Патент USA US2411590код для вставки
Patented Nov. 28, 1946 _ 2,411,590 'UNITED STATES PATENT OFFICE 2,411,500 _ vnvrr. aesnz ooarma com'osmos George M. Powell. 8rd, South Charlesion, W. Va” ‘ arbido and Carbon Chemicals Cor nation, a corporation of New York assignortoc No Drawing. Appliestion July 3, 1848, Serial No. 498,42‘! a claims.- (Cl. 148-“) 1 . compositions activity on h 2 now Patent No. 2,848,097, March 14, 1944. How ever, vegetable oils and alkyd resins may be pres ent in the coating compositions of this invention. This invention relates to vinyl resin coating ving a controlled and limited re . In addition to improving the ‘ Vinyl resins formed by the copolymerization of co to water and solvents of coatings containing the vinyl halide polymers or copolymers modi?ed with the alpha. beta-oleiinic carboxylic acids, the urea formaldehyde and melamine-formaldehyde resins vinyl compounds with alpha, beta-oleiinic car boxylic acids are known. Those resins which contain a relatively large amount of the copoly merized acid are soluble in dilute alkalies and in act as heat stabilizers for the vinyl halide resins many common organic solvents. It has hereto tore been proposed to insolubilize these resins by 10 in a manner set forth in the above-identi?ed ap plication of Powell and McKnight. An important feature of the present inven esterii'ying them with polyhydric alcohols, such as glycerine and polyvinyl alcohol. Such alkyd type condensation products have insumcient re tion is that the amount of the heat-reactive aminoplasts employed may becontrolled so as According to this invention, copolymers of vinyl 15 to improve the softening point and solvent re sistance to water for many purposes. sistance of the vinyl resin coatings in accordance with speci?c requirements, without seriously de creasing the ?exibility, toughness, and chemical halides, vinyl esters of lower fatty acids, and alpha, beta-ole?nic carboxylic acids, as well as copolymers of vinyl halides with alpha, beta resistance of the resins. Films of the urea-for ole?nic carboxylic acids, which are soluble in a number of common organic solvents, are rendered 20 maldehyde and melamine-formaldehyde resins alone, usually tend to- be brittle, because of the more resistant to solvents by an essentially new extensive three dimensional polymerization or type of treatment. This treatment involves ap condensation involved in the thermosetting re plying such copolymers admixed with alcohol action. On the other hand, the vinyl resins are soluble, heat-reactive aminoplasts, such as urea tormaldehyde or melamine-formaldehyde resins, 25 believed to have essentially one and two dimen sional molecular structures, which may account to a surface to be coated, and then baking the for their ?exibility. However, the three dimen coating. As a result of the' heat treatment, a sional aminoplasts in minor amounts, do not water-resistant coating is obtained which is either insoluble in the original solvents-for the copoly mer resins, or which has much enhanced resist seriously decrease the ?exibility of the vinyl resins 30 and eilect the speci?c improvements mentioned ance to these solvents. In addition, the heat treated coating has a higher softening point than - coatings formed of the original copolymers. Y above. ' ' _ In more detail, the types ‘of vinyl resins to which this invention is applicable are those formed by the copolymerization of vinyl halides, The presence of the combined-,carboxylic acid in the copolymers plays an important part in the 35 such as vinyl chloride or vinyl bromide, with insolubilization and the improvement in waterf; resistance which occurs, slnceoomparative tests have established that these phenomena are not observed when vinyl halide polymers or copoly aliphatic, alpha, beta-ole?nic carboxylic acids, boxylic acids combined in the polymer, are heat The copolymerization may be carried out in the or by the copolymerization of vinyl halides, vinyl esters of lower fatty acids, such as acetic, pro pionic and butyric acids. and the aliphatic, alpha, , mers ofvinyl halides with vinyl'fatty acid esters, 40 beta-ole?nic carboxylic acids. In this latter in stance, three component copolymers are