JP7154946B2 - Method for producing hydraulic composition for plastering - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a hydraulic composition for plastering.

Hydraulic compositions to be applied with a trowel, such as plastering materials, used to ensure workability during application by adding seaweed paste such as natural "Tsunomata". After that, methyl cellulose was developed as a semi-synthetic resin and has been commonly used since then.
The physical properties required for such a hydraulic composition include good workability (ease of application and ease of finishing), high water retention (prevention of poor curing due to dryout, etc.), and anti-sagging (misalignment) properties. (Prevention of deformation due to the weight of the applied mortar, prevention of slippage of the tiles attached), etc. are required, and these requirements are becoming more and more sophisticated in recent years as the rationalization of work sites progresses.

Patent Document 1 describes a vinyl polymer (A) comprising a specific vinyl polymer, (meth)acrylic acid (salt), and (meth)acrylic acid ester having 4 to 12 carbon atoms as essential constituent monomers, a specific vinyl monomer and An additive for a cement composition having excellent water retention and shape retention is disclosed, which is characterized by containing a vinyl polymer (B) comprising an unsaturated carboxylic acid (salt) as an essential constituent monomer. .
In Patent Document 2, a specific monomer (1b) having a group selected from an ethyleneoxy group and a propyleneoxy group as a component (A) and an alkali-thickening polymer as a component (A), and methacrylic acid and acrylic acid and a specific monomer (2b) as a constituent monomer, and the total amount of the monomer (1b) and the monomer (2b) in the constituent monomer is 90% by mass or more and 100% by mass or less Disclosed is an admixture for a one-component hydraulic composition that contains a copolymer and can impart excellent fluidity and material separation resistance to the hydraulic composition and has better storage stability. ing.

JP 2007-1844 A JP 2017-206393 A

When the hydraulic composition used for the plastering material is thickly applied with a trowel, the weight of the applied hydraulic composition causes sagging, resulting in loss of smoothness and cracking. In order to prevent this sagging, a hydraulic composition containing a thickening agent is used, but the thickening of the hydraulic composition deteriorates the workability with a trowel, and it is difficult for workers such as plasterers. It becomes a problem when the load increases.

The present invention provides a method for producing a hydraulic composition for plastering, which has good workability when the composition is applied with a trowel and is excellent in preventing dripping of the applied hydraulic composition.

TECHNICAL FIELD The present invention relates to a method for producing a hydraulic composition for plastering, which comprises mixing an emulsion containing (A) an alkali-thickening polymer (hereinafter referred to as component (A)), hydraulic powder, and water.

The present invention also relates to a hydraulic composition for plastering, which comprises an emulsion containing component (A), hydraulic powder, and water.

In the present invention, the hydraulic composition for plastering is, for example, a hydraulic composition that is used for finishing coating walls, floors, earthen walls, etc. of buildings using a trowel. It refers to a hydraulic composition that requires less sagging and workability with a trowel.
In addition, hydraulic compositions used for plastering must stand on their own (low fluidity) to prevent sagging, unlike concrete structures and concrete products that need to be pumped or poured into forms. It is also a special application in that it is preferable not to cause sagging even under weak vibration conditions that occur during work, and it is necessary to stand on its own even under vibration conditions (low fluidity).

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the hydraulic composition for plastering which has the favorable workability|operativity at the time of applying a hydraulic composition with a trowel, and is excellent in the drip prevention property of the applied hydraulic composition is provided.

Although the mechanism by which the effects of the present invention are exhibited is unknown, it is considered as follows.
In the present invention, the alkali-thickening polymer, which is the component (A), is in the form of an emulsion and is mixed with hydraulic powder and water. It is believed that the powder can be uniformly acted upon. In addition, since the component (A) is a polymer, it is believed that the hydraulic powder in the slurry can be aggregated. By the action of these two effects, the component (A) forms a uniform crosslinked structure with respect to the entire hydraulic powder particles in the slurry, and uniformly agglomerates the particles, thereby preventing sagging during operation. It is thought that a self-sustaining (low fluidity) slurry can be realized. Even when the slurry has a high salt concentration, if the component (A) is mixed in the form of an emulsion, the component (A) has low water retention and does not thicken water, which is the continuous phase. It is thought that it is possible to realize the

[Method for producing hydraulic composition for plastering]
<(A) Component>
Component (A) is an alkali-thickening polymer.
The alkali-thickening polymer has the property of being neutralized when it comes into contact with an alkali, such as the alkali of cement, becoming soluble in water, and increasing the viscosity of a mixture containing the polymer and water. Say. For example, the alkali-thickening polymer may be a polymer that thickens a mixture containing the polymer and water at a pH of 9 or higher. Whether or not the polymer is an alkali thickening type can be confirmed, for example, by checking that the viscosity of the mixture containing the polymer and water at pH 12.5 is at least twice the viscosity at pH less than 9. The ratio of polymer and water in the mixture is arbitrary, and the pH and viscosity measurement temperature can be selected to be 20°C. Mixtures include aqueous solutions, emulsions and slurries. In addition, as a method for measuring the viscosity, the method described in Examples can be mentioned.

The alkali-thickening polymer of component (A) includes a copolymer containing an unsaturated compound (1a) containing an acidic group and an ethylenically unsaturated compound (2a) as constituent monomers. In this copolymer, the total amount of (1a) and (2a) in the constituent monomers is preferably 80% by mass or more, more preferably 90% by mass or more, and preferably 100% by mass or less. Yes, and may be 100% by mass.

Examples of the acidic group of the unsaturated compound (1a) containing an acidic group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, and a phenolic hydroxyl group. These may be salts.

An unsaturated carboxylic acid (1a ₁ ) is mentioned as the unsaturated compound (1a) containing an acidic group.
As the unsaturated carboxylic acid (1a ₁ ),
unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, aconitic acid, and crotonic acid;
Unsaturated carboxylic acid anhydrides such as maleic anhydride and citraconic anhydride, and unsaturated carboxylic half-esters such as monomethyl itaconate, monobutyl itaconate and monoethyl maleate,
etc.

Further, as the unsaturated compound (1a) containing an acidic group,
unsaturated sulfonic acids such as vinylsulfonic acid, methallylsulfonic acid, 2-(meth)acrylamido-2-methylpropanesulfonic acid;
Unsaturated phosphoric acids such as 2-((meth)acryloyloxy)ethyl phosphate, bis[2-((meth)acryloyloxy)ethyl hydrogen phosphate],
unsaturated phenols such as vinylphenol,
etc.

As the unsaturated compound (1a) containing an acidic group, an unsaturated carboxylic acid (1a ₁ ) is preferred. The unsaturated carboxylic acid (1a ₁ ) is preferably a monomer (1a′) selected from acrylic acid and methacrylic acid, more preferably acrylic acid.

