JP7126706B2 - Anti-algae long-lasting antifouling agent composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a water-based paint composition that is used for building interior materials, exterior materials, and the like, and has antifungal and/or antialgae persistence.

Organic solvent-diluted paints have been widely used as paints for exterior materials, etc., but in recent years, environmental problems such as sick house syndrome and VOC regulations, such as the emission of organic solvents into the atmosphere, have been raised. , conversion to water-based paint is progressing.

In addition, in recent years, the development of products such as exterior materials with high design has become active, and from the viewpoint of color tone and dirt, it has high transparency and long-term low staining function (especially the function of preventing biological contamination by mold etc.) There is an increasing need for a coating agent that maintains

Patent Document 1 discloses a hydrophilic composition containing photocatalytic metal oxide particles and colloidal silica. However, photocatalysts such as titanium oxide are generally expensive, and cannot exhibit sufficient functions in places where they are not exposed to ultraviolet rays. Furthermore, the photocatalytic composition containing an inorganic binder has insufficient film-forming properties and water resistance and tends to peel off with rainwater, etc., so it has long-term hydrophilic antifouling properties, especially antifungal and / or antialgal persistence. There is room for improvement.

JP-A-11-140432

An object of the present invention is to provide a water-based coating composition having transparency, storage stability, and antifungal/antialgae persistence.

As a result of intensive studies, the present inventors have found that an aqueous composition comprising metal oxides and/or metal hydroxides, colloidal silica, clay minerals, and an inorganic binder dispersed in water exhibits excellent transparency. , storage stability, and antifungal/antialgae persistence, and completed the present invention.

That is, the present invention provides [1] an antifungal and/or antialgal composition comprising an aqueous dispersion containing a metal oxide and/or metal hydroxide, colloidal silica, a clay mineral, and an inorganic binder. A composition in which the content of the inorganic binder in the composition is 0.05% by weight or more,
[2] The composition of [1], further comprising an anionic surfactant,
[3] metal oxide and / or metal hydroxide contains one or more selected from the group consisting of copper (I) oxide, copper (II) oxide and copper (II) hydroxide [1] or [2 ] the composition described in
[4] The composition according to any one of [1] to [3], wherein the metal oxide and/or metal hydroxide comprises copper (I) oxide and/or copper (II) hydroxide;
[5] The metal oxide and/or metal hydroxide is one or more selected from the group consisting of copper (I) oxide, copper (II) oxide and copper (II) hydroxide, and one or more other metal oxides The composition according to any one of [1] to [4], which contains a substance and / or a metal hydroxide,
[6] The metal oxide and/or metal hydroxide is one or more selected from the group consisting of copper (I) oxide, copper (II) oxide and copper (II) hydroxide, zinc oxide, silver oxide and nickel oxide The composition according to any one of [1] to [5], comprising one or more selected from the group consisting of
[7] of [1] to [5], wherein the metal oxide and/or metal hydroxide consists of copper (I) oxide and/or copper (II) hydroxide and one or more other metal oxides a composition according to any
[8] The composition according to any one of [1] to [7], wherein the inorganic binder is a silicon binder containing a silicate;
[9] The composition according to any one of [1] to [8], wherein the clay mineral is smectite.

ADVANTAGE OF THE INVENTION According to this invention, the water-based coating composition which has transparency, storage stability, and mildew-proof / algae-proof persistence can be provided.

An antifungal and/or antialgal composition, which is one embodiment of the present invention, comprises metal oxides and/or metal hydroxides, colloidal silica, clay minerals, and inorganic binders dispersed in water. be. Since it is an aqueous composition, it has no solvent odor and can be dried at room temperature, so it is easy to handle.

In this specification, when a numerical range is indicated by using "-", the numerical values at both ends are included.

The "composition comprising an aqueous dispersion containing a metal oxide and/or metal hydroxide, colloidal silica, a clay mineral, and an inorganic binder" according to the present embodiment includes metal oxides and/or metal hydroxides. , colloidal silica, clay minerals, and inorganic binders. In addition, the composition is a substance in which compounding components such as metal oxides, metal hydroxides, colloidal silica, clay minerals, and inorganic binders are chemically changed during storage or use (for example, oxidation as metal oxides). When copper (I) is blended, the case where it contains copper (II) hydroxide, etc.) that is generated over time is also included.

