WO1997024397A1 - Automobile underbody coating composition - Google Patents

Automobile underbody coating composition Download PDF

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Publication number
WO1997024397A1
WO1997024397A1 PCT/US1996/000255 US9600255W WO9724397A1 WO 1997024397 A1 WO1997024397 A1 WO 1997024397A1 US 9600255 W US9600255 W US 9600255W WO 9724397 A1 WO9724397 A1 WO 9724397A1
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WO
WIPO (PCT)
Prior art keywords
coating composition
styrene
rubber
underbody
copolymer
Prior art date
Application number
PCT/US1996/000255
Other languages
French (fr)
Inventor
Bengt Jungqvist
Finn Bergishagen
Original Assignee
Bengt Jungqvist
Finn Bergishagen
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bengt Jungqvist, Finn Bergishagen filed Critical Bengt Jungqvist
Priority to PCT/US1996/000255 priority Critical patent/WO1997024397A1/en
Publication of WO1997024397A1 publication Critical patent/WO1997024397A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • 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
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures

Definitions

  • the present invention relates generally to coating compositions for protecting automobile underbodies and, more particularly, to automobile underbody coating compositions which allow road debris to embed therein.
  • the underbody coatings be sprayable, i.e., have a low enough viscosity to be spray-applied. It is also desirable that the underbody coating be recyclable, solventless, and resistant to oxygen, ozone, ultraviolet light, abrasion, and high temperatures, have high cohesive strength, and adhere well to the underbody of an automobile to protect the underbody from the environment.
  • underbody coating which allows small particulates of road debris, such as dust, dirt, and sand, to embed into the surface of the underbody coating while the automobile is traveling to provide a further barrier to moisture and other factors of the environment.
  • EP '635 European Patent Application 0 546,635 Al to DeKeyzer, et al.
  • the coating compositions disclosed in EP '635 have much higher than desirable viscosities due to higher than desirable weight percentages of polymer content, which make it difficult, if not impossible for the coating to be spray-applied, even though it was stated therein that they had actually sprayed it.
  • the coating compositions disclosed in EP '635 do not allow road debris, such as dust, dirt, and sand, to effectively embed into the coating surface.
  • the underbody coating of '635 incorporates too much polymer, which is the most expensive part of the composition. This high polymer content also hinders the use of additives or other types of polymer.
  • an object of the present invention to provide a protective coating composition for an underbody of an automobile which is not based on halogenated materials and which may be uniformly spray- applied to the underbody, is recyclable, is solventless, is resistant to oxygen, ozone, ultraviolet light, abrasion, and high temperatures, has high cohesive strength, and adheres well to the underbody.
  • one embodiment of the present invention is a coating composition which uniformly coats and adheres to the underbody of an automobile and protects the underbody from the environment.
  • the coating composition includes a polymeric composition which, when coated onto an automobile underbody, allows small road debris to embed into the coated composition while traveling to provide further protection to the underbody.
  • our coating is sprayable when hot applied and has a gummy consistency which gives certain desirable properties, most notably a self-healing quality. Furthermore, this gummy coating invites the embedding of small road debris, rather than protecting against it. Most prior art coatings are damaged and chipped during bombardment of road debris.
  • the present invention not only receives the small stone chips and dirt that make up the small road debris, but we utilize those stones and dirt to act as a barrier within our coating to substantially reduce any further damage.
  • the coating composition can be disposed of without harming the environment.
  • the prior art PVC coatings give off toxic gases when the car is ultimately burned or the underbody is melted.
  • the automotive industry is looking for new products which are more earth friendly and better performing than old ways.
  • Our invention is such a new product.
  • the coating composition has a viscosity of at most about 1000 centipoise at 150°C and includes a styrene-rubber diblock copolymer, a styrene-rubber-styrene triblock copolymer, and a polar-functionalized polymeric material.
  • the rubber portions of the diblock and triblock copolymers may be individually selected from the group consisting of ethylene-butylene, ethylene-propylene, and mixtures thereof.
  • FIG. 1 shows prior art PVC coating sprayed onto a test panel, before impingement testing
  • FIG. 2 shows the same test panel after impingement, illustrating how the coating chips and flakes off
  • FIG. 3 shows prior art polyester coating, sprayed onto a test panel, before impingement testing
  • FIG. 4 shows that prior art polyester coating on a test panel after the impingement test, showing how the coating is completely worn away down to the metal test panels;
  • FIG. 5 shows our new hot melt polymer coating sprayed onto a test panel, before impingement testing;
  • FIG. 6 shows our new hot melt polymer coating after the impingement test, illustrating how the road debris has embedded into the coating, without exposing the underlaying metal test panel;
  • FIG. 7 illustrates the results of a smear test, using a key, and the gummy consistency of the present invention hot melt polyester coating on a test panel
  • FIG. 8 shows the uniform spray pattern which can be achieved by the present invention hot melt polymer coating on a test panel
  • FIG. 9a shows a corrosion test of the present invention hot melt coating which has been coated onto a test panel to a thickness of between 350-400 micrometers thick scratched down through to the bare metal, illustrating the anti-rust properties;
  • FIG. 9b shows a similar test, although the polymer coating of the present invention was coated to a thickness of between 600-700 micrometers and also having been scratched down through to the metal test panel.
  • the present invention provides new coating compositions which adhere to the underbody of an automobile and protect the underbody from the environ ent.
  • One embodiment of the present invention is a hot melt, sprayable polymeric coating composition which is soft and self-healing yet has high cohesive strength such that, when coated onto an automobile underbody and impinged with road debris, the coating composition not only resists chipping when road debris impinges it, road debris (such as fine dirt and light gravel) is likely to embed into the coating composition, providing further protection to the underbody.
  • road debris such as fine dirt and light gravel
  • the road debris has an average diameter of about 1-10 micrometers. It should embed into the surface at a level of from about 5% to 40% percent based on the weight of the coated composition.
  • the coating composition preferably includes a triblock copolymer, a diblock copolymer, and a polar- functionalized polymeric material.
  • This coating composition adheres to the underbody of an automobile, protects the underbody from the environment, and contains a mixture of thermoplastics and other rubbers.
  • the preferred thermoplastics and rubbers include a styrene-rubber diblock copolymer; a styrene-rubber-styrene triblock copolymer; cross-lining polymers; and a polar-functionalized polymeric materials.
  • the criteria for polymer selection includes any polymer as long as it has a low enough viscosity when added to the polar functionalization polymeric materials to be sprayable.
  • selected polymers should be elastomeric in order to receive road debris.
  • Our invention is intended to be "softer" than the prior art, yielding its two-fold main functional advantages of being both resistant to chipping, and receiving road debris to provide an additional protective layer.
  • the preferred rubber portions of the diblock and triblock copolymers are saturated olefin rubbers individually selected from the group consisting of ethylene-butylene, ethylene-propylene, and mixtures thereof.
  • the rubber portion is the major portion in the copolymers and the polystyrene portion is the minor portion of the copolymers.
  • Such diblock and triblock copolymers may be prepared by anionic polymerization.
  • U.S. Patent Nos. 3,030,346, 3,231,635, 3,251,905, 3,265,765, 3,281,383, 3,639,521, 4,033,888, and 4,077,893 teach methods for making the above-described block copolymers, which patents are incorporated herein by reference.
  • the molecular weight distribution i.e., the weight average molecular weight divided by the number average molecular weight, of the copolymers is from about 0.8 to about 1.1, most preferably, about 1.0.
  • the preferred properties of the triblock copolymer are that it be a styrene-(ethylene-butylene)-styrene triblock copolymer having a styrene:rubber ratio of from about -9-
  • polar-functionalized copolymers Although it is helpful to use a triblock copolymer which has been polar-functionalized to aid in adhesion, it is preferred not to employ polar- functionalized copolymers at very high levels. Use of high levels of polar-functionalized copolymers decreases the pot life of the coating composition at elevated temperatures due to occurrence of crosslinking of the polar-functionalized copolymers. It is most preferred to employ polar-functionalized polymeric materials at levels of at most about 5 weight percent of the coating composition.
  • KRATON G 1652 is a styrene-(ethylene-butylene)-styrene triblock copolymer having a styrene:rubber ratio of about 29:71; a tensile strength of about 6300 psi; an elongation of about 500%; a Shore A hardness of about 75; a specific gravity of about 0.91 grams per cubic centimeter; a solution viscosity of about 475 centipoise; and a rubber block having a glass transition temperature of -42°C.
  • the tensile strength is as determined using ASTM method D412 with a tensile tester jaw separation speed of 10 inches per minute, and the solution viscosity is measured on a solution consisting of 20 weight percent copolymer in toluene at 25°C using a BROOKFIELD Model D RVT viscometer with a number 21 spindle.