Examples of ethylenically unsaturated compounds (2a) include (2a ₁ ) ethylene, (2a ₂ ) cyanovinyl such as acrylonitrile and methacrylonitrile, (2a ₃ ) acrylic acid such as methyl acrylate, ethyl acrylate, and butyl acrylate. esters, (2a ₄ ) methacrylate esters such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate and glycidyl methacrylate; (2a ₅ ) vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, Vinyl esters of aliphatic carboxylic acids having 1 to 18 carbon atoms such as vinyl stearate, vinyl octylate, and vinyl neodecanoate; vinyl ether monomers such as (2a ₆ ) methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and phenyl vinyl ether; 2a ₇ ) polyfunctional vinyl monomers such as allyl methacrylate, (2a ₈ ) unsaturated hydrocarbons such as styrene and butadiene, and (2a ₉ ) acrylamide, methacrylamide, N-isopropylacrylamide, N-isopropylmethacrylamide, N - Unsaturated amide compounds such as vinylpyrrolidone.
Compounds containing an acidic group are excluded from the ethylenically unsaturated compound (2a). Therefore, the unsaturated compound (1a) containing an acidic group does not correspond to the ethylenically unsaturated compound (2a).

As the ethylenically unsaturated compound (2a), a monomer (2a') selected from acrylic acid esters and methacrylic acid esters is preferred. The number of carbon atoms in the ester portion of the acrylic acid ester and methacrylic acid ester is preferably 1 or more, more preferably 2 or more, and preferably 8 or less, more preferably 5 or less, and still more preferably 3 or less. The number of carbon atoms in the ester moiety is the number of carbon atoms in -C(O)-O-R ^1a (R ^1a is a hydrocarbon group) including carbon atoms in -C(O)-O-.
The monomer (2a') selected from acrylic acid esters and methacrylic acid esters is preferably one or more monomers selected from methyl acrylate, ethyl acrylate, methyl methacrylate and ethyl methacrylate.

Component (A) is preferably a copolymer containing an unsaturated carboxylic acid (1a ₁ ) and an ethylenically unsaturated compound (2a) as constituent monomers.
When component (A) is a copolymer of unsaturated carboxylic acid (1a ₁ ) and ethylenically unsaturated compound (2a), the mass ratio of unsaturated carboxylic acid/ethylenically unsaturated compound is From the viewpoint of obtaining viscosity, it is preferably 0.05 or more, more preferably 0.2 or more, still more preferably 0.4 or more, still more preferably 0.6 or more, and preferably 20 or less, more preferably 5 Below, more preferably 2.5 or less, still more preferably 1.5 or less. In this copolymer, the total amount of unsaturated carboxylic acid and ethylenically unsaturated compound in the constituent monomers is preferably 80% by mass or more, more preferably 90% by mass or more, and preferably 100% by mass or less. and may be 100% by mass.
Methods for polymerizing the unsaturated carboxylic acid and the ethylenically unsaturated compound include methods such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization.

Component (A) is a copolymer containing a monomer (1a') selected from acrylic acid and methacrylic acid and a monomer (2a') selected from acrylic acid esters and methacrylic acid esters as constituent monomers. Coalescence [hereinafter referred to as copolymer (A)] is more preferred.
Also in the copolymer (A), the monomer (2a′) has an ester moiety with preferably 1 or more carbon atoms, more preferably 2 or more carbon atoms, and preferably 8 or less, more preferably 5 or less carbon atoms, and further Monomers selected from acrylates and methacrylates, preferably 3 or less, are preferred. The number of carbon atoms in the ester moiety is the number of carbon atoms in -C(O)-O-R ^1a (R ^1a is a hydrocarbon group) including carbon atoms in -C(O)-O-.
In the copolymer (A), from the viewpoint of anti-sagging properties, the proportion of the monomer (1a') in the total of the monomer (1a') and the monomer (2a') is preferably 20% by mass. above, more preferably 30% by mass or more, still more preferably 35% by mass or more, still more preferably 40% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 55% by mass 50% by mass or less, more preferably 50% by mass or less.
In the copolymer (A), the total amount of the monomer (1a′) and the monomer (2a′) in the constituent monomers is preferably 60% by mass or more, more preferably 70% by mass or more, More preferably 80% by mass or more, still more preferably 85% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, and preferably 100% by mass or less, and 100% by mass may be

The component (A) preferably has a weight average molecular weight of 100,000 or more and 10,000,000 or less from the viewpoint of sagging prevention. The weight average molecular weight of component (A) is more preferably 150,000 or more, still more preferably 200,000 or more, still more preferably 250,000 or more, and preferably 8,000,000 or less, more preferably 5 ,000,000 or less, even more preferably 3,000,000 or less, even more preferably 2,000,000 or less, even more preferably 1,700,000 or less, still more preferably 1,200,000 or less be.

Component (A) has a number average molecular weight of preferably 20,000 or more, more preferably 30,000 or more, still more preferably 35,000 or more, and even more preferably 40,000 or more, from the viewpoint of anti-sagging properties. And preferably 8,000,000 or less, more preferably 5,000,000 or less, even more preferably 2,000,000 or less, still more preferably 1,000,000 or less, still more preferably 500,000 Below, more preferably 300,000 or less, still more preferably 250,000 or less, still more preferably 200,000 or less, still more preferably 180,000 or less.

Component (A) has a weight average molecular weight (Mw) to number average molecular weight (Mn) ratio Mw/Mn of preferably 1.1 or more, more preferably 2.0 or more, and even more preferably 2.0 or more, from the viewpoint of anti-sagging properties. is 4.0 or more, still more preferably 5.0 or more, and preferably 10.0 or less, more preferably 8.0 or less, and even more preferably 7.0 or less.

The weight-average molecular weight and number-average molecular weight of component (A) were each measured by gel permeation chromatography (GPC) under the following conditions.
* GPC conditions Apparatus: GPC (HLC-8320GPC) manufactured by Tosoh Corporation Column: TsKgelα-M + TsKgelα-M (manufactured by Tosoh Corporation)
Eluent: 60 mmol/L phosphoric acid, 50 mmol/L LiBr-DMF
Flow rate: 1.0 mL/min
Column temperature: 40°C
Detection: RI
Sample size: 1 mg/mL
Standard material: polystyrene conversion (monodisperse polystyrene with known molecular weight, molecular weight: 590, 3,600, 30,000, 96,400, 929,000, 8,420,000)

In the present invention, the component (A) is preferably the copolymer (A). In the present invention, the component (A) is more preferably the copolymer (A) having a weight average molecular weight within the above range.

Component (A) is available in the form of an emulsion using water as a dispersion medium. In the method for producing a hydraulic composition for plastering of the present invention, an emulsion containing component (A) is mixed with hydraulic powder and water from the viewpoint of anti-sagging.

