[go: up one dir, main page]

US20110144232A1 - Biocide composition comprising pyrithione and pyrrole derivatives - Google Patents

Biocide composition comprising pyrithione and pyrrole derivatives Download PDF

Info

Publication number
US20110144232A1
US20110144232A1 US12/930,458 US93045811A US2011144232A1 US 20110144232 A1 US20110144232 A1 US 20110144232A1 US 93045811 A US93045811 A US 93045811A US 2011144232 A1 US2011144232 A1 US 2011144232A1
Authority
US
United States
Prior art keywords
coating composition
alkyl
pyrrole
hydrogen
composition
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.)
Abandoned
Application number
US12/930,458
Inventor
Craig Waldron
Robert Martin
Gareth Williams
Tina Williams
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.)
Arch Chemicals Inc
Original Assignee
Arch Chemicals Inc
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 Arch Chemicals Inc filed Critical Arch Chemicals Inc
Priority to US12/930,458 priority Critical patent/US20110144232A1/en
Publication of US20110144232A1 publication Critical patent/US20110144232A1/en
Assigned to ARCH CHEMICALS, INC. reassignment ARCH CHEMICALS, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: WALDRON, CRAIG, WILLIAMS (DECEASED, SIGNED BY LEGAL REPRESENTATIVE TINA WILLIAMS), GARETH, MARTIN, ROBERT
Abandoned legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-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
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1625—Non-macromolecular compounds organic
    • 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
    • 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
    • A01N55/02—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing metal atoms
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31692—Next to addition polymer from unsaturated monomers
    • Y10T428/31699—Ester, halide or nitrile of addition polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • Y10T428/31906—Ester, halide or nitrile of addition polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31935—Ester, halide or nitrile of addition polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31971—Of carbohydrate
    • Y10T428/31989—Of wood

