WO2017095335A1 - Biocides micro-encapsulés, compositions de revêtement comprenant des biocides micro-encapsulés, et utilisation de compositions de revêtement pour filets de pêche - Google Patents

Biocides micro-encapsulés, compositions de revêtement comprenant des biocides micro-encapsulés, et utilisation de compositions de revêtement pour filets de pêche Download PDF

Info

Publication number
WO2017095335A1
WO2017095335A1 PCT/SI2015/000034 SI2015000034W WO2017095335A1 WO 2017095335 A1 WO2017095335 A1 WO 2017095335A1 SI 2015000034 W SI2015000034 W SI 2015000034W WO 2017095335 A1 WO2017095335 A1 WO 2017095335A1
Authority
WO
WIPO (PCT)
Prior art keywords
biocide
water
microcapsules
oil
coating composition
Prior art date
Application number
PCT/SI2015/000034
Other languages
English (en)
Other versions
WO2017095335A8 (fr
Inventor
Fabrizio Calenti
Denis Jahic
Masenka Mikuz
Aljosa Vrhunec
Dejean STEFANEC
Jurij Puslar
Original Assignee
Aquafil S.P.A.
Microcaps D.O.O.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Aquafil S.P.A., Microcaps D.O.O. filed Critical Aquafil S.P.A.
Priority to PCT/SI2015/000034 priority Critical patent/WO2017095335A1/fr
Publication of WO2017095335A1 publication Critical patent/WO2017095335A1/fr
Publication of WO2017095335A8 publication Critical patent/WO2017095335A8/fr

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/26—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests in coated particulate form
    • A01N25/28—Microcapsules or nanocapsules
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group

