AU2001245983A1 - Peelable foam coating composition - Google Patents
Peelable foam coating compositionInfo
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Description
TITLE : PEELABLE FOAM COATING COMPOSITION
Technical Field
This invention relates generally to a water resistant p eelable protective coating compositions, and, more specifically, to water and/or solventbased, polymeric coating compositions which form a protective and/or decorative coating with the ability to adhere to a variety of porous, solid, or liquid substrates, including automotive paints, metals, glass, plastics, vinyl, cloth, paper, asphalt, concrete, porcelain, ceramics, and solutions of water and/or oil, etc.
Description of the Prior Art
A demand exists for a coating composition suitable for the temporary protection of the surface of an article through the depositing on the surface of a coating which can be subsequently be easily removed, and more specifically, peeled off, from the surface without altering the surface or requiring a surface pretreatment.
For example, in the case of painted or polished metal manufactured articles such as automobiles, a need exists for such a coating composition to protect the automobile against weathering, contamination from the atmosphere, chemical attack or accidental damage during handling. Moreover, often the paint on the front end of a motor vehicle or around the outer edges of the fenders is chipped or otherwise damaged by rocks or other small hard objects flying from the road. If dead bugs and bird droppings are left to remain on the paint for a prolonged period of time, permanent stain marks may appear even after cleaning of the automotive body surface.
The vehicle's body surface may also be scratched by pets, during delivery from the dealership, or even during transportation and storage from shipping.
A need also exists for a temporary, peelable coating for the purpose of decoration, either seasonal or occasional, which is easily applied and removed to items such as windows, doors, hood and trunk lids, tailgates, or buildings and other objects whether metal, plastic, glass, wood, brick, or block, etc. A three-dimensional coating film is more desirable to the consumers/users since it offers better visibility and greater design possibilities. The peelable foam coating can be applied to a painted surface, or coated surface such as chrome or chrome plated plastic, to prevent damage to the paint.
SUMMARY OF THE INVENTION
This invention relates generally to water resistant peelable protective and decorative clear, translucent, reflective, phosphorescent, or pigmented coating composition and, more specifically, to water and/or solvent based, polymeric coating compositions which form a protective and/or decorative coating on a variety of substrates, including automotive paints, metals, plastics, glass, cloth, paper, asphalt, concrete, porcelain, and ceramics.
The peelable foam coatings are solvent based and include a gas carrier and may form a generally flat raised ribbon of film on the substrate, or expand providing a raised three-dimensional coating whereby the dimensions of the foamy coating can be controlled by the formulation and applicator to form an expandable cord, string, lines, or figures, and/or for filling in a template in the shape of a desired design, be it a letter, symbol, or other art form.. The coating may be formulated for temporary or long-term protection and/or for decorative art pur oses. The peelable foam coating is fast drying due to the evaporation of the solvent carrier and does not depend upon cross-linking of the resin polymer(s) or application of radiation to cure. The adhesive properties of the foam resists migration, yet foams a peelable film on the substrate and
foams a skin over a gas filled cellular matrix providing a means to control the depth or thickness of a single application of the peelable foam coating or multiple layers. The adhesion of the multiple layers can be controlled based on the time of curing to produce layers peelable from one another, or layers adhering to one another with a selected amount of migration between selected layers providing a means to control the color, thickens, and/or texture or the layers.
The coating may be formulated for temporary or long term protection, and may be either thin or thick . The thickness and density of a single layer or multiple layers can be designed with a porosity to maximum the energy absorbing characteristics of the peelable foam coating as well. The invention also relates generally to water based and solvent based peelable foam coating composition and their method of application by brush, roll, squeeze tube, crayon, marker, ink pen, foam, jell, paste, spraying, dipping, and as an aerosol. The coating can be applied in a single or multiple layers which adhere to one another without bleeding together. The layers may be separated from one another upon drying enabling the user to position cords or strands of the coating composition for decorative purposes or portraying a written or graphic message. The peelable foam coatings may be applied according to their rate of curing (evaporation of the solvent carrier) in order to minimize or maximize the adhesive properties of the peelable coating layers and their capability to adhere and bond to one another.
In one preferred method, the peelable foam coating may be applied using an aerosol filled applicator with a tube or spout of a selected length and width to control the expansion of the foam creating a strand or cord of uniform width and depth. The resulting strand or cord will generally form a smooth sealed exterior skin enclosing a porous interior providing structural integrity thereto.
It is an object of the present invention to provide a decorative, scratch resistant means for protecting the paint, glass, plastic, or metal portions of automotive vehicles during storage and shipping, and against road hazards, debris, bugs, etc. depending
upon the particular embodiment selected imparting a tough resistant, impact absorbing characteristic or more elastic film characteristic. The peelable coating may also be formulated to be an excellent insulating material against scratch or damage to individual parts and may used as packaging material to spray or paint particular parts, such as automotive parts or military equipment prior to shipping.
The present invention provides a protective peelable coating which can be applied to a painted or coated surface of a motor vehicle such as an automobile, airplane, boat, snowmobile, motorcycle, or other vehicle forming a removable coating which can be peeled away leaving a fresh paint surface in a condition at least as good as before application of the removable coating.
Moreover, removal of the film often removes dirt and contaminants covering the painted surface. The present invention may also be utilized as a removable protective coating for transporting and storing tools and equipment and applied to the bottom surface of snow and water skis, surfboards, snow boards, and other sporting accessories which require a smooth slick surface for optimum performance.
A clear and colorless, tinted, or pigmented coating of up to 100 miles and generally of from about 5 to 50 mils and preferably from 20 to 40 mils and most preferably of about 30 mils may be applied to the goods to be protected in the form of an expandable foam of a particular width and depth depending upon the application. Moreover, logos, writing and other graphic designs may be formed by and/or imprinted on the coatings using paint, ink, dye, or the like, and removed from the substrate by peeling the coating from the substrate surface. For example, an advertisement displayed on an automobile windshield or even the painted portions of the auto.. It is also contemplated that multiple layer of coatings may be applied providing means to decorate an object. It is contemplated that an effective amount of micro beads or small glass spheres or other particles composed of other materials may be added to the formulation to aid in the release of the coating and may be used alone or in combination with the chemical release agents set forth hereafter.
Although not required, the peelable foam coating may be applied to a substrate such as a painted surface after pretreating the substrate with a pretreatment composition such as a fatty acid soap, water and/or alcohol solution, silicon, polish, paste, or wax in order to minimize or eliminate any surface marks left on the substrate from removal of the peelable film together contaminants adsorbed by the peelable foam coating from the substrate leaving a clean surface outline due to dirt or grim left on the surface surrounding the peelable foam coating.
