KR101752578B1 - Coating composition for use in ship with reduced friction drag utilizing gas-lubricating function in water, coating film formed from said composition, ship coated with said coating film, method for manufacturing said ship, method for predicting said friction drag reduction effect, device used for predicition of said friction drag reduction effect, and friction drag reduction system for use in said ship with reduced friction drag - Google Patents

Abstract

An object of the present invention is to provide a frictional resistance reducing vessel which is economical and has little influence on the environment because the gas affinity of air or the like in water continues to be maintained over a long period of time for a large effect of reducing fluid friction resistance, And which is capable of forming a coating film having an antifouling function even under a standing condition even during a running under the influence of friction resistance. The present invention is a coating composition for use in a frictional resistance reducing vessel that utilizes a gas lubrication function in water, capable of forming a coating film having a specific static bubbling contact angle underwater and a specific underwater bubble roll (slip) angle. Further, the present invention relates to an antifouling coating for a friction reducing abatement vessel using a gas lubrication function in water, comprising a specified amount of a specific organopolysiloxane (A), a specific organosilane (B) and a specific hydrophobic material (C) Coating composition.

Description

A coating composition for use in a ship, a coating film formed from the composition, a vessel covered with the coating film, a method for manufacturing the vessel, a method for predicting the frictional resistance reducing effect, Technical Field [0001] The present invention relates to an apparatus for predicting a resistance reduction effect and a friction resistance reducing system used for the friction resistance reducing vessel, a friction drag reduction effect, and a friction drag reduction system for use in said friction drag reduction effect, a device for predicting said drag coating effect,

The present invention relates to a coating composition for use in a ship with reduced frictional resistance mainly utilizing gas lubrication function in water, a coating film formed from the composition, a vessel coated with the coating film, a method for manufacturing the vessel, A device used for predicting the frictional resistance reducing effect, and a frictional resistance reducing system used in the frictional resistance reducing vessel.

The ship undergoes a wave resistance due to the generation of waves, a pressure shape resistance due to the shape of the bottom, and a frictional resistance (water friction resistance) due to the viscosity of water. Though the wave resistance and the shape resistance are greatly reduced by the researches so far, the frictional resistance occupies 60% to 80% of the total resistance of the hull, and it is urgently required to reduce the frictional resistance in order to save energy. As a method for reducing the resistance to water flow, there has been proposed and proposed an air lubrication method for supplying air to the bottom and a method of adding a polymer in a fluid such as seawater (a method using a Toms effect) .

For example, Patent Documents 1 to 4 disclose a method of treating a bottom surface with a coating agent or the like to impart water repellency to the bottom surface to retain bubbles or an air layer to reduce frictional resistance. In all of these methods, air is supplied to the bottom of the bottom where the specific hydrophobic coating film is formed, and the bottom surface of the bottom is covered with the air layer to reduce the frictional resistance by the air lubrication effect.

The hydrophobic coating film is formed of hydrophobic (fine) particles and a hydrophobic binder resin contained in the coating agent, and has a hydrophobic irregular surface having high affinity with air. The hydrophobic coating film (hereinafter also referred to as " hydrophobic uneven coating film ") having a hydrophobic concavo-convex pattern surface has air adhesion to the concave portion in the air to be retained as an air layer and exhibits high water repellency due to the small surface free energy of the convex portion . However, such a hydrophobic uneven coating film undergoes aging change in water to lose its water repellency and lose air compatibility. Especially in the bottom of the ship where the ship is running, this change over time is remarkable. That is, since the intermolecular interaction force between the air (gas molecule) and the hydrophobic uneven coating film (surface constituent molecule) is small, water (molecules) gradually enters into the concave portion and air is excluded. This phenomenon is described as "immersion wetting ". If there is water on the surface of the hydrophobic irregular coating film, the exclusion of air is further promoted. If the air (layer) is excluded due to the entry of water into the recesses of the hydrophobic concavo-convex coating film, even if fresh air is supplied to the surface, the cohesion energy and mass of water (molecules) are overwhelmingly larger than air, It can not enter the concave portion of the coating film. That is, the air (layer) holding performance is not revived. Therefore, the hydrophobic uneven coating film forms an air layer in the concave portion in the air, but it exhibits air affinity. However, since the surface of the coating film is covered with water penetrating into the concave portion in water, the hydrophilic unevenness coating film is lost in affinity with air.

In addition, the hydrophobic uneven coating film has small cohesive energy (surface free energy) and low mechanical strength. Therefore, such a hydrophobic concavo-convex coating film is fragile and insufficient in adhesion, so that the fine particles and the hydrophobic concavo-convex coating film peel off from the bottom surface due to the action of water flow during navigation or the like, and the air retention performance of the hydrophobic concave-

Furthermore, the hydrophobic uneven coating film has no antifouling performance. From the viewpoint that the roughness of the bottom surface is increased by the contamination of the bottom surface due to the attachment of aquatic organisms at the time of berth in the ship, and the frictional resistance is prevented from being increased, it is desired that the coat formed on the bottom has antifouling property. Patent Document 5 discloses that an oxidizing gas or an oxidizing liquid is supplied to the sea so that these gases or liquids flow through the bottom to impart antifouling properties to the uneven surface. However, it is difficult to always keep all of the bottom surface under such atmosphere, There is a concern about pollution of the ocean due to an oxidizing gas or an oxidizing liquid.

Thus, these conventional techniques are not effective as a method of reducing the frictional resistance of a ship used for a long period of time.

As described in Patent Document 6, there is also known a method of judging the effect of reducing the frictional resistance by the contact angle of the film surface with water. However, this method has a problem that the state and behavior of the bubbles on the surface of the coating film It is difficult to say that

Japanese Patent No. 2890340 Japanese Patent Application Laid-Open No. 08-268380 Japanese Patent Laid-Open No. 10-273617 Japanese Patent Application Laid-Open No. 11-131007 Japanese Patent Application Laid-Open No. 09-262563 Japanese Patent Application Laid-Open No. 2003-277691

As described above, in the prior art, by injecting air into the hydrophobic concavo-convex coating film having air affinity, the coating film retains the air layer and exhibits a frictional resistance reducing effect. In the water, the surface of the hydrophobic concave- The affinity with the air is lost, and the effect of reducing the frictional resistance as described above is lowered. Moreover, since the hydrophobic uneven coating film has no antifouling performance, the roughness of the coating film is remarkably increased due to contamination by microorganisms and the like, and the friction resistance tends to be increased.

In addition, attempts have been made to supply a large amount of air to the bottom so as to maintain the effect of reducing the frictional resistance. However, a large power is required to supply the air, and the energy saving effect due to the reduction in frictional resistance is canceled.

In consideration of the above, there is a method of predicting the frictional resistance reducing effect using the air lubrication function in the water of the coating film more easily, and it is useful if there is a device usable for the above prediction.

In view of the above, it is an object of the present invention to provide a coating film having an antifouling function even under a traveling condition or under a standing condition while exhibiting a high frictional resistance reducing effect by supplying a small amount of gas, A coating film formed from the composition, a friction resistance reducing vessel formed with the coating film, and a method of manufacturing a boat with reduced frictional resistance.

The present invention also provides a method for forming a coating film which is economical and has less effect on the environment because the gas affinity of air or the like in water continues for a long period of time, And a method for predicting the frictional resistance reducing effect using the gas lubrication function in the water of a coating film and a method for predicting the frictional resistance reducing effect of the coating film, A second object of the present invention is to provide a used device.

Another object of the present invention is to provide a frictional resistance reducing system for use in a frictional resistance reducing vessel as described above, and a frictional resistance reducing vessel that uses the gas lubrication function in water with the system.

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that a composition containing a specific organopolysiloxane (A), a specific hydrophobic material (C) and, if necessary, a specific organosilane and / It has been found that the above-mentioned first problem can be solved by the antifouling paint composition used for a ship having reduced frictional resistance using a gas lubrication function in water.

The present inventors have also found that an antifouling paint composition for use in a ship having a frictional resistance reduction utilizing a gas lubrication function in water and having a coating film having static air bubble contact angle and underwater bubble roll angle A method for predicting said frictional resistance reducing effect using a contact angle and underwater bubble roll (slip) angle, a method for predicting said frictional resistance reduction effect by means of a device having a specific configuration capable of measuring underwater underwater bubble contact angle and underwater bubble roll And found that the problem can be solved.

The present inventors have also found that by a frictional resistance reduction system comprising a coating film formed of a composition capable of solving the first or second problem described above and a gas supply device for supplying a gas such as air to the surface of the coating film, And found that the third problem can be solved.

The present invention is based on the following findings newly discovered by the present inventors.

A coating film formed from an antifouling paint composition containing a specific organopolysiloxane, a specific hydrophobic material and, if necessary, a specific organosilane and / or a partial condensate thereof efficiently exhibits an air lubrication effect, .

When compounds having a polysiloxane skeleton structure are incorporated in the antifouling paint composition, the leveling property of the compounds affects the shape of the antifouling coating film formed from the antifouling paint composition, and it is presumed that a coating film of a specific shape to be described later is formed .

The coating film formed by the above-described antifouling paint composition has a small roughness and a long average peak-valley interval (surface roughness of 50 占 퐉 or less and peak-valley average spacing of 700 占 퐉 or more). This coating film shape contributes to the demonstration of the characteristic that the contact angle of the bubbles in static water is less than 90 degrees and the bubble roll (slip) angle is less than 30 degrees. Unlike the conventional coating films (for example, the above-mentioned Patent Documents 1 to 4) which require that conventional fine irregularities are formed, this coating film shape is a coating film having gentle undulations relative to these coating films, Effect.

The hydrophobic component is liquid or grease-like at 25 占 폚. In a ship having a coating film formed of the coating composition on the water-immersed surface of the outer shell of the ship, the hydrophobic component bleeds out during the course of navigation to cover the surface of the coating film, The coating film formed of the composition exhibits antifouling property.

If the bubble and / or gas layer in the static water underwater contact angle of the coating film is less than 90 degrees and the bubble roll (slip) angle is less than 30 degrees, Since the fluid flows without delay, the air lubrication effect is efficiently expressed, and the water flow friction resistance is effectively reduced.

The above-mentioned coating film can maintain the properties and properties for a long period of time, and exhibits a high frictional resistance reducing effect with a small amount of air. Therefore, the frictional resistance reduction vessel formed on the water-immersed surface of the shell plating of the coating film does not require a large power for air supply, and thus the energy saving effect is large.

· In the case of a coating film formed of an antifouling paint composition containing a hydrophobic material and an antifouling agent, the friction resistance of a ship formed on a submerged surface of a shellboard is reduced, and the attachment of aquatic organisms is prevented, .

That is, the present invention is as follows.

The antifouling paint composition for use in a ship having reduced frictional resistance using a gas lubrication function in water according to the present invention comprises (A) a reactive curing organopolysiloxane having a viscosity of 20 to 400,000 mm 2 / s at 25 ° C, (C) (A) and the following organosilane and / or a partial condensate thereof (B)), and optionally (B) a hydrophobic material which is liquid or grease in the presence of a hydroxyl group and a hydrolyzable group (Hereinafter also referred to as " first coating composition ") (hereinafter referred to as " friction resistance using a gas lubrication function in water Abatement ship "is also called" special friction resistance abatement ship ").

The antifouling paint composition of the present invention is preferably such that the hydrophobic material (C) contains at least one kind selected from silicone oil, fluorine-based oil and paraffin from the viewpoint that the antifouling paint composition has better antifouling properties.

It is preferable that the antifouling paint composition of the present invention further contains antifouling agent (D) in an amount of 5 to 100 parts by weight based on 100 parts by weight of the organopolysiloxane from the viewpoint that the antifouling paint composition has better antifouling properties.

The antifouling coating film used in the special friction resistance reducing vessel of the present invention is characterized by being formed of the antifouling paint composition (also referred to as a first coating film).

The surface shape of the antifouling coating film of the present invention is such that the maximum height from the bottom of the recess to the top of the convex portion measured according to JIS B 0601 is 30 탆 or less and one convexity measured in accordance with JIS B 0601, It is preferable that the peak-valley mean spacing of 700 mu m or more, which is the average of the length of one period of one concave of the concavity, is more effective in reducing the frictional resistance.

The antifouling coating film of the present invention is characterized in that the bubble contact angle in static water measured by the static water contact angle measurement method is less than 90 degrees and the bubble roll angle (slip angle) measured by the measurement method of the water bubble roll (slip) And less than 30 degrees is preferable from the viewpoint that the frictional resistance can be more effectively reduced.

<Measurement method of static water bubble contact angle>

A hard polyvinyl chloride test plate (maximum height measured in accordance with JIS B 0601) of 1 占 퐉 or less coated with the coating composition was soaked in water at 25 占 폚 for 30 days so as to form a coating film having a dry film thickness of 150 占 퐉, A rigid polyvinyl chloride test plate was placed in water so that the surface of the coating film was horizontal and the lower side of the test plate. 0.1 cc of air was injected into the water to form one bubble on the surface of the coating film. (A) and the diameter (b) of the contact portion between the coating film surface and the bubbles were measured, and the static bubbling contact angle? _S (unit: degree) I ask.

&Lt; Measurement method of water bubble roll (slip) angle &gt;

In the method of measuring the static bubble contact angle in water, an underwater bubble roll angle (? _M , unit (? _M )), which is an inclination angle with respect to a horizontal plane of a coated film surface when bubbles start to move by gradually inclining the coated film surface on which bubbles are formed, : Degrees).

The special frictional resistance reducing ship of the present invention is characterized in that the antifouling coating film is coated with a submerged surface of the outer shell of the ship (also referred to as a first special frictional resistance reducing vessel).

The first special frictional resistance reducing ship manufacturing method of the present invention is characterized in that the antifouling coating film is formed on a surface of a shell plating to be submerged in water.

