JP6041897B2 - Paint composition used for ship with reduced frictional resistance utilizing gas lubrication function in water, coating film formed from the composition, ship coated with the coating film, method for manufacturing the ship, and reduction of frictional resistance Method for predicting effect, apparatus used for predicting frictional resistance reduction effect, and frictional resistance reducing system used for frictional resistance-reducing ship - Google Patents

Description

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

  The navigating ship is subjected to wave-making resistance due to the generation of waves, pressure shape resistance due to the shape of the bottom of the ship, and frictional resistance due to water viscosity (water frictional resistance). Wave resistance and shape resistance have been greatly reduced by previous research, but friction resistance accounts for 60% to 80% of the total resistance of the hull, and reduction of friction resistance is eagerly desired to save energy. ing. As methods for reducing the water friction resistance, air lubrication for supplying air to the ship bottom and methods for adding polymers to fluids such as seawater (methods utilizing the Toms effect) have been proposed and studied. Practical application to ships is underway.

  For example, Patent Documents 1 to 4 disclose a method in which a ship bottom surface is treated with a coating agent, water repellency is imparted to the ship bottom surface, air bubbles and an air layer are held, and frictional resistance is reduced. In any of these methods, air is supplied to the ship bottom on which a specific hydrophobic coating film is formed to cover the surface of the ship bottom with an air layer, and friction resistance is reduced by an air lubrication effect.

  The hydrophobic coating film is formed of hydrophobic (fine) particles contained in a coating agent and a hydrophobic binder resin, and has a hydrophobic rough surface having a high affinity with air. A hydrophobic coating film having a hydrophobic rough surface (hereinafter also referred to as a “hydrophobic uneven coating film”) is that air adheres to the concave portion in the air and is retained as an air layer, and Due to the small surface free energy, high water repellency is exhibited. However, such hydrophobic concavo-convex coating film loses its water repellency over time in water and loses its air affinity. In particular, this change over time is remarkable at the bottom of a ship that is sailing. That is, since the intermolecular interaction force between air (gas molecules) and the hydrophobic concavo-convex coating film (surface constituent molecules) is small, water (molecules) gradually permeates into the concave portions and air is excluded. This phenomenon is described as “immersion wet”. When there is a water flow on the surface of the hydrophobic uneven coating film, the elimination of air is further promoted. If water intrudes into the recesses of this hydrophobic uneven coating and air (layer) is eliminated, even if new air is supplied to this surface, the cohesive energy and mass of water (molecules) will be higher than that of air Since it is overwhelmingly large, air cannot permeate into the recesses of the hydrophobic uneven coating film. That is, the air (layer) retention performance is not restored. Therefore, the hydrophobic uneven coating film exhibits air affinity because an air layer is formed in the recesses in the air, but in water, the surface of the coating film is covered with water that has penetrated into the recesses, so that it becomes hydrophilic. Loses affinity.

  Further, the hydrophobic uneven coating film has a small cohesive energy (surface free energy) and a low mechanical strength. Therefore, such a hydrophobic uneven coating film is fragile and poor in adhesion, and the above-mentioned fine particles and hydrophobic uneven coating film are peeled off from the ship bottom surface due to the action of water flow during navigation, etc. Air retention performance due to the uneven coating film is reduced.

  Furthermore, the hydrophobic uneven coating film has no antifouling performance. From the viewpoint of preventing the surface of the ship bottom from becoming dirty due to the contamination of the bottom of the ship due to the adhesion of aquatic organisms when the ship is anchored, the coating film formed on the ship bottom has antifouling properties. It is desirable to have. In Patent Document 5, in order to impart antifouling properties to the uneven surface, it is described that an oxidizing gas or an oxidizing liquid is supplied into the sea so that the gas or liquid flows through the bottom of the ship. It is difficult to keep all of them in the atmosphere at all times. Furthermore, since there is concern about the pollution of the ocean by oxidizing gas and oxidizing liquid, it is not practical.

As described above, these conventional techniques are not effective as a method for reducing the frictional resistance of a ship used for a long time.
Further, as described in Patent Document 6, there is also known a method for judging the effect of reducing the frictional resistance by the contact angle of the film surface with respect to water. It is hard to say that it accurately reflects the state and behavior of bubbles.

Japanese Patent No. 2890340 Japanese Unexamined Patent Publication No. 08-268380 Japanese Patent Laid-Open No. 10-273617 Japanese Patent Laid-Open No. 11-131007 JP 09-262563 A JP 2003-277691 A

  As described above, the conventional technology injects air into a hydrophobic uneven coating film having air affinity, and this coating film retains the air layer and expresses the frictional resistance reduction effect. The surface of the hydrophobic uneven coating film changes with time to become hydrophilic and loses its affinity with air, and the frictional resistance reducing effect as described above is reduced. Furthermore, since this hydrophobic uneven film has no antifouling performance, the roughness of the coating film tends to be significantly increased due to fouling by microorganisms and the like, and the frictional resistance tends to increase.

  In addition, attempts have been made to supply a large amount of air to the bottom of the ship to maintain the frictional resistance reduction effect. However, this air supply requires a large amount of power, which offsets the energy-saving effect of reducing frictional resistance and is practical. Disappears.

  Moreover, in examining the above, it is useful to have a method for predicting the frictional resistance reduction effect using the air lubrication function of the coating film in water and an apparatus that can be used for the prediction.

In view of the above, the present invention has a long-term affinity with water and other gases such as air, provides a high frictional resistance reduction effect by supplying a small amount of gas , and prevents both navigation and stationary conditions. To provide a coating composition capable of forming a coating film having a soiling function, a coating film formed from the composition, a frictional resistance-reducing ship formed with the coating film, and a method for producing the frictional resistance-reducing ship Is the first issue.

Furthermore, the present invention has a long-term affinity for gas such as air in water, has a great effect of reducing fluid frictional resistance without introducing large power into the gas supply, is economical, and has an impact on the environment. Coating composition capable of forming a coating film with a small amount of coating, a coating film formed from the composition, a frictional resistance-reducing ship formed with the coating film, a method for producing the frictional resistance-reducing ship, A second problem is to provide a method for predicting the frictional resistance reduction effect using the gas lubrication function in the above and a device used for the prediction.

  The third object of the present invention is to provide a frictional resistance reduction system for use in a frictional resistance-reducing ship as described above, and a frictional resistance-reducing ship that uses a gas lubrication function in water that includes the system. To do.

  As a result of intensive studies to solve the above problems, the present inventors have found that a specific organopolysiloxane (A), a specific hydrophobic material (C), and, if necessary, a specific organosilane and / or its It has been found that the above first problem can be solved by an antifouling paint composition used for a frictional resistance-reducing ship that contains a partial condensate (B) and uses a gas lubrication function in water.

  Furthermore, the present inventors have a coating film in which a static underwater bubble contact angle and underwater bubble rolling (sliding) angle, which will be described later, are in a specific range, and to a ship with reduced frictional resistance that utilizes a gas lubrication function in water. Antifouling paint composition used, method for predicting the frictional resistance reduction effect using the static underwater bubble contact angle and underwater bubble rolling (sliding) angle, the static underwater bubble contact angle and underwater bubble rolling (sliding) It has been found that the second problem can be solved by an apparatus having a specific configuration capable of measuring an angle.

In addition, the present inventors include a coating film formed from a composition that can solve the first problem or the second problem, and a gas supply device that supplies a gas such as air to the surface of the coating film. It has been found that the third problem can be solved by the frictional resistance reduction system provided.

The present invention is based on the following findings newly discovered by the present inventors.
A coating film formed by an antifouling paint composition containing a specific organopolysiloxane, a specific hydrophobic material, and, if necessary, a specific organosilane and / or a partial condensate thereof has an air lubrication effect. The water frictional resistance is effectively reduced by efficiently expressing.
When compounds having a polysiloxane skeleton structure are blended in the antifouling paint composition, the leveling properties of these compounds affect the shape of the antifouling coating film formed from the antifouling paint composition, which will be described later. It is estimated that a specific shape of the coating film is formed.
-The coating film formed with the antifouling paint composition described above has a low roughness and a long average interval between the peaks and valleys (the surface roughness is 50 μm or less and the average valley interval is 700 μm or more). This coating film shape contributes to exhibiting the characteristics that the static water bubble contact angle is less than 90 degrees and the bubble rolling (slip) angle is less than 30 degrees. And unlike the conventional coating film (for example, the said patent documents 1-4) which requires that this fine-film unevenness | corrugation is formed, this coating-film shape has gentle undulation compared with those coating films. It has a coating film having an excellent effect of reducing frictional resistance.
The hydrophobic component is liquid or grease-like at 25 ° C., and the hydrophobic component bleeds out during navigation on a ship that has a coating film formed from the coating composition on the submerged surface of the ship's outer plate. The coating film surface is covered, and the coating film formed from the coating composition exhibits antifouling properties.
-When the static underwater bubble contact angle of the coating film is less than 90 degrees and the bubble rolling (slip) angle is less than 30 degrees, in the ship in which the coating film is formed on the submerged surface of the outer plate, bubbles and / or Since the gas layer flows without stagnation while sufficiently in contact with the coating film, the air lubrication effect is efficiently exhibited and the water frictional resistance is efficiently reduced.
-The said coating film can maintain the said property and characteristic for a long term, and there exists a high frictional resistance reduction effect with little air quantity. Therefore, the frictional resistance reduction ship in which the coating film is formed on the submerged surface of the ship outer plate has a large energy saving effect because it does not require large power for air supply.
・ If the coating film formed from an antifouling paint composition containing a hydrophobic material or an antifouling agent is a ship with reduced frictional resistance formed on the submerged surface of the ship's outer plate, further adhere to aquatic organisms. This can prevent the air lubrication effect over a longer period.

That is, the present invention is as follows.
The antifouling paint composition used for a ship with reduced frictional resistance utilizing the gas lubrication function in water according to the present invention is (A) a reaction-curable organopolysiloxane having a viscosity of 20 to 400,000 mm ² / s at 25 ° C. And (C) a hydrophobic material that is liquid or grease-like at 25 ° C. (excluding the above organopolysiloxane (A) and the following organosilane and / or its partial condensate (B)), and if necessary (B) an organosilane having at least two hydroxyl groups and hydrolyzable groups in one molecule and / or a partial condensate thereof (first paint) Also called composition). (Hereinafter, “a ship with reduced frictional resistance utilizing a gas lubrication function in water” is also referred to as “a ship with reduced special frictional resistance”.)
In the antifouling paint composition according to the present invention, the hydrophobic material (C) contains at least one selected from silicone oil, fluorine oil and paraffins. It is preferable from the viewpoint that the soiling is more excellent.

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

The antifouling coating film used for the special frictional resistance reducing ship according to the present invention is formed from the antifouling coating composition (also referred to as a first coating film).
As for the surface shape of the antifouling coating film according to the present invention, 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 μm or less, and in accordance with JIS B 0601. It is preferable from the viewpoint of more effectively reducing the frictional resistance that the average interval between the peaks and valleys, which is the average of the length of one convex and one concave adjacent to it, is 700 μm or more.

The antifouling coating film according to the present invention has a static underwater bubble contact angle of less than 90 degrees as measured by the following static underwater bubble contact angle measurement method, and is measured by the underwater bubble rolling (slip) angle measurement method. The underwater bubble rolling (sliding) angle is preferably less than 30 degrees from the viewpoint of more effectively reducing the frictional resistance.
<Measurement method of static underwater bubble contact angle>
A hard polyvinyl chloride test plate (maximum height measured in accordance with JIS B 0601 of 1 μm or less) coated with a coating composition so that a coating film having a dry film thickness of 150 μm is formed at 25 ° C. for 30 days. Immerse in water and place the hard polyvinyl chloride test plate 30 days after immersion in water so that the coating surface is horizontal and below the test plate, so that one bubble is formed on the coating surface 0.1 cc of air was injected into the water, and the height a of the bubbles formed on the coating surface from the coating surface and the diameter b of the contact portion between the coating surface and the bubbles were measured. From the following equation (1), a static underwater bubble contact angle (θ _s , unit: degree) which is a contact angle between the coating film surface and bubbles is obtained.

<Measurement of underwater bubble rolling (slip) angle>
In the method for measuring the static underwater bubble contact angle, an underwater bubble having an inclination angle with respect to a horizontal plane of a coating film surface when bubbles are gradually tilted with respect to the horizontal plane and the bubble starts to move. Measure the rolling (sliding) angle (θ _m , unit: degree).

The special frictional resistance reduction ship according to the present invention is characterized in that the submerged surface of the ship outer plate is covered with the antifouling coating film (also referred to as a first special frictional resistance reduction ship).
The first method for producing a special frictional resistance-reducing ship according to the present invention is characterized in that the antifouling coating film is formed on a planned submerged surface of the outer plate of the ship to be painted.

A frictional resistance reduction system according to the present invention includes the above-described coating film (first coating film) and a gas supply device that supplies a gas such as air to the surface of the coating film (first). Also called a frictional resistance reduction system.

