Impact and abrasion resistant coating composition
0 United States Patent 1191 1111 3,875,090  
 Levy Apr. 1, 1975 IMPACT AND ABRASION RESISTANT [56] References Cited COATING COMPOSITION UNITED STATES PATENTS [75] Inventor: Stanley S. Levy, North Caldwell, 2,512,726 6/1950 Penn eta]. 260/19 UA N J 3,293,728 12/1966 Hill 260/22 TN 3,346,524 10/1967 Skreckoski 260/22 TN Asslgneel N L Industries, New York. 3,403,721 10/1968 Robins et a1. 260/22 TN NY. 3,642,936 2 1972 Hodge et a1. 260/827 Filed: y 1974 3,748,294 7/1973 Kershaw et a1&#34;; 26O/S22 TN 1 pp NOI: 472,078 FOREIGN PATENTS 01&#39;! AP LICATION 1,182,884 3/1970 United Kingdom 260/77.5 R Related US. Application Data [63] Continuation-in-part of Ser. No. 363,732, May 24, Primary Examiner-Ronald W. Griffin 1973, abandoned.  
  [57] ABSTRACT [52] Cl 260/22 117/125 117/132 A high impact and abrasion resistant coating composi- 117/132 BS, 117/148, 117/161 KP, 260/22 CB 260 22 S 260 23 P 26 23 TN tlon is described comprising a mixture of a partially 2 6 R v hydrolyzed vinyl chloride-vinyl acetate copolymer, an 60/33&#39;6 l /77&#39;5 alkyd and an isocyanate terminated urethane prepoly- 2 &#39;g g gg mer. The composition is cured at ambient tempera- 1 o earc l tures to form a urethane reaction product.  
 20 Claims, N0 Drawings IMPACT AND ABRASION RESISTANT COATING C()l\IPOSITION BACKGROUND OF THE INVENTION This application is a continuation-in-part of my copending application Ser. No. 363.732. filed May 24. 1973. now abandoned.  
  This invention is concerned with a novel coating composition which can be cured at ambient temperatures to form a durable. adhesive. impact resistant and abrasive resistant coating on metallic. wood and cementitious substrates.  
  In the past. various coatings which are cured under ambient conditions such as alkyd. acrylic. epoxy. urethane and vinyl coatings have been used for the protection of metal surfaces where high durability is required as for example maintenance coatings or for freight moving vehicles. However. these coatings generally fail where coating properties such as high impact and abrasion resistance are required. Modification of these systems to increase crosslinking such as when thermosetting resins such as urea-formaldehyde or melamineformaldehyde are reacted with functional acrylic polymers may sometimes improve abrasion resistance. but reduce flexibility of the coatings. Conversely. abrasion resistance may be poor although the film will have considerable flexibility. In addition. many of these systems require primers or anti-corrosive pigments depending on the particular metal substrate in order to prevent corrosion or require high film thicknesses of as much as 10 mils to maintain resistance to an industrial atmosphere.  
  The vinyl coatings which include polymers and copolymers of ethylene. styrene. acrylic esters and vinyl chloride are extremely inert to chemical environments. However. because they are thermoplastic they cannot be used on surfaces which attain a temperature of l50F or higher. In addition they generally require more than 2 days curing for sufficient release of solvents in order to develop their coating properties.  
  Coal tar epoxy coatings do not usually require primer coatings but must be applied in thick films of about 10 mils to perform satisfactorily. Coating compositions containing alkyd baking enamels or thermosetting acrylics require curing at elevated temperatures after application which renders them costly to the user.  
  The instant invention provides a coating composition which can be rapidly cured at ambient temperatures to form a durable coating on most any surface. The coating has excellent adhesion. abrasion resistance and impact resistance. The composition can be applied as a clear coating or a pigmented coating by the addition of a pigment such as titanium dioxide. In another embodiment of this invention special solvents are added to the coating composition which allows for spraying a film of the composition on to substrate surfaces and which also allows efficient release of air bubbles from the film formed on the substrate surfaces during curing.  
 It is an object of this invention to provide a clear or pigmented. durable. adhesive. impact resistant and abrasion resistant cured coating.  
 It is an even further object of this invention to provide a coating composition which can be applied to substrates by spraying.  
 SUMMARY OF THE INVENTION The instant invention comprises a self-priming poly- \inyl chloride-acetate based polyurethane coating composition which is rapidly cured at ambient temperatures to provide a durable. adhcsi\e..impactresistant and abrasion resistant coating for substrates such as wood. metal and cementitious materials. Curing of the composition is generally complete within about 48 hours. Adhesion to sandblasted steel. cold-rolled steel. magnesium. wood and cementitious substrates is excellent. Impact resistance of these coated substrates as measured by reverse impact tests have shown values of lot) inch-pounds which is unusually high for urethanetype coatings.  
