WO2006131147A1 - Emulsions de cire destinees a augmenter les proprietes biocides des peintures - Google Patents

Emulsions de cire destinees a augmenter les proprietes biocides des peintures Download PDF

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Publication number
WO2006131147A1
WO2006131147A1 PCT/EP2005/052596 EP2005052596W WO2006131147A1 WO 2006131147 A1 WO2006131147 A1 WO 2006131147A1 EP 2005052596 W EP2005052596 W EP 2005052596W WO 2006131147 A1 WO2006131147 A1 WO 2006131147A1
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Prior art keywords
pbw
water
weight
composition
paint
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PCT/EP2005/052596
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English (en)
Inventor
Amaro Izquierdo Ramis
Joan Seguer Bonaventura
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Laboratorios Miret, S.A.
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Application filed by Laboratorios Miret, S.A. filed Critical Laboratorios Miret, S.A.
Priority to BRPI0520315-5A priority Critical patent/BRPI0520315A2/pt
Priority to EP05766763A priority patent/EP1890535A1/fr
Priority to PCT/EP2005/052596 priority patent/WO2006131147A1/fr
Publication of WO2006131147A1 publication Critical patent/WO2006131147A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
    • 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
    • A01N27/00—Biocides, pest repellants or attractants, or plant growth regulators containing hydrocarbons
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/02—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0058—Biocides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/205—Compounds containing groups, e.g. carbamates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C08K5/47—Thiazoles

