Патент USA US2408175код для вставки
Patented-Sept. 24, 11946 i I ' ' _ ‘ * "2,408,174: ‘ cums a‘ itssm coa'rmo coluroslrrolvs - , Glen H. ,. Morey, Terre “Haute, 'Indg assig'nor to, " Commercial Solvents Corporation, Terre'Haute, ‘ l ' ' Ind., a'corporation-of'Maryland" No Drawing. Application March 20, 1944; I sensmaszmsi ‘6 _ (01. 260-32) ~ , My invention relates to‘c'oating compositions,’ , I have now discovered,thatthealkyl esters of and more particularly to coatingcompositions levulinic acid serve as particularly good vsolvents containing polymerizedvinyl ‘compounds e‘Numerous types: and grades of synthetic resins for certain grades ofvinyl resins, alld'that solu-' tlons oitheSeresins in the aforesaid solvents 'possess [none of the disadvantages mentioned abovewhich'were attributable'to the use of prior solvents. vIn this connection it should be pointed have been produced ‘by the polymerization of vinyl compounds. _Among these resinsLlcertainl typesare particularly adapted for use in coating compositions, “for example, resins resulting from out that the vinyl resinssuitable for use in'the 5 ~ the,‘ cop'olymerization' 01a vinyl halide with a coating ‘compositions of my invention are -'those'_ vinyl ester or a'lower aliphatic acid; ‘,These‘res ins, .ien'l'general, possess very ,"interesting and use-‘‘ having a molecular weight above‘4000and‘which are insoluble in toluene. These resins are pro ful ‘properties. particularly "those ‘resulting jirom duced by thecopolymerizationjcf a vinyl‘halide, such asjvinylchloride, with a vinyl ester, ‘.ror the polymerization ‘ofimixtures of vinylechlorlde vexample, vinyl acetate, and I have found that chloride. j, Such; resins, have great physical. and 15 such.» copolymers ,cont'ainlng aboutv85% vinyl, chloride land,15% vinyl acetate are particularly I chemical-stability'and are'notjreadily ailfected'by; suitable i'or preparingfthe coating compositions concentrated ' hydrochloric, or hydro?uoric‘ acids,v ' of ‘my inventiong-The lower molecular'weight,,, 50 ‘per cent‘ sodium hydroxide solution, alcoholsj oreven'by a mixture offpotassiumnichromate‘ toluenesoluble grades oi the aforesaid type of and sulfuric acid. 'Because 01 this-superiorsta 20 resins are substantially insoluble in alkyl esters bility, synthetic ‘resinsloi‘ ‘this type have been ' 0i.’ levulinic acid, yieldinggels when'incorporated insaid esters. @ . suggestedfor numerous usesfinthej'l?nishing and - and vinyl acetate with’ahigh proportion‘ oi’ the cosnngznems. I i ' 1 ' ' ' Itis an object oi myfinvention to provide vinyl" . resin coating comp0sitions._which employ ‘alkyl. Although ‘coating compositions, ‘which employ such resins as the principal'fllm forming .rnate 25 esters oilevulinic acid, either ,alone orin con- .7 junction with suitable diluents. , The alkyl, esters of levulinic acid, that I__ use > as solvents for the.‘ vinyl resins in my improved jvrial, are capable , of solving numerous] and‘ long existing problems in the ?nisl'iin‘gvileld, thereex; ist certain icommonzdei'ects‘which make the use coating compositions, may be conveniently pre-' of such resins for coatingpurposes infparticular ‘lines somewhat diilicult. _"For. example, contact so pared by reacting approximately equimolecular quantities of levulinic acid with the desired alco hol in the presence of a catalytic amount or a at elevated ‘temperatures with: certain metals, such as zinc, ‘iron, or tin, causes rapid decompo-, sition of polymerized vinyl compounds'prepared mineral acid, such as sulfuric acid. Puri?cation oi the resulting esters may be eii’ected by means from vinyl chloride with ‘the liberation oihydro chloric acid. The presence oi’ pigments contain ing iron or'zinc has‘ thesame eil'ect. [Another 01' 35 of fractional distillation in the customary man- ' ner. Any of thealkylesters of levulinic acidof vthe important handicaps" preventing ,extensive' use of vinyl resins incoating compositions, has" suitable boiling‘ points and rates of evaporation, maybe used-as solvents for the-preferred form been the, lack of. satisfactory solvents therefor,‘ ' of .vinyl resinsdisclosed above. :Examples of such‘ and while there‘ha'vebeen found certain mate, 40 compounds are the methyl, ethyl, ipropyl, butyl, rials which are comparatively good'solventslfor ‘isobutyl, isoamyl,qand;capryl esters of .levulinic the vinyl ‘resins; boththe solutions asjwell as'the resulting v?lm "formed, when Iutilizingjsuch‘ sol vents possess defects‘ which restrict‘ greatly‘the .acid- Certain ofthese compounds, such as the , a capryl ester of levulinic acid, possess asu?lcient 1y high boillngpoint, as well as...other desirable free and general application of such coating come 45 properties, to renderthem useful, as plasticizers positions. fvF'or example, lacquers prepared from‘ vinyl resins of the type described and materials previously found to beisatisiac'tory solventsfor saidjresins possesslvery‘poor color stability. 