  The coating composition is divided into two components; a functional polymer component and a urethane prepolymer component. The functional polymer component comprises polymeric resins containing pendant hydroxyl groups which are capable of reaction with isocyanate groups. The urethane prepolymer component is an elastomeric isocyanate-terminated urethane prepolymer. The functional polymer component may also contain solvents to aid in mixing the polymeric resins and to adjust the viscosity of the coating composition. Upon mixing the two components a reaction begins between the reactive hydrogen groups of the functional polymer component and the isocyanate groups of the urethane prepolymer. After mixing the components. the so-formed composition is then applied to a substrate as for example by brushing. rolling or dipping. The composition is then cured at ambient temperatures for about 48 hours during which time any solvents which are present are evaporated and a cured polyurethane coating is formed comprising the reaction product of the polymeric resins and urethane prepolymer.  
  The cured coating is durable. adhesive to the substrate. and is both impact and abrasion resistant. In addition to such properties. the coating may also provide corrosion assistance and sound deadening properties to a substrate. such&#39;as the undercarriage of a car or other types of vehicles.  
  The polymeric resins in the functional polymer component comprise a partially hydrolyzed vinyl chloridevinyl acetate copolymer and an alkyd resin. The vinyl chloride-vinyl acetate copolymer has been partially hydrolyzed to convert some of the combined vinyl acetate groups to vinyl alcohol groups.  
  These vinyl alcohol groups are preferably present in an amount of from 2 to 2071 of the weight of the copolymer. For purposes of convenience this copolymer will be hereinafter referred to as the vinyl copolymer.  
  The alkyd resin in the functional polymer component is a saturated or unsaturated alkyd resin containing at least l% by weight of hydroxyl groups ahd having a molecular weight of at least 1000.  
  The functional polymer component may optionally contain a high molecular weight silicone polymer having a viscosity greater than 5,000 centistokes at 25C. The silicone polymer improves the rheology of the coating composition and allows for efficient leveling and bubble suppression of the coating film on the substrate during cu ring. A secondary crosslinking reaction may also occur between the silicone polymer and the urethane prepolymer due to the presence of about 0.5% of free hydroxyl groups in the silicone. This type of crosslinking is believed to contribute to the formation of a slick coating surface which prevents materials from adhering to it. This is advantageous in some areas of coating applications such as in hopper car linings to 3 ease the discharge of the material being freighted. lt is also advantageous where -graffitiresistance is desired. The coating decidedly minimizes the adhesion of pen. ink. crayon markings or spray paint on to its surface.  
  The urethane prepolymer component is an elastomeric isocyanate-terminated urethane prepolymer comprising the reaction product of organic polyisocyanates and polyol esters of ricinoleic acid. The amount of free isocyanate groups in the prepolymer is from about 5 to 30% by weight. Thus. when the two components are mixed the hydroxyl groups of the polymeric resins in the functional polymer component form a urethane reaction product with the isocyanate groups of the prepolymer which is completed on curing.  
  Solvents are preferably added to the functional polymer component to enable efficient application of the coating composition to substrate materials and in maintaining uniform films on the substrate during curing. These solvents are used with the functional polymer component to provide homogeneous mixing of the polymeric resins with the urethane prepolymer. The solvents are also used to adjust the viscosity or density of the composition as required for a particular method of application. Thus airless spraying ofthe composition requires a lower viscosity than conventional spraying which in turn is lower than for brushing or rolling. The basic requirements for the solvent are that it be inert to the functional polymer component. the prepolymer and the cured product and be capable of complete evaporation from the coating composition within about 48 hours.  
  Among these solvents include lower alkyl ketones having up to 8 carbon atoms such as acetone. methyl ethyl ketone. methyLn-butyl-ketone. methyl isobutyl ketone. acetone. methyl amylketone. cyclohexanone and 4-methoxy-4-methyl pentane2-one; aromatic hydro-carbon solvents containing up to 10 carbon atoms such as xylene. toluene. ethyl benzene and pseudocumene; organic esters containing up to 8 carbon atoms such as ethyl acetate. propylacetate. butyl acetate and cellosolve acetate: and mixtures thereof.  
  The coating composition of this invention can also be pigmented by adding a pigment such as titanium dioxide to either the functional polymer component or urethane prepolymer component to provide sufficient hiding. In addition an array of colored coatings can be made by incorporating other pigment additives or tinting agents in the composition.  
  The amount of alkyd used in the functional polymer component is generally from to 8071 of the weight of the vinyl copolymer. If a silicone oil is to be employed it should generally comprise from 2 to 20% by weight of the vinyl copolymer. The amount of solvent for the functional polymer component may vary according to the desired viscosity of the coating composition. However, generally a range of from 1 to 3 parts of solvent by weight for each part of functional polymer component is sufficient for most mechanical applications of the coating to the substrate such as brushing or rolling.  
  Sufficient amounts of urethane prepolymer are used to provide a molar ratio of isocyanate groups in the prepolymer to hydroxyl groups in the polymeric resins of from about 1.0/. to 5.0/1 and preferably from 20/ to 3.5/ for excellent curing and performance properties of the coating.  
