KR102560679B1 - Modified ether-polydialkyl polysiloxane compound, method for manufacturing the same and antifouling paint composition containing the same - Google Patents

Abstract

Amphiphilic modified ether polydialkylsiloxane compound having a structure in which a hydrophilic ether group is bonded to a hydrophobic silicone compound, a manufacturing method thereof, and an amphiphilic modified ether polydialkylsiloxane compound having both hydrophobic and hydrophilic properties for marine use It is about antifouling paint technology. The modified ether polydialkylsiloxane compound is represented by the following Structural Formula 1, and is formed by synthesizing and reacting an ether compound, which is a reactive monomer, with a polydialkylsiloxane compound.
[Structural Formula 1]

Description

Modified ether polydialkylsiloxane compound, manufacturing method thereof, and marine antifouling paint containing the same

The present invention is a modified ether polydialkylsiloxane compound applied to marine antifouling paints. It relates to a method for producing the same and a technology for marine antifouling paint including the same, and more specifically, an amphiphilic modified ether polydialkylsiloxane compound having a structure in which a hydrophilic ether group is bonded to a hydrophobic silicone compound, a method for preparing the same, and a hydrophobicity and an amphiphilic modified ether polydialkylsiloxane compound having both hydrophilic and hydrophilic properties.

Aquatic organisms such as barnacles, mussels, and algae tend to adhere to underwater structures, ships, fishing nets, and the like. Due to the attachment of such organisms, problems such as obstructing efficient operation of ships and the like and causing waste of fuel occur. In addition, in fishing nets, etc., problems such as clogging of the mesh and shortening of service life occur. For this reason, in order to prevent the adhesion of aquatic organisms, it has been conventionally performed to form an antifouling coating film by applying an antifouling coating composition to the surface.

Therefore, conventionally, there is an antifouling paint using a hydrolyzed resin containing tin, but this induces toxicity to marine organisms and the phenomenon of biological impo-sex by accumulation in the body of the tin compound eluted from the resin, which is gradually becoming unregulated. It has been subject to regulations in 2003 and has been completely banned since 2008.

As described in Korean Patent Publication No. 1999-006147, the self-wearing antifouling paint as described above is prepared by adding half-ester or half-amide to the end of the side chain of the polymer. An antifouling paint containing a self-abrasive binder as a colorant and a metal-containing antifouling agent is known, and as described in Korean Patent Registration No. 10-0254651, a plurality of Schiff base-type primary amino groups in the molecule as a vehicle resin. Antifouling paints made of vinyl polymers are known.

However, in the antifouling paints described in Patent Publication No. 1999-006147 and Patent Registration No. 10-0254651, antifouling components are eluted into seawater by reaction with seawater, so the durability of the coating film is lowered, requiring frequent repair painting, and long-term anchoring. In the case of patent publication 10-2020-0029154, there is a problem in that a large amount of marine life adheres to the ship because the elution of the antifouling component is not active.

As a more advanced technology, there is an antifouling paint that does not contain tin, which is produced by mixing cuprous oxide and organic antifouling agent with resin that does not contain tin. A problem has been raised, and it has a problem of re-painting every 5 years at the longest.

Alternative paints for organic tin-containing antifouling paints should have antifouling performance equivalent to those of known antifouling paints containing at least TBTO or cuprous oxide, while at the same time having a beneficial effect on the general performance of ships. In addition, it is advantageous that alternative paints have environmental friendliness. When the surface free energy is low and the contact angle is large, marine organisms may not be attached to the surface of the ship or their adhesion may be weakened, and if moisture is difficult to attach, the marine organisms once attached may easily fall off.

On the other hand, if the surface roughness of the coating film is small or the friction coefficient is small, the fuel consumption of the ship can be reduced. Therefore, alternative paints for organic tin-containing antifouling paints need to be developed based on this point of view.

Recently, in addition to the function to prevent or control the attachment and growth of marine organisms that cause pollution, a function that can be used for a long time, a function to reduce frictional resistance with seawater to reduce fuel costs, and a function to reduce the content of volatile organic compounds (VOC) Additional functions, such as the ability to reduce, are being added.