  • the preferred properties of the copolymer composition containing a diblock copolymer are that it contain at least about 20 weight percent diblock copolymer, the remainder preferably being triblock copolymer, that it have a styrene:rubber ratio of from about 25:75 to about 35:65; a tensile strength of from about 300 to about 400 psi determined using ASTM method D412 with a tensile tester jaw separation speed of 10 inches per minute; an elongation of from about 150 to about 250%; a specific gravity of from about 0.85 to about 0.95 grams per cubic centimeter; a solution viscosity of about 100 to about 300 centipoise measured on a solution consisting of 25 weight percent copolymer in toluene at 25°C using a BROOKFIELD Model D RVT viscometer with a number 21 spindle; a Shore A hardness of from about 50 to about 70; and a rubber block having a glass transition temperature of about -42°C
  • KRATON G 1726 is a blend of about 30 weight percent styrene-(ethylene-butylene) diblock copolymer and about 70 weight percent styrene-(ethylene-butylene)- styrene triblock copolymer and has a styrene/rubber ratio of about 30:70; a tensile strength of about 350 psi; an elongation of about 200%; a Shore A hardness of about 60; a specific gravity of about 0.91 grams per cubic centimeter; a solution viscosity of about 200 centipoise; and a rubber block having a glass transition temperature of -42°C.
  • the tensile strength is as determined using ASTM method D412 with a tensile tester jaw separation speed of 10 inches per minute.
  • the solution viscosity was measured on a solution consisting of 25 weight percent copolymer in toluene at 25°C using a BROOKFIELD Model D RVT viscometer with a number 21 spindle.
  • the polar-functionalized polymeric material improves the adhesion of the coating composition to the automobile underbody.
  • the adhesion promoting function of the polar-functionalized polymeric material is discussed in U.S. Statutory Invention Registration No. H1022, which statutory invention registration is incorporated herein by reference.
  • Examples of a polar-functionalized polymeric material usable in the coating compositions of the present invention are the anhydride-modified FUSABOND Adhesive Resins, available from E. I. Du Pont de Nemours & Co. , Inc., Wilmington, Delaware.
  • the FUSABOND Adhesive Resins include FUSABOND E, FUSABOND P, and FUSABOND C Adhesive Resins.
  • FUSABOND E Adhesive Resins are polyethylene-based adhesive resins and include products based on LDPE, LLDPE, and HDPE with a range of melt flows.
  • FUSABOND P Adhesive Resins are polypropylene- based adhesive resins and include three types of base polypropylene: homopolymer, impact copolymer, and random copolymer.
  • FUSABOND C Adhesive Resins are ethylene copolymer-based adhesive resins and include products with from 18 to 33 percent ethylene vinyl acetate content and melt indexes of from 2 to 400. FUSABOND may be employed in amounts from about 0 to about 5 weight percent of the coating composition.
  • Suitable polar-functionalized polymeric materials are ethylene-vinyl silane and ethylene-vinyl acetate-vinyl silane polymers which are produced by free radical copolymerization of ethylene, vinyltrimethoxysilane, and, optionally, vinyl acetate. Such polymers are described in the article, "Properties of EVS and EVAVS Moisture Crosslinkable Polymers", by Alex M. Henderson, published in Adhesives Age , November 1994, pages 18-24, which article is incorporated herein by reference.
  • Other suitable polar-functionalized polymeric materials are the vinyl-modified butadiene styrene- butadiene block polymers discussed in the article, "New Modified TPE Polymers for Hot Melt Formulations, by David J. Dougherty, published in Adhesives Age , November 1994, pages 29-31, which article is also incorporated herein by reference.
  • a suitable polar- functionalized polymeric material is a styrene-rubber- styrene triblock copolymer functionalized with groups that render the copolymer more polar.
  • Compounds which will polar-functionalize polymeric materials include acids or anhydrides or derivatives thereof, other carboxy1-containing compounds, sulfonates, alcohols, i ides, acid chlorides, aldehydes, amines, amides, epoxies, isocyanates, and esters.
  • Polar-functionalized polymeric materials containing carboxylic groups reacted onto vinyl aromatic hydrocarbons are described in U.S. Patent No. 4,868,245, which patent is incorporated herein by reference.
  • Polar-functionalized polymeric materials incorporating sulfonate groups are described in U.S.S.N. 198,543, filed May 24, 1988, which application is incorporated herein by reference.
  • U.S. Patent No. 4,578,429 which is incorporated herein by reference, teaches of polymers being functionalized with acids, anhydrides, derivatives of acids or anhydrides, esters, imides, and amides.
  • Preferred functionalizing compounds are unsaturatedmono- and polycarboxylic-containing acids and anhydrides and derivatives of the acids or anhydrides. Examples of such compounds include maleic acid, maleic anhydride, fumaric acid, and fumaric anhydride.
  • the preferred properties of the polar- functionalized triblock copolymer are that it have a styrene:rubber ratio of from about 25:75 to about 35:65; a tensile strength of from about 4000 to about 6000 psi determined using ASTM method D412 with a tensile tester jaw separation speed of 10 inches per minute; an elongation of from about 400 to about 600%; a specific gravity of from about 0.85 to about 0.95 grams per cubic centimeter; a solution viscosity of about 5000 to about 7000 centipoise measured at 25°C using a BROOKFIELD Model D RVT viscometer with a number 21 spindle on a solution consisting of 20 weight percent copolymer in toluene; a Shore A hardness of from about 65 to about 85; a rubber block having a glass transition temperature of about - 42°C, and from about one to about 4 weight percent bound functionality.
  • a suitable commercially-available polar- functionalized copolymer which has the above-described preferred properties is KRATON FG 1901X, a maleic anhydride-functionalized styrene-(ethylene-butylene)- styrene triblock copolymer, available from the Shell Chemical Company.
  • KRATON FG 1901X has a styrene/rubber ratio of about 28:72; a specific gravity of 0.91 grams per cubic centimeter; a tensile strength of about 5000 psi; an elongation at break of about 500%; a Shore A hardness of about 75; a solution viscosity of about 6000 centipoise measured at 25°C on a solution consisting of 20 weight percent copolymer in toluene; a rubber block having a glass transition temperature of -42°C; and about a two weight percent bound functionality.
  • the elongation at break was determined using a film cast from toluene, ASTM D412, "D" die, and a separation speed of 10 inches per minute.
  • the coating compositions contain a ratio of one weight part polar-functionalized polymeric material, such as KRATON FG 1901X, to from about two to about three weight parts triblock copolymer, such as KRATON G 1652, and from about three to about five weight parts of the mixture of diblock and triblock copolymers, such as KRATON G 1726. It is desirable that the polar-functionalized polymeric material, such as KRATON FG 190IX, be employed in less than about 5 weight percent of the coating composition. A typical suitable range for the polar-functionalized polymeric material is from about 2 to about 5 weight percent of the coating composition.
  • cross-linking polymers include; Butyl rubber, chlorinater rubber, ethylene-propylene rubber, block polymers, butadiene- acrylonitrile rubber, butadiene styrene rubber, butyl rubber, fluoropolymers, natural rubber, polybutadiene rubber, polychloroprene, polyisobutylene, polyisoprene, polysulfide, polyurethane, reclaimed rubber, silicone rubber, and others.
  • thermoplastic rubbers such as styrene-butadiene and/or styrene-isoprene copolymers may be used in place of the styrene-(ethylene- butylene) type and/or styrene-(ethylene-propylene) type diblock and triblock copolymers. If such a substitution is done, it is best if done by substituting less than about ten (10%) percent of the total diblock and triblock copolymers.
  • Exemplary commercial styrene-butadiene copolymers and styrene-isoprene copolymers are EUROPRENE SOL T Thermoplastic Rubbers, available from EniChem Elastomers Ltd, Southampton, United Kingdom.
  • EUROPRENE SOL T Thermoplastic Rubbers are block copolymers of the (S-B) literalX type, where S represents the polystyrene block, B represents the polybutadiene or polyisoprene block and X represents the coupling agent.
  • EUROPRENE SOL T Thermoplastic Rubbers 161, 162, 163, 171, 172, 174, 175, and 176 are styrene-butadiene type copolymers where the weight ratio of styrene to butadiene ranges from 30:70 to 55:45.
  • EUROPRENE SOL T 166 is a styrene-butadiene type copolymer.
  • EUROPRENE SOL T 190 is a styrene-isoprene type copolymer having a weight ratio of styrene to isoprene of 15:85.
  • the hot-melt coating compositions of the present invention contain from about 5 to about 25 weight percent polymer which includes any diblock copolymer, triblock copolymer, and polar-functionalized polymeric material.
  • the coating compositions of the present invention which are in the form of water-based emulsions are also preferably from about 5 to about 25 weight percent polymer, based on the dry weight of the coating composition, i.e., the coating composition devoid of water.
  • the tackifying resin is a liquid resin (being liquid at room temperature) , such as a liquid aliphatic hydrocarbon resin.
  • Suitable liquid aliphatic hydrocarbon resins include HERCURES C 10 and REGALREZ, both available from the Hercules Chemical Corporation, Wilmington, Delaware, and BEVILITE 621, a rosin ester available from Bergvik Kemi AB, of Sandarne, Sweden.
  • HERCURES C 10 has a viscosity at 50°C of 3500- 4500 Pa sec using a Brookfield viscometer.
  • BEVILITE 621 has a Ring & Ball Softening Point of from about 18 to about 23°C.
  • the tackifying resin gives the composition body and is typically employed from about 40 to about 70 weight percent of the coating composition, preferably, up to about 4 weight parts of tackifying resin to one weight part polymer which includes diblock copolymers, triblock copolymers, and polar-functionalized polymeric material.
  • a detackifier or deblocker is also a preferred ingredient in the coating composition to detackify the coating composition, plasticize the rubber phase, and maintain integrity of the coating composition.
  • An exemplary detackifier is paraffin wax, such as Paraffin 5205 or TOTAL, both available from Ter Hell Paraffin Co. of Hamburg, Germany or PARAFF 52/54 available from the Chemo Li pex Company.
