KR20010005870A - Coating compositions comprising busoxinone - Google Patents

Abstract

The present invention relates to an auxiliary sinon-containing coating composition which can form a coating film having excellent antifouling performance and can provide such excellent performance for a long time. The invention also relates to a method of protecting a surface or an object in frequent or continuous contact with water.

Description

Coating compositions comprising busoxinone

Surfaces or objects that are moist or exposed to an aqueous environment include algae, fungi, bacteria, microorganisms, and tunicates, hydroids, bivalves, and mosquito bryozoans. It is easily settled by aquatic organisms such as aquatic animals such as polychaete worms, sponges, barnacles, molluscs and crustacea. Because these organisms settle or adhere to the surface, the value of the exposed object is low. Attachment or fixation of the organism is also known as 'contamination' of the structure. The exterior, possibly also inside, of the object may deteriorate, and the surface may, for example, change from smooth, clean, streamline to coarse, dirty and rugged, and the weight of the object may be due to the deposition of organisms and their residues. Increasingly, the proximity of the object may be blocked or blocked. The function of the objects and systems involved is degraded and the quality of the aqueous environment is degraded. A common way to control the attachment of contaminating organisms is to treat the structure to be protected with a coating containing an antifouling agent.

Coating compositions containing organotin compounds have been used for many years primarily because of their good antifouling properties. However, the negative effects on the environment of highly toxic organotin compounds and the accumulation of these toxic compounds in the organism have been pointed out as problems. The Ministry of Transportation issued a warning to limit their use. Therefore, it is worth developing alternative antifouling coating compositions as substitutes.

The major factor in determining the effectiveness of an antifouling coating composition is the rate of release of the antifouling agent from this coating into the aquatic environment. If the antifouling agent is released too quickly, it is quickly consumed and has to be reapplied to the surface to be protected, thus shortening the interval between normal service periods. The reapplication of antifouling coatings is costly and time consuming.

Contamination of surfaces or objects that are moist or exposed to an aqueous environment often begins with the attachment or settlement of algae. This roughens the smooth surface, thereby facilitating the settlement of other contaminating organisms such as cysts, barnacles, shellfish, mollusks and the like. Therefore, the algicidal nature of the coating that protects the surface from contamination is of primary concern.

(±) -3- [5- (1,1-dimethylethyl-3-isoxazolyl] -4-hydroxy-1-methyl-2-imidazolidinone, also known as aduxinone or PPG 1259 First disclosed in US Pat. No. 4,268,679 as herbicide.

EP-0,044,185, and US Pat. No. 4,421,546, published January 20, 1982, disclose adnexonone as an effective herbicide for pre- or post-emergence control of aquatic weeds, including ground weeds and algae. The technical literature also discloses aqueous sprays, drenches, solid powders or invert emulsions containing auxinone. EP-0,127,433, published December 5, 1984, also includes synergistic compositions containing pluridone and accessorysinone which are useful as agicides and as aquatic herbicides.

The herbicide activity before and after germination of adnexon is also described by W.Bond in Test Agrochem. Cultiv., 8, p. 106-107, 1987 (CAN 107: 54066) and in A.K. Wilson et al. Abstract no.859,090 Gov. Rep. Announce Index U.S., 88 (23) 1988, (CAN 111: 35070).

The above prior art documents, in particular EP-0,044,185 and US-4,421,546, are parts which are applied directly to aquatic plants or are used to control or eliminate the growth of aquatic plants by dispersing them in an aqueous environment containing submerged or floating aquatic plants. Synon's formulations are disclosed. The present invention differs from the above technical documents in that it provides a coating composition containing adjunction.

Unexpectedly, despite the high solubility of accessory sinon in water, it has been found that the rate of release or escape of accessory sinon from the coating composition to the aqueous environment is low enough to provide a coating having good antifouling properties for a long time. .

The present invention relates to a coating composition containing aduxinone which protects a surface or an object that is frequently or continuously in prolonged contact with water from the settlement of aquatic organisms, also known as contamination.

Therefore, the present invention provides a coating composition containing an algae effective amount of accessory sinon that inhibits the attachment or settlement of algae to a surface in a humid or aqueous environment. The coating composition can form a coating with good antifouling performance and can provide good antifouling performance for a long enough time to bridge the gap between normal service life.