A preferred embodiment of the foamy peelable coating composition comprises a film former, a release agent, a surfactant profoamer, and a liquid propellant in an aerosol can. Dyes and/or pigments, thickening agents, anti-skinning agents, stabilizers, and bactericides may be incorporated into the peelable coatings formula to enhance particular physical and decorative characteristics of the product.
Accordingly, it is an object of the present invention to provide a clear, translucent, pigmented, flourescent, dyed, tinted, or illuminative coating for application to a wet or dry metal, plastic, glass, cloth, ceramic, clay, fiber, concrete, brick, rock, cinder block, paper, film, or wood surface, in addition to application directly onto a liquid substrate for the expandable composition can formulated to float..
It is an object of the present invention to provide a peelable coating in which metal flake, powder, or other decorative particles can be embedded throughout.
It is an object of the present invention to be applicable in a pressurized container; tube, or syringe.
It is an object of the present invention to provide a peelable coating which can be removably placed upon a solid substrate such as paints, metals, plastics, concrete, natural and synthetic elastomers, and ceramics and used as a means of removably
supporting another substrate such as a metal foil, a plastic film, STYROFOAM, foam product, paper, or one or more additional layers of peelable coating forming a sandwich therewith.
It is an object of the present invention to provide a water based or solvent based carrier for the peelable foam coating for use on metal, plastic, glass, paper, or wood surfaces having existing protective coatings of paint, varnish, film, without damaging the existing protective coatings.
It is another object of the present invention to produce a peelable coating which does not damage the surface.
It is yet another object of the present invention to produce a protective coating which will not damage paint, chrome, plastic, fiberglass, or other substrate to be coated therewith.
It is another object of the present invention to produce a coating which is easily to apply as a liquid, foam, jell, paste, semi-solid, or aerosol.
It is another object of the invention to provide a coating embodiment having an interior cellular matrix formed by gas bubbles entrapped within a polymeric skin providing a three-dimensional aspect to the peelable coating so that the coating can be seen from an angle yet minimize the amount of pigment and other effective components in the formulation. And the three-dimensional aspect adds to the design possibilities for the consumers/users.
It is another object of the peelable foam coating embodiment to be applied to surfaces without complicated apparatus.
It is yet another object of the peelable foam coating embodiment to include a propellant so that the coating can be sprayed from a can as an aerosol.
It is yet another object of the foamy coating embodiment to be applied through an extension tube to control the size and shape of the coating, and offer more structural design to the three-dimensional foams.
It is another object of the present invention to foam a expandable polymeric peelable foam coating having structural integrity formed by cells which exhibits memoiy and a tendency to retain its shape and appearance upon curing.
It is yet another object of the foamy coating embodiment to be applied at ambient temperature and dry on a surface (becomes non-tacky) within about 5 to 10 minutes of application and become peelable from the surface within an hour of the application.
It is another object of the present invention to provide a peelable foam coating composition which is soluble in an aromatic and/or chlorinated solvent, but not water.
The foregoing objects are accomplished by providing an expandable foam coating including a film forming effective amount of: a film forming polymeric resin such as an aqueous polyurethane dispersion; a selected release agent such as soy lecithin for a polyurethane resin or a polyglycol may be used for a PVA resin; a propellant such as a hydrocarbon propellant; a thickening agent such as a sodium polyacrylic polymer; a surfactant such as akanolamide; and a profoamer such as an amide alkanolamide. Optionally, an effective amount of a plasticizer such as an aliphatic polyurethane; an antiskinning agent such as an antioxidant; an aqueous carrier and/or solvent carrier such as alcohol or preferably alcohol water blend. Other components such as pigments, dyes, stabilizers, lubricants, waxes, and dispersing agents although not required may be added to provide desired special characteristics and properties to the peelable foam coating formed thereby.
More particularly, a preferred embodiment comprises a peelable foam coating composition comprising a selected resin, such as an aqueous polyurethane dispersion,
in an effective amount ranging of up to 95 percent by weight and generally from between 60 to 95 percent by weight, and more preferably from about 80 to 90 percent by weight; in an effective amount of a solvent in an effective range of up to 50 percent by weight and generally from between about 5 to 30 percent by weight; and a release agent in an effective amount of up to 10 percent by weight and generally ranging from between about 0.1 to 5.0 percent by weight can be used to provide a peelable film having a thickness of up to about 80 mils and preferably from about 20 to 40 mils. Effective amounts of other components such as pigments for color and stability such as titanium dioxide and organic pigments, thickening agents such as acrylic polymers, surfactants such as silicone surfactants, each one in effective amounts up to 10 percent by weight and preferably from about 0,001 to 5.0 percent by weight, may also be utilized in with the selected resin and more particularly with one preferred embodiment utilizing an aqueous polyur ethane dispersion.
The resulting peelable coating exhibits excellent toughness, gloss, elasticity, resiliency, flexibility, abrasion resistance, and adhesion. It is resistant to impact and absorbs impacts, weathering, acids, and alkalies. It is a coating which is impervious to water, and is resistant to most of the chemical solvents. It may be applied by brush, roll, spray, extrusion, or dipping or wet or dry surfaces.
BRIEF DESCRIPTION OF THE DRAWINGS
A better understanding of the present invention will be had upon reference to the following description in conjunction with the accompanying drawings in which like numerals refer to like parts throughout the several views and wherein:
Figure 1 is a partial perspective view of a peelable foam coating container, dispenser, and nozzle;
Figure 2 is a top view of Figure 1;
- Si - Figure 3 is a front view of Figure 1;
Figure 4 is a side view of the entire container, dispenser, and nozzle for the expandable and peelable foam container of Figure 1;
Figure 5 is a perspective view showing the container, dispenser, and nozzle, of the invention of Figure 1 including a funnel for spreading and controlling the dimensions of the foam expanding therefrom;
Figure 6 is a perspective view showing a portion of generally cylindrical piece of strand extruded from the expanded peelable foam coating and showing the smooth outer surface forming a skin and the porous interior structure thereof;
Figure 7 is a perspective view showing a portion of generally flattened piece of peelable foam strand having an ovular cross-section extruded from the expanded foam and showing the smooth outer skin surface and porous interior structure thereof;
Figure 8 is a sectional view of a dry mound of foam showing the cellular interior formed by the expansion and trapping of the gas bubbles and showing the formation of a smooth membrane or skin on the exterior surface, and formation of a film on the substrate surface; and
Figure 9 is a perspective view showing application of the peelable foam coating in a decorative manner applied to an automobile shown in phantom lines.