Japanese Patent Laid-open Publication No. 1990-196869 describes a hydrolyzable copolymer composed of trimethylsilyl (meth)acrylate and a known unsaturated monomer, and trimethylsilyl acrylate has a hydrolysis degree of about 70% compared to conventional tin-based binders. , and this is believed to be due to the relatively strong covalent bonding of silicon compared to tin in the metal ester structure, resulting in a lower degree of hydrolysis in seawater. Therefore, the content of hydrolyzed trimethylsilyl (meth)acrylate should be higher than that of other antifouling paint compositions. Trimethylsilyl (meth) acrylate monomer is relatively very expensive in terms of price, and when the content is higher than necessary, there is a problem in that the crack resistance of the binder is poor.

In addition, when a material having a low carbon number of an alkyl group bonded to silicon is applied in order to increase hydrolysis, long-term storage property is poor.

Korean Patent Publication No. 1997-7004840 discloses a method of mixing a plastic (meth)acrylate copolymer to solve the problem of the copolymer composed of the trimethylsilyl (meth)acrylate monomer, but in this case, in seawater As a large amount of non-hydrolyzable binder remains after long-term wear, the wear rate gradually decreases.

Korean Patent Publication No. 2013-0093840 discloses an organic acid containing a carboxylic acid group and an amine group prepared by radical reaction of a monomer containing a divalent metal, a double bond and a carboxylic acid group, and a monomer containing a double bond and an alkyl group. Although a resin for antifouling paint prepared by a condensation reaction with an acrylic resin and an antifouling paint composition containing the same are described, discoloration resistance and crack resistance are improved by applying an organic acid containing a carboxylic acid group and an amine group. , it is insufficient to express low viscosity and high solid differentiation characteristics.

Bacteria, fungi, and "soft fouling" by marine organisms such as sponges, bryozoans, multicellular algae such as Ulva, and brown algae are present in the marine contamination layer that pollutes ships. And there is shellfish or "hard fouling" by barnacles, mussels, polychaetes, etc. The process of contamination by marine organisms occurs over several months, but the formation of an adsorption layer by adsorption of substances such as polysaccharides, proteins, and glycoproteins present in the sea occurs within minutes. This slime layer is known to cause the adsorption of marine microorganisms and the adsorption of large shellfish.

Therefore, it is known that effectively preventing the occurrence of organic film or microfouling at the beginning determines the antifouling performance of the coating layer. As for the method of controlling the surface energy of the coating layer, a method of forming a coating layer having a low surface energy is mainly used, and an elastomer having a fluorine-based or silicon-based molecular structure having a low surface energy is mainly used, and it is very resistant to water when immersed in water. Hydrophilic polymers capable of exhibiting very low friction by exhibiting a low contact angle are also being studied for this purpose.

The adhesion of the coating layer by marine organisms is highly dependent on the surface properties of the substrate. That is, it is common for hydrophilic marine organisms to exhibit high adhesion to hydrophilic substrates and hydrophobic aquatic organisms to hydrophobic substrates. Because it is very difficult to assert about the surface of the water, the hydrophobic antifouling coating layer alone cannot prevent the formation of a mucus-like slime layer formed by the adhesion of substances such as bacteria, proteins, and diatoms in the early stage of being supported on the sea. It is known that the formation of a hydrophilic surface is essential for If the coating layer is made of only hydrophilic properties, it is easily decomposed and dissolved in water, making it impossible to maintain the coating layer for a long period of time. Therefore, research and development are focused on antifouling paints that can form both hydrophobic and hydrophilic surfaces at the same time.

(01) Korean Patent Publication No. 1997-7004840 (02) Korean Patent Publication No. 2013-0093840

An object of the present invention is to solve the above problems, and modified ether polydialkylsiloxane is an amphiphilic silicone binder in which a hydrophilic ether is substituted for a hydrophobic silicone structure formed by connecting silicon and oxygen in a chain or network form in a certain repeating unit. It is a technical task to provide a compound and a method for preparing the same.

In addition, antifouling paint is prepared using a modified ether polydialkylsiloxane compound, which is an amphiphilic silicone binder in which hydrophilic ether is substituted for a hydrophobic silicone structure, to prevent marine organisms or foreign substances from attaching to the bottom of the ship during sailing or anchoring. The technical task is to provide antifouling paints for ships and marine vessels that have excellent antifouling performance and are environmentally friendly.

In order to achieve the above object, a modified ether polydialkylsiloxane compound, which is an amphiphilic silicone binder according to an embodiment of the present invention, is applied to marine paints and is represented by Structural Formula 1 below.

