WO2002043881A9 - An engineered composite system, system component compositions, and methods of use - Google Patents
An engineered composite system, system component compositions, and methods of useInfo
- Publication number
- WO2002043881A9 WO2002043881A9 PCT/US2001/044497 US0144497W WO0243881A9 WO 2002043881 A9 WO2002043881 A9 WO 2002043881A9 US 0144497 W US0144497 W US 0144497W WO 0243881 A9 WO0243881 A9 WO 0243881A9
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ranging
- basecoat
- agents
- substrate
- topcoat
- Prior art date
Links
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- 238000000227 grinding Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229920006247 high-performance elastomer Polymers 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000000752 ionisation method Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 230000003137 locomotive effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229960003574 milrinone Drugs 0.000 description 1
- VWUPWEAFIOQCGF-UHFFFAOYSA-N milrinone lactate Chemical compound [H+].CC(O)C([O-])=O.N1C(=O)C(C#N)=CC(C=2C=CN=CC=2)=C1C VWUPWEAFIOQCGF-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 235000012015 potatoes Nutrition 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010107 reaction injection moulding Methods 0.000 description 1
- 230000029058 respiratory gaseous exchange Effects 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000013020 steam cleaning Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-M urea-1-carboxylate Chemical compound NC(=O)NC([O-])=O AVWRKZWQTYIKIY-UHFFFAOYSA-M 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
- B05D7/148—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using epoxy-polyolefin systems in mono- or multilayers
-
- 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
- C08G18/003—Polymeric products of isocyanates or isothiocyanates with epoxy compounds having no active hydrogen
-
- 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
- C08G18/698—Mixtures with compounds of group C08G18/40
-
- 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
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
- B05D1/08—Flame spraying
- B05D1/10—Applying particulate materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/08—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by flames
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249987—With nonvoid component of specified composition
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31511—Of epoxy ether
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31844—Of natural gum, rosin, natural oil or lac
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31844—Of natural gum, rosin, natural oil or lac
- Y10T428/31848—Next to cellulosic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
Definitions
- the present invention relates to an engineered composite system, system component compositions and methods of use, and in particular to a system employing a thermosetting asphalt extended cross-linked hybrid basecoat for resting on a porous substrate, and for receiving a thermoplastic top coating.
- a number of coating materials have been proposed for thermal field applied applications, particularly flame-sprayed coatings.
- One problem with these types of field-applied coatings is that the substrate may be porous, e.g., wood or concrete, and is subject to off-gassing or thermal decomposition. Consequently, it is very difficult to coat these types of materials.
- the present invention solves this need by providing a field applied coating system that is ideally adapted for porous substrates.
- Another object of the invention is a field applied and/or shop applied, engineered composite system comprising: 1) an asphalt extended, chemically cross linked - urethane/epoxy hybrid basecoat, 2) an alcohol / silane primer, 3) a thermoplastic powder coating topcoat, 4) a optional fabric or fiber reinforcement layer, and the system components of the basecoat, the topcoat, and the primer.
- the present invention provides a coating system that comprises a basecoat of an thermosetting asphalt extended, chemically cross linked - urethane/epoxy hybrid basecoat resting on a substrate, preferably a porous substrate such as concrete or wood that off-gas when coated with a thermoplastic material; and a thermoplastic powder coating topcoat overlying at least the base coat.
- An alcohol-silane primer can be on the substrate and surrounding at least a portion of the basecoat while leaving a portion of the substrate exposed, the topcoat overlying both the primer and the portion of exposed substrate.
- the system can further comprise a reinforcing layer disposed between the basecoat and the topcoat, and the reinforcing layer can be one of a metallic or non- metallic fiber such as glass, a natural fiber such as cotton, a polymeric fiber, a carbon fiber, or combinations thereof.
- thermosetting basecoat composition comprises, in weight percent based on final formulation: between 10 and 90%, preferably 20 and 70, and most preferably 30 and 60% of a petroleum asphalt; between 10 and 90%, preferably 20 and 70, and most preferably 30 and 60% of a hydroxy-terminated homopolymer; between 0.1 and 30%, preferably 3 and 25, and most preferably 5 and 15% of a functional epoxy reactive diluent for reducing the viscosity of the composition; up to 5%, preferably 0.2 and 3%, and most preferably 0.3 and 1.0% of a surfactant for improving surface imperfections; up to 5%, preferably 0.2 and 3%, and most preferably 0.3 and 1.0% of an anti- oxidant; and up to 25%, preferably 0.1 and 10%, and most preferably 0.5 and 2.0% of an thickening agent.