DESCRIPTION OF THE PREFERRED EMBODIMENT
A preferred embodiment of the peelable foam coating composition comprising a film former, a carrier or solvent, and a release agent. Dyes and/or pigments, thickening agents, surfactants, anti-skinning agents, stabilizers, bactericides, and
plasticizers may be incorporated into the peelable coatings formula to enhance particular physical and decorative characteristics of the product.
The expanded foam may be applied by attachment of a straw or tube 10 attached to the nozzle 12 of a pressurized container 14 such as is shown in Figures 1 - 4. A round or ovular funnel 16 as best illustrated in Figure 5 may be used to aid in controlling the expansion of the foam as it exits the straw and before application to the surface of the substrate. It is anticipated that dies or templates can be attached to the distal end of the straw to provide strings of foam having selected cross-sectional shapes such as are shown in Figure 6 showing a string 18 having a cylindrical shape and Figure 7 showing a string 20 having an ovular shape. Moreover, an extension onto the straw may provide a depth gauge by holding the nozzle tip at a selected distance above the substrate surface to provide for application of the peelable foam coating at a selected uniform depth for applications such as the decorative coatings shown in Figure 9, wherein the peelable foam coating is applied to a vehicle providing decorative logos 22.
One preferred composition for the peelable foam coating composition comprises a film forming polymeric resin such as an aqueous polyurethane dispersion having about 25% solids at between 75 to 98 percent by weight, and more preferably 85 to 92 percent by weight. A selected release agent such as soy lecithin or polyglycol of from 0.01 to 5 percent by weight and more preferably from 2 to 3 percent by weight is used for a polyurethane resin, PVA resin or other aqueous based resin. A propellant such as a hydrocarbon or chloroflorinated hydrocarbon propellant of up to 30 percent by weight and more preferably from 5 to 20 percent by weight provides the gas. A thickening agent such as a sodium polyacrylic polymer is typically utilized in an amount of up to 5 percent by weight. A surfactant such as alkanolamide may be added in an amount of from between 0.01 and 10.0 percent by weight. A profoamer such as an amide alkanolamide or oleates or other foaming agents can be added in an amount up to 1.0 percent by weight and more preferably up to 0.5 percent by weight.
Optionally, a preferred embodiment includes a plasticizer such as an aliphatic polyurethane in amount of from between 0.01 to 20 percent by weight. An antiskinning agent such as an antioxidant may also be added in an amount of from between 0.01 and 1.0 percent by weight and more preferably between 0.01 and 0.2 percent by weight. An aqueous carrier and/or solvent carrier such as alcohol or preferably alcohol water blend may be used in an amount of up to 90 percent by weight. Other components such as pigments, dyes, stabilizers, lubricants, waxes, and dispersing agents in effective amounts up to 10 percent by weight, and preferably from 0.01 to 10 percent by weight may be added to provide desired special characteristics and properties to the peelable foam coating formed thereby.
The peelable foam coating produced therefrom provides a three-dimensional peelable coating with thickness ranging from 0.1 to 1 inch, more preferably 0.25 to 0.5 inch. The foamy coating embodiment having a glossy or semi-glossy surface preferably utilizes an effective amount of resin content of a polyurethane dispersion generally of 25 percent or more and preferably of about 40 percent or more of solids in order to prevent unwanted porosity and prevent collapse of the foam upon application. Moreover, the three-dimensional aspect of the preferred embodiment is preserved by using a polyurethane dispersion of about 40 percent solids or greater, producing a coating having structural integrity from the moment of application to days and weeks after the application of the coating to the substrate.
In the present invention, a selected detergent is used to produce the foam. The resin content of the present invention is high enough to provide structural support for the foam during drying so that the formation of the foam formed by expulsion of the of the selected gas from the container expands at a predictable rate and volume, and forms a peelable foam coating having a density in a selected range, with cellular cavities formed by bubbles in a desired size range. The evaporation of the water, solvent, or water/solvent blend carrier results in curing of the expanded peelable foam coating forming the film on the substrate, the skin on the exterior surface, and cells having dimensions in a particular range providing structural support therefor.
Although the top surface of the expandable peelable foam is solid upon curing, during the drying and curing process tiny pores are formed in the skin by evaporation of the aqueous or solvent based carrier. An alkconoid may be utilized to retain foam stability and control shrinkage. The use of additives such as plasticizers, lubricants, waxes, and/or pigments which have a tendency to migrate to the surface of the skin may reduce or eliminate visibility of the pores.
As shown in Figure 8, the present invention is shown as a sectional view of a mound of peelable foam coating showing the interior cellular matrix 24 containing a plurality of cells 26 formed by the expansion and trapping of the gas bubbles and showing the formation of a smooth membrane or skin 28 forming the exterior surface, and formation of a film 30 on the substrate surface.
Moreover, the expandable foam of different colors or having other different properties may be contained within a single container or a plurality of containers leading to a manifold, or combining straws, or having a nozzle which combines the streams of expanded peelable foam in the same manner as is conventionally used to create toothpaste having stripes.
The polyurethane resin and plasticizer compounds are thermoplastic polymers typically produced by the condensation reaction of a polyisocyanate and an alcohol, more particularly, a hydroxyl-containing material such as polyol derived from polypropylene oxide or trichlorobutylene oxide. The basic polymer unit is formed as follows: RjNCO + R2OH --> R1NHCOOR2, typically derived from forming "prepolymers" containing isocyanate groups (toluene and 4,4'-diphenylmethane diisocyanates) and hydroxyl containing materials such as polyols and drying oils. Resin dispersions are typically derived from the reaction of polyisocyanates with linear polyesters or polyethers containing hydroxyl groups.
The film former is a polymeric resin, or a mixture of polymeric resins, which form a film after curing or drying. The resin in the preferred embodiments is a
polyurethane dispersion, which can be obtained from Bayer, Ruco Polymers, NeoResins, Witco, Reichhold, etc. Other resins such as polyvinyl styrene butadiene copolymers, polyvinyl toluene butadiene copolymers, styrene acrylate, vinyl toluene acrylate copolymers, styrene acrylate copolymers, vinyl toluene acrylate terpolymers, amino-formaldehyde resins, polyvinyl butyral and polyisocyanate resins may be used in combination therewith.
Polyurethane provides a tough but flexible film for use in the peelable coating. The resin selected is preferably UV resistant and may have a stabilizer incorporated therein. The resins may vary in molecular weight and viscosity depending upon the characteristics desired in the resulting peelable coating. Preferred compositions of a film-type peelable coating typically contain a resin in an amount ranging from about 60 to 99 percent, more preferably from about 75 to 95 percent, and most preferably from about 80 to 90 percent by weight of the total weight percent of the composition.
