WO2012161692A1 - Résines barrières contre l'humidité pour revêtements résistant à la corrosion - Google Patents

Résines barrières contre l'humidité pour revêtements résistant à la corrosion Download PDF

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WO2012161692A1
WO2012161692A1 PCT/US2011/037599 US2011037599W WO2012161692A1 WO 2012161692 A1 WO2012161692 A1 WO 2012161692A1 US 2011037599 W US2011037599 W US 2011037599W WO 2012161692 A1 WO2012161692 A1 WO 2012161692A1
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cross
polymer
hydrolyzed
linkable
composition
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Robert G. Bayless
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Encap Technologies LLC
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Encap Technologies LLC
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    • 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
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/04—Homopolymers or copolymers of ethene
    • C09D123/08—Copolymers of ethene
    • C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09D123/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0853—Ethylene vinyl acetate copolymers
    • 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
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/08—Cellulose derivatives
    • C09D101/26—Cellulose ethers

Definitions

  • Coatings can be employed for a number of reasons.
  • Product coatings or industrial coatings are typically applied in a factory on a given metal substrate or product, such as appliances, automobiles, aircraft, and the like, to reduce the susceptibility of the metal substrate or product to corrosion from environmental exposure.
  • corrosion inhibitive sacrificial components or additives are typically used in coatings applied to the substrate.
  • coatings applied to the substrate For example, painting and/or application of enamel are common anti-corrosion treatments. These anti-corrosion treatments work by providing a barrier of corrosion-resistant material between the damaging environment and the substrate material. Aside from cosmetic and
  • Patent literature includes US Patent Publications 2003/0235690; 2004/0105979;
  • compositions, methods of making compositions, and methods of using compositions are described herein.
  • one embodiment provides corrosion resistant coatings and methods for inhibiting corrosion of a substrate with corrosion resistant coatings.
  • a corrosion resistant coating comprises a cross-linkable hydrolyzed polymer and a cross-linking agent.
  • the cross-linkable hydrolyzed polymer has a dielectric constant less than about 2.2.
  • the cross-linkable hydrolyzed polymer comprises a
  • hydrolyzable, cross-linkable ethylene-vinyl acetate copolymer such as partially hydrolyzed poly (ethylene-vinyl acetate).
  • the cross-linkable hydrolyzed polymer comprises partially hydrolyzed poly (ethylene-vinyl acetate)related embodiments, the partially hydrolyzed poly (ethylene-vinyl acetate) may comprise about 60 to about 88 mol percent ethylene.
  • the partially hydrolyzed poly (ethylene-vinyl acetate) is about 38 to about 55 percent hydrolyzed; such as about 44 to about 46 percent hydrolyzed.
  • the partially hydrolyzed poly (ethylene-vinyl acetate) comprises about 70 percent ethylene, about 10 to about 14 percent vinyl alcohol, and about 16 to about 20 percent vinyl acetate. In some related embodiments, the partially hydrolyzed poly (ethylene-vinyl acetate) comprises about 12.5 to about 13 percent vinyl alcohol. In other related
  • the partially hydrolyzed poly (ethylene-vinyl acetate) comprises about 17 to about 18 percent vinyl acetate. In other embodiments, the partially hydrolyzed poly
  • the cross-linkable hydrolyzed polymer may comprise a poly( vinyl-formal) polymer, a poly (vinyl-butyral) polymer, an alkylated cellulose, or an acylated cellulose; such as ethyl cellulose and/or cellulose acetate butyrate.
  • the cross-linking agent comprises one or more of a
  • the cross-linking agent may comprise an aliphatic diisocyanate, a non-aliphatic diisocyanate such as toluene diisocyanate, an aliphatic polyisocyanate, a non-aliphatic polyisocyanate, a toluene diisocyanate-trimethylol propane adduct, and/or a diacid halide, such as a dicarboxylic acid chloride, including adipoyl chloride, terephthaloyl chloride, or phosgene (carbonic dichloride).
