WO1994007612A1 - Polymeres peints electrostatiquement et leur procede de production - Google Patents

Polymeres peints electrostatiquement et leur procede de production Download PDF

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Publication number
WO1994007612A1
WO1994007612A1 PCT/US1993/008470 US9308470W WO9407612A1 WO 1994007612 A1 WO1994007612 A1 WO 1994007612A1 US 9308470 W US9308470 W US 9308470W WO 9407612 A1 WO9407612 A1 WO 9407612A1
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WIPO (PCT)
Prior art keywords
polymer
electrostatically
metal salt
volatile metal
polymers
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PCT/US1993/008470
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English (en)
Inventor
Robert Carswell
Martin C. Cornell
Cynthia K. Groseth
James R. Porter
Ralph D. Priester, Jr.
Ricky L. Tabor
Melissa J. Zawisza
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Dow Chemical Co
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Dow Chemical Co
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Priority to DE69320644T priority Critical patent/DE69320644T2/de
Priority to BR9307150A priority patent/BR9307150A/pt
Priority to EP93920503A priority patent/EP0662867B1/fr
Priority to JP6509074A priority patent/JPH08501981A/ja
Priority to KR1019950701219A priority patent/KR100282103B1/ko
Publication of WO1994007612A1 publication Critical patent/WO1994007612A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
    • B05D1/04—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field
    • B05D1/045—Processes for applying liquids or other fluent materials performed by spraying involving the use of an electrostatic field on non-conductive substrates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material

