KR100913938B1 - Antifouling coating composition - Google Patents

Abstract

The present invention discloses an antifouling coating composition comprising an inorganic salt as an antifouling agent or an antifouling additive, and comprising a self-wearing polymer as a binder.

The antifouling coating composition according to the present invention can significantly improve the antifouling ability by using an inorganic salt having basicity as an antifouling agent or an antifouling additive, and can alleviate or prevent the problem of environmental pollution of the conventional antifouling agent.

Inorganic salt, tourmaline

Description

Anti-fouling Paint Composition

The present invention relates to an antifouling coating composition which provides improved antifouling performance while reducing environmental pollution by using an environmentally friendly antifouling agent or an antifouling additive, unlike the prior art using only a highly toxic antifouling agent. The present invention relates to an antifouling coating composition having improved antifouling performance by using an inorganic salt as an antifouling agent or an antifouling additive.

The antifouling coating composition aims to prevent or control the attachment and growth of marine organisms causing seawater deposition and surface contamination of the coating film.

The hull bottom (aquatic bottom), aquatic structures, etc. may be attached to the surface of animals such as shellfish, oysters, shellfish mussels and shellfish, plants such as shellfish (seaweed) and various aquatic organisms such as aquatic bacteria when exposed to water, Multiplication results in poor appearance or loss of function. In particular, when these aquatic organisms adhere to and propagate at the bottom, the surface roughness of the entire ship's outer shell may increase, which may lower ship speed or increase fuel consumption. Removing aquatic creatures from the bottom requires more effort and longer working time. In addition, mucus (mud) or slime adheres to and propagates on bacteria that attach to and propagate to underwater structures, or large, sticky organisms adhere to and propagate on underwater structures (eg steel structures). Thus, when damaging the corrosion-resistant coating of the underwater structure, there is a problem in reducing the strength or function of the underwater structure to significantly shorten the life.

In order to prevent such a problem, it is common to coat an antifouling coating composition containing a copolymer of tributyltin methacrylate, methyl methacrylate and copper nitrous oxide (Cu ₂ O) as an antifouling paint having excellent antifouling properties on the bottom. to be. The copolymer constituting the antifouling coating composition is hydrolyzed in seawater, thereby forming bistributyl tin oxide (Bu ₃ Sn-O-SnBu ₃ (Bu is a butyl group)) or tributyltin halide (Bu ₃ SnX (X is Organic tin compounds such as halogen atoms)) are released to exhibit antifouling effects. In addition, since the copolymer is a hydrolyzable self-polishing type, the hydrolyzed copolymer itself is also changed to water solubility and dissolved in seawater, so that no residue of resin remains on the surface of the bottom coating film and thus remains active. Keep the surface.

However, the above-described organotin compounds are very toxic and are likely to cause marine pollution, the occurrence of malformed fish or shellfish, the destruction of aquatic ecosystems through the food chain, and the like. Due to these problems, the development of a tin free antifouling paint that can replace the conventional organic tin antifouling paint has been required.

As such non-organic tin-based antifouling paint, there is Korea Patent Publication 2005-0010681.

Such non-organic tin-based antifouling paints also use non-tin antifouling agents, and thus there is still a toxicity problem.

The first technical problem to be achieved by the present invention is to provide an antifouling coating composition to improve the antifouling ability by using an environmentally friendly antifouling agent or antifouling additive in order to solve the above problems.

The present invention to achieve the first technical problem,

An antifouling coating composition comprising an inorganic salt as an antifouling agent or an antifouling additive and comprising a self-wearing polymer as a binder is provided.

The antifouling coating composition according to the present invention can significantly improve the antifouling ability by using an inorganic salt having basicity as an antifouling agent or an antifouling additive, and can alleviate or prevent the problem of environmental pollution of the conventional antifouling agent.

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

The present invention provides an antifouling coating composition comprising an inorganic salt as an antifouling agent or an antifouling additive, and comprising a self-wearing polymer as a binder.

