TWI426954B - A photocatalyst film preventing microorganism adhesion and the use thereof - Google Patents

Description

Photocatalyst film for resisting biological adhesion and use thereof

The present invention relates to a film for bioadhesion that is bonded to the surface of an article to enable the article to be resistant to biofouling.

Conventional anti-biofouling film, such as the Republic of China No. 200923037 "antifouling coating composition, antifouling coating film, substrate with coated film, antifouling substrate, method for forming a coating film on the surface of the substrate, and substrate The anti-fouling method patent application discloses that an antifouling coating composition can be applied to any underwater structure such as an outer panel of a ship, a fishing net or a fishing gear, and an anti-biofouling film is formed on the surface of the underwater structure, so that The underwater structure is not attached to marine organisms such as stone scorpions, barnacles, bryozoans, etc., but can avoid the problem of the strength or function of the structures in the water, or reduce the service life of the structure in the water. However, the antifouling coating composition has the function of reducing the attachment of the underwater structure to the organism, but does not inhibit the growth of the adhering organism to enhance its anti-bioadhesive effect.

Photocatalyst materials have been widely used in various fields due to their redox properties, such as air purification, odor removal or water purification by photocatalytic materials. For example, anatase TiO ₂ is a photocatalyst material, and a photocatalyst material is irradiated by a specific light source to generate a pair of free electron holes. When a medium such as air or water is in contact with the photocatalyst material, The harmful substances (organic or inorganic substances) in the medium are subjected to a redox reaction. Therefore, conventional TiO ₂ has an effect of inhibiting the growth of bacteria and mold.

Please refer to the Patent No. 350752 of the Republic of China on "Water Purification Methods for Aquatic Animal Breeding Boxes", which discloses a method for purifying aquatic animals in aquaculture tanks by oxidation-reduction of TiO ₂ . However, although the anatase phase TiO ₂ can inhibit bacterial growth, due to the anatase phase TiO ₂ hydrophilic material (the contact angle is nearly 0°), adherent organisms such as moss, algae, etc. can be The biofilm or anchoring structure is similar to the hydrophilicity of the anatase phase TiO ₂ and adheres to the surface of the water tank. Therefore, the anatase phase TiO ₂ cannot be used as an anti-moss or other adhering organism. It is used to suppress the growth of bacteria in the water tank. It takes time and labor for the user to clean the surface of the water tank to keep the inner wall surface of the culture tank clean, resulting in an increase in the workload of the user.

The main object of the present invention is to improve the above disadvantages to provide a photocatalyst film for resisting bio-adhesion, which can be applied to the surface of any object in contact with water, to prevent the article from being bio-adhered, and to inhibit the growth of the adherent organism.

A second object of the present invention is to provide a photocatalytic film for resisting bioadhesion, which is applied to the surface of any object in contact with water for enhancing the anti-bioadhesive effect of the surface of the article.

In order to achieve the foregoing object, the photocatalyst film for a submerged structure of the present invention comprises at least one of ZnTiO ₃ , Zn ₂ TiO ₄ and Zn ₂ Ti ₃ O ₈ ; and a photocatalyst for resisting biological adhesion For the use of a film, the photocatalyst film is bonded to a water-contacting surface of an object to prevent the organism from adhering to the water-contacting surface.

Wherein, the contact surface of water on the photocatalyst film preferably has a contact angle of 50 to 90°.

Preferably, the photocatalyst film further comprises rutile phase TiO ₂ .

The thickness of the photocatalyst film is preferably 10 to 300 nm; if the object is composed of a light transmissive material, the thickness of the photocatalyst film is preferably 10 to 100 nm.

The above and other objects, features and advantages of the present invention will become more <RTIgt;

The photocatalyst film for bioadhesion according to the present invention comprises at least one of ZnTiO ₃ , Zn ₂ TiO ₄ and Zn ₂ Ti ₃ O ₈ , and the contact surface of the photocatalyst film with water has a contact angle of 50 to 90°. A hydrophobic film can be used for anti-bioadhesion, in particular, it can resist the adhesion of hydrophilic bioadhesive tissues, such as mucosa, biofilm, sessile tissue, etc. of aquatic organisms.

