JP2014125372A - Surface treatment material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a surface treatment material having excellent adhesiveness and durability.SOLUTION: The surface treatment material comprises a liquid composition containing a powdery composition containing cement and a synthetic resin emulsion, the powdery composition contains cement of 50 wt.% or more, a vinyl acetate resin emulsion and a cationic group- and/or nitrile group-containing synthetic resin emulsion are contained as the synthetic resin emulsion in the liquid composition, and the cement and the synthetic resin emulsion are mixed to have a solid content weight ratio of 100:1 to 50.

Description

  The present invention relates to a novel surface treatment material.

  Conventionally, as the finishing of buildings, inorganic base materials such as concrete, mortar, ALC board, PC board, calcium silicate board, plaster, etc., which are the main materials constituting building floors, walls, ceilings, columns, beams, etc. Alternatively, an organic material such as a styrene foam plate or a urethane foam plate as a heat insulating material is used as a base material, and a finishing material such as a finish coating material, ceramic tile, or wallpaper is applied thereto. Such a base material generally has irregularities such as unevenness, burrows, and defects, and the aesthetics are impaired as it is, so surface treatment materials can be used to smooth the base and repair defective areas. Has been done.

As such a surface treatment material, a material in which a synthetic resin is blended with cement is often used. For example, Patent Document 1 describes a cement composition in which an ethylene vinyl acetate resin emulsion is blended with cement. . However, if the synthetic resin emulsion is simply added to the cement as in Patent Document 1, the adhesion to the base material may be insufficient depending on conditions such as the curing temperature. On the other hand, Patent Document 2 describes a cement composition in which two or more kinds of powder polymers having different glass transition temperatures are blended, and describes that adhesion can be improved.

JP-A-6-329455 Japanese Patent Laid-Open No. 9-2860

However, even when two or more powder polymers are used in combination as in Patent Document 2, sufficient adhesion strength may not be obtained, and durability may be insufficient.

  The present invention has been made in view of the above problems, and an object thereof is to obtain a surface treatment material having excellent adhesion and durability.

  As a result of intensive studies to achieve the above object, the present inventors have conceived a surface treatment material comprising a powdery composition containing cement and a liquid composition containing a specific synthetic resin emulsion, thereby completing the present invention. It reached.

That is, the present invention has the following characteristics.
1. A surface treatment material comprising a powdery composition containing cement and a liquid composition containing a synthetic resin emulsion,
The powdery composition contains 50% by weight or more of cement,
The synthetic resin emulsion in the liquid composition includes a vinyl acetate resin emulsion and a synthetic resin emulsion containing a cationic group and / or a nitrile group,
A surface treatment material, wherein the cement and the synthetic resin emulsion are mixed at a solid content weight ratio of 100: 1 to 50.
2. The synthetic resin emulsion includes a vinyl acetate resin emulsion and a cationic group and / or nitrile group-containing synthetic resin emulsion in a solid content weight ratio of 99.5: 0.5 to 10:90. The surface treatment material as described in 2.

The surface treatment material of the present invention is excellent in adhesion and durability.

  Hereinafter, modes for carrying out the present invention will be described.

The surface treatment material of the present invention comprises a powder composition (I) containing cement (hereinafter also referred to as “powder composition (I)”) and a liquid composition (II) containing a specific synthetic resin emulsion (hereinafter referred to as “the powder composition (I)”). , Also referred to as “liquid composition (II)”) in a specific weight ratio. As a synthetic resin emulsion in the liquid composition (II), a vinyl acetate resin emulsion and a cationic group and / or a nitrile group are contained. A synthetic resin emulsion is included.

The powdery composition (I) of the present invention contains at least cement (a) (hereinafter also referred to as “component (a)”). Examples of the component (a) include ordinary Portland cement, early-strength Portland cement, ultra-high-strength Portland cement, moderately hot Portland cement, sulfate-resistant Portland cement, white Portland cement and other Portland cement, alumina cement, Examples thereof include cement, expanded cement, acidic phosphate cement, silica cement, blast furnace cement, fly ash cement, and keens cement. These may be used alone or in combination of two or more. Among these, Portland cement is preferable.