In the method for producing a hydraulic composition for plastering of the present invention, the solid content concentration of component (A) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and still more preferably 1% by mass or more, Still more preferably 5% by mass or more, still more preferably 10% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, still more preferably 20% by mass Mix with hydraulic powder and water as an emulsion containing:

The emulsion containing component (A) preferably contains water as a dispersion medium and component (A) as dispersed particles. In the emulsion containing component (A), the average particle size of dispersed particles of component (A) is preferably 0.01 µm or more, more preferably 0.05 µm or more, and preferably 20 µm or less, more preferably 10 µm or less. be. The average particle size of the dispersed particles of component (A) is measured by diluting with ion-exchanged water to a solid content of 0.3% by mass and using a particle size/zeta potential measuring device, Zetasizer Nano ZS (manufactured by Malvern). be able to.

<(B) Component>
In the method for producing the hydraulic composition for plastering of the present invention, it is preferable to further mix a dispersant as the component (B) from the viewpoint of good workability.

Component (B) is preferably a hydraulic powder dispersant, more preferably one or more dispersants selected from polycarboxylic acid polymers, naphthalene polymers, and cationic polymers.

As the polycarboxylic acid-based polymer of the component (B), a monomer (1b) represented by the following general formula (1b) and a monomer (2b) represented by the following general formula (2b) are constituent monomers. Copolymers containing as a body are preferred.

[In the formula,
R ^1b , R ^2b : may be the same or different, hydrogen atom or methyl group R ^3b : hydrogen atom or —COO(AO) _n1 X ¹
X ¹ : a hydrogen atom or an alkyl group having 1 to 4 carbon atoms AO: a group selected from an ethyleneoxy group and a propyleneoxy group n1: the average number of added moles of AO, the number of 2 to 300 q: 0 to 2 Indicates the number of: ]

[In the formula,
R ^4b , R ^5b , R ^6b : may be the same or different and is a hydrogen atom, a methyl group or (CH ₂ ) _r COOM ² , (CH ₂ ) _r COOM ² is COOM ¹ or other (CH ₂ ) may form an anhydride with _r COOM ² , in which case M ¹ , M ² of those groups are absent.
M ¹ , M ² : may be the same or different, hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium group, alkylammonium group, substituted alkylammonium group, alkyl group, hydroxyalkyl group, or Alkenyl group r: A number of 0 or more and 2 or less. ]

In general formula (1b), R ^1b is preferably a hydrogen atom.
In general formula (1b), R ^2b is preferably a methyl group.
In general formula (1b), R ^3b is preferably a hydrogen atom.
In general formula (1b), X ¹ is preferably a hydrogen atom or a methyl group, more preferably a methyl group.
In general formula (1b), AO is preferably an ethyleneoxy group. AO preferably contains an ethyleneoxy group.
In general formula (1b), n1 is the average number of added moles of AO, and from the viewpoint of anti-sagging and good workability, 2 or more, preferably 5 or more, and 300 or less, preferably 140 or less, or more. The number is preferably 120 or less.
In general formula (1b), q is preferably 0.

In general formula (2b), R ^4b is preferably a hydrogen atom.
In general formula (2b), R ^5b is preferably a methyl group.
In general formula (2b), R ^6b is preferably a hydrogen atom.
(CH ₂ ) _r COOM ² may form an anhydride with COOM ¹ or another (CH ₂ ) _r COOM ² , in which case M ¹ , M ² of those groups are absent.
M ¹ and M ² may be the same or different, and may be a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), an ammonium group, an alkylammonium group, a substituted alkylammonium group, an alkyl group, a hydroxyalkyl group, or It is an alkenyl group.
The alkyl group, hydroxyalkyl group, and alkenyl group of M ¹ and M ² each preferably have 1 or more and 4 or less carbon atoms.
M ¹ and M ² may be the same or different, preferably a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), an ammonium group, or an alkylammonium group, a hydrogen atom, an alkali metal, an alkaline earth A metal group (1/2 atom) or an ammonium group is more preferred, a hydrogen atom, an alkali metal or an alkaline earth metal (1/2 atom) is more preferred, and a hydrogen atom or an alkali metal is even more preferred.
r of (CH ₂ ) _r COOM ² in general formula (2b) is preferably 1.

In the copolymer containing the monomer (1b) and the monomer (2b) as constituent monomers, the total amount of the monomer (1b) and the monomer (2b) in the constituent monomers is preferably is 90% by mass or more, more preferably 92% by mass or more, still more preferably 95% by mass or more, and preferably 100% by mass or less. This total amount may be 100% by mass.

In a copolymer containing the monomer (1b) and the monomer (2b) as constituent monomers, the ratio of the monomer (2b) to the total of the monomer (1b) and the monomer (2b) is , From the viewpoint of anti-sagging and good workability, preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, still more preferably 40 mol% or more, and preferably 90 mol % or less, more preferably 80 mol % or less, still more preferably 60 mol % or less, and even more preferably 50 mol % or less.

The weight-average molecular weight of the polycarboxylic acid-based polymer and further the copolymer containing the monomer (1b) and the monomer (2b) as constituent monomers is preferably 20,000 from the viewpoint of good workability. more preferably 30,000 or more, more preferably 40,000 or more, still more preferably 50,000 or more, and preferably 100,000 or less, more preferably less than 100,000, even more preferably 70,000 Below, more preferably below 60,000.

The number average molecular weight of the polycarboxylic acid-based polymer and further the copolymer containing the monomer (1b) and the monomer (2b) as constituent monomers is preferably 15,000 from the viewpoint of good workability. Above, more preferably 25,000 or more, still more preferably 35,000 or more, and preferably 80,000 or less, more preferably 50,000 or less.

From the viewpoint of good workability, the polycarboxylic acid-based polymer and further the copolymer containing the monomer (1b) and the monomer (2b) as constituent monomers have a weight average molecular weight (Mw) and a number average The molecular weight (Mn) ratio Mw/Mn is preferably 1.0 or more, more preferably 1.1 or more, still more preferably 1.2 or more, and preferably 7.0 or less, more preferably 4.5 or less. , more preferably 2.0 or less.

The weight-average molecular weight and number-average molecular weight of the polycarboxylic acid-based polymer and further the copolymer containing the monomer (1b) and the monomer (2b) as constituent monomers are gel permeation under the following conditions: It was measured by a chromatographic (GPC) method.
* GPC conditions Equipment: GPC (HLC-8320GPC) manufactured by Tosoh Corporation Column: G4000PWXL + G2500PWXL (manufactured by Tosoh Corporation)
Eluent: 0.2M phosphate buffer/ _CH3CN =9/1
Flow rate: 1.0 mL/min
Column temperature: 40°C
Detection: RI
Sample size: 0.2 mg/mL
Standard substance: Polyethylene glycol equivalent (monodisperse polyethylene glycol with known molecular weight, molecular weight 87,500, 250,000, 145,000, 46,000, 24,000)

The naphthalene-based polymer preferably includes a naphthalenesulfonic acid formaldehyde condensate or a salt thereof. The naphthalenesulfonic acid-formaldehyde condensate or its salt is a condensate of naphthalenesulfonic acid and formaldehyde or its salt. Naphthalenesulfonic acid-formaldehyde condensates may be used as monomers, for example, methylnaphthalene, ethylnaphthalene, butylnaphthalene, hydroxynaphthalene, naphthalenecarboxylic acid, anthracene, phenol, cresol, creosote oil, tar, melamine, as long as the performance is not impaired. It may be co-condensed with an aromatic compound capable of co-condensing with naphthalenesulfonic acid, such as urea, sulfanilic acid and/or derivatives thereof.