A particularly useful embodiment incorporates the polyurethane within a controlled foam which quickly dries imparting body to the film leaving a smooth outside surface. The term "foam", as used herein, designates a mixture of liquid, gas, and a surfactant that gives the liquid a film strength which permits the formation of long lasting bubbles when the mixture is agitated to convert it into a mass of bubbles. The liquid used is normally water, and the gas is usually air, because these ingredients are of low cost, but other liquid and/or gas can be used when compatible with the surfactant, for example, a pressurized hydrocarbon as the gas component. The strength of the film depends upon the characteristics of the polyurethane dispersion and the surfactant, and the relative amount of liquid and surfactant in the liquid-gas- surfactant mixture.
In the film-type coating embodiment a solvent such as aromatic and/or aliphatic solvents, ethyl, methyl, isopropyl, and butyl alcohol, water, and combinations thereof may be used to provide a carrier for the resin polymer. The amount of total solvent (including the water in the resin dispersion) may range up to about 90 percent
by weight, more preferably from about 50 percent to 85 percent by weight, and most preferably from about 60 to about 80 percent by weight of the total weight percent of the composition.
In the foamy coating embodiment no extra solvent is necessary for the formulation; water introduced from the resin dispersion itself acts as the solvent to the system. However, an optional amount of water or other solvent up to the amount of 10 percent by weight may be introduced into the embodiment to enhance the solubility of other co p onents .
One or more release agents and/or aids may be utilized individually or in combination in either the water based or solvent based peelable coating compositions of the present inventions. Preferred release agents include soy lecithin, organosilicone fluids, nonylphenoxypoly(ethyleneoxy)ethanol, oleic acid polyethylene glycol mono stear ate, petrolatum, sodium alkyl benzene, sulfonates, siloxanes, polyglycols, silicone surfactants, polyvinyl alcohol resins, paraffin and polymeric waxes, and synthetic waxes including low molecular weight polyethylene waxes. It is contemplated that the formulas in the examples set forth herein could utilize any of these release agents wherein the selected release agent depends upon its solubility, availability, and cost and environmental considerations.
A typical release agent used in the examples is soy lecithin which may be defined as C2H1705NRR' , R and R' being fatty acid groups. The lecithins are mixtures of diglycerides of fatty acids linked to the choline ester of phosphoric acid and may be classified a phosphoglycerides or phosphatides (phospholipids). Moreover, the lecithin may be a mixture of acetone-insoluble phosphatides of not less than 50% acetone-insoluble matter. The soy lecithin is derived from soybeans.
Thickeners applicable to all of the formulas are utilized to control the application properties of the coating composition, such as sodium polyacrylate, Carbopol EZ-2 (acrylic polymers), Polyox WSR (high molecular weight, (mol. wt.),
poly ers of ethylene oxide) from Union Carbide, xanthan gums, guar gums, polyacrylic acid, polysaccharides. Fillers such as silica, cellulose, wood flour, and clays may be utilized with the resins of the preferred compositions.
Moreover, a flow resistant component may beused and defined as athickening agent to impart body in the film coating. Solvent soluble/dispersible compounds which have good filmfoammg characteristics such as Drewthix (Drew Chemicals) may be utilized independently or in combination with other thickening agents to impart desirable characteristics to the film.
Another water-soluble thickening agent is carboxymethylcellulose (CMC). A preferred embodiment utilizes at least some CMC together with other thickeners such as acrylic polymers. The CMC may be dissolved at about 1.5% in water and be added to the formulation in an effective amount of up to 25 percent by weight, preferably from about 0.01 to 10 percent by weight, and more preferably from about 0.1 to 5.0 percent by weight.
The preferred composition of a film-type coating may contain up to 10% thickeners and more preferably from 0.01 to 8 weight percent thickeners, and more preferably from about 0.1 to 3 weight percent thickeners.
An anti-skinning agent may be added to the formulation and is particularly useful for prop ellant carried fo amy co atings and is preferably used in combination with a foam stabilizer. Typical anti-skinning agents are antioxidants used to inhibit formation of an oxidized film on the exposed surface. The anti-skinning agent provides a means for rapid drying and curing of the foam from the "bottom-up" so that the resulting film dries more quickly and thoroughly and provides a smoother, more glossy appearance having some body. An effective amount of an anti-skinning agent such as Exkin No. 2 up to 1 percent by weight may be utilized in a preferred embodiment, and preferably from about 0.01 to about 0.2 weight percent.
In the foamy coating embodiment, a surfactant may be added as an option, in order to enhance the foamability and reduce the bubble size in the foams, in an effective amount of from between 0.01 to about 10 percent by weight, more preferably from about 0.1 to 5 percent by weight, and most preferably about 1 to 2 percent by weight. The term "surfactant", as used herein, refers to surface-active agents which comprise polar compounds consisting of an amphophilic molecule (a molecule with a hydrophilic head attached to a long hydrophobic tail). The hydrophilic group may be anionic, cationic, amphoteric or nonionic. As used in the present invention, the addition of a surfactant to a liquid system reduces the liquid's surface tension and in the presence of gas, promotes foaming. Typical foaming agents include alkanolamides, silicone glycols, alkyl benzene sulfonates, alcohol ethoxylated, phosphate esters, betaines, alkylphenol ether sulfates, alkylaryl sulfonates. Alkanolamide type surfactant is preferably used because it also functions as a foam stabilizer once the foam is formed. It is anticipated that other foam stabilizers such as proteins and fatty acids may be utilized in combination with the surfactants.
A pressurized liquid propellant may be utilized as a carrier to apply the foamed film coating. The preferred embodiments of the present invention use a nonfloronated propellant. A commercial liquid hydrocarbon propellant which is compatible with the preferred composition may be selected from the group of A-31 , A-46, A-70, or A- 108 propane/isobutane blends, with A-46 and A-70 being the most preferred propellant for use with particular compositions. The composition may contain up to 25 weight percent of the propellant, and more preferably from 5 to 20 weight percent of the propellant.
Moreover, the addition of water soluble resins, fillers, solvents, orplasticizers, such as polyvinyl alcohol, cellulose, and a polyglycol, may assist in the application of the peelable composition to a substrate having a residual amount of water in the form of droplets, a film, or moisture absorbed thereon by combining with the preexisting moisture of the substrate.
Inorganic and organic dye or pigments, preferably pigments, such as the 896 Aqueous Industrial Colorants series, and/or stabilizer/pigment combinations, such as titanium dioxide, may be utilized in an effective amount of up to about 10.0 percent by weight, more preferably from about 0.01 to 5 percent by weight, and most preferably from 0.5 to 2 percent by weight.