  • a dicarboxylic acid chloride including adipoyl chloride, terephthaloyl chloride, or phosgene (carbonic dichloride).
  • the cross-linkable hydrolyzed polymer and the cross-linking agent are present in solution at a ratio of cross-linkable hydrolyzed polymer to cross-linking agent within the range of about 10:1 to 1 : 1 by weight; such as within the range of about 5 : 1 to 4:3 by weight; such as within the range of about 5: 1 to 2: 1 by weight; such as within the range of about 4:1 to 2: 1.
  • Cross-linkable hydrolyzed polymer and cross-linking agent present at these ranges preferably lead to cross linking occurring at a percentage of hydroxyl groups in the polymer within the range of about 8.73% to 87.3%; such as within the range of about 21.8% to 65.4%; such as within the range of about 21.8% to 43.6%, such as within the range of about 21.8 to about 35%, such as within the range of about 21.8 to about 25%.
  • the cross-linkable hydrolyzed polymer and the cross-linking agent are present in solution at a ratio of cross-linkable hydrolyzed polymer to cross-linking agent within the range of about 5:1 to 10:3 by weight; such as within the range of about
  • Cross-linkable hydrolyzed polymer and cross-linking agent present at these ranges preferably lead to cross linking occurring at a percentage of hydroxyl groups in the polymer within the range of about 17% to 26%; such as within the range of about 18% to 26%; such as within the range of about 18% to 22%; such as about 22%.
  • the corrosion resistant coating has a permeance less than about 3.00 x 10 - " 7 g/Pa*s*m 2 ; such as less than about 1.00 x 10 - " 7 g/Pa*s*m 2 ; such as less than about 5.00 x 10 - " 8 g/Pa*s*m 2 ; such as less than about 1.00 x 10 - " 8 g/Pa*s*m 2.
  • the corrosion resistant coating has a thickness within the range of about 1 to 33 mils; such as within the range of about 5 to 33 mils; such as within the range of about 10 to 33 mils; such as within the range of about 15 to 33 mils.
  • methods of inhibiting corrosion of a substrate include the steps of: dissolving a cross-linkable hydrolyzed polymer in an organic solvent to generate a cross- linkable hydrolyzed polymer solution; adding a cross-linking agent to the cross-linkable hydrolyzed polymer solution to generate a cross-linked hydrolyzed polymer solution; and applying the cross-linked hydrolyzed polymer solution to a substrate to form a corrosion inhibiting coating on the substrate.
  • the step of applying cross-linked hydrolyzed polymer solution to a substrate comprises applying two or more coats of cross-linked hydrolyzed polymer solution to the substrate. In some embodiments, the step of applying cross-linked hydrolyzed polymer to the substrate comprises spraying cross-linked hydrolyzed polymer solution on the substrate.
  • the cross-linkable hydrolyzed polymer has a dielectric constant less than about 2.2.
  • the cross-linkable hydro lyzed polymer comprises a
  • hydrolyzable, cross-linkable ethylene-vinyl acetate copolymer such as partially hydrolyzed poly (ethylene-vinyl acetate).
  • the partially hydrolyzed poly (ethylene-vinyl acetate) may comprises about 60 to about 88 mol percent ethylene. In some embodiments, the partially hydrolyzed poly (ethylene-vinyl acetate) is about 38 to about 55 percent hydrolyzed; such as about 44 to about 46 percent hydrolyzed. In other embodiments, the partially hydrolyzed poly (ethylene-vinyl acetate) comprises about 70 percent ethylene, about 10 to about 14 percent vinyl alcohol, and about 16 to about 20 percent vinyl acetate. In some related embodiments, the partially hydrolyzed poly (ethylene-vinyl acetate) comprises about 12.5 to about 13 percent vinyl alcohol. In other related
  • the partially hydrolyzed poly (ethylene-vinyl acetate) comprises about 17 to about 18 percent vinyl acetate. In other embodiments, the partially hydrolyzed poly
  • (ethylene-vinyl acetate) comprises vinyl alcohol groups and vinyl acetate groups at a mole ratio of vinyl alcohol groups to the sum of vinyl alcohol groups and the vinyl acetate groups at about 0.15 to about 0.7.