The frictional resistance reducing system of the present invention is characterized by including a coating film (first coating film) and a gas supplying device for supplying a gas such as air to the surface of the coating film (also referred to as a first frictional resistance reducing system).

The special frictional resistance reducing ship of the present invention is characterized by having a first frictional resistance reducing system (also referred to as a third special frictional resistance reducing vessel).

The coating composition of the present invention is used for a ship with reduced frictional resistance using a gas lubrication function in water and has a bubble contact angle in static water measured by a static water bubbling contact angle measurement method below below 90 deg. (Slip) angle of less than 30 degrees measured by an angular measurement method (also referred to as a second coating composition).

<Measurement method of static water bubble contact angle>

A hard polyvinyl chloride test plate (maximum height measured in accordance with JIS B 0601) of 1 占 퐉 or less coated with the coating composition was soaked in water at 25 占 폚 for 30 days so as to form a coating film having a dry film thickness of 150 占 퐉, A rigid polyvinyl chloride test plate was placed in water so that the surface of the coating film was horizontal and the lower side of the test plate. 0.1 cc of air was injected into the water to form one bubble on the surface of the coating film. (A) and the diameter (b) of the contact portion between the coating film surface and the bubbles were measured, and the static bubbling contact angle? _S (unit: degree) I ask.

[Equation 1]

&Lt; Measurement method of water bubble roll (slip) angle &gt;

In the method of measuring the static bubble contact angle in water, an underwater bubble roll angle (? _M , unit (? _M )), which is an inclination angle with respect to a horizontal plane of a coated film surface when bubbles start to move by gradually inclining the coated film surface on which bubbles are formed, : Degrees).

The antifouling coating film of the present invention has a peak height measured in accordance with JIS B 0601 of 30 占 퐉 or less and a peak-valley average spacing measured in accordance with JIS B 0601 of 700 占 퐉 or more, .

The coating film of the present invention is characterized by being formed by a coating composition used for a special friction resistance reducing vessel (also referred to as a second coating film).

The special frictional resistance reducing ship of the present invention is characterized in that the coating film is provided on the water-immersed surface of the outer shell of the ship (also referred to as a second special frictional resistance reducing vessel).

The frictional resistance reducing system of the present invention is characterized by comprising a coating film (second coating film) and a gas supply device for supplying a gas such as air to the surface of the coating film (also referred to as a second frictional resistance reduction system).

The special frictional resistance reducing vessel of the present invention is characterized by having a second frictional resistance reducing system (also referred to as a fourth special frictional resistance reducing vessel).

The second special frictional resistance reducing ship manufacturing method of the present invention is characterized in that the coating film is formed on a surface of a shell plating to be immersed in water.

The method of predicting the frictional resistance reduction effect using the gas lubrication function of the coating film of the present invention in water is characterized by measuring the bubbling contact angle in the static water by the measurement method of the bubbling contact angle in static water below, (Slip) angle is measured by the measurement method, and the frictional resistance reducing effect using the gas lubrication function in the water of the coating film is predicted from the bubbling contact angle in static water and the bubble roll (slip) angle in water.

<Measurement method of static water bubble contact angle>

The test plate coated with the coating composition was immersed in water so that the test plate after the immersion was installed in water so that the surface of the coating film was horizontal and the lower side of the test plate, air was introduced into the water to form bubbles on the surface of the coating film , The height (a) of the bubbles formed on the surface of the coating film from the surface of the coating film and the diameter (b) of the contact portion between the coating film surface and the bubbles were measured to calculate a static water bubble contact angle θ _s , unit: degrees).

[Equation 1]

&Lt; Measurement method of water bubble roll (slip) angle &gt;

In the method of measuring the static bubble contact angle in water, an underwater bubble roll angle (? _M , unit (? _M )), which is an inclination angle with respect to a horizontal plane of a coated film surface when bubbles start to move by gradually inclining the coated film surface on which bubbles are formed, : Degrees).

The apparatus used for predicting the frictional resistance reducing effect using the gas lubrication function of the coating film of the present invention is a device equipped with a test stand, an inclination angle control device, a dipping container, and an observing device. And a test plate having a coating film formed on its surface is mounted so that the back surface of the test plate is in contact with the underside of the test plate so that the test plate is immersed in the water immersion container to form bubbles on the surface of the test plate Wherein the observation apparatus is provided so as to observe the state of the test plate and the bubbles, and the state of the bubbles formed on the surface of the coating film of the test plate when the test plate is horizontal And the tilt angle of the test plate is inclined with respect to the horizontal by the tilt angle control device And observing the behavior of the bubble by the observation apparatus and measuring the bubble roll (slip) angle of the bubble formed on the surface of the coating film of the test plate.

Since the antifouling paint composition used in the special friction resistance reducing vessel of the present invention is blended with specific components, even when a small amount of gas is supplied, the frictional resistance against the water-immersed surface of the shell plating (hereinafter simply referred to as &quot; Frictional resistance &quot;) can be reduced, and the energy saving effect is also great. Since the coating film formed of the antifouling paint composition contains a specific hydrophobic material, it exhibits excellent antifouling properties and can prevent the adhesion of aquatic organisms, thereby preventing an increase in frictional resistance of the hull due to adhesion of aquatic organisms have. Furthermore, the coating film formed of the antifouling paint composition can maintain these effects for a long period of time.

When the hydrophobic material (C) contained in the antifouling paint composition used in the special friction resistance reducing vessel of the present invention contains at least one selected from the group consisting of silicone oil, fluorinated oil and paraffin, the antifouling paint composition has higher antifouling performance Whereby the effect of reducing the friction of the coating film can be maintained over a longer period of time. When the antifouling paint composition contains the antifouling agent (D), the effect is further increased.

The surface shape of the antifouling coating film of the present invention is such that the maximum height from the bottom of the concave portion to the top of the convex portion measured in accordance with JIS B 0601 is 30 占 퐉 or less and one convexity measured in accordance with JIS B 0601, Since the average peak-valley interval of one period length of one concave is 700 mu m or more, the holding force of the bubbles and / or the gas layer is high, and peeling and separation from the ship outer plate and the like are difficult to occur, Can be stably reduced.

Since the first special friction resistance reducing vessel coated with the antifouling coating film formed of the antifouling coating composition of the marine shell plating of the present invention has the antifouling coating film formed of the antifouling coating composition described above, The effect of reducing the water friction resistance is exhibited even if the amount is small, and the effect can be exhibited stably over a long period of time.

The first method of producing a special friction resistance reducing vessel of the present invention can manufacture a specific ship exhibiting the above effect by a simple method of forming an antifouling coating film formed of the antifouling paint composition on the water-immersed surface of the outer shell of the ship.

Since the coating composition used in the special friction resistance reducing vessel of the present invention can form a coating film having a bubble contact angle of less than 90 deg. And a bubble roll (slip angle) of less than 30 degrees in water under static water, the bubble and / And flows without delay while sufficiently contacting the coating film. Therefore, in the case of the (second) reduced special friction resistance vessel having the coating film formed on the water-immersed surface of the shell plating, an efficient gas lubrication effect is exhibited, and even if the amount of air supplied is small, And the energy saving effect is also great.

The second method of manufacturing a frictional resistance reducing vessel according to the present invention forms the coating film on the surface of the shell plating of the vessel to be covered with water so that even if the amount of air to be supplied is small, The frictional resistance to the locked surface is effectively reduced, and a special frictional resistance reducing vessel having a large energy saving effect can be manufactured.

The method of predicting the effect of reducing the friction resistance using the gas lubrication function in the water of the coating film of the present invention can be carried out by measuring the static contact angle of the bubbles formed on the surface of the coating film in water or the roll (slip) angle. That is, it can be predicted that, when they are in a specific range, the frictional resistance reducing effect using the gas lubrication function in water is superior due to the measurement results of the static contact angle and the roll (slip) angle of the bubbles formed on the surface of the coating film in water.

Further, the method of predicting the frictional resistance reducing effect of the present invention can evaluate the ease of formation of bubbles in water from the measurement results of the static contact angle and the roll (slip) angle of the bubbles of the coating film in water, It is possible to observe the state or behavior of the bubbles of the coating material (for example, the ease of flow of bubbles to the coating material).

The above-described prediction method of the present invention is capable of evaluating the hydrophobicity of the coating film from the contact angle in view of the above, but is superior to the prior art method in which the behavior of bubbles in water can not be evaluated.

The apparatus used for predicting the frictional resistance reducing effect using the gas lubrication function in the water of the present invention does not require a complicated apparatus configuration and can easily measure the bubble contact angle and the bubble roll angle It can be suitably used for prediction of the frictional resistance reducing effect as described above.

The first and second frictional resistance reduction systems used in the frictional resistance reducing vessel using the gas lubrication function in water of the present invention are characterized in that the first or second coating film and the gas such as air are supplied to the surface of the coating film It is possible to provide a friction resistance reduction system for use in a reduced frictional resistance vessel that utilizes a gas lubrication function in water, which exhibits an excellent frictional resistance reducing effect because it has a gas supply device. Therefore, the gas affinity of air or the like in water continues for a long period of time, so that the effect of reducing the fluid friction resistance is increased without introducing a great power into the supply of the gas, which is economical and has little influence on the environment.

The third and fourth special frictional resistance reducing vessels according to the present invention are provided with a frictional resistance reducing system, thereby exhibiting an excellent frictional resistance reducing effect. Therefore, the gas affinity of air or the like in water continues for a long period of time, so that the effect of reducing the fluid friction resistance is increased without introducing a great power into the supply of the gas, which is economical and has little influence on the environment.

1 is a schematic view of a contact angle measuring apparatus used for predicting a frictional resistance reducing effect by measurement of static bubbles contact angle in water or underwater bubble roll (slip) angle measurement.
2 is a schematic explanatory view showing a method for obtaining a static bubble contact angle in a static water underwater bubble contact angle measurement method.
3 is a schematic explanatory diagram showing a measurement method of an underwater bubble roll (slip) angle.
Fig. 4 is a schematic view of a model line used for measuring the resistance to water flow.
5 is a graph showing the relationship between the equivalent air thickness and the frictional resistance reduction ratio (comparison before immersion and after 30 days after immersion).

Hereinafter, the present invention is broadly classified into three groups as follows, and the best mode will be described in detail for each group in order.

First group: Antifouling coating composition (first coating composition) used in a special friction resistance abatement ship, antifouling coating film (first coating film) formed from the composition, vessel coated with the first coating film (first special friction resistance reduction And a method for manufacturing the first vessel.

The second group is a coating composition (second coating composition) used in a special friction resistance reducing vessel, a coating film (second coating film) formed from the composition, a vessel coated with the coating film (second special friction resistance reducing vessel) A method for manufacturing a second vessel, a method for predicting a frictional resistance reducing effect using a gas lubrication function in a water film of a coating film, and an apparatus for predicting the frictional resistance reducing effect.

Group 3: Reduction of Friction Resistance using gas lubrication in water. Friction Resistance Reduction System (First and Second Friction Resistance Reduction System) used in ships and Special Friction Resistance Reduction Ship equipped with the system 4 Special Friction Resistance Reduced Vessel).

In addition, when there is no specific designation, the pressure condition is at normal pressure (about 0.1013 MPa) and the temperature condition is at room temperature (about 25 deg. C).

The first, second, third and fourth special frictional resistance reducing vessels of the present invention are common in the following respects.

In order to reduce the frictional resistance by the gas lubrication function, it is necessary that the bubbles and / or the gas layer sufficiently contact with the surface (submerged surface of the shell plating) contacting the water of the special frictional resistance reducing vessel.

In this specification, &quot; water &quot; includes seawater, river water, lake, etc. in addition to fresh water.

In this specification, the term &quot; gas &quot; means a gas which does not damage a ship such as air, nitrogen gas, carbon dioxide gas, oxygen gas and hydrogen gas. Air, particularly from the standpoint of environmental impact, cost, and the like.

1. Group 1

In the case of the first special friction resistance reducing vessel of the present invention, for example, a specific organopolysiloxane (A), a specific hydrophobic material (C) and, if necessary, a specific organosilane and / An antifouling coating film formed of a special resistance reducing abatement antifouling coating composition containing a specific amount is formed in a water-immersed portion of the outside sheathing.

By using such a special resistance reducing marine antifouling coating composition, it is possible to form a coating film having various characteristics such as the above-mentioned friction reduction characteristics.

1-1. An antifouling paint composition having a specific composition

The antifouling paint composition of the present invention is compounded with a compound having a polysiloxane skeleton structure, and it is presumed that the leveling property unique to these compounds affects the shape of the coating film formed from the antifouling paint composition. Therefore, it is presumed that the antifouling coating composition of the present invention can form a coating film having a height of roughness of 30 탆 or less and a peak-valley average spacing of 700 탆 or more as described later. Further, the antifouling coating composition of the present invention can form a coating film having such a shape, and its shape is very suitable for exhibiting gas lubrication performance such as gas retention and gas fluidity on the surface of the coating film, It is presumed that an antifouling coating film having a contact angle in water of less than 90 degrees and a roll (slip) angle of bubbles of usually less than 30 degrees can be formed.

The hydrophobic material (C) in the antifouling paint composition is present in the cured coating film in the same form as the filler as described later. The hydrophobic material (C) gradually bleeds out and covers the surface of the coated film during the course of the ship formed on the water-immersed surface of the outer plate portion. Since the hydrophobic material is liquid or grease at 25 占 폚, it is possible to improve the lubricity of the surface, for example, as a lubricant, thereby preventing adhesion of microorganisms in the water and imparting antifouling properties to the antifouling coating film.

Each component in the antifouling paint composition will be described below.

1-1-1. The reactive curing organopolysiloxane (A)

The reaction-curable organopolysiloxane (A) has a viscosity of 20 to 400,000 mm 2 / s at 25 ° C.