  • Paraffin 5205 has a melting point of 52°C.
  • paraffin waxes having a low melting point of about 52°C are particularly well suited when combined in a 70% wax to 30% Fusabond ratio by weight.
  • paraffin wax is a very good deblocker, we experienced poor adhesion, so Fusabond was added to raise the adhesion to an acceptable level. Paraffin wax seems to be the best diluent, but adding too much causes a loss of elasticity.
  • Thixotropes are generally a part of the coating compositions of the present invention to prevent the coating compositions from sagging from the coated underbody of the automobile either during application of the composition or when the automobile passes through a paint-curing oven during the manufacturing of the automobile.
  • a thixotrope is typically an agent that swells and disperses in a liquid thixotrope activator to form a stable network of colloidal particles. The network of particles is broken under high shear stresses but reforms when the shear stresses are removed.
  • thixotropes are employed from about 0 to about 5 weight percent of the coating composition.
  • Suitable thixotropes include carbon black, aluminum powder, fumed silica, and overbased calcium sulfonate.
  • Suitable fumed silicas include CARBOSIL H 5 available from Cabot Corporation, and AEROSIL 300 available from the Degussa Corporation, Frankfurt, West Germany.
  • Overbased calcium sulfonate is available from the Witco Corporation, and also serves in the coating composition as a plasticizer, a viscosity reducer, and a corrosion inhibitor.
  • a thixotrope activator such as water, alcohol, or water- or alcohol-based liquids, is usually employed with the thixotrope.
  • a suitable thixotrope activator is CARBOWAX 8000 available from the Union Carbide Corporation, New York, New York.
  • the thixotrope activator is typically employed in amounts from about 0 to about 1 weight percent of the coating composition.
  • Antioxidants may also be employed in the coating composition of the present invention to prevent degradation of the polymers and resins during processing and the normal life of the coating composition.
  • Suitable antioxidants include the hindered phenols, IRGANOX 1010 and IRGANOX 1076, both available from the Ciba-Geigy Corporation, Basel, Switzerland.
  • Fillers, blowing agents, and curing agents may also be used in the coating compositions of the present invention.
  • Fillers such as calcium carbonate, are preferably added in amounts less than about 10 weight percent of the composition.
  • Exemplary blowing agents include p-toluene sulfonyl semicarbazide, available from Uniroyal, Incorporated, New York, New York, and modified cyclodextrin, available from American Maize Company, Hammond, Indiana.
  • Curing agents for KRATON FG 1901X include overbased calcium sulfonate, available from the Witco Corporation, calcium sulfonate in the presence of water, and the melamine type resin, CYMEL 303, available from American Cyanamid Company, Wayne, New Jersey. Use of the calcium sulfonate in the presence of water is taught in U.S. Patent No. 5,063,251, which patent is incorporated herein by reference. The following table provides general ratios that may be employed of the composition components described hereinabove.
  • Antioxidant 0.5-3-' Helps lifetime
  • Emulsifying 0-5% If emulsification agent is needed
  • the coating composition of the present invention may be spray-applied as a hot-melt composition or as a water-based emulsion and exhibits little or no "cob-webbing".
  • "Cob-webbing” is when sprayed material forms strings of material rather than discrete droplets. When “cob-webbing” occurs, the coverage is not as uniform and does not adhere well to the surface.
  • the spray pattern consists of uniform droplets that coalesce when impacted against the underbody surface.
  • a viscosity of between 350 and 400 centipoise was ideal for our spraying conditions with a nozzle pressure of 400kg ⁇ cm 2 . It appears that 1000 centipoise would be the upper limit to achieve sprayability.
  • the coating compositions of the present invention are sprayable using, for example, a spray nozzle having a diameter of from about 0.015 inch to about 0.031 inch at an angle of from about 25° to about 110°.
  • the spray delivered from such a spray nozzle and angle meets the typical automotive industry production requirements with respect to the amount of coating composition delivered in one or two passes so that a uniform continuous coating is provided on the underbody.
  • a hot-melt composition As a hot-melt composition, the composition is solventless and devoid of flammable materials to avoid occurrence of fire or explosion.
  • Flammable materials are those materials which are flammable according to the definition provided in the United States Code of Federal Regulations, Title 49, Part 173, Section 10.5 (49 CFR 173.10.5). Briefly restated, a flammable liquid means any liquid having a flash point below 100°F, where flash point means the minimum temperature at which a liquid gives off vapor within a test vessel in sufficient concentration to form an ignitable mixture with air near the surface of the liquid.
  • Title 49 of the Code of Federal Regulations provides proper testing conditions for measuring flash point and is incorporated herein by reference. If flammable materials are included in the composition, the coating operation could be done in a non-combustible atmosphere, such as nitrogen, to avoid fires.
  • the hot-meltable coating composition will reduce to a suitable viscosity for hot-melt spray techniques at temperatures of at least about 120°C, more specifically, at temperatures from about 120°C to about 180°C. It is desirable that the hot-meltable coating compositions have a viscosity of at most about 1000 centipoise at 150°C, more preferably at most about 350 centipoise at 150°C. The viscosity of the hot-meltable coating compositions are typically at least 1 centipoise at 150°C, but more typically at least about 100 centipoise at 150°C.
  • Preparing the hot-meltable coating compositions of the present invention may be done in several ways.
  • One method of preparing the hot-meltable compositions is by preparing two premixes.
  • a first premix may consist of, e.g., part of the tackifying resin, the deblocker or detackifier, the antioxidant, the diblock and triblock copolymers, the polar- functionalized polymeric material, and the thixotrope.
  • the amount of tackifying resin in the first premix may be, for example, from about one-fourth to about one- half the total amount of tackifying resin to be included in the coating composition.
  • the first premix may be prepared by blending the above-mentioned ingredients in a mixer, advantageously, a high-shear mixer, while heating to about 180°C and constantly stirring.
  • the temperature is preferably held at 180°C until all of the polymers are dissolved in the premix.
  • a second premix may consist of the thixotrope activator and the remainder of the tackifying resin.
  • the second premix may be prepared by merely blending the thixotrope activator and the tackifying resin together. To complete the preparation of the coating composition, the second premix is then admixed into the first premix until a uniform composition is achieved.
  • the coating composition, thus prepared may then be extruded, pelletized, and dusted with an antiblocking powder, if desired.
  • the coating composition is first loaded into a hot-melt spraying apparatus, such as that described in International Patent Application WO 91/00152, which patent application is incorporated herein by reference. The apparatus is then allowed to heat the coating composition, and the coating composition is then sprayed onto the underbody of an automobile.
  • a hot-melt spraying apparatus such as that described in International Patent Application WO 91/00152, which patent application is incorporated herein by reference.
  • the apparatus is then allowed to heat the coating composition, and the coating composition is then sprayed onto the underbody of an automobile.
  • To form a water-based emulsion of the coating composition of the present invention the coating composition is dispersed in water with the aid of at least one surface active agent to form an emulsion.
  • the surface active agent is typically used in an amount from about 1 to about 3 weight percent of the coating composition.
  • the solvent is then stripped from the emulsion to form the emulsified coating composition.
  • An exemplary suitable surface active agent is a nonionic nonylphenol compound, such as IGEPAL CO-430, available from Rhone-Poulenc, Paris, France.
  • the nonionic nonylphenol compound is especially effective when used in combination with an oleic amine soap.
  • the emulsified coating compositions of the present invention are loaded into a spraying apparatus and sprayed onto the underbody of an automobile.
  • the sprayed coating tends to be in the form of discrete or agglomerated particles rather than a coherent film.
  • the coating is heated to cause the discrete or agglomerated particles to coalesce to form a uniform film.
  • a suitable way of heating the coated film on the automobile is by passing the automobile through a paint-curing oven, which procedure is typically done during the production of an automobile.
  • the coating compositions of the present invention are useful for protecting the underbody of an automobile from rust and corrosion and provide a further barrier to the environment.
  • the present coating compositions are not based on halogenated materials, may be spray-applied to the underbody, may be formulated to be recyclable, solventless, resistant to oxygen, ozone, ultraviolet light, abrasion, and high temperatures, to have high cohesive strength, and to adhere well to the underbody.
  • the Opel General Motors Europe (GME) Abrasion Resistance Test is used in the following examples, specification GME 60400, to measure the loss of coating in liters per micron caused by the direct impingement of split steel sand on a coated panel.
  • a test panel positioned at a 45° angle relative to horizontal and having a known thickness of the coating composition thereon is subjected to the impingement of two liters of split steel sand, having a diameter of 4 to 5 mm, passing through a 914 cm long vertically-positioned steel guide tube. The impingement is continued until failure, i.e., when a space is seen where the coating is worn off and the panel is exposed.
  • the results are reported in liters per micron at failure.
  • a test panel coated with 400 microns of coating composition and withstanding 50 liters of sand before failure would have a wear factor of 0.125 liters per micron (50 liters/400 microns) .
  • all references to "parts” are intended to mean parts by weight.
  • the "points" which are assigned as the results of the test indicate how many kilograms of material was impinged against the surface before it goes through the coatings.
  • HERCURES C 10 25 parts of HERCURES C 10, 11 parts paraffin 5205, 1 part IRGANOX 1010, 2.5 parts KRATON FG 1901X,
  • Coating Composition I had a viscosity of 350 centipoise at 150°C as measured on a Brookfield HL viscometer using Spindle #3.
