KR101886579B1 - Self-polishing and anti-fouling composition - Google Patents

Abstract

The present invention relates to a self-polishing silicone-based polymer, anti-fouling composition including the same, and a self-polishing coating film manufactured therefrom. It is possible to effectively prevent marine organisms from adhering to a surface of a ship or the like due to gradual decomposition of the silicone-based polymer by being self-polished. The adhesion force between the surface of the ship and the coating film is excellent so that self-polishing properties can be maintained for a long time. To achieve the above objectives of the present invention, one embodiment of the present invention relates to an acrylic monomer, an acrylic resin in which a functional monomer is copolymerized, and an anti-fouling polymer containing a copolymer including a monomer containing a trialkylsilyl group as a copolymer component.

Description

[0001] Self-polishing and anti-fouling composition [0002]

The present invention relates to a self-tuning silicone polymer, a polymer for an antifouling paint comprising the same, and a self-tuning coating film prepared therefrom, wherein the silicone polymer is gradually decomposed and self-abraded to effectively adhere marine life to the surface of a ship or the like And it has an advantage that the adhesion between the surface of the ship and the coating film is excellent and the self-wear characteristics can be maintained for a long time.

The purpose of the antifouling paint polymer is to prevent or control the attachment and growth of marine life causing seawater deposition and surface contamination of the coating film. When exposed to water for a long period of time, various kinds of aquatic organisms, such as seashells, oysters, mussels such as shellfishes and shellfishes, plants such as seaweeds, and aquatic bacteria, And the appearance becomes poor or its function is lost. Particularly, when these aquatic organisms adhere to the bottom of the ship and proliferate, surface roughness of the entire outer shell of the ship may increase, leading to deterioration of linear velocity or fuel consumption. Removing aquatic organisms from the bottom requires more than necessary effort and long working time. In addition, when bacteria adhere to a submerged structure attached to an underwater structure and mucus (slime material) or slime adheres to it, or when large-scale adherent creatures adhere to an underwater structure (such as a steel structure) In the case of damaging the corrosion-resistant coating film of an underwater structure, there is a problem that the strength or function of an underwater structure is lowered and the service life is remarkably shortened.

Therefore, there is a demand for an antifouling paint that allows excellent antifouling performance and fine hydrolysis. Fouling is also related to the difference in seawater temperature. When the sea water temperature is high, the polishing of the antifouling paint is increased, and the amount of the antifouling agent is increased, resulting in the fouling of the antifouling coating film leading to deep fouling.

When such aquatic organisms adhere to the bottom of the bottom and proliferate, the hull is corroded, the strength is lowered, and the abrasion can be more easily caused, so that the life can be remarkably shortened and it is common to paint the antifouling paint. An antifouling paint composition is disclosed in Patent Publication No. 10-2008-0010956 (published on Aug. 19, 2008).

The copolymer constituting such an antifouling paint is hydrolyzed in seawater and is converted into bistributyltin oxide (Bu ₃ Sn-OSnBu ₃ (Bu is butyl group)) or tributyltin halide (Bu ₃ SnX (X is halogen atom) Since most of the antifouling paints are hydrolyzable self-polishing type resins, the hydrolytic action on the surface of the polymer that comes into contact with the seawater causes the bond When it is broken and deposited with the dissolution of the antifouling agent, the residual state that is deposited may cause severe environmental pollution. Since tin-based antifouling paints are subject to regulation due to biological problems of tin-based compounds eluted during hydrolysis, development of anti-fouling antifouling paints capable of replacing conventional organic tin-based antifouling paints has been required.

Korean Patent Publication No. 10-2008-0010956 (published on Aug. 19, 2008).

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a self- A polymer for an antifouling paint containing the same, and a self-adhesive model coating film prepared from the same.

In order to accomplish the above object, one aspect of the present invention relates to an antifouling paint polymer comprising a copolymer comprising an acrylic monomer copolymerized with an acrylic monomer and a functional monomer and a monomer containing a trialkylsilyl group as copolymer components.

In addition, the antifouling paint polymer of the present invention is an acrylic monomer, such as methyl methacrylate and methacrylic acid monomer, and the functional monomer is 2-hydroxyethyl acrylate. .

The antifouling paint polymer of the present invention is produced by polymerizing 5 to 10 parts by weight of the acrylic monomer and 10 to 25 parts by weight of the functional monomer with respect to 5 to 10 parts by weight of the monomer containing the trialkylsilyl group do.

Further, the antifouling paint polymer of the present invention is characterized in that the monomer containing the trialkylsilyl group is triethylsilyl (meth) acrylate.