Definitions

  • This invention relates to a composition comprising a biocidal compound to be used in water-borne paints.
  • compositions comprising a biocidal compound containing an effective amount of wax or paraffin to improve the efficacy of the water-borne paint compositions,
  • the paints used on jobsites today are a blend of pigments, resins, solvents, and additives.
  • the pigments provide colour and hiding ability and the resins determine the physical properties such as adhesion, abrasion resistance, and exterior durability.
  • Common types of resins found in paint include ⁇ ?alkyd, acrylic, vinyl, and poly-urethane.
  • Solvents- keep paints in liquid form so they can be applied easily.
  • the solvent may constitute up to 90% of the paint by weight or volume.
  • Solvent-borne (oil- based) paints use hydrocarbons produced from oil as the solvent.
  • Water- borne (latex) paints use water as the main solvent, but usually in combination with one or more other solvents made from hydrocarbons.
  • solvent-borne paints contain hydro-carbon solvents such as stoddard solvent, mineral spirits, and varsol.
  • High performance coatings such as epoxy paints may contain other solvents such as ketones, xylene, or toluene.
  • Water-borne paints use mostly water as the solvent. Glycols or other solvents are also commonly present in water-borne paints but they typically constitute at most 10% of the total weight.
  • the chemistry of water-borne paints is more diverse and complex than that of solvent-based paints.
  • a water-borne paint composition is composed of four basic components: binder, aqueous carrier, pigments and additives.
  • binder aqueous carrier
  • pigments e.g., a preservative agent needs to added.
  • water-borne paints contain many additives such as preservatives and fungicides, surfactants, and solvents.
  • Additives in paints are used to adjust the acidity (pH) of the paint, or add special properties, such as resistance to microorganisms.
  • pH acidity
  • special properties such as resistance to microorganisms.
  • water-borne paints there may be small amounts (typically less than 1%) of ammonia, alcohol, glycol ether, and formaldehyde.
  • Most manufacturers have stopped using ammonia and formaldehyde because of the unpleasant odours and
  • Paint components usually enter the body through inhalation of vapour and skin contact with liquid paint.
  • the hydrocarbon solvents used in 20 conventional alkyd paints can produce high vapour concentrations during painting and for several hours afterward. Painters and other workers have complained about eye irritation, the unpleasant odour, and even dizziness and nausea from the use of solvent-borne paints. In areas with poor ventilation, deaths have occurred.
  • Skin contact with solvent-borne paints and the solvents needed to remove paint from the skin can dry out the skin and in some cases lead to long- term skin problems (dermatitis).
  • Contact with water-borne paints can also lead to skin problems because some preservatives are known to cause allergic reactions.
  • Water-borne paints generally pose less of a hazard than solvent-based paints.
  • the use of a half-mask respirator with dust/mist cartridges is recommended for spraying water-borne paint.
  • a half-mask respirator with organic vapour cartridges and a dust/mist prefilter is recommended.
  • Water-borne paints are far less harmful to the environment.
  • Conventional paints use solvents which contribute to the formation of smog and ozone in the atmosphere.
  • Antifouling paints containing biocides are used on ship hulls to prevent organisms from growing on the bottom of boats.
  • Fouling organisms include both animals (e.g. barnacles, molluscs, polychaete worms, encrusting hydroids, bryozoa and sea squirts) and plants (e.g. green, red and brown algae and diatoms). By settling or clinging onto a ship's hull, these fouling organisms can cause higher fuel consumption due to increased drag, and interfere with the performance and durability of the craft.
  • TBT Tributyltin
  • Formaldehyde releasers are compounds that are synthesized by the condensation of formaldehyde, an amine and eventually a glycol.
  • sodium pyrithione is a water-soluble fungicide used primarily in metalworking fluids. Bacteria can also be controlled with sodium pyrithione, though at a high cost. This cost can be offset if it is also desirable to have a dry film fungicide in the paint, since sodium pyrithione and zinc oxide together provide protection of the paint film against the growth of mildew and algae. Soluble zinc from the zinc oxide will react with sodium pyrithione in a water-based system to produce zinc pyrithione. The rate is influenced by the pH. The higher the pH, the more soluble the zinc oxide becomes, allowing the reaction with sodium pyrithione to proceed faster.
  • This reaction also occurs in latex paint. Since there are many materials in latex paint, the rate of reaction will vary and will be influenced by additional factors other than pH. Adsorption of pyrithione onto the zinc oxide particle can occur and will be influenced by pH as well. Other metals can also react to produce additional salts of pyrithione, but this reaction can be used to an advantage.