Naphthalenesulfonic acid formaldehyde condensates or salts thereof include, for example, Mighty 150, Demol N, Demol RN, Demol MS, Demol SN-B, Demol SS-L (all manufactured by Kao Corporation), Celluflow 120, and Labelin FD-40. , Labelin FM-45 (both manufactured by Daiichi Kogyo Co., Ltd.) and the like can be used.

The naphthalenesulfonic acid formaldehyde condensate or its salt preferably has a weight average molecular weight of 1,000 or more, more preferably 3,000 or more, and still more preferably 4,000 or more, from the viewpoint of anti-sagging property and good workability. , more preferably 5,000 or more, and preferably 200,000 or less, more preferably 100,000 or less, even more preferably 80,000 or less, even more preferably 50,000 or less, still more preferably 30, 000 or less. The naphthalenesulfonic acid formaldehyde condensate may be in the acid state or neutralized.

The molecular weight of the naphthalenesulfonic acid-formaldehyde condensate or salt thereof can be measured using gel permeation chromatography under the following conditions.
[GPC conditions]
Column: G4000SWXL + G2000SWXL (Tosoh)
Eluent: ₃₀ mM CH3COONa/ _CH3CN =6/4
Flow rate: 0.7ml/min
Detection: UV280nm
Sample size: 0.2mg/ml
Standard material: Nishio Kogyo Co., Ltd. polystyrene sodium conversion (monodisperse sodium polystyrene sulfonate: molecular weight, 206, 1,800, 4,000, 8,000, 18,000, 35,000, 88,000, 780,000)
Detector: Tosoh Corporation UV-8020

The cationic polymer is preferably a cationic polymer having a structural unit derived from a polymerizable monomer having an amine or quaternary ammonium group.
The cationic polymer contains monomer units [hereinafter referred to as monomer units (3b)] derived from one or more compounds selected from compounds represented by the following general formula (3b), acid salts thereof, and quaternary salts thereof. A cationic polymer containing is more preferred.

[In general formula (3b), R ^11b and R ^12b each independently represent a hydrogen atom or a methyl group, and R ^13b is —C(O)OM ³ (M ³ is a hydrogen atom or an alkali metal atom) or Indicates a hydrogen atom. X ² represents -C(O) ^{OR 16b} -, -C(O)NR ^17b -R ^18b - or -CH ₂ -. R ^14b has the general formula (3b′) when X ² is —CH ₂ —

In other cases, X ² is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms. R ^15b represents an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a hydrogen atom. R ^16b and R ^18b each independently represent an alkylene group having 1 to 4 carbon atoms, and R ^17b represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]

Among the compounds represented by the general formula (3b) from which the monomer unit (3b) is derived, the compound in which X ² in the general formula (3b) is —C(O) ^{OR 16b} — includes acrylic acid (or methacrylic acid) N,N-dimethylaminomethyl, acrylic acid (or methacrylic acid) N,N-dimethylaminoethyl, acrylic acid (or methacrylic acid) N,N-dimethylaminopropyl, acrylic acid (or methacrylic acid) ) N,N-dimethylaminobutyl, N,N-diethylaminomethyl acrylate (or methacrylate), N,N-diethylaminoethyl acrylate (or methacrylate), N,N-diethylaminopropyl acrylate (or methacrylate) , acrylic acid (or methacrylic acid), N,N-diethylaminobutyl, and the like.

Further, among the compounds represented by general formula (3b), the compound in which X ² in general formula (3b) is —C(O)NR ^17b —R ^18b — includes N,N-dimethylaminopropylacryl acid (or methacrylic acid) amide, N,N-dimethylaminomethyl acrylic acid (or methacrylic acid) amide, N,N-dimethylaminoethyl acrylic acid (or methacrylic acid) amide, N,N-dimethylaminobutyl acrylic acid ( or methacrylic acid) amide and the like.

Further, when X ² in general formula (3b) is —CH ₂ —, R ^14b is a group represented by general formula (3b′). Examples of such compounds include diallylamine and the like.

The acid salt or quaternary salt thereof can be used for the compound represented by the general formula (3b). Examples of the acid salt include neutralized salts of the compound represented by the general formula (3b) with an inorganic acid such as hydrochloric acid or sulfuric acid, and neutralized salts with various organic acids. The quaternary salt includes a quaternary salt obtained by quaternizing the compound represented by the general formula (3b) with an alkyl halide having 1 to 3 carbon atoms or an alkyl sulfuric acid having 1 to 3 carbon atoms. . Examples of quaternary salts include N,N,N-trimethyl-N-(2-methacryloyloxyethyl)ammonium chloride, N,N-dimethyl-N-ethyl-N-(2-methacryloyloxyethyl)ammonium ethylsulfate, diallyldimethyl Ammonium chloride is mentioned. These compounds are sold, for example, by MRC Unitek Co., Ltd. under the trade names of QDM and MOEDES.

Among the compounds represented by the general formula (3b), more preferred compounds are N,N-dimethylaminoethyl methacrylate, N,N-dimethylaminomethyl methacrylate, N,N-dimethylaminoethyl acrylate, N acrylate , N-dimethylaminomethyl, and one or more selected from acid salts or quaternary salts thereof.

The cationic polymer comprises a monomer unit (3b) and a monomer unit derived from a polymerizable vinyl compound copolymerizable with the compound represented by general formula (3b) [hereinafter referred to as monomer unit (4b)]. It may be a copolymer having

Examples of the monomer unit (4b) include monomer units derived from compounds represented by the following general formula (4b).

[In the formula, R ^21b and R ^22b each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Y is an aryl group, -OC(O)-R ^23b , -C(O ) O—(R ^24b —O) _n2 —R ^25b , or —C(O)NR ^26b —R ^27b . R ^23b , R ^25b , and R ^27b each independently represent a linear, branched, or cyclic alkyl or alkenyl group having 1 to 22 carbon atoms, or an arylalkyl group having 6 to 14 carbon atoms in total; R ^24b is an alkylene group having 2 or 3 carbon atoms, n2 is a number of 0 to 50, and R ^26b is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]

Y in general formula (4b) is preferably -C(O)O-(R ^24b -O) _n2 -R ^25b .
In —C(O)O—(R ^24b —O)nR ^{25b of Y, R 25b is} preferably an alkyl group having 8 or more, more preferably 10 or more, and 18 or less, further 14 or less carbon atoms. R ^24b is preferably ethylene. n2 is a number of 0 or more, preferably 20 or less, more preferably 10 or less. n is more preferably 0.

