KR20060074046A - Anti-fouling paint composition - Google Patents

Abstract

The present invention provides an antifouling coating composition characterized in that a mixture of a triphenylborane-amine mixture represented by the following formula (1) and a polyhexamethyleneguanidine salt represented by the following formula (2), which is a triphenylborane-amine mixture alone It is useful as antifouling paints for fishing nets, ships, marine structures, etc., since it has improved antifouling performance and storage stability compared to those used as an antifouling effective ingredient.

In the above formula, each X is independently an inorganic acid salt or an organic acid salt, and each R 1 is independently a linear or branched alkyl group having 1 to 20 carbon atoms, or is phenyl, chlorophenyl, bromophenyl, iodophenyl, benzyl, chlorobenzyl, Bromobenzyl, iodobenzyl, phenethyl, naphthyl or hydrogen, n is an integer of 1 or greater.

Description

 Anti-fouling paint composition

The present invention relates to an antifouling coating composition, and more particularly, to an antifouling coating composition comprising a mixed antifouling agent of a triphenylborane-amine mixture and a polyhexamethyleneguanidine salt as an antifouling active ingredient.

The surface of all aquatic environments is under intense attachment pressure by bacteria, protozoa, algae and invertebrates. In the following, the process is referred to as "attachment".

The prevention of attachment is of particular interest in marine transport operations and marine engineering, such as offshore construction, heat exchangers, marine sensors, underwater inserts, farm construction, and the like.

For example, the attachment on a ship's cover increases the frictional drag, thereby reducing the corresponding speed and mobility, increasing fuel consumption, and increasing the maintenance cost of removing the attachment. Moreover, even a very small number of living organisms attached to the ship's propellers significantly reduce the propeller's efficiency or cause problems such as corrosion.

On the other hand, an important group of marine organisms involved in the attachment process are those belonging to the crustaceans collectively referred to as shellfish. Of these, living bodies, called barnacles or rock shells, are generally involved in the attachment of submerged surfaces, such as ship covers.

In order to solve such a problem, antifouling paints have been used. Until recently, as an active ingredient of antifouling paints, tin-based compounds, tributyltin and triphenyltin were mainly used.

However, tin-based compounds continue to accumulate toxic substances in living organisms, causing great disruption in marine ecosystems and are currently prohibited for use in many countries. Therefore, the development of a low-toxic underwater antifouling agent having excellent antifouling properties over a long period of time, high stability to humans and fish and shellfish, and includes antipyretic effect and antifouling, for example, including pyrithione metal salts and triphenylborane-amine mixture Antifouling paints of various compositions have been tried with improved performance in sustainability.

Therefore, the inventors of the present invention have been searching for a method of using a triphenylborane-amine mixture as an antifouling active ingredient more efficiently, and compared to using a triphenylborane amine mixture as an antifouling active ingredient alone with a polyhexamethyleneguanidine salt. When used as a mixed antifouling agent was found to show a higher level of antifouling performance was completed the present invention.

Accordingly, it is an object of the present invention to provide an antifouling coating composition which can exhibit improved antifouling performance compared to using a triphenyl borane-amine mixture as an antifouling active ingredient.

The antifouling coating composition of the present invention for achieving the above object includes a coating film-forming resin, an additive and an antifouling active ingredient, wherein the antifouling active ingredient is a triphenylborane-amine mixture represented by the following Chemical Formula 1 and the following Chemical Formula 2 Characterized in that it is a mixture of polyhexamethyleneguanidine salt represented by.

Formula 1

Formula 2

In the above formula, each X is independently an inorganic acid salt or an organic acid salt, and each R 1 is independently a linear or branched alkyl group having 1 to 20 carbon atoms, or is phenyl, chlorophenyl, bromophenyl, iodophenyl, benzyl, chlorobenzyl, Bromobenzyl, iodobenzyl, phenethyl, naphthyl or hydrogen, n is an integer of 1 or greater.