  • the partially hydrolyzed poly (ethylene- vinyl acetate) has a hydroxyl content of about 204 ⁇ 5% mg KOH / g.
  • the cross-linkable hydrolyzed polymer may comprise a poly( vinyl-formal) polymer, a poly (vinyl-butyral) polymer, an alkylated cellulose, or an acylated cellulose; such as ethyl cellulose and/or cellulose acetate butyrate.
  • the cross-linking agent comprises one or more of a diisocyanate and a polyisocyanate, with or without a catalyst present.
  • the cross-linking agent may comprise an aliphatic diisocyanate, a non-aliphatic diisocyanate such as toluene diisocyanate, an aliphatic polyisocyanate, a non-aliphatic polyisocyanate, a toluene diisocyanate-trimethylol propane adduct, and/or a diacid halide, such as a dicarboxylic acid chloride, including adipoyl chloride, terephthaloyl chloride, or phosgene (carbonic dichloride).
  • a dicarboxylic acid chloride including adipoyl chloride, terephthaloyl chloride, or phosgene (carbonic dichloride).
  • the cross-linkable hydrolyzed polymer and the cross-linking agent are present in solution at a ratio of cross-linkable hydrolyzed polymer to cross-linking agent within the range of about 10:1 to 1 : 1 by weight; such as within the range of about 4 : 1 to 4:3 by weight; such as within the range of about 4:1 to 2: 1 by weight.
  • Cross-linkable hydrolyzed polymer and cross-linking agent present at these ranges preferably lead to cross linking occurring at a percentage of hydroxyl groups in the polymer within the range of about 8.73% to 87.3%; such as within the range of about 21.8% to 65.4%>; such as within the range of about 21.8%) to 43.6%, such as within the range of about 21.8%) to about 35%, such as within the range of about 21.8 to about 25%.
  • the cross-linkable hydrolyzed polymer and the cross-linking agent are present in solution at a ratio of cross-linkable hydrolyzed polymer to cross-linking agent within the range of about 5:1 to 10:3 by weight; such as within the range of about 100:21 to 10:3 by weight; such as within the range of about 100:21 to 4: 1 by weight; such as about 4: 1.
  • Cross-linkable hydrolyzed polymer and cross-linking agent present at these ranges preferably lead to cross linking occurring at a percentage of hydroxyl groups in the polymer within the range of about 17% to 26%; such as within the range of about 18% to 26%; such as within the range of about 18% to 22%; such as about 22%.
  • the corrosion resistant coating has a permeance less than about 3.00 x 10 - " 7 g/Pa*s*m 2 ; such as less than about 1.00 x 10 - " 7 g/Pa*s*m 2 ; such as less than about 5.00 x 10 - " 8 g/Pa*s*m 2 ; such as less than about 1.00 x 10 - " 8 g/Pa*s*m 2.
  • the corrosion resistant coating has a thickness within the range of about 1 to 33 mils; such as within the range of about 5 to 33 mils; such as within the range of about 10 to 33 mils; such as within the range of about 15 to 33 mils.
  • the substrate comprises a metal, particularly a metal susceptible to corrosion due to environmental exposure.
  • Corrosion refers to degradation of a material or substrate due to chemical reaction with its surroundings. Many metals, including structural alloys, corrode merely from exposure to moisture in the air. Corrosion can be concentrated locally to form a pit or crack, or can extend across a wide exposed area.
  • Polymer refers to a large molecule comprising repeating structural units typically connected by covalent chemical bonds.
  • Cross-linking refers to bonding that occurs between two or more polymer molecules. The degree of cross-linking may be expressed stoichiometrically, as the percentage of hydroxyl groups in the polymer that are involved in cross-linking bonds.
  • Bulk substrate refers to a material suitable for coating by the methods or materials described herein.