  • Pelletized Coating Composition I was then charged into a Graco FP 13 hot-melt apparatus, manufactured by Graco Corporation, Farmington Hills, Michigan USA, heated to 150°C, and sprayed to a thickness of 400-600 microns on standard steel panels measuring 20 centimeters long by 10 centimeters wide. The coated panels were then hung vertically in an oven at 150°C for 30 minutes to simulate the automotive paint-curing oven cycle.
  • a panel coated with 350 microns of Coating Composition I was subjected to the Opel GME Abrasion Resistance Test.
  • the panel had a wear factor rating of 0.165 liters per micron. See Figures 5 and 6.
  • a panel coated with 400 microns of our own prior art GEVESEAL 2511 polyester, a conventional underbody coating available from Geveko Corporation of Goteborg, Sweden had a wear factor rating of 0.16 liters per micron using the Opel GME Abrasion Resistance Test. See Figures 3 and 4.
  • Figures 7 and 8, respectively, show the results of a smearing test, and the uniform coating which is achievable by spraying the hot melt composition of the present invention.
  • a suitable coating composition of the present invention was prepared by blending, while heating, 43 parts HERCURES C 10, 18 parts BEVILITE 621, 10 parts Paraffin 5205, 1 part IRGANOX 1010, 4.2 parts KRATON FG 1901X, 15.8 parts EUROPRENE SOL T 166, 2.7 parts CABOSIL H-5, 0.5 parts CARBOWAX 8000, and 4.8 parts OREVAC 9305, a maleic anhydride of an ethylene-vinyl acetate copolymer, available from Elf Autochem. The OREVAC 9305 was added to reduce surface tackiness and improve adhesion. The coating composition, thus prepared, was soft and self-healing.
  • overbased calcium sulfonate was first dehydrated by heating it in an oven at a temperature of 150-170°C for a period of four hours with occasional stirring.
  • 25 parts of the dehydrated overbased calcium sulfonate, 11 parts Paraffin 5205, 1 part IRGANOX 1010, 2.5 parts KRATON FG 1901X, 6.2 parts KRATON G 1652, 9.5 parts KRATON G 1726, and 2.3 parts CABOSIL H 5 were blended together as Premix A in a mixing tank by constant stirring and gradual heating to 180°C. The temperature of Premix C was held at 180°C until all of the polymers were dissolved.
  • Premix D 0.5 parts of Carbowax 8000 and 42 parts of HERCURES C 10 were blended together to form Premix D. Premix D was then added to Premix C with continuous stirring until uniform to form Coating Composition II.
  • Coating Composition II was coated onto a panel by spray-applying at a temperature of 150°C. The coated panel and a container of water were then placed for 12 hours in an oven heated to 100°C. The surface of the coated panel showed increased toughness and less tack than the panel coated with Composition I, evidence that the KRATON FG 190IX cured in the presence of the calcium sulfonate and water.
  • overbased calcium sulfonate was first dehydrated by heating it in an oven at a temperature of 150-170°C for a period of four hours with occasional stirring. 27.3 parts of the dehydrated overbased calcium sulfonate, 11 parts Paraffin 5205, 1 part IRGANOX 1010, 2.5 parts KRATON FG 1901X, 6.2 parts KRATON G 1652, and 9.5 parts KRATON G 1726 were blended together in a mixing tank by constant stirring and gradual heating to 180°C to form Premix E. The temperature of Premix E was held at 180°C until all of the polymers were dissolved.

Abstract

A coating composition which adheres to the underbody of an automobile and protects the underbody from the environment. The coating composition includes a polymeric composition which, when coated onto an automobile underbody, allows small road debris to embed into the coated composition while traveling to provide further protection to the underbody. An acceptable level of weight gain of sand in the coating is at least about five to forty weight percent based on the weight of the coated composition. Another embodiment is a coating composition having a viscosity of at most about 1000 centipoise at 150 °C and includes a styrene-rubber diblock copolymer, a styrene-rubber-styrene triblock copolymer, and a polar-functionalized polymeric material. The rubber portions of the diblock and triblock copolymers are individually selected from the group consisting of ethylene-butylene, ethylene-propylene, and mixtures thereof.

Description

AUTOMOBILE UNDERBODY COATING COMPOSITION
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to coating compositions for protecting automobile underbodies and, more particularly, to automobile underbody coating compositions which allow road debris to embed therein.
2. Description of the Related Art
It is commonplace to provide a coating to the metallic underbody of an automobile to protect the underbody from attack by road salt, water, and impinging road debris which cause rust and corrosion of the automobile underbody. In the past, conventional underbody coatings based on polyvinylchloride were attractive to the industry because they are relatively inexpensive and easy to apply.
Recently, however, the burning of halogenated materials, such as polyvinylchloride, have been suspected of contributing to the depletion of the ozone layer in the atmosphere. During exposure to high temperatures, polyvinylchloride releases chlorine usually in the form of hydrogen chloride or dioxins, which are some of the materials suspected of causing depletion of the ozone layer and its associated problems. Such high temperatures occur, e.g., when the automobile is junked and the unused parts are incinerated under uncontrolled conditions. It is both expensive and difficult to design incineration plants which can incinerate polyvinylchloride in a controlled manner. It is, therefore, desirable to provide an underbody coating which is not based on PVC or other halogenated materials.
In addition, for the underbody coatings to be attractive to the industry, it is desirable that the underbody coatings be sprayable, i.e., have a low enough viscosity to be spray-applied. It is also desirable that the underbody coating be recyclable, solventless, and resistant to oxygen, ozone, ultraviolet light, abrasion, and high temperatures, have high cohesive strength, and adhere well to the underbody of an automobile to protect the underbody from the environment.
It is also desirable to have an underbody coating which allows small particulates of road debris, such as dust, dirt, and sand, to embed into the surface of the underbody coating while the automobile is traveling to provide a further barrier to moisture and other factors of the environment.
One attempt at providing an improved automobile underbody coating is discussed in European Patent Application 0 546,635 Al to DeKeyzer, et al. (EP '635). However, the coating compositions disclosed in EP '635 have much higher than desirable viscosities due to higher than desirable weight percentages of polymer content, which make it difficult, if not impossible for the coating to be spray-applied, even though it was stated therein that they had actually sprayed it. Also, the coating compositions disclosed in EP '635 do not allow road debris, such as dust, dirt, and sand, to effectively embed into the coating surface. Besides that, the underbody coating of '635 incorporates too much polymer, which is the most expensive part of the composition. This high polymer content also hinders the use of additives or other types of polymer.
It is, therefore, an object of the present invention to provide a protective coating composition for an underbody of an automobile which is not based on halogenated materials and which may be uniformly spray- applied to the underbody, is recyclable, is solventless, is resistant to oxygen, ozone, ultraviolet light, abrasion, and high temperatures, has high cohesive strength, and adheres well to the underbody.
It is another object of the present invention to provide a protective coating composition for an underbody of an automobile which, when coated onto an automobile underbody, allows road debris, such as dust, dirt, and sand, to embed into the surface upon impact to provide a further protection to the automobile underbody.
SUMMARY OF THE INVENTION
To achieve the foregoing objects, one embodiment of the present invention is a coating composition which uniformly coats and adheres to the underbody of an automobile and protects the underbody from the environment. The coating composition includes a polymeric composition which, when coated onto an automobile underbody, allows small road debris to embed into the coated composition while traveling to provide further protection to the underbody.
In the preferred embodiment, our coating is sprayable when hot applied and has a gummy consistency which gives certain desirable properties, most notably a self-healing quality. Furthermore, this gummy coating invites the embedding of small road debris, rather than protecting against it. Most prior art coatings are damaged and chipped during bombardment of road debris. The present invention not only receives the small stone chips and dirt that make up the small road debris, but we utilize those stones and dirt to act as a barrier within our coating to substantially reduce any further damage.
One of the main advantages over the prior art is that our coating composition can be disposed of without harming the environment. The prior art PVC coatings give off toxic gases when the car is ultimately burned or the underbody is melted. Needless to say, the automotive industry is looking for new products which are more earth friendly and better performing than old ways. Our invention is such a new product. In the most preferred embodiment, the coating composition has a viscosity of at most about 1000 centipoise at 150°C and includes a styrene-rubber diblock copolymer, a styrene-rubber-styrene triblock copolymer, and a polar-functionalized polymeric material. The rubber portions of the diblock and triblock copolymers may be individually selected from the group consisting of ethylene-butylene, ethylene-propylene, and mixtures thereof.
Other objects, features, and advantages of the present invention will be readily appreciated as the same becomes better understood after reading the subsequent description taken in conjunction with the appendant drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows prior art PVC coating sprayed onto a test panel, before impingement testing;
FIG. 2 shows the same test panel after impingement, illustrating how the coating chips and flakes off;
FIG. 3 shows prior art polyester coating, sprayed onto a test panel, before impingement testing;
FIG. 4 shows that prior art polyester coating on a test panel after the impingement test, showing how the coating is completely worn away down to the metal test panels; FIG. 5 shows our new hot melt polymer coating sprayed onto a test panel, before impingement testing;
FIG. 6 shows our new hot melt polymer coating after the impingement test, illustrating how the road debris has embedded into the coating, without exposing the underlaying metal test panel;
FIG. 7 illustrates the results of a smear test, using a key, and the gummy consistency of the present invention hot melt polyester coating on a test panel;
FIG. 8 shows the uniform spray pattern which can be achieved by the present invention hot melt polymer coating on a test panel;
FIG. 9a shows a corrosion test of the present invention hot melt coating which has been coated onto a test panel to a thickness of between 350-400 micrometers thick scratched down through to the bare metal, illustrating the anti-rust properties;
FIG. 9b shows a similar test, although the polymer coating of the present invention was coated to a thickness of between 600-700 micrometers and also having been scratched down through to the metal test panel.