The special frictional resistance reduction ship according to the present invention includes the first frictional resistance reduction system (also referred to as a third special frictional resistance reduction ship).
The coating composition according to the present invention is used for a ship with reduced frictional resistance utilizing a gas lubrication function in water, and the static underwater bubble contact angle measured by the following static underwater bubble contact angle measurement method is less than 90 degrees. In addition, a coating film having an underwater bubble rolling (sliding) angle of less than 30 degrees measured by a method for measuring an underwater bubble rolling (sliding) angle can be formed (also referred to as a second coating composition).

<Measurement method of static underwater bubble contact angle>
A hard polyvinyl chloride test plate (maximum height measured in accordance with JIS B 0601 of 1 μm or less) coated with a coating composition so that a coating film having a dry film thickness of 150 μm is formed at 25 ° C. for 30 days. Immerse in water and place the hard polyvinyl chloride test plate 30 days after immersion in water so that the coating surface is horizontal and below the test plate, so that one bubble is formed on the coating surface 0.1 cc of air was injected into the water, and the height a of the bubbles formed on the coating surface from the coating surface and the diameter b of the contact portion between the coating surface and the bubbles were measured. From the following equation (1), a static underwater bubble contact angle (θ _s , unit: degree) which is a contact angle between the coating film surface and bubbles is obtained.

<Measurement of underwater bubble rolling (slip) angle>
In the method for measuring the static underwater bubble contact angle, an underwater bubble having an inclination angle with respect to a horizontal plane of a coating film surface when bubbles are gradually tilted with respect to the horizontal plane and the bubble starts to move. Measure the rolling (sliding) angle (θ _m , unit: degree).

  The antifouling coating film according to the present invention has a maximum height measured in accordance with JIS B 0601 of 30 μm or less and an average interval between peaks and valleys measured in accordance with JIS B 0601 of 700 μm or more. From the viewpoint of more effectively reducing frictional resistance.

The said coating film which concerns on this invention is formed with the coating composition used for a special frictional resistance reduction ship (it is also called 2nd coating film).
The special frictional resistance-reducing ship according to the present invention has the coating film on the submerged surface of the ship's outer plate (also referred to as a second special frictional resistance-reducing ship).

A frictional resistance reduction system according to the present invention includes the above-described coating film (second coating film) and a gas supply device that supplies a gas such as air to the surface of the coating film (first) This is also called the second frictional resistance reduction system).

The special frictional resistance reduction ship according to the present invention includes a second frictional resistance reduction system (also referred to as a fourth special frictional resistance reduction ship).
The second method for manufacturing a special frictional resistance reducing ship according to the present invention is characterized in that the coating film is formed on a planned submerged surface of the outer plate of the ship to be painted.

The method for predicting the frictional resistance reduction effect using the gas lubrication function in water of the coating film according to the present invention measures the static underwater bubble contact angle by the following static underwater bubble contact angle measurement method, and Underwater bubble rolling (sliding) angle is measured by measuring the underwater bubble rolling (sliding) angle. From the static underwater bubble contact angle and underwater bubble rolling (sliding) angle, the film can be lubricated in water. It is characterized by predicting the frictional resistance reduction effect used.
<Measurement method of static underwater bubble contact angle>
The test plate coated with the coating composition is immersed in water so that a coating film is formed, and the immersed test plate is placed in water so that the coating surface is horizontal and below the test plate. Air is injected into water so that bubbles are formed on the coating surface, and the height a of the bubbles formed on the coating surface from the coating surface and the contact portion between the coating surface and the bubbles are The diameter b is measured, and the static underwater bubble contact angle (θ _s , unit: degree), which is the contact angle between the coating film surface and the bubble, is obtained from the following formula (1).

<Measurement of underwater bubble rolling (slip) angle>
In the method for measuring the static underwater bubble contact angle, an underwater bubble having an inclination angle with respect to a horizontal plane of a coating film surface when bubbles are gradually tilted with respect to the horizontal plane and the bubble starts to move. Measure the rolling (sliding) angle (θ _m , unit: degree).

  The apparatus used for predicting the frictional resistance reduction effect using the gas lubrication function in water of the coating film according to the present invention is an apparatus comprising a test bench, an inclination angle control device, an immersion vessel, and an observation device. The tilt angle control device is connected to the test stand, and the test stand is mounted so that the test plate having the coating film formed on the surface thereof is in contact with the lower surface of the test stand. The test plate is immersed in the immersion container containing water, and is installed in a state where bubbles are formed on the coating film surface of the test plate. The observation device includes the test plate and the bubbles. The state of bubbles formed on the surface of the coating film on the test plate when the test plate is horizontal is observed with the observation device, and the static underwater bubble contact angle is determined. Measure and tilt the test plate with respect to the horizontal using the tilt angle control device. By observing the behavior of the bubbles by the microscopy apparatus, and measuring the coating rolling water bubbles bubbles was formed on the surface of the membrane (slip) angle of the test plate.

  Since the antifouling paint composition used in the special frictional resistance-reducing ship of the present invention is blended with specific components, the frictional resistance against the submerged surface of the ship's outer plate (hereinafter referred to as “low-gas”) can be efficiently supplied even with a small amount of gas supply. In other words, it is possible to form a coating film that can reduce the frictional resistance of the hull. And since the coating film formed from the antifouling paint composition contains a specific hydrophobic material, it can exhibit excellent antifouling properties and prevent the attachment of underwater organisms, The increase in the frictional resistance of the hull due to the adhesion of the hull can be prevented. And the coating film formed from this antifouling coating composition can maintain those effects over a long period of time.

  When the hydrophobic material (C) blended in the antifouling paint composition used for the special friction resistance-reducing ship of the present invention contains at least one selected from silicone oil, fluorine-based oil and paraffins, The dirty paint composition can form a coating film exhibiting higher antifouling performance, and as a result, the friction reducing effect of the coating film is maintained for a longer period of time. When the antifouling coating composition contains an antifouling agent (D), the effect is further increased.

  The surface shape of the antifouling coating film of the present invention has a maximum height of 30 μm or less from the bottom of the concave portion to the top of the convex portion measured in accordance with JIS B 0601, and is measured in accordance with JIS B 0601. In addition, since the average interval between the peaks and valleys, which is the average of the length of one convex and one concave adjacent to it, is 700 μm or more, the retention force of the bubbles and / or the gas layer is high. Since the peeling and dropping of the hull are difficult to occur, the frictional resistance of the hull can be stably reduced over a long period.

  The first special frictional resistance reducing ship in which the submerged surface of the ship outer plate of the present invention is coated with the antifouling coating film formed from the antifouling paint composition is formed from the above antifouling paint composition. Since it has an antifouling coating film, even if a small amount of gas is supplied to the outer skin of the ship, a high water frictional resistance reduction effect can be achieved and the effect can be stably achieved over a long period of time.

  The first method for producing a ship with reduced special frictional resistance according to the present invention provides the above-described effect by a simple method of forming an antifouling coating film formed from the antifouling paint composition on the submerged surface of the ship outer plate. A specific ship can be manufactured.

  Since the coating composition used in the special frictional resistance reducing ship of the present invention can form a coating film having a static underwater bubble contact angle of less than 90 degrees and a bubble rolling (slip) angle of less than 30 degrees in water. And / or the gas layer flows without stagnation while in sufficient contact with the coating. Therefore, in the (second) special frictional resistance reduced ship having the coating film formed on the submerged surface of the outer plate, an efficient gas lubrication effect is exhibited, and the frictional resistance of the hull is supplied even if the amount of air supplied is small. Is effectively reduced and the energy-saving effect is great.

  In the second method for manufacturing a ship with reduced frictional resistance according to the present invention, the coating film is formed on the submerged planned surface of the outer plate of the ship to be coated. The frictional resistance against the submerged surface of the plate can be efficiently reduced, and a special frictional resistance-reducing ship with a large energy saving effect can be manufactured.

  The method of predicting the frictional resistance reduction effect of the coating film of the present invention utilizing the gas lubrication function in water measures the static contact angle and rolling (slip) angle of bubbles formed on the surface of the coating film in water. This can be done. That is, when the static contact angle and rolling (slip) angle of the bubbles formed on the surface of the coating film in water are within a specific range, the frictional resistance is reduced by utilizing the gas lubrication function in water. It can be predicted that the effect is excellent.

  Further, the method for predicting the frictional resistance reduction effect of the present invention can only evaluate the ease of formation of bubbles in water from the measurement results of the static contact angle and rolling (slip) angle of the bubbles in the coating film in water. In addition, it is possible to observe the state and behavior of bubbles in actual water (for example, ease of flow of bubbles with respect to the paint).

The above prediction method of the present invention is superior to the prior art method in that it can evaluate the hydrophobicity of the coating film from the contact angle but cannot evaluate the behavior of bubbles in water.
The apparatus used for predicting the frictional resistance reduction effect using the gas lubrication function in water of the coating film of the present invention does not require a complicated apparatus configuration, and the operation is simple, static underwater bubble contact angle and bubble rolling. Since the (slip) angle can be measured, it can be suitably used for prediction of the frictional resistance reduction effect as described above.

The first and second frictional resistance reduction systems used in the frictional resistance reduction ship utilizing the gas lubrication function in water of the present invention are the first or second coating film as described above, and the surface of the coating film. And a gas supply device for supplying a gas such as air to the friction resistance reduction system used in a friction resistance reduction ship using a gas lubrication function in water that exhibits an excellent friction resistance reduction effect. Can be provided. Therefore, the affinity of gas such as air in water is maintained for a long period of time, and the effect of reducing fluid friction resistance is great without introducing large power into the gas supply, which is economical and has little impact on the environment.

Since the 3rd and 4th special frictional resistance reduction ship of this invention comprises a frictional resistance reduction system, it exhibits the outstanding frictional resistance reduction effect. Therefore, the affinity of gas such as air in water is maintained for a long period of time, and the effect of reducing fluid friction resistance is great without introducing large power into the gas supply, which is economical and has little impact on the environment.

FIG. 1 is a schematic view of a contact angle measuring device used for predicting a frictional resistance reduction effect by measuring a static underwater bubble contact angle or underwater bubble rolling (slip) angle. FIG. 2 is a schematic explanatory diagram showing how to obtain the static underwater bubble contact angle in the static underwater bubble contact angle measurement method. FIG. 3 is a schematic explanatory diagram showing a method for measuring the underwater bubble rolling (slip) angle. FIG. 4 is a schematic view of a model ship used for measurement of water friction resistance. FIG. 5 is a view showing the relationship between the equivalent air thickness and the frictional resistance reduction rate (comparison between before immersion and after 30 days of immersion).

Below, for convenience, the present invention is roughly classified into three groups as follows, and the best mode will be specifically described in order for each group.
First group: Antifouling paint composition (first paint composition) used for ships with reduced special frictional resistance, antifouling paint film (first paint film) formed from the composition, first paint A ship covered with a film (first special frictional resistance reducing ship) and a manufacturing method of the first ship.

  Second group: paint composition (second paint composition) used for ships with reduced special frictional resistance, paint film (second paint film) formed from the composition, ship coated with the paint film (second paint composition) Second special frictional resistance reduction ship), method for producing the second ship, method for predicting the frictional resistance reduction effect using the gas lubrication function of the coating film in water, and the prediction of the frictional resistance reduction effect apparatus.

  Third group: Friction resistance reduction system (first and second friction resistance reduction systems) used in a frictional resistance reduction ship using a gas lubrication function in water and a special frictional resistance reduction ship (third) And the fourth special frictional resistance reduction ship).

Note that various characteristic measurements described below are performed at normal pressure (about 0.1013 MPa) and temperature conditions at room temperature (about 25 ° C.) unless otherwise specified.
Moreover, the 1st, 2nd, 3rd, 4th special frictional resistance reduction ship which concerns on this invention is common in the following points.

In order to reduce the water flow frictional resistance by the gas lubrication function, it is necessary that the bubbles and / or the gas layer are sufficiently in contact with the surface (the submerged surface of the ship outer plate) in contact with the water flow of the special frictional resistance reduced ship.

Here, in this specification, “water” includes seawater, river water, lake water, and the like in addition to fresh water.
Moreover, in this specification, "gas" comprehensively represents gas which does not damage a ship, such as air, nitrogen gas, carbon dioxide gas, oxygen gas and hydrogen gas. Air is particularly preferred from the viewpoint of environmental impact and cost.

1. First group
In the first special frictional resistance reduction ship according to the present invention, for example, a specific organopolysiloxane (A), a specific hydrophobic material (C), and a specific organosilane and / or a partial condensation thereof as necessary. An antifouling coating film formed from a special resistance-reducing marine antifouling paint composition containing a specific amount of the product (B) is formed on the submerged portion of the outer plate.

Moreover, the coating film which has various characteristics, such as the above-mentioned friction reduction characteristic, can be formed by using such a special resistance reduction marine antifouling paint composition.
1-1. Antifouling paint composition having a specific composition The antifouling paint composition according to the present invention is formulated with compounds having a polysiloxane skeleton structure, and the characteristic leveling properties of these compounds are formed from the antifouling paint composition. It is inferred that it affects the shape of the coated film. Therefore, it is speculated that the antifouling paint composition according to the present invention can form a coating film having a roughness height of 30 μm or less and an average interval between peaks and valleys of 700 μm or more, as will be described later. In addition, the antifouling paint composition according to the present invention can form a coating film having such a shape, which is very useful for exhibiting gas lubrication performance such as gas retention and gas fluidity on the coating film surface. It is presumed that an antifouling coating film having a small static underwater bubble contact angle in water of usually less than 90 degrees and a bubble rolling (slip) angle of usually less than 30 degrees in water can be formed.