Definitions

  • This invention relates to a biocidal composition. More particularly, this invention relates to a biocidal composition comprising a blend of at least one selected pyrithione compounds and at least one selected pyrrole derivatives that prevent, or inhibit growth of microbes and the method of using such biocidal composition.
  • compositions and formulations are known in the art for the prevention, inhibition, and treatment of growth or infestation of microbes.
  • compositions and coatings specifically formulated for the prevention, inhibition, and treatment of growth or infestation of fouling organisms are known in the art for the prevention, inhibition, and treatment of growth or infestation of microbes.
  • Fouling organisms present a large problem for substrates and objects that are exposed to water.
  • the term “fouling organism” includes both hard and soft fouling organisms. Hard fouling organisms include barnacles, mollusks, and the like, while soft fouling organisms include algae, fungi, and the organisms listed in U.S. Pat. No. 5,712,275, which is incorporated by reference herein. Such organisms present a constant problem for objects and substrates that are exposed to marine water, fresh water, brackish water, sewage water, waste water, rain water, and the like.
  • wood and wood products often experience growth and infestation of microbes such as fouling organisms, termites and the like. Growth and infestation of such microbes leads to warping, cracking, and deterioration of the wood and wood products. Consequently the wood and wood products lose value, visual appeal, and usefulness.
  • microbes such as fouling organisms, termites and the like.
  • biocides found useful include tributylin compounds, pyrithione compounds, oxathiazine compounds, pyrrole compounds, triphenylboron compounds and terbutyn.
  • Pyrithione compounds and select pyrrole compounds are separately known and used as biocidal or antifouling agents. However, it is not known in the art, nor is it obvious to combine the two compounds. Examples of prior art references teaching the use of pyrithione compounds and selected pyrrole compounds include the following:
  • U.S. Pat. No. 5,057,153 to Ruggiero relates to an improved paint or paint base composition characterized by enhanced biocidal efficacy.
  • the paint contains a biocide comprising pyrithione salt and a copper salt.
  • a process for generating copper pyrithione biocide in-situ in a paint formulation is disclosed.
  • the paint and paint bases of this patent comprise pyrithione compounds as the only biocide present in the formulation.
  • U.S. Pat. No. 5,098,473 to Hani et al. relates to paints and paint bases, and more specifically to a process for providing a stable gel-free dispersion of zinc pyrithione plus cuprous oxide biocide in paint (see also U.S. Pat. Nos. 5,098,473; 5,112,397; 5,137,569; 5,185,033; 5,232,493; 5,298,061; 5,342,437; PCT Patent Application No. WO 95/10568 and EP 0610251).
  • U.S. Pat. No. 4,565,856 to et al. relates to pyrithione-containing polymers.
  • the polymers described in this patent are used as biocides in paints and wood preservative products.
  • U.S. Pat. No. 4,610,993 to Wedy et al. describes a method of administering an effective mount of at least one selected pyridine-N-oxide disulfide compound to treat or prevent bovine mastitis.
  • European patent number EP 0746979 describes a method for controlling or combating the attachment of a fouling organism to an underwater surface by contacting the organism with an antifouling-effective amount of a 2-arylpyrrole compound.
  • U.S. Pat. No. 6,069,189 to Kramer et al. describes antifouling paints that contain selected pyrrole derivatives.
  • Specific pyrrole compounds incorporated into the antifouling paint include 2-trihalogenomethyl-3-halogeno-4-cyano pyrrole and derivatives thereof.
  • Kramer et al. found these compounds to be particularly effective against barnacle infestation. Additionally, this Kramer et al. reference found that bright or light colored anti-fouling paint could be created despite the addition of these compounds.
  • PCT Patent Application No. WO 03/039256 describes an antifouling composition that comprises an amount of at least 3.5 wt. % based on the total weight of the dry mass of the composition of 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, or a salt thereof together with another biocide.
  • the other biocide is selected from bethoxazin, tolylfluanide, dichlofuanide, or DCOIT.
  • one aspect of the present invention is directed to a biocidal composition
  • a biocidal composition comprising one or more pyrithione compounds, and one or more pyrrole compounds of Formula I:
  • X is halogen, CN, NO 2 or S(O) n R 1 ; Y is hydrogen, halogen or S(O) n R 1 ; Z is halogen, C 1 -C 4 haloalkyl or S(O) n R 1 ; n is an integer of 0, 1 or 2; R 1 is C 1 -C 4 haloalkyl; L is hydrogen or halogen; M and Q are each independently hydrogen, halogen, C 1 -C 4 allyl, C 1 -C 4 haloalkyl, C r C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, CN, NO 2 , R 2 CO or NR 3 R 4 , or when M and Q are on adjacent positions and are taken together with the carbon atoms to which they are attached MQ represents the structure —OCH 2 O—, —OCF
  • halogen designates Cl, Br, I or F
  • haloalkyl designates any alkyl group C n H 2n+1 having from 1 halogen atom to 2n+1 halogen atoms wherein the halogen atoms are the same or different.
  • Another aspect of the present invention is directed to a coating composition
  • a coating composition comprising an effective biocidal amount of a biocidal composition comprising one or more pyrithione compounds and one or more pyrrole compounds of Formula (I) as described above wherein said biocidal composition is copper free or low copper content.
  • Still another aspect of the present invention is directed to a method of coating a substrate comprising applying a coating composition that contains a biocidal composition comprised of one or more pyrithione compounds and one or more pyrrole compounds of Formula (I) as described above, to the substrate and drying the coating composition on the substrate.
  • a coating composition that contains a biocidal composition comprised of one or more pyrithione compounds and one or more pyrrole compounds of Formula (I) as described above
  • Yet another aspect of the present invention is directed to a coated substrate comprising the coating composition that contains a biocidal composition of the present invention and a substrate, wherein said substrate is selected from a group consisting of wood, plastic, leather, vinyl and metal.
  • One expected advantage of the present invention includes increased protection against a large spectrum of microbes.
  • Another expected advantage of the present invention includes preservation of wood and wood-products. Additionally, it is expected that the present invention will be long-lasting, have low toxicity, and be easily and inexpensively produced.
  • an effective biocidal amount as used in the present specification and claims relates to the amount of the biocidal composition that has a positive effect on reducing, eliminating, or preventing attachment or growth of microbes on a substrate.
  • microbe as used in the present specification and claims includes algae, fungi, biofilm, insects, fouling organisms (including both hard and soft fouling organisms), or any organism that can attach to, grow on, or damage materials such as wood, concrete, paper, plastic, and the like.
  • copper free or low copper content means that the compositions do not contain copper or contain copper at a total weight percent of less than 3% by weight, based on the total weight of formulation.
  • wood products as used in the present specification and claims includes materials that contain or are derived from wood, including, but not limited to, particle board, chipboard, plywood, wafer board, wood laminated material, pressed wood, and the like.
  • one aspect of the present invention is a biocidal composition
  • a biocidal composition comprising one or more pyrithione compounds and one or more pyrrole compounds according to Formula (I) as described above.
  • pyrithione compounds and one or more pyrrole compounds according to Formula (I) as described above.
  • Pyrithiones in general are widely known and frequently used in a variety of applications including paint and personal care products. Pyrithiones are excellent biocides, and can be found in antifouling marine paint. Additionally, metal salts of pyrithione including tin, cadmium and zirconium, are suitable for use in shampoo.
  • the pyrithione in the biocidal composition are compounds with the following basic structure:
  • Pyrithione compounds suitable for use in the present invention include zinc pyrithione, copper pyrithione, sodium Omadine®, pyridine-N-oxide disulfide, Omadine® disulfide, 2,2′-dithio-pyridine-1,1-dioxide, or pyridine-2-thione-N-oxide.
  • Such pyrithione compounds have excellent biocidal effects. Zinc and copper pyrithione are most preferable because of the low soluable in salt water therefore making it more durable than other pyrithione salts.
  • the zinc and copper pyrithione compounds can be prepared by methods described in U.S. Pat. No. 2,809,971 to Berstein et al. Other patents disclosing similar compounds and processes for making them include U.S. Pat. Nos. 2,786,847; 3,589,999; and 3,773,770.
  • the biocidal composition of the present invention comprises one or more pyrrole compounds of Formula (I) as shown above.
  • the pyrrole compounds are 2-trihalogenomethyl-3-halogeno-4-cyano pyrrole derivatives substituted in position 5 and optionally in position 1, the halogens in positions 2 and 3 being independently selected from the group consisting of fluorine, chlorine and bromine, the substituent in position 5 being selected from the group consisting of C1-8 alkyl, C1-8 monohalogenoalkyl, C5-6 cycloalkyl, C5-6 monohalogenocycloalkyl, benzyl, phenyl, mono- and di-halogenobenzyl, mono- and dihalogenophenyl, mono- and di-C1-4 alkyl benzyl, mono- and di-C1-4 alkyl phenyl, monohalogeno mono-C1-4-alkyl benzyl and monohalogeno mono-C1-4-alkyl phenyl, any hal
  • 2-arylpyrrole compounds suitable for use in the methods and composition of the invention are: 4,5-dichloro-2-(alpha, alpha, alpha-trifluoro-p-tolyl)pyrrole-3-carbonitrile; 4-bromo-5-chloro-2-(p-chlorophenyl)pyrrole-3-carbonitrile; 4-bromo-2-(p-chlorophenyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile; 3,4-dichloro-2-(3,4-dichlorophenyl)pyrrole-5-carbonitrile; 4-chloro-2-(p-chlorophenyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile; 4,5-dibromo-2-(p-chlorophenyl)-3-(trifluoromethylsulfonyl)pyrrole; 4-bromo-2-(3,5-dichlorophenyl)-5-(trifluoromethyl)pyr
  • the pyrithione compounds and the compounds of Formula (I) are preferably present in the biocidal composition in a weight ratio of 9:1 to 1:9. More preferably, the pyrithione compounds and compounds of Formula (I) are present in the biocidal composition in a weight ratio of 3:2 to 2:3. Most preferably, the pyrithione compounds and the compounds of Formula (I) are present in the biocidal composition in a weight ratio of 3:1 to 1:3.
  • Another aspect of the invention comprises a coating composition that contains the above biocidal composition.
  • the biocidal composition is present in the coating composition in an effective biocidal amount.
  • the effective biocidal amount is between 1%-15% by weight, based on the total weight of the coating composition.
  • the biocidal composition is present in an amount between 1% and 15% by weight, based on the total weight of the coating composition.
  • the biocidal composition is present in an amount between 1% and 10% by weight, based on the total weight of the coating composition.
  • the biocidal composition is present in an amount between 3% and 8% by weight, based on the total weight of the coating composition.
  • the coating composition may also include additives.
  • additives may include, but are not limited to, organic binding agents; processing additives; fixatives such as polyvinyl alcohol; plasticizers; UV stabilizers; dyes; color pigments; anti-settling agents; antifoaming agents; additional insecticides such as chlorinated hydrocarbons, organophosphates and, the like; additional fungicides and bactericides such as alcohols, aldehydes, formaldehyde releasing compounds, and the like; phenols; organic acids such as propionic acid, benzoic acids and the like; inorganic acids such as boric acid; amides; azoles; heterocyclic compounds; N-haloalkylthio compounds; and the like.
  • Acrylic polymers such as acrylic polymers or acrylic co-polymers, that are self-polishing for use in, for example, marine antifouling coatings may also be employed. Preferably, these polymers are free of tin.
  • acrylic polymers and copolymers that may be implemented in the composition of the invention include copper acrylate polymer or co-polymer, zinc acrylate polymer or co-polymer, silyl acrylate polymer or co-polymer, and the like. Additional polymers known in the paint and coating arts may also be employed in the composition of the invention.
  • the additives present in the coating composition will depend on the preferences of the user or manufacturer as well as the end use of the coating composition.
  • the coating composition is formed by combining the biocidal composition and additives into a paint base material, such as a marine paint base.
  • a paint base material such as a marine paint base.
  • Methods of forming such a coating composition are well known in the art. Examples of such methods include, but are not limited to combining the biocidal composition and the additives in a blending mechanism. The blending mechanism would evenly disperse the biocidal composition throughout the additives. Additional methods of forming the coating composition can be used as known to those skilled in the art.
  • any base paint material that is suitable for marine applications including water or solvent-based formulations, may be used in the coating composition of the invention.
  • Such marine paints are known in the art, as shown, for example, in U.S. Pat. Nos. 6,710,117; 4,981,946; 4,426,464; 4,407,997; and 4,021,392.
  • the coating composition can take a variety of forms. Those forms include, but are not limited to paint, (especially anti-fouling paint), varnish, lacquer, a wash, a wood sealant, or any form that may be used to coat the material.
  • Another aspect of the invention comprises a method comprising applying the coating composition described above to material being sought to protect.
  • the coating composition may be applied in a variety of manners that include, but are not limited to brushing on, spraying on, sponging on, atomizing on, or dipping, immersing, or soaking the material in.
  • the coating composition is applied in an even fashion to the material.
  • it should be allowed to dry to ensure proper adhesion to the material. Drying can be accomplished by exposure to the air, or by using a mechanism that allows for faster drying such as heat lamps, or a hot air generator.
  • Material that can be protected by the coating composition includes wood, leather, vinyl, plastic, concrete, plaster, paper, and any other material that may be exposed to microbes or to water containing such microbes. Ideally, the material should be porous enough to allow the coating composition to penetrate and adhere to the material.
  • the coated substrate comprises a material as described above that has been coated with the coating composition.
  • Substrates that would benefit the most from application of the coating composition include traditional marine substrates such as ship hulls, docks, piers, buoys, fishing gear, fishnets, lobster traps, bridges, and pilings.
  • substrates coated with the coating composition may also include concrete, wallboard, decks, siding, or any other substrate that is in constant or frequent contact with water or microbes.
  • the substrate is expected to exhibit biocidal properties when it is coated with the coating composition.
  • the biocidal properties will prevent, inhibit, or treat attachment or growth of microbes on or in the substrate. Prevention or treatment of such growth will allow the substrate to be microbe free. In addition to the substrate being visually appealing, being microbe free will allow it to be used in the manner it was intended to be used.
  • wood or wood products that are coated with the coating composition will exhibit resistance to microbes.
  • Application of the coating composition to wood and wood products is expected to prevent microbes such as fungi, algae, termites, and the like from destroying the visual appeal and use of the wood and wood products.
  • Commercial and residential products and structures that would benefit from such application include staircases, floors, cabinets, decks, piers, shingles, pilings, fences, furniture, mailboxes, and the like.
  • a series of nine paint formulations containing 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile (referred to in below table as Pyrrole) and zinc pyrithione (ZPT) were tested by Duke University off the Beaufort, N.C. coast in 2004 for their antifouling effectiveness against barnacles and other fouling organisms.
  • the formulations were created in the laboratory by the addition of various amounts of biocides to a resin base-formulation (vinyl resin/wood rosin with Zn oxide filler).
  • Formulations include 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile alone and in combination with ZPT.
  • a solvent based zinc oxide coating was used as a control.
  • Unprimed fiberglass rods (8 mm diameter ⁇ 11 cm length) were dip-coated with each formulation (5 rods/formulation) and suspended from a test rack in the ocean (one-meter below the surface). Rods were evaluated each month for number of barnacles and bryozoans. The most promising results came from the formulations in which 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile was blended with ZPT (See Table 1 below).
  • Bryozoans are highly complex colonial animals constructed of individual “zooids”, all connected by living tissue. The zooids are protected within a cup- or box-shaped exoskeleton of calcified chitinous tissue. The degree of calcification governs how rigid or flexible is the overall structure. Bryozoans are eaten by a variety of grazing animals, such as sea urchins and various molluscs.

Landscapes

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

Abstract

The present invention is directed to a biocidal composition comprising a blend of one or more pyrithione compounds, and one or more pyrrole compounds of Formula I wherein said biocidal composition is copper free or low copper content.

