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
  • C09D5/02—Emulsion paints including aerosols
• • 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
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
  • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
• • 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
  • C09D5/16—Antifouling paints; Underwater paints
  • C09D5/1687—Use of special additives
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
  • C09K15/02—Anti-oxidant compositions; Compositions inhibiting chemical change containing inorganic compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
  • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
  • C09K15/28—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen, oxygen and sulfur

Definitions

• This invention relates generally to coating compositions, and, more specifically, to such compositions that are characterized by enhanced antimicrobial efficacy and resistance to discoloration, both in their wet state and, after drying, in the form of a dry film on a substrate.
• Sodium pyrithione (also called the sodium salt of l-hydroxy-2-pyridinethione, sodium pyridine-2-thiol-N-oxide, or 2-pyridinethiol-l- oxide, Na salt) is one pyrithione salt having excellent antimicrobial properties, and is typically employed as a biocide and preservative in functional fluids, such as metalworking fluids, lubricants, cosmetics and toiletries.
• Sodium pyrithione is a well-known commercial product commonly made by reacting 2 -chloropyridine-N-oxide with NaSH and NaOH, as disclosed, for example, in U.S. Patent No. 3,159,640.
• zinc pyrithione also known as zinc pyridine-2-thiol-N-oxide or bis [l-hydroxy-2 (H) pyridinethionato] -zinc
• Zinc pyrithione may be made by reacting l-hydroxy-2-pyridinethione or a soluble salt thereof with a zinc salt (e.g., ZnS0 4 ) to form a zinc pyrithione precipitate, as disclosed, for example in U.S. Patent No. 2,809,971.
• Zinc pyrithione has been employed as a broad-spectrum anti-microbial agent and preservative in metalworking fluids, plastics, paints, adhesives and cosmetics.
• any ingredient which causes the formulation to vary much from a desired white or color may make the colorant formulators' task very difficult.
• paint bases i.e., the partially formulated paint before pigment addition
• adhesives, caulks and sealants any unwanted color in an additive can adversely affect the color of the formulated product, Such discoloration typically adversely affects the desired product color, producing an off -color product.
• Patents 4,957,658 and 4,818,436 disclose solutions to the above-discussed discoloration problem attributable to the presence of ferric ion plus pyrithione, ih paints and functional fluids (e.g., metalworking fluids) respectively, by adding to the paint or functional fluid an alkali metal or alkaline earth metal salt of 1-hydroxyethane-l , 1-diphosphonic acid.
• functional fluids e.g., metalworking fluids
• U.S. Patent 4,161,526 discloses a white to cream yellow pyrithione, pyrithione salt or dipyrithione for application to skin or hair containing from about 0.01 percent to about 1 percent of the zinc salt of an organic carboxylic or inorganic acid, zinc hydroxide or zinc oxide, or a mixture thereof.
• the composition of the '526 patent is said to be effective in preventing or removing discoloration caused by formation of a colored pyrithione, pyrithione salt, or dipyrithione contaminant (said to be iron pyrithione) in the composition.
• the '526 patent does not teach a solution to the discoloration problem in compositions unrelated to skin or hair care, and not containing iron pyrithione.
• unwanted ions such as ferric ion
• ferric ion can cause a functional problem with respect to the antimicrobial performance of pyrithione. It is believed by the present inventors that this performance problem results from the fact that the pyrithione tends to form a blue precipitate in the presence of ferric ion, and precipitation of pyrithione reduces the amount of available pyrithione throughout the composition, thereby diminishing the biocidal protection thereof.
• the present inventors have found that the presence of a large amount of zinc oxide in a pyrithione-containing paint can surpress the short- term (or initial stage) of antimicrobial efficacy imparted by the pyrithione to the paint when dried to form a dry film on a substrate. This diminished short term efficacy adversely affects the performance of the paint, particularly in regard to resistance of the paint film to mildew growth.