The inventors of the present invention have found that the use of basic inorganic salts by adding a basic inorganic salt to a conventional general antifouling paint or replacing a part of an antifouling agent or an antifouling additive significantly improves the antifouling ability and completed the present invention. These inorganic salts are environmentally friendly because they do not cause a separate environmental pollution. Therefore, in order to obtain a similar antifouling ability compared to the conventional general antifouling paint, it is possible to significantly reduce or not use the existing highly toxic antifouling agent or antifouling additive.

The inorganic salts used in the antifouling coating composition are preferably metal salts of hypochlorous acid, metal salts of chloric acid, metal salts of chlorite, metal salts of carbonate, sodium carbonate and sodium hydroxide (NaOH) and the like.

The metal used for the inorganic salt is preferably at least one metal selected from the group consisting of alkali metals and alkaline earth metals. Lithium, sodium, potassium, rubidium, etc. are preferable as alkali metal, and magnesium, calcium, strontium, etc. are preferable as alkaline earth metal. Mixtures of the alkali metals with alkaline earth metals are also possible.

The inorganic salt is basic and has, for example, sodium hypochlorite (NaClO), potassium chlorate (KClO ₃ ), sodium chlorate (NaClO ₃ ), sodium chlorite (NaClO ₂ ), sodium carbonate (Na ₂ Co ₃ ), sodium hydrogencarbonate (NaHCo ₃ ), sodium hydroxide (NaOH) and the like are preferred, but are not necessarily limited to these, and provided with basicity is not particularly limited as long as it is an inorganic salt having antifouling ability.

The inorganic salts are described below for the purpose of understanding the present invention and not for the purpose of limiting the present invention, but the inorganic salts, when used in antifouling paints, maintain strong base conditions in a binder or chlorine when contacted with seawater. It is thought to suppress the growth of bacteria and microorganisms in water by generating gas. When the growth of bacteria and microorganisms in the water is suppressed, diatomaceous earth or slime adhered to them is eliminated, and as a result, it is thought that seaweeds cannot be reproduced.

In particular, these inorganic salts are less suitable for the antifouling agents or antifouling additives, and thus are more suitable for marine environmental regulations that are expected to be environmentally friendly and strengthened in the future.

On the other hand, the inorganic salt may include an acid corresponding to the salt in the solution. For example, sodium hypochlorite may also include hypochlorous acid. This can be caused by the equilibrium of the salts and the corresponding acids.

The inorganic salt preferably comprises 1 to 50 parts by weight based on 100 parts by weight of the binder in the composition. When the inorganic salt content is less than 1 part by weight, there is a problem that the antifouling ability is lowered, and when the content exceeds 50 parts by weight, there is a problem that the adhesion of the coating film is inferior.

The inorganic salt may be prepared and used in the form of an aqueous solution containing water as necessary. For example, the inorganic salt may be mixed with distilled water and used as it is. The aqueous solution may further include tourmaline and ferrous chloride (FeCl ₃ ).

When prepared in the form of an aqueous solution of the inorganic salt, it is also possible to configure no organic solvent in the antifouling coating composition. In this case, the antifouling coating composition may be more environmentally friendly.

It is possible to further comprise tourmaline as the antifouling paint composition as the antifouling additive. The tourmaline has the effect of inhibiting the production of bacteria or microorganisms that propagate on the bottom or the underwater structure as a rock having antimicrobial properties. It is considered that the antifouling performance is improved by the interaction between the tourmaline and the inorganic salt.

The tourmaline may be represented by the following Chemical Formula 1, and the main production sites of the tourmaline include China, Japan, and Brazil.

<Formula 1>

(Ca, K, Na) (Al, Fe, Li, Mg, Mn) ₃ (Al, Cr, Fe, V) ₆ (BO ₃ ) ₃ (Si, Al, B) ₆ O ₁₈ (OH, F) ₄