The reaction-curable organopolysiloxane is an organopolysiloxane having at least two condensation reactors per molecule, preferably an organopolysiloxane having two or more condensation reactors at both ends, and the organopolysiloxane alone Or an organopolysiloxane that can be cured by a curing reaction with a compound such as an organosilane and / or a partial condensate thereof (B) which will not be cured by the organopolysiloxane alone but which will be described later.

Both ends of the molecule refer to the two ends of the main chain, and the condensation reaction unit is usually a hydroxyl group or a hydrolyzable group, and the two terminal groups may be the same or different. In addition to the hydroxyl group or hydrolyzable group present at both ends of the molecule, a functional group capable of reacting with organosilane and / or its partial condensate (B) described later may be contained in the main chain or side chain. Having two or more condensation reactors at both ends means, in other words, one or more condensation reactors at each end of the two ends.

Specific examples of the hydrolyzable group are the same as the specific examples of X of X _3-b R ³ _b SiO (R ¹ R ² SiO) _m R ³ _b SiX _3-b as the organopolysiloxane (A) described later.

In view of the ability to react with the organosilane and / or its partial condensate (B) described later, the hydrolyzable group of the organopolysiloxane (A) is preferably a hydrolyzable group of the organosilane and / or its partial condensate (B) It is preferably the same as the decomposable group.

The viscosity is preferably from 25 to 200,000 mm 2 / s from the viewpoints of coating properties such as hardenability, rubber strength of a cured coating film, thickening and handling properties, prevention of sagging when the resulting composition is diluted with a solvent, , And more preferably 500 to 100,000 mm 2 / s.

In the present specification, the viscosity is measured using a capillary viscometer (Ube load viscometer) according to &quot; JIS Z 8803 Viscosity of Liquid-Measuring Method &quot;.

Examples of the organopolysiloxane (A) include an organopolysiloxane represented by HO (R ¹ R ² SiO) _m H and having silanol groups at both ends of the molecule. R ¹ and R ² are monovalent hydrocarbon groups of 1 to 10 carbon atoms such as a methyl group, a phenyl group and a vinyl group, and m is a positive number corresponding to the degree of polymerization and is within a range satisfying the range of the above viscosity.

Other examples include organopolysiloxanes represented by X _3-b R ³ _b SiO (R ¹ R ² SiO) _m R ³ _b SiX _3-b and having a hydrolyzable group at the end of the molecule. R ¹ and R ² are the same as the above structural formula, R ³ is the same monovalent hydrocarbon group as R ¹ and R ² , X is the following hydrolyzable group, b is 0, 1 or 2, and m is a degree of polymerization And is within a range that satisfies the above range.

Examples of the hydrolyzable group of X include an alkoxy group, an acyloxy group, an alkenyloxy group, an imino group, an amino group, an amide group and an aminooxy group, and an alkoxy group is preferable.

The alkoxy group preferably has 1 to 10 carbon atoms in total, and at least one oxygen atom may be interposed between the carbon atoms. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxyethoxy group , Ethoxyethoxy group, and the like.

The acyloxy group is preferably an aliphatic or aromatic group represented by the formula: R ⁴ COO- (wherein R ⁴ is an alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 12 carbon atoms), and for example, A propionyloxy group, a propionyloxy group, a propionyloxy group, a propionyloxy group, and a benzoyloxy group.

The alkenyloxy group preferably has about 3 to 10 carbon atoms, and examples thereof include an isopropenyloxy group, an isobutenyloxy group, and a 1-ethyl-2-methylvinyloxy group. As the already-fused (= N-OH, oxyimino group, ketoxime group), the number of carbon atoms is preferably about 3 to 10, and examples thereof include a ketoxime group, a dimethyl ketoxime group, a methyl ethyl ketoxime group, , A cyclopentanediyl group, and a cyclohexanediyl group.

The amino group preferably has 1 to 10 carbon atoms, and examples thereof include N-methylamino group, N-ethylamino group, N-propylamino group, N-butylamino group, N, N-dimethylamino group, Hexylamino group and the like. The amide group preferably has 2 to 10 carbon atoms in total, and examples thereof include N-methylacetamide group, N-ethylacetamide group and N-methylbenzamide group.

The aminooxy group preferably has 2 to 10 carbon atoms in total, and examples thereof include N, N-dimethylaminooxy group, N, N-diethylaminooxy group and the like.

Each of R ¹ , R ² and R ³ independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 8 carbon atoms. Such a monovalent hydrocarbon group For example, an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, and an aralkyl group.

The alkyl group may be any of straight chain, branched or aliphatic cyclic alkyl groups, linear or branched alkyl groups having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, cycloalkyl groups having 3 to 6 carbon atoms Is preferred. Examples of such a linear or branched alkyl group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a 2-ethylbutyl group and an octyl group, particularly preferably a methyl group. As the aliphatic cyclic alkyl group , For example, a cyclohexyl group and a cyclopentyl group.

The alkenyl group preferably has 2 to 10 carbon atoms, preferably about 2 to 8 carbon atoms, and examples thereof include a vinyl group, a hexenyl group and an allyl group.

The aryl group preferably has about 6 to 15 carbon atoms, preferably about 6 to 12 carbon atoms, and examples thereof include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and a diphenyl group.

The cycloalkyl group preferably has 3 to 8 carbon atoms, and examples thereof include a cyclohexyl group and the like. As the aralkyl group, the total number of carbon atoms is preferably 7 to 10, preferably 7 to 8, and examples thereof include a benzyl group and a 2-phenylethyl group.

Some or all of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with a halogen atom such as F, Cl, Br or I, a cyano group or the like, and examples of the halogenated alkyl group include chloromethyl groups, -Trifluoropropyl group, 2-cyanoethyl group and the like.

As R ¹ , R ² and R ³ , an unsubstituted monovalent hydrocarbon group is preferable, and methyl group and phenyl group are particularly preferable. Also, if a plurality of R ^3, a plurality of R ^1, R ² present in the organopolysiloxane having hydrolyzable groups at the molecular terminal thereof represented by the general formula, the plurality of R ³ to each other, a plurality of R ^1, R ² together, or R ³ and R ¹ and R ² may be the same or different.

As described above, the reaction-curing organopolysiloxane (A) can be produced by reacting a functional group that reacts with organosilane and / or its partial condensate (B) described below in addition to the hydroxyl group or hydrolyzable silyl group present at both ends of the molecule For example, HO (R ¹ R ² SiO) _m H or X _3-b R ³ _b SiO (R ¹ R ² SiO) _m R ³ _{b in} SiX _3-b ¹ , R ² and R ³ are functional groups capable of reacting with the above-mentioned organosilane and / or its partial condensate (B) can also be used as the organopolysiloxane (A).

Examples of such organopolysiloxane (A) include dimethylpolysiloxane (both trade names: "XF3905", manufactured by Momentive Performance Materials Co., Ltd.) in which both ends of the molecular chain are encapsulated with silanol groups, decoupled organopolysiloxanes , Trade name &quot; KE-445 &quot;, manufactured by Shin-Etsu Chemical Co., Ltd.).

The organopolysiloxane (A) is preferably self-condensed from the viewpoints of cost reduction and handling of coating compositions, and is more preferably self-condensing at around room temperature (usually about 10 ° C to 30 ° C).

Among the organopolysiloxanes (A) exemplified above, dimethylpolysiloxane (for example, trade name "XF3905" manufactured by Momentive Performance Materials Co., Ltd.) in which both ends of the molecular chain are bound with silanol groups, decoupled organopolysiloxane Trade name &quot; KE-445 &quot;, manufactured by Shin-Etsu Chemical Co., Ltd.) is a self-condensation polysiloxane.

These organopolysiloxanes (A) may be incorporated in the antifouling paint composition used for the frictional resistance reducing ship alone, or two or more kinds thereof may be blended.

1-1-2. The specific organosilane and / or its partial condensate (B)

Component (B) is an organosilane and / or a partial condensate thereof having at least two of a hydroxyl group and a hydrolyzable group in one molecule.

The hydroxyl group and the hydrolyzable group may be either two or more of either or both of the organosilanes.

Component (B) preferably serves as a crosslinking agent for the organopolysiloxane (A) from the viewpoints described below.

The organosilane and / or its partial condensate (B) may optionally be blended in the antifouling paint composition as required.

When the organopolysiloxane (A) is cured by the condensation reaction (that is, by self-condensation) of the organopolysiloxane (A), even if the organosilane and / or the partial condensate (B) A cured coating film having excellent hardness can be obtained from the composition. However, when the organosilane and / or its partial condensate (B) is blended, there is an advantage that the curing rate and the degree of curing of the coating film can be controlled more precisely.

In this case, room temperature vulcanization is possible when the organopolysiloxane (A) is self-condensed near room temperature by a catalyst or the like.

Even if the organopolysiloxane (A) is not self-condensed at around room temperature, the organosilane and / or its partial condensate (B) may be blended so that the coating of the antifouling paint A condensation reaction of the organopolysiloxane (A) with the organosilane and / or its partial condensate (B) is generated by using a hydrolysis reaction, and a cured coating film can be obtained even at a room temperature.

When the organopolysiloxane (A) does not undergo self-condensation, the organosilane having a functional group capable of condensation with the condensation-reactive functional group of the organopolysiloxane not self-condensing and / or a partial condensate thereof (B ) Is preferable from the viewpoints of the curing rate and the curing degree of the resulting coating film.

The hydrolyzable group of the organosilane and / or the partial condensate (B) used in the present invention is a functional group capable of condensation reaction with the condensation reaction reactor of the reaction-curing organopolysiloxane (A). As the component (B), an organosilane represented by the following formula [?] Can be used.

In the above formula [?], R ⁵ may be the same or different and represents a hydroxyl group, a hydrolyzable group or a monovalent hydrocarbon group of 1 to 8 carbon atoms. With the proviso that at least one of R ⁵ at both ends is a hydroxyl group or a hydrolyzable group (both of which have at least two hydroxyl groups and / or hydrolyzable groups at both ends). And two or more, preferably three or more, of R &lt; ⁵ &gt; including a hydroxyl group and / or a hydrolyzable group at both ends thereof are condensation reactive groups. and z represents an integer of 0 to 10, preferably 0 to 8.

Examples of the monovalent hydrocarbon group having 1 to 8 carbon atoms in the formula [?] Include a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, and an aralkyl group. The formula [α] hydrolyzable group as either ^{_{X 3-b R 3 b SiO}} (R 1 R 2 SiO) as an example of the reaction-curing organopolysiloxane ^{_{(A) m R 3 b SiX}} 3-b of the X in the The same as the case of the hydrolyzable group, and among them, an oxepi group, an acetyloxy group or an alkoxy group is preferable.

It is also possible to use, for example, an organosilane in which a hydrolyzable group such as an acetyloxy group or an alkoxy group is partially hydrolyzed (for example, an organosilane having two or more hydrolysable groups A partially hydrolyzed condensate can be used as the component (B)).

It is also possible to use an organosilane partially dehydrated and condensed between two or more hydroxyl groups as the component (B) (that is, a partial condensate of organosilane having two or more hydrolysable groups is referred to as the component (B) .

In the present invention, an organosilane containing an alkoxy group, that is, an alkoxysilane (alkylsilicate) or a partial condensate thereof may be suitably used.

Examples of the alkoxysilane include tetraalkylorthosilicate (alkyltetraalkoxysilane) such as tetraethylorthosilicate (TEOS), or alkyltrialkoxysilane such as methyltrimethoxysilane, ethyltrimethoxysilane or methyltriethoxysilane. And alkoxysilane. The alkoxysilane is more preferably an alkyltetraalkoxysilane or an alkyltrialkoxysilane in view of the curability of the resulting cured coating film.

In particular, when an organopolysiloxane having hydroxyl groups at both terminals is used as component (A), it is preferable to use these alkyl silicates (alkoxysilane) and / or a partial condensate thereof as component (B) in combination. These organosilanes and / or their partial condensates (B) may be those commercially available. Examples of the tetraethyl orthosilicate include "ethyl silicate 28" (trade name, manufactured by Colcoat Co., Ltd.), "ortho silicate ethyl" (trade name, manufactured by DAMAR CHEMICALS), "partially hydrolyzed tetraethyl orthosilicate" TES40 WN &quot; (manufactured by Wako Asahi Kasei Silicone), and &quot; KBM-13 &quot; (manufactured by Shinetsu Chemical Co., Ltd.) as the alkyltrialkoxysilane.

The organosilane and / or its partial condensate (B) can be used in an amount of 1 to 60 parts by weight, based on 100 parts by weight of the organopolysiloxane (A). In view of physical properties of the curable and cured coating film, Is contained in the antifouling paint composition in an amount of 20 to 20 parts by weight, preferably 2 to 10 parts by weight.

These organosilanes and / or their partial condensates (B) may be blended with one kind of organosilane or partial condensates thereof in the antifouling paint composition used for the abrasion resistance reducing vessel, Or may be blended. The organosilane and the partial condensate thereof may be used alone or in combination of two or more.

1-1-3. Hydrophobic material (C)

Component (C) is a hydrophobic material in liquid or grease at 25 占 폚.

The hydrophobic material (C) may be any of silicone oil, fluorine-containing silicone oil, fluorine-based oil, paraffin or wax, liquid or grease at room temperature. For example, the hydrophobic material (C) includes at least one selected from these.

However, the hydrophobic material corresponding to the organopolysiloxane (A) and the hydrophobic material corresponding to the organosilane and / or the partial condensate (B) thereof are not included in the hydrophobic material (C).

<Silicone oil>

The silicone oil is not particularly limited as long as it is a silicone oil which is bleeding out from a cured product of a non-reactive (non-condensable) silicone oil or an antifouling paint composition used for a special friction resistance reducing vessel. , And a silicone oil having a group represented by the following formula [III] are preferable.