• New solutions to the yellow, blue and green discoloration problem in various pyrithione- containing aqueous coating compositions, particularly paints, adhesives, caulks and sealants would be highly desired.
• Preferred solutions would includes those that enable pyrithione to be utilized in coating compositions containing iron or copper, without encountering any resulting discoloration of the composition, and that is cheaper, longer lasting, and/or uses lower levels of additives than required by the above-discussed prior art.
• a particularly preferred solution namely one providing improved short-term and long-term antimicrobial resistance of the coating composition and resulting coating against microbial attack, would be highly desired by the paint, adhesives, caulks and sealants manufacturing community. The present invention provides one such solution.
• the present invention relates to an aqueous coating composition
• an aqueous coating composition comprising: a) water, b) a base medium, c) a pyrithione salt, in an amount of from 0.01% to 2.0% based upon the weight of the composition, and d) zinc oxide compound selected from the many grades suitable for paint manufacture at a concentration of from 0.001% to 10% based upon the weight of the composition.
• Typical coating compositions include aqueous compositions of a paint, adhesive, caulk, sealant, latex emulsion, pigment slurry, patching compound, joint compound, or concrete admixture.
• the present invention relates to a process for inhibiting dry film- discoloration of a pyrithione-containing coating composition, attributable to ultraviolet light degradation of said pyrithione, which comprises incorporating into said coating composition an effective amount of a zinc compound selected from the group consisting of zinc salts of organic acids, zinc salts of inorganic acids, zinc hydroxide, zinc oxide, and combinations thereof.
• the present invention relates to a process for removing an undesirable discoloration in an aqueous antimicrobial composition containing a dissolved metal ion selected from the group consisting of ferric ion, cupric ion, and combinations thereof, and containing pyrithione, which comprises contacting said composition with a zinc ion in a molar amount at least equal to the amount of said dissolved metal ion in said composition.
• the present invention relates to an aqueous antimicrobial coating composition, characterized by antimildew efficacy and protected against discoloration attributable to the presence of pyrithione therein, said composition being selected from the group consisting of water- based paints, adhesives, caulks and sealants, and combinations thereof, said composition comprising water, a pyrithione salt or acid, an organic base medium and a zinc compound, said zinc ion being present in said composition in an amount of from 0.001% to 10% based upon the weight of the coating composition.
• the present invention relates to a coated substrate comprising a substrate selected from the group consisting of wood, metal, plastic substrates, and combinations thereof, and a coating on said substrate, said coating comprising pyrithione and a zinc compound selected from the group consisting of zinc salts of organic acids, zinc salts of inorganic acids, zinc hydroxide, zinc oxide, and combinations thereof
• a zinc compound such as a zinc salt, zinc oxide or zinc hydroxide
• a pyrithione compound preferably zinc pyrithione
• ultraviolet radiation a component of natural, outdoor light, tends to cause yellow discoloration of dry- film coatings containing pyrithione. It has now been found that the presence of zinc oxide within the preferred range of from 0.02% to 0.5% by weight, based upon the weight of the coating composition, in a pyrithione-containing coating composition contributes both to antimicrobial efficacy and avoidance of undesirable blueing or other discoloration of the coating composition, as well as avoidance of undesirable yellowing or other discoloration of the dry film resulting from the coating of a substrate with the coating composition.
• discoloration as employed herein with respect to pyrithione-containing coating compositions is intended to describe any unacceptable gray, blue, black, purple, green, or color other than the natural color or desired artificial color of the paint or paint base formulation.
• discoloration is also intended to describe any yellow or brown discoloration of the dry film resulting from coating a substrate with the coating composition. Such yellow or brown discoloration is typically caused by photodegradation of pyrithione in the coating.
• Discoloration of the coating composition can be attributable to unwanted metal ions (such as iron or copper) entering the coating composition from the starting materials employed in the preparation of the coating composition.