  • Bulk substrates are not limited in composition, but are limited in size and shape in that bulk substrates are not particulate substrates, such as nanoparticles or microparticles. Certain properties of a coating, such as adhesion, may be different when applied to a bulk substrate as compared to a particulate substrate.
  • the present invention relates, in some embodiments, to corrosion resistant resins which are derived from a solution comprising a film-forming, cross-linkable, partially hydrolyzed polymer and a cross-linking agent.
  • these two reagents When these two reagents are mixed in an appropriate ratio, they form a cross-linked polymer which can be applied to the surface of a variety of corrodible substrates.
  • the cross-linked polymer acts as a moisture barrier, and may be used as a corrosion resistant coating.
  • the corrosion resistant coatings described herein form films on the surface of the substrate.
  • the coatings may be applied in one or more coats to achieve any desired thickness.
  • corrosion resistant coatings as described herein may have thicknesses of about 1 to about 100 mils, such as about 1 to about 75 mils, such as about 1 to about 50 mils.
  • the cross-linkable hydrolyzed polymer and the cross-linking agent are present in solution at a ratio of cross-linkable hydrolyzed polymer to cross-linking agent within the range of about 10:1 to 1 : 1 by weight; such as within the range of about 4 : 1 to 4:3 by weight; such as within the range of about 4:1 to 2: 1 by weight.
  • Cross-linkable hydrolyzed polymer and cross-linking agent present at these ranges preferably lead to cross linking occurring at a percentage of hydroxyl groups in the polymer within the range of about 8.73% to 87.3%; such as within the range of about 21.8% to 65.4%; such as within the range of about 21.8%) to 43.6%>; such as within the range of about 21.8 to about 35%; such as within the range of about 21.8 to about 25%.
  • certain degrees of cross-linking and certain thickness result in improved moisture impermeability.
  • cross-linkable hydrolyzed polymer to cross-linking agent may be present in solution at a ratio within the range of about cross-linkable hydrolyzed polymer to cross-linking agent between about
  • the cross-linkable hydrolyzed polymer and the cross-linking agent are present in solution at a ratio of cross- linkable hydrolyzed polymer to cross-linking agent within the range of about 5:1 to 10:3 by weight; such as within the range of about 100:21 to 10:3 by weight; such as within the range of about 100:21 to 4: 1 by weight; such as about 4: 1.
  • Cross-linkable hydrolyzed polymer and cross-linking agent present at these ranges preferably lead to cross linking occurring at a percentage of hydroxyl groups in the polymer within the range of about 17% to 26%; such as within the range of about 18% to 26%; such as within the range of about 18% to 22%; such as about 22%.
  • the corrosion resistant coating has a permeance less than about 3.00 x 10 "7 g/Pa*s*m 2 ; such as less than about 1.00 x 10 "7 g/Pa*s*m 2 ; such as less than about 5.00 x 10 - " 8 g/Pa*s*m 2 ; such as less than about 1.00 x 10 - " 8 g/Pa*s*m 2.
  • the corrosion resistant coating has a thickness within the range of about 1 to 33 mils; such as within the range of about 5 to 33 mils; such as within the range of about 10 to 33 mils; such as within the range of about 15 to 33 mils.
  • the cross-linked corrosion resistant coating may be applied in thicknesses of about 15 mils or greater, such as about 15 mils to about 75 mils, such as about 15 to about 50 mils, such as about 15 mils to about 35 mils.
  • the polymer should be substantially dielectric, preferably with a dielectric constant less than about 2.2, preferably in the range of from about 1.8 to about 2.2.
  • Various polymers may be utilized to form the cross-linked corrosion resistant coating.
  • a preferred polymer is a hydrolyzable, cross-linkable ethylene-vinyl acetate copolymer.
  • the polymer should be pyrolyzable.
  • the polymeric material can be any film-forming polymeric material that wets the substrate material.