  The instant coating composition can be applied to most any substrate by dipping. rolling or brushing to form an adhesive coating.  
  For example. application of the coating to a cementitious material such as porous brick forms a glazed. hard and durable coating. Both ferrous metals such as sand blasted steel or cold rolled steel and non-ferrous metals such as magnesium and aluminum can also be coated using the instant coating composition to form a highly durable. impact and abrasion resistant coating. On hard woods and soft woods the cured coating forms an adhesive. highgloss protective finish.  
  The functional polymer component is prepared by forming a solution of the partially hydrolyzed vinyl acetate-vinyl chloride copolymer in a solvent; adding the alkyd to said solution to form the functional polymer component: and mixing the urethane prepolymer component with the so-formed functional polymer component. The resulting coating composition is then ready for application to substrate surfaces.  
  If the silicone oil is to be included in the functional polymer component it is preferably added together with the alkyd or after the alkyd is added. If a pigment is to be added. a portion of vinyl copolymer is first dissolved in a portion of the solvent. The pigment is then dispersed in this solution under strong agitation until a uniform dispersion is formed as for example to a 5 reading on a Hegman Grind Guage. The remaining vinyl copolymer and solvent is added to the pigment dispersion under strong agitation followed by addition of alkyd and silicone oil. if desired. as described above. Procedures may vary for dispersing the pigment in the polymer-solvent combination. as well known to those skilled in the coating art.  
  The above procedure is only given by way of example. In some cases it may be possible to add all pigment to the solventvinyl copolymer solution depending on the amount of pigment. type of solvent and dispersing equipment.  
  After forming the coating composition it is applied to substrate surfaces in any manner known to the art as for example. brushing. rolling. dipping or blading on the substrate surfaces. After about 48 hours of curing at ambient temperatures all solvents are released and the reaction between the hydroxyl groups of the polymeric resins and the isocyanate groups of the urethane prepolymer is completed.  
  The curing can of course be accelerated by employing high temperatures or by employing metal catalyst salts such as tin octoate or amine catalysts.  
  In another embodiment of this invention. a sprayable coating composition. is produced by the addition of pseudocumene and the silicone oil. The pseudocumene must be included as a solvent for the functional polymer along with other solvents such as the ketone and organic esters in an amount of from about 15 to 55% by weight of total solvents. The total weight of solvents should be from L5 to 3.0 times the weight of functional polymer component. The silicone oil must also be added to the functional polymer component as described above in an amount from 2% to 20% by weight of the vinyl copolymer. The coating composition can then easily be applied to substrates by spraying such as by conventional. airless or electrostatic spraying. The pseudocumene and silicone oil enhance sprayability and allow efficient bubble release from the sprayed film. The organic esters and ketones help hold the sprayed film open so as to allow uniform solvent release thereby preventing film discontinuity or cracking during curing. This embodiment of the instant coating composition also achieves &#34;Good wrap around is a term which applies to the ability of a sprayed film to lap around curved or irregular surfaces so that the position of the spray nozzle need not be constantly moved to insure covering of these surfaces.  
  In still another embodiment of this invention. a storable coating composition is provided having excellent shelf-life wherein the functional polymer component and urethane prepolymer component are premixed and stored together indefinitely without any reaction between the components. This is accomplished by reacting blocking groups with the isocyanate groups of the urethane prepolymer. The resulting blockedisocyanate groups are thus rendered incapable of reacting with the hydroxyl groups of the polymeric resins. The composition can be packaged and stored indefinitely until ready for application. The blocking groups are removed by heating the composition form about 350C to 335C after coating the substrate whereafter the free&#34; isocyanate groups begin to react with the hydroxyls of the polymeric resins. Among such blocking groups include phenol. lower alkyl ketosimes having up to 6 carbon atoms such as 3-butanone oxime and lower alkyl aldoximes having up to 6 carbon atoms such as butyraldoxime.  
 DESCRIPTION OF THE PREFERRED EMBODIMENTS The partially hydrolyzed vinyl-chloride vinyl acetate copolymers ofthis invention are those which have a degree of hydrolysis such that the resin contains by weight from 70 to 96.5% combined vinyl chloride. from about 3 to about combined vinyl alcohol and from 1.5 to about combined vinyl acetate. These copoly mers and their preparation are described in more detail in US. Pat. No. 3.513.736 issued June 37. 1950. The preferred partially hydrolyzed vinyl chloride-vinyl acetate copolymer is one having 3 percent by weight of combined vinyl acetate and about 6% by weight of combined vinyl alcohol. Useful molecular weights for the vinyl copolymer range from 5.000 to 35.000.  
  By virtue ofthe hydroxyl functionality ofthe vinyl alcohol groups of the copolymer. a reaction occurs between the hydroxyl groups and some of the isocyanate groups of the urethane prepolymer to form urethane bonds.  