formed. which do not contain alpha, beta-ole?nic car treated with the heat-reactive urea-formaldehyde or melamine-formaldehyde resins. Furthermore, absence of any solvent or diluent, or the mon omers may be dissolved in solvents or emulsi?ed water prior to polymerization. The tempera the urea-formaldehyde and melamine-formalde 45 in ture of polymerization may be between 30° and hyde resins are slightly more compatible with 80° 0., and oxygen-yielding catalysts, such as the copolymers containing combined alpha, beta hydrogen peroxide, benzoyl peroxide, and potas ole?nic carboxylic acids. They show much less sium persulphate may be employed. Certain tendency towards formation of a prominent retic ulated pattern in the baked coatings, than they 60 alpha, beta-ole?nic carboxylic acids, such as maieic acid, copolymerize at a faster rate than the exhibit in the unmodi?ed vinyl‘halide polymers vinyl halides or mixtures of vinyl halides and or copolymers in the absence of a‘, blending in vinyl aliphatic esters. In such instances, allow gredient, such as a vegetable oil or alkyd resin as ance for this can be made by adjusting the described in an application of vPowell and Mc Knight, Serial No. 429,112, ?led January 31, 1942, 55 charslns ratio of the monomers, or by adding 2,411,590 - 4 the maleic acid in small amounts during the poly merization. . The aliphatic, alpha, beta-oleilnic carboxylic acids all contain the resinophoric group, cause of the obvious diiliculties, this has not been experimentally established, however, but in any events. distinct improvement in resistance of the ?lm to attack by solvents, to softening under heat, and to thermal decomposition is observed. The amount of heat reactive resin in such mix tures may vary from about 5 to 30 parts of such resin per 100 parts of the modi?ed vinyl resin, depending, to some extent, on the amount of and the term "acids" also includes the anhydrides 10 carboxylic acid combined 'in the vinyl resin. About 10 to 20 parts of the heat-reactive resin oi’ the acids. The acids may be either monobasic per 100 parts of the modified vinyl resin are pre or polybasic and may contain one or more ole?nic groups in addition to the one which is in a con ferred. jugated position with the 0:0 linkage. Ex The coating composition of this invention may amples of suitable acids include maleic acid, fu 15 be applied tojany surface which will withstand maric acid, mono-esters of fumaric and maleic the heat-treatment required. Thus, it may be acids, maleic anhydride, acrylic acid, a-meth applied as a protective coating to foils, sheets, acrylic acid, crotonic acid, citraconic acid and its panels, wires, rods and tubes made of metals, anhydride, itaconic acid and its anhydride, chlor such as iron, tin plate, zinc, copper, aluminum, maleic acid, and the like. Examples of mono 20 lead, magnesium, and their alloys; it may also esters of maleic and fumaric acids include mono- . methyl fumarate and mono-2-ethyl-hexyl male serve as a water-resistant coating for cellulosic sheet material, such as porous papers, glassine ate, as well as other lower mono-alkyl esters of paper, waxed papers, and regenerated cellulose these acids. sheeting. It may be used to coat textile fabrics The amount of the alpha, beta-ole?nic car 25 made of yarns composed of cotton, wool, viscous boxylic acid which need be combined in the vinyl rayon, cellulose acetate, or linear polyamides. It halide polymers or copolymers is not large in may also serve as an oxidation-resistant and order that insolubilization of the coating may solvent-resisting coating for natural rubber, occur on heat-treatment with the urea-formal butadiene-styrene rubbers, butadiene-acryloni dehyde or melamine-formaldehyde resins. 