The present invention will be described in more detail as follows.

In general, the antifouling paint contains a coating film-forming resin, an additive, and an antifouling active ingredient. In the present invention, the polyhexamethyleneguanidine salt represented by the above formula (2) together with the triphenylborane-amine mixture represented by the above formula (1) as an antifouling active ingredient It is mixed and used.

In the polyhexamethyleneguanidine salt represented by the formula (2), X is preferably HCl, HBr, HI, HNO 3, carbonic acid, sulfuric acid, phosphoric acid, acetic acid, benzoic acid, dehydroacetic acid, propionic acid, gluconic acid, sorbic acid, fumaric acid , Maleic acid, and epichlorohydrinic acid, more preferably phosphoric acid.

The polyhexamethyleneguanidine salt of the formula (2) preferably has a molecular weight of 500 to 20,000 in consideration of handling properties such as homogeneous mixing with other components, ease of preparation, maintenance of antifouling properties, and the like, and more preferably. Preferably 800 to 10000, most preferably 900 to 5000.

Polyhexamethyleneguanidine salts are conventional and can be prepared according to a polymer polymerization method, and for example, the monomer having a guanidine salt and a diamine group can be obtained by condensation polymerization at a high temperature of about 180 ° C. Polyhexamethylenegudine salts are easily soluble in water, and by electrostatic attraction, they access cell membranes of contaminants, in particular to phospholipids such as phosphatidyl glycerol and then to membranes. It causes substance leakage and cell membrane destruction action by structural disturbance, and prevents adhesion of contaminating organisms.

In order to exhibit sufficient antifouling effect by using triphenylborane-amine mixture in antifouling paint, antifouling paint should be prepared to contain at least 2% of triphenylborane-amine mixture. If it exceeds, there may be a problem that the paint properties such as cracks in the coating film is bad. In addition, the use of polyhexamethylene guadine salt is most appropriate when using about 1 to 10% of the paint in consideration of the physical properties and antifouling efficacy of the antifouling paint.

In addition to the above antifouling active ingredients, it is also possible to further add nitrous oxide, zinc pyrithione and copper pyrithione in some cases.

The other antifouling paint composition depends on the normal antifouling paint composition, and is not particularly limited.

For example, the coating film forming resin that can be used for the antifouling paint is vinyl acetate resin, vinyl resin such as vinyl chloride resin, urethane resin, rubber chloride resin, phthalic acid resin, alkyd resin, epoxy resin, phenol resin, melanin resin, acrylic resin And natural resins such as synthetic resins such as fluorine resins and silicone resins or rosin. In addition to such synthetic or natural resins, various water-soluble resins or fat-soluble resins may be used in combination. Usually, the content of the coating film-forming resin is preferably 10 to 40% by weight of the total coating composition.

On the other hand, the additive can be optionally selected from pigments, plasticizers, surfactants, anti-settling agents, thickeners and organic solvents necessary for viscosity adjustment as known in the art, and of course, they are not particularly limited.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.

Examples 1-3

Next, as shown in Table 1, triphenylborane-amine mixture and toluene were introduced into a 1000 ml vessel while stirring at a rotational speed of 2,000 rpm using a mechanical stirrer, and polyhexamethyleneguanidine phosphate and a film forming resin were added thereto. After mixing, the mixture was sufficiently mixed for 2 hours.

As the film-forming resin, n-butyl acrylate polymer sold under the trade name Acronal 4F, which is a rosin and a hydrolyzable resin, and an acrylic acid copolymer, are used as a non-hydrolyzable resin, and an acrylic acid unit is bound to a naphthenic acid residue. It is a material shielded by copper atoms. The composition ratio of these coating film-forming resins is 50% rosin, 25% acronal 4F, and 25% acrylic acid copolymer.