  • any sodium pyrithione that is not converted to zinc pyrithione will provide good short-term protection of the dry film against mildew. Due to the water solubility of the sodium pyrithione, this protection will not last as long as might be desired. However, the high water solubility will help to kill any mildew that might already be established on the surface before being painted, therefore preventing mildew from growing through the paint film.
  • the pyrithione is the active part of both the sodium and zinc pyrithione molecules. The higher water solubility of sodium pyrithione provides a much higher concentration of pyrithione to kill microorganisms but will wash out of a paint film in a relatively short time.
  • the zinc pyrithione, formed from zinc oxide and sodium pyrithione will only be soluble at about 8 ppm with a pH of 7.
  • the solubility is higher above and below pH 7, but is still quite low. This property makes zinc pyrithione (a good fungicide for long-term protection of a paint film, but sometimes the short-term efficacy is not always as good as other available fungicides when compared at low concentrations. This is because some of these fungicides have a higher water solubility (160 ppm for iodo propynyl butyl carbamate (IPBC) and 460 ppm for n- octyl-isothiazolone(OIT)). This higher water solubility provides a higher concentration of available fungicide on the paint surface.
  • IPBC iodo propynyl butyl carbamate
  • OIT n- octyl-isothiazolone
  • biocides are generally used at a level of 1% or less by weight, U.S. paint makers add some 32 million Ib, or $110 million worth, of them annually to the paints they ship to users. Most of the opportunity for biocide suppliers is in preserving dry paint films. About 56% of biocides by volume are soid to keep paint films wholesome looking. Another 27% preserve liquid latex paints, solvent-based paints generally do not require in-can preservation. Antifoulants to preserve marine paints make up the remaining 17% of biocides sold.
  • the water-borne paint compositions contain perishable materials and must therefore be preserved. These emulsions are mainly preserved with 0,5 - 2% of a formulation which contains between 10-30% of biocides.
  • composition comprising an effective amount of a wax or a paraffin in combination with a biocide.
  • composition of the invention contains a wax or a paraffin.
  • wax has traditionally referred to a substance that is secreted by bees (beeswax) and used by them in constructing their honeycombs.
  • Wax is a generic name for a large range of products consisting of long- chain fatty acids esterified with long-chain fatty alcohols, triterpene alcohols or steroid alcohols. Chemically, a wax may also be an ester of ethylene glycol (ethane 1,2-diol) and two fatty acids, as opposed to a fat which is an ester of glycerin (propane 1,2,3-triol) and three fatty acids. It is a type of lipid.
  • Waxes generally include the following subgroups:
  • wax is defined according to its properties such as hardness, melting point, viscosity, colors etc. All these properties define the potential applications.
  • wax is an imprecisely defined term generally understood to be a substance with properties similar to beeswax, namely
  • Paraffin is a common name for a group of high molecular weight alkane hydrocarbons with the general formula C n H 2n+ 2, where n is greater than about 20.
  • paraffin oil or just paraffin
  • paraffin wax the solid forms of paraffin
  • straight-chain hydrocarbons with 18 or higher carbons in the molecule are called petroleum wax or paraffin wax, because they are solid at room temperature but become liquid quickly upon heating.
  • straight-chain hydrocarbons with 13 carbons in the molecule is called Liquid Petroleum Wax or Liquid Paraffin Wax because it is also straight-chain hydrocarbon as paraffin wax, although it is liquid at the room temperature.
  • Paraffin is also a technical name for an alkane in general, but in most cases it refers specifically to a linear, or normal alkane, while branched, or isoalkanes are also called isoparaffins (Latin para+affinis with the meaning here of "lacking affinity", or "lacking reactivity").
  • Paraffins are mostly found as a white, odorless, tasteless, waxy solid, with a typical melting point between about 47°C and 65°C. They are insoluble in water, but soluble in ether, benzene and certain esters. Paraffins are unaffected by most common chemical reagents, but burn readily.
  • Food-grade paraffin wax is used in some candies to make them look shiny. Although edible, it is nondigestible; it passes right through the body without being broken down. Non-food grade paraffin wax can contain oils and other impurities which may be toxic or harmful.
  • Paraffin wax is not used much to make original models for casting, as it is relatively brittle at room temperature and usually cannot be cold-carved without excessive chipping and breaking. Soft, pliable waxes such as beeswax are preferred for modelling.
  • composition of the invention is provided as an emulsion. It is an advantage of the paraffins that they are emulsified easily and this makes them particularly suitable to be used in the compositions of the invention.
  • wax Any kind of wax is in principle suitable to be used in the composition according to the invention. It is preferred to use paraffin waxes in the compositions of the invention.
