of the defoaming agent used can be reduced, and the compatibility between the defoaming agent and the copolymer is also excellent. Is. The oxyalkylene-based defoaming agent is not particularly limited as long as it is a compound having an oxyalkylene group in the molecule and having an action of reducing bubbles in an aqueous liquid, and among them, the following is also represented by the following formula (14). The specific oxyalkylene antifoaming agent represented is preferred.
R ¹⁷ {-W- (R ¹⁸ O) u1-R ¹⁹ } u2 (14)
In the above formula (14), R ¹⁷ and R ¹⁹ are the same or different, and have a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 1 to 22 carbon atoms, an alkynyl group having 1 to 22 carbon atoms, and phenyl. Represents a group or an alkylphenyl group (the alkyl group in the alkylphenyl group has 1 to 22 carbon atoms). R ¹⁸ O represents one kind or a mixture of two or more kinds of oxyalkylene groups having 2 to 4 carbon atoms, and in the case of two or more kinds, it may be added in a block shape or randomly. u1 is the average number of moles of the oxyalkylene group added, and represents a number from 0 to 300. When u1 is ^0, it never R ^{17, R 19} are not hydrogen atoms at the same time, W is _{-O -, - CO 2 -,} - SO 4 -, - represent or -NH- groups - PO _4. u2 represents an integer of 1 or 2, and when R ¹⁷ is a hydrogen atom, u2 is 1.

Examples of the oxyalkylene-based defoaming agent represented by the above formula (14) include polyoxyalkylenes such as (poly) oxyethylene (poly) oxypropylene adduct; diethylene glycol heptyl ether, polyoxyethylene oleyl ether, and poly. (Poly) oxyalkylene alkyl ethers such as oxypropylene butyl ether, polyoxyethylene polyoxypropylene-2-ethylhexyl ether, oxyethylene oxypropylene adduct to higher alcohols having 12 to 14 carbon atoms; polyoxypropylene phenyl ether, poly (Poly) oxyalkylene (alkyl) aryl ethers such as oxyethylene nonylphenyl ether; 2,4,7,9-tetramethyl-5-decine-4,7-diol, 2,5-dimethyl-3-hexin- Acetylene ethers obtained by addition-polymerizing an alkylene oxide to an acetylene alcohol such as 2,5-diol and 3-methyl-1-butin-3-ol; such as diethylene glycol oleic acid ester, diethylene glycol lauric acid ester, and ethylene glycol distearate ester. (Poly) oxyalkylene fatty acid esters; (poly) oxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolauric acid ester and polyoxyethylene sorbitan trioleic acid ester; polyoxypropylene methyl ether sodium sulfate, polyoxyethylene dodecylphenol (Poly) oxyalkylene alkyl (aryl) ether sulfate esters such as sodium ether sulfate; (poly) oxyalkylene alkyl phosphates such as (poly) oxyethylene stearyl phosphate; (poly) such as polyoxyethylene laurylamine ) Oxyalkylene alkylamines; etc., and one or more of these can be used.

In the water-hard material composition, ^{the unit water amount, cement usage amount and water / cement ratio per 1 m 3} are not particularly limited. For example, the unit water amount is 100 to 300 kg / m ³ , and the cement amount used is 300 to 500 kg / m. ^{3. The} water / cement ratio (weight ratio) is preferably 0.35 to 0.6. More preferably, the unit water amount is 140 to 240 kg / m ³ , the cement amount used is 350 to 480 kg / m ³ , and the water / cement ratio (weight ratio) is 0.4 to 0.5.

