WO2005123847A1 - Free radical curable conductive primer - Google Patents
Free radical curable conductive primer Download PDFInfo
- Publication number
- WO2005123847A1 WO2005123847A1 PCT/US2005/020575 US2005020575W WO2005123847A1 WO 2005123847 A1 WO2005123847 A1 WO 2005123847A1 US 2005020575 W US2005020575 W US 2005020575W WO 2005123847 A1 WO2005123847 A1 WO 2005123847A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- composition
- peroxide
- acrylates
- initiator
- butyl
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
-
- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
- C09D167/07—Unsaturated polyesters having carbon-to-carbon unsaturation having terminal carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
Definitions
- the present invention concerns coating compositions, particularly conductive, sprayable primers.
- the coating composition of the present invention is more particularly a substantially 100% solids, sprayable, free radical curable electroconductive coating compositions.
- SMC sheet molded compound
- sheet molded compound is a thermoset resin mixture comprising a polymer, glass fibers, and fillers.
- the polymer is selected according to the desired properties of the product produced therefrom, as well as the processing parameters.
- the SMC resin is processed into a mat or pre- form and, then, placed under heat and several tons of pressure in a suitable mold to form the item, although other manufacturing processes may exist.
- the mold conforms the mat to the requisite part or shape. After forming the mat into the desired shape, the item produced is removed from the mold and it is, then, finished such as by painting or the like.
- a finish may be applied through electrostatic spraying.
- other spray application methods may be used, such as, for example, siphon feed spray guns, gravity feed spray guns, High Volume Low Pressure (HVLP) spray guns, airless spray systems, air assisted airless spray systems, rotary atomizer, disk rotators and the like, as well as combinations thereof.
- SMC panels When exposed to electrostatic spray finishes, SMC panels present certain unique problems. Because SMC is a non-conductive plastic, it does not have the capacity to carry an electrical current. Therefore, a conductive solution or coating, such as a conductive primer, conductive preparation coat, conductive undercoat or the like must be applied to the SMC surface so that subsequent coatings can be applied thereover via electrostatic application.
- a conductive solution or coating such as a conductive primer, conductive preparation coat, conductive undercoat or the like must be applied to the SMC surface so that subsequent coatings can be applied thereover via electrostatic application.
- Such conductive solutions or coatings are known in the prior art.
- these prior art primers are either solvent-based, water based, powder coatings, or combinations thereof. These primers, generally, require a cure at elevated temperatures in a suitable oven after application.
- SMC SMC materials are porous. When solvent evaporates or is removed from the coating, there is a tendency for surface irregularities, which are manifested by bubbly looking voids or "pops" to appear or be created on the surface of the finished product. Oftentimes, the "pops" may not be noticed until a final topcoat is applied and cured. Obviously, this causes a great expense in labor and materials to correct the problem.
- the present invention alleviates many of the problems encountered heretofore by providing a substantially 100% solids, sprayable composition that is curable through a number of methods, such as conventional ovens or via infra red (IR).
- the present invention is directed toward a conductive coating 1 composition that not only functions as a primer but may also be utilized as a sealer or a combination, as well.
- This new primer provides a sealed surface that minimizes popping or outgassing, in turn saving repair costs, and provides a conductive surface to allow electrostatic application of subsequent paint layers. Because the initiator results in a thermally cured composition, there is no need to employ UV light or electron beam (EB), and accordingly accompanying equipment, such as is necessary with the use of photoinitiators, to achieve the cured composition as herein described.
- compositions include reduced repair costs due to minimal popping, lower VOC emissions and lower energy costs attributed to the curing process.
- the composition hereof generally, comprises a mixture of: (a) a free-radical curable, polymerizable compound which may be a polymer, a pre-polymer, a monomer, and mixtures thereof; (b) a initiator which may be a blend of initiators. In one embodiment, a conductive pigment or a mixture of pigments is included in the composition. [0013]
- the composition hereof generally, comprises (a) from about 50% to about 95%, by weight, based on the total weight of the composition of a free-radical curable, polymerizable compound, (b) from about 0.1% to about 4%, by weight, based upon the total weight of the composition, of the initiator. Additionally, the composition may include from about 0.5% to about 10%, by weight, based upon the total weight of the composition, of a conductive pigment.