Definitions

  • Microencapsulated biocides coating compositions with microencapsulated biocides and use of coating compositions for fishing nets
  • the invention relates to heavy metal free, copper free antifouling treatment for protection of fishing nets for controlling and preventing of biofouling from algae, fungi, and bacteria on wetted surface of the netting.
  • a method of the microencapsulation process of organic biocide in particular 4,5-dichloro-2-n-octyl-3(2H)-isothiazolone (DCOIT) which is incorporated into a polymeric microcapsule with a porous wall enabling a controlled and prolonged release of biocide from the microcapsule.
  • DCOIT 4,5-dichloro-2-n-octyl-3(2H)-isothiazolone
  • Water based coating composition containing biocide microcapsules are provided as well.
  • Biofouling assemblages are a complex phenomenon resulting from several processes, the rate and extent of which are influenced by numerous physical, chemical and biological factors in the immediate proximity of the surface and affects most of the wet surfaces, resulting in significant financial costs. Accumulation of algae and barnacles increases the ship's drag, reduces the flux in water cooling pipes and destroys protection and the equipment used in aquaculture.
  • the released biocides have to be bioavailable to the target organisms at the surface.
  • the release rate of biocides from the paint matrix called leaching rate, has to be kept above a limit threshold in order to reach and maintain a minimum inhibition concentration of the biocide at the exposed surface.
  • anti-fouling paints are formulated with toxic copper or other biocides-special chemicals, in order to prevent the growth of sessile marine organisms. Copper is an effective and still widely used biocide; however its effectiveness is relatively short, often only few months, so cleaning and paint reapplication are frequently required. Besides economics, leaching of copper or other biocides causes contamination of the sea water and problems to not target organisms.
  • Fishing nets waste typical composition includes approximately 50%-99% of synthetic polymer fibres forming the netting and ropes fixed to these nettings, examples of such polymer fibres are Polyamide6, Polyamide6.6, Polypropylene, Polyethylene or Polyester. High percentage of polymeric components in this waste is considered as valuable resource of material that can be recycled. Most of fishing nets are made of Polyamide6 fibres, which can be regenerated back into Polyamide6 offering exactly the same performances as that of the "virgin" Polyamide6, produced out of crude oil, crude oil intermediates and derivates.
  • Typical composition of these coatings contain copper based biocides, for example copper(l) oxide Cu 2 0, pigments, binders and waxes, in particular paraffinic waxes and film forming polymeric or copolymer resins, for example Ethylene- Vinyl Acetate copolymers, Polyacrylic polymer, etc., which remains on the fibres surface and can not be easily removed.
  • copper based biocides for example copper(l) oxide Cu 2 0, pigments, binders and waxes, in particular paraffinic waxes and film forming polymeric or copolymer resins, for example Ethylene- Vinyl Acetate copolymers, Polyacrylic polymer, etc.
  • other impurities can be present on the surface of the netting, for example sea shells, or impurities coming from the sea silt sediments or the landfill area, but these are usually in low level approximately 0.1 %-1%.
  • the coating components are removed, as they are dissolved in the cleaning solution, such as water, chemicals, washing agents, or are being mechanically removed from the fibres surface using high pressure or high friction cleaning equipment.
  • the cleaning solution such as water, chemicals, washing agents, or are being mechanically removed from the fibres surface using high pressure or high friction cleaning equipment.
  • Copper (I) oxide particles in cleaning solutions settle on the bottom or remain partially floating on top and often remain attached to waxes or binders, causing formation of foams or sediments during washing process. These solid materials are further removed from the cleaning solutions and this increases costs of the cleaning process.
  • Typical filtration and separation technologies are used for removal of solid particles, and thus a high amount of solid material waste which contains high level of copper(l) oxide Cu 2 0, waxes and other coating components are obtained, which must be safely handled and properly disposed, usually sent for incineration or to further recycling of metal components.
  • the biocide releasing can be additional and more precisely controlled by involving microencapsulation technology.
  • Microencapsulation enables variations of the membrane, i.e. shell properties hence controlling the release of the active biocide. It is a process that allows isolating an active product from the external medium by forming microspheres or microcapsules.
  • Microspheres correspond to a polymeric network in which a solid active substance is enclosed and microcapsules are constituted by a liquid core with active substance, i.e. biocide or antifouling agent and a polymeric wall, i.e. shell.
  • active substance i.e. biocide or antifouling agent
  • a polymeric wall i.e. shell.
  • Many industrial sectors are interested in microencapsulation processes, including biocidal applications.
  • the biocide in the paint is previously encapsulated into microcapsules with various properties which enable controlled release and lover skin toxicity.
  • EP0679333 describes much lower skin sensation potential than non-encapsulated isothiazolons achieved by encapsulation via interfacial polymerisation with polyurea based capsules. Described capsules of so encapsulated isothiazolons contain volatile organic solvent within the capsules.
  • WO2013101889 describes antifouling composition with increased release comprising an encapsulated active component and metal additives.
  • Active component should be encapsulated in the presence of organic solvents if the active component is solid at temperatures above 20°C. Beside the organic solvents, which are potentially present in the antifouling paint, the residual formaldehyde content is present in the higher concentration as well resulting in the leaching of both components into the environment. Furthermore said compositions contain one or more metal additive.
  • EP2201836 describes antifouling solutions by using encapsulated DCOIT where capsules are essentially impermeable to xylene and where the core contains partially water soluble solvent as well.
