KR102141764B1 - Resin composition for metal type self-polishing an antifouling paint - Google Patents

Abstract

The present invention relates to a resin composition for an antifouling coating material and a manufacturing method thereof, and more particularly, to a resin composition for an antifouling coating material and a manufacturing method thereof, in which: when an antifouling coating material is manufactured by using the composition, since a metal salt which imparts high stickiness and adhesion is used, the antifouling coating material exhibits high mixability with an antifouling agent; since the metal salt exhibits a self-wear property, marine organisms are effectively prevented from adhering to a surface of a ship or the like; adhesion between the surface of the ship and a coating film is excellent so that the self-wear property is maintained for a long time; and excellent crack resistance and wear performance are obtained. The resin composition for the antifouling coating material includes: 100 to 150 parts by weight of an acrylic monomer; a metal salt such as copper acetate or zinc acetate; 10 to 30 parts by weight of an organic solvent; and 30 to 40 parts by weight of first silica particles which are surface-modified with SO_3 and represented by Chemical formula 1.

Description

Resin composition for metal type self-polishing an antifouling paint}

The present invention relates to a resin composition for a metal-based self-wearing antifouling paint and a method for manufacturing the same, and more specifically, because it uses a metal salt that provides high adhesion and adhesion, it has high mixing property with an antifouling agent, and the metal salt is self-wearing. It can effectively prevent marine organisms from adhering to the surface of a ship, etc., because of the excellent adhesion between the ship's surface and the coating film, it can maintain self-wear properties for a long time, and has excellent effects such as crack resistance and wear performance. The present invention relates to a resin composition for a metal-based self-wearing antifouling paint and a method for manufacturing the same.

The resin for antifouling paints serves to prevent or control the attachment and growth of marine organisms that cause seawater deposition and surface contamination of the coating, and the bottom of the hull, aquatic structures, etc., are exposed to water for long periods of time, such as shellfish, oysters, mussels, and hats. Animals such as shellfish, plants such as green grass (seaweed), and various aquatic organisms such as aquatic bacteria attach to and multiply on the surface, resulting in poor appearance or loss of function. In particular, when such aquatic organisms attach to the bottom of the ship and multiply, the surface roughness of the entire ship's outer shell may increase, resulting in a decrease in ship speed or an increase in fuel consumption.

In order to remove aquatic organisms from the bottom, a lot of manpower and cost are consumed. Mucus or slime attaches to the bacteria that attach to and reproduce in the aquatic structure, thereby causing the bacteria to decay or adhere to a large organism that has adhesion. There was a problem in that the function of the coating film was reduced or damaged by adhesion and propagation, thereby significantly shortening the life.

In addition, since the surface or underwater structure of the ship is exposed to sea water or water for a long period of time, it must exhibit excellent corrosion resistance. The resin for antifouling paints used in the past is a toxic substance that inhibits the growth of bacteria or organic matter to show antifouling performance. Since it contained a large amount, there was a problem of polluting the environment, and since it only suppresses contamination of the surface of the ship or the structure of the underwater structure, there is a demand for an anti-corrosion coating resin showing excellent corrosion resistance.

Accordingly, in order to compensate for the above-mentioned problems, the present inventors recognized that the development of a resin composition for an antifouling paint having excellent antifouling ability, crack resistance and abrasion performance and a manufacturing method thereof is urgent, and completed the present invention.

Republic of Korea Registered Patent Publication No. 10-1828661 Republic of Korea Registered Patent Publication No. 10-1270522 Republic of Korea Registered Patent Publication No. 10-1683970 Japanese Patent Application Publication No. 2006-265560

Progress in Organic Coatings Volume 53, Issue 4, 1 August 2005, Pages 256-275 Progress in Organic Coatings Volume 55, Issue 3, 1 March 2006, Pages 207-217

The object of the present invention is to use a metal salt that gives high adhesion and adhesion, and exhibits excellent mixing properties with an antifouling agent, can improve antifouling ability, exhibits an excellent curing rate, and has excellent metal resistance to crack resistance and abrasion performance. It is to provide a resin composition for abrasive antifouling paint.