- the pigment may me a mixture or blend comprising both conductive and non- conductive pigments, including (a) mixtures of conductive pigments and (b) mixtures of conductive and non-conductive pigment.
- the composition is substantially free of a photoinitiator.
- the composition hereof may contain adjuvants such as flow additives, dispersion aids, defoamers, deaerators, suspension aids, and mixtures thereof. Other adjuvants, as needed, may also, be incorporated hereinto.
- the composition may also contain fillers or extenders that may be organic or inorganic, as well as mixtures thereof.
- composition hereof is used to coat SMC surfaces and, in particular, automotive panels. It is to be understood, however, that the present invention also contemplates coating SMC surfaces other than automotive panels, as well as other substrates such as, but not limited to, reaction injection molding (RIM), reaction thermal molding (RTM), hand lay up, acrylonitrile butadiene styrene (ABS), thermoplastic olefin (TPO), polycarbonate (PC), and the like.
- RIM reaction injection molding
- RTM reaction thermal molding
- TPO thermoplastic olefin
- PC polycarbonate
- the viscosity of the composition is less than about 3000 centipoise at 25°C. In one useful embodiment, the composition is at least about 95% nonvolatile material.
- compositions for sealing and priming porous plastic substrates are provided.
- the composition is a low VOC, substantially 100% solids curable primer.
- the composition is at least about 95% nonvolatile materials.
- the primer utilizes free-radical cure technology by cross-linking acrylate monomers and oligomers with thermally generated free radicals from organic peroxide(s).
- cross-linkable and non-functional resins can be used that are not acrylate functional.
- composition hereof generally, comprises a mixture of: (a) a free-radical curable, polymerizable compound which may be either a polymer, a monomer, an oligomer, and mixtures thereof, (b) a thermal initiator; and (c) a conductive pigment or a mixture of pigments.
- composition disclosed herein comprises: (a) from about 50% to about 95%, by weight, based on the total weight of the composition, of a free-radical curable, polymerizable compound, (b) from about 0.1% to about 4%, by weight, based upon the total weight of the composition of the initiator and (c) from about 0.5% to about 10%, by weight, based upon the total weight of the composition, of a conductive pigment.
- the pigment mixture may comprise both conductive and non-conductive pigments in admixture including (a) a mixture of conductive pigments and (b) a mixture of conductive and non-conductive pigment.
- Dispersion aids may be incorporated into the composition to tailor the properties of the primer/sealer.
- Other adjuvants may also, be incorporated hereinto.
- the composition may, also, contain fillers or extenders that may be organic or inorganic, as well as mixtures thereof.
- the present coating composition functions not only as a primer but as a sealer, thus, eliminating the need for separate primer and sealer coatings.
- the first component of the present composition is a substantially solvent free, sprayable, free-radical curable polymerizable compound that utilizes unsaturated monomers and/or oligomers in order to minimize the viscosity and provide the highest application solids of the curable coatings.
- the polymerizable reactants suitable for use in this invention can be any compound having polymerizable ethylenic unsaturation such as unsaturated polymers, oligomers, monomers or combinations thereof.
- Representative polymeric or oligomeric polyunsaturated compounds are well known in the art and can include, for example, unsaturated polyesters obtained by the reaction of polyols and maleic or fumaric acid, reaction products of polyacids or polyisocyanates with unsaturated alcohols, reaction products of polyepoxides and unsaturated acids such as acrylic or methacrylic acids, reaction products of polyols and unsaturated acids or esters, and other methods well known in the art.
- the polymerizable compound is acrylate functional.
- the acrylate may be monofunctional or polyfunctional.
- mixtures of acrylate functional compounds may be used. Such a mixture may comprise all monofunctional acrylate, all polyfunctional compounds, or mixtures thereof.
- the monomeric acrylates generally function as adhesion promoters as well as controlling the viscosity of the final composition and provide various characteristics upon cure. It should be noted that a single acrylate may, also, be used herein.
- Especially useful monomers include vinyl and allyl compounds such as styrene, vinyl acetate, vinyl ethers, vinyl esters, unsaturated polyesters, unsaturated resins, vinylidene chloride, and (meth)acrylates of monohydric alcohols, acrylamides and similar (meth)acrylate acid derivatives, such as methylmethacrylate, hydroxyethyl acrylate, acrylonitrile, and acrylamide.
- vinyl and allyl compounds such as styrene, vinyl acetate, vinyl ethers, vinyl esters, unsaturated polyesters, unsaturated resins, vinylidene chloride, and (meth)acrylates of monohydric alcohols, acrylamides and similar (meth)acrylate acid derivatives, such as methylmethacrylate, hydroxyethyl acrylate, acrylonitrile, and acrylamide.
- acrylates or acrylate functional components include monoacrylates, diacrylates, triacrylates, polyacrylates, aliphatic and aromatic urethane- modified acrylates, urethane acrylates, polyester-modified acrylates, polyester acrylates, vinyl acrylates, epoxy acrylates, epoxy modified acrylates, polyether acrylates, amine modified acrylates, acrylic polymer modified acrylates, acid functional acrylates, acid modified acrylates, silicone acrylates, silicone modified acrylates, acrylate functional cycloaliphatic resins, acrylate functional cationic resins, and mixtures thereof.
- the polymerizable compound comprises a mixture of acrylates that are selected from the group consisting of aliphatic diacrylate, urethane acrylate, tetrahydrofufuryl acrylate, urethane dimethacrylate, and polyester acrylate, as well as mixtures and derivatives thereof.
- the polyester acrylate is particularly useful in the composition described herein because of its characteristic as an adhesion promoter.
- An example of a urethane acrylate oligomer which can be used in accordance with this invention is a hexafunctional aliphatic urethane acrylate oligomer that is sold by UCB Chemicals Corp under the trade name Ebecryl® 8301.
- a polyester acrylate that can be used in accordance with this invention is a polyester resin diluted with tripropylene glycol diacrylate, which is sold by UCB Group under the trade name Ebecryl® 525.
- the mixture of acrylates will be present in the composition in an amount ranging from about 50% to about 95%, by weight, based on the total weight of the composition. In another useful embodiment the mixture of acrylates is from about 80% to about 95%, by weight, based upon the total weight of the composition.
- the second component of the present invention is an activator, which includes an initiator.
- the initiator that is used in the composition of the present invention may be of the free radical type. A mixture or blend of initiators may be also used. In one embodiment of the present invention, the initiator or initiators that may be use are not photoinitiators.
- the peroxide initiator should be used in an amount sufficient to overcome the effect of the inhibitor and to cause crosslinking or curing of the ethylenically unsaturated materials.
- the peroxide initiator is used in an amount of about 0.1% to about 5% by weight based on the weight of the ethylenically unsaturated materials employed in the coating composition.
- the initiator is present in an amount ranging from about 1% to about 2%, by weight, based upon the total weight of the composition. It is to be appreciated that the amount of thermal initiator required in a given formulation will depend on the bake cycle specifications, for example, the time and temperature of the bake.
- the coating composition also includes a conductive pigment.
- conductive pigments of the type contemplated for use herein ordinarily, include conductive carbon black pigment. These conductive pigments are well-known and commercially available compounds and are, generally, defined as dry conductive carbon black pigment. Dispersions can be made of any of a number of pigments in monomers or oligomers or combinations thereof. In one useful embodiment, a mixture of conductive pigments is employed.
- Additional conductive pigments other than those enumerated above and include antimony doped tin oxide, and metallic pigments such as gold, platinum, silver, titanium, aluminum, copper, and the like, as well as mixtures thereof. These conductive metal pigments may be supported or unsupported. These pigments come in forms such as flakes, powders, spheres, microballoons, microencapsulated, or other physical forms.
- Other conductive materials that are contemplated for use herein include encapsulated pigments; conductive polymers; conductive fibers (fibrols or fibrils); conductive additives, as well as mixtures thereof. These additional conductive materials may be used conjointly with the conductive pigments identified above. Where used, the conductivity enhancers will be present in an amount dependent on the desired conductivity level of the composition.
- the total amount of conductive material i.e., pigment with or without enhancer, is, generally, employed in an amount ranging from about 0.5% to about 10%, by weight, based upon the total weight of the composition.
- the amount of conductive pigment generally is dependent upon the final desired conductivity level of the composition.
- conductive carbon black is used in the coating composition in an amount of from about 1 to 2 parts by weight per 100 parts by weight of the polymerizable oligomer.
- the conductive carbon black pigment that is used is sold under the trade name Printex XE2 by Degussa Corporation.
