Patented Dec. 3, 1946 2,411,989 umi‘Eo' STATES PATENT OFFICE PAPER Cosmo HenryV. Dunham, Bainbridze, N. Y., assignor to H The Borden Company, New York, N. Y., acor poration of ‘New Jersey '- No Drawing. Application February 5, 1942, ' 1 . Serial N0. 429,680 .9 Claims. This invention has for its object the use ofv .certain well de?ned constituents present in seeds of relatively high protein content,_such as for example soybean, peanut, cottonseed, sun?ower and the like in the manufacture of coated paper, tein seed'meals. One method is known as'the extraction process, where the seeds are crushed and extracted with a highly volatile oil solvent such as hexane. Another process, known as the ‘ hydraulic process, relates to crushing the beans or wall papers and the like. I have found that such products derived from certain portions of high protein seeds are very’suitable for use in the , making of coated papers, wall papers and /the like, e. g., the sizing of coated paper in connection 10 with mineral ?llers and pigments. _ (Cl. 117-156) ‘ seeds, heating to various degrees, and compress ing with an hydraulic press toremove ‘the oil. A third process isv of the expeller type, wherein the beans or seeds are run through an expeller at various degrees of . temperature. Under the ex-. peller process high pressure is applied to the seeds One object of this invention is to utilize a high protein seed residue which has been substantially increased in protein content above the protein content of the unenriched seed meal as ordinarily 15 by means of a screw in the expeller chamber, with the result that the oil is pressed from the seeds and the relatively oil-free meal expelled from the expeller. In general, a solvent extracted obtained. meal will analyze very low in oil, only about 0.5% Another object is to utilize for paper coating in many cases‘ remaining in the meal. By the purposes a seed residue of relatively high protein hydraulic or expeller processes the resulting meals content as distinguished from the seed residue may contain from 4 to perhaps 7 to 8% oil re prior to its enrichment as heretofore used in 20 maining in the meal. Any .of the meals resulting coating. The’ process is sharply distinguished from the above mentioned‘ processes are suitable from the use of chemically isolated seed meal for utilization in my invention, although I pre proteins, several processes for which have been fer seed meals resulting from low temperature heretofore proposed. treatment of the seed rather than high tempera A further object is to provide a means for uti lizing the product of this invention in a simple and easy manner. Another object is the utilization of the seed reduce of increased protein content for paper 25 ture. In the utilization of products relating to this invention, I ?nd that products produced from cottonseed, peanut, or sun?ower meal usually re sult in producing a rather dark colored product. coating, without greatly changing the charac 30 Often for the purposes of this invention a light ter and properties of the major portion of the colored material is desired. ‘Because of the above, protein present in the seed substance, as would occur by chemical reaction. .in most cases ‘I use soybean meal of light color ' as the starting material. In some types of coated A still further object is to obtain greater ad paper it would be undesirable to use these dark hesive values for paper coating over and. above 35 colored products because of color, although for the adhesive values of the raw material hereto dark coated papers this would not be objection able. ' fore employed in utilization of seed meal prod ucts for paper ‘coating. In‘ general, my invention consists in the use Other objects will be apparent to those skilled of a high protein seed substance from which a in the art. _ 40 major portion of substances soluble in weak acid In describing the'process and its results for solutions, and in solutions of certain types of the purpose of this application, I shall refer to salts, as mentioned below, have been removed, products made from commercially de-oiled, rela and these substances which are removed with tively high protein content soybean meal as the such solutions I shall refer to as “gummy sub- _ raw material used in many of ‘my tests in develop ing this process, although in general, the same methods may be used and similar results secured, using other high protein seed substances such as peanut meal, cottonseed meal, sun?ower seed meal and the like. In all cases, the object of this process is to utilize, as a starting material, the 45 stances.” After the gummy substances have been removed from the seed residue, the degummed material may be dried or washed and dried, and ?nally ground when it is ready to be used as a glue or adhesive for paper coating purposes. Many acids, acid salts, and‘ some normal or neu tral salts, when used in very weak solutions in water, have the property of retarding or pre de-oiled commercial high protein seed meals, The process of de-oiling seed meals is well venting solution or undue swelling of the major known in the art. There are three commercially portion of the protein (including water-soluble used methods for removing the oil from high pro 55 protein and water-insoluble protein) present in 2,411,989 the de—oiled seed residue, but permit certain sub stances (gummy substances) in the seed residues to dissolve without dissolving the major portion of the protein material present in the meal. Thus, it is quite simple in commercial operations to remove the major portion of these gummy substances from the seed residue, without dissolving much of the proteins therefrom. This treated product is preferably then dried and grounii. The ‘product is then in an excellent physical condition for handling (drying) in com mercial operations. It is not in a sticky, exces sively swollen condition as would be the case if water were substituted for the extracting solu 4 removal of fibrous material can be accomplished later on, after the degumming process. In order to better illustrate this invention, and to show how ‘the same can be performed, I give herewith the following data and examples. Un less otherwise speci?ed, all parts mentioned in the examples are by weight. Emu‘. I The following ingredients are employed: 100 pounds of the so called “mechanically mill re?ned” soybean mealv analyzing 54% protein, which has been ?nely ground. 1000 pounds of degumming solution contain- - tion referred to above. This step of removing 15 ing 4.5 pounds of dissolved ammonium bi?uoride. the material which I refer to as gummy sub stance from seeds of high protein content has been referred to in the literature as a means The procedure is as follows: ' ' Into a suitable mixer in which a rather slow agitation is provided, say an agitator rotating . at 30 to 60 R. P. M., I place the 1000 pounds of of preparing such seed residues for the isolation of protein. That is to say (in a prior process), 20 degumming solution, which may be at or below room temperature. Thereafter I add the 100 after the degumming treatment, the material has pounds of soybean meal, the mixer is started, then been treated with a protein solvent in the and the agitation continued without heating, the presence of water to dissolve the protein portion same, for approximately 30 minutes.v Thereafter of the seed residue.‘ Thereafter the rather dilute protein solution has been ?ltered or otherwise 25 the mixing apparatus is stopped, the material allowed to settle for about an hour, after which separated from the, ?nely suspended insoluble time it will be found that a large portion of the substance present in the seed residue substance, insoluble residue or degummed material will have and which is not dissolved by any of the protein settled tolthe bottom of the mixer. The super solvents. After removing all, or substantially natant liquid is drawn o? as much as possible 30 all, of the insoluble substance by means of a without removing appreciable quantities of any ?lter press, a centrifugal, or some satisfactory suspended degummed material. Thereafter the mechanical means, the protein solution has been balance of the material which contains the solids dried by any of the convenient methods such as or degummed material and a portion of the liq spray drying and the like, or the solution has been concentrated to a greater or less extent 35 uid degumming solution containing the gummy substances may be run through a ?lter press or (in vacuum, for example), and utilized in that placed in a hydraulic press, or may be put through condition.. Furthermore, the protein has been a centrifugal to remove the greater portion of precipitated from such solutions by the action the remaining gummy substances in the degum of acids or acid salts. In the latter case, the precipitate is allowed to settle out as much as 40 ming solution. The solid undissolved material possible, the supernatant liquid removed, the pre cipitated material pressed, dried and ground. This latter product is commonly referred to as can also be given a water ‘wash, if desired. The liquid can be separated from the undissolved degummed material in any suitable manner. The resulting pressed cake of degummed material is I make no claim for any of the procedures 45 broken up, preferably by putting it through an ordinary casein picker which breaks the cake into outlined above wherein the suspended insoluble relatively small pieces in order that the same. material is removed from the protein solution. may dry rapidly. Neither do I make any claim herein for the The drying operation may be carried out by process per se, of extracting the gummy sub stances from seed residues by the utilization of 50 any convenient means, such as utilization of an ordinary continuous casein drier, or the ma any particular salt or acid. My invention in a "chemically isolated precipitated protein." terial may be dried in a casein tunnel drier,. or volves also the use of the degummed material by any other suitable drying method. I prefer as outlined above, preferably produced as de that the material be dried at a temperature of scribed herein, without the removal of the other non-protein substances which are ordinarily re 55 not more than 150° F., although this exact tem perature is not absolutely essential. After the", moved only by dissolving the protein in a pro degummed material is thoroughly dry it is ;tein solvent, and ?ltering or otherwise removing ground to a powder, for example 80 mesh, or i ?ner if desired, when it is .ready to use as‘ an centration or drying,vand the like, and the in 60 adhesive in paper coating compositions. 'the'suspended insoluble material therefrom, and 1 thereafter further treatment of the same by con corporation thereof with fillers, pigments, etc. It will be understood that in my present process, the hulls or husks of the seeds are largely re During the treatment with the degumming solution, the gums,’sugars, some coloring matter. and perhaps other substances, all of which are herein included under the term "gummy mag. moved at any suitable stage of the process. This can in many cases be‘ accomplished prior to the 65 terial," are removed; but only very little of the 1 protein is removed from the seed material dur-' de-oiling of the seed material. ing the degumming treatment. Since the con In-many cases the seed meal is "mechanically stituents so removed appear to be largely car mill refined" by purely mechanical operations in bohydrates, the per cent of protein in the leached cluding grinding, sieving and blowing operations, and the like to‘ separate some of the ?brous mate 70 and dried residue will be found to have been iggeased up to about 60 to 73% (usually 67 to rial (which step may give an increase in the pro 0 tein content of the seed meal material say from This dried material is then ready to be shipped. 40-44% up to 47-54% protein content, also giv to a paper-coating mill, wall paper factory, etc. ing a “protein-poor" materialthat may be suit able as a stock feed). Or in some cases such 75 Various other methods for the degumming of 5 2,411,989 6 seed meals are given in the following examples, together with tables showing analyses on the Exunm: VI Same procedure as in Example I, but using a soybean meal showing a protein content of 49.7%, the meal being prepared by what is known as resulting products, etc. In every case the pro tein ?gures appearing in the analyses are based on calculating the nitrogen on a moisture-free sample and multiplying by the conversion factor the expeller process, showing a ?ber content of .. 6.25. approximately 7%, and an oil content of about ' . In this and the other examples given, the de 0.5%. ' gummed material prior to'drying may, if so de EXAMPLE VII sired, be washed with water to further remove 10 ~ Same procedure as in Example I, with the small amounts of the gummyvsubstances which exception that a high grade 011 extracted peanut would not be removed by simply pressing the ' meal was substituted for a soy product as the degummed material in a ?lter press or by other raw material. ' means. This may be accomplished by any de EXAMPLE VIII sired means, as, for example, by use of continu 15 ous ?lters which are now on the market. Some Same procedure as in Example I, with the of these include a rotating ‘drum covered with exception that a high grade cottonseed meal cloth, and inside of which there is produced a was substituted for the soybean meal as the raw vacuum. The drum rotating in a suspension of material. the degummed material and the gummy solution, 20 EXAMPLE IX that is, prior to any separation, picks up due to Same procedure as in Example I, with the exception that a South American pressed type of sun?ower meal was used in place of soybean the vacuum a uniform layer of the degummed material, and as the drum slowly revolves, the interior suction causes the solution of gummy materials to be sucked away from the degummed 25 meal as the raw material. material, to the point where there is, e. g. about EXAMPLE X 70% of moisture‘still present in the cake as it Same procedure as in Example I with the ex comes from the revolving drum. Now if one de ception that the soybean meal was ?rst added to sires, there may be applied a spray of water at some point on this vacuum drum and thus wash 30 cold water in the'proportions indicated (1. e. 100 lbs. of meal to 1000' lbs. of water)‘, thoroughly the degummed material. Of course other meth mixed for about 5 minutes, and thereafter the ods of separation and/or washing would be pos dissolved ammonium bi?uoride, 4.5 pounds, was sible. Thus in Example I, after removing the 1 added to the mixture, and the procedure con supernatant liquid as described, a volume of wa ter can be added, to wash the degummed ma 35 tinued as in Example I. I consider this pro cedure to be less advisable than that given in terial. Thereafter the degummed material can be allowed to settle without becoming sticky or gummy because of the removal of most of the Example I. - > By the above procedure, Example X, a consid gummy substances. Then the wash water can erable amount of the water soluble protein orig be drawn off, and the resulting mass then 40 inally present in the raw material is dissolved in pressed and dried in any suitable manner. Any the water, since the solvent retarding degumming chemical is not present in the mix at the begin other suitable means may be used if desired for washing the degummed material. ning of the treatment, but after the addition of the degumming chemical (ammonium bi?uo It will be apparent that the removal of all the gummy material, if no substantial amount of 45 ride) the water soluble protein as such appears to be substantially all (or mostly) precipitated proteins is removed, will increase the percentage by the addition of degumming material and after of protein in thegproduct, in contrast to the re properly mixing and allowing the mix to stand. moval of a part only of the gummy material. At this stage the supernatant liquid is about the EXAMPLE II 50 same in appearance as in Example I, but the set Same procedure as indicated in Example I with tling of the degummed material is somewhat less the exception that a high grade soybean meal rapid after the mixing operation than when the was used as the raw material, analyzing 51.3% degumming chemical is added to the water prior protein, and showing a fiber content of approxi to the addition of the material to be degummed, mately 7%. This is a solvent extracted type 55 although there is no di?iculty encountered in ?l meal, and the product used was in an unground tering the degummed material or pressing out form, that is to say, in a ?ake form. the excess liquid as described in the operation under Example I. As has been indicated, other EXAMPLE III degumming chemicals may be used, and the uti Same procedure as in Example I, with the ex lization of the ammonium bi?uoride in the exam 60 ception that the raw material used was unground ples cited above are only by way of illustration. ?akes‘ of solvent-extracted soybean, showing a The results as to increase in protein content protein content of 49.2%. over the raw material, raise of protein obtained’ EXAMPLE IV by the treatment, yield of the degummed material Same procedure as in Example I, with the 65 based on the raw material used, and per cent of raw material retained in the treated degummed exception that there was used a soybean meal material appear in Table I, given below. analyzing 51.8% protein, and which is believed Many di?erent degumming chemicals have to have been a solvent extracted type of meal. been used in my researches, and the results have EXAMPLE V 70 shown substantially the same quality of de Same procedure as in Example I with the ex gummed material from the standpoint of its sub ception that a soybean meal was used showing by sequent use as a sizing in coated paper. To more analysis 57.5% protein, and a low ?ber content, fully illustrate the results that may be obtained namely approximately 0.5%. This was a solvent with other degumming chemicals I give the fol extracted meal. 75 lowing examples: - 8,411,”? 7 8 Exunu: XXIV Same procedure as Example X, with ‘the excep Same procedure as in Example I-with-the exa tion that 3.7 pounds 01' sulphur dioxide gas were' ception that the degumming solution was‘ made substituted in this test for the ammonium bi with 3.8 pounds oi hydrochloric acid having a ’ ?uoride indicated in Example X. speci?c gravity of 1.18 to 1.19. ‘and 3.3 pounds 0! tin chloride (stannous chloride) in place of the EXAMPLE XII: use of ammonium bi?uoride. Same as Example I, with the exception that ExmLsXXV the degumming solution was made with 3 pounds 10 of phosphorous acid in place oi’ the ammonium Same procedure as in Example x with the ex ception that the degumming solution was made bi?uoride. ' v _ EXAMPLE XIII with '6 pounds of hydrochloric acid having a spe citlc gravity 01' 1.18 to 1.19, said hydrochloric acid Same as Example X except that the degum being saturated with calcium ?uoride prior to ming solution was made with 4.4 pounds 01' com 15 its addition to the mixture oi’ meal and ‘water, mercial hydrochloric acid having a speci?c grav indicated in Example X, and this mixture was ity of 1.18 to 1.19 in place of the ammonium bi used as the degumming chemical. ?uoride as the degumming agent. It will be noted that this gives hydrochloric acid solution Exmu: XXVI . of about 0.155% to 0.17% strength. 20 Same procedure‘ as in Example I with the ex Exmm XIV ception that the degumming solution was made with 12.5 pounds of saturated solution of citric Same as Example 1, except that the degum acid and lead chloride in which the ratio of the ming solution was made with 4.2 pounds of gla citric acid to the lead chloride was as 5 to 1. Said cial acetic acid as the degumming chemical. mixture of acid and the salt was added to the Exmu: XV diluting water in the proportions indicated in , Same procedure as in Example I except that Example I in place of the ammonium bi?uoride. the degumming solution was made with 5 pounds Exsxru XXVII of tartaric acid as the degumming chemical in 30 Same procedure as in Example I, with the ex place or the ammonium bi?uoride. ception that the degumming solution was made Exsuru: XVI with 25 pounds of acetin and 6.3 pounds of glacial Same procedure as in Example I excepting that acetic acid in the place of the ammonium bi?uo the degumming chemical used was 6 pounds of ride used in Example X. ‘ ' EXAMPLE XI ‘ citric acid as the degumming chemical. ‘ 35 ' EXAIPLE xxvm EXAMPLE XVII Same procedure as in Example X with the ex Same procedure as in Example I except that ception that the- degumming solution was made the degumming solution was made with 4 pounds of oxalic acid in place of the ammonium bi?uo 40 with 8.5 pounds of a mixture of triethanolamine and glacial acetic acid, the mixture being pre ride. pared by the addition of suillcient glacial acetic ExAMPLn XVIII acid to the triethanolamine so that the resulting Same as Example I with the exception that mixture had a ‘pl-I of 3.9, and this degumming the degumming solution was made with 6 pounds chemical was substituted for the ammonium bi of tin chloride (stannous chloride) instead of ?uoride. ' ammonium bi?uoride. The analyses, yields, etc., resulting from ex amples in to XXVIII inclusive, are indicated in EXAMPLE XIX Table II, given below. It should be noted that Same procedure as in Example I with the ex the .various examples listed above were made at a ception that the degumming solution was made temperature of approximately 60 to 70° F., room with 10 pounds of magnesium chloride in place temperature, 100 pounds of meal and 1000 pounds of the ammonium bi?uoride. ‘ jams as Example X with the exception that tii€desumming solution was made with 5 pounds of calcium sulphate in place of the ammonium bi?uoride. EXAMPLE XXI Other examples are given, however, with different temperatures used during the de summing process as illustrated by the following I oi.’ water. Exnnna XX ‘ Same as Example X with the exception that the degumming solution was made with 5 pounds of magnesium silico-?uoride in place of the am monium bi?uoride. examples. ExsurLsXXIX Same procedure as Example I, with the ex ception that the degumming solution was made with 2.1 pounds of sulphur dioxide gas, and the degumming solution maintained at a temperature of 110° F. Exam?“ XXX Same procedure as Example I with the ex 65 ception that the degumming solution was made EXAMPLE IQIII with 2 pounds of sulphur dioxide gas, and the de Same as Example X with the exception that the gumming solution was maintained at a tempera degumming solution used was 5 pounds of mono ture of 160° F. calcium phosphate in place of the ammonium bi Exmu XXXI ?uoride. 70 EXAMPLE XXIII Same procedure as Example I with the excep Same as Example X with the exception that ‘ tion that the degumming solution was made with the degumming solution was made with 5 pounds 2 pounds of sulphur dioxide gas. and that the de of neutral sodium ?uoride in place of the ammo gumming solution'during the process was main nium bi?uoride. ' . 75 tained at a temperature of 180° 1". 9,41 1,989 9 I . 10' Exsurnr: XL Exulru XXXII Same procedure as indicated in Example X . Same procedure as in Example I, with the ex ception that the degumming solution was made was made with 5 pounds of hydrochloric acid 5 with 6 pounds of tin chloride (stannous chloride) and 500 pounds of water. having a specific gravity of 1.18 to 1.19, and that The analysis, yields, etc., the washed products the degumming solution was maintained of Examples XXXVI to XL inclusive are indi throughout at a temperature of 100° F, The de with the exception that the degumming solution gumming solution accordingly contains. about 0.18 to 0.19% H01. . ExAmrLa xxxm Same as Example X, with the exception that the degumming “solution was made with 3.4 cated in Table IV. > 130° F. . . _elieve it would be readily possible to use even smaller amounts of water, in the degumming treatment, e. g.,_400 of water to 100 of the seed meal. pounds of glacial acetic acid, and that the de 15 gumming was carried out at a temperature of ‘ 1N Based on the above and other experiments, I . In order to demonstrate the improved adhesive value of the degummed material from the stand point of paper coating‘ the following results are EXAMPLE XXXIV given. The ?nely ground. degummed and dried" I material which may be ground to any desired Same procedure as Example X with the ex ception that the degumming solution was made 20 mesh, for example 80 mesh or ?ner, and made for instance according to the method described with 5.6 pounds of glacial acetic acid, and that in Example I, is mixed with cold water, the par the degumming solution was maintained through out the operations of degumming at a tempera-v . ticles thoroughly wetted, and the mixture may be allowed to soak in water for a short time, say ture of 190° F. 25 15 or 20 minutes. _(Here, as above, all parts are _ . 'EXAMPLE XXXV given by weight.) Thereafter an alkaline ma Same procedure as Example X with ‘the excep terial (or protein solvent as is the usual accepted tion that the degumming'solution was made with term for-such substances) .is added to this mix 5 pounds of ammonium-bi?uoride and that the ture, the mixture then thoroughly stirred, and degumming solution was maintained throughout 30 preferably heated to. about 120 or 130° F., while the operations of degumming at a temperature of. stirring to assist in' the dissolving. When the 180° F. . ~ degummed substance is dissolved, with the ex The Table III given below, is a tabulation of ception of the suspended insoluble non-protein the analyses, yields, etc., obtainedfrom the pro material, it is ready to be used as a sizing for cedure as described under Examples XXIX to 35 paper coatings; XXXV, inclusive. , Generally, there appears to be no substantial advantage now apparent in the useof tempera tures above room temperature (60-80‘ F.) in the degumming treatment. There are some disad vantages in the use of heat‘ in this treatment, notably that when the degumming treatment is effected at 30° F., the ?nal coating solution has somewhat better ?owing properties, when applied The exact proportions in pre paring the liquid size from the degummed mate rial and in they preparation _of the regular seed meal size, for comparative purposes, is as follows: Parts 40 ‘ Degummed material _____________________ __ 100 Water _____ ' - _ 500 10% solution of sodium hydroxide ________ __ 100 ' Here, as will be noted, 100 parts'of a 10% so to the paper. lution of caustic soda is mixed with 500 parts of It will be noted that in the examples thus far 45 water, to form a mild (1.67%) solution of caustic given, the amount of water used was on the basis soda which is used as the solvent or vehicle for of approximately 1000 parts of water to 100 parts the degummed material and pigmentary mate of the meal to be treated. However, the water rial. ratio may be adjusted to obtain the most favor For preparing the paper coating mixture, able factory handling conditi ns during the de- 50 (which is ordinarily referred to as "coating color” gumming process without in terially changing whether the pigment and ?ller are colored or the quality of the treated d summed seed ma white) , the following formula was used: terials. The following, exa ples illustrate the , Parts use of less quantities of water during the degum 5 Clay ___________________________________ __ 100 ming process: - ‘ EXAMPLE XXXVI Water _________________ __~_ ____________ __ 100 Liquid size ______________ __' ___________ _..~_.. 126 Same procedure as Example I except that the The clay is added to the water and mixed until a degumming solution was made with 3.2 pounds of smooth slip is formed. The liquid size is then sulphur dioxide gas added to 500 pounds of water. 60 introduced and mixed until smooth and until the I ' clay is completely dispersed. The above propor EXAMPLE IDIXVII tions give a concentration of 18 parts of dry siz Same procedure as Example 1 except that the degumming solution was made with 2.5 pounds of sulphur dioxide gas and 500 pounds of water. EXAMPLE XXXVIII Same procedure as in Example 1, with the ex ing material to 100 parts of dry clay. The prepared paper coating color is preferably 65 strained through an 80 to 100 mesh wire screen . and thereafter brushed on to the type or paper ordinarily used in the paper coating industry. .or applied to the paper by some coating machine ception that the degumming solution was made such as for example the laboratory coating ma with 4.4 pounds of glacial acetic acid using-500 pounds of water instead of 1000 pounds of water. 70 chine known as the Martinson, wherein an ex act amount of the coating color can be applied EXAMPLE XXXIX per unit area in each test. After the sheets of paper have been coated they are allowed to dry Same procedure as in Example I, except that and to season for approximately 18 hours in an the degumming solution was made by using 500 pounds of water instead of 1000 pounds of water. 75 air-conditioned room with a relative humidity of aunties 11 -. \ 50%, and a temperature of 70° F., in order to maintain uniform conditions during the test pe riod. After the proper aging. of the coated sheets their relative qualities were tested. In mytests I have employed the almost universal procedure . known “the Dennison wax test, which may be . described as follows: The end of the wax stick is softened by hold ing over. a flame. The softened end is then, 12 outside shell or hull of the bean, that the result ing degummed dried material is thereafter ground by any suitable mealre?ning method to remove the major portion of the outside shells or husks of the bean, and at the same time reduce the re maining material to a relatively ?ne mesh, prei- ' erably 80 mesh or ?ner. This relatively ?ne ground condition, in the ?nished product is im portant from the standpoint of its use for-paper pressed by hand against the coated surface to 10 coating purposes. The coarser the ?nished ma terial may be, the more slowly will it dissolve or be tested, using moderate pressure. The wax is allowed to cool and harden. Then it is pulled disperse in the alkaline solvent in the presence of water when being prepared for paper coating away from the surface of the paper. The wax sticks are supplied in graduated degrees oi’ hard purposes. I do not restrict the invention to the particular alkali mentioned (numerous others. ness, the lowest number being the softest and including trisodium phosphate, ammonia,sodium giving the least pull on the paper suri'a'ce,the higher numbers becoming progressively harder carbonate, etc., can be used). I do not restrict and giving more pull to the surface. By applying the invention to the use of clay, water and size onlyfin the “coating. color" since colored pig a series of the wax sticks to the paper, a point will be found where no failure of the coating or 20 ments, dyes, etc., can be added, and the clay paper stock takes place with a given wax stick, can be substituted by satin white, calcium car bonate, and other ?llers. ‘Such pigments, dyes but when applying the next harder wax stick and ?llers will hereinafter be referred to for there will be failure. The end point ofthe test brevity, as “a suspended pigmentary material." (the number recorded to indicate the strength of sizingin the coating) is the number oi‘ the hard 25 The degummed material made as described in this speci?cation may if desired be mixed with est wax which does not cause failure. other adhesive materials for paper coating pur Coated sheets were prepared and tested, as de poses such as combinations of casein, animal glue, scribed above, coated with colors prepared from modi?ed starches, and the like in such propor the products of several of the above examples as the sizing material for the clay. Papers coated 80 tions as might be desired. 01 the proteinsol vents mentioned, caustic alkali (e. g. NaOH) with several untreated seed meals were tested for seems to be better than the others tested. = comparison. The results of these tests are tabu The above mentioned and similar seeds in their lated and appear in Table V, below. original condition include cellulose in two dis It will be noted that there is a very large ‘in crease in the ‘adhesive value of the sheets coated 35 tinct forms, namely (a) a hull or shell composed of one or several layers, which hull is composed with my degummed product as compared with largely of cellulose in a relatively tough and use the sheets coated-with the raw seed meals used less condition and (b) cell walls in the interior in preparing the degummed material. or'kemel of the seed, which latter is softer, and It will be understood that the above examples oi’ paper coating are for the purposeof illustra 40 less tough in character. The former will be re ferred toas “hull,” and the latter as “non-hull tion only. I do not restrict the invention to cellulose," for brevity. In the process of the pres , grinding the degummed material to 80 mesh or ent case, the “hull" is‘ all or substantially all re ?ner. Thusv in Example II, the product was moved from the seed material during the process treated by the degumming process in the un ground or ?ake form. This coarser material has 45 ing, whereas the "non-hull cellulose” is not re moved, at least to any considerable extent, and the advantage that it does not tend to lumpor remains in the treated dried product. In the ball up when mixed with water and the acidic process very little of the protein content of the degumming material. Furthermore. after proper seedmeal is dissolved out and very little of the treatment, such coarse degummed ?ake material settles from the. supernatant liquid more rapidly 50' "non-hull cellulose” is removed, and accordingly the ratio of protein to non-hull cellulose, as orig than a ?ner ground material would do. It should inally existing in the seedmeal and in the me be borne in mind, however, that if the unground chanically mill re?ned material practicallyis sub or‘?ake form of material has been treated either stantially preserved throughout the treatment. with or without a considerable proportion of the TABLE I Degumming treatment of various seed meals with 4.5 parts of ammonium bi?uoride per 100 parts 0;! meal and 1000 parts of water Emmple numbe' Peroent pro- Percent pro tein in raw “in iilngg‘ material gum Raw material treated material Soybean meal ............... _. Rise in per- Percent yield Percent pro cent of pro- on raw matein ro am ierial tained I 53. 0 70. 3 17. 3 65. 0 ._-..d 51.3 62.4 11.1 81.8 _-_._do- ' 49. 2 63. 1 13. 9 78.0 .-___do_ ...-.do. 51.8 57. 5 64.4 68. 6 12.6 11. 1 79.8 76. 1 ..___do __________ _. Peanut meal .......... .. 49.7 64. 2' 63.5 74. 3 13.8 l0. 1 76.5 84. 0 97.6 97. 3 48. 2 58. 8 l0. 6 80. 2 9s 0 _ Cottonseed meal ...... __ _ Soy ............... -. 1 Used 5.0 parts oi ammonium bi?uoride. ' Moisture contents disregarded in values. 40.3 53.8 53.0 69. 0 _ 7.5 84.3 l6. 0 65. 1 8o. 2 99.6 1i!) 99.2 90. 9 _ 01.7 85. 0 2,411,989 13 ~ _ Tm: II - . Deyumming treatment of soybean meal (from the same lot) having 53.0 per cent protein with various chemicals and chemical miztures Dcgummlng Percent pro chemical Chemical used in degumming treatment percent 01' tcin in de- mos] ééhdtiliééiié'h'cié‘i?ii iii} 87916305 87916305 7042835 aving a Rise in per Percent yield Percent otto cent protein in do gummed tal protein in raw material produced men] retained mw%wm .1 6G.750m392Q4n 376 376 68. 9 70'. 9 15.9 17. 9 64.5 83.0 68.0 62.0 88.3 . . 82.9 TABLE III Treatment of soybean meal of 53.0% protein con tent with various chemicals and 1000 parts of water to 100 parts of meal at higher tempera tures Chemical used percent of meal Tmmt,mm .r 046 8 sum1mm.mw m Ppdoreimam m amw nMad$61026 w e, RmanD.or rm m a n :mM7.5a?w& to1 mm...“ 1 nde. UW_ m mm D " 86102 m d mm"7?%"a.5..&.ml?. "60571 Hfor m“n‘mwmw6.11“a0 0. tnm"11 . TABLE IV Degumming treatment of soybean meal having 53.0 per cent protein with 500 parts of water and 100 parts of meal and various chemicals Chemical per 100 of meal Chemical used xx XEXL0xxxxm. wmwmmm0. a f m I _ . degummed mamamamamama when m Teen: V Parts Parts Wax test Sizing material Soybean meal (not treated)..-“ Product of Example I. Product of Example X . _ . Peanut meal (not treated).______ Peanut product (treated as m Example I). on meal Percent of protein re tained in degummed I claim 1. In paper coating, the process which consists in ?rst leaching a high protein content seedmeal ‘0 with about 4-to 10 times its own weight of an acid aqueous solution having an acid content equal to about 3.8 to 6 lbs. of hydrochloric acid solution of sp. gr. 1.18 to 1.19, per 100 lbs. of said seedmeal, said seedmeal material to a protein-denaturing treatment, mixing the degummed seedmeal ma 18 18 100 100 Partial on 2.I 5. 1 No. 2 is lowest wax available. The minimum wax test, for a coated paper, for a useful product for being printed upon is about 4.5 (four and a half). Percent yield thereby dissolving and removing the bulk of the '35 carbohydrate gums, and without subjecting the Product of Example IX. _ Product of Example XIV Product of Example xI.___..-. Cottonseed meal (not treated)__ Cottonseed product (treated as in Example I). Rise in per cent protein 3.24%16 2540 ,50287 1 6.5 L 50287 w .mn 03 8 .27 7089 phur dioxide._... .. __ KATs Percent protein . terial with an aqueous alkaline liquid of an alka linity equal to about 1.67% of NaOH, and with 70 a pigmentary material, and coating paper with said mixture. 2. A process as covered in claim 1, in which the seedmeal material is one selected from the group consisting of soybean, cottonseed, peanut, 75 sun?ower seed and mixtures thereof. 2,411,900 15v -4 3. In the paper coating process of claim 1, the . 16 therefrom by means 0! an extremely dilute addition of a water-washing step after the leach aqueous solution of an acidulous material, which ing operation. ahueou's solution is not an effective protein sol ‘ ‘ ‘ in ?rst leaching a high protein‘ content seedmeal vent, whereby a material richer in protein than ' the de-olled seed residue and low in water-soiuole _ with several times its own weight or an acid aqueous solution having an acid content equal to gums and vother soluble carbohydrates is pro duced, and at some stage of the process removing - 4. In paper coating, the pr ess which consists substantially all hull material, incorporating such degummed seed meal with an‘ alkaline solution therebyv dissolving and removing the bulk of the 10 which is an eil'ective protein solvent, and without about 3.8 to 6_ lbs. of hydrochloric acid solution of sp. gr. 1.18 to 1.19, per 100 lbs. of said seedmeal, carbohydrate gums, and without subjecting the . said seedmeal material to a protein-denaturing thereafter removing the bulk of the swollen un dissolved constituents, incorporating a paper treatment, mixing the degummed seedmeal mate coloring pigmentary material with the liquid rial with an-aqueous liquid which is capable of mass,‘ and applying the same as a coating on dissolving the protein content of such material, 15 paper, and drying the same. 1 8. In the art of coating paper, the improvement and with a pigmentary material, and coating which comprises separating at least the principal paper with such mixture. part of the oil content from‘ proteinaceous oil 5. In paper coating, the process which consists in ?rst leaching a high protein content seedmeal bearing seed material, leaching the de-oiled ma* with several times its own weight of an aqueous 20 terial with a dilute solution of a compound con liquid which is a good solvent’for carbohydrate taining an acid radical, which solution is a less gums contained in ‘said seedmeal but which is less active as a solvent for‘water soluble proteins present in said seedmeal than is pure water, effective solvent than water alone for water-sol ‘uble protein present in the seed residue, and which is a good solvent for soluble carbohydrates thereby dissolving and removing from said seed 25 including gummy substances, whereby a material meal the water soluble carbohydrates including richer in protein than the de-oiled seed residue carbohydrate gums, and without denaturing the and low in water-soluble gums and other water soluble carbohydrates is produced, and at some proteins present'in said seedmeal, thereafter mix stage of the process removing substantially all ing the degummed seedmeal residue with an aqueous protein-solvent liquid and'with a pig 30 hull material, incorporating such degummed ma mentary material, and coating a fully formed terial in which material the proteins present re paper with the resulting liquid. main in substantially the same condition as in the 6. In the art of coating paper, the improvement original seedmeal with an alkaline solution which which comprises separating at least the principal ‘is an e?ective protein solvent, and without there- , part of the oil content of proteinaceous oil-bear 35 after removing the bulk of the swollen undissolved ing- seed material, raising the protein content of constituents, incorporating a paper-coloring, pig the proteinaceous solid material by the removal - mentary material with the liquid mass, and apply-v of cellulosic hull therefrom, leaching out gummy material therefrom by means of an extremely dilute aqueous solution of an acidulous material,‘ 40 corresponding in acidity to KC! solution of about 0.155 to 0.19%‘ strength, which solution is not an effective protein solvent, but which is a solvent for water soluble carbohydrates including gums, whereby a material richer in protein than the 45 de-oiled seed residue and low in gums and other soluble carbohydrates is produced, and at some stage of the process removing substantially all ing the same as a coating. on paper, and drying the same. 9. In the art of coating paper, the improve ment which comprises separating at least the principal part of the oil content from protein aceous oil-bearing material, leaching the de-oiled material with a dilute solution in which water soluble proteins are largely insoluble. and are for the most part in the undissolved state and in a condition readily soluble in alkaline casein sol vents, whereby a material richer in protein than the de-oiled seed residue and low in water-soluble hull material, and drying the said material, while still containing substantially all of the compo 50 gums and other water-soluble carbohydrates is nents of the seed meal except those removed by produced, and at some stage of the process re the above steps, thereafter incorporating the de ‘ moving substantially all hull material, incorpo gummed material with an alkaline solution which rating such degummed material, while still con is a protein solvent, and without thereafter re moving the bulk .of the swollen but undissolved constituents, incorporating a paper-coloring pig _ mentary material with the liquid mass, and there after applying the same as a coating on paper. 7. In the art of coating paper, the improvement ' taining substantially all of its protein in a chemi cally unmodi?ed condition, with. an alkaline solu tion which is an effective protein solvent, and without thereafter removing the bulk of the swollen undissolved constituents, incorporating a paper-coloring pigmentary material with the which comprises separating at least the principal 60 liquid mass, and applying the same as a coating part o'i'the oil content of proteinaceous oil-bear- . ing seed material, leaching out gummy material on paper, and drying the same. HENRY V. DUNHAI'. 1? Certi?cate of Correction Patent No. 2,411,989.- - 18 _ December 3, 1946. HENRY v. DUNHAM It is hereby certi?ed that error appears in the printed speci?cation of the above numbered patent requiring correction asfollows: Column 1, line 29, for the word “reduce” read residue; and that the said Letters Patent should be read with this cor réegion therein that the same may conform to the record of the case in the Patent ce. - Signed and sealed this 11th day of November, A. D. 1947. [81m] THOMAS F. MURPHY, Assistant Oommissioner of Patents.