  The preferred alkyds ofthe invention are oil-free and have an average equivalent weight of at least l000 and preferably between 1000 and 1500. The alkyd must also contain at least one percent by weight of hydroxyl groups to serve as a reactant with the urethane prepolymer. Low water content and low acid number of the alkyd is also preferred. Particularly preferred is a linear saturated oil-free alkyd having an average equivalent weight of l300 and which contains about from 1 to 3 percent of hydroxyl groups by weight.  
  It is also preferred to add a plasticizer to the alkyd which will enhance the flexibility of the alkyd and in turn the final cured coating of this invention. The preferred plasticizer is a copolymer of butyl acrylate and vinyl isobutyl ether contained as a 50% solution in ethyl acetate. The amount of plasticizer required is generally about 0.3% of the weight of the alkyd. The hydroxyl groups of the alkyd reacts with some of the isocyanate groups of the urethane prepolymer to form additional urethane linkages.  
  The high molecular weight silicone preferred in this invention is a 100% dimethyl silicone polymer having a viscosity of 60.000 Ctks. at 35C. The invention is not limited to this silicone polymer and any silicone polymer can be used which has a viscosity of from 5000 Ctks. to l00.000 Ctks. at room temperature and preferably from 60.000 to 80.000 Ctks. at 35C. In addition siliconized resins such as siliconized alkyds or acrylics having the desired viscosity may also be employed as a silicone polymer for the invention.  
  lt is also preferred to use a silicone polymer having available at least 0.5% of hydroxyl groups by weight to serve as a further reactive material with the urethane prepolymer.  
  The urethane prepolymer component of this invention comprises an isocyanate terminated urethane prepolymer made by reacting an organic polyisocyanate and a polyol ester of ricinoleic acid.  
  By organic polyisocyanate is meant organic com pounds containing two or more isocyanate (NCO) groups. This definition also includes polymeric organic polyisocyanates which are polyisocyanates of organic polymers. such as polymeric diphenyl methane diisocyanate and toluene diisocyanate.  
  By polyol ester is meant ricinoleic acid-esters prepared by reacting ricinoleic acid with alcohols having at least two hydroxyl groups. The esterification may be complete or partial; that is the polyol hydroxyls may have all reacted wtih ricinoleic acid such as in the case of castor oil. the triglyceryl ester of ricinoleic acid or propylene glycol diricinoleate. or a fraction of the polyol hydroxyls may have reacted. such as in the case of propylene glycol mono ricinoleate or ethylene glycol mono ricinoleate. Mixtures of the ricinoleate esters may also be employed.  
  Suitable polyisocyanates include toluene diisocyanate, hexamethylene diisocyanate. isophorone diisocyanate. diphenyl methane 4.4 diisocyanate. and trimethyl hexamethylene diisocyanate and mixtures thereof. Other isocyanates. either alone or in admixture. may also be used to vary the durability. nonyellowing and physicochemical properties of the coating.  
  The urethane prepolymer should contain from about 5 to 30% free isoc &#34;anate groups by weight and preferably from 15 to 35% by weight. If less than 5% NCO groups are present the cured film will be too inflexible. lf greater than about 30% NCO groups are present, these excess NCO groups may react with moisture and destroy the coating film properties. The solvents or solvent mixtures which are employed in this invention can be used in varying amounts depending on the viscosity desired. When using aromatic solvents it is preferred to combine them with ketonic solvents or organic esters in order to efficiently dissolve the vinyl copolymer.  
  The amount of alkyd preferred in the functional polymer component should generally be from about 30 to by weight of the vinyl copolymer and preferably about 50%. If below about 30% is employed. the flexibility of the cured film may be diminished. lf greater than about 80% is used. the coating generally may not cure to a hard and durable finish.  
  The urethane prepolymer should be present in the composition in sufficient amounts to provide a molar NCO to OH ratio of from about 10/ to 50/ and preferably from about 2.0/ to 3.5 At less than about 1.0, ratio there will not be complete reaction with the polymeric resins. At ratios greater than about 5.0/,. no real advantage in coating properties is gained. There may even be a detrimental effect on film properties due to side reactions which may occur between the excess isoeyanate groups and other functional groups in the polymeric resins.  
  If a silicone oil is to be employed in the functional polymer component it should comprise from about 2 to 21))? of the weight of the vinyl copolymer and preferably from o to Amounts of silicone oil less than about I&#34;? render it ineffective in suppressing bubble formation in the coated film. Amounts greater than about 204&#39; may diminish hardness of the coating.  
  The cured coating on the substrate is the reaction product of the polymeric resins containing hydroxyl functionality and the urethane prepolymer. Where the composition also contains the silicone oil it remains in the cured coating. Any hydroxyl groups contained in the silicone oil also react with the isoeyanate groups of the urethane prepolymer.  