- a conductive additive that can be employed is sold under the trade name Efka® 8860.
- the composition may also contain various pigments to introduce color to the composition.
- Common pigments used may include, titanium dioxide, phthalos, iron oxides, lamp black, carbon black, various organic and inorganic pigments, and mixtures thereof.
- dispersions can be made of any of a number of pigments.
- a number of dispersing agents can be employed for this purpose.
- Such dispersing agents include polymeric dispersants.
- some dispersants that may be used in accordance with this invention include a dispersant sold under the trade name Nuosperse by Condea Servo LLC, and SolsperseTM 5000 and 32500 which are sold by Lubrizol Ltd.
- adjuvants may be incorporated herein such as, flow additives, dispersing aids (such as, for example, polymeric dispersants), defoamers, deaerators, suspension aids, scavengers, stabilizers, antioxidants, plasticizers, nonfunctional or nonreactive diluents, hydrocarbon oils, conductive additives, and the like, as well as mixtures thereof.
- the flow agent that is used is sold under the trade name Tego® Flow 300 by Degussa Corporation.
- Suitable fillers or extenders which may be added to the composition for various properties include the commonly used fillers or extenders, such as carbonates, silicates, sulfates, silicas, silicates, sulf ⁇ tes, clays, carbides, oxides, polyfluorinated ethylenes, ferrites, aluminas, nitrides, polymeric fillers, fibers, cellulosics, ceramics, and the associated precipitates, derivatives, and hydrates and the like, as well as mixtures thereof.
- These extenders may be in a treated or non-treated form, and may be natural occurring products or synthetically manufactured, and may be reclaimed or recycled, as well as combinations thereof.
- Thermal initiators that are suitable for use in the practice of the present invention include organic free-radical or free radical generating initiator (catalyst) to catalyze the polymerization, copolymerization, and/or crosslinking of the ethylenically unsaturated oligomers and the other ethylenically unsaturated materials.
- organic free-radical or free radical generating initiator catalyst
- thermal initiator that can be used in accordance with this invention is peroxide.
- peroxides include diacyl peroxides, dialkyl peroxides, hydroperoxides, ketone peroxides, monoperoxycarbonates, peroxydicarbonates, peroxyesters, peroxyketals and blends and mixtures thereof, including but not limited to tertiary butyl perbenzoate, tertiary butyl peroctoate in diallyl phthalate, diacetyl peroxide in dimethyl phthalate, dibenzoyl peroxide, di( ⁇ -chlorobenzoyl) peroxide in dibutyl phthalate, di(2,4- dichlorobenzoyl) peroxide with dibutyl phthalate, dilauroyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide in dibutyl phthalate, 3,5-dihydroxy-3,4-dimethyl-l,2- dioxacyclopentane, t-butylper
- One useful peroxide that may be used in accordance with this invention is di- (4-t-butyl cyclohexyl) peroxydicarbonate, which is sold by Crompton Corporation under the trade name Espercarb® 1043. h one useful embodiment, a peroxide that has a 10- hour half-life at about 35-45°C is used, and it is particularly useful to employ the use of a peroxide that has a 10-hour half-life at about 43 °C. It has been discovered that an initiator with this range of half-life provides for a thermally cured coating, with a low level of VOCs, through the use of conventional ovens to decrease cure time.
- the coating composition is generally a mixture of polymeric compound and activator.
- the initiator(s) is dispersed in an acrylate or other curable material and dissolved therewithin to form an activator or initiator solution.
- the initiator solution is then added to the remaining composition that comprises, for example, a polymerizable compound and any desired additives, including but not limited to dispersing agents, conductive additives, and flow agents, fillers, extenders, and adjuvants.
- the resulting composition is sprayable onto an SMC surface through conventional electrostatic spraying equipment as well as standard siphon feed spray guns, HVLP spray guns, airless spray equipment, air assisted airless spray equipment, disk rotators, rotary atomizers, and the like depending on the mode of application, as denoted above.
- the polymer is cured by a rapid polymerization reaction that is initiated by the initiator component of the composition when it is exposed to suitable heat source(s) or other catalyzing effect.
- the composition once applied to a part, can be cured in an oven where the part temperature attains at least about 107°C (225°F) for at least about 30 minutes, however, other cure schedules may be employed.
