EP0801666A1 - Flavonoid-aldehyde und verwendung in lacken - Google Patents

Flavonoid-aldehyde und verwendung in lacken

Info

Publication number
EP0801666A1
EP0801666A1 EP95944566A EP95944566A EP0801666A1 EP 0801666 A1 EP0801666 A1 EP 0801666A1 EP 95944566 A EP95944566 A EP 95944566A EP 95944566 A EP95944566 A EP 95944566A EP 0801666 A1 EP0801666 A1 EP 0801666A1
Authority
EP
European Patent Office
Prior art keywords
substituent containing
formulation
paint
compound
carbon atoms
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP95944566A
Other languages
English (en)
French (fr)
Inventor
Ralph W. Emerson
Bradford G. Crandall, Jr.
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.)
Proguard Inc
Original Assignee
Proguard 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 Proguard Inc filed Critical Proguard Inc
Publication of EP0801666A1 publication Critical patent/EP0801666A1/de
Withdrawn legal-status Critical Current

Links

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
    • C09D5/16—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
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aliphatically bound aldehyde or keto groups, or thio analogues thereof; Derivatives thereof, e.g. acetals
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
    • B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
    • B27K3/34—Organic impregnating agents
    • B27K3/38—Aromatic compounds

Definitions

  • This invention relates to flavonoid aldehydes as biocides in paints and wood preservative products for use in, and on the surfaces of. homes, boats, offices and industrial buildings.
  • Biocides are required in many paint and wood preservative formulations to prevent microbial degradation during shipment, storage or use. Biocides are also required in these formulated products to help protect a substrate subsequently coated with these formulated products from harmful microorganisms such as bacteria and fungi and the like. Biocides used in paint products may be grouped into three major classes: preservatives, mildewicides and antifoulants. Preservatives are widely used in water-based paint systems to prevent in-can bacterial and fungal degradation during storage and shipment. They are particularly useful in latex systems such as synthetic rubber, polyacrylate, and natural rubber latexes. Mildewicides are employed to prevent degradation of the dried paint films and underlying substrate by microorganisms. Antifoulant paints are used to prevent the growth of organisms on the hulls of both commercial and pleasure boats. The attachment of such organisms decreases the operating efficiency of the boats and increases their maintenance costs.
  • Mercurial-type biocides have been widely used as both preservatives and mildewicides in paints. They have excellent performance in both functions in many situations. They offer fast kill time and can control high levels of bacterial contamination. Unfortunately, they are hazardous to handle and may present environmental problems. Thus, their use may be limited to certain applications. Various nonmercurial preservatives and mildewicides have been increasingly considered as substitutes for mercurial compounds.
  • a wide variety of biocides have been tried as marine antifoulants, but the marketplace has been dominated by formulations of cuprous oxide and organotin compounds. Cuprous oxide has been popular because it is efficient, relatively economical, and is specified in many military antifouling paint formulations as the exclusive biocide.
  • Biocides also are employed as wood preservative products in order to prevent deterioration of wood products that are exposed to conditions which promote microbial growth and decay.
  • utility poles, cross ties, piling timbers, freshly milled lumber and fence posts as well as wood chip piles used in pulp manufacture require the incorporation of biocides to stop or control fungal attachment.
  • two classes of biocides have been employed as wood preservatives.
  • One class is oil-borne preservatives (e.g., creosote and pentachlorophenol) while the second class is water-borne salts (e.g., mixtures of inorganic compounds such as copper, chromium, arsenic and zinc salts).
  • the oil- bome preservatives have been the most widely used biocides for wood preservation. However, products treated with these mixtures may have messy oily surfaces. Also both creosote and pentachlorophenol have been objected to as being environmentally hazardous.
  • the water-borne salts are also toxic chemicals which are dissolved in water and injected into wood products where they become bound to or within the wood. These salts have certain advantages over the oil-borne treatments. They leave a cleaner surface that may be more readily painted. Also, their water soluble characteristics provide savings in solvent costs. However, the use of chromium and arsenic salts in particular presents environmental problems.