The photocatalyst film of the present embodiment is a zinc titanate prepared by a sputtering method, a sol-gel method or other conventional methods by using a mixture of zinc oxide (ZnO) and titanium oxide (TiO ₂ ). ZnTiO ₃ , Zn ₂ TiO ₄ or Zn ₂ Ti ₃ O ₈ films of different crystal phases are formed by different annealing temperatures, and the photocatalyst film has a contact angle of 50 to 90°, and the photocatalyst film is hydrophobic and resistant to living things. The effect of inhibiting the growth of bacteria, microorganisms and the like of the photocatalyst film is enhanced by adhering to an excitation light source, thereby further enhancing the anti-bioadhesion effect of the present invention.

In addition, the thickness of the photocatalyst film is preferably 10 to 300 nanometers (nm). If the thickness of the photocatalyst film is less than 10 nm, the anti-bioadhesive effect is not good. If the thickness is greater than 300 nm, the deposition is uneven. , reducing the bonding strength of the photocatalyst film to the object.

The photocatalyst film for bioadhesion of the present invention can be bonded to a water contacting surface of an object to prevent the object from being attached to the organism. The object refers to any material of any material whose inner wall surface or outer wall surface is in contact with water. The object may be completely or partially immersed in water or used to hold a water body, and the object is not limited to plastic, glass, fiber, metal. The material is preferably made of a light transmissive material, such as glass or plastic, and the surface of the water touch refers to the surface in contact with water, for example, the inner wall surface for water holding of the water tank, the inner and outer wall surfaces of the water pipe, The surface of the ship's board, submersible motor, etc.

If the object is selected from a light transmissive material, the thickness of the photocatalyst film is preferably 10 to 100 nm, so that light can penetrate the light transmissive object and the photocatalyst film at the same time. It can be applied to objects such as aquariums, culture tanks, etc., and it can make the water-repellent surface of the object have anti-bio-adhesion effect.

In this embodiment, ZnO and TiO ₂ are prepared into a film-type photocatalyst by sputtering, and are plated on a glass substrate at a weight ratio of 1:1, and different annealing temperatures are controlled. To form photocatalyst films having different crystal phases, such as ZnTiO ₃ , Zn ₂ TiO ₄ or Zn ₂ Ti ₃ O ₈ . More specifically, the photocatalyst film must be sintered at a temperature above 1100 ° C for a mixture of ZnO and TiO ₂ . After sintering, an annealing process is required to obtain photocatalysts of different zinc titanate crystal phases, when annealing temperature When 700~800°C, the crystal phase of ZnTiO ₃ can be formed. When the annealing temperature is 800~820°C, the crystal phase of Zn ₂ Ti ₃ O ₈ can be formed. When the annealing temperature is 900~945°C, the crystal of Zn ₂ TiO ₄ can be formed. phase, and forming the respective crystal phases, due to the annealing temperature is higher than 700 deg.] C, so that the photocatalyst film generally contains a little rutile phase (rutile) TiO _2, the rutile TiO ₂ based photocatalyst material having the hydrophobic, not Reducing the hydrophobicity of the photocatalyst film of the present invention also contributes to the effect of inhibiting bacterial growth of the photocatalyst film of the present invention.

In order to confirm that the photocatalyst films of different crystal phases of the present embodiment have anti-bioadhesive effects, in this embodiment, a glass substrate (having an area of 10 mm ² ) is prepared into a glass having different crystal phases of zinc titanate in the above manner. For the substrate, please refer to Table 1, (A) is a glass substrate without any treatment, (B) is a glass substrate with a ZnTiO ₃ film, and (C) is a glass with ZnTiO ₃ and TiO ₂ (rutile) film. a substrate, (D) is a glass substrate having a Zn ₂ Ti ₃ O ₃ film, and (E) is a glass substrate having a film of Zn ₂ TiO ₄ and TiO ₂ (rutile), and the glass substrate of the above different zinc titanate crystal phases is placed After a predetermined time (20 days) in a tap water irradiated with blue light (wavelength: 470 nm), the algae adhesion on each glass substrate was observed under a microscope.