The content ratio of the component (a) is 50% by weight or more (preferably 55% by weight or more and 80% by weight or less, more preferably 60% by weight or more and 70% by weight or less) with respect to the entire powder composition (I). . When the component (a) has such a ratio, it is possible to obtain sufficient effects in adhesion and durability, which is also preferable in terms of water absorption suppression.

As the powdery composition (I) of the present invention, in addition to the above components, a filler (b) (hereinafter also referred to as “component (b)”) can be further mixed. By including the component (b), the strength of the coating film to be formed and the adhesion to the base material can be enhanced. Examples of such component (b) include silica powder, silica sand, calcium carbonate, magnesium carbonate, titanium oxide, aluminum oxide, aluminum hydroxide, fly ash, limestone powder, talc, kaolin, clay, mica, silicafame, Examples thereof include inorganic powders such as glass hollow fine particles and ceramic glass hollow fine particles. These may be used alone or in combination of two or more. In the present invention, it is particularly preferable to include silica sand, and it is particularly preferable to include silica sand having an average particle diameter of 0.05 to 1 mm (more preferably 0.1 to 0.5 mm). In this case, a smooth film can be formed, and excellent effects can be exhibited in improving the strength of the film and adhering to the base material. The content ratio of the component (b) is preferably 1 to 90 parts by weight (more preferably 5 to 80 parts by weight) with respect to 100 parts by weight of the component (a).

As the powdery composition (I) of the present invention, in addition to the above components, a fiber material (c) (hereinafter also referred to as “component (c)”) can be mixed. By including (c) component, the intensity | strength of the film formed and adhesiveness with a base material can be improved. As such component (c), acrylic fiber, acetate fiber, aramid fiber, copper ammonia fiber (cupra), nylon fiber, novoloid fiber, pulp fiber, viscose rayon, vinylidene fiber, polyester fiber, polyethylene fiber, polychlorinated Organic fibers such as vinyl fiber, polyclar fiber, vorinosic fiber, polypropylene fiber; inorganic fibers such as carbon fiber, rock wool, wollastonite, glass fiber, silica fiber, silica-alumina fiber, carbon fiber, silicon carbide fiber, etc. It is done. These may be used alone or in combination of two or more. In the present invention, it is particularly preferable to include inorganic fibers. The content ratio of the component (c) is preferably 0.1 to 20 parts by weight (more preferably 0.5 to 10 parts by weight) with respect to 100 parts by weight of the component (a). In such a range, the effect of the present invention is easily obtained.

  In addition to the above components, the powdery composition (I) of the present invention includes coloring pigments, extender pigments, rust preventive pigments, thickeners, dispersants, curing accelerators, anti-oxidants to the extent that the effects of the present invention are not impaired. Various additives such as a foaming agent, a reaction adjusting agent, a water reducing agent, a corrosion inhibitor, an antiseptic, an algaeproofing agent, an antifungal agent, an antibacterial agent, an ultraviolet absorber, and an antioxidant can be mixed.

  The liquid composition (II) of the present invention comprises at least a vinyl acetate resin emulsion (d) (hereinafter also referred to as “component (d)”), a cationic group and / or nitrile-containing synthetic resin emulsion (e) (hereinafter referred to as “the resin composition”). , (Also referred to as “component (e)”). By including such a component (d) and component (e) in combination, the strength and adhesion of the formed film can be increased, the water absorption suppressing effect can be improved, and excellent durability can be exhibited.

The component (d) is a synthetic resin emulsion containing vinyl acetate as a resin constituent component. As the component (d), any known vinyl acetate resin emulsion can be used without any particular limitation. Examples thereof include a vinyl acetate emulsion and an ethylene-vinyl acetate copolymer emulsion obtained by copolymerizing ethylene and vinyl acetate. These may be used alone or in combination of two or more. In the present invention, it is particularly preferable to contain an ethylene-vinyl acetate copolymer emulsion.

