JPH08501981A - Electrostatically coated polymer and method of making same - Google Patents

Abstract

Polyurethane/polyurea polymers can be electrostatically painted without first being coated with a conductive primer. Disclosed is an improvement in a process for electrostatically painting polyurethane/polyurea polymers, the improvement being to prepare the polymer from a formulation including a non-volatile metal salt conductivity inducing material. The polymers painted by the process of the present invention can have physical properties and aesthetic properties substantially similar to those of otherwise identical polymers prepared without the non-volatile metal salt conductivity inducing materials of the present invention. The increased conductivity of the polymers can allow them to be charged with sufficient charge density to permit efficient paint transfer to the polymer surface. Also disclosed is a composition of at least two layers, one layer being an outer layer of electrostatically applied paint, and the other an inner layer of polyurethane/polyurea polymer.

Description

Detailed Description of the Invention Electrostatically coated polymer and method of making same   The present invention relates to a method for electrostatically coating a polymer. The present invention is specifically described in The present invention relates to an electrostatically coatable polymer having a retan or urea group.   It is well known that most painting methods are not 100% efficient. For example, A small amount of paint directed at an object when the paint is applied to the object as a spray The part will not adhere to the object. In even less efficient environments, paints and objects acquire an electrostatic charge of the same polarity As a result, the paint may be partially repelled from the object. Commonly observed Another inefficiency may be the uneven thickness of the paint layer on the painted object. It Yet another commonly observed inefficiency is the particularly complex shape of spray-coated objects. In, the paint is relatively straight from the spray device to the object to be painted. Can cover surfaces that are prone to Would not.   Painting applications that require very high quality paint finishes, such as automotive body parts In painting, the object to be painted is completely and uniformly coated with the minimum consumption of paint. It is generally desirable. This is desirable for several reasons. First, this Paints for applications such as are often very effective. Therefore, paint consumption is reduced Providing a direct benefit of reduced paint costs. Secondly, it is painted Paint that does not adhere to the object to be lost will be lost to the environment, and this loss is environmentally desirable. It won't be. Therefore, the amount of paint lost to the surroundings during painting is reduced. Reduces the cost of treating lost paint solids and reduces paint solvent emissions. It Third, the object on the object Paint layers that are too thin can sometimes be tolerated, but paint layers that are too thin can be tolerated more often. Can't be done. In addition to improving the appearance of objects, modern paints are often painted. The role of protecting the stored objects from the environment. For example, paint is corrosive to gold Can protect genus objects or protect plastic objects by UV Can be protected from deterioration. Therefore, because of the area of paint that is too thin on the object The failure of the painted object is that the paint layer is uniform and has a sufficient thickness. This can be avoided by applying paint to the object.   To minimize the problem of inefficient painting, paint should be applied when painting certain materials. Electrostatic application is commonly done. Painted with paint in electrostatic painting An electrostatic potential difference is generated between the target object and the paint to be drawn to the target object. Electrostatic attraction As a result, less paint is lost to the surroundings, and the entire surface is sprayed with paint. Paint more homogeneously on the object without direct access to Is applied.   However, the object to be electrostatically coated is not always a problem. Electrostatic coating on target In order to achieve a potential difference between the object to be painted and the paint to be applied to the object. Must be generated. If the object is not conductive or very low If conductive, it cannot be electrostatically charged efficiently, and therefore efficiency Statically cannot be electrostatically painted.   One of the means of electrostatically coating a polymer is to first include the polymer with a conductive filler. To make them more conductive by making polymers from the formulation. It European patent application 0 363 103 to Suzuki et al. Describes a fiber conductive filler of 2 to 50% by weight. , For example, carbon fiber, metal fiber, metallized glass fiber, metal coated carbon fiber and And conductivity Disclosed is a thermoplastic polymer having a strong potassium titanate whisker. Po The limmer is etched and then electrostatically painted. But like this Adding a large amount of fiber filler to the polymer will affect the physical properties of the polymer and the paint finish. Both can be adversely affected. A separate etching process step would also be undesirable.   Japanese Patent No. 2-180960 granted to Kanto Auto Works has improved conductivity. The manufacture of a polyurethane substrate is disclosed. The polyurethane of this reference is n-a It is prepared using an ammonium salt such as rukyl dimethyl sulfate. this One of the problems with such additives is that they promote conductivity only when they are wetted Is Rukoto. This would be problematic for coating applications where ambient humidity is not constant. Apart Deliberately wetting before electrostatic painting is a waste of time, and expensive Is.   Another means of electrostatically coating a polymer is to use a conductive agent called a "prepcoat". The application is first to make the polymer conductive. These pre Upcoat is a conductive agent that adheres to the polymer surface. Such drugs are quaternary Materials such as min can be included. One of the problems with such compounds is that Is often hydrophilic. Reaction injection molding (RIM) polyurethane In, the absorbed water can cause defects on the polymer surface. Hydrophilic coating It can exacerbate the tendency of objects to absorb water before painting. This promotes the formation of defects. And therefore, is not desirable for applications requiring high quality finishes. U   Yet another solution to the problem of electrostatically painting plastics is the first plus The tick object is coated with a conductive coating and then the coated object Is to electrostatically paint. For example, U.S. Pat.No. 5,071,593 to Ta Kahashi et al. Conductive agent before electrostatic coating Cover problem plastics such as impregnated polyacetal and polyester. It is disclosed to be applied. However, it is ineffective to coat an object with a conductive agent. Can be a rate. It is a expense for additional painting equipment, for applying conductive agents Additional processing time, additional processing time to cure the conductive agent and cost of the conductive agent. Need to pay for   Polymers, especially reaction injection molded polyurethane / polyureas, are for example Materials useful for making automotive components such as plates and interior and exterior panels Is known in the art. In the current automobile manufacturing industry Paint products made from such polymers, as required, and First applied a conductive primer to produce a high quality paint finish It is later known to electrostatically paint these products. Electrostatic coating of polymer products Known methods for coating are at least (1) polyurethane / polyurea polymers -Preparing the object to be coated from the composition, (2) applying this object to a conductive agent (Or a conductive undercoating agent), (3) applying a first polarity charge (4) applying a second charge of opposite polarity to the object, (or Alternatively, simply charge either the paint or the product against the grounding One remains neutral with respect to the grounding body), and (5) from the coating device onto the object. The step of discharging the paint is included.   