When the coating film for marine use is formed by using the silicone polymer of the present invention, the coating film is gradually decomposed in seawater to self-wear, thereby effectively preventing marine organisms from adhering to the surface of the ship, The wear characteristics can be maintained for a long period of time.

Fig. 1 is a photograph of a coating film prepared by applying and drying the antifouling paint polymer prepared in Examples 1 to 3 and Comparative Examples 1 to 10; Fig.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a polymer for an antifouling paint of the present invention and a self-primer coating film prepared therefrom will be described in detail with reference to the accompanying drawings. The following drawings are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. Therefore, the present invention is not limited to the following drawings, but may be embodied in other forms.

Hereinafter, the technical and scientific terms used herein will be understood by those skilled in the art without departing from the scope of the present invention. Descriptions of known functions and configurations that may be unnecessarily blurred are omitted.

The present invention is an antifouling paint polymer containing as a copolymer component a monomer containing an acrylic resin and a trialkylsilyl group copolymerized with an acrylic monomer and a functional monomer.

According to an embodiment of the present invention, the acrylic monomer may be selected from the group consisting of butylacrylate, styrene, methylmethacrylate, ethyl methacrylate, Butyl acrylate, n-butyl methacrylate, t-butyl methacrylate, acrylonitrile, methacrylonitrile, isobornyl acrylate, And may be at least one monomer selected from 2-hydroxyethyl acrylate and methacrylic acid.

Most preferably, it may be a monomer such as methyl methacrylate and methacrylic acid. Methyl mthacrylate or methacrylic acid is superior in chemical resistance and strength to acrylate monomers having the same side chain.

According to an embodiment of the present invention, the acrylic monomer may be 1: 1 of methyl methacrylate and methacrylic acid.

Further, preferably, the acrylic monomer may be at least one monomer selected from ethyl acrylate and 2-methoxyethyl acrylate. The ethyl acrylate and 2-methoxyethyl acrylate have flexibility and give flexibility and are excellent in adhesion to organs.

Next, since the acrylic monomer alone can not exert sufficient performance, resin designing should be performed in consideration of compatibility with various derivatives. Acrylic resins copolymerize two or more monomers, and since the copolymer is synthesized using a functional monomer, the kind and the capacity of the monomer are important considering the reactivity between the monomers. In the case of a monomer having a functional group, there is a problem that the functional groups are not uniformly distributed in the polymer when the initial charge is determined without considering the reaction ratio because of the high reactivity. If the degree of polymerization of the resin is too low, the coating film is weak and durability, chemical resistance and physical properties deteriorate. If the degree of polymerization is too high, the viscosity of the resin solution becomes too high and the film becomes less susceptible to scratching, This can be bad.

 It is necessary to develop an antifouling resin having a low viscosity. However, if the polymerization molecular weight is simply lowered, the physical and chemical performance of the coating will be deteriorated. If the average molecular weight of the antifouling resin is less than 5000, the weatherability will be deteriorated. Therefore, it is necessary to introduce a proper type of functional group. In order to maintain the dispersibility and stability of the pigment in the application of the coating material, attention must be paid to the molecular weight distribution.

According to one embodiment of the present invention, the functional monomer is selected from the group consisting of 2-HEMA (2-Hydroxyethyl methacrylate), HEA (Hydroxyethyl acrylate), 2-HEA (2-Hydroxyethyl acrylate), HPMA (Hydroxypropyl methacrylate) ), IA (Itaconic acid), and GMA (Glycidylmethacrylate). Most preferably, the functional monomer may be 2-HEA (2-Hydroxyethyl acrylate). When 2-hydroxyethyl acrylate (2-HEA) is polymerized as a functional monomer, an antifouling effect of preventing contamination of an antifouling paint containing a polymerized polymer is advantageous.

Next, the monomer containing the trialkylsilyl group may be more specifically trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, tripropylsilyl (meth) acrylate, triisopropylsilyl (Meth) acrylate, trioctylsilyl (meth) acrylate, tridecylsilyl (meth) acrylate, triisobutylsilyl (meth) acrylate, (Meth) acrylate, dimethyldimethylsilyl (meth) acrylate, butyldimethylsilyl (meth) acrylate and octyldibutylsilyl (meth) acrylate.

The antifouling paint polymer of the present invention is obtained by copolymerizing an acrylic monomer copolymerized with an acrylic monomer and a functional monomer and a monomer containing a trialkylsilyl group as copolymer components and 5 to 10 parts by weight of the monomer containing the trialkylsilyl group, To 10 parts by weight, and the functional monomer is preferably polymerized in an amount of 10 to 25 parts by weight.