Another object of the present invention includes a first silica particle surface-modified with SO ₃ represented by [Formula 1] and a second silica particle surface-modified with SO ₃ represented by [Formula 2] in an antifouling coating composition, It is to provide a method for preparing a resin composition for a metal-based self-abrasive antifouling coating that exhibits significantly improved crack resistance and abrasion performance compared to an antifouling coating composition.

The problems of the present invention are not limited to the problems mentioned above, and other problems that are not mentioned will be clearly understood by those skilled in the art from the following description.

In order to achieve the above object, the present invention provides a resin composition for a metal-based self-wearing antifouling paint and a method for manufacturing the same.

Hereinafter, the present specification will be described in more detail.

The present invention is an acrylic monomer; Metal salts; Organic solvents; And it provides a resin composition for an antifouling coating comprising the first silica particles surface-modified with SO ₃ represented by the following [Formula 1].

[Formula 1]

In the present invention, the resin composition for antifouling paint is characterized in that it further comprises; second silica particles surface-modified with SO ₃ represented by the following [Formula 2].

[Formula 2]

In the present invention, the resin composition for antifouling paint is 100 to 150 parts by weight of the acrylic monomer; 10 to 30 parts by weight of the organic solvent; And 30 to 40 parts by weight of the first silica particles surface-modified with SO ₃ represented by [Formula 1], wherein the metal salt comprises 1.85 to 2.65% by weight in the total weight% of the acrylic monomer. It is characterized by.

In the present invention, the acrylic monomer is styrene (styrene); n-butyl acrylate; Methyl mthacrylate; 2-hydroxyethyl acrylate; And methacrylic acid.

In the present invention, the acrylic monomer is 70 to 85 parts by weight of n-butyl acrylate relative to 100 parts by weight of styrene (styrene); 50 to 60 parts by weight of methyl methacrylate; 2-hydroxyethyl acrylate 150 to 250 parts by weight; And 20 to 30 parts by weight of methacrylic acid.

In the present invention, the metal salt is characterized in that copper acetate (copper acetate) or zinc acetate (zinc acetate).

In the present invention, the organic solvent is xylene; Or a mixture of xylene and butyl acetate, and the mixture of xylene and butyl acetate is a mixture of 3 to 5 parts by weight of butyl acetate with respect to 100 parts by weight of xylene.

In the present invention, the resin composition for antifouling paint may further include 2 to 3 parts by weight of the initiator relative to 100 parts by weight of the acrylic monomer, and the initiator may be azo bis-isobutylonitrile (azobisisobutyronitrile), Benzoyl peroxide, tert-butyl perbenzoate, di-butyl peroxide, di-tert-butyl peroxide, and Characterized in that at least one member selected from the group consisting of 2-(tert-butoxy)-2-methylpropane).

In addition, the present invention provides a method for producing a resin composition for antifouling paints comprising the following steps.

(S1) mixing the initiator and the organic solvent, and heating to 50 to 90 ℃;

(S2) adding the first silica particles surface-modified with an acrylic monomer, a metal salt, and SO ₃ represented by the following [Formula 1] to the mixture; And

(S3) adding an organic solvent, and cooling to 30 to 50° C. to terminate the reaction.

[Formula 1]

In the present invention, the (S2) step is characterized in that it further comprises; second silica particles surface-modified with SO ₃ represented by the following [Formula 2].

[Formula 2]

The same applies to all the matters mentioned in the resin composition for antifouling paints of the present invention and a method for manufacturing the same, unless contradictory to each other.

The metal-based self-abrasive antifouling coating resin composition of the present invention and its manufacturing method can effectively prevent marine organisms from adhering to the surface of a ship or the like by using a metal salt that has self-abrasion and provides high adhesion and adhesion, It can improve the excellent mixing property and antifouling ability with the antifouling agent, exhibits an excellent curing rate, and has excellent effects in crack resistance and abrasion performance.

In addition, town self of the invention metal-based model antifouling coating resin composition and a method for the surface modified with SO ₃ represented by the above Formula 1 the surface-modified first silica particles and a SO ₃ represented by [Formula 2] The second silica particles are included in the antifouling coating composition to exhibit significantly improved crack resistance and abrasion performance compared to the conventional antifouling coating composition.