  • the most suitable waxes and paraffins are such waxes or paraffins which display a melting point at a temperature between 50 and 60 0 C.
  • paraffin The most suitable paraffin is the type of product which is sold under the commercial names Redezon 100 or Cera 100 (manufacturer Repsol).
  • the types of paraffin which may be used vary from the types 50/52 to 68/70, the most preferred type is the one 55/60.
  • the most suitable type of wax is Cera LP (Licowax LP flakes; manufactured by Clariant). This type of wax comprises a fatty acid of 24 to 34 carbon atoms with CAS number 68476-03-9.
  • the amount of wax or paraffin in the composition of the invention is 1 to 50 % by weight. According to a preferred embodiment the amount of wax or paraffin is 5 to 45 % by weight, according to an even more preferred embodiment the amount of wax or paraffin is 15 to 40 % by weight, according to yet a further preferred embodiment the amount of wax or paraffin is 25 to 35 % by weight.
  • compositions according to the invention contain both a wax and a paraffin.
  • a composition on the basis of paraffin alone displays the wanted improvement of the biocidal efficacy and the presence of paraffin leads to highly stable compositions. Addition of a minor amount of wax leads to a further improvement of the properties.
  • composition on the basis of wax alone may display a viscosity value which is too high for easy handling. This phenomenon makes the combined presence of wax and paraffin the more preferable embodiment.
  • wax and paraffin in the combined application of wax and paraffin in the composition of the invention the same types of wax and paraffin are preferred as in the use of wax or paraffin alone.
  • the preferred amount of paraffin is 10 to 40 % by weight, the amount of wax 1 to 5 % by weight, a more preferred amount in the combined application is 15 to 30 % by weight for the paraffin and 2 to 4,5 % by weight for the wax.
  • a further component of the present invention is a thickener.
  • Different thickeners can be used. Historically, cellulose based materials (such as hydroxyethyl cellulose and sodium carboxymethyl cellulose), and to a lesser extent certain polyacrylates, have dominated the emulsion paint thickener market. While such cellulose based materials and polyacrylates are still commonly used for this application, a new class of thickeners, associative thickeners, has become available to the paint manufacturer. These are low molecular weight synthetic polymers or modified cellulose based materials which have several advantages over the conventional cellulose based materials. They impart a more Newtonian rheology, are stable to enzymatic degradation and can impart good gloss, flow, and anti-spatter properties to emulsion paints.
  • Casein is a natural phosphoprotein obtained from milk through extraction at the isolectric point.
  • Commercial names of the casein products which can be used in the composition of the invention are Caseina® (manufactured by Brenntag), Industrial acid casein (manufactured by Unilait, France) and Caseina Acide industrial (manufactured by Becamo).
  • the amount of the thickener in the composition of the invention is 1 to 10 % by weight, more preferred 3 to 8 % by weight.
  • Another component of the composition of the invention is a surfactant.
  • the presence of the surfactant shall allow the emulsification of wax and paraffin and shall provide the required stability to the emulsion, so that an acceptable shelf-life can be achieved.
  • Any conventional surfactant which is known in the art can be used, such as in particular the general groups of the non-ionic surfactants and the anionic surfactants.
  • a surfactant is a linear molecule with a hydrophilic (attracted to water) head and a hydrophobic (repelled by water) end. Surfactants tend to clump together when in solution, forming a surface between the fluid and air with the hydrophobic tails in the air and the hydrophilic heads in the fluid. Often surfactants will form "bubbles" within the fluid, leading to a small sphere of heads surrounding a pocket of air containing the tails. They can also form bubbles in air, leading to two nested spheres of surfactant, between them a thin layer of water, surrounding a pocket of air - and antibubbles in fluid - a layer of air surrounding a pocket of water.
  • Suitable surfactants for the purpose of the invention are such surfactants which are capable to provide the composition of the invention its character of a stable emulsion which can be shelved for a substantial time without showing signs of instability such as clouding, separation of layers or deposit.
  • Non-ionic surfactants comprise the following options:
  • Natural alcohol ethoxylates (C12-C16 alkylethoxylate containing n mols of ethoxy, n can be between 1 and 80, most suitably 20); a commercial product is Genapol C 200 (manufactured by Clariant);
  • n can be between 1 and 80, most suitably 20; a commercial product is Genapol O 200 (manufactured by Clariant);
  • Tallow fatty alkyl ethoxylate with n mols of ethoxy, n can be between 1 and 80, most suitably 20; a commercial product is
  • Oxoalkylethoxylates C12-C15 oxoalkylethoxylate with n mols of ethoxy, n can be between 1 and 80, most suitably 20
  • a commercial product is Genapol OX 100 (manufactured by -Glariant)