  • Mosses are a nuisance in horticultural and landscape maintenance. More importantly, in certain geographic zones favoring moss growth on surfaces frequented by people (e.g., stairs, walkways, paths, decks, patios), there is an ongoing concern about slip and fall injuries. Particular interest has been expressed concerning the safety of senior citizens in outdoor areas of nursing and rehabilitation centers where the results of such slip and fall accidents are of more medical (particularly orthopedic) concern. Products on the market for control of moss include zinc chloride and ferric sulfate. Zinc chloride solutions have several disadvantages.
  • Antifouling paint is disclosed in USPN 4,313,860. Mildew resistant paint compositions are disclosed in USPN 5,073,582. Skin diseases and contact sensitivity in house painters using water-based paints, glues and putties is described in Fischer, et al., (1995) Contact Dermatitis 32:39-45.
  • the present invention provides compositions and methods for controlling pathogenic organisms using flavonoid aldehydes in paint and wood preservatives.
  • the method includes the step of including an antipathogenic agent in the paint or wood preservative formulation in an amount sufficient to control growth of target pathogenic organisms.
  • the growth modulating product has a formula shown in (1) below:
  • R represents -CH 2 OH or -CHO; n is an integer from 0 to 3; each R, independently represents OH or an organic substituent containing from 1 to 10 carbon atoms and from 0 to 5 heteroatoms, wherein the total number of carbon and heteroatoms in all R t substituents of said compound is no more than 15, and R 4 represents hydrogen or an organic constituent containing from 1 to 10 carbon atoms.
  • These compounds include natural compounds such as cinnamaldehyde, coniferyl aldehyde, and closely related compounds.
  • alpha substituted aldehydes such as ⁇ -hexyl cinnamic aldehyde (HCA). The method finds use in treating ornamentals and agricultural crops for pathogenic organisms.
  • Paint and wood preservatives substantially free of pathogenic organisms such as fungi and bacteria are provided together with a method to biocontrol pathogen infestations on painted or treated surfaces using flavonoid aldehydes.
  • biocontrol is intended control of pathogens via direct antipathogenic activity.
  • a fungus and/or bacteria colonizing formulation or coated substrate such as a roof and roof shingles, bams, boat hulls, railroad ties, tree trunks, wooden "jungle gyms,” decks, docks, walkways, stairs, wooden patios, or wharves with brick surfaces, are contacted with a paint or preservative containing a flavonoid aldehyde.
  • colonizing is intended association of a microorganism or insect with a surface or with a paint or preservative formulation.
  • the flavonoid aldehydes can be isolated from a natural source, be wholly or partially synthetic, or be produced by recombinant techniques.
  • the method of the subject invention is carried out by adding an effective pathogen-inhibiting amount of a compound of the invention to a paint or preservative formulation.
  • the compound preferably is added at the time of placing the formulation in a shipping container, but can be added immediately prior to use of the product.
  • the amount of antipathogenic agent that is added depends to some extent upon the paint or preservative formulation and the specific compounding used and therefore is empirically determined for best results.
  • antipathogenic is intended controlling the growth of pathogens and can involve killing the pathogen and/or slowing or arresting its proliferation.
  • the compounds of the present invention offer several advantages over those currently in use. They possess good antimicrobial activity and are not incompatible with components of conventional paint and wood preservative products.
  • the compounds also are non-volatile, hydrolytically stable, thermally stable, and depending upon their chemical structure, may be soluble in water and organic solvents. Furthermore, generally they form no undesirable colors in the paint and wood preservative formulations or in the resulting dried films. Still further, they are cost competitive with known biocides used in various paints and wood preservative products while having low or no toxicity toward humans and wildlife.
  • the present invention also overcomes the problem of migration of previously available preservatives by bonding the bioactive compounds to the wood.
  • a preferred preservative compound is shown in formula (2) below:
  • R represents-CHO
  • R 2 represents-OH or an organic substituent containing from 1 to 10 carbon atoms
  • R 3 represents a methoxy group or organic substituent containing from 1 to 10 carbon atoms
  • R t represents a hydrogen or an organic substituent containing from 1 to 10 carbon atoms.