  As will be described later, the hydrophobic material (C) in the antifouling coating composition is present in the cured coating film in the form of a filler. The hydrophobic material (C) gradually bleeds out to cover the coating film surface during the navigation of the ship in which the cured coating film is formed on the submerged surface of the outer plate. Since this hydrophobic material is liquid or grease-like at 25 ° C., for example, it can improve the surface lubricity like a lubricant and prevent the adhesion of microorganisms in the water, etc. Dirty is imparted.

Hereinafter, each component in the antifouling coating composition will be described.
1-1-1. Reaction-curing organopolysiloxane (A)
The reaction curable organopolysiloxane (A) has a viscosity at 25 ° C. of 20 to 400,000 mm ² / s.

  Here, the reaction-curable organopolysiloxane is an organopolysiloxane having at least two condensable reactive groups in one molecule, preferably an organopolysiloxane having at least two condensable reactive groups at both ends. Yes, it can be cured by a curing reaction only with the organopolysiloxane, or it cannot be cured only with the organopolysiloxane, but by a curing reaction with a compound such as an organosilane and / or a partial condensate thereof (B) described later. An organopolysiloxane that can be cured.

  Both ends of the molecule refer to the two ends of the main chain, and the condensable reactive group is usually a hydroxy group or a hydrolyzable group, and the two end groups may be the same or different. Good. In addition to the hydroxy group and hydrolyzable group present at both ends of the molecule, the main chain or side chain may have a functional group that reacts with an organosilane and / or its partial condensate (B) described later. . Having at least two condensable reactive groups at both ends means, in other words, having at least one condensable reactive group at each of the two ends.

Specific examples of the hydrolyzable group are the same as the specific examples of X in X _3-b R ³ _b SiO (R ¹ R ² SiO) _m R ³ _b SiX _3-b as organopolysiloxane (A) described later. It is.
Further, from the viewpoint that it can be reacted with an organosilane and / or its partial condensate (B) described later, the hydrolyzable group of the organopolysiloxane (A) is an organosilane and / or its partial condensation described below. It is preferable that they are the same as the hydrolyzable group of the product (B).

The viscosity is 25 to 200,000 mm ² / s from the viewpoint of curability, coating strength such as rubber strength of a cured coating film, thickening and handling properties, and prevention of sagging when the resulting composition is diluted with a solvent. It is preferable that it is 500 to 100,000 mm ² / s.

In the present specification, the viscosity is measured using a capillary viscometer (Ubbelohde viscometer) according to “JIS Z 8803 liquid viscosity—measurement method”.
Examples of the organopolysiloxane (A) include organopolysiloxanes 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 having 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 above viscosity range. It is in.

Other are represented by ^{_{X 3-b R 3 b SiO}} (R 1 R 2 SiO) m R 3 b SiX 3-b, organopolysiloxanes having a hydrolyzable group at the terminal of the molecule. R ¹ and R ² are the same as in the above structural formula, R ³ is a monovalent hydrocarbon group similar to R ¹ and R ² , X is the following hydrolyzable group, b is 0, 1 or 2 And m is a positive number corresponding to the degree of polymerization and is in a range satisfying the above viscosity range.

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

  As the alkoxy group, those having 1 to 10 carbon atoms are desirable, and one or more oxygen atoms may be interposed between carbon atoms. For example, methoxy group, ethoxy group, propoxy group, butoxy group, A methoxyethoxy group, an ethoxyethoxy group, etc. are mentioned.

As the acyloxy group, an aliphatic group or an aromatic group represented by the formula: R ⁴ COO— (wherein R ⁴ is an alkyl group having 1 to 10 carbon atoms and an aromatic group having 6 to 12 carbon atoms) is used. Desirable examples include an acetoxy group, a propionoxy group, a butyroxy 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. The iminoxy group (= N-OH, oxyimino group, ketoxime group) is preferably one having about 3 to 10 carbon atoms, for example, a ketoxime group, a dimethyl ketoxime group, a methyl ethyl ketoxime group, a diethyl ketoxime group, A cyclopentanoxime group, a cyclohexanoxime group, etc. are mentioned.

  The amino group is preferably one having 1 to 10 carbon atoms, for example, N-methylamino group, N-ethylamino group, N-propylamino group, N-butylamino group, N, N-dimethylamino group, N , N-diethylamino group, cyclohexylamino group and the like. The amide group preferably has 2 to 10 carbon atoms, and examples thereof include an N-methylacetamide group, an N-ethylacetamide group, and an N-methylbenzamide group.

The aminooxy group preferably has 2 to 10 carbon atoms in total, and examples thereof include an N, N-dimethylaminooxy group and an N, N-diethylaminooxy group.
R ¹ , R ² and R ³ each 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. Examples of such monovalent hydrocarbon groups include alkyl groups, alkenyl groups, aryl groups, cycloalkyl groups, aralkyl groups, and the like.

  The alkyl group may be any type of linear, branched or alicyclic alkyl group, and the linear or branched alkyl group having 1 to 10, preferably about 1 to 8 carbon atoms. A cycloalkyl group having 3 to 6 carbon atoms is preferred. Examples of such linear or branched alkyl groups include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, 2-ethylbutyl group and octyl group, particularly preferably methyl group. Examples of the cyclic alkyl group include 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 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, a diphenyl group, and the like, and a phenyl group is particularly preferable.

  As a cycloalkyl group, a C3-C8 thing is desirable, for example, a cyclohexyl group etc. are mentioned. The aralkyl group preferably has a total carbon number of 7 to 10, preferably about 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 halogen atoms such as F, Cl, Br, and I, cyano groups, etc. Examples of halogenated alkyl groups include: Examples include chloromethyl group, 3,3,3-trifluoropropyl group, 2-cyanoethyl group and the like.

R ¹ , R ² and R ³ are preferably an unsubstituted monovalent hydrocarbon group, particularly preferably a methyl group or a phenyl group. In the case where a plurality of R ³ , a plurality of R ¹ , and R ² are present in the organopolysiloxane having a hydrolyzable group at the molecular end represented by the above formula, the plurality of R ³ , A plurality of R ¹ , R ² , or R ³ and R ¹ , R ² may be the same or different from each other.

Further, as described above, the reaction-curable organopolysiloxane (A) reacts with the organosilane and / or its partial condensate (B) described later in addition to the hydroxy group and hydrolyzable silyl group present at both ends of the molecule. May be present in the main chain or side chain, 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 A compound in which R ¹ , R ² and R ³ in SiX _3-b are a functional group that reacts with the aforementioned organosilane and / or its partial condensate (B) can also be used as the organopolysiloxane (A).

  Examples of such organopolysiloxane (A) include dimethylpolysiloxane having both ends of molecular chains sealed with silanol groups (for example, trade name “XF3905”, manufactured by Momentive), deoxime-type organopolysiloxane (for example, Trade name “KE-445”, manufactured by Shin-Etsu Chemical Co., Ltd.).

  The organopolysiloxane (A) is preferably self-condensable from the viewpoints of cost reduction and handling of the coating composition, and is self-condensable near room temperature (usually about 10 ° C. to 30 ° C., the same applies hereinafter). It is more preferable.

  Among the organopolysiloxanes (A) exemplified above, dimethylpolysiloxane (for example, trade name “XF3905” manufactured by Momentive Co., Ltd.) in which both ends of the molecular chain are sealed with silanol groups, deoxime-type organopolysiloxane (For example, trade name “KE-445”, manufactured by Shin-Etsu Chemical Co., Ltd.) is a self-condensable polysiloxane.

These organopolysiloxanes (A) may be blended singly or in combination of two or more in the antifouling paint composition used in a ship with reduced frictional resistance.
1-1-2. Specific organosilane and / or its partial condensate (B)
Component (B) is an organosilane having at least two of at least one of a hydroxy group and a hydrolyzable group in one molecule and / or a partial condensate thereof.

Only one of the hydroxy group and the hydrolyzable group may be present in the organosilane, or two or more in combination.
The component (B) desirably functions as a crosslinking agent for the organopolysiloxane (A) from the following viewpoints.

Organosilane and / or its partial condensate (B) are optional components and may be blended into the antifouling coating composition as necessary.
When the organopolysiloxane (A) is cured by a condensation reaction between the organopolysiloxanes (A) (ie, by self-condensation), the organosilane and / or its partial condensate (B) At least, a cured coating film having excellent hardness can be obtained from the antifouling coating composition. However, when organosilane and / or its partial condensate (B) are blended, the curing speed, the degree of curing of the coating film, etc. There is an advantage that can be controlled more accurately.

In this case, room temperature vulcanization is possible when the organopolysiloxane (A) is self-condensing at around room temperature with a catalyst or the like.
Even if organopolysiloxane (A) does not self-condense at around room temperature, it can be mixed with organosilane and / or its partial condensate (B) at room temperature at the time of application of antifouling paint. Utilizing a hydrolysis reaction with water such as moisture in the interior, a condensation reaction between organopolysiloxane (A) and organosilane and / or its partial condensate (B) is caused, and a cured coating film is formed even at around room temperature. There is also an advantage that it can be obtained.

  When the organopolysiloxane (A) is not self-condensed, organosilane having a functional group that undergoes a condensation reaction with the condensation-reactive functional group of the organopolysiloxane that does not self-condense and / or a partial condensate thereof ( It is desirable to blend B) from the viewpoints of the curing speed and the degree of curing of the resulting coating film.

  The hydrolyzable group of the organosilane and / or its partial condensate (B) used in the present invention is a functional group capable of undergoing a condensation reaction with the condensable reactive group of the reaction-curable organopolysiloxane (A). As this component (B), an organosilane represented by the following general formula (α) can be used.

In the general formula (α), R ⁵ may be the same or different from each other, and represents a hydroxyl group, a hydrolyzable group, or a monovalent hydrocarbon group having 1 to 8 carbon atoms. However, at least one of R ^{5 at} both ends is a hydroxy group or a hydrolyzable group at each end (both are two or more hydroxy groups and / or hydrolyzable groups at both ends). At least two, preferably three or more of R ⁵ , including the hydroxyl groups and / or hydrolyzable groups at both ends, are condensation-reactive groups. 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 general formula (α) include a substituted or unsubstituted alkyl group, alkenyl group, aryl group, cycloalkyl group, and aralkyl group. Examples of the hydrolyzable group in the general formula (α) include X _3-b R ³ _b SiO (R ¹ R ² SiO) _m R ³ _b SiX _3- mentioned as an example of the reaction-curable organopolysiloxane (A). _Although the same thing as the case of the hydrolysable group among X of _b is mentioned, Especially, an oxime group, an acetyloxy group, or an alkoxy group is preferable.

  In addition, for example, an organosilane in which a hydrolyzable group such as the acetyloxy group or alkoxy group is partially hydrolyzed can be used as the component (B) (that is, it has two or more hydrolyzable groups). A partially hydrolyzed condensate of organosilane can be used as the component (B)).

  Alternatively, an organosilane partially dehydrated and condensed between at least two hydroxy groups can also be used as the component (B) (that is, a partial condensate of an organosilane having two or more hydrolyzable groups is used as the above component (B). Can be used as component (B)).

In the present invention, in particular, the above-mentioned alkoxysilane-containing organosilane, that is, alkoxysilane (alkyl silicate) or a partial condensate thereof can be suitably used.
Examples of the alkoxysilane include tetraalkylorthosilicate (alkyltetraalkoxysilane) such as tetraethylorthosilicate (TEOS), or alkyltrialkoxysilane such as methyltrimethoxysilane, ethyltrimethoxysilane, and methyltriethoxysilane. Can be mentioned. As the alkoxysilane, alkyltetraalkoxysilane and alkyltrialkoxysilane are more preferable from the viewpoint of curability of the resulting cured coating film.

  In particular, when an organopolysiloxane having hydroxyl groups at both ends is used as the component (A), it is preferable to use these alkyl silicates (alkoxysilanes) and / or partial condensates thereof in combination as the component (B). As such organosilane and / or its partial condensate (B), those marketed can be used. For example, “ethyl silicate 28” (manufactured by Colcoat Co.) and “normal ethyl silicate” (manufactured by Tama Chemical Industry) are used as tetraethyl orthosilicate, and “silicate 40” (manufactured by Tama Chemical Industry Co., Ltd.) is used as a partial hydrolyzate of tetraethyl orthosilicate. ), “TES40 WN” (manufactured by Asahi Kasei Wacker Silicone), and alkyltrialkoxysilanes include “KBM-13” (manufactured by Shin-Etsu Chemical Co., Ltd.).

  The organosilane and / or the partial condensate thereof (B) can be used in a total amount of 1 to 60 parts by weight with respect to 100 parts by weight of the organopolysiloxane (A). From the viewpoint of the physical properties of the film, it is usually desirable to be contained in the antifouling coating composition in an amount of 1 to 20 parts by weight, preferably 2 to 10 parts by weight.

  These organosilanes and / or partial condensates thereof (B) are blended in an antifouling coating composition used for ships with reduced frictional resistance, either of organosilanes or their partial condensates alone. Alternatively, both of them may be blended. Moreover, about each of organosilane and its partial condensate, it can also mix | blend individually by 1 type or in mixture of 2 or more types.

