JPH08164359A - Antifouling member and production thereof - Google Patents

Abstract

PURPOSE: To obtain an antifouling member keeping excellent antifouling function for a long period. CONSTITUTION: A film of an antifouling substance is formed on the surface of a base of metal, coating film, plastics, rubber, ceramics, fiber or the like by an ion beam support vacuum deposition method or an ion implantation method. Cu, Ag, Zn, Sn, Cr, Co, H, F, Cl, B, He, Ne, Ar, O and N, etc., are cited as antifouling substances performed ion implantation. In the ion beam support vacuum deposition method, Cu, Ag, Zn, Sn, Cr and Co, etc., are vapor- deposition, while the surface of the base is irradiated with ion beams of He, Ar and O, etc. Thus, since a dense surface layer superior in adhesive strength to the base is formed, a work for preventing sticking of aquatic living thing is sustained for a long period.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface-treated antifouling member for preventing adhesion of aquatic organisms and a method for producing the same.

[0002]

2. Description of the Related Art Algae, barnacles, shellfish such as mussels tend to adhere to members that are in constant contact with water, such as underwater structures, cooling water pipes, drain pipes, and ship bottoms. When aquatic organisms adhere to the pipes, the cross-sectional area of the flow path is reduced and the smooth flow of cold water, hot water, etc. passing through the inside is hindered. Further, if aquatic organisms separated from the inner wall of the pipe flow into equipment such as a pump, a serious accident may occur. The aquatic organisms attached to the bottom of the ship become a great resistance and weaken the propulsive force of the ship, which also causes the corrosion of the steel material forming the bottom of the ship. Therefore, it is necessary to periodically scrape off the underwater organisms attached to the bottom of the ship. To prevent the attachment of aquatic organisms that cause such problems,
Conventionally, various antifouling measures have been adopted. Above all,
The method of applying various antifouling agents and the method of coating the surface of the substrate with a metal or metal compound having a bactericidal effect are general-purpose.

For example, in Japanese Patent Laid-Open No. 59-145074, an insulating coating is applied to the surface of a structure immersed in seawater, and then Cu or a Cu alloy having a bactericidal effect is sprayed. In Japanese Patent Laid-Open No. 61-97480, Cu, S
The structure is covered with a fibrous tape sprayed with n, Zn or the like. In Japanese Patent Laid-Open No. 64-21086, a base material coated with a resin is sprayed with Cu or a Cu alloy, and then a synthetic resin coating is applied. Cu, Sn, Zn with bactericidal effect
Metals or alloys such as the above may be applied to the surface of the base material by plating, sputtering, vacuum deposition or the like. Also, by applying an organic tin compound, a copper-based compound such as cuprous oxide, or an antifouling agent such as an alkylphenol, a surface having resistance to biofouling can be obtained.

[0004]

When an antifouling agent is applied to the surface of a substrate by thermal spraying, plating, sputtering, vacuum deposition, etc., the functional layer formed often has insufficient adhesion to the substrate. Therefore, the functional layer is easily peeled off from the base material by friction or impact before sufficiently exerting the original antifouling function.
The more intense the tidal currents and water currents, the more frequently friction and impact due to suspended matter in the water are applied, and the adhesion of aquatic organisms cannot be sufficiently suppressed. In addition, in the functional layer formed by the conventional method, Cu, Ag, etc., which are active ingredients, are often eluted in water, and as a result, the antifouling function is reduced in a short period of time. Moreover, some treatment methods require high temperatures, which limits the types of substrates that can be treated. The present invention has been devised to solve such problems, and a functional layer for a substrate is obtained by injecting or depositing an antifouling substance on the surface of the substrate by an ion implantation method or an ion beam assisted vapor deposition method. It is an object of the present invention to obtain an antifouling member that suppresses excessive elution of an antifouling substance by improving the adhesion of the above and densifying the functional layer, and maintaining an excellent antifouling action for a long period of time.