  • the corrosion resistant coating material preferably is partially hydrolyzed poly (ethylene-vinyl acetate) containing about 60 mol % to about 88 mol % ethylene, in which some of the vinyl acetate groups are hydrolyzed to form vinyl alcohol groups that provide reaction sites for subsequent cross-linking.
  • the degree of hydrolysis for the poly (ethylene-vinyl acetate) can be within the relatively broad range of about 38 % to about 55 %, preferably within the range of about 44 % to about 46 %.
  • a preferred film-forming polymer for use in the presently claimed inventions is a poly (ethylene-vinyl acetate) containing about 60 mol % to about 88 mol % ethylene and having about 38 % to about 55 % (preferably between about 44 % and about 46 %) of the vinyl acetate groups hydrolyzed to vinyl alcohol groups to provide reaction sites for cross-linking.
  • the partially hydrolyzed copolymers of ethylene and vinyl acetate contain ethylene groups, vinyl acetate groups, and vinyl alcohol groups, and can be represented by the general formula:
  • x, y and z represent mol fractions of ethylene, vinyl alcohol and vinyl acetate, respectively.
  • the mol ratio of the vinyl alcohol groups to the sum of vinyl alcohol groups and the vinyl acetate groups present is about 0.15 to about 0.7.
  • the amount of ethylene groups present is also important and can be about 60 to about 88 mol percent. Stated another way, the mol ratio of ethylene groups to the sum of ethylene groups, vinyl alcohol groups and vinyl acetate groups can be about 0.6 to about 0.88.
  • the suitable partially-hydrolyzed poly (ethylene -vinyl acetate) has a molecular weight of about 50,000 and a melt index (using a 2160 gram force at 190 °C, for 10 minutes) of about 5 to about 70, preferably a melt index of about 35 to about 45.
  • the molecular weight of the copolymer is not overly critical, except that if the molecular weight is too high, the copolymer will be relatively insoluble.
  • cross-linkable polymeric materials include poly( vinyl-formal) polymers, poly (vinyl-butyral) polymers, alkylated cellulose (e.g., ethyl cellulose), acylated cellulose (e.g., cellulose acetate butyrate) and the like.
  • the preferred polymer is poly (ethylene-vinyl acetate) having a melt index of about 35 to about 37 and having about 44 % to about 46 % of the vinyl acetate groups hydro lyzed to vinyl alcohol groups.
  • This polymer has an ethylene content of about 70 %, a vinyl alcohol content of about 10 % to about 14 % (most preferably about 12.5 % to about 13 %) and a vinyl acetate content of about 16 % to about 20 % (most preferably about 17 % to about 18 %).
  • Suitable cross-linking agents useful for preparation of the corrosion resistant coatings include the diisocyanates or polyisocyanates, e.g., aliphatic diisocyanates, non-aliphatic diisocyanates such as toluene diisocyanate, aliphatic polyisocyanates, and non-aliphatic polyisocyanates, with or without a catalyst present. Particularly preferred is a toluene diisocyanate-trimethylol propane adduct.
  • cross-linking agents are diacid halides, such as dicarboxylic acid chloride, including adipoyl chloride, terephthaloyl chloride, or phosgene (carbonic dichloride) and the like, as well as difunctional hydrides.
  • diacid halides such as dicarboxylic acid chloride, including adipoyl chloride, terephthaloyl chloride, or phosgene (carbonic dichloride) and the like, as well as difunctional hydrides.
  • cross-linking of the polymer may be accomplished by any other method known in the art.
  • Application of the cross-linking / polymer mixture to a substrate may be
  • the cross-linking / polymer mixture may be applied to a substrate by dipping, spraying, and the like.
  • the corrosion resistant coating may be applied to the substrate in one or more coats. In preferred embodiments, one to three coats are applied to the substrate. In especially preferred embodiments, two coats are applied to the substrate. [0043] Moisture permeability of the corrosion resistant coating is dependent to a considerable extent on the degree of cross-linking that has been effected. However, excessive cross- linking also negatively impacts the adhesion of the coating to the surface of a bulk substrate.