Silicone oils [I] and [II] of these silicone oils do not exhibit reactivity with the organopolysiloxane (A) or the like and do not undergo autocontinuous condensation, and bleed out without accompanying any specific chemical change, It is believed to have an action of forming a layer (film).

On the other hand, the silicone oil [III] reacts with the organopolysiloxane (A) or the like to become a coating film forming component to form a cured coating film. When immersed in seawater for a long period of time, it hydrolyzes with time, SiR ⁸ OH &quot; and the like and bleed out to the surface of the coating film, thereby exerting an effect of preventing seawater adherence.

(In the formula [I], a plurality of R ^{6 s} may be the same or different and each represents an alkyl group, an aryl group, an aralkyl group or a fluoroalkyl group having 1 to 10 carbon atoms, a plurality of R ^{7 s} may be the same or different and each R ⁷ represents an alkyl group having 1 to 10 carbon atoms, an aryl group, an aralkyl group or a fluoroalkyl group, and n represents a number of 0 to 150)

(In the formula [III], R ⁸ represents an unsubstituted or substituted divalent hydrocarbon group or a divalent hydrocarbon group containing an ether bond, R ⁹ is an unsubstituted or substituted monovalent hydrocarbon group, Y is a hydrolyzable group, b is 0, 1 or 2.)

(Wherein R ¹⁰ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group each having 1 to 10 carbon atoms, and R ¹¹ represents an alkyl group having 1 to 10 carbon atoms which may contain an ether group, an ester group or -NH- Z represents a monovalent polar group which is an amino group, a carboxyl group, an epoxy group or a polyethylene glycol or polypropylene glycol group which may be blocked with an alkyl group having 1 to 6 carbon atoms or an acyl group, and x and y are each 0.01 X &lt; 3.99, 0.01 &lt; y &lt; 3.99, and 0.02 x + y &lt;

As the silicone oil [I] in the silicone oil, those described in JP-A-10-316933 can be used, and the number average molecular weight measured by the GPC method is 180 to 20,000, preferably 1,000 to 10,000, The viscosity measured by the Uberode viscometer is preferably 20 to 30,000 mm 2 / s, more preferably 50 to 3,000 mm 2 / s.

Examples of such a silicone oil [I] include dimethylsilicone oil in which all of R ⁶ and R ⁷ are methyl groups, and phenylmethylsilicone oil in which a part of methyl groups in these dimethylsilicone oils are substituted with phenyl groups. Among them, methylphenylsilicone Oil is preferred. Specific examples of such methylphenyl silicone oil include "KF-54, KF-56, KF-50" (manufactured by Shinetsu Chemical Co.), "SH510, SH550" (manufactured by Dow Corning Toray Silicone Co., Ltd.) , &Quot; TSF433 &quot; (manufactured by Toshiba Silicones), and the like.

As the silicone oil (silicone oil [III]) having a group represented by the above formula [III], those described in Japanese Patent No. 2522854 proposed by the present applicants can be used, and the number average molecular weight Is in the range of 250 to 20,000, preferably 1,000 to 10,000, and the viscosity measured by the above method is preferably 20 to 30,000 mm 2 / s, more preferably 50 to 3,000 mm 2 / s.

Specific examples of the R ⁸ include unsubstituted or substituted divalent hydrocarbon groups such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexamethylene group, and the like, or a group of the formula: - (CH ₂ ) _p -O- CH ₂ ) _q - "(wherein p and q each independently represents an integer of 1 to 6), and the like.

R ⁹ represents an unsubstituted or substituted monovalent hydrocarbon group of 1 to 8 carbon atoms. Y represents the same group as the hydrolyzable group X of X _{3 -b} R ³ _b SiO (R ¹ R ² SiO) _m R ³ _b SiX _3-b as an example of the reaction-curable organopolysiloxane (A). Specific examples of the silicone oil [III] having at least one group represented by the formula [III] include (CH ₃ ) ₃ SiO [(CH ₃ ) _{2 ^{SiO] h [R 12 R 13}} SiO] i (CH 3) 2 SiC 3 H 6 -OH, HO-C 3 H 6 - [(CH 3) 2 SiO] [(CH 3) 2 SiO] h [R 12 _{^{R 13 SiO] i - (CH}} 3) 2 Si-C 3 h 6 -OH, (CH 3) 3 SiO [(CH 3) 2 SiO] h [R 12 R 13 SiO] i [(CH 3) (C ₃ H ₆ -OH) SiO] _j [(CH ₃ ) ₂ SiCH ₃ ] in which the hydroxyl group of the silicone oil is blocked with a hydrolyzable group. However, each of the formula, R ^12, R ¹³ as phenyl, tolyl, etc. of the aryl group; a benzyl group, phenylethyl group, etc. β- aralkyl group; such as halogenated alkyl groups such as propyl group trifluoromethyl, R ^12, R ^An unsubstituted or substituted monovalent hydrocarbon group in which at least one of R &lt; ¹³ &gt; and R &lt; ¹³ &gt; is selected from groups other than the methyl group. h, i, j are both positive numbers.

In view of the storage stability of the resulting composition, the silicone oil is represented by the formula: R ⁹ _b SiY _{3 -b} (R ⁹ , Y, and b are the same as in the case of formula (III)) as exemplified below May be reacted with an organosilane.

For example _{(CH 3) 3 SiO [(} CH 3) 2 SiO] h [R 12 R 13 SiO] i (CH 3) 2 SiC 3 H 6 -OR 9 b SiY 3-b, HO-C 3 H 6 _{- [(CH 3) 2 SiO} ] [(CH 3) 2 SiO] h [R 12 R 13 SiO] i - (CH 3) 2 Si-C 3 H 6 -OR 9 b SiY 3-b, (CH 3 _{) 3 SiO [(CH 3)} 2 SiO] m [R 12 R 13 SiO] i [(CH 3) (C 3 H 6 -OR 9 b SiY 3-b) SiO] l [(CH 3) 2 SiCH 3 ] And the like.

Specific examples of the silicone oil [II] include those described in JP-A-10-316933, and have a number average molecular weight of 250 to 30,000, preferably 1,000 to 20,000, as measured by GPC, The viscosity measured by the above method is preferably 20 to 30,000 mm 2 / s, more preferably 50 to 3,000 mm 2 / s.

As such silicone oil [II], it is preferable that R ¹⁰ in the formula [II] is a methyl group or a phenyl group, and R ¹¹ is a methylene group, an ethylene group or a propylene group. When Z is a polyethylene glycol or polypropylene glycol group which may be blocked with an alkyl group having 6 or less carbon atoms or an acyl group at the terminal, the number of oxyethylene and oxypropylene as repeating units is preferably 10 to 60. Examples of the alkyl group for terminal blocking include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the acyl group for terminal blocking include a ketoxyl group, an acetyl group, and a propionyl group.

Specific examples of the silicone oil in which the polar group Z is an amino group include "SF8417" (manufactured by Dow Corning Toray Co.), "ISI4700, ISI4701" (manufactured by Toshiba Silicones), "FZ3712, AFL- . Examples of the silicone oil in which the polar group Z is a carboxyl group include "XI42-411" (manufactured by Toshiba Silicone), "SF8418" (manufactured by Dow Corning Toray Silicone), and "FXZ4707" (manufactured by Nippon Unicar). Examples of the silicone oil whose polar group is an epoxy group include "SF8411" (manufactured by Dow Corning Toray Silicone Co., Ltd.), "XI42-301" (manufactured by Toshiba Silicones), "L-93, T-29" . (Silicone oil), "KF6009" (manufactured by Shin-Etsu Chemical Co., Ltd.), "SHI", "SHI" Ltd.) and the like.

<Fluorine-Containing Silicone Oil>

Examples of the fluorine-containing silicone oil include X-22-821 (manufactured by Shin-Etsu Chemical Co., Ltd.) and X-22-822 (silicon-modified fluoroalkyl-modified silicone oil manufactured by Shinetsu Chemical Co., Ltd.).

<Fluorine-based oil>

Examples of the fluorine-based oil include DEMNUM S-65 (manufactured by Daikin Industries, Ltd .; perfluoropolyether oil).

<Paraffin or wax>

As paraffins or waxes, Sumoi P-350 (manufactured by Matsumura Kogyo Co., Ltd., liquid paraffin) can be mentioned.

The amount of the hydrophobic material (C) in the antifouling paint composition used in the special friction resistance reducing vessel of the present invention is usually 0.1 to 200 parts by weight, preferably 20 to 100 parts by weight, per 100 parts by weight of the organopolysiloxane component (A) .

When the amount of the hydrophobic material (C) is in the above range, a coating film excellent in antifouling property and coating film strength (antifouling) is obtained. When the amount of the hydrophobic material (C) is less than the above range, the antifouling property is lowered. When the amount is more than the above range, the film strength may be lowered.

These hydrophobic materials (C) may be incorporated in the antifouling paint composition used in the special friction resistance reducing ship alone, or two or more kinds thereof may be blended.

1-2. Preparation of Antifouling Coating Composition for Special Friction Resistance Reduced Ship

The antifouling paint composition used in the special friction resistance reducing vessel of the present invention can be produced by the following method. A part or all of the organopolysiloxane (A), a hydrophilic silica or a hydrophilic silica and a hydrophobic silica to be described later may be added to the decomposition temperature of the compounded components at 100 ° C. or higher under atmospheric pressure or reduced pressure, preferably 100 to 300 ° C. , More preferably at a temperature of about 140 ° C to 200 ° C for about 30 minutes to 3 hours. Subsequently, in the case where hydrophilic silica or hydrophobic silica is used, in addition to the remainder of the organopolysiloxane (A), hydrophilic silica or hydrophilic silica and hydrophobic silica, and, if necessary, organosilane and / or its partial condensate (B) (C) as the hydrophobic material. When hydrophilic silica or hydrophobic silica is not used, it can be produced by further compounding the organopolysiloxane (A) and the hydrophobic material (C) in addition to the organosilane and / or the partial condensate (B) . In either case, any of the conventionally known organosiloxane curing catalysts, antifouling agents, thixotropic agents, plasticizers, inorganic dehydrating agents (stabilizers), anti-sagging agents (thickening agents), pigments and dyes, A silane coupling agent having a reactive organic group such as a fungicide, a fungicide, an antioxidant, an antioxidant, an antistatic agent, a flame retardant, a heat conduction improver, an amino group, an epoxy group or a mercapto group, At a time or in any order, stirring, mixing, and dissolving and dispersing in a solvent.

When mixing and mixing the above-mentioned ingredients, conventionally known mixing and stirring devices such as a Ross mixer, a planetary mixer, and a universal Shinagawa stirrer are suitably used.

<Optional ingredients>

(catalyst)

As the catalyst, those described in, for example, Japanese Patent No. 2522854 can be suitably used. Specific examples thereof include carboxylic acid pomegranates such as tin naphthenate and tin oleate; dibutyltin diacetate Tin compounds such as dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin diolate, dibutyltin oxide, dibutyltin dimethoxide and dibutylbis (triethoxysiloxy) tin; Titanium acid esters such as tetraisopropoxytitanium, tetra n-butoxytitanium, tetrakis (2-ethylhexoxy) titanium, dipropoxy bis (acetylacetonato) titanium and titanium isopropoxy octyl glycol, Compounds such as zinc naphthenate, zinc stearate, zinc 2-ethyloctoate, iron 2-ethylhexoate, cobalt-2-ethylhexoate, manganese- Aminoalkyl substituted alkoxysilanes such as 3-aminopropyltrimethoxysilane and N -? (Aminoethyl)? - aminopropyltrimethoxysilane, hexylamine, Amine compounds such as dodecyldodecylamine phosphate, dimethylhydroxylamine and diethylhydroxylamine, and salts thereof; quaternary ammonium salts such as benzyltriethylammonium acetate; alkali metal salts such as potassium acetate, sodium acetate and lithium bromate; Silane containing a guanidyl group such as tetramethylguanidylpropyltrimethoxysilane, tetramethylguanidylpropylmethyldimethoxysilane, tetramethylguanidylpropyltris (trimethylsiloxy) silane, or the like; Siloxanes, and the like.

These catalysts are used in an amount of not more than 10 parts by weight, preferably not more than 5 parts by weight, more preferably not more than 1 part by weight, based on 100 parts by weight of the organopolysiloxane (A), and a preferable lower limit is 0.001 part by weight More preferably 0.01 part by weight or more.

(Hydrophobic silica, hydrophilic silica)

Silica includes hydrophilic silica (surface untreated silica) such as wet process silica (hydrated silica), dry process silica (fumed silica, ahydrous silica), hydrophobic silica treated with hydrophobic wet silica and hydrophobic fumed silica.

These silicas may be used singly or in combination of two or more. Use of hydrophobic silica in combination with hydrophilic silica is preferable from the viewpoint of obtaining an antifouling paint composition for use in a special frictional resistance reducing vessel which is excellent in stability at the time of preparation, storage and storage, and which has sufficient thixotropy and can be thickened by one painting. In addition, the coating film obtained from the antifouling coating composition used for the special friction resistance reducing vessel has excellent balance of rubber properties such as hardness, tensile strength and elongation, and is also excellent in antifouling property and the like.

In the present invention, as the silica component, those having the following characteristics may be used as they are. In the preferred embodiment, from the viewpoint of improving the physical properties and strength of the obtained thixotropy of the coating and the obtained coating film, It is preferable that at least the hydrophilic silica in the hydrophilic silica is heat-treated together with a part or all of the organopolysiloxane (A), and furthermore, both the hydrophilic silica and the hydrophobic silica are heat-treated together with a part or the whole of the component (A) Is more preferable.