The additive for a hydraulic material of the present invention is not particularly limited as long as it is used in a hydraulic material composition, and can be used for ready-mixed concrete, sprayed concrete, and the like. It is preferably used for sprayed concrete applications. The method of using the additive for hydraulic materials of the present invention in sprayed concrete is also one of the present inventions. The present invention is also a method in which the additive for a hydraulic material of the present invention is sprayed onto a construction surface together with a hydraulic material.
The above-mentioned usage method is not particularly limited as long as the additive for hydraulic material of the present invention is sprayed on the construction surface together with the hydraulic material, but a mixture of the additive for hydraulic material and the hydraulic material is sprayed on the construction surface. Is preferable. The above-mentioned usage methods include a step of mixing an additive for a hydraulic material and a hydraulic material, a step of pumping the hydraulic material composition obtained by the mixing step with compressed air, a pump, or the like, and pumped water. It is more preferable to include a step of spraying the hard material composition.
Preferred forms and the like of the hydraulic material composition are as described above.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".

<Measurement of weight average molecular weight of compound (B)>
The weight average molecular weight was measured under the following measurement conditions.
Equipment: Waters Alliance (2695)
Analysis software: Waters, Emper2 Professional + GPC option used Column: Tosoh Co., Ltd., TSKgroundvolumesSWXL + TSKgel G4000SWXL + G3000SWXL + G2000SWXL
Detectors: Differential Refractometer (RI) Detector (Waters 2414), Multi-Wavelength Visible Ultraviolet (PDA) Detector (Waters 2996)
Eluent: 115.6 g of sodium acetate trihydrate dissolved in a mixed solvent of 10999 g of water and 6001 g of acetonitrile, and the pH was adjusted to 6.0 with acetic acid.
Standard Material for Calibration Curve Creation: Polyethylene Glycol (Peak Top Molecular Weight (Mp) 272500, 219300, 107000, 50000, 24000, 12600, 7100, 4250, 1470)
Calibration curve: Prepared by a cubic formula based on the Mp value and elution time of the above standard substance.
Flow rate: 1 mL / min Column temperature: 40 ° C
Measurement time: 45 minutes Standard substance sample solution injection amount: 100 μL (polymer concentration 0.1% by mass eluent solution)
Polymer sample solution injection amount: 100 μL (eluent solution with polymer concentration of 0.5% by mass)

<GPC analysis conditions (polymer analysis)>
In the obtained RI chromatogram, the flat and stable portions at the baseline immediately before and immediately after elution of the polymer were connected by a straight line, and the polymer was detected and analyzed. However, when the peaks of the monomer and impurities derived from the monomer partially overlap the polymer peak and are measured, the polymer portion and the monomer are vertically divided at the innermost recess of the overlapping portion of the polymer and the polymer portion. The part and the impurity part were separated, and the molecular weight and molecular weight distribution of only the polymer part were calculated. When there was no recess, the calculation was done collectively.
The pure polymer content was calculated as follows from the ratio of the peak areas by the RI detector.
Polymer pure content = (polymer peak area) / (polymer peak area + peak area of monomers and impurities)

<Adhesion evaluation by texture analyzer>
(1) Equipment: Texture Analyzer TA., manufactured by Eiko Seiki Co., Ltd. XT Plus
(2) Outline of the device: A mechanism consisting of a probe, a sample table, and a stress detector that can apply a constant load for a certain period of time, and the speed at which the mortar can be contacted and peeled off at a constant speed. It has a controllable mechanism.
Adhesion test probe: Tsukisashi, cylindrical probe for compression P / 35 (material: aluminum, diameter 35 mm)
(3) Evaluation method: The mortar sample prepared (kneaded) as follows was transferred to a 200 mL descup and placed on a sample table. The probe was then penetrated to a depth of 20 mm from the surface of the sample at a rate of 1 mm per second, followed immediately by 1 mm / sec. The probe was pulled out at the speed of, and the maximum load required for the probe to peel off from the mortar was calculated and used as the value of the probe tack test. The unit is N / cm ² . The maximum load ratio of each system when the maximum load of the systems of the comparative example was 100% was defined as adhesiveness. When the maximum load ratio was 110% or more, the adhesiveness was considered to be high.