As a specific polymerizable vinyl compound represented by the general formula (4b) and copolymerizable with the starting material of the monomer unit (3b), the alkyl group has 1 or more, preferably 8 or more, and 22 or less carbon atoms. , preferably 14 or less, alkyl acrylates or alkyl methacrylates are preferred.

Examples of polymerizable vinyl compounds copolymerizable with the starting material of the monomer unit (3b) other than the compound of general formula (4b) [hereinafter referred to as other polymerizable compounds] include (1) vinyl alcohol and (2) hydroxyethyl. (Meth)acrylic acid ester or (meth)acrylamide having a hydroxyalkyl group having 1 to 22 carbon atoms such as (meth)acrylate, hydroxypropyl (meth)acrylamide, (3) Polyhydric alcohol such as glycerin (meth)acrylate (meth)acrylic acid ester of (4) diacetone (meth)acrylamide, (5) N-vinyl cyclic amides such as N-vinylpyrrolidone, (6) N-(meth)acryloylmorpholine, (7) vinyl chloride, (8) acrylonitrile, (9) (meth)acrylic acid, maleic acid, itaconic acid, vinyl compounds having a carboxyl group such as styrenecarboxylic acid, (10) 2-acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, etc. vinyl compounds having a sulfonic acid group, and the like.

The cationic polymer is (1) a compound selected from compounds represented by the general formula (3b), acid salts thereof and quaternary salts thereof, specifically N,N-dimethylaminoethyl methacrylate, methacrylic acid Cationic homopolymers of monomers selected from N,N-dimethylaminomethyl, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminomethyl acrylate, and acid salts or quaternary salts thereof, and (2 ) One or more compounds selected from the compounds represented by the general formula (3b), acid salts thereof and quaternary salts thereof, specifically N,N-dimethylaminoethyl methacrylate, N,N-methacrylate A monomer selected from dimethylaminomethyl, N,N-dimethylaminoethyl acrylate, and N,N-dimethylaminomethyl acrylate, and a compound represented by the general formula (4b), specifically, the number of carbon atoms in the alkyl group is Cationic copolymers obtained by copolymerization with one or more compounds selected from 8 to 14 acrylic acid alkyl esters and methacrylic acid alkyl esters are preferred.

When the cationic polymer is a copolymer having monomer units derived from the compounds represented by the monomer units (3b) and (4b), such copolymers are monomer units (3b)/ The molar ratio of the monomer unit (4b) is preferably 20/80 or more and 99/1 or less, more preferably 50/50 or more and 95/5 or less, and even more preferably 70/30 or more and 95/5 or less. The sum of the monomer units (3b) and (4b) is preferably 60 mol% or more, more preferably 80 mol% or more, and preferably 100 mol% or less, of the total monomer units of the cationic polymer. The ratio of the monomer units may be the molar ratio of the polymerizable compounds of general formula (3b) and general formula (4b) used during polymerization.

The weight average molecular weight (Mw) of the cationic polymer is preferably 2,000 or more, more preferably 3,000 or more, still more preferably 6,000 or more, still more preferably 12,000 or more, and preferably 2 ,000,000 or less, more preferably 1,500,000 or less, even more preferably 100,000 or less, and even more preferably 60,000 or less. The ratio Mw/Mn between Mw and Mn (number average molecular weight) is preferably 1.0 or more, more preferably 1.5 or more, and preferably 40 or less, more preferably 35.

Mw, Mn and Mw/Mn of the cationic polymer use values obtained by gel permeation chromatography (GPC) measurement. Water, alcohol, chloroform, dimethylformamide, tetrahydrofuran, acetonitrile, or a combination of these solvents can be used as the eluent. If the cationic polymer is relatively hydrophilic, use polyethylene glycol as the standard. Since it is used as a molecular weight in terms of polyethylene glycol (hereinafter sometimes referred to as PEG conversion), and if it is relatively hydrophobic, polystyrene is used as a standard, so polystyrene conversion (hereinafter sometimes referred to as PSt conversion) molecular weight.

That is, when the polymer to be measured is considered to be relatively hydrophilic with a large proportion of the monomer unit (3b), a mixed solvent of (1% acetic acid/ethanol): water = 3:7 (mass ratio) Using the prepared 50 mmol / L solution of LiBr as a solvent, two GPC columns for polar solvents "α-M (manufactured by Tosoh Corporation)" are used in series, and the molecular weight is calculated in terms of polyethylene glycol (measurement method A). . If the polymer is considered to be relatively hydrophobic, a 1 mmol/L-CHCl3 solution of Firmin DM20 (manufactured by Kao Corporation) was added to the organic solvent GPC column "K-804 (manufactured by Showa Denko Co., Ltd.). ” are used in series, and the molecular weight is calculated in terms of polystyrene (measurement method B).

<Hydraulic powder>
The hydraulic powder used in the method for producing a hydraulic composition for plastering of the present invention is a powder that hardens when mixed with water. Portland cement, ultra-early-strength Portland cement, sulfate-resistant Portland cement, low-heat Portland cement, white Portland cement, ecocement (for example, JIS R5214, etc.). Among these, cement selected from early-strength Portland cement, ordinary Portland cement, sulfuric acid-resistant Portland cement, and white Portland cement is preferable from the viewpoint of shortening the time required for the hydraulic composition to reach the required strength. Cements selected from Portland cement and ordinary Portland cement are more preferred.

Hydraulic powders may include blast furnace slag, fly ash, silica fume, anhydrous gypsum, and the like, and may also include non-hydraulic limestone fine powder. As the hydraulic powder, blast furnace cement, fly ash cement, and silica fume cement, which are mixtures of cement, blast furnace slag, fly ash, silica fume, and the like, may be used.
Hydraulic powders include cement or a mixed powder of cement and bentonite.

<Mixed composition, etc.>
In the method for producing a hydraulic composition for plastering of the present invention, the amount of component (A) mixed with 100 parts by mass of hydraulic powder is preferably 0.01 part by mass or more, from the viewpoint of sagging prevention. Preferably 0.02 parts by mass or more, more preferably 0.03 parts by mass or more, and preferably 2 parts by mass or less, more preferably 1.5 parts by mass or less, even more preferably 1.2 parts by mass or less, and even more The emulsion containing component (A) is mixed in an amount of preferably 0.9 parts by mass or less, more preferably 0.6 parts by mass or less, and even more preferably 0.3 parts by mass or less.

In the method for producing a hydraulic composition for plastering of the present invention, when the component (B) is mixed, the amount of the component (B) mixed with respect to 100 parts by mass of the hydraulic powder is, from the viewpoint of good workability, Preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, still more preferably 0.03 parts by mass or more, and preferably 1 part by mass or less, more preferably 0.7 parts by mass or less, still more preferably 0.5 parts by mass or less, more preferably 0.3 parts by mass or less, even more preferably 0.25 parts by mass or less, still more preferably 0.2 parts by mass or less, and mixing component (B) do.

