EP3331954A1 - Revêtement contenant du benzoxaborole résistant à un champignon susceptible d'être porté par la cellulose - Google Patents

Revêtement contenant du benzoxaborole résistant à un champignon susceptible d'être porté par la cellulose

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Publication number
EP3331954A1
EP3331954A1 EP16751753.1A EP16751753A EP3331954A1 EP 3331954 A1 EP3331954 A1 EP 3331954A1 EP 16751753 A EP16751753 A EP 16751753A EP 3331954 A1 EP3331954 A1 EP 3331954A1
Authority
EP
European Patent Office
Prior art keywords
fungus
paint
growth
benzoxaborole
cellulose
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP16751753.1A
Other languages
German (de)
English (en)
Inventor
Stephen J. Benkovic
Chunyu Liu
Edward Q. KAISER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Penn State Research Foundation
Original Assignee
Penn State Research Foundation
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 Penn State Research Foundation filed Critical Penn State Research Foundation
Priority claimed from PCT/US2016/045329 external-priority patent/WO2017024022A1/fr
Publication of EP3331954A1 publication Critical patent/EP3331954A1/fr
Withdrawn legal-status Critical Current

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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
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • A01N55/08—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing boron
    • 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
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C09D5/025—Preservatives, e.g. antimicrobial agents
    • 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
    • C08K5/55—Boron-containing compounds

Definitions

  • the present invention contemplates a latex paint composition that contains an effective amount of one or more cellulose-supportable fungus growth- inhibiting benzoxaborole compounds of Formula C.
  • Fungi are eukaryotic microorganisms. Fungi can occur as yeasts, molds, including mildews, or as a combination of both forms. Yeasts are microscopic fungi consisting of solitary cells that reproduce by budding. Molds, in contrast, occur in long filaments known as hyphae, which grow by apical extension.
  • Hyphae can be sparsely septate to regularly septate and possess a variable number of nuclei. Regardless of their shape or size, fungi are all heterotrophic and digest their food externally by releasing
  • fungus and "yeast” and their various grammatical forms are generally used interchangeably herein except where a particular taxon is discussed. Molds reproduce by releasing seed-like spores into their environment . Mold spores are seemingly ubiquitous. Given a suitable environment of appropriate temperature, humidity and nutrients, spores germinate and can infect one' s living space leading to decay and discoloration of affected surfaces, as well as offensive odors and allergic reactions of inhabitants. [McGinnis et al.,
  • Such wood product-growing fungi are referred to herein as cellulose-supportable fungi. They possess specific enzymes that can digest
  • cellulose and related polysaccharides cellulose and related polysaccharides. These fungi can typically also utilize another source of sugars for growth, but share an ability to grow on cellulose as a food source.
  • antifungals can display very different inhibitory efficacy for cellulose-supportable fungi when the food source (paper/cellulosic substrate vs. potato dextrose broth) or the antifungal delivery system (inside dried latex paint matrix vs. in liquid culture medium) are different .
  • Fungal growths, or colonies can start to grow on a damp surface within 24 to 48 hours. Fungi digest organic material, eventually destroying the material they grow on, and then spread to destroy adjacent organic material. In addition to the damage fungi can cause in a home, they can also cause mild to severe health problems.
  • fungi Of the thousands of fungi that exist, some are or produce known allergens (aggravating or causing skin, eye, and respiratory problems), and a few fungi produce harmful mycotoxins that can cause serious problems. But all fungi, in the right conditions and at high enough concentrations, are capable of adversely affecting human health.
  • Fungal infection can also occur on the skin of a person's body. Infants, children, immune- compromised patients, pregnant women, individuals with existing respiratory conditions, and the elderly are at higher risks for adverse health effects from mold .
  • Some of the common molds (fungi) present in indoor environments that can have an impact on human health are: Stachybotrys chartarum, Alternaria alternata r Penicillium chrysogenum , Aspergillus niger, Chaetomium globosum and Auerobasidium
  • Stachybotrys atra also called Stachybotrys chartarum.
  • the mold is greenish-black and slimy, resembling tar or black paint. Spores of
  • Stachybotrys chartarum are allergenic just like the spores from other mold species. Stachybotrys chartarum is classified as a toxic mold because it produces toxic chemicals called mycotoxins.
  • Stachybotrys typically feeds and grows only on repeatedly wetted materials that contain cellulose - from paper to ceiling tiles, drywall and any kind of wood. In most cases, this mold can be removed by a thorough cleaning with a 10% bleach solution.
  • Severe mold infestations may require the assistance of a professional with experience in dealing with Stachybotrys . Dealing With Mold & Mildew In Your Flood Damaged Home, U.S. Department of Homeland
  • Alternaria alternata is another commonly encountered cellulose-supportable allergenic fungus. Brown segmented mycelia give rise to simple or solitary conidiophores , which may produce solitary apical spores, or a string of spores. Alternaria is one of the main allergens affecting children. In temperate climates, airborne Alternaria spores are detectable from May to November, with peaks in late summer and autumn.
  • A. alternata can be found on foodstuffs and textiles, with favorite habitats being soils, corn silage, rotten wood, compost, bird nests, and various forest plants. It is frequently found on water condensed on window frames. It is one of the most common mold spores found in dwelling dust in both North America and Europe.
  • the number of allergens in A. alternata extracts can range from 10 to 30, and few allergens are present in nearly all extracts studied [De Vouge et al., Int Arch Allergy Immunol 116 (4) : 261-268 (1998)].