• Typical starting materials include tap water, and fillers (such as calcium carbonate) used to prepare coating compositions, as well as a source of pyrithione in the form of sodium pyrithione, zinc pyrithione, and combinations thereof. It is noted, for example, that the natural color of sodium pyrithione itself is a clear yellow. It is quite common, however, for iron and/or copper contaminants to be introduced into the aqueous composition from the tap water or fillers used in preparing the coating compositions, causing discoloration of the composition.
• One way of quantifying the extent of discoloration is by measuring the reflectance color parameters, and calculating a whiteness value from them. Another method is to visually inspect the composition for any signs of off -whiteness, as compared to the desired or white color.
• the amount of the above described zinc salt of an organic acid or inorganic acid, zinc hydroxide or zinc oxide, or combination thereof, needed to prevent discoloration in the coating composition in which it is employed, and the resulting dry film made by coating a substrate with the coating composition can vary over a wide range of from 0.001% or lower to 10% or greater (advantageously from 0.001% to 3%, more advantageously from 0.02% to 0.5%)," based upon the weight of the coating composition in which it is employed.
• the amount of zinc oxide preferably should not exceed 0.5% by weight (advantageously from 0.002% to 0.2%) based upon the weight of the coating composition.
• the pyrithione used in the process and composition of this invention is preferably a pyrithione salt, such as sodium pyrithione, zinc pyrithione, chitosan pyrithione, magnesium disulfide pyrithione, and the like, although pyrithione acid can be used if desired. More preferable pyrithione salts include sodium pyrithione, and zinc pyrithione, most preferably zinc pyrithione.
• the sodium pyrithione useful in the present invention is a well-known commercial product that is commonly made by reacting 2-chloropyridine-N-oxide with NaSH and NaOH, as illustrated by the disclosures of U.S. Pat. No. 3,159,640.
• Zinc pyrithione may be made by reacting 1- hydroxy-2-pyridinethione (i.e., pyrithione acid) or a soluble salt thereof with a zinc salt (e.g., ZnS0 4 ) to form a zinc pyrithione precipitate, as illustrated by the disclosures of U.S. Pat. No. 2,809,971.
• a zinc salt e.g., ZnS0 4
• aqueous compositions of the present invention are suitable for a variety of uses, such as, for example as soap, shampoo, skin care medicaments, paint, or incorporated into or onto plastic or a woven or non-woven fibers, when formulated to contain the requisite components in addition to the antimicrobial component.
• the antimicrobial compositions of the present invention are particularly useful in the form of paints, including indoor and outdoor household paints, industrial and commercial paints.
• the antimicrobial compositions provide desirable results when the antimicrobial component is incorporated into exterior paints of the latex types .
• the coating compositions of the present invention are suitably applied to a substrate, such as a wood, plastic or metal substrate, and allowed to dry to form a dry coating.
• the dry film formed by coating and drying the coating composition of the present invention onto a substrate exhibits excellent resistance to the growth of fungus and algae, as show by outdoor exposure tests using boards painted with the coating composition.
• certain paint formulations namely those that are rich in hydrophilic components, might provide an environment that is more favorable to the growth of both mildew and algae, as compared to the coatings tested. Mildew needs moisture to survive.
• Hydrophilic materials in a paint film will keep the moisture level of the film higher. This provides a better environment for mildew and also may contribute to accelerated leaching out of hydrophilic materials.
• the hydrophilic components in these formulations tend to cause relatively soluble antimicrobial additives to leach out of the formulation, thus providing good short-term antimicrobial protection at the expense of longer- term antimicrobial protection due to this leaching effect.
• zinc pyrithione a relatively water- insoluble antimicrobial additive
• a relatively water-soluble antimicrobial additive in combination with a relatively water-soluble antimicrobial additive provides an excellent combination of desired short-term and long-term antimicrobial protection in dry paint films made using paint formulations containing high levels of hydrophilic components.