<Dispersiveness (workability) evaluation>
The mortar test was conducted in an environment where the temperature was 20 ° C. ± 1 ° C. and the relative humidity was 60% ± 15%. The mortar composition was C / S / W = 560/1350/250 (g) in Examples and Comparative Examples (1) and (4), and C / S / W in Examples and Comparative Examples (2) and (3). = 690/1600 / 331.2 (g).
However,
C: Cement (ordinary Portland cement, manufactured by Taiheiyo Cement)
S: Fine aggregate (land sand from Oi River)
W: An ion-exchanged aqueous solution of the sample and the defoaming agent was prepared, and W contained the additives for water-hardening materials and the defoaming agent shown in Tables 1 to 3 below, and was sufficiently uniformly dissolved in the ion-exchanged water.
Using a mortar mixer (Mixer manufactured by Hobart, model number: N-50), C and S were put into a kneading container and kneaded at 1st speed for 10 seconds. Further, while kneading at the 1st speed, W was added over 10 seconds. The mixer was stopped 60 seconds after the start of kneading, and the mortar was scraped off for 30 seconds. Then, kneading was further carried out at 2nd speed for 60 seconds to prepare a mortar. Half of the mortar obtained as described above is packed in a mini slump cone (JIS microconcrete slump cone, upper end inner diameter 50 mm, lower end inner diameter 100 mm, height 150 mm) placed on a flow measuring plate (60 cm × 60 cm). The surface of the mini slump cone was smoothed after piercing with a piercing rod, filling the mortar to the full extent of the mini slump cone, and piercing with the piercing rod 15 times. Then, 3 minutes and 30 seconds after starting the mixer for the first time, the mini slump cone was pulled up vertically, and the diameter of the expanded mortar (the diameter of the longest part (major diameter) and the diameter of the part 90 degrees to the long diameter). ) Was measured at two points, and the average value was taken as the mortar flow value. The amount of air was adjusted to less than 3.0% by adding an oxyalkylene defoaming agent which is a defoaming agent.

Synthesis example <Production of compound (B-1)>
An aqueous solution (B1a) prepared by dissolving 0.4 parts of L-ascorbic acid and 0.8 parts of 3-mercaptopropionic acid in 50.0 parts of water was prepared.
Unsaturated poly with 90.4 parts of water and an average of 50 mol of ethylene oxide added to 3-methyl-3-butene-1-ol in a reaction vessel equipped with a thermometer, agitator, dropping device, nitrogen introduction tube, and reflux condenser. 191.0 parts of alkylene glycol ether-based monomer (IPN-50) and 0.3 part of acrylic acid (AA) were charged, and then the inside of the reaction vessel was replaced with nitrogen under stirring, and the temperature was raised to 60 ° C. under a nitrogen atmosphere. After warming, 0.9 part of a 35% aqueous solution of hydrogen peroxide was added.
After 30 minutes, the above-mentioned mixed solution (B1a) was weighed and dropped at a constant rate over 3.5 hours and 25.5 parts of acrylic acid (AA) over 3.0 hours. The temperature during this period was kept constant at 60 ° C.
After the completion of dropping the mixed solution (B1a), the temperature was continuously maintained at 60 ° C. for 1 hour to complete the polymerization reaction. Then, the pH of the reaction solution was neutralized to pH = 6.3 using an aqueous sodium hydroxide solution at a temperature equal to or lower than the polymerization reaction temperature. In this way, an aqueous polymer solution containing the copolymer (B-1) was obtained. The weight average molecular weight Mw of the obtained copolymer (B-1) was 32000.