  • Oxo-alcohol ethoxylates C14-C15 oxoalkylethoxylate with n mols of ethoxy, n can be between 1 and 80, most suitably 20
  • a commercial product is Genapol OA 080 (manufactured by Clariant);
  • Isotridecyl ethoxylate with n mols of ethoxy f n can be between 1 and 80 / most suitably 20; a commercial product is Genapol X150 (manufactured by Clariant) and Imbentin T/150 (manufactured by
  • Ethylene/propylene oxide block copolymer a commercial product is Pluronic PE9400 (BASF): ;
  • Ethoxylated Castor oil • Ethoxylated Castor oil; commercial products are Hedipin-R/300 (Dr. KoIb), Emulsogen EL (Clariant) and Eumulgin PRT36 (Cognis).
  • Anionic surfactants comprise the following options: • Aryl sulphonates sodium salt,
  • Preferred surfactants are the surfactants belonging to the class of the non-ionic surfactants.
  • the amount of the thickener to be added in the composition of the invention in particular the amount of casein according to the preferred embodiment should be at least 3 % by weight.
  • the active ingredient of the composition of the invention is the biocide.
  • the biocide shall protect the paint against any kind of attack of fungi or algae, accordingly it is appropriate to add a biocide with a fungicidal or algaecidal effect.
  • any product known in the art with an effect on the growth of bacteria, algae or fungi may be used.
  • the most preferred biocides to be used in the composition of the invention are IPBC, terbutryn, cybutryne, OIT, thiabendazole, and zinc-2-pyridine thiol 1-oxide.
  • IPBC, OIT, thiabendazole and zinc-2-pyridine thiol 1-oxide are fungicidal compounds.
  • Terbutryn and cybutrin are algaecidal compounds.
  • Combinations of the biocidal compounds are possible as well.
  • Two fungicidal compounds may be combined in a product, such as IPBC and zinc-2-pyridine thiol 1-oxide, just as well as two algaecidal compounds such as terbutryn and cybutrin.
  • a product such as IPBC and zinc-2-pyridine thiol 1-oxide
  • two algaecidal compounds such as terbutryn and cybutrin.
  • it is more suitable to combine a fungicidal compound with an algaecidal compound.
  • the concentration of the biocide in the composition of the invention has to be selected td provide the wanted biocidal, algaecidal or fungicidal effect.
  • the usual concentration of the biocide in the composition of the invention is 1 to 20 % by weight.
  • a preferred concentration of the biocide in the composition of the invention is 2 to 15 % by weight, an even more preferred amount is 5 to 10 % by weight.
  • the composition of the invention comprises a combination of a fungicidal compound with an algaecidal compound it is preferred that in this embodiment the concentration of the fungicidal compound in the composition is 1 to 10 % by weight and the concentration of the algaecidal compound 1 to 10 % by weight, more preferred the concentration of the fungicidal compound 2 to 7,5 % by weight and the concentration of the algaecidal compound 2 to 7,5 % by weight.
  • the liquid basis for the composition of the invention is water.
  • Water in the context of the invention means any kind of aqueous liquid, such as tap water, purified water, desalted water, distilled water, demineralised water, buffers, etcetera.
  • aqueous liquid is not essential, but demineralised water is preferred.
  • Certain amounts of an organic solvent may be present, but this amount should be not more than 10 % by volume based on the total volume of the aqueous liquid and the organic solvent.
  • biocidal composition comprises additional components such as preservatives and antioxidants which may support the stability of the composition.
  • composition of the invention is based on processes which are known in the art. It is for instance possible to combine all components in a container and finally add water. In order to obtain the emulsion, treatment with an ultrasonic device may be required.
  • composition of the invention is added to a water-borne paint to provide the required biocidal activity. It is preferred to combine the paint basis and the composition of the invention immediately before use. The combination can be achieved while using conventional mixing techniques, intensive manual agitation is usually sufficient.
  • the amount of the composition of the invention which is added to the water-borne paint depends on the intended use and on the properties of the water-borne paint and the biocidal composition of the invention.
  • the usual amount of the composition to be added to the water-borne paint is 0.5 to 5 % by weight based on the total weight of the water-borne paint.
  • the assays were performed with three kinds of water-borne paints, based on acrylic, acrylic styrene and vinyl veove resins.
  • Vinyl veove resins are copolymers of vinyl acetate and a VeoVa monomer.
  • VeoVa products are monomers that can offer a variety of unique properties to polymers prepared from it and other co-monomers.
  • VeoVa is a vinyl ester of Versatic acid, a synthetic saturated monocarboxylic acid of highly branched structure containing nine or ten carbon atoms. Inclusion of such a monomer in polymer systems introduces very good alkali resistance, UV resistance and hydrophobicity to the polymer.
  • the inclusion of VeoVa monomers can provide hydrocarbon solubility or a low-energy coating surface and also adds steric bulk to the polymer providing protection to less stable monomers like vinyl acetate.