Among these silicas, wet process silica usually has an adsorbed water content (also referred to as water content) of about 4 to 8%, a bulk density of 200 to 300 g / L, a primary particle size of 10 to 30 μm, a specific surface area ) Is 10 m &lt; 2 &gt; / g or more, preferably 50 to 800 m &lt; 2 &gt; / g, and more preferably 100 to 300 m &

The dry process silica (fumed silica) has a moisture content of usually 1.5% or less. In addition, the dry moisture content of the dry process silica is as low as 0.3% or less, for example, immediately after the production, but the moisture content is gradually increased by moisture absorption if left untreated, and about 0.5-1.0% do. The bulk density of this dry process silica is not uniformly determined depending on the kind thereof but is, for example, from 50 to 100 g / L, the primary particle size is from 8 to 20 μm, the specific surface area (BET surface area) is from 10 m 2 / g or more, preferably about 100 to 400 m 2 / g, and more preferably about 180 to 300 m 2 / g.

The hydrophobic fumed silica is obtained by surface-treating the silica of the dry process with an organosilicon compound such as methyltrichlorosilane, dimethyldichlorosilane, hexamethyldisilazane, hexamethylcyclotrisiloxane or octamethylcyclotetrasiloxane. The water content is usually 0.3% or less, in most cases 0.1 to 0.2%, and the specific surface area is 10 m 2 / g or more, preferably 100 to 300 m 2 / g, more preferably 120 to 230 m 2 / The primary particle diameter is 5 to 50 μm and the bulk density is 50 to 100 g / L.

Further, in the case of the hydrophobic fumed silica heat-treated with the organopolysiloxane (A) (heat-treated hydrophobic fumed silica), water adsorbed on the surface of the hydrophobic silica is physically reduced and removed, and the water content is usually 0.2% Preferably 0.1% or less, particularly 0.05 to 0.1%, and other physical properties such as bulk density are the same as those of the hydrophobic silica.

Such a silica component is usually added in an amount of 1 to 100 parts by weight, preferably 2 to 50 parts by weight, particularly preferably 5 to 30 parts by weight, based on 100 parts by weight of the component (A) It is preferably contained in the antifouling paint composition to be used. When the silica component is contained in the antifouling coating composition used in the special friction resistance reducing vessel in such an amount, the coating film strength and the coating film hardness are excellent, the thixotropy is good, the appropriate viscosity is obtained, For example, even a vertically standing substrate surface or the like is preferable because it is possible to achieve thickening of the coating film by one coating.

When the amount of the silica component is less than the above range, sufficient film strength and coating film hardness can not be obtained, and a desired thixotropy can not be obtained. Thus, a desired thick film can not be obtained by one coating, When the amount of the silica component is larger than the above range, the viscosity of the coating becomes excessively high, and it is necessary to dilute the coating composition with a solvent such as a thinner to a suitable viscosity suitable for coating, so that thickening by spraying once may not be achieved .

In the present invention, hydrophobic silica (a) such as hydrophobic fumed silica and hydrophilic silica (b) such as surface-untreated silica are preferably used in a weight ratio ((a) / (b)) of 1/99 to 99/1, It is preferable to use them in an amount of 20/80 to 80/20, particularly preferably 30/70 to 70/30. An antifouling paint composition used for a ship having a reduced special friction resistance obtained by using hydrophobic fumed silica (a) and hydrophilic silica (b) in combination with hydrophobic fumed silica (a) in this proportion is excellent in paint stability at the time of preparation, storage and storage, has sufficient thixotropy, Further, the coating film obtained by curing the composition tends to have excellent coating film strength and coating film hardness.

&Lt; Antifouling agent (D) &gt;

As described above, the antifouling paint composition used in the special friction resistance reducing vessel of the present invention exhibits excellent antifouling property by blending the hydrophobic material (C). By further adding the antifouling agent (D) Can be exercised.

As the antifouling agent (D), any of inorganic and organic antifouling agents may be used.

Examples of the inorganic antifouling agent include copper, copper oxide, copper rod, and inorganic copper compound, among which copper and an inorganic copper compound are preferable.

As the organic antifouling agent, metal-pyrithiones represented by the following formula [?]: Wherein R ¹⁴ to R ¹⁷ each independently represent hydrogen, an alkyl group, an alkoxy group or a halogenated alkyl group; M represents Cu, Zn, Na , Mg, Ca, Ba, Pb, Fe, and Al, and n represents valence]

, Tetramethylthiuram disulfide, carbamate-based compounds (e.g., zinc dimethyldithiocarbamate, manganese-2-ethylenebisdithiocarbamate, zinc ethylenebisdithiocarbamate), 2,4,5,6- Tetrachloroisophthalonitrile, N, N-dimethyldichlorophenyl urea, 4,5-dichloro-2-n-octyl-3 (2H) isothiazoline, 2,4,6- trichlorophenylmaleimide, 4-t-butylamino-6-cyclopropyltriazine, N- (fluorodichloromethylthio) phthalimide, N, N'-dimethyl-N'- phenyl- (N-fluorodichloromethylthio ) Sulfamide, N-dichlorofluoromethylthio-N ', N'-dimethyl-Np-tolylsulfamide, 2,3,5,6-tetrachloro-4- (methylsulfonyl) Triphenylborane (PK), 4- [1- (2,3-dichlorobenzyl) -2,3-dimethylphenylcarbamoylmethyl] biphenyldithiocarbamate, Dimethylphenyl) ethyl] -1H-im Diazo (madethomidine), and the like.

Of the organic antifouling agents, copper pyrithione (in the formula [beta], M = Cu), zinc pyrithione (in the formula [beta], M = Zn), N, N-dimethyldichlorophenyl element, 2,4,6 2-methylthio-4-t-butylamino-6-cyclopropyltriazine, 4,5-dichloro-2-n-octyl-4-isothiazolin- , 4,5,6-tetrachloroisophthalonitrile are preferable.

Of these organic antifouling agents, metal pyrithiones are particularly preferred. The metal pyrithiones and 5-dichloro-2-n-octyl-4-isothiazolin-3-one may be used in combination. These antifouling agents may be used alone or in combination of two or more, and they are preferably contained in an amount of 1 to 150 parts by weight, preferably 1 to 100 parts by weight, based on 100 parts by weight of the organopolysiloxane (A) .

The antifouling paint composition used for a special friction resistance reducing vessel containing such an antifouling agent includes, for example, an amount of the inorganic copper compound and / or organic antifouling agent and the amount of the antifouling paint composition excluding the amount of the solvent in an amount of 100% , It is preferably contained in an amount of usually 0.1 to 50% by weight, preferably 0.5 to 40% by weight.

<Plasticizer (chlorinated paraffin)>

Examples of the plasticizer include TCP (tricresyl phosphate), chlorinated paraffin, and polyvinyl ethyl ether. These plasticizers may be used alone or in combination of two or more. These plasticizers contribute to improvement in crack resistance of a coating film (hereinafter also referred to as &quot; antifouling coating film &quot;) made of an antifouling coating composition used in a special reduced friction resistance vessel to be obtained.

&Lt; Sagging prevention and sedimentation inhibitor (thickener) &gt;

Examples of the anti-sagging / anti-sediment agent include salts of stearate salts of organic clays such as Al, Ca and Zn, lecithin salts and alkylsulfonates, polyethylene waxes, amide waxes, hydrogenated castor waxes, polyamide waxes And a mixture of the two, synthetic fine silica, oxidized polyethylene wax, and the like, and preferably polyamide wax, synthetic fine silica, oxidized polyethylene wax and organic clay are used. Examples of such anti-sagging and anti-settling agents include "DIPARON 305", "DIPARON 4200-20" manufactured by Goosmotochemicals Co., Ltd., and those sold under the trade names "DIPARON A630-20X" .

Such anti-sagging and anti-sedimenting agents are compounded in an amount of 0.1 to 10% by weight, for example, in the antifouling coating composition used in the special friction resistance reducing vessel.

<Pigment, Dye>

As the pigment, conventionally known various organic or inorganic pigments can be used. Examples of the organic pigments include carbon black, phthalocyanine blue, and persulfate. Examples of the inorganic pigments include those which are neutral and unreactive such as titanium white, red iron oxide, barite powder, silica, calcium carbonate, talc, chalk and iron oxide; zinc (ZnO), lead white, (Active pigment), which is basic and reactive with an acidic substance in the paint, such as red lead, lead powder, lead oxide lead powder and the like.

Metal oxides such as diatomaceous earth and alumina or their surface treated with a silane compound; metal carbonates such as magnesium carbonate and zinc carbonate; other asbestos, glass fiber, quartz powder, aluminum hydroxide, Surface-treated calcium carbonate, and glass balloons.

Also, various coloring agents such as dyes may be included.

These pigments, dyes and the like may be used singly or in combination of two or more.

Such various pigments and dyes are preferably blended in an amount of about 0.5 to 45% by weight, for example, in total in the antifouling coating composition used for a special friction resistance reducing vessel. It is also preferable that these various pigments and dyes are blended in an amount of 1 to 40 parts by weight based on 100 parts by weight of the organopolysiloxane (A).

&Lt; Other Coating Film Forming Component &gt;

As the coating film forming component, other coating film forming components other than the organopolysiloxane (A) described above may be included within the scope contrary to the object of the present invention. Examples of the "other coating film forming component" include acrylic resin, acryl Butadiene copolymer resin, a styrene-butadiene copolymer resin, a styrene-butadiene copolymer resin, a styrene-butadiene copolymer resin, a polyolefin resin, Soluble or non-water-soluble resins (hereinafter referred to as &quot; water-soluble resins &quot;) such as ethylene-vinyl acetate copolymer resins, vinyl chloride resins, alkyd resins, coumarone resins, trialkylsilyl acrylate (co) polymers , Also referred to as an egg / water-insoluble resin).

<Other Thixotropic Properties-giving Agent, Flame Retardant, Heat Conducting Conditioner, Adhesion-giving Agent, etc.>

Examples of the thixotropic property-imparting agent include polyethylene glycol, polypropylene glycol, and derivatives thereof. Examples of the flame retardant include antimony oxide and paraffin oxide. Examples of the heat conduction improver include boron nitride and aluminum oxide. As the adhesive component, a substance containing one or more reactive organic groups such as an amino group, a mercapto group, an alkoxysilyl group, an epoxy group, a hydrosilyl group, an acryl group, and a hydroxysilyl group, for example, a silane coupling agent or the like And mixtures of these materials.

<Solvent>

The antifouling paint composition used in the special friction resistance reducing vessel of the present invention may or may not contain a solvent. Such various components may be dissolved or dispersed in a solvent as required. As the solvent to be used herein, various solvents commonly used in antifouling paints, such as aliphatic solvents, aromatic solvents, ketone solvents, ester solvents, ether solvents and alcohol solvents, are used. Examples of the aromatic solvent include xylene and toluene. Examples of the ketone solvent include MIBK and cyclohexanone. Examples of the ether solvent include propylene glycol monomethyl ether , Propylene glycol monomethyl ether acetate (PMAC), and the like. Examples of the alcohol-based solvent include isopropyl alcohol and the like.

Such a solvent can be used in an arbitrary amount, and is used in an amount of, for example, 0.1 to 9999 parts by weight, preferably 1 to 50 parts by weight, based on 100 parts by weight of the component (A). It is also used in an amount of 1 to 99% by weight, preferably 5 to 50% by weight, in the antifouling paint composition of the present invention. Reduction of Special Friction Resistance such as Antifouling Coating Composition Used in Reduced Special Friction Resistance Vessel as Diluted as Required by Such Solvent The viscosity (25 ° C, B type viscometer, No. 3 rotor) of the antifouling paint composition used for the ship was evaluated by coating In consideration of the film thickness obtained by one-time coating and the like, it is usually about 0.001 to 50 Pa · s, preferably about 0.01 to 20 Pa · s.

<Others>

The antifouling paint composition may be a one-pack type or a multi-pack type such as a two-pack type or a three-pack type.

For example, in the case of a combination which can utilize the hydrolysis reaction between the hydrolyzable group and the water in the air, the curing reaction does not occur if the water source is cut off just before coating, so that it can be made into one-component type.

For example, when a component causing a curing reaction at room temperature is added by the addition of a catalyst, a multi-component type in which a catalyst and a component that undergoes a reaction by the addition of a catalyst are mixed with another solution can be used.

As specific examples of the one-pack type antifouling paint composition, there may be mentioned, as the organopolysiloxane (A), an organopolysiloxane, which is a hydrolyzable group such as a defoaming or the like, and a organosilane and / or a partial condensate thereof B), an organosilane such as oxime silane.

Examples of the three-pack type antifouling paint composition include a mixture of organopolysiloxane (A) containing organopolysiloxane having hydroxyl groups at both ends of the molecule as hydroxyl groups, organosilane and / or a partial condensate thereof (B) , And a curing accelerator blended with a catalyst. The antifouling paint composition of the present invention can be used as an antifouling paint composition.

1-3. Antifouling coating (first coating), special friction resistance reduction vessel (1st special friction resistance reduction vessel)

The coating film formed by the antifouling coating composition used in the special friction resistance reducing vessel of the present invention is characterized in that the static bubble contact angle in water measured in the method described below is usually as small as less than 90 degrees and the roll (slip) angle Is usually less than 30 degrees, the height of the roughness is 30 mu m or less, and the peak-valley mean spacing is 700 mu m or more.

From the viewpoint of effectively reducing the frictional resistance of the hull and reducing the frictional resistance over the long term, it is preferable that the bubble contact angle in static water in water is 80 DEG or less, and the roll (slip) angle of the bubbles is 20 Deg.] Or less, and the maximum height of the roughness is preferably 25 [micro] m or less, and the interval between the peak of the roughness and the valley is preferably 800 [micro] m or more.

