JP2640270B2 - Algae-proof powder and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an anti-algal powder having an algal-inhibiting metal supported on the surface of hydrous titanium oxide or titanium oxide particles and a method for producing the same.

[Technical background of the invention]

In general, in addition to mold, greenery algae and other plants are liable to develop on the exterior walls of the building, as well as in bathrooms and kitchens, and as a result, their aesthetics are impaired, the durability is reduced, and the sanitary environment is deteriorated. Or For this reason, various proposals have hitherto been made in order to prevent the adhesion and propagation of algae and to avoid the above-mentioned fouling of structures and the like. For example, a method of applying a construction with a paint to which an organic anti-algal agent such as benzothiazole or phenylurea is added is well known. However, in general, when using this kind of organic anti-algal agent, for example, the persistence of the anti-algal effect is not sufficient, or the coating film is yellowed by the anti-algal agent or the coating film strength is reduced. The effect on the physical properties of the coating film cannot be avoided, for example, and the improvement is strongly demanded.

By the way, the present inventors have been conducting various studies on high value-added or composite materials as a functional material of a powder of hydrous titanium oxide or titanium oxide for some time. Attention was paid to its application as a substrate particle of powder, and further studies were conducted. As a result, these titanium oxide-based or hydrated titanium oxide-based powders have a high value-added material as a material having a long-lasting anti-algal effect by allowing a specific metal component to be supported on the particle surface. What can be achieved, especially in recent years,
Propagating on the outer walls of buildings in high-temperature, humid areas such as tropical or subtropical areas, severely contaminating the painted outer wall, or corroding it and impairing durability,
The solution is urgently needed Trentepohl
ia), Anacystis, etc., have been found to have extremely excellent algal protection properties against contamination, and the present invention has been completed.

[Disclosure of the Invention]

That is, the present invention provides: 1) the surface of a particle of hydrous titanium oxide or titanium oxide;
An anti-algal powder comprising at least one metal selected from the group consisting of copper, zinc and alloys thereof.

2) The anti-algal powder according to claim 1, wherein the metal is copper.

3) The anti-algal powder according to claim 1, wherein the metal is a copper alloy.

4) On the surface of the particles of hydrous titanium oxide or titanium oxide,
A method for producing an algal-proof powder, comprising electroless plating at least one of copper, zinc or an alloy thereof to carry the metal.

5) On the surface of the particles of hydrous titanium oxide or titanium oxide,
A method for producing an algal-proof powder, comprising depositing at least one of copper, zinc or an alloy thereof and supporting the metal.

6) A method for producing an alga-proof powder, comprising compacting and mixing at least one of copper, zinc, and an alloy thereof on the surface of hydrous titanium oxide or titanium hydroxide particles to carry the metal.

7) An anti-algae characterized in that particles of hydrous titanium oxide or titanium oxide and at least one compound of copper, zinc or an alloy thereof are mixed and then reduced to carry the metal on the surface of the particles. Method for producing conductive powder.

8) An anti-algal powder characterized in that at least one of an organocopper compound, an organozinc compound or a mixture thereof is thermally decomposed and the decomposed metal is supported on the surfaces of particles of hydrous titanium oxide or titanium oxide. Production method.

9) An anti-algal resin composition comprising the thermosetting resin or the thermoplastic resin and the antibacterial powder according to claim 1 mixed therein.

10) A rubber composition comprising the antibacterial powder according to claim 1 and rubber; 11) a glass composition comprising the antialgal powder according to claim 1. It is an anti-algal glass composition.

In the present invention, the hydrous titanium oxide or titanium oxide (hereinafter referred to as “substrate particles”) carrying an anti-algal metal component includes various hydrated titanium dioxides in addition to hydrous titanium oxide represented as so-called TiO ₂ .nH ₂ O. What
Normal titanium dioxide, Ti: O in a ratio of approximately 1: 2, Ti: O
Is present in various proportions, so-called low titanium oxide, titanium-nickel-antimony based on titanium dioxide, titanium-chromium-antimony based, titanium oxide composite based pigment, synthetic rutile pigment, etc. It is. These have an average particle size of usually 0.01 to 3 μm, preferably 0.02 to 1 μm.
μm, and more preferably 0.03 to 0.4 μm. As the base particles, those manufactured by various production methods can be used. For example, (1) titanium dioxide powder obtained by gas phase oxidative decomposition of titanium tetrachloride, (2) titanium sulfate solution, titanium tetrachloride solution or Hydrous titanium dioxide obtained by hydrolyzing the organic titanium compound solution in the presence of seeds for nucleation as necessary (3) powdered titanium dioxide obtained by calcining hydrous titanium dioxide; 1), (2), various low-order titanium oxide powders obtained by heating and reducing the hydrated titanium dioxide precipitate or titanium dioxide powder obtained in (3), and (5) the above (2) And a titanium oxide composite pigment obtained by adding a metal component for coloring to the precipitated titanium oxide precipitate obtained by the above and reacting by heating.