1-1-3. Hydrophobic material (C)
Component (C) is a hydrophobic material that is liquid or grease-like at 25 ° C.
As the hydrophobic material (C), any of silicone oil, fluorine-containing silicone oil, fluorine-based oil, paraffins, wax and the like may be used as long as it is liquid or grease-like 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 non-reactive (non-condensable) silicone oil or a silicone oil that bleeds out from a cured product of an antifouling coating composition used in ships with reduced special frictional resistance. Silicone oils represented by [I] and [II] and silicone oils having a group represented by the following formula [III] are preferred.

  Of these silicone oils, silicone oils [I] and [II] do not exhibit reactivity or self-condensation with organopolysiloxane (A) or the like and bleed out without any particular chemical change. Thus, it is considered that the antifouling functional layer (film) is formed on the coating film surface (layer).

On the other hand, silicone oil [III] reacts with organopolysiloxane (A) or the like as a coating film forming component to form a cured coating film, and is hydrolyzed over time when immersed in seawater for a long time. It is considered that the terminal group becomes a group “≡SiR ⁸ OH” having an alcoholic hydroxyl group, and the like, bleeds out to the surface of the coating film and exhibits an effect of preventing the adhesion of marine organisms.

(In the formula [I], a plurality of R ^{6 s} may be the same or different from each other and represent an alkyl group, aryl group, aralkyl group or fluoroalkyl group having 1 to 10 carbon atoms, and a plurality of R ^{7 s} are the same Or 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 from 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 represents an unsubstituted or substituted monovalent hydrocarbon group, and Y represents a hydrolyzed group. A decomposable group, b is 0, 1 or 2)

(In the formula [II], R ¹⁰ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group, and R ¹¹ has an ether group, an ester group or —NH— interposed therebetween. Represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and Z may be blocked with an amino group, a carboxyl group, an epoxy group, or an alkyl group or acyl group having 1 to 6 carbon atoms. 1 represents a monovalent polar group that is a polyethylene glycol or polypropylene glycol group, and x and y are 0.01 ≦ x <3.99, 0.01 ≦ y <3.99, and 0.02 ≦ x + y <4.)

Among the silicone oils, as the silicone oil [I], 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 The viscosity is 1,000 to 10,000, and the viscosity measured with the Ubbelohde viscometer is 20 to 30,000 mm ² / s, preferably 50 to 3,000 mm ² / s.

Examples of such silicone oil [I] include, for example, dimethyl silicone oil in which all of R ⁶ and R ⁷ are methyl groups, and phenylmethyl silicone in which a part of the methyl groups of these dimethyl silicone oils are substituted with phenyl groups. Examples of the oil include methylphenyl silicone oil. Specifically, as such methylphenyl silicone oil, for example, “KF-54, KF-56, KF-50” (manufactured by Shin-Etsu Chemical Co., Ltd.), “SH510, SH550” (manufactured by Toray Dow Corning Silicone Co., Ltd.) ), “TSF431, TSF433” (manufactured by Toshiba Silicone Co., Ltd.), etc.

Further, as the silicone oil having a group represented by the above formula [III] (silicone oil [III]), those described in Japanese Patent No. 2522854 proposed by the applicants of the present application can be used. The measured number average molecular weight is 250 to 20,000, preferably 1,000 to 10,000, and the viscosity measured by the above method is 20 to 30,000 mm ² / s, preferably 50 to 3000 mm ² / s. Is desirable.

Specific examples of R ⁸ include unsubstituted or substituted divalent hydrocarbon groups such as a methylene group, an ethylene group, a propylene group, a butylene group, and a hexamethylene group; or “— (CH ₂ ) _p -O- (CH _{2) q} - "(wherein, p, q can be mentioned each independently represent an integer of 1-6) divalent hydrocarbon group containing an ether bond represented by like..

R ⁹ represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms. Y is a group similar to the hydrolyzable group X of X _3-b R ³ _b SiO (R ¹ R ² SiO) _m R ³ _b SiX _3-b mentioned as an example of the reaction-curable organopolysiloxane (A). Indicates. Specific examples of the silicone oil [III] having at least one group represented by the formula [III] include (CH ₃ ) ₃ as described in the above-mentioned Japanese Patent No. 2522854. 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 Examples include those obtained by blocking the hydroxyl group of silicone oil represented by [(CH ₃ ) (C ₃ H ₆ —OH) SiO] _j [(CH ₃ ) ₂ SiCH ₃ ] with a hydrolyzable group. In the above formulas, R ¹² and R ¹³ are each an aryl group such as a phenyl group or a tolyl group; an aralkyl group such as a benzyl group or a β-phenylethyl group; a halogenated alkyl group such as a trifluoropropyl group; Thus, an unsubstituted or substituted monovalent hydrocarbon group in which at least one of R ¹² and R ¹³ is selected from a group other than a methyl group can be mentioned. h, i, and j all represent positive numbers.

In addition, from the viewpoint of storage stability of the resulting composition, as exemplified below, the above silicone oil is represented by the formula: “R ⁹ _b SiY _3-b ” (R ⁹ , Y, and b are represented by the formula [III]. It may be the same as in the case of the above)).

For example, (CH ₃ ) ₃ SiO [(CH ₃ ) ₂ SiO] _h [R ¹² R ¹³ SiO] _i (CH ₃ ) ₂ SiC ₃ H ₆ —O—R 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 —O—R 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 —O—R ⁹ _b SiY _3-b ) SiO] _l [(CH ₃ ) ₂ SiCH ₃ ] and the like.

As the silicone oil [II], specifically, those described in JP-A-10-316933 can be used, and the number average molecular weight measured by GPC method is 250 to 30,000, preferably 1, The viscosity is 000 to 20,000, and the viscosity measured by the above method is 20 to 30,000 mm ² / s, preferably 50 to 3,000 mm ² / s.

As such a silicone oil [II], preferably, in the above formula [II], R ¹⁰ is a methyl group or a phenyl group, and R ¹¹ is a methylene group, an ethylene group or a propylene group. . In addition, as Z, when the terminal is a polyethylene glycol or polypropylene glycol group which may be blocked with an alkyl group or an acyl group having 6 or less carbon atoms, the number of oxyethylene and oxypropylene as a repeating unit is 10 to 60. Is preferred. Examples of the alkyl group for end-capping include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the acyl group for end-capping include a ketoxime group, an acetyl group, and a propionyl group. .

  Specifically, as silicone oils in which the polar group Z is an amino group, “SF8417” (manufactured by Toray Dow Corning), “ISI4700, ISI4701” (manufactured by Toshiba Silicone), “FZ3712, AFL-40” (Japan) Unicar) and the like. 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 Toray Dow Corning Silicone), “FXZ4707” (manufactured by Nihon Unicar), and the like. . Silicone oils whose polar groups are epoxy groups include “SF8411” (manufactured by Toray Dow Corning Silicone), “XI42-301” (manufactured by Toshiba Silicone), “L-93, T-29” (Nihon Unicar Company). Manufactured) and the like. Examples of the silicone oil in which the polar group Z is an alkyl group or an acyl group include “ISI4460, ISI4445, ISI4446” (manufactured by Toshiba Silicone), “SH3746, SH8400, SH3749, SH3700” (manufactured by Toray Dow Corning Silicone), “KF6009”. (Shin-Etsu Chemical Co., Ltd.).

<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 (manufactured by Shin-Etsu Chemical Co., Ltd .; side chain type fluoroalkyl-modified silicone oil).

<Fluorine oil>
Examples of the fluorinated oil include demnum S-65 (manufactured by Daikin Industries, Ltd .; perfluoropolyether oil).

<Paraffins or wax>
Examples of paraffins or waxes include Sumoyle P-350 (manufactured by Matsumura Oil Co., Ltd .; liquid paraffin).

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

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

These hydrophobic materials (C) may be blended singly or in combination of two or more in the antifouling paint composition used in the special frictional resistance-reducing ship.
1-2. Manufacture of antifouling paint composition used for ship with reduced special friction resistance Such antifouling paint composition used for ship with reduced special friction resistance according to the present invention can be manufactured by the following method. First, if necessary, a part or all of the organopolysiloxane (A) and the later-described hydrophilic silica, or both hydrophilic silica and hydrophobic silica are heated at 100 ° C. or higher under normal pressure or reduced pressure. The heat treatment is usually performed for about 30 minutes to 3 hours at a temperature equal to or lower than the decomposition temperature of the blended components, preferably about 100 to 300 ° C, more preferably about 140 to 200 ° C. Next, when hydrophilic silica or hydrophobic silica is used, the remaining organopolysiloxane (A), hydrophilic silica, or both hydrophilic silica and hydrophobic silica, and if necessary, organosilane and / or Or in addition to the partial condensate (B), it can manufacture by mix | blending hydrophobic material (C) further. When no hydrophilic silica or hydrophobic silica is used, in addition to the organopolysiloxane (A) and, if necessary, the organosilane and / or its partial condensate (B), a hydrophobic material (C) is further added. It can manufacture by mix | blending. In any case, conventionally known organosiloxane curing catalysts, antifouling agents, thixotropy imparting agents, plasticizers, inorganic dehydrating agents (stabilizers), sagging and anti-settling agents (thickening agents), pigments and dyes , Other film forming components, solvents (eg xylene), bactericides, fungicides, anti-aging agents, antioxidants, antistatic agents, flame retardants, heat conduction improvers, amino groups, epoxy groups, mercapto groups It is also possible to add an adhesion-imparting agent such as a silane coupling agent having a reactive organic group such as at a predetermined ratio all at once or in any order, and stir and mix to dissolve / disperse in a solvent.

In the case of stirring and mixing the above-described blending components, conventionally known mixing and stirring devices such as a loss mixer, a planetary mixer, and a universal Shinagawa stirrer are appropriately used.
<Optional component>
(catalyst)
As the catalyst, for example, those described in Japanese Patent No. 2522854 can be preferably used. Specifically, for example, tin carboxylates such as tin naphthenate and tin oleate; dibutyltin diacetate, Tin compounds such as dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin dioleate, dibutyltin oxide, dibutyltin dimethoxide, dibutylbis (triethoxysiloxy) tin; tetraisopropoxy titanium, tetra n-butoxy titanium, tetrakis (2-ethylhexoxy) In addition to titanate esters or titanium chelate compounds such as titanium, dipropoxybis (acetylacetonato) titanium, titanium isopropoxyoctyl glycol; etc., zinc naphthenate, zinc stearate, zinc-2-ethyl octoate, iron- 2 Organometallic compounds such as ethylhexoate, cobalt-2-ethylhexoate, manganese-2-ethylhexoate, cobalt naphthenate, alkoxyaluminum compound; 3-aminopropyltrimethoxysilane, N-β (amonoethyl ) Aminoalkyl group-substituted alkoxysilanes such as γ-amonopropyltrimethoxysilane; amine compounds such as hexylamine, dodecyldodecylamine phosphate, dimethylhydroxylamine, diethylhydroxylamine, and salts thereof; and benzyltriethylammonium acetate Quaternary ammonium salts; lower fatty acid salts of alkali metals such as potassium acetate, sodium acetate and lithium odorate; tetramethylguanidylpropyltrimethoxysilane, tetramethylguanidylpropylmethyldimethoxy Orchids, silanes or siloxanes containing tetramethylguanidylpropyltrimethoxysilane (trimethylsiloxy) guanidyl group such as a silane; and the like.

  These catalysts are used in an amount of 10 parts by weight or less, preferably 5 parts by weight or less, and more preferably 1 part by weight or less based on 100 parts by weight of the organopolysiloxane (A). 0.001 part by weight or more, particularly 0.01 part by weight or more.

(Hydrophobic silica, hydrophilic silica)
Silica includes hydrophilic silica (surface untreated silica) such as wet method silica (hydrated silica) and dry method silica (fumed silica, anhydrous silica); surface treatment such as hydrophobic wet silica and hydrophobic fumed silica There is an improved hydrophobic silica.

  These silicas may be used alone or in combination of two or more. When used in combination with hydrophobic silica and hydrophilic silica, it has excellent stability during preparation, storage and storage, has sufficient thixotropy, and can be used for ships with special frictional resistance that can be thickened with a single coating. This is preferable from the viewpoint of obtaining an antifouling coating composition. In addition, the coating film obtained from the antifouling paint composition used in the ship with reduced special frictional resistance has a good balance of rubber properties such as hardness, tensile strength, elongation, etc., and also has excellent antifouling properties. Yes.

  In the present invention, as these silica components, those having the following characteristics may be used as they are, but in a preferred embodiment thereof, from the viewpoint of improving the thixotropy of the paint, the physical properties of the obtained coating film, strength, etc. As will be described in detail later, at least the hydrophilic silica of the hydrophobic silica and the hydrophilic silica is preferably heat-treated together with a part or all of the organopolysiloxane (A). More preferably, both the functional silica and the hydrophobic silica are heat treated together with a part or all of the component (A).

Among these silicas, wet-process silica usually has an adsorbed moisture content (also referred to as moisture content) of about 4 to 8%, a bulk density of 200 to 300 g / L, and a primary particle size of 10 to 10%. The specific surface area (BET surface area) may be 10 m ² / g or more, preferably 50 to 800 m ² / g, and more preferably about 100 to 300 m ² / g.