  • the presence of specific allergens, including the major allergens, depends very much on the growth conditions, and may vary during the growth cycle, being higher one day than another [Breitenbach et al., Chem Immunol 81:48-72 (2002); Portnoy et al., J Allergy Clin Immunol 91:773-782 (1993)].
  • Penicillium is a common fungal contaminant in indoor environments.
  • the spores of this mold are produced in dry chains and can easily be dispersed in the air.
  • One of the most common species is
  • Penicillium chrysogenum that produces several toxins of moderate toxicity, are allergenic and can infect immunocompromised individuals. Penicillium
  • chrysogenum has been shown to induce a more robust allergic and inflammatory response at lower doses than house dust mite [Ward et al., Indoor Air 20:380- 391 (2010) ] .
  • Penicillium chrysogenum and other common household molds may play an important role in asthma development.
  • Aspergillus is another ubiquitous fungal contaminant whose spores can often be isolated from indoor air, but does not normally cause illness on healthy individuals. Allergens produced by
  • Aspergillus niger and Aspergillus fumigatus can produce allergic reactions in humans. Aspergillosis is a group of diseases that can result from
  • Aureobasidium is another common mold found in soil, wood, textiles, and indoor air environments. This yeast-like fungus is commonly found on caulking or damp window frames. Chronic exposure to
  • Aureobasidium pullulans can lead to hypersensitivity pneumonitis. [Microorganisms in Home and Indoor Work Environments : Diversity, Health Impacts,
  • Latex paint is a general term that covers paints that use synthetic polymers such as acrylic, vinyl acrylic (PVA) , styrene-acrylic, and the like as film-forming binders that are dispersed along with a colorant in an aqueous medium as the vehicle.
  • synthetic polymers such as acrylic, vinyl acrylic (PVA) , styrene-acrylic, and the like as film-forming binders that are dispersed along with a colorant in an aqueous medium as the vehicle.
  • PVA vinyl acrylic
  • styrene-acrylic and the like
  • latex is used because these paints form milky white emulsions in water when free of other pigments, just as does the true latex formed from a Hevea rubber plant.
  • a clear coating like a varnish primarily contains the binder and the vehicle. If a colorant such as a pigment is added to provide color and opacity to a varnish, one makes a paint.
  • fungus growth-inhibiting ingredients Many commercially available latex paints contain fungus growth-inhibiting ingredients. Aside from usually-observed differences in activity against microbes such as fungi that are exhibited in aqueous media, incorporation of a fungus growth-inhibiting ingredient (fungicide) can provide a greater fungus growth-inhibiting ingredient (fungicide)
  • the coating When there is a balance between the biocide rate of depletion from the surface and the biocide rate of migration from within the film, the coating will have long-term protection from microbial attack. When there is not a balance, the coating will fail more quickly. Where the selected biocide has too high a water solubility, the coating will be well protected during an initial period of perhaps 12 to 18 months, but the biocide reservoir in the film will be quickly depleted and the coating will fail after that short initial period.
  • the selected biocide has too low a water-solubility and a coated surface is first placed in the outdoor environment, there is an initial period where the coating will have high susceptibility to fungal attack because some of the non-fungicidal small-molecule paint ingredients leach from the coating film and serve as a nutrient source for the fungi. After the nutrients are washed away and the coating becomes less susceptible to fungal attack, if the fungicide selected has too low a water solubility, fungi can start to become established during the initial period of high susceptibility. In this case, there is biocide present at the surface of the film, but not enough biocide migrates from the biocide reservoir in the film to prevent the fungi from becoming established.
  • One common strategy for achieving long-term protection of the coating film is to combine a very low water solubility fungicide with a relatively high water solubility fungicide. The more water-soluble fungicide will migrate quickly through the film and will prevent the fungi from becoming established during the initial period of the coating' s high microbial susceptibility. Over longer term of outdoor exposure, the less water-soluble biocide will continue to slowly migrate from the biocide reservoir in the coating film to the coating surface. Because the coating has lower microbial susceptibility after the initial time period, the level of the less- soluble biocide delivered to the coating' s surface is sufficient to prevent microbial defacement. With this strategy, long-term protection of the coating can be achieved. [Brown, "The Development of High- Performance Paint Film Biocides for Architectural Coatings", Paint & Coatings Industry, BNP Media (July 1, 2014).]
  • the Brown article lists ten typical fungicides and algaecides used in the paint industry for dry film preservation.
  • the article grouped the antifungal compounds by relative solubility in water to include: zinc pyrithione (ZnPT) [or zinc omadine (ZnOM)], chlorothalonil (CTL) , carbendazim (BCM) , and
  • Irgarol® as low water solubility compounds (6-8 mg/L) ; diuron, dichlorooctylisothiazolinone (DCOIT) , and terbutryn as having medium solubility in water [14-35 mg/L] ; and octylisothiazolinone (OIT) , n-butyl-benzisothiazolinone (BBIT) , and
  • IPBC iodopropynylbutyl-carbamate
  • 5-Fluorobenzoxyborole is an antifungal agent in that it suppresses the ability of fungal growth, inter alia, by inhibiting leucyl-transfer RNA synthetase, an enzyme that plays a pivotal role in fungal protein synthesis.
  • Trichophyton rubrum or Trichophyton mentagrophytes from Anacor Pharmaceuticals, Inc., under the name
  • R' and X amount to more than 100 million compounds.