'Also the ?lms ‘resulting from" thejapplication ‘of such compositions, are objectionable‘ because oi’v the ~ disagreeable residualv odor. which .they possess. Thus the use of vinyl resin coating compositions in which such solvents =werepemployed, hasbeen limited considerably.‘ ’ for vinyl resins ‘of. the aboVe-described‘type, particularly, where thelatter are emploxedaslbond ing agents in the manufacture of laminated glassy. _In order‘ to cheapenvthe compositions, and fre-_ quently- ior' other reasons? it ‘is ‘desirable not to use materials’ consisting onlyjof 'a single solvent or solvent mixture. ‘ Owing to the high tolerances ' of, the levulinic acid esters for they coal-tar hydro-_ _ ' carbons,isuch as, forexample, benzene, and tolu-’ used'as dilu'. 55 ene, large volumes thereof may 2,408,174 3 4 cuts for the levulinic ester solutions of vinyl resins. Various hydrocarbon mixtures may, of C., was found to be 95 centipoises, as compared course, also be used as diluents and other mate rials ordinarily used in synthetic resin coating compositions, may likewise be employed in my improved vinyl resin compositions. For example, plasticizers such as cresyl phosphate, butyl phtha~ late, butyl phosphate,- or as mentioned above, the to 180 centipoises for a solution employing a mix ture of 20‘ per cent ethyl levulinate, and 80 per cent toluene. Where the viscosity is found to be . too high for a particular given solvent mixture, it can be very materially lowered by only a slight decrease in the concentration of ‘the vinyl resin incorporated therein. ‘ ' ' . The following examples are illustrative of the higher alcohol esters of levulinic acid, may be use of alkyl esters of levulinic acid in unpigmen’red incorporated in such compositions. Other resins, vinyl resin coating compositions. either natural or synthetic, may likewise be used therein. Also pigments or dyes may be added, Example I provided care is taken to avoid the presence of ' Vinyl resin copolymer consisting of approxi zinc and iron compounds. mately 85% vinyl chloride and 15% vinyl The viscosities of vinyl resin coating composi 15 tions, as in the case of most other coating com acetate.‘ _____________ __grams per 100 00.. 16 positions, are of considerable importance regard Butyl phthalate __' ___________ __d0 _______ __ less of the method of application utilized. Inas much- as the character of the solvent mixture em ployed affects not only the character of the de posited ?lm obtainable, but also the viscosities Ethyl levulinate ________________ __per cent__ 20 Ethyl isobutyl ketone ______________ __do_____ 20 Toluene __ _ do 2 60 ’ Example II of the liquid coating compositions, the choice of proper solvents to use with vinyl resins is highly Vinyl resin copolymer consisting of approxi solutions with the, vinyl resins, which likewise damar and mastic, may be incorporated in any mately>85% vinyl chloride and 15% vinyl important, and depends to a large extent‘on the acetate ________ __» ____ __grams per 100 cc__ l6 viscosity characteristics of the solutions obtained 25 Butyle levulin'a'te____ ___________ "per cent__ 20 therewith. The majority of the solvents previ l-nitropropane ___-____; __________ __do_____ 10 ously suggested for use‘with vinyl resins are un Toluene _________ _'_ ___________ __y___do___>__ "10 suitable for the preparation of satisfactory coat ing compositions, because solutions of the resin If desired, other solvents such as ethyl acetate, made with such solvents. not only possess high 30 butyl acetate, nitroethane, 2-nitropropane, etc., initial viscosities, but in addition, tend to increase or other diluents or diluent mixtures, such as in viscosity on aging andultimately set to a solid xylene, petroleum naphtha, and hydrogenated gel. While the alkyl esters of levulinic acid form petroleum» diluents, and. other resins, such as possess such characteristics to a certain extent, 35 of the above formulas. In adding such materials, they exhibit these undesirable properties to a however, care should ordinarily be exercised not lesser degree than solutions employing the com mon types of‘ ‘solvent compositions previously to incorporate substantial amounts of materials tending to increase the viscosity 0r accelerate the used. This coupled with the fact that the odor rate of gelling in the solution, such as, for ex of the ‘coating compositions‘of my invention‘ is 40 ample, the alcohols, which when present in only very mild and agreeable, as compared to that of very small proportions, will increase the gelling such compositions formerly available, make them tendency of the solution. I ‘ , much better suited for most types of vinyl coat This is a continuation-in-part of my copending ing compositions than those containing the previ application U. S. Serial No. 465,801, filed Novem ously available solvents. Another advantage of 45 ber 16, 1942._ , ' ' the solvents of my’invention, over those previ What I claim is: ‘ ' n ' ' ously employed, is the fact that the former have l. A coating composition possessing decreased higher boiling points and