Definitions

  • This invention relates to a process for electrostatically painting polymers. This invention particularly relates to
  • electrostatically painting polymers having urethane or urea groups having urethane or urea groups.
  • paint for such applications is often very expensive. Therefore, reducing paint consumption offers the immediate benefit of reduced paint cost.
  • paint which is not deposited upon the object to be painted can be lost to the environment and this loss can be environmentally undesirable. Therefore, reducing the quantity of paint lost to the environment in a painting process reduces the costs of disposing of the lost paint solids and reduces emissions of paint solvents.
  • paint can protect a metal object from corrosion or protect a plastic object from degradation by ultraviolet radiation. Therefore, failures of painted objects due to areas of too thin paint on the objects can be avoided by applying paint to objects wherein the layer of paint is of a consistent and sufficient thickness. In order to minimize problems with inefficient painting, it is common practice in painting some materials to apply paint
  • electrostatically In electrostatic painting, a static electric potential is generated between paint and an object to be painted causing the paint to be attracted to the object. As a result of the electrostatic attraction, less paint can be lost to the environment and the paint can be more evenly applied to the object without the entire surface being directly accessible to the paint spraying apparatus.
  • electrostatically painting objects is not always trouble free. In order to electrostatically paint an object, an electric charge potential must be generated between the object to be painted and a paint to be applied to the object. If an object is either not conductive or of very low conductivity, it cannot be efficiently electrostatically charged and cannot, therefore, be efficiently electrostatically painted.
  • One means of electrostatically painting polymers is to first make them more conductive by preparing the polymers from formulations including conductive fillers.
  • European Patent Application 0 363 103 to Suzuki, et al. discloses preparing a thermoplastic polymer having 2 to 50 percent by weight of a fibrous conductive filler such as carbon fibers, metallic fibers, metalized glass fibers, metal coated carbon fibers and conductive potassium titanate whiskers. The polymer is etched and then electrostatically painted.
  • adding such large amounts of fibrous fillers to a polymer can adversely affect both the polymer's physical properties and paint finish. A separate etching step can also be undesirable.
  • JP II 2-180960 assigned to Kanto Auto Works discloses preparing polyurethane substrates having improved conductivity.
  • polyurethanes of this reference are prepared with ammonium salts such as n-alkyldimethyl ammonium sulphates.
  • ammonium salts such as n-alkyldimethyl ammonium sulphates.
  • One problem with such additives are that they promote conductivity only when humidified.
  • prepcoats are conductive agents which adhere to the surface of the polymer.
  • agents can include materials such as quaternary amines.
  • One problem with such compounds is that they are often hydrophilic. In reaction injection molding (RIM) polyurethanes, the adsorbed water can cause blemishes on the surfaces of the polymer. Hydrophilic coatings can aggravate the tendency of objects to adsorb water prior to painting, thus promoting the formation of blemishes and thereby be undesirable in applications requiring high quality finishes.
  • RIM reaction injection molding
  • electrostatically paint polymers without having to pretreat the polymer by priming or prep-coating the polymer with a conductive material. It would also be desirable in the art to more efficiently electrostatically paint a polymer which has been primed or prepcoated with a conductive substance. It would be desirable in the art to prepare a polymer with sufficient native conductivity to efficiently electrostatically paint the polymer. It would be desirable in the art that the polymer to be painted not require special treatment such as humidification. And it would also be desirable in the art that the painted polymer have a sufficiently high quality painted surface and sufficiently strong physical properties such that the polymer could be used in very demanding applications such as the manufacture of automobiles. Finally, it would be desirable in the art if objects of dissimilar composition, for example, metal and plastic, can be painted as a unit rather than painted separately and then joined together.
  • the present invention is a process for electrostatically painting cured urea and/or urethane group containing polymers comprising the steps of: (A) preparing a cured polymer from a polymer formulation including (1) materials which include or form urea groups, urethane groups or mixtures thereof, and (2) a non-volatile metal salt conductivity inducing material, and (B) electrostatically painting the polymer, wherein (a) the polymer can be efficiently electrostatically painted, and (b) the polymer would not be conductive but for the inclusion of the non-volatile metal salt conductivity inducing materials in the polymer.
  • Another aspect of the present invention is in a process for electrostatically painting a cured urea and/or urethane group containing polymer wherein the polymer is formed into a shaped article, coated with a conductive preparatory substance and then electrostatically painted, the improvement comprising preparing the polymer from a polymer formulation including (1) materials which include or form urea groups, urethane groups or mixtures thereof, and (2) a non-volatile metal salt conductivity inducing material.
  • Still another aspect of the present invention is an
  • electrostatically painted object comprising at least two layers, a first layer being a layer of polymer prepared from a polymer
  • the present invention is an improvement to known processes for electrostatically painting polymers. This improvement includes preparing an object to be painted from a from a polymer formulation including (1) materials which include or form urea and/or urethane groups and (2) a non-volatile metal salt conductivity inducing material.
  • the resultant polymers can be electrostatically painted without the use of a conductive primer or other preparatory coating.
  • a cured polymer is painted.
  • a cured polymer is one wherein the reaction to produce the polymer is substantially complete and the polymer is in a solid and preferably fixed shape. Even more preferably, the polymer is in a shape appropriate for painting.
  • the polymer can be in the shape of an automobile body panel, side cladding or fascia.
  • the conductivity inducing materials of the present invention are non-volatile metal salts.
  • the conductivity inducing materials of the present invention will have both a cation and an anion.
  • the cation of the salts can be a cation of any metal which forms an ionizable salt with one or more anions, including Li, Be, Na, Mg, Al, K, Ca, Ga, Ge, Cu, Zn, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Rb, Sr, In, Sn, Sb, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, Cs, Ba, Tl, Pb, Bi, Po, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Fr, Ra and the Lanthanide series of the Periodic Table of the Elements.
  • the cation is a cation of an alkali metal (Li, Na, K, Rb, Cs, Fr), an alkaline earth metal (Ca, Ba, Sr, Ra), Co, Ni, Fe, Cu, Cd, Zn, Sn, Al or Ag; more preferably the cation is a cation of an alkaline earth or alkali metal; even more preferably the cation is a monovalent cation, especially an alkali metal cation; and most preferably the cation is a cation of Li, Na, K or mixtures thereof.
  • the non-volatile metal salt cations of the present invention can be selected from the group consisting of cations of Li, Na, K and mixtures thereof.
  • the non-volatile metal salt conductivity inducing materials of the present invention are salts of certain anions with the cations described above.
  • One group of preferred non-volatile metal salts are fluoroalkyl sulfonic acid salts.
  • the fluoroalkyl sulfonic acid anion (fluoroalkyl sulfonate) is suitably any fluoroalkyl sulfonic acid anion compatible with a specific composition in which it is used.
  • preferred fluoroalkyl sulfonates have from one to twenty carbon atoms and are either straight chained, branched or cyclic.
  • Fluoroalkyl sulfonates are sulfonate anions having an alkyl group having fluorine substitution, that is, fluorine atoms bonded to the carbon atoms of the alkyl groups.
  • the alkyl groups optionally, also have hydrogen atoms and/or other halogen atoms bonded to the carbon atoms.
  • at least 25 percent, more preferably 75 percent, (by number) of the atoms other than carbon which are bonded to carbon atoms of the fluoroalkyl groups are halogen, preferably fluorine.
  • the fluoroalkyl groups are perhaloalkyl groups, that is, alkyl groups having only halogen substitution.
  • Suitable halogens include fluorine, chlorine, bromine and iodine, preferably fluorine and chlorine.
  • Suitable perhaloalkyl sulfonic acid anions include, for instance, C 2 H 2 F 3 SO 3 - (tresylate), C 2 HF 4 SO 3 -, C 2 HClF 3 SO 3 -, C 3 H 2 F 5 SO 3 -, C 4 H 2 F 7 SO 3 -, C 5 H 2 F 9 SO 3 -, C 7 ClF 14 SO 3 -, C 8 Cl 2 H 2 F 13 SO 3 -, C 20 ClHF 39 SO 3 -.
