Патент USA US2132869код для вставки
Patented Oct. 11, 1938 ‘ v ~ * 2,132,869 PATENT. ‘OFFICE UNITED . ‘ , ' ,I 21132369. 'CELLULO-SE ACETATE LACQUERS ‘CONTAIN- . ING‘OXIDIZE‘D CEIJJULOSE ACETATE’ 5' Charles‘R. Fordyceva'nd Martti" Salo', ‘Rochester, . N.‘-Y., assignors to Eastman Kodak Company, 1 Rochester, ZN.’ Y.,ga. corporation. of ,lflew Jett Application December 15, 1936, Serial No. 115,971 q , q ' Claims. ,(01. 134.49) ' ' . . bylour preferred method, were dissolved in ' This invention relates to celluloseacetate lac-~ pared 10 parts by ‘weight of a solvent mixture com quers, and has as its objectjto provide a cellulose acetate lacquer which will adhere ?rmly to metal and other surfaces which it is desired to coat." , 5;; ' The use of cellulose‘ acetate ' inflacquers ‘has been greatly restricted by the insuf?cient adhesion of cellulose acetate lacquer" ?lms to surfaces to which they are, ap=plied.~ In the case of cellulose , posed fcf I 1i ' I . V » Auetnne . » Percentiby weight v ' ' 50‘ Ethylene glycol \monomethyl ether acetate__ 20 Toluene__;-;__'__‘_' ______________________ _-__ 15 Methyl acetate"; ______ __- _______ __'_Y____.;_‘ 15 nitrate lacquers, adhesion‘ can be improved by . and the solution was» coated on a strip of cold Very rolled steel. Stripping .tests were carriedout by few resins,rhowever, are compatible with cellulose theGardner Laboratory adhesion method, de acetate, and even those which are compatible do scribed on page 217 of the 6th edition of “Physi 10 the incorporation of resins in the lacquer. not always confer the property of good. adhesion on cellulose acetate lacquers in which they are 15 incorporated. . . 1 We have discovered that the adhesion of cellu lose acetate lacquers to metal and other surfaces can be improved by the incorporationof oxidized cellulose acetate in the cellulose acetate lacquer.v 20 ‘cal and Chemical Examination of Paints, Var nishes, Lacquers and Colors”, by H. A. Gardner.‘ A stripping load of over 600 grams was necessary to remove the ?lm from the metal,‘ as compared to a load of only 50 grams necessary to remove a ?lm of a cellulose acetate lacquer made in the same way except for the omission of the oxidized The method by which we prefer toi prepare ' cellulose acetate. The load required for strip ping the cellulose acetate lacquer containing oxi oxidized cellulose acetate is as follows: A sus; pension of 100 parts of cellulose acetate'of 38% acetyl content in a solution of 10 parts of po tassium permanganate, 13.5 parts of sulfuric acid, N). U1 and 1500 parts of distilled water is held at 25° C. until the permanganate color, hasentirely ‘dis appeared, which requires approximately three hours. The suspended, oxidized cellulose acetate is then treated with water vcontaining sulfur 30 dioxide to remove the manganese dioxide ad dized cellulose acetate was approximately the same as that required for stripping a typical, commercial cellulose nitrate lacquer. The ratio of the Weight of oxidized cellulose 2-5 acetate to cellulose acetate in 'a lacquer may range from 1:4 to 3:1. Proportions much less than 1:4-v do not give satisfactory adhesion, while proportions much greater than 3:1 do not give satisfactory ?exibility or stability upon aging. 30 hering to it, and ?nally is washed with distilled ' In most cases, it is desirable to use a cellulose acetate plasticizer.v in the lacquer. The lower water and dried. . . r The preparation of oxidized‘cellulose acetate alkyl phthalates, such as dimethyl, diethyl and is described in U. S. Patent 1,976,758 of George dibutyl phthalates are very satisfactory, as are tripropionin, tributyl phosphate, and dibutyl ' 35 B. Watkins and Joseph D. Ryan, which shows its use as an adhesive layer between cellulose tartrate. The quantity of plasticizer may vary ‘widely, but best results are obtained if the weight acetate sheeting and glass sheeting in the manu facture of safety glass. Oxidized celluloseace-r of plasticizer is from 40% to 60% of the com tate, however, is too water-absorbent vandf the bined weight of ‘cellulose acetate and oxidized 40 cellulose acetate. . 