- the basecoat can also comprise an effective amount of a hardener to cross link with the hydroxyl functional polybutadiene and reactive diluent components and active hydrogen contained in the asphalt, wherein the hardener is preferably an isocyanate type hardener, but can be diamine or an equivalent hardener.
- the basecoat composition can optionally including one or more of a catalyst in a range between 0.0001 and 5%, preferably 0.005 and 2%, and most preferably 0.1 and 2.0%, polyols for higher strength, other fillers for viscosity adjustment between 0.1 and 75%, functional silanes at 0.001 to 10%, thermal conductivity agents between 0.1 and 75% of the formulation such as zinc oxide for resiliency and conductivity, other fillers such as hollow and / or solid glass spheres (.001 to 5%), drying agents ranging up to 20 gram/gram of water present, flame retardants in amounts between 0.1 and 60%, corrosion inhibitors ranging from 0.1 and 50%, antistatic agents ranging from 0.1 to 50%, biostabilizers ranging from 0.1 to 10%, chemical blowing agents ranging from .1 to 10%, scent additives ranging from 0.1 to 25%, bittering agents ranging from 0.1 to 25%, pigments ranging from 0.1 to 40%, fluorescent whiting agents, ranging from 0.1 to 10%, lubricants, UV
- a topcoat thermoplastic composition comprises, in weight percent, based on final formulation: between 10 and 90%, preferably 20 and 70, and most preferably 30 and 60% of a modified ethylene terpolymer with a temperature stable ester and high acidic functionality; between 5 and 95, preferably 20 and 70, and most preferably 30 and 60% of a polyethylene/methacrylic acid copolymer; between 5 and 95, preferably 5 and 70, and most preferably 7.5 and 20% of a polyethylene/methacrylic acid copolymer ionomer; up to 50% of a coloring pigment; up to 5% of an anti-oxidant; up to 5% of an ultraviolet stabilizer; up to 5%, preferably 0.2 and 3%, and most preferably 0.3 and 1.0% of a surfactant for improving surface imperfections; and up to 25%, preferably 0.1 and 10%, and most preferably 0.5 and 2.0% of a thickening agent.
- the topcoat composition can optionally contain one or more of other fillers for viscosity adjustment between 0.1 and 75%, thermal conductivity agents between .1 and 75% of the formulation such as zinc oxide for resiliency and conductivity, drying agents ranging up to 20 gram/gram of water present, flame retardants in amounts between 0.1 and 60%, corrosion inhibitors ranging from 0.1 and 50%, antistatic agents ranging from 0.1 to 50%, biostabilizers ranging from 0.1 to 10%, chemical blowing agents ranging from .1 to 10%, scent additives ranging from 0.1 to 25%, bittering agents ranging from 0.1 to 25%, pigments ranging from 0.1 to 40%, fluorescent whiting agents, raging from 0.1 to 10%, and lubricants, and plasticizers each ranging from 0.1 to 25%.
- other fillers for viscosity adjustment between 0.1 and 75% such as zinc oxide for resiliency and conductivity
- drying agents ranging up to 20 gram/gram of water present
- flame retardants in amounts between 0.1 and 60%
- Coating nuclear plant equipment loading the topcoat and basecoat with powder Tungsten, or other like materials, allows the composite to shield against certain levels of radiation.
- the material provides excellent adhesion to a variety of materials. Item • tested to date include: concrete, aluminum, steel, glass, fiberglass, plastic, paper, wood, Teflon ® , roofing shingles, rubber, ceramic, leather, and synthetic foam.
- the basecoat material when used as a stand-alone coating, provides excellent adhesion, chemical resistance, resiliency, impact resistance, flexibility, and elongation. It successfully bridges gaps in areas such as concrete seems.
- topcoat resin chemistries and additives may be utilized to provide for different end uses, such as - more abrasion resistance, increased hardness, different chemical resistance profiles, different service temperatures, etc.
- any virtual array of blends utilizing the aforementioned thermoplastic resins, modified resins, or co - and poly - polymers of above listed resins may be used.
- All coatings can be made available in virtually an unlimited array of color selections and finishes. From fluorescent to jet-black; from smooth - high gloss, dimple and pinhole free surface - to wrinkled textures; as well as colors and finishes between these extremes.
