JPH11323185A - Composition for covering - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition the cured material of which has excellent adhesion to a substrate and adhesion strength and exhibits excellent effects of preventing the attack and growth of fungi or the like and still further maintains the effects for a prolonged period of time. SOLUTION: A composition for covering comprises (A) a polymer comprising a (meth)acrylate as an essential constituent monomer unit, (B) a zeolite carrying a basic copper thereon, (C) a cement and (D) water, wherein the content of the component B is 2-30 wt.% of the composition and the content of the component C is not less than 100 pts.wt. per 100 pts.wt. of the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition for suppressing the generation of algae and fungi that adhere to and proliferate on the foundation of a waterway such as a waterway and an agricultural waterway of a hydroelectric power plant.

[0002]

2. Description of the Related Art Algae proliferate and adhere, or viscous substances produced by proliferated fungi adhere in layers to the walls of waterways such as headraces and agricultural canals of hydroelectric power plants. Since the cross-sectional area of the channel becomes small or the surface roughness increases, there is a problem that the amount of flowing water decreases. Until now, methods for removing deposits such as products of these algae and fungi have been carried out by hand, or methods of physically removing high-pressure water through a water channel, and the like. Is very time-consuming, and cannot be operated unless the running water is stopped, resulting in a large economic loss.

On the other hand, as a method for preventing fungi, molds, algae and the like (hereinafter referred to as fungi) from adhering to and growing on the surface of concrete structures such as sewers and marine structures and ships, etc., silver and silver are used. A method of applying a composition such as a metal such as copper or a compound thereof as it is or a hydraulic material such as cement or a paint to a paint (Japanese Patent Application Laid-Open No. 5-170983) has been studied. In the method, the metal or the compound is zeolite, apatite or glass in order to obtain a greater effect with a small amount of the metal or the compound and to control the elution amount to maintain the effect for a long time. A method of using a material supported on a material such as the one described in Japanese Patent Application Laid-Open No. 9-284 is also being studied.
9).

Among the above metal compounds, patina, which is a copper compound, has antibacterial, antifungal and antialgal properties (hereinafter referred to as antibacterial properties) for a long period of time, and antibacterial, antifungal and antialgal materials ( (Hereinafter referred to as antibacterial material) in many fields such as plastics and building materials. What is patina?
When copper is exposed to the atmosphere or water containing water and carbon dioxide for a long time (weeks to months), it is a green substance that forms on this surface and consists of basic copper, copper and suboxides. Since it has lower solubility in water than copper and the like, it can maintain long-term antibacterial properties and the like more than copper and cuprous oxide (JP-A-9-194901).

[0005]

When an antibacterial material or the like is installed in a waterway or the like, it is required that the initial shape is maintained for several years and the effects such as antibacterial properties are maintained. However, conventional antibacterial materials and the like, physical properties such as antibacterial properties and water-resistant adhesiveness are not compatible, and sufficient effects such as antibacterial properties cannot be obtained,
Or, in a waterway, etc., the surface on which the antibacterial material or the like is applied is immersed in water for a long period of time, so that the adhesiveness is reduced, and as a result, the surface is floated, peeled off, or the surface is worn. Was. The present inventors have studied diligently to provide a composition in which the cured product is excellent in adhesion and strength to a base, and excellent in inhibiting adhesion and growth of fungi and the like, and furthermore, maintaining these effects for a long period of time. Was done.

[0006]