<Manufacturing of compound (B-2)>
A solution (a) was prepared in which 0.2 part of L-ascorbic acid and 0.6 part of 3-mercaptopropionic acid were dissolved in 140.2 parts of water. Ethylene oxide in 43.6 parts of water, 43.6 parts of 2-propanol, and 2-methyl-2-propen-1-ol in a reaction vessel equipped with a thermometer, agitator, dropping device, nitrogen introduction tube, and reflux cooler. 193.5 parts of an 80% aqueous solution of unsaturated polyalkylene glycol ether-based monomer added with an average of 150 mol and 0.8 parts of a 70% aqueous solution of paratoluenesulfonic acid monohydrate were charged, and then reacted under stirring. The inside of the container was replaced with ethylene, the temperature was raised to 60 ° C. under a nitrogen atmosphere, and then 5.4 parts of a 2% aqueous solution of hydrogen peroxide was added. After 30 minutes, the above-mentioned mixed solution (a) was weighed and dropped at a constant rate over 3.5 hours and 17.0 parts of a 90% aqueous solution of acrylic acid over 3 hours. The temperature during this period was kept constant at 60 ° C.
After the completion of dropping the mixed solution (a), the temperature was continuously maintained at 60 ° C. for 1 hour to complete the polymerization reaction. Then, the pH of the reaction solution is neutralized to pH = 5.0 using an aqueous sodium hydroxide solution at a temperature equal to or lower than the polymerization reaction temperature, and the polycarboxylic acid of the present invention comprising an aqueous polymer solution having a weight average molecular weight of 52,000 is used. A polymer was obtained.

<Manufacturing of compound (B-3)>
A solution (a) in which 3.3 parts of ammonium pervertate was dissolved in 107.3 parts of water was prepared. A solution (b) in which 19.7 parts of methacrylic acid was mixed was prepared. A solution (c) was prepared in which 123.8 parts of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added 23) and 1.2 parts of 3-mercaptopropionic acid were dissolved in 53.6 parts of water. Add 70.6 parts of water to a reaction vessel equipped with a thermometer, agitator, dropping device, nitrogen introduction tube, and reflux condenser, and then replace the inside of the reaction vessel with nitrogen under stirring to reach 80 ° C. under a nitrogen atmosphere. After the temperature was raised, the above-mentioned mixed solution (a) was weighed and dropped over 5 hours, and the above-mentioned mixed solutions (b) and (c) were weighed and dropped at a constant rate over 4 hours. The temperature during this period was kept constant at 80 ° C. After the completion of dropping the mixed solution (a), the temperature was continuously maintained at 80 ° C. for 1 hour to complete the polymerization reaction. Then, the pH of the reaction solution is neutralized to pH = 5.0 using an aqueous sodium hydroxide solution at a temperature equal to or lower than the polymerization reaction temperature, and the polycarboxylic acid co-weight of the present invention consisting of a polymer aqueous solution having a weight average molecular weight of 20,000 is obtained. I got a coalescence.

Example (1) -1 and Comparative Examples (1) -1, (1) -2
Table 1 shows polyethyleneimine (Epomin P-1000 manufactured by Nippon Catalyst Co., Ltd.) as the nitrogen-containing compound (A) and the copolymer (B-1) synthesized in the above synthesis example as the compound (B). Additives for water-hard materials were prepared by blending in proportions. The prepared additives for hydraulic materials were evaluated for dispersibility and adhesiveness by the method described above. As for the adhesiveness, the adhesiveness of Example (1) -1 and Comparative Example (1) -2 was calculated with the adhesiveness of Comparative Example (1) -1 as 100%. The results are shown in Table 1.

Example (2) -1 and Comparative Example (2) -1
Table 2 shows polydiallyldimethylammonium chloride (manufactured by SIGMA-ALDRICH, product code 522376) as the nitrogen-containing compound (A) and lignin sulfonic acid (manufactured by BASF, Pozoris No. 8) as the compound (B). Additives for water-hard materials were prepared by blending in proportions. The prepared additives for hydraulic materials were evaluated for dispersibility and adhesiveness by the method described above. As for the adhesiveness, the adhesiveness of Example (2) -1 was calculated with the adhesiveness of Comparative Example (2) -1 as 100%. The results are shown in Table 2.

Examples (3) -1 to 19 and Comparative Examples (3) -1 to 4
Polydiallyl dimethylammonium chloride (manufactured by SIGMA-ALDRICH) or poly-2-hydroxypropyldimethylammonium chloride (manufactured by Yokkaichi Synthetic Co., Ltd.) was used as the nitrogen-containing compound (A), and the copolymer (B) synthesized in the above synthesis example. -1) to (B-3) were compounded as compound (B) in the proportions shown in Table 3 to prepare an additive for a water-hard material. The prepared additives for hydraulic materials were evaluated for dispersibility and adhesiveness by the method described above. The adhesiveness was calculated with the adhesiveness of Comparative Example (3) -1 as 100%. The results are shown in Table 3.