- Coating of a part generally requires two steps (but not necessarily in this order): 1. deposition of the powder, and 2. Oven (heat) to flow the powder into a film.
- a spray booth is very desirable, and in some instances necessary. The booth keeps the powder overspray contained so that it is not a hazard (high concentrations of air-borne powder can be an explosion hazard). Other hazards that are curbed include breathing of the dust. The booth also promotes good "industrial hygiene.” Also, by use of a spray booth, powder overspray may be reclaimed for reuse.
- Figure 2 shows one of the simplest methods in which to coat parts.
- a fluidized-bed canister is filled with powder.
- a small amount of air is introduced into the bottom of the canister and rises through a porous fluidizing board. This "fluffs" the powder and causes it to behave like a liquid, or to become “fluidized.”
- the part is preheated and dipped into the fluidized bed, and treated afterwards if necessary with additional heating for the proper finish.
- Figures 3 and 4 illustrate electrostatic spray methods. As the powder paint cloud gently leaves the spray gun, it is charged with static electricity to attract the powder paint to the part being coated. The part is then placed in an oven (typically 250-600°F) and allowed to melt and flow to a "proper durable and beautiful finish.” In Figure 3, the part can be preheated.
- an oven typically 250-600°F
- Figures 5 and 6 show electrostatic fluid-bed methods.
- powder particles are aerated in a fluidizing chamber.
- the powder is electrostatically charged by ionized air, which passes through a porous plate at the base of the fluidized bed.
- the part is preheated in Figure 5 prior to passing through the cloud of particles, whereas Figure 6 merely conveys the part through the cloud, and then subjects the part to post heating if necessary.
- the charged powder particles which repel one another, rise above the fluidizing bed, forming a cloud of charged particles.
- a hood above the fluidizing bed prevents powder from entering the plant atmosphere. When a grounded part is placed in the cloud or conveyed through it, the charged particles are attracted to the part.
- a hardener e.g., a modified diphenylmethane diisocyanate
- 1 : 9 resin by wt. corresponding to a NCO/OH ratio of approximately 1.10
- other hardeners may be used as would be recognized by those skilled in the art.
- the asphalt is incorporated into the formulation to provide tack, and to extend the hydroxy-terminated, 1 ,3-butadiene homopolymer (cost effective).
- Lower loadings of asphalt will produce a harder, less elastic material - as well as reducing the viscosity of the blended resin system.
- Higher loadings of the asphalt will produce a more viscous resin, which cures to yield a softer material that has more residual tack and elasticity.
- a broad range of 10-90%, final formulation is obtainable.
- Materials such as petroleum asphalt grade PG 64-22 are noted to increase the tensile properties by upwards of 20%.
- other petroleum based, hydrocarbon crudes may substitute.
- Petroleum hydrocarbon oil may also be used in conjunction with the asphalt, as an extender and diluent.
- Other thermoplastic and non-thermoplastic resins, and other thermoplastic and non- thermoplastic resins with select fillers may be added at a range of 10-90% to modify end physical (such as topcoat/basecoat inter-adhesion).
- a list of generally compatible extenders that may substitute include: dioctyl phthalate, diundecyl phthalate, tricresyl phosphate, halogenated paraffin, aromatic process oil, naphthenic process oil, alkyl naphthalenes, asphalt, coal tar, linseed oil, tung oil, detergent alkylate, and others as recognized by those skilled in the art.
- the hydroxy-terminated, 1 ,3-butadiene homopolymer is incorporated into the formulation to provide resiliency and crosslinkability (through the hydroxyl groups on the terminus of the butadiene polymer). Increasing the loading of this ingredient (and the corresponding amount of hardener) will result in a harder material that has reduced elasticity. Decreasing the ingredient (and the corresponding amount of hardener) will result in a softer mastic with greater elongation properties. A range of 10-90%, final formulation is obtainable.
- other functionalized polymers, with either aromatic or aliphatic type backbones may be substituted (also copolymers and modified homo/co polymers).
- the functional groups may include: alkyd, hydroxy, carboxy, amine, and virtually any other compound containing an active hydrogen.