In the method for producing a hydraulic composition for plastering of the present invention, when the component (B) is mixed, the mass ratio (B)/(A) of the mixing amount of the component (A) and the mixing amount of the component (B) is From the viewpoint of anti-sagging and good workability, it is preferably 0.05 or more, more preferably 0.1 or more, still more preferably 0.2 or more, and preferably 3 or less, more preferably 2.5 or less. More preferably, the emulsion containing component (A) and component (B) are mixed so that the ratio is 2 or less.

In the method for producing a hydraulic composition for plastering of the present invention, the water/hydraulic powder ratio (W/C) is preferably 20% by mass or more, more preferably 30% by mass, from the viewpoint of anti-sagging and good workability. Water and hydraulic powder are mixed so that the content is at least 200% by mass, preferably 150% by mass or less, and even more preferably 100% by mass or less.
Here, the water/hydraulic powder ratio (W/C) is the mass percentage (mass %) of water and powder in the hydraulic composition, and is calculated by water/powder×100.
In addition, the hydraulic powder is selected from powder having a physical property of hardening by hydration reaction such as cement, powder having pozzolanic action, powder having latent hydraulic property, and stone powder (calcium carbonate powder). When powders are included, their amount is also included in the amount of hydraulic powder in the present invention. Moreover, when the powder having the property of hardening by hydration contains a high-strength admixture, the amount of the high-strength admixture is also included in the amount of the hydraulic powder. This is the same for other mass parts related to the mass of the hydraulic powder.

In the method for producing a hydraulic composition for plastering of the present invention, an aggregate can be further mixed. Aggregates include fine aggregates, coarse aggregates, and the like. Fine aggregates are preferably mountain sand, land sand, river sand, and crushed sand, and coarse aggregates are preferably mountain gravel, land gravel, river gravel, and crushed stone. Depending on the application, lightweight aggregate may be used. The term "aggregate" is based on "Concrete Overview" (June 10, 1998, published by Gijutsu Shoin).
When coarse aggregate is used, it is preferably 1000 kg/m ³ or less, more preferably 850 kg/m ³ or less, even more preferably 700 kg/m ³ or less, and 500 kg/m ³ . 300 kg/m ³ or less, even more preferably 100 kg/m ³ or less, even more preferably 50 kg/m ³ or less, and 25 kg/m 3 or less. It is more preferably m ³ or less, even more preferably 10 kg/m ³ or less, and even more preferably 1 kg/m ³ or less. It is preferable that coarse aggregate is not mixed in the method for producing the hydraulic composition for plastering of the present invention.

In the method for producing the hydraulic composition for plastering of the present invention, other components other than the components described above can be further mixed within a range that does not affect the effects of the present invention. Examples include AE agents, retarders, foaming agents, thickeners, foaming agents, waterproofing agents, flow agents, antifoaming agents and the like.

In the method for producing a hydraulic composition for plastering of the present invention, a liquid composition is prepared by mixing water, an emulsion containing component (A), and an optional component (B) in advance, and the liquid composition is mixed with water. It is preferable to add to a mixture of hard powder, moreover, to a mixture of hydraulic powder and aggregate, and to produce a hydraulic composition for plastering.
That is, as a method for producing a hydraulic composition for plastering of the present invention, a liquid composition containing water, an emulsion containing component (A), and an optional component (B) is prepared, and the liquid composition is prepared. is added to the hydraulic powder, and further to the mixture of the hydraulic powder and the aggregate, and mixed.

In the method for producing the hydraulic composition for plastering of the present invention, all existing devices can be used for mixing each component, for example, tilting mixer, pan mixer, twin-screw forced mixer, omni mixer, Henschel mixer, Examples include V-type mixers and Nauta mixers.

The hydraulic composition for plastering obtained by the production method of the present invention has workability when applying the prepared hydraulic composition with a trowel (ease of application with a trowel due to suppression of thickening, lightness of the trowel during work ) and can suppress dripping of the applied hydraulic composition, it is suitable for plasterers who mainly apply with a trowel.

[Hydraulic composition for plastering]
TECHNICAL FIELD The present invention relates to a hydraulic composition for plastering, which comprises an emulsion containing component (A), hydraulic powder, and water.
For the hydraulic composition for plastering of the present invention, the aspects described in the manufacturing method of the hydraulic composition for plastering of the present invention can be appropriately applied.
In the hydraulic composition for plastering of the present invention, the component (A), the hydraulic powder, the optional component (B), the aggregate, and other optional components are prepared in the method for producing the hydraulic composition for plastering of the present invention. Same as described embodiment. In addition, the mixing amount of component (A), the mixing amount of component (B), and the mass ratio (B)/(A) described in the manufacturing method of the hydraulic composition for plastering of the present invention are obtained by replacing the mixing amount with the blending amount. , can be applied to the hydraulic composition for plastering of the present invention.

The components (A), (A') (comparative components for component (A)), and (B) shown in Tables 2 and 3 were as follows.

(A) component (A-1): as constituent monomers, a copolymer composed of acrylic acid, ethyl acrylate, and ethyl methacrylate, acrylic acid/ethyl acrylate/ethyl methacrylate = 40 mass%/30 Mass %/30 mass %, polymerization average molecular weight (Mw) 557,000, number average molecular weight (Mn) 84,900
An aqueous emulsion of the copolymer (A-1) having a solid content of 1.0% by mass gave a pH of 2.7 and a viscosity of 5.5 mPa s, whereas a 10% by mass aqueous sodium hydroxide solution gave a pH of 12.5 and a solid Since the aqueous emulsion of copolymer (A-1) adjusted to 1.0% by mass gave a viscosity of 20 mPa s, copolymer (A-1) was judged to be an alkali-thickening polymer. . Both pH and viscosity are values at 20°C (the same applies to component (A) below). The viscosity was measured with a B-type viscometer (BM-type VISCOMETER: manufactured by TOKIMEC INC., measurement conditions: rotor No. 2, 60 rpm). The pH was measured with a pH meter (HM-30S: manufactured by Toa DKK).

(A-2): A copolymer composed of acrylic acid, ethyl acrylate, and ethyl methacrylate as constituent monomers, acrylic acid/ethyl acrylate/ethyl methacrylate = 50% by mass/25% by mass/25 mass %, polymerization average molecular weight (Mw) 267,000, number average molecular weight (Mn) 43,400
An aqueous emulsion of the copolymer (A-2) having a solid content of 1.0% by mass gave a pH of 2.7 and a viscosity of 4.5 mPa s, while a 10% by mass sodium hydroxide aqueous solution gave a pH of 12.5 and a solid Since the aqueous emulsion of copolymer (A-2) adjusted to 1.0% by mass gave a viscosity of 30 mPa s, copolymer (A-2) was judged to be an alkali-thickening polymer. .

