JP2006111832A - Covered film composition of naturally hardenable type electroconductive polyurethane prepolymer, and antifouling apparatus by using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antifouling apparatus for preventing the structures, ships, waterways and piping that lie in the seawater and are in contact with the seawater from depositing and settling of marine organisms, which apparatus comprises (A) an electroconductive polyurethane prepolymer covered film, (B) an electrode material arranged in the covered film and (C) at least one kind of a source among a direct current power source, a battery and a solar cell, and additionally in which apparatus a suitable antifouling current is energized in the covered film surface by installing (B) the electrode material inside (A) the naturally hardenable type electroconductive polyurethane and by connecting to (C) a variety of electric power sources and which apparatus is characterized in that the apparatus involves the above (A) and (B) and besides a satisfactory antifouling current flows during a time to bring about an antifouling effect. <P>SOLUTION: The electroconductive polyurethane prepolymer covered film composition is a composition as the electroconductive polyurethane which is obtained by kneading a one-pack, naturally hardenable type polyurethane prepolymer with an emulsified pigment of an elecroconductive carbon and a hardening accelerating, electroconduction-inducing activated water and which has an electrical resistivity of 5-200 KΩ cm. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a so-called antifouling technique for preventing marine organisms from adhering to the surface of a ship or structure in seawater and in contact with seawater.

  Ships are made of steel, aluminum, FRP (reinforced plastic) and equipment structures are often made of steel or concrete. Antifouling paint is applied to the surface that contacts the seawater as a means of antifouling to prevent marine organisms from adhering to and staying in the seawater and the surface that contacts the seawater of the ship, equipment, and As chemical methods, chemical substances such as chlorine used for tap water as a bactericidal agent have been used, but none is preferable from the viewpoint of environmental compatibility. In recent years, electrical antifouling technology with few environmental problems is being used, but the cost of equipment becomes expensive.

  As for the electrical antifouling method, the method of generating chlorine by electrolyzing seawater is recognized as an adhesion and seizure prevention effect, but it is necessary to consider corrosion measures for antifouling facilities.

  The mechanism by which microorganisms adhere to and settle on the surface of ships and facilities that are in contact with seawater forms marine microorganisms to form a microbial film, on which large organisms such as corals, barnacles, and oysters adhere and settle. It is known that they are formed in this order, and an effective solution is to prevent microorganisms from attaching and staying on the surface.

JP 2002-309042 PR

  However, this publicity has a vulcanization process in the factory and on-site when rubber lining is enforced. There is also a natural vulcanization method, but there are some physical difficulties, and the manufacturing cost is high, and lining construction Those skilled in the art need skilled engineers, and it is likely that enforcement will be difficult depending on the construction structure, material and shape.

  The purpose is to deal with the above-mentioned problems in electrical antifouling, and it is easy to implement regardless of the structure and shape of the actual ship / equipment / equipment. Is to provide an antifouling method and an antifouling device with a natural curing type conductive polyurethane-based prepolymer coating film that realizes a uniform potential distribution at low cost, but there are significant differences from conductive rubber lining. First, the cost is about 1/2 to 1/3, and the workability of the conductive rubber lining is the in-house work, after a skilled engineer installs the vulcanization process, and large articles enter the vulcanizer, In other words, it is constrained by the size that can be transported on land, and it seems difficult to repair at the time of breakage. On the other hand, the coating film of the present invention is a self-curing type, which can be applied on-site and can be easily repaired.

  In general, it is sufficient to place a cathode and an anode on the left and right, but when using a power source of minute power, it is preferable to use a plurality of power sources in combination, in which case the cathode and anode are arranged alternately. For example, it may be arranged so that a current flows.

  Depending on the material of the base material to be enacted, surface treatment is required. (A) Metallic and non-ferrous metal structures and ships with conductive polyurethane-based prepolymer composition have electrical conductivity, which may cause galvanic phenomena and needs to be an insulator. Alternatively, in the case of an inorganic material and concrete, an epoxy coating film is desirable as a base treatment in order to increase the adhesive strength.

  (X) One-part naturally curing polyurethane-based prepolymer composition that achieves the object of the present invention is a moisture-curable polyisocyanate non-yellowing type coronate 2234 or 100 parts of coronate 2298 by Nippon Polyurethane Industry Co., Ltd. A hexamethylene isocyanate raw material having an isocyanate bond, combined with 0.5 to 7.0 parts, preferably 0.5 to 3.0 parts, and further containing 10 to 40 parts of a silicon oil processed product It is characterized by having a fluid film-forming property.

  (X) One-pack spontaneously curable conductive polyurethane prepolymer composition (Y) Examples of conductive carbon emulsion pigments include carbon black and metal powder (silver, copper, nickel, etc.). In particular, carbon black is preferably used. Examples of carbon black include ketjen black EC, acetylene black, XCE carbon, SRF carbon, graphite, activated carbon, etc. Among them, ketjen black EC is excellent for the purpose of the present invention. In the present invention, Lion paste W-356A, W370C, W-310A, 100 parts manufactured by Lion Co., Ltd. are mixed and dispersed, and the silicon oil processed product is 10-50 parts, preferably 15-25 parts. And (Z) 1-5 parts of cured conductive inductive active water was found to be emulsified.

(Z) Curing accelerating conductivity-inducing active water is an ionic acidic water 100 parts by weight. Purified wood vinegar with a small water molecule cluster and an aqueous solution containing 0.05 to 2.0 parts by weight is used as an activation device. When treated for 24 to 36 hours, the water molecule cluster becomes a water molecule cluster of 50 to 70% smaller than tap water. When blended with a polyurethane-based prepolymer, (Z) curing promoting conductivity-inducing active water is evenly dispersed. (A) a naturally curable conductive polyurethane-based prepolymer composition having a property of electrical resistance of 5 to 200 kΩ, which is imparted with curing accelerating property and electrical inductivity, and synergistically with the conductive carbon emulsion pigment (Y) Become.

  Furthermore, (X) 30 to 38 parts of (Y) conductive carbon emulsion pigment (Z) 10 to 20 parts of hardening-accelerating conductive inductive activated water is added to 100 parts of the one-component naturally curing polyurethane prepolymer. (A) A naturally curable polyurethane prepolymer composition coating film characterized by having a coating film in a short time and having a very high electrical resistance value of 5 to 200 kΩ as a resin coating film.

  When the electrode is a highly conductive material, a carbon woven fabric made of copper foil double-sided conductive adhesive strip, copper strip, titanium strip, aluminum strip, graphite nonwoven strip, long fiber or short fiber Among the highly conductive band electrodes selected from banded fabrics, woven fabrics made by coating / depositing / welding conductive materials on natural / synthetic fibers and bands, (B) Bands with copper foil double-sided conductive adhesive material are priced It is also cheap and desirable from the viewpoint of workability.

A 20-foot (6.06 m) long work boat, the bottom of the ship, approximately 10.0 m ^{2 is} powered by a single AA battery DC1.5V x 2 = DC3.0V. No adhesion or settlement of microorganisms or marine organisms is observed during the month. Also, no damage or change of the electrode part is observed. By applying a DC voltage of 3.0 V, the antifouling device (A) gives an electric shock to marine organisms that approach or come into contact with the coating film surface of the (A) naturally-curing type conductive polyurethane-based prepolymer composition. The purpose is to prevent adhesion. This electric antifouling device has a single battery DC1.5V x 2 = DC3.0V as a power source, so it works only on organisms trying to adhere to the surface and does not release harmful substances. It does not harm the environment. The power supply voltage is an antifouling device using at least one of a battery, a constant potential DC power supply, a photovoltaic power generation battery and a storage battery equipment. A battery, DC 3.0-6.0 V is desirable for anti-fouling of a ship class of 20 to 35 feet (6.06 to 10.6 m) ship class.

  After attaching the above-mentioned (B) copper foil double-sided adhesive band on the surface on which marine organisms can adhere and settle on a base material made of steel, FRP, inorganic material, wood, etc. (C) After wiring to the power source, the above-mentioned (A) natural curing type conductive polyurethane-based prepolymer composition is included with (B) a copper foil double-sided adhesive material contacted with a brush, roller, spray machine, etc. The antifouling purpose is applied to the entire surface by applying a coating film 5 times (dry film 200 to 300 μm) and energizing to provide an antifouling device.

The invention's effect

Industrial applicability

  The (A) conductive polyurethane-based prepolymer composition of the present invention is antifouling and the base material is metal, non-ferrous metal steel, FRP, concrete, etc. Not limited to the need for local implementation, the composition of the present invention is excellent in coating workability, and the composition of the present invention is colored in the market, and has excellent workability, low cost, short work period, mechanization, etc. An excellent composition that can be repaired in the field even when the membrane is damaged.

  The purpose is to deal with the above-mentioned problems in electrical antifouling, and it is easy to realize regardless of the structure and shape in an actual ship, structure, equipment, or device, and a relatively uniform potential distribution can be realized at low cost. (A) It is to provide an antifouling method and an antifouling device by energizing electricity with a coating film of a natural curable conductive polyurethane prepolymer composition.

  In general, it is sufficient to place a cathode and an anode on the left and right, but when using a power source of minute power, it is preferable to use a plurality of power sources in combination, in which case the cathode and anode are arranged alternately. For example, it may be arranged so that a current flows.

Measurement Equipment Custom Co., Ltd. Product Name Multi Tester CX-270N
Measurement function used DC voltage DCV range 0-10V Accuracy F. Within S ± 3% Resistance Ω × 1K: 0 to 200Ω to 2MΩ Scale length within ± 3%
Inside the measuring instrument, internal power supply UM-3 (1.5V) x 2
Inside power supply, internal power supply 006P (9V) x 1

  It is a form figure of the antifouling device which installed (A), (B), and (C) in the ship exterior side and the ship bottom concerning the present invention, and is a circuit diagram from a power source.   The form figure of the antifouling apparatus in the seawater intake concrete water channel and water channel concerning this invention, and the circuit diagram by multiple power supplies.   Cross section of the main coating film

Explanation of symbols

A Self-curing conductive polyurethane-based prepolymer composition coating film B Electrode Copper foil double-sided adhesive band C Power supply Battery DC3.0V DC1.5V x 2 pieces D Epoxy coating film E Concrete channel

Claims (7)

(X) A composition obtained by kneading (Y) a conductive carbon emulsified pigment and (Z) curing-accelerating conductive conductivity-inducing active water into a one-component spontaneous curing polyurethane prepolymer, A naturally curable conductive polyurethane prepolymer composition. The (A) naturally curable conductive polyurethane-based prepolymer composition according to claim 1, comprising (Y) a conductive carbon emulsified pigment. (A) The natural curing type conductive polyurethane-based prepolymer composition of (A) according to claim 1 containing (Z) a curing accelerating conductivity-inducing active water. The conductive polyurethane prepolymer composition according to any one of claims 1.2 to 3, which has an electrical resistivity of 5 to 200 KΩ. A facility device for preventing fouling caused by adhesion and occupancy of marine organisms to seawater and structures, ships and waterways / pipings that come into contact with seawater, and (A) a naturally curable conductive polyurethane-based prepolymer composition ( B) It is comprised from at least 1 type with the electrode material arrange | positioned in contact with a coating film, (C) DC power supply, a battery, and a photovoltaic power generation battery and storage battery equipment.
(B) After setting the anode and cathode for the electrode material and connecting and wiring to various power sources, (A) Covering the entire surface of the antifouling objective part including the place where the natural curing type conductive polyurethane is in contact with the power source and then connecting to various power sources Thus, the antifouling device is characterized by having (A) and (B) in which a sufficient antifouling current is applied for a period of time when the current is applied to the coating film surface. (B) When the electrode is a highly conductive material, it consists of a copper foil double-sided conductive adhesive strip, a copper strip, a titanium strip, an aluminum strip, a graphite nonwoven strip, a long fiber or a short fiber. It is characterized by being a highly conductive band electrode selected from a carbon woven band, a woven cloth in which a conductive material is coated / deposited / welded on natural / synthetic fiber, and a band. (A) Anti-fouling coating film and anti-fouling device using the natural curable polyurethane pre-polymer composition according to any one of claims 1 to 6 as a natural curable conductive polyurethane pre-polymer composition .

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