- the diglycidyl ether reactive diluent is used to reduce the viscosity of the resin and cross-link with the hardener. Increasing the loading of this ingredient (and the corresponding amount of hardener) will result in a harder material that has reduced elasticity. Decreasing the ingredient (and the corresponding amount of hardener) will result in a softer mastic with greater elongation properties, although the viscosity increases dramatically. This material provides for better topcoat-basecoat adhesion. A range of 0.1 - 30%, final formulation is obtainable.
- other functionalized polymers, with either aromatic or aliphatic type backbones may be substituted.
- the functional groups may include: alkyd, hydroxy, carboxy, amine, and virtually any other compound containing an active hydrogen.
- the polymers may have a range of functionality / molecule. Harder, less flexible films are expected as functionality increases. Also, viscosity may range from 1cP upwards of 5000cP. It is also plausible to consider non-reactive diluents, such as plasticizers, oils, etc. Other glycilyl reactive diluents can be used as well. As another example, a mono- functional glycidyl ether diluent results in a very soft "gel" mastic, which enhances the system where foot traffic and ergonomics are important.
- the acrylic is used to improve flow, eliminate air entrapment, orange peel, pinholes, craters, and other surface imperfections. This ingredient improves the flexibility of the coating and provides for better topcoat-basecoat adhesion.
- a range of 0.1 to 5%, final formulation is obtainable.
- Other acrylic (supplied as both liquid or on solid carrier particles) and non-acrylic modifiers yield virtually the same results (i.e., benzoin and Acetylenic diol's).
- Anti-foam agents such as silicone oils may be used, when the basecoat is used as a stand alone coating. Ranges are from 0.1 to 5%, final formulation.
- Other material typically considered to be utilized as surfactants by formulators in the art, may be utilized.
- This material is used as an anti-oxidant to protect the cured resin from thermal decomposition, upon exposure to the flame applied topcoat. Higher loading levels show improvement in thermal stability, where lower levels decrease the thermal stability of the basecoat. Other phenol and "Non-phenol" type anti-oxidants generally give the same results.
- An example includes thioester antioxidants. Loadings range from 0.01 to 5%, final formulation.
- Light stabilizers that may be incorporated include: benzophenone, benzotriazole, triazine, benzoxazinone, hindered amines, and hindered benzoate. Loadings may range from 0.01% to 5%, final formulation.
- This material is used as a thickening agent / anti-sag agent. It prevents phase separation of material when stored for long periods of time. Decreasing the loading of this material into the resin decreases the viscosity. Increasing the loading of this material (up to 10%) increases the viscosity, such that the resin is trowel-able, to apply to vertical surfaces. The addition of the silica does not significantly affect the performance of the basecoat.
- the material may be loaded at 0.01 to 10%, final formulation.
- Other thickening agents that may substitute include, but are not limited to the materials listed in the filler portion of this disclosure. Loadings are anticipated to be 0.1 to 25%, final formulation.
- the MDI is used to cross link with the hydroxy terminated polybutadiene, diglycidyl ether reactive diluent, and active hydrogens contained in the petroleum asphalt. It is incorporated according to stoichiometric equivalents. Increasing the amount of hardener results in a harder film, and reducing the amount of hardener results in a softer film.
- MDI or other poly-functional isocyanates
- Other multi-functional isocyanates may also be used including: aliphatic, aromatic, TDl, etc.
- diamines and other hardeners recognized by those skilled in the art may substitute. Catalysts
- Catalysts may be used to accelerate the crosslinking of the basecoat.
- Three candidates have been found to date: 1) dibutyltin dilaurate, 2) aminopropyltriethoxysilane, and 3) triethylenetetramine.
- most amines will catalyze the reaction, as well as, the tin dilaurate.
- Many catalysts known in the urethane formulation art, may be utilized. Loadings are typically at 0.0001 to 5%, final formulation.
- auxiliary polyols Physical properties of the system can be improved by the addition of auxiliary polyols to the formulation.
- short chain diols i.e., polyether and polyester backbone
- Voranol 220-530 phenyl diisopropanolamine
- the use of a short chain diol in conjunction with the required additional isocyanate increases the urethane concentration in the final polymer backbone. This combination leads to increased hydrogen bonding between polymer chains and thus higher strength properties in the cured elastomer.
- short chain diamines or mixed alcohol diamines are employed as auxiliary reactants with the system.