----- [Structural Formula 1]

As an example, in Structural Formula 1, R1 is an alkyl group, R2 includes any one selected from a vinyl group, a hydroxyl group, and an alkoxy group, R3 is hydrogen or a methyl group, and R is any one selected from methyl, ethyl, and propyl groups. Including, n is an integer from 10 to 100, n1 is an integer from 5 to 10.

According to one embodiment, the modified ether polydialkylsiloxane compound may have a structure in which a hydrophilic ether compound is bonded by substitution to a hydrophobic polydialkylsiloxane compound.

According to one embodiment, the ether compound included in the modified ether polydialkylsiloxane compound may include an alkyl oxide.

In order to achieve the above object, the modified ether polydialkylsiloxane compound, which is an amphiphilic silicone binder according to an embodiment of the present invention, synthesizes and reacts an ether compound of structural formula 3, which is a reactive monomer, with a polydialkylsiloxane compound of structural formula 2 below. characterized by manufacturing.

----- [Formula 2]

------ [Formula 3]

In Structural Formulas 2 and 3, R1 is an alkyl group, R2 includes any one selected from a vinyl group, a hydroxyl group, and an alkoxy group, R3 is hydrogen or a methyl group, and R includes any one selected from methyl, ethyl, and propyl groups, , n is an integer from 10 to 100, and n1 is an integer from 5 to 10.

According to one embodiment, the polydialkylsiloxane compound includes at least one selected from polydimethylsiloxane, polydipropylsiloxane, and polydipentylsiloxane, and the ether compound has a mass average molecular weight of 100 to 500 in the range of polyethylene glycol acryl. It may include at least one selected from latex and polypropylene glycol acrylate.

According to one embodiment, it is preferable to synthesize and react 60 to 80% by weight of the polydialkylsiloxane compound and 20 to 40% by weight of the ether compound under a catalyst.

In order to achieve the above object, a marine antifouling paint according to an embodiment of the present invention has a composition including a modified ether polydialkylsiloxane compound represented by Structural Formula 1 and a pigment as a binder.

----- [Structural Formula 1]

In Structural Formula 1, R1 is an alkyl group, R2 includes any one selected from a vinyl group, a hydroxyl group, and an alkoxy group, R3 is hydrogen or a methyl group, R includes any one selected from methyl, ethyl, and a propyl group, and n is an integer from 10 to 100, and n1 is an integer from 5 to 10.

In order to achieve the above object, the marine antifouling coating film according to an embodiment of the present invention is an antifouling paint having a composition including a modified ether polydialkylsiloxane compound represented by Structural Formula 1 and a pigment, which causes adhesion and contamination of marine organisms. It is formed by being applied to the surface of articles and products.

The antifouling paint prepared by applying a modified ether polydialkylsiloxane compound, which is an amphiphilic silicone binder in which a hydrophilic ether is substituted for a hydrophobic silicone structure of the present invention, has both hydrophilic and hydrophobic properties and is well adsorbed on a hydrophilic coating film due to its amphiphilic property. It is possible to prevent not only organisms but also marine organisms that are well adsorbed to the hydrophobic coating film from being attached to ships or marine structures. The antifouling coating formed in this way has an eco-friendly advantage of not discharging harmful marine substances at all.

1 is a graph showing surface characteristics by measuring contact angles for 10 minutes after water was dropped on the antifouling coating films of Examples and Comparative Examples.
2 is a photograph of a result of a seawater immersion test comparing the degree of adhesion of marine organisms after immersing antifouling coatings of Examples and Comparative Examples in seawater for 2 months.

Hereinafter, a modified ether polydialkylsiloxane compound applied to a marine antifouling paint according to an embodiment of the present invention. The manufacturing method thereof and the marine antifouling paint including the same will be described in detail.

Since the present invention can have various changes and various forms, specific embodiments will be described in detail in the text. However, it should be understood that this is not intended to limit the present invention to the specific disclosed form, and includes all modifications, equivalents, and substitutes included in the spirit and scope of the present invention. Terms such as first and second may be used to describe various components, but the components should not be limited by the terms. These terms are only used for the purpose of distinguishing one component from another. For example, a first element may be termed a second element, and similarly, a second element may be termed a first element, without departing from the scope of the present invention.

Terms used in this application are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this application, terms such as "comprise" or "having" are intended to designate that a combination of features, numbers, steps, and elements described in the specification exists, but one or more other features, numbers, steps, It should be understood that the presence or addition of components or combinations thereof is not precluded.

Meanwhile, unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by a person of ordinary skill in the art to which the present invention belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and unless explicitly defined in the present application, they should not be interpreted in an ideal or excessively formal meaning. don't

Modified ether polydialkylsiloxane compound and its preparation method

A modified ether polydialkylsiloxane compound according to an embodiment of the present invention is represented by the following Structural Formula 1 and can be used as a silicone binder for ships or marine paints requiring antifouling properties.

[Structural Formula 1]

As an example, in Structural Formula 1 of the modified ether polydialkylsiloxane compound, R1 is an alkyl group, specifically including a methyl group, an ethyl group, a propyl group, and the like, and any one selected from among them may be used.

In addition, R2 in Structural Formula 1 may include a vinyl group, a hydroxyl group, or an alkoxy group, and R2 in Structural Formula 1 may be used in a curing reaction when preparing a coating film of an antifouling paint using a modified ether polydialkylsiloxane compound of Structural Formula 1. there is.

As an example, in Structural Formula 1, R3 is hydrogen or a methyl group, R includes methyl, ethyl, or a propyl group, any one selected from among them may be used, n is an integer from 10 to 100, and n1 is 5 to 10 is an integer of

The modified ether polydialkylsiloxane compound according to an embodiment of the present invention preferably has a structure in which a hydrophilic ether compound is bonded by substitution to a hydrophobic polydialkylsiloxane compound.

Specifically, the modified ether polydialkylsiloxane compound is obtained by adding a hydrophilic ether compound including an alkyl oxide represented by structural formula 3 to a hydrophobic polydialkylsiloxane compound represented by structural formula 2 below in the presence of a catalyst or by addition reaction. can be manufactured.

That is, hydrogen in the polydialkylsiloxane compound and the vinyl functional group of the hydrophilic ether compound ((ex) polyethylene glycol acrylate) are added by a platinum catalyst to produce a modified ether polydialkylsiloxane compound silicone having amphoteric characteristics. can

[Structural Formula 2]

In Structural Formula 2, R2 may include a vinyl group, a hydroxyl group, an alkoxy group, etc., and R2 may use any one selected from among them. In Structural Formula 2, n is preferably an integer ranging from 10 to 100 in order to have the characteristics of a polymer resin.

As an example, examples of the polydialkylsiloxane compound represented by Structural Formula 2 include polydimethylsiloxane, polydipropylsiloxane, and polydipentylsiloxane. It is preferable to use at least one selected from these.

[Structural Formula 3]

A hydrophilic ether compound containing an alkyl oxide represented by Structural Formula 3 is used to introduce an ether, a hydrophilic group, into Structural Formula 2, and examples of the hydrophilic ether compound include polyethylene glycol 　 acrylate, polypropylene glycol 　 acrylate, polyethylene glycol 　 polypropylene 　 glycol methacryl Rate, methoxy polyethylene glycol acrylate, polyethylene glycol acrylate, etc. are mentioned. These may be used alone or in combination of two or more.

As an example, the ether compound represented by Structural Formula 3 is preferably selected and used within a weight average molecular weight range of 100 to 500.

Specifically, when the weight average molecular weight of the ether compound is 100 or less, it is difficult to exhibit hydrophilic performance, and when the weight average molecular weight is 500 or more, compatibility with silicone is not good, and finally synthesis of a modified ether polydialkylsiloxane compound of structural formula 1 This is because it causes problems that become more difficult.

Marine antifouling paint and antifouling coating

A marine antifouling paint according to an embodiment of the present invention has a composition including a modified ether polydialkylsiloxane compound represented by Structural Formula 1 and a pigment as an amphiphilic silicone compound binder. Specifically, it may have a composition including 75 to 85% by weight of the modified ether polydialkylsiloxane compound and 15 to 25% by weight of the pigment.

---- [Formula 1]

In Structural Formula 1, R1 is an alkyl group, R2 includes any one selected from a vinyl group, a hydroxyl group, and an alkoxy group, R3 is hydrogen or a methyl group, and R includes any one selected from a methyl, ethyl, and propyl group, and n is an integer from 10 to 100, and n1 is an integer from 5 to 10.

In the marine antifouling paint, since the detailed description of the modified ether polydialkylsiloxane compound represented by Structural Formula 1 has been described in detail above, it will be omitted to avoid redundancy.

As an example, the pigment applied to the marine antifouling paint is used to improve the strength of the formed antifouling paint film, control the wear rate, and impart roles such as coloring. Examples of the pigment include titanium white, red iron oxide, and black. Iron oxide, zinc oxide, talc, etc. are mentioned. These may be used alone or in combination of two or more.

As an example, the marine antifouling paint includes a modified ether polydialkylsiloxane compound represented by the following Structural Formula 1 and a pigment, and may further include other components such as a solvent or an additive. The other components include, for example, solvents for adjusting viscosity, surfactants, silicone fluids, wetting agents, and the like, which are known to those skilled in the art.

When the content of the modified ether polydialkylsiloxane compound applied to the marine antifouling paint of the present invention is less than 75% by weight, the antifouling performance is significantly lowered, and when the content exceeds 85% by weight, the content of the pigment is relatively low, so that it is used for ships. It is difficult to implement the reddish-brown color required by Therefore, the marine antifouling paint preferably contains 75 to 85% by weight of the modified ether polydialkylsiloxane compound.

As an example, when the marine antifouling paint includes a solvent, any solvent such as alcohol, ester, ether, ketone, ether-alcohol, aromatic hydrocarbon, aliphatic hydrocarbon, halogenated hydrocarbon, and volatile silicone may be used.

The antifouling coating film formed from the marine antifouling paint containing the above-mentioned modified ether polydialkylsiloxane compound is amphiphilic with both hydrophilic and hydrophobic properties, so marine organisms that are well adsorbed to hydrophilic coating films as well as marine organisms that are well adsorbed to hydrophobic coating films They can be prevented from attaching to ships or offshore structures. In addition, it has the advantage of being eco-friendly because it does not emit any harmful marine substances.

Hereinafter, the present invention will be described in more detail based on comparative synthesis examples, synthesis examples, examples and comparative examples, but the present invention is not limited to the following synthesis examples and examples.

<Comparative Synthesis Example>

90g of a polydialkylsiloxane compound (hydropolydimethylsiloxane (n = 30)) and 10g of an ether compound (polyethylglycol acrylate (Mw = 400)) After adding 0.01 g of a platinum catalyst (3000 ppm), stirring was performed at about 100° C. for 5 hours to obtain a modified ether polydialkylsiloxane compound.

<Synthesis Example 1>

80 g of a polydialkylsiloxane compound (hydropolydimethylsiloxane (n = 30)) and 20 g of an ether compound (polyethyl glycol acrylate (Mw = 400)) After adding 0.01 g of a platinum catalyst (3000 ppm), stirring was performed at about 100° C. for 5 hours to obtain a modified ether polydialkylsiloxane compound.

<Synthesis Example 2>

70 g of a polydialkylsiloxane compound (hydropolydimethylsiloxane (n = 30)) and 30 g of an ether compound (polyethylglycol acrylate (Mw = 400)) After adding 0.01 g of a platinum catalyst (3000 ppm), stirring was performed at about 100° C. for 5 hours to obtain a modified ether polydialkylsiloxane compound.

<Synthesis Example 3>

60 g of a polydialkylsiloxane compound (hydropolydimethylsiloxane (n = 30)) and 40 g of an ether compound (polyethyl glycol acrylate (Mw = 400)) After adding 0.01 g of a platinum catalyst (3000 ppm), stirring was performed at about 100° C. for 5 hours to obtain a modified ether polydialkylsiloxane compound.

Comparative Example 1

A marine antifouling paint of Comparative Example 1 was prepared by mixing 80 parts by weight of hydropolydimethylsiloxane and 20 parts by weight of a pigment and then dispersing at a high speed of 2000 rpm.

Comparative Example 2 and Examples 1 to 3

The modified ether polydialkylsiloxanes of Comparative Synthesis Example 1, Synthesis Example 1, Synthesis Example 2, and Synthesis Example 3 were mixed with pigments in the contents shown in Table 1, respectively, and then dispersed at a speed of 2000 rpm at high speed to obtain Comparative Example 2 and Example 1 , Examples 2 and 3 of the marine antifouling paints were prepared, respectively.