The coating compositions of the present invention provide a safer and ecologically more acceptable alternative to current coatings comprising antifouling products based on heavy metals such as copper oxide, or antifouling products based on organometallic derivatives such as organotin compounds. to provide. Toxicity of auxinone to mammals is acceptable, and auxinone is itself less risky to humans when reaching the human body by direct physical contact (eg, during handling or application) or through the food chain. . The biodegradability of adnexinone ensures that adductinone is less persistent in the environment and less and shortens environmental pollution and irritation. In addition, the chemical stability of auxinone by itself means that it is compatible with most inanimate substances and does not require special attention, such as the addition of an agent for stabilization of auxinone.

The term "pollutant organisms" includes, in particular, organisms that adhere to, settle, grow, or adhere to various surfaces in a humid or aqueous environment, such as seawater, freshwater, saline, rainwater, and cooling water, drainage, wastewater, and sewage. . Contaminating organisms include algae such as Microalgae, such as Amphora, Achnanthes, Navicula, Amphiorora, Mellosira, and Cockonese. Cocconeis, Chlamydomonas, Chlorella, Ulothrix, Anabaena, Paeodactylum, Porphyridium; Macroalgae, for example, enteromorpha, Cladophora, Ectocarpus, Acrochaetium, Ceramium, Polysiphonia And Hormidium species (sp.); Fungi; microbe; Members of the Ascidiacea class, including Ciona intestinalis, Diplosoma listerianium, and Botryllus schlosseri Cysts; Members of the Hydroworm family, such as Clava squamata, Hydractinia echinata, Obelia geniculata and Tubularia larynx; Bivalve shells, such as Mytilus edulis, Crassostrea virginica, Ostrea edulis, Ostrea chilensia, and Lacea Lusaea rubra; Moss-like animals such as Electra pilosa, Bugula neritina, and Bowervania gracilis; Polymorphic worms, for example Hydroydes norvegica; sponge; And members of the Crustacea River, including Artemia and Cirripedia (barnacles), for example Balanus amphitrite, Lepas anatifera, Balanus bala Balanus balanus, Balanus balanoides, Balanus hameri, Balanus crenatus, Balanus improvisus, Balanus galleatus Balanus galeatus, and Balanus eburneus; Elminius modestus, and Veruca.

The coating composition of the present invention comprises an alginate effective amount of adjunction; And polymers or air derived from monomers such as dialkyl siloxanes, (meth) acrylic acid, (meth) acrylic acid esters, vinyl and allyl alcohols and derived esters, maleic acid, styrene, vinylchloride, butadiene, acrylamide, acrylonitrile Coalescing or resins such as alkyd resins, polyurethanes, epoxy resins, phenol-resins and urea-formaldehyde resins; And mixtures thereof.

The coating composition of the present invention is a waterproofing agent; Surface slippers; diluent; Organic binders; Pesticide; Fungicides; Bactericides; Auxiliary solvent; Processing additives; Fixing agent; Thickeners; Plasticizers; UV-stabilizers; Stabilizers against heat or light; dyes; Color pigments; drier; Corrosion inhibitors; Fixation inhibitors; Anti-skinning agents; It may further comprise one or more additives selected from the group consisting of antifoams.

Useful additives in such compositions include water repellents and surface sliding agents capable of imparting low surface tension to the coating film formed by the polymer or copolymer in the coating composition.

Auxinone may be added to the coating composition in pure form or may be dissolved or suspended in a sufficient amount of diluent. Preferably, the diluent consists of one or more solvents in the final composition. The diluents used to prepare the coating composition should preferably not be easily burned and, if possible, should be as nontoxic to animals or plants and humans as are not intended to be in the relevant environment. Suitable diluents for this purpose include, for example, water or organic solvents such as aromatic hydrocarbons such as methylbenzene, dimethylbenzene mixtures, substituted naphthalenes; Alcohols and glycols and ethers and esters thereof, such as ethanol, ethylene glycol, ethylene glycol monomethyl or mono ethyl ether; Ketones such as 2-propanone, cyclohexanone and the like; Strong polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide; Vegetable oils or epoxidized vegetable oils such as epoxidized peanut oil or soybean oil, and mixtures thereof. Coating compositions can be prepared by conventional methods, with the aid of a solution promoter, if necessary. Other coating compositions that can be used consist of emulsions, dispersions or suspensions in water or suitable diluents, or concentrates for preparing such emulsions, dispersions or suspensions which can be directly adjusted to the desired concentrations. To this end, appendixone is mixed, for example, with a dispersant, suspending agent or emulsifier. Auxinone may also be dissolved or dispersed in a suitable inert solvent and mixed with the dispersant or emulsifier simultaneously or sequentially.