(A-3): A copolymer composed of acrylic acid and ethyl acrylate as constituent monomers, acrylic acid/ethyl acrylate = 50 mass%/50 mass%, polymerization average molecular weight (Mw) 1,050 ,000, number average molecular weight (Mn) 174,000
An aqueous emulsion of the copolymer (A-3) having a solid content of 1.0% by mass gave a pH of 2.7 and a viscosity of 5.5 mPa s. Since the aqueous emulsion of copolymer (A-3) adjusted to 1.0% by mass gave a viscosity of 30 mPa s, copolymer (A-3) was judged to be an alkali-thickening polymer. .

(A-4): A copolymer composed of acrylic acid, ethyl acrylate, and ethyl methacrylate as constituent monomers, acrylic acid/ethyl acrylate/ethyl methacrylate=50% by mass/30% by mass/20 Mass %, polymerization average molecular weight (Mw) 86,4000, number average molecular weight (Mn) 170,000
An aqueous emulsion of the copolymer (A-4) having a solid content of 1.0% by mass gave a pH of 2.7 and a viscosity of 5.5 mPa s. Since the aqueous emulsion of copolymer (A-4) adjusted to 1.0% by mass gave a viscosity of 150 mPa s, copolymer (A-4) was judged to be an alkali-thickening polymer. .

Copolymers (A-1) to (A-4) were produced based on the production example of JP-A-2017-206393.

(A') component (comparative component of (A) component)
(A'-1): bentonite, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. (A'-2): hydroxyethyl cellulose, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

Component (B) (B-1): as a constituent monomer, a copolymer composed of monomer (1b) and monomer (2b), monomer (2b)/monomer (1b) = methacrylic acid/methoxypolyethylene glycol (9) monomethacrylate (average addition mole number in parentheses) = 47 mol%/53 mol%, weight average molecular weight (Mw) = 70,000
(B-2): Naphthalenesulfonic acid formalin condensate (Mighty 150: manufactured by Kao Corporation)
(B-3): Homopolymer consisting of monomer units derived from N,N-dimethylaminoethyl methacrylate sulfate, weight average molecular weight (Mw) 56,000, Caosera MD-P, manufactured by Kao Corporation ( B-4): Copolymer composed of monomer (1b) and monomer (2b) as constituent monomers, monomer (2b)/monomer (1b) = methacrylic acid/methoxy Polyethylene glycol (120) monomethacrylate (average addition mole number in parentheses) = 60 mol%/40 mol%, weight average molecular weight (Mw) = 60,000
(B-5): as a constituent monomer, a copolymer composed of monomer (1b) and monomer (2b), monomer (2b)/monomer (1b) = methacrylic acid/ Methoxypolyethylene glycol (120) monomethacrylate (average addition mole number in parentheses) = 90 mol%/10 mol%, weight average molecular weight (Mw) = 55,500

[Mortar test for plastering]
<Preparation of plastering mortar>
Cement and sand were added to a Hobart mixer (KC-8, manufactured by Kansai Kiki Seisakusho Co., Ltd.) according to the formulation shown in Table 1, and the mixture was kneaded for 10 seconds. Next, water mixed with each component shown in Table 2 is added to the dry-kneaded mixture of cement and sand, and stirred for 2 minutes (stirring speed: revolution 62 rpm, rotation 141 rpm) to prepare mortar for plastering. did. In Examples 1-1 to 1-12 in Table 2, when component (A) was mixed with water, component (A) was an emulsion having a solid concentration of 15% by mass. Further, in Comparative Examples 1-2 to 1-4 in Table 2, when component (A') was mixed with water, component (A') was powder (solid concentration: 100% by mass). In Comparative Example 1-5 in Table 2, the copolymer (A-1) is used as the component (A). Instead, an aqueous solution prepared by adjusting the copolymer (A-1) to a pH of 12.5 and a solid content of 15% by mass with a 10% by mass sodium hydroxide aqueous solution was used.
The amount of water to be added was adjusted so that the amount of water in the formulation shown in Table 1 was achieved. The amount of water to be added includes the amount of component (A), component (A') and component (B) added.

In Table 1, each material used in the mortar formulation is as follows.
Water: tap water (the blending amount includes components (A), (A'), and (B))
Cement: Ordinary Portland cement, a mixture of Taiheiyo Cement and Sumitomo Osaka Cement at a mass ratio of 50/50, specific gravity 3.16
Sand: Made in Joyo, Kyoto Prefecture, surface dry specific gravity 2.54 g/cm ³

<Evaluation of fluidity of mortar>
According to JIS R 5201, the mortar for plastering immediately after kneading is filled into a flow cone (upper diameter 70 mm x lower diameter 100 mm x height 60 mm), and the initial mortar spreads 1 minute after being lifted vertically on the flow table. Measured as flow. Table 2 shows the results. From the viewpoint of suppression of sag, the initial mortar flow is preferably 120 mm or less. Next, immediately after measuring the initial mortar flow, measure the mortar flow when the flow table is tapped 15 times in 10 seconds (referred to as "mortar flow after tapping" in Table 2), and calculate the flow difference from the initial mortar flow. did. Table 2 shows the results. From the viewpoint of workability with a trowel, the flow difference is preferably 95 mm or more.

<Sagging test>
A plate made of mortar was placed on a horizontal surface, a frame of 100×100×30 (thickness) mm was placed thereon, and the prepared mortar for plastering was filled in the frame. After that, the frame was removed, and the plate made of mortar was allowed to stand at an angle of 90° with the ground. The mortar was allowed to stand until it stopped sagging due to its own weight, and after confirming that the sagging had stopped, the vertical length from the ground of the part protruding from the mortar shape when the formwork was present was measured. Table 2 shows the results. From the viewpoint of preventing sagging, the length is preferably within 200 mm.

<Workability sensory evaluation>
The prepared mortar for plastering was applied to a board made of mortar with a trowel to a thickness of about 5 mm, and stickiness and lightness of the trowel were evaluated. After the sticky mortar was applied, the load on the arm when the trowel was removed from the smeared mortar was sensorily evaluated according to the following criteria. As for the lightness of the trowel, the lightness of the trowel and the smoothness when applying to a thickness of about 5 mm were sensorily evaluated according to the following criteria. Table 2 shows the results.
Stickiness 1: When the trowel is removed from the mortar, stickiness is felt and the arm is burdened.
2: Stickiness is felt when the trowel is removed from the mortar, but no burden is felt on the arm.
3: The trowel can be easily separated, and the arm does not feel a burden.
Lightness of trowel 1: It is heavy and feels a load on the arm.
2: The burden is light, but force is required when applying.
3: Can be applied smoothly with almost no effort.

In Table 2, the content of component (A) and component (B) is the content (parts by mass) per 100 parts by mass of hydraulic powder. In addition, the component (A'), which is a comparative component of the component (A), is described in the column of the component (A) for convenience.