40 ?lms it forms are too brittle to permit of its use In lacquer compositions to be applied by spray as the sole ?lm forming; component of a lacquer which is to form the surface layer of an object. ing, solvent combinations already known for use We have found that oxidized ‘cellulose acetate 7 with cellulose acetate may be employed. We have is compatible in all proportions with cellulose ace- - found the following mixtures very satisfactory: tate, and that lacquers made .from mixtures, in Per cent suitable‘ porportions, of cellulose acetate, oxi ' ' by weight dized cellulose acetate, and a plasticizer, are very (A) Acetone ________ -4 ________________ __V_ 50 satisfactory with respect to adhesion, ?exibility Ethylene glycol monomethyl ether_-____ 20 Methyl acetate_________________ _;____ 15 As an illustration of the effect of an’admix'ture of oxidized cellulose acetate on the adhesion of vToluene ___________________________ __ 15 cellulose acetate, we give thefollowing examples: (B) Acetone ___________________________ __ 50 Example I .—10 parts by weight of low-viscosity cellulose .acetate of 40%, acetyl-content and 2 parts by weight of oxidized cellulose acetate pre . Ethyl lactate ____________ ___ _________ __ 20 and water resistance. a ' . i ' Ethyl ‘acetate ___________________ _'____ Toluene ____' __________________ _'___._‘__ l5 15 55 2 t 2,132,869 The concentration of the lacquer solution will vary somewhat, depending upon the viscosity de sired, but ordinarily the combined weight of cel lulose acetate and oxidized cellulose acetate will Cl be from 6% to 9% of the combined weight of cellulose acetate, oxidized cellulose acetate, and solvent mixture. Pigments may be incorporated if 'desired. I acetate of high acetyl content were, dissolved im a mixture of 2500 parts of ethylene chloride and; 500 parts of ethyl alcohol. All parts are expressed by weight. By means of a suitable coating ma chine this solution was applied a thin surface 5 coating to paper. The resulting coated paper exhibited good appearance and ?rm adhesion of Example II.—400 parts, of low;viscosity; ace-'1 the applied coating to the paper. . 10 tone-soluble cellulose acetate and 400. partslofz ‘ 'lWhat we claiin as our invention and desire to’ oxidized celluloseiacetate‘ were dissolved in a .be secured by Letters. Patent of the United States 10 mixture of 5000 parts of acetone, 2000 parts. of 1. A cellulose acetate lacquer comprising oxii= ethylene glycol mcn‘ometh'yl ether, 1500 parts of cellulose acetate in the proportion of from methyl acetate and 1500 parts of toluene. 400 dized 15 parts of diethyl phthalate' was then adde'gl as a' 1' to ‘12 parts of‘oxidized cellulose acetate per 4 pliasticizer; All parts are expressed by weight. parts of cellulose acetate, the lacquer having the 15 property of adhering ?rmly to ‘metal and other Panels of polished steel were coated by spraying surfaces to which'it is. applied, and of continuing this solution under standard spraying conditions. to adhere when the lacquered surface is bent. 1S: When thoroughly dry, the lacquerjcoatings were 90 found to adhere very tenaciously to the metal. For uses which'require coatingfrom heavy so- ' V . . V V 2. A ?exible ‘article of manufacture having a closely adhering coating of a cellulose acetate 20 lacquer comprising oxidized cellulose acetate lutions, ordinary celluloseeacetate solvents, such the proportion of from 1 to 12 parts oi oxidized vas acetone, ethylene chloride-methyl ‘alcohol, cellulose acetate per 4 parts of cellulose acetate, mixtures, methyl acetate, etc., may be employed the, lacquer forming the surface layer of the 25 without diluents, and the concentration in the ?nished article, and maintaining its adhesion to 25 sclution adjusted’ to give the required viscosity. the article when, the article is bent. ' Example, [IL-400 parts of oxidized cellulose acetateand 600, parts of, low-viscosity cellulose CHARLES R. FORDYCE. j MART'I'I SALO.