  • antifouling paint contains the free isothiazolone based biocides and organic solvent.
  • the antifouling paint is a solvent based paint; the active substance is completely sealed within the capsules.
  • WO2010133548 proposes polyacrylate based microparticles for paints however the core of capsules contains volatile solvent as well.
  • US7429392 patent describes melamine formaldehyde based capsules of active biocide for alkaline environment.
  • VOC volatile organic compounds
  • the VOC compound shall mean any organic compound having at 293,15 K a vapour pressure of 0,01 kPa or more, or having a corresponding volatility under the particular conditions of use. So far there is no commercialised solution available which would solve the VOC leaching drawbacks due to other antifouling paint compositions.
  • the object of the present invention is therefore to provide a highly effective water based antifouling coating composition, wherein said coating composition comprising a water based binder and a heavy-metal-free biocide that has previously been microencapsulated resulting in a long-term activity and low impact to the environment.
  • the invention refers to a process for synthesis of the microencapsulated heavy metal free biocide in the melted state without the VOC addition enabling to provide zero VOC coating composition by using zero VOC water based binder and other proper paint additives.
  • the shell of the microcapsules is porous, so that the active substance, i.e. biocide, is controlled released through the pores into the layer of the coating composition.
  • the present invention refers also to the use of the antifouling coating composition for the coating of fishing materials for their easier recycling after use. DETAILED DESCRIPTION OF THE INVENTION
  • a coating composition according to the invention comprises a mixture of water based binder and a water dispersion of microencapsulated biocide, wherein microcapsules comprise a porous polymeric membrane as capsule's wall and at least one heavy-metal-free biocide without volatile organic compounds as a core material within the polymeric membrane. Heavy-metal-free biocide without volatile organic compounds was microencapsulated by interfacial polymerisations via oil- in-water emulsion to obtain water dispersion of microencapsulated biocide wherein said water dispersion of microencapsulated biocide is without free biocide.
  • interfacial polymerisation process There are various types of interfacial polymerisation process but all involve reaction at the interface of a dispersed phase and a continuous phase in an emulsion system.
  • interfacial polymerisation process the in situ interfacial polymerisation reaction, all of the wall- forming monomers are contained in one phase of the emulsion, i.e. in the aqueous phase.
  • Another type of microencapsulation process is the interfacial condensation polymerisation reaction where reactants, i.e. wall-forming monomers, are contained in the oil and aqueous phase respectively and are brought together at the oil/water interface where they react by condensation to form the microcapsule wall.
  • the biocide is present in an internal (oil) phase of the emulsion.
  • the oil phase comprises pure biocides or biocides mixed with free VOC solvents and optionally mixed with oil soluble monomers.
  • the aqueous phase is water based solution of the emulsifier and comprises a mixture of at least one anionic or a non-ionic protective colloid and/or a non-ionic surfactant.
  • Oil phase is then transferred into the water based solution of the emulsifier, i.e. into the aqueous phase, while stirring.
  • high sheer mixer can be used.
  • the water based reactant solution is added to the emulsion and polymerisation reaction is started by increasing the temperature and optionally changing a pH.
  • Curing of the both types of polymers at the oil/water phase interface is initiated by heating the emulsion to a temperature of between about 20°C to about 95°C, optionally lowering the pH to values from 3 to 6 or optionally by initiation activity by a catalyst.
  • the heating occurs for a sufficient period of time to allow substantial completion of the (pre)polymers to convert the droplets to capsules consisting of porous polymer membrane entrapping the core materials, i.e. biocides, and is optionally between 1 and 3 hours.
  • a water dispersion of microencapsulated biocide with 20-50 wt% of capsules content based on the total weight of the dispersion with a concentration of biocide from 10-40 wt% based on the total weight of the dispersion is thus obtained.
  • the capsules consist of 50-90 wt% of the core (active component) and 10-50 wt% of polymeric membrane based on the total weight of the microcapsules and the size of the capsules so obtained is between 0,1 and 40 micrometres.
  • Suitable biocides in the context of the invention are preferably heavy-metal-free biocides such as isothiazolinones, carbamates, pyrithiones, aldehydes, ketones, quinones, amines, amidines, guanidines, hydrazo and azo compounds, aromatic earbonitriles, carboxylic esters, carboxamides and carboximides, benzimidazoles, quinoxalines, imidazoles, triazoles, pyrimidines, triazines, halogenated and nitrated alcohols and phenols, perhaloalkyl mercaptan derivatives, phosphoric and phosphonic esters, tetrahydro-1 ,3,5-thiadiazinethiones, thiocyanates and isothiocyanates, thiophenes, antibiotics, and active plant substances.
  • isothiazolinones such as isothiazolinones, carbamates, pyrithiones
  • biocides in the context of the invention are triazines, ⁇ , ⁇ -dimethylureas, and uracils.
  • algicides in accordance with the invention are N2-t-butyl-N4-ethyl-6-methylthio- 1 ,3,5-triazine-2,4-diyldiamine (terbutryn), 2-chloro-4,6-bis(isopropylamino)-s-triazine, 2-t- butylamino-4-ethylamino-6-methoxy-s-triazine, N'-(3,4-dichlorophenyl)-N,N-dimethylurea, 4- butylamino-2-chloro-6-ethylamino-s-triazine, 3-(4-isopropylphenyl)-1 ,1-dimethylurea, and 3-t- butyl-5-chloro-6-methyluracil.
  • biocides according to the invention are methyl 4,5-dichloro-octylisothiazolin-3-one (DCOIT), 2-n-octylisothiazolin-3-one (OIT), 3-iodo-2-propynyl N-butylcarbamate (IPBC), 1 H-benzimidazol-2-ylcarbamate (carbendazim).
  • an internal, i.e. oil phase of the emulsion consists of the pure biocide only, i.e. without solvent, melting of biocide before emulsification is needed in some cases.
  • the biocide is in a solid state at room temperature the heating of the oil phase above its melting point is necessary which is usually above 35°C.