Although the minimum film-forming temperature (MFT) of (d) component can be set suitably, it is preferable that it is 10 degrees C or less (preferably 0 degrees C or less). The average particle size of the component (d) is preferably 0.1 to 5 μm (more preferably 0.2 to 3 μm, still more preferably 0.4 to 2 μm). The average particle diameter is a value measured by a dynamic light scattering method.

The component (e) is not particularly limited as long as it is a synthetic resin emulsion containing a cationic group and / or a nitrile group (however, the component (d) is excluded). Of these, the cationic group-containing synthetic resin emulsion is not particularly limited and can be used as long as it is a synthetic resin emulsion provided with a cationic group. As a method for imparting cationicity to the synthetic resin emulsion, for example,
A method of copolymerizing a cationic group-containing monomer during the production of a synthetic resin emulsion,
-After obtaining a synthetic resin emulsion, a method of modifying the emulsion particle surface charge to cationic with a cationic surfactant,
A method for obtaining a synthetic resin emulsion in the presence of a cationic surfactant;
Etc. Examples of such synthetic resin emulsions include acrylic resin emulsions, urethane resin emulsions, epoxy resin emulsions, vinyl chloride resin emulsions, fluororesin emulsions, synthetic rubber resin emulsions, and mixed / composite resin emulsions thereof. These can be used alone or in combination of two or more.

In the present invention, it is particularly preferable to include a cationic group-containing acrylic resin emulsion as the component (e). As such a cationic group-containing acrylic resin emulsion, for example,
-Copolymerized monomer group including (meth) acrylic acid alkyl ester and cationic group-containing monomer,
A copolymer obtained by copolymerizing a polymerizable monomer group containing (meth) acrylic acid alkyl ester to obtain an acrylic resin emulsion, which is then modified with a cationic surfactant,
・ A product obtained by copolymerizing a polymerizable monomer group containing a (meth) acrylic acid alkyl ester in the presence of a cationic surfactant,
Etc. can be used.

  Examples of (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, and isobutyl (meth). Acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, Examples include octadecyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, and benzyl (meth) acrylate. These can be used alone or in combination of two or more. In the present invention, the acrylic acid alkyl ester and the methacrylic acid alkyl ester are collectively referred to as (meth) acrylic acid alkyl ester.

Examples of the polymerizable monomer other than the above (meth) acrylic acid alkyl ester include acrylic acid, methacrylic acid, crotonic acid, maleic acid or a monoalkyl ester thereof, itaconic acid or a monoalkyl ester thereof, fumaric acid or a monoalkyl ester thereof. Carboxyl group-containing monomers such as
Hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate;
Vinyl ester monomers such as vinyl acetate and vinyl propionate;
Nitrile group-containing monomers such as acrylonitrile and methacrylonitrile;
Aromatic monomers such as styrene, 2-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene, vinylanisole, vinylnaphthalene, divinylbenzene;
Amide group-containing monomers such as acrylamide, methacrylamide, maleic acid amide, N-methylol (meth) acrylamide and diacetone acrylamide;
Epoxy group-containing monomers such as glycidyl (meth) acrylate, diglycidyl (meth) acrylate, and allyl glycidyl ether;
Carbonyl group-containing monomers such as acrolein, diacetone (meth) acrylamide, vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone;

Alkoxysilyl groups such as vinyltrimethoxysilane, vinyltriethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane Containing monomers;

Vinylidene halide monomers such as vinylidene chloride and vinylidene fluoride;
Other examples include ethylene, propylene, isoprene, butadiene, vinyl pyrrolidone, vinyl chloride, vinyl ether, vinyl ketone, vinyl amide, and chloroprene. These can be used alone or in combination of two or more.

Moreover, as a cationic group containing monomer, for example,
Contains amino groups such as N-methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminoethyl vinyl ether, N- (2-dimethylaminoethyl) acrylamide, N- (2-dimethylaminoethyl) methacrylamide monomer;
Examples thereof include pyridine monomers such as vinyl pyridine. These can be used alone or in combination of two or more.