DESCRIPTION OF THE PREFERRED EMBODIMENT (Si
The present invention provides new coating compositions which adhere to the underbody of an automobile and protect the underbody from the environ ent. One embodiment of the present invention is a hot melt, sprayable polymeric coating composition which is soft and self-healing yet has high cohesive strength such that, when coated onto an automobile underbody and impinged with road debris, the coating composition not only resists chipping when road debris impinges it, road debris (such as fine dirt and light gravel) is likely to embed into the coating composition, providing further protection to the underbody. Like chewing gum on the side of a road, it picks up dust and fine road debris first, after which very little else will stick to it.
One way to measure the debris-embedding quality of the coating composition is by an impingement test with road debris. This test is described more fully hereinbelow. The road debris has an average diameter of about 1-10 micrometers. It should embed into the surface at a level of from about 5% to 40% percent based on the weight of the coated composition.
In a broad concept of our invention, the coating composition preferably includes a triblock copolymer, a diblock copolymer, and a polar- functionalized polymeric material.
This coating composition adheres to the underbody of an automobile, protects the underbody from the environment, and contains a mixture of thermoplastics and other rubbers. The preferred thermoplastics and rubbers include a styrene-rubber diblock copolymer; a styrene-rubber-styrene triblock copolymer; cross-lining polymers; and a polar-functionalized polymeric materials. The criteria for polymer selection includes any polymer as long as it has a low enough viscosity when added to the polar functionalization polymeric materials to be sprayable. Furthermore, selected polymers should be elastomeric in order to receive road debris. Our invention is intended to be "softer" than the prior art, yielding its two-fold main functional advantages of being both resistant to chipping, and receiving road debris to provide an additional protective layer.
The preferred rubber portions of the diblock and triblock copolymers are saturated olefin rubbers individually selected from the group consisting of ethylene-butylene, ethylene-propylene, and mixtures thereof. The rubber portion is the major portion in the copolymers and the polystyrene portion is the minor portion of the copolymers.
Such diblock and triblock copolymers may be prepared by anionic polymerization. U.S. Patent Nos. 3,030,346, 3,231,635, 3,251,905, 3,265,765, 3,281,383, 3,639,521, 4,033,888, and 4,077,893 teach methods for making the above-described block copolymers, which patents are incorporated herein by reference.
Preferably, the molecular weight distribution, i.e., the weight average molecular weight divided by the number average molecular weight, of the copolymers is from about 0.8 to about 1.1, most preferably, about 1.0.
In accordance with the present invention, the preferred properties of the triblock copolymer are that it be a styrene-(ethylene-butylene)-styrene triblock copolymer having a styrene:rubber ratio of from about -9-
25:75 to about 35:65; a tensile strength of from about 5000 to about 7000 psi determined using ASTM method D412 with a tensile tester jaw separation speed of 10 inches per minute; a Shore A hardness of from about 65 to about 85; an elongation of from about 300 to about 600%; a specific gravity of from about 0.85 to about 0.95 grams per cubic centimeter; a solution viscosity of about 400 to about 600 centipoise measured at 25°C using a BROOKFIELD Model D RVT viscometer with a number 21 spindle, and measured on a solution consisting of 20 weight percent copolymer in toluene; and a rubber block having a glass transition temperature of about -42°C.
Although it is helpful to use a triblock copolymer which has been polar-functionalized to aid in adhesion, it is preferred not to employ polar- functionalized copolymers at very high levels. Use of high levels of polar-functionalized copolymers decreases the pot life of the coating composition at elevated temperatures due to occurrence of crosslinking of the polar-functionalized copolymers. It is most preferred to employ polar-functionalized polymeric materials at levels of at most about 5 weight percent of the coating composition.
By way of clarification, it should be stated that all trademarks listed throughout the rest of the specification belong to the companies which are mentioned immediately thereafter.
A triblock copolymer having the above-described preferred properties is available from the Shell Chemical Company, Houston, Texas, as KRATON G 1652. KRATON G 1652 is a styrene-(ethylene-butylene)-styrene triblock copolymer having a styrene:rubber ratio of about 29:71; a tensile strength of about 6300 psi; an elongation of about 500%; a Shore A hardness of about 75; a specific gravity of about 0.91 grams per cubic centimeter; a solution viscosity of about 475 centipoise; and a rubber block having a glass transition temperature of -42°C. The tensile strength is as determined using ASTM method D412 with a tensile tester jaw separation speed of 10 inches per minute, and the solution viscosity is measured on a solution consisting of 20 weight percent copolymer in toluene at 25°C using a BROOKFIELD Model D RVT viscometer with a number 21 spindle.
The preferred properties of the copolymer composition containing a diblock copolymer are that it contain at least about 20 weight percent diblock copolymer, the remainder preferably being triblock copolymer, that it have a styrene:rubber ratio of from about 25:75 to about 35:65; a tensile strength of from about 300 to about 400 psi determined using ASTM method D412 with a tensile tester jaw separation speed of 10 inches per minute; an elongation of from about 150 to about 250%; a specific gravity of from about 0.85 to about 0.95 grams per cubic centimeter; a solution viscosity of about 100 to about 300 centipoise measured on a solution consisting of 25 weight percent copolymer in toluene at 25°C using a BROOKFIELD Model D RVT viscometer with a number 21 spindle; a Shore A hardness of from about 50 to about 70; and a rubber block having a glass transition temperature of about -42°C. As with the diblock copolymers, it is possible to use a mixture of diblock and triblock copolymers which has been polar- functionalized. However, it is preferred not to employ polar-functionalized copolymers at high levels, as discussed above.
A copolymer composition containing a diblock copolymer having the preferred properties discussed above is KRATON G 1726, also available from the Shell Chemical Company. KRATON G 1726 is a blend of about 30 weight percent styrene-(ethylene-butylene) diblock copolymer and about 70 weight percent styrene-(ethylene-butylene)- styrene triblock copolymer and has a styrene/rubber ratio of about 30:70; a tensile strength of about 350 psi; an elongation of about 200%; a Shore A hardness of about 60; a specific gravity of about 0.91 grams per cubic centimeter; a solution viscosity of about 200 centipoise; and a rubber block having a glass transition temperature of -42°C. The tensile strength is as determined using ASTM method D412 with a tensile tester jaw separation speed of 10 inches per minute. The solution viscosity was measured on a solution consisting of 25 weight percent copolymer in toluene at 25°C using a BROOKFIELD Model D RVT viscometer with a number 21 spindle.
The polar-functionalized polymeric material improves the adhesion of the coating composition to the automobile underbody. The adhesion promoting function of the polar-functionalized polymeric material is discussed in U.S. Statutory Invention Registration No. H1022, which statutory invention registration is incorporated herein by reference. Examples of a polar-functionalized polymeric material usable in the coating compositions of the present invention are the anhydride-modified FUSABOND Adhesive Resins, available from E. I. Du Pont de Nemours & Co. , Inc., Wilmington, Delaware. The FUSABOND Adhesive Resins include FUSABOND E, FUSABOND P, and FUSABOND C Adhesive Resins. FUSABOND E Adhesive Resins are polyethylene-based adhesive resins and include products based on LDPE, LLDPE, and HDPE with a range of melt flows. FUSABOND P Adhesive Resins are polypropylene- based adhesive resins and include three types of base polypropylene: homopolymer, impact copolymer, and random copolymer. FUSABOND C Adhesive Resins are ethylene copolymer-based adhesive resins and include products with from 18 to 33 percent ethylene vinyl acetate content and melt indexes of from 2 to 400. FUSABOND may be employed in amounts from about 0 to about 5 weight percent of the coating composition.
Other examples of suitable polar-functionalized polymeric materials are ethylene-vinyl silane and ethylene-vinyl acetate-vinyl silane polymers which are produced by free radical copolymerization of ethylene, vinyltrimethoxysilane, and, optionally, vinyl acetate. Such polymers are described in the article, "Properties of EVS and EVAVS Moisture Crosslinkable Polymers", by Alex M. Henderson, published in Adhesives Age , November 1994, pages 18-24, which article is incorporated herein by reference. Other suitable polar-functionalized polymeric materials are the vinyl-modified butadiene styrene- butadiene block polymers discussed in the article, "New Modified TPE Polymers for Hot Melt Formulations, by David J. Dougherty, published in Adhesives Age , November 1994, pages 29-31, which article is also incorporated herein by reference.