When the acrylic monomer is polymerized in an amount of less than 5 parts by weight with respect to 5 to 10 parts by weight of the monomer containing the trialkylsilyl group, problems may arise in the storage stability of a paint prepared thereafter. When the acrylic monomer is mixed in an amount exceeding 10 parts by weight The content of the trialkylsilyl group may be reduced, and thus the antifouling effect of the resulting paint may be deteriorated.

When the functional monomer is mixed in an amount of less than 10 parts by weight based on 5 to 10 parts by weight of the monomer containing the trialkylsilyl group, a suitable viscosity can not be realized due to a small number of functional groups. Therefore, And if the functional monomer is mixed in an amount exceeding 25 parts by weight, the viscosity of the coating material may increase and the workability may be lowered. Therefore, the polymerization is preferably carried out under the above conditions.

Most preferably, the antifouling paint polymer of the present invention may be copolymerized with 6 parts by weight of an acrylic monomer and 5 parts by weight of the functional monomer with respect to 14 parts by weight of the monomer containing the trialkylsilyl group.

Next, the polymer for an antifouling paint according to an example of the present invention may further include an organic solvent.

The organic solvent is used for dissolving the silicone-based polymer, and is not particularly limited as long as it is commonly used in the art, and in one specific example, xylene. But are not limited to, hydrocarbons including toluene, xylene, ethylbenzene, cyclopentane, octane, heptane or white splits, dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, diethylene glycol mono Ethers including methyl ether or diethylene glycol monoethyl ether, acetates including butyl acetate, propyl acetate, benzyl astate, ethylene glycol monomethyl ether acetate or ethylene glycol monoethyl ether acetate, ethyl isobutyl ketone or methyl Ketones including isobutyl canon and alcohols including butanol or propanol, or mixtures thereof, but are not limited thereto.

According to one embodiment of the present invention, the antifouling paint composition comprising the antifouling paint polymer is at least one selected from an antifouling release modifier, a plasticizer, a flow inhibitor, a sedimentation inhibitor, a defoaming agent, a coloring pigment, an organic auxiliary antifouling agent, The additive is contained in an amount of 1 to 10 parts by weight based on the total weight of the antifouling paint composition. The amount of each additive can be appropriately adjusted within the above range.

As the colored pigment, various organic and inorganic pigments known in the art can be used. Examples of the organic pigments include carbon black, phthalocyanine blue and the like. Examples of the inorganic pigments include neutral pigments such as titanium white, iron oxide red, iron oxide powder and chalk, ZnO, zinc oxide), white lead, red lead, and the like, which are reactive to acidic materials in the paint, but the present invention is not limited thereto.

Examples of the organic auxiliary antifouling agent include N-3,4-dichlorophenyl-N, N-dimethylurea, zinc ethylene-1,2-bisdithiocarbamate, metal salt pyrithione type (zinc salt pyrithione, , 2-methylthio-4-t-butylamino-6-cyclopropylamino-triazine, triphenylboron pyridine.

According to one embodiment of the present invention, a flow inhibitor such as a plasticizer such as chlorinated paraffin or an amide wax which contributes to improving the crack resistance of the antifouling paint film is exemplified, and among those commonly used in the art And is not particularly limited.

In addition, the polymer for an antifouling paint according to an exemplary embodiment of the present invention may further include components commonly used in the art within a range that does not impair the physical properties such as the self-abrasion rate or adhesion force, which is the object of the present invention.

The present invention provides a self-assembled monolithic coating film prepared from the polymer for an antifouling paint. The self-priming coating may be one prepared by coating and drying a polymer for an antifouling paint on a substrate.

Hereinafter, the present invention will be described in more detail with reference to a zymma model silicone polymer according to the present invention, a polymer for an antifouling paint containing the same, and a zymology model coating film prepared therefrom. It should be understood, however, that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention. Unless otherwise defined, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Also, the singular forms as used in the specification and the appended claims are intended to include the plural forms as well, unless the context clearly indicates otherwise. In addition, the unit of the additives not specifically described in the specification may be% by weight.

[Synthesis Example 1] Production process of antifouling paint polymer

2-Hydroxyethyl acrylate and triethylsilyl (meth) acrylate were injected into either one of methyl methacrylate or methacrylic acid in the reactor, At 18 rpm and 28 rpm, and then slowly heated to 70 ° C. The type and concentration of the polymerization initiator are determined depending on the molecular weight and the polymerization temperature. When the reaction temperature reached 70 ° C., xylene was polymerized while being added dropwise at 18 Hz and 28 rpm for 7 hours, and then xylene was injected, and the mixture was reacted at 95 ° C. at 18 Hz and 28 rpm for 2 hours . When polymerization is initiated and polymerization is terminated by recombination after the propagation reactions (Combination, Terminated by Combinations), both ends of the molecule become decomposition compounds of the polymerization initiator. If the molecular weight is low, the concentration of the terminal group becomes high, and the influence of the polymerization initiator on the coating film may be large. After that, xylene is added dropwise, reacted at 95 ° C for 18 minutes at 28 rpm for 60 minutes, and then xylene is injected to react and terminate for 20 minutes. When the reaction temperature was lowered to 50 캜, the viscosity was measured.