Pre-coat the polymer by pre-coating or pre-coating it with a conductive agent. Efficient electrostatic coating of polymers without the need for pretreatment is a key practice in the art. Would be desired. Polymers primed or pre-coated with conductive material It would be desirable in the art to more efficiently electrostatically coat. A polymer with sufficient intrinsic conductivity to effectively electrostatically coat the polymer It would be desirable in the art to prepare Poly to be painted It is desirable in the art that mers do not require special treatments such as wetting. Will be lost. Painted polymer is of sufficiently high quality for a painted surface and It has strong physical properties that make the polymer very demanding in applications such as automobiles. It would also be desirable in the art that it could be used in manufacturing. Finally , If different compositions, eg metal and plastic objects, are If it can be painted as a unit rather than painted and then combined , Would be desirable in the art. In one aspect, the invention is a curing By electrostatically coating the prepared polyurea and / or polyurethane group-containing polymer Or (A) (1) containing a urea group, a urethane group or a mixed group thereof, or And (2) blending of polymer containing conductive inductive material of non-volatile metal salt Preparing a cured polymer from the object, (B) electrostatically coating this polymer (A) the polymer can be electrostatically coated efficiently, and (B) Does the polymer contain a non-volatile metal salt conductive inductive material? If not, it would not have been conductive.   Another aspect of the invention contains cured, urea and / or urethane groups. A method of electrostatically painting a polymer, where the polymer is processed into a shaped article and To be coated with an electrically conductive preparation and then electrostatically coated, improved Is (1) a material containing a urea group, a urethane group or a mixed group thereof, and (2) Preparing polymers from polymer blends containing non-volatile metal salt conductive inductive materials Including that.   Yet another embodiment of the present invention is that the first layer comprises (1) a urea group, a urethane group or a combination thereof. Materials containing mixed groups, and (2) conductivity of non-volatile metal salts A layer of polymer prepared from a polymer blend containing an inductive material, the second layer being An electrostatically coated object comprising at least two layers which are layers of electrostatically applied paint. It Here, (a) the polymer can be efficiently electrostatically coated, and (b) ) The polymer does not include non-volatile metal salt conductive inductive material It would not have been conductive.   The present invention is an improvement over known methods for electrostatically coating polymers. this The improvements are (1) a material containing a urea group and / or a urethane group, and (2) a non-volatile material. Objects to be coated from polymer blends containing conductive inductive materials of foaming metal salts To prepare. The resulting polymer is a conductive primer or other preparation It can be electrostatically coated without the use of a coating.   In the method of the present invention, the cured polymer is painted. For the purposes of the present invention, The cured polymer is such that the reaction giving rise to the polymer is substantially complete and the poly The mer is a solid, and is preferably a fixed shaped article. Even more preferred In other words, the polymer is in a suitable shape for painting. For example, car body panels, It can be in the form of id cladding or instruments.   The conductive inductive material of the present invention is a non-volatile metal salt. As a salt, the conductivity of the present invention The sex-inducing material will have both cations and anions. Salt cation Is a cation of any metal that forms an ionizable salt with one or more anions , For example, Li, Be, Na, Mg, Al, K, Ca, Ga, Ge, Cu, Zn, SC, Ti, V, Cr, Mn, Fe, Co, Ni, Rb, Sr, In, Sn, Sb, 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 Z It can be a lanthanide series element of the periodic table. Preferably, the cation is al Potassium metal (Li, Na, K, Rb, Cs, Fr),   Alkaline earth metals (Ca, Ba, Sr, Ra), Co, Ni, Fe, Cu, Cd, Zn, Sn, Al Is a cation of Ag, and more preferably, the cation is an alkaline earth or cation. Lucari metal cation, and even more preferably, the cation is a monovalent cation. And especially an alkali metal cation, and most preferably a cation Is a cation of Li, Na, K or a mixture thereof. Nonvolatile metal salt of the present invention Is selected from the group consisting of Li, Na, K cations or mixtures thereof. Can be   The non-volatile metal salt conductive inducing material of the present invention is specified as the cation described above. It is a salt with the anion of. One group of preferred non-volatile metal salts is fluoro It is an alkyl sulfonate. Anion of fluoroalkyl sulfonic acid (Alkyl sulfonate) is suitably compatible with the particular composition used. Is an anion of all fluoroalkyl sulfonic acids. Advantageously, preferred Fluoroalkyl sulfonates have 1 to 20 carbon atoms and are straight chain, branched It is either chain or cyclic. Fluoroalkyl sulfonates are fluorine substituted Having an alkyl group, ie having a fluorine atom bonded to a carbon atom of the alkyl group Is an anion of sulfonate. The alkyl group is optionally attached to a carbon atom It may also have a hydrogen atom and / or another halogen atom. Preferably Is 25% of the atoms other than carbon bonded to the carbon atom of the fluoroalkyl group, more preferably 75% halogen (by number) is preferable, and fluorine is preferable. Better Preferably, the fluoroalkyl group is a perhaloalkyl group, that is, only halogen substitution. Is an alkyl group having. Suitable halogens are fluorine, chlorine, bromine and iodine. And preferably fluorine and chlorine. Suitable perhaloalkyl sulfone The acid anion is, for example, C₂H₂F₃SO₃ ^-(Tresile), C₂ HF_FourSO₃ ^-, C₂HClF₃SO₃ ^-, C₃H₂F_FiveSO₃ ^-, C_FourH₂F₇SO₃ ^-, C_Five H₂F₉SO₃ ^-, C₇ClF₁₄SO₃ ^-, C₈Cl₂H₂F₁₃SO₃ ^-,C₂₀ClHF₃₉S O₃ ^-including.   The fluoroalkyl group is most preferably a perfluoroalkyl group. representative Perfluoroalkyl sulfonate anions include, for example, CF₃SO₃ ^-(bird Freight), C₂F_FiveSO₃ ^-, C₃F₇SO₃ ^-, C_FourF₉SO₃ ^-(Nonaflate), C_Five F₁₁SO₃ ^-(Nonaflate), C₆F₁₃SO₃ ^-, C₇F_FifteenSO₃ ^-, C₈F₁₇SO₃ ^- , C₉F₁₉SO₃ ^-, C₂₀F₄₁SO₃ ^-, Their isomers and their mixtures. Mu. Perfluoroalkyl sulfonates are available and compatible with polymers. For reasons preferably having 1 to 20 and more preferably 1 to 10 carbon atoms It   Other non-volatile metal salts have also been used as conductive inductive materials to make the formulations of this invention. Can be used. The anions of such salts are π-bonded, halogen atoms To those skilled in the art for properties such as electron withdrawing groups such as Can be done. The anion is preferably capable of accepting charge and delocalizing Relatively large polyatoms with substituents such as phenyl, sulfur and phosphorus atoms Anions, more preferably one or more, more preferably few, anions. It has at least 4, and most preferably at least 5 non-metal atoms.   Non-metal atoms are generally boron, carbon, silicon, phosphorus, arsenic, oxygen, sulfur, selenium. Selected from the group consisting of, tellurium, fluorine, chlorine, bromine, iodine and astatine. It is thought to be. Preferred non-metal atoms are boron, phosphorus, sulfur and fluorine in aromatic groups. Elementary and carbon, with sulfur and carbon in the aromatic groups being more preferred. The anion is Preferably monovalent Is. The anion is more preferably a fluoroalkyl sulfonate or a None containing one or more delocalizable electrons, such as traorganoboron ions It is a conjugate base of organic acid. Such anions include, for example, NO₃ ^-, SCN^-, S O_Four ^2-, HSO_Four ^-, SO₃ ^-2, PX₆ ^-, HSO₃ ^-, CNSO₃ ^-, XSO₃ ^-(X in the formula Is halogen. ), SXSO₃ ^-(In the formula, X is hydrogen or anion.), ClO_Four ^-, PO_Four ^3-, H₂PO_Four ^-, HPO_Four ^2-, PO₃ ^3-, HPO₃ ^2-, H₂PO₃ ^-To In particular tetraalkyl and tetraarylboron ions and non-alkyl Alternatively, it contains a non-aryl substituted sulfonate ion.   