  In order to more fully describe the instant invention the following examples are given:  
 EXAMPLE 1 This example illustrates the preparation of a coating composition wherein the functional polymer component comprises 1-161 vinyl copolymer. 7% linear satunated urethane prepolymer (Yorite o2oM-l. N L 1ndustries. lne. made by reacting castor oil and a polyol ester of ricinoleic acid with organic polyisocyanates. to provide 217/ by weight of free isocyanate groups. The mixture was then stirred until a homogeneous composition was achieved. The resulting composition was then hrushed onto sand blasted steel panels and allowed to cure for about 48 hours. The coated film after curing contained the reaction product of the vinyl copolymer and linear saturated alkyd with the urethane prepolymer component. The coating contained 28.3% ofcom&#39; bined vinyl copolymer. 14% of combined linear saturated polyester. 22.7% of combined urethane prepolymer and 35.292 of pigment by weight. To compare the instant coating with other pigmented coatings known in the art for their durability properties. four sand-blasted steel panels were respectively coated with a paint formulation containing a non-hydrolyzed vinyl chloridevinyl acetate copolymer. (Vinyl). a vinyl urethane coating made by reacting a hydrolyzed vinyl chloridevinyl acetate copolymer with a polyol diisocyanate. (Vinyl Urethane). a polyol urethane coating. (Polyol Urethane). and a polyamide catalyzed epoxy coating. (Epoxy). None of the above pigmented coatings contained the alkyd or urethane prepolymer of this invention. Reverse Impact Tests after one week aging. Abrasion Falling Sand. Slip. Rockwell Hardness and Gardner Adhesion Tests were performed on all coatings.  
 Table 1 below summarizes the results.  
 rated polyester. 61.571 solvents and 17.5% pigment by weight. The urethane prepolymer component contained 21% by weight of free NCO groups and the molar ratio of NCO in the urethane prepolymer to OH in the polymeric resins of the functional polymer component was about 25/ A partially hydrolyzed vinyl acetate-vinyl chloride copolymcr containing approximately 91% by weight of combined vinyl chloride. 3% by weight of combined vinyl acetate and 671 by weight of combined vinyl alcohol. 12.5 parts. was dissolved in 6.1 parts of methyl isobutyl ketone. To this solution was dispersed 15.5 parts of titanium dioxide pigment under strong agitation until a sample of this dispersion showed a No. 5 reading on a Hegman Grind Guage. To this dispersion was added a solution of 1 1.25 parts of additional vinyl copolymer in 14.3 parts of methyl isobutyl ketone under strong agitation. To this dispersion was added 6.2 parts of a linear saturated oil-free alkyd having an equivalent weight of 1300 and containing about 1 to 1.5% of hydroxyl groups by weight. Xylene. 20.9 parts and cellosolve acetate. 135 parts were also added to the dispersion to form the functional polymer component. To this component was added 10.1 parts of an isocyanate termi- As the table shows the instant coating was superior to all other coatings in the aged Reverse Impact Test except the Vinyl coating which showed equal performance. Resistance to abrasion as shown in the results of the Abrasion Falling Sand Test and Slip test reveals that the instant composition is superior to all other coatings tested. In hardness and adhesion, the instant composition shows equal or better performance than the other coatings.  
  The coating composition was applied to a cementitious substrate. namely a porous brick substrate. A glazed-tile coating was formed after curing which had a hardness similar to that coated in sand-blasted steel in Example 1. The brick was immersed in a tank full of fresh water. After an extended period of immersion the coating was essentially uneffected. and had excellent adhesion and abrasion resistance.  
 EXAMPLE 2 This example illustrates the cure properties of the instant composition. A clear coating composition was prepared using the procedure of Example 1 except without addition of pigment. The vinyl copolymer of 1 Example 1. 12.5 parts was dissolved in 20.4 parts of methyl isobutyl ketone followed by the addition of linear alkyd to this solution. The remainder of the procedure of Example l was used to form the clear coating composition. (Example l clear). This composition was then coated on a sand-blasted steel panel. For comparison a clear epoxy coating was applied to a steel panel (Epoxy Clear). The pigmented coating of Example 1 and the pigmented epoxy coating of Example 1 (Epoxy) were also coated on sand-blasted steel panels. Sward Hardness measurements were taken of the four compositions after curing for 1, 3, 7. 14 and days. The clear coating composition of this example after curing contained 43% of combined vinyl polymer, 22% of combined linear saturated alkyd and of combined urethane prepolymer.  
 Table 2 below summarizes the cure properties of theisobutyl ether in ethyl acetate was used with the alkyd. In all cases the amount of al-kyd was 509? of the weight ofthe vinyl copolymer and the ratio of NCO in the urethane prepolymer to total OH in the vinyl copolymer and the alkyd was about 3.1/  
  The compositions were prepared by dissolving about 10% of the vinyl copolymer in a portion of the solvents (about 20% of total solvents by weight). To this solution was added all of the pigment under high shear until the pigment was completely dispersed. The remaining vinyl copolymer was then added together with the remaining solvents. Next the linear saturated alkyd containing the plasticizer was added to form the functional polymer component. Finally, the urethane prepolymer was added to form the coating composition. Table 3 summarizes the types and amounts of all items in the coatings. composition.  