In addition, the metal-based self-wearing antifouling coating resin composition of the present invention and a method for manufacturing the same exhibit an acid value of 10 mg KOH/g or less, thereby exhibiting an excellent curing rate, and can exhibit excellent effects in crack resistance and abrasion performance.

The effects of the present invention are not limited to the effects mentioned above, and other effects not mentioned will be clearly understood by those skilled in the art from the description of the claims.

1 is an embodiment 1 to 3 of the present invention; And the anti-fouling paint prepared by using the resin for anti-fouling paint of Comparative Example 1, showing the degree of contamination (anti-fouling property) of the specimen.

The present invention provides a resin composition for a metal-based self-wearing antifouling paint and a method for manufacturing the same.

Hereinafter, the present specification will be described in more detail.

Resin composition for antifouling paint

The present invention provides a resin composition for antifouling paints.

More specifically, the present invention is an acrylic monomer; Metal salts; Organic solvents; And it provides a resin composition for an antifouling coating comprising first silica particles surface-modified with SO ₃ represented by the following [Formula 1].

[Formula 1]

In addition, the composition for antifouling paints may further include; second silica particles surface-modified with SO ₃ represented by the following [Formula 2].

[Formula 2]

The resin composition for antifouling paint is 100 to 150 parts by weight of the acrylic monomer; 10 to 30 parts by weight of the organic solvent; And 30 to 40 parts by weight of the first silica particles surface-modified with SO ₃ represented by [Formula 1]; and the metal salt may include 1.85 to 2.65% by weight in the total weight% of the acrylic monomer. have.

The acrylic monomer is styrene (styrene); n-butyl acrylate; Methyl mthacrylate; 2-hydroxyethyl acrylate; And methacrylic acid.

The acrylic monomer is 70 to 85 parts by weight of n-butyl acrylate relative to 100 parts by weight of styrene; 50 to 60 parts by weight of methyl methacrylate; 2-hydroxyethyl acrylate 150 to 250 parts by weight; And 20 to 30 parts by weight of methacrylic acid.

The styrene can be applied to a wide range of industrial applications by supplementing and improving mechanical properties while maintaining the transparency of the resin, and it is applied to paints because it has good fluidity while increasing stability and strength against heat, etc. of the resin. When it does, it not only maintains its properties stably, but also can exhibit an effect of, for example, a continuous release of the antifouling agent in the antifouling resin composition.

The metal salt may include 1.85 to 2.65% by weight based on the total weight of the acrylic monomer.

The metal salt is less than 1.85% by weight in the total weight% of the acrylic monomer, the above effect is insignificant, and when the content of the metal salt exceeds 2.65% by weight, the effect is not significantly improved, and adhesion when antifouling paint is applied It can degrade sex.

The metal salt may be a copper salt or a zinc salt, and more preferably copper acetate or zinc acetate.

The copper acetate or zinc acetate not only inhibits the growth and adhesion of microorganisms and corrosion of the metal substrate, but also can be suppressed from being contaminated with the surface of the ship or underwater structure while gradually eluting after being contained in the antifouling paint.

The copper acetate or zinc acetate may be applied in the form of anhydride or first hydrate.

In the resin composition for antifouling paint, the organic solvent may be included in an amount of 10 to 30 parts by weight.

The organic solvent serves to uniformly mix all the reaction substances involved in the preparation of the resin composition for antifouling paints of the present invention and to exhibit homogeneous properties.

If the content of the holding solvent is less than 10 parts by weight, the above effect is negligible. When the content of the oil-soluble solvent exceeds 30 parts by weight, the effect of the above is not significantly improved, and the content of the metal salt and acrylic monomer is relatively reduced, thereby preventing contamination. When applying a paint, the antifouling performance effect can be reduced.

The organic solvent is xylene; Or xylene and butyl acetate.

The mixture of xylene and butyl acetate may be an organic solvent mixed with 3 to 5 parts by weight of butyl acetate with respect to 100 parts by weight of xylene.

The first silica particles surface-modified with SO ₃ represented by [Formula 1] may be included in 30 to 40 parts by weight.