  • C4alkyl optionally substituted by -NR3 ⁇ 44 wherein R3 and R ⁇ are each independently hydrogen, optionally substituted C]_-C4alkyl.
  • a composition containing a compound of Formula B-1 was said to be useful in a method of protecting plants or plant propagation materials against phytopathogenic fungi belonging to several classes. The above published application teaches the use of several oxaboroles at
  • concentrations ranging from 200 to 20 parts per million (ppm) to obtain between 80 and 20 percent control of fungal growth on infected plants, seeds and plant propagation materials.
  • the present invention contemplates a fungus-resistant latex paint composition.
  • contemplated fungus-resistant latex paint composition contains the typical amounts of aqueous vehicle, film-forming binder, pigment and other additives as is commonly found in commercial latex paint, but also further contains a cellulose-supportable fungus growth-inhibiting amount of a benzoxaborole of
  • X is H (hydrido) , halogen (fluoro, chloro or bromo) , C]_-Cg hydrocarbyl, C1-C7 acyl, cyano, carboxyl [C(0)OH], C ⁇ -Cg hydrocarbyloxy carboxylate [C(0)OC]_-Cg hydrocarbyl], carboxamido whose amido nitrogen atom is unsubstituted [C(0)NH2], mono- substituted with a C_-Cg hydrocarbyl group (R ⁇ -)
  • R 2 form a 5- or 6-membered ring that can contain one additional hetroatom that is oxygen or nitrogen and wherein the nitrogen atom when present in that ring can be unsubstituted or substituted with one C ⁇ -Cg hydrocarbyl group.
  • benzoxaborole of Formula C is about 5 to about 2,000 ⁇ g/mL or about 0.005 to about 2.0 g/L.
  • a method of inhibiting the growth of cellulose-supportable fungus on a cellulosic surface free of visible fungal growth comprises the step of coating a
  • cellulose-based surface that is free of visible fungus growth, preferably an interior wall or ceiling surface, with a latex paint as described above that contains a cellulose-supportable fungus growth- inhibiting amount of a benzoxaborole of Formula C .
  • Another aspect of the invention is a method of inhibiting the growth of a cellulose-supportable fungus on a cellulosic surface that has a visible fungus infection.
  • the fungus- infected surface preferably an interior wall or ceiling surface
  • a latex paint as described above that contains a fungus growth- inhibiting amount of a benzoxaborole of Formula C , particularly where "n" is 1.
  • this contemplated paint composition is particularly useful for painting over a fungus-infected interior wall or ceiling surface as compared to using the same paint with the currently available antifungal additives such as chlorothalonil, captan, triclosan, IPBC, OIT, and thiabendazole.
  • the present invention has several benefits and advantages.
  • One benefit is that the use of a contemplated benzoxaborole additive provides fungus protection when utilized in a latex paint.
  • An advantage of the invention is that the relatively high water solubility of a contemplated benzoxaborole permits easy formulation of an antifungal agent into a latex paint, particularly a latex paint intended for use in coating interior walls or ceilings.
  • a particular benefit of the invention is that in many cases, a latex paint containing a contemplated benzoxaborole additive performed better than did a similar paint formulated with an equal amount of another commercial antifungal additive, such as chlorothalonil, captan, octylisothiazolinone (OIT) , 3-iodo-2-propynylbutyl-carbamate (IPBC) , thiabenzaole, and triclosan, in that it not only provided superior fungal growth inhibition to an initial fungal infection, but also suppressed fungal growth "bleed through" when painted over a fungus- infected surface.
  • another commercial antifungal additive such as chlorothalonil, captan, octylisothiazolinone (OIT) , 3-iodo-2-propynylbutyl-carbamate (IPBC) , thiabenzaole, and triclosan
  • a contemplated benzoxaborole additive appears to be UV stable so that the antifungal protection in paint will not decrease rapidly due to prolonged UV- exposure .
  • Another advantage of the invention is that it is not necessary to use two antifungals with high and low water solubilities for long term benefits.
  • Fig. 1 is a depiction of a circular filter paper disc divided into 20 sections of equal area that is used to estimate the percentage of defacement of a painted surface area caused by fungal growth.
  • a fungus-resistant latex paint composition is contemplated by the present invention.
  • Such a contemplated fungus-resistant latex paint composition contains the typical amounts of vehicle (water) , film-forming binder, pigment and other additives that are found in a commercially available latex paint, but also further contains a cellulose-supportable mold (fungal) growth-inhibiting (effective) amount of one or more benzoxaboroles of Formula C , below,
  • X is H (hydrido) , C1-C7 acyl, cyano, halogen (fluoro, chloro or bromo) , C_-Cg hydrocarbyl,
  • R2 form a 5- or 6-membered ring that can contain one additional heteroatom that is oxygen or nitrogen and wherein the nitrogen atom when present in that ring can be unsubstituted or substituted with one C ] _-Cg hydrocarbyl group.
  • a substituent X preferably has a positive Hammett sigma constant for one or both of para and meta substituents .
  • a halogen or a C ] _-Cg hydrocarbyl group is a preferred substituent, and that substituent is preferably bonded at position 5 of a compound of Formula C , below.
  • a contemplated latex paint composition is preferably free of a cellulose-supportable fungus growth-inhibiting amount of a second antifungal agent (i.e., a non-Formula C antifungal agent).
  • a second antifungal agent i.e., a non-Formula C antifungal agent.