- a flash or dwell time of about 5-15 minutes is typical prior to baking.
- Conventional ovens can be employed to cure the composition once it is applied onto a surface.
- Typical primers are based at about 149°C (300°F) for at least about 30 minutes.
- the primer alternatively has the capacity to be cured with IR radiation or other devices.
- the cure time is 1 minute at 100%, or 4 minutes at 50%, and a part surface temperature of about 149°C (300°F).
- the material polymerizes in and about the substrate, providing adhesion thereto.
- composition of the present invention does not contain any significant water or organic solvent, which must be evaporated before curing is complete. Rather, the present invention includes low molecular weight polymerizable monomers and/or oligomers that are polymerized in place upon exposure to an adequate cure schedule. Therefore, the composition of the present invention is much less hazardous to the environment than the previously available compounds, which included organic solvents that had to be evaporated into the atmosphere in order to cure the finish.
- Possible methods of application include spraying, brushing, curtain coating, dipping, and rolling.
- the composition has the ability to control viscosity by the use of low molecular weight monomers which take the place of organic solvents but which also participate and contribute to final polymer properties.
- the formulation can be applied through various application means. By controlling the viscosity of the material, depth and speed of penetration before curing can be controlled.
- the viscosity of the composition hereof is less than about 3500 centipoise at 25°C at about 100% solids. In one embodiment, the viscosity is less than about 1000 centipoise at about 100% solids.
- the present invention enables the production of a substantially solvent-free composition.
- the present invention precludes the necessity of nonreactive solvents, such as water, alcohols, volatile organics and the like. However, minor amounts of such may be included without deleteriously affecting the present invention.
- the polymer of the present invention is cured by thermal exposure, such as by exposure in a conventional oven or through an IR cure, or combinations thereof.
- the present coating composition is useful both as an electrically conductive primer and sealer.
- other electrically conductive or non-electroconductive coatings may be applied via electrostatic or other application method or methods thereunto because of the electrically conductive nature of the coating in the liquid and cured state.
- composition hereof may be used to coat SMC surfaces and, in particular, automotive panels. It is to be understood, however, that the present invention also contemplates coating SMC surfaces other than automotive panels, as well as other substrates such as, but not limited to, reaction injection molding (RIM), reaction thermal molding (RTM), hand lay up, acrylonitrile-butadiene styrene (ABS), thermoplastic olefin (TPO), polycarbonate (PC), hybrid molding, and mixtures thereof.
- RIM reaction injection molding
- RTM reaction thermal molding
- TPO thermoplastic olefin
- PC polycarbonate
- hybrid molding and mixtures thereof.
- EXAMPLE This example illustrates a thermal curable, substantially 100% solids, sprayable conductive primer.
- Ingredient Amount (parts by weight)
- Activator Formula Tefrahydrofurfuryl acrylate 91.5 Espercarb 1043 7 5.6
- the Activator ingredients are mixed until all of the Espercarb® 1043 is dissolved.
- the Activator solution is then added to the first component to form the curable composition.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Sealing Material Composition (AREA)
- Conductive Materials (AREA)
- Polymerization Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE602005010095T DE602005010095D1 (en) | 2004-06-10 | 2005-06-10 | RADICALLY HARDENABLE CONDUCTIVE PRIMER |
BR122015007235A BR122015007235B1 (en) | 2004-06-10 | 2005-06-10 | electroconductive sealant / initiator composition |
EP05761166A EP1784459B1 (en) | 2004-06-10 | 2005-06-10 | Free radical curable conductive primer |