As a result of various studies, the present inventors have found that a composition comprising a (meth) acrylate polymer, a zeolite supporting basic copper, and a cement, has a cured product. The inventors have found that they have excellent adhesiveness to a base or the like, have sufficient strength, and are also excellent in effects such as antibacterial properties, and can maintain these effects over a long period of time, and have completed the present invention. Hereinafter, the present invention will be described in detail.
In this specification, an acrylate or a methacrylate is referred to as a (meth) acrylate, and an acrylic acid or a methacrylic acid is referred to as a (meth) acrylic acid.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Polymer Having (Meth) Acrylate as an Essential Constituent Monomer Unit Polymer Having (A) Component (A) of the Present Invention Having an Essential Constituent Monomer Unit [Hereinafter also referred to as (meth) acrylic acid ester polymer] is intended to make the cured product thereof excellent in adhesiveness to a base and strength by being blended into the composition. In the (meth) acrylate polymer, the (meth) acrylate as a raw material monomer includes methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylate. Iso-propyl acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, n-pentyl (meth) acrylate, is (meth) acrylate
o-pentyl, hexyl (meth) acrylate, (meth)
Heptyl acrylate, octyl (meth) acrylate,
2-ethylhexyl (meth) acrylate, alkyl (meth) acrylates such as nonyl (meth) acrylate and decyl (meth) acrylate, and hydroxyalkyl (meth) acrylate such as hydroxyethyl (meth) acrylate No. The polymer may be a copolymer of two or more of these monomers. Further, the polymer may be a copolymer of (meth) acrylic acid ester with other monomers, and specifically, (meth)
Acrylic acid, styrene, acrylonitrile, ethylene,
Butadiene, vinyl chloride, vinylidene chloride, vinyl acetate, (meth) acrylamide, N-methylol (meth) acrylamide and the like. As the polymer,
Those obtained by copolymerizing two or more of these other monomers may be used. As the polymer, the carbon number of the alkyl group is 1 to
Preferably, it contains 20 to 100% by weight of one or more of 10 alkyl (meth) acrylates and has a glass transition temperature of 20 ° C or lower. A composition containing the polymer,
Adhesion and strength of the cured product to the base are particularly excellent. Further, as the form of the polymer, an emulsion of the polymer is preferable because it is easily mixed with the composition. The emulsion may be obtained by subjecting the monomer to emulsion polymerization in the presence of a surfactant in accordance with a conventional method. Particularly, a secondary, tertiary amine type or quaternary ammonium salt type surfactant may be used. The cationic emulsion obtained by the emulsion polymerization used is more preferable because of its excellent adhesion to the substrate. A preferable ratio of the polymer is 1 to 20% by weight, more preferably 2 to 10% by weight in the composition. When the proportion of the polymer is less than 1% by weight, the adhesion of the cured product to the substrate may be reduced, while the proportion of the polymer may be 20% by weight.
If it exceeds 3, the viscosity of the composition becomes high, and the coatability may decrease.

Zeolite supporting basic copper (B) In the zeolite supporting the basic copper of the component (B), the basic copper is basic copper carbonate [CuCO ₃ Cu (O
H) ₂ ], basic copper acetate [Cu (CH ₃ CO ₂ ) CuO
6H ₂ O], basic copper chloride [CuCl ₂ 3Cu (OH)
₂ ] and basic copper sulfate [CuSO ₄ 3Cu (OH) ₂ ]
And the like, and basic copper carbonate is preferred in terms of excellent antibacterial properties and the like. Also, patina, which is a mixture of basic copper, can be used. Various types of zeolite supporting basic copper can be used, and examples include unsubstituted zeolite and those substituted with an alkali metal salt or an alkaline earth metal salt. Here, examples of the metal include sodium, potassium and calcium. Zeolites include natural zeolites and synthetic zeolites, but natural products are preferred. or,
As the zeolite, a powdery zeolite is preferable because of excellent mixability and workability of the composition. The particle size of the zeolite may be appropriately selected depending on the purpose, and may be 5 μm to 2 mm.
Is preferable. When the particle size is smaller than 5 μm, the viscosity of the composition increases, and the workability may be deteriorated.
If it exceeds mm, it may be too large as an aggregate, resulting in poor workability such as ironing and spraying, or a poor finished appearance. In the present invention, the term “support” refers to a state in which basic copper is physically or chemically attached or adsorbed on the zeolite surface. The amount of basic copper supported on the zeolite is preferably 30% by weight or less based on the weight of the zeolite. If the amount of basic copper exceeds 30% by weight, zeolite cannot be supported, and the effects of the present invention may not be exhibited, and it is not economical. Zeolite powder supporting basic copper is commercially available, and preferable examples thereof include "green-blue zeolite PO-Z series" manufactured by Future Force Co., Ltd.

The mixing ratio of the component (B) is determined from the viewpoints of adhesion to a base such as concrete, compressive strength and antibacterial properties.
It is 2 to 30% by weight, preferably 5 to 20% by weight, based on the total weight of the composition. If it is less than 2%, the antibacterial properties are insufficient, while if it exceeds 30%, the adhesiveness and compressive strength of the cured product of the composition to the base surface are reduced, and the composition is liable to float, peel and crack. , Wear resistance is significantly reduced.