- Fillers common the industry include: aluminum oxide, calcium carbonates, dolomite, calcium sulfate, silicates, glass spheres (solid and hollow), asbestos, talk, kaolin, mica, feldspar and nepheline syenite, wollastonite, silicate spheres, silica, natural silicas, synthenic silicas, adhesion promoters (silanes, titanate, zirconate, and aluminate coupling agents), molybdenum disulfide, polytetrafluoroethylene, barium sulfate, metals and metal oxides, aluminum hydroxide, carbon, fibers (natural and synthetic - basalt, carbon polyamide, glass, boron, ceramic), electrically conducting fillers (stainless steel, carbon, carbon fibers, silver coated glass particles), radar absorbing materials, radiation shielding / EMI shielding (Tungsten powder), magnetic additives (strontium ferrite and ceramics), rubber (virg
- Zinc Oxide in addition to reinforcement, also provides resilience and heat conductivity. This is an important filler, where enhanced thermal conductivity is of concern. Loadings are typically at 0.1 to 75%, final formulation. Anti-thermal conductive materials (glass and ceramic) may also be used for the opposite effect. Loadings are at 0.1 to 75%, final formulation.
- Alkali-metal alumino-silicate materials may be used as a molecular sieve adsorbent for static dehydration in the formulation, increasing shelf life of the product.
- This material is also useful when the removal of water is of interest; i.e., One-Step mechanism, as described below.
- PTSI para-Toluenesulfonyl Isocyanate
- isocyanate reactive groups such as free acid in powdered aluminum alkanoates and active hydrogen present in carbon black pigments. This prevents the thickening of the formulation during storage.
- Loadings are typically 13 grams / gram of water.
- Flame ' retardants for the formulation are plentiful. Some of these include (but are not limited to): halogen liberating flame retardants, antimony oxide, phosphorous containing agents, modified silicones, alumina trihydrate, magnesium hydroxide, organically modified montmorillonite clay, expandable graphite, boric oxide, zinc borate, etc. Loadings are typically 0.1 to 60%, final weight.
- Corrosion protection agents may include polyaniline, amino tri (methylene- phosphonic acid) - (ATMP), ammonium benzoate, sodium nitrite, 2- benzothiazolylthio-succinic acid (MBTS), primary, secondary, and tertiary aliphatic amines, aliphatic diamines, cycloaliphatic and aromatic amines, polymethylimines, long-chain ethanolamines, imidazolines, amine salts of carbonic, carbamic, acetic, benzoic, oleic, nitrous, and chromic acids, acetylenic alcohols, lauric alcohol, alkyl chromates, organic esters of nitrous acid, organic esters of phthalic acid, organic esters of carbonic acid, nitronaphthalene, nitrobenzene, etc.
- the anticipated loadings may range from 0.1 to 50%, final formulation.
- Antistatic Agents may range from 0.1 to 50%, final formulation.
- Antistatic agents prevent dust attraction, discharge process that may damage the product (i.e., packaging and handling of electronic chips), and curbing spark discharge that can produce serious accidents.
- Additives in loadings ranging between 0.1 to 50%, final formulation include: a) Cationic compounds (best effect in polar substrates), generally consisting of a voluminous cation which often contains a long alkyl residue (i.e., quaternary ammonium, phosphonium or sulfonium salt, etc.). In most cases, the anion is the chloride, methosulfate or nitrate originating from the quatemization process.
- Anionic compounds mostly an alkyl sulfonate, sulfate or phosphate, a dithiocarbamate or carboxylate, alkali metals, etc.
- Nonionic compounds, uncharged surface-active molecules including: polyethylene glycol esters or ethers, fatty acid esters or ethanolamides, mono- or diglycerides or ethoxylated fatty amines, etc.
- These materials are often used as package preservative, can corrosion inhibitor, mold inhibitor (fungicide), and tannin stain blocking agent.
- fungicide fungicide
- tannin stain blocking agent Several commercially available agents are available, which typically base their chemistry on organic materials (i.e., Buckman Laboratories). Other materials may include zinc oxide, copper oxides, etc.
- the anticipated loadings range between about 0.1 to 10%, final formulation.
- Chemical blowing agents when incorporated into the basecoat, release small amounts of gas - resulting in a foamed material.
- Examples include (but are not limited to) a mixture of sodium bicarbonate and acetic acid, chloro-fluorocarbons, etc. This material typically ranges between about 0.1 to 10%, final formulation.