Description

    BACKGROUND OF THE INVENTION
  • 1. Field of the Invention
  • This invention relates to a biocidal composition. More particularly, this invention relates to a biocidal composition comprising a blend of at least one selected pyrithione compounds and at least one selected pyrrole derivatives that prevent, or inhibit growth of microbes and the method of using such biocidal composition.
  • 2. Brief Description of Art
  • Many compositions and formulations are known in the art for the prevention, inhibition, and treatment of growth or infestation of microbes. Likewise, there are many compositions and coatings specifically formulated for the prevention, inhibition, and treatment of growth or infestation of fouling organisms.
  • Fouling organisms present a large problem for substrates and objects that are exposed to water. The term “fouling organism” includes both hard and soft fouling organisms. Hard fouling organisms include barnacles, mollusks, and the like, while soft fouling organisms include algae, fungi, and the organisms listed in U.S. Pat. No. 5,712,275, which is incorporated by reference herein. Such organisms present a constant problem for objects and substrates that are exposed to marine water, fresh water, brackish water, sewage water, waste water, rain water, and the like.
  • Fouling organisms grow on, infest, or adhere to various kinds of substrates and objects that are exposed to any type of water. Growth or infestation of fouling organisms on surfaces is visually unappealing. Additionally, growth may cause some problems in using the substrates and objects that fouling organisms have attached or infested. For example, one problem that occurs frequently is the attachment of hard fouling organisms to a ship hull. The organisms cause the surface of the ship to become rough, thereby reducing the ship's speed.
  • Additionally, wood and wood products often experience growth and infestation of microbes such as fouling organisms, termites and the like. Growth and infestation of such microbes leads to warping, cracking, and deterioration of the wood and wood products. Consequently the wood and wood products lose value, visual appeal, and usefulness.
  • To combat this problem, coatings comprising biocides were developed. Examples of biocides found useful include tributylin compounds, pyrithione compounds, oxathiazine compounds, pyrrole compounds, triphenylboron compounds and terbutyn.
  • Pyrithione compounds and select pyrrole compounds are separately known and used as biocidal or antifouling agents. However, it is not known in the art, nor is it obvious to combine the two compounds. Examples of prior art references teaching the use of pyrithione compounds and selected pyrrole compounds include the following:
  • U.S. Pat. No. 5,057,153 to Ruggiero relates to an improved paint or paint base composition characterized by enhanced biocidal efficacy. The paint contains a biocide comprising pyrithione salt and a copper salt. Additionally, in U.S. Pat. No. 5,246,489 to Farmer Jr. et al. a process for generating copper pyrithione biocide in-situ in a paint formulation is disclosed. The paint and paint bases of this patent comprise pyrithione compounds as the only biocide present in the formulation.
  • U.S. Pat. No. 5,098,473 to Hani et al. relates to paints and paint bases, and more specifically to a process for providing a stable gel-free dispersion of zinc pyrithione plus cuprous oxide biocide in paint (see also U.S. Pat. Nos. 5,098,473; 5,112,397; 5,137,569; 5,185,033; 5,232,493; 5,298,061; 5,342,437; PCT Patent Application No. WO 95/10568 and EP 0610251).
  • U.S. Pat. No. 4,957,658 to French et al. related to paint and paint bases and more specifically to a process and composition for providing reduced discoloration of paints and paint bases containing a pyrithione and ferric ion.
  • U.S. Pat. No. 4,399,130 to Davidson et al. describes a method using an effective amount of at least one metallic salt of pyridine-2-thione-N-oxide to treat or prevent swine exudate epidermitis.
  • U.S. Pat. No. 4,496,559 to Henderson et al. describes selected derivatives of 2-selenopyridine-N-oxide for use as fungicides and bactericides.
  • U.S. Pat. No. 4,565,856 to Trotz et al. relates to pyrithione-containing polymers. The polymers described in this patent are used as biocides in paints and wood preservative products.
  • U.S. Pat. No. 4,610,993 to Wedy et al. describes a method of administering an effective mount of at least one selected pyridine-N-oxide disulfide compound to treat or prevent bovine mastitis.
  • European patent number EP 0746979 describes a method for controlling or combating the attachment of a fouling organism to an underwater surface by contacting the organism with an antifouling-effective amount of a 2-arylpyrrole compound.
  • U.S. Pat. No. 6,069,189 to Kramer et al., describes antifouling paints that contain selected pyrrole derivatives. Specific pyrrole compounds incorporated into the antifouling paint include 2-trihalogenomethyl-3-halogeno-4-cyano pyrrole and derivatives thereof. Kramer et al. found these compounds to be particularly effective against barnacle infestation. Additionally, this Kramer et al. reference found that bright or light colored anti-fouling paint could be created despite the addition of these compounds.
  • PCT Patent Application No. WO 03/039256 describes an antifouling composition that comprises an amount of at least 3.5 wt. % based on the total weight of the dry mass of the composition of 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, or a salt thereof together with another biocide. The other biocide is selected from bethoxazin, tolylfluanide, dichlofuanide, or DCOIT.
  • Despite the advances made in the art, what is still needed is a coating that comprises an biocidal composition that would be effective against a large spectrum of microbes, and also demonstrates high durability and low toxicity. Ideally, the coating and the composition would be easily and inexpensively produced. This invention is believed to be an answer to the above discussed problems.
    • BRIEF SUMMARY OF THE INVENTION
  • Therefore, one aspect of the present invention is directed to a biocidal composition comprising one or more pyrithione compounds, and one or more pyrrole compounds of Formula I:
  • Figure US20110144232A1-20110616-C00001
  • wherein X is halogen, CN, NO2 or S(O)nR1; Y is hydrogen, halogen or S(O)nR1; Z is halogen, C1-C4haloalkyl or S(O)nR1; n is an integer of 0, 1 or 2; R1 is C1-C4haloalkyl; L is hydrogen or halogen; M and Q are each independently hydrogen, halogen, C1-C4allyl, C1-C4haloalkyl, Cr C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, CN, NO2, R2CO or NR3R4, or when M and Q are on adjacent positions and are taken together with the carbon atoms to which they are attached MQ represents the structure —OCH2O—, —OCF2O—, or —CH═CH—CH═CH—; R is hydrogen, C1-C4alkoxyalkyl, C1-C4alkylthioalkyl or R6CO; R2 is C1-C4haloalkyl, C1-C4alkoxy or NR3R4; R3 is hydrogen or C1-C4alkyl; R4 is hydrogen, C1-C4alkyl or R5CO; R5 is hydrogen or C1-C4alkyl; and R6 is C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C2-C6 alkenyloxy, C1-C4haloalkoxy, phenyl optionally substituted with one to three C1-C4alkyl groups, benzyl, phenoxy, benzyloxy, C1-C4alkylcarbonyloxy, C3-C6cycloalkyl, naphthyl, pyridyl, thienyl or furanyl, wherein said biocidal composition is copper free or low copper content.
  • As defined herein, the term halogen designates Cl, Br, I or F, and the term haloalkyl designates any alkyl group CnH2n+1 having from 1 halogen atom to 2n+1 halogen atoms wherein the halogen atoms are the same or different.
  • Another aspect of the present invention is directed to a coating composition comprising an effective biocidal amount of a biocidal composition comprising one or more pyrithione compounds and one or more pyrrole compounds of Formula (I) as described above wherein said biocidal composition is copper free or low copper content.
  • Still another aspect of the present invention is directed to a method of coating a substrate comprising applying a coating composition that contains a biocidal composition comprised of one or more pyrithione compounds and one or more pyrrole compounds of Formula (I) as described above, to the substrate and drying the coating composition on the substrate.
  • Yet another aspect of the present invention is directed to a coated substrate comprising the coating composition that contains a biocidal composition of the present invention and a substrate, wherein said substrate is selected from a group consisting of wood, plastic, leather, vinyl and metal.
  • One expected advantage of the present invention includes increased protection against a large spectrum of microbes. Another expected advantage of the present invention includes preservation of wood and wood-products. Additionally, it is expected that the present invention will be long-lasting, have low toxicity, and be easily and inexpensively produced.
    • DETAILED DESCRIPTION OF THE INVENTION
  • The term “an effective biocidal amount” as used in the present specification and claims relates to the amount of the biocidal composition that has a positive effect on reducing, eliminating, or preventing attachment or growth of microbes on a substrate.
  • The term “microbe” as used in the present specification and claims includes algae, fungi, biofilm, insects, fouling organisms (including both hard and soft fouling organisms), or any organism that can attach to, grow on, or damage materials such as wood, concrete, paper, plastic, and the like.
  • The term “copper free or low copper content” as used in the present specification and claims means that the compositions do not contain copper or contain copper at a total weight percent of less than 3% by weight, based on the total weight of formulation.
  • The term “wood products” as used in the present specification and claims includes materials that contain or are derived from wood, including, but not limited to, particle board, chipboard, plywood, wafer board, wood laminated material, pressed wood, and the like.
  • As indicated above, one aspect of the present invention is a biocidal composition comprising one or more pyrithione compounds and one or more pyrrole compounds according to Formula (I) as described above. Each of these components is discussed in more detail below.
  • Pyrithiones in general are widely known and frequently used in a variety of applications including paint and personal care products. Pyrithiones are excellent biocides, and can be found in antifouling marine paint. Additionally, metal salts of pyrithione including tin, cadmium and zirconium, are suitable for use in shampoo.
  • Preferably, the pyrithione in the biocidal composition are compounds with the following basic structure:
  • Figure US20110144232A1-20110616-C00002
  • Pyrithione compounds suitable for use in the present invention include zinc pyrithione, copper pyrithione, sodium Omadine®, pyridine-N-oxide disulfide, Omadine® disulfide, 2,2′-dithio-pyridine-1,1-dioxide, or pyridine-2-thione-N-oxide. Such pyrithione compounds have excellent biocidal effects. Zinc and copper pyrithione are most preferable because of the low soluable in salt water therefore making it more durable than other pyrithione salts.
  • The zinc and copper pyrithione compounds can be prepared by methods described in U.S. Pat. No. 2,809,971 to Berstein et al. Other patents disclosing similar compounds and processes for making them include U.S. Pat. Nos. 2,786,847; 3,589,999; and 3,773,770.