[Plaster paste test using commercially available repair material]
<Preparation of paste for plastering>
Using a commercially available repair material (Himolmax #10, manufactured by Showa Denko Kenzai Co., Ltd.), the following evaluations were performed.
To Hymolmax #10, water mixed with each component listed in Table 3 was added and stirred for 30 seconds (stirring speed 950 rpm) with a hand mixer (manufactured by Panasonic Corporation, model number MK-H4) to prepare a paste for plastering. . In addition, when (A) component was mixed with water, the (A) component used the emulsion whose solid content concentration was 30 mass %.
The amount of water added was prepared by mixing 42 parts by mass of water with 100 parts by mass of Hymolmax #10. The amount of water to be added includes the amount of component (A) and component (B) added.

<Evaluation of liquidity>
The prepared paste for plastering was filled in a cylindrical cone (φ50 mm × 50 mm), and the spread when pulled up vertically (the average value of the length of the longest diameter and the length in the vertical direction) was measured as a paste flow. The measurement was made immediately after the end of kneading (after 0 minutes). Table 3 shows the results. The paste flow is preferably 75 mm or less from the viewpoint of preventing sagging.

<Evaluation of rheology>
As evaluation of rheology, the prepared plastering paste was measured for shear stress dependence of shear rate at 20° C. under the following conditions. The shear stress when the shear rate reached 0.5 (1/s) was taken as the yield value, and the slope of the shear rate and shear stress at 1500 Pa from the yield value was taken as the plastic viscosity. Table 3 shows the results.
・Measurement device name: MCR301 manufactured by Anton Paar Japan Co., Ltd.
・Application: RHEOPLUS
・Measurement jig: Parallel plate PP-25 (d=1mm)
・ Range of shear stress: 1 to 1500 (Pa)
The yield value is the stress required to fluidize the fluid, and the higher the yield value, the more the sagging can be suppressed. On the other hand, the plastic viscosity indicates the deformation resistance of the fluid under shear stress, and the lower the plastic viscosity, the better the workability can be achieved.

<Sensory evaluation of plastering characteristics>
The prepared paste for plastering was applied to a plywood board using a trowel, and the sagging property and the lightness of the trowel were evaluated. As for sagging, the plastering paste was applied to a thickness of about 3 cm on a plywood board placed vertically from the ground, and the plastering paste was allowed to stand still. As for the lightness of the trowel, the lightness of the trowel and the smoothness when applying to a thickness of about 5 mm were sensorily evaluated according to the following criteria.
Sagging property 1: Sagging occurs when left standing.
2: Sag does not occur even when left standing, but sag occurs when a little vibration is applied.
3: Sagging does not occur even when vibration is applied.
Lightness of the trowel 1: It is heavy and feels a load on the arm. 2: It is light, but it requires force when applying. 3: It can be applied smoothly with almost no effort.

In Table 3, the content of component (A) and component (B) is the content (parts by mass) per 100 parts by mass of Hymolmax #10.

Claims (13)

(A) an emulsion containing an alkali-thickening polymer (hereinafter referred to as component (A)) in an amount of 0.02 parts by mass or more and 0.9 parts by mass based on 100 parts by mass of hydraulic powder in terms of the amount of component (A) mixed; The following is a method for producing mortar for plastering, comprising mixing hydraulic powder, fine aggregate, optionally coarse aggregate of 1 kg/m ³ or less, and water. The production of mortar for plastering according to claim 1, wherein the component (A) is a copolymer containing an unsaturated compound (1a) containing an acidic group and an ethylenically unsaturated compound (2a) as constituent monomers. Method. The plastering mortar according to claim 1 or 2, wherein the component (A) is a copolymer containing an unsaturated carboxylic acid (1a ₁ ) and an ethylenically unsaturated compound (2a) as constituent monomers. Production method. (A) Component is a copolymer containing a monomer (1a') selected from acrylic acid and methacrylic acid and a monomer (2a') selected from acrylic acid esters and methacrylic acid esters as constituent monomers The method for producing a mortar for plastering according to any one of claims 1 to 3, wherein the mortar is coalesced. 5. The method for producing a mortar for plastering according to claim 4, wherein the ester portion of the acrylic acid ester and the methacrylic acid ester in the monomer (2a') has from 1 to 8 carbon atoms. The method for producing mortar for plastering according to any one of claims 1 to 5 , further comprising mixing (B) a dispersant (hereinafter referred to as component (B)). 7. The method for producing a mortar for plastering according to claim 6 , wherein the component (B) is one or more dispersants selected from polycarboxylic acid-based polymers, naphthalene-based polymers, and cationic polymers. Component (B) is a copolymer containing a monomer (1b) represented by the following general formula (1b) and a monomer (2b) represented by the following general formula (2b) as constituent monomers. , The method for producing a mortar for plastering according to claim 6 or 7 .

[In the formula,
R ^1b , R ^2b : may be the same or different, hydrogen atom or methyl group R ^3b : hydrogen atom or —COO(AO) _n1 X ¹
X ¹ : a hydrogen atom or an alkyl group having 1 to 4 carbon atoms AO: a group selected from an ethyleneoxy group and a propyleneoxy group n1: the average number of added moles of AO, the number of 2 to 300 q: 0 to 2 Indicates the number of: ]

[In the formula,
R ^4b , R ^5b , R ^6b : may be the same or different and is a hydrogen atom, a methyl group or (CH ₂ ) _r COOM ² , (CH ₂ ) _r COOM ² is COOM ¹ or other (CH ₂ ) may form an anhydride with _r COOM ² , in which case M ¹ , M ² of those groups are absent.
M ¹ , M ² : may be the same or different, hydrogen atom, alkali metal, alkaline earth metal (1/2 atom), ammonium group, alkylammonium group, substituted alkylammonium group, alkyl group, hydroxyalkyl group, or Alkenyl group r: A number of 0 or more and 2 or less. ] The method for producing a mortar for plastering according to claim 8 , wherein the ratio of the monomer (2b) to the total of the monomer (1b) and the monomer (2b) is 10 mol% or more and 80 mol% or less. The emulsion and the component (B) are mixed so that the mass ratio (B)/(A) of the mixed amount of the component (A) and the mixed amount of the component (B) is 0.05 or more and 3 or less. A method for producing a mortar for plastering according to any one of claims 6 to 9 . (A) an emulsion containing an alkali thickening polymer (hereinafter referred to as component (A)) in an amount of 0.02 parts by mass or more and 0.9 parts by mass based on 100 parts by mass of hydraulic powder in terms of the amount of component (A) Mortar for plastering, which is obtained by blending hydraulic powder, fine aggregate, optionally 1 kg/m ³ or less of coarse aggregate , and water. The mortar for plastering according to claim 11, further comprising (B) a dispersant (hereinafter referred to as component (B)). The mortar for plastering according to claim 12, wherein the mass ratio (B)/(A) of the blending amount of component (A) and the blending amount of component (B) is 0.05 or more and 3 or less.