Microbiocides, pH control agents, UV stabilizers, etc., may be incorporated in the composition in an amount of from between about 0.01 to about 1.0 percent by weight of the total composition.
In coating embodiments which contain aqueous polyurethane dispersions, no extra plasticizer is necessary since the peelable foam coating formed by the resin already possesses enough plasticity and flexibility. Although not required for use with a polyurethane dispersion resin, a plasticizer may be used to impart flexibility other selected resins or even added to the polyurethane formulation to impart special physical characteristics to the selected resin such as to facilitate processing and to increase the flexibility and toughness of the final product by internal modification (solvation) of the polymer molecule. Numerous plasticizers are available for utilization in the present invention and may be selected from the group including phthalate, adipates, sebacate esters, and more particularly: glyceryl tri(acetoxystearate), epoxidized soybean oil, epoxidized linseed oil, N,n-butyl benzene sulfonamide, aliphatic polyurethane, epoxidized soy oil, polyester glutarate, polyester glutarate, triethylene glycol caprate/caprylate, long chain alkyl ether, dialkyl diester glutarate, monomeric, polymer, and epoxy plasticizers, polyester based on adipic acid, hydrogenated dimer acid, distilled dimer acid, polymerized fatty acid trimer, ethyl ester of hydrolyzed collagen, isostearic acid and sorbian oleate and cocoyl hydrolyzed keratin, PPG-12/PEG-65 lanolin oil, dialkyl adipate, alkylaryl phosphate, alkyl diaryl phosphate, modified triaryl phosphate, triaryl phosphate, butyl benzyl phthalate, octyl benzyl phthalate, alkyl benzyl phthalate, dibutoxy ethoxy ethyl adipate, 2- ethylhexyldiphenyl phosphate, dibutoxy ethoxy ethyl formyl, diisopropyl adipate, diisopropyl sebacate, isodecyl oleate, neopentyl glycol dicaprate, neopenty glycol
diotanoate, isohexylneopentanoate, ethoxylated lanolins, polyoxyethylene cholesterol, propoxylated (2 moles) lanolin alcohols, propoxylated lanoline alcohols, acetylated polyoxyethylene derivatives of lanoline, and dimethylpolysiloxane. Other plasticizers which may be substituted for and/or used with the above plasticizers including glycerine, polyethylene glycol, dibutyl phthalate, and 2,2,4-trimethyl-l,3-pentanediol monoisobutyrate, and diisononyl phthalate all of which are soluble in a solvent carrier.
Plasticizers especially useful are differentiated primarily by the molecular weights. The plasticizers are generally classified as formulated aliphatic polyurethane compounds. Either one or a combination of plasticizers of different molecular weights may be used in the formula depending upon the desired viscosity of the coating. Of course, it is contemplated that aromatic polyurethane compounds will also be applicable in the formula for the coating. The amount of plasticizer may range from about 0.1 percent to about 20 percent by weight, more preferably from about 0.5 percent to about 10.0 percent by weight, and more preferably from about l.O to about 5.0 percent by weight of the total weight percent of the composition.
EXPERIMENTAL EVALUATION
The following examples are presented to illustrate the claimed invention and are not intended to be otherwise limiting.
A preferred embodiment of a water resistant, peelable, protective and decorative clear or pigmented water based polymeric dispersion coating composition producing a three-dimensional foamy film of about lA in thick for use on a variety of substrates, including automotive paints is set forth in Example 1, as follows:
EXAMPLE 1
INGREDIENT PERCENT BY WEIGHT
Aqueous polyurethane dispersion 75.0-98.0
Release agent 0.1-5.0
Hydrocarbon propellant 5.0-15.0
Surfactant 0.0-5.0
Pigment (red, blue, yellow, etc.) 0.0-5.0
Thickening agent 0.1-2.0
Anti-skinning agent 0.0-0.2
S olvent (optional) 0.0-5.0
The aqueous polyurethane dispersion was mixed with the rest of the constituents except the propellant in a container, and then the mixture was transferred into an aerosol can where the pressurized liquid propellant was forced into the said aerosol can to mix with the said mixture. A regular spray nozzle with a push-down button, or with a push-down cap, may be used to apply the coating, and more preferably, an extension tube may be added onto the snout of the push-down button or cap to control the size and shape of the coating, and offer more structural design to the coating. The extension tube may be tapered at the opening and extending outwardly at a constant dimension as shown in Figure 1 , or spread in a cone or generally flat "V" shaped nozzle to control the spread or width, and depth of the expansion of the foam depending upon the application. Within seconds after application, the expandable foam will assume shape and form a skin on the exterior holding in the gas and forming a porious interior matrix as shown in Figure 2, providing structural strength to the resulting cord, strand, or other graphic art or the selected dimensions.
The preferred water based compositions include an effective amount of an aqueous polyurethane resin dispersion. The aqueous polyurethane dispersion is a waterborne, colloidal dispersion of aliphatic urethane. The average molecular weight
is between about 50,000 and 5,000,000, more preferably between about 500,000 and 1,000,000. The foamy coating embodiment preferably utilizes a resin content of polyurethane dispersion above 40 percent solids, or non-volatile (NV) components, in order to prevent unwanted porosity and prevent collapse of the foam upon application. Moreover, the three-dimensional aspect of the preferred embodiment is preserved by using a polyurethane dispersion of about 40 percent solids or greater, producing a coating having structural integrity from the moment of application to weeks after the application of the coating to the substrate. The aqueous polyurethane ranges in amount from about 75 to 98 percent by weight, and more preferably from about 80 to 95 percent by weight. About 89 percent by weight of the aqueous polyurethane dispersion was used in Example 1.
Water in the aqueous polyurethane dispersion itself provides enough solvency/dispersing medium for the rest of the components, therefore, no extra solvent is necessary in the formulation. However, an optional amount of water or other polar solvent up to 5 percent by weight may be added into the formulation to cut down cost, to enhance the evaporation of the solvent in the system, and/or to enhance the solubility of other components in the mixture.
The preferred embodiments of the present invention use a nonfloronated propellant, although pressurized air, N2, C02 may also be used. A commercial liquid hydrocarbon propellant which is compatible with the preferred composition may be selected from the group of A-31, A-46, A-70, or A-108 propane/isobutane blends, with A-46 and A-70 being the most preferred propellant for use with particular compositions. The composition may contain up to 25 weight percent of propellant, and more preferably from 5 to 20 weight percent of propellant. About 7.5 percent by weight of the propellant A-46 was used in Example 1.