The small static air bubble contact angle indicates that the air is wetted (affinity-imparted) to the coating film, the air bubbles have a small roll (slip) angle and the roughness is small and the peak- . That is, a surface excellent in gas lubrication. These properties can be inspected using the underwater bubble contact angle meter. The gas lubrication effect (the effect of reducing the resistance to water flow friction) can be obtained by applying the paint composition to the bottom of the model line and measuring the water flow resistance when air is supplied to the formed bottom coat film (Circulating water tank test).

A coating film having such a shape can be obtained, for example, by applying an antifouling paint composition used for the above-mentioned special friction resistance reducing vessel to a substrate. Since the antifouling paint composition used in the special friction resistance reducing vessel has a specific composition capable of forming the coating film having the above-mentioned shape, there is no need for a special operation other than a very general method of coating and drying the antifouling paint composition on the substrate, A coating film having the above-described shape can be obtained only by such a simple coating method.

These anti-fouling coatings have a special frictional resistance reducing vessel formed on the water-immersed side of the shell plating, exhibiting excellent anti-fouling effects as well as exhibiting excellent frictional resistance reduction effects even with a small amount of gas supply. Further, they exhibit their effects stably over a long period of time .

The static underwater bubble contact angle and underwater bubble roll (slip) angle can be measured using a contact angle measuring apparatus described later.

<Measurement method of static water bubble contact angle>

The measurement method of the static underwater bubble contact angle is as follows.

A hard polyvinyl chloride test plate (maximum height measured in accordance with JIS B 0601 of 1 占 퐉 or less) coated with a coating composition is immersed in water at 25 占 폚 for 30 days so that a coating film having a dry film thickness of 150 占 퐉 is formed. Specifically, a test plate is mounted on the inner wall of a cylindrical rotary immersion bath and water is generated by rotating the center portion of the water in the water (main speed: 15 knots), and immersed in this state for 30 days. A rigid polyvinyl chloride test plate after immersion was placed in water so that the surface of the coating film was horizontal and the lower side of the test plate. 0.1 cc of air was injected into water so that one air bubble was formed on the surface of the test film, (A) and the diameter (b) of the contact portion between the coating film surface and the bubbles were measured, and the static bubbling contact angle? _S (unit: degree) .

[Equation 1]

&Lt; Measurement method of water bubble roll (slip) angle &gt;

The measurement method of the underwater bubble roll (slip) angle is as follows.

In the method of measuring the static bubble contact angle in water, the angle of inclination (underwater bubble roll (slip) angle (? _M ,?) With respect to the horizontal plane of the surface of the coating film when bubbles start to move by gradually inclining the coated film surface, Unit: degree) is measured.

1-4. Manufacturing method of special friction resistance reducing ship

In the method of manufacturing a special frictional resistance reducing vessel of the present invention, the antifouling coating film is formed on a surface of a shell plating to be immersed in water. The antifouling coating film can be formed from the antifouling paint composition.

The antifouling paint composition used in the special friction resistance reducing vessel of the present invention is applied to the surface of the portion of the outer shell of the ship which is submerged in water by one or a plurality of times according to a usual method and cured, A coating film which can be imparted can be formed, and the performance can be maintained over a long period of time. Conventionally known painting means such as a brush, a roll, a spray, and a dip coater are widely used for such painting.

The antifouling coating film formed by curing the antifouling coating composition used in the special friction resistance reducing vessel of the present invention can continuously prevent adhesion of aquatic organisms such as a coral reef, a barnacle, a palaea, a cera pula, an oyster, And is excellent in antifouling property.

The antifouling paint composition used in the special friction resistance reducing vessel of the present invention is preferably applied on a conventional anticorrosion coating film previously coated on the outer shell of a ship from the viewpoints of adhesion and corrosion resistance.

The antifouling coating composition used for the special abrasion resistance reducing vessel of the present invention may be topcoated on the surface of the ship which is coated with the antifouling paint composition used for the special friction resistance reducing vessel of the present invention. The thickness of the antifouling coating film formed on the water-immersed side of the outer shell of the ship is not particularly limited, but is, for example, about 30 to 150 占 퐉 / hour.

The antifouling paint composition used in the special friction resistance reducing vessel of the present invention is preferably coated on the water-immersed surface of the outer shell of the ship from the viewpoint of frictional resistance reducing performance.

2. Group 2

2-1. Second Coating Composition, Coating Film, Special Friction Resistance Reduced Vessel

The second coating composition is a coating composition capable of forming a coating film satisfying the conditions of static bubble contact angle and water bubble roll (slip angle) shown below.

The coating composition capable of forming a coating film satisfying these conditions includes the above-described antifouling coating composition (first coating composition). Details of the first coating composition are as described above.

&Lt; Static underwater bubble contact angle and underwater bubble roll (slip) angle &gt;

The underwater bubble contact angle measured by the static water bubble contact angle measurement method below is less than 90 degrees and the underwater bubble roll (slip) angle measured by the below-mentioned measurement method of underwater bubble roll (slip) angle is less than 30 degrees.

The static underwater bubble contact angle and underwater bubble roll (slip) angle can be measured using a contact angle measuring apparatus described later.

The measurement method of the static underwater bubble contact angle is as follows.

A hard polyvinyl chloride test plate (maximum height measured in accordance with JIS B 0601 of 1 占 퐉 or less) coated with a coating composition is immersed in water at 25 占 폚 for 30 days so that a coating film having a dry film thickness of 150 占 퐉 is formed. Specifically, a test plate is mounted on the inner wall of a cylindrical rotary immersion bath and water is generated by rotating the center portion of the water in the water (main speed: 15 knots), and immersed in this state for 30 days. A rigid polyvinyl chloride test plate after immersion was placed in water so that the surface of the coating film was horizontal and below the test plate. Air of 0.1 cc was injected into the water to form one bubble on the surface of the coating film, (B) of the bubbles from the surface of the coating film and the diameter (b) of the contact portion between the coating film surface and the bubbles were measured to calculate the static bubbling contact angle? _S in units of degrees ).

[Equation 1]

The measurement method of the underwater bubble roll (slip) angle is as follows.

In the method of measuring the static bubble contact angle in water, the angle of inclination (underwater bubble roll (slip) angle (? _M ,?) With respect to the horizontal plane of the surface of the coating film when bubbles start to move by gradually inclining the coated film surface, Unit: degree) is measured.

The static underwater bubble contact angle indicates the degree of wetting (degree of affinity) of the gas in the coating film. The smaller static bubble contact angle indicates that the gas is wetted (affinity) to the coating film, and the larger the bubble contact angle in static water indicates that the gas is less wetted (affinity) to the coating film.

The roll (slip) angle of the bubble indicates the ease of air flow on the surface of the coating film. The smaller roll (slip) angle of the bubbles indicates that air can easily flow on the surface of the coated film, and the larger roll (slip) angle of the bubbles indicates that the air hardly flows on the surface of the coated film.

That is, these physical properties serve as an index for judging whether or not the water-immersed portion of the shell plating on which the coating film is formed has a surface with excellent gas-lubricating properties, so that the bubble contact angle in static water is small and the roll (slip) Excellent lubricity.

It is preferable that the contact angle in static water bubbles is 80 degrees or less from the viewpoint of reducing the frictional resistance and further maintaining the property of the coating film formed on the surface of the outer shell of the ship for a long period of time. Or less.

Since the special friction resistance reducing vessel formed on the water-immersed side of the coating film having the bubble contact angle in water and the underwater bubble roll (slip) angle in the above range is excellent in gas lubrication on the water-immersed side of the side plate, The air supply can also effectively reduce the frictional resistance of the ship, resulting in excellent energy saving. In addition, since the frictional resistance of the special frictional resistance reducing vessel with respect to the water-immersed surface of the outer shell of the ship is reduced by the above-mentioned coating film, the abrasion of the water- It also shows the effect that the property is maintained over a long period of time.

<Friction resistance reduction rate after immersion in water, difference in frictional resistance reduction rate before and after immersion in water>

The gas lubrication effect (water friction resistance reduction effect) can be confirmed by applying a coating composition to the bottom of a model line and measuring the water flow friction resistance (circulating water tank test) when air is supplied to the surface of the formed bottom coating film. In the present specification, a test plate having a coating film formed of a coating composition is dipped in water (preferably at about 25 ° C) in water (preferably seawater) or mounted on the inner wall of a rotary dipping bath and water Is referred to as &quot; after immersion X &quot; (X is elapsed time, for example, 30 days after immersion if immersed for 30 days). do. In addition, those without such treatment are referred to as before immersion.

For example, a test plate is mounted on the inner wall of a cylindrical rotary immersion tank, and the center portion of the test piece is rotated in water (15 knots at a main speed) to generate a water flow. The friction resistance reduction rate measured before and after immersion Is the difference in the friction resistance reduction rate before immersion and 30 days after immersion.

Specific examples of the measurement method of difference in friction resistance reduction rate before and after immersion are as follows.

As shown in Fig. 4, a length of 2.05 m, a width of 0.24 m and an area of 2.8 m, a molded breadth of 0.24 m and a molded depth of 0.14 m were immersed in the bottom of a model line for 30 days A 0.492 m 2 test plate is mounted so that the surface of the coating is exposed (the surface of the coating is in contact with water). The coating film portion of the test plate is used as the test coat film portion 9. Subsequently, the model line was installed in a vertical circulation type circulating water tank having a length of 8 m, a width of 1.5 m and a depth of 1.2 m, and the test plate was mounted under the condition that the flow rate of water (12 캜) was 1.4 m / s The frictional resistance of the hull is measured when the air is blown out from the air blow-out port 8 provided at the bottom of the model line (for example, equivalent air thickness ta = 1.0 mm) and not blown out. Next, the frictional resistance reduction rate eta F of the test plate portion is obtained from the following equation (2) and the following equation (3). The difference in the friction resistance reduction rate before and after immersion can be obtained by subtracting the frictional resistance reduction rate after immersion for 30 days from the frictional resistance reduction rate before immersion (the flow rate of water or the equivalent air thickness value can be appropriately set).

R _t0 is the total resistance of the hull when air is not blown [kgf],

R _t : total resistance of the hull when air is blown [kgf],

R _f0 is the frictional resistance [kgf] in the case where air is not ejected from the test plate expressed by the following equation (4)

ρ: density of water [Kgf · s ² / m ⁴ ] (12 ° C.),

S: Area of test plate [m2],

U: Flow rate of water [m / s],

C _f0 : coefficient of friction when the test plate shown in the following formula (5) does not eject air,

R _n : Reynolds number of the test plate expressed by the following equation (6)

U: Flow rate of water [m / s],

L: length of test plate [m],

ν: Number of kinetic constants of water [㎡ / s] (12 ℃).

The above-described equivalent air thickness ta [mm] represents the amount of air ejected, and is represented by the following equation (7).

Qa: Amount of air ejected [m ³ / s],

U: Flow rate of water [m / s],

Ba: Width of air outlet [m].

Here, the term &quot; total resistance &quot; refers to the sum of all the resistances involved in the measurement, such as wave resistance, shape resistance, and frictional resistance.

The test plate shall be an aluminum plate (material: A5052P).

The difference in the reduction rate of the frictional resistance before and after immersion shows how the reduction of the frictional resistance by the coating film is maintained over a certain period of time.

That is, the smaller the difference in frictional resistance reduction rate before and after immersion, the smaller the change with time in the properties of the coating film after a certain period of time.

The special friction resistance reducing vessel formed on the water-immersed side of the shell plating that meets the above requirements has a small difference in friction resistance reduction rate before and after immersion (change over time of the coating film) . Also, even with a small amount of air (for example, ta = 1.0 mm), a sufficient resistance reduction effect can be obtained, and energy for supplying air required for reducing frictional resistance is also minimized.

2-2. Second Special Friction Resistance Reduction Ship Manufacturing Method

The manufacturing method of the second special frictional resistance reducing vessel as described above may be complied with a method of manufacturing a special frictional resistance reducing vessel (the first special frictional resistance reducing vessel) coated with a coating film formed of the above-mentioned antifouling paint composition.

2-3. A method of predicting the effect of reducing the friction resistance using the gas lubrication function in the water of a coating film

The method of predicting the frictional resistance reducing effect using the gas lubrication function of the coating film of the present invention in the water is a method of measuring the bubble contact angle in static water by the measurement method of the static bubble contact angle in water and the method of measuring the bubble roll angle (Slip) angle in water under the static water bubble contact angle and underwater bubble roll (slip) angle is measured to predict the frictional resistance reducing effect using the gas lubrication function in the water of the coating film formed of the coating composition .

The static water bubble contact angle and the underwater bubble roll angle (slip angle) are as follows, and the static water bubble contact angle indicates the degree of wetting (affinity) of the gas with respect to the film, and the roll (slip) The flow of air in the case of the present invention is easy.

<Measurement method of static water bubble contact angle>

The test plate coated with the coating composition is immersed in water so that the test plate before and after the immersion is placed in water such that the surface of the coating film is horizontal and is located below the test plate and air is injected into the water to form bubbles on the surface of the coating film (A) from the surface of the coating film formed on the surface of the coating film and the diameter (b) of the contact portion between the coating film surface and the bubbles were measured, and from the following formula (1) (θ _s , unit: degree) is obtained.

[Equation 1]

&Lt; Measurement method of water bubble roll (slip) angle &gt;

In the method of measuring the static bubble contact angle in water, an underwater bubble roll angle (? _M , unit (? _M )), which is an inclination angle with respect to a horizontal plane of a coated film surface when bubbles start to move by gradually inclining the coated film surface on which bubbles are formed, : Degrees).

That is, these physical properties serve as an index for judging whether or not the water-immersed portion of the shell plating on which the coating film is formed has a surface with excellent gas-lubricating properties, so that the bubble contact angle in static water is small and the roll (slip) Excellent lubricity.