  • VeoVa monomers essentially differ in the glass transition temperature of their homopolymers. VeoVa 10 provides a balance of flexibility and hardness whereas VeoVa 9, containing shorter and more heavily branched carbon chains, provides rigidity to the polymer. VeoVa monomers are used as modifying co-monomers in the preparation of vinyl acetate based polymer latices, which are used for the manufacture of speciality emulsion paints. VeoVa monomers are also used as co-monomers with acrylates for the production of emulsion-, solution- and bulk polymers such as acrylic automotive and powder coatings.
  • VeoVa monomers react readily with vinyl acetate to prepare binders for interior and exterior paint.
  • the ease of preparation and the superior performance of these latex systems have enabled VeoVa-based systems to capture a large portion of the latex paint market in Western Europe, Latices can also be made from VeoVa and various acrylates that can be used as coatings for wood and plastics.
  • VeoVa/ vinyl acetate system can also be used to prepare cement additives or adhesives.
  • biocides have been assayed in the composition according to the invention, these biocides are particularly preferred:
  • IPBC 3-iodo-2-propynyl butyl carbamate
  • OIT 2-n-octyl-2H-isothiazol-3-one
  • Zinc-2-pyridine thiol 1-oxide (CAS Number: 13463-41-7) 2-tert-butylamino-4-cyclopropylamino-6-methyl-thio-l,3,5-triazine (cybutryne) (CAS Number: 28159-98-0)
  • pbw. refers to parts by weight.
  • Paint 1 pure acrylic based paint
  • Hydroxyethylcelluiose was supplied by the company Dow Chemicals under the tradename Cellosize®, hexametaphosphate was provided as the sodium salt by the company Brenntag, the acrylic resin used in the example was the product sold under the tradename Craymul 2167 XP® by the company Cray Valley, titanium oxide was purchased from American elements, barium sulfate from Alkemi and butyl glycol acetate from BASF.
  • Two further examples 8 and 9 are provided in which the biocide terbutryn has been replaced for the biocide cybutrin.
  • the Refinated paraffin is bought as the product Redezon 100 from the company Repsol
  • Cera LP is bought as the product Licowax LP FL from the company Clariant
  • thiabendazole was purchased under the trademark Metasol TK 100® from the company Bayer
  • BHT antioxidant
  • Ionol CP 2,6-di-tert-butyl-4-methylphenol
  • Ionol CP from the company Quimidroga
  • Casein was bought as the product Casein ind. from the company Brenntag
  • BIT preservative was bought under the trademark Proxel Press Paste from the company Arch Chemicals B.
  • IPBC was bought under the trademark Preventol MP 100 from the company Bayer
  • Terbutryn was bought as the product Terbutryn Tech from the company Ciba
  • OIT was bought under the trademark Kathon 893 F from the company Rohm & Haas
  • C13 oxo alcohol ethoxylate was bought under the trademark Emulan TO 4070 from the company BASF
  • zinc-2-pyridine thiol 1-oxide was bougt as Zinc Omadine Powder from the company Arch Chemicals B. V. and cybutryne was bought as the product Cybutryn Tech from the company Ciba.
  • Paint 1 was prepared by providing 640 g of water into a beaker. Under stirring under high speed (1000 rpm) 970 g of hydroxyethylcellulose was added as a 2% solution in water, together with 120 g of hexametaphosphate as a 10 % solution in water. Then 1600 g of titanium oxide and 220 of barium sulfate were added. Finally, 150 g of butyl glycol acetate were added, thereafter, the stirring speed was reduced to 400 rpm and 6300 g acrylic resin were added.
  • the formulations 1 to 9 were prepared as follows:
  • Casein and the non-ionic surfactant were added.
  • the addition of casein had to be monitored in order to be sure of the absence of lumps.
  • the temperature was maintained at 80-85 0 C and stirring was continued at 80 rpm. Stirring was continued until homogeneity of the composition was observed.
  • Table I shows the inhibition halos (in mm) against fungi and algae in an acrylic paint:
  • w (*) lixiviation during 48 hours of the pieces of the painted papers in water.
  • Hydroxyethylcellulose was supplied by the company Dow Chemicals under the tradename Cellosize®, hexametaphosphate was provided as the sodium salt by the company Brenntag, the acrylic styrene resin used in the example was the product sold under the tradename Craymul 2110® by the company Cray Valley, titanium oxide was purchased from American elements, barium sulfate from Al'kemi and butyl glycol acetate from BASF.
  • Table II shows the inhibition halos (in mm) against fungi and algae in an acrylic styrene based paint: Table II. Inhibition halos (in mm) against fungi and algae in an acrylic styrene paint
  • w (*) lixiviation during 48 hours of the pieces of the painted papers in water.
  • Hydroxyethylcellulose was supplied by the company Dow Chemicals under the tradename Cellosize®, hexametaphosphate was provided as the sodium salt by the company Brenntag, the vinyl veove used in the example was the vinyl versate product sold under the tradename Craymul 2326® by the company Cray Valley, titanium oxide was purchased from American elements, calcium carbonate from SA Reverte and butyl glycol acetate from BASF.
  • w (*) lixiviation during 48 hours of the pieces of the painted papers in water.