- Scent additives such as Stanley S. Schoenmann's products provide an array of different fragrances that may be incorporated into the formulation. Loadings range between about 0.1 to 25%, final formulation. Bittering agents and pepper
- Bitter agents such as ground buffalo gourd may be incorporated into the coating to prevent damage by livestock (via oral degradation of the coating).
- Other ingredients include cyanine pepper powder, etc. Loadings are typically 0.1 to 25%, final formulation.
- Carbon black will cause tensile, modulus, tear, and hardness to increase, as the carbon loading is increased.
- carbon black gives the formulation the color of black. Typical loadings range from 0.1 to 40%, final formulation.
- Many other organic and inorganic pigments may be used. Specialty pigments, such as pearl and glow-in-dark may be incorporated. Fluorescent Whiting Agents
- Typical lubricants include: fatty alcohols ant their dicarboxylic acid esters, fatty acid esters of glycerol and other short chain alcohols, fatty acids, fatty acid amides, metallic soaps, oligomeric fatty acid esters (fatty acid complex esters), fatty acid esters of long-chain alcohols, montanic acid, esters and soaps, polar polyethylene waxes and their derivatives, nonpolar polyolefin waxes, natural and synthetic paraffin waxes, fluoropolymers, and molybdenum disulfide.
- This basecoat material may also be formulated into a one-step urethane reaction.
- the components of the desired formulation are weighed; i.e., hydroxy-terminated, 1 ,3-butadiene homopolymer resin, petroleum asphalt, filler(s), extender oil(s), anti-oxidants, plasticizers, and catalyst.
- one preferred basecoat formula (based on weight % of final formulation) is: 44.5 % Petroleum Asphalt (U.S. Oil and Refining Co. PG 52-28)
- the completed formulation is mixed until homogeneous (the reaction of the isocyanate with hydroxyl groups will generate heat - a cooling jacket may be required on the mixing vessel).
- the finished material is then pumped into suitable containers (care is taken not to expose formulation to atmospheric moisture).
- the system prepared as described above, is applied as a one step curing basecoat.
- the applied material reacts with atmospheric water to give urea structures, or can form allophanate crosslinks (especially at elevated temperatures).
- Upon proper cure longer cure to be anticipated compared to A + B mixture) no differences in properties should be noted, as compared to the A + B mixture. Potlifes and physicals can be tuned for this system by engineering the formulation properly.
- All of the above auxiliary ingredients may be incorporated into this system, as outlined above.
- isocyanate functional silanes may be utilized in place of the poly-functional isocyanate.
- one preferred basecoat formula (based on weight % of final formulation) is:
- the materials are charge to a suitable mixing device and allowed to mix until the ingredients are well dispersed.
- This "master-batch" may be degassed under vacuum - it may also be necessary to dry fillers at elevated temperatures to remove moisture. If degassing is not possible, a gaseous nitrogen blanket should be used.
- the petroleum asphalt is heated under dry nitrogen to 140-360 deg F and removed from the heat source.
- the hydroxy-terminated 1 ,3-butadiene homopolymer is added with the aid of mechanical stirring.
- the remainder of ingredients are added and the resin is mixed with mechanical stirring until a uniform dispersion is obtained.
- the resin is allowed to cool completely to room temperature.
- the calculated amount of isocyanate functional silane is added to the mixture to give the desired NCO/OH ratio. Optimum properties are usually obtained at NCO/OH ratios between 1.0 and 1.2.
- the completed formulation is mixed until homogeneous (the reaction of the isocyanate with hydroxyl groups will generate heat - a cooling jacket may be required on the mixing vessel).
- the finished material is then pumped into suitable containers (care is taken not to expose formulation to atmospheric moisture).
- This prepared system is applied as a one step curing basecoat.
- the applied material crosslinks (cures) when exposed to moisture.
- an isocyanate terminated prepolymer (quasi-pre- polymer) is first formed and subsequently converted to a high molecular weight cured elastomer by further reaction with glycols, diamines, or other chain extending agents.
- an isocyanate terminated prepolymer (quasi-pre- polymer) is first formed and subsequently converted to a high molecular weight cured elastomer by further reaction with glycols, diamines, or other chain extending agents.
- one preferred basecoat formula (based on weight % of final formulation) is:
- the pressure was adjusted to 60 mm mercury and benzoyl chloride added.
- the addition of benzoyl chloride was found to greatly enhance the stability of the prepolymer.
- the diisocyanate with an equivalent weight of 136 (corresponding to a necessary 34 gm load) was added over a 5 minute interval. The exotherm was found to increase the temperature by 20 deg F.