  • the preferential ratios of cross-linkable hydrolyzed polymer to cross-linking agent may be less than 1 : 1 by weight; such as between about 4: 1 to 1 : 1 by weight; such as between about 4:1 and 4:3 by weight; such as between about 4: 1 to about 2: 1 by weight; such as about 2: 1 by weight.
  • Cross-linkable hydrolyzed polymer and cross-linking agent present at these ranges preferably lead to cross linking occurring at a percentage of hydroxyl groups in the polymer within the range of about 43.6% to 87.3%; such as between about 43.6%> to 65.4%>; such as about 43.6%>.
  • a solution of a film-forming polymeric material comprising partially hydrolyzed ethylene -vinyl acetate copolymer (HEVA), having from about 38 % to about 55 %, and preferably from about 44 % to about 46 %, of the vinyl acetate groups hydrolyzed to form vinyl alcohol groups, is prepared in a liquid vehicle such as toluene at an elevated dissolution temperature (e.g., typically above about 70 °C, and preferably from about 75 °C to about 100 °C).
  • HEVA ethylene -vinyl acetate copolymer
  • this admixture is cooled, and a solution of a cross-linking agent, such as toluene diisocyanate (TDI) adducted with trimethylol propane in toluene, is added and the solution mixed.
  • a cross-linking agent such as toluene diisocyanate (TDI) adducted with trimethylol propane in toluene
  • the solution prepared above may then be applied to a substrate as a surface coating, for example, by dipping the substrate in the mixture at room temperature.
  • the cross-linked polymeric coating is then allowed to set at room temperature. Multiple coatings may be applied by re-dipping the substrate in the solution. Preferably, each coating is allowed some period of time to set, such as about 10 to 20 minutes, before application of a subsequent coat. Preferably, two coats are applied.
  • a plural-spray or proportional spray system may be used to apply the corrosion resistant coating. Plural-spray or proportional spray systems do not mix the polymeric material and the cross-linking agent until immediately prior to spray application.
  • a HEVA / tolulene admixture may be prepared as described above, and loaded into the sprayer system.
  • the cross-linking agent may then be loaded into a separate chamber of the sprayer system. Mixing of the two components then only occurs immediately prior to spraying of the coating.
  • each coating is allowed some period of time to set, such as about 10 to 20 minutes, before application of a subsequent coat.
  • test panels Fourteen 1010 cold-rolled steel test panels were prepared with polymer/primer, or polymer/primer/enamel top coat for cyclic corrosion testing. All test panels were first dipped into a cross linked polymer made from hydrolyzed ethylene vinyl acetate (HEVA) (dissolved in toluene at about 10% HEVA by weight) and Desmodur® L 75 (an aromatic polyisocynate cross linking agent by Bayer Material Science) at about a 1 : 1 ratio by weight, and allowed to dry.
  • HEVA hydrolyzed ethylene vinyl acetate
  • Desmodur® L 75 an aromatic polyisocynate cross linking agent by Bayer Material Science
  • Cyclic exposure testing was conducted according to ASTM D5894-96, Standard Practice for Cyclic Salt Fog/UV Exposure of Painted Metal, (Alternating Exposures in a Fog/Dry Cabinet and a UV /Condensation Cabinet). Three polymer/primer panels were diagonally scribed prior to exposure testing. All test panels were subjected to a cycle of alternating fluorescent UV/condensation and alternating salt fog/drying. [0053] The test panels were first subjected to 168 hours of fluorescent UV/condensation consisting of alternating every four hours between exposure to UV light (UVA 340 bulbs at 0.77 W/m 2 /nm at 340 nm) at 60°C and condensation at 50°C.
  • salt fog/drying consisting of alternating every hour between exposure to a salt fog (dilute electrolyte solution of 0.05% sodium chloride and 0.35% ammonium sulfate) at ambient temperature and drying at 35°C.
  • polymer/primer/enamel panels showed no sign of corrosion or discoloration.