A release agent such as a soy lecithin in an amount ranging from about 0.1 to about 5 percent by weight, more preferably from about 1 to 3 percent by weight, is utilized in the aqueous polyurethane dispersion. Other water soluble or dispersible
release agents described heretofore may be utilized with or substituted for the soy lecithin. About 2 percent release agent was use in the embodiment of Example 1.
Additional preferred compositions of the above formulation may be formulated to provide foamy peelable coatings with particular characteristics by blending the compounds as follows.
The above-composition may be formed as a clear foamy peelable coating composition or tinted with a dye or pigment in an effective amount of up to 5.0 percent by weight. At least one preferred embodiment utilizes a pigment (red, blue, yellow, green, etc.), either organic or inorganic, in an effective amount of between 0.01 to 5 percent by weight, more preferably from between about .1 to 3 percent by weight, and most preferably from between about 1 to about 2 percent by weight. The composition of Example 1 utilized 1.0 percent by weight of red, blue, or yellow pigment, or a water-dispersible titanium dioxide pigment for color and stability.
A profoamer may be added into the formulation too enhance the foaming ability during applying the coating. Surfactants are used for this purpose, which can be either anionic, cationic, amphoteric or nonionic. Typical foaming agents include alkanolamides, silicone glycols, alkyl benzene sulfonates, alcohol ethoxylated, phosphate esters, betaines, alkylphenol ether sulfates, alkylaryl sulfonates. Super amide may function as a foam enhancer and stabilizer, so it is preferably used in the embodiment of the foamy coating formulation. In the present Example 0.5 percent by weight of the super amide is used as the preferred profoamer.
A thickening agent may optionally be added to control the application properties of the coating composition. Preferred thickeners for the aqueous polyurethane based dispersion include the acrylic polymers (sodium polyacrylate, CarbopolEZ-2), Polyox WSR (high mol. wt. polymers of ethylene oxide) from Union Carbide, organoclays such as Bentone, etc. Other thickeners considered applicable include xanthan gums, guar gums, polyacrylic acid, polysaccharides, fillers such as silica, cellulose, wood
flour, clays, etc. The preferred embodiment of Example 2 includes a thickening agent in an effective amount of from about 0.01 to about 5 percent by weight, and more preferably from about 0.1 to 2 percent by weight. Moreover, the water-soluble or solvent-soluble thickeners may be used in conjunction with the above-said solvent in the formulation. The formulation of Example 1 includes about 0.2 to 0.3 percent by weight of thickening agent.
An anti-skinning agent may be added to the formulation. An effective amount of an anti-skinning agent such as Exkin No. 2 up to 1 percent by weight may be utilized in a preferred embodiment, and preferably from about 0.01 to about 0.2 weight percent. In the present Example about 0.05 percent of the anti-skinning agent, preferably Exkin No. 2, was used.
EVALUATION OF PEELABLE FILM IN EXAMPLE 1
The foamy films were applied onto an automotive paint panel using a push-down cap with a extension tube connected to the snout and let dry in ambient temperature and humidity. The thickness of the foamy coating can range from 0.1 to 1 inch, more preferable 0.25 to 0.5 inch. The resulting dry films were foamy, three-dimensional, with a semi-glossy outside surface, and with the bulk structure sponge like. The panel was then immersed in tap water and examined at selected intervals to determine if any of the component leached out. No color change of water was found during the test, and water did not show any impact on the film's integrity. The surface tension of the water was reduced a little, indicating that some of the surfactant was leaching out. Since the foam structure had already be formed and become rigid through air dry, the leaching out of the surfactant didn't affect the dry film structure at all. The films were also heated to 150°F for 72 hours and then taken out from the oven and dipped in cool tap water at about 18°C. No adverse effects were demonstrated on the film coating which remained on the painted substrate.
The peelabilty of the above-mentioned films were excellent, which could be peeled away from the substrate as a whole piece. The film was foamy and very elastic.
Long-term peelability was demonstrated by letting the coated paint panel in the open-air environment for a certain amount of time, and then peeled off from the substrate, and the surface of the substrate was evaluated both visually and with a microscope. Coatings of 200 days in open-air environment were peelable from the substrate as a whole piece. No apparent fading of the color was noticed for the coatings in open-air environment for 200 days, and no surface damage on the substrate was noticed.
Resins other than polyurethane dispersions can also be used as film former in the formulation. A preferred embodiment of a water resistant, peelable, protective and decorative clear or pigmented solvent-based polymeric coating composition for use on a variety of substrates, including automotive paints is set forth in Example 2, resulting in a film of abut 30 mils, as follows:
Example 2
INGREDIENT PERCENT BY WEIGHT
Vinyl toluene acrylate copolymer resin 27.0-30.0
Aromatic solvent (xylene) 12.0-15.0
Aliphatic solvent (mineral spirits) 38.0-40.0
Pigment (red, blue, yellow, etc.) 3.0-5.0
Polypropylene Glycol release agent 5.0-7.0
Propellant (CO.) Up to 5 or hydrocarbon propellant Up to 25
2-Ethylhexyldiphenyl phosphate plasticizer 6.0-9.0
Thickner Wood flour 0.1-2.0
The solvents were mixed together and the resin and pigment(s) were added to the solution at about 120°F over a period of about two hours. The remaining constituents were added thereafter. An important consideration is the Kauri-Butanol value of the peelable coating composition which measures the aromaticity of the film components. If the aromaticity is too high the solvent carrier of the peelable coating will tend to dissolve certain substrates. Thus, the peelable coating must dry quickly before dissolving substrates susceptible to the solvent used as the carrier in a selected composition.
Preferred compositions include an effective amount of a resin soluble in aliphatic and/or aromatic solvents such as a vinyl toluene acrylate copolymer resin, alkyd resins, polystyrene, and combinations thereof in an amount ranging from about 10 to about 50 percent by weight, more preferably from about 20 to 40 percent by weight, and most preferably from about 25 to 35 percent by weight.
An effective amount of an aromatic solvent, such as xylene, aliphatic solvent, such as heptane, or combination thereof in an amount ranging from about 20 to about 90 percent by weight, more preferably from about 40 to 80 percent by weight, and more preferably from about 50 to 75 percent by weight is also included in the composition. Alternatively, an combination of an aliphatic solvent in an effective amount ranging from between 0.01 to about 90 percent by weight, more preferably from about 20 to about 60 percent by weight and most preferably form about 30 to about 50 percent by weight may be utilized together with an effective amount of an aromatic solvent in an amount of between 0.01 to 90 percent by weight, more preferably from about 1 to 50 percent by weight, and most preferably from about 5 to 25 percent by weight.
Additional preferred compositions of the above formulation may be formulated to provide peelable coatings with particular characteristics by blending the compounds as follows.