In the present invention, as the anti-algal metal supported on the base particles, metal copper, in addition to metal zinc, Cu-Zn, Cu-Sn, Cu
Alloys based on copper and / or zinc, such as -Al, Cu-Ag, Zn-Sn, Zn-Sn-Cu, Zn-Al-Cu-Mg; Also, two or more kinds may be supported. The supported amount of the metal component is
Usually 0.00 as a supporting metal based on the weight of the base particles.
It is 1 to 35%, preferably 0.01 to 30%. If the supported amount is less than the above range, the desired alga-proofing effect cannot be obtained, and if it is more than the above-mentioned range, not only is it not advantageous in terms of cost but also the dispersibility and toning in the algal-proofing treatment medium. The properties are easily impaired. In the present invention, the treatment for supporting the algal-proof metal on the base particles can be carried out by various methods. For example, (1) a reducing agent, and Various auxiliary agents such as a buffering agent, a complexing agent, and a pH adjusting agent are added to form a plating bath, and the base particles are immersed in the plating bath, and agitated for a predetermined time to remove the metal ions. A method of supporting the particles by a so-called electroless plating method of depositing a metal film on the surface of the particles. In this case, prior to the deposition of the film of the anti-algal metal, the base particles are immersed in an aqueous solution such as palladium or tin in advance. By adhering them to the surface of the particles, it is possible to more efficiently deposit the film of the anti-algal metal component, and it is easy to form a strong film with good adhesion.
(2) a method of heating and dissolving an anti-algal metal in a vacuum evaporation apparatus to evaporate it and deposit it on the surface of the base particles; (3) an alkyl metal compound containing an algal anti-metal component, an organometallic complex compound, and the like. A method in which various organometallic compounds are thermally decomposed and supported on the base particles, (4) the base particle powder and the algal-proof metal powder are loaded into a dry or wet compaction pulverizer such as a vol mill or an edge runner mill. And compacting and mixing, a method of supporting an algal-proof metal on the surface of the substrate particles,
(5) An anti-algal metal compound is added to the hydrous titanium oxide precipitate, the anti-algal metal component is supported on the surface of the hydrous titanium dioxide particles, and the titanium oxide is subjected to heat treatment in a reducing gas atmosphere. It can be carried out by a method of supporting an anti-algal metal on the particle surface.
Among these methods, the methods (1) and (2) are particularly easy to show the algal-proof metal on the surface of the base particles in a tight manner, and further enhance the expression and sustainability of the algal-proof effect. it can. When carrying out the above (1), (3) or (4), it is desirable to carry out the supporting treatment in an atmosphere of an inert gas such as nitrogen gas so as to prevent oxidation as much as possible.

The algae-proof powder of the present invention is useful for various algae. Examples of the algae include Trentepohlia lagenifera and Trentepohlia odorat.
a), Chlorella vulgaris,
Oscillatoria tenuis,
Scenedesmus quadrica
uda), Chlorolobion br
aunii), Tetracystits
pampae), Anacystis mont
ana).

The algae-preventive powder supported and treated as described above can be applied as various known algae-treating materials. For example, in addition to being added to various aqueous or non-aqueous paint compositions, it can be added to resin moldings and the like. It is very suitable for imparting an anti-algal effect to buildings, facilities, equipment and the like for a long period of time.

Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples.

(Example of the present invention)

Example 1 10 g of titanium dioxide powder (using rutile-type titanium dioxide obtained by vapor-phase oxidative decomposition of titanium tetrachloride and having the composition shown in Table 1 as base particles) was converted to 20% hydrofluoric acid. After immersion and stirring for 60 minutes, filtration, washing with water, drying,
5 g of the solution was first immersed in an aqueous solution of stannous chloride (0.5 g /) 1 and then immersed in an aqueous solution of palladium chloride (0.5 g /) 1 to attach palladium to the surface of the titanium dioxide particles. The titanium dioxide pretreated in this manner is added to a plating bath solution (copper sulfate 70 g /, Rochelle salt 35).
0 g /, sodium hydroxide 100 g /)
When the liquid temperature reached 25 ° C with gentle stirring,
100 ml of a 37% formalin solution was gradually added, and after completion of the addition, stirring was further continued at the same solution temperature for 90 minutes to deposit a metal copper film on the surface of the base particles by electroless plating. Thereafter, the titanium dioxide particles were separated by filtration, washed with water, and dried to obtain a target alga-proof powder.