(metal oxides and metal hydroxides)
Metal oxides and metal hydroxides that can be used in this embodiment include, for example, silicon, aluminum, iron, titanium, zirconium, copper, silver, magnesium, calcium, tin, zinc, manganese, nickel, cobalt, tungsten, Oxides and hydroxides of metals such as cerium, yttrium, vanadium, osmium, cadmium, thallium, ruthenium, hafnium, strontium, bismuth, and niobium, and oxides and hydroxides of copper, zinc, silver, nickel, etc. is preferred. The metal oxides and/or metal hydroxides may be used singly or in combination of two or more, preferably in combination of two or more. Composite oxides of a plurality of metal components can also be used. In particular, by combining copper (I) oxide, which has strong redox and antibacterial properties, with one or more other metal oxides, sufficient film strength and a wide antibacterial spectrum can be obtained. The anti-mold/algae effect can be sustained over a long period of time. Copper (II) oxide and copper (II) hydroxide can also be suitably used as substitutes for copper (I) oxide. Metal oxides that can be combined with copper (I) oxide, copper (II) oxide and copper (II) hydroxide include, for example, zinc oxide, silver oxide, nickel oxide and the like, with zinc oxide being preferred. As the metal oxide and metal hydroxide in this embodiment, an aqueous dispersion in which metal oxide and metal hydroxide particles are dispersed in water may be used. Photocatalytic activity of these metal oxides and metal hydroxides is not particularly required.

The total amount of copper (I) oxide, copper (II) oxide and copper (II) hydroxide in the total amount of metal oxides and metal hydroxides is 0 from the viewpoint of antifungal and / or antialgal persistence. .1 to 100% by weight is preferred, 0.2 to 80% by weight is more preferred, 0.3 to 50% by weight is even more preferred, and 0.5 to 30% by weight is particularly preferred.

The average particle size of the metal oxide and metal hydroxide is preferably 1 to 5000 nm, more preferably 10 to 1000 nm, even more preferably 50 to 500 nm. When the average particle size is within the above range, sufficient film strength can be obtained, and poor appearance such as white turbidity of the coating film can be prevented. The average particle size can be measured with a commercially available laser diffraction/scattering particle size distribution analyzer.

The total content of metal oxides and metal hydroxides is preferably 0.1 to 10% by weight, more preferably 0.3 to 8.0% by weight, and 0.5 to 6.0% by weight relative to the composition. % is more preferred, and 1.0 to 4.0% by weight is particularly preferred. If it is less than 0.1% by weight, the antifungal and/or antialgal persistence tends to be insufficient. Moreover, when it exceeds 10 weight%, there exists a tendency for coating-film durability and transparency to fall.

(colloidal silica)
As colloidal silica in the present embodiment, an aqueous dispersion in which silica particles are colloidally dispersed in water can be used. By blending such aqueous colloidal silica, the coating film surface becomes hydrophilic immediately after the coating film is formed, improving water wettability, and rainwater permeates the interface between the coating film and contaminants to wash away contaminants. and the antifouling effect can be maintained for a long period of time.

Specific examples of colloidal silica are commercially available under trade names such as Snowtex manufactured by Nissan Chemical Industries, Ltd., Cataloid S series manufactured by JGC Shokubai Kasei Co., Ltd., and Adelite AT series manufactured by ADEKA Corporation. There are some. Colloidal silica may be used singly or in combination of two or more types selected from those exemplified above. It should be noted that colloidal silica is more preferable as it has better product stability. Specifically, colloidal silica that does not gel for one month or more in an atmosphere of 40° C. can be preferably used as colloidal silica with good product stability. The shape of the colloidal silica includes spherical, chain, rod-like, pearl-like, and irregular shapes, but is not particularly limited.

The average particle size of colloidal silica is not particularly limited, but is preferably 1 to 300 nm, more preferably 10 to 250 nm, even more preferably 10 to 100 nm. If the average particle size is less than 1 nm, the particles tend to aggregate and lack stability. On the other hand, when the average particle size exceeds 300 nm, the silica tends to settle and the storage stability tends to decrease.

Although the pH of colloidal silica is not particularly limited, it is preferably 8-12.

The solid content concentration of silica in colloidal silica is not particularly limited, but it is generally about 1 to 50% by weight, about 1 to 40% by weight, and more generally 1 to 30% by weight. In addition, colloidal materials containing acids such as nitric acid, hydrochloric acid, and acetic acid can be used as stabilizers. The solid content of colloidal silica refers to the amount of residue after heating these at 100° C. for 1 hour.

The content of colloidal silica is preferably 0.5 to 20% by weight, more preferably 1.0 to 15% by weight, based on the solid content of these components. 3.0 to 10% by weight is more preferred. If the amount is less than 0.5% by weight, the hydrophilicity of the coating film is insufficient.