 TABLE 3 Example 3 Example 4 Example 5 Item lbs. Gals. lbs. Gals. lbs. Gals.  
 1. Vinyl Copolymcr 100.0 8.64 100.0 8.64 100.0 8.64 2. TiO Pigment (Rutile) 125.0 2.93 125.0 2.93 125.0 2.93 3. Gellant (Bcntone 5.0 0.59  
  38. NL Industries, Inc.) 4. Alkyd 50.0 5.04 50.0 5.04 50.0 0.59 5. Plasticizer 1.2 0.16 1.2 0.16 1.2 0.16 6 Urethane Prepolymer 103.3 11.00 107.3 11.00 107.3 11.00 7. Methyl lsobutyl Ketone 126.0 18.88 126.1 18.88 8. Methyl Ethyl Ketone 145.7 21.71 42.7 6.36 42.7 6.36 9. Cellosolve Acetate 145.7 17.99 42.7 5.27 100.3 11.15 10. Toluene 36.4 5.04 94.3 13.06 94.4 13.06 1 l. Butyl Acetate 36.4 4.97 10.7 1.46 10.7 1.46 12. 4-Methoxy-4-Methyl Pentane-Z-Onc 47.6 6.33 13. High Flash Naphtha 189.3 26.22 189.3 26.22 189.3 26.22 TOTAL 933. 103.70 936. 105.35 952.0 101.04  
  TABLE 2 All compositions were brushed on steel panels and allowed to cure for 48 hours. The cured coatings all SWARD HARDNESS had similar properties to the pigmented coating of Ex- Example 1 Epoxy Example 1 Epoxy am 1e 1 Time Clear Clear Pigmented Pigmented p 1 day 16 2x 22 12 EXAMPLE 6 3 days 40 50 26 7days 60 44 50 In this example, a pigmented coating composrtion 14 days 60 44 50 4 c 30 days 60 44 43 48 5 was prepared containing 7/: of a silicone 011 based on As the example shows, the instant compositions after approximately 3 days curing time formed a hard and durable coating film far superior than the Epoxy coatingsl In addition the hardness of the film is maintained at high levels over one month of curing.  
  The clear coating of this example (Example 1 clear) was applied to a wood surface and cured. A high-gloss, clear protective finish was formed which had excellent abrasion resistance, scuff resistance and adhesion. A Sward Hardness of 60 was attained after 1 week aging.  
 EXAMPLES 35 the weight of vinyl copolymer.  
  The procedure of Example 1 was followed except 0.9 parts of a dimethyl silicone oil having a viscosity of 60,000 Ctks. at 25C was added to the dispersion along with the linear saturated alkyd.  
  The formed coating was then brushed onto a magnesium metal surface and allowed to cure. The silicone oil imparted excellent bubble-releasing properties to the coated film during curing. After curing, impact and abrasion resistance of the coating were tested and found to be comparable to the pigmented coating of Example 1. The cured coating was adhesive, uniform, hard and resistant to scarring and chipping after being subjected to contact with a high velocity object.  
 EXAMPLE 7 This example illustrates the preparation of a clear coating composition comprising the vinyl copolymer and linear saturated alkyd of Example 1 the silicone oil of Example 6. and solvent mixtures. The urethane prepolymer of Example 1 was added after combining the above materials to form the coating composition.  
  The amount of linear saturated alkyd used was 80% by weight of the vinyl copolymer; the amount of sili cone oil was 20% of the vinyl copolymer; and the ratio of NCO in the urethane prepolymer to total OH in the vinyl copolymer, alkyd and silicone was about 110/ The coating composition was prepared by adding the vinyl copolymer under agitation to approximately 70% of the total solvents to form a solution. Then the re-&#39; maining solvents were added to this solution followed by the linear saturated alkyd and silicone oil. The urethane prepolymer was then added using moderate agitation.  
 The coating composition is given below:  
 Item Parts by Weight l l. Vinyl Copolymer 50 2 Linear Saturated Alkyd 40 3. Silicone Oil 4. Urethane-Prepolymer 5. Xylene 72.4 6. Methyl lsobutyl Ketone l(l-l.7 7. Pseudocumene 29.9 8. Cellosolve Acetate 31.8 9. 4-Methoxy-4-Methyl Pentane-l-One 511 The coating composition was applied to a cold-rolled steel substrate and allowed to cure at room temperature for 48 hours. After 1 week of aging the impact resistance of the coating as measured by Reverse Impact Test was 160 in-lbs. Abrasion Falling Sand measurements after 1 week was 35 liter/mil; and after 5 weeks it increased to 49 liter/mil.  
