JPH0615825Y2 - FRP ship - Google Patents

Description

[Detailed Description of the Invention] (Industrial field of application) The present invention is an FR which prevents adhesion of underwater microorganisms to the bottom of a ship.
It relates to a P (fiber reinforced plastic) ship.

(Prior Art) Various methods have been conventionally used for the antifouling method of the FRP bottom plate, but a definitive method has not been found yet.

Conventionally, it has been generally practiced to apply various antifouling agents to the surface of a substrate to prevent the adhesion of microorganisms and algae. In particular, organic tin compounds, for example, low molecular weight organic tin compounds such as tolbutyltin oxide and tributyltin fluoride, and high molecular weight organic tin compounds such as a copolymer of tolbutyltin methacrylate have been widely used.

However, with regard to antifouling agents centering on these organotin compounds, in recent years, their toxicity and persistence to fish and shellfish have come to be problematic, and the use of low molecular weight organotin compounds is particularly limited. It's starting to happen.

On the other hand, copper and copper alloys have long been known to be less susceptible to aquatic organisms, and the effects of fish and shellfish and the food chain through them on the human body can be almost ignored. Has desirable characteristics.

Therefore, it is known to use a copper or copper alloy plate or a structure in which a plate is adhered to the surface by utilizing this advantage, but there are problems such as strength, durability or economical efficiency of the structure, and it is practical. Is not used to much.

Further, various methods have been proposed in which a resin composition obtained by mixing copper or copper alloy powder in a resin is applied to various base materials. However, at present, satisfactory results have not been obtained in terms of long-term adhesion on a substrate and antifouling property.

In particular, when the FRP is a substrate, it was very difficult to obtain a coating having high adhesion because of its surface smoothness.

On the other hand, a method of spraying copper or a copper alloy on a substrate to form a sprayed coating is also known (Japanese Patent Laid-Open No. 59-145074).
However, in order to maintain the adhesiveness of the sprayed coating or improve the coating efficiency during spraying, it was necessary to sufficiently roughen the surface of the substrate. Such roughening treatments include physical methods such as blasting and polishing, or chemical methods, but all of them require a great deal of labor and treatment of dust or waste liquid after the roughening treatment. There were many problems.

(Purpose of the Invention) The present invention aims to solve or improve the problems of the conventional techniques as described above, and has an antifouling film having excellent adhesion and, as a result, capable of maintaining the antifouling property for a long time.
It intends to provide an RP ship.

(Means for Solving Problems) The above-mentioned object is to provide a particle size of 5 to 200 in the submerged portion of the FRP ship.
To provide a resin layer having a surface roughness (Rz) of 30 to 250 μm containing 25 to 400% by volume of non-conductive solid particles of μm with respect to the resin, and a copper or copper alloy sprayed coating layer on the resin layer. Achieved by

Hereinafter, the present invention will be described in detail.

In the present invention, the resin layer as the thermal spray pretreatment layer provided between the FRP and the metal thermal spray coating layer has an average particle size of 5 to 2
It is obtained by applying and drying a resin composition containing non-conductive solid particles of 00 μm.

Examples of the non-conductive solid particles include oxides, nitrides and carbides of metals such as copper, nickel, aluminum, zinc, iron and silicon.

Specific examples include aluminum oxide, silicon oxide, iron oxide, silicon carbide, boron nitride, and the like.

Further, depending on the solvent composition of the composition, powders of acrylic resin, styrene resin, epoxy resin and the like may be used.

These particles can be used alone or as a mixture of two or more kinds.

Considering the chemical stability with respect to the resin used, the fact that it does not form a corrosion battery with the thermal spray material, is hard, and is unlikely to precipitate in the composition, it is particularly preferable to use silica sand, alumina, silicon carbide or the like.

In the present invention, the particle size of the particles is in the range of 5 to 200 μm, preferably 30 to 100 μm. If the particle diameter exceeds 200 μm in the above range, the particles are likely to precipitate in the resin composition and the nozzles are likely to be clogged when spray coating. Further, even if it can be applied, the surface roughness becomes too rough, and the surface of the metal sprayed film becomes rough, so that the appearance becomes very poor. On the other hand, when the particle size is smaller than 5 μm, the desired surface roughness cannot be obtained even when the resin composition is applied to the surface of the substrate, and thus it becomes difficult to obtain a metal sprayed coating having excellent adhesion.