  • Biocides can be optionally mixed with free VOC compounds in order to improve the physical and chemical properties, such as viscosity, surface tension, density and other properties for the emulsion stability and controlled released of biocide after the applying of the coating composition according to the invention.
  • suitable solvents are free VOC isoparaffins, paraffins, silicon oils, vegetable oils, fatty acids, perfluorinated aliphatic ethers, glycol ethers, glycol ether esters, esters, or ketones.
  • oil phase of the emulsion contains oil soluble monomers as well.
  • Suitable oil soluble monomers used in this process are isocyanates, like diphenylmethane diisocyanates, toluene diisocyanates, xylylene diisocyanates, dicyclohexylmethane diisocyanates, tetramethylxylene diisocyanate, naphthalene diisocyanate, para-phenylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, mixtures thereof, and the like.
  • Polymeric polyisocyanates, biurets, blocked polyisocyanates, and mixtures of polyisocyanates with melting point modifiers and mixtures thereof can also be used.
  • Oil phase is dispersed in the aqueous phase in the presence of a mixture of at least one anionic or a non-ionic protective colloid and/or a non-ionic surfactant thus forming an oil-in-water emulsion.
  • Aqueous phase of the emulsion contains of 0,1-10 wt. % of protective colloids based on the amount of the aqueous phase, which are critical for use in the invented emulsion preparation.
  • suitable protective colloids which may be used are polyacrylates, polyvinyl alcohols, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinylpyrrolidone, polyethylene oxide (polyoxyethylene), styrene copolymers, polystyrene sulfonate, polyvinylsulfonates, maleic anhydride styrene copolymer, maleic anhydride-isobutylene copolymer, maleic anhydride-ethylene copolymer, maleic anhydride-methyl vinyl ether copolymer, gum arabic, acrylate copolymers, gelatine, pectin, pullulan, phthalate gelatine, succinate gelatine and other gelatine derivatives.
  • non-ionic surfactants are the products which can be obtained by reaction of ethylene oxide, or by the combined reaction of ethylene oxide and propylene oxide, with fatty alcohols, alkylphenols, fatty acids, fatty acid esters of polyhydroxy compounds, fatty acid amides and fatty amines.
  • additives such as thickeners, density balancing agents, dispersants, dyes, salts, anti-freeze agents, and the like can be added to improve stability and ease of capsules' synthesis itself and incorporation into the coating system as well.
  • poly(urea-urethane) membrane by interfacial condensation polymerisation reaction amines or polyols are used as a reactant solution.
  • Suitable polyols used for polyurethanic wall formation may include simple low molecular weight aliphatic di, tri or tetraols or polymeric polyols.
  • the polymeric polyols may be members of any class of polymeric polyols, for example: polyether, polycarbonates, polyesters and polyesteramides.
  • the diols suitable for use in the present invention are ethyleneglycol, diethylene glycol, propylene glycol, 1 ,4-butane diol, 1,4 hexane diol, dipropylene glycol, cyclohexyl 1,4 dimethanol, 1 ,8 octane diol and polyols such as poly (ethylene glycols), poly (propylene glycols) and their copolymers, poly (tetramethylene glycols), butyleneglycol.
  • Preferred amines which are suitable for interfacial reaction with the isocyanates and which also function as "crosslinking agents" are aliphatic, primary or secondary di- and polyamines, for example: ethylene-1 ,2-diamine, bis(3-aminopropyl)amine, hydrazine-2-ethanol, bis(2- methylaminoethyl)methylamine, 1 ,4-diaminocyclohexane, 3-amino-1-methyl-aminopropane, N- hydroxy-ethyl-ethylene-diamine, N-methyl-bis(3-aminopropyl)amine, 1 ,4-diamino-n-butane, 1 ,6- diamino-n-hexane, ethylene-1 ,2-diamine-N-ethyl-sulphonic acid (as an alkali metal salt), 1- amino-ethylene-1 ,2-diamine and bis(N,N'-aminoethyl
  • prepolymers and polymers thereof are used as a reactant solution.
  • Particularly preferred according to the invention are melamine-formaldehyde resins and prepolymers thereof.
  • a microencapsulated DCOIT according to this invention was prepared by in situ polymerisation forming the melamine-formaldehyde wall polymers or by interfacial condensation polymerisation resulting in polyurethane, polyurea or poly(urea-urethane) microcapsules.
  • the formaldehyde scavenger is added in order to reduce free-formaldehyde content in the dispersion and polycondensation reaction is stopped by changing pH again.
  • the membrane properties (such as elasticity, porosity, releasing properties etc.) can be varied by changing its composition and thickness.
  • the capsules size has a strong influence on the capsules properties as well. Faster releasing of the core, i.e. of the active substance, is usually achieved by reducing the concentration of wall-forming monomers, increasing the surfactants concentration or by reducing capsules diameter.
  • Water dispersion of microencapsulated biocide thus obtained is further mixed into a water based coating binder in order to prepare coating compositions according to the invention.
  • suitable water based coating binders can be used. Examples include water based acrylics, alkyds, amides, epoxies, ethylene co-terpolymers, urethanes, silicates, styrene or vinyls coatings.
  • Suitable binder type is selected from ethylene-vinyl acetate copolymer, polyacrylate, and polyurethane, preferably ethylene-vinyl acetate copolymer or polyacrylate.
  • Proportion of each of the components in the coating composition is (in weight % based on total weight of the composition): 60-90 wt. % of water-based binder and 10-40 wt. % of water dispersion of microencapsulated biocide, wherein the water based binder contains 30-50 wt. % of pure binder and the rest water (based on the total weight of binder).
  • Water dispersion of microencapsulated biocide is typically added to the water based coating system while stirring at room temperature for 5 to 30 minutes.
  • the concentration of the active component, i.e. biocide in the coating composition is between 0,01 wt% and 18 wt. % based on total weight of the composition.
  • Coating compositions according to the invention are used for coating of objects which come into contact with sea water such as yachts, ships, boats, floating object, buoys, preferably for coating fish nets.
  • Example 1 An aqueous dispersion of melamine-formaldehyde capsules of DCOIT