  • Additionally, the biocidal composition of the present invention comprises one or more pyrrole compounds of Formula (I) as shown above. Preferably, the pyrrole compounds are 2-trihalogenomethyl-3-halogeno-4-cyano pyrrole derivatives substituted in position 5 and optionally in position 1, the halogens in positions 2 and 3 being independently selected from the group consisting of fluorine, chlorine and bromine, the substituent in position 5 being selected from the group consisting of C1-8 alkyl, C1-8 monohalogenoalkyl, C5-6 cycloalkyl, C5-6 monohalogenocycloalkyl, benzyl, phenyl, mono- and di-halogenobenzyl, mono- and dihalogenophenyl, mono- and di-C1-4 alkyl benzyl, mono- and di-C1-4 alkyl phenyl, monohalogeno mono-C1-4-alkyl benzyl and monohalogeno mono-C1-4-alkyl phenyl, any halogen on the substituent in position 5 being selected from the group consisting of chlorine and bromine, the optional substituent in position 1 being selected from C1-4 alkyl and C1-4 alkoxy C1-4 alkyl. Among the 2-arylpyrrole compounds suitable for use in the methods and composition of the invention are: 4,5-dichloro-2-(alpha, alpha, alpha-trifluoro-p-tolyl)pyrrole-3-carbonitrile; 4-bromo-5-chloro-2-(p-chlorophenyl)pyrrole-3-carbonitrile; 4-bromo-2-(p-chlorophenyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile; 3,4-dichloro-2-(3,4-dichlorophenyl)pyrrole-5-carbonitrile; 4-chloro-2-(p-chlorophenyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile; 4,5-dibromo-2-(p-chlorophenyl)-3-(trifluoromethylsulfonyl)pyrrole; 4-bromo-2-(3,5-dichlorophenyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile; 2-(p-chlorophenyl)-5-(trifluoromethyl)-4-(trifluoromethylthio)pyrrole-3-carbonitrile; 4-bromo-2-(2,3,4-trichlorophenyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile; 4-bromo-2-(2,3,5-trichlorophenyl)-5-(trifluoromethyl)-pyrrole-3-carbonitrile; 4-bromo-2-(p-chlorophenyl)-5-(alpha, alpha, beta, beta-tetrafluoroethylthio)pyrrole-3-carbonitrile; 4-bromo-2-(m-fluorophenyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile; 2-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4-(trifluoromethylthio)pyrrole-3-carbonitrile; and 4-bromo-2-(p-chlorophenyl)-5-[(beta-bromo-beta, alpha, alpha-trifluoro)-ethylthio]pyrrole-3-carbonitrile. Most preferably, Formula (I) is 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile.
  • The compounds of Formula (I) as discussed above can be prepared by methods described in U.S. Pat. Nos. 5,310,938 and 5,328,928.
  • To ensure biocidal effectiveness, the pyrithione compounds and the compounds of Formula (I) are preferably present in the biocidal composition in a weight ratio of 9:1 to 1:9. More preferably, the pyrithione compounds and compounds of Formula (I) are present in the biocidal composition in a weight ratio of 3:2 to 2:3. Most preferably, the pyrithione compounds and the compounds of Formula (I) are present in the biocidal composition in a weight ratio of 3:1 to 1:3.
  • Another aspect of the invention comprises a coating composition that contains the above biocidal composition. The biocidal composition is present in the coating composition in an effective biocidal amount. The effective biocidal amount is between 1%-15% by weight, based on the total weight of the coating composition. Preferably, the biocidal composition is present in an amount between 1% and 15% by weight, based on the total weight of the coating composition. More preferably, the biocidal composition is present in an amount between 1% and 10% by weight, based on the total weight of the coating composition. Most preferably, the biocidal composition is present in an amount between 3% and 8% by weight, based on the total weight of the coating composition.
  • In addition to the biocidal composition, the coating composition may also include additives. Such additives may include, but are not limited to, organic binding agents; processing additives; fixatives such as polyvinyl alcohol; plasticizers; UV stabilizers; dyes; color pigments; anti-settling agents; antifoaming agents; additional insecticides such as chlorinated hydrocarbons, organophosphates and, the like; additional fungicides and bactericides such as alcohols, aldehydes, formaldehyde releasing compounds, and the like; phenols; organic acids such as propionic acid, benzoic acids and the like; inorganic acids such as boric acid; amides; azoles; heterocyclic compounds; N-haloalkylthio compounds; and the like. Polymers, such as acrylic polymers or acrylic co-polymers, that are self-polishing for use in, for example, marine antifouling coatings may also be employed. Preferably, these polymers are free of tin. Examples of acrylic polymers and copolymers that may be implemented in the composition of the invention include copper acrylate polymer or co-polymer, zinc acrylate polymer or co-polymer, silyl acrylate polymer or co-polymer, and the like. Additional polymers known in the paint and coating arts may also be employed in the composition of the invention. The additives present in the coating composition will depend on the preferences of the user or manufacturer as well as the end use of the coating composition.
  • The coating composition is formed by combining the biocidal composition and additives into a paint base material, such as a marine paint base. Methods of forming such a coating composition are well known in the art. Examples of such methods include, but are not limited to combining the biocidal composition and the additives in a blending mechanism. The blending mechanism would evenly disperse the biocidal composition throughout the additives. Additional methods of forming the coating composition can be used as known to those skilled in the art. In addition, any base paint material that is suitable for marine applications, including water or solvent-based formulations, may be used in the coating composition of the invention. Such marine paints are known in the art, as shown, for example, in U.S. Pat. Nos. 6,710,117; 4,981,946; 4,426,464; 4,407,997; and 4,021,392.
  • The coating composition can take a variety of forms. Those forms include, but are not limited to paint, (especially anti-fouling paint), varnish, lacquer, a wash, a wood sealant, or any form that may be used to coat the material.
  • Another aspect of the invention comprises a method comprising applying the coating composition described above to material being sought to protect. The coating composition may be applied in a variety of manners that include, but are not limited to brushing on, spraying on, sponging on, atomizing on, or dipping, immersing, or soaking the material in. Preferably the coating composition is applied in an even fashion to the material. Once the coating composition is applied to the material, it should be allowed to dry to ensure proper adhesion to the material. Drying can be accomplished by exposure to the air, or by using a mechanism that allows for faster drying such as heat lamps, or a hot air generator.
  • Material that can be protected by the coating composition includes wood, leather, vinyl, plastic, concrete, plaster, paper, and any other material that may be exposed to microbes or to water containing such microbes. Ideally, the material should be porous enough to allow the coating composition to penetrate and adhere to the material.
  • Another aspect of the invention comprises a coated substrate. The coated substrate comprises a material as described above that has been coated with the coating composition. Substrates that would benefit the most from application of the coating composition include traditional marine substrates such as ship hulls, docks, piers, buoys, fishing gear, fishnets, lobster traps, bridges, and pilings. However, substrates coated with the coating composition may also include concrete, wallboard, decks, siding, or any other substrate that is in constant or frequent contact with water or microbes.
  • The substrate is expected to exhibit biocidal properties when it is coated with the coating composition. The biocidal properties will prevent, inhibit, or treat attachment or growth of microbes on or in the substrate. Prevention or treatment of such growth will allow the substrate to be microbe free. In addition to the substrate being visually appealing, being microbe free will allow it to be used in the manner it was intended to be used.
  • Additionally, it is expected that wood or wood products that are coated with the coating composition will exhibit resistance to microbes. Application of the coating composition to wood and wood products is expected to prevent microbes such as fungi, algae, termites, and the like from destroying the visual appeal and use of the wood and wood products. Commercial and residential products and structures that would benefit from such application include staircases, floors, cabinets, decks, piers, shingles, pilings, fences, furniture, mailboxes, and the like.
    • Examples
  • The following Examples further illustrate the present invention. All parts and percentages are by weight unless explicitly stated otherwise. All temperatures are degrees Celsius unless explicitly stated otherwise.
    • Paint Efficacy Testing
  • A series of nine paint formulations containing 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile (referred to in below table as Pyrrole) and zinc pyrithione (ZPT) were tested by Duke University off the Beaufort, N.C. coast in 2004 for their antifouling effectiveness against barnacles and other fouling organisms. The formulations were created in the laboratory by the addition of various amounts of biocides to a resin base-formulation (vinyl resin/wood rosin with Zn oxide filler). Formulations include 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile alone and in combination with ZPT. A solvent based zinc oxide coating was used as a control. Unprimed fiberglass rods (8 mm diameter×11 cm length) were dip-coated with each formulation (5 rods/formulation) and suspended from a test rack in the ocean (one-meter below the surface). Rods were evaluated each month for number of barnacles and bryozoans. The most promising results came from the formulations in which 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile was blended with ZPT (See Table 1 below).
  • Bryozoans are highly complex colonial animals constructed of individual “zooids”, all connected by living tissue. The zooids are protected within a cup- or box-shaped exoskeleton of calcified chitinous tissue. The degree of calcification governs how rigid or flexible is the overall structure. Bryozoans are eaten by a variety of grazing animals, such as sea urchins and various molluscs.
  • The study confirms that 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile is an effective antifouling agent for hard fouling organisms such as barnacles, that it is compatible with ZPT, and that it performs better with ZPT as a co-biocide than it does alone.
  • TABLE 1
    2 months Average 3 months Average 4 months Average 5 months Average
    DATES Jul. 16, 2004 Aug. 13, 2004 Sep. 15, 2004 Oct. 13, 2004
    ROD # of # of # of # of
    CODE # Bryozoans BARNACLES BARNACLES Bryozoans BARNACLES Bryozoans BARNACLES
    CONTROL - 1 7.8 18.2 0 14 4 14.5 M M
    No Biocide
    8% Pyrrole 2 0.4 1 0 4 2.2 8.6 M 1
    Biocide
    6% Pyrrole 3 0.4 1.4 0 7 0.6 5.6 0.2 0.8
    Biocide
    4% Pyrrole 4 0 0.8 0 5.6 0.4 4 0.4 1.6
    Biocide
    5% Pyrrole 5 0 0.4 0 1 0 3.4 0 0.8
    4% ZPT
    5% Pyrrole 6 0 0.6 0 1.8 0 1.4 0 0.4
    2% ZPT
    2% Pyrrole 7 0 1 0 16 0 3.2 0.2 1.2
    2% Pyrrole 8 0 0.2 0 12.2 0.4 4.4 0 2
    4% ZPT
    2% Pyrrole 9 0 0.8 0 9.4 0 3.8 0 1.2
    2% ZPT
    Notes:
    “M” refers to a mature fouling community. The growth cycle of certain marine organisms can cause a difference in the average number per month reading in the above table.
  • While the invention has been described above with reference to specific embodiments thereof, it is apparent that many changes, modifications, and variations can be made without departing from the inventive concept disclosed herein. Accordingly, it is intended to embrace all such changes, modifications and variations that fall within the spirit and broad scope of the appended claims. All patent applications, patents and other publications cited herein are incorporated by reference in their entireties.