In the present invention, the first silica particles surface-modified with SO ₃ represented by [Formula 1] may be silica particles surface-modified with SO ₃ in a form in which the surface of the glass bubble is modified.

The term used in the present invention, the glass bubble is a compound made of soda-lime-borosilicate (soda-lime-borosilicate), has excellent water resistance, and has excellent mechanical properties.

In the present invention, the glass bubble is not limited to the type of average particle size, specific gravity, and the like, and can be used without limitation if there is no inconvenience in using it commercially.

In addition, the second silica particles surface-modified with SO ₃ represented by [Formula 2] may be included in 30 to 40 parts by weight. The second silica particles may be included as a substitute for the first silica particles, and may be included in a 1:1 mixture with the first silica particles surface-modified with SO ₃ represented by [Formula 1].

In the present invention, by including the first silica particles surface-modified with SO ₃ represented by [Formula 1] and the second silica particles surface-modified with SO ₃ represented by [Formula 2], antifouling at the time of manufacturing the antifouling coating It has the effect of amplifying the performance and exhibiting excellent antifouling performance.

The resin composition for antifouling paint may additionally include 2 to 3 parts by weight of the initiator with respect to 100 parts by weight of the acrylic monomer.

Since the resin composition for antifouling paints further includes an initiator, monomers selected according to various known polymerization methods such as solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization of the metal salt, organic solvent, and acrylic monomer can be randomly copolymerized. .

The initiator is azo bis-isobutylonitrile (azobisisobutyronitrile), benzoyl peroxide, tert-butyl perbenzoate, di-butyl peroxide, di-butyl peroxide, di- It may be one or more selected from the group consisting of di-tert-butyl peroxide and 2-(tert-butoxy)-2-methylpropane. And preferably, may be one or more selected from the group consisting of azo bis-isobutylonitrile, benzoyl peroxide, and tert-butyl perbenzoate.

When the content of the initiator is less than 2 parts by weight, the polymerization rate and the degree of polymerization of the resin composition for antifouling paint are lowered to decrease the adhesion performance of the antifouling paint polymer prepared from the composition, and the initiator content is more than 3 parts by weight. When the polymerization degree of the resin composition for antifouling paint is excessively increased, the viscosity is excessively improved, and thus, the efficiency of the process may be lowered when the antifouling paint is applied to the surface of a ship or an underwater structure.

The initiator acts to polymerize the resin composition for antifouling paint so as to exhibit an appropriate viscosity when the antifouling paint is applied, and because the viscosity is improved by polymerizing with the oligomer or polymer by the initiator, the surface of the ship may be applied when the antifouling paint is applied. It becomes possible to adhere to the surface of the underwater structure.

Manufacturing method of resin composition for antifouling paint

The present invention provides a method for producing a resin composition for antifouling paints comprising the following steps.

(S1) mixing the initiator and the organic solvent, and heating to 50 to 90 ℃;

(S2) adding the first silica particles surface-modified with an acrylic monomer, a metal salt, and SO ₃ represented by the following [Formula 1] to the mixture; And

(S3) adding an organic solvent, and cooling to 30 to 50° C. to terminate the reaction.

[Formula 1]

The resin composition for antifouling paint is as described above.

The organic solvent used in step (S1) may be xylene; and the organic solvent used in step (S3) may be a mixture of xylene and butyl acetate.

The mixture of xylene and butyl acetate may be a mixture mixed with 3 to 5 parts by weight of butyl acetate, based on 100 parts by weight of xylene.

The first silica particles surface-modified with SO ₃ represented by the following [Chemical Formula 1] used in the step (S2) may be prepared by the following steps.

(S2-1A) A glass bubble combined with one hydroxy group represented by the following [Formula 3] and a (3-mercaptopropyl)trimethoxysilane represented by the following [Formula 4] ( Preparing a mixture by mixing (3-Mercaptopropyl)trimethoxysilane) at 100 to 120°C;

(S2-2A) Step of preparing the first silica particles surface-modified with SO ₃ represented by [Formula 1] by adding hydrogen peroxide (H ₂ O ₂ ) and sulfur (H ₂ SO ₄ ) to the mixture.