CN2005800187426A CN1973004B (en) | 2004-06-10 | 2005-06-10 | Free radical curable conductive primer |
BRPI0511887A BRPI0511887B1 (en) | 2004-06-10 | 2005-06-10 | coating composition containing free radical curable polymerizable compound |
MXPA06012945A MXPA06012945A (en) | 2004-06-10 | 2005-06-10 | Free radical curable conductive primer. |
CA2565982A CA2565982C (en) | 2004-06-10 | 2005-06-10 | Free radical curable conductive primer |
BR122015007227A BR122015007227B1 (en) | 2004-06-10 | 2005-06-10 | method of initiation and sealing of a non-conductive plastic substrate |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US57880904P | 2004-06-10 | 2004-06-10 | |
US60/578,809 | 2004-06-10 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2005123847A1 true WO2005123847A1 (en) | 2005-12-29 |
Family
ID=34972587
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2005/020575 WO2005123847A1 (en) | 2004-06-10 | 2005-06-10 | Free radical curable conductive primer |
Country Status (9)
Country | Link |
---|---|
US (1) | US20060009570A1 (en) |
EP (1) | EP1784459B1 (en) |
CN (1) | CN1973004B (en) |
AT (1) | ATE409730T1 (en) |
BR (3) | BR122015007227B1 (en) |
CA (1) | CA2565982C (en) |
DE (1) | DE602005010095D1 (en) |
MX (1) | MXPA06012945A (en) |
WO (1) | WO2005123847A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1842885A1 (en) * | 2006-04-05 | 2007-10-10 | Ivm S.R.L. | styrene-free varnish based on polyunsaturated polyester resins |
CN110655813A (en) * | 2018-06-29 | 2020-01-07 | 常州格林感光新材料有限公司 | Light-cured composition for repairing composite material and application thereof |
CN110655812A (en) * | 2018-06-29 | 2020-01-07 | 常州格林感光新材料有限公司 | Composite material composition for rapid repair and application thereof |
US20200248006A1 (en) * | 2017-08-17 | 2020-08-06 | Khalifa University of Science and Technology | Mesoporous carbon based nanocontainer coatings for corrosion protection of metal structures |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8378017B2 (en) | 2005-12-29 | 2013-02-19 | Designer Molecules, Inc. | Thermosetting adhesive compositions |
US8287686B2 (en) * | 2006-07-24 | 2012-10-16 | Designer Molecules, Inc. | Derivatives of poly(styrene-co-allyl alcohol) and methods for use thereof |
US20080139700A1 (en) * | 2006-12-11 | 2008-06-12 | Roden Don R | Methods for devolatilizing resin solutions and resins produced thereby |
US8344076B2 (en) * | 2006-12-19 | 2013-01-01 | Designer Molecules, Inc. | Hydrolytically resistant thermoset monomers |
US8039663B2 (en) * | 2007-04-09 | 2011-10-18 | Designer Molecules, Inc. | Monomers derived from pentacyclopentadecane dimethanol |
US7928153B2 (en) * | 2007-08-14 | 2011-04-19 | Designer Molecules, Inc. | Thermosetting polyether oligomers, compositions and methods for use thereof |
ES2319068B1 (en) * | 2007-10-30 | 2010-02-12 | Fepyr S.A. | COATING SYSTEM FOR SURFACE LACQUERING. |
US8541531B2 (en) * | 2008-03-21 | 2013-09-24 | Designer Molecules, Inc. | Anti-bleed compounds, compositions and methods for use thereof |
US8008419B2 (en) * | 2008-08-13 | 2011-08-30 | Designer Molecules, Inc. | Siloxane monomers and methods for use thereof |
US8217120B2 (en) * | 2008-08-13 | 2012-07-10 | Designer Molecules, Inc. | Functionalized styrene oligomers and polymers |
US8158748B2 (en) * | 2008-08-13 | 2012-04-17 | Designer Molecules, Inc. | Hetero-functional compounds and methods for use thereof |
CN105419573A (en) * | 2015-12-23 | 2016-03-23 | 东莞市纳利光学材料有限公司 | Nano metal slurry used for transparent electric-conductive thin film and preparation method thereof |
CN107043564A (en) * | 2017-02-07 | 2017-08-15 | 欧振云 | A kind of conducting function coating and its prepare conductive fiber method |
EP4011617A4 (en) * | 2019-08-06 | 2023-09-13 | Resonac Corporation | Primer-equipped thermoplastic resin member, and resin-resin conjugate |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5453451A (en) * | 1991-05-15 | 1995-09-26 | Sokol; Andrew A. | Finishing composition which is curable by UV light and method of using same |
US6025031A (en) * | 1996-05-08 | 2000-02-15 | Basf Coatings Ag | Coating agent consisting of at least 3 components |
US20010018467A1 (en) * | 1999-12-20 | 2001-08-30 | Robert Dunkle | Method of priming SMC parts |