The coating composition of the present invention may also include other adjuvants commonly used in the art of formulation. These depend on the particular application and the user's preference. Such adjuvants include, for example, organic binders (eg, chemically dried organic binder-forming polymers such as alkyd resins or physically dried organic binder-forming solids by solvent evaporation); Pesticides such as, for example, chlorinated hydrocarbons (e.g., endosulfans, organophosphates (e.g. chloropyriphos), pyrethroids (e.g. permethrin, etc.)); Further fungicides and fungicides such as alcohols (eg, ethanol, 2,3,3-triiodalyl alcohol); Aldehydes (eg formaldehyde, glutaraldehyde); Formaldehyde releasing compounds (eg, 2-bromo-2-nitro-propane-1,3-diol (bronopol), 2-bromo-2-nitro-propan-1-ol); Reaction products of amines with formaldehyde (eg, triazines, 3,5-dimethyl-tetrahydro-1,3,5-2H-thiadiazine-2-thione); Reaction products of amides with formaldehyde (eg 1-hydroxymethyl-2-thiono-1: 2-dihydro-benzothiazole-N-hydroxymethyl-benzothiazolinthion); Phenols (eg 2-phenylphenol, pentachlorophenol); Organic acids (eg, propionic acid, benzoic acid, salicylic acid, naphthenic acid copper salts); Inorganic acids (eg, boric acid); Amides (eg, 2,5-dimethyl-N-cyclohexyl-N-methoxy-furan-3-carbonamide); Carbamate (eg 3-iodopropargyl-N-butylcarbamate (IPBC), methyl-N-benzimidazol-2-ylcarbamate (carbendazim), methyl-N- (1-Butylcarbamoyl) benzimidazol-2-ylcarbamate (benomil), zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, bis- (dimethylthiocarbamoyl) disulfide ); Pyridine derivatives (eg 2-mercapto-pyridine-N-oxide, 2-chloro-6- (trichloromethyl) pyridine, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine , Copper 8-hydroxyquinoline, 1-ethyl-1,4-dihydro-7-methyl-4-oxo-1,8-naphthyridine-3-carboxylic acid); Azoles (eg, tebuconazole, propicosol, azaconazole, imajaryl); Heterocycle compounds (e.g. 2-methyl-3 (2H) -isothiazolone, 5-chloro-2-methyl-3 (2H) -isothiazolone, 2-n-octyl-4-isothiazoline- 3-one, 4,5-dichloro-2- (n-octyl) -4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, 2-methyl-4,5-tri Methylene-4-isothiazolin-3-one, 2- (4-thiazolyl) -benzimidazole, 2-mercaptobenzothiazole, 2- (thiocyanomethylthio) benzthiazole); N-haloalkylthio compounds (e.g., N-trichloromethylthioptalimide, folpet, N-trichloromethylthio-4-cyclohexane-1,2-dicarboximide, captan , N-1,1,2,2-tetrachloroethylthio-4-cyclohexene-1,2-dicarboximide, captapol, diclofluanide, tolylufluoride); Compounds having an activated halogen group (eg, chlorotalonyl); Surfactants (eg guanidine and biguanide); Various compounds (eg fimaricin, tridemorph, methylene bisthiocyanate, tolyl sulfone, dicyanobutane) active natural products (eg streptomycin); auxiliary solvents such as ethylglycol acetate and methoxypropylacetate; processing additives; Fixing agents such as carboxymethyl-cellulose, polyvinyl alcohol, paraffins; thickeners; plasticizers such as benzoic acid esters and phthalates (e.g. dibutyl phthalate, dioctyl phthalate, dododecyl phthalate); UV-stabilizers; heat or Stabilizers against light; dyes; color pigments; desiccants such as cobalt octoate, lead octoate, and cobalt naphthenate; corrosion inhibitors; antisettling agents; antidermal agents such as methylethylketoxime; antifoaming agents, etc. Is not essential to the practice of the invention, but in particular the formulation, in particular the overall effect and ease of application, is It is included in coating formulations for compatibility, which can be used in conventional amounts.