Claims (21)

1-31. (canceled)
32. A biocidal composition comprising:
A.) a pyrithione compound being copper pyrithione and
B.) one or more pyrrole compounds of Formula (I):
Figure US20110144232A1-20110616-C00003
wherein X is halogen, CN, NO2 or S(O)nR1; Y is hydrogen, halogen or S(O)nR1; Z is halogen, C1-C4haloalkyl or S(O)nR1; n is an integer of 0, 1 or 2; R1 is C1-C4haloalkyl; L is hydrogen or halogen; M and Q are each independently hydrogen, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, CN, NO2, R2CO or NR3R4, or when M and Q are on adjacent positions and are taken together with the carbon atoms to which they are attached MQ represents the structure —OCH2O—, —OCF2O—, or —CH═CH—CH═CH—; R is hydrogen, C1-C4alkoxyalkyl, C1-C4alkylthioalkyl or R6CO; R2 is C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or NR3R4; R3 is hydrogen or C1-C4alkyl; R4 is hydrogen, C1-C4alkyl or R5CO; R5 is hydrogen or C1-C4alkyl; and R6 is C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C2-C6 alkenyloxy, C1-C4haloalkoxy, phenyl optionally substituted with one to three C1-C4alkyl groups, benzyl, phenoxy, benzyloxy, C1-C4alkylcarbonyloxy, C3-C6cycloalkyl, naphthyl, pyridyl, thienyl or furanyl; and
wherein said biocidal composition is low copper content.
33. The biocidal composition of claim 32, wherein said pyrrole compound of Formula (I) is selected from a group consisting of 2-trihalogenomethyl-3-halogeno-4-cyano pyrrole derivative substituted in position 5 and optionally in position 1, the halogens in positions 2 and 3 being independently selected from the group consisting of fluorine, chlorine and bromine, the substituent in position 5 being selected from the group consisting of phenyl, mono- and dihalogenophenyl, mono- and di-C1-4 alkyl phenyl, and monohalogeno mono-C1-4-alkyl phenyl, any halogen on the substituent in position 5 being selected from the group consisting of chlorine and bromine, the optional substituent in position 1 being selected from C1-4 alkyl and C1-4 alkoxy C1-4 alkyl.
34. The biocidal composition of claim 32, wherein said pyrrole compound is 2-trihalogenomethyl-3-halogeno-4-cyano-5-(p-chlorophenyl)pyrrole.
35. The biocidal composition of claim 32, wherein the pyrithione compound and said compound of formula I are present in a weight ratio of 9:1 to 1:9.
36. The biocidal composition of claim 32, wherein the pyrithione compound and said pyrrole compound of Formula I are present in a weight ratio of 3:2 to 2:3.
37. The biocidal composition of claim 32, wherein the pyrithione compound and said pyrrole compound of Formula I are present in a weight ratio of 3:1 to 1:3.
38. The biocidal composition of claim 32, further comprising at least one acrylic polymer or co-polymer selected from the group consisting of copper acrylate polymer or co-polymer, zinc acrylate polymer or co-polymer, silyl acrylate polymer or co-polymer, and combinations thereof.
39. A coating composition comprising an effective biocidal amount of a biocidal composition comprising:
A) a pyrithione compound being copper pyrithione; and
B) one or more pyrrole compounds of Formula (I):
Figure US20110144232A1-20110616-C00004
wherein X is halogen, CN, NO2 or S(O)nR1; Y is hydrogen, halogen or S(O)nR1; Z is halogen, C1-C4haloalkyl or S(O)nR1; n is an integer of 0, 1 or 2; R1 is C1-C4haloalkyl; L is hydrogen or halogen; M and Q are each independently hydrogen, halogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, CN, NO2, R2CO or NR3R4, or when M and Q are on adjacent positions and are taken together with the carbon atoms to which they are attached MQ represents the structure —OCH2O—, —OCF2O—, or —CH═CH—CH═CH—; R is hydrogen, C1-C4alkoxyalkyl, C1-C4alkylthioalkyl or R6CO; R2 is C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy or NR3R4; R3 is hydrogen or C1-C4alkyl; R4 is hydrogen, C1-C4alkyl or R5CO; R5 is hydrogen or C1-C4alkyl; and R6 is C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C2-C6 alkenyloxy, C1-C4haloalkoxy, phenyl optionally substituted with one to three C1-C4alkyl groups, benzyl, phenoxy, benzyloxy, C1-C4alkylcarbonyloxy, C3-C6cycloalkyl, naphthyl, pyridyl, thienyl or furanyl; and
wherein said biocidal composition is low copper content.
40. The coating composition of claim 39, wherein said pyrrole compound of Formula (I) is 2-trihalogenomethyl-3-halogeno-4-cyano-5-(p-chlorophenyl)pyrrole.
41. The coating composition of claim 39, wherein the effective biocidal amount is between 1% and 15% by weight, based on the total weight of said coating composition.
42. The coating composition of claim 39, wherein the effective biocidal amount is between 2% and 10% by weight, based on the total weight of said coating composition.
43. The coating composition of claim 42, wherein the effective biocidal amount is between 3% and 8% by weight, based on the total weight of said coating composition.
44. The coating composition of claim 42, wherein the pyrithione compound and said compound of formula I are present in a weight ratio of 9:1 to 1:9.
45. The coating composition of claim 42, wherein the pyrithione compound and said pyrrole compound of Formula I are present in a weight ratio of 3:2 to 2:3.
46. The coating composition of claim 42, wherein the pyrithione compound and said pyrrole compound of Formula I are present in a weight ratio of 3:1 to 1:3.
47. The coating composition of claim 42, wherein said coating composition is paint.
48. The coating composition of claim 42, wherein said coating composition is a varnish.
49. The coating composition of claim 42, wherein said coating composition is a lacquer.
50. The coating composition of claim 42, wherein said coating composition is a wood sealant.
51. The coating composition of claim 42, further comprising at least one acrylic polymer or co-polymer selected from the group consisting of copper acrylate polymer or co-polymer, zinc acrylate polymer or co-polymer, silyl acrylate polymer or co-polymer, and combinations thereof.
US12/930,458 2006-03-03 2011-01-07 Biocide composition comprising pyrithione and pyrrole derivatives Abandoned US20110144232A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US12/930,458 US20110144232A1 (en) 2006-03-03 2011-01-07 Biocide composition comprising pyrithione and pyrrole derivatives

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11/368,244 US7893047B2 (en) 2006-03-03 2006-03-03 Biocide composition comprising pyrithione and pyrrole derivatives
US12/930,458 US20110144232A1 (en) 2006-03-03 2011-01-07 Biocide composition comprising pyrithione and pyrrole derivatives

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US11/368,244 Continuation US7893047B2 (en) 2006-03-03 2006-03-03 Biocide composition comprising pyrithione and pyrrole derivatives

Publications (1)

Publication Number Publication Date
US20110144232A1 true US20110144232A1 (en) 2011-06-16

Family

ID=38471723

Family Applications (4)

Application Number Title Priority Date Filing Date
US11/368,244 Active 2027-10-22 US7893047B2 (en) 2006-03-03 2006-03-03 Biocide composition comprising pyrithione and pyrrole derivatives
US12/928,983 Active 2026-05-03 US8481523B2 (en) 2006-03-03 2010-12-22 Biocide composition comprising pyrithione and pyrrole derivatives
US12/930,419 Expired - Fee Related US8372829B2 (en) 2006-03-03 2011-01-06 Biocide composition comprising pyrithione and pyrrole derivatives
US12/930,458 Abandoned US20110144232A1 (en) 2006-03-03 2011-01-07 Biocide composition comprising pyrithione and pyrrole derivatives

Family Applications Before (3)