The contact angle of the (A) glass substrate is 38.76°, and the contact angle of the (B) to (E) glass substrate falls between 50 and 90°, thereby confirming that the glass substrates of the embodiment do have different The photocatalyst film has an anti-bioadhesive effect by the hydrophobicity of the photocatalyst film of each crystal phase.

According to each of the glass substrates (A to E) shown in Table 1, after 20 days passed, the algae adhesion was observed under a microscope, and the algae was counted at a magnification of 100× unit field, the (A) glass substrate The observed algae includes Scenedesmus, N. algae, Chlorella, etc., and calculates algae in a unit field of view, and calculates the (B) to (E) based on the number of algae in the (A) glass substrate. The percentage of anti-adhesion can reach more than 40% of the anti-adhesion effect, and the anti-adhesion effect of (D) is the best (the percentage of anti-adhesion is 78.1%), which is due to the addition of ZnTiO on the glass substrate of (D). _{In addition to the} film, rutile phase TiO _{2 is included} , which can slow the growth of microorganisms. Therefore, the hydrophobicity of the ZnTiO ₃ film can prevent bio-adhesion, and the rutile phase TiO _{2 can} inhibit the growth of algae. Decreasing the rate at which algae grow and multiply on the glass substrate has the effect of enhancing the anti-bioadhesion of the present invention.

In addition, the present embodiment can be applied to other marine appliances, underwater appliances, fishing gears, etc., such as a ship bottom, a ship board, a submersible motor, a water pipe, a water tank, a water tank or a fishing net, etc., in addition to being applicable to aquaculture or aquarium appliances. Therefore, the tools can not reduce the efficiency of the operation due to the attachment of the organism, and can help the use of the appliances without the need for frequent cleaning operations, and has the effect of reducing the workload of the user.

The photocatalyst film for anti-bioadhesion of the invention can be applied to the surface of any object which is in contact with water, avoiding the object being bio-adhered, and at the same time suppressing the growth of the adherent organism, and having the effect of suppressing bio-adhesion.

The use of the photocatalyst film for anti-biofouling of the present invention is applied to the surface of any object in contact with water to improve the anti-bioadhesive effect on the surface of the object, and can reduce the workload of the user for cleaning the attached organism. Improve the efficiency of work efficiency.

While the invention has been described in connection with the preferred embodiments described above, it is not intended to limit the scope of the invention. The technical scope of the invention is protected, and therefore the scope of the invention is defined by the scope of the appended claims.

Claims (9)

The photocatalyst film for resisting bio-adhesion comprises at least one of ZnTiO ₃ , Zn ₂ TiO ₄ and Zn ₂ Ti ₃ O ₈ , wherein water has a contact angle of 50° to 90° on the contact surface of the photocatalyst film . The photocatalyst film for bioadhesion according to the first aspect of the patent application, wherein the photocatalyst film further comprises TiO _{2 of} a rutile phase. The photocatalyst film for bioadhesion according to the first aspect of the patent application, wherein the photocatalyst film has a thickness of 10 to 300 nm. The use of a photocatalyst film for resisting bio-adhesion, the photocatalyst film being bonded to a water-contacting surface of an object to prevent biological adhesion to the water-contacting surface, wherein the contact surface of water on the photocatalyst film has 50 ~90° contact angle. The photocatalyst film according to claim 4, wherein the photocatalyst film comprises at least one of ZnTiO ₃ , Zn ₂ TiO ₄ and Zn ₂ Ti ₃ O ₈ . The use of a photocatalyst film for bioadhesion according to item 4 of the patent application scope, wherein the photocatalyst film further comprises TiO _{2 of} a rutile phase. The use of the photocatalyst film for bioadhesion according to item 4 of the patent application scope, wherein the photocatalyst film has a thickness of 10 to 300 nm. The use of the photocatalyst film for bioadhesion according to item 4 of the patent application scope, wherein the object is composed of a light transmissive material. The use of the photocatalyst film for bioadhesion according to item 8 of the patent application scope, wherein the photocatalyst film has a thickness of 10 to 100 nm.