- the vessel contents were heated to 150 deg F and allowed to stir for 1 hour. The remainder of the ingredients were then added. The mixture was allowed to stir for a two hour period at 60 mm mercury. The finished material was then transferred into suitable containers - under dry nitrogen (care is taken not to expose formulation to atmospheric moisture).
- This prepolymer material may then be cured by use of a variety of chain- extending diols or diamines.
- a polyether polyol (Dow Voranol 220-530).
- a weight ratio of 1 :5 prepolymer was found to give good result.
- Isocyanate prepolymers are widely used for producing high performance elastomers of castable, millable, and moldable types. Other applications include foams, and one and two component coatings, caulks, sealants, etc.
- AH materials are mechanically pre-blended. This blended material is then passed through a 1 :24 single screw plastic extruder at a temperature of 240 - 280 deg F. The extruder melts and disperses the ingredients. The material exits the extruder as a molten strand and is cooled and re-solidified in a water trough. The solidified strand is then pelletized.
- the processed pellets are then cryogenically ground to a powder, screened to the correct particle size, and then dried and packaged.
- the powder is the finished product.
- Cryogenic grinding of the material will yield particles of a specific size.
- -40mesh seems to work the best for thermal application equipment (- 80 for powder coating grade).
- a range of -35 to -500 mesh may find utility in the marketplace.
- fumed silica may be incorporated at up to 5.0 % by weight to aid in dry flow-ability of the powder.
- thermoplastic olefins, functionalized or non-functionalized, co, ter polymers, other thermoplastic and non-thermoplastic resins may be added at a range of 10-90% to modify end physicals.
- other functionalized polymers, with either aromatic or aliphatic type backbones may be substituted.
- the functional groups may include: alkyd, hydroxy, carboxy, amine, and virtually any other compound containing an active hydrogen. Melt flow ranges are from 1 to 1000. Loadings may range from 5 to 95%, final formulation.
- Loadings may range from 5 to 95%, final formulation.
- Other thermoplastic olefins, functionalized or non-functionalized, co, ter polymers, other thermoplastic and non-thermoplastic resins may be added at a range of 10-90% to modify end physicals. Melt flow ranges are from 1 to 1000. Loadings may range from 5 to 95%, final formulation.
- the acrylic is used to improve flow, eliminate air entrapment, orange peel, pinholes, craters, and other surface imperfections. This ingredient improves the flexibility of the coating and provides for better topcoat-basecoat adhesion.
- a range of 0.1 to 5%, final formulation is obtainable.
- Modaflow 2100 - direct substitute) and non-acrylic modifiers are expected to yield the same results (i.e., benzoin and Acetylenic diol's). Ranges are from 0.1 to 5%, final formulation.
- This material if incorporated into the formulation during the melt mixing portion of the manufacturing, is used as a thickening agent / anti-sag agent. Decreasing the loading of this material into the resin decreases the viscosity. Increasing the loading of this material (up to 10%) increases the viscosity. The addition of the silica does not significantly affect the performance, although gloss is matted with incorporation of silica.
- the material may be loaded at 0.001 to 10%, final formulation.
- Other thickening agents that may substitute include, but are not limited to the materials listed in the filler portion of this disclosure (i.e., aluminum oxide). Loadings are anticipated to be 0.1 to 25%, final formulation.
- Fillers common the industry include: aluminum oxide, calcium carbonates, dolomite, calcium sulfate, silicates, glass spheres (solid and hollow), asbestos, talk, kaolin, mica, feldspar and nepheline syenite, wollastonite, silicate spheres, silica, natural silicas, synthetic silicas, adhesion promoters (silanes, titanate, zirconate, and aluminate coupling agents), molybdenum disulfide, polytetrafluoroethylene, barium sulfate, metals and metal oxides, aluminum hydroxide, carbon, fibers (natural and synthetic - basalt, carbon polyamide, glass, boron, ceramic), electrically conducting fillers (stainless steel, carbon, carbon fibers, silver coated glass particles), radar absorbing materials, radiation shielding / EMI shielding (Tungsten powder), magnetic additives (strontium ferrite and ceramics), rubber (virgin and
- Anti-thermal conductive materials may also be used for the opposite effect. Loadings are at 0.1 to 75%, final formulation.