Application Number Title Priority Date Filing Date
US11/368,244 Active 2027-10-22 US7893047B2 (en) 2006-03-03 2006-03-03 Biocide composition comprising pyrithione and pyrrole derivatives
US12/928,983 Active 2026-05-03 US8481523B2 (en) 2006-03-03 2010-12-22 Biocide composition comprising pyrithione and pyrrole derivatives
US12/930,419 Expired - Fee Related US8372829B2 (en) 2006-03-03 2011-01-06 Biocide composition comprising pyrithione and pyrrole derivatives

Country Status (16)

Country Link
US (4) US7893047B2 (en)
EP (2) EP3231283A1 (en)
JP (2) JP2009528356A (en)
KR (3) KR102033921B1 (en)
CN (2) CN101400256A (en)
AU (1) AU2007221987B8 (en)
CA (1) CA2644087C (en)
DK (1) DK1998619T3 (en)
ES (1) ES2636810T3 (en)
HK (1) HK1213738A1 (en)
MY (1) MY145917A (en)
NO (1) NO341341B1 (en)
PL (1) PL1998619T3 (en)
PT (1) PT1998619T (en)
TW (1) TWI394532B (en)
WO (1) WO2007103013A2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104356818A (en) * 2014-12-10 2015-02-18 李永志 Antibacterial coating

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2007211466B2 (en) * 2006-02-01 2012-05-17 Janssen Pharmaceutica N.V. Combinations of 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1h-pyrrole-3-carbonitrile and metal compounds
US7893047B2 (en) 2006-03-03 2011-02-22 Arch Chemicals, Inc. Biocide composition comprising pyrithione and pyrrole derivatives
RU2426313C2 (en) * 2006-04-10 2011-08-20 Янссен Фармацевтика Н.В. Combinations of 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1h-pyrrole-3-carbonitrile and biocidal compounds
JP5432925B2 (en) * 2008-02-06 2014-03-05 ジヤンセン・フアーマシユーチカ・ナームローゼ・フエンノートシヤツプ Combination of phenylpyrrole and pillion compounds
TW201033308A (en) * 2008-12-11 2010-09-16 Janssen Pharmaceutica Nv Antifouling combination comprising 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile
JP2010150355A (en) * 2008-12-25 2010-07-08 Nippon Paint Marine Kk Anti-fouling coating composition, anti-fouling coating film, and method for controlling hydrolysis rate of anti-fouling coating film
US8541493B2 (en) * 2010-02-19 2013-09-24 Arch Chemicals, Inc. Synthesis of zinc acrylate copolymer from acid functional copolymer, zinc pyrithione, and copper compound
KR101464898B1 (en) * 2010-06-17 2014-11-24 닛뽄 페인트 마린 가부시키가이샤 Antifouling material composition, antifouling film, and method for controlling hydrolysis rate of antifouling film
CN102958363B (en) * 2010-07-01 2014-10-29 詹森药业有限公司 Antifouling benzoate combinations
KR20140057609A (en) 2011-08-17 2014-05-13 아크 캐미컬스 인크 Synthesis of copper pyrithione from zinc pyrithione and copper compound
PT3000857T (en) * 2013-05-22 2018-11-05 Chugoku Marine Paints Antifouling paint composition, antifouling paint film, substrate having an antifouling paint film, and production method for said substrate
US10131799B2 (en) 2014-01-16 2018-11-20 Akzo Nobel Coatings International B.V. Antifouling coating composition and its use on man-made structures
KR102626623B1 (en) 2015-04-09 2024-01-17 요툰 에이/에스 Antifouling Composition
CN105123751A (en) * 2015-08-21 2015-12-09 泰兴市和庆机械配件厂 Tropical fish culture fish tank protein insect scavenging agent and preparation method thereof
CN105622598B (en) * 2016-02-26 2017-12-22 河南好年景生物发展有限公司 Aryl-pyrrolidine nitrile compounds and preparation method and purposes and agricultural insecticide and pest control method for desinsection
CN112832028B (en) * 2021-02-05 2023-06-30 浙江红督服饰有限公司 Preparation method of natural antibacterial silk cloth
CN112826156B (en) * 2021-02-05 2023-12-15 江西梦娜袜业有限公司 Preparation method of socks with deodorizing and antibacterial functions

Citations (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2786847A (en) * 1956-07-23 1957-03-26 Reilly Tar & Chem Corp 2-mercapto, alkanol pyridine-nu-oxides
US2809971A (en) * 1955-11-22 1957-10-15 Olin Mathieson Heavy-metal derivatives of 1-hydroxy-2-pyridinethiones and method of preparing same
US3589999A (en) * 1968-10-25 1971-06-29 Ionics Deionization process
US3615744A (en) * 1967-07-03 1971-10-26 Takeda Chemical Industries Ltd Antifouling paints
US3773770A (en) * 1968-09-30 1973-11-20 Procter & Gamble Process for preparing pyridine n-oxide carbanion salts and derivatives thereof
US4021392A (en) * 1974-04-03 1977-05-03 The International Paint Company Limited Marine paint
US4039312A (en) * 1972-07-04 1977-08-02 Marcel Joseph Gaston Patru Bacteriostatic, fungistatic and algicidal compositions, particularly for submarine paints
US4399130A (en) * 1982-02-01 1983-08-16 Olin Corporation Use of metallic salts of pyridine-2-thione-N-oxide to treat or prevent swine exudative epidermitis
US4407997A (en) * 1980-10-29 1983-10-04 The International Paint Company Limited Marine paint
US4426464A (en) * 1981-07-03 1984-01-17 International Paint Public Limited Company Marine paint
US4496559A (en) * 1981-09-02 1985-01-29 Olin Corporation 2-Selenopyridine-N-oxide derivatives and their use as fungicides and bactericides
US4565856A (en) * 1984-10-12 1986-01-21 Olin Corporation Pyrithione-containing bioactive polymers and their use in paint and wood preservative products
US4581351A (en) * 1982-11-23 1986-04-08 Sutton Laboratories, Inc. Composition of matter containing imidazolidinyl urea and pyrithione and its derivatives
US4610993A (en) * 1984-08-08 1986-09-09 Olin Corporation Use of selected pyridine-N-oxide disulfide compounds to treat or prevent bovine mastitis
US4957658A (en) * 1987-08-31 1990-09-18 Olin Corporation Process and composition for providing reduced discoloration caused by the presence of pyrithione and ferric ion in water-based paints and paint bases
US4981946A (en) * 1986-07-28 1991-01-01 Semih Erhan Marine paint composition comprising quinone/polyamine polymer
US5057153A (en) * 1990-05-03 1991-10-15 Olin Corporation Paint containing high levels of a pyrithione salt plus a copper salt
US5098473A (en) * 1991-03-04 1992-03-24 Olin Corporation Process for stabilizing zinc pyrithione plus cuprous oxide in paint
US5112397A (en) * 1991-06-17 1992-05-12 Olin Corporation Process for stabilizing zinc pyrithione plus cuprous oxide in paint
US5137569A (en) * 1991-10-10 1992-08-11 Olin Corporation Process for stabilizing zinc pyrithione plus cuprous oxide in paint
US5185033A (en) * 1992-09-01 1993-02-09 Olin Corporation Gel-free paint containing copper pyrithione or pyrithione disulfide plus cuprous oxide
US5232493A (en) * 1992-09-01 1993-08-03 Olin Corporation Process for stabilizing zinc pyrithione plus cuprous oxide in paint
US5238490A (en) * 1992-09-04 1993-08-24 Olin Corporation Process for generating copper pyrithione in-situ in a paint formulation
US5246489A (en) * 1992-09-04 1993-09-21 Olin Corporation Process for generating copper pyrithione in-situ in a paint formulation
US5298061A (en) * 1993-05-14 1994-03-29 Olin Corporation Gel-free paint containing zinc pyrithione, cuprous oxide, and amine treated rosin
US5310938A (en) * 1987-07-29 1994-05-10 American Cyanamid Company Substituted arylpyrrole compounds
US5328928A (en) * 1990-05-11 1994-07-12 American Cyanamid Company N-acylated arylpyrroles useful as insecticidal, agents
US5342437A (en) * 1993-10-15 1994-08-30 Olin Corporation Gel-free paint containing zinc pyrithione cuprous oxide and carboxylic acid
US5712275A (en) * 1993-08-24 1998-01-27 Janssen Pharmaceutica, N.V. Antibacterial and antifouling oxathiazines and their oxides
US5717007A (en) * 1995-01-26 1998-02-10 Etat Francais As Represented By The Delegue General Pour L'armement Anti-fouling self-polishable paints
US5932520A (en) * 1995-05-23 1999-08-03 American Cyanamid Company Use of pyrrole compounds as antifouling agents
US6069189A (en) * 1996-09-19 2000-05-30 Sigma Coatings, B.V. Light-and bright-colored antifouling paints
US6228382B1 (en) * 1996-12-10 2001-05-08 Etc C.V. Microbiocidal mixtures
WO2003039256A1 (en) * 2001-11-08 2003-05-15 Janssen Pharmaceutica N.V. Synergistic antifouling compositions comprising 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1h-pyrrole-3-carbonitrile
US20030162924A1 (en) * 2000-02-25 2003-08-28 Marcel Vos Metal-free binders for self-polishing antifouling paints
US6710117B2 (en) * 2000-02-25 2004-03-23 Sigma Coatings B.V. Marine paint compositions
US20050065232A1 (en) * 2002-10-23 2005-03-24 Chugoku Marine Paints, Ltd. Antifouling paint composition, antifouling paint films, and, ships, underwater underwater structures, fishing gear and fishing nets covered with the films
US20050123503A1 (en) * 2002-03-15 2005-06-09 Yasuhiro Kozasa Underwater antifouling coating composition with excellent storage stability
US20090017135A1 (en) * 2006-02-01 2009-01-15 Tony Mathilde Jozef Kempen COMBINATION OF 4-BROMO-2-(-4-CHLOROPHENYL)-5-TRIFLUOROMETHYL)-1h- PYRROLE-3-CARBONITRILE AND METAL COMPOUNDS