The coating composition of the present invention may comprise additional ingredients known to be used in coatings, such as plasticizers, thickeners, anti-fixing agents, auxiliary film-forming agents and stabilizers against heat and light. Suitable formulations may be formulated according to procedures known in the art below. For example, accessory sinone may be admixed with any surfactant, such as extenders composed of liquid, semisolid or solid carriers, and emulsifiers and / or dispersants.

Coatings formed by the present coating compositions can include many forms, including paints, gelcoats, varnishes, and the like.

The coating composition may comprise 1 to 75% by weight based on the total weight of the dry mass of the composition, in particular 10 to 50% by weight of adsynonone (ie 50% by weight or less based on the total weight of the coating composition, Especially from 5 to 25% by weight of appendynone). The term "dry lump" refers to the total solids content of the coating composition.

Coating compositions of the present invention may be prepared by dispersing an effective amount of auxinone in other components, such as polymers or copolymers, resins, and other optional additives such as waterproofing agents; Surface slippers; diluent; Organic binders; Pesticide; Fungicides; Bactericides; Auxiliary solvent; Processing additives; Fixing agent; Thickeners; Plasticizers; UV-stabilizers; Stabilizers against heat or light; dyes; Color pigments; drier; Corrosion inhibitors; Fixation inhibitors; Dermabrasion inhibitors; It is prepared by intimate mixing with an antifoaming agent.

The coating composition of the present invention is particularly suitable for applying a coating composition containing adjunction to a surface or object that is in constant or frequent contact with water to protect the surface and object from contamination or attachment or fixation of algae. Examples of such surfaces and objects include, for example, hulls; Recreational devices such as surfboards, jet skis, and water skis; Port equipment; Small bridges and piles; Dry dock; water gate; Lock; Mooring masts, buoys; Offshore oil rigging equipment; Training ground; bridge; Pipeline; fish net; Cables and other objects in constant or frequent contact with water.

In addition, the coating compositions according to the invention can be used in swimming pools, baths, cooling water circuits and in various installations, for example in manufacturing plants or air purifiers, which may be impaired by the presence and / or propagation of algae. It can be used to protect structures such as industrial baths. Another example is building accessories such as buildings and floors, exterior and interior walls or ceilings, or places that are damaged by moisture, such as basements, bathrooms, kitchens, laundry, etc., which are hotbeds of contamination. Pollution is not only a problem from a sanitary and aesthetic point of view, but also causes economic losses because the building and / or decoration materials are damaged faster than intended.

Therefore, the present invention also provides the use of the coating composition according to the invention for protecting surfaces or objects that are in frequent or continuous contact with water from contamination or the attachment or settlement of algae.

The invention also provides a method of protecting a surface comprising applying a coating composition to the surface according to the invention. Particularly important uses of the method of the invention include a method of suppressing contamination of a hull characterized by applying the coating composition according to the invention to the hull.

The method applies a coating composition containing adxinone to an inanimate material, optionally in the form of a suitable formulation, by techniques known in the art such as, for example, brushing, spraying, spraying, soaking, dipping, impregnating, dispersing and pouring. Also includes.

The following examples illustrate the scope of the invention.

A. Biological Examples

The algae properties of adductinone were compared to that of diuron, a common name for the well-known algae, N '-(3,4-dichlorophenyl) -N, N-dimethyl-urea.

Example 1 Bleeding Test from Coating Film

The solubility of accessory sinenone in water at 25 ° C. is 656 mg / l, and the solubility of diuron in water at 25 ° C. is 42 mg / l.

The test compound, accessory sinone and diuron were added to the solvent-based alkyd coating composition of composition example B.1 and mixed at a concentration of 0.2% to 0.5%. Filter paper strips (4 cm x 4 cm) were treated with the above coating composition containing anuxinone or diuron and dried. The filter paper strip was immersed in 60 ° C. water (70 ml) for 24 hours. The concentration of test compound released from the coating in aqueous solution was measured by HPLC method.

Table 1:

As illustrated in Table 1, in spite of the high water solubility of accessory sinon compared to diuron, about 10 times less amount of accessory sinon is leaked from the coating into the aqueous solution.

Example 2: Long-Term Efficacy of Coating Compositions Containing Adnexon

a) The coating composition of Example 1 was coated on both sides of the filter paper test strip (4 cm x 4 cm) containing 0.3% of appendixone or diuron. The filter paper strips were dried and weathered by placing the paper strips in water at 50 ° C. for 1 or 5 days.