Examples of the cationic surfactant include quaternary ammonium salts such as lauryl trialkyl ammonium salt, stearyl trialkyl ammonium salt, trialkyl benzyl ammonium salt, alkyl amine acetate, alkenyl amine acetate, alkenyl amine salt and the like. Examples thereof include amine salts, lauryl pyridinium salts, benzalkonium salts, benzethonium salts, and lauryl amine acetate. These can be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a quaternary ammonium salt represented by the following formula.
[NR ₄ ] ⁺ (Formula 1)
(R represents H, an alkyl group, a hydroxyalkyl group, a urea-containing alkyl group, or an amide bond-containing alkyl group.)
Examples of these cationic surfactants include alkyl dimethyl benzyl ammonium chloride and alkyl dimethyl methacrylate ammonium chloride. These can be used alone or in combination of two or more.

  Moreover, the said cationic surfactant and a nonionic surfactant can also be mixed and used. Examples of such nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester, and the like. These can be used alone or in combination of two or more.

The nitrile group-containing synthetic resin emulsion of the present invention is not particularly limited as long as it contains a nitrile group as a synthetic resin component, but the present invention includes the above (meth) acrylic acid alkyl ester and a nitrile group-containing monomer. An acrylic resin emulsion obtained by copolymerizing a polymerizable monomer group is preferable. The content ratio of the nitrile group-containing monomer is preferably 5 to 50% by weight (more preferably 10 to 40% by weight) with respect to all monomers constituting the component (e). The production method is not particularly limited, and various methods such as emulsion polymerization, soap-free emulsion polymerization, dispersion polymerization, feed emulsion polymerization, feed dispersion polymerization, seed emulsion polymerization, and seed dispersion polymerization can be employed.

  In particular, the component (e) of the present invention preferably contains a cationic group and a nitrile group. Thereby, the intensity | strength and adhesiveness of the film which are formed can be improved further, and the outstanding durability can be exhibited.

Although the minimum film-forming temperature (MFT) of (e) component can be set suitably, it is preferable that it is 10 degrees C or less (preferably 0 degrees C or less). Moreover, it is preferable that the average particle diameter of (e) component is 50-500 nm (preferably 100-300 nm).

In the liquid composition (II) of the present invention, the component (d) and the component (e) are mixed in a solid content weight ratio of 99.5: 0.5 to 10:90 (more preferably 99.2: 0.0.0). 8 to 50:50, more preferably 99: 1 to 70:30). In such a range, the effect of the present invention is easily obtained.

In addition to the above components, the liquid composition (II) of the present invention has water, a film-forming aid, a thickener, a dispersant, a curing accelerator, an antifoaming agent, a reaction to the extent that the effects of the present invention are not impaired. Mixing various additives such as regulators, water reducing agents, corrosion inhibitors, antiseptics, antialgae agents, fungicides, antibacterial agents, plasticizers, antifreezing agents, pH adjusters, UV absorbers, antioxidants, etc. You can also.

The surface treatment material of the present invention is obtained by mixing the powder composition (I) and the liquid composition (II). The blending ratio of the cement (the above component (a)) and the synthetic resin emulsion (the sum of the above component (d) and the above component (e)) is 100: 1 to 50 (preferably 100: 1 to 1) in terms of solid content. 30). In such a range, the effect of the present invention is easily obtained.

  The surface treatment material of the present invention can be applied mainly to an interior surface or an exterior surface of a building. Examples of the base material (base material) constituting the base to be painted include gypsum board, plywood, concrete, mortar, porcelain tile, brick, fiber-mixed cement board, cement calcium silicate board, slag cement perlite board, ALC board , Siding plate, extrusion molding plate and the like. These base materials may be those already coated in some way.