 
 

 

Claims (13)

1. An additive for hydraulic materials containing a nitrogen-containing compound (A).
   The nitrogen-containing compound (A) has a nitrogen atom content of 6.8% by mass or more with respect to 100% by mass of the nitrogen-containing compound (A).
   The additive for a water-hard material further contains a compound (B) having at least one selected from the group consisting of a carboxyl group, a sulfonic acid group, a phosphoric acid group, a group of salts thereof, and a phosphoric acid ester group.
   An additive for hydraulic materials, which is characterized by being used for sprayed concrete applications.
2. The compound (B) is derived from at least one selected from the group consisting of an unsaturated carboxylic acid-based monomer (B1), a sulfonic acid-based monomer (B2) and a phosphoric acid-based monomer (B3). The additive for a water-hard material according to claim 1, wherein the polymer has a structural unit.
3. The additive for a water-hard material according to claim 1 or 2, wherein the compound (B) is a polymer having a structural unit (b1) derived from an unsaturated carboxylic acid-based monomer (B1). ..
4. The addition for a hydraulic material according to any one of claims 1 to 3, wherein the compound (B) further has a structural unit (c) derived from a (poly) alkylene glycol-based monomer (C). Agent.
5. The additive for a hydraulic material according to any one of claims 1 to 4, wherein the compound (B) has a weight average molecular weight of 10 to 5 million.
6. The nitrogen-containing compound (A) is a structural unit having an alkylene group and an amino group and / or a structural unit derived from a nitrogen atom-containing monomer (A1) having a nitrogen atom content of 6.8% by mass or more (A1). The additive for a water-hard material according to any one of claims 1 to 5, which is a polymer having a1).
7. The nitrogen atom-containing monomer (A1) has the following formulas (3) to (6);
   

   

   (In formulas (3) to (6), R ² to R ⁴ represent the same or different alkyl groups having a hydrogen atom or 1 to 5 carbon atoms, and X represents a direct bond or a divalent linking group. In formulas (3) and (4), R ⁵ and R ⁶ represent hydrogen atoms or hydrocarbon groups having 1 to 12 carbon atoms, which are the same or different. In formulas (5) and (6), R ⁷ ~ R ⁹ represents the same or different hydrocarbon groups having 1 to 12 carbon atoms ^{. Y −} represents an anion.) A monomer represented by any of the above; a nitrogen-containing heterocyclic group-containing simple substance. The additive for a water-hard material according to any one of claims 1 to 6, wherein the weight is at least one selected from the group consisting of N-vinylformamide.
8. The nitrogen-containing compound (A) has at least one selected from the group consisting of a structural unit having an alkylene group and an amino group, a structural unit derived from an allylamine-based monomer, and a structural unit derived from a dialkylamine. The additive for a water-hard material according to any one of claims 1 to 7, which is a polymer.
9. The nitrogen-containing compound (A) is selected from the group consisting of polyethyleneimine, a polymer having a structural unit derived from an allylamine-based monomer, and a polymer having a structural unit derived from a reaction product of an epoxy compound and an amine compound. The additive for a water-hard material according to any one of claims 1 to 8, wherein the additive is at least one kind.
10. The additive for a hydraulic material according to any one of claims 1 to 9, wherein the nitrogen-containing compound (A) has a weight average molecular weight of 10 to 5 million.
11. The additive for a water-hard material according to any one of claims 1 to 10, wherein the ratio of the nitrogen-containing compound (A) to 100% by mass of the compound (B) is 0.1 to 200% by mass. The additive for water-hardening materials described.
12. A hydraulic material composition comprising the additive for a hydraulic material according to any one of claims 1 to 11 and a hydraulic material.
13. A method in which the additive for a hydraulic material according to any one of claims 1 to 11 is sprayed onto a construction surface together with the hydraulic material.