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
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  • Environmental Sciences (AREA)
  • Paints Or Removers (AREA)
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Abstract

L'invention concerne une composition contenant une quantité efficace d'une cire et/ou d'une paraffine en combinaison avec un biocide. La composition comprenant de la cire et/ou de la paraffine est ajoutée à des peintures à base d'eau augmentant ainsi l'efficacité des biocides. La peinture présente une propriété biocide améliorée. La lixiviation des biocides de la couche de peinture est réduite.
PCT/EP2005/052596 2005-06-07 2005-06-07 Emulsions de cire destinees a augmenter les proprietes biocides des peintures WO2006131147A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
BRPI0520315-5A BRPI0520315A2 (pt) 2005-06-07 2005-06-07 emulsões em cera para aumentar as propriedades biocidas em tintas
EP05766763A EP1890535A1 (fr) 2005-06-07 2005-06-07 Emulsions de cire destinees a augmenter les proprietes biocides des peintures
PCT/EP2005/052596 WO2006131147A1 (fr) 2005-06-07 2005-06-07 Emulsions de cire destinees a augmenter les proprietes biocides des peintures

Applications Claiming Priority (1)

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PCT/EP2005/052596 WO2006131147A1 (fr) 2005-06-07 2005-06-07 Emulsions de cire destinees a augmenter les proprietes biocides des peintures

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009001983A1 (de) 2008-05-10 2009-11-12 Wachs-Chemie Elsteraue E.K. Mikronisierte Wachspartikel und Verfahren zu ihrer Herstellung
EP2471365A3 (fr) * 2010-11-09 2012-12-12 Dow Global Technologies LLC Combinaison synergique de flumetsulam et de thiabendazole
WO2014085740A1 (fr) * 2012-11-30 2014-06-05 Rohm And Haas Company Combinaison synergique de lénacile et de pyrithione de zinc pour la protection de film sec
US9756859B1 (en) * 2016-08-11 2017-09-12 Troy Technology Ii, Inc. Stable aqueous dispersions of biocides
EP4328257A1 (fr) 2022-08-22 2024-02-28 Clariant International Ltd Particules de cire dispersibles

Citations (8)

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Publication number Priority date Publication date Assignee Title
EP0003389A1 (fr) * 1978-01-19 1979-08-08 The British Petroleum Company p.l.c. Procédé de revêtement de surfaces sous-marines avec de la cire et compositions de revêtement ainsi appliquées
EP0040106A2 (fr) * 1980-05-14 1981-11-18 Roberts Consolidated Industries, Inc. Composition hydrofuge/protectrice pour matériaux cellulosiques
EP0623656A2 (fr) * 1993-05-05 1994-11-09 The Thompson Minwax Company Revêtements aqueux hydrofuges
WO1996000264A1 (fr) * 1994-06-27 1996-01-04 Kop-Coat, Inc. Procede d'impermeabilisation du bois et composition associee
GB2304574A (en) * 1995-08-24 1997-03-26 Advanced Engineering Services Fungicidal composition using a water-based wax emulsion as a carrier
WO1997023327A1 (fr) * 1995-12-22 1997-07-03 Bauer, Wulf Dispersion aqueuse et son utilisation comme agent de protection pour materiaux
US5882731A (en) * 1996-07-24 1999-03-16 Owens; Richard L. Method of applying a mildewcide laden film and composition for the use therewith
EP1466526A2 (fr) * 2003-04-07 2004-10-13 Rohm And Haas Company Composition microbicide