US20030008934A1 (en) * | 2001-03-07 | 2003-01-09 | Zychowski Frank David | 100% solids radiation curable conductive primer |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4169825A (en) * | 1975-05-15 | 1979-10-02 | The Sherwin-Williams Company | High solids coating compositions |
US4235833A (en) * | 1977-07-11 | 1980-11-25 | The General Tire & Rubber Company | In-the-mold coating apparatus and method |
US4239808A (en) * | 1979-06-13 | 1980-12-16 | The General Tire & Rubber Company | In-mold coating of sheet molding compound moldings |
US4422996A (en) * | 1980-05-01 | 1983-12-27 | Freeman Chemical Corporation | Method for making coated molded articles |
US4366109A (en) * | 1980-05-01 | 1982-12-28 | Freeman Chemical Corporation | Method for making coated molded articles |
US4293659A (en) * | 1980-05-01 | 1981-10-06 | Freeman Chemical Corporation | Composition for coating molded articles |
US4414173A (en) * | 1981-11-02 | 1983-11-08 | The General Tire & Rubber Company | In-mold coating |
US4477405A (en) * | 1981-12-31 | 1984-10-16 | Ppg Industries, Inc. | Method of in-mold coating |
US4668460A (en) * | 1985-04-02 | 1987-05-26 | The Sherwin-Williams Company | Method of molding and coating a substrate in a mold. |
US4908230A (en) * | 1988-12-22 | 1990-03-13 | The Sherwin-Williams Company | Process for coating polycarbonates with UV curable coatings |
US5244941A (en) * | 1989-11-02 | 1993-09-14 | Ralph Wilson Plastics Company | Artificial stone compositions, process of producing the same, and apparatus employed in the production thereof |
US5773487A (en) * | 1991-05-15 | 1998-06-30 | Uv Coatings, Inc. | Finishing composition which is curable by UV light and method of using same |
US5319003A (en) * | 1992-09-30 | 1994-06-07 | Union Carbide Chemicals & Plastics Technology Corporation | Method for improving the mechanical performance of composite articles |
US5387750A (en) * | 1993-08-27 | 1995-02-07 | The Sherwin-Williams Company | Two-component urethane in-mold coating composition |
US5410078A (en) * | 1994-01-03 | 1995-04-25 | The Sherwin-Williams Company | Styrene-based dicarboxylic acid-functional monomers and polymers prepared from same |
US5632838A (en) * | 1994-08-08 | 1997-05-27 | The Sherwin-Williams Company | Coating composition for pultrusion/extrusion process and method of application |
US5627230A (en) * | 1994-08-08 | 1997-05-06 | The Sherwin-Williams Company | Coating composition for pultrusion process and method of application |
US6296932B1 (en) * | 1998-12-14 | 2001-10-02 | 3M Innovative Properties Company | Microsphere adhesive coated article for use with coated papers |
US20010043995A1 (en) * | 1999-03-02 | 2001-11-22 | Sgro Joseph Charles | Method of coating a substrate with a structural polymer |
US6448302B1 (en) * | 2000-01-19 | 2002-09-10 | The Sherwin-Williams Company | Radiation curable coatings having low gloss and coated articles made therefrom |
US6706810B2 (en) * | 2001-03-16 | 2004-03-16 | Illinois Tool Works, Inc. | Primer/primer surfacer |
-
2005
- 2005-06-10 BR BR122015007227A patent/BR122015007227B1/en not_active IP Right Cessation
- 2005-06-10 AT AT05761166T patent/ATE409730T1/en not_active IP Right Cessation
- 2005-06-10 US US11/150,513 patent/US20060009570A1/en not_active Abandoned
- 2005-06-10 EP EP05761166A patent/EP1784459B1/en not_active Not-in-force
- 2005-06-10 WO PCT/US2005/020575 patent/WO2005123847A1/en active Search and Examination
- 2005-06-10 DE DE602005010095T patent/DE602005010095D1/en active Active
- 2005-06-10 BR BRPI0511887A patent/BRPI0511887B1/en not_active IP Right Cessation
- 2005-06-10 CA CA2565982A patent/CA2565982C/en not_active Expired - Fee Related
- 2005-06-10 CN CN2005800187426A patent/CN1973004B/en not_active Expired - Fee Related
- 2005-06-10 BR BR122015007235A patent/BR122015007235B1/en not_active IP Right Cessation
- 2005-06-10 MX MXPA06012945A patent/MXPA06012945A/en active IP Right Grant
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5453451A (en) * | 1991-05-15 | 1995-09-26 | Sokol; Andrew A. | Finishing composition which is curable by UV light and method of using same |