  • the fluoroalkyl groups are most preferably perfluoroalkyl groups.
  • Exemplary perfluoroalkyl sulfonic acid anions include, for example CF 3 SO 3 -(triflate), C 2 F 5 SO 3 -, C 3 F 7 SO 3 -, C 4 F 9 SO 3 - (nonaflate), C 5 F 11 SO 3 -, C 6 F 13 SO 3 -, C 7 F 15 SO 3 -, C B F 17 SO 3 -, C 9 F 19 SO 3 -, C 20 F 41 SO 3 -, isomers thereof and mixtures thereof.
  • the salts of perfluoroalkyl sulfonates preferably have from 1 to 20, more preferably from 1 to 10, carbon atoms for reasons of availability and compatibility with polymers.
  • non-volatile metal salts can be used as conductivity inducing materials to prepare the formulations of the present invention also.
  • the anion of such salts is recognizable by those skilled in the art by such characteristics as pi bonding, electron withdrawing groups such as halogen atoms and the possibility of resonance structures.
  • the anion is preferably a relatively large, multiatomic anion having substituents like phenyl groups, sulfur atoms, and phosphorus atoms that can accept and delocalize an electron charge; more preferably the anion has more than one, more preferably at least 4, most preferably at least 5, non-metallic atoms.
  • Non-metallic atoms are generally considered to be selected from the group consisting of boron, carbon, silicon, phosphorus, arsenic, oxygen, sulfur, selenium, tellurium, fluorine, chlorine, bromine, iodine and astatine.
  • Preferred non-metallic atoms are boron, phosphorus, sulfur, fluorine and carbon in aromatic groups; sulfur and carbon in aromatic groups are more preferred.
  • the anion is preferably monovalent.
  • the anion is more preferably the conjugate base of an inorganic acid having one or more delocalizable electrons, for example, a fluoroalkyl sulfonate or a tetraorganoboron ion.
  • Such anions include, for example, NO 3 -, SCN-, SO 4 2- , HSO 4 -, SO 3 2- , PX 6 -, HSO 3 -, CNSO 3 -, XSO 3 - wherein X is a halogen, SXSO 3 - wherein X is a hydrogen or an anion, ClO 4 -, PO 4 3- , H 2 PO 4 -, HPO 4 2- , PO 3 3- , HPO 3 2- , H 2 PO 3 -, particularly tetraalkyl and tetraarylboron ions and non-alkyl or non-aryl
  • non-volatile metal salt is further defined to exclude those salts which are incompatible with or undesirable in formulations for polymers having urethane and/or urea groups.
  • the anion of a non-volatile metal salt of the present invention is not an SCN- anion because the salts of these anions can cause handling problems due to viscosity growth in polyurea formulations.
  • SCN- anions are also known to be water extractable in some polyurethane formulations. This property can cause handling problems in some painting applications.
  • non-volatile metal salts having good compatibility with formulations for polymers having urethane and/or urea groups are included and are preferred.
  • non-volatile metal salts of the present invention are salts wherein the non-volatile metal salt anion is selected from the group consisting of a perfluoroalkyl sulfonate, a tetraphenylboron anion, a hexafluorophosphate anion, or mixtures thereof.
  • the amount of conductivity inducing material which will be included in the polyurethane/polyurea formulations of the present invention will vary with the polymer. In the practice of the present invention, sufficient conductivity enhancing material is included in the formulation to render the material sufficiently conductive to allow efficient electrostatic painting.
  • comparatively nonconductive can require more conductivity inducing material than a polymer which is comparatively more conductive.
  • the amount of conductivity inducing material added to a polymer formulation useful for preparing polyurethane/polyurea polymers to be electrostatically painted is preferably from 0.02 percent to 1.5 percent, more preferably from 0.05 percent to 1.0 percent and even more preferably from 0.10 to 0.75 percent.
  • the non-volatile metal salt conductivity inducing materials of the present invention are preferably those which, when included in a polymer formulation, result in a polymer which has physical properties substantially similar to those of otherwise identical polymers prepared without the non-volatile metal salt conductivity inducing materials.
  • the physical properties relevant to this are those properties which determine if the polymer is useful in the application for which it is intended. For example, one such property is aesthetic appearance. If a non-volatile metal salt produces an undesirable appearance in a polymer at the minimum concentration necessary to efficiently paint the polymer, it is not a preferred conductivity inducing material of the present invention.
  • flex modulus tear strength
  • tensile strength tensile strength
  • two polymers have substantially similar physical properties if the values for those properties are within 15 percent, preferably within 12 percent, and most preferably within 10 percent of each other.
  • the non-volatile metal salts of the present invention can interact with the polymers they are incorporated into to actually improve some polymer physical
  • the polymers of the present invention can be any polymers of the present invention.
  • the efficiency of the painting process is determined by measuring the amount of paint deposited onto the object during the electrostatic painting process.
  • electrostatically painted is defined as the condition wherein the same thickness of paint is deposited upon a polymer object as is deposited upon a steel object when electrostatically painted under the same or substantially similar conditions.
  • the process of the present invention can be used with polymers that would not be conductive but for the inclusion of the non-volatile metal salt conductivity inducing materials of the present invention.
  • conductive is defined as having sufficient electrical conductivity to be efficiently electrostatically painted.
  • efficient electrostatically painted is used as defined in the paragraph immediately above.
  • the polymers of the present invention have urea groups, urethane groups and mixtures thereof. That is the polymers can be prepared from materials which include or react to form only polyurethane or polyurea groups, or the polymers of the present invention can be prepared from materials which include or react to form both polyurethane and polyurea groups. Other polymer linkages can be formed in the practice of the present invention too. For example, a polymer having polyurethane, polyurea and isocyanurate groups can be prepared.
  • the polymers of the present invention can also be polymer blends and polymer interpenetrating network polymers.
  • a polyurethane of the present invention can be blended with another polymer such as, for example, an acrylonitrile-butadiene-styrene polymer and then be electrostatically painted.
  • Other blendable polymers useful with the present invention include but are not limited to nylon, polyethyl terephthalate and polyacrylate.
  • Interpenetrating network polymers can be prepared with polymers of the present
  • the network polymers can be prepared by including one or more monomers in the formulations of the present invention such that the materials form a co-continuous or phase segregated in-situ polymer network.
  • the urea/urethane group containing polymers are the predominant component of multipolymer compositions of the present invention.
  • the polymers of the present invention can be either thermoplastic or thermoset .
  • Polyurethanes are prepared from
  • formulations including both polyisocyanate and a polyalcohol.
  • Polyureas are prepared from formulations including both a
  • polyisocyanate and a polyamine are often prepared from formulations including a polyisocyanate and both a polyalcohol and a polyamine.
  • the polyisocyanate formulation component can be advantageously selected from organic polyisocyanates, modified polyisocyanates, isocyanate-based
  • prepolymers and mixtures thereof.
  • These can include aliphatic and cycloaliphatic isocyanates, but aromatic and especially
  • multifunctional aromatic isocyanates are preferred. Preferred are 2,4- and 2,6-toluenediisocyanate and the corresponding isomeric mixtures; 4,4'-, 2,4'- and 2,2'- diphenylmethanediisocyanate and the corresponding isomeric mixtures; mixtures of 4,4'-, 2,4'- and 2,2'-diphenylmethanediisocyanates and polyphenyl polymethylene polyisocyanates (PMDI); and mixtures of PMDI and toluene diisocyanates. Also useful with the present invention are aliphatic and cycloaliphatic isocyanate compounds such as 1,6-hexamethylenediisocyanate;
  • modified multifunctional isocyanates that is products which are obtained through chemical reactions of the above diisocyanates and/or polyisocyanates.
  • modified multifunctional isocyanates that is products which are obtained through chemical reactions of the above diisocyanates and/or polyisocyanates.
  • exemplary are polyisocyanates containing esters, ureas, biurets, allophanates and preferably carbodiimides and/or uretone imines; isocyanurate and/or urethane group containing diisocyanates or polyisocyanates.
  • polyisocyanates containing carbodiimide groups, uretonimine groups and/or isocyanurate rings, having isocyanate groups (NCO) contents of from 10 to 40 weight percent, more preferably from 20 to 35 weight percent, can also be used.
  • NCO isocyanate groups