In addition to the above mixed composition components, pigments, plasticizers, additives, thickeners, curing agents and other resins may be blended as necessary, or water-repellent components such as petroleum wax and paraffin silicone oil may be added. Additives include organo-clay structuring agents, silica, carbon black and molecular sieve zeolites.

Comparative Example 1

In Comparative Example 1, as the antifouling active ingredient, triphenyl borane-amine mixture alone was added so as to be 15% by weight in the total coating composition, and the other methods were the same as in Example 1.

Comparative Example 2

In Comparative Example 2, zinc pyrithione was added in an amount of 5% by weight in the paint composition and 10% by weight of cuprous oxide in place of the triphenylborane-amine mixture and polyhexamethyleneguanidine phosphate as an antifouling active ingredient. Same as Example 1.

The antifouling paint thus obtained was tested for storage stability, and the antifouling paint was coated on a polyethylene plate to test the antifouling performance. The results are shown in Table 1 below.

Specific evaluation method is as follows.

(1) storage stability

After the prepared antifouling paint was stored at room temperature (25 ° C.) for 3 months, the state gauge was evaluated by visual observation. After 3 months, no sedimentation sedimentation was observed and the redispersibility was judged to be good as "PASS".

(2) Antifouling performance of coating film

The prepared antifouling paint was immersed in a polyethylene plate of 40 cm x 60 cm and dried. The dry coating film thickness was 0.1-0.2 micrometer. Thus, the plate coated with antifouling paint was immersed at a depth of 1.5 m from the coast of Geoje, Gyeongsangnam-do and tested for antifouling performance. After immersion for 8 months from January 2004 to the end of August, it was pulled up and observed by the naked eye for the attachment state of plants and slime and evaluated by the following 5 steps.

A: No attachment of flora and fauna and slime                     

B: There are plants and animals attached but no slime

C: Less than 10% of the immersion area of sea animals and plants

D: 10 to 50% of the immersion area is attached to plants and animals

E: Over 50% of the area of immersion

As described in detail above, the antifouling coating composition comprising the polyhexamethyleneguanidine salt together with the triphenylborane-amine mixture as the antifouling active ingredient according to the present invention may be a triphenylborane-amine mixture alone or a pyrithione salt. Compared with the use of copper nitrous oxide as an antifouling active ingredient, antifouling performance is improved and storage stability is equal, which is useful as antifouling paint for fishing nets, ships, and marine structures.

Claims (5)

In the antifouling coating composition comprising a coating film-forming resin, an additive and an antifouling active ingredient, The antifouling effective component is an antifouling coating composition, characterized in that a mixture of a triphenylborane-amine mixture represented by the following formula (1) and a polyhexamethyleneguanidine salt represented by the following formula (2). Formula 1

Formula 2

In the above formula, each X is independently an inorganic acid salt or an organic acid salt, and each R 1 is independently a linear or branched alkyl group having 1 to 20 carbon atoms, or is phenyl, chlorophenyl, bromophenyl, iodophenyl, benzyl, chlorobenzyl, Bromobenzyl, iodobenzyl, phenethyl, naphthyl or hydrogen, n is an integer of 1 or greater. The antifouling coating composition according to claim 1, comprising 2 to 20% by weight of a triphenylborane-amine mixture. The antifouling coating composition according to claim 1 or 3, comprising 1 to 10% by weight of polyhexamethyleneguanidine salt. According to claim 1, wherein the polyhexamethyleneguanidine salt represented by the formula (1) is X is independently HCl, HBr, HI, HNO3, carbonic acid, sulfuric acid, phosphoric acid, acetic acid, benzoic acid, dehydroacetic acid, propionic acid, gluconic acid, sorbic acid , Fumaric acid, maleic acid, and epichlorohydric acid selected from the group consisting of antifouling paint composition. The antifouling coating composition according to claim 1 or 4, wherein the polyhexamethyleneguanidine salt represented by Chemical Formula 1 has a molecular weight of 500 to 20,000.