More specifically the tourmaline is, for _{example, NaMg 3 Cr 6 Si 6 O} 18 (BO 3) 3 (OH), NaMg 3 Al 6 Si 6 O 18 (BO 3) 3 (OH), Na (Li 1 .5 _{, Al 1 .5) Al 6 Si} 6 O 18 (BO 3) 3 (OH), CaFe 2 + 3 (MgAl 5) Si 6 O 18 (BO 3) 3 (OH), (Fe 2+ 2 Al) Al ₆ Si ₆ O ₁₈ (BO ₃ ) ₃ (OH), Ca (Li ₂ Al) Al ₂ Si ₆ O ₁₈ (BO ₃ ) ₃ (OH) ₃ , (Mg ₂ Al) Al ₆ Si ₆ O ₁₈ (BO ₃ ) ₃ (OH), NaAl ₃ Al ₆ Si ₆ O ₁₈ (BO ₃ ) ₃ O ₃ , NaFe ³⁺ ₃ (Fe ³⁺ ₄ Mg ₂ ) Si ₆ O ₁₈ (BO ₃ ) ₃ (OH) ₃ , (LiAl ₂ ) Al ₆ Si ₆ O ₁₈ (BO ₃ ) ₃ (OH), NaFe ²⁺ ₃ Al ₆ Si ₆ O ₁₈ (BO ₃ ) ₃ (OH), CaMg ₃ (MgAl ₅ ) Si ₆ O ₁₈ (BO ₃ ) ₃ (OH) ₃ , NaMg ₃ V ₆ Si ₆ O ₁₈ (BO ₃ ) ₃ (OH) and the like may be used, but are not necessarily limited thereto and all tourmaline used in the art may be used.

Preferably, the antifouling coating composition comprises 1 to 50 parts by weight of inorganic salt and 1 to 100 parts by weight of tourmaline with respect to 100 parts by weight of the binder. When the tourmaline content exceeds 100 parts by weight, it is not easy to form a coating film, and when the tourmaline content is less than 1 part by weight, it is difficult to substantially obtain an antifouling effect.

In the antifouling coating composition, the self-wearing polymer preferably includes a polymer prepared by using at least one ethylenically unsaturated monomer selected from carboxylic acid derivatives and sulfonic acid derivatives that generate acidic groups upon hydrolysis, but not necessarily The polymer is not limited thereto, and any polymer may be used as long as it is a magnetic wear polymer in the art.

In particular, the self-wearing polymer preferably includes a polymer prepared using at least one monomer selected from the group consisting of a monomer containing a trialkylsilyl group and a (meth) acrylate-based monomer. For example, the polymer is preferably zinc acrylate, copper acrylate or the like.

As the monomer containing the trialkylsilyl group, more specifically, as the monomer used in the preparation of the polymer, trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, tripropylsilyl (meth) acrylate, triiso Propylsilyl (meth) acrylate, tributylsilyl (meth) acrylate, triisobutylsilyl (meth) acrylate, trihexylsilyl (meth) acrylate, trioctylsilyl (meth) acrylate, tridodecylsilyl ( Meta) acrylate, ethyldimethylsilyl (meth) acrylate, butyldimethylsilyl (meth) acrylate, octyldibutylsilyl (meth) acrylate, and the like are preferred.

The (meth) acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, Isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, methoxyethyl (meth) acrylate, etc. are preferable.

The self-wearing polymer may also further comprise a vinyl unsaturated monomer. The vinyl unsaturated monomers may be styrene or vinyl esters. More specifically, styrene, vinyl toluene, methyl styrene, vinyl acetate, vinyl benzoate, vinyl propionate, vinyl butyrate and the like are possible.

The self-wearing polymer may be prepared by random copolymerization according to various known polymerization methods such as solution polymerization, bulk polymerization, emulsion polymerization and suspension polymerization in the presence of a radical polymerization initiator.

The antifouling coating composition of the present invention may further include general components used in conventional antifouling coatings in addition to the inorganic salt and the self-wearing polymer.

These ingredients include antifouling agents, pigments, thickeners, organic solvents, dehumidifying agents, anti-sagging agents, anti-flooding agents, thixotropic agents, anti-solidifying agents, stabilizers, dispersants and antifoam agents. can do.

In addition, fluorine-based resins can be selectively used. The fluorine-based resin may be used a fluorinated polysiloxane-based resin, a fluorinated polyether-based resin and the like, as long as it is used in the art. Since they are used as a kind of additive, any kind of fluorine resin does not affect the achievement of the object of the present invention.

The antifouling agent used as other essential components in the antifouling coating composition of the present invention may be any of conventionally known antifouling agents. Known antifouling agents are roughly divided into inorganic compounds, metal-containing organic compounds, and organic compounds containing no metals.

Examples of inorganic compounds include copper compounds (e.g. copper sulfate, copper powder, cupric thiocyanate, copper carbonate, copper chloride and conventional preferred cuprous oxide), zinc sulfate, zinc oxide, zinc sulfide, nickel sulfate And copper nickel alloys.

Examples of metal-containing organic compounds include organo-copper compounds, organo-nickel compounds and organo-zinc compounds. Also useful are manganese ethylene bis dithiocarbamate (maneb), propineb and the like.

Examples of organo-copper compounds include copper nonylphenol-sulfonate, copper bis (ethylenediamine) bis (dodecylbenzenesulfonate), copper acetate, copper naphthenate, copper pyrithione and copper bis (pentachlorophenolate) There is. Examples of organo-nickel compounds are nickel acetate and nickel dimethyldithiocarbamate. Examples of organo-zinc compounds include zinc acetate, zinc carbamate, bis (dimethylcarbamoyl) zinc ethylene-bis (dithiocarbamate), zinc dimethyldithiocarbamate, zinc pyrithione and zinc ethylene- Bis (dithiocarbamate). Examples of mixed metal-containing organic compounds include (polymer) manganese ethylene bis (dithiocarbamate) and a complex salt of zinc (mancozeb).

Examples of organic compounds containing no metal include N-trihalomethylthioptalimide, trihalomethylthiosulfamide, dithiocarbamic acid, N-arylmaleimide, 3- (substituted amino) -1 , 3-thiazolidine-2,4-dione, dithiocyano compound, triazine compound, oxathiazine, and the like.

Examples of N-trihalomethylthioptalimide include N-trichloromethylthioptalimide and N-fluorodichloromethylthioptalimide. Examples of dithiocarbamic acid are bis (dimethylthiocarbamoyl) disulfide, ammonium N-methyldithiocarbamate and ammonium ethylene bis (dithiocarbamate). Examples of trihalomethylthiosulfamides include N- (dichlorofluoromethylthio-N ', N'-dimethyl-N-phenylsulfamide and N- (dichlorofluoromethylthio) -N', N'-dimethyl -N- (4-methylphenyl) sulfamide Examples of N-arylmaleimides are N- (2,4,6-trichlorophenyl) maleimide, N-4-tolylmaleimide, N-3 chlorophenyl Maleimide, N- (4-n-butylphenyl) maleimide, N- (anilinophenyl) maleimide and N- (2,3-xylyl) maleimide 3- (substituted amino) -1 Examples of, 3-thiazolidine-2,4-dione include 2- (thiocyanomethylthio) -benzothiazole, 3-benzylideneamino-1, 3-thiazolidine-2,4-dione, 3 -(4-methylbenzylideneamino) -1,3-thiazolidine-2,4-dione, 3- (2-hydroxybenzylideneamino) -1,3-thiazolidine-2,4-dione, 3- (4-dimethylaminobenzylideamino) -1,3-thiazolidine-2,4-dione, and 3- (2,4-dichlorobenzylideneamino) -1,3-thiazolidine-2, There is 4-dione dithiosia Examples of compounds are dithiocyanomethane, dithiocyanoethane and 2,5-dithiocyanothiophene Examples of triazine compounds are 2-methylthio-4-butylamino-6-cyclopropylamino-s-tria Examples of the oxathiazines include 1,4,2-oxathiazine and mono- and di-oxides thereof.

Other examples of organic compounds that do not include metals include 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethyl-dichlorophenylurea, 4,5-dichloro-2-n-octyl-4-iso Thiazolin-3-one, N, N-dimethyl-N'-phenyl- (N-fluorodichloromethylthio) sulfamide, tetramethylthiuramidesulfide, 3-iodo-2-propynylbutyl carbamate , 2- (methoxycarbonylamino) benzimidazole, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, pyridine, diiodomethyl-p-tolyl sulfone, phenyl (bispyridine ) Bismuth dichloride, 2- (4-thiazolyl) benzimidazole, dihydroabiethyl amine, N-methylol formamide and pyridine triphenylborane.

In the present invention, one or more antifouling agents selected from such antifouling agents may be used. The amount of the antifouling agent is about 0.1 to 90% by weight, preferably 0.1 to 80% by weight, more preferably 1 to 60% by weight based on the solids content of the coating film composition. If the antifouling agent content is too small, there is no antifouling effect, while if too high, the antifouling effect is reduced by forming a coating film which easily causes defects such as cracking and peeling.

The antifouling paint of the present invention may further include an antifouling additive to further improve the performance of the antifouling agent.

The antifouling additive may act as both an antifouling agent or an antifouling additive.

For example, when two or more antifouling agents are used, one of the two may be referred to as an antifouling additive.

The antifouling paint of the present invention further comprises a pigment (or filler), a solvent and an additive. The coating composition may comprise one or more "active pigments" which are dissolved in traces in sea water. These pigments have seawater solubility that the pigment particles cannot withstand on the paint surface. These pigments have the effect of evenly inducing the overall force of the relatively moving seawater on the paint film and minimizing local corrosion to preferentially remove the abnormal products formed during the paint application process. Trace-soluble pigments have long been used in self-wear antifouling paints. Typical examples are cupric thiocyanate, cuprous oxide, zinc oxide, cupric metabisate, zinc chromate, zinc dimethyl dithiocarbamate, zinc ethylene bis (dithiocarbamate) zinc and diethyl dithiocar It is zinc chestnut. Preferred pigments dissolved in trace amounts are zinc oxide, cuprous oxide, cuprous thiocyanate.

The coating composition may comprise one or more pigments that are almost insoluble in seawater, such as titanium dioxide, talc or ferric oxide. The almost insoluble pigment may be used at 40% by weight or less relative to the total weight of the total pigment component of the paint. Almost insoluble pigments have the effect of delaying the corrosion of the paint.

Examples of organic solvents include aromatic hydrocarbons such as xylene or toluene; Aliphatic hydrocarbons such as hexane and heptane; Esters such as ethyl acetate and butyl acetate; Amides such as N-methylpyrrolidone and N, N-dimethylformamide; Alcohols such as propyl alcohol, isopropyl alcohol and butyl alcohol; Dioxane; THF; Ethers such as diethyl ether; And ketones such as methyl ethyl ketone, methyl isobutyl ketone and isoamyl ketone. And water can be used as a solvent. The solvents may be used alone or in combination.

The antifouling coating composition of the present invention can optionally introduce an additive component. Examples of ingredients of the additives are conventional in coating compositions as dehumidifying agents and anti-sagging agents, anti-flooding agents, thixotropic and anti-solidifying agents, stabilizers, desiccants, coating strength modifiers and antifoaming agents. There are additives used.

In addition, the antifouling coating composition of the present invention may include benzoic acid, hydroxypyridine, zinc and copper salts of benzoic acid, metal salts of hydroxypyridine and mixtures thereof.

Cellulose derivatives such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose as thickeners; Poly (vinyl alcohol), poly (vinyl pyrrolidone), poly (ethylene glycol), salts of polyacrylic acid, salts of acrylic acid / acrylamide copolymer, and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, these are for illustrating the present invention and the scope of the present invention is not limited thereto.

Preparation of antifouling paint composition

Example 1

30 parts by weight of a 33% by weight aqueous solution of sodium hypochlorite, 8 parts by weight of tourmaline, 10 parts by weight of zinc oxide, 2 parts by weight of Al (OH) _3, 2 parts by weight of titanium dioxide (TiO ₂ ), and a disper as a dispersant 0.01 parts by weight of BYK-323 (BYK-Chemie GMBH, Lot No 0110282870-01), 5 parts by weight of Sea-Nine 211 (manufactured by Rohm & Haas) as an antifouling additive, and 3 parts by weight of xylene as a solvent to prepare an antifouling coating composition. It was.

The binder is composed of 25 parts by weight of zinc acrylate, 20 parts by weight of rosin and 2 parts by weight of fluororesin (fluoropolyether).