Dry process silica (fumed silica) usually has a moisture content of 1.5% or less. This dry silica has a low initial moisture content of, for example, 0.3% or less, such as immediately after production. However, the moisture content gradually increases if left untreated, and after several months have passed since production. Then, for example, it becomes about 0.5 to 1.0%. In addition, the bulk density of such dry process silica varies depending on the type and is not unconditionally determined. For example, it is 50 to 100 g / L, the primary particle diameter is 8 to 20 mμ, and the specific surface area (BET surface area) is: 10m may be any ² / g or more, but is preferably 100 to 400 m ² / g, more preferably 180～300M ² / g approximately.

Hydrophobic fumed silica is a surface-treated dry process silica with an organosilicon compound such as methyltrichlorosilane, dimethyldichlorosilane, hexamethyldisilazane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, etc. The water content is usually 0.3% or less, in many cases 0.1 to 0.2%, and the specific surface area may be 10 m ² / g or more, preferably 100 to 300 m ^2. / G, more preferably 120 to 230 m ² / g, the primary particle size is 5 to 50 mμ, and the bulk density is 50 to 100 g / L.

  In addition, in the hydrophobic fumed silica (heat treated hydrophobic fumed silica) heat-treated with the organopolysiloxane (A), the moisture adsorbed on the surface of the hydrophobic silica is physically reduced and removed. The content is usually 0.2% or less, preferably 0.1% or less, particularly 0.05 to 0.1%, and other physical property values such as bulk density are the same as those of the hydrophobic silica.

  Such a silica component is usually 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 desirable that it be contained in an antifouling paint composition used for resistance-reducing ships. When the silica component is contained in such an amount in an antifouling coating composition used for ships with reduced special frictional resistance, it has excellent coating strength and coating hardness, good thixotropy, and moderate viscosity. In addition, it can be applied particularly well by spray coating. For example, even on a vertically upright base material surface or the like, it is preferable because the coating film can be thickened by a single coating.

  If the silica component is less than the above range, sufficient coating strength and coating hardness cannot be obtained, the desired thixotropy cannot be obtained, and the desired film thickness cannot be increased by a single coating, particularly spray coating. In addition, if the silica component is more than the above range, the viscosity of the coating becomes excessively high, and it is necessary to dilute with a solvent such as thinner to an appropriate viscosity suitable for coating. May not be achieved.

  Further, in the present invention, as a silica component, a hydrophobic ratio ((i) / (b)) of hydrophobic silica (b) such as the above-described hydrophobic fumed silica and hydrophilic silica (b) such as untreated surface silica is used. ) Is 1/99 to 99/1, preferably 20/80 to 80/20, particularly preferably 30/70 to 70/30. When hydrophobic fumed silica (I) and hydrophilic silica (B) are used in combination in such a quantitative ratio, the resulting antifouling paint composition used in ships with reduced special frictional resistance can be obtained during preparation, storage and storage. A coating film having excellent coating stability, sufficient thixotropy, and a film obtained by curing the composition tends to be excellent in coating film strength and coating film hardness.

<Anti-fouling agent (D)>
As described above, the antifouling paint composition used in the special frictional resistance reducing ship according to the present invention exhibits excellent antifouling properties by blending the hydrophobic material (C). By further blending the soiling agent (D), more excellent antifouling properties can be exhibited.

The antifouling agent (D) may be either inorganic or organic.
Examples of the inorganic antifouling agent include copper, cuprous oxide, rhodan copper, inorganic copper compounds, etc. Among them, copper and inorganic copper compounds are preferable.

As other organic antifouling agents, metal-pyrithiones represented by the following formula (β) [wherein R ^{14 to} R ¹⁷ each independently represent hydrogen, an alkyl group, an alkoxy group, or a halogenated alkyl group. , M represents a metal such as Cu, Zn, Na, Mg, Ca, Ba, Pb, Fe, Al, and n represents a valence]:

, Tetramethylthiuram disulfide, carbamate compounds (eg, zinc dimethyldithiocarbamate, manganese-2-ethylenebisdithiocarbamate, zincethylenebisdithiocarbamate), 2,4,5,6-tetrachloroisophthalonitrile, N , N-dimethyldichlorophenylurea, 4,5-dichloro-2-n-octyl-3 (2H) isothiazoline, 2,4,6-trichlorophenylmaleimide, 2-methylthio-4-t-butylamino-6-cyclopropyl striazine, 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) pyridine, 3-iodo-2-propynylbutylcarbamate, diiodomethylparatolylsulfone, bisdimethyldithiocarbamoyl zinc ethylenebisdithiocarbamate, pyridine-triphenylborane (PK) ), 4- [1- (2,3-dimethylphenyl) ethyl] -1H-imidazole (medetomidine), and the like.

  Among the organic antifouling agents, copper pyrithione (in formula (β), M = Cu), zinc pyrithione (in formula (β), M = Zn), N, N-dimethyldichlorophenylurea, 2,4,6- Trichlorophenylmaleimide, 2-methylthio-4-t-butylamino-6-cyclopropylstriazine, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2,4,5,6- Tetrachloroisophthalonitrile is preferred.

  Among these organic antifouling agents, metal pyrithiones are particularly preferable. The metal pyrithione 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 are 1 to 150 parts by weight, preferably 1 to 100 parts by weight, based on 100 parts by weight of organopolysiloxane (A). It is desirable to be included in the amount of.

  In the antifouling paint composition used in a special frictional resistance reducing ship containing such an antifouling agent, for example, an inorganic copper compound and / or an organic antifouling agent removes the amount of the solvent from the total amount of the antifouling paint composition. When the amount is 100% by weight, it is usually contained in an amount of 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, polyvinyl ethyl ether, and the like. These plasticizers can be used alone or in combination of two or more. These plasticizers contribute to the improvement of crack resistance of a coating film (hereinafter, also referred to as “antifouling coating film”) made of the antifouling coating composition used in the special friction resistance-reducing ship obtained.

<Anti-sagging and anti-settling agent (thickener)>
Anti-sagging and anti-settling agents (fading agents) include organoclay Al, Ca, Zn stearate salts, lecithin salts, alkyl sulfonate salts, polyethylene wax, amide wax, hydrogenated castor oil wax system Polyamide wax and mixtures thereof, synthetic fine powder silica, oxidized polyethylene wax, and the like. Polyamide wax, synthetic fine powder silica, oxidized polyethylene wax, and organic clay are preferably used. Examples of such anti-sagging and anti-settling agents are those marketed under the trade names such as “DISPARON 305” and “DISPARON 4200-20” manufactured by Enomoto Kasei Co., Ltd. and “DISPARON A630-20X”. Is mentioned.

Such an anti-sagging / settling-preventing agent is blended in an amount of 0.1 to 10% by weight, for example, in the antifouling coating composition used in the special frictional resistance-reducing ship.
<Pigments and dyes>
As the pigment, various conventionally known organic and inorganic pigments can be used. Examples of organic pigments include carbon black, phthalocyanine blue, and bitumen. Examples of the inorganic pigment include neutral and non-reactive pigments such as titanium white, bengara, barite powder, silica, calcium carbonate, talc, chalk, iron oxide powder; zinc white (ZnO, zinc oxide), Examples are basic (active pigments) that are basic and reactive with acidic substances in the paint, such as lead white, red lead, zinc dust, and lead oxide powder.

  In addition, metal oxides such as diatomaceous earth and alumina, or surfaces thereof treated with a silane compound; metal carbonates such as magnesium carbonate and zinc carbonate; others, asbestos, glass fiber, quartz powder, aluminum hydroxide , Gold powder, silver powder, surface treated calcium carbonate, glass balloon and the like.

Various colorants such as dyes may also be included.
These pigments and dyes may be used alone 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 the antifouling coating composition used in a ship with reduced special frictional resistance. Moreover, it is preferable that 1-40 weight part of such various pigments / dyes are mix | blended with respect to 100 weight part of organopolysiloxane (A).

<Other coating film forming components>
As the coating film forming component, a coating film forming component other than the above-described organopolysiloxane (A) may be contained within a range not contrary to the object of the present invention. For example, acrylic resin, acrylic silicone resin, unsaturated polyester resin, fluorine resin, polybutene resin, silicone rubber, urethane resin (rubber), polyamide resin, vinyl chloride copolymer resin, chlorinated rubber (resin), chlorinated Olefin resins, styrene / butadiene copolymer resins, ethylene-vinyl acetate copolymer resins, vinyl chloride resins, alkyd resins, coumarone resins, trialkylsilyl acrylate (co) polymers (silyl resins), petroleum resins, etc. Examples thereof include water-soluble resins (hereinafter also referred to as difficult / non-water-soluble resins).

<Other thixotropic agents, flame retardants, heat conduction improvers, adhesion promoters, 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. Adhesive components include substances containing one or more reactive organic groups such as amino groups, mercapto groups, alkoxysilyl groups, epoxy groups, hydrosilyl groups, acrylic groups, hydroxysilyl groups, such as silane coupling agents, etc. Or a mixture of these substances.

<Solvent>
The antifouling paint composition used in the special frictional resistance-reducing ship of the present invention may or may not contain a solvent. It can be used by dissolving or dispersing in a solvent. As the solvent used here, for example, various solvents such as aliphatic, aromatic, ketone, ester, ether, alcohol and the like which are usually blended in antifouling paints 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 and propylene glycol monomethyl. Ether acetate (PMAC) etc. are mentioned, As an alcohol solvent, isopropyl alcohol etc. are mentioned, for example.

  Such a solvent can be used in any amount, but for example, in an amount of 0.1 to 9999 parts by weight, preferably in an amount of 1 to 50 parts by weight with respect to 100 parts by weight of the component (A). Used. The antifouling coating composition of the present invention is used in an amount of 1 to 99% by weight, preferably 5 to 50% by weight. Viscosity of the antifouling paint composition used in the special frictional resistance-reducing ship such as antifouling paint composition used in the special frictional resistance-reducing ship diluted with such a solvent as necessary (25 ° C., B-type viscometer, The No. 3 rotor) is usually about 0.001 to 50 Pa · s, preferably about 0.01 to 20 Pa · s, considering the coating property (sagging property) and the film thickness obtained by one-time coating.

<Others>
The antifouling coating composition may be a one-component type or a multi-component type such as a two-component type or a three-component type.

  For example, in the case of a formulation that can utilize a hydrolysis reaction between a hydrolyzable group and moisture in the air, the curing reaction does not occur if the moisture source is turned off until just before coating, so that it can be a one-pack type.

Further, for example, when a component that causes a curing reaction at room temperature by addition of a catalyst is blended, a multi-liquid type in which a catalyst and a component that undergoes a reaction by addition of the catalyst are separate liquids can be used.
As a specific example of the one-pack type antifouling coating composition, an organopolysiloxane (A) is blended with an organopolysiloxane in which the condensable reactive groups at both ends of the molecule are hydrolyzable groups such as deoxime. And / or the antifouling paint composition which mix | blended organosilanes, such as oxime silane, can be mentioned as the partial condensate (B).

  In addition, as a three-component antifouling paint composition, a main agent, organosilane and / or partial condensation thereof in which organopolysiloxane (A) is mixed with an organopolysiloxane having a condensable reactive group at both ends of the molecule as a hydroxy group. Examples of the product (B) include an antifouling coating composition composed of three liquids: a curing agent blended with a polyalkoxysilane such as ethyl silicate and a curing accelerator blended with a catalyst.

1-3. Antifouling coating (first coating), special friction resistance reduction ship (first special friction resistance reduction ship)
The coating film formed from the antifouling paint composition used in the special frictional resistance reducing ship according to the present invention has a static underwater bubble contact angle in water as small as less than 90 degrees, as measured by the method described below, and The bubble has a shape in which the rolling (sliding) angle is usually as small as less than 30 degrees, the roughness is 30 μm or less, and the average interval between peaks and valleys is 700 μm or more.

  From the standpoint of efficiently reducing the frictional resistance of the hull and realizing a long-term reduction in the frictional resistance, the static underwater bubble contact angle in water is preferably 80 ° or less, and the bubble rolling (sliding) The angle is preferably 20 ° or less, the maximum height of the roughness is preferably 25 μm or less, and the distance between the peak of the roughness and the valley bottom is preferably 800 μm or more.

  A small static water bubble contact angle indicates that the air gets wet with the coating film (affinity), that the bubble rolling (slip) angle is small, the roughness is small, and the average interval between the peaks and valleys is long. The property that air easily flows. That is, it indicates that the surface is excellent in gas lubricity. These properties can be examined using an underwater bubble contact angle meter, and the gas lubrication effect (water frictional resistance reduction effect) is applied to the bottom of the model ship by applying a coating composition and supplying air to the formed ship bottom coating. This can be confirmed by measuring the water flow resistance in the case of a test (circulating water tank test).

  The coating film having such a shape can be obtained, for example, by applying an antifouling coating composition used in the special frictional resistance reducing ship to an object to be coated. Since the antifouling paint composition used in the special frictional resistance reducing ship has a specific composition capable of forming a coating film having the above-mentioned shape, the antifouling paint composition is applied to an object to be coated and dried. No special operation is required except for such a general method, and a coating film having the above-described shape can be obtained only by coating by such a simple method.