For the purposes of the present invention, the non-volatile metal salt further comprises urethane and / or urea groups. Incompatible or undesirable in formulations for polymers with Defined to exclude salt. For example, the anion of the non-volatile metal salt of the present invention is SCN^-Not an anion. It is because this salt is due to the increased viscosity of the polyurea formulation This can cause handling problems. SCN^-Anions in specific formulations It is also known to be water extractable. This property is It can cause handling problems. In contrast, urethane and / or urea groups Contains non-volatile metal salts that have good compatibility with the formulations for polymers that have , And preferred. For example, tetraphenylboron and hexafluorophosphate Due to their compatibility and handleability, anions are considered as the conductive inductive material of the present invention. Is particularly preferable. Mixtures of non-volatile metal salts of the present invention can also be used to practice the present invention. May be used. Most preferably, the non-volatile metal salt of the present invention is a non-volatile metal salt. Anion is perfluoroalkyl sulfonate tetraphenylboron anion , Selected from the group consisting of hexafluorophosphate anions or mixtures thereof. It is salt.   The amount of electrically conductive inducing material included in the polyurethane / polyurea of the present invention is poly It will change depending on the mar. In the practice of the present invention, sufficient conductivity improving material The material is distributed to make the material sufficiently conductive to enable efficient electrostatic coating. Included in compound. A relatively non-conductive polymer is a relatively conductive polymer Would require more conductive inductive material. However, in general, electrostatic coating Polymer blends useful for preparing polyurethane / polyurea polymers to be loaded The amount of conductive inductive material added is preferably 0.02% to 1.5%, more preferably 0. 0.05% to 1.0%, and even more preferably 0.10 to 0.75%.   The non-volatile metal salt conductive inductive material of the present invention is included in a polymer formulation. When the same non-volatile metal salt was prepared without the conductive inductive material It is such that it results in a polymer having substantially the same physical properties as the polymer. The physical properties associated with this determine whether a polymer is useful for its intended use. It has physical properties that For example, one such physical property is aesthetic appearance. if , Non-volatile metal salts at the minimum concentration needed to coat the polymer efficiently If it produces an undesired appearance to the mer, it is the conductive inductive material of the present invention. As undesirable. Polymers are useful in applications where electrostatic coating is often used Other properties that are often useful in determining whether are flexural modulus, tear strength and Including tensile strength. For the purposes of the present invention, the physical properties are within 15% of each other, preferably within 12%. , And most preferably within 10% the two polymers are substantially similar Has physical properties. In certain cases, the non-volatile metal salts of the present invention can be incorporated into the incorporated polymer. Can actually improve certain polymer physical properties.   The polymers of the present invention are the same as steel controls coated under the same conditions. It can be electrostatically coated with one efficiency. The efficiency of the painting method is that it adheres to the object during electrostatic painting. Determined by measuring the amount of paint applied. For the purposes of the present invention, "effectively electrostatic The term "painted" means electrostatically painted under the same or substantially similar conditions. The same thickness of paint that was deposited on the steel object is deposited on the polymer object Is defined as a situation.   The method of the present invention does not include the non-volatile metal salt conductive inductive material of the present invention. Used in polymers that would not be conductive. For the purposes of the present invention, The term "electrically conductive" has sufficient electrical conductivity to be effectively electrostatically coated. Specified as one. The term "effectively electrostatically coated" is the immediately preceding paragraph. F is as prescribed.   The polymer of the present invention has a urea group, a urethane group or a mixed group thereof. Immediately Then, the polymer is reacted so as to generate only polyurethane groups or only polyurea groups. Prepared from materials containing or containing them, or the polymers of the present invention are React to or generate both polyurethane groups and polyurea groups Can be prepared from a material containing Other polymer linkages are also practiced in the present invention. Can be generated. For example, polyurethane groups, polyurea groups and polyisocyanates. Polymers with pendant groups can be prepared.   The polymers of the present invention are polymer blends and polymer interpenetrating network polymers. It can also be. For example, the polyurethane polymer of the present invention may be another polymer, eg Is blended with acrylonitrile-butadiene-styrene polymer and then Can be electrostatically coated. Other blendable polymers useful in the present invention are , But not limited to nylon, polyethyl terephthalate and poly Including crelate. Interpenetrating network polymer is epoxy resin and It can be prepared with materials such as polycarbonate and the polymers of the present invention. Mesh polymer Form a polymer network in the field where materials are continuous or phase separated from each other. As prepared by including one or more monomers in the formulations of the present invention. Can be Preferably, the urea / urethane group-containing polymer is a polymer of the present invention. It is the main component of the thipolymer composition.   The polymers of the present invention can be thermoplastic or thermosetting. Is polyurethane a blend containing both polyisocyanates and polyalcohols? Can be prepared from Polyurea is a polyisocyanate and polyamine It can be prepared from a formulation containing both. Polyurethane / Polyurea Poly Mers often contain polyisocyanates and polyalcohols and polyamines. It can be prepared from a formulation containing both.   In the practice of the present invention, the polyisocyanate compounding ingredient is an organic polyisocyanate. Nates, modified polyisocyanates, isocyanate-based prepolymers , And mixtures thereof can be advantageously selected. These are aliphatic and And cycloaliphatic isocyanates, but may be aromatic, especially polyfunctional aromatic esters. Socyanate is preferred. 2,4- and 2,6-toluene diisocyanate and corresponding Mixture of isomers; 4,4'-, 2,4'- and 2,2'-diphenylmethylene diisocyanate And corresponding isomer mixtures; 4,4'-, 2,4'- and 2,2'-diphenylmethyle Diisocyanate and polyphenyl polymethylene polyifocyanate (PMDI) A mixture of PMDI and toluene diisocyanate is preferred. Also aliphatic Is an alicyclic isocyanate compound, for example, 1,6-hexamethylene diisocyanate 1-isocyanato-3,5,5-trimethyl 1-3-isocyanatomethyl-cyclohexane ; 2,4- and 2,6-hexahydrotoluene diisocyanate And corresponding isomer mixtures; 4,4'-2,2'- and 2,4'-dicyclohexyl Methane diisocyanate, as well as the corresponding isomer mixture, are also useful in the present invention.   So-called modified polyfunctional isocyanates, that is, the above-mentioned diisocyanates and Products obtained through the chemical reaction of polyisocyanates and / or polyisocyanates are also of advantage. Used for lysocyanate component. Typical examples include polyisocyanate Esters, ureas, burettes, and allophanates, preferably carbodiyl Mines and / or uretone imines; containing isocyanate and / or urethane groups Diisocyanate or polyisocyanate. Carbodiimide group, urea Containing tonimine group and / or isocyanurate ring, 10 to 40% by weight, more preferably More preferably, a liquid polyimide having an isocyanate group (NCO) content of 20 to 35% by weight. Sociate can also be used. These include, for example, 4,4'-, 2,4'- and And 2,2'-diphenylmethane diisocyanate and the corresponding isomer mixture. Polyisocyanate, 2,4- and / or 2,6-toluene diisocyanate And corresponding isomer mixtures, 4,4'-, 2,4'- and 2,2'-diphenylmethanedi Isocyanates and corresponding isomer mixtures, diphenylmethane diisocyanate And PMDI, as well as toluene diisocyanate with PDMI and / or diisocyanate. Includes a mixture with phenylmethane diisocyanate.   Prepolymer having an NCO content of 5-40% by weight, more preferably 15-30% by weight Is also appropriate. These prepolymers are di- and / or polyisocyanates It is prepared by the reaction of materials containing diols, triols, di- and tri- Also with amines and polyvalent active hydrogen compounds such as di- and trithiols Can be prepared. Individual examples include urethane groups, preferably 5-40% by weight, More preferably an aromatic polyisocyanate having an NCO content of 20-35% by weight. And diisocyanates and polyisocyanates, for example, low molecular weight , Triol, oxyalkylene glycol, dioxyalkylene glycol Or obtained from reaction with polyoxyalkylene glycols up to a molecular weight of 800 It These polyols are di- and / or polyoxyalkylene glycols. Can be used individually or as a mixture. For example, diethylene glycol Cole, dipropylene glycol, polyoxyethylene glycol, polyoxy Propylene glycol and polyoxypropylene polyoxyethylene glyco Can be used.   Particularly useful in the present invention is (i) 4,4'-diphenylmethane diisocyanate or Derived from a mixture of 4,4'- and 2,4'-diphenylmethane diisocyanate, 8 It has an NCO content of ~ 40% by weight and contains carbodiimide groups and / or urethane groups. (Ii) preferably having a functionality of 2 to 4 and 800 to 15,000 Polyoxyalkylene having a molecular weight of 0 and 4,4'-diphenylmethane diisocyanate Of 4,4'- and 2,4'-diphenylmethane diisocyanate with nates or A prepolymer prepared by a reaction with a substance, which is based on the weight of the prepolymer. A prepolymer containing NCO groups having an NCO content of 20-35% by weight, and (i) and And (ii); and (iii) 2,4- and 2,6-toluene diisocyanate and And the corresponding isomer mixture. PMDI in all its forms can also be used , And preferred. In this case it is preferably 125-300, more preferably 13 It has an equivalent weight of 0 to 175 and an average functionality of greater than 2. With an average functionality of 2.5-3.5 Some are more preferred. The viscosity of the polyisocyanate component is preferably 25 at 25 ° C. ~ 5,000 centipoise (cps) (0.025 ~ 5Pa.s), but 100 ~ 1, OOOOcps at 25 ℃ (0.1 ~ The value of 1 Pa.s) is preferable from the viewpoint of processability. Select another polyisocyanate component A similar viscosity is preferred when exposed.   In the practice of the present invention, the polyalcohol compounding ingredients are advantageously used alone or A mixture of (a) an alkylene oxide adduct of a polyhydroxyalkane; (b) Alkylene oxide adducts of non-reducing sugars and sugar derivatives, (c) phosphorus and phosphorus Alkylene adducts of acids and (d) alkylene oxide adducts of polyphenols Is selected from the group of compositions: These types of polyols are now referred to as "Substrate Called "polyol". Polyhydroxyalkanes of the alkylene groups useful herein Examples of xide adducts are ethylene glycol, propylene glycol, 1,3-dihydride. Roxypropane, 1,4-dihydroxybutane, and 1,6-dihydroxyhexane , Glycerol, 1,2,4-trihydroxybutane, 1,2,6-trihydroxyhexane , 1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, pentaerythite Litol, polycaprolactone, xylitol, arabitol, sorbitol, It is an adduct of mannitol. Polyhydroxyalkane alkyleneoxy Preferred as the adduct is ethylene oxide of trihydroxyalkane. It is an adjunct. Other useful adducts are ethylenediamine, glycerin, ammonium A, 1,2,3,4-tetrahydroxybutane, fructose and sucrose.   Poly (oxypropylene) glycol, triol, tetrol, pentol And any of these capped with hexol and ethylene oxide It is also preferable. These polyols are also poly (oxypropyleneoxy) (Tylene) polyol. The oxyethylene content is preferably 80 of the total It should be included at less than 40% by weight, and more preferably less than 40% by weight. When used, the ethylene oxide will not be aligned along the polymer chain. May be incorporated in any manner, such as internal blocks, end blocks or runs. It can be captured as a dam distribution block, or a combination thereof.   Another preferred class of polyols are "copolymer polyols", which are , Including stably dispersed polymers such as acrylonitrile-styrene copolymers. It is a base polyol. The production of these copolymer polyols is described, for example, in Catalysts such as zobisisobutyronitrile: copolymer polyol stabilizers; and Reaction mixtures containing various other materials including chain transfer agents such as isopropanol Can be manufactured from.   Polyisocyanate polyaddition active hydrogen containing compounds (PIPA) also prepared formulations of the present invention. It is useful to make. PIPA compounds are usually TDI and triethanolamine. Reaction product. Methods for preparing PIPA compounds are given, for example, in Rawlands. Can be found in US Pat. No. 4,374,209.   Polyester polyols are used to prepare the polymers of the present invention Can be. For example, polyols prepared from caprolactone are useful. Bu Polyols prepared from tandiol and adipic acid may also be used. Poly One skilled in the art will know that it is useful in the art of preparing urethanes and polyureas. Any of the polyesters mentioned can be used in the present invention.   Low molecular weight diols and triols may also be used to prepare the polymers of this invention. You can Ethylene glycol is particularly useful, but other similar compounds are also used Can be done. Propylene glycol and diethylene glycol are also used in the present invention. Suitable for.   In the practice of this invention, the polyamine compounding ingredients are polyamine and amine terminated. It can be selected from the group consisting of polyols. Book Preferred polyamines for preparing the inventive polyurethane / polyurea blends are less than 800, Known low molecular weight isocyanate-reactive with preferably a molecular weight of less than 500 Compounds, such as aromatic polyamines, especially diamines.   A preferred amine group-containing compound is at least in the ortho position with respect to the primary amino group. Also has an ortho to one linear or branched alkyl substituent and a secondary amino group. At least one containing at least one, preferably one to three carbon atoms in position Sterically hindered containing one, preferably two straight chain or branched chain alkyl substituents Containing aromatic diamine. These aromatic diamines are 1-methyl-3,5-diethyl- 2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3,5- Trimethyl-5-t-butyl-2,4-diaminobenzene, 1-methyl-5-t-butyl-2,4-dia Minobenzene, 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 Le-5-t-butyl-2,6-diaminobenzene, 1,3,5-triethyl-2,4-diaminobenze 1,3,5,3 ', 5'-Tetraethyl-4,4'-diaminodiphenylmethane, 3,5,3', 5'-teto Laisopropyl-4,4'-diaminodiphenylmethane, 3,5-diethyl-3 ', 5'-diiso Propyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-5,5'-diisopropyl Le-4,4'-diaminodiphenylmethane, 1-methyl-2,6-diamino-4-isopropyl ester Benzene and mixtures of the above diamines. The most preferred mixture is 1-methyl-3 , 5-Diethyl-2,4-diaminobenzene and 1-methyl-3,5-diethyl-2,6-diamino A mixture of benzene in a weight ratio of 50:50 to 85:15, preferably 65:35 to 80:20. .   Unhindered aromatic polyamines should be used with sterically hindered extenders. And 4-, and / or 2,6-diaminotoluene, 2,4 ′ and / Or 4,4'-diaminodiphenylmethane, 1,2'- and / or 1,4-phenylene Diamine, naphthalene-1,5-diamine and triphenylmethane-4,4 ', 4 "-tri Contains amines. Difunctional and polyfunctional aromatic amine compounds also include 4,4'-di- (Methyl) amino-diphenylmethane or 1-methyl-2-methylamino-4-amino Secondary amino groups such as benzene can be included exclusively or partially. A Polyphenyl polymer of the type obtained by condensation of niline and formaldehyde Liquid mixtures of tylene polyamines are also suitable.   Generally, non-sterically hindered aromatic diamines and polyamines are RIM polyurethanes and polyamines. And to provide sufficient processing time to prepare polymers such as polyurea Is too reactive. Therefore, these diamines and polyamines are listed above. Should be used in combination with one or more of the listed sterically hindered diamines . One exception to this is in the case of methylenedioltochloroaniline. This Certain diamines of RIM Polyurethane / Polyurea are not sterically hindered Is a suitable material for preparing.   