  • a typical amount of a benzoxaborole of Formula C is about 5 to about 2,000 ⁇ g/mL or about 0.005 to about 2.0 g/L. More preferably, that amount is about 10 to about 500 ⁇ g/mL .
  • the substituent "X" is preferably in the 5-position of a compound of Formula C .
  • the ring numbering for a compound of Formula C is shown in the structural formula below
  • a paint contains three main categories of ingredients: film-forming binder, vehicle and
  • the vehicle is typically water in which the binder and pigment are dispersed. Additional ingredients can also be present as discussed below.
  • the binder imparts properties such as gloss, durability, flexibility, and toughness.
  • Binders include natural resins and oils such as shellac and linseed oil, as well as synthetic resins and oils, as well as synthetic resins and oils.
  • polymers and co-polymers such as alkyds, acrylics, vinyl-acrylics, styrenated acrylics ( styrene/acrylic and/or methacrylic co-polymer), vinyl
  • Flat paints have a very high pigment loading and have high PVCs (often of about 35% to about 80%, and more usually about 35% to about 50%) .
  • Primers and undercoats vary from 30% to about 50% PVC as do semi-gloss, satin and low sheen paints. Gloss colored paints can vary from 3% to about 20% PVC depending on the color of the paint.
  • Binders can be categorized according to the mechanisms for drying or curing. Although drying may refer to evaporation of the solvent or thinner, it usually refers to oxidative cross-linking of the binder resins and is indistinguishable from curing.
  • a latex paint is a water-borne dispersion of sub-micrometer polymer particles.
  • dispersions are prepared in water by emulsion
  • Latex paints cure by a process called coalescence where first the water, and then the trace, or coalescing, solvent, evaporate and draw together and soften the binder particles and fuse them together into irreversibly bound, film-forming networked structures, so that the paint does not re- dissolve in the solvent/water that originally carried it.
  • the residual emulsifying surfactants in paint, as well as hydrolytic effects with some polymers cause the paint to remain susceptible to softening and, over time, degradation by water.
  • the main purpose of the diluent is as the carrier for the non-volatile components.
  • the vehicle disperses the polymer and pigment, and adjusts the viscosity of the paint.
  • the vehicle is volatile and does not become part of the paint film.
  • the vehicle also controls flow and application properties, and in some cases can affect the
  • Pigments are finely ground granular solids incorporated in the paint to contribute color. Fillers are granular solids incorporated to impart toughness, texture, give the paint special
  • paints contain dyes instead of o in combination with pigments.
  • Pigments can be classified as either natural or synthetic. Natural pigments include various clays, calcium carbonate, mica, silicas, and talcs. Synthetic pigments include engineered molecules, calcined clays, blanc fixe, precipitated calcium carbonate, and synthetic pyrogenic silicas.
  • Hiding pigments in making paint opaque, also protect the substrate from the harmful effects of ultraviolet light.
  • Hiding pigments include titanium dioxide, phthalo blue, red iron oxide, and many others .
  • Fillers are a special type of pigment that serve to thicken the film, support its structure and increase the volume of the paint. Fillers are usually inexpensive and inert materials, such as diatomaceous earth, talc, lime, barytes, clay, and similar compounds.
  • paint can have a wide variety of miscellaneous additives that are usually added in small amounts, and yet can provide a significant effect on the product.
  • Some examples include additives to modify surface tension improve flow properties, improve the finished appearance, increase wet edge, improve pigment stability as with hydroxypropyl cellulose, impart antifreeze properties using polyols such as ethylene glycol and propylene glycol, control foaming, and control skinning.
  • Other types of additives include catalysts, thickeners, stabilizers, emulsifiers , texturizers, adhesion promoters, UV stabilizers, flatteners (de-glossing agents) , and biocides to fight microbial growth. Additives normally do not significantly alter the percentages of individual components in a formulation. Illustrative latex paint compositions can be found in U.S. Patents No. 3,215,660, No. 3,483,148, and No. 7,482,395.
  • a primer is a paint that is applied directly to the bare substrate. Primers have varying roles on different substrates. The main functions of a primer include providing adhesion to the substrate for the new paint system and providing a surface to which subsequent coats of paints can easily adhere. A primer is often used to seal the surface and prevent subsequent coats of paint from sinking into the substrate and losing gloss.
  • Primers are usually pigmented and typically have a middle range pigment volume concentration (PVC) of about 35-45%. This pigment level permits a primer to have spare binder resin (left over from pigment holding together duties) for adhesion to substrate purposes. A relatively large pigment content is needed to provide hiding power and to help seal off the substrate surface.
  • PVC pigment volume concentration
  • a method of inhibiting the growth of a cellulose-supportable fungus on a cellulosic surface comprises the step of coating a surface that is free of visible fungus growth with a latex paint as described above that contains a cellulose-supportable fungus growth- inhibiting amount of a benzoxaborole of Formula C .
  • the coated surface is preferably an interior (indoor) wall or ceiling that contains cellulose.
  • the surface to be coated is itself cellulosic such as the paper-coated exterior surfaces of drywall (plasterboard) . That surface can have one or more previously applied and dried coats of paint, or be paint-free as in a newly erected plasterboard wall or ceiling, a cellulosic ceiling tile,
  • Another aspect of the invention is a method of inhibiting the growth of cellulose-supportable fungus on a painted surface that has a visible fungus infection.
  • the cellulose-supportable fungus-infected cellulosic surface preferably an interior (indoor) wall or ceiling surface as
  • a latex paint as described above that contains a cellulose- supportable fungus growth-inhibiting amount of a benzoxaborole of Formula C . It has been found that a contemplated paint composition is particularly useful for painting over a fungus-infected cellulosic wall or ceiling surface as compared to using the same paint with a currently available antifungal agent such as chlorothalonil, thiabendazole, OIT,
  • the antifungal compound of Formula C that is used be a compound of Formula C-l .
  • X of Formula C-l is a halogen such as fluorine or chlorine or C_-Cg hydrocarbyl.
  • hydrocarbyl is used herein as a short hand term for a non-aromatic group that
  • alkyl, alkenyl and alkynyl groups are straight and branched chain aliphatic as well as cyclic groups or radicals that contain only carbon and hydrogen. Inasmuch as alicyclic groups are cyclic aliphatic groups, such substituents are deemed to be subsumed within the aliphatic groups. Thus, alkyl, alkenyl and alkynyl groups are
  • hydrocarbyl ether is referred to as a
  • hydrocarbyloxy rather than a “hydrocarboxy” group as may possibly be more proper when following the usual rules of chemical nomenclature.
  • Illustrative hydrocarbyloxy groups include methoxy, ethoxy, and cyclohexenyloxy groups.
  • a contemplated cyclohydrocarbyl substituent ring contains 3 to 6 carbon atoms.
  • a preferred cyclohydrocarbyl substituent is a cycloalkyl group.
  • the term "cycloalkyl" means a cyclic alkyl radical that is saturated. Examples of such cycloalkyl radicals include cyclopropyl, cyclobutyl,
  • hydrocarbyl substituent group i.e., C]_-C4 alkyl, methyl or tert-butyl.
  • exemplary hydrocarbyl groups contain a chain of 1 to 6 carbon atoms, and preferably 1 or 4 carbon atoms.
  • a C ] _, methyl, group is most preferred.
  • a particularly preferred hydrocarbyl group is an alkyl group.
  • a generalized, but more preferred substituent can be recited by replacing the descriptor "hydrocarbyl” with “alkyl” in any of the substituent groups enumerated herein.
  • a specific aliphatic hydrocarbyl substituent group is intended, that group is recited; i.e., C1-C4 alkyl, methyl or 2-propyl.
  • straight and branched chain alkyl radicals include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl.
  • Illustrative cyclic alkyl groups include cyclopropyl, cyclopentyl, 3-methylcyclopentyl and cyclohexyl.
  • suitable alkenyl radicals include ethenyl (vinyl) , 2-propenyl,
  • alkynyl radicals include ethynyl, 2-propynyl, 1- propynyl, 1-butynyl, 2-butynyl, 3-butynyl, and 1- methyl-2-propynyl, 3-methyl-l-butynyl and 2-methyl-1- pentynyl.
  • Cyclic alkynes are analogous to the cyclic alkenes .
  • a substituent that cannot exist such as a alkenyl or alkynyl group or a C]_-C2 cyclic group is not intended to be encompassed by the word "hydrocarbyl", although such substituents with two or more carbon atoms are intended for other than cyclic substituents.
  • hydrocarbyl group containing a -C(0)- functionality such as a keto group or a portion of a carboxyl group is referred to as a hydrocarboyl
  • acyl group.
  • exemplary hydrocarboyl (acyl) groups include acyl groups such as formyl, acetyl,
  • a C]_-Cg hydrocarbyl ester of a carboxyl group is referred to herein, for example, as a C ⁇ -Cg
  • a typical amount of a benzoxaborole of Formula C used in an antifungal (mold growth- inhibiting or fungus growth-inhibiting) paint is about 5 to about 2,000 ⁇ g/mL, and more preferably about 10 to about 500 ⁇ g/mL. It is presently
  • a compound of Formula C be the only anti-cellulose-supportable mold growth-inhibiting additive present in a contemplated paint composition.
  • the specific fungus species whose infection of a painted surface is inhibited can depend on the geographical location of that surface. Thus, more generally, those fungi whose growth is to be
  • Rhizopus r Mucor Penicillium r Cladosporium t
  • Fusarium and Stachybotrys include one or more of Alternaria alternata r Aspergillus niger r Aspergillus fumigatus, Aureobasidium pullulans, Rhizopus spp,. r Mucor spp. , Penicillium brevicompactum r Penicillium corylophilum, Penicillium purpurogenum r Penicillium chrysogenum r Cladosporium spp. , Epicoccum spp. r
  • BIO 200 100
  • IPBC 3-Iodo-2- propynylbutylcarbamate
  • OIT 2-Octyl-4-isothiazolin ⁇ 3-one
  • Compound B5 can be viewed as a homolog of Compound B9, having an extra CH2 group in one ring, whereas Compound B7 can be viewed as a combination of a homolog (as in B5) with a
  • Tables 2 and 3 lists results for paint formulations coated twice on both sides of a cellulosic surface of a filter paper disc to provide a surface that is visibly free of any fungal growth after the paint coating has dried.
  • Table 3 lists results for a painted cellulosic surface in which fungal growth was painted over by a contemplated latex paint containing an antifungal additive as disclosed herein.
  • a Defacement Rating is measured by estimating the percentage of surface defacement with 10 being no defacement and 0 begin completely defaced.
  • ASTM test method D3273-12 Standard Method for Resistance to Growth of Mold on the Surface of Interior Coatings in an Environmental Chamber; ASTM D3273-12, American Society for Testing Materials International, West Conshohocken, PA, USA] .
  • Valspar® QuikHide white flat interior paint (The Valspar Corporation, Minneapolis, MN) . According to the product label and information sheet, Olympic® Home paint does not contain an antimicrobial additive. In contrast, both Valspar® ceiling paint and Valspar® QuikHide paint both contain mildewcidal additives according to a
  • Sherwin-Williams Property Advantage® interior paint "does not contain anti-microbials and is not a mildew proof product" according to a representative from the company' s Customer Support department .
  • Valspar® QuikHide paint which contains some level of added mildewcide, was not effective at inhibiting fungal growth under these experimental conditions (elevated humidity and temperature) . It is also noted that this study subjected a treated surface to a very high level of freshly prepared fungal inoculum, meaning that the experimental condition used presented a very challenging system (strongly encourages fungal/mold growth) for anti-mildew/antifungal samples.
  • Valspar® Ceiling paint were not able to prevent fungal/mold growth after 14 days under the experimental conditions (Valspar® Ceiling paint did show inhibition for Alternaria alternata, but not as much for Stachybotrys chartarum) .
  • Valspar® bonding primer was able to resist fungal/mold growth for over 21 days.
  • Valspar ® bonding primer behaved as if it contained an antimicrobial agent. However, that could not be confirmed by company representatives. It is also likely that this product contains a higher percentage of organic solvents in its composition, creating a less favorable environment to support living organisms.
  • indoor/architectural fungal/mold species (Alternaria alternata r Stachybotrys chartarum r and Penicillium chrysogenum) were used to represent fungal/mold contaminants that one might find in a typical
  • the average defacement ratings (mold coverage level) was 0.9 ⁇ 1.8 over 18 samples in just 7 days after fungal spore inoculation (Table 2) .
  • the defacement levels were very high for the unaltered paint at the 14 and 21 day time points.
  • the average defacement rating was essentially 0 (100% fungus coverage) , suggesting no capability to inhibit fungal growth.
  • Valspar® QuikHide paint which contains a proprietary antimicrobial additive, also performed poorly for inhibiting the growth of Stachybotrys chartarum and Alternaria alternata on painted
  • Penicillium chrysogenum past 7 days after fungal inoculation Sherwin-Williams Property Advantage® interior paint also failed to inhibit fungal growth 7-14 days after being inoculated with the spores of Stachybotrys chartarum or Alternaria alternata.
  • the filter paper discs separately painted with the same Olympic® Home interior flat latex paint that was pre-mixed with Compounds B9 or B8 performed significantly better at resisting fungal/mold growth on the painted surfaces; i.e., the difference was greater than 2 standard deviations .
  • the averaged defacement rating on samples containing 100 g/mL of Compound B9 was found to be 7.4 + 1.8 for 9 samples. After 21 days, an average defacement value of 3.8 ⁇ 0.9 was found. In other words, about 38% of the painted surfaces containing 100 pg/mL of Compound B9 were free of fungal growth. Compound B0 did not show any significant ability to inhibit fungal growth on the painted surface at the 100 pg/inL concentration level despite showing complete inhibition of fungal growth at 12.5 pg/mL in a liquid medium (Table 1) .
  • thiabendazole all showed no inhibitory activity towards fungal/mold growth on the painted surfaces when present dispersed within that painted surface.
  • Paints containing 10 pg/mL of Compound B8 were not very effective at preventing fungal growth on painted surfaces.
  • a preferred antifungal surface coating composition should contain more than 10 pg/mL of the antifungal benzoxaborole additive.
  • Compound B0 did not inhibit the growth of Stachybotrys chartarum as an antifungal additive present in dried paint .
  • OIT-containing paints also displayed a similar level of fungal growth inhibition.
  • OIT and IPBC can be considered industry standards because they have been used as anti-mildew/anti-microbial additives for various surface coating products.
  • the data in Table 2 show that antifungal benzoxaboroles, such as B8 and B9, demonstrated similar antifungal activity as OIT and IPBC in a surface coating matrix (i.e. latex paint) .
  • antifungal compounds that have been used as antifungal/antimildew additives for surface protecting products were also assayed under the same experimental conditions using 100 pg/mL of each.
  • An antifungal chemical can behave very unpredictably inside a dried surface coating matrix.
  • An antifungal chemical might completely lose its antifungal activity when it is inside a dried surface coating matrix.
  • Penicillium chrysogenum two different paints were used as the base into which antifungal agents were mixed. Table 2 shows that discs
  • Paints containing 200 pg/mL of Captan or OIT were unable to provide decent inhibition of fungal growth on the surfaces of painted discs past 7 days. Paints containing 200 pg/mL of thiabendazole were unable to prevent fungal growth on the surfaces of painted discs past 14 days. Paints containing 200 pg/mL of chlorothalonil did not perform much better at preventing fungal growth on the surfaces.
  • the benzoxaborole antifungal agents also worked very well to inhibit existing fungal growth on painted or treated surfaces.
  • fungal growth was allowed to cover a painted surface (surface containing 2 coats of the unaltered paint) to a defacement rating of 3-5, forming a ' 'contaminated surface' .
  • These contaminated surfaces were then painted over with one coat of the same paint either with or without antifungal
  • Table 3 shows that one week after repainting and maintenance under high humidity and elevated temperature incubating conditions, latex paints containing either Compound B8 (100 pg/mL;
  • Contaminated surfaces that were re-painted with paints containing 200 pg/mL of Compounds B8 or B9 showed even greater ability to inhibit the re- emergence of fungal/mold growth.
  • the fungus-containing samples that were painted over with the un-modified paint yielded an average defacement rating of 1.8 ⁇ 1.9 after one week of incubation.
  • the fungi/molds were able to completely reclaim the samples where 2 coats of un-modified paints were re-painted over the contaminated surfaces.
  • Table 3 shows complete re-emergence of fungus/mold (Alternaria alternata) growth in 7 days when contaminated surfaces were re-painted with paints containing 100 pg/mL of Compound B0, IPBC, triclosan, thiabendazole, OIT, or captan.
  • chlorothalonil can completely inhibit the growth of Alternaria alternata at 1000 times lower
  • Table 2 shows paints containing 100 pg/mL of OIT or IPBC to have good antifungal activity when the paints were applied to clean cellulose-based discs prior to the introduction of fungal spore inoculum.
  • paints containing 100 pg/mL of the antifungal benzoxaborole compounds (B0, B8, and B9) were effective at significantly reducing the re-emergence of fungus/mold on re-painted surfaces (Table 3) .
  • contaminated surfaces that were painted over with paints containing 100 pg/mL of Compound B8 managed to suppress fungus/mold re- emergence by about 50% for 21 days (averaged
  • Stachybotrys chartarum re-emergence on the surfaces after 7 days.
  • paints containing 200 pg/mL of Compound B8 provided mild inhibitory
  • Penicillium chrysogenum after 14 days Penicillium chrysogenum after 14 days.
  • the benzoxaborole-containing latex paint's ability to inhibit the re-emergence of fungus growth on a re-painted contaminated surface compares favorably against other antifungal agents.
  • the data from Tables 1, 2 and 3 do not show a clear correlation between water solubility, MIC value determined in liquid medium, and antifungal activity in a dried latex paint formulation for the group of antifungal compounds examined.
  • the antifungal efficacy determined in liquid media or other means does not
  • benzoxaborole compounds to be a singular class of compounds because they demonstrated good antifungal efficacy in three areas: in liquid medium (Table 1), in dried latex paint formulation for preventing fungus/mold growth (Table 2), and in dried latex paint formulation for suppressing the re-emergence of fungus/mold growth when painting over a contaminated surface (Table 3). All the other industry standard antifungal additives tested can only satisfy 1 or 2 of the above three areas, and none of them seems to be capable of suppressing the re-emergence of fungus/mold growth on a contaminated surface.
  • painted filter paper discs were irradiated with ⁇ UV light from a 30 watt bulb for 2 hours and then inoculated with Alternaria alternata spores ("+ UV” in the table below) , or were inoculated without prior UV irradiation ("no UV” in the Table 4) .
  • the painted filter papers were incubated as discussed elsewhere herein, evaluated at 13 and 21 days post-inoculation for defacement by fungal growth and compared to similar painted filter paper discs that were not irradiated prior to inoculation. The results of this study are shown below in Table 4.
  • the benzoxaborole antifungal was stable against UV light exposure.
  • the antifungal capacity of painted surfaces exposed to UV irradiation was the same as surfaces not exposed to UV irradiation.
  • IPBC is the active ingredient found in BIOBANTM IPBC antimicrobial products including paint, stain, cordage coating, plastic, plastic coating, paper coating, and wood preservative to inhibit
  • Penicillium corylophilum was cultured from either cryogenic storage stock, silica gel storage stock, or lyophilized (with skim milk) stock in the Plant Pathology and Environmental
  • a fungal isolate of Stachybotrys chartarum was purchased from American Type Culture Collection (ATCC) Manassas, VA.
  • a fungal isolate of Stachybotrys chartarum was purchased from American Type Culture Collection (ATCC) Manassas, VA.
  • CBS 112388 Cladosporium cladosporioides
  • Valspar' QuikHide White flat interior paint (satin; RPM International Inc., Medina, OH), Valspar' QuikHide White flat interior paint (The Valspar
  • Valspar® Ultra ceiling white flat interior paint (The Valspar
  • DMSO sterile 25% potato dextrose broth
  • the spore inoculum was prepared fresh prior to each study, and the inoculum was appropriately diluted to a final concentration of 0.4 - 1 x 10 5 spores/mL or colony- forming unit (CFU) /mL in each study.
  • the spore suspension can be stored in a refrigerator at 4 ° C for up to one week.
  • MICs minimal inhibitory concentrations
  • the individual MIC values were determined in triplicate in a final volume of 0.2 mL/well with antifungal concentrations of 0 - 200 ⁇ g/mL (12 serial dilutions down from 200 ⁇ g/mL [200, 100, 50, 25, 12.5, 6.25, 3.13, 1.56, 0.78, 0.39, 0.20, and 0.098 pg/mL] ; control studies with 0 ⁇ g/mL of antifungals were performed in parallel for each plate) . Plates sealed with clear polyester film (VWR, Radnor, PA) were incubated at a temperature of about 25 °C. The progress of fungal growth was monitored at 48 hours and 72 hours. The MICs were determined as the lowest antifungal concentrations that completely inhibited fungal growth (no visible growth) or the concentrations that inhibited fungal growth by greater than 95% (determined as relative absorbance using the Bio-Tek® PowerWaveTM HT
  • microplate reader at 530 or 630 nm) relative to the corresponding antifungal-free control.