  • Melamine formaldehyde microcapsules were prepared by in-situ polymerisation of the oil-in- water emulsion. 396g of 3% aqueous solution of styrene-maleic acid anhydride copolymer with 200.000 average molecular weight pre-heated to 50°C was mixed with 142, 3g of 4,5-Dichloro-2- octyl-4-isothiazolin-3-one (DCOIT) pre-heated to 50°C . The mixed solution was then emulsified with homogeniser at 13,000 rpm for 30 minutes at 50°C to obtain stable emulsion of oil-in-water.
  • DCOIT 4,5-Dichloro-2- octyl-4-isothiazolin-3-one
  • the emulsion was then transferred into a 800 mL polymerisation reactor pre-heated to 50°C and 107,2g of 50% aqueous solution of partly methylated trimethylolmelamine pre-heated to 50°C was added.
  • the emulsion was mixed with the stirrer at 500 rpm and heated from 50 to 75 °C to induce polycondensation reaction. Polycondensation process was taking place for about 1 ,5 hours then polycondensation was terminated by raising pH to 7 with sodium hydroxide. At 50°C 7g of ammonia was added for removal of residual formaldehyde. Then the dispersion of microcapsules was cooled down to the room temperature. Microcapsules dispersion with an average particle size 14 ⁇ and 22 % DCOIT content has been obtained.
  • Example 2 An aqueous dispersion of melamine-formaldehyde capsules of DCOIT
  • Melamine formaldehyde microcapsules were prepared by in-situ polymerisation of the oil-in- water emulsion. 375g of 3% aqueous solution of styrene-maleic acid anhydride copolymer with 200.000 average molecular weight pre-heated to 50°C was mixed with 142, 3g of 4,5-Dichloro-2- octyl-4-isothiazolin-3-one (DCOIT) pre-heated to 50°C . The mixed solution was then emulsified with homogeniser at 13,000 rpm for 30 minutes at 50°C to obtain stable emulsion of oil-in-water.
  • DCOIT 4,5-Dichloro-2- octyl-4-isothiazolin-3-one
  • the emulsion was then transferred into a 800 ml_ polymerisation reactor pre-heated to 50°C and 128,6g of 50% aqueous solution of partly methylated trimethylolmelamine pre-heated to 50°C was added.
  • the emulsion was mixed with the stirrer at 500 rpm and heated from 50 to 75 °C to induce of polycondensation reaction. Polycondensation process was taking place for about 1 ,5 hours then polycondensation was terminated by raising pH to 7 with sodium hydroxide. At 50°C 9 g of ammonia was added for removal of residual formaldehyde. Then the dispersion of microcapsules was cooled down to the room temperature. Microcapsules dispersion with an average particle size 15 m and 22% DCOIT content has been obtained.
  • Example 3 An aqueous dispersion of melamine-formaldehyde capsules of DCOIT with free VOC solvent
  • Example 2 The procedure is analogous to Example 1 except that oil phase comprise of 1 13,8 g of DCOIT and 28,5 g of linseed oil instead of the pure DCOIT. Microcapsules dispersion with an average particle size 2-20 ⁇ and 17% DCOIT content has been obtained.
  • Example 4 An aqueous dispersion of polyurethane capsules of DCOIT An oil phase was prepared by mixing 100 g of DCOIT, 50 g of linseed oil and 10 g of methylene diphenyl diisocyanate. Water phase was prepared by dissolving 4 g of polyvinyl alcohol and 2 g of carboxymethyl cellulose in 200 g of water by heating up to 85 °C for 30 min.
  • the oil phase was emulsified in the cooled water phase using a high shear mixer.
  • the mixing with high shear mixer (15,100 rpm) was continued for 15 min at room temperature.
  • a solution of 15 g of butane diol in 15 g of water was added.
  • the emulsion was heated up to 80°C and mixed (400 rpm) for 2 hours at this temperature.
  • the dispersion of microcapsules was cooled to room temperature. Microcapsules dispersion with an average particle size 13 ⁇ and 27% DCOIT content has been obtained.
  • Microcapsules dispersions obtained from example 1 and 2 were mixed with pre-prepared water- based binders.
  • Ethylene-vinyl acetate copolymer (EVA), polyacrylate (PA), and polyurethane (PU) were used as binder type.
  • Stabile water-based coating compositions (CC) were prepared by introducing the microcapsules dispersion into binder while stirring at room temperature with a spiral propeller blade at 3000 rpm for 15 minutes.
  • One coating compositions (CC13) has been prepared by adding pure, nonencapsulated DCOIT for efficiency comparison. Examples of coating compositions are shown in Table 1.
  • Table 1 Comparative examples of coating compositions (CC).
  • First step was preparation of different coating compositions with the addition of microcapsules dispersions and with the nonencapsulated DCOIT, i.e. DCOIT water based emulsion.
  • DCOIT nonencapsulated water based emulsion
  • coating samples CC1 and CC4 from table 1 with microcapsules dispersions obtained from example 1 and 2 were used.
  • nonencapsulated water based emulsion of DCOIT has been used in same amount (CC13) as with both encapsulated samples.
  • Samples of coatings has been then applied on stainless steel (SS) plates by dipping followed by drying at 60°C degrees for 90 minutes so that conditions of applying to fishing nets has been simulated.
  • the SS plates were immersed in a flow cell with a constant temp. 24 °C, and constant inflow of seawater - 1 ,8 l/h. After 2 weeks, the plates were removed from sea water and remaining DCOIT content in the coatings was determinate by extraction in ethanol and analysis on UV VIS spectroscopy.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne des compositions de revêtement antisalissures, exemptes de cuivre, exemptes de métaux lourds, pour la protection de filets de pêche pour lutter et prévenir l'encrassement biologique provenant d'algues, de champignons et de bactéries sur une surface mouillée du filet. L'invention concerne un procédé du processus de microencapsulation de biocide organique, en particulier 4,5-dichloro-2-n-octyl-3(2H)-isothiazolone (DCOIT) qui est incorporé dans une microcapsule polymère avec une paroi poreuse permettant une libération contrôlée et prolongée de biocide à partir de la microcapsule. L'invention concerne également des compositions de revêtement à base d'eau contenant des microcapsules de biocide.
PCT/SI2015/000034 2015-11-30 2015-11-30 Biocides micro-encapsulés, compositions de revêtement comprenant des biocides micro-encapsulés, et utilisation de compositions de revêtement pour filets de pêche WO2017095335A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/SI2015/000034 WO2017095335A1 (fr) 2015-11-30 2015-11-30 Biocides micro-encapsulés, compositions de revêtement comprenant des biocides micro-encapsulés, et utilisation de compositions de revêtement pour filets de pêche

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/SI2015/000034 WO2017095335A1 (fr) 2015-11-30 2015-11-30 Biocides micro-encapsulés, compositions de revêtement comprenant des biocides micro-encapsulés, et utilisation de compositions de revêtement pour filets de pêche

Publications (2)

Publication Number Publication Date
WO2017095335A1 true WO2017095335A1 (fr) 2017-06-08
WO2017095335A8 WO2017095335A8 (fr) 2017-08-17

Family

ID=55485257

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SI2015/000034 WO2017095335A1 (fr) 2015-11-30 2015-11-30 Biocides micro-encapsulés, compositions de revêtement comprenant des biocides micro-encapsulés, et utilisation de compositions de revêtement pour filets de pêche

Country Status (1)

Country Link
WO (1) WO2017095335A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109769807A (zh) * 2018-11-14 2019-05-21 浙江农林大学 一种具有双分子结构的缓释灭藻微胶囊及其制备方法
WO2019133483A1 (fr) * 2017-12-28 2019-07-04 Dow Global Technologies Llc Stabilisation de dcoit dans des systèmes aqueux
CN110003703A (zh) * 2019-04-25 2019-07-12 海南大学 一种防污微胶囊、其制备方法及应用
US10457015B1 (en) * 2019-01-11 2019-10-29 Tru-View LLC Mesh material for flexible structures and methods of fabricating same
WO2020068748A1 (fr) * 2018-09-28 2020-04-02 Rohm And Haas Company Agents de conservation du bois
WO2020099567A1 (fr) 2018-11-16 2020-05-22 Lonza Ltd Biocides encapsulés
US10926511B2 (en) 2019-01-11 2021-02-23 Tru-View LLC Mesh material for flexible structures and methods of fabricating same
CN112970749A (zh) * 2021-01-25 2021-06-18 湖北福力德鞋业有限责任公司 一种缓释型抗菌微胶囊及其制备方法
WO2022002846A1 (fr) 2020-07-01 2022-01-06 Laboratorios Miret, S.A. Tcmtb microencapsulé
US12082583B2 (en) 2017-03-31 2024-09-10 Nutrition & Biosciences Usa 2, Llc Wood preservatives

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0679333A2 (fr) 1994-04-28 1995-11-02 Rohm And Haas Company Composition biocide non-sensibilisatrice
US6221374B1 (en) 1997-05-28 2001-04-24 Rohm And Haas Company Controlled release compositions
US6365066B1 (en) 1996-10-24 2002-04-02 Bayer Aktiengesellschaft Antifouling paint
US6635692B1 (en) 1997-07-04 2003-10-21 Aquaculture Crc Limited Antifouling polymers
WO2004000953A1 (fr) * 2002-06-19 2003-12-31 Thor Gmbh Materiau d'enduction contenant des microcapsules de biocide
EP1457531A1 (fr) 2002-10-23 2004-09-15 Chugoku Marine Paints, Ltd. Composition de peinture antifouling, films de peinture antifouling, et navires, structures sous marines, materiel de peche et filets de peche recouverts par ces films
WO2007039055A2 (fr) * 2005-09-19 2007-04-12 Sipcam S.P.A. Formulations à base de carbamate de 3-iodo-2-propynyle butyle
EP1834524A2 (fr) * 2006-03-16 2007-09-19 Rohm and Haas Company Mélanges de biocides encapsulés
WO2008000797A2 (fr) * 2006-06-30 2008-01-03 Thor Gmbh Microparticules antimicrobiennes
WO2008080963A1 (fr) * 2006-12-28 2008-07-10 Thor Gmbh Masses de collage et d'étanchéité présentant un apprêt antimicrobien
EP2201836A2 (fr) 2004-09-14 2010-06-30 Microtek Laboratories, Inc. Microencapsulation de biocides et d'agents antisalissures
WO2010133548A2 (fr) 2009-05-19 2010-11-25 Capeco Ab Microcapsules et microsphères à libération lente comprenant une substance active
WO2013101657A1 (fr) * 2011-12-27 2013-07-04 Dow Global Technologies Llc Microcapsules
WO2013101889A1 (fr) 2011-12-29 2013-07-04 Rohm And Haas Company Principes actifs encapsulés
WO2013101887A2 (fr) * 2011-12-27 2013-07-04 Dow Global Technologies Llc Microcapsules
WO2015128382A1 (fr) * 2014-02-27 2015-09-03 Lanxess Deutschland Gmbh Microcapsules biocides

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0679333A2 (fr) 1994-04-28 1995-11-02 Rohm And Haas Company Composition biocide non-sensibilisatrice
US6365066B1 (en) 1996-10-24 2002-04-02 Bayer Aktiengesellschaft Antifouling paint
US6221374B1 (en) 1997-05-28 2001-04-24 Rohm And Haas Company Controlled release compositions
US6635692B1 (en) 1997-07-04 2003-10-21 Aquaculture Crc Limited Antifouling polymers
US7429392B2 (en) 2002-06-19 2008-09-30 Thor Gmbh Coating material with biocide microcapsules
WO2004000953A1 (fr) * 2002-06-19 2003-12-31 Thor Gmbh Materiau d'enduction contenant des microcapsules de biocide
EP1457531A1 (fr) 2002-10-23 2004-09-15 Chugoku Marine Paints, Ltd. Composition de peinture antifouling, films de peinture antifouling, et navires, structures sous marines, materiel de peche et filets de peche recouverts par ces films
EP2201836A2 (fr) 2004-09-14 2010-06-30 Microtek Laboratories, Inc. Microencapsulation de biocides et d'agents antisalissures
WO2007039055A2 (fr) * 2005-09-19 2007-04-12 Sipcam S.P.A. Formulations à base de carbamate de 3-iodo-2-propynyle butyle
US20070215000A1 (en) 2006-03-16 2007-09-20 Reybuck Sarah E Blends of encapsulated biocides
EP1834524A2 (fr) * 2006-03-16 2007-09-19 Rohm and Haas Company Mélanges de biocides encapsulés
WO2008000797A2 (fr) * 2006-06-30 2008-01-03 Thor Gmbh Microparticules antimicrobiennes
WO2008080963A1 (fr) * 2006-12-28 2008-07-10 Thor Gmbh Masses de collage et d'étanchéité présentant un apprêt antimicrobien
WO2010133548A2 (fr) 2009-05-19 2010-11-25 Capeco Ab Microcapsules et microsphères à libération lente comprenant une substance active
WO2013101657A1 (fr) * 2011-12-27 2013-07-04 Dow Global Technologies Llc Microcapsules
WO2013101887A2 (fr) * 2011-12-27 2013-07-04 Dow Global Technologies Llc Microcapsules
WO2013101889A1 (fr) 2011-12-29 2013-07-04 Rohm And Haas Company Principes actifs encapsulés
WO2015128382A1 (fr) * 2014-02-27 2015-09-03 Lanxess Deutschland Gmbh Microcapsules biocides

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Solvesso 200 MSDS", 21 May 2014 (2014-05-21), pages 1 - 10, XP055264166, Retrieved from the Internet <URL:http://www.pure-chemical.com/assets/uploads/products/solvesso_200.pdf> [retrieved on 20160411] *
ELIZABETH HASLBECK: "FINAL REPORT: Microencapsulation of Biocides for Reduced Copper, Long-life Antifouling Coatings", 1 February 2007 (2007-02-01), West Bethesda, MD, U.S.A., pages 1 - 39, XP055264410, Retrieved from the Internet <URL:http://db.materialoptions.com/ASETSDefense/SEDB/CrPrimer_VOC_Alts/Qual_Eng_Data/Microencapsulation of biocides WP-0306-FR.pdf> [retrieved on 20160412] *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US12082583B2 (en) 2017-03-31 2024-09-10 Nutrition & Biosciences Usa 2, Llc Wood preservatives
WO2019133483A1 (fr) * 2017-12-28 2019-07-04 Dow Global Technologies Llc Stabilisation de dcoit dans des systèmes aqueux
CN114845548A (zh) * 2018-09-28 2022-08-02 营养与生物科技美国第二有限公司 木材防腐剂
CN114845548B (zh) * 2018-09-28 2024-04-02 营养与生物科技美国第二有限公司 木材防腐剂
WO2020068748A1 (fr) * 2018-09-28 2020-04-02 Rohm And Haas Company Agents de conservation du bois
CN109769807B (zh) * 2018-11-14 2021-01-12 浙江农林大学 一种具有双分子结构的缓释灭藻微胶囊及其制备方法
CN109769807A (zh) * 2018-11-14 2019-05-21 浙江农林大学 一种具有双分子结构的缓释灭藻微胶囊及其制备方法
CN109769807B9 (zh) * 2018-11-14 2021-02-09 浙江农林大学 一种具有双分子结构的缓释灭藻微胶囊及其制备方法
CN113226026A (zh) * 2018-11-16 2021-08-06 隆萨解决方案股份公司 包封的杀菌剂
WO2020099567A1 (fr) 2018-11-16 2020-05-22 Lonza Ltd Biocides encapsulés
US20200223173A1 (en) * 2019-01-11 2020-07-16 Tru-View LLC Mesh material for flexible structures and methods of fabricating same
US10744741B2 (en) * 2019-01-11 2020-08-18 Tru-View LLC Mesh material for flexible structures and methods of fabricating same
US10926511B2 (en) 2019-01-11 2021-02-23 Tru-View LLC Mesh material for flexible structures and methods of fabricating same
US10457015B1 (en) * 2019-01-11 2019-10-29 Tru-View LLC Mesh material for flexible structures and methods of fabricating same
CN110003703A (zh) * 2019-04-25 2019-07-12 海南大学 一种防污微胶囊、其制备方法及应用
WO2022002846A1 (fr) 2020-07-01 2022-01-06 Laboratorios Miret, S.A. Tcmtb microencapsulé
CN112970749A (zh) * 2021-01-25 2021-06-18 湖北福力德鞋业有限责任公司 一种缓释型抗菌微胶囊及其制备方法
CN112970749B (zh) * 2021-01-25 2022-02-15 湖北福力德鞋业有限责任公司 一种缓释型抗菌微胶囊及其制备方法

Also Published As

Publication number Publication date
WO2017095335A8 (fr) 2017-08-17

Similar Documents

Publication Publication Date Title
WO2017095335A1 (fr) Biocides micro-encapsulés, compositions de revêtement comprenant des biocides micro-encapsulés, et utilisation de compositions de revêtement pour filets de pêche
CN101037554B (zh) 包囊的生物杀伤剂的混合物
DK2201836T3 (en) Microencapsulation of biocides and antifouling agents.
CN107708853B (zh) 包封
US20110274763A1 (en) Slow releasing microcapsules and microspheres containing an active substance
CN107083094B (zh) 一种微胶囊、其制备方法、仿生防污涂料和仿生防污涂层
CN1103540C (zh) 含生物活性化合物悬浮液的微囊
EP3916058A1 (fr) Utilisation de compositions d&#39;aérogel dans des peintures et revêtements marins
KR100957986B1 (ko) 무기화합물 함유 마이크로 캡슐을 포함하는 자기 보수성 피막이 코팅된 표면처리강판 및 강판의 자기 보수성 표면처리 피막 형성용 수지 조성물
US20070053950A1 (en) Composition of polymer microcapsules of biocide for coating material
US4253877A (en) Anti-fouling marine paints containing microencapsulated anti-fouling agents and the process of microencapsulation
TW201231572A (en) Antifouling coating composition
JP2023014073A (ja) 防汚物品
US8722071B2 (en) Microcapsules containing biocide and preparation thereof by solvent evaporation technique
Patil et al. Synthesis, characterization, and controlled release study of polyurea microcapsules containing metribuzin herbicide
US20180037749A1 (en) Biocidal protective formulations
CN104039141B (zh) 包封的活性物质
CN104508058A (zh) 包含杀生物剂的涂料组合物
DK2779831T3 (en) Microcapsules
EP3298895A1 (fr) Microcapsules biocides pour la lutte contre l&#39;encrassement biologique
Kulkarni et al. Polyurea and polyurethane microcapsules containing mosquito repellent DEET: preparation and characterization
DK3036032T3 (en) Process for preparing concentrates of preferably water-soluble active substances
JPH1059810A (ja) 水中付着生物忌避剤およびそれを含有する防汚塗料
EP4175473A1 (fr) Tcmtb microencapsulé
KR20050055844A (ko) 방오 도료 조성물

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15840999

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15840999

Country of ref document: EP

Kind code of ref document: A1