In applying the surface treatment material of the present invention, a trowel is preferably used, and the surface treatment material may be applied so that a flat surface is formed to some extent. In the case where irregularities such as unevenness, burrows, and defects are present on the base, the surface treatment material can be filled in the irregularities.
At the time of application, the surface treatment material of the present invention can be diluted with water as necessary. The dilution ratio is preferably about 0 to 50% by weight.
The coating amount is not particularly limited, but is preferably about 0.2 to 10 kg / m ² , more preferably about 0.3 to 8 kg / m ² , and still more preferably about 0.5 to 5 kg / m ² , The number of times of application can be set as appropriate.
The drying time is preferably about 3 to 24 hours at room temperature.

After the surface treatment material of the present invention is applied, various finishing materials can be applied. Specific finishes that can be used include, for example, synthetic resin emulsion paint, glossy synthetic resin emulsion paint, non-water-dispersed resin enamel and other flat paints, JIS
Architectural finishing coatings specified in A 6909, for example, thin finishing coating materials such as lysine paints, single-layer elastic coating materials, thick finishing coating materials such as stucco coatings, and multi-layer finishing coating materials Examples thereof include paints, stone finish finishing coating materials, and sandstone finishing coating materials. These finishing materials may be applied through various undercoat materials. It is also possible to construct dry finishing materials such as various decorative sheet building materials and ceramic tiles through known adhesives.

A known applicator can be used for application of a finishing material or an adhesive. As a coating device, for example, a spray, a roller, a brush, a trowel or the like can be used. What is necessary is just to set the coating amount of a finishing material suitably according to the kind of coating material and coating instrument to be used, the surface shape of a finishing coating film, etc. At the time of application, the paint can be diluted as necessary.

  Examples are given below to clarify the features of the present invention.

<Manufacture of powdery composition (I)>
Powder compositions I-1 to 4 were produced by mixing and stirring the respective raw materials by a conventional method according to the formulation (% by weight) shown in Table 1.
<Manufacture of liquid composition (II)>
Liquid compositions II-1 to 10 were produced by mixing and stirring the respective raw materials by the conventional method according to the formulation (% by weight) shown in Table 2. In addition, the following were used as a raw material.

In addition, the following were used as a raw material of powdery composition (I) and liquid composition (II) (a) Cement: Portland cement (b) Filler: Silica sand (average particle diameter of 0.1-0. 3mm)
(C) Inorganic fiber: wollastonite (d) ethylene-vinyl acetate copolymer resin emulsion (solid content: 55% by weight, average particle size: 0.9 μm, minimum film-forming temperature: 0 ° C. or less)

(E1) Cationic group-containing acrylic resin emulsion In the presence of a cationic surfactant (alkyldimethylbenzylammonium chloride) and a nonionic surfactant (polyoxyethylene alkyl ether), methyl methacrylate: methacrylic acid: butyl acrylate = Emulsion polymerization of 40: 2: 58 gave a cationic group-containing acrylic resin emulsion (e1) having a solid content of 45% by weight, an average particle size of 220 nm, and a minimum film-forming temperature of 0 ° C. or less.

(E2) Methyl methacrylate: methacrylic acid: butyl acrylate: acrylonitrile = 28: 2: 58: 12 is emulsion-polymerized in the presence of a nitrile group-containing acrylic resin emulsion nonionic surfactant (polyoxyethylene alkyl ether) As a result, a nitrile group-containing acrylic resin emulsion (e2) having a solid content of 45% by weight, an average particle size of 250 nm, and a minimum film forming temperature of 0 ° C. or less was obtained.

(E3) A cationic group and nitrile group-containing acrylic resin emulsion In the presence of a cationic surfactant (alkyldimethylbenzylammonium chloride) and a nonionic surfactant (polyoxyethylene alkyl ether), methyl methacrylate: methacrylic acid: Emulsion polymerization of butyl acrylate: acrylonitrile = 37: 2: 58: 3 to solid content: 45% by weight, average particle size: 240 nm, minimum film forming temperature: 0 ° C. or lower cationic group and nitrile group-containing acrylic resin An emulsion (e3) was obtained.