  • Suitable also are prepolymers having NCO contents of from 5 to 40 weight percent, more preferably from 15 to 30 weight percent. These prepolymers are prepared by reaction of the di- and/or
  • poly-isocyanates with materials including diols, triols, but also they can be prepared with multivalent active hydrogen compounds such as di- and tri-amines and di- and tri-thiols.
  • aromatic polyisocyanates containing urethane groups preferably having NCO contents of from 5 to 40 weight percent, more preferably 20 to 35 weight percent, obtained by reaction of diisocyanates and/or polyisocyanates with, for example, lower molecular weight diols, triols, oxyalkylene glycols, dioxyalkylene glycols or polyoxyalkylene glycols having molecular weights up to 800.
  • These polyols can be employed individually or in mixtures as di- and/or polyoxyalkylene glycols.
  • polyoxypropylenepolyoxyethylene glycols can be used. Particularly useful in the present invention are: (i) polyisocyanates having an NCO content of from 8 to 40 weight percent containing carbodiimide groups and/or urethane groups, from
  • PMDI in any of its forms can also be used and is preferred. In this case it preferably has an equivalent weight between 125 and 300, more preferably from 130 to 175, and an average functionality of greater than 2. More preferred is an average functionality of from 2.5 to 3.5.
  • the viscosity of the polyisocyanate component is preferably from 25 to 5,000 centipoise (cps) (0.025 to 5 Pa ⁇ s), but values from 100 to 1,000 cps (0.1 to 1 Pa ⁇ s)at 25°C are preferred for ease of processing. Similar viscosities are preferred where alternative polyisocyanate components are selected.
  • a polyalcohol formulation component can be advantageously selected from the following classes of compositions, alone or in admixture: (a) alkylene oxide adducts of polyhydroxyalkanes; (b) alkylene oxide adducts of non-reducing sugars and sugar derivatives; (c) alkylene oxide adducts of phosphorus and polyphosphorus acids; and (d) alkylene oxide adducts of polyphenols.
  • Polyols of these types are referred to herein as "base polyols”. Examples of alkylene oxide adducts of
  • polyhydroxyalkanes useful herein are adducts of ethylene glycol, propylene glycol, 1,3-dihydroxypropane, 1,4- dihydroxybutane, and 1,6-dihydroxyhexane, glycerol, 1,2,4-trihydroxybutane,
  • alkylene oxide adducts of polyhydroxyalkanes are the ethylene oxide adducts of trihydroxyalkanes.
  • Other useful adducts include ethylene diamine, glycerin, ammonia, 1,2,3,4-tetrahydroxy butane, fructose, and sucrose.
  • poly (oxypropylene) glycols triols, tetrols, pentols and hexols and any of these that are capped with ethylene oxide.
  • These polyols also include poly (oxypropyleneoxy ethylene)polyols.
  • the oxyethylene content should preferably comprise less than 80 weight percent of the total and more preferably less than 40 weight percent.
  • the ethylene oxide when used, can be incorporated in any way along the polymer chain, for example, as internal blocks, terminal blocks, or randomly distributed blocks, or any combination thereof.
  • copolymer polyols are base polyols containing stably dispersed polymers such as acrylonitrile-styrene copolymers. Production of these copolymer polyols can be from reaction mixtures comprising a variety of other materials, including, for example, catalysts such as azobisisobutyronitrile; copolymer polyol stabilizers; and chain transfer agents such as isopropanol.
  • PIPA Polyisocyanate polyaddition active hydrogen containing compounds
  • PIPA compounds are typically the reaction products of TDI and triethanolamine.
  • a process for preparing PIPA compounds can be found in, for example, United States Patent 4,374,209, issued to Rowlands.
  • Polyester polyols can be used for preparing the polymers of the present invention.
  • polyols prepared from caprolactone are useful.
  • Polyols prepared from butanediol and adipic acid can also be used. Any polyester known to one skilled in the art of preparing polyurethanes and polyureas to be useful can be used with the present invention.
  • Low molecular weight diols and triols can also be used in preparing the polymers of the present invention.
  • Ethylene glycol is particularly useful but other, similar compounds can also be used.
  • Propylene glycol, diethylene glycol are also suitable for use in the present invention.
  • the polyamine formulation component can be selected from the group including polyamines, and amine terminated polyols.
  • Polyamines are preferred for preparing the polyurethane/polyurea formulations of the present invention include the known low molecular isocyanate-reactive compounds such as aromatic polyamines, especially diamines, having molecular weights of less than 800, preferably less than 500.
  • Preferred amine group containing compounds include the sterically hindered aromatic diamines which contain at least one linear or branched alkyl substituent in the ortho position to the first amino group and at least one, preferably two, linear or branched alkyl substituents containing at least one, preferably one to three carbon atoms in the ortho position to the second amino group.
  • aromatic diamines include 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3,5-trimethyl-2,4-diaminobenzene, 1-methyl5-t-butyl-2,4-diaminobenzene, 1-methyl-5-t-butyl-2,6-diaminobenzene, 1,3,5-triethyl-2,4-diaminobenzene, 1-methyl-5-t-butyl-2,4-diaminobenzene, 1-methyl-5-t-butyl-2,6-diaminobenzene, 1,3,5-triethyl-2,4- diaminobenzene, 3,5,3', 5'-tetraethyl-4,4'- diaminodiphenyImethane, 3,5,3',5'-tetraisopropy1-4,4'- di
  • Unhindered aromatic polyamines can be used with the sterically hindered chain extenders and include 2,4- and/or
  • the difunctional and polyfunctional aromatic amine compounds may also exclusively or partly contain secondary amino groups such as 4,4'-di- (methylamino)-diphenylmethane or 1-methyl-2-methylamino-4-aminobenzene.
  • Liquid mixtures of polyphenyl polymethylene polyamines of the type obtained by condensing aniline with formaldehyde are also suitable.
  • nonsterically hindered aromatic diamines and polyamines are too reactive to provide sufficient processing time in preparing polymers such as RIM polyurethanes and polyureas.
  • polyurethane/polyureas are also suitably used with the present invention.
  • the catalyst is preferably incorporated in the formulation in an amount suitable to increase the rate of reaction between the isocyanate groups of the composition of the present invention and a hydroxyl-reacting species.
  • the most widely used and preferred catalysts are the tertiary amine catalysts and the organotin catalysts.
  • tertiary amine catalysts examples include, for example, triethylenediamine, N-methyl morpholine, N-ethyl morpholine, diethyl ethanolamine, N-coco morpholine, 1-methyl-4-dimethylaminoethyl piperazine, 3-methoxy-N-dimethylpropylamine, N,N-diethyl-3-diethyl aminopropylamine, and dimethylbenzyl amine.
  • Tertiary amine catalysts are advantageously employed in an amount from 0.01 to 2 percent by weight of the polyol formulation.
  • organotin catalysts examples include dimethyltin dilaurate, dibutyltin dilaurate, dioctyltin dilaurate, and stannous octoate.
  • Other examples of effective catalysts include those taught in, for example, U.S. Patent No. 2,846,408.
  • the organotin catalyst is employed in an amount from 0.001 to 0.5 percent by weight of the polyol formulation.
  • Catalysts which promote the formation of isocyanurate groups can also be used with the present invention.
  • Suitable catalysts for use with the present invention include such as those mentioned in Saunders and Frisch, Polvurethanes. Chemistry and Technology in 1 High Polymers Vol. XVI, pp. 94-97 (1962). Such catalysts are referred to herein as trimerization catalysts. Examples of these catalysts include aliphatic and aromatic tertiary amine compounds,
  • trimerization catalysts are potassium salts of carboxylic acids such as potassium octoate and tertiary amines such as, for instance,
  • the process of the present invention can include an additional step wherein the polymer is formed into an -article prior to painting it.
  • RIM as already discussed above is a preferred method of preparing an article.
  • Injection molding of thermoplastics is also a preferred means of preparing an article.
  • Polymer casting can also be practiced with the process of the present invention as well as blow molding, extrusion and compression molding.
  • One advantage of the present invention is that articles so formed can be attached to metal articles and the two painted together as a unit.
  • the polyurethane/polyurea formulations of the present invention can also include materials known to be useful in preparing polyurethane/polyurea polymers by those skilled in the art. Included in these
  • additives such as fillers, mold release agents, pigments, blowing agents, surfactants, and flame retardants.
  • the polymers of the present invention are not sufficiently conductive in the absence of the non-volatile metal salt conductivity inducing materials of the present invention to be efficiently electrostatically painted.
  • formulation components of the formulations of the present invention can be brought together to form a polymer in any way known to be useful to those skilled in the art of preparing
  • RIM reaction injection molding