Example 2 70 g of rutile-type titanium dioxide powder having the composition shown in Table 1 was suspended in 500 ml of 3% hydrofluoric acid, stirred at normal pressure for about 30 minutes, filtered, washed with water, dried and pulverized. Separately, 0.1 g of silver nitrate was added to 1 water, and a solution was added until aqueous ammonia was formed and the precipitate was re-dissolved.
50 g was added, and the mixture was stirred and dispersed for about 60 minutes. Next, a previously prepared reducing solution (45 g glucose, 4 g tartaric acid, 100 alcohol)
1) 30 ml was gradually added to the above-mentioned dispersion liquid, followed by filtration and washing until the specific resistance of the filtrate became 125 μs or less, followed by drying and pulverization. This pulverized product is plated with a plating solution (copper sulfate 70g /
, Rochelle salt 350g /, Sodium hydroxide 100g /)
When the liquid temperature reached 50 ° C. with gentle stirring, 37% formalin solution 1 was gradually added to deposit a metallic copper film on the surface of the titanium dioxide particles.
Filtration, washing and drying yielded the desired alga-proof powder.

Example 3 10 g of rutile-type titanium dioxide powder having the composition shown in Table 1 was spread in a glass Petri dish (65 mm in diameter), and placed in a vacuum evaporation apparatus (HUS-5GB, manufactured by Hitachi, Ltd.). A piece was placed and a predetermined amount of brass was vapor-deposited on the surface of the titanium dioxide particles to obtain a desired algal-proof powder.

The powders supporting the antialgal metal obtained in Examples 1 to 3 were each stored in a container which had been previously replaced with nitrogen gas. Table 2 shows the physical properties of these samples.

Test Example The algae-proof powders A ₁ , A ₂ and A ₃ obtained in Examples ₁ , ₂ and ₃ were used as test samples, and titanium dioxide A ₀ having no algae-proof metal on the particle surface was used as a blank sample. An anti-algal test was performed.

The test method was a Proteose agar medium (Proteoseagar
edium) Add a predetermined amount of anti-algal powder so that the concentration of copper or copper + zinc becomes 350 ppm in 10 ml, stir well with a test tube mixer, suspend in agar, and pour into a 6 cm diameter petri dish. Of green algae, Trentepohlia lagenifera and Trentepohli
a odoreta), Chlorella (Chlorella vulgaris), Tetracystis (Tetracystis pampae)
Incubate for 14 days in a 20 ° C constant temperature bath under fluorescent light irradiation,
The effect according to the degree of growth on agar was determined. Table 3 shows the results. An emulsion paint (PVC 40%, test sample 1.5% by weight) prepared by using Boncoat EC-833 (Acrylic styrene emulsion resin, manufactured by Dainippon Ink and Chemicals, Inc.) was added to the glass surface. (2 cm × 2 cm), the above-mentioned Trentepohlia odoreta algal cells were applied to the glass surface, and the temperature was 25 ° C.
Was left under a fluorescent lamp irradiation in a constant temperature bath, and the effect of the growth degree after one month and three months was determined. Table 4 shows the results.
Shown in

[Effect of the Invention] The anti-algal powder obtained by the present invention is a powder in which an algal-proof metal component is firmly supported on the surface of the substrate particles, and an anti-algal effect can be expected to increase in sustainability. In particular, it exhibits excellent algicidal properties against algae that are rapidly breeding in the tropics, such as Trentporia, etc., and this is the high hidden power of titanium dioxide powder as the base particles. It has excellent optical characteristics such as high whiteness and high dispersibility, and is of great industrial value as a treatment material for imparting anti-algal properties in a wide range of applications and as a coloring material.

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Claims (12)

(57) [Claims] (1) An anti-algal powder characterized in that at least one kind of metal composed of copper, zinc or an alloy thereof is supported on the surface of particles of hydrous titanium oxide or titanium oxide. 2. The algal-proof powder according to claim 1, wherein said metal is copper. 3. The anti-algal powder according to claim 1, wherein said metal is a copper alloy. 4. A method for producing an algal-proof powder, characterized in that at least one of copper, zinc or an alloy thereof is electrolessly plated on the surface of particles of hydrous titanium oxide or titanium oxide to carry the metal. Method. 5. A method for producing an algae-resistant powder, comprising depositing at least one of copper, zinc or an alloy thereof on the surface of particles of hydrous titanium oxide or titanium oxide and supporting the metal. 6. A method for producing an algal-proof powder, characterized in that at least one of copper, zinc and their alloys is compacted and mixed on a surface of a particle of hydrous titanium oxide or titanium oxide to carry the metal. Method. 7. A method comprising mixing particles of hydrous titanium oxide or titanium oxide with at least one compound of copper, zinc or an alloy thereof, reducing the mixture, and supporting the metal on the surface of the particles. A method for producing an algae-proof powder. 8. An anti-algae characterized in that at least one of an organocopper compound, an organozinc compound or a mixture thereof is thermally decomposed and the decomposed metal is supported on the surfaces of particles of hydrous titanium oxide or titanium oxide. Method for producing conductive powder. 9. An anti-algal resin composition comprising a thermosetting resin or a thermoplastic resin and the anti-algal powder of claim 1 mixed therein. 10. An anti-algal rubber composition comprising a rubber and the anti-algal powder of claim 1 blended therein. 11. An algal-proof glass composition comprising a glass and the algal-proof powder of claim 1 blended therein. 12. An antibacterial coating composition comprising the antialgal powder of claim 1 blended therein.