• Relatively water-soluble antimicrobials that are useful as co-biocides for dry- film efficacy when used in combination with zinc pyrithione in accordance with the present invention include iodopropynyl butylcarbamate (“IPBC”), n- octyl isothiazolin-one (“OIT”), methylene thiocyanate (“MTC”), thiocyanomethylthio benzothiazole (“TCMTB”), thiazolyl benzimidazole (“TBZ”), benzimidazolyl carbamic acid methylester (“BCM”), triazoles, such as chlorophenylethyl dimethylethyl triazole ethanol ( “Tebuconazole” , commercially available from Bayer) , substituted triazines such as tert-butylamino cyclopropylamino methylthio-s-triazine, and dichlorophenyl dimethylurea ("Diur
• cobiocides are suitably added either alone, or in admixture with zinc pyrithione, to the desired paint, to provide a paint containing a molar ratio of zinc pyrithione to co-biocide of from 1:10 to 10:1.
• a paint composition will contain, in addition to the antimicrobial component, a resin, a pigment, and various optional additives such as thickening agent (s), wetting agents and the like, as is well known in the art.
• the resin is preferably selected from the group consisting of vinyl, alkyd, epoxy, acrylic, polyurethane and polyester resins, and combinations of thereof.
• the resin is preferably employed in an amount of between about 20% and about 80% based upon the weight of the paint or paint base.
• the paint composition of the present invention optionally additionally contains optional additives which have a favorable influence on the viscosity, the wetting power and the dispersibility, as well as on the stability to freezing and electrolytes and on the foaming properties.
• the paint preferably contains a swelling agent to cause the paint to gradually "slough off" in its marine environment, thereby causing renewed biocidal efficacy of newly exposed biocide at the surface of the paint in contact with the water medium of the marine ' environment .
• Illustrative swelling agents are naturally occurring or synthetic clays, such as kaolin, montomorillonite, and bentonite) , clay mica (muscovite) , and chlorite (hectonite) , and the like.
• clays other swelling agents, including natural or synthetic polymers, such as that commercially available as POLYMERGEL, have been found to be useful in the compositions of the present invention to provide the desired "sloughing off" effect.
• Swelling agents can be used singly or in combination.
• the total amount of optional additives is preferably no greater than 20% by weight, more preferably between about 1% and about 5% by weight, based upon the total weight of the paint composition.
• thickening agents include cellulose 30 derivatives, for example methyl, hydroxyethyl , hydroxypropyl and carboxy ⁇ nethyl cellulose, poly(vinyl alcohol), poly (vinylpyrolidone) , poly (ethyleneglycol) , salts of poly (acrylic acid) and salts of acrylic acid/acrylamide copolymers.
• Suitable wetting and dispersing agents include sodium polyphosphate, salts of low molecular weight poly (acrylic acid), salts of poly (ethane sulfonic acid) , salts of poly (vinyl phosphonic acid) , salts of poly (maleic acid) and salts of copolymers of maleic acid with ethylene, 1 olefins 3 to 18 carbon atoms and/or styrene.
• ком ⁇ онент 1.2-diols for example glycol, propylene glycol (1.2) and butylene glycol 1.2) or polymers thereof, or ethoxylated compounds.
• monomer 1.2-diols for example glycol, propylene glycol (1.2) and butylene glycol 1.2) or polymers thereof, or ethoxylated compounds.
• the minimum temperature of film formation of the paint composition may be reduced by adding solvents, such as ethylene glycol, butyl glycol, ethyl glycol acetate, ethyl diglycol acetate, butyl diglycol acetate, or alkylated aromatic hydrocarbons.
• solvents such as ethylene glycol, butyl glycol, ethyl glycol acetate, ethyl diglycol acetate, butyl diglycol acetate, or alkylated aromatic hydrocarbons.
• defoaming agents there are suitable for example poly (propylene glycol) and polysiloxanes .