  • the polymers of the present invention can be molded with fewer defects due to flash imperfections. Small particles of polymer which remain in the mold after a molded article has been removed from the mold are known as flash. Since the polymers of the present invention are comparatively more conductive than otherwise identical polymers prepared without conductivity inducing materials, they can be less subject to a static-attraction to the mold and can be more easily removed. Therefore, the flash particles are less likely to remain behind and be an imperfection on the surface of the next article to be molded.
  • cured polymers are electrostatically painted.
  • electrostatic painting includes at least the steps of: (1) charging an object to be painted with an electrical charge, (2) charging a paint with an electrical charge of opposite polarity to that of the object or at least grounding the paint relative to the charged article and (3) dispensing the paint from an electrostatic painting apparatus onto the object. It is also possible and even more routine, in some industries, to charge the paint and ground the object to be painted. Any means and apparatus known to be useful for electrostatic painting to those skilled in the art can be used with the process of the present invention. For example, an apparatus such as a BINKS MODEL 85* can be used to electrostatically paint the cured polymers of the present invention (*BINKS MODEL 85 is a trade designation of Binks Manufacturing Company).
  • the material which can be "painted” onto an object by the method the present invention includes any material which can be electrostatically deposited onto an object.
  • these materials include but are not limited to liquid pigment paints, liquid transparent paints (also known as clear coats), powder pigments, powder coatings, conductive coatings such as primers and prepcoats.
  • the materials can be neat or solvent born, water born or both solvent and water born. As with the case of powders, for example, the materials can also be applied as a solid.
  • the process of electrostatic painting includes the process of electrodeposition as well wherein rather than applying the material onto the article in an aerosol, the article is dipped into the material while an
  • electrostatic potential is maintained between the article and the material being applied thereto.
  • a preferred embodiment of the present invention is an electrostatically painted object comprising at least two layers, a first layer being a layer of polymer prepared from a polymer
  • formulation including (1) materials which include or form urea groups, urethane groups or mixtures thereof, and (2) a non-volatile metal salt conductivity inducing material, and a second layer, the second layer being a layer of electrostatically applied paint, wherein (a) the polymer can be efficiently electrostatically painted, and (b) the polymer would not be conductive but for the inclusion of the non-volatile metal salt conductivity inducing materials in the polymer. While the present invention is useful for electrostatically painting articles not primed or coated with a conductive material, that is the two layers being adjacent, the present invention can also be used advantageously to prepare articles having a third layer interposed between the electrostatically applied paint and the polymer.
  • the third layer can be a non-conductive or a conductive coating.
  • the non-volatile metal salts of the present invention increase the bulk conductivity of polymers prepared therewith. Surface coating of a polymer with a conductive material increases surface conductivity but has little effect on bulk conductivity. It is believed that surface conductivity alone is inefficient in charging an article to be electrostatically painted. Therefore, the method of the present invention can be employed to more efficiently paint a polymer coated with a non-conductive layer or even a polymer having a preparatory conductive coating such as a conductive primer or prep-coat.
  • the method of the present invention can be advantageous compared to conventional methods of electrostatically painting polymers for several reasons.
  • One of these reason is that a very small amount of material is added to a polymer which both imparts sufficient conductivity to permit efficient electrostatic painting but does not substantially degrade polymer physical properties.
  • the non-volatile metallic salts of the present invention can be selected such that they are compatible with the polymer formulation in which they will be included.
  • the salt can be mixed with a compatibilizer. If a compatibilizer is used, it should be selected such that it does not impart undesirable properties to the polymer and that it does not degrade the physical properties of the polymer.
  • n-methyl-2-pyrrolidone can be used to compatibilize a non-volatile salt of the present invention and yet not cause a substantial degradation of polymer physical properties prepared therewith.
  • a polyurethane/polyurea polymer was prepared by reacting an isocyanate prepolymer (A side) and a polyol diamine mixture (B side) by means of a reaction injection molding apparatus to produce
  • the polyurethane/polyurea polymer formulation was of two components.
  • the first component was a methylene diphenyl diisocyanate based soft segment prepolymer, the prepolymer being prepared with a polyether polyol sold commercially as SPECTRIM 50A* (*SPECTRIM 50A is a trade designation of The Dow Chemical Company).
  • the second component was a blended active hydrogen containing component based on a polyether polyol and
  • SPECTRIM 50B* diethyltoluenediamine sold commercially as SPECTRIM 50B* (*SPECTRIM 50B is a trade designation of The Dow Chemical Company). 0.164 percent of total polymer weight of a sodium perfluroalkyl sulfonic acid salt was included in the SPECTRIM 50B component, the SPECTRIM 50B component and sodium perfluroalkyl sulfonic acid salt, FLUORAD FC-98*, were mixed and placed into a reservoir of the RIM apparatus (*FLUORAD FC-98 is a trade designation of 3M and is a mixture of potassium perfluoro cyclohexyl alkylsulfonates). The SPECTRIM 50A was also placed in a reservoir of the RIM apparatus. Plaques were prepared by molding and postcuring.
  • the plaques were washed using a five step process including the steps of a 60 second rinse in ISW 32*, a 30 second deionized water rinse, a 30 second rinse in ISW 33**, a 30 second deionized water rinse, a 15 second deionized water rinse (*ISW-32 is a trade
  • the plaques were painted by first weighing the plaques on an analytical balance (Original Plaque Weight (OP Wt)) and then mounting the plaques on a curved metal support having an 8.6 inch (21.8 cm) radius. The support was then mounted on a conveyor travelling 320 inches/minute (8.13 m/minute). The distance through which the plaques were moved during painting was 20 inches (50.8 cm).
  • the plaques were painted with a BINKS MODEL 85* gun having a 0.046 inch (1.24 mm) orifice equipped with a an E63PB* air cap and a D63B* fluid tip
  • a polyurethane/polyurea polymer was prepared, painted and tested substantially identically to Example 1 except that instead of 0.164 percent FLUORAD FC-98, the formulation includes no FLUORAD FC-98. The result is displayed in Table 2 below.
  • a polyurethane/polyurea polymer was prepared substantially identically to Example 1 except that instead of 0.164 percent FLUORAD FC-98, the formulation includes 0.761 percent FLUORAD FC-98.
  • the plaques were tested for physical properties. The results are displayed in Table 3 below.
  • a polyurethane/polyurea polymer was prepared and tested substantially identically to Example 3 except that instead of 0.761 percent FLUORAD FC-98, the formulation includes 0.200 percent FLUORAD FC-98. The results are displayed in Table 3.
  • a polyurethane/polyurea polymer was prepared and tested substantially identically to Example 3 except that instead of 0.761 percent FLUORAD FC-98, the formulation includes no FLUORAD FC-98. The results are displayed in Table 3. EXAMPLES 6-18 AND COMPARATIVE EXAMPLES 19-24
  • Polymers were prepared with the non-volatile metal salts of the present invention.
  • the additives detailed below in Table 4A-4C were admixed into the polymer formulations and then injection molded or reaction injection molded into articles suitable for painting.
  • a white basecoat (CBC9753) was applied with a SPRAYMATION MODEL 310160* automatic panel sprayer.
  • the fixed conditions for the panel spraying system are:
  • ⁇ BINKS MODEL 80A* electrostatic spray gun including a 63B fluid tip, N63 air cap, and a 111-1271 fluid needle;
  • the process conditions used during the application and the specific paint preparation conditions are shown below. Painted panels were cured after paint application in an electric air circulation oven.
  • the paints used were Pittsburgh Paint and Glass (PPG)* paints.
  • the paints had the following properties:
  • the standard metal panel support rods on the SPRAYMATION were replaced with fiberglass rods of the same dimensions.
  • the rack cross-members were replaced with oak which was glued on with epoxy.
  • a metal bolt was flush mounted to the face of the metal plates. The bolt was centered on the plate and it protruded on the back where it serves as a grounding point.
  • a grounding wire was attached with a nut and a washer. The ground had a resistivity of 0.15 ohms.