Example 2

Except for adding 1.42 parts by weight of an aqueous solution of 33% by weight of sodium hypochlorite and 4.7 parts by weight of tourmaline, 47 parts by weight of the binder was used in the same manner as in Example 1 to prepare an antifouling coating composition.

Example 3

An antifouling coating composition was prepared in the same manner as in Example 1, except that 71.21 parts by weight of an aqueous 33% sodium hypochlorite solution and 47 parts by weight of tourmaline were added to 47 parts by weight of the binder.

Comparative Example 1

KCC model name A / F 795 was obtained and used as it is.

Comparative Example 2

International Marine Coatings' model name Intersleek 757 was obtained and used as is.

Antifouling Performance test

Sandblasted 20mm × 50mm × 2mm sized steel plate with epoxy-based anticorrosive coat 200μm, binder coat 100μm and antifouling paints prepared in Examples 1 to 3, Comparative Examples 1 and 2 The paint was continuously prepared at intervals of one day, and cured and dried at room temperature for one week to prepare specimens.

The specimens were immersed at a position below 1m by sea level using a raft-type pontoon installed in the sea near Dadaepo (hereinafter referred to as A) and millet (hereinafter referred to as B). Every two weeks after immersion, the degree of contamination of the coating due to the attachment of a hanger organism was observed, and the antifouling performance was evaluated according to the criteria described below.

Level 5: Without marine life

Grade 4: Thin organic film formed

Class 3: The condition of vegetable contamination is less than 30% of the effective area of the specimen

Level 2: Vegetable contaminated area over 60% of the effective area of the specimen

Level 1: Condition of Animal Contamination

Deposition time Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 A B A B A B A B A B 2 weeks 5 5 5 5 5 5 5 5 5 5 4 Weeks 5 5 5 5 5 5 5 5 4 4 6 Weeks 5 5 5 5 5 5 5 4 4 4 8 Weeks 5 5 5 5 5 5 4 4 4 4 10 Weeks 5 5 5 5 5 5 4 4 4 4 12 Weeks 5 5 5 5 5 5 4 4 4 4 14 Weeks 5 5 5 5 5 5 4 4 4 4 16 Weeks 5 5 5 5 5 5 4 4 3 3 18 Weeks 5 5 5 5 5 5 3 3 4 3 20 Weeks 5 5 5 5 5 5 3 3 3 3 22 Weeks 5 5 5 5 5 5 4 4 3 3 24 Weeks 5 5 5 5 5 5 4 4 3 3 Week 26 5 5 5 5 5 5 4 4 3 3 28 Weeks 5 5 5 5 5 5 4 4 4 4

 As shown in Table 1, the antifouling paint of the present invention was remarkably superior in antifouling performance compared to the conventional antifouling paint.

Claims (9)

Antifouling agents or antifouling additives, including inorganic salts, A binder comprising a self-wearing polymer, The inorganic salt is in contact with sea water and has a strong base or generates chlorine gas in the binder, The inorganic salt is at least one compound selected from the group consisting of metal salts of hypochlorous acid, metal salts of chloric acid, metal salts of chlorite, metal salts of carbonate, and sodium hydroxide (NaOH), The antifouling coating composition wherein the metal used for the inorganic salt is at least one metal selected from the group consisting of alkali metals and alkaline earth metals. delete delete The antifouling coating composition according to claim 1, wherein the composition comprises 1 to 50 parts by weight of the inorganic salt with respect to 100 parts by weight of the binder. The antifouling coating composition according to claim 1, further comprising a tourmaline as the antifouling additive. The antifouling coating composition according to claim 1, wherein the composition comprises 1 to 50 parts by weight of inorganic salt and 1 to 100 parts by weight of tourmaline with respect to 100 parts by weight of the binder. The antifouling coating composition according to claim 1, wherein the composition comprises water. The antifouling coating composition according to claim 1, wherein the self-wearing polymer is a polymer prepared using at least one ethylenically unsaturated monomer selected from carboxylic acid derivatives and sulfonic acid derivatives which generate acidic groups upon hydrolysis. The antifouling coating composition according to claim 1, wherein the self-wear polymer is a polymer prepared using at least one monomer selected from the group consisting of a monomer containing a trialkylsilyl group and a (meth) acrylate-based monomer. .