[0005]

In order to achieve the object, the antifouling member of the present invention has a functional layer containing an antifouling substance formed on the surface of a substrate by an ion beam assisted vapor deposition method or an ion implantation method. It is characterized by being As the base material, materials and processed products such as metal, coating film, plastics, rubber, ceramics, fiber are used. As antifouling substances, Cu, A
One or more selected from g, Zn, Sn, Cr, Co and alloys thereof are used. Ion-implanted hydrogen, fluorine, chlorine, boron, helium, neon, argon, oxygen, nitrogen, etc. also exhibit antifouling action. In the ion implantation method, an ionized antifouling substance is implanted on the surface of the base material.
The types of ions are Cu, Ag, Zn, Sn, C
There are metal ions such as r and Co. Also, hydrogen, fluorine, chlorine, boron, helium, neon, argon, oxygen, nitrogen, etc. are used as long as they are ionizable. In the ion beam assisted deposition method, an antifouling substance is deposited while irradiating the surface of the base material with an ion beam. The antifouling substance to be deposited includes metals or alloys such as Cu, Ag, Zn, Sn, Cr and Co. The types of ion beams supported include ions such as helium, argon, and oxygen.

[0006]

[Function] The antifouling substance injected into the substrate by the ion implantation method is
It does not form a coating layer different from the base material formed by thermal spraying, plating, sputtering, vacuum deposition, etc., but is taken into the inside of the base material surface layer. Therefore, unlike a coating film or a vapor deposition film, there is no possibility of peeling from the base material. C with toxicity
In those in which metal elements such as u, Zn, Sn, Cr, and Co are ion-implanted, the concentrations of these metal elements are high in the surface layer of the base material. Therefore, Cu, Zn, Sn, Cr, C
A toxic effect such as o extends to the periphery of the member, and aquatic organisms dislike this toxicity and do not adhere to the surface of the base material. Also,
Aquatic organisms that have already adhered are Cu, Zn, Sn, C
Growth is hindered by toxicity of r, Co, etc., and eventually they die. Ag has a catalytic action, produces | generates active oxygen from oxygen in water, and suppresses adhesion of aquatic organisms by active oxygen. Hydrogen, fluorine, chlorine, boron, helium, neon, argon, oxygen, nitrogen and the like other than metals are similarly taken into the inside of the surface layer of the base material by ion implantation to form a surface layer portion which is not likely to peel off. The surface layer portion has a high concentration of a non-metal element, the surface condition such as wettability is modified, and the aquatic organism hardly adheres to the surface. In addition, since fluorine, chlorine, boron, etc. put out into the water ions that aquatic organisms dislike, they also have an action of suppressing attachment of aquatic organisms.

In the ion beam assisted vapor deposition method, a base material is placed in a vacuum atmosphere and one or more metal elements of Cu, Ag, Zn, Sn, Cr and Co are irradiated while irradiating the surface of the base material with an ion beam. Is vapor deposited. An ion beam is used to ionize helium, argon, oxygen, etc. with an ion gun,
It is generated by applying an acceleration voltage of 1 kV or more. Since the formed vapor deposition film is vapor-deposited on the surface of the base material activated by the irradiation of the ion beam, the adhesion to the base material is extremely high. The metal element itself of the deposited film generates toxicity and active oxygen that aquatic organisms dislike. Toxic or active oxygen inhibits and kills the growth of aquatic organisms around the substrate. The antifouling effect of the vapor-deposited film is synergistically improved with the metal or non-metal implanted on the surface of the substrate due to the assisted ion beam. Further, since the vapor deposition film formed by the ion beam assisted vapor deposition method is densified, the amount of metal eluted from the vapor deposition film into water is suppressed and the antifouling action is maintained for a long time.

[0008]

【Example】

(Preparation of test piece) Example 1: A 100 mm x 200 mm aluminum alloy (1100) plate having a plate thickness of 1 mm, which was subjected to electrodeposition coating with a film thickness of 10 µm, was used as a substrate. To this substrate, Table 1
Cu was ion-implanted under the conditions shown in. Example 2: A Cu vapor deposition film was formed on the aluminum alloy substrate coated with the same electrodeposition coating as in Example 1 by the ion beam assisted vapor deposition method under the conditions shown in Table 2. Example 3: A vinyl chloride plate having a thickness of 5 mm and a size of 100 mm × 200 mm was used as a substrate, and Cu was used under the conditions shown in Table 1.
Was ion-implanted. Example 4: The same vinyl chloride plate base material as in Example 3 was added to Table 2.
A Cu vapor deposition film was formed by the ion beam assisted vapor deposition method under the conditions shown in. Example 5: An Ag vapor deposition film was formed on the aluminum alloy base material coated with the same electrodeposition coating as in Example 1 by the ion beam assisted vapor deposition method under the conditions shown in Table 2.

The antifouling performance of each treated substrate was investigated by the method described below. The following comparative materials were prepared to clarify the effectiveness of the surface layer treated by the ion implantation method and the ion beam assisted vapor deposition method. Comparative Example 1: An aluminum alloy plate which has been subjected to the same electrodeposition coating as in Examples 1, 2, 5 Comparative Example 2: Untreated vinyl chloride plate as in Examples 3 and 4 Comparative Example 3: Examples 1, 2 , An aluminum alloy plate on which the same electrodeposition coating as that of No. 5, 5 was formed with a Cu vapor deposition film by a vacuum vapor deposition method. Comparative Example 4: A vapor deposition of Cu by a vacuum vapor deposition method on Examples 3 and 4 and a vinyl chloride substrate.

[0010]

[Table 1]

[0011]

[Table 2]

(Evaluation of Antifouling Performance) Each treated material was immersed 1.5 m below the sea surface in Orido Bay, Shimizu City, and periodically pulled up to observe the adhesion state of organisms attached to the surface of the test piece. As can be seen from Table 3 showing the observation results, in Examples 1 to 5 according to the present invention, almost no aquatic organisms were observed to adhere and the clean surface condition at the beginning of the test was maintained for a long period of time. On the other hand, in Comparative Examples 1 and 2, a large amount of aquatic organisms became attached as the test period passed. Also, C
In Comparative Examples 3 and 4 in which the u vapor-deposited film was formed, the initial antifouling performance was almost the same level as in Examples 1 to 5, but the adhesion of aquatic organisms increased rapidly as the test period became longer. This indicates that the Cu vapor deposition film formed by vacuum vapor deposition has been consumed.

[0013]

[Table 3]

[0014]

As described above, the antifouling member of the present invention is an ion implantation method or an ion beam assisting method on the surface of a material such as metal, coating film, plastics, rubber, ceramics, fiber or processed product. A surface layer having an antifouling effect is formed by a vapor deposition method. This surface layer is coated, plated, sputtered,
Compared to a film formed by a vacuum deposition method or the like, it has excellent adhesion to a substrate and maintains an excellent antifouling function for a long period of time. In this way, the member with the antifouling function is
It is used in a wide range of applications such as structures in contact with fresh water and seawater, piping, and ship bottoms.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location B05D 7/14 Z 7/24 303 B 7415-4F (72) Inventor Kuji Hori 1 Kabahara, Kambara-cho, Anbara-gun, Shizuoka 34th-1st Nichiru Giken Co., Ltd.

Claims (7)

[Claims] 1. An antifouling member in which a functional layer containing an antifouling substance is formed on the surface of a substrate by an ion beam assisted vapor deposition method or an ion implantation method. 2. An antifouling member, wherein the base material according to claim 1 is a metal, a coating film, plastics, rubber, ceramics or fibers. 3. The antifouling substance according to claim 1 is Cu, Ag,
An antifouling member which is one or more selected from Zn, Sn, Cr, Co and alloys thereof. 4. A method for producing an antifouling member, which comprises injecting an ionized antifouling substance on the surface of a base material. 5. Cu, Ag, Zn, Sn, Cr, Co,
The method for producing an antifouling member according to claim 4, wherein one or more ions selected from H, F, Cl, B, He, Ne, Ar, O and N are used. 6. A method for producing an antifouling member, which comprises depositing an antifouling substance on the surface of a base material while irradiating the surface of the base material with an ion beam. 7. The method for producing an antifouling member according to claim 6, wherein one or more selected from Cu, Ag, Zn, Sn, Cr, Co and alloys thereof are used as an antifouling substance.