Polyurethane catalysts are also suitable for use in the present invention. The catalyst is preferably of the invention. Increases the reaction rate between isocyanate groups and hydroxyl-reactive species in the composition Incorporated into the formulation in an appropriate amount to allow Various materials are useful for this purpose However, the most widely used and preferred catalysts are tertiary An amine catalyst and an organotin catalyst.   Examples of tertiary amine catalysts are, for example, triethylenediamine, N-methylmorpholine. N, N-ethylmorpholine, diethyl ethanolamine, N-cocomorpholine, 1-methyl-4-dimethylaminoethylpiperazine, 3-methoxy- N-dimethylpropylamine, N, N-diethyl-3-diethylaminopropylamine And dimethylbenzylamine. Tertiary amine catalysts are used in polyol formulations of 0. It is advantageously used in an amount of 01 to 2% by weight.   Examples of organotin catalysts are dimethyltin dilaurate, dibutyltin dilaurate, dioxin. Includes octyltin dilaurate and stannous octoate. Other examples of effective catalysts are For example, it is taught in US Pat. No. 2,846,408. Preferably, the organotin catalyst is Used in an amount of 0.001-0.5% by weight of the polyol formulation.   Catalysts that promote the formation of isocyanurate groups can also be used in the present invention . Suitable catalysts for use in the present invention are those of Saunders and Frisch.Polyurethanes, Che mistry and Technology, lHighPolymers Vol. XVI, pp. 94 to 97 (1962) Including those. Such catalysts are referred to herein as trimerization catalysts. These catalysts Examples of are aliphatic and aromatic tertiary amine compounds, organometallic compounds, carboxylic acids Includes alkali metal salts and symmetrical triazine derivatives. The preferred trimerization catalyst is oku Potassium salts of carboxylic acids such as potassium tannate and, for example, 2,4,6-tris It is a tertiary amine such as (dimethylaminomethyl) phenol.   The method of the present invention may include the additional step of product processing the polymer prior to painting. Wear. RIM, already described above, is the preferred method for manufacturing the product. heat Injection molding of plastic plastics is also a preferred means of making products. Polymer -Casting can also be carried out by the method of the present invention, and further, blow molding, pressing. Demolding and compression molding can also be used. One advantage of the present invention is that processing in this way The assembled product is attached to the metal product and the two are united together. It can be painted as   In addition to the above ingredients, the polyurethane / polyurea formulations of the present invention Materials known by those skilled in the art to be useful in the preparation of tan / polyurea polymers Fees can also be included. Fillers, mold release agents, pigments, foaming agents, surfactants and difficult Additives such as flame retardants can be included in these materials. Other conductive filling Agents are specifically excluded. The polymer of the present invention is a conductive derivative of the non-volatile metal salt of the present invention. Without conductive material, it is not sufficiently conductive for efficient electrostatic coating.   The formulation components of the formulations of the present invention are used to prepare polyurethane / polyurea polymers. The polymer is produced by any method known to be useful by those skilled in the art. Can be adapted to. Of the polyurethane / polyurea polymers of the present invention One preferred method of production is by means of reaction injection molding (RIM). RIM polymer Although it is well known in the art to prepare, in general, mutually reactive materials are Including introducing into the mold through a mixer with at least two streams of material. At this point, the material polymerizes to produce a molded polymeric product.   In addition to the advantage of being able to paint without the use of a conductive primer, The polymer can be shaped to have fewer defects due to flash defects. Small particles of polymer that remain in the mold after the molded article is removed from the mold And is known. The polymers of the present invention were prepared without conductive inductive materials. They are relatively more conductive than the same It is less susceptible to electrostatic attraction and can be easily retrieved. Therefore, Burr particles are unlikely to remain and are less likely to be a surface defect on the next product to be molded .   In the practice of the present invention, the cured polymer is electrostatically coated. For the purposes of the present invention , Electrostatic coating is (1) charging an object to be coated with electric charge, (2) pair Charge the paint with a charge of the opposite polarity to the charge of the elephant, or compare to charged products Ground the paint at least, and (3) from the electrostatic coating device to the object. Discharging the paint toward. In a particular industry It is also possible to charge the paint and ground the object to be painted , Even better. It is known to those skilled in the art that it is useful for electrostatic coating. Any means and devices can be used in the method of the present invention. For example, BINK MODEL 85 * Can be used to electrostatically coat the cured polymer of the present invention (* B INK MODEL 85 (is a trademark of Binks Manufacturing Company).   Although the present invention can be used in liquid paints, the term "paint" is such a narrow term. Is not intended to be interpreted. For the purposes of the present invention, an object according to the method of the present invention A material that can be "painted" on is any material that can be electrostatically deposited on an object. Including materials. These materials are not limited to liquid pigment paints, they are liquid transparent. Bright paint (also known as clear coat), powder pigment, powder paint, primer And a conductive coating such as a prep coat. The material is neat or Can be solvent-borne, water-borne or both solvent and water-borne. Wear. In the case of powders, for example, the material can also be applied as a solid It The method of electrostatic coating is to apply the material to the product by aerosol, rather than applying it on the product. The product is immersed in the material while maintaining a potential difference between it and the product to which it is applied. Including electrostatic deposition method.   In a preferred embodiment of the present invention, the first layer comprises (1) a urea group, a urethane group or a mixture thereof. Group-containing material, and (2) conductive conductivity of non-volatile metal salt A polymer layer prepared from a polymer blend containing a conductive material, and a second An electrostatically coated object comprising at least two layers, the layers being electrostatically applied paints Where (a) the polymer can be electrostatically coated and (b) poly. If the mer did not include the non-volatile metal salt conductive inductive material in the polymer Will not be conductive. The present invention uses a conductive material so that the two layers are adjacent to each other. Useful for electrostatic coating of painted or uncoated products Ming also has products that have a third layer sandwiched between the electrostatically applied paint and the polymer. Can be used to conveniently prepare. The third layer is non-conductive or conductive. It can be a membrane. The non-volatile metal salt is of the polymer prepared with it. Increase bulk conductivity. Surface conductivity of polymer with conductive material is surface conductivity , But has little effect on bulk conductivity. Surface conductivity alone , Believed to be insufficient to electrostatically charge products that are electrostatically coated. Therefore, The method of the present invention comprises a polymer coated with a non-conductive layer, or More polymers with a preliminary conductive coating such as a paint or prep coat It can be used to paint efficiently.   