  • Test samples were mounted in such a way that half of the sample was backed by the grounded aluminum plate and half was unbacked.
  • the test samples were held in place by clamping them on the outside edge (left handed part on the left side, right handed part on the right side) onto the aluminum plate with a conductive metal clip ( ⁇ 0.15 ohms resistivity). This ensures that the plastic articles were grounded.
  • the aluminum plates were 4 inches (10.2 cm) wide by 6 inches (15.2 cm) long, the optimum part size was 4 (10.2 cm) inches wide by 12 inches (30.5 cm) long so that half of the part would be backed and half would not be backed.
  • Some of the parts were 10 inches (25.4 cm) long, in which case, 5 inches (12.7 cm) of the parts were backed with the aluminum and 5 inches (12.7 cm) were not.
  • polyurethane plaque was taped, from the back, onto the aluminum plate.
  • the metal clip used to hold the parts in place was centered over the interface between the aluminum plate and the polyurethane. Half of the clip was on each of the 5 inch (12.7 cm) long parts. Masking tape was used to cover any exposed aluminum.
  • ELCOMETER 245 * portable film thickness meter (*ELCOMETER 245 is a trade designation of Elcometer Instruments Ltd.). Film thickness was measured visually on the plastic panels. A piece of the painted substrate was dug out of the painted plastic substrate with a razor knife. The chip was placed painted side down on a flat cutting surface. A cross-section was cut through the plastic and paint layers. The cross sectional piece was placed on a microscope slide. The paint thickness was measured at a magnification of 200 times with a graduated ocular. On the 12 inch (30.5 cm) long panels, film thickness measurements were made at 2 (5.1 cm) and 4 (12.7) inches from the top of the aluminum backed half of the test panels.
  • paint wrap made by comparing a sample to both an electrostatically painted steel control and a steel control similarly painted except that the electrostatic power supply was turned off during the painting. These parts have paint wrap values of excellent and none respectively.
  • the hierarchy of paint wrap values are:
  • SPECTRIM 50S is a polyurethane/polyurea polymer prepared by admixing two commercially available components (SPECTRIM 50S is a trade designation of The Dow Chemical Company).
  • the first component was a methylene diphenyl diisocyanate based soft segment prepolymer, the prepolymer being the prepared with a polyether polyol sold commercially as SPECTRIM 50A* (*SPECTRIM 50A is a trade designation of The Dow Chemical Company).
  • the second component was a blended active hydrogen containing component based on a polyether polyol and diethyltoluenediamine sold commercially as SPECTRIM 50B* (*SPECTRIM 50B is a trade designation of The Dow Chemical Company) .
  • the articles were prepared by reaction injection molding.
  • FC-98 is a mixture of potassium perfluoro cyclohexyl alkylsulfonates available from 3M. FC-98 is a trade designation of 3M.
  • C SPECTRIM 25 is a polyurethane/polyurea polymer prepared by admixing two commercially available components (SPECTRIM 25 is a trade designation of The Dow Chemical Company).
  • the first component was a methylene diphenyl diisocyanate based soft segment prepolymer, the prepolymer being the prepared with a polyether polyol sold commercially as SPECTRIM 25A* (*SPECTRIM 25A is a trade designation of The Dow Chemical Company).
  • the second component was a blended active hydrogen containing component based on a polyether polyol and diethyltoluenediamine sold commercially as SPECTRIM 25B* (*SPECTRIM 25B is a trade designation of The Dow Chemical Company) .
  • the articles were prepared by reaction injection molding.
  • D SPECTRIM HF85 is a polyurethane/polyurea polymer prepared by admixing two commercially available components (SPECTRIM HF85 is a trade designation of The Dow Chemical Company).
  • the first component was a methylene diphenyl diisocyanate based soft segment prepolymer, the prepolymer being the prepared with a polyether polyol sold commercially as SPECTRIM HF85A* (*SPECTRIM HF85A is a trade designation of The Dow Chemical Company).
  • the second component was a blended active hydrogen containing component based on an aminated polyether polyol sold commercially as SPECTRIM HF85B* (*SPECTRIM HF85B is a trade designation of The Dow Chemical Company) .
  • the articles were prepared by reaction injection molding.
  • E TPU is a thermoplastic urethane based on methylene diphenyl diisocyanate and a polyester polyol sold commercially as PELLETHANE 2354-65D by The Dow chemical Company.
  • PELLETHANE 2354-65D is a trade designation of The Dow Chemical Company.
  • the additive was admixed into the liquid precursors used to prepare the TPU.
  • the articles were prepared by injection molding.
  • F DEHYQUAT C is lauryl pyridinium chloride and is a trade designation of Henkel Corporation.
  • Sample polyurethane/polyurea plaques were prepared using the polymers and non-volatile metal salts as shown in Table 5 (*SPECTRIM 50S is a trade designation of The Dow Chemical Company).
  • the plaques were prepared by admixing the non-volatile metal salts with the B side of the formulation and the reaction injection molding the plaques. The samples were tested for physical properties and the results are displayed below in Table 6.
  • SPECTRIM 50S is a polyurethane/polyurea polymer prepared by admixing two commercially available components (SPECTRIM 50S is a trade designation of The Dow Chemical Company).
  • the first component was a methylene diphenyl diisocyanate based soft segment prepolymer, the prepolymer being the prepared with a polyether polyol sold commercially as SPECTRIM 50A* (*SPECTRIM 5QA is a trade designation of The Dow Chemical Company).
  • the second component was a blended active hydrogen containing component based on a polyether polyol and diethyltoluenediamine sold commercially as SPECTRIM 50B* (*SPECTRIM 50B is a trade designation of The Dow Chemical Company).
  • the articles were prepared by reaction injection molding.
  • SPECTRIM 25 is a polyurethane/polyurea polymer prepared by admixing two commercially available components (SPECTRIM 25 is a trade designation of The Dow Chemical Company).
  • the first component was a methylene diphenyl diisocyanate based soft segment prepolymer, the prepolymer being the prepared with a polyether polyol sold commercially as SPECTRIM 25A* (*SPECTRIM 25A is a trade designation of The Dow Chemical Company).
  • the second component was a blended active hydrogen containing component based on a polyether polyol and diethyltoluenediamine sold commercially as SPECTRIM 25B* (*SPECTRIM 25B is a trade designation of The Dow Chemical Company) .
  • the articles were prepared by reaction injection molding.
  • FC-98 is a mixture of potassium perfluoro cyclohexyl alkylsulfonates available from 3M. FC-98 is a trade designation of 3M.
  • Sample plaques were prepared with the polymers and additives indicated in Table 7 below .
  • the plaques were powder coated using the following procedure :
  • a clear powder coating was applied electrostatically to test panels using a Nordson NPE CC8 Model 246152H* electrostatic Powder coating applicator .
  • the applicator gun was mounted on an ECLIPSE MODEL 50-6528 panel sprayer using a rack speed of 300 inches/minute (762 cm/minute) , a 10 inch (25 . 4 cm) gun to part distance , and a 3 inch (7 . 6 cm) gun index .
  • the fol lowing condit ions were keep constant on the powder applicator :
  • the powder coating was applied in one coat and then cured for 15 minutes at 325°F (163°C).
  • the Powder coating formulation was composed of the following components by weight: DER 662UH* 100 parts, EPON P-108** 4 parts,
  • the melt was mixed on a Buss Condux PLK-46 extruder with a kneader rate of 200 revolutions per minute at 70°F (21°C).
  • the extrudate was ground into powder with a Mikropul Bantam grinder using a 0.013 inch herringbone screen.
  • the powder was sieved through a 150 mesh screen.
  • a SPECTRIM HF85 is a polyurethane/polyurea polymer prepared by admixing two commercially available components (SPECTRIM HF85 is a trade designation of The Dow Chemical Company).
  • the first component was a methylene diphenyl diisocyanate based soft segment prepolymer, the prepolymer being the prepared with a polyether polyol sold commercially as SPECTRIM HF85A* (*SPECTRIM HF85A is a trade designation of The Dow Chemical Company).
  • the second component was a blended active hydrogen containing component based on an aminated polyether polyol sold commercially as SPECTRIM HF85B* (*SPECTRIM HF85B is a trade designation of The Dow Chemical Company).
  • the articles were prepared by reaction injection molding.
  • B GTX is NORYL GTX 910-A*, an engineering thermoplastic based on a
  • polydimethylphenylene oxide and nylon blend available from General Electric Company (*N0RYL GTX 910-A is a trade designation of General Electric Company).
  • the additive is first admixed in high concentration with the plastic to form a concentrate.
  • This concentrate is then admixed with virgin plastic in a ratio to achieve the indicated concentration.
  • Articles were formed by injection molding.
  • FC-98 is a mixture of potassium perfluoro cyclohexyl alkylsulfonates available from 3M. FC-98 is a trade designation of 3M.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Paints Or Removers (AREA)