[Table 1]

Evaluation of marine antifouling paints

Microbial antifouling performance and seawater immersion antifouling performance of the marine antifouling paints of Comparative Example 1, Comparative Example 2, Example 1, Example 2 and Example 3 were performed in the following manner, and the results are shown in Table 2 and FIG. 1 and It is disclosed in FIG. 2 .

[Table 2]

As can be seen from the results disclosed in Table 2, the marine antifouling paints of the present invention according to Examples 1 to 3 have an increased content of modified ether contained in the modified ether polydialkylsiloxane compound (of the ether compound used in Synthesis Example). As the usage amount increased), it was confirmed that the antifouling performance of microorganisms and the antifouling performance of seawater immersion were also excellent while having hydrophilic characteristics on the surface. On the other hand, as in the case of Comparative Example 1, when the modified ether polydialkylsiloxane compound was not used as the resin, it was found that the surface properties showed only hydrophobic properties and the antifouling performance was also very poor.

In addition, as can be seen in FIG. 1, as a result of measuring the contact angle of water in the antifouling coating for 10 minutes, the initial contact angles of Comparative Example 2, Example 1, Example 2, and Example 3 were all similar. Looking at the contact angle results after 10 minutes, Comparative Example 1 maintained a contact angle similar to the initial contact angle, but Comparative Example 2, Example 1, Example 2, and Example 3 samples had a decrease in contact angle, and the range of change was greater depending on the modified ether content. appeared large. However, in Comparative Example 2, although the contact angle was decreased, it was confirmed that some marine animals/plants were attached to the seawater immersion evaluation result.

The reason for the change in the contact angle of the antifouling paint containing the modified ether polydialkylsiloxane compound is that the hydrophobic characteristics of silicone appear initially, but the surface properties change to hydrophilic characteristics due to modified ether over time. Since these characteristics are a major obstacle to the growth of marine organisms, it was confirmed that the antifouling paints of Examples 1 to 3 had excellent antifouling performance, as can be seen from the photos shown in FIG. 2 .

* Anti-fouling performance test evaluation method

(1) Microbiological evaluation

- To evaluate the antifouling performance of the antifouling film against marine microorganisms, an adhesion test of one type of Escherichia Coli and three types of microalgae (NItzschia sp., Navicula annexa., Amphora sp.) was conducted.

- Anti-fouling film specimen size 5 x 9 cm was produced and microorganism attachment was cultured for 30 days

- Recover the microorganisms attached to the surface of the specimen and measure the amount of microorganisms attached through the chlorophyll-a analysis method based on the water pollution process test method.

(2) seawater immersion assessment

A seawater immersion test was conducted for two months from September to November using seawater immersion equipment.

Visual evaluation of microbial adhesion on the surface of antifouling paint subjected to seawater immersion

(3) Seawater immersion evaluation criteria

5: State without attachment of marine life (non-contaminated state)

4: state in which a thin layer of slime is observed

3: A thick slime layer is observed or the vegetable contamination area is less than 20% of the effective area of the specimen

2: A state in which the vegetable contamination area is 20 to 50% of the effective area of the specimen

1: A state in which the vegetable contamination area is 50 to 100% of the effective area of the specimen

X: state of animal contamination

Claims (11)

delete delete delete delete delete delete As a binder, 75 to 85% by weight of a modified ether polydialkylsiloxane compound represented by Structural Formula 1 below; and
A marine antifouling paint comprising 15 to 25% by weight of a pigment.
---[Structural Formula 1]
(In Structural Formula 1, R1 is an alkyl group, R2 includes any one selected from a vinyl group, a hydroxyl group, and an alkoxy group, R3 is hydrogen or a methyl group, and R includes any one selected from methyl, ethyl, and propyl groups, n is an integer from 10 to 100, and n1 is an integer from 5 to 10.) 8. The marine antifouling paint according to claim 7, wherein the modified ether polydialkylsiloxane compound is formed by synthesizing and reacting 60 to 80% by weight of the polydialkylsiloxane compound and 20 to 40% by weight of the ether compound under a catalyst. The method of claim 8, wherein the polydialkylsiloxane compound includes polydimethylsiloxane or polydipentylsiloxane, and the ether compound is polyethylene glycol acrylate and/or polypropylene glycol acrylate having a mass average molecular weight in the range of 100 to 500. Marine antifouling paint, characterized in that it comprises. delete An antifouling coating film formed by applying the antifouling coating according to claim 7 to the surface of an article or product to which marine organisms adhere and become contaminated.