Cement As the cement of the component (C), various portland cements, white cements, blast furnace cements, alumina cements and the like can be mentioned.

The proportion of component (C) must be at least 100 parts by weight per 100 parts by weight of component (A).
5000 parts by weight are preferable, and 200 to 3 parts by weight are more preferable.
000 parts by weight. If this ratio is less than 100 parts by weight, the viscosity of the composition increases, and the workability of the composition such as troweling and spraying is deteriorated, and the adhesion and compression of the cured product of the composition to the substrate are reduced. In some cases, the cured product of the composition may be peeled off or cracked due to sand and stones flowing along with water in a water channel or the like, and the abrasion resistance may be significantly impaired.

Water The water of the component (D) of the present invention is a component that is blended to cure the cement of the component (C), and is usually water derived from the emulsion of the (meth) acrylate polymer. Yes, and if the blending ratio is insufficient, it can be further blended. The preferred proportion of water is between 3 and 40 in the composition.
%, More preferably 5 to 30% by weight.
When the proportion of water is less than 3% by weight, the coatability and curability of the composition may be reduced. On the other hand, when the proportion is more than 40% by weight, sagging may occur when the composition is applied. In some cases, the curability of the composition may be reduced, and the strength of the cured composition may be reduced.

Other components Other components can be added to the composition of the present invention, if necessary. For example, an inorganic aggregate, a swelling agent, a water reducing agent, a thickening agent, a curing accelerator, a curing retarder and the like can be mentioned. In the present invention, the composition is added to give fluidity,
In order to improve the dimensional stability of the cured composition, it is preferable to add an inorganic aggregate. As inorganic aggregate, silica sand,
Examples include river sand, silica, talc, mica, diatomaceous earth, calcium carbonate, kaolin, silica powder, sepiolite and the like, and inorganic lightweight aggregates. As the mixing ratio of the inorganic aggregate,
It is only necessary to follow the mixing ratio conventionally used in cement mortar, and preferably cement: inorganic aggregate = 1: 0.5
１ ： 1: 4 (weight ratio).

Production and Use Method In the production method of the composition of the present invention, the components (A), (B), (C) and (D) may be mixed in a conventional manner.

As a method of using the composition of the present invention, a method conventionally known as a method for applying mortar, concrete or the like may be applied. Specific examples include application with a trowel, brush, roller and spatula, spraying with a spray gun or the like, pouring into a mold, injection into cracks and gaps in concrete, and the like.

The composition of the present invention can be applied to concrete, mortar, block, stone wall, bedrock, etc., in which the growth of fungi is concerned. Specifically, the present invention can be applied to a water channel, a ditch, and other facilities through which hydroelectric water, agricultural water, industrial water, domestic water, drainage, and the like flow. Examples of the facilities for hydroelectric power generation include a headrace, a spillway, a tailrace, a pumping canal, a sand basin, a regulating pond, a surge tank, and a dam. In addition, it can also be used for embankments such as rivers and canals. Since the composition of the present invention has excellent adhesive strength to a substrate, it can be particularly preferably applied to a waterway such as a headrace of a hydroelectric power plant and an agricultural canal.

[0017]

The present invention will be described more specifically below with reference to examples and comparative examples. In the following, "parts" means parts by weight, and "%" means% by weight. Production Example (Production of acrylate polymer emulsion) 2-Ethylhexyl acrylate 48 parts, styrene 50
Parts, 2 parts of methyl acrylate and 2 parts of polyoxynonylphenyl ether, 1 part of trimethylammonium chloride stearate as a surfactant, and 0.2 parts of 2,2-azobis (2-diaminopropane) hydrochloride as a polymerization initiator. Emulsion polymerization was carried out in 100 parts of water using 4 parts. The obtained acrylic acid ester polymer emulsion had a solid content of 48%, and the glass transition temperature of the polymer was 4 ° C.