[Formula 3]

[Formula 4]

More specifically, in the step (S2-1A), a glass bubble combined with one hydroxy group represented by [Formula 3] and (3-mercaptopropyl) trime represented by [Formula 4] The mixture can be prepared by dissolving oxysilane in a solvent, and more preferably, dissolving in toluene.

The mixture dissolved in the solvent in the step (S2-1A) can be carried out for agitation reaction for 4 to 12 hours at 100 to 120 ℃.

In the present invention, after the mixing is completed in the step (S2-1A), the mixture may further include a step of drying and washing. More specifically, after the stirring reaction, the mixture is removed through a filter through a solvent to obtain a powder, and the obtained powder can be dried. The powder drying may be performed at room temperature or room temperature, and may be performed for 1 to 24 hours, but is not limited to this, as long as the moisture of the powder is removed.

The (S2-2A) step may be a step of preparing the first silica particles surface-modified with SO ₃ represented by [Formula 1] by reacting the mixture with hydrogen peroxide and sulfuric acid.

More specifically, hydrogen peroxide (H ₂ O ₂ ) and sulfuric acid (H ₂ SO ₄ ) may be added to the powder dried in the step (S2-2A) to react at 40 to 80° C., preferably 50 to 50 It can be reacted at 70°C.

In the present invention, the (S2-2A) step may be performed for 1 to 8 hours, more preferably 2 to 6 hours.

In the present invention, when adding hydrogen peroxide water performed in the step (S2-2A), a solvent or a solution may be added, and the solvent or solution may be water, ethanol, sulfuric acid or a mixture thereof, preferably water And ethanol and sulfuric acid.

The (S2) step may further include; second silica particles surface-modified with SO ₃ represented by the following [Formula 2];

[Formula 2]

The third silica particles surface-modified with SO ₃ represented by [Formula 2] used in the step (S2) may be prepared by the following steps.

(S2-1B) The three hydroxy group represented by the following [Formula 5] glass bubbles and (3-mercaptopropyl) trimethoxysilane represented by [Formula 4] 100 to 120 ℃ Mixing in to prepare a mixture;

(S2-2B) Step of preparing the second silica particles surface-modified with SO ₃ represented by [Formula 2] by adding hydrogen peroxide (H ₂ O ₂ ) and sulfur (H ₂ SO ₄ ) to the mixture.

[Formula 5]

More specifically, in the (S2-1B) step, three hydroxy groups represented by [Formula 5] are combined with a glass bubble and (3-Mercaptopropyl) trime represented by [Formula 4] The mixture can be prepared by dissolving oxysilane in a solvent, and more preferably, dissolving in toluene.

The mixture dissolved in the solvent in the step (S2-1B) may be carried out for agitation reaction for 4 to 12 hours at 100 to 120 ℃.

In the present invention, after the mixing is completed in the step (S2-1B), the mixture may further include a step of drying and washing. More specifically, after the stirring reaction, the mixture is removed through a filter through a solvent to obtain a powder, and the obtained powder can be dried. The powder drying may be performed at room temperature or room temperature, and may be performed for 1 to 24 hours, but it is not limited thereto, as long as the moisture of the powder is removed.

The (S2-2B) step may be a step of preparing the second silica particles surface-modified with SO ₃ represented by [Formula 2] by reacting the mixture with hydrogen peroxide and sulfuric acid.

More specifically, hydrogen peroxide (H ₂ O ₂ ) and sulfuric acid (H ₂ SO ₄ ) may be added to the powder dried in the step (S2-2B) to react at 40 to 80° C., preferably 50 to 50 It can be reacted at 70°C.

In the present invention, the (S2-2B) step may be performed for 1 to 8 hours, more preferably for 2 to 6 hours.

In the present invention, when adding hydrogen peroxide water performed in the step (S2-2B), a solvent or a solution may be added, and the solvent or solution may be water, ethanol, sulfuric acid, or a mixture thereof, preferably water And ethanol and sulfuric acid.

Advantages and features of the present invention, and methods for achieving them will be clarified with reference to embodiments described below in detail. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various different forms, and only the embodiments make the disclosure of the present invention complete, and common knowledge in the technical field to which the present invention pertains. It is provided to fully inform the person having the scope of the invention, and the present invention is only defined by the scope of the claims.