 EXAMPLE 8 This example illustrates the preparation of a coating composition wherein the alkyd comprises of the vinyl copolymer and the silicone oil comprises 6% of the vinyl copolymer; and wherein the rate of NCO in the urethane polymer to OH in the functional polymercomponent is about 4.8/,.  
  Following the procedure of Example 7, a coating was prepared having the following composition:  
 Parts by Weight Item  1. Vinyl Copolymer 75 2. Linear Saturated Alkyd 20 3. Silicone Oil 5 4. Urethane-Piepolymer l l0 5. Xylene 72.4 6. Methyl lsobutyl Ketone 166.4 7. -l Methoxy-4-Methyl Pentane-2-One 5.6  
  The composition was brushed onto cold rolled steel panels and cured for 48 hrs. After 1 week aging, lmpact Resistance was 160 in-lbsl as measured by the Reverse lmpact Test; Abrasion resistance was 56 L./mil as measured by the Falling Sand Abrasion Test.  
 EXAMPLE 9 The results of impact and abrasion resistance after curing was similar to the coating of Example 1.  
 EXAMPLES l0-ll These examples illustrate the formation of a storable coating composition in which the urethane prepolymer contains aliphatic oxime-blocked isocyanate groups.  
  Exactly 88 g. ofa 2-butanone oxime was added with stirring at ambient temperature to 200 g. of the urethane prepolymer described in Example 1. This amount of oxime constituted a 1% molar excess with respect to the isocyanate groups of the prepolymer. After the addition. the oxime blocked urethane prepolymer was cooled and 73.7 g. of it was added to a functional polymer component comprising 64 g. of vinyl copolymer and 32 g. of linear alkyd dissolved in a mixture of methyl amyl ketone and cellosolve acetate. A homogeneous composition resulted which was stored in a metal container. After 2 months storage, there was no indication of any reaction between the components. The composition was then applied to a cold-rolled steel substrate, and heated to a temperature of about 275F for 15 minutes to drive off the oxime blocking group. The cured coating had similar abrasion and impact resistance to the clear coating of Example 2.  
  In a similar experiment, 88 g. of butyraldoxime was substituted for the Z-butanone oxime described above, to prepare another oxime blocked urethane prepolymer. Another coating composition was prepared, stored for 2 months, and coated on a sandblasted steel substrate. After removal of the oxime blocking group by heating, the cured coating was identical in abrasion and impact resistance to the clear coating of Example 2 and the pigmented coating ofExammple l.  
 EXAMPLE 12 This example illustrates the preparation of a sprayable composition of the instant invention wherein pseudocumene, a silicone oil and oxygenated solvents are employed in forming the functional polymer component.  
  The vinyl copolymer. linear saturated alkyd and urethane polymer used herein is described in Example 1. The silicone oil is described in Example 6.  
 Following the procedure of Examples 3-6 a pigmented coating composition was formed having the following composition:  
 Parts by. Weight Item  1. Vinyl copolymer 12.5 2. Alkyd 6.2 3. Silicone Oil 0.9 4. Pigment (TiO l5.5 5. Urethane Prepolymer 10.] 6. Pseudocumenc 20.9 7. Methyl lsobutyl Ketonc 20.4 8. Cellosolve Acetate l3,5  
 ness. abrasion resistance and impact resistance (see Examples l and 2).  
 &#39; EXAMPLE 13 A coating composition was prepared using the proce-&#39; dure of Example 1 except that 10.6 parts of a urethane prepolymer prepared as follows was employed: 18.9 parts of castor oil reacted with 76.1 parts of toluene diisocyanate and extended with&#39;38.3 parts of polypropylene glycol (m. w. 420) to provide by weight of free isocyanate groups. The resulting coating composition was applied to steel panels and after air drying was tested for reverse impact after 3 days of aging. The results indicated 160 in-lbs.  
 EXAMPLE 14 EXAM PLE 15 A coating composition was prepared using the procedure of Example 1 except that 13.1 parts of a urethane prepolymer prepared as follows was employed:  
 10.5 parts of a mixed ester of ricinoleic acid (Polycin-5l, N L Industries. Inc.) reacted with 75 parts of polymeric polymethylene polyphenyl diisocyanate and extended with 21.3 parts of polypropylene glycol (m. w. 420) to provide 16.2% by weight of free isocyanate groups.  
  The resulting coating composition was applied to steel panels and after air drying was tested for reverse impact after 3 days of aging. The results indicated 160 in-lbs.  
 I claim:  
  1. A curable coating composition comprising a mixture of:  
 a. a partially hydrolyzed vinyl chloride-vinyl acetate co-polymer;  
 b. an alkyd containing at least 1% hydroxyl groups by weight; and  
 c. a urethane prepolymer terminated with free isocyanate groups comprising the reaction product of an organic poly-isocyanate and a polyol ester of ricinoleic acid.  
 2. The coating composition of claim 1 which further comprises a silicone oil having a viscosity of at least 5000 ctks. at C.  