  • ASTM test method D3273-12 Standard Method for Resistance to Growth of Mold on the Surface of Interior Coatings in an Environmental Chamber
  • ASTM D3273-12 American Society for Testing Materials International, West Conshohocken, PA, USA
  • ASTM test method G21-13 Standard Practice for Determining Resistance of Synthetic Polymeric
  • Test surfaces were prepared in triplicate. In most cases, the tested conditions were repeated on a different date, again in triplicate. Spiked paint solutions were applied to autoclaved (for 15-20 minutes) #413 filter paper discs, 4.25 cm in diameter from VWR, Radnor, PA. Two coats of paint were applied with a polyester brush to completely cover both faces of the filter paper disc, allowing at least four hours drying time between coats.
  • Nutrient-Salts Agar (NSA) medium was prepared according to ASTM method G21-13 in 100 x 15 mm sterile polystyrene petri dishes (VWR® Radnor, PA) with a solidified agar layer of about 3 to about 6 mm (1/8 to 1/4 in.) in depth. The agar was allowed to solidify for at least 24 hours before being used. The painted test filter paper discs were placed in the center of the agar plates in a biosafety hood while wearing clean nitrile gloves.
  • the paint coatings were evaluated against three representative cellulose-supportable fungi: Stachybotrys chartarum, Penicillium chrysogenum r and Alternaria alternata. Fungal isolates of S.
  • chartarum (ATCC 16026) was purchased from American Type Culture Collection (ATCC) Manassas, VA. Fungal isolates of Alternaria alternata and Penicillium chrysogenum were obtained from the Plant Pathology and Environmental Microbiology Department at Penn State University.
  • a sterile cell scraper (Falcon® #35085, Corning, NY) was used to gently scrape the surface growth from the fungal culture.
  • a spore suspension of each of these fungi was prepared by pouring a 20- mL portion of autoclaved deionized water containing
  • Painted test surfaces were inoculated with a spray bottle or with a sterile cotton-tipped applicator.
  • the spore suspension was sprayed twice on the painted test discs with an autoclaved spray bottle that delivered approximately 0.14 g of fluid per spray.
  • an autoclaved cotton-tipped applicator was submerged in approximately 400 ⁇ of the spore inoculum solution (spore concentrations described above) and applied evenly over the surface of the painted test surface twice. A fresh autoclaved cotton-tipped applicator was used for the application of each painted disc.
  • a grid that divides the circular area into 20 equal sections as shown in Fig. 1 was used to estimate the extent (percent defacement) of fungal growth .
  • Nutrient-Salts Agar (NSA) media was prepared according to ASTM method G21-13 in 100 x 15 mm sterile polystyrene petri dishes (VWR® Radnor, PA) with a solidified agar layer from 3 to 6 mm (1/8 to 1/4 in.) in depth. The agar was allowed to solidify for at least 24 hours before being used. The painted test filter paper discs were placed in the center of the agar plates in a biosafety hood while wearing clean nitrile gloves .
  • ATCC Manassas
  • VA Fungal isolates of Alternaria alternata and Penicillium chrysogenum were obtained from the Plant Pathology and Environmental Microbiology Department at Penn State University.
  • a sterile cell scraper (Falcon® #35085, Corning, NY) was used to gently scrape the surface growth from the fungal culture.
  • a spore suspension of each of these fungi was prepared by pouring a 20- mL portion of autoclaved deionized water containing 0.01% Tween® 20 onto a subculture of each fungal species. Spores were counted with the use of a hemocytometer (Hausser Scientific, Horsham, PA) under a microscope. Spore suspensions of Stachybotrys chartarum and Penicillium chrysogenu were diluted to 1 X 10 6 spores/mL with autoclaved deionized water. Spore suspensions of Alternaria alternata were used "as is" in the range of 200,000 to 400,000 spores/mL.
  • Painted test surfaces were inoculated with a spray bottle or with a cotton-tipped applicator. To inoculate the sample with a spray bottle, the spore suspension was sprayed twice on the painted test discs with a spray bottle that delivered
  • Samples showing similar levels of fungal growth were collected based on the number of samples needed for testing. These samples were randomly assigned to each of the testing categories.
  • the paint formulation was painted over the fungal growth with one coat of paint using a nylon polyester brush to completely cover the appearance of the existing fungus growth.
  • the paint application was extended approximately 1-2 cm beyond the edge of the disc onto the NSA medium. Each formulation used a separate brush to avoid cross contamination.
  • Samples were stored inverted to prevent the pooling of condensate on the sample surface.

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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)
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Abstract

L'invention concerne une composition de peinture au latex qui contient un liant filmogène et un pigment dispersé dans un véhicule aqueux et qui contient également une quantité efficace d'un ou de plusieurs composés de benzoxaborole inhibant la croissance d'un champignon susceptible d'être porté par la cellulose de Formule C. L'invention concerne également un procédé d'utilisation de cette peinture au latex destinée à inhiber la croissance d'un champignon susceptible d'être porté par la cellulose sur une surface cellulosique, ainsi qu'un procédé d'inhibition de cette croissance par peinture d'une surface infectée par un champignon avec une peinture au latex de l'invention.
EP16751753.1A 2015-08-06 2016-08-03 Revêtement contenant du benzoxaborole résistant à un champignon susceptible d'être porté par la cellulose Withdrawn EP3331954A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201562201836P 2015-08-06 2015-08-06
PCT/US2016/045329 WO2017024022A1 (fr) 2015-08-06 2016-08-03 Revêtement contenant du benzoxaborole résistant à un champignon susceptible d'être porté par la cellulose

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EP3331954A1 true EP3331954A1 (fr) 2018-06-13

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