  A special frictional resistance-reducing ship with such an antifouling coating film formed on the submerged surface of the ship's outer plate exhibits an excellent frictional resistance reducing effect even when a small amount of gas is supplied, and also exhibits an excellent antifouling effect. In addition, these effects can be exhibited stably over a long period of time.

The static underwater bubble contact angle and underwater bubble rolling (sliding) angle can be measured using a contact angle measuring device described later.
<Measurement method of static underwater bubble contact angle>
The measurement method of the static underwater bubble contact angle is specifically as follows.

A hard polyvinyl chloride test plate (maximum height measured in accordance with JIS B 0601 of 1 μm or less) coated with a coating composition so that a coating film having a dry film thickness of 150 μm is formed at 25 ° C. for 30 days. Immerse in water. Specifically, the test plate is attached to the inner wall of a cylindrical rotary dipping bath, and its central portion is rotated in water (peripheral speed 15 knots) to generate a water flow, and dipped in that state for 30 days. The hard polyvinyl chloride test plate after immersion is placed in water so that the coating surface is horizontal and below the testing plate, and 0.1 cc of air is formed so that one bubble is formed on the coating surface. And the height a of the bubbles formed on the coating film surface from the coating film surface and the diameter b of the contact portion between the coating film surface and the bubbles are measured. Then, a static underwater bubble contact angle (θ _s , unit: degree), which is a contact angle between the coating film surface and bubbles, is determined.

<Measurement of underwater bubble rolling (slip) angle>
The method for measuring the underwater bubble rolling (slip) angle is specifically as follows.
In the method for measuring the static underwater bubble contact angle, the coating surface on which bubbles are formed is gradually tilted with respect to the horizontal plane, and the tilt angle of the coating surface with respect to the horizontal plane when the bubbles begin to move (underwater bubble rolling) (Slip) angle) (θ _m , unit: degree) is measured.

1-4. Method for Manufacturing Special Friction Resistance-Reducing Ship In the method for manufacturing a special friction resistance-reducing ship according to the present invention, the antifouling coating film is formed on the submerged planned surface of the outer plate of the ship to be painted. The antifouling coating film can be formed from the above antifouling coating composition.

  The antifouling paint composition for use in a special frictional resistance-reducing ship of the present invention reduces the frictional resistance to the surface of the submerged portion of the outer plate of the ship if applied and cured one or more times in accordance with a conventional method. A coating film capable of imparting performance and antifouling performance can be formed, and the above performance can be maintained over a long period of time. For such coating, conventionally known coating means such as brushes, rolls, sprays, dip coaters, etc. are widely used.

  The antifouling coating film obtained by curing the antifouling paint composition used in the special frictional resistance reducing ship according to the present invention has a long adhesion to aquatic organisms such as Aosa, Barnacles, Aonori, Cell plastic, Oysters, and Flies. It has excellent antifouling properties such as continuous prevention during the period.

It is desirable that the antifouling paint composition used in the special frictional resistance-reducing ship according to the present invention is applied on an anticorrosion coating film that has been previously applied to the outer plate of the ship from the viewpoints of adhesion and anticorrosion.
The antifouling paint composition used in the special frictional resistance-reducing ship of the present invention is overcoated on the surface of the ship that is coated with the antifouling paint composition used in the special frictional resistance-reducing ship of the present invention. May be. Thus, although the thickness of the antifouling coating film formed in the submerged surface of a ship outer plate is not specifically limited, For example, it is about 30-150 micrometers / time.

The antifouling paint composition used in the special frictional resistance-reducing ship according to the present invention is preferably applied to the entire submerged surface of the ship's outer plate from the viewpoint of the frictional resistance-reducing performance.
2. Second group
2-1. Second paint composition, paint film, special friction resistance reducing ship second paint composition is a paint composition that can form a paint film satisfying the following conditions of static underwater bubble contact angle and underwater bubble rolling (slip) angle It is.

Examples of the coating composition that can form a coating film satisfying such conditions include the aforementioned antifouling coating composition (first coating composition). The details of the first coating composition are as described above.
<Static underwater bubble contact angle and underwater bubble rolling (sliding) angle>
The static underwater bubble contact angle measured by the following static underwater bubble contact angle measurement method is less than 90 degrees, and the underwater bubble rolling (slip) angle measured by the following underwater bubble rolling (slip) angle measurement method is 30 degrees. Is less than.

The static underwater bubble contact angle and underwater bubble rolling (sliding) angle can be measured using a contact angle measuring device described later.
The measurement method of the static underwater bubble contact angle is specifically as follows.

A hard polyvinyl chloride test plate (maximum height measured in accordance with JIS B 0601 of 1 μm or less) coated with a coating composition so that a coating film having a dry film thickness of 150 μm is formed at 25 ° C. for 30 days. Immerse in water. Specifically, the test plate is attached to the inner wall of a cylindrical rotary dipping bath, and its central portion is rotated in water (peripheral speed 15 knots) to generate a water flow, and dipped in that state for 30 days. The hard polyvinyl chloride test plate after immersion is placed in water so that the coating surface is horizontal and below the testing plate, and 0.1 cc of air is formed so that one bubble is formed on the coating surface. And the height a of the bubbles formed on the coating film surface from the coating film surface and the diameter b of the contact portion between the coating film surface and the bubbles are measured. Then, a static underwater bubble contact angle (θ _s , unit: degree), which is a contact angle between the coating film surface and bubbles, is determined.

The method for measuring the underwater bubble rolling (slip) angle is specifically as follows.
In the method for measuring the static underwater bubble contact angle, the coating surface on which bubbles are formed is gradually tilted with respect to the horizontal plane, and the tilt angle of the coating surface with respect to the horizontal plane when the bubbles begin to move (underwater bubble rolling) (Slip) angle) (θ _m , unit: degree) is measured.

  The static underwater bubble contact angle represents the degree of wetting of the gas to the coating film (degree of affinity). A small static underwater bubble contact angle indicates a large degree of gas wetting (affinity) on the coating, and a large static underwater bubble contact angle indicates that the gas wets (affinity) the coating. ) Indicates that the degree is small.

  The rolling (slip) angle of the bubbles represents the ease of air flow on the coating film surface. A small bubble rolling (sliding) angle indicates that air easily flows on the coating surface, and a large bubble rolling (sliding) angle indicates that air does not easily flow on the coating surface. Represent.

  That is, these physical properties serve as an index for determining whether or not the submerged portion of the ship outer plate on which the coating film is formed has a surface excellent in gas lubricity, the static water bubble contact angle is small, and the bubbles Those having a small rolling (sliding) angle are more excellent in gas lubricity.

  From the viewpoint of reducing the frictional resistance and thus maintaining the properties of the coating film formed on the surface of the ship outer plate for a long period of time, the static underwater bubble contact angle is preferably 80 degrees or less. The bubble rolling (slip) angle is preferably 20 degrees or less.

  The special friction resistance reducing ship in which the coating film having the underwater bubble contact angle and the underwater bubble rolling (sliding) angle in the above range is formed on the submerged surface of the outer plate, as described above, has the gas lubricity of the submerged surface of the outer plate. Because it is excellent, the frictional resistance of the ship can be reduced efficiently even with a small amount of air supplied, and energy saving is also excellent. In addition, since the special frictional resistance reducing ship has reduced frictional resistance against the submerged surface of the ship outer plate by the coating film, the wear of the submerged surface of the outer plate due to the frictional resistance is greatly suppressed, and the coating film There is also an effect that the property of is maintained for a long 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) is to measure the water friction resistance when a paint composition is applied to the bottom of the model ship and air is supplied to the surface of the formed bottom paint film (circulating water tank test). Can be confirmed. In the present specification, a test plate having a coating film formed from a coating composition is immersed in water (usually about 25 ° C.) in water (preferably seawater) or attached to the inner wall of a rotary immersion tank. Rotating water (preferably about 25 ° C.) (preferably seawater) to generate a water flow with a peripheral speed of 15 knots, and “after X immersion” (X is the elapsed time. For example, immersion for 30 days) 30 days later.) In addition, the fact that such treatment is not performed is expressed as before immersion.

  For example, a test plate is attached to the inner wall of a cylindrical rotary immersion bath, and its center is rotated in water (circumferential speed 15 knots) to generate a water flow. The difference in the frictional resistance reduction rate is referred to as the difference in the frictional resistance reduction rate before immersion and 30 days after immersion.

The specific example of the measuring method of the difference of the frictional resistance reduction rate before and behind immersion is as follows.
As shown in FIG. 4, a length of 2.05 m and a width of 0.24 m immersed for 30 days in the bottom of a model ship having a total length of 2.8 m, a mold width of 0.24 m, and a mold depth of 0.14 m. Then, a test plate having an area of 0.492 m ² is attached so that the surface of the coating film becomes front (so that the coating film surface is in contact with water). Let the coating film part of the test plate be the test coating film part 9. Next, the above model ship is installed in a vertical circulation type circulating water tank having a measuring part length of 8 m, a width of 1.5 m, and a water depth of 1.2 m, and the flow rate of water (12 ° C.) is 1.4 m / s. Under the conditions, when air is blown out from the air outlet 8 installed in the bottom of the model ship to the bottom of the ship to which the test plate is attached (for example, equivalent air thickness (ta) = 1.0 mm) Measure the frictional resistance of the hull when it does not spout. Next, the total resistance reduction rate (ηT) is obtained from the following equation (2), and the frictional resistance reduction rate (ηF) of the test plate portion is obtained from the following equation (3). The difference between the frictional resistance reduction ratios before and after immersion can be obtained by subtracting the frictional resistance reduction ratio after 30 days immersion from the frictional resistance reduction ratio before immersion (values of water flow rate and equivalent air thickness are appropriately set. be able to).

R _t0 : Total hull resistance [kgf] when air is not blown out,
R _t : Total resistance of the hull when air is blown out [kgf],
R _f0 : Friction resistance [kgf] when air of the test plate represented by the following formula (4) is not blown out,

ρ: density of water [Kgf · s ² / m ⁴ ] (12 ° C.),
S: Area of test plate [m ² ],
U: Flow rate of water [m / s],
C _f0 : Friction resistance coefficient when the test plate air represented by the following formula (5) is not blown out,

R _n : Reynolds number of the test plate represented by the following formula (6),

U: Flow rate of water [m / s]
L: length of test plate [m],
ν: Kinematic viscosity coefficient of water [m ² / s] (12 ° C.).

  In addition, the above-mentioned equivalent air thickness (ta) [mm] indicates the amount of air ejected and is represented by the following equation (7).

Qa: amount of air blown out [m ³ / s],
U: Flow rate of water [m / s],
Ba: The width of the air ejection port [m].

Here, “total resistance” refers to a combination of all the resistances related to the measurement, such as wave resistance, shape resistance, and friction resistance.
The test plate is an aluminum plate (material: A5052P).

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

  Special friction resistance-reduced ships with coatings that satisfy the above requirements on the submerged surface of the outer plate are formed on the surface of the outer plate of the ship because the difference in the frictional resistance reduction rate before and after immersion (the change with time of the coating) is small. The properties of the coated film can be maintained for a long time. In addition, even with a small amount of air (for example, ta = 1.0 mm), a sufficient resistance reduction effect can be achieved and less energy is required to supply the air necessary for reducing the frictional resistance. Is also expensive.

2-2. Second Special Friction Resistance Reduction Ship Manufacturing Method Regarding the second special friction resistance reduction ship manufacturing method as described above, the special friction resistance reduction covered with the coating film formed from the antifouling paint composition described above. What is necessary is just to follow the manufacturing method of a ship (1st special frictional resistance reduction ship).

2-3. Method for Predicting Friction Resistance Reduction Effect Utilizing Gas Lubricating Function of Coating Film Underwater Method for predicting frictional resistance reduction effect utilizing gas lubrication function of coating film according to the present invention is a static underwater bubble The static underwater bubble contact angle is measured by the contact angle measurement method, and the underwater bubble roll (slip) angle is measured by the underwater bubble roll (slip) angle measurement method. From the bubble rolling (slip) angle, the effect of reducing the frictional resistance of the coating film formed from the coating composition using the gas lubrication function in water is predicted.

The measurement method of the static underwater bubble contact angle and underwater bubble rolling (slip) angle is as follows, respectively, and the static underwater bubble contact angle represents the degree of gas wetting to the coating film (degree of affinity). The bubble rolling (sliding) angle represents the ease of air flow on the surface of the coating film.
<Measurement method of static underwater bubble contact angle>
The test plate coated with the coating composition is immersed in water so that a coating film is formed, and the immersed test plate is placed in water so that the coating surface is horizontal and below the test plate. Air is injected into water so that bubbles are formed on the coating surface, and the height a of the bubbles formed on the coating surface from the coating surface and the contact portion between the coating surface and the bubbles are The diameter b is measured, and the static underwater bubble contact angle (θ _s , unit: degree), which is the contact angle between the coating film surface and the bubble, is obtained from the following formula (1).

<Measurement of underwater bubble rolling (slip) angle>
In the method for measuring the static underwater bubble contact angle, an underwater bubble having an inclination angle with respect to a horizontal plane of a coating film surface when bubbles are gradually tilted with respect to the horizontal plane and the bubble starts to move. Measure the rolling (sliding) angle (θ _m , unit: degree).