- Flame retardants for the formulation are plentiful. Some of these include: halogen liberating flame retardants, antimony oxide, phosphorous containing agents, modified silicones, alumina trihydrate, magnesium hydroxide, organically modified montmorillonite clay, expandable graphite, boric oxide, zinc borate, etc. Loadings are typically 0.1 to 60%, final weight.
- Corrosion protection agents may include polyaniline, amino tri (methylene- phosphonic acid) - (ATMP), ammonium benzoate, sodium nitrite, 2- benzothiazolylthio-succinic acid (MBTS), primary, secondary, and tertiary aliphatic amines, aliphatic diamines, cycloaliphatic and aromatic amines, polymethylimines, long-chain ethanolamines, imidazolines, amine salts of carbonic, carbamic, acetic, benzoic, oleic, nitrous, and chromic acids, acetylenic alcohols, lauric alcohol, alkyl chromates, organic esters of nitrous acid, organic esters of phthalic acid, organic esters of carbonic acid, nitronaphthalene, nitrobenzene, etc.
- the anticipated loadings may range from 0.1 to 50%, final formulation.
- Additives with loadings are at 0.1 to 50%, final formulation include.
- Cationic compounds best effect in polar substrates, generally consisting of a voluminous cation which often contains a long alkyl residue (i.e., quaternary ammonium, phosphonium or sulfonium salt, etc.).
- the anion is the chloride, methosulfate or nitrate originating from the quaternization process.
- Anionic compounds mostly an alkyl sulfonate, sulfate or phosphate, a dithiocarbamate or carboxylate, alkyli metals, etc.
- Nonionic compounds uncharged surface-active molecules including: polyethylene glycol esters or ethers, fatty acid esters or ethanolamides, mono- or diglycerides or ethoxylated fatty amines, etc.
- Carbon black will cause tensile, modulus, tear, and hardness to increase, as the carbon loading is increased.
- carbon black gives the formulation the color of black. Typical loadings range from 0.1 to 40%, final formulation.
- Many other organic and inorganic pigments may be used. Specialty pigments, such as pearl and glow-in-dark may be incorporated.
- silanes that may substitute include (but not limited to): alkyd, hydroxy, carboxy, amine, isocyanate functionality and virtually any other compound containing an active hydrogen. Also, ionic and anionic silane salts may substitute. Blends of any above may also work.
- thermoplastic resin systems include (but not limited to) these plausible thermoplastic resin systems: ethylene-vinyl acetate, polypropylene, ethylene-methyl acrylate EMA and ethylene-methyl methacrylate EMAA / polyethylene copolymers, polyethylene, polyethylene acid terpolymers, polyethylene ionomers, polyamide co- and ter- polymers, thermoplastic elastomers (TPE's), acrylonitrile-butadiene-styrene, acrylonitrile halogenated polyethylene, acrylonitrile halogenated styrene, acrylic-styrene-acryonitrile, cellulose acetate, cellulose acetate- butyrate, cellulose acetate-propionate, halogenated polyethylene, halogenated polyvinyl chloride, polymonochlorotrifluoroethylene, diallyl phthalate, ethyl cellulose, ethylene-chlorotrifluroethylene, ethylene-
- modifications to the above listed material including silane grafting, maleic anhydride grafting, acrylic acid grafting, and grafting of any functional group containing an active hydrogen may be used.
- polyethylene may be modified (peroxide grafting) to include silane, maleic anhydride, acrylic acid, or virtually any functional group containing an active hydrogen.
- co- and poly- polymers utilizing the above resins and/or modified resins may be used.
- any virtual array of blends utilizing the aforementioned thermoplastic resins, modified resins, or co - and poly - polymers of above listed resins may be used.
Abstract
Description
Claims
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-
2001
- 2001-11-28 US US09/994,787 patent/US6544596B2/en not_active Expired - Fee Related
- 2001-11-29 WO PCT/US2001/044497 patent/WO2002043881A1/en not_active Application Discontinuation
- 2001-11-29 AU AU2002219906A patent/AU2002219906A1/en not_active Abandoned
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2003
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US20030113566A1 (en) | 2003-06-19 |
US6849338B2 (en) | 2005-02-01 |
AU2002219906A1 (en) | 2002-06-11 |
WO2002043881A8 (en) | 2003-01-30 |
WO2002043881A1 (en) | 2002-06-06 |
US20020114940A1 (en) | 2002-08-22 |
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