[Example 1]

In Example 1, the mixing amount of each additive in Synthesis Example 1 was changed to 280 g of triethylsilyl (meth) acrylate, 60 g of methyl methacrylate, 60 g of methacrylic acid, 100 g of 2-hydroxyethyl acrylate was mixed, and all other steps were carried out in the same manner as in Synthesis Example 1.

[Example 2]

In Example 2, the mixing amount of each additive in Synthesis Example 1 was changed to 280 g of triethylsilyl (meth) acrylate, 70 g of methyl methacrylate, 50 g of methacrylic acid, 100 g of ethyl acrylate (2-hydroxyethyl acrylate) was mixed, and all other processes were carried out in the same manner as in Synthesis Example 1. [

[Example 3]

In Example 3, 280 g of triethylsilyl (meth) acrylate, 50 g of methyl methacrylate, 70 g of methacrylic acid, 2 g of 2-hydroxypropyl methacrylate were added in the same manner as in Synthesis Example 1, 100 g of ethyl acrylate (2-hydroxyethyl acrylate) was mixed, and all other processes were carried out in the same manner as in Synthesis Example 1. [

[Comparative Example 1]

In Comparative Example 1, 280 g of the triethylsilyl (meth) acrylate, 120 g of methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate, Were mixed in the same manner as in Synthesis Example 1, and all the other steps were carried out in the same manner as in Synthesis Example 1.

[Comparative Example 2]

In Comparative Example 2, 280 g of the triethylsilyl (meth) acrylate, 120 g of methacrylic acid, and 2-hydroxyethyl acrylate were added in the same manner as in Synthesis Example 1, And all the other steps were carried out in the same manner as in Synthesis Example 1. [

[Comparative Example 3]

In Comparative Example 3, 100 g of the triethylsilyl (meth) acrylate, 120 g of methyl methacrylate, 120 g of methacrylic acid, 2 g of 2-hydroxystearic acid, 160 g of 2-hydroxyethyl acrylate was mixed, and all other processes were carried out in the same manner as in Synthesis Example 1. [

[Comparative Example 4]

In Comparative Example 4, 350 g of the triethylsilyl (meth) acrylate, 50 g of methyl methacrylate, 50 g of methacrylic acid, 2 g of 2-hydroxystyrene 50 g of 2-hydroxyethyl acrylate was mixed, and all other steps were carried out in the same manner as in Synthesis Example 1. [

[Comparative Example 5]

In Comparative Example 5, 140 g of the triethylsilyl (meth) acrylate, 80 g of methyl methacrylate, 80 g of methacrylic acid, 2-hydroxystyrene 200 g of 2-hydroxyethyl acrylate was mixed, and all other processes were carried out in the same manner as in Synthesis Example 1. [

[Comparative Example 6]

In Comparative Example 6, the mixing amount of each additive in Synthesis Example 1 was changed to 200 g of triethylsilyl (meth) acrylate, 30 g of methyl methacrylate, 30 g of methacrylic acid, 240 g of 2-hydroxyethyl acrylate was mixed, and all other steps were carried out in the same manner as in Synthesis Example 1. [

[Comparative Example 7]

In Comparative Example 7, the mixing amount of each additive in Synthesis Example 1 was changed to 200 g of the triethylsilyl (meth) acrylate, 110 g of methyl methacrylate, 110 g of methacrylic acid, 80 g of 2-hydroxyethyl acrylate was mixed, and all other steps were carried out in the same manner as in Synthesis Example 1. [

[Comparative Example 8]

In Comparative Example 8, the mixing amount of each additive in Synthesis Example 1 was changed to 280 g of polyethylene, 60 g of methyl methacrylate, 60 g of methacrylic acid, 2 g of 2-hydroxyethyl acrylate ) Were mixed, and all other steps were carried out in the same manner as in Synthesis Example 1. [

[Comparative Example 9]

In Comparative Example 9, 280 g of the tripropylsilyl (meth) acrylate, 60 g of methyl methacrylate, 60 g of methacrylic acid, 60 g of 2-hydride 100 g of 2-hydroxyethyl acrylate was mixed, and all other steps were carried out in the same manner as in Synthesis Example 1.