Reagents and solvents mentioned below were purchased from Sigma-Aldrich Korea unless otherwise specified.

Preparation Example 1. SO represented by [Formula 1] ₃ First silica particles surface-modified with

The glass bubble containing one hydroxy group represented by [Formula 3] and the (3-mercaptopropyl) trimethoxysilane represented by [Formula 4] are mixed and dissolved in toluene, and the dissolved The mixture was stirred at 110° C. for 6 hours. The mixture was removed with toluene using filter paper to obtain a powder, and the obtained powder was dried at room temperature for 24 hours. Water, hydrogen peroxide and yellow phase were added to the dried powder. The reaction was performed at 60° C. for 4 hours to prepare first silica particles surface-modified with SO ₃ represented by the following [Chemical Formula 1].

[Formula 1]

Production Example 2. SO represented by [Formula 2] ₃ Second silica particles surface-modified with

A glass bubble containing three hydroxy groups represented by [Formula 5] and (3-mercaptopropyl)trimethoxysilane represented by [Formula 4] are mixed and dissolved in toluene, and the dissolved mixture Was stirred at 110° C. for 6 hours. The mixture was removed with toluene using filter paper to obtain a powder, and the obtained powder was dried at room temperature for 24 hours. Water, hydrogen peroxide and yellow phase were added to the dried powder. The reaction was performed at 60° C. for 4 hours to prepare second silica particles surface-modified with SO ₃ represented by the following [Chemical Formula 2].

[Formula 2]

Example 1. Resin for antifouling paints of the present invention 1

Xylene was added to the initiator bis-isobutylonitrile (azobisisobutyronitrile) and mixed. And stirred while heating to 60 ℃, styrene 100: 80 parts by weight of n-butyl acrylate; 55 parts by weight of methyl methacrylate; 2-hydroxyethyl acrylate 200 parts by weight; And 25 parts by weight of methacrylic acid; 120 parts by weight of the acrylic monomer as a mixture, 35 parts by weight of the first silica particles surface-modified with SO ₃ represented by [Formula 1] and 2.4 parts by weight of copper acetate (the acrylic monomer 2.0% by weight). Finally, while adding a mixed solution of xylene and butyl acetate (100:4 weight ratio), the temperature was reduced to 40° C. to prepare a resin 1 for the antifouling paint of the present invention.

Example 2. Resin 2 for antifouling paints of the present invention

Xylene was added to the initiator bis-isobutylonitrile and mixed. And stirred while heating to 60 ℃, styrene 100: n-butyl acrylate 80 parts by weight; 55 parts by weight of methyl methacrylate; 2-hydroxyethyl acrylate 200 parts by weight; And 25 parts by weight of methacrylic acid; 120 parts by weight of the acrylic monomer as a mixture, 35 parts by weight of the second silica particles surface-modified with SO ₃ represented by [Formula 2], and 2.4 parts by weight of zinc acetate (the acrylic monomer 2.0% by weight). Finally, while adding a mixed solution of xylene and butyl acetate (100:4 weight ratio), the temperature was reduced to 40° C. to prepare Resin 2 for the antifouling paint of the present invention.

Example 3. Resin 3 for antifouling paints of the present invention

Xylene was added to the tert-butyl perbenzoate initiator and mixed. And stirred while heating to 70 ℃, styrene 100: n-butyl acrylate 75 parts by weight; 55 parts by weight of methyl methacrylate; 2-hydroxyethyl acrylate 220 parts by weight; And methacrylic acid 25 parts by weight of surface-SO ₃ represented by a mixture of acrylic monomer 135 parts by weight of the Formula 1 the surface modification of the first silica particles and the by SO ₃ represented by the [formula 2] mixed in a 38 parts by weight of a 1:1 mixture of modified second silica particles, and 3.375 parts by weight of copper acetate (2.25% by weight based on the total weight of the acrylic monomer) were added. Finally, while adding a mixed solution of xylene and butyl acetate (100:4 weight ratio), the temperature was reduced to 40° C. to prepare Resin 3 for the antifouling paint of the present invention.