 3. The coating composition of claim 1 which further comprises a solvent.  
  4. The coating composition of claim 1 wherein said composition further comprises a pigment.  
  5. The coating composition of claim 1 wherein said isocyanate groups are blocked with a blocking agent selected from the group consisting of phenol, lower alkyl ketoximes having up to 6 carbon atoms and lower alkyl aldoximes having up to 6 carbon atoms.  
  14 6. A c&#39;urablecoating composition comprising a mixtureof: H  
  aua partially hydrolyzed f jin&#39;yl chloride-vinyl acetate copolymer containing from aboutl&#39;to about 20% by weight of combined alcoholhand from 1.5 to 25% by weight of combined&#39;vinyl acetate; M  
 b. an alkyd containing at least 1% hydroxyl groups by weight and having a molecular weight of at least 1000;  
 c. a solvent; and y I &#39;d. a urethane prepolymer terminated with from 5% to 30% by weight of isocyanate groups: said prepolymer comprising the reaction product of an organic polyisocyanate and a polyol ester of ricinoleic acid; wherein the ratio of NCO in said urethane prepolymer to total OH in said copolymer and alkyd is from. 1.0/1 to 5.0/1.  
  7. The coating composition of claim 6 which further comprises a silicone oil having a viscosity of at least 5000 ctks. at 25C.  
  8. The coating composition of claim 6 wherein said alkyd further comprises a plasticizer.  
  9. The coating composition of claim 6 which further comprises a pigment.  
  10. The coating composition of claim 6 wherein the amount of alkyd is from 30 to of the weight of said vinyl copolymer.  
  11. The coating composition of claim 6 wherein said solvent is selected from the group consisting of lower alkyl ketones having up to 8 carbon atoms, aromatic hydrocarbons having up to 10 carbon atoms. organic esters having up to 8 carbon atoms and mixtures thereof.  
  12. The coating composition of claim 6 wherein said isocyanate groups contain a blocking agent selected from the group consisting of phenol, alkyl ketoximes having up to 6 carbon atoms and alkyl aldoximes having up to 6 carbon atoms.  
  13. A curable coating composition comprising a mixture of:  
 a. a partially hydrolyzed vinyl chloride-vinyl acetate copolymer containing about 6% of combined vinyl alcohol and about 3% of combined vinyl acetate by weight.  
 b. A linear saturated oil-free alkyd containing from about 1 to 2% hydroxyl groups by weight and having a molecular weight of about 1300; the amount of said alkyd being about 50% by weight of said vinyl copolymer;  
 c. a solvent selected from the group consisting of lower alkyl ketones having from 3 to 8 carbon atoms, aromatic hydrocarbons having up to 10 carbon atoms, organic esters having up to 8 carbon atoms and mixtures thereof; and  
 d. a urethane prepolymer terminated with about from 5 to 30% of NCO groups by weight; said prepolymer being the reaction product of an organic polyisocyanate and a polyol ester of ricinoleic acid; wherein the ratio of NCO in said urethane prepolymer to total OH in said vinyl copolymer and polyester is from 1.0/1 to 5.0/1.  
  14. The coating composition of claim 13 which further comprises from 2 to 20% of a dimethyl silicone oil based on the weight of said vinyl copolymer; said 011 having a viscosity of about 60.000 ctks. at 25C.  
  15. The coating composition of claim 13 which further comprises a titanium dioxide pigment.  
  1 5 l6 16. The coating composition ofclaim 13 wherein said mixture of; solvent comprises from 15 to 55% of pseudocumene. a. a partially hydrolyzed vinyl chloride-vinyl acetate 17. The coating composition of claim 13 wherein said copolymer; isocyanate groups are blocked with a blocking agent b. an alkyd containing at least 1% by weight of hyselected from the group consisting of 2 butanoneox- 5 droxyl groups and having a molecular weight of at ime and butyraldoxime. least I000;  
 18. A substrate coated with the reaction product of: c. a silicone oil having a viscosity of at least 5000 a. a partially hydrolyzed vinyl chloride-vinyl acetate ctks. at 25C;  
  copolymer and an alkyd; said alkyd containing at d. a solvent containing from 15% to 55% by weight least 1% hydroxyl groups by weight; and of pseudocumene; and b. a urethane prepolymer terminated with isocyanate e. a urethane prepolymer terminated with isocyanate groups; said prepolymer comprising the reaction groups; said prepolymer comprising the reaction product of an organic polyisocyanate and a polyol product of an organic polyisocyanate and a polyol ester of ricinoleic acid. ester of ricinoleic acid; wherein the molar ratio of 19. The substrate of claim 18 wherein said reaction NCO in said urethane prepolymer to total OH in product further comprises a silicone oil having a viscossaid copolymer, alkyd and silicone oil is from 1.0/1 ity of at least 5000 ctks. at C. to 5.0/1.  
 20. A sprayable coating composition comprising a