(clay mineral)
The antifungal and/or antialgal composition according to this embodiment is characterized by containing a clay mineral. The solubility, swelling property, and dispersibility of the clay mineral in water impart viscosity to the composition, prevent precipitation of silica and sagging of the composition, and improve the transparency of the composition. can.

In the present embodiment, "clay mineral" means a natural, synthetic, or modified layered silicate mineral, and is not particularly limited as long as it swells in water and is ion-exchangeable. From the viewpoint of solubility in water, swellability, and dispersibility, clay minerals having alkali metal ions between clay layers are preferred. Among them, clay minerals in which the alkali metal is sodium (Na-type clay minerals) It is most preferably used because it is highly soluble and swellable in water and is inexpensive.

Specific examples of clay minerals include zeolite, talc, chlorite, kaolinite, illite, gloconite, sericite, and smectite. Among them, kaolinite and smectite are preferred because of their high hydrophilicity. Smectite is appropriately selected from montmorillonite, beidellite, nontronite, stevensite, sauconite, hectorite, saponite and bentonite, preferably montmorillonite, hectorite, saponite, bentonite and mixtures thereof, more preferably hectorite. Examples of various natural, synthetic, and modified smectites include layered inorganic additives commercially available from BYK-Chemie Japan Co., Ltd. under trade names such as LAPONITE, OPTIGEL, OPTIBENT, GARAMITE, TIXOGEL, CLAYTONE, and CLOISITE. mentioned. Any one of the clay minerals exemplified above may be used alone, or two or more thereof may be used in combination.

The content of the clay mineral is preferably 0.01 to 10% by weight, more preferably 0.05 to 5.0% by weight, even more preferably 0.1 to 2.0% by weight, relative to the composition. If it is less than 0.01% by weight, colloidal silica tends to precipitate during storage, and the transparency of the composition tends to be insufficient. On the other hand, if it exceeds 10% by weight, the composition tends to gel during storage.

(Inorganic binder)
Examples of inorganic binders that can be used in the present embodiment include silicon-based binders such as hydrolyzable silanes, alkylsilicates, polyorganosilanes, polyorganosiloxanes, silanols, and silicates; zinc phosphate and aluminum phosphate. , hydroxyapatite, calcium phosphate; Titanium oxide, alumina, titania, organic zirconium compounds, zirconia and the like can be mentioned, and silicon-based binders are preferred. Among them, a silicate-containing silicon-based binder is preferably used because the silicate functions as a pH adjuster and stabilizes the viscosity of the composition. Any one of the above-exemplified inorganic binders may be used alone, or two or more thereof may be used in combination. In addition, the inorganic binder is selected from the above-exemplified ones (preferably in the silicon binder), and further includes a base such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium hydrogen carbonate, aqueous ammonia, and the like. may contain a polar pH adjuster. Incidentally, the inorganic binder can be dissolved or suspended in water and incorporated into the composition.

Examples of silicates include sodium silicate, potassium silicate, borosilicate, magnesium silicate, aluminum silicate, zirconium silicate, potassium aluminum silicate, magnesium aluminum silicate, sodium aluminum silicate, and sodium methyl silicate. , potassium methyl silicate, sodium butyl silicate, sodium propyl silicate, lithium propyl silicate, triethanolammonium silicate, tetramethanolamine silicate, zinc hexafluorosilicate, ammonium hexafluorosilicate, cobalt hexafluorosilicate, hexa iron fluorosilicate, potassium hexafluorosilicate, nickel hexafluorosilicate, barium hexafluorosilicate, hydroxyammonium hexafluorosilicate, sodium hexafluorosilicate and calcium fluorosilicate; Preference is given to sodium silicate, potassium silicate, sodium methyl silicate and potassium methyl silicate, and mixtures thereof.

The content of the inorganic binder (preferably silicon binder) is 0.05% by weight or more, preferably 0.06% by weight or more, and preferably 0.10% by weight, based on the solid content of these components. % by weight or more is more preferred, 0.12% by weight or more is even more preferred, and 0.15% by weight or more is particularly preferred. If the content is less than 0.05% by weight, the composition tends to gel during storage, resulting in reduced storage stability. From the viewpoint of the water resistance and hydrophilicity of the coating film, it is preferably 3.0% by weight or less, more preferably 2.5% by weight or less, and even more preferably 2.0% by weight or less.