A plasticizer, such as any set forth and described heretofore, and preferably a phosphate plasticizer is added in an effective amount of from between about 0.1 to about 40 percent by weight, more preferably from about 1 to 20 percent by weight, and most preferably from about 5 to about 15 percent by weight.
A filler such as set forth and described heretofore and preferably wood flour may optionally be added to the composition in an effective amount of between about 0.1 and 10 percent, more preferably between about 0.5 and 5 percent, and most preferably from between about 1 and 2 percent by weight.
Apolyglycol such as polypropylene glycolmay optionally be added to thepeelable coating composition as a release agent in an effective amount of from between about 0.1 and 20 percent by weight, more preferably from between about 1 and 10 percent by weight, and most preferably of from between about 3 and 8 percent by weight of the total composition.
The above composition may be formed as a clear peelable coating composition or tinted with a dye/pigment in an effective amount of from between about 0.1 and 5.0 percent by weight. At least one preferred embodiment utilizes a day or pigment (red, blue, yellow, green, etc.) either organic or inorganic in an effective amount of between 0.1 to 10 percent by weight, more preferably from between about 1.0 and 5 percent by weight, and most preferably from between about 3 to about 5 percent by weight.
EXPERIMENTAL RESULTS AND EVALUATION OF PEELABLE FILM IN
EXAMPLE 2
The films were cast using a drawdown bar (15, 30 and 50 mil) onto an automotive paint panel and let dry in ambient temperature and humidity. The resulting films were generally flat and smooth, with little amount of tiny bubbles trapped in it. The panel was then immersed in tap water and examined at selected intervals to determine if any of the component leached out. No color change of water was found during the test,
and water did not show any impact on the film's integrity. The films were also heated to 150°F for 72 hours and then taken out from the oven and dipped in cool tap water at about 18°C. No adverse effects were demonstrated on the film coating which remained on the painted substrate.
The peelabilty of the above-mentioned films were excellent, which could be peeled away from the substrate, although the film integrity could not be preserved completely during peeling. The film was a little brittle compared with the film formed by polyurethane resin.
The following examples 3-11 illustrate some additional water based polymeric emulsions which can be used in the preparation of water resistant, peelable, protective and decorative clear or pigmented three-dimensional foamy film compositions of the present invention. Unless otherwise indicated in the following examples and elsewhere in the specification and claims, all parts and percentages are by weight, temperatures are in degree Centigrade, and pressures are at or near atmospheric pressure.
The following general procedure is utilized for preparing the water based polymeric foamy emulsion of Examples 3-11. The aqueous polymeric dispersions is mixed with the colorants, release agents, surfactants, thickening agent, except the propellant in a container, and then the mixture was transferred into an aerosol can where the pressurized liquid propellant was forced into the said aerosol can to mix with the mixture.
Example 3
Component Pts. wt.
Polyurethane 84.75
Soy Lecithin (Soy Lecthin) 3.00
Dow Corning organo silicone fluid 1.15
Aqueous Industrial Colorant (Creanova, Inc.) 1.00
Acrylic copolymer thickener 0.10
Hydrocarbon Propellant 10.00
Example 4
Component Pts/wt.
Silicone polyurethane copolymer (BF Goodrich) 83.40
Soy Lecithin 4.00
Dow Corning Q4-3667 fluid (Dow Corning) which is a polydimethyl- polyether-siloxane blockcopolymer 1.50 Aqueous Industrial Colorant (Creanova, Inc.) 1.00
Acrylic copolymer (Drew Chemical) 0.10
Hydrocarbon Propellant (Aeropres Corp) 10.00
Example 5
Component Pts/wt.
Polyurethane (Reichhold) 84.94 Soy Lecithin 2.98
Dow Corning organo silicone fluid 1.06
896 Aqueous Industrial Colorant (Creanova, Inc.) 0.99 an acrylic copolymer (Drew Chemical 0.10
Hydrocarbon Propellant (Aeropres Corp) 9.93
Example 6
Component Pts/wt.
Vinyl Acetate- Vinyl Chloride-Ethylene Terpolymer (Air Products) 84.61
Soy Lecithin 3.25
Organo silicon fluid (Dow Corning) 1.20
Aqueous Industrial Colorant (Creanova, Inc.) 0.84
Acrylic copolymer (Drew Chemical) 0.10
Hydrocarbon Propellant (Aeropres Corp) 10.00
Example 7 Component Pts/wt. Silicone Acrylic Copolymer (Avery) 85.60 Soy Lecithin 2.80
Organo silicon fluid (Dow Corning) 1.06 Aqueous Industrial Colorant (Creanova, Inc.) 1.00 Acrylic copolymer (Drew Chemical) 0.10 Hydrocarbon Propellant (Aeropres Corp) 9.44
Example 8 Component Pts/wt. Styrene Butadiene Copolymer (BF Goodrich) 84.61 Soy Lecithin 3.25
Organo Silicon Fluid (Dow Corning) 1.20 Aqueous Industrial Colorant (Creanova, Inc.) 0.84 Acrylic copolymer (Drew Chemical) 0.10 Hydrocarbon Propellant (Aeropres Corp) 10.00
Example 9 Component Pts/wt. Acrylic Nitrile Copolymer (BF Goodrich) 85.40 Soy Lecithin 2.50
Organo Silicon fluid (Dow Corning) 1.05 Aqueous Industrial Colorant (Creanova, Inc.) 0.95 Acrylic copolymer (Drew Chemical) 0.10 Hydrocarbon Propellant (Aeropres Corp) 10.00
Example 10 Component Pts/wt. Polyvinyl Butytral (Solution) 85.30 Soy Lecithin 2.50
Organo Silicon fluid (Dow Corning) 1.10 Aqueous Industrial Colorant (Creanova, Inc.) 1.00 Acrylic copolymer (Drew Chemical) 0.10 Hydrocarbon Propellant (Aeropres Corp) 10.00
Example 11 Component Pts/wt. Polyurethane (Richhold) 56.28
Si-acrylic copolymer (Avery) 28.47 Soy Lecithin 3.00
Organo Silicon fluid (Dow Corning) 1.15 Aqueous Industrial Colorant (Creanova, Inc.) 1.00 Acrylic Copolymer (Drew Chemical) 0.10 Hydrocarbon Propellant (Aeropres Corp) 10.00
The following general procedure is utilized for characterizing the polymeric foamy properties of the following examples. Aqueous polymeric dispersion
formulations as set forth in (Examples 3-11) were contained in a pressurized aerosol can with pushdown button spray nozzle is applied on the polystyrene standard Petri Dishes (95X15 mm, Fishevbrand). The excess of coating material is removed by wiping with ruler from the dish surface then let the coating dry in humility control room at ambient temperature. The drying time of coating is determined by the coating weight reaching constant and foam coating removability. The foam volume is measured by adding the water to the dry foam coating until the water level reaching coating surface and using water weight as the volume of the coating.