• other biocides can additionally be incorporated into the paint formulations of the present invention.
• the paint composition of the present invention may be used as a paint for natural or synthetic materials, for example wood, paper, metals, textiles and plastics. It is particularly suitable as an outdoor paint, and is excellent for use as a marine paint .
• aqueous composition of the present invention is as a latex tile adhesive typically containing, for example, in addition to the antimicrobial component, a latex emulsion, an optional rosin emulsion, an optional plasticizer, an optional antioxidant, and an optional pigment or filler (such as calcium carbonate) .
• a latex caulk typically containing, in addition to the antimicrobial component, an acrylic latex, a nonionic surfactant, a dispersant, an optional plasticizer, and an optional pigment or filler (such as calcium carbonate) .
• aqueous antimicrobial compositions of the present invention are useful, in any of the variety of applications described herein, as disinfectants and preservatives, in a liquid or spreadable solid form, alone or in combination with an inert carrier such as water, liquid hydrocarbons, ethanol , isopropanol, or the like. They can be employed using conventional procedures to control bacteria and fungi on various substrates, and can be applied to bacterial or fungal organisms or on substrates in an antimicrobial amount by conventional procedures such as spraying, dipping, drenching impregnation, and the like.
• a paint was prepared having the following composition:
• Latex Paint Formulation Containing Zinc Oxide Ingredient Grams Water 240. ,0
• Colloid 643 2 2. ,0 Triton ® CF-103 5. ,0
• a paint was prepared having the following composition:
• the paint was applied by brush in two coats to an unprimed white pine substrate to determine whether the coating supported the growth of mildew on the coating. After four months of outdoor aging, the growth was rated in accordance with the procedure of ASTM D 3274-82 to a rating of 8 (light growth) .
• a paint was prepared having the following composition:
• Attapulgite Clay 6 Attapulgite Clay 6, .0
• a nonionic surfactant a product of Union Carbide Corp.
• Example 1 demonstrates that the combination of zinc pyrithione and zinc oxide suitably provides total resistance to the growth of mildew on painted wood substrates, whereas zinc oxide or zinc pyrithione alone (Comparative Examples A and B) does not provide such resistance.
• aqueous latex paint formulation (below) containing zinc pyrithione and one not containing zinc pyrithione were applied to a panel and exposed in a QUV weatherometer for 500 hours.
• the yellowness index (“YI") was measured at time zero and after 500 hours of exposure.
• the difference in YI for the paint without zinc pyrithione after 500 hours of exposure was an increase in yellowness of 1.34.
• the difference in YI for the paint with 0.3% by weight of active zinc pyrithione was an increase of 3.68, indicating an increase in yellowing on exposure to UV with the paint containing zinc pyrithione.
• Attapulgite Clay 4 .0 4 , ,0
• Example 2 To determine if a lower concentration of zinc oxide could be used to provide effectiveness in avoiding, eliminating or reducing yellow discoloration caused by ultraviolet in a pyrithione- containing paint, the following experiment was conducted. Following the procedure of Example 2, two paints were prepared as follows: to Example 2 were prepared as follows:
• Titanium Dioxide 200.0 200 .0
• zinc pyrithione-containing paint compositions In the presence of ferric ion, zinc pyrithione- containing paint compositions also tended to turn blue to gray, although at a much slower rate than did the sodium pyrithione-containing paints.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Wood Science & Technology (AREA)
• Plant Pathology (AREA)
• Dentistry (AREA)
• Pest Control & Pesticides (AREA)
• Health & Medical Sciences (AREA)
• Agronomy & Crop Science (AREA)
• General Health & Medical Sciences (AREA)
• Zoology (AREA)
• Environmental Sciences (AREA)
• Inorganic Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Paints Or Removers (AREA)
• Sealing Material Composition (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)

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• 1997
  • 1997-02-21 US US08/804,225 patent/US5939203A/en not_active Expired - Lifetime
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