In the method for evaluating the frictional resistance reducing effect of the present invention, as a result of the above two kinds of measurement methods, it has been found that the static water bubble contact angle is less than 90 degrees (preferably 80 degrees or less) and the underwater bubble roll (Preferably 20 degrees or less) is excellent in gas lubrication and is excellent in the effect of reducing friction resistance using a gas lubrication function in water.

Also, as shown by the results of Examples described later, the paint having a high evaluation in the method of evaluating the friction resistance reducing effect of the present invention is highly evaluated even in the evaluation result of the resistance to water flow using the model wire, and vice versa. same.

Therefore, the method of predicting the frictional resistance reducing effect using the gas lubrication function in the coating film of the present invention is simple and suitable, and thus, is effective for selection of the coating film.

2-4. Apparatus used for prediction of frictional resistance reduction effect using gas lubrication function in coating water

The apparatus (contact angle measuring apparatus) used for predicting the frictional resistance reducing effect using the gas lubrication function of the coating film of the present invention comprises a test stand, a tilt angle control device, a dipping container, and a monitoring device.

The inclination angle control device is connected to the test stand.

The test table is mounted so that a test plate having a coated film formed on its surface is brought into contact with the underside of the test bench, and the test plate is immersed in the immersed container containing water to form bubbles on the surface of the test plate Respectively.

The observation apparatus is installed so as to observe the state of the test plate and the bubbles.

The static water bubbling contact angle of the bubbles is measured by observing the state of the bubbles formed on the surface of the coating film of the test plate when the test plate is in a horizontal position, and measures the bubbling contact angle in static water.

The underwater bubble roll (slip) angle of the bubble is measured by obliquely tilting the test plate with respect to the horizontal by the inclination angle control device, observing the behavior of the bubble by the observation device, and forming it on the surface of the test film.

Hereinafter, the contact angle measuring apparatus will be described in detail with reference to the apparatus shown in Fig. 1 as an example of the contact angle measuring apparatus.

1, a test table 5 for mounting a test plate 6 having a coated film on its surface is connected to a tilt angle control mechanism including a rotation drive handle 4, and by rotating the rotation drive handle 4, The inclination angle with respect to the horizontal direction of the screen 5 is controlled. The angle is measured by the goniometer (3). The test bench 5 is installed underwater by a dipping vessel 7 designed to be able to mount the test bench 5 underwater. In the apparatus shown in Fig. 1, at least a part or the whole of the dipping container 7 is made of a member having transparency (for example, acrylic or glass) And the shape of the bubble formed in the test plate 6 can be observed. The test plate 6 is mounted on the lower side of the test table 5 so that the surface on which the coated film is formed faces downward of the test table 5.

The formation of bubbles on the surface of the coating film of the test plate 6 may be performed using, for example, a syringe 2.

The observation of the bubbles is carried out by using the camera 1. Bubbles can be observed with the naked eye, but the use of the camera 1 can more accurately observe the behavior of bubbles.

The measurement of the static water bubble contact angle and the underwater bubble roll (slip) angle may be performed as described above. The type of test plate, the dry film thickness of the coated film, the immersion time, the volume of the bubble, and the like may be appropriately set according to the purpose.

In this case, although it depends on the purpose, the type of the test plate is vinyl chloride plate, and the dried film thickness of the coating film is usually in the range of 50 to 500 μm, the immersion time is usually in the range of 1 to 180 days, Is usually in the range of 0.1 to 3 cc. As the test plate, a test piece having a maximum height measured in accordance with JIS B 0601 of 1 占 퐉 or less is used.

3. Group 3

3-1. Friction resistance reduction system (first and second frictional resistance reduction system) used for a special frictional resistance reduction ship and special frictional resistance reduction ship (third and fourth frictional resistance reduction vessel)

The first and second frictional resistance reduction systems used in the special frictional resistance abatement ship of the present invention comprise a first coating film (antifouling coating film) and a second coating film, respectively, and a gas supply unit for supplying gas to the surfaces of the first coating film or the second coating film And a gas supply device.

Such a frictional resistance reduction system, as described above, is provided with a coating film having specific physical properties excellent in frictional resistance reduction performance or a gas such as air from a gas supply device on the surface of the antifouling coating film, It can be greatly reduced.

The gas supply device and the gas to be used are as described above.

The third and fourth special frictional resistance reducing vessels each having such a first and second frictional resistance reducing system are greatly reduced in frictional resistance in the water of the ship by the above system, It is economical and has less environmental impact because the effect of reducing fluid friction resistance is large without introducing large power into the supply.

Example

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples at all. Unless otherwise noted, the pressure conditions are atmospheric pressure (about 0.1013 MPa) and the temperature conditions are room temperature (about 25 ° C).

Details of various tests conducted in the following Examples and Comparative Examples are as follows.

&Lt; Measurement of coating film surface roughness &

The surface state of each coating film was measured using a contact type surface roughness meter (Handysurf E-35A, manufactured by Tokyo Seimitsu Co., Ltd.) in accordance with JIS B 0601.

&Lt; Measurement of change in contact angle and roll (slip) angle with time>

The coating composition prepared in the following examples was coated on a hard polyvinyl chloride plate (having a maximum height of 1 占 퐉 or less measured in accordance with JIS B 0601) of 50 占 50 占 2 mm so as to have a dry film thickness of 150 占 퐉, And dried at room temperature for 5 days to prepare a test plate. The test plate was mounted on the inner wall of a cylindrical rotary immersion tank, and the coating film formed on the test plate was immersed. And the central part of the water was rotated in the water (main speed: 15 knots) to generate water flow. The static water bubble contact angle and underwater bubble roll (slip) angle of the coating film formed on the test plate were measured as follows using the "contact angle measuring device" before immersion, 14 days after immersion and 30 days after immersion (FIGS. 4).

(Measurement of Static Underwater Bubble Contact Angle)

The test plate before or after immersion for the specific period as described above was attached to a test stand (5) so that the surface of the coating film was horizontal and the lower side of the test plate was set in water. 0.1 cc of air was injected into the water using a syringe (2) so that a bubble was formed on the surface of the coating. The height (a) of the bubbles formed on the surface of the coating film and the diameter (b) of the contact portion of the coating film surface and the bubbles were measured from the side using the camera 1 (video microscope) 1, the contact angles of the coating film surface and the bubbles were determined (see FIGS. 1 and 2). The affinity between the surface of the coating film and the air bubble can be evaluated by the static water bubble contact angle (? _S ) at this angle. The smaller the value of? _S is, the greater the affinity between the coating film surface and the air is.

[Equation 1]

(Measurement of underwater bubble roll (slip) angle)

0.1 cc of air was injected into the water so as to form bubbles on the surface of the coating film under the same conditions as in the measurement of the static bubbling contact angle in water, and then the rotation drive handle 4 was rotated to gradually tilt the surface of the coating film against the horizontal plane (See Figs. 1 and 3). With this angle being the underwater bubble roll (slip) angle (? _M ), the fluidity of the air bubbles on the coated film surface can be evaluated. The smaller the? _M , the better the fluidity.

<Method of Static Antifouling Test>

(Epikone Zinc Rich Primer B-2, manufactured by Chukogyo Kogyo Co., Ltd.), epoxy-based anticorrosive paint (manufactured by Chikugo Kogyo Co., Ltd.), and the like were coated on a sandblasted steel sheet of 100 mm x 300 mm x 2.3 mm (CMP Bioclean SG, manufactured by Chukogyo Kogyo Co., Ltd.) were coated in the above order using air spray so as to have a dry film thickness of 20 탆, 150 탆 and 100 탆, respectively . The antifouling paint composition prepared in the later-described examples was coated on the surface of a urethane-based binder coat formed from a urethane resin-based paint to prepare a test plate having a dry film thickness of 100 탆 to 200 탆. The obtained test plate was dried in a room (room temperature 20 ° C, relative humidity 60%) for 1 week, immersed in a raft 1 m under the surface of the water in Hiroshima bay, and 1, 3, 6, 12 The condition of bioadhesion for months was visually observed.

The evaluation was made by visual observation of the attachment area (%) of the marine creatures.

The evaluation criteria were as shown in Table 3.

<Dynamic Antifouling Test Method>

A sandblast steel sheet having a size of (lengthwise) 170 mm x (width) 70 mm x (thickness) of 2.3 mm was prepared by bending such that it could be mounted on the side of a rotary drum installed in seawater of Kurehishi Hiroshima. This sandblast steel plate was coated with an epoxy-based zinc rich primer (Epikone Zinc Rich Primer B-2 manufactured by Chugoku Kogyo Co., Ltd.), an epoxy based coating material (Banano 500 manufactured by Chukogyo Kogyo Co., Ltd.) ("CMP Bio Clean SG" manufactured by Chukyo Kogyo Co., Ltd.) was overlaid in the above order using air spray so that the dry film thicknesses were 20 μm, 150 μm and 100 μm, respectively. The antifouling paint composition prepared in the later-described examples was coated on the surface of a urethane-based binder coat formed from a urethane resin-based paint to prepare a test plate having a dry film thickness of 100 탆 to 200 탆. The obtained test plate was dried in a room (room temperature 20 ° C, relative humidity 60%) for 1 week, mounted on the rotary drum and spin-dipped at a peripheral speed of 15 knots, The bioadhesive condition in the dynamic environment of the liver was visually observed.

&Lt; Measurement of water flow resistance &gt;

A test plate (length 2.05 m, width 0.24 m, area 0.492 m &lt; 2 &gt;) coated with the antifouling paint composition prepared in Examples described later was placed on the bottom of a model line (total length 2.8 m, width 0.24 m, Base: Aluminum plate (A5052P)) is mounted so that the surface of the coating film is exposed. The coating film portion of the test plate was used as the test coat film portion 9. Subsequently, under the condition that the flow rate of water (12 ° C) was a specific rate, the bottom of the test vessel (the test coat portion (Ta: mm) is ejected from the air blow-out port (8) provided at the bottom of the model line with the air blower (9), and the frictional resistance of the hull when it is not blown out is measured before and after the immersion And then measured. The air was jetted from an arrayed porous plate (2 mm diameter x 46 holes) provided at the front edge of the test plate by controlling the flow rate of the compressed air from the compressor. Then, the total resistance reduction rate eta T and the frictional resistance reduction ratio eta F of the test plate portion at each of the water flow rate, the air flow rate, and the air flow rate were obtained according to the following equations (2) and (3). The difference in the frictional resistance reduction rate before and after immersion was obtained by subtracting the frictional resistance reduction rate after immersion for 30 days from the frictional resistance reduction rate before immersion.

&Quot; (2) &quot;

&Quot; (3) &quot;

&Lt; Preparation of antifouling paint composition &gt;

[Production Example 1]

900 parts by weight of dimethylpolysiloxane (XF3905, manufactured by Momentive Performance Materials Co., Ltd.) having both ends of the molecular chain blocked with silanol groups and having a viscosity at 25 DEG C of 700 mm &lt; 2 &gt; / s, 100 parts by weight of hydrophobized fumed silica (manufactured by Nippon Aerosil Co., Ltd., R-972) were uniformly mixed at 150 DEG C for 2 hours using a stirring mixer (5NDMV, manufactured by Dalton) to obtain a base compound 1. The viscosity of base compound 1 was 1530 mm 2 / s.

[Production Examples 2 to 4]

YF3057 (viscosity: 3,000 mm 2 / s, manufactured by Momentive Performance Materials Company) and YF3807 (viscosity: 20,000 mm 2 / s, manufactured by Momentive Performance Materials Co., Ltd.) as the dimethylpolysiloxane having both ends of the molecular chain blocked with silanol groups in Production Example 1 ) And YF3802 (viscosity: 80,000 mm &lt; 2 &gt; / s, manufactured by Momentive Performance Materials Company) were used in place of the base compounds 2, 3 and 4. The viscosities of base compounds 2 and 3 were 8,670 mm 2 / s and 46,000 mm 2 / s, respectively. Since BASE COMPOUND 4 has a high viscosity, viscosity measurement was impossible.

[Example 1]

100 parts by weight of the base compound 1, 10 parts by weight of silicone oil KF-50-3000 (trade name: KF-50-3000, manufactured by Shinetsu Chemical Co., Ltd., methylphenyl silicone oil) obtained in Production Example 1, 12 parts by weight of a pigment 1.5 parts by weight of black iron oxide (trade name &quot; KN320 &quot;, manufactured by Toda Kogyo Co., Ltd.) as a pigment were placed in a paint shaker using glass beads as a medium, After shaking for a time, the resulting mixture was filtered through a filter of 120 mesh to prepare a composition (I solution).

Just prior to coating, 123.5 parts by weight of the above solution I, 5 parts by weight of ethyl silicate (trade name "TES40WN", ethyl silicate oligomer, manufactured by Wako Asahi Kasei Silicone Co., Ltd.) as a solution II, and tin catalyst (trade name "GLECK TL" 10 parts by weight of dibutyl tin dilaurate, 10% xylene solution) were thoroughly mixed with solution I and solution II, and the solution III was added and stirred to prepare an antifouling paint composition.

The obtained antifouling paint composition was subjected to various tests described above under the conditions shown in Tables 1 and 3 to 6 below.

The results are shown in Tables 1 and 4-6.

[Examples 2 to 10]

As shown in Table 1, an antifouling paint composition was prepared in the same manner as in Example 1 except that the kinds and blending amounts of the respective components were changed.

The obtained antifouling paint composition was subjected to various tests described above under the conditions shown in Tables 1 and 3 to 6 below.

The results are shown in Tables 1 and 4-6.

[Example 11]

100 parts by weight of a reactive organopolysiloxane KE-445 (trade name "KE-445", Shin-Etsu Chemical Co., Ltd., defoaming type organopolysiloxane, viscosity: 4,500 mm 2 / s), silicone oil KF- 40 parts by weight of KF-50-100, a methylphenyl silicone oil manufactured by Shinetsu Chemical Co., Ltd.) and 22 parts by weight of KF-50-3000 (trade name: KF-50-3000, manufactured by Shinetsu Chemical Co., And 20 parts by weight of xylene were placed in a paint shaker using glass beads as a medium, shaken for 1 hour, and filtered through a filter of 120 mesh to prepare an antifouling paint composition.