Examples 1 to 3 According to the formulation shown in Table 1, the acrylic acid ester polymer emulsion containing the component (A) obtained in Production Example 1 and the patina containing the basic copper carbonate as the component (B) as a main component [PO-70Z manufactured by Future Force Co., Ltd., particle size 1]
0-100 μm], Portland cement of component (C),
A composition was prepared by mixing silica sand and water. The obtained composition was evaluated according to the following evaluation method. Table 2 shows the results. The composition of the present invention exhibited good antibacterial properties and the like, and also had excellent adhesive strength and uniaxial compressive strength.

Evaluation method: Adhesion strength The composition was applied to a concrete plate having a size of 30 cm × 30 cm × 6 cm to a thickness of 10 mm, and was applied at 20 ° C. and 60% RH.
After curing on a day, it was used as a test specimen. The test specimens were each measured for adhesion three times by a Kenken-type tensile tester. After dipping in water for 7 days, the adhesive strength was measured three times in the same manner.

Uniaxial compressive strength A cured product of the composition was measured according to JIS A 6203.

Test for antibacterial activity, etc. A test specimen was prepared by applying 4 kg / m ² of the composition to a 30 cm × 30 cm iron plate and curing at 20 ° C. and 60% RH for 14 days. The test body was fixed to the inner wall of the headrace in Nagano Prefecture with anchor bolts, and the adhesion of mold, algae, scale, etc. after one year was examined. The evaluation criteria are as follows. A: No adhesion at all. ；: Almost no adhesion. Δ: adhered to 20% of the surface. ×: adhered to almost the entire surface, but can be removed by lightly rubbing with a finger. XX: Adhered in layers over the entire surface and could not be removed by rubbing with a finger.

[0022]

[Table 1] 1) The number in parentheses is the ratio to the whole composition. 2) The number in parenthesis is the ratio to 100 parts by weight of the polymer.

[0023]

[Table 2]

Comparative Example 1 The procedure of Example 1 was repeated except that the composition shown in Table 3 was used.
(B) A composition containing no component was produced. About the obtained composition, it evaluated similarly to the Example. Table 4 shows the results. The composition of Comparative Example 1 did not exhibit any antibacterial properties or the like.

Comparative Example 2 A composition was prepared in the same manner as in Example 1 except that the composition shown in Table 3 was used, in which the component (B) contained 32% by weight, which exceeds the upper limit of the present invention. About the obtained composition, it evaluated similarly to the Example. Table 4 shows the results. The composition of Comparative Example 2 had good antibacterial properties and the like, but was immersed in water 7
The adhesive strength after a day dropped sharply, and the uniaxial compressive strength was also insufficient.

Comparative Example 3 The procedure of Example 1 was repeated except that the composition shown in Table 3 was used.
A composition was prepared which contained 97 parts by weight of the component (C), which was less than the lower limit of the present invention, based on 100 parts by weight of the component (A). About the obtained composition, it evaluated similarly to the Example. Table 4 shows the results. The composition of Comparative Example 3 had good antibacterial properties and the like, but had very low adhesive strength and uniaxial compressive strength.

Comparative Example 4 The procedure of Example 1 was repeated except that the composition shown in Table 3 was used.
(A) A composition containing no component was produced. About the obtained composition, it evaluated similarly to the Example. Table 4 shows the results. The composition of Comparative Example 4 had good antibacterial properties and the like, but did not have sufficient adhesive strength.

[0028]

[Table 3] 1) The number in parentheses is the ratio to the whole composition. 2) The number in parenthesis is the ratio to 100 parts by weight of the polymer.

[0029]

[Table 4]

[0030]

The composition of the present invention has excellent antibacterial properties and the like, and its cured product also has excellent water-resistant adhesiveness and physical strength with respect to a base, and there is a concern that fungi and the like may be generated. By installing on the inner walls of waterways, such as waterways for agricultural power generation and agricultural waterways, it is possible to control the adhesion and proliferation of fungi to the building for a long period of time without deterioration such as floating, peeling, cracking and severe abrasion. can do.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // (C04B 28/02 24:26)

Claims (1)

[Claims] 1. A composition comprising (A) a polymer having a (meth) acrylate ester as an essential constituent monomer unit, (B) a zeolite carrying basic copper, (C) cement and (D) water. Wherein the proportion of the component (B) is 2 to 30% by weight in the composition and the proportion of the component (C) is 1 to 100 parts by weight of the component (A).
The coating composition is at least 00 parts by weight.