(E4) Cationic group and nitrile group-containing acrylic resin emulsion In the presence of a cationic surfactant (alkyldimethylbenzylammonium chloride) and a nonionic surfactant (polyoxyethylene alkyl ether), methyl methacrylate: methacrylic acid: Emulsion polymerization of butyl acrylate: acrylonitrile = 28: 2: 58: 12 solid content: 45% by weight, average particle size: 210 nm, minimum film forming temperature: 0 ° C. or lower cationic group and nitrile group-containing acrylic resin An emulsion (e4) was obtained.

(E5) A cationic group and nitrile group-containing acrylic resin emulsion In the presence of a cationic surfactant (alkyldimethylbenzylammonium chloride) and a nonionic surfactant (polyoxyethylene alkyl ether), methyl methacrylate: methacrylic acid: Emulsion polymerization of butyl acrylate: acrylonitrile = 10: 2: 58: 30 to solid content: 45% by weight, average particle size: 230 nm, minimum film-forming temperature: 0 ° C. or lower cationic group and nitrile group-containing acrylic resin An emulsion (e5) was obtained.

<Manufacture of surface treatment material>
(Surface treatment materials 1-10, 13-15)
According to the combinations shown in Table 3, surface treatment material 1 was prepared by mixing and stirring 100 parts by weight of powdered composition (I), 25 parts by weight of liquid composition (II), and 25 parts by weight of diluent (water) by a conventional method. -10, 13-15 were produced.
(Surface treatment material 11)
According to the combinations shown in Table 3, the surface treatment material 11 was prepared by mixing and stirring 100 parts by weight of the powdery composition (I), 45 parts by weight of the liquid composition (II), and 10 parts by weight of the diluent (water) by a conventional method. Manufactured.
(Surface treatment material 12)
According to the combinations shown in Table 3, the surface treatment material 12 was prepared by mixing and stirring 100 parts by weight of the powdery composition (I), 15 parts by weight of the liquid composition (II), and 30 parts by weight of the diluent (water) by a conventional method. Manufactured.

(Test Examples 1-15)
<Adhesion strength test>
According to the method prescribed in JIS A6916: 2000, 7.13 adhesion strength test, a test specimen was prepared (surface treatment material coating amount: 2.0 kg / m ² , low temperature curing), and an adhesion strength test was performed. It was. The results are shown in Table 3. The evaluation criteria are shown below.
A: 1.3 N / mm ² or more B: 1.0 N / mm ² or more and less than 1.3 N / mm ² C: 0.7 N / mm ² or more and less than 1.0 N / mm ²

<Durability test>
JIS A6916: 2000, 7.17 According to the method prescribed in the durability test, a test specimen is prepared (surface treatment material coating amount: 2.0 kg / m ² , type of multilayer finish coating material: multilayer coating material) RS) and a durability test was conducted. The results are shown in Table 3. The evaluation criteria are shown below.
A: 1.4 N / mm ² or more B: 1.2 N / mm ² or more 1.4 N / mm ² lower than C: 1.0 N / mm ² or more 1.2 N / mm less than ²

<Water absorption test>
According to the method prescribed | regulated to JISA6916: 2000, 7.14 water absorption test, the test body was produced (application amount of surface treatment material: 2.0kg / m < ² >), and the water absorption test was done. The results are shown in Table 3. The evaluation criteria are shown below.
A: Less than 0.7 g B: 0.7 g or more and less than 0.8 g C: 0.8 g or more and less than 1.0 g

Claims (2)

A surface treatment material comprising a powdery composition containing cement and a liquid composition containing a synthetic resin emulsion,
The powdery composition contains 50% by weight or more of cement,
The synthetic resin emulsion in the liquid composition includes a vinyl acetate resin emulsion and a cationic group and / or nitrile group-containing synthetic resin emulsion,
A surface treatment material, wherein the cement and the synthetic resin emulsion are mixed at a solid content weight ratio of 100: 1 to 50. The synthetic resin emulsion includes a vinyl acetate resin emulsion and a cationic group and / or nitrile group-containing synthetic resin emulsion in a solid content weight ratio of 99.5: 0.5 to 10:90. The surface treatment material according to 1.