30 trile rubbers, and other synthetic rubbers and Amounts of combined acid between about 0.5% rubber substitutes, such as sodium polysul?de and 20% of the polymer are usually su?flcient, ethylene dichloride or dichlorethylether conden and for most purposes, a resin containing from sation products, gamma polyvinyl chloride and copolymers of vinyl chloride and vinyl acetate isfactory. Dibasic acids, such as maleic acid, are 35 having molecular weights above 18,000 and vinyl usually effective in smaller amounts than mono chloride contents of about 95%, containing about basic acids. When vinyl esters are present in 30% to 45% plasticizer. It may be used to apply the copolymer, in addition to vinyl halides and a solvent-resistant coating on resinous sheet ma the carboxylic acids, their amount may vary‘ terial which otherwise may be attacked by sol from 3.2% or 5% to 15, 20, 35 or 40% by weight 40 vents, such as sheets composed of cellulose ace of the copolymer. The molecular weight of the tate, cellulose nitrate and vinyl resins, for in resins as determined by Staudinger’s method may stance, copolymers of vinylv chloride and vinyl vary from 5,000 to 30,000, or higher. The resins acetate. It may be used to protect wood and con 0.5% to 10% of combined carboxylic acid is sat described above are insoluble in dilute solutions crete articles from moisture, or to impart chem of sodium hydroxide. 45 ical resistance to articles molded from phenol The heat-reactive urea-formaldehyde resins formaldehyde resins. or melamine-formaldehyde resins are well known. They are usually formed by heating urea or The metal sheets may already contain a dec orative or primer coating before the composition melamine with a molar excess of formaldehyde. of this invention is applied, and such coatings The initial heating is under non-acidic condi 50 may consist of solid color coatings, varnishes, tions, and the ?nal heating is in the presence lacquers, or lithographic prints. Similarly, the of an acidic catalyst, and a solvent, such as plastic sheets to be protected may have press butanol. Water is removed during the latter polished, matte or embossed surfaces. stage, and the reaction is stopped while the The coating composition exhibits good adhesion resin is still soluble in alcohol. The resins may 55 to various types of surfaces, but it ?nds its most be modi?ed during manufacture with other in useful adaptation in applications where the gredients such as ethylene glycol phthalate resins chemical inertness; acid, alkali, oil, and grease having unreacted hydroxyl groups. polyhydric resistance; ?exibility; abrasive resistance, and alcohols, vegetable oils, and the like. In addi toughness of the vinyl resins are desired, but a tion, both urea and melamine may be used in 60 coating. of higher softening point and greater the same resin if desired, or other nitrogen de rivatives, such as dicyandiamid, thiourea, and the various diazine and triazine derivatives, may be resistance to solvents and boiling water is re quired. Thus, the coating composition of this invention gives excellent service as an adherent, used alone or in combination with other start 65 non-toxic lining for food or beverage containers ing materials. In general, resins of these types magic of metal, in which the food or beverage is are capable of undergoing insolubilization reac packaged at temperatures of 212° F. or higher tions after deposition in film form, and are char to insure sterility. Also, many of the present acterized by the relative speed of these ther vinyl resin coatings for paper do not have a suf mosetting reactions even at baking temperatures 70 ficiently high softening temperature to prevent “blocking" at summer temperatures, especially in warehouses exposed to the sun.v However, paper blended with the acid modi?ed vinyl resin and coatings containing the modi?ed vinyl resin heat films are deposited from such mixtures and treated in situ with the heat-reactive urea-form baked, it is possible that some degree of reaction as low as 200° F. When such heat reactive aminoplasts are between the two resinous ingredients occurs. Be 75 aldehyde or melamine-formaldehyde resins have 2,411,500 5 ' In this manner, damage to the heat-sensitive a!’ ticle can be minimized or avoided. at temperatures'of 180° 1'‘. It has also been found that the presence in the Another illustration of the utility of the new coating of phosphoric acid or acid esters of coatings in this respect is as a top or ?nishing phosphoric acid, such as the mono- or dialkyl coating for cloth coated with a highly plasticized acid phosphates, will accelerate the curing reac vinyl resin, such as a copolymer of vinyl chloride