The obtained antifouling paint composition was subjected to various tests described above under the conditions shown in Tables 1 and 3 to 6 below.

The results are shown in Tables 1 and 4-6.

[Comparative Example 1]

<Super water repellent coating film 1>

12.6 parts by weight of a fluororesin LF-200 (trade name: Lumipulon LF-200, manufactured by Asahi Glass Co., Ltd., fluorinated polyol), 10 parts by weight of fluorine powder L- 24.2 parts by weight of a low molecular weight tetrafluoroethylene ultrafine powder manufactured by Daikin Industries, Ltd.), 1.8 parts by weight of an additive SF-1265-1000 (trade name: SF-1265-1000, manufactured by Toray-Dow, fluorinated silicone oil) 60.6 parts by weight of butyl acetate and 0.8 parts by weight of a tin catalyst (trade name "GLECK TL", Dibutyltin dilaurate, 0.1% xylene solution) as a curing accelerator were placed in a paint shaker using glass beads as a medium, After that, the resulting mixture was filtered through a filter of 60 mesh to prepare a super water repellent coating composition.

Immediately before painting, 100 parts by weight of the super water repellent coating composition and 1.7 parts by weight of DN-980 (trade name: "Bernok DN-980, manufactured by DIC Corporation, isocyanurate type polyisocyanate") as a curing agent were mixed to prepare a super water- Lt; / RTI &gt;

The obtained antifouling paint composition was subjected to various tests described above under the conditions shown in Tables 1 and 3 to 6 below.

The results are shown in Tables 1 and 4-6.

[Comparative Example 2]

&Lt; Super water repellent coating film 2 &gt;

34.7 parts by weight of an acrylic resin TZ-343 (trade name: "ACRIDIC TZ-343", manufactured by DIC Corporation), 19.6 parts by weight of hydrophobic fine silica (trade name "Nipsil SS-70" And 44.3 parts by weight of xylene were placed in a paint shaker using glass beads as a medium and shaken for 1 hour. Then, 1.4 parts by weight of an additive (trade name: DIPARON A630-20X manufactured by Gusumoto Chemicals Co., Ltd.) was further added After shaking for 15 minutes, the resulting mixture was filtered through a filter of 60 mesh to prepare a super water repellent coating composition.

The obtained antifouling paint composition was subjected to various tests described above under the conditions shown in Tables 1 and 3 to 6 below.

The results are shown in Tables 1 and 4-6.

[Comparative Example 3]

<Aluminum plate>

An anti-corrosion aluminum plate (material A5052P) was provided for the test as a non-coated plate, and the anti-corrosion aluminum plate was subjected to various tests described above under the conditions shown in Tables 1 and 3 to 6 below.

The results are shown in Tables 1 and 4-6.

In the following Table 1, the blending amount is expressed in parts by weight.

In the following Tables 4 to 6, R _t0 (total resistance of the hull when air is not blown) and R _t (total resistance of the hull when air is blown out) are expressed as [kgf] Reduction rate) and? F (frictional resistance reduction rate) are indicated as [%].

5 shows the relationship between the equivalent air thickness ta and the frictional resistance reduction rate (comparison before immersion and after 30 days of immersion).

The abbreviations of the raw materials listed in Table 1 are as shown in Table 2, and the evaluation criteria of the antifouling test are as shown in Table 3.

As shown in Tables 1 and 4 to 6, the coating film obtained from the compositions of Examples 1 to 11 in which the organopolysiloxane was the main component had a smaller bubble contact angle (less than 90 degrees) in comparison with the unpainted aluminum plate (Comparative Example 3) The roll angle or slip angle was small, and the change with time in immersion in water at these angles was small. In Comparative Examples 1 and 2, the change with time in immersion in water was great and became hydrophilic, and the affinity with air disappeared. These water resistance reduction rates of Examples 1 to 11 were larger than those of Comparative Examples 1 and 2.

As shown in Table 6 and Fig. 5, the coating film obtained from the composition of Example exhibited a friction reducing effect in a small air amount (ta = 1.0 mm) as compared with the unpainted aluminum plate (Comparative Example 3) It is possible to reduce the energy to be used, which is effective for energy reduction, which is the net taste of the ship.

As shown in Table 6 and FIG. 5, the change in the frictional resistance reduction rate before and after immersion in the coating film obtained from the composition of the example is clearly smaller than that in the super water repellent coating films 1 and 2 (Comparative Examples 1 and 2).

In the antifouling property test, as shown in Tables 1 and 3, the compositions of Examples 1 to 11 did not show any fouling at the immersion period of 12 months, but the compositions of Comparative Examples 1 and 2 showed remarkable dirtiness despite the super water- And the function as an antifouling paint was not sufficient.

The special friction resistance reducing vessel according to the present invention exhibits an effective gas lubrication effect, so that the frictional resistance of the hull is effectively reduced even if the amount of air to be supplied is small, and the energy saving effect is also large.

The antifouling paint composition used in the special friction resistance reducing vessel of the present invention can form a coating film capable of effectively reducing the frictional resistance of the hull even by supplying a small amount of gas, and thus has a large energy saving effect. In addition, the coating film formed of the antifouling paint composition exerts excellent antifouling property and can prevent an increase in frictional resistance of the hull due to adhesion of aquatic organisms or the like. Moreover, the antifouling paint composition can maintain their effects over a long period of time.

The method for producing a special friction resistance reducing vessel of the present invention can produce a specific ship exhibiting the above effect by a simple method of forming an antifouling coating film formed of the antifouling paint composition on a water-immersed surface of the outer shell of a ship.

The method of predicting the frictional resistance reducing effect of the present invention can predict the frictional resistance reducing effect by a simple and low-cost facility or technique.

Therefore, the special friction resistance reducing vessel of the present invention, the antifouling paint composition used for the special friction resistance reducing vessel, and the manufacturing method of the special friction resistance reducing vessel can all be used in various ships requiring reduction in frictional resistance, Can be used.

1 Camera
2 syringes
3 goniometer
4 rotation drive handle
5 Testbed
6 Trial
7 Containment vessel
8 Air outlet
9 test film portion

Claims (18)

(A) a reactive curing organopolysiloxane having a viscosity at 25 ° C of 20 to 400,000 mm 2 / s,
(C) a hydrophobic material (except for at least one selected from the organopolysiloxane (A) and the organosilane and its partial condensate (B)) in liquid or grease at 25 ° C, and
(B) an organosilane having at least two groups of at least one of a hydroxyl group and a hydrolyzable group in one molecule, and partial condensates thereof.
An antifouling paint composition for use in a marine vessel having a gas supply device for supplying a gas and reducing a frictional resistance using a gas lubrication function in water. The method according to claim 1,
Wherein the hydrophobic material (C) comprises at least one selected from the group consisting of silicone oil, fluorine-based oil, paraffin and wax. The method according to claim 1,
Wherein the antifouling agent (D) is contained in an amount of 1 to 150 parts by weight based on 100 parts by weight of the organopolysiloxane (A). An antifouling coating film for use in a ship having a gas supply device for supplying a gas, which is formed of the antifouling paint composition according to claim 1, and which reduces frictional resistance using a gas lubrication function in water. 5. The method of claim 4,
The maximum height from the bottom of the concave portion to the top of the convex portion measured according to JIS B 0601 is 30 占 퐉 or less and one convexity measured in accordance with JIS B 0601 and one convexity of one concave adjacent thereto Wherein an average peak-valley interval is 700 mu m or more. 5. The method of claim 4,
An antifouling coating film having a bubble contact angle in static water of less than 90 deg. And a water bubble roll angle (slip) angle of less than 30 deg. Measured by the following method of measurement of bubble roll (slip) angle measured by the following static static bubble contact angle measurement method:
<Measurement method of static water bubble contact angle>
A hard polyvinyl chloride test plate (maximum height measured in accordance with JIS B 0601) of 1 占 퐉 or less coated with the coating composition was soaked in water at 25 占 폚 for 30 days so as to form a coating film having a dry film thickness of 150 占 퐉, A rigid polyvinyl chloride test plate was placed in water so that the surface of the coating film was horizontal and the lower side of the test plate. 0.1 cc of air was injected into the water to form one bubble on the surface of the coating film. (A) and the diameter (b) of the contact portion between the coating film surface and the bubbles were measured, and the static bubbling contact angle? _S (unit: degree) Seek;
[Equation 1]

&Lt; Measurement method of water bubble roll (slip) angle &gt;
In the method of measuring the static bubble contact angle in water, an underwater bubble roll angle (? _M , unit (? _M )), which is an inclination angle with respect to a horizontal plane of a coated film surface when bubbles start to move by gradually inclining the coated film surface on which bubbles are formed, : Degrees). A gas supply device for supplying a gas, characterized in that the antifouling coating film according to any one of claims 4 to 6 is coated with a submerged surface of the outer shell of the ship, Friction resistance reduction vessel used. An antifouling coating film according to any one of claims 4 to 6, which is formed on a surface of a shell plating to be immersed in water on the outside of a coated vessel, comprising a gas supply device for supplying a gas, A method of manufacturing a ship with reduced frictional resistance using a lubrication function. A frictional resistance reducing system comprising the antifouling coating film according to any one of claims 4 to 6 and a gas supply device for supplying gas to the surface of the antifouling coating film. A frictional resistance reducing vessel comprising a gas supply device for supplying a gas and using the gas lubrication function in water, characterized by comprising the frictional resistance reduction system according to claim 9. (Slip) angle of less than 30 degrees as measured by the static water bubbling contact angle measured by the static water underwater contact angle measuring method below and less than 90 deg. Lt; RTI ID = 0.0 &gt;
A coating composition for use in a ship having a gas supply device for supplying gas and reducing frictional resistance using a gas lubrication function in water:
<Measurement method of static water bubble contact angle>
A hard polyvinyl chloride test plate (maximum height measured in accordance with JIS B 0601) of 1 占 퐉 or less coated with the coating composition was soaked in water at 25 占 폚 for 30 days so as to form a coating film having a dry film thickness of 150 占 퐉, A rigid polyvinyl chloride test plate was placed in water so that the surface of the coating film was horizontal and the lower side of the test plate. 0.1 cc of air was injected into the water to form one bubble on the surface of the coating film. (A) and the diameter (b) of the contact portion between the coating film surface and the bubbles were measured, and the static bubbling contact angle? _S (unit: degree) Seek;
[Equation 1]

&Lt; Measurement method of water bubble roll (slip) angle &gt;
In the method of measuring the static bubble contact angle in water, an underwater bubble roll angle (? _M , unit (? _M )), which is an inclination angle with respect to a horizontal plane of a coated film surface when bubbles start to move by gradually inclining the coated film surface on which bubbles are formed, : Degrees). A coated film formed by a coating composition used for a friction resistance reducing vessel according to claim 11. A reduced frictional resistance vessel using a gas lubrication function in water, comprising a gas supply device for supplying a gas, characterized in that the coated film according to claim 12 is provided on a water immersed surface of a shell external plate. A frictional resistance reducing system comprising the coating film according to claim 12 and a gas supply device for supplying gas to the surface of the coating film. A frictional resistance reducing vessel comprising the gas supply device for supplying a gas and using the gas lubrication function in water, characterized by comprising the frictional resistance reduction system according to claim 14. Characterized in that the coating film according to claim 12 is formed on the surface of the outer plate of the coated steel plate intended to be immersed in water, characterized by comprising a gas supply device for supplying a gas, Gt; The bubble contact angle in static water was measured by the static water contact angle measurement method in the following manner, and the underwater bubble roll (slip) angle was measured by the below-mentioned measurement method of bubble roll (slip)
And estimating the frictional resistance reducing effect using the gas lubrication function in the water of the coating film from the static water bubbling contact angle and the underwater bubble roll (slip) angle.
A method for predicting the effect of reducing the frictional resistance by using the gas lubrication function in the water of a coating film:
<Measurement method of static water bubble contact angle>
The test plate coated with the coating composition was immersed in water so that the test plate after the immersion was installed in water so that the surface of the coating film was horizontal and the lower side of the test plate, air was introduced into the water to form bubbles on the surface of the coating film , The height (a) of the bubbles formed on the surface of the coating film from the surface of the coating film and the diameter (b) of the contact portion between the coating film surface and the bubbles were measured to calculate a static water bubble contact angle θ _s , unit: degrees);
[Equation 1]

&Lt; Measurement method of water bubble roll (slip) angle &gt;
In the method of measuring the static bubble contact angle in water, an underwater bubble roll angle (? _M , unit (? _M )), which is an inclination angle with respect to a horizontal plane of a coated film surface when bubbles start to move by gradually inclining the coated film surface on which bubbles are formed, : Degrees). An apparatus comprising a test bed, a tilt angle control device, a dipping container, and a viewing device,
The inclination angle control device is connected to the test stand,
The test stand is mounted in such a state that a test plate having a coated film formed on its surface is brought into contact with the underside of the test stand so that the test plate is immersed in the immersed container containing water and bubbles are formed on the surface of the test film And,
Wherein the observation apparatus is installed so as to observe the state of the test plate and the bubble,
The state of the bubbles formed on the surface of the coating film of the test plate when the test plate is horizontal is observed by the observation apparatus and the contact angle of the bubbles in static water is measured,
The tilt angle control device tilts the test plate horizontally to observe the behavior of the bubbles by the observation device, and measures the bubble roll (slip) angle of the bubbles formed on the surface of the coating film of the test plate. , A device used for prediction of frictional resistance reduction effect using gas lubrication function in a coating film.

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