In the present invention, the particles are added to the resin described later in 25
~ 400% by volume [pigment volume concentration (PVC) 20 ~
80%], preferably 65 to 150% by volume [pigment volume concentration (PVC) 40 to 60%].
In the above range, when the content with respect to the resin is less than 25% by volume, the amount of the resin is large and therefore the surface roughness is small, and as a result, the adhesion of the metal sprayed coating is deteriorated.

On the other hand, if the content of the particles with respect to the resin exceeds 400% by volume, the resin content is extremely reduced and the bonding force between the particles is weakened, and as a result, the adhesiveness of the metal spray coating is deteriorated, which is not preferable.

The "resin" used in the present invention is not particularly limited as long as it has a certain degree of drying property, hardness, adhesion, water resistance and durability.

Specific examples thereof include thermoplastic acrylic resin that is a one-liquid room temperature drying type resin, vinyl resin, chlorinated rubber, alkyd resin, unsaturated polyester resin that is a two-component curing type resin, acrylic-urethane resin, polyester-urethane resin, and epoxy. Resin, melamine-alkyd resin which is a thermosetting resin,
Examples include melamine-acrylic resin, melamine-polyester resin, acrylic resin, acrylic-urethane resin and the like.

These may be used alone or as a mixture of two or more.

If necessary, an organic solvent for dissolving or dispersing the resin, water or the like is added to the composition of the present invention as a component other than the resin.

Further, additives such as dyes, pigments, dispersants, antifoaming agents and anti-sagging agents (thixotropic agents) can also be used in combination.

The composition may take any form such as a solvent system, a water-soluble system, a water dispersion system, and a solvent dispersion system.

In the present invention, the composition is prepared by adding the above-mentioned resin and particles, if necessary, a solvent or dispersion medium, various additives and the like, and mixing them by a usual dispersion and mixing method.

The thus-obtained (resin) composition is applied onto a substrate by the same method as in a general coating composition. In particular, it is preferable to use the air spray method because it is easy to control the coating amount. However, as with ordinary paints,
It goes without saying that brush coating and roll coating are also possible by appropriately adjusting the viscosity and the like.

The thickness of the resin layer in the present invention is freely selectable, the film thickness obtained by coating at a rate of approximately 10 to 300 g / m ^2, particularly preferably is applied at a rate of about 20 to 150 g / m ² It is about the film thickness obtained. If the coating amount is less than 10 g / m ² , the surface roughness will be small, the thermal spraying efficiency of the metal will be low, and the adhesion of the thermal spray coating will also be low, such being undesirable. On the other hand, when the coating amount exceeds 300 g / m ² , the surface roughness becomes too rough, or the coating becomes too smooth depending on the composition and properties of the composition, so that the adhesion of the metal spray coating decreases. This is not preferable.

In the present invention, the surface roughness (Rz) of the coating film after application of the composition
Is 30 to 250 μm, preferably 60 to 120
It is preferably in the range of μm. [In addition, the said surface roughness (Rz) shows the ten-point average roughness of JISB-0601 (1982) "definition and display of surface roughness", and the surface roughness (Rz) is measured by Tokyo Seimitsu ( The surface roughness profile measuring instrument Surfcom 554A manufactured by K.K. In the range of the surface roughness, when the thickness is not 30 μm, the thermal spraying efficiency is low and the adhesion of the metal sprayed coating is deteriorated. On the other hand, when the surface roughness exceeds 250 μm, the surface of the sprayed coating is Both are not preferable because they are rough and have a significantly deteriorated appearance, and when the sprayed coating is rubbed, the coating of the underlying resin composition may be exposed.

The surface roughness as described above is determined by the particle size of the particles contained in the resin composition and the content thereof, and the coating amount on the substrate.

For example, when the specific composition as described above is applied by an air spray method in a slightly dry spray manner within the above application amount range, a desired surface roughness can be obtained. Further, for example, it is possible to obtain the desired surface roughness by applying thixotropic property to the above-mentioned specific composition, if necessary, and applying it with a brush or the like.

In the present invention, the target FRP ship can be obtained by providing the copper or copper alloy spray coating on the resin layer as described above.

Examples of the method for obtaining the metal sprayed coating include a plasma spraying method, a gas flame spraying method, an electric arc spraying method, and a low temperature spraying method using a reduced pressure arc sprayer.
Either method may be used.

However, since the resin layer is formed on the FRP that is sprayed, the decomposition or flow of these resins does not occur, and the FRP substrate is not exposed to extremely high temperatures.
It is necessary to consider the spraying method and conditions. For example, it is necessary to control the amount of gas, the amount of air, the current, the voltage, the spray rate, the spray distance, and the like.