Yet another example of a suitable polar- functionalized polymeric material is a styrene-rubber- styrene triblock copolymer functionalized with groups that render the copolymer more polar. Compounds which will polar-functionalize polymeric materials include acids or anhydrides or derivatives thereof, other carboxy1-containing compounds, sulfonates, alcohols, i ides, acid chlorides, aldehydes, amines, amides, epoxies, isocyanates, and esters. Polar-functionalized polymeric materials containing carboxylic groups reacted onto vinyl aromatic hydrocarbons are described in U.S. Patent No. 4,868,245, which patent is incorporated herein by reference. Polar-functionalized polymeric materials incorporating sulfonate groups are described in U.S.S.N. 198,543, filed May 24, 1988, which application is incorporated herein by reference. U.S. Patent No. 4,578,429, which is incorporated herein by reference, teaches of polymers being functionalized with acids, anhydrides, derivatives of acids or anhydrides, esters, imides, and amides. Preferred functionalizing compounds are unsaturatedmono- and polycarboxylic-containing acids and anhydrides and derivatives of the acids or anhydrides. Examples of such compounds include maleic acid, maleic anhydride, fumaric acid, and fumaric anhydride. The preferred properties of the polar- functionalized triblock copolymer are that it have a styrene:rubber ratio of from about 25:75 to about 35:65; a tensile strength of from about 4000 to about 6000 psi determined using ASTM method D412 with a tensile tester jaw separation speed of 10 inches per minute; an elongation of from about 400 to about 600%; a specific gravity of from about 0.85 to about 0.95 grams per cubic centimeter; a solution viscosity of about 5000 to about 7000 centipoise measured at 25°C using a BROOKFIELD Model D RVT viscometer with a number 21 spindle on a solution consisting of 20 weight percent copolymer in toluene; a Shore A hardness of from about 65 to about 85; a rubber block having a glass transition temperature of about - 42°C, and from about one to about 4 weight percent bound functionality.
A suitable commercially-available polar- functionalized copolymer which has the above-described preferred properties is KRATON FG 1901X, a maleic anhydride-functionalized styrene-(ethylene-butylene)- styrene triblock copolymer, available from the Shell Chemical Company. KRATON FG 1901X has a styrene/rubber ratio of about 28:72; a specific gravity of 0.91 grams per cubic centimeter; a tensile strength of about 5000 psi; an elongation at break of about 500%; a Shore A hardness of about 75; a solution viscosity of about 6000 centipoise measured at 25°C on a solution consisting of 20 weight percent copolymer in toluene; a rubber block having a glass transition temperature of -42°C; and about a two weight percent bound functionality. The elongation at break was determined using a film cast from toluene, ASTM D412, "D" die, and a separation speed of 10 inches per minute.
It is preferred that the coating compositions contain a ratio of one weight part polar-functionalized polymeric material, such as KRATON FG 1901X, to from about two to about three weight parts triblock copolymer, such as KRATON G 1652, and from about three to about five weight parts of the mixture of diblock and triblock copolymers, such as KRATON G 1726. It is desirable that the polar-functionalized polymeric material, such as KRATON FG 190IX, be employed in less than about 5 weight percent of the coating composition. A typical suitable range for the polar-functionalized polymeric material is from about 2 to about 5 weight percent of the coating composition.
Other curing or cross-linking polymers may also play a part in this composition. Possible cross-linking polymers include; Butyl rubber, chlorinater rubber, ethylene-propylene rubber, block polymers, butadiene- acrylonitrile rubber, butadiene styrene rubber, butyl rubber, fluoropolymers, natural rubber, polybutadiene rubber, polychloroprene, polyisobutylene, polyisoprene, polysulfide, polyurethane, reclaimed rubber, silicone rubber, and others.
Although not preferred, thermoplastic rubbers such as styrene-butadiene and/or styrene-isoprene copolymers may be used in place of the styrene-(ethylene- butylene) type and/or styrene-(ethylene-propylene) type diblock and triblock copolymers. If such a substitution is done, it is best if done by substituting less than about ten (10%) percent of the total diblock and triblock copolymers. Exemplary commercial styrene-butadiene copolymers and styrene-isoprene copolymers are EUROPRENE SOL T Thermoplastic Rubbers, available from EniChem Elastomers Ltd, Southampton, United Kingdom. EUROPRENE SOL T Thermoplastic Rubbers are block copolymers of the (S-B)„X type, where S represents the polystyrene block, B represents the polybutadiene or polyisoprene block and X represents the coupling agent. EUROPRENE SOL T Thermoplastic Rubbers 161, 162, 163, 171, 172, 174, 175, and 176 are styrene-butadiene type copolymers where the weight ratio of styrene to butadiene ranges from 30:70 to 55:45. EUROPRENE SOL T 166 is a styrene-butadiene type copolymer. EUROPRENE SOL T 190 is a styrene-isoprene type copolymer having a weight ratio of styrene to isoprene of 15:85.
Preferably, the hot-melt coating compositions of the present invention contain from about 5 to about 25 weight percent polymer which includes any diblock copolymer, triblock copolymer, and polar-functionalized polymeric material. The coating compositions of the present invention which are in the form of water-based emulsions are also preferably from about 5 to about 25 weight percent polymer, based on the dry weight of the coating composition, i.e., the coating composition devoid of water.
It is desirable to include tackifying resins in the coating compositions of the present invention to provide tack to and to lower viscosity of the coating compositions. Preferably, the tackifying resin is a liquid resin (being liquid at room temperature) , such as a liquid aliphatic hydrocarbon resin. Suitable liquid aliphatic hydrocarbon resins include HERCURES C 10 and REGALREZ, both available from the Hercules Chemical Corporation, Wilmington, Delaware, and BEVILITE 621, a rosin ester available from Bergvik Kemi AB, of Sandarne, Sweden. HERCURES C 10 has a viscosity at 50°C of 3500- 4500 Pa sec using a Brookfield viscometer. BEVILITE 621 has a Ring & Ball Softening Point of from about 18 to about 23°C.
The tackifying resin gives the composition body and is typically employed from about 40 to about 70 weight percent of the coating composition, preferably, up to about 4 weight parts of tackifying resin to one weight part polymer which includes diblock copolymers, triblock copolymers, and polar-functionalized polymeric material.
A detackifier or deblocker is also a preferred ingredient in the coating composition to detackify the coating composition, plasticize the rubber phase, and maintain integrity of the coating composition. Typically, at most about 1 weight part detackifier to five parts tackifying resin is desired or from about 5 to about 15 weight percent in the coating composition. An exemplary detackifier is paraffin wax, such as Paraffin 5205 or TOTAL, both available from Ter Hell Paraffin Co. of Hamburg, Germany or PARAFF 52/54 available from the Chemo Li pex Company. Paraffin 5205 has a melting point of 52°C. Specifically, paraffin waxes having a low melting point of about 52°C are particularly well suited when combined in a 70% wax to 30% Fusabond ratio by weight. As paraffin wax is a very good deblocker, we experienced poor adhesion, so Fusabond was added to raise the adhesion to an acceptable level. Paraffin wax seems to be the best diluent, but adding too much causes a loss of elasticity.
Thixotropes are generally a part of the coating compositions of the present invention to prevent the coating compositions from sagging from the coated underbody of the automobile either during application of the composition or when the automobile passes through a paint-curing oven during the manufacturing of the automobile. A thixotrope is typically an agent that swells and disperses in a liquid thixotrope activator to form a stable network of colloidal particles. The network of particles is broken under high shear stresses but reforms when the shear stresses are removed.
Typically, thixotropes are employed from about 0 to about 5 weight percent of the coating composition. Suitable thixotropes include carbon black, aluminum powder, fumed silica, and overbased calcium sulfonate. Suitable fumed silicas include CARBOSIL H 5 available from Cabot Corporation, and AEROSIL 300 available from the Degussa Corporation, Frankfurt, West Germany. Overbased calcium sulfonate is available from the Witco Corporation, and also serves in the coating composition as a plasticizer, a viscosity reducer, and a corrosion inhibitor.
A thixotrope activator, such as water, alcohol, or water- or alcohol-based liquids, is usually employed with the thixotrope. A suitable thixotrope activator is CARBOWAX 8000 available from the Union Carbide Corporation, New York, New York. The thixotrope activator is typically employed in amounts from about 0 to about 1 weight percent of the coating composition.
Antioxidants may also be employed in the coating composition of the present invention to prevent degradation of the polymers and resins during processing and the normal life of the coating composition. Suitable antioxidants include the hindered phenols, IRGANOX 1010 and IRGANOX 1076, both available from the Ciba-Geigy Corporation, Basel, Switzerland.
Fillers, blowing agents, and curing agents may also be used in the coating compositions of the present invention. Fillers, such as calcium carbonate, are preferably added in amounts less than about 10 weight percent of the composition. Exemplary blowing agents include p-toluene sulfonyl semicarbazide, available from Uniroyal, Incorporated, New York, New York, and modified cyclodextrin, available from American Maize Company, Hammond, Indiana. Curing agents for KRATON FG 1901X include overbased calcium sulfonate, available from the Witco Corporation, calcium sulfonate in the presence of water, and the melamine type resin, CYMEL 303, available from American Cyanamid Company, Wayne, New Jersey. Use of the calcium sulfonate in the presence of water is taught in U.S. Patent No. 5,063,251, which patent is incorporated herein by reference. The following table provides general ratios that may be employed of the composition components described hereinabove.