After the weathering step, the filter paper strips were placed in algal culture (Anabaena sp., Hormidium sp. And Chlorella vulgaris) at 25 ° C. for 28 days. The test results are summarized in Table 2.

Table 2: Deposition of Algae after 28 Day Exposure

As exemplified in Table 2, despite the high solubility of Adjuncion in comparison with Diuron, no coating of algae occurred in the coating containing Adjuncion after 28 days of exposure.

b) Compositions Containing Annexone or Diuron on Both Sides of the Filter Paper Test Strip (4 cm x 4 cm) The solvent-based acrylic silicone coating composition of Example B.2 was coated. The filter paper strips were dried and weathered in water at 50 ° C. for 14 days.

After the weathering step, the filter paper strips were placed in algal cultures (Anavaena species, Hormidium species and Chlorella vulgaris) at 25 ° C. Deposition of algae was measured weekly and summarized in Table 3.

Table 3: Deposition of Algae

As illustrated in Table 3, despite the high water solubility of accessory sinon and 14 days of weathering at 50 ° C., no 28 or only slightly deposited algae were found in the accessory sinonone containing coating after 28 days of exposure.

B. Composition Examples

Suitable coating compositions are illustrated in Composition Examples B.1 to B.4. An algae effective amount of acsinone was added to these compositions. The amount of accessory sinonone may range from 0.1 to 50% by weight, based on the total weight of the coating composition (including solvent).

B.1. Polyurethane resin enamels and varnishes (all percentages by weight)

Titanium Dioxide 22.50

Precipitated Barium Sulfate 3.80

Castor Oil-Phthalic Acid Resin 45.00

Antiprecipitation 0.08

Toluene 2.60

Butyl Acetate 1.00

Additive 0.08

Polyisocyanate 11.25

Toluene 10.00

Butyl Acetate 3.69

B.2. Acrylic urethane resin enamels and varnishes (all putts are by weight)

Titanium Dioxide 17.600

Precipitated Barium Sulfate 2.400

Poly-Acrylic Resin Varnish 52.000

Antiprecipitation 0.800

Dispersant 0.160

Toluene 2.000

Xylene 2.000

Butyl Acetate 3.037

Silicone oil 0.003

Polyisocyanate 13.400

Ethyl acetate 6.600

B.3. Polyvinyl Acetate Emulsion Paint (All Percent by Weight)

Clear Polyvinyl Acetate 85.0

Titanium Dioxide 15.0

B.4. Polyacrylic styrene emulsion paint (all percentages by weight)

Titanium Dioxide Paste 33.884

Polyacrylic Styrene Emulsion 50.452

Texanol 3.542

Thickener Aqueous Solution 3.492

Defoamer 0.208

Water 8.422

Claims (7)

(a) an effective amount of adjuncino in algicidal; And (b) polymers derived from monomers such as dialkyl siloxanes, (meth) acrylic acid, (meth) acrylic acid esters, vinyl and allyl alcohols and derived esters, maleic acid, styrene, vinylchloride, butadiene, acrylamide, acrylonitrile Or copolymers or resins such as alkyd resins, polyurethanes, epoxy resins, phenolic resins and urea-formaldehyde resins; And coating compositions containing the mixtures thereof. The method of claim 1, further comprising: a waterproofing agent; Surface slippers; diluent; Organic binders; Pesticide; Fungicides; Bactericides; Auxiliary solvent; Processing additives; Fixing agent; Thickeners; Plasticizers; UV-stabilizers; Stabilizers against heat or light; dyes; Color pigments; drier; Corrosion inhibitors; Fixation inhibitors; Dermabrasion inhibitors; And at least one additive selected from the group consisting of antifoaming agents. 3. The coating composition of claim 1 or 2, wherein the coating composition contains from 1% to 75% by weight of adsynonone based on the total weight of the dry mass of the coating composition. A process for preparing a coating composition according to any one of claims 1 to 3, in which an algae effective amount of accessory sinonone is intimately mixed with other components. Use of a coating composition according to any one of claims 1 to 3 for protecting surfaces or objects from frequent or continuous contact with water from contamination. Use of a coating composition according to any one of claims 1 to 3 for protecting a surface or object from frequent or continuous contact with water from the attachment or settlement of algae. A method of protecting a surface or object comprising applying the coating composition according to claim 1 to a surface or an object.