Abstract

Des polymères de polyuréthane/polycarbamide peuvent être peints électrostatiquement sans avoir été auparavant revêtus d'une première couche conductrice. L'invention concerne l'amélioration apportée à un procédé permettant de peindre électrostatiquement des polymères de polyuréthane/polycarbamide, et qui consiste à préparer le polymère à partir d'une formulation comprenant un matériau inducteur de conductivité à sel métallique non volatil. Les polymères peints par le procédé de l'invention peuvent avoir des propriétés physiques et esthétiques sensiblement similaires à celles d'autres polymères identiques préparés sans les matériaux inducteurs de conductivité à sel métallique non volatil de la présente invention. La conductivité accrue des polymères permet de les charger d'une densité de charge suffisante pour pouvoir transférer efficacement la peinture sur la surface polymère. L'invention concerne également une composition d'au moins deux couches, une couche étant une couche externe de peinture appliquée électrostatiquement, et l'autre, une couche interne de polymère de polyuréthane/polycarbamide.
PCT/US1993/008470 1992-09-30 1993-09-09 Polymeres peints electrostatiquement et leur procede de production Ceased WO1994007612A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
DE69320644T DE69320644T2 (de) 1992-09-30 1993-09-09 Elektrostatische beschichtung von polymergegenständen und verfahren zur herstellung
BR9307150A BR9307150A (pt) 1992-09-30 1993-09-09 Polímeros eletrostaticamente pintados e um processo para fazer os mesmos
EP93920503A EP0662867B1 (fr) 1992-09-30 1993-09-09 Polymeres peints electrostatiquement et leur procede de production
JP6509074A JPH08501981A (ja) 1992-09-30 1993-09-09 静電塗装されたポリマーおよびそれを製造する方法
KR1019950701219A KR100282103B1 (ko) 1992-09-30 1993-09-09 정전도장된 중합체 및 이의 제조방법

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US95462892A 1992-09-30 1992-09-30
US07/954,628 1992-09-30

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WO1994007612A1 true WO1994007612A1 (fr) 1994-04-14

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JP (1) JPH08501981A (fr)
KR (1) KR100282103B1 (fr)
AT (1) ATE170109T1 (fr)
BR (1) BR9307150A (fr)
CA (1) CA2145191A1 (fr)
DE (1) DE69320644T2 (fr)
MX (1) MX9306078A (fr)
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WO (1) WO1994007612A1 (fr)

Cited By (9)