Comparative Example 1. Resin composition for antifouling paint of Korean Patent Registration No. 10-1828661

In order to confirm the effect of the resin composition for antifouling paints of the present invention, the Republic of Korea Patent Publication No. 1 does not contain alkoxysilane monomers and metal salts containing sulfonic acid groups represented by [Formula 1] A resin composition for antifouling paint of 10-1828661 was prepared. All manufacturing processes were prepared according to Preparation Example 1 of Korean Patent Publication No. 10-1828661.

Experimental Example 1. Confirmation of acid value

Examples 1 to 3 above; And in order to confirm the acid value of the resin for antifouling paint of Comparative Example 1, the resin for antifouling paint (solid content or solution) was weighed in an Erlenmeyer flask and dissolved by adding a solvent. Then, an indicator (1% phenolphthalein ethyl alcohol solution) was added, titrated with a 0.1 mol/l potassium hydroxide solution (alcoholic), and calculated by the following equation when the pink color disappeared as an end point.

Acid value (mgKOH/g) = F x V/S

F: Factor of 0.1 mol/l potassium hydroxide solution (concentration correction factor)

V: titration amount of 0.1 mol/l potassium hydroxide solution (ml)

S: sampling amount (g)

Referring to Table 1 below, the acid values of Examples 1 to 3 to which metal salts (copper acetate or zinc acetate) were added were in the range of 6 to 7 mgKOH/g, while Comparative Example 1 without metal salts It can be seen that represents a value of 68 mgKOH/g acid value.

[Table 1]

As in the above Examples 1 to 3, when the paint exhibits a high acid value of 10 mgKOH/g or less, the curing speed of the paint increases, thereby showing an effect of increasing work efficiency, and has the effect of extending the life of the paint. . On the other hand, when the acid value of the paint is low, as in Comparative Example 1, the curing speed of the paint may be slowed to lower the working efficiency and the paint itself may be dilute.

From the above results, it can be seen that the paint of the present invention shows an acid value in the range of 6 to 7 mgKOH/g, and thus exhibits an excellent effect in terms of the curing speed of the paint.

Experimental Example 2. Confirmation of crack resistance and wear performance effect

Examples 1 to 3 above; And to confirm the crack resistance and abrasion performance effect of the resin for antifouling paint of Comparative Example 1, to prepare an antifouling paint by adding the reactants in Table 2 in weight%.

[Table 2]

In order to check the effect of crack resistance and abrasion performance using an antifouling coating prepared by mixing the reactants of [Table 2], the surface of the AF (Anti-Finger) is visually inspected on a weekly basis using QUV, a weather resistance evaluation device It was checked to determine the presence or absence of cracks. It was evaluated as ○ without cracks and X with cracks.

In addition, the above Examples 1 to 3; And the antifouling paint of Comparative Example 1 was continuously coated at intervals of one day to cure and dry at room temperature for one week. The specimens thus prepared were installed on the outside of a rotating drum having a diameter of 600 mm and a height of 300 mm, and then rapidly rotated at a rate of 20 knot at constant temperature of 25°C to measure the change in the film thickness for 6 months at 1-month intervals. Was evaluated. The degree of abrasion performance was automatically measured and quantified by a laser coating film measuring machine, and 0 to 8 was evaluated as △, 8 to 15 were evaluated as ○, and 16 to 30 were evaluated as ◎, and the results are shown in Table 3 below.

[Table 3]

As can be seen from the [Table 3], it can be seen that the coating films coated with the antifouling coatings of Examples 1 to 3 containing metal salts were excellent in crack resistance and abrasion performance effects. On the other hand, it can be seen that the coating film coated with the anti-fouling paint of Comparative Example 1, which does not contain a metal salt, has a remarkably poor crack resistance and wear performance effect.

Experimental Example 3. Confirmation of seawater contamination (antifouling)

Examples 1 to 3 above; And in order to confirm the degree of seawater contamination of the resin for antifouling paint of Comparative Example 1, the Examples 1 to 3 prepared in Experimental Example 2; And the antifouling paint of Comparative Example 1.