Component % wt Possible types Reason
Polymer 5-25% diblock: KratonG 1726 Wear resistant tribloc :KratonG 1652 Elastomeric Polar functionalized: properties KratonFG 1901X Smearing cross-linkable: EVA: Cariflex TKX 1395 SBS
Deblocker 5-15^ Paraffin Wax Lowers viscosity
Resm 40-60* Liq. aliphatic HC Gives body resin (clear) HERCURES CIO BEVITACK 220
Thixotrope 0-5% Carbonblack-Carbosil Holds particles in Aluminum powder suspension fumed silica
Thixotrope 0-1? water activator alcohol silica:activator 3
Antioxidant 0.5-3-' Helps lifetime
Fillers 0-20% Calcium carbonate Gives body and weight to product
(CaCQj) and reduces cost
Blowing 0-3% P-toluene sulfonyl Helps impact Agent semicarbazide resistance (makes thermoplastic "spongy")
Curing 0-5% Calcium sulfonate If using Kraton Agent 1901X
Emulsifying 0-5% If emulsification agent is needed The coating composition of the present invention may be spray-applied as a hot-melt composition or as a water-based emulsion and exhibits little or no "cob-webbing". "Cob-webbing" is when sprayed material forms strings of material rather than discrete droplets. When "cob-webbing" occurs, the coverage is not as uniform and does not adhere well to the surface. When the coating composition is sprayed in the most desirable fashion, the spray pattern consists of uniform droplets that coalesce when impacted against the underbody surface. A viscosity of between 350 and 400 centipoise was ideal for our spraying conditions with a nozzle pressure of 400kg\cm2. It appears that 1000 centipoise would be the upper limit to achieve sprayability.
The coating compositions of the present invention are sprayable using, for example, a spray nozzle having a diameter of from about 0.015 inch to about 0.031 inch at an angle of from about 25° to about 110°. The spray delivered from such a spray nozzle and angle meets the typical automotive industry production requirements with respect to the amount of coating composition delivered in one or two passes so that a uniform continuous coating is provided on the underbody.
As a hot-melt composition, the composition is solventless and devoid of flammable materials to avoid occurrence of fire or explosion. Flammable materials, as the term is used herein, are those materials which are flammable according to the definition provided in the United States Code of Federal Regulations, Title 49, Part 173, Section 10.5 (49 CFR 173.10.5). Briefly restated, a flammable liquid means any liquid having a flash point below 100°F, where flash point means the minimum temperature at which a liquid gives off vapor within a test vessel in sufficient concentration to form an ignitable mixture with air near the surface of the liquid. Title 49 of the Code of Federal Regulations, provides proper testing conditions for measuring flash point and is incorporated herein by reference. If flammable materials are included in the composition, the coating operation could be done in a non-combustible atmosphere, such as nitrogen, to avoid fires.
Preferably, the hot-meltable coating composition will reduce to a suitable viscosity for hot-melt spray techniques at temperatures of at least about 120°C, more specifically, at temperatures from about 120°C to about 180°C. It is desirable that the hot-meltable coating compositions have a viscosity of at most about 1000 centipoise at 150°C, more preferably at most about 350 centipoise at 150°C. The viscosity of the hot-meltable coating compositions are typically at least 1 centipoise at 150°C, but more typically at least about 100 centipoise at 150°C.
Preparing the hot-meltable coating compositions of the present invention may be done in several ways. One method of preparing the hot-meltable compositions is by preparing two premixes. A first premix may consist of, e.g., part of the tackifying resin, the deblocker or detackifier, the antioxidant, the diblock and triblock copolymers, the polar- functionalized polymeric material, and the thixotrope. The amount of tackifying resin in the first premix may be, for example, from about one-fourth to about one- half the total amount of tackifying resin to be included in the coating composition. The first premix may be prepared by blending the above-mentioned ingredients in a mixer, advantageously, a high-shear mixer, while heating to about 180°C and constantly stirring. The temperature is preferably held at 180°C until all of the polymers are dissolved in the premix.
A second premix may consist of the thixotrope activator and the remainder of the tackifying resin. The second premix may be prepared by merely blending the thixotrope activator and the tackifying resin together. To complete the preparation of the coating composition, the second premix is then admixed into the first premix until a uniform composition is achieved. The coating composition, thus prepared, may then be extruded, pelletized, and dusted with an antiblocking powder, if desired.
To use the hot-meltable coating compositions of the present invention, the coating composition is first loaded into a hot-melt spraying apparatus, such as that described in International Patent Application WO 91/00152, which patent application is incorporated herein by reference. The apparatus is then allowed to heat the coating composition, and the coating composition is then sprayed onto the underbody of an automobile. To form a water-based emulsion of the coating composition of the present invention, the coating composition is dispersed in water with the aid of at least one surface active agent to form an emulsion. The surface active agent is typically used in an amount from about 1 to about 3 weight percent of the coating composition. The solvent is then stripped from the emulsion to form the emulsified coating composition.
An exemplary suitable surface active agent is a nonionic nonylphenol compound, such as IGEPAL CO-430, available from Rhone-Poulenc, Paris, France. The nonionic nonylphenol compound is especially effective when used in combination with an oleic amine soap.
To use the emulsified coating compositions of the present invention, the emulsified coating compositions are loaded into a spraying apparatus and sprayed onto the underbody of an automobile. The sprayed coating tends to be in the form of discrete or agglomerated particles rather than a coherent film. To form a coherent film from the discrete or agglomerated particles, the coating is heated to cause the discrete or agglomerated particles to coalesce to form a uniform film. A suitable way of heating the coated film on the automobile is by passing the automobile through a paint-curing oven, which procedure is typically done during the production of an automobile.
Accordingly, the coating compositions of the present invention are useful for protecting the underbody of an automobile from rust and corrosion and provide a further barrier to the environment. The present coating compositions are not based on halogenated materials, may be spray-applied to the underbody, may be formulated to be recyclable, solventless, resistant to oxygen, ozone, ultraviolet light, abrasion, and high temperatures, to have high cohesive strength, and to adhere well to the underbody.
EXAMPLES
The following examples are illustrative only and should not be construed as limiting the invention which is properly delineated in the appended claims.
The Opel General Motors Europe (GME) Abrasion Resistance Test is used in the following examples, specification GME 60400, to measure the loss of coating in liters per micron caused by the direct impingement of split steel sand on a coated panel. A test panel positioned at a 45° angle relative to horizontal and having a known thickness of the coating composition thereon is subjected to the impingement of two liters of split steel sand, having a diameter of 4 to 5 mm, passing through a 914 cm long vertically-positioned steel guide tube. The impingement is continued until failure, i.e., when a space is seen where the coating is worn off and the panel is exposed. The results are reported in liters per micron at failure. For example, a test panel coated with 400 microns of coating composition and withstanding 50 liters of sand before failure would have a wear factor of 0.125 liters per micron (50 liters/400 microns) . In the following examples, all references to "parts" are intended to mean parts by weight. The "points" which are assigned as the results of the test indicate how many kilograms of material was impinged against the surface before it goes through the coatings.
EXAMPLES
Example 1-Coatinα Composition I
25 parts of HERCURES C 10, 11 parts paraffin 5205, 1 part IRGANOX 1010, 2.5 parts KRATON FG 1901X,
6.2 parts KRATON G 1652, 9.5 parts KRATON G 1726, and
2.3 parts CABOSIL H 5 were blended together as Premix A in a mixing tank by constant stirring and gradual heating to 180°C. The temperature of Premix A was held at 180°C until all of the polymers were dissolved.
0.5 parts of Carbowax 8000 and 42 parts of HERCURES C 10 were blended together until uniform to form Premix B. Premix B was then added to Premix A with continuous stirring until uniform to form Coating Composition I. Coating Composition I was then extruded, pelletized, and dusted with CABOSIL H 5 to prevent blocking. Coating Composition I had a viscosity of 350 centipoise at 150°C as measured on a Brookfield HL viscometer using Spindle #3.
Pelletized Coating Composition I was then charged into a Graco FP 13 hot-melt apparatus, manufactured by Graco Corporation, Farmington Hills, Michigan USA, heated to 150°C, and sprayed to a thickness of 400-600 microns on standard steel panels measuring 20 centimeters long by 10 centimeters wide. The coated panels were then hung vertically in an oven at 150°C for 30 minutes to simulate the automotive paint-curing oven cycle.
In accordance with the present invention, a panel coated with 350 microns of Coating Composition I, was subjected to the Opel GME Abrasion Resistance Test. The panel had a wear factor rating of 0.165 liters per micron. See Figures 5 and 6. In a comparative test, a panel coated with 400 microns of our own prior art GEVESEAL 2511 polyester, a conventional underbody coating available from Geveko Corporation of Goteborg, Sweden had a wear factor rating of 0.16 liters per micron using the Opel GME Abrasion Resistance Test. See Figures 3 and 4. In another comparative test, a panel coated with 400 microns of our own prior art GEVESEAL 2610 polyvinyl chloride, another conventional underbody coating available from Geveko, had a wear factor rating of 0.12 liters per micron. See Figures 1 and 2.
Panels coated with 350 to 400 microns and 600 to 700 microns of Coating Composition I were subjected to ASTM B-117 salt spray corrosion test. No serious corrosion was evident after 1000 hours of testing. See Figures 9(A) and, respectively 9(B).
Another panel coated with 600 microns of Coating Composition I was subjected to a 180° bend on a 32 mm diameter mandrel at -30°C. The coating showed no loss of adhesion upon bending. Flexibility thus is Another panel coated with 600 microns of Coating Composition I was subjected to a 180° bend on a 32 mm diameter mandrel at -30°C. The coating showed no loss of adhesion upon bending. Flexibility thus is sufficient to meet the specification requirements of General Motors Corporation.