  That is, these physical properties serve as an index for determining whether or not the submerged portion of the ship outer plate on which the coating film is formed has a surface excellent in gas lubricity, the static water bubble contact angle is small, and the bubbles Those having a small rolling (sliding) angle are more excellent in gas lubricity.

  In the method for evaluating the frictional resistance reduction effect according to the present invention, as a result of the two kinds of measurement methods, the static underwater bubble contact angle is less than 90 degrees (preferably 80 degrees or less), and underwater bubble rolling ( A coating film having a slip angle of less than 30 degrees (preferably 20 degrees or less) is evaluated to be excellent in gas lubricity and excellent in frictional resistance reduction effect utilizing a gas lubrication function in water.

  In addition, as shown in the results of Examples to be described later, the paint that was highly evaluated by the method for evaluating the frictional resistance reduction effect according to the present invention has a high evaluation even in the evaluation result of the water flow frictional resistance using a model ship, The reverse is also true.

Therefore, the method of predicting the frictional resistance reduction effect using the gas lubrication function in water of the coating film according to the present invention is simple and appropriate, and is effective for selecting a coating film.
2-4. Apparatus used for prediction of frictional resistance reduction effect using gas lubrication function of coating film in water Apparatus used for prediction of frictional resistance reduction effect of coating film according to present invention using gas lubrication function in water The angle measuring device includes a test bench, an inclination angle control device, a dipping container, and an observation device.

An inclination angle control device is connected to the test table.
And, the test plate is attached with a test plate having a coating film formed on the surface thereof so that the back surface of the test plate is in contact with the lower surface of the test table. The test plate is immersed and installed in a state in which bubbles are formed on the coating film surface of the test plate.

The observation device is installed so that the state of the test plate and the bubbles can be observed.
The static underwater bubble contact angle of bubbles is determined by observing the state of bubbles formed on the surface of the coating film of the test plate when the test plate is horizontal, using the observation device, and calculating the static underwater bubble contact angle. taking measurement.

  The underwater bubble rolling (sliding) angle of the bubbles is determined by inclining the test plate with respect to the horizontal by the inclination angle control device, observing the behavior of the bubbles with the observation device, and applying it to the surface of the coating film on the test plate. Form and measure.

Hereinafter, a specific description will be given with reference to the apparatus shown in FIG. 1 as an example of the contact angle measuring apparatus.
In the apparatus shown in FIG. 1, a test table 5 to which a test plate 6 having a coating film formed on a surface is attached is connected to an inclination angle control mechanism including a rotation drive handle 4, and the rotation drive handle 4 is rotated. The inclination angle of the test table 5 with respect to the horizontal is controlled. The angle is measured by the goniometer 3. The test table 5 is installed in the water by an immersion container 7 designed so that the test table 5 can be installed in the water. In the apparatus shown in FIG. 1, at least a part or all of the immersion container 7 is made of a permeable member (for example, made of acrylic or glass), and the test table 5 or The state of bubbles formed on the test plate 6 can be observed. The test plate 6 is attached to the lower side of the test table 5 such that the surface on which the coating film is formed faces the lower side of the test plate table 5.

Formation of bubbles on the coating film surface of the test plate 6 may be performed using, for example, the syringe 2.
Bubbles are observed using the camera 1. Although the observation of bubbles can be performed with the naked eye, the behavior of the bubbles can be observed more accurately by using the camera 1.

  The measurement of the static underwater bubble contact angle and underwater bubble rolling (sliding) angle may be carried out as described above, but the type of test plate, dry film thickness of coating film, immersion time, bubble volume, etc. It can also be set as appropriate.

  In that case, depending on the purpose, the type of test plate includes a vinyl chloride plate, the dry film thickness of the coating is usually in the range of 50 to 500 μm, the immersion time is usually in the range of 1 to 180 days, The volume of the bubbles is usually in the range of 0.1 to 3 cc. Further, as the test plate, one having a maximum height of 1 μm or less measured according to JIS B 0601 is used.

3. Third group
3-1. Friction resistance reduction system (first and second friction resistance reduction system) used for special friction resistance reduction ship and special friction resistance reduction ship (third and fourth friction resistance reduction ship) equipped with the system
The first and second frictional resistance reduction systems used in the special frictional resistance reducing ship according to the present invention are the first coating film (antifouling coating film) and the second coating film, respectively, and the first coating film. Or a gas supply device for supplying gas to the surface of the second coating film.

Such a frictional resistance reduction system is special because, as described above, gas such as air is supplied from the gas supply device to the surface of the coating film having specific properties excellent in the frictional resistance reduction performance or the antifouling coating film. Friction resistance reduction The frictional resistance of a ship can be greatly reduced.

The gas supply device and the gas used are as described above.
In addition, the third and fourth special frictional resistance reduction ships equipped with such first and second frictional resistance reduction systems, respectively, greatly reduce the frictional resistance of the ship in water by the above-described system. Therefore, the effect of reducing fluid frictional resistance is great without introducing large power into the supply of gas such as air, and it is economical and has little impact on the environment.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail, referring an Example, this invention is not limited to these Examples at all. Unless otherwise noted, the pressure condition is normal pressure (about 0.1013 MPa), and the temperature condition is room temperature (about 25 ° C.).

Details of various tests conducted in the following examples and comparative examples are as follows.
<Measurement of coating film surface roughness>
In accordance with JIS B 0601, the surface state of each coating film was measured using a stylus type surface roughness meter (Handy Surf E-35A, manufactured by Tokyo Seimitsu Co., Ltd.).

<Measurement of changes over time in contact angle and rolling (slip) angle>
The coating composition produced in the examples described later is dried on a 50 × 50 × 2 mm hard polyvinyl chloride plate (maximum height measured in accordance with JIS B 0601 is 1 μm or less) to 150 μm. And dried at room temperature for 5 days to prepare a test plate. The test plate was attached to the inner wall of a cylindrical rotary dipping bath, and the coating film formed on the test plate was dipped. The center part was rotated in the water (circumferential speed 15 knots), and the water flow was generated. The static underwater bubble contact angle and underwater bubble rolling (sliding) angle of the coating film formed on the test plate were as follows using a “contact angle measuring device” before immersion, after 14 days of immersion, and after 30 days of immersion. (See also FIGS. 1 to 4).

(Measurement of static underwater bubble contact angle)
The test plate before immersion or after immersion for a specific period was attached to the test table 5 and placed in water so that the coating surface was horizontal and below the test plate. Using syringe 2, 0.1 cc of air was injected into water so that one bubble was formed on the surface of the coating film. Observe from the side using the camera 1 (video microscope), and measure the height a of the bubbles formed on the coating surface from the coating surface and the contact portion diameter b between the coating surface and the bubbles. From the following formula (1), the contact angle between the coating surface and the bubbles was determined (see FIGS. 1 and 2). This angle is the static underwater bubble contact angle (θ _s ), and the affinity between the coating film surface and air bubbles can be evaluated. The smaller this θ _{s, the} greater the affinity between the coating film surface and air.

(Measurement of underwater bubble rolling (slip) angle)
0.1 cc of air is injected into the water so that bubbles are formed on the surface of the coating film under the same conditions as the measurement of the static underwater bubble contact angle, and then the rotation driving handle 4 is turned to gradually increase the coating surface. Was gradually tilted with respect to the horizontal plane, and the angle when the bubbles started to move was measured (see FIGS. 1 and 3). This angle is the underwater bubble rolling (sliding) angle (θ _m ), and the fluidity of the air bubbles on the coating surface can be evaluated. The smaller θ _m is, the better the fluidity is.

<Standing antifouling test method>
Epoxy zinc rich primer ("Epicon zinc rich primer B-2" manufactured by China Paint Co., Ltd.), epoxy anticorrosive paint ("Banno 500" manufactured by China Paint Co., Ltd.) on 100mm x 300mm x 2.3mm sandblasted steel plate The urethane resin anticorrosive paint (“CMP Bioclin SG” manufactured by China Paint Co., Ltd.) was repeatedly applied in the order described above using air spray so that the dry film thicknesses were 20 μm, 150 μm, and 100 μm, respectively. On the surface of the urethane binder coating formed from the urethane resin anticorrosive paint, the antifouling paint composition produced in the examples described later was applied so that the dry film thickness was 100 μm to 200 μm, and a test plate was prepared. . The obtained test plate was dried in a room (room temperature 20 ° C., relative humidity 60%) for one week, and then immersed in a 1 m below the surface of the water from a bowl installed in Hiroshima Bay. The state of biofouling on the surface for 1, 3, 6, 12 months was visually observed.

Evaluation was made by visual observation of the adhesion area (%) of marine organisms.
Evaluation criteria were as shown in Table 3.
<Dynamic antifouling test method>
A sandblasted steel plate that is bent so that it can be attached to the side of a rotating drum installed in seawater in Kure City, Hiroshima Prefecture, and has a size of (vertical) 170 mm x (horizontal) 70 mm x (thickness) 2.3 mm Prepared. Epoxy zinc rich primer ("Epicon Zinc Rich Primer B-2" manufactured by China Paint Co., Ltd.), epoxy anticorrosive paint ("Banno 500" manufactured by China Paint Co., Ltd.), urethane resin anticorrosive paint (“CMP Bioclin SG” manufactured by China Paint Co., Ltd.) was overcoated in the order described above using air spray so that the dry film thicknesses were 20 μm, 150 μm, and 100 μm, respectively. The antifouling paint composition produced in the examples described later was applied onto the surface of the urethane binder coat formed from the urethane resin anticorrosive paint so that the dry film thickness was 100 μm to 200 μm to prepare a test plate. The obtained test plate was dried in a room (room temperature 20 ° C., relative humidity 60%) for one week, then attached to the rotary drum and rotationally immersed at a peripheral speed of 15 knots. The state of biofouling in a dynamic environment for 3, 6, 12 months was visually observed.

<Measurement of water friction resistance>
A test plate (length 2) coated with the antifouling paint composition produced in the examples described later on the bottom of the model ship (total length 2.8 m, mold width 0.24 m, mold depth 0.14 m) shown in FIG. 0.05 m, width 0.24 m, area 0.492 m ² , base material: aluminum plate (A5052P)) is attached so that the coating film surface becomes the front. The coating film part of the test plate was designated as test coating film part 9. Then, using the vertical circulation type circulating water tank (measurement part dimensions: length 8m, width 1.5m, water depth 1.2m), the above test plate under the condition that the flow rate of water (12 ° C) becomes a specific speed. When the air of a specific equivalent air thickness (ta: mm) is ejected from the air ejection port 8 installed on the bottom of the model ship to the bottom of the ship (test coating film part 9) to which is attached. The frictional resistance of the hull in the absence was measured before immersion and after a specific period after immersion. The flow of compressed air from the compressor was controlled, and the air was ejected from an arrayed perforated plate (2 mm diameter × 46 holes) provided at the front edge of the test plate. Next, the total resistance reduction rate (ηT) and the frictional resistance reduction rate (ηF) at each water flow rate and each air flow rate were determined 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 30 days immersion from the frictional resistance reduction rate before immersion.

<Manufacture of antifouling paint composition>
[Production Example 1]
Both ends of the molecular chain are blocked with silanol groups, 900 parts by weight of dimethylpolysiloxane (XF3905, manufactured by Momentive Co., Ltd.) having a viscosity of 700 mm ² / s at 25 ° C., a specific surface area of 200 m ² / g, and the surface is hydrophobized. 100 parts by weight of fumed silica (produced by Nippon Aerosil Co., Ltd., R-972) was uniformly mixed at 150 ° C. for 2 hours using a stirring mixer (manufactured by Dalton Co., 5NDMV) to obtain a base compound 1. . The viscosity of the base compound 1 was 1530 mm ² / s.

[Production Examples 2 to 4]
In Production Example 1, YF3057 (viscosity: 3000 mm ² / s, manufactured by Momentive), YF3807 (viscosity: 20000 mm ² / s, manufactured by Momentive) and YF3802 were used as dimethylpolysiloxanes having both molecular chain ends blocked with silanol groups. Base compounds 2, 3 and 4 were obtained in the same manner as in Production Example 1 except that (viscosity: 80000 mm ² / s, manufactured by Momentive) was used. The viscosity of the base compound 2 and 3, in order respectively, 8670mm ² / s, was 46000mm ² / s. Since the base compound 4 had a high viscosity, the viscosity could not be measured.

[Example 1]
100 parts by weight of base compound 1 obtained in Production Example 1, 10 parts by weight of silicone oil KF-50-3000 (trade name “KF-50-3000”, manufactured by Shin-Etsu Chemical Co., Ltd., methylphenyl silicone oil), pigment 12 parts by weight of titanium oxide (trade name “R-5N”, manufactured by Sakai Chemical Co., Ltd.), 1.5 parts by weight of black iron oxide (trade name “KN320”, manufactured by Toda Kogyo Co., Ltd.) ) Was placed in a paint shaker using glass beads as a medium and shaken for 1 hour, and then the resulting mixture was filtered through a 120 mesh filter to prepare a composition (liquid I).