US6025031A (en) * | 1996-05-08 | 2000-02-15 | Basf Coatings Ag | Coating agent consisting of at least 3 components |
US20010018467A1 (en) * | 1999-12-20 | 2001-08-30 | Robert Dunkle | Method of priming SMC parts |
US20030008934A1 (en) * | 2001-03-07 | 2003-01-09 | Zychowski Frank David | 100% solids radiation curable conductive primer |
Non-Patent Citations (1)
Title |
---|
STOYE, D.; ED.: "Paints, Coatings and solvents", 1993, VCH, WEINHEIM, NEW YORK, XP002345560 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1842885A1 (en) * | 2006-04-05 | 2007-10-10 | Ivm S.R.L. | styrene-free varnish based on polyunsaturated polyester resins |
US20200248006A1 (en) * | 2017-08-17 | 2020-08-06 | Khalifa University of Science and Technology | Mesoporous carbon based nanocontainer coatings for corrosion protection of metal structures |
US11859104B2 (en) * | 2017-08-17 | 2024-01-02 | Khalifa University of Science and Technology | Mesoporous carbon based nanocontainer coatings for corrosion protection of metal structures |
CN110655813A (en) * | 2018-06-29 | 2020-01-07 | 常州格林感光新材料有限公司 | Light-cured composition for repairing composite material and application thereof |
CN110655812A (en) * | 2018-06-29 | 2020-01-07 | 常州格林感光新材料有限公司 | Composite material composition for rapid repair and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CA2565982C (en) | 2011-01-11 |
CN1973004B (en) | 2010-10-13 |
BR122015007227B1 (en) | 2016-03-08 |
US20060009570A1 (en) | 2006-01-12 |
CA2565982A1 (en) | 2005-12-29 |
CN1973004A (en) | 2007-05-30 |
BRPI0511887B1 (en) | 2015-12-08 |
MXPA06012945A (en) | 2007-02-12 |
ATE409730T1 (en) | 2008-10-15 |
BR122015007235B1 (en) | 2016-03-01 |
BRPI0511887A (en) | 2008-01-15 |
EP1784459A1 (en) | 2007-05-16 |
DE602005010095D1 (en) | 2008-11-13 |
EP1784459B1 (en) | 2008-10-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2565982C (en) | Free radical curable conductive primer | |
US6784222B2 (en) | 100% solids radiation curable conductive primer | |
US5614581A (en) | Conductive gray in-mold coating | |
CA1192453A (en) | Method for repairing glass fiber reinforced plastic parts | |
EP0396837B1 (en) | Thermosetting in-mold coating compositions | |
EP0950071B1 (en) | New polymers, process for making them and coating compositions containing them, especially thermosetting acrylic gel coat compositions | |
JPH0139690B2 (en) | ||
CA2232483C (en) | Coating composition with improved water and mar resistance | |
JP2008231220A (en) | Hard coating agent and hard coat film | |
KR930009209B1 (en) | Coating compositions in mold | |
EP4028478B1 (en) | Method of coating a substrate using an accelerator-free coating composition | |
KR101705196B1 (en) | Water based aerosol coating composition and manufacturing method thereof | |
JP7370341B2 (en) | Composition with excellent coating properties | |
KR100533343B1 (en) | A polymer-coating method of face to metal-paint | |
CN115651509A (en) | Photocuring floor coating and preparation method thereof | |
US20080153932A1 (en) | Uses of waste stream from the production of powder coat | |
WO2005108512A1 (en) | In-mold coating with improved adhesion | |
MXPA99003985A (en) | New polymers, process for making them and coating compositions containing them, especially thermosetting acrylic gel coat compositions |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KM KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DPEN | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed from 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2565982 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: PA/a/2006/012945 Country of ref document: MX |
|
WWE | Wipo information: entry into national phase |
Ref document number: 200580018742.6 Country of ref document: CN |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWW | Wipo information: withdrawn in national office |
Country of ref document: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2005761166 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 2005761166 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: PI0511887 Country of ref document: BR |
|
DPE2 | Request for preliminary examination filed before expiration of 19th month from priority date (pct application filed from 20040101) |