Figures 7 and 8, respectively, show the results of a smearing test, and the uniform coating which is achievable by spraying the hot melt composition of the present invention.
Example 2
A suitable coating composition of the present invention was prepared by blending, while heating, 43 parts HERCURES C 10, 18 parts BEVILITE 621, 10 parts Paraffin 5205, 1 part IRGANOX 1010, 4.2 parts KRATON FG 1901X, 15.8 parts EUROPRENE SOL T 166, 2.7 parts CABOSIL H-5, 0.5 parts CARBOWAX 8000, and 4.8 parts OREVAC 9305, a maleic anhydride of an ethylene-vinyl acetate copolymer, available from Elf Autochem. The OREVAC 9305 was added to reduce surface tackiness and improve adhesion. The coating composition, thus prepared, was soft and self-healing.
Example 3
For this example, overbased calcium sulfonate was first dehydrated by heating it in an oven at a temperature of 150-170°C for a period of four hours with occasional stirring. 25 parts of the dehydrated overbased calcium sulfonate, 11 parts Paraffin 5205, 1 part IRGANOX 1010, 2.5 parts KRATON FG 1901X, 6.2 parts KRATON G 1652, 9.5 parts KRATON G 1726, and 2.3 parts CABOSIL H 5 were blended together as Premix A in a mixing tank by constant stirring and gradual heating to 180°C. The temperature of Premix C was held at 180°C until all of the polymers were dissolved.
0.5 parts of Carbowax 8000 and 42 parts of HERCURES C 10 were blended together to form Premix D. Premix D was then added to Premix C with continuous stirring until uniform to form Coating Composition II.
Coating Composition II was coated onto a panel by spray-applying at a temperature of 150°C. The coated panel and a container of water were then placed for 12 hours in an oven heated to 100°C. The surface of the coated panel showed increased toughness and less tack than the panel coated with Composition I, evidence that the KRATON FG 190IX cured in the presence of the calcium sulfonate and water.
Example 4
For this example, overbased calcium sulfonate was first dehydrated by heating it in an oven at a temperature of 150-170°C for a period of four hours with occasional stirring. 27.3 parts of the dehydrated overbased calcium sulfonate, 11 parts Paraffin 5205, 1 part IRGANOX 1010, 2.5 parts KRATON FG 1901X, 6.2 parts KRATON G 1652, and 9.5 parts KRATON G 1726 were blended together in a mixing tank by constant stirring and gradual heating to 180°C to form Premix E. The temperature of Premix E was held at 180°C until all of the polymers were dissolved.
0.5 parts of Carbowax 8000 and 42 parts of HERCURES C 10 were blended together to form Premix F. stirring to form Coating Composition III.
The present invention has been described in an illustrative manner. It is to be understood that the terminology which has been used is intended to be in the nature of words of description rather than of limitation.
Many modifications and variations of the present invention are possible in light of the above teachings. Therefore, within the scope of the appended claims, the present invention may be practiced otherwise than as specifically described.

Claims

WHAT IS CLAIMED IS:
1. A coating composition which adheres to the underbody of an automobile and protects the underbody from the environment, the coating composition comprising: a polymeric composition, which allows road debris to embed into the surface when impacting the surface of the polymeric composition, so that, once coated onto an automobile underbody, small road debris can embed into the polymeric composition to provide further protection to the underbody.
2. The coating composition of claim 1, wherein the coating composition has a viscosity of at most about 1000 centipoise at 150°C.
3. The coating composition of claim 1, wherein the coating composition has a viscosity of at most about 350 centipoise at 150°C.
4. The coating composition of claim 1, wherein the coating composition is a solventless composition which reduces to a viscosity suitable for hot-melt spray techniques at temperatures of at least about 120°C.
5. The coating composition of claim 1, wherein the coating composition is in the form of a water-based emulsion.
6. The coating composition of claim 1, wherein the coating composition contains a polar- functionalized styrene-rubber-styrene triblock copolymer and a copolymer selected from the group consisting of a styrene-butadiene copolymer, a styrene- isoprene copolymer, and mixtures thereof, wherein the rubber portion of the styrene-rubber-styrene triblock copolymer is selected from the group consisting of ethylene-butylene, ethylene-propylene, and mixtures thereof.
7. The coating composition of claim 1, wherein the coating composition contains from about 5 to about 25 weight percent polymer.
8. The coating composition of claim 1, wherein the coating composition contains a styrene- rubber diblock copolymer and a styrene-rubber-styrene triblock copolymer, wherein the rubber portions of the diblock copolymer and the triblock copolymer are individually selected from the group consisting of ethylene-butylene, ethylene-propylene, and mixtures thereof.
9. The coating composition of claim 8, wherein the coating composition further contains a polar-functionalized styrene-rubber-styrene triblock copolymer, wherein the rubber portion is selected from the group consisting of ethylene-butylene, ethylene- propylene, and mixtures thereof.
10. The coating composition of claim 8, wherein the coating composition further contains a tackifying resin.
11. The coating composition of claim 8, wherein the coating composition further contains a deblocker.
12. The coating composition of claim 8, wherein the coating composition further contains a thixotrope.
13. A coating composition which adheres to the underbody of an automobile and protects the underbody from the environment, the coating composition comprising: a styrene-rubber diblock copolymer; a styrene-rubber-styrene triblock copolymer, wherein the rubber portions of the diblock copolymer and the triblock copolymers are individually selected from the group consisting of ethylene-butylene, ethylene-propylene, and mixtures thereof; and a polar-functionalized polymeric material, the coating composition having a viscosity of at most about 1000 centipoise at 150°C.
14. The coating composition of claim 13, wherein the coating composition has a viscosity of at most about 350 centipoise at 150°C.
15. The coating composition of claim 13, wherein the polar-functionalized polymeric material is a functionalized styrene-rubber-styrene copolymer, wherein the rubber portion is selected from the group consisting of ethylene-butylene, ethylene-propylene, and mixtures thereof.
16. The coating composition of claim 13, wherein the coating composition allows road debris to embed into the composition.
17. The coating composition of claim 13, wherein the coating composition is a solventless composition which reduces to a viscosity suitable for hot-melt spray techniques at temperatures of at least about 120°C.
18. The coating composition of claim 13, wherein the coating composition is in the form of a water-based emulsion.
19. The coating composition of claim 13, further comprising a tackifying resin.
20. The coating composition of claim 13, further comprising a deblocker.
21. The coating composition of claim 13, further comprising a thixotrope.
22. The coating composition of claim 13, wherein the coating composition contains from about 5 to about 25 weight percent polymer, the polymer including the styrene-rubber diblock copolymer, the styrene-rubber-styrene triblock copolymer, and the polar-functionalized polymeric material.
23. A coating composition which adheres to the underbody of an automobile and protects the underbody from the environment, the coating composition comprising: a styrene-rubber diblock copolymer; a styrene-rubber-styrene triblock copolymer; a maleic anhydride of a styrene-rubber- styrene triblock copolymer, wherein the rubber portions of the diblock copolymer and the triblock copolymers are individually selected from the group consisting of ethylene-butylene, ethylene-propylene, and mixtures thereof; a tackifying resin; and a thixotrope, wherein the coating composition contains from about 5 to about 25 weight percent polymer, the polymer including the styrene-rubber diblock copolymer, the styrene-rubber-styrene triblock copolymer, and the maleic anhydride, and the coating composition allows road debris to embed into the composition, has a viscosity of at most about 350 centipoise at 150°C, and is solventless.
PCT/US1996/000255 1996-01-02 1996-01-02 Automobile underbody coating composition WO1997024397A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/US1996/000255 WO1997024397A1 (en) 1996-01-02 1996-01-02 Automobile underbody coating composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1996/000255 WO1997024397A1 (en) 1996-01-02 1996-01-02 Automobile underbody coating composition

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3689596A (en) * 1971-04-19 1972-09-05 Dow Chemical Co Impact resistant styrene-maleic anhydride/hydroxylated diene block copolymer compositions
US4355139A (en) * 1980-03-10 1982-10-19 Monsanto Company Compatibilized polymer blends
US4968747A (en) * 1990-03-30 1990-11-06 Arco Chemical Technology, Inc. Compatibilized blends of crystalline propylene polymers and styrenic copolymers
US5061753A (en) * 1989-03-22 1991-10-29 Sumitomo Chemical Company, Ltd. Resin composition
US5349015A (en) * 1989-12-08 1994-09-20 Shell Oil Company Melt blending acid or anhydride-crafted block copolymer pellets with epoxy resin

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3689596A (en) * 1971-04-19 1972-09-05 Dow Chemical Co Impact resistant styrene-maleic anhydride/hydroxylated diene block copolymer compositions
US4355139A (en) * 1980-03-10 1982-10-19 Monsanto Company Compatibilized polymer blends
US5061753A (en) * 1989-03-22 1991-10-29 Sumitomo Chemical Company, Ltd. Resin composition
US5349015A (en) * 1989-12-08 1994-09-20 Shell Oil Company Melt blending acid or anhydride-crafted block copolymer pellets with epoxy resin
US4968747A (en) * 1990-03-30 1990-11-06 Arco Chemical Technology, Inc. Compatibilized blends of crystalline propylene polymers and styrenic copolymers

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