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WO1997007901A1 (fr) * 1995-08-30 1997-03-06 The Dow Chemical Company Procede de production d'articles revetus
WO1997035930A1 (fr) * 1996-03-26 1997-10-02 Minnesota Mining And Manufacturing Company Compositions a polymerisation radicalaire pouvant former un revetment a l'aide d'un procede electrostatique
WO1997035929A1 (fr) * 1996-03-26 1997-10-02 Minnesota Mining And Manufacturing Company Compositions polymerisables par liberation de cations pouvant s'appliquer a l'aide d'un procede electrostatique
US5844037A (en) * 1996-07-24 1998-12-01 The Dow Chemical Company Thermoplastic polymer compositions with modified electrical conductivity
US5858545A (en) * 1996-03-26 1999-01-12 Minnesota Mining And Manufacturing Company Electrosprayable release coating
US5962546A (en) * 1996-03-26 1999-10-05 3M Innovative Properties Company Cationically polymerizable compositions capable of being coated by electrostatic assistance
WO2003001299A1 (fr) * 2001-06-22 2003-01-03 Agfa-Gevaert Materiau comportant un motif conducteur; materiau et procede utilises pour former un motif conducteur
US6746751B2 (en) 2001-06-22 2004-06-08 Agfa-Gevaert Material having a conductive pattern and a material and method for making a conductive pattern
US20250276343A1 (en) * 2024-03-04 2025-09-04 Zhejiang Dingsheng Outdoor Living Products Co., Ltd. Treatment Method on a Surface of a Plastic Flowerpot

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KR19980046324A (ko) * 1996-12-12 1998-09-15 위르겐 에르트만, 베른트 뮐러 비전도성 합성 수지 부재들의 코팅 방법
IL145077A0 (en) * 1999-03-02 2002-06-30 Skc Acquisition Corp Conductive or static dissipative coating
DE10032558B4 (de) * 2000-07-05 2014-10-23 Volkswagen Ag Verfahren zum elektrostatischen Beschichten von Fahrzeuganbauteilen, danach hergestelltes Fahrzeuganbauteil und dessen Verwendung
CN101283027A (zh) * 2005-08-08 2008-10-08 卡伯特公司 包含纳米管的聚合物组合物
RU2343010C1 (ru) * 2007-05-30 2009-01-10 Общество с ограниченной ответственностью "Производственная компания "Теплофон" Способ электростатического окрашивания диэлектрических изделий
US8574414B2 (en) * 2010-07-14 2013-11-05 Ppg Industries Ohio, Inc Copper prerinse for electrodepositable coating composition comprising yttrium

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EP0443767A1 (fr) * 1990-02-20 1991-08-28 Hughes Aircraft Company Articles contenant un polymère conducteur ionique et leur méthode de fabrication
EP0475360A1 (fr) * 1990-09-14 1992-03-18 Dai-Ichi Kogyo Seiyaku Co., Ltd. Procédé pour améliorer la conductibilité électrique d'une résine

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US3535294A (en) * 1966-12-08 1970-10-20 Lion Fat Oil Co Ltd Method for electrostatically coating synthetic resin moldings
EP0309286A2 (fr) * 1987-09-25 1989-03-29 Polyplastics Co. Ltd. Agent conducteur pour le revêtement électrostatique de matières plastiques et masses de moulage de matières plastiques revêtues par le procédé électrostatique
EP0443767A1 (fr) * 1990-02-20 1991-08-28 Hughes Aircraft Company Articles contenant un polymère conducteur ionique et leur méthode de fabrication
EP0475360A1 (fr) * 1990-09-14 1992-03-18 Dai-Ichi Kogyo Seiyaku Co., Ltd. Procédé pour améliorer la conductibilité électrique d'une résine

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997007901A1 (fr) * 1995-08-30 1997-03-06 The Dow Chemical Company Procede de production d'articles revetus
US5629050A (en) * 1995-08-30 1997-05-13 The Dow Chemical Company Process for preparing coated articles
US5858545A (en) * 1996-03-26 1999-01-12 Minnesota Mining And Manufacturing Company Electrosprayable release coating
WO1997035929A1 (fr) * 1996-03-26 1997-10-02 Minnesota Mining And Manufacturing Company Compositions polymerisables par liberation de cations pouvant s'appliquer a l'aide d'un procede electrostatique
US5817376A (en) * 1996-03-26 1998-10-06 Minnesota Mining And Manufacturing Company Free-radically polymerizable compositions capable of being coated by electrostatic assistance
WO1997035930A1 (fr) * 1996-03-26 1997-10-02 Minnesota Mining And Manufacturing Company Compositions a polymerisation radicalaire pouvant former un revetment a l'aide d'un procede electrostatique
US5962546A (en) * 1996-03-26 1999-10-05 3M Innovative Properties Company Cationically polymerizable compositions capable of being coated by electrostatic assistance
US5844037A (en) * 1996-07-24 1998-12-01 The Dow Chemical Company Thermoplastic polymer compositions with modified electrical conductivity
WO2003001299A1 (fr) * 2001-06-22 2003-01-03 Agfa-Gevaert Materiau comportant un motif conducteur; materiau et procede utilises pour former un motif conducteur
US6746751B2 (en) 2001-06-22 2004-06-08 Agfa-Gevaert Material having a conductive pattern and a material and method for making a conductive pattern
US6759083B2 (en) 2001-06-22 2004-07-06 Agfa-Gevaert Material having a conductive pattern; and a material and method for making a conductive pattern
US6863955B2 (en) 2001-06-22 2005-03-08 Agfa-Gevaert Material having a conductive pattern; and a material and method for making a conductive pattern
KR100883215B1 (ko) * 2001-06-22 2009-02-13 아그파-게바에르트 도전성 패턴을 갖는 물질, 및 도전성 패턴 형성용 물질과형성방법
US20250276343A1 (en) * 2024-03-04 2025-09-04 Zhejiang Dingsheng Outdoor Living Products Co., Ltd. Treatment Method on a Surface of a Plastic Flowerpot
US12427542B2 (en) * 2024-03-04 2025-09-30 Zhejiang Dingsheng Outdoor Living Products Co., Ltd. Treatment method on a surface of a plastic flowerpot

Also Published As

Publication number Publication date
CA2145191A1 (fr) 1994-04-14
EP0662867B1 (fr) 1998-08-26
ATE170109T1 (de) 1998-09-15
KR100282103B1 (ko) 2001-02-15
EP0662867A1 (fr) 1995-07-19
KR950703414A (ko) 1995-09-20
RU95112572A (ru) 1997-01-10
RU2119830C1 (ru) 1998-10-10
BR9307150A (pt) 1999-03-30
JPH08501981A (ja) 1996-03-05
DE69320644D1 (de) 1998-10-01
DE69320644T2 (de) 1999-01-14
MX9306078A (es) 1995-01-31

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