Family Cites Families (63)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3573975A (en) * 1968-07-10 1971-04-06 Ibm Photochemical fabrication process
JPS5754317A (en) * 1980-09-19 1982-03-31 Hitachi Ltd Method and device for forming pattern
US4346164A (en) * 1980-10-06 1982-08-24 Werner Tabarelli Photolithographic method for the manufacture of integrated circuits
US4509852A (en) * 1980-10-06 1985-04-09 Werner Tabarelli Apparatus for the photolithographic manufacture of integrated circuit elements
US4390273A (en) * 1981-02-17 1983-06-28 Censor Patent-Und Versuchsanstalt Projection mask as well as a method and apparatus for the embedding thereof and projection printing system
JPS57153433A (en) * 1981-03-18 1982-09-22 Hitachi Ltd Manufacturing device for semiconductor
US4929634A (en) * 1987-10-23 1990-05-29 American Cyanamid Company Method of and bait compositions for controlling mollusks
US5040020A (en) * 1988-03-31 1991-08-13 Cornell Research Foundation, Inc. Self-aligned, high resolution resonant dielectric lithography
US5121256A (en) * 1991-03-14 1992-06-09 The Board Of Trustees Of The Leland Stanford Junior University Lithography system employing a solid immersion lens
JP2753930B2 (en) * 1992-11-27 1998-05-20 キヤノン株式会社 Immersion type projection exposure equipment
US5939203A (en) 1995-02-03 1999-08-17 Arch Chemicals, Inc. Discoloration prevention in pyrithione-containing coating compositions
MY115462A (en) 1995-06-01 2003-06-30 Chugoku Marine Paints Antifouling coating composition, coating film formed from said antifouling coating composition, antifouling method using said antifouling coating composition and hull or underwater structure coated with said coating film
US6104687A (en) * 1996-08-26 2000-08-15 Digital Papyrus Corporation Method and apparatus for coupling an optical lens to a disk through a coupling medium having a relatively high index of refraction
US5825043A (en) * 1996-10-07 1998-10-20 Nikon Precision Inc. Focusing and tilting adjustment system for lithography aligner, manufacturing apparatus or inspection apparatus
DE19725017A1 (en) * 1997-06-13 1998-12-17 Bayer Ag Use of 2-mercapto-pyridine-N-oxide
US5900354A (en) * 1997-07-03 1999-05-04 Batchelder; John Samuel Method for optical inspection and lithography
WO2000054589A1 (en) 1999-03-17 2000-09-21 Yoshitomi Fine Chemicals, Ltd. Coated bis(2-pyridinethiol 1-oxide) copper salt
TWI242111B (en) * 1999-04-19 2005-10-21 Asml Netherlands Bv Gas bearings for use in vacuum chambers and their application in lithographic projection apparatus
TW591653B (en) * 2000-08-08 2004-06-11 Koninkl Philips Electronics Nv Method of manufacturing an optically scannable information carrier
WO2002091078A1 (en) * 2001-05-07 2002-11-14 Massachusetts Institute Of Technology Methods and apparatus employing an index matching medium
JP2003029989A (en) * 2001-07-16 2003-01-31 Matsushita Electric Ind Co Ltd Distributed processing system and job distributed processing method
US6600547B2 (en) * 2001-09-24 2003-07-29 Nikon Corporation Sliding seal
KR20050044371A (en) * 2001-11-07 2005-05-12 어플라이드 머티어리얼스, 인코포레이티드 Optical spot grid array printer
DE10229818A1 (en) * 2002-06-28 2004-01-15 Carl Zeiss Smt Ag Focus detection method and imaging system with focus detection system
DE10210899A1 (en) * 2002-03-08 2003-09-18 Zeiss Carl Smt Ag Refractive projection lens for immersion lithography
JP4695390B2 (en) * 2002-08-09 2011-06-08 アクゾ ノーベル コーティングス インターナショナル ビー ヴィ Acid-capped quaternized polymers and compositions comprising such polymers
US6988326B2 (en) * 2002-09-30 2006-01-24 Lam Research Corporation Phobic barrier meniscus separation and containment
US6954993B1 (en) * 2002-09-30 2005-10-18 Lam Research Corporation Concentric proximity processing head
US7093375B2 (en) * 2002-09-30 2006-08-22 Lam Research Corporation Apparatus and method for utilizing a meniscus in substrate processing
US6788477B2 (en) * 2002-10-22 2004-09-07 Taiwan Semiconductor Manufacturing Co., Ltd. Apparatus for method for immersion lithography
SG121819A1 (en) * 2002-11-12 2006-05-26 Asml Netherlands Bv Lithographic apparatus and device manufacturing method
DE60335595D1 (en) * 2002-11-12 2011-02-17 Asml Netherlands Bv Immersion lithographic apparatus and method of making a device
CN101424881B (en) * 2002-11-12 2011-11-30 Asml荷兰有限公司 Lithography projection apparatus
KR100492773B1 (en) * 2002-12-02 2005-06-07 주식회사 하이닉스반도체 Ferroelectric Memory Device Comprising Extended Memory Region
DE10258718A1 (en) * 2002-12-09 2004-06-24 Carl Zeiss Smt Ag Projection lens, in particular for microlithography, and method for tuning a projection lens
SG150388A1 (en) * 2002-12-10 2009-03-30 Nikon Corp Exposure apparatus and method for producing device
US6992750B2 (en) * 2002-12-10 2006-01-31 Canon Kabushiki Kaisha Exposure apparatus and method
MXPA05006325A (en) * 2002-12-19 2005-12-12 Arch Chem Inc Pyrithione biocides enhanced by zinc metal ions and organic amines.
US6781670B2 (en) * 2002-12-30 2004-08-24 Intel Corporation Immersion lithography
US7684008B2 (en) * 2003-06-11 2010-03-23 Asml Netherlands B.V. Lithographic apparatus and device manufacturing method
US6867844B2 (en) * 2003-06-19 2005-03-15 Asml Holding N.V. Immersion photolithography system and method using microchannel nozzles
JP4029064B2 (en) * 2003-06-23 2008-01-09 松下電器産業株式会社 Pattern formation method
JP4084712B2 (en) * 2003-06-23 2008-04-30 松下電器産業株式会社 Pattern formation method
JP2005019616A (en) * 2003-06-25 2005-01-20 Canon Inc Immersion type exposure apparatus
EP1498778A1 (en) * 2003-06-27 2005-01-19 ASML Netherlands B.V. Lithographic apparatus and device manufacturing method
US6809794B1 (en) * 2003-06-27 2004-10-26 Asml Holding N.V. Immersion photolithography system and method using inverted wafer-projection optics interface
US7175968B2 (en) * 2003-07-28 2007-02-13 Asml Netherlands B.V. Lithographic apparatus, device manufacturing method and a substrate
US7326522B2 (en) * 2004-02-11 2008-02-05 Asml Netherlands B.V. Device manufacturing method and a substrate
US6961186B2 (en) * 2003-09-26 2005-11-01 Takumi Technology Corp. Contact printing using a magnified mask image
US7369217B2 (en) * 2003-10-03 2008-05-06 Micronic Laser Systems Ab Method and device for immersion lithography
US7678527B2 (en) * 2003-10-16 2010-03-16 Intel Corporation Methods and compositions for providing photoresist with improved properties for contacting liquids
US7924397B2 (en) * 2003-11-06 2011-04-12 Taiwan Semiconductor Manufacturing Company, Ltd. Anti-corrosion layer on objective lens for liquid immersion lithography applications
US7545481B2 (en) * 2003-11-24 2009-06-09 Asml Netherlands B.V. Lithographic apparatus and device manufacturing method
US20050185269A1 (en) * 2003-12-19 2005-08-25 Carl Zeiss Smt Ag Catadioptric projection objective with geometric beam splitting
US7460206B2 (en) * 2003-12-19 2008-12-02 Carl Zeiss Smt Ag Projection objective for immersion lithography
GB0330023D0 (en) * 2003-12-24 2004-01-28 Basf Ag Microbicidal compositions
US20050153424A1 (en) * 2004-01-08 2005-07-14 Derek Coon Fluid barrier with transparent areas for immersion lithography
KR101417706B1 (en) * 2004-01-14 2014-07-08 칼 짜이스 에스엠테 게엠베하 Catadioptric projection objective
US7391501B2 (en) * 2004-01-22 2008-06-24 Intel Corporation Immersion liquids with siloxane polymer for immersion lithography
EP1753829B1 (en) * 2004-02-03 2008-03-12 Akzo Nobel Coatings International BV Antifouling compositions comprising a polymer with salt groups
EP1723467A2 (en) * 2004-02-03 2006-11-22 Rochester Institute of Technology Method of photolithography using a fluid and a system thereof
US7050146B2 (en) * 2004-02-09 2006-05-23 Asml Netherlands B.V. Lithographic apparatus and device manufacturing method
US7893047B2 (en) 2006-03-03 2011-02-22 Arch Chemicals, Inc. Biocide composition comprising pyrithione and pyrrole derivatives