The content of silicate in the silicon-based binder is not particularly limited, but is, for example, 1 to 99 wt%, 5 to 95 wt%, 10 to 90 wt%, 1 to 30 wt%, 5 to 40 wt%, 10 ~50 wt%, 20-60 wt%, 30-70 wt%, 40-80 wt%, or 50-90 wt%, preferably 5-95 wt%, more preferably 10-50 wt%. preferable.

(Anionic surfactant)
The antifungal and/or antialgal composition according to the present embodiment preferably contains an anionic surfactant from the viewpoint of transparency of the resulting composition. Anionic surfactants include, for example, carboxylates such as soap; sulfonates; alkyl sulfates, sulfates such as polyoxyethylene alkyl sulfates; alkyl phosphates; acyl-N-methyltaurate, etc.; Fatty acid ester salts and dialkyl sulfosuccinates are more preferred. Any one of the above-exemplified anionic surfactants may be used alone, or two or more thereof may be used in combination.

The content of the anionic surfactant is preferably 0.1 to 10% by weight, more preferably 0.2 to 5.0% by weight, even more preferably 0.3 to 2.0% by weight, relative to the composition. If it is less than 0.1% by weight, colloidal silica tends to precipitate during storage, and the transparency of the composition tends to be insufficient. On the other hand, when it exceeds 10% by weight, there is a tendency that film properties such as film formability and adhesion are lowered.

The anti-mold and/or anti-algae composition according to the present embodiment is suitably used as a water-based paint for architectural interior materials, exterior materials, and the like. When used as a paint, only the paint composition can be used as a clear paint. , mica, alumina, alum, clay, magnesium hydroxide, magnesium oxide, diatomaceous earth, and other extender pigments, as well as titanium oxide with photocatalytic activity, flypontite with anti-stain and adsorption functions, active zinc white, magnesium silicate, etc. of functional pigments can also be added. In order to impart various functions as a paint, a plasticizer, an antioxidant, a thickener, a dispersant, an anti-settling agent, an ultraviolet absorber, a light stabilizer, etc. may be added as appropriate.

The coating composition thus obtained can be applied to various inorganic materials, metal materials, wood materials, plastic materials, etc., and an excellent coating film can be obtained by natural drying or forced drying at a temperature of 50°C or higher. It is possible to form In the film formation, an organic solvent (film-forming aid) such as ethylene glycol monobutyl ether, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate is optionally added for the purpose of lowering the film formation temperature. It is also possible to add to

Furthermore, the anti-mold and/or anti-algae composition according to this embodiment can also be made into an aerosol spray by encapsulating compressed gas such as LPG, dimethyl ether, nitrogen, carbon dioxide, or air.

The present invention will be described based on examples, but the present invention is not limited only to the examples.

Various materials used in Examples and Comparative Examples are listed below.
Metal oxide 1: Copper oxide (I) manufactured by Sekisui Jushi Co., Ltd. was dispersed in ultrapure water (milliQ water) so as to have a concentration of 5% by weight. (Average particle size: 150 nm)
Metal oxide 2: Zinc oxide manufactured by Sakai Chemical Co., Ltd. was dispersed in ultrapure water (milliQ water) to a concentration of 20% by weight. (Average particle size: 150 nm)
Metal oxide 3: Copper (II) oxide manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd. was passed through 200 mesh and dispersed in ultrapure water (milliQ water) to a concentration of 5% by weight. . (Average particle size: 2400 nm)
Metal hydroxide 1: Copper (I) hydroxide manufactured by FUJIFILM Wako Pure Chemical Co., Ltd. was passed through 200 mesh and dispersed in ultrapure water (milliQ water) to a concentration of 5% by weight. used. (Average particle size: 3200 nm)
Colloidal silica: Cataloid SI-40 manufactured by Nikki Shokubai Kasei Co., Ltd. (solid concentration: 40% by weight, pH: 9, average particle size: 18 nm)
Clay mineral: Synthetic smectite anionic surfactant manufactured by BYK-Chemie Japan Co., Ltd. ADEKA CORPORATION EC-8600 (diethylhexyl sodium sulfosuccinate)
Inorganic binder: 15 to 30% by weight of potassium methylsilicate and polyorganosilane, and about 3% by weight of potassium hydroxide dispersed in ultrapure water (milliQ water) were used.

(Examples and Comparative Examples)
Test paints were prepared according to the formulations shown in Tables 1 and 2. Specifically, an inorganic binder dispersion is added to a mixture of water, a metal oxide or metal hydroxide dispersion, a colloidal silica dispersion, a clay mineral, and an anionic surfactant, Stirring at 20° C. for 30 minutes using a homodisper gave the test paint. 25 g/m ² of the obtained test paint was applied to the surface of a synthetic resin product (fluoroemulsion clear coating manufactured by Kawakami Toryo Co., Ltd.) by spraying, and then dried at 80°C for 3 minutes to prepare a test panel. was made. In Tables 1 and 2, not the solid content of each component, but the amount of the dispersion as a whole is shown.

<Measurement of contact angle>
After each test plate was sprayed with pure water, the contact angle was estimated by photography. The static contact angles of the test plates of Examples 1-8 were less than 50°, confirming that the surfaces of these test plates had good hydrophilicity.

<Storage stability>
Each test paint was placed in a 100 mL glass sample bottle, sealed and stored in a constant temperature room at 43° C. for 30 days, and its condition was observed.

<Transparency>
The paint was applied to a microslide glass using a #7 bar coater and dried sufficiently to prepare a specimen. Using a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd.), the transparency of each test paint was measured according to JIS K7136. The performance target value of transparency haze is 0.5% or less.

<Anti-algae sustainability>
The test plate was exposed using a metal weather tester (KW-R5TP manufactured by Daipla Wintes Co., Ltd.). Specifically, light of 295 to 780 nm was irradiated with a KF-1 filter using a metal halide lamp light source, and irradiation (75 mW/cm ² at 63 ° C., 50% RH) and darkness (30 ° C., 98%) for 4 hours. RH) Cycle conditions were 4 hours, and the cycle was repeated to expose each test panel for 0 to 900 hours.
The anti-algae persistence of the test plates after exposure was evaluated by the agar medium method. A liquid medium for algae culture is placed in a glass container, a test plate is placed, an algae suspension (test strain: Protcoccus sp, Pleurococcus Chlorella vulgaris 3 kinds of mixture) is sprayed, a temperature of 23 ° C., an illumination of 2500 lx (light period of 16 Time: 8 hours dark period) and cultured for 4 weeks. After exposing the test panels for a specified time (0 to 900 hours), the degree of algal growth on the test panels was examined. Tables 1 and 2 show the exposure times for the test panels that had 0% algae. The performance target value for the anti-algae persistence is 400 hours (similar to commercially available photocatalytic compositions).

From the results in Tables 1 and 2, it can be seen that the water-based coating composition of the present invention has good transparency, storage stability, and antifungal/antialgae persistence. On the other hand, in Comparative Example 6, precipitation of metal oxides was confirmed after storage, and in Comparative Examples 7 and 8, the composition gelled after storage and satisfactory storage stability was not obtained.

The water-based paint composition of the present invention has good transparency, storage stability, and antifungal/algae resistance, and is therefore particularly useful as a paint used for building interior materials, exterior materials, and the like.

Claims (7)

An antifungal and/or antialgal composition comprising an aqueous dispersion containing metal oxides and/or metal hydroxides, colloidal silica, clay minerals, and an inorganic binder,
The metal oxide and/or metal hydroxide is one or more selected from the group consisting of copper (I) oxide, copper (II) oxide and copper (II) hydroxide, zinc oxide, silver oxide, and nickel oxide. and one or more selected from the group consisting of
The total content of metal oxides and metal hydroxides in the composition is 0.1 to 10% by weight,
A composition having an inorganic binder content of 0.12 % by weight or more. An antifungal and/or antialgal composition comprising an aqueous dispersion containing metal oxides and/or metal hydroxides, colloidal silica, smectite, and an inorganic binder,
The metal oxide and / or metal hydroxide contains one or more selected from the group consisting of copper (I) oxide, copper (II) oxide and copper (II) hydroxide,
The total content of metal oxides and metal hydroxides in the composition is 2.0 to 10% by weight,
A composition having an inorganic binder content of 0.12% by weight or more. 3. The composition according to claim 1, wherein the average particle size of the metal oxide and metal hydroxide is 50-5000 nm . Claims 1 to 3, wherein the total amount of copper (I) oxide, copper (II) oxide and copper (II) hydroxide in the total amount of metal oxide and metal hydroxide is 0.1 to 80% by weight. A composition according to any one of the preceding claims. Claims 1 to 1, wherein the metal oxide and/or metal hydroxide comprises one or more selected from the group consisting of copper (I) oxide, copper (II) oxide and copper (II) hydroxide, and zinc oxide. 5. The composition according to any one of 4. A composition according to any one of claims 1 to 5 , further comprising an anionic surfactant. The composition according to any one of claims 1 to 6 , wherein the inorganic binder is a silicon binder containing silicate.