correspondingly lower > gelling tendencies, comprising a tough and strong rates of evaporation than the latter. arti?cial resin insolublein toluene, having a mo Although it is frequently desired to use a dilu 50 lecular weight in excess of 4000, and prepared by ent in vinyl resin coating compositions, it should the copolymerization of vinyl chloride, with vinyl » be noted that the incorporation of such material acetate, said resin being dissolved in ,a suii‘icient ordinarily results in an increase in the viscosity quantity of a solvent having a low rate of evap of the‘composition, and under certain conditions oration to decrease the gelling‘ tendency of the the viscosity increase with leaner mixtures be 55 composition, comprising an alkyl ester of levulinic comes very great. This increase in viscosity, in acid and a liquid coal-tar hydrocarbon, tomake general, depends upon such factors as tempera a readily ?owable composition adapted to produce ture of the solution, the concentration of the resin in solution, the viscosity characteristics of resistant, adhesive, and stable protective orbrna the particular resin employed, etc. Therefore, mental'surface coatings. _ ' to obtain lacquers possessing the desired prop erties. For example, the viscosity of a solution containing 15 grams of vinyl resin per 100 cc. of solvent mixture which consisted of 40 per cent protective or ornamental'surface coatings. z 2. A coating-composition possessing decreased it will be evident that the proportion of diluent 60 gelling tendencies, comprising a tough and strong to levulinic ester utilized, in any speci?c coating arti?cial resin insoluble'in toluene, having a mo composition, will vary with the particular dilu lecular weight in excess of 4000, and prepared by ent, the character and concentration of the resin, the copolymerization of vinyl chloride with vinyl the probable length of time before use of ‘the 65 acetate, said resin ‘being dissolved in a suilicient composition, and other such factors. By proper quantity of a volatile solvent having a low rate » selection of the particular alkyl ester of levulinic of evaporation to decrease the gelling tendency of acid and the‘ diluent and proportion thereof-1', both the resulting composition comprising ethyl levu the viscosity and the rate of evaporation of the linate, to make a ‘readily ?owable composition coating composition can be widely varied so as 70 adapted to produce ‘resistant, adhesive, and stable ethyl levulinate, and 60 per cent toluene at 30° AA 3. A coating composition possessing decreased gelling tendencies, comprising a‘tough' and strong arti?cial resin insoluble in toluene, having a mo lecular weight in excess of 4000, and prepared by 2,408,174 6 the copolymerization of vinyl chloride‘ with vinyl I lecular weight in excess of 4000, and prepared by acetate, said resin being ‘dissolved in a suf?cient -. the copolymerization of vinyl chloride with vinyl quantity of a volatile solvent having a low rate acetate, said resin being dissolved in a sufficient ' > of evaporation‘to decrease the gelling tendency quantity of a volatile solvent having a low rate of ' of the composition, comprising ethyl levulinate 5 and a liquid coal-tar hydrocarbon, to make a , readily ?owable composition adapted to produce resistant, adhesive, and stable protective or orna mental surface coatings. . a liquid coal-tar hydrocarbon, to make a readily ,?owable composition adapted to produce resist ant, adhesive, and stable protective orornamental Y 4. A coating composition possessing decreased l0 gelling tendencies, comprising a tough and strong surface coatings. v . 6. A coating composition possessing decreased gelling tendencies, comprising a tough and strong yinylresin copolymer having a molecular weight , arti?cial resin insoluble in toluene, having a mo lecular weight in excess of 4000, and prepared ' by the copolymerization of vinyl chloride with vinyl acetate, said resin being dissolved in a suf evaporation to decrease the gelling tendency of the composition, comprising butyl levulinate and in excess of 4000 insoluble in toluene, and con 15 ?cient quantity of a volatile solvent having a low , rate 01’; evaporation to‘decrease the gelling tend ency of the resulting‘ composition comprising _ butyl levulinate, to make a readily ?owable com sisting of approximately 85% vinyl chloride and 15% vinyl acetate, said resin being dissolved in a sufiicient quantity of a solvent having a low rate of evaporation to decrease the gelling tendency of the resulting- composition comprising alower position adapted to produce resistant, adhesive, alkyl ester of levulinic acid, to make a readily and stable protective or ornamental surface coat~ ?owable composition adapted to produce resistant, ings. adhesive, and stable protective vor ornamental sur ' ' ' ‘ 5. A coating composition possessing decreased gelling tendencies, comprising a tough and strong arti?cial resin insoluble in toluene, having a. mo 25 face coatings. I , GLEN H. MOREY.