PEELABLE FOAM COATING PROPERTIES
Example Polymeric Type Coating Drying Time Foam Density (g/cm 3)
3 Polyurethane (PU) 2-2 ^ hrs. 0.214
4 Silicone Polyurethane Copolymer (Si-PU) 24 hrs. 0.236
5 Polyurethane (PU) 3-3 hrs. 0.159
6 Vinyl Acetate- Vinyl Chloride-Ethylene Terpolymer 45-50 min. 0.629
7 Silicone Acrylic Copolymer (Si-Acrylic) 80-90 min. 0.486
8 Styrene Butadiene Rubber (SBR) 3-3 1/2 hrs. 0.330
9 Acrylic Nitrile Rubber 90-95 min. 0.740
10 Polyvinyl Butytral 2-2 1/2 hrs. 0.212
11 Mixture of Si-Acrylic Polyurethane 1 1/2 - 2 hrs. 0.085
These peelable foam coatings as set forth in Examples 4- 12 are formulated with aqueous based resins which exhibit different physical properties and characteristics.
MODIFICATIONS
The foregoing detailed description is given primarily for clearness of understanding and no unnecessary limitations are to be understood therefrom, for modification will become obvious to those skilled in the art upon reading this disclosure and may be made upon departing from the spirit of the invention and scope of the appended claims. Accordingly, this invention is not intended to be limited by the specific exemplifications presented herein above. Rather, what is intended to be covered is within the spirit and scope of the appended claims.
Specific compositions, methods, or embodiments discussed are intended to be only illustrative of the invention disclosed by this specification. Variation on these compositions, methods, or embodiments are readily apparent to a person of skill in the art based upon the teachings of this specification and are therefore intended to be included as part of the inventions disclosed herein.
Reference to documents made in the specification is intended to result in such patents or literature cited are expressly incorporated herein by reference, including any patents or other literature references cited within such documents as if fully set forth in this specification.
Claims (9)
1. A peelable foam coating composition, comprising an effective amount of:: an aqueous film forming polymeric resin; a release agent; a propellant; a thickening agent; a surfactant; and a profoamer.
2. The peelable coating of Claim 1 including a dye or pigment in an effective amount of from .01 to 10.0 percent by weight.
3. The peelable coating of Claim 1 including a thickening agent in an effective amount of from 0.01 to 5.0 percent by weight.
4. The peelable coating of Claim 1 including an antifoam in an effective amount of from 0.01 to 1.0 percent by weight.
5. The peelable coating of claim 1 , including an effective amount of a plasticizer.
6. The peelable coating of claim 1 including an effective amount of an antiskinning agent.
7. The peelable coating of claim 1 including an effective amount of an antioxidant.
8. The peelable coating of claim 1 including an effective amount of a carrier selected from the group consisting of an aqueous carrier, a solvent carrier, or combination thereof.
9. A foamy peelable coating composition, comprising: an aqueous polyurethane dispersion resin in an effective amount ranging from about 75.0 percent to about 98.0 percent by weight of the total weight percent of the composition; a release agent in an amount of from between 0.1 and 5.0 percent of the total weight percent of the composition; and a propellant in an amount of from 5.0 to 20.0 percent of the total weight percent of the composition.
10. The peelable coating of Claim 9 including a dye or pigment in an effective amount of from 0.01 to 10.0 percent by weight.
11. The peelable coating of Claim 9 including a thickening agent in an effective amount of from 0.01 to 5.0 percent by weight.
12. The peelable coating of Claim 9 including a surfactant in an effective amount of from 0.01 to 10.0 percent by weight.
13. The peelable coating of Claim 9 including an anti-skinning agent in an effective amount of from 0.01 to 1.0 percent by weight.
14. The peelable coating of Claim 9 including an effective amount of a carrier selected from the group consisting of an aqueous carrier, a solvent carrier, or combination thereof.
9. A peelable foam coating composition comprising: a vinyl toluene acrylate copolymer resin in an amount of from between 27.0 to 30.0 weight percent; an aromatic solvent in an amount of from between 12.0 to 15.0; an aliphatic solvent in an amount of from b etween 38.0 to 40.0 weight p ercent; a pigment in an amount of from between 3.0 to 5.0 weight percent; release agent in an amount of from between 5.0 to 7.0 weight percent; a propellant in an effective amount selected from the group consisting of a carbon dioxide and a hydrocarbon propellant; a plasticizer in an amount of from 6.0 to 9.0 weight percent; and a thickner in an amount of from 0.1 to 2.0 weight percent.
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| US19150600P | 2000-03-23 | 2000-03-23 | |
| US60/191,506 | 2000-03-23 | ||
| US09/693,366 | 2000-10-20 | ||
| US09/693,366 US6822012B1 (en) | 2000-03-23 | 2000-10-20 | Peelable polymeric coating composition |
| PCT/US2001/009532 WO2001070834A1 (en) | 2000-03-23 | 2001-03-23 | Peelable foam coating composition |
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| AU2001245983A1 true AU2001245983A1 (en) | 2001-12-13 |
| AU2001245983B2 AU2001245983B2 (en) | 2006-07-27 |
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| AU4598301A Pending AU4598301A (en) | 2000-03-23 | 2001-03-23 | Peelable foam coating composition |
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| AU4598301A Pending AU4598301A (en) | 2000-03-23 | 2001-03-23 | Peelable foam coating composition |
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| EP (1) | EP1268578A4 (en) |
| AU (2) | AU2001245983B2 (en) |
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| NZ (1) | NZ522488A (en) |
| WO (1) | WO2001070834A1 (en) |
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-
2000
- 2000-10-20 US US09/693,366 patent/US6822012B1/en not_active Expired - Fee Related
-
2001
- 2001-03-23 US US09/815,874 patent/US6713522B2/en not_active Expired - Fee Related
- 2001-03-23 WO PCT/US2001/009532 patent/WO2001070834A1/en active IP Right Grant
- 2001-03-23 NZ NZ522488A patent/NZ522488A/en not_active IP Right Cessation
- 2001-03-23 MX MXPA02010464A patent/MXPA02010464A/en active IP Right Grant
- 2001-03-23 AU AU2001245983A patent/AU2001245983B2/en not_active Ceased
- 2001-03-23 AU AU4598301A patent/AU4598301A/en active Pending
- 2001-03-23 EP EP01918969A patent/EP1268578A4/en not_active Withdrawn
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