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0003389A1 (fr) * 1978-01-19 1979-08-08 The British Petroleum Company p.l.c. Procédé de revêtement de surfaces sous-marines avec de la cire et compositions de revêtement ainsi appliquées
EP0040106A2 (fr) * 1980-05-14 1981-11-18 Roberts Consolidated Industries, Inc. Composition hydrofuge/protectrice pour matériaux cellulosiques
EP0623656A2 (fr) * 1993-05-05 1994-11-09 The Thompson Minwax Company Revêtements aqueux hydrofuges
WO1996000264A1 (fr) * 1994-06-27 1996-01-04 Kop-Coat, Inc. Procede d'impermeabilisation du bois et composition associee
GB2304574A (en) * 1995-08-24 1997-03-26 Advanced Engineering Services Fungicidal composition using a water-based wax emulsion as a carrier
WO1997023327A1 (fr) * 1995-12-22 1997-07-03 Bauer, Wulf Dispersion aqueuse et son utilisation comme agent de protection pour materiaux
US5882731A (en) * 1996-07-24 1999-03-16 Owens; Richard L. Method of applying a mildewcide laden film and composition for the use therewith
EP1466526A2 (fr) * 2003-04-07 2004-10-13 Rohm And Haas Company Composition microbicide

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009001983A1 (de) 2008-05-10 2009-11-12 Wachs-Chemie Elsteraue E.K. Mikronisierte Wachspartikel und Verfahren zu ihrer Herstellung
RU2565447C2 (ru) * 2010-11-09 2015-10-20 Дау Глоубл Текнолоджиз Ллк Синергетическая комбинация флуметсулама и тиабендазола
EP2471365A3 (fr) * 2010-11-09 2012-12-12 Dow Global Technologies LLC Combinaison synergique de flumetsulam et de thiabendazole
KR101344740B1 (ko) 2010-11-09 2013-12-26 다우 글로벌 테크놀로지스 엘엘씨 플루메트설람과 티아벤다졸의 상승적 배합물
US9288991B2 (en) * 2012-11-30 2016-03-22 Rohm And Haas Company Synergistic combination of a lenacil compound and zinc pyrithione for dry film protection
US20150296791A1 (en) * 2012-11-30 2015-10-22 Rohm And Haas Company Synergistic combination of a lenacil compound and zinc pyrithione for dry film protection
JP2016502541A (ja) * 2012-11-30 2016-01-28 ローム アンド ハース カンパニーＲｏｈｍ Ａｎｄ Ｈａａｓ Ｃｏｍｐａｎｙ 乾燥フィルム保護用のレナシルおよびジンクピリチオンの相乗的組合せ物
CN105307496A (zh) * 2012-11-30 2016-02-03 罗门哈斯公司 用于干膜保护的环草定与吡硫鎓锌的协同性组合
WO2014085740A1 (fr) * 2012-11-30 2014-06-05 Rohm And Haas Company Combinaison synergique de lénacile et de pyrithione de zinc pour la protection de film sec
CN105307496B (zh) * 2012-11-30 2017-06-06 罗门哈斯公司 用于干膜保护的环草定与吡硫鎓锌的协同性组合
WO2018031429A1 (fr) * 2016-08-11 2018-02-15 Troy Technology Ii, Inc. Dispersions aqueuses stables de biocides
US9756859B1 (en) * 2016-08-11 2017-09-12 Troy Technology Ii, Inc. Stable aqueous dispersions of biocides
EP3307836A4 (fr) * 2016-08-11 2018-07-04 Troy Technology II, Inc. Dispersions aqueuses stables de biocides
US10149475B2 (en) * 2016-08-11 2018-12-11 Troy Technology Ii, Inc. Stable aqueous dispersions of biocides
US10721931B2 (en) 2016-08-11 2020-07-28 Troy Technology Ii, Inc. Stable aqueous dispersions of biocides
AU2017311045B2 (en) * 2016-08-11 2021-08-19 Troy Technology Ii, Inc. Stable aqueous dispersions of biocides
EP4328257A1 (fr) 2022-08-22 2024-02-28 Clariant International Ltd Particules de cire dispersibles
WO2024041874A1 (fr) 2022-08-22 2024-02-29 Clariant International Ltd Particules de cire dispersibles

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BRPI0520315A2 (pt) 2009-05-05

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