  • flavonoid aldehydes particularly aromatic aldehydes.
  • aromatic aldehydes of use in the present invention are cinnamic aldehyde ((3) below):
  • Other compounds of interest include analogs of the compound of formula (1) such as compounds substituted at the alpha position with an alkyl, such as a hexyl group, or a branched alkyl group such as an amyl group. Generally the group at the alpha position is from C-5 to C-10. Such compounds include alpha hexyl cinnamaldehyde and alpha amyl cinnamaldehyde.
  • alpha- hexylcinnamic aldehyde (HCA) is shown in (5) (below).
  • HCA The Chemical Abstracts Service (CAS) name of HCA is 2-(phenylmethylene) octanal and the CAS Registry Number is [101-86-0]. The compound is also described by the chemical name of 2-hexyl-3-phenyl-2-propenal. The formula of the compound is C 15 H 20 O and the molecular weight is 216.3.
  • HCA is a low to moderately volatile compound, having a vapor pressure of 70 x 10 s mm Hg at 25°C. Its parent compound, cinnamic aldehyde, has a vapor pressure approximately 40 times higher (2970 x lO "5 mm Hg at 25°C). (Reifenrath, W.G. (1995) Volatile Substances.
  • the aromatic and aliphatic aldehydes of the subject invention can be prepared by various synthetic methods known to those skilled in the art. For example, see, J. March, ed., Appendix B, Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, 2nd Ed., McGraw-Hill, New York, 1977. Cinnamaldehyde can be prepared synthetically, for example, by oxidation of cinnamyl alcohol (Traynelis et al., J. Am. Chem. Soc. (1964) 86:298) or by condensation of styrene with formylmethylaniline (Brit, patent 504,125).
  • the subject aldehydes also can be obtained by isolation from natural sources.
  • cinnamaldehyde can be isolated from woodrotting fungus, Stereum subpileatum. Birkinshaw et al., Biochem. 7. (1957) 66:188.
  • HCA can be synthesized as described, for example, in USPN 5,055,621.
  • HCA can be synthesized by reaction of benzaldehyde with octanal under a nitrogen atmosphere (aldol condensation) (Personal Communication, Eric Walborsky, Firmenich Chemical Manufacturing Center, Port Newark, New Jersey). The reaction is conducted in a stirred flask charged with methanol, 309 ppm diphenylamine, potassium hydroxide and benzaldehyde. Following the slow addition of octanal, the reaction mixture is brought to a pH of 7.5-9.5 with acetic acid. Following evaporation of methanol and wash of the reaction mixture with water, the organic phase is transferred to a distillation unit.
  • the "heart cut” is subjected to an additional fractionation, in which 1-5% (by weight) of the material is removed in "light” fractions, depending upon odor evaluation.
  • the final product is a light yellow oil having a specific gravity of 0.955-0.965 at 20°C, a refractive index of 1.548-1.562 at 20°C, a boiling point of 305 °C at 1 atmosphere, and a melting point of 26°C.
  • HCA also can be obtained from Firmenich; their product is composed principally of the (E)-cis isomer (93.8% maximum), and the (Z)-trans isomer (6% maximum). Among minor components is the self aldol condensation product of octanal (1-1.5% (Personal Communication, June Burkhardt, Firmenich, Plainsboro, New Jersey). The commercial product is stabilized with the addition of 0.04% 2, 6- di-tert-butyl-p-cresol (butylated hydroxy toluene or BHT), which serves as an anti- oxidant (Technical Data Sheet, Hexylcinnamic aldehyde 907600, Revision 853, Firmenich Inc., Plainsboro, New Jersey). HCA can be isolated from rice where it has been reported to occur naturally. (Givaudan-Roure Index, Givaudan-Roure Corporation, Clifton, New Jersey, 1994, p. 89).
  • the compounds can be used by incorporating an effective paint preservative amount of the compound into a paint or wood preservative.
  • an effective paint preservative amount is intended any amount which will prevent or control degradation of the paint. In-can degradation of paints is often caused by gram- positive bacteria such as Bacillus cereus and Staphylococcus aureus or gram-negative bacteria such as those of the Pseudomonas or Xanthomonas classes. This degradation of the paint ingredients results in viscosity loss or generation of offensive odors.
  • paint preservatives are employed in aqueous-based paint systems such as latex systems.
  • Solvent-based paints usually do not require a preservative since the nonaqueous formulation will not support fungal and/or bacterial growth.
  • preservatives are fungicidal and/or bactericidal and their killing action preferably is rapid to prevent production of enzymes by the microorganisms which are actually the cause of the latex paint destruction.
  • bioactive compounds When the present bioactive compounds are employed as paint preservatives, it is usually desirable to add them to the paint formulation in the same manner as other ingredients are incorporated. It is preferred to incorporate them as a substitute for substantially all of the non-bioactive non-paint components in the paint formulation.
  • the actual amount of preservative used varies depending upon many parameters. Generally, it is preferred to employ from about 0.5 to 5 volume % of a compound of formula (1) as'part of a total paint formulation for this purpose.
  • the compounds of the subject invention also find use for the prevention and/or killing of mildew (mildewicides). Accordingly, the term "effective mildewicidal amount" is intended to include any amount which will kill or control the growth of mildew-causing microorganisms. Mildew or mold causing microorganisms vary according to the exposure environment. Aureobasidium pullulans is the most commonly found species in temperate and colder climates. Tropical and subtropical conditions favor the growth of microorganisms of the classes Aureobasidium,
  • the effective mildewicidal amount is varied empirically based up changes in the parameters of the environment and the substrate having the compounds of the subject invention incorporated therein. Generally, it is preferred to employ from about 0.5 to 5 volume % of a compound shown in formula (1) as part of a total paint formulation.
  • An effective antifoulant amount of one or more of the compounds of formula (1) is incorporated into a hull coating formulation.
  • effective antifouling amount is intended any amount which will prevent or control fouling on the hull.
  • Fouling organisms include plant forms such as algae and animal forms such as those of the classes Anthropeda, Coelenterata and Mollusca.
  • the green algae Enteromorpha is the organism most often found on the hulls of large ships.
  • the effective antifouling amount will vary because of changes in the parameters of the environment and the substrate on which it is applied to the hulls. Generally, it is preferred to employ from about 0.5 to 5 volume % of the active moiety shown in formula (1) as part of a total paint formulation for this purpose.
  • An additional use of the subject formulation is as a wood preservative.
  • An effective wood-preserving amount of one or more of these compounds is incorporated into a wood treatment product.
  • the term "effective wood-preserving amount" is intended to include an amount of the compound which prevents or controls degradation of the wood product to which it is applied.
  • Wood products not in water are subject to two forms of fungal attack, surface attack (e.g., soft rot) and internal attack (e.g., white and brown rots).
  • Fungi imperfecti and Ascomycetes are the major cause of soft rot and the Basidiomycetes class of fungi is the major cause of internal attack.
  • White rots attack the lignin and brown rots attack the cellulose.
  • the commonly known dry rot is a brown rot.
  • the effective amount of compound employed in this application is empirically determined based upon parameters which include the specific preserving compound(s) employed, the type of wood product to be protected, and the type of environment the wood product is exposed to. Generally, it is preferred to employ from about 0.5 to 5 volume % of the active moiety shown in formula (1) as part of a total wood preservative formulation.
  • the biocides of the present invention can be added to the wood products by either pressure or nonpressure impregnation. If pressure impregnation is employed, air, hydrostatic pressure or vacuum methods, or combinations thereof, can be used. If nonpressure impregnation of wood is desired, dipping, spraying, brushing or the like can be used.
  • the bioactive compounds of the present invention can be either added directly to cellulosic materials such as the wood products in a preformed state, or the compounds of formula (1) can be added to, for example, bound to a cellulose binding protein. In this latter case, the bioactive compounds bond to the polysaccharide structure of the cellulosic material (e.g., wood, paper and the like) upon contact. Paper products can be treated to make a mildew-resistant paper, cardboard boxes or the like using the flavonoid compound - polysaccharidase binding conjugate. A sufficient portion of a cellulose binding domain up to the full length cellulose can be used when the target polysaccharide is a cellulose. The preparation of cellulose binding domains is described in U.S. Patent Nos.
  • Binding proteins from scaffold proteins also can be used. See Shoseyev et al. (PCT application EP/0594/04132).
  • the conjugate can be prepared with or. without a cleavable bond using methods known to those skilled in the art.
  • Paint and wood preservative products which may contain the biocidal compositions of the invention as preservatives and mildewicides include such as latex and solvent interior and exterior paints, coatings for new and existing architectural structures.
  • Other paint products include industrial finishing products such as interior and exterior maintenance coatings and marine antifouling paints.
  • the total slide is exposed to the challenge of either fungi or algae with the expectation that the half of the slide containing the active agent will prevent growth of the challenging organism, while the untreated half will not.
  • the slide In the fungal test, the slide is placed on the surface of an agar plate which is seeded with fungi. After incubation for about 14 days, the slide is examined for extent of growth or lack thereof on the treated surface of the slide. Since leaching of the active agent would create an undesirable zone-of-inhibition outside the perimeter of the treated surface of the slide, no growth on the treated surface along with a small, or no, zone of inhibition is the desired result.
  • the slide In the algal test, the slide is immersed in a nutrient broth which has been inoculated with the algae Pleurochloris pyrenoidosa. After an incubation for 30 days (under light) and a water rinse, the slide is examined microscopically and the extent of algal attachment is noted. Total lack of attachment on the treated surface is the desired result. Additional information is obtained by comparing the extent of growth of algae throughout the broth. Significant leaching of the active agent from the treated surface would inhibit growth in the broth as well as on the treated surface.
  • Example 3 Wood Preservation Testing This aspect of the present invention extends the utility of the above described antimicrobial compounds to the wood preservation area. Two general techniques are shown. In one, a solution of the compound is applied to the wood directly. In the second, a solution of compound bound to a cellulose binding protein is applied to the wood.
  • Example 4 Wood Rot Test The test procedure is based upon the following published procedure: H.P. Sutter, International Biodeterioration Bulletin, 14 (3), 95-99 (1978). The organisms employed are Coniophora souna ATCC 36336 and Lentinus lepideus ATCC 12653 (a creosote-resistant fungus). Duplicates are run in each case. The growth of brown rot (cellulose-degrading) fungi on pine blocks after 25 days at 28° C. is evaluated as:
  • print wood blocks are surface treated with either a wood preservative comprising a test concentration of a compound according to formula (1) or a commercial wood preservative.
  • the wood blocks are brush coated on all surfaces and in some cases multiple coats are applied. Pressure treatment is not used. These present examples correspond to what a consumer would do to apply a wood preservative.
  • the amount of biocide applied to each wood block is calculated by determining the weight increase of each wood block after treatment and calculating the biocide present in the weight increase.
  • Biofunctional compounds are tested in a standard Minimum Inhibitory Concentration (MIC) test against 8 different bacteria and 8 different fungi. Also tested in this MIC test are Tween 80 (2%), NaHCO 3 (6%) and Tween 80 (2%) plus NaHCO 3 (6%) as blanks.
  • MIC Minimum Inhibitory Concentration
  • the organisms included in the MIC test are:
  • Example 6 Brvophvtacide Activity of Flavonoid Aldehyde Bryophyta (moss) bioassay studies were carried out as follows: fifteen 9 cm plastic petri dishes were lined with Whatman filter paper discs (7.5 cm). Three ml water were pipetted onto each filter paper disc. Mosses were placed in groups of five; each moss section was about 3.5 cm x 3.5 cm. Two ml of test solution were sprayed as a fine mist (Gilmour sprayer) from a distance of 10 cm. and the petri dishes placed on a table at ambient room temperature and observed at 24, 48 and 60 hours. The area of desiccation was measured at each observation time point. See Table 1 (below) for results.
  • F2 Saponin (10° Brix) 0.86 ml cone, diluted in 50 ml water.
  • Example 8 Formulation for Interior Latex Flat Paint A latex paint formulation is mixed according to the proportions in Table 3, below.
  • Cinnamic aldehyde is substituted for Kathon and propylene glycol in various percentages.
  • One gallon batches are produced and stored in sealed one gallon paint pails. At 30, 60, 120 and 180 days, lids are removed and the paint compared to commercial batches. Inspection for molds, skimming and settling is conducted. Test paints also are compared to commercial flat latex on wood surfaces over the same time frame. Inspections are made for mold and general coating deterioration.
EP95944566A 1995-06-07 1995-12-29 Flavonoid-aldehyde und verwendung in lacken Withdrawn EP0801666A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US48503295A 1995-06-07 1995-06-07
US485032 1995-06-07
PCT/US1995/017048 WO1996040831A1 (en) 1995-06-07 1995-12-29 Flavonoid aldehydes and use in paint

Publications (1)

Publication Number Publication Date
EP0801666A1 true EP0801666A1 (de) 1997-10-22

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EP (1) EP0801666A1 (de)
CN (1) CN1159819A (de)
AU (1) AU4691196A (de)
BR (1) BR9508562A (de)
CA (1) CA2196975A1 (de)
WO (1) WO1996040831A1 (de)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19611825A1 (de) * 1996-03-26 1997-10-02 Desowag Materialschutz Gmbh Holzschutzmittel
CA2343267A1 (en) * 1998-09-30 2000-04-06 The Procter & Gamble Company Laundry detergent and/or fabric care compositions comprising chemical components linked to a cellulose binding domain
DE19847964A1 (de) * 1998-10-17 2000-04-20 Knoell Hans Forschung Ev Holzschutzmittel mit Langzeitwirkung gegen Trockenholzschädlinge
CN101536687B (zh) * 2008-03-20 2013-12-18 香港科技大学 黄酮和异黄酮衍生物作为抗生物污损物质的应用以及防止海洋生物污损的方法和涂料
DE102011077067A1 (de) * 2011-06-07 2012-12-13 Beiersdorf Ag Wirkstoffkombinationen aus å-Polylysin (Epsilon-Polylysin) und einem odermehreren aromatischen Aldehyden
CN103788917A (zh) * 2012-10-29 2014-05-14 广东盈然木业有限公司 一种改性大豆蛋白胶及其在生产实木复合地板中的应用
CN106272789A (zh) * 2015-06-04 2017-01-04 东北林业大学 一种水载型肉桂醛基木材保护剂的制备方法
CN107322719A (zh) * 2017-07-13 2017-11-07 阜南县铭钰柳木工艺品有限公司 一种柳编制品表面疏水防虫处理方法
CA3133586A1 (en) 2019-03-15 2020-09-24 VERINLEGNO S.p.A. Wood coating products containing vegetal-origin anti-oxidants, and methods to make the same

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU520990B2 (en) * 1979-01-29 1982-03-11 Kureha Kagaku Kogyo Kabushiki Kaisha Preservative
JP2796588B2 (ja) * 1989-08-24 1998-09-10 大日本除蟲菊株式会社 屋内用殺ダニ剤
JPH04306269A (ja) * 1989-12-29 1992-10-29 D & D Kk 防汚塗料
JPH04300801A (ja) * 1991-03-29 1992-10-23 Nippon Paint Co Ltd 抗菌性物質インターカレート組成物
FR2697133B1 (fr) * 1992-10-28 1995-01-13 Transbiotech Composition biocide et/ou biostatique et ses applications.

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9640831A1 *

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BR9508562A (pt) 1997-11-25
CA2196975A1 (en) 1996-12-19
CN1159819A (zh) 1997-09-17
AU4691196A (en) 1996-12-30
WO1996040831A1 (en) 1996-12-19

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