  • Ten of the sixteen test panels were first coated with a cross-linked polymer base coat by dipping into a cross-linked polymer made from HEVA (dissolved in toluene at about 10% HEVA by weight) and Desmodur® L 75 (an aromatic polyisocyanate cross linking agent by Bayer Material Science) at about a 2: 1 ratio by weight, and allowed to dry.
  • HEVA dissolved in toluene at about 10% HEVA by weight
  • Desmodur® L 75 an aromatic polyisocyanate cross linking agent by Bayer Material Science
  • Cyclic exposure testing was conducted according to ASTM D5894-05, Standard Practice for Cyclic Salt Fog/UV Exposure of Painted Metal, (Alternating Exposures in a Fog/Dry Cabinet and a UV /Condensation Cabinet). All panels were diagonally scribed and subjected to three cycles of fluorescent UV/condensation and salt fog/drying.
  • test panels were evaluated for surface corrosion (per ASTM D610-01 , Standard Test Method for Evaluating Degree of Rusting on Painted Steel Surfaces), blistering (per ASTM D714-02, Standard Test Method for Evaluating Degree of Blistering of Paints), and creep from scribe (per ATSM D 1654-05, Standard Test Method for Evaluation of Painted or Coated Specimens Subjected to Corrosive Environments).
  • the scale of Rust Rating according to ASTM D610-01 is presented above in Table 2.
  • test panels were first subjected to 168 hours of fluorescent UV/condensation cycling consisting of alternating every four hours between exposure to UV light (UVA 340 bulbs at 0.89 W/m 2 /nm at 340 nm) at 60°C, and condensation at 50°C ⁇ 3°C.
  • test panels were then subjected to 168 hours of salt fog/drying cycling consisting of alternating every hour between exposure to a salt fog (dilute electrolyte solution of 0.05%> sodium chloride and 0.35% ammonium sulfate) at ambient temperature, and drying time at 35°C.
  • salt fog dilute electrolyte solution of 0.05%> sodium chloride and 0.35% ammonium sulfate
  • Eighteen of the twenty two test panels were first coated with a cross-linked polymer base coat by dipping into a cross-linked polymer made from HEVA (dissolved in toluene at about 10% HEVA by weight) and Desmodur® L 75 (an aromatic polyisocynate cross linking agent by Bayer Material Science) at about a 4: 1 ratio by weight, and allowed to dry.
  • HEVA dissolved in toluene at about 10% HEVA by weight
  • Desmodur® L 75 an aromatic polyisocynate cross linking agent by Bayer Material Science
  • Cyclic exposure testing was conducted according to ASTM D5894-05, Standard Practice for Cyclic Salt Fog/UV Exposure of Painted Metal, (Alternating Exposures in a Fog/Dry Cabinet and a UV/Condensation Cabinet). Panels 1, 3, 9, 10, and 13 were diagonally scribed prior to exposure testing. All test panels were subjected to three cycles of fluorescent UV/condensation and salt fog/drying.
  • test panels were visually evaluated for surface corrosion (per ASTM D610-01, Standard Test Method for Evaluating Degree of Rusting on Painted Steel Surfaces), blistering (per ASTM D714-02, Standard Test Method for Evaluating Degree of Blistering of Paints), and creep from scribe (per ATSM D 1654-05, Standard Test Method for Evaluation of Painted or Coated Specimens Subjected to Corrosive Environments).
  • the scale of Rust Rating according to ASTM D610-01 is presented above in Table 2.
  • test panels were first subjected to 168 hours of fluorescent UV/condensation consisting of alternating every four hours between exposure to UV light (UVA 340 bulbs at 0.89 W/m 2 /nm at 340 nm) at 60°C and condensation at 50°C ⁇ 3°C.
  • salt fog/drying consisting of alternating every hour between exposure to a salt fog (dilute electrolyte solution of 0.05% sodium chloride and 0.35% ammonium sulfate) at ambient temperature and drying at 35°C.