tion, and result in more insoluble and adherent with vinyl acetate or a plasticized polyvinyl par coatings of higher softening point and better re tial butyral resin, which may itself be of a ther sistance to boiling water. The amount of the mosetting or heat-curing type. Upon heat-treat phosphoric acid or organic acid phosphate may ment, the top coating is converted to‘ its insoluble be varied from less than 1% to over 30% by weight form and insures that the coated cloth does not of the urea or melamine resin. About 10% of block at temperatures of 180° F. or higher. An such compounds appears preferable because of other advantage is that such top coatings tend to the increasing incompatibility of higher propor prevent excessive loss of plasticizer by evapora tion, and prevent plasticizer exudation or "sweat 15 tions. Suitable alcohols for making the mono and dialkyl phosphoric acid esters include methe out,” both 'where this is caused by the underly anol, ethanol, isopropanol, butanol, 2-ethyl bu ing resin absorbing water, as is sometimes the tanol and 2-ethyl hexanol. The phosphoric acid case with highly plasticized base coatings of may also be spread over the surfaceof ferrous thermoplastic polyvinyl partial butyral resins, or where “sweat-out" iscaused by diffusion of the 20 metals to be coated, but better results are. ob tained“ the surface of the iron or steel is lightly plasticizer to the surface. For coating cloth, it is phosphatized by any of the known chemical .or desirable that the top coating also be plasticized, higher softening points and do not "block" even electrochemical treatments, such as the “Bond but not necessarily to such an extent as to equal erizing process,” to form a coating which does not the ?exibility of the base coating. To prevent crack on subsequent forming operations. The the plasticizer of the base coating from penetrat composite coating of this invention is then ap ing the‘clotb, a primer coating of the modified plied and baked for 10 to 15 minutes at 325° to vinyl~ resin and heat-reactive vresin may be ap 400° F. plied tothe cloth. In many instances, copolymers of vinyl chlo Composite coatings prepared in this manner o?er advantages not easily obtainable by other 30 ride and vinyl acetate containing from 60% to 95%, and preferably from 85% to 88% of vinyl methods. Thus coated fabrics of very good ?ex chloride may be included in the coating. These ibility can be prepared by using high proportions resins may be blendedwith the other resinous of plasticizer in the intermediate coats, while the ingredients of the coating in amounts of 10, 20, less soluble top coat and base coat, based upon composit‘ons of heat reactive‘ aminoplasts 35 30, 40, 50, 60, 70, 80 or 90% depending on the solvent resistance and softening point which is blended with the modi?ed vinyl resins, prevent ‘required for the particular application. Where escape of the excess plasticizer, which otherwise the larger amounts of the vinyl acetate-vinyl would occur and make the surface "tacky” at chloride oopolymers are employed, it is usually temperatures of l50°~200° F. _ The coating composition in combination with 40 necessary to include a small amount of a vegeta ble oil, an alkyd resin, or a vegetable oil-modi suitable plasticizers may also be applied in dilute ?ed alkyd resin in the composite coatinglto avoid solution to impregnate cotton fabrics of the type difficulties from “checking” of the film after bak used in shirts, collars and overalls, whereby ing. Castor oil or a castor oil-modi?ed glyceryl about 1% to 5% of the composition by weight of phthalate resin are preferred for this purpose. The usual ketone solvents for vinyl resins may of the cloth to improve the wearing qualities of be employed in the coating compositions, but a the cloth and its resistance to abrasion. The-un coupling or blending solvent in addition to the plasticized coating composition may also be used hetone solvent is frequently desirable in order to to improve the sti?ness and crease-resistance of fabrics, such as curtain fabrics, or pile fabrics by 50 obtain clear solutions of the vinyl resins and mel amine or urea resins. Suitable coupling agents spreading a dilute solution