The method of the present invention may be advantageous over conventional methods for several reasons. it can. One of these reasons is that there is sufficient conductivity to allow efficient electrostatic painting. A very small amount of material that imparts properties but does not substantially deteriorate the physical properties of the polymer. Is to be added to the limmer. The non-volatile metal salts of the present invention are those to which they are added. It can be chosen to be compatible with the intended polymer formulation. Apart The salt can be mixed with the compatibilizer. If a compatibilizer is used Does not give undesired physical properties to the polymer and does not deteriorate the physical properties of the polymer. Should be chosen. For example, n- Methyl-2-pyrrolidone is used to compatibilize the non-volatile metal salts of the present invention. However, it does not substantially deteriorate the physical properties of the polymer prepared with it. Absent.   The following examples and comparative examples are intended to be illustrative of the present invention. These fruits The examples and comparative examples are not intended to limit the scope of the claims of the present invention, and Should not be interpreted as.Example 1   17.5in. (44.4cm) x10.0in. (25.4cm) x0.0063in. An error measuring (0.16 cm) Isocyanate is produced by means of a reaction injection molding machine to produce storm plaques. And react the nate prepolymer (A side) with the polyoldiamine mixture (B side) To prepare a polyurethane / polyurea polymer. Of reaction injection molding equipment The parameters are shown in Table 1 below. Polyurethane / polyurea polymer blends It consisted of two components. The first component is methylene diphenyl diisocyanate. It is a soft segment prepolymer which is made of SPECTRIM 50A * (* SPECTRIM 50A is a product name of The Dow Chemical Company) It is prepared using terpolyol. The second component is SPECTRIM 50B * (* SPECTR IM 50B is a commercial product of The Dow Chemical Company) Mixed active hydrogen containing compounds based on amine and polyether polyols It was a minute. 0.164% of total polymer weight perfluoroalkyl sulfonate sodium Um was contained in the SPECTRIM 50B component. SPECTRIM 50B ingredient and sodium salt Rufluoroalkyl sulfonate, FLUORAD FC-98 * is mixed and RIM equipment (* FLUORAD FC-98 is a trade name of 3M It is a mixture of potassium cyclohexylalkyl sulfonate. ). SPECTRIM 50A Was also placed in the reservoir of the RIM device. Plaque is successful Prepared by shape and post cure.   The plaques are rinsed in ISW 32 * for 60 seconds, deionized water for 30 seconds, and ISW 33 **. Rinse for 30 seconds, rinse in deionized water for 30 seconds, rinse in deionized water for 15 seconds Washed using a 5-step process including (* ISW-32 is from DuBios Chemicals Corp. Trade name and a phosphoric acid based detergent, ** ISW-33 is a DuBios Chemical s Corp. , And is a phosphoric acid-based paint control agent). After that, The lark was dried.   First, weigh the plaques on an analytical balance (initial plaque weight (OP Wt), Then attach this plaque to a bent metal support with an 8.6 inch (21.8 cm) radius The plaque was painted by brushing. After that, the support is 320 inches / minute (8.13 It was attached to a conveyor moving at torr / min). Plaques move during painting The distance traveled was 20 inches (50.8 cm). E63PB * air cap and D63B * full BINKS MODEL 85 with 0.046 inch (1.24 mm) orifice with id tip * Painted with gun (* BINKS MODEL 85, E63PB and D63B are Binks M Product name of anufacturing Company). Paint a metal coupon on 1.4 mils (0.036mm) The optimum conditions for the operation are 50 psi (345 mPa) air atomization pressure and 8 psi (55.2 mPa) It was up pressure. Gun is 3inch (7.62cm) downward with 6 passes for each paint film I was indexed. The applied voltage is 70-75 kilovolts, 40-45 microamps It was accompanied by the electric current. The paint used was PPG CBC8554 *, which is Fisher # Dilute with isobutyl acetate to give a spray viscosity of 22 seconds using 2 cups. (* PPG CBC8554 is a product name of PPG Industries Inc.). First coat of paint After being applied, the paint is flushed for 1.5 minutes, and then a second of paint The coating was applied.   After the plaque has been painted, flush the painted plaque for 5 minutes and then Then plaque is allowed to cure for 45 minutes at 260 ° F (127 ° C) in a ventilated oven. The transport efficiency of the paint was measured. Allow the plaques to cool to ambient temperature for 30 minutes and then After that, it was re-weighed (final plaque weight (FP Wt)) with an analytical balance. Spray gun The discharge rate (TP) of the air will turn off the air stream, and the amount of paint collected in 1 minute. It was measured by weighing the amount of material. Weight percentage of solids in paint (WT solids Min) flash solvent from 5-10g of paint, cure at 120 ° C for 1 hour, and It was determined by measuring the weight difference on a balance. The paint spray time (PST) was 44.4 seconds. The paint transportation efficiency is calculated by the following formula: (FP Wt)-(OP Wt)} / {Tp X PST X Wt solids} and determined in Table 2 below. Shown in.Comparative example 2   Preparing and coating a polyurethane / polyurea polymer substantially identical to Example 1, And tested, except that the formulation was FLUORAD FC-98, but not 0.164% FLUORAD FC-98. Was not included. The results are shown in Table 2 below. Example 3   A polyurethane / polyurea polymer was prepared substantially the same as in Example 1, except that The formulation contained 0.761% FLUORAD FC-98, but not 0.164% FLUORAD FC-98. Step The physical properties of the larks were tested. The results are shown in Table 3 below.Example 4   A polyurethane / polyurea polymer was prepared and tested substantially identically to Example 3. However, the formulation was 0.200% FLUORAD FC-, not 0.761% FLUORAD FC-98. Including 98. Table 3 shows the results.Comparative Example 5   A polyurethane / polyurea polymer was prepared and tested substantially identically to Example 3. Tested, but the formulation contains FLUORAD FC-98, but not 0.761% FLUORAD FC-98 There wasn't. Table 3 shows the results. * FC-98 is a 3M product name, and potassium perfluorosiloxyhexyl alkyl sulfonate It is a mixture of um. 1 ASTM-D-638-89, plastic tensile property test method 2 ASTM-D-790-86, unreinforced and reinforced plastic and electrical insulation Bending property test method for green materials 3 ASTM-D-624-86, Rubber Property Test Method--Tear Resistance 4 ASTM-D-3796-85, Microporous Urethane Test Method--High Temperature Slack 5 ASTM-D-256-88, Impact resistance test method for plastic and electrical insulation materials 6 ASTM-D-2240-86, Rubber Property Test Method--Durometer Hardness 7 ASTM-D-570-81, Plastic water absorption test methodExamples 6-18 and Comparative Examples 19-24   Polymers were prepared with the non-volatile metal salts of the present invention. Shown in Tables 4A-4C below These additives are mixed into the polymer blend and then injection molded into a product suitable for painting. Or reaction injection molded. White base coat (CBC9753) SPRAYMATION MODEL  310610 * Applied with automatic panel sprayer. The fixed conditions for the panel spray system are: --850 "/ min (2.16m / min) gun traversing speed; --2 "(5.1cm) spray gun split feed, 50% fan overlap; --40psig (276kPa) air atomization pressure; Includes --63B Fluid Tip, N63 Air Cap and 111-1271 Fluid Needle MUBINKS MODEL 80A * Electrostatic coating gun; --BINKS MODEL 111-3800 *, 0-100 kV output source; --Gun distance 10 "(25.4cm); --Number of coatings = 2; --Number of gun passes per coating = 8; and --80kw (* BINKS MODEL 80A and BINKS MODEL 111-3800 are Binks Manufacturing ComPan SPRAYMATION MODEL 310160 is a product name of Spraymation Equipment Company Is the product name. )   Specify the process conditions and specific paint preparation conditions used during application. Shown below. The painted panels were cured after application of the paint in an electric draft oven. used The paint was Pittsburgh Paint and Glass (PPG) * paint. The paint has the following characteristics did. Designation type CBC9753 *                                       white Lot number 64233C Unconverted viscosity 60 Spray viscosity 21 Diluent IBA % Diluent 25 Number of coatings 2 Flash: coating, min 0.5 Pre-cure flash-min 5 Cure time-min 30 40 Curing temperature 260 ° F (127 ° C) * PPG and CBC9753 are product names of Plttsburgh Paint and Glass. calibration: With bare steel panel of size 0.032x4x12inch (0.81mmx10.2cmx30.48cm) Calibration was performed. The panels were painted without static for calibration. Steel calibration panel Target film thickness was 0.8 mil +/- 0.1 mil (0.02 +/- 0.0025 mm). Target film thickness using pot pressure 6 PSIG with some exceptions Was achieved. Panel holder and ground   Use the standard metal panel support rod on the SPRAYMATION Replaced with a fiber rod. Replace the hook cross member with an oak and replace it Bonded with epoxy. 