Patent Citations (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2809971A (en) * 1955-11-22 1957-10-15 Olin Mathieson Heavy-metal derivatives of 1-hydroxy-2-pyridinethiones and method of preparing same
US2786847A (en) * 1956-07-23 1957-03-26 Reilly Tar & Chem Corp 2-mercapto, alkanol pyridine-nu-oxides
US3615744A (en) * 1967-07-03 1971-10-26 Takeda Chemical Industries Ltd Antifouling paints
US3773770A (en) * 1968-09-30 1973-11-20 Procter & Gamble Process for preparing pyridine n-oxide carbanion salts and derivatives thereof
US3589999A (en) * 1968-10-25 1971-06-29 Ionics Deionization process
US4039312A (en) * 1972-07-04 1977-08-02 Marcel Joseph Gaston Patru Bacteriostatic, fungistatic and algicidal compositions, particularly for submarine paints
US4021392A (en) * 1974-04-03 1977-05-03 The International Paint Company Limited Marine paint
US4407997A (en) * 1980-10-29 1983-10-04 The International Paint Company Limited Marine paint
US4426464A (en) * 1981-07-03 1984-01-17 International Paint Public Limited Company Marine paint
US4496559A (en) * 1981-09-02 1985-01-29 Olin Corporation 2-Selenopyridine-N-oxide derivatives and their use as fungicides and bactericides
US4399130A (en) * 1982-02-01 1983-08-16 Olin Corporation Use of metallic salts of pyridine-2-thione-N-oxide to treat or prevent swine exudative epidermitis
US4581351A (en) * 1982-11-23 1986-04-08 Sutton Laboratories, Inc. Composition of matter containing imidazolidinyl urea and pyrithione and its derivatives
US4610993A (en) * 1984-08-08 1986-09-09 Olin Corporation Use of selected pyridine-N-oxide disulfide compounds to treat or prevent bovine mastitis
US4565856A (en) * 1984-10-12 1986-01-21 Olin Corporation Pyrithione-containing bioactive polymers and their use in paint and wood preservative products
US4981946A (en) * 1986-07-28 1991-01-01 Semih Erhan Marine paint composition comprising quinone/polyamine polymer
US5310938A (en) * 1987-07-29 1994-05-10 American Cyanamid Company Substituted arylpyrrole compounds
US4957658A (en) * 1987-08-31 1990-09-18 Olin Corporation Process and composition for providing reduced discoloration caused by the presence of pyrithione and ferric ion in water-based paints and paint bases
US5057153A (en) * 1990-05-03 1991-10-15 Olin Corporation Paint containing high levels of a pyrithione salt plus a copper salt
US5328928A (en) * 1990-05-11 1994-07-12 American Cyanamid Company N-acylated arylpyrroles useful as insecticidal, agents
US5098473A (en) * 1991-03-04 1992-03-24 Olin Corporation Process for stabilizing zinc pyrithione plus cuprous oxide in paint
US5112397A (en) * 1991-06-17 1992-05-12 Olin Corporation Process for stabilizing zinc pyrithione plus cuprous oxide in paint
US5137569A (en) * 1991-10-10 1992-08-11 Olin Corporation Process for stabilizing zinc pyrithione plus cuprous oxide in paint
US5185033A (en) * 1992-09-01 1993-02-09 Olin Corporation Gel-free paint containing copper pyrithione or pyrithione disulfide plus cuprous oxide
US5252123A (en) * 1992-09-01 1993-10-12 Olin Corporation Gel-free paint containing cuprous oxide plus 2,2'-dithiobis (pyridine-1-oxide) compound
US5232493A (en) * 1992-09-01 1993-08-03 Olin Corporation Process for stabilizing zinc pyrithione plus cuprous oxide in paint
US5246489A (en) * 1992-09-04 1993-09-21 Olin Corporation Process for generating copper pyrithione in-situ in a paint formulation
US5238490A (en) * 1992-09-04 1993-08-24 Olin Corporation Process for generating copper pyrithione in-situ in a paint formulation
US5298061A (en) * 1993-05-14 1994-03-29 Olin Corporation Gel-free paint containing zinc pyrithione, cuprous oxide, and amine treated rosin
US5712275A (en) * 1993-08-24 1998-01-27 Janssen Pharmaceutica, N.V. Antibacterial and antifouling oxathiazines and their oxides
US5342437A (en) * 1993-10-15 1994-08-30 Olin Corporation Gel-free paint containing zinc pyrithione cuprous oxide and carboxylic acid
US5717007A (en) * 1995-01-26 1998-02-10 Etat Francais As Represented By The Delegue General Pour L'armement Anti-fouling self-polishable paints
US5932520A (en) * 1995-05-23 1999-08-03 American Cyanamid Company Use of pyrrole compounds as antifouling agents
US6069189A (en) * 1996-09-19 2000-05-30 Sigma Coatings, B.V. Light-and bright-colored antifouling paints
US6228382B1 (en) * 1996-12-10 2001-05-08 Etc C.V. Microbiocidal mixtures
US20030162924A1 (en) * 2000-02-25 2003-08-28 Marcel Vos Metal-free binders for self-polishing antifouling paints
US6710117B2 (en) * 2000-02-25 2004-03-23 Sigma Coatings B.V. Marine paint compositions
WO2003039256A1 (en) * 2001-11-08 2003-05-15 Janssen Pharmaceutica N.V. Synergistic antifouling compositions comprising 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1h-pyrrole-3-carbonitrile
US20050123503A1 (en) * 2002-03-15 2005-06-09 Yasuhiro Kozasa Underwater antifouling coating composition with excellent storage stability
US20050065232A1 (en) * 2002-10-23 2005-03-24 Chugoku Marine Paints, Ltd. Antifouling paint composition, antifouling paint films, and, ships, underwater underwater structures, fishing gear and fishing nets covered with the films
US20090017135A1 (en) * 2006-02-01 2009-01-15 Tony Mathilde Jozef Kempen COMBINATION OF 4-BROMO-2-(-4-CHLOROPHENYL)-5-TRIFLUOROMETHYL)-1h- PYRROLE-3-CARBONITRILE AND METAL COMPOUNDS

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104356818A (en) * 2014-12-10 2015-02-18 李永志 Antibacterial coating

Also Published As

Publication number Publication date
KR102033921B1 (en) 2019-10-18
DK1998619T3 (en) 2017-08-28
MY145917A (en) 2012-05-15
EP1998619A2 (en) 2008-12-10
AU2007221987B8 (en) 2012-03-08
EP1998619B1 (en) 2017-05-10
US8481523B2 (en) 2013-07-09
NO20083590L (en) 2008-09-26
AU2007221987A1 (en) 2007-09-13
PT1998619T (en) 2017-07-14
KR20070080261A (en) 2007-08-09
WO2007103013A3 (en) 2008-12-11
JP2014040444A (en) 2014-03-06
CA2644087A1 (en) 2007-09-13
TW200803746A (en) 2008-01-16
WO2007103013A2 (en) 2007-09-13
EP3231283A1 (en) 2017-10-18
US7893047B2 (en) 2011-02-22
HK1213738A1 (en) 2016-07-15
PL1998619T3 (en) 2017-11-30
US20110104375A1 (en) 2011-05-05
ES2636810T3 (en) 2017-10-09
US20070207178A1 (en) 2007-09-06
US20110143153A1 (en) 2011-06-16
KR20140131908A (en) 2014-11-14
CN104982435A (en) 2015-10-21
US8372829B2 (en) 2013-02-12
CN101400256A (en) 2009-04-01
JP5956400B2 (en) 2016-07-27
NO341341B1 (en) 2017-10-16
CA2644087C (en) 2011-06-14
KR20160124926A (en) 2016-10-28
TWI394532B (en) 2013-05-01
JP2009528356A (en) 2009-08-06
EP1998619A4 (en) 2012-08-15
AU2007221987B2 (en) 2012-02-23

Similar Documents

Publication Publication Date Title
US8372829B2 (en) Biocide composition comprising pyrithione and pyrrole derivatives
JP3665335B2 (en) Antibacterial and antifouling oxathiazines and their oxides
TWI399173B (en) Combinations of 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1h-pyrrole-3-carbonitrile and metal compounds
JP7436481B2 (en) Copper chelate complex composition for antifouling protection
KR100751005B1 (en) Controlled release compositions
TWI327057B (en) Synergistic antifouling compositions comprising 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1h-pyrrole-3-carbonitrile
JP4098375B2 (en) Use of pyrrole compounds as antifouling agents
JP4275214B2 (en) Underwater antifouling composition
US20060217456A1 (en) Non-toxic coating composition, methods of use thereof and articles protected from attachment of biofouling organisms
JP2001518970A (en) Coating composition comprising busoxinone

Legal Events

Date Code Title Description
AS Assignment

Owner name: ARCH CHEMICALS, INC., CONNECTICUT

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:WALDRON, CRAIG;MARTIN, ROBERT;WILLIAMS (DECEASED, SIGNED BY LEGAL REPRESENTATIVE TINA WILLIAMS), GARETH;SIGNING DATES FROM 20060509 TO 20060515;REEL/FRAME:028536/0942

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION