[go: up one dir, main page]

WO1997002135A1 - Bois modifie dote de revetements de surface - Google Patents

Bois modifie dote de revetements de surface Download PDF

Info

Publication number
WO1997002135A1
WO1997002135A1 PCT/US1996/012356 US9612356W WO9702135A1 WO 1997002135 A1 WO1997002135 A1 WO 1997002135A1 US 9612356 W US9612356 W US 9612356W WO 9702135 A1 WO9702135 A1 WO 9702135A1
Authority
WO
WIPO (PCT)
Prior art keywords
wood
resin
isocyanate
composition
coating
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.)
Ceased
Application number
PCT/US1996/012356
Other languages
English (en)
Inventor
Darrel D. Nicholas
Charles U. Pittman
Lichang Wang
Ahmed Kabir
Tor P. Shultz
Leonard L. Ingram
Moon G. Kim
Eugene M. Ivankoe
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Priority to AU65086/96A priority Critical patent/AU6508696A/en
Publication of WO1997002135A1 publication Critical patent/WO1997002135A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • B27K3/02—Processes; Apparatus
    • B27K3/15—Impregnating involving polymerisation including use of polymer-containing impregnating agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes

Definitions

  • the present invention relates to impregnated, surface coated wood products. More particularly, the present invention relates to the use of isocyanate-based polymers that are highly lightfast and de-contaminatable to impregnate and surface coat solid wood products with tight film formation via polymer grafting on wood cell surfaces when the prepolymers cure.
  • One object of the present invention is therefore to provide wood impregnation and coatings materials for enhancing various wood properties including the de-contaminability of the chemical warfare agent VX before and after a long exposure to the degradation effect of sunlight.
  • Another object of the present invention is to provide impregnation and coating procedures for manufacturing the treated wood products using the impregnation and coatings materials of this invention.
  • Still another object of the present invention is to provide various impregnated and coated wood materials that have various enhanced properties including the de-contaminability of the chemical warfare agent VX before and after long exposure to the degradation effect of sunlight.
  • the invention comprises a method and process for treating wood.
  • the steps of the method include preparing isocyanate-based reactive prepolymer resins for impregnation, impregnating wood with these impregnation resins, curing the impregnated wood at elevated temperatures, preparing isocyanate resin-based coating materials and applying these coating materials on the cured impregnated wood and curing the coatings at room or elevated temperatures.
  • the final product is novel and useful in a variety of applications including those applications described herein.
  • This invention is intended for use with a variety of woods.
  • the first step comprises the preparation of isocyanate-based reactive prepolymer resins for wood impregnation.
  • This may be accomplished using various commercially available isocyanate materials such as toluene diisocyanates (TDI). methylene-bisphenylene diisocyanates (MDI). and low molecular weight derivatives of MDI or other aliphatic isocyanates.. All are suitable for the present invention.
  • Polyols suitable for reaction with these isocyanates are linear polyols having a molecular weight range from about 500 to about 5000 daltons and a hydroxyl group functionality of about 2.0. Also polyols having a major amount of hydrophobic segments, such as propylene oxide or butadiene groups, are preferred over those of the more hydrophilic groups, such as ethylene oxide groups.
  • Polyols suitable ⁇ for this invention are linear polyols. such as. for example, ethylene oxide-propylene oxide copolymers, polytetrahydrofurans, and hydroxyl group-terminated polybutadienes.
  • the isocyanate/polyol ration should be in a range that will keep the amount of isocyanate (NCO) functional groups, left unreacted at the end of the synthesis reaction, at a level between about 3% and 20% by weight based on the total weight of the isocyanate and polyol materials used in the reaction.
  • This excess isocyanate functionality is designed for later reactions with hydroxyl groups and moisture in the wood during the curing process, so that a tightly coupled wood-polymer composite material is obtained. Too high levels of isocyanate group are not desirable because of the slow curing rate in the wood and also because of the rough cured surfaces caused by excessive curing with the moisture in the air.
  • the prepolymer resin synthesis reaction must be conducted in the absence of moisture, preferably under a stream of dry nitrogen, and at an elevated temperature until all hydroxyl groups of the polyol are reacted. This completeness of reaction is determined when no further increase in viscosity is occurring.
  • the reaction mixture is then cooled to room temperature and may at that time be diluted with a suitable water-dry solvent such as methyl ethyl ketone or Cellosolve Acetate, or the like.
  • the mixture should be stored in a dry. closed container.
  • the preferred prepolymer resin is a polyurethane resin identified as L-18.
  • L-18 is manufactured by reacting a methylene diphenyl diisocyanate resin, a hydroxy-terminated polypropylene glycol and a hydroxy-terminated polybutadiene resin. The resulting polymer is diluted with methyl ethyl ketone.
  • Methylene diphenyl diisocyanate resin consists of a mixture of monomeric and oligomeric methylene diphenyl diisocyanates in liquid form, having 29% by weight -NCO group content, an equivalent weight of 144.5 (g/more) and a functionality of 2.1 per mole.
  • the resis should contain less than 2.0% of triethylphosphate as a viscosity reducing agent.
  • the methylene diphenyl diisocyanate resin should exhibit a viscosity of about 35 cP at 25 °C and the resin may he stored In glass, plastic or metal vessels, as long as water is rigorously excluded, so that it is preferably stored under slight dry nitrogen pressure.
  • the polypropylene glycol has a molecular weight of 2000 g/mole, a functionality of 2/mole and an equivalent weight of 1000 g/mole. It too is stored under slight dry nitrogen pressure to prevent moisture uptake.
  • the water content should be less than 0.05% and the pH value measured in a 10: 1 methanol /water solution should be less than 3.0.
  • the hydroxy-terminated polybutadiene resin has a molecular weight of 2800 g/mole and a functionality of 2.4 to
  • This viscous liquid having a viscosity of 50P at 30 °C, is stored under a slight pressure of dry nitrogen. It has a hydroxy value of 0.83 meg/g and the polymer structure contains olefin groups (iodine value of 398), composed of 60% trans- 1 ,4 unites, 20%S cis-1.4 unites and 20% vinyl 1.2 units. The nonvolatile content should be greater than 99.9%.
  • the methyl ethyl ketone (MEK) is a solvent having a boiling point of 79.6 °C and is used to reduce the L-18 viscosity. MEK that has no more than 0.1% water is then dried over 4 or 5 A molecular sieve before use. Care should be taken to keep water from the MEK as water will cause the -NCO groups to react with the water, which in turn will cause uncontrolled polymer formation and loss of isocyanate functionality.
  • the three components, methylene diphenyl diisocyantate resin, hydroxy-terminated propylene glycol and hydroxy-terminated polybutadiene are used in a weight ratio of 41.0% to 13.80% to 45.20%, respectively.
  • MEK is added after prepolymer formation so that the MEK constitutes @5-35% by weight of the final solution. If more MEK is used in the formulation, the resulting solution viscosity will be lower; however, a larger void volume fraction will remain inside the - wood after treatment and other treatment difficulties might arise.
  • Preparation of the L- 18 prepolymer solution is accomplished in a chemical reactor equipped with an agitator, thermometer, condenser, dry nitrogen cover, and heating and cooling mechanisms. Both the reactor and the storage containers or drums should be clean, dry and cool before work is begun. Presented below is an example of the preparation of a drum of prepolymer.
  • a reactor is filled with a slow stream of dry nitrogen and maintained at a positive pressure of nitrogen throughout the entire procedure.
  • 1501 pounds of methylene diphenyl diisocyanate resin is charged into the reactor.
  • the agitator is operated at about 15-20 rpm and heat is applied to reach 60 °C in about 20-30 minutes.
  • 505 pounds of hydroxy-terminated polypropylene glycol is charged, followed by 1654 pounds of hydroxy-terminated polybutadiene under heat so that the temperature reaches 80 °C at about 20 minutes from the polybutadiene charge. This temperature is maintained for the entire charging period which may take 90 minutes or more.
  • the reactor contents are heated to 85°C in ten minutes and held at that temperature for an additional 20 minutes.
  • the second step comprises the impregnation of wood with the prepolymer resins, followed by curing them.
  • the wood should first be dried to a moisture content ranging from about 2% to 14%. based on the oven dry wood weight and the free isocyanate group content of the prepolymer resin should be adjusted to approximate the wood moisture content level. Any wood impregnation procedure may be used as long as the impregnation is sufficiently complete.
  • One such process is generally described as a 'full cell' process, used here to illustrate the process using the prepolymers of the present invention.
  • the preferred lumber is derived from either Aspen. Southern Yellow Pine or Red Oak. Wood quality should be good, being free of decay which can easily be detected visually or by abnormal brashness when picked with a sharp instrument.
  • the lumber should be free from insects, beetles, powder post beetle deterioration and other infestation at the time of treatment. To ensure that the wood is completely free of the oak wilt fungus, all would used in the present invention should be absolutely free from bark.
  • a wood sample is placed on a plan in a cylinder and a vacuum is applied to the cylinder, preferably 26 inches of Hg up to about 28 inches of vacuum for a minimum of 20 minutes. Dry nitrogen is introduced to break the vacuum and a second vacuum is applied and held for a minimum of 30 minutes. A prepolymer is introduced to the pan through an opening to completely cover the wood sample. The vacuum is then continued for about 30 minutes and, after release of the vacuum, a positive pressure of a minimum of 50 psig to about
  • the third step includes preparation of surface coating materials for use in the present invention.
  • Two package formulations based on aliphatic isocyanates and multi-functional polymeric polyols are preferred for this invention.
  • Aliphatic isocyanates such as hexane diisocyanate and isophorone diisocyanate or their oligomeric adduct products are suitable.
  • the isocyanate is formulated as one part of the coating system with suitable solvents for adjustment of the viscosity and other properties.
  • the multi-functional polyol is the major component of the second part of the coating system, again with suitable solvents for adjustment of the viscosity. It is preferred that the polyol should be polymeric molecules with a molecular weight range from about 500 to about 15,000 daltons and having more than two hydroxyl groups per molecule with a background structure of either aliphatic or aromatic carbon chains.
  • additives particularly useful for the coating system of this invention are flow promoters such as certain acrylic copolymers.
  • hydroxy group-cross linking additives such as methylolated melamine-formaldehyde resins, pigment hydrophobicizing and cross linking agents such as epoxyalkylsilanes. and graft promoters between the polymer and wood surface such as acrylic ester monomers with attendant initiators.
  • the hydroxyl groups of the polyol are mostly cured with the isocyanate groups by forming urethane bonds but also they are cured by forming bonds with the melamine formaldehyde and epoxysilane components.
  • the two part coating system should be mixed well before its application in a proportion such that the number of isocyanate functionality should be somewhat higher than the number of available hydroxyl groups. This is done to assure adequate self-cross linking by reacting with moisture in the air and for forming urea bonds. Excess isocyanate functionality as well as any deficiency of it in this final mixed coating system should be avoided.
  • a preferred coating composition is formed from an aliphatic polyisocyanate, melamine resis, acrylic resin, epoxy silane and other additives designed to bind tightly and provide a uniform coverage of porous surfaces.
  • the preferred two part system is identified herein as P- 13 and includes the following individual components.
  • a high molecular weight epoxy resin is employed.
  • This resin is a hydroxyl group containing, high molecular weight bisphenol-A-based epoxy resin that provides a good flexible coating.
  • Resin solids should be about 40% to 50%, with non-chlorine type solvents such as MEK, monoproply glycol, monomethyl ether acetate and cyclohexane.
  • the epoxy- resin shall have a hydroxyl group content of 1.80- 1.90 meg/g, based on solid resin weight.
  • the solvents for the first part should be technical grade or better but with a water content less than 0.10% and dried over 4-5 Angstrom molecular sieves before use.
  • Xylene and Cellosolve acetate are useful solvents for the second part of this component.
  • An acrylic resin based flow promoter may be used.
  • One preferred flow promoter is Modaflow, supplied in a 10% solid solution by Monsanto Co.
  • An epoxyalkyl silane to promote adhesion may be used, such as the epoxy group containing silyl ester supplied by Union Carbide Corp.
  • the cross linking agent is a multifunctional acrylate cross liking agent such as propane trimethylmethacrylate, supplied by Sartorner Co.
  • the preferred melamin-formaldehyde resin based thermosetting component is hexamethoxymethyl melamine resin supplied by American Cyanamid Co. Cross linking is initiated by use of benzoyl peroxide and silver perchlorate, in 1% and 0.1% MEK respectively.
  • An aliphatic polyisocyanate is also employed in the preferred composition.
  • An 1 ,6-hexamethylene diisocyanate-based adduct that has less than 1.6% monomer concentration, dissolved in a mixed solvent of an aliphatic ester and an aromatic solvent is used to control the evaporation rate when applied as a coating.
  • the -NCO group content needs to be 16.5% and the resin solids content shall be 75% or more.
  • Preparation of the P-13 coating solution is also accomplished in a chemical reactor equipped with an agitator. thermometer, condenser, dry nitrogen cover, and heating and cooling mechanisms. Both the reactor and the storage containers or drums should be clean, dry and cool before work is begun. Presented below is an example of the preparation of a drum of prepolymer.
  • the coating formula used in this preparation is as follows:
  • the above formulation was used to prepare the preferred coating formulation.
  • First Part A was prepared, then Part B.
  • a reactor was filled with a slow stream of dry nitrogen and maintained at a positive pressure of nitrogen throughout the entire procedure.
  • the high MW epoxy resin is charged and agitation at about 15-20 rpm started. While agitating at that speed, all the other materials are charge in the order given above. After charging, agitation is continued for 20 minutes so that viscosity is 50 cP +/- 10 cP.
  • Part B components are charged in sequence as listed above to reach a mixed solution with a viscosity of 5- 10 cP. Both parts are then stored in dry drums until needed. When the coating material is to be used, they are combined is a mixing tank filled with dry nitrogen.
  • Part A 33 parts of Part A are added with mixing at 15-20 rpm, followed by 10 parts of Part B, followed by 20 minutes agitation as a smooth solution is obtained.
  • the viscosity of the mixed solution should be 30 cP +/- 10 cP initially, but will increase as the mixture stands to 60-70 cP over a period of about 10-15 hours.
  • the next step is the application of the surface coating materials followed by curing it.
  • the surface coating materials prepared as described above should be applied within an hour or two of preparation.
  • the viscosity may be adjusted to some extent by adding a solvent such as methyl ethyl ketone or Cellosolve Acetate.
  • Application of the coating is done using a brush, or preferably, by spraying methods. Of course, the fumes in the application area are to be well controlled.
  • the spraying should not continue once the viscosity has reached about 150 cP. although dilution with up to about 10% MEK is allowed.
  • the treated wood should have a minimum film thickness of 0.3 mils.
  • the coated object After the application of the coating, the coated object should be kept in a well ventilated area until all solvent evaporates and the system cures completely.
  • a faster curing can be achieved by using slightly elevated temperatures such as up to about 40°C to 60°C. in a properly ventilated oven.
  • a material charge formula comprising 55 parts of isocyanate (Isonate 1143L, from Dow Chemical Co.) and 45 parts of polymeric polyol (Voranol 220- 1 19, from Dow Chemical Co.) were charged in a dry reactor under dry nitrogen and reacted for two hours at 75-80°C. After cooling to room temperature, the prepolymer resin was diluted with methyl ethyl ketone to a 90% resin solids level resulting in a viscosity of about 200 cP. The free NCO group content of the prepolymer resin was calculated to be 15.0%, based on the total resin solids.
  • Part A and Part B were made, separately, by mixing the materials in the given order in a dry reactor.
  • the final coating composition was obtained by mixing 33 parts of Part A and 10 parts of Part B to a uniform mix in a blender.
  • a six inch by 1 /2 inch piece of southern pine was coated with Example Seven material using a soft-bristled brush to give a dried film thickness of four to five mil.
  • the coating was dried in a ventilated hood for 24 hours and cured at 40°C for 24 hours, resulting in a uniform clear glossy coating.
  • Example Seven was tinted with a solvent-borne white tinting base and a green pigment base by mixing in, respectively. 1.5 parts and 1.0 parts to 98.5 parts of Example Seven. Part A. Mixing this tinted material and Example Seven, Part B, in a ration of 33 parts to 10 parts resulted in a pigmented coating formulation. Coating a piece of southern pine and solvent cleaned mild steel with this coating formula to a three to five mil dry film thickness resulted in a green coating with a good hiding and film adhesion properties.
  • a phenol-formaldehyde resol resin was prepared by reading 64.2 parts of 90% phenol and 35.2 parts of 50% formaldehyde in the presence of 1.1 parts sodium hydroxide at 75°C for eight hours. The resulting resin showed a viscosity of 50 cP and a solids content of 60.0%. The resin was impregnated into southern pine wood in the exact way as in Example Three and the sample was cured in a hot press at 194°C for 10 minutes under a platen pressure of 50 psi.
  • the polymer weight gain was 46.0% and the sample surface showed a shiny coating with the cured PF polymer resin and the toughness test result obtained according to the ASTM C 143 using a sample length of 5.5 inches showed a decrease to a 58% of the untreated control sample.
  • a six inch by 1/2 inch piece of southern pine was coated using a soft-bristled brush with a two-package epoxy resin system
  • a melamine-formaldehyde resin was obtained from Astro Industries. Its formaldehyde/melamine mole ratio was reported to be five to six, solids content was 80.0%, and its pH value was 8.8.
  • the resin was catalyzed with a 0.3% ammonium chloride in the laboratory and impregnated into southern pine wood in the exactly same way as described in Example Three and cured in an oven for four hours with a temperature schedule of gradually increasing from 40°C to 150°C during the curing period.
  • the polymer weight gain was 25% and the toughness test result, obtained according to ASTM D143 using a sample length of 5.5 inches, showed an improvement of 6% over an untreated control sample.
  • Impregnated wood samples obtained using the procedure and materials of Example Five were coated with the coating formula of Example Seven using the procedure of Example Eight. Pine, aspen, and oak were used in this experiment.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Un procédé de traitement du bois consiste à préparer des résines de prépolymères réactives, à base d'isocyanate, destinées à l'imprégnation, et à en imprégner du bois, à polymériser le bois imprégné à des températures élevées, à préparer des matériaux de revêtement à base de résines d'isocyanate et à appliquer ces revêtements sur le bois imprégné polymérisé, puis à polymériser ces revêtements à température ambiante ou plus élevée. Le bois traité résultant présente une aptitude améliorée à la décontamination concernant l'agent VX utilisé pour la guerre chimique, tant au début qu'après une longue exposition aux effets de dégradation provenant de la lumière solaire.
PCT/US1996/012356 1995-07-06 1996-07-03 Bois modifie dote de revetements de surface Ceased WO1997002135A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU65086/96A AU6508696A (en) 1995-07-06 1996-07-03 Modified wood with surface coatings

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US90995P 1995-07-06 1995-07-06
US60/000,909 1995-07-06
US96795P 1995-07-07 1995-07-07
US49951895A 1995-07-07 1995-07-07
US08/499,518 1995-07-07
US60/000,967 1995-07-07

Publications (1)

Publication Number Publication Date
WO1997002135A1 true WO1997002135A1 (fr) 1997-01-23

Family

ID=27356770

Family Applications (3)

Application Number Title Priority Date Filing Date
PCT/US1996/012283 Ceased WO1997002134A1 (fr) 1995-07-06 1996-07-03 Bois impregne de polyurethane, procedes d'impregnation utilises et articles ainsi produits
PCT/US1996/012357 Ceased WO1997002136A1 (fr) 1995-07-06 1996-07-03 Bois modifie par un revetement de surface
PCT/US1996/012356 Ceased WO1997002135A1 (fr) 1995-07-06 1996-07-03 Bois modifie dote de revetements de surface

Family Applications Before (2)

Application Number Title Priority Date Filing Date
PCT/US1996/012283 Ceased WO1997002134A1 (fr) 1995-07-06 1996-07-03 Bois impregne de polyurethane, procedes d'impregnation utilises et articles ainsi produits
PCT/US1996/012357 Ceased WO1997002136A1 (fr) 1995-07-06 1996-07-03 Bois modifie par un revetement de surface

Country Status (2)

Country Link
AU (3) AU6508696A (fr)
WO (3) WO1997002134A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE20112198U1 (de) * 2001-07-24 2001-09-13 Jakob Schmid Söhne GmbH & Co. KG, 72108 Rottenburg Holzelement für Bodenbeläge
DE10160572A1 (de) * 2001-12-10 2003-07-17 Bayer Ag Herstellverfahren für Schichtstoffe auf Holzfurnierbasis
EP1447189A1 (fr) * 2003-02-11 2004-08-18 Materia Nova A.S.B.L Procédé de traitement d'un élément en bois
FR2886196B1 (fr) * 2005-05-26 2007-08-17 Arc Nucleart Procede de stabilisation d'un substrat en un materiau comprenant du bois
FR2902685B1 (fr) * 2006-06-21 2010-02-26 Michel Faivre Procede d'etancheification d'un element de menuiserie en bois, et element ainsi obtenu
CA3058624A1 (fr) 2017-03-31 2018-10-04 Dow Global Technologies Llc Agents de conservation du bois
CA3114218A1 (fr) 2018-09-28 2020-04-02 Rohm And Haas Company Agents de conservation du bois
CA3114102A1 (fr) * 2018-09-28 2020-04-02 Rohm And Haas Company Agents de conservation du bois
CA3114101A1 (fr) * 2018-09-28 2020-04-02 Rohm And Haas Company Agents de conservation du bois
CN114845547B (zh) * 2018-09-28 2024-04-02 营养与生物科技美国第二有限公司 木材防腐剂

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4383070A (en) * 1982-05-27 1983-05-10 Mobay Chemical Corporation Storage stable polyurethane compositions

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4019171A1 (de) * 1990-06-15 1991-12-19 Henkel Kgaa Beschichtungsmittel

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4383070A (en) * 1982-05-27 1983-05-10 Mobay Chemical Corporation Storage stable polyurethane compositions

Also Published As

Publication number Publication date
AU6508696A (en) 1997-02-05
AU6602996A (en) 1997-02-05
WO1997002136A1 (fr) 1997-01-23
WO1997002134A1 (fr) 1997-01-23
AU6680696A (en) 1997-02-05

Similar Documents

Publication Publication Date Title
EP0391166B2 (fr) Revêtements résistant à l'écaillement et procédés d'application
FI112084B (fi) Vettä sisältäviä itsesilloittuvia polyuretaani-vinyylihybrididispersioita
KR102246054B1 (ko) 다층 코팅 및 이의 제조 방법
US4499151A (en) Color plus clear coating method utilizing addition interpolymers containing alkoxy silane and/or acyloxy silane groups
EP0304816B1 (fr) Méthode de revêtement par vernis de base-vernis clair à réparabilité améliorée utilisant un additif anhydride dans un vernis de base contenant un polymère thermoplastique
US5066733A (en) Chip resistant coatings and methods of application
JP3055197B2 (ja) ポリウレタン接着剤組成物
KR102692142B1 (ko) 방사선 경화성 조성물
EP0304817A1 (fr) Composition de revêtement non jaunissante à base d'un composant hydroxy et d'un composant anhydride et utilisation dans un procédé de revêtement
EP3428199B1 (fr) Composition de revêtement durcissable par rayonnement pour améliorer les propriétés de surface de matières plastiques
US4387194A (en) High solids internally U.V. stabilized melamine cured urethane paint
JPS6111971B2 (fr)
WO1997002135A1 (fr) Bois modifie dote de revetements de surface
EP4073178B1 (fr) Compositions de revêtement durcissables à basse température
KR102678559B1 (ko) 다층 코팅 및 이의 제조 방법
GB2038346A (en) Inhibition coating for propellant charges
KR102786885B1 (ko) 저온 경화 코팅 조성물
CA1129584A (fr) Peinture de finition en polyurethane durcissant a l'humidite et d'un lustre plus stable
JPH085872B2 (ja) ポリウレタンポリアンハイドライドオリゴマーおよび調製法
US6602605B2 (en) Modified wood with surface coatings
US5674565A (en) Liquid thermoset sealers and sealing process for molded plastics
EP4259680A1 (fr) Dispersion aqueuse comprenant un nucléophile basé sur l'effet alpha
KR20240116793A (ko) 카바제이트 작용성 화합물
US6174947B1 (en) Low volatile organic component polyurethane varnish
JP2890324B2 (ja) ウレタンプレポリマー及びポリウレタン組成物

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AT AU CA CH CN DE DK ES FI GB JP KR LU MX NO PT SE SG US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA