UNITED STATES PATENT OFFICE,

CARL GUSTAV HAGEMANN AND FRIEDRICHOTTO CORN ELIUS ZIMMER MANN, OF LUDWIGSHAFEN, GERMANY. MANUFACTURE OF CELLULOD. SPECIFICATION forming part of Letters Patent No. 657,535, dated September 11, 1900. Application filed Jtine, 25, 1898, Serial No. 684,503, (No specimens.) To all, whom it may concern: incorporation there with of the hydrate or hy Be it known that we, CART, GUSTAV HAGE droxid of a metal. In order to remove all MANN and FRIEDRICHOTTO CORNELIUS ZIM danger of explosion, we convert the nitrocel MERMANN, of Ludwigshafen-on-the-Rhine, lulose while wet into celluloid or into a cellu 55 Germany, have invented certain new and loidal body, which we have called “hydrocel useful Improvements in the Manufacture of lite,’ as will hereinafter appear. We are thus Celluloid; and we do hereby declare the fol enabled to save the expense involved in first lowing to be a full, clear, and exact descrip drying the nitrocellulose. tion of the invention, such as will enable In carrying out our invention we dissolve others skilled in the art to which it apper the nitrocellulose while wet (containing fifty tains to make and use the same. per cent., more or less, water) in a suitable This invention relates to the manufacture solvent, as acetone, so as to form a semifluid of celluloid, which, as is well known, consists, or more or less, doughy mass. With this essentially, of nitrocellulose and camphor, mass We incorporate a concentrated aqueous 65 which latter imparts the required plasticity solution of a salt of a metal-as, for instance, to nitrogellulose. It is also well known that a sulfate of alumina-which may be done by celluloid is a highly-combustible substance trituration, kneading, or otherwise, whereby which is not only readily ignited, but burns We obtain a homogeneous plastic transpar with great violence. Furthermore, the man ent compound. With this compound we in ufacture of celluloid, as is well known, is corporate a concentrated solution of a salt of fraught with great danger, while the cost of an alkali metal having the property of neu the substance is comparatively high. tralizing such compound-as, for instance, This invention has for its object, primarily, caustic soda-which is preferably gradually the production of a practically non-inflam added to and incorporated with the compound 75 25 mable and non-combustible celluloidal body by trituration, kneading, or otherwise until of any desired degree of plasticity, the man the compound is neutralized, which can read ufacture of which is free from danger, while ily be ascertained by the fact that the mass the cost of the product is materially reduced. becomes almost suddenly more or less crum The primary object of this invention we bly or friable, while the hydroxid of alumina, attain by molecularly combining with nitro is precipitated, and thus molecularly and cellulose a hydrate or hydroxid of a metal, quantitatively combined with the nitrocellu and this is best effected by incorporating lose, as clearly shown by the following for With a solution of nitrocellulose a concen mula: m trated Solution of the salt of a metal, then 35 precipitating from said salt the hydroxid by chemically decomposing the same by treating The crude hydrocellite thus obtained and the compound with a correspondingly-con which consists, essentially, of hydrate of alu Centrated Solution of a salt of a metal of the mina, sodium sulfate, (Glauber salt,) nitro alkalies having the property of neutralizing cellulose, and water is then freed from so 40 the compound, as a solution of caustic soda, dium sulfate and acetone by Washing with after which the solvent for the nitrocellulose water, then freed from moisture by pressure as well as the soluble products formed under or centrifugal action, leaving the intimately the action of the precipitant are removed, combined nitrocellulose and hydrate of alu the remaining compound being then dried mina in a more or less gritty or friable con 95 and gelatinized in the usual manner, with or dition, while the solvent and sodium sulfate without the addition of camphor. In some can be removed from the waste liquor by dis cases we also incorporate with the compound tillation and crystallization, respectively. an oleaginous body, preferably castor-oil, The compound of nitrocellulose and hydrate when we desire to obtain a smooth and duc of alumina obtained as described is then C So tile final product, the oil being incorporated dried, gelatinized in the usual manner by With the nitrocellulose solution before the means of acetone or a solution of camphor in a 657,535 acetone or a solution of camphorin-alcohol or Having thus described our invention, what the like, and then molded into any desired we claim as new-therein, and desire to secure form: The degree of plasticity of the final. by Letters Patent, is product depends, of course, upon the propor 1. The process, which consists in combining 5 tion of camphor incorporated therewith. On with nitrocellulose a hydrate or hydroxid of a 7o the other hand, in the absence of camphor metal, for the purpose set forth, the final product is a very hard one, possess- 2. The process, which consists in combining ing but little plasticity when heated. If it a hydrate or hydroxid of a metal with nitro is desired to obtain a very smooth ductile cellulose and gelatinizing the compound, sub To final product, an oleaginous body, preferably stantially as and for the purposes set forth. 75 castor-oil, is mixed with the solution of nitro- 3. The process, which consists in combining cellulose before the incorporation therewith a hydrate or hydroxid of a metal with nitro of the hydrate or hydroxid of a metal. In cellulose, and gelatinizing the compound with the following examples we have given pro- a nitrocellulose solvent holding camphor in I5 portions of ingredients which have yielded solution, for the purpose set forth. 8o excellent results, the parts being given by 4. The process, which consists in combining, weight: with a solution of nitrocellulose, a solution of Hydrocellite without camphor or oil: nitro- a hydrate or hydroxid of a metal, reacting cellulose, seventy parts; hydrate of alumina, tupon the compound with a solution of an 20 thirty parts. - ‘. . agent capable of neutralizing the same and 85 Hydrocellite without oil: nitrocellulose, precipitating the hydroxid, and removing the fifty-six parts; hydrate of lumin, twenty nitrocellulose solvent and the soluble con four parts; camphor, twenty parts. . . in. stituents resulting from the reaction, for the Hydrocellite without camphor: nitrocellu- purpose set forth. 25 lose, sixty-three parts; hydrate of Alumina, 5. The process, which consists in molecu- 9o twenty-seven parts; castor-oil, ten parts. . i larly combining, with a solution of nitrocellu Hydrocellite with camphor and oil: nitro-lose, a solution of a hydrate or hydroxid of a cellulose, fifty parts; hydrate of alumina, metal; reacting upon the compound with a twenty parts; camphor, twenty parts; castor-concentrated solution of a salt of a metal ca 30 oil, ten parts. pable of neutralizing said compound, and pre-95 - The proportions of concentrated solutions cipitating the hydroxid, and removing the of the salt of alumina and caustic soda are de-cellulose solvent and the soluble constituents termined by well-known stoicheiometric rules, resulting from the reaction, for the purpose due consideration being had of the degree of set forth. - . . . 35 purity of the chemicals. 6. The process, which consists in combining, Too Hydrocellite can be colored in the same with a solution of nitrocellulose, a concen imanner as celluloid, as the hydrate of alu-ltrated solution of a hydrate or hydroxid of a mina fixes colors, metal, reacting upon the compound with a - In the process described and as hereinbe-concentrated solution of caustic soda, remov 40 fore stated hydroxids of other metals can being the cellulose solvent and soluble constitu- Io5 used and intimately incorporated with the ni-ents resulting from the reaction, drying, and trocellulose, provided, of course, the salts of gelatinizing the compound, for the purpose the metals can be readily dissolved, while set forth. . . . Very attenuated solutions do not readily com- 7. The process, which consists in combining, 45 bine with the nitrocellulose. with a solution of nitrocellulose, a concen- IIo From what has been said it will readily be trated solution of a hydrate or hydroxid of a seen that hydrocellite has very material ad-metal, reacting upon the compound with a vantages over celluloid-as, for instance, its concentrated solution of caustic soda, remov comparatively-low degree of inflammabilitying the cellulose solvent and soluble constitu 5o and its possibility of varying the density of ents resulting from the reaction, drying, and II5 the product and its degree of hardness with-gelatinizing the compound with a solvent of in very wide limits. The manufacture of the nitrocellulose holding camphor in solution, hydrocellite is free from danger, because the for the purposes set forth. nitrocellulose is worked up while in such a 8. The herein-described product consisting 55 Wet condition that it cannot even be ignited, essentially of gelatinized nitrocellulose and a 120 much less exploded, while the drying is ef hydrate or hydroxid of a metal, substantially fected after incorporation there with of a salt as set forth. of a metal which renders the compound prac In testimony that we claim the foregoing as stically non-explosive at the degree of heat our invention we have signed our names in necessary to dry the same, so that the drying presence of two subscribing witnesses. operation is also not fraught with danger. CARI, GUSTAW HAGEMANN. Finally, the cost of the hydrocellite is very ma FRIEDRICHOTTO CORNELIUS ZIMMERMANN, - terially less than that of celluloid, while the Witnesses: range of use of the former is equally as great JACOB ADRIAN, 65 and in fact greater than that of celluloid. FRIEDRICH MARDO.