  Immediately before coating, 123.5 parts by weight of the above liquid I, ethyl silicate (trade name “TES40WN”, manufactured by Asahi Kasei Wacker Silicone Co., Ltd., ethyl silicate oligomer) as liquid II, and tin catalyst (trade name “GLECK” as liquid III) TL ", manufactured by DIC Corporation, dibutyltin dilaurate, 10% xylene solution) 10 parts by weight were mixed well with liquid I and liquid II, and then liquid III was added and stirred to prepare an antifouling paint composition. did.

About the obtained antifouling paint composition, the above-mentioned various tests were performed under the conditions shown in the following Tables 1 and 3-6.
The results are shown in Tables 1 and 4-6.

[Examples 2 to 10]
As shown in Table 1, an antifouling coating composition was prepared in the same manner as in Example 1 except that the types and amounts of the components were changed.

About the obtained antifouling paint composition, the above-mentioned various tests were performed under the conditions shown in the following Tables 1 and 3-6.
The results are shown in Tables 1 and 4-6.

[Example 11]
Reactive organopolysiloxane KE-445 (trade name “KE-445”, manufactured by Shin-Etsu Chemical Co., Ltd., deoxime organopolysiloxane, viscosity: 4500 mm ² / s) 100 parts by weight, silicone oil KF-50-100 (product Name "KF-50-100", manufactured by Shin-Etsu Chemical Co., Ltd., methyl phenyl silicone oil) 40 parts by weight and KF-50-3000 (trade name "KF-50-3000", manufactured by Shin-Etsu Chemical Co., Ltd., methyl phenyl silicone oil) ) 22 parts by weight and 20 parts by weight of xylene were charged in a paint shaker using glass beads as a medium, shaken for 1 hour, and then filtered through a 120 mesh filter to prepare an antifouling paint composition.

About the obtained antifouling paint composition, the above-mentioned various tests were performed under the conditions shown in the following Tables 1 and 3-6.
The results are shown in Tables 1 and 4-6.

[Comparative Example 1]
<Super water-repellent coating film 1>
As the super water-repellent coating film 1, 12.6 parts by weight of fluorine resin LF-200 (trade name “Lumiflon LF-200”, manufactured by Asahi Glass Co., Ltd., fluorine polyol), fluorine powder L-2 (trade name “Lublon”) L-2 ", Daikin Industries, Ltd., low molecular weight tetrafluoroethylene ultrafine powder) 24.2 parts by weight, additive SF-1265-1000 (trade name" SF-1265-1000 ", Toray Dow Manufactured, fluorinated silicone oil) 1.8 parts by weight, butyl acetate 60.6 parts by weight and tin catalyst (trade name "GLECK TL" manufactured by DIC Corporation, dibutyltin dilaurate, 0.1% xylene solution) ) Charge 0.8 parts by weight into a paint shaker using glass beads as a medium, shake for 1 hour, and filter the resulting mixture through a 60 mesh filter for super water repellency. The charge composition was prepared.

  Immediately before coating, 100 parts by weight of the super water-repellent coating composition and 1.7 parts by weight of DN-980 (trade name “Bernock DN-980, manufactured by DIC Corporation, isocyanurate type polyisocyanate”) as a curing agent are mixed. Thus, a super water-repellent coating composition was prepared.

About the obtained antifouling paint composition, the above-mentioned various tests were performed under the conditions shown in the following Tables 1 and 3-6.
The results are shown in Tables 1 and 4-6.

[Comparative Example 2]
<Super water-repellent coating film 2>
As the super water-repellent coating film 2, acrylic resin TZ-343 (trade name “Acridick TZ-343”, manufactured by DIC Corporation) 34.7 parts by weight, hydrophobic fine silica (trade name “Nipsil SS-70”) 19.6 parts by weight of Tosoh Silica Co., Ltd. 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, and then an additive (trade name “DISPARON A630- After adding 1.4 parts by weight of “20X” (Enomoto Kasei Co., Ltd.) and shaking for 15 minutes, the resulting mixture was filtered through a 60-mesh filter to prepare a super water-repellent coating composition.

About the obtained antifouling paint composition, the above-mentioned various tests were performed under the conditions shown in the following Tables 1 and 3-6.
The results are shown in Tables 1 and 4-6.

[Comparative Example 3]
<Aluminum plate>
A corrosion-resistant aluminum plate (material A5052P) was used as an uncoated plate, and the various tests described above were performed on the corrosion-resistant aluminum plate under the conditions shown in Tables 1 and 3-6 below.

The results are shown in Tables 1 and 4-6.
In Table 1 below, the compounding amount is expressed in parts by weight.
In Tables 4 to 6 below, R _t0 (total resistance of the hull when air is not blown out) and R _t (total resistance of the hull when air is blown out) are expressed in [kgf] and ηT (total Resistance reduction rate) and ηF (friction resistance reduction rate) are expressed in [%].

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

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

  As shown in Tables 1 and 4-6, the coating film obtained from the compositions of Examples 1 to 11 containing organopolysiloxane as a main component was in contact with bubbles in water as compared to the uncoated aluminum plate (Comparative Example 3). The angle was small (less than 90 degrees), the rolling or sliding angle was small, and there was little change with time in immersion in water at these angles. In Comparative Examples 1 and 2, there was a great change over time in immersion in water, and hydrophilicity was lost and the affinity with air disappeared. In these water flow resistance reduction rates, Examples 1 to 11 were larger than Comparative Examples 1 and 2.

  As shown in Table 6 and FIG. 5, the coating film obtained from the composition of the example is frictionless with a small amount of air (ta = 1.0 mm) as compared with the uncoated aluminum plate (Comparative Example 3). The reduction effect is expressed, and it is possible to reduce the energy for generating air, which is effective in reducing the net energy of the ship.

  As shown in Table 6 and FIG. 5, the coating film obtained from the composition of the example shows a change in the frictional resistance reduction rate before and after the immersion in the super water-repellent coating films 1 and 2 (Comparative Examples 1 and 2). In comparison, the amount of change is clearly small.

  Also in the antifouling test, as shown in Tables 1 and 3, the compositions of Examples 1 to 11 showed no fouling in the immersion period of 12 months, but the compositions of Comparative Examples 1 and 2 were super repellent. Despite the water paint film, significant fouling was observed, and the function as an antifouling paint was not sufficient.

The special frictional resistance reduction ship of the present invention exhibits an efficient gas lubrication effect, and even if the amount of air supplied is small, the frictional resistance of the hull is efficiently reduced, and the energy saving effect is also great.
The antifouling paint composition used in the special frictional resistance-reducing ship of the present invention can form a coating film that can efficiently reduce the frictional resistance of the hull even by supplying a small amount of gas, and has a great energy saving effect. Furthermore, the coating film formed from the antifouling coating composition exhibits excellent antifouling properties and can prevent an increase in the frictional resistance of the hull due to adhesion of aquatic organisms. Moreover, the antifouling coating composition can maintain these effects over a long period of time.

  The method for manufacturing a ship with reduced special friction resistance according to the present invention is a specific ship that exhibits the above effect by a simple method of forming an antifouling coating film formed from the antifouling paint composition on a submerged surface of a ship outer plate. Can be manufactured.

The method for predicting the frictional resistance reduction effect of the present invention can predict the frictional resistance reduction effect by a simple and low-cost facility or technique.
Therefore, the antifouling paint composition used for the special frictional resistance-reducing ship, the special frictional resistance-reducing ship of the present invention, and the method for manufacturing the special frictional resistance-reducing ship are both used for various ships that require reduced frictional resistance. Can be used in fields such as maritime transportation.

DESCRIPTION OF SYMBOLS 1 Camera 2 Syringe 3 Angle meter 4 Rotation drive handle 5 Test stand 6 Test board 7 Dipping container 8 Air outlet 9 Test coating part

Claims (16)

(A) a reaction-curable organopolysiloxane having a viscosity at 25 ° C. of 20 to 400,000 mm ² / s;
(C) a hydrophobic material that is liquid or grease-like at 25 ° C. (excluding the organopolysiloxane (A) and the following organosilane and / or its partial condensate (B));
Optionally containing (B) an organosilane having at least two hydroxyl groups and hydrolyzable groups in one molecule and / or a partial condensate thereof.
An antifouling paint composition for use in a ship having a reduced frictional resistance , comprising a gas supply device for supplying gas and utilizing a gas lubrication function in water.   The antifouling paint composition according to claim 1, wherein the hydrophobic material (C) contains at least one selected from silicone oil, fluorine oil, paraffins and wax.   Furthermore, 1-150 weight part of antifouling agents (D) are contained with respect to 100 weight part of said organopolysiloxane (A), The antifouling paint composition of Claim 1 or 2 characterized by the above-mentioned. A ship having a gas supply device for supplying gas , wherein the antifouling paint composition according to any one of claims 1 to 3 is used, and a frictional resistance reducing ship using a gas lubrication function in water Antifouling coating used in   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 μm or less, and one convex portion and one concave portion adjacent thereto measured in accordance with JIS B 0601. The antifouling coating film according to claim 4, wherein an average interval between peaks and valleys, which is an average of the length of one cycle, is 700 μm or more. The static underwater bubble contact angle measured by the following static underwater bubble contact angle measurement method is less than 90 degrees, and the underwater bubble rolling (slip) angle measured by the following underwater bubble rolling (slip) angle measurement method is 30 degrees. The antifouling coating film according to claim 4 or 5, wherein:
<Measurement method of static underwater bubble contact angle>
A hard polyvinyl chloride test plate (maximum height measured in accordance with JIS B 0601 of 1 μm or less) coated with a coating composition so that a coating film having a dry film thickness of 150 μm is formed at 25 ° C. for 30 days. Immerse in water and place the hard polyvinyl chloride test plate 30 days after immersion in water so that the coating surface is horizontal and below the test plate, so that one bubble is formed on the coating surface 0.1 cc of air was injected into the water, and the height a of the bubbles formed on the coating surface from the coating surface and the diameter b of the contact portion between the coating surface and the bubbles were measured. From the following formula (1), a static underwater bubble contact angle (θ _s , unit: degree), which is a contact angle between the coating film surface and bubbles, is obtained;

<Measurement of underwater bubble rolling (slip) angle>
In the method for measuring the static underwater bubble contact angle, an underwater bubble having an inclination angle with respect to a horizontal plane of a coating film surface when bubbles are gradually tilted with respect to the horizontal plane and the bubble starts to move. Measure the rolling (sliding) angle (θ _m , unit: degree). A submerged surface of a ship outer plate is coated with the antifouling coating film according to any one of claims 4 to 6, comprising a gas supply device for supplying gas, and a gas lubrication function in water A ship that reduces frictional resistance. The submerged scheduled surface of the skin of the painted ship and forming an antifouling coating film according to claim 4, comprising a gas supply device for supplying a gas, in water A method of manufacturing a ship with reduced frictional resistance utilizing the gas lubrication function of the ship.   A frictional resistance reduction system comprising: the antifouling coating film according to any one of claims 4 to 6; and a gas supply device that supplies gas to the surface of the antifouling coating film. A ship for reducing frictional resistance comprising a gas supply device for supplying gas and utilizing a gas lubrication function in water, comprising the frictional resistance reduction system according to claim 9. The static underwater bubble contact angle measured by the following static underwater bubble contact angle measurement method is less than 90 degrees, and the underwater bubble rolling (slip) angle measured by the following underwater bubble rolling (slip) angle measurement method is 30 degrees. It is possible to form a coating film that is less than,
The coating composition according to any one of claims 1 to 3, which comprises a gas supply device for supplying a gas and is used for a frictional resistance-reducing ship using a gas lubrication function in water.
<Measurement method of static underwater bubble contact angle>
A hard polyvinyl chloride test plate (maximum height measured in accordance with JIS B 0601 of 1 μm or less) coated with a coating composition so that a coating film having a dry film thickness of 150 μm is formed at 25 ° C. for 30 days. Immerse in water and place the hard polyvinyl chloride test plate 30 days after immersion in water so that the coating surface is horizontal and below the test plate, so that one bubble is formed on the coating surface 0.1 cc of air was injected into the water, and the height a of the bubbles formed on the coating surface from the coating surface and the diameter b of the contact portion between the coating surface and the bubbles were measured. From the following formula (1), a static underwater bubble contact angle (θ _s , unit: degree), which is a contact angle between the coating film surface and bubbles, is obtained;

<Measurement of underwater bubble rolling (slip) angle>
In the method for measuring the static underwater bubble contact angle, an underwater bubble having an inclination angle with respect to a horizontal plane of a coating film surface when bubbles are gradually tilted with respect to the horizontal plane and the bubble starts to move. Measure the rolling (sliding) angle (θ _m , unit: degree).   The coating film formed with the coating composition used for the frictional resistance reduction ship of Claim 11. A ship having a gas supply device for supplying gas and having a coating film according to claim 12 on a submerged surface of a ship outer plate, and using a gas lubrication function in water.   A frictional resistance reduction system comprising: the coating film according to claim 12; and a gas supply device that supplies a gas to a surface of the coating film. A ship for reducing frictional resistance comprising a gas supply device for supplying gas and utilizing a gas lubrication function in water, comprising the frictional resistance reduction system according to claim 14. A coating device according to claim 12 is formed on a surface to be submerged of an outer plate of a ship to be coated, which comprises a gas supply device for supplying a gas and utilizing a gas lubrication function in water A method for manufacturing a ship with reduced frictional resistance.

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