The anti-fouling paints of Examples 1 to 3 and Comparative Example 1 prepared in Experimental Example 2 were coated on a 100×300×3.2 mm sandblast-treated steel sheet to prepare a specimen with a dry film thickness of 100 μm. The specimens were dried at room temperature for 7 days, and still immersed in the East Coast, and the adhesion area of attached organisms was measured with the naked eye every 3 months, and the results are shown in Tables 4 and 1 below.

[Table 4]

As can be seen from [Table 4] and [Figure 1], it can be seen that the pollution degree of seawater in the anti-fouling paints of Examples 1 to 3 of the present invention containing the metal salt after 12 months is impossible from 2 to 9%. For this reason, it can be confirmed that the antifouling paint of the present invention exhibits very good antifouling properties. On the other hand, in Comparative Example 1, which does not contain a metal salt, it can be seen that after 3 to 6 months, it shows a seawater pollution degree of 17%, and after 12 months, it shows a high seawater pollution degree of 38%.

From the above results, it can be seen that the antifouling paint of the present invention containing a metal salt exhibits a remarkably excellent antifouling effect of up to 7.6 times or more compared to the antifouling paint of Comparative Example 1 that does not contain a metal salt.

Above, the present invention is not limited to the above-described embodiments, and it is obvious to those skilled in the art that various modifications and variations can be made without departing from the spirit and scope of the present invention. Therefore, it should be said that such modifications or variations belong to the claims of the present invention.

Claims (10)

100 to 150 parts by weight of an acrylic monomer; Metal salts of copper acetate or zinc acetate; 10 to 30 parts by weight of an organic solvent; And 30 to 40 parts by weight of the first silica particles surface-modified with SO ₃ represented by the following [Formula 1];
The metal salt is 1.85 to 2.65% by weight of the total weight of the acrylic monomer, characterized in that it comprises a resin composition for antifouling paint.
[Formula 1]

According to claim 1,
The resin composition for antifouling paints further comprises second silica particles surface-modified with SO ₃ represented by [Formula 2] below.
[Formula 2]

delete According to claim 1,
The acrylic monomer,
Styrene; n-butyl acrylate; Methyl methacrylate; 2-hydroxyethyl acrylate; And methacrylic acid. According to claim 4,
The acrylic monomer,
With respect to 100 parts by weight of styrene,
70 to 85 parts by weight of n-butyl acrylate; 50 to 60 parts by weight of methyl methacrylate; 2-hydroxyethyl acrylate 150 to 250 parts by weight; And 20 to 30 parts by weight of methacrylic acid; an antifouling coating resin composition, characterized in that it is mixed. delete According to claim 1,
The organic solvent,
Xylene; Or a mixture of xylene and butyl acetate,
The mixture of xylene and butyl acetate,
With respect to 100 parts by weight of the xylene,
A resin composition for antifouling paint, characterized in that it is a mixture mixed with 3 to 5 parts by weight of butyl acetate. According to claim 1,
The resin composition for antifouling paints,
With respect to 100 parts by weight of the acrylic monomer, the initiator may further include 2 to 3 parts by weight,
The initiator is azo bis-isobutylonitrile (azobisisobutyronitrile), benzoyl peroxide, tert-butyl perbenzoate, di-butyl peroxide, di-butyl peroxide, di- One or more selected from the group consisting of di-tert-butyl peroxide and 2-(tert-butoxy)-2-methylpropane A resin composition for an antifouling paint, characterized in that. (S1) mixing the initiator and the organic solvent, and heating to 50 to 90 ℃;
(S2) adding the first silica particles surface-modified with an acrylic monomer, a metal salt, and SO ₃ represented by the following [Formula 1] to the mixture; And
(S3) adding an organic solvent, and cooling to 30 to 50 ℃ to terminate the reaction; includes,
The metal salt is copper acetate (copper acetate) or zinc acetate (zinc acetate) method of manufacturing a resin composition for antifouling paint, characterized in that.
[Formula 1]

The method of claim 9,
The (S2) step, the second silica particles surface-modified with SO ₃ represented by the following [Formula 2]; further comprising a method for producing a resin composition for antifouling paint.
[Formula 2]

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