  • Example 4 Polymer Adhesion as a Function of Cross-Linking
  • polymer adhesion is increased for cross-linked polymers prepared from mixtures of cross-linkable hydrolysable polymer to cross linking agent at ratios greater than 1 : 1 cross-linkable polymer : cross linking agent.
  • cross-linkable polymer : cross linking agent ratio by weight
  • Adhesion is the ability of a coating to be continuously attached the object upon which it is applied throughout its normal service life. Thin films prepared according to various embodiments described herein were tested to determine their adhesion characteristics.
  • Adhesion testing was conducted according to ASTM D4541, Standard Method for Pull-Off Strength of Coatings Using Portable Adhesion Testers. Adhesion is measured as the force per square inch required to pull a coating off of a metal panel's surface and is expressed as pounds per square inch (psi).
  • Embodiments of the present invention were measured to have adhesion pull-off strengths in the range of about 1870 to about 2050 psi.

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  • Wood Science & Technology (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

L'invention concerne une composition permettant de préparer un revêtement résistant à la corrosion destiné à un substrat massif, ladite composition comprenant: un polymère hydrolysé réticulable; et un agent de réticulation, l'agent de réticulation étant présent en quantité suffisante pour réticuler d'environ 21,8 % à 65,4 % des groupes réticulables du polymère hydrolysé réticulable. L'invention concerne de plus un procédé visant à inhiber la corrosion d'un substrat massif, ledit procédé comprenant les étapes suivantes: dissoudre un polymère hydrolysé réticulable dans un solvant organique afin de former une solution de polymère hydrolysé réticulable; ajouter un agent de réticulation à ladite solution de polymère hydrolysé réticulable, en quantité suffisante pour produire un polymère hydrolysé réticulé contenant d'environ 21,8 % à 65,4 % groupes hydroxyle réticulés; et appliquer ledit polymère hydrolysé réticulé sur le substrat massif. L'invention concerne aussi un substrat massif revêtu, qui comprend: un substrat massif; un revêtement résistant à la corrosion, qui comprend un polymère hydrolysé réticulé présentant un taux de réticulation d'environ 21,8 % à 65,4 %, ledit revêtement résistant à la corrosion étant en contact avec au moins une partie d'une surface dudit substrat massif.
PCT/US2011/037599 2011-05-23 2011-05-23 Résines barrières contre l'humidité pour revêtements résistant à la corrosion Ceased WO2012161692A1 (fr)

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PCT/US2011/037599 WO2012161692A1 (fr) 2011-05-23 2011-05-23 Résines barrières contre l'humidité pour revêtements résistant à la corrosion

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PCT/US2011/037599 WO2012161692A1 (fr) 2011-05-23 2011-05-23 Résines barrières contre l'humidité pour revêtements résistant à la corrosion

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WO2012161692A1 true WO2012161692A1 (fr) 2012-11-29

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JP2018009108A (ja) * 2016-07-14 2018-01-18 ユケン工業株式会社 防錆用コーティング処理液

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US5418014A (en) * 1992-01-21 1995-05-23 Eastman Chemical Company Aqueous dispersion useful in coatings containing hydrolyzed cellulose ester and acrylic resin
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US20040105979A1 (en) 2002-08-14 2004-06-03 Encap Technologies, Inc. Microencapsulated and nanoencapsulated particles, moisture barrier resins, and processes for manufacturing same
US20040130045A1 (en) 2001-11-20 2004-07-08 Bayless Robert G. Microencapsulated particles and process for manufacturing same
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US4137364A (en) * 1976-11-05 1979-01-30 Monsanto Research Corporation Transparent laminate and adhesive film
US5418014A (en) * 1992-01-21 1995-05-23 Eastman Chemical Company Aqueous dispersion useful in coatings containing hydrolyzed cellulose ester and acrylic resin
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US20070167561A1 (en) * 2006-01-12 2007-07-19 Dynea Oy Polymer-aldehyde binding system for manufacture of wood products

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018009108A (ja) * 2016-07-14 2018-01-18 ユケン工業株式会社 防錆用コーティング処理液

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