The metal used for the thermal spray is copper or copper and nickel,
It is an alloy with metals such as aluminum, zinc, tin, manganese, and iron. The content of copper in the alloy is at least 10% by weight, preferably 50% by weight or more, in consideration of antifouling property.

The thickness of the copper or copper alloy coating layer is about 100
It is preferable that the film thickness is such that it can be obtained by thermal spraying at a rate of up to 3000 g / m ² .

Thus, according to the present invention, it is possible to easily provide a copper or copper alloy coating on the FRP that has been conventionally hard to adhere to a metal spray coating, and as a result, an FRP ship having a long-term stable antifouling coating. Can be obtained.

Hereinafter, the present invention will be described in more detail with reference to the drawings and embodiments.

Example 1 100 g of an epoxy resin (Epiclon 4051, manufactured by Dainippon Ink and Chemicals, Inc., epoxy equivalent: 950) was mixed with 8 parts of xylene.
After adding 0 g, 60 g of methyl ethyl ketone and 25 g of butanol and dissolving, a polyamide resin (Epicure 89
2, 275 g of epoxy-polyamide resin B having a heating residue of 40% by weight (resin solid content volume of 100 cm ³ ) obtained by adding 10 g of active hydrogen equivalent 133 manufactured by Celanese, and silicon carbide having an average particle diameter of 48 μm (green silicon carbide CG320) Product made in Nagoya polishing machine industry specific gravity 3.16 221 g (particle volume 7
0 cm ³ , PVC 41%) and thoroughly mixed with resin composition A
Was produced.

When the resin composition A was applied to the bottom submerged portion of a FRP boat having a length of about 1.5 m by air spray at 60 g / m ² , the surface roughness (Rz) was 70 μm. After drying for 24 hours, cupro nickel (copper: nickel = 90: 10 alloy) was sprayed at a low temperature to 110 μm.

The conditions for low-temperature spraying are as follows: arc-spraying machine PA600 (manufactured by Pan Art Craft Co., Ltd.) under reduced pressure, using cupro-nickel wire with a wire diameter of 1.1 mm, wire speed 5 m / min, voltage 20 V
I went there.

The vertical tensile strength of this sprayed coating was good at 55 kg / cm ² .

The results of the antifouling test are shown in Table 1.

In addition, the state of the film after 1 year was observed.
No peeling or blistering was observed and it was good.

Example 2 Acrylic polyol resin (hydroxyl value 100, heating residue 5
0%) 170 g, isocyanate resin Sumidule N
75 (Sumitomo Bayer Urethane, heating residue 75% by weight)
203 g of solvent type urethane-acrylic resin having a heating residue of 54% by weight obtained by adding 33 g (volume 100 cm ³ ) and aluminum oxide having an average particle size of 20 μm (white fused alumina WA800, manufactured by Nagoya Abrasive Equipment Industry, specific gravity 3.96). 11
9 g (particle volume 30 cm ³ , PVC 23%) were sufficiently stirred to prepare a resin composition B.

When the resin composition B was applied to the same article as in Example 1 by air spray at a rate of 80 g / m ² , the surface roughness (Rz) was 90 μm. After drying for 24 hours, P
A copper wire rod having a diameter of 1.1 mm and containing 5% zinc was sprayed by A600 to a film thickness of 80 μm. The thermal spraying conditions were a carrying speed of 8 m / min and a voltage of 19V.

The obtained film had a vertical tensile strength of 50 kg / cm ² and good antifouling property.

In FIG. 1, a partial cross-sectional view (outline) of the FRP ship bottom skin obtained in Example 2 is shown, and a resin layer obtained from the resin composition B on the FRP ship bottom skin 1 is shown. 2 and a copper alloy sprayed coating layer 3 coated thereon.

In the test, the FRP boats of Examples and Comparative Examples were laid up in Toba Bay, Mie Prefecture, and the adhesion of shellfish such as barnacles and seaweeds such as sea lettuce and sea lions was observed in area ratio, and the results are shown in Table 1. It is a thing.

[Brief description of drawings]

FIG. 1 is a partial cross-sectional view (schematic diagram) of a bottom plate of a FRP ship of the present invention. 1 ... FRP outer plate, 2 ... resin layer, 3 ... sprayed coating layer.

Claims (1)

[Scope of utility model registration request] 1. A submerged portion of a ship has a resin layer and a copper or copper alloy sprayed coating layer provided on the resin layer, and the resin layer is a non-conductive solid having a particle diameter of 5 to 200 μm. An FRP ship containing particles in an amount of 25 to 400% by volume with respect to the resin and having a surface roughness (R _z ) of 30 to 250 μm.