of the composition include aloohol-ethers, such as ethylene glycol over the fabric, and subjecting it to a heat-treat the cloth is deposited as a coating over the ?bers rnégnoethyi ether and ethylene. glycol monoethyl ment. Such fabrics are adapted to resist discol oration and deterioration on exposure to light and oxygen. ' The temperature and duration of the heat e 55 er. The following examples will serve to illustrate the invention: ' treatment will vary depending on the surface to Example 1 be protected. For metal coatings, a baking pe riod of 10 to 15 minutes at temperatures of 350° Two clear lacquers of the following composi to 400° F‘. is usually su?icient to convert the coat 60 tion were prepared: ing to its insoluble form. At lower temperatures, longer baking periods are usually required. For , cloth orpaper coatings, temperatures of 200° to 300° F. areusually the maximum the cloth or pa per will withstand for prolonged periods, and,_ at 65 these temperatures, baking times of about 30 to ~60 minutes are usually necessitated to obtain coatings of .improved softening point. For wire coatings,’ temperatures up to about 800° F., for A Vin lohloride(8ii ). vinyl acetate 15 M'olecularwe 2%1 , co 1 B er. Parts Parts ........ _ ______ -. Vinyl chloride (86%), vinyl acetate (14%), maleic acid (1%), oopolymer. . Molecular weight 10,000 ......... _ . Heat-reactive nrea-iormaldelgde resin (50% solution iii-butanol, 2 , eapryl cohol, 1 part) __________ __ 4 20 4 aci 0.10l 0.10l periods ofabout 1 to 2 minutes may be employed. 70 Phosphoric Iiltliyl one glycol monomethyl ether __________________ -. Met ylisobutyl ketone _____________________________ __ 60 60 Where the surface to be protected is sensitive Toluene 00 60 to heat, thin, films of the composite coating can be cured by exposureof the coated side to intense Two coats of each lacquer were sprayed over radiant heat for a brief period, as for instance, in an. even having a continuous conveyor belt. 75 sanded steel panels, and each panel was baked at 2,411,090 . with coating A exhibited a prominent reticulated pattern or checks and cracks, whereas the panel with coating 13 was smooth. After 45 minutes heating, coating 3 exhibited better heat stability than coating A. After baking, coating 3 did not soften appreciably in contact with acetone, where as coating A was distinctly softened and swollen. , A clear lacquer was prepared as follows: . Parts Vinyl chloride (95%), vinyl acetate (3.2%), 10 Example 2 8 iron panels, coating 1" was somewhat better than. coating 1:. Example 4 375' 1". After baking for 15 minutes, the panel nasal: acid (1.8%). Molecular weight about Heat-reactive, alkyd modi?ed melamine-form aldehyde resin, 50% solids in solvent mix ture consisting of 30% butanol, 20% capryl Two clear lacquers of the following composi tion were prepared: alcohol, and 50% mineral spirits ________ _- 6 15 Phosphoric acid, 10% solution in ethylene glycol monomethyl ether _______________ __ 1 Ethylene glycol monomethyl ether_______ -_ 13 Methyl isobutyl ketone ___________________ _- 50 Vinyl chloride (85.0%), vinyl acetate (13.3%), maleic Parts acid (L7 a) copolymer ____________ .2 ............... _. Heat-react ve urea-formaldehyde resin (25% solution in ethylene glycol monoethyl ether, 5 parts, butanol, 20 Ethy 2.8 ne rtsglycol and capryl monomethyl alcoho ,ether. 1.4 parts . __..... ._ Toluene 50 Two coats of the lacquer were applied by spray ing to black iron panels and to tin plated steel panels having a primer coating of baked oleo resinous varnish. All panels were baked at 375° F. for 15 minutes. The resultant ?nishes were 25 amber in color and very tough and adherent. Two- coats of each lacquer were sprayed onto They did not soften appreciably on soaking the brightly sanded steel panels, and then baked for panels in methyl ethyl ketone, nor did they blush one hour at 350° F. Coating D showed better or lose any of their adherent qualities after im- _ resistance to acetone than coating C, but both mersion of the panels in boiling water for one were distinctly better than coating A of Ex 30 hour. ‘ ample 1. The softening point of coating D was Phosphoric acid 'lil‘loelthyl isobutyl ketone .......... _ _ Example 5 somewhat higher than coating 0, but the soften ing points of both coatings were about 30° to Example 4 was repeated with equivalent re 40° F. higher than that of coatings which con tain only the modi?ed copolymer of vinyl chlo 85 sults using monobutyi phosphoric acid in place of phosphoric acid. ride, vinyl acetate and maleic acid, which have a softening point of about 170° F. The softening points are determined by placing a piece of cheese Example 6 cloth on the baked film under a one pound per Example 4 was repeated employing a copoly mer of vinyl chloride (84%), vinyl acetate (14%) and methacrylic acid (1%), and a ?nish was ob tained which was resistant to solvents and to water. square inch weight. The softening point is taken 40 at the temperature at which the ?bers of the cloth will print on the ?lm after the pressure is applied for 30 minutes. 45 Example 3 Two clear lacquers were prepared as follows: Vinyl chloride (85%), vinyl acetate (14%), malelc acid (1%). Molecular weight 10,000 _______________ _. Heat-reactive alkyd modi?ed melamine-formalde h do resin, 50% solids in solvent mixture consisting o 30% butanol, 20% capryl alcohol, and 60% min eral spirits Ethy Example 7 The following lacquer was prepared: Parts 50 Vinyl chloride (92%), maleic acid (8%), co polymer. Molecular weight about 20,000-- 20 Heat-reactive alkyd modi?ed melamine formaldehyde resin, 50% solids in solvent mixture consisting of 30% butanol, 20% capryl alcohol, and 50% mineral spirits" Phosphoric acid, 10% solution in ethylene 6 glycol monomethyl other. . Methyl isobutyl ketone .......... . _ _ _. glycol monomethyl ether ______________ _- l Toluene _____________________________________________ __ Ethylene glycol monomethyl ether ________ _- l3 Cyclohexanone _________________________ .... 100 Two coats of each lacquer were applied to tin 60 Two coats were applied by spraying to steel plated steel panels which contained a baked oleo panels, and the coating baked for 15 minutes at resinous varnish of the type used for priming 375° F. The resultant ?nish showed good re cans for packaging beverages, such as beer. Du sistance to ketone solvents and to boiling water. plicate coats were also applied to black iron panels . and both sets of panels were baked for 15 min 65 Example 8 utes at 275° F. Coating F had somewhat better resistance to solvents than did coating E, and This example illustrates a cloth coating in it showed better adhesion after immersion in which the partially heat-reactive vinyl resin boiling water for 15 minutes. However, both coat ings were much superior in these respects to 70 composition is employed as a solvent-resistant, non-blocking, finishing coating over a highly coatings of unmodi?ed copolymers of vinyl chlo plasticized base coating containing a copolymer ride and vinyl acetate, irrespective of whether of vinyl chloride and vinyl acetate of relatively such coatings contained urea or melamine resins. low molecular weight which has good ?exibility The heat stability of both coatings E and F was satisfactory, although in the tests on the black 75 but exhibits a tendency to “block” at tempera 8,411,590 . 0 turescfiwlltoiwl'. 'i‘hebaseeoatinghad thefollowing composition: ' ' Per-cent Vinyl chloride (88%). vinyl acetate (14%) copolymer. Average molecular weight 10,000 ............. -'_ ....... -- 'pliedtotheclothbyusingadoctorkniiafolr lcwedbyonecostoftbetopcoating.'1‘heilnal coatingwasbakedforwtowminutesatml'. The coating did not "block” when sterilised with ' steam under 15 pounds per square inch pressure. 21.2 In determining this, samples of the coated cloth Yellow iron oxide pigment............ -Black iron oxide pigment. ............ ..- 1. 43 1. 84 Lead titanate ....................... __ 1.09 Whiting 8.44 .10 Dloctyl phthalate.................... __ 4. 75 were placed face to face under a pressure of one .pound per square inch. . Dicapryl phthalate __________________ __ 7.78 water-repellent, treatment. 3.19 Light hydrocarbon distillate __________ .. 25. 3 Methylethyl ketone __________________ __ 12.8 Methyl isobutyl ketone _______________ __ 12. 8 The coated cloth is useful for raincoats, tar paulins, tents, ski clothing, gun coverings and the like. The cloth may be coated on both sides with the composition, or the uncoated side given a Butyl ester of acetylated polymerized ricinoleic acid-__-. _________________ ..- 10' Beveraicoatsofthebasecompositionwereap 15 100.00 Several coats of this composition were applied to cloth and then a ilnishing coating of the fol The above composition without the pigments is useful for coating paper and rubber articles. and may be applied by conventional methods. For instance, the paper may be coated employing a reverse roller machine, and the rubber articlesv may be coated by a spraying technique, after suit able thinning of the composition. lowing composition was applied: ‘ _ Modi?cations of the invention other than as Per cent specifically described in the examples will be ap Vinyl chloride (85%). vinyl acetate parent to those skilled in the art, and are in (14%), maleic acid (1.0%) copolymer. cluded within the scope of the invention. Average molecular weight about 10,000- 22. 5 I claim: Heat-reactive alkyd modified melamine1. A vinyl resin coating composition of a lim formaldehyde resin, 50% solids in sol ited heat-reactive type comprising an acid-react vent mixture consisting of 30% butanol, ing vinyl resin of the group consisting of a co 20% capryl alcohol and 50% mineral polymer of vinyl chloride, a vinyl ester of a lower 30 spirits ' 4. 53 saturated fatty acid, and an aliphatic, alpha, Yellow iron oxide pigment ____________ __ 1. 52 beta-ole?nic carboxylic acid, in which from 3.2% Black iron oxide pigment_____________ __ 1. "('1 to 40% of said ester and from 0.5% to 20% of Lead titanate ______________________ -_'_ 1. 18 acid, by weight of the copolymer, are combined Whiting 8. 94 35 therein, and a copolymer of vinyl chloride and an Dioctyl phthalate __________________ __ 1.76 aliphatic, alpha, beta-ole?nic carboxylic acid, in Butyl ester of acetylated polymerized ricinoleic acid _____________________ __ Dicapryl phthalate __________________ __ Light hydrocarbon distillate__________ .._ Methylethyl ketone __________________ _Methyl isobutyl ketone ______________ .._ 30% by weight of said ‘acid-reacting vinyl resin of a heat-reactive, alcohol-soluble resin of the group consisting of urea-formaldehyde and mel amine-formaldehyde resins, the composition be ing dispersed in an organic solvent. 2. A vinyl resin coating composition of a lim Each coat was baked for a few minutes at 210° 45 ited heat-reactive type comprising an acid-react ing vinyl resin of the group consisting of a co F. to remove solvents and the ?nal cost was polymer of vinyl chloride, a vinyl ester of a lower baked 30 minutes at 230° F. The total coating weight was -3.5Ito 4.2 ounces ' saturated fatty acid, and an aliphatic, alpha, beta-ole?nic carboxylic acid, in whichfrom 3.2% per square yard. The coating was ?exible at 0° 1". and it did not block at a temperature of 50 to 40% of said ester and from 0.5% to 20% of acid, by weight of the copolymer, are combined 210° F. therein, and a copolymer of vinyl chloride and an Example 9 aliphatic, alpha, beta-ole?nic carboxylic acid, in To obtain coated cloth of better resistance to which from 0.5% to 20% of acid by weight of the solvents and boiling water, it is preferable to em is combined therein, from 5% to 30% ploy the heat-reactive vinyl resin composition in 55 copolymer by weight of said acid-reacting vinyl resin of a Synthetic wax ______________________ _. ' 3. 00 1.18 15. 82 40 18. 48 18.48 which from 0.5% to 20% of acid by weight of the copolymer is combined therein, and from 5% to 0.84 100. 00 both the base coating and the top coating. The following compositions are suitable for this purpose: - Base coat- Top coat in: Vinyl chloride (85% , vinyl acetate (14%), his Per cm! 22. maleic acid (1.0%) copolymer. Average molecular weight about 10,000 __________ _ . Heat-reactive melamine-formaldehyde resin solution of Example 8_____________ A titanate ___________ __ Methyl isobutyl keione ...... __ Metbylethyl ketone __________ _ 60 weight of said heat-reactive resin of one of the group consisting of phosphoric acid and acid es ters of phosphoric acid, the composition being dispersed in an organic solvent. 3. A coating composition of a limited heat-re active type comprising a copolymer of vinyl chloride, vinyl acetate and maleic acid, in which from 3.2% to 40% of vinyl acetate and from 0.5% to 10% of maleic acid, by weight of the copolymer, are combined therein. from 5% to 70 30% by. weight of said copolymer of a heat-re active, alcohol-soluble resin of the group con uy as r o ace ym m... surrenders-am. pwlel?tiidngm heat-reactive, alcohol-soluble resin of the group consisting of urea-formaldehyde and melamine formaldehyde resins, and from 1% to 30% by ‘3o""""" " Dlcapryrphtbalate.................... ..I: §8 5. e sisting of urea-formaldehyde and melamine i’ormaldehyde resins, and an organic solvent. 4. A coating composition of a limited heat-re 75 active type comprising a copolymer of vinyl 2,411,590 l1 chloride, vinyl acetate and maleic acid, in which from 3.2% to 40% of vinyl acetate ‘and from 0.5% to 10% of maleic acid, by weight of the co polymer, are combined therein, from 5% to 30% by weight of said copolymer of a heat-reactive, alcohol-soluble resin of the group consisting of urea-formaldehyde and melamine-formaldehyde resins, a copolymer oi! vinvl chloride with vinyl acetate containing irom 60% to 95% vinyl chlo ride, and an organic solvent. 5. A coating composition oi’ a limited heat 12 on said surface by baking the coating at tem peratures between 200' 1". and 800' 1".. and heat treating said acid-reacting vinyl resin with said heat-reactive resin to form a coating on said article which is resistant to water and solvents. '1. Process for coating metals which comprises applying a primer coating comprising an oleo resinous varnish, baking said primer coating, and then applying a composition comprising a dis 10 persion in an organic solvent of a copolymer of vinyl‘chloride, vinyl acetate and maleic acid, in reactive type comprising a copolymer of vinyl which from 3.2% to 40% of vinyl acetate and chloride and maleic acid, the amount of maleic from 0.5% to- 10% of maleic acid, by weight of acid combined in the copolymer being from 0.5% the copolymer, are combined therein, and from to 10% by weight of the copolymer, from 5% to 15 5% to 30% by weight 01' the copolymer 0! an 30% by weight of said copolymer oil a heat-re alcohol-soluble, heat-reactive resin of the group active, alcohol-soluble resin 0! the group consist consisting of urea-formaldehyde resins and me] ing of urea-formaldehyde and melamine form amine-formaldehyde resins, baking said compo aldehyde resins, and an organic solvent. sition at a temperature of 325° F. to 400° F.. and 6. Process for coating smooth and extended 20 i'orming a coating on the metal which is resist surfaces which comprises applying to said sur ant to solvents and to water. faces a coating composition of a limited heat 8. Process for coating ferrous metal which reactive type comprising a dispersion in an or comprises phosphatizing the metal surface. and ganic solvent of an acid-reacting vinyl resin of then applying a composition comprising a dis the group consisting of a copolymer of vinyl chlo persion in an organic solvent of a copolymer of ride, a vinyl ester of a lower saturated fatty acid, vinyl chloride, vinyl acetate and maleic acid, in and an aliphatic, alpha, beta-ole?nic carboxylic which from 3.2% to 40% of vinyl acetate and acid, in which from 3.2% to 40% of said ester from 0.5% to 10% of maleic acid, by weight oi’ and from 0.5% to 20% of acid, by weight of the the copolymer, are combined therein, and from copolymer, are combined therein. and a copoly 30 5% to 30% by weight of the copolymer of an mer of vinyl chloride and an aliphatic, alpha, alcohol-soluble, heat-reactive resin 01 the group beta-ole?nic carboxylic acid, in which from 0.5% consisting of urea-formaldehyde resins and mel to 20% of acid by weight of the copolymer is amine-formaldehyde resins. baking said com combined therein, and from 5% to 30% by weight position at a temperature of 325° F. to 400° I-.. of said acid-reacting vinyl resin 0! a heat-re 36 and forming a coating on the metal which is re active, alcohol-soluble resin 01 the group con sistant to solvents and to water. sisting oi’ urea-formaldehyde and melamine iormaldehyde resins, forming a continuous ?lm GEORGE ll. POWELL, 3RD.