4x4x1 / 4 inch (10.2x15.2x0.64cm) size The minium plate (2) is 1 inch (2.54 cm) away from the upper oak crossbar with wood screws. Installed. The metal bolt was flush mounted on the metal plate surface . The bolt is in the center of the plate, which penetrates through the back, where it Functions as a ground point. Ground wire attached with nuts and washers . The ground had a resistance of 0.15 ohms. Ground test   WOODHEAD MODEL 7040 * Performed grounding test with grounding loop impedance tester ( * WOODHEAD MODEL 7040 is a product name of Daniel Woodhead Company). Sample mounting   Half of the sample is supported by a grounded aluminum plate, half is supported The test sample was mounted as if it were not. Conductive metal clip (≧ 0.15 ohm resistance) Place the outer edge (left side on the left side, right side on the right side) on the aluminum plate with To fix the test sample. This allows the plastic products to It is confirmed that the land has been grounded.   Aluminum plate is 4inch (10.2cm) wide and 6inch (15.2cm) long Therefore, the optimum molded product size is 4inch (10.2cm) wide and 12inch (30.5cm) long. And in this way half of the part is aluminum-supported and half is Not supported. Some of the molded parts are 10inch (25.4cm) long, in this case, 5inch (12.7cm) of the molding is supported, and 5inch (12.7cm) is supported did not exist.   Many molded products had a length of only 5 inches (12.7 cm). In this case, experiment For that purpose, two 5 inch (12.7 cm) long molded parts were clipped together. 4inch ( 10.2cm) width x 2.5inch (6.4cm) length x 1 / 4inch (0.64cm) thickness non-conductive modified Polyurethane plaque is taped from the back onto an aluminum plate Was done. The metal clip used to secure the part is made of aluminum. Centered on the interface between polyurethane and polyurethane. Half of each clip is 5inch (12.7cm) ) Length was on the molded part. Masking to cover all exposed aluminum Tape was used. Film thickness   ELCOMETER 245 * Portable Film Thickness Meter (* ELCOMETER 245 is Elcometer  Instruments Ltd. Film thickness on a steel anel using Decided Film thickness was visually measured on a plastic panel. Painted The prepared substrate pieces were cut from the plastic substrate with a razor knife. Chip is flat The cut side was placed face down on the painted side. Plastics and paints A section was cut through the face. Section pieces were placed on microscope slides. Scaled contact The paint thickness was measured at 200 times magnification with an eye lens. 12inch (30.5cm) long panel , Film thickness measurement is 2 in from the top of the aluminum supported half of the test panel It was performed in ch (5.1 cm) and 4 inch (12.7 cm). Clipped 5inch (12.7c m) length panel and 10inch (2.54cm) length panel on the film thickness measurement Done 1.5 inch (3.81 cm) from the top of the aluminum-supported half of the test panel It was All samples were measured 3.5 inches (8.9 cm) below the metal support. Paint siege   Instead of only going straight out of the atomizer towards the part to be painted, the part The extent to which the paint surrounds the area was also measured. This is known as paint siege It is a subjective measurement, with electrostatically coated steel controls and charging powder supply between paintings. By comparing the sample with both a similarly painted steel control but without stopping. Is carried out. Each of these moldings has a paint envelope value from excellent to none . The paint siege class is Excellent> Good> Equivalent> Some> None Is. The results are shown in Tables 4A-4C below. ^A SPECTRIM 50S is a polyurethane prepared by mixing two commercially available ingredients. / Polyurea polymer (SPECTRIM 50S is a trade name of The Dow Chemical Company) . The first component is a soft segment prepolymer based on methylene diphenyl diisocyanate. A polymer, wherein the prepolymer is commercially available as SPECTRIM 50A * Prepared with Le Polyol (* SPECTRIM 50A is The Dow Chemical Company Is the product name). The second component is diethyltoluene dichloride commercially available as SPECTRIM 50B *. Mixed active hydrogen containing compounds based on amine and polyether polyols Minutes (* SPECTRIM 50B is a trade name of The Dow Chemical Company). Made The article was prepared by reaction injection molding.^B  FC-98 is a perfluorocyclohexylalkyl sulfonic acid available from 3M It is a mixture of potassium. FC-98 is a product name of 3M.^C  SPECTRIM 25 is a polyurea prepared by mixing two commercially available ingredients. / Polyurea polymer (SPECTRIM 25 is a trade name of The Dow Chemical Company Is). The first component is a soft segment based on methylene diphenyl diisocyanate. Is a prepolymer, which is commercially available as SPECTRIM 25A *. Prepared with ether polyol (SPECTRIM 25A is a product of The Dow ChemicalComp is the product name of any). The second component is diethyltoluene commercially available as SPECTRIM 25B * Mixed active hydrogen containing based on diamine and polyether polyols It was an ingredient (* SPECTRIM 25B is a trade name of The Dow Chemical Company). The product was prepared by reaction injection molding.^D  SPECTRIM HF85 is a polyurea prepared by mixing two commercially available ingredients. Tan / polyurea polymer (SPECTRIM HF85 is a commercial product of The Dow Chemical Company. The product name). The first component is methylene diph A soft segment prepolymer based on phenyl diisocyanate, The repolymer was prepared with the commercially available polyether polyol as SPECTRIM HF85A *. Manufactured (SPECTRIM HF85A is a trade name of The Dow Chemical Company). second Ingredients are based on aminated polyether polyols commercially available as SPECTRIM HF85B * Was a mixed component containing active hydrogen (* SPECTRIM HF85B is The Dow Chemi The product name of cal Company). The product was prepared by reaction injection molding.^E  TPU is a poly available commercially as PELLETHANE 2354-65D from The Dow Chemical Company. Thermoplastics based on ester polyols and methylene diphenyl diisocyanate It is a urethane. PELLETHANE 2354-65D is a trade name of The Dow Chemical Company Is. Additives were mixed with the liquid precursor used to prepare the TPU. The product was molded by injection molding.^F  DEHYQUAT C is laurylpyridinium chloride, a product of Henkel Corporation n Is the name.Examples 25, 27-29 and Comparative Examples 26 & 30   The sample polyurethane / polyurea plaques are polymer and non-volatile as shown in Table 5. Prepared using metal salts (SPECTRIM 50S is a product of The Dow Chemical Company Name). Plaque mixes the B side of the formulation with a non-volatile metal salt, and plaque Was prepared by reaction injection molding. Test the physical properties of the sample and It shows in Table 6. ¹ SPECTRIM 5OS is a polyurethane prepared by mixing two commercially available ingredients. / Polyurea polymer (SPECTRIM 50S is a trade name of The Dow Chemical Company ). The first component is a methylene diphenyl diisocyanate-based soft segment Repolymer, which is a polypolymer commercially available as SPECTRIM 50A *. Prepared with Terpolyol (* SPECTRIM 50A is The Dow Chemical Compan y is the product name). The second component is diethyltoluene dichloride commercially available as SPECTRIM 50B *. Mixed active hydrogen containing compounds based on amine and polyether polyols Minutes (* SPECTRIM 50B is a trade name of The Dow Chemica1 Company). Made The article was prepared by reaction injection molding.²  SPECTRIM 25 is a polyurea prepared by mixing two commercially available ingredients. / Polyurea polymer (SPECTRIM 25 is a trade name of The Dow Chemical Company Is). The first component is a soft segment based on methylene diphenyl diisocyanate. Is a prepolymer, which is commercially available as SPECTRIM 25A *. Prepared with ether polyol (* SPECTRIM 25A is from The Dow Chemical Co is the product name of mpany). The second component is diethyltoluene commercially available as SPECTRIM 25B *. Mixed active hydrogen containing based on diamine and polyether polyol It was an ingredient (* SPECTRIM 25B is a product name of The Dow Chemical Company) . The product was prepared by reaction injection molding.³  FC-98 is a perfluorocyclohexylalkyl sulfonic acid available from 3M It is a mixture of potassium. FC-98 is a product name of 3M.