[Comparative Example 10]

In Comparative Example 10, the mixing amount of each additive in Synthesis Example 1 was changed to 280 g of triethylsilyl (meth) acrylate, 60 g of methyl methacrylate, 60 g of methacrylic acid, 100 g of ethyl methacrylate (2-hydroxyethyl methacrylate) was mixed, and all other processes were carried out in the same manner as in Synthesis Example 1. [

[Property evaluation]

Antifouling performance test

To 35 parts by weight of the antifouling paint polymer prepared in Examples 1 to 3 and Comparative Examples 1 to 10, 6 parts by weight of iron oxide, 30 parts by weight of zinc oxide, 4 parts by weight of talc, 10 parts by weight of an organic antifouling agent, And 8 parts by weight of xylene were mixed and dispersed using a dispersing machine at a rotation speed of 2,500 rpm and dispersed, and then filtered using a 200-mesh filter. Each of the antifouling paint compositions was applied to a sandblast-treated steel sheet, . The coating film thus formed was observed for 20 days from January 20, 2016 to August 25, 2016, and the degree of fouling of the coating film was evaluated by observing the coated state of the polymer for antifouling paint.

The coating films on which the antifouling paint polymers of Examples 1 to 3 and Comparative Examples 1 to 10 were formed were evaluated for physical properties on the same date and clean step> formation of a biofilm> Film formation step> partial plant formation step> overall plant formation step> partial animal formation step, and it was confirmed that the effect of self-abrasion was lowered as the step toward partial animal formation step was progressed.

As shown in Fig. 1, the coated film coated with the antifouling paint polymer of Examples 1 to 3 was found to be very clean as compared with Comparative Examples 1 to 10, and in the case of Examples 2 to 3, In particular, in Example 1, it was confirmed that the biofilm was formed only partially on the coated film, and thus the abrasion effect was excellent.

On the other hand, the antifouling paint polymer prepared by Comparative Examples 1 to 10 was confirmed to be a partial plant forming step, an overall plant forming step and a partial animal forming step, as shown in Fig. 1, 3, it can be confirmed that the self-wear effect is low.

Wear performance test

To measure the abrasion rate of the magnetic resin mold resin, 6 parts by weight of iron oxide, 30 parts by weight of zinc oxide, 4 parts by weight of talc, 10 parts by weight of an organic antifouling agent were added to 35 parts by weight of the antifouling paint polymer prepared in Example 1 and Comparative Example 11, , 2 parts by weight of a plasticizer and 8 parts by weight of xylene were mixed and dispersed using a dispersing machine at a rotation speed of 2,500 rpm and dispersed. Then, the resulting antifouling paint composition was filtered using a 200 mesh filter, M, dried at room temperature for more than 24 hours, immersed in artificial seawater, and weighed using a precision scale over a period of time. Table 1 below shows the results of the wear rate test under static conditions.

Result of coating wear test 0.5 months 1 month 1.5 months 2 months 2.5 months Rest% Example 1 1.00 0.90 0.87 0.85 0.83 83 Example 2 1.00 0.91 0.89 0.87 0.85 85 Example 3 1.00 0.90 0.86 0.83 0.82 82 Comparative Example 1 1.00 0.92 0.87 0.84 0.82 82 Comparative Example 2 1.00 0.91 0.88 0.85 0.83 83 Comparative Example 3 1.00 0.94 0.91 0.88 0.87 87 Comparative Example 4 1.00 0.87 0.82 0.79 0.76 76 Comparative Example 5 1.00 0.97 0.96 0.95 0.93 93 Comparative Example 6 1.00 0.99 0.98 0.98 0.97 97 Comparative Example 7 1.00 0.89 0.85 0.82 0.80 90 Comparative Example 8 1.00 0.91 0.88 0.84 0.82 82 Comparative Example 9 1.00 0.93 0.89 0.86 0.84 84 Comparative Example 10 1.00 0.92 0.89 0.87 0.85 85

While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. Therefore, the above description does not limit the scope of the present invention, which is defined by the limitations of the following claims.

Claims (5)

3 parts by weight of methyl methacrylate relative to 14 parts by weight of triethylsilyl (meth) acrylate; 3 parts by weight of methacrylic acid monomer; And 5 parts by weight of 2-hydroxyethyl acrylate as a copolymerization component,
Wherein the weight ratio remaining after self-abrasion after one month in artificial seawater is 90%.
The antifouling paint composition according to claim 1, wherein the copolymer further comprises ethyl acrylate and 2-methoxyethyl acrylate as copolymer components. delete delete delete

Images