^Four  Lithium trifluoromethanesulfonate^A  ASTM-D-790-86, Unreinforced and Reinforced Plastic and Electrical Insulation Material Bending Characteristics test method^B  ASTM-792-86, a test of specific gravity (relative density) and density of plastics by substitution Test method^C  ASTM-624-86, Rubber Property Test Method--Tear Resistance^D  ASTM-D-638-89, Plastic Tensile Property Test MethodExample 31 and Comparative Examples 32-36   Sample plaques were prepared using the polymers and additives shown in Table 7 below. Step Larks were powder coated using the following procedure. Powder coating application device   Nordson NPE CC8 Model 246152H * with electrostatic powder coating applicator The transparent powder coating was then electrostatically applied to the test panel. This applicator gun Is molded from a 300 inch / min (762 cm / min) hooking speed and a 10 inch (25.4 cm) gun ECLIPSE MODEL 50-65 using item distance and 3 inch (7.6 cm) gun indexing Attached to a 28 panel sprayer. The following conditions were fixed with a powder applicator . --Fine air = 20PSIG (138kPa) --Fluidization 0.2PSIG (1.4RPa) input --Flow velocity 30PSIG (207RPa) --90 kV potential difference Specimen mounting and grounding Tape four 12.5 "Lx1.75" Wx0.125 "inch (31.75cmLx4.45cmWx3.18mm) pieces Mounted on a cardboard holder manufactured by I attached the fee. The holder was screwed onto the Eclipse support rod. For grounding The wire was attached to the top of the test molding. Powder coating applications and formulations   Apply one coat of powder coating, and then cure 15 powders at 325 ° F (163 ° C) It was   The powder coating formulation contained the following components: DER 662UH * 100 copies, EPON P-108 ** 4 copies, RESIFLW P-67 *** 1 part (* DER 662UH is a product name of The Dow Chemical Company , ** EPON P-108 is a trade name of Shell Chemical Company, *** RESIFLOW P-108 Is the trade name of Esrton Chemical Company. ).   Buss Condux PLK-46 extruder with kneader speed of 200 rev / min at 70 ° F (21 ° C) Mixed the melt. Extrudate is 0.013 inch (0.33 inch) with a Mikropu I Bantam grinder. mm) Milled into powder using a scroll screen. 150 mesh powder Sifted lean. ^A SPECTRIM HF85 is a polyurea prepared by mixing two commercially available ingredients. Tan / polyurea polymer (SPECTRIM HF85 is a product of The Dow Chemical Company The product name). The first component is a methylene diphenyl diisocyanate based soft A segmented prepolymer, which is marketed as SPECTRIM HF85A * Prepared with Polyether Polyol on sale (SPECTRIM HF85A is The Dow Ch Product name of emical Company). The second component is commercially available as SPECTRIM HF85B *. A mixed active hydrogen-containing component based on a minated polyether polyol (* SPECTRIM HF85B is a trade name of The Dow Chemical Company). Products Prepared by reaction injection molding.^B  GTX is NORYL GTX 910-A *, available from General Electric Company Engines based on polydimethylphenylene oxide and nylon blends. A nearing thermoplastic (* NORYL GTX 910-A is a General Electr ic Company is the product name). The additive is initially mixed with the plastic in high concentration. To form a concentrate. This concentrate is then proportioned to achieve the indicated concentration. Mix with unfilled plastic. The product was manufactured by injection molding.^C  FC-98 is a mixture of potassium perfluoroalkyl sulfonates available from 3M Things. FC-98 is a product name of 3M.

─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Grosses, Cynthia K.             Bra, United States, Texas 77422             Zoria, Pee. Oh. Box 6537             ー 、 Route 6 (72) Inventor Porter, James Earl.             Ray, United States, Texas 77566             Peacock spouse 103 (72) Inventor Prestar, Ralph Dee, Jr.             Ray, United States, Texas 77566             Kuja Jackson, Huckleberry 428 (72) Inventor Taber, Ricky El.             Ray, United States, Texas 77566             Peacock, garland drive             420, apartment 1408 (72) Inventor Zawisza, Melissa Jay.             United States, Michigan 48640, Mi             Drand, Pine Oak Court 2562

Claims (1)

[Claims]   1. For electrostatically coating cured urea group and / or urethane group containing polymer The law, (A) (1) A material containing or forming a urea group, a urethane group or a mixed group thereof. Fee, and (2) Conductive inductive material of non-volatile metal salt, Preparing a cured polymer from a polymer blend comprising: (B) electrostatically coating this polymer, Including the steps of (A) the polymer can be efficiently electrostatically coated, and (B) Does the polymer contain a non-volatile metal salt conductive inductive material? If not, the method that is not conductive.   2. The polymer does not include the non-volatile metal salt conductive inductive material of the present invention. Has substantially the same physical properties as the polymer except that it was prepared The method according to claim 1.   3. The method of claim 1, further comprising the step of molding the polymer into a shaped article before painting. Method.   4. The polymer is molded into a shaped article by injection molding or reaction injection molding. The method according to range 3.   5. The method according to claim 4, wherein the polymer is molded into a shaped article by reaction injection molding. Law.   6. The non-volatile metal salt consists of Li, Na, K cations and mixtures thereof. The method of claim 1 comprising a cation selected from the group:   7. The non-volatile metal salt is perfluoroalkyl sulfonate anion, tetraphe Nylboron anion, Hexafluorophosphate anion and And an anion selected from the group consisting of a mixture thereof. Law.   8. The non-volatile metal salt is present in the polymer blend at 0.02-1.5%. The method according to range 1.   9. For electrostatically coating cured urea group and / or urethane group containing polymer A polymer is molded into a shaped article, coated with a conductive formulation, and In the method of electrostatic coating, (1) materials containing or forming urea groups, urethane groups or mixed groups thereof, And (2) Conductive inductive material of non-volatile metal salt, Preparing a cured polymer from a polymer blend comprising: A method characterized by an improvement including.   10. An electrostatically coated object comprising at least two layers, wherein the first layer But, (1) materials containing or forming urea groups, urethane groups or mixed groups thereof, And (2) Conductive inductive material of non-volatile metal salt, Is a layer of polymer prepared from a polymer blend comprising A layer of paint applied electrostatically, (A) the polymer can be painted efficiently, and (B) Does the polymer contain a non-volatile metal salt conductive inductive material? Electrostatically coated objects that are not electrically conductive.   11. The polymer does not include the non-volatile metal salt conductive inductive material of the present invention Has the same physical properties as the polymer except that it was prepared in The electrostatically painted object according to claim 10.   12. Nonvolatile metal salts from Li, Na, K cations and mixtures thereof The electrostatically-coated object according to claim 10, comprising a cation selected from the group consisting of .   13. The non-volatile metal salt is perfluoroalkyl sulfonate anion, tetraf From phenylboron anion, hexafluorophosphate anion and their mixtures 13. The electrostatically coated object according to claim 12, which contains an anion selected from the group consisting of .   14. Nonvolatile metal salts are present in the polymer blend at 0.02-1.5%. An object which is electrostatically coated according to claim 10.   15. Claims wherein the electrostatically applied paint layer and the polymer layer are adjacent. 10. The electrostatically coated object according to 10.   16. Claims comprising an additional layer between the electrostatically applied paint layer and the polymer layer 11. An electrostatically coated object according to range 10.   17． The additional layer is a conductive primer or a conductive modified coating. 6. The electrostatically coated object according to item 6.   18. The polymer is an object molded by injection molding or reaction injection molding. The electrostatically painted object according to claim 10.   19. 20. The polymer is an object molded by reaction injection molding. The electrostatically painted object described.