[1]Patented May 16, 1933 11908 716 UNITED STATES PATENT OFFIC'E. FRANK M. WILLIAMS, OF WATFRTOWN, NFW YORK XETHOI) OF PF.ODUCING DRY SIZE No Drawing. Application filed April 26,1930. Serial No. 447,768. This iiivention relates to sizing compositions aiid metliods of preparing the same, and it has ptrticular reference to water dispersible sizing composition . rod-Liced dip rectly from materials in the dry state and solid phase. In a copending application, Serial No. 429@210, filed February 17,1930, 1 hltve poiint- - ed oiit ,t nuiiiber of @ f tetors involved in tlie 10 in-,intif -,icture and tise of sizing coinpositions. I may here state that a sizing composition is a iiiiterial employed to impart water repellent properties ,ind ink bearidg pr6 ties .per alid to re,-Iiiee the c,@ipillarity of tl-ie fibei-s in 15 Stich materials as textile fabrics and paper. For sizing Pqper, it has heretofore been proposed to employ soclium resinate or a rosin soap, made by the action of a hot or cold alkaline solution on ordinary rosin, or by fus2,3, i _Ilg too, th r the alkali ,tnd the rosin. These ,@e e prodiiets yield rosin soap or sodilim resinate, which may b6 dil-Lited with water, added to the paper stock, and subsequently precipitated on the fibers by the use of ,t suitable 25, aq:ent, such as iltim or stilphuric acid. As expl,,iined more fully in the aforesaid copen(ling ,tpplication of -which the instant case mty be regarded as a continliation in part, I hi-ve fotind that it is unnecessary, in the preparation of water-clispersibl6 sizin .9 niaterial, to resort 'uo the tise of hot or cold alkaline solutions, or to ihe relatively high teiiiperatiires eniployed in f-Lision methods. In accordance -w.ith the phases herein set f ortli tnd claimed, I treat the solid material iii the solid ph,,ise, tnd at a temperature below its flision point or softening point, wllile in the dry state, or substantially f-ree 40 fi-ol-n excess water, with a substance which is@ capable of beino, pepti@ed,,tn(I dispersed,with water. The sL@Gstance which I employ - niay be chemically. lionreactive toward the siziii(y material, or may react therewith to form e t reaction prodtict or soap; or, I may us a 4u, iiiaterial ivhich, iii accordance with the methods that I have developed, is i-ilert wheii used incert-,ii,n proportions, and which is ehemically reactive when Lised in 6ther propprtions. For a b,,tse or sizing iuaterial I may refer to co,lophony or ordiiiary rosin as a typical example. This inaterial is insoluble in water in its natural form, and is not readily dispersible in stich medium, even at elevated temperatures. By my method of treatment, however, I am able to produce a rosi n size capable of forming a complete and perma-, nent dispersion of rosinthroughout an aqlieous, iiiedilim ivhich is a substantially homogeneous, - dispersed inixture of rosin, protect- 60 ecl in its dispersed f ori-n, - by tl-ie substances re-,tdily peptized by ivater, and whivh aid iii the peptization of the rosin in the liquid or aqueous n-teditim. Such dispersion will occur only subsequent to the intimate rind- 65 9 ing, crushina, and inter-dispersion of one si-ibstance within the other, such as is contemplated by improved process and not I,ny by a mere mixing action. As extmples of 70 substances, ",hich wh n intimately intere ii-iixed with. rosin, stibsequently produce a dispersible rosill wlien, gr,ound iiiinutely tl).erewith are,starch, (yelatin, alli:aline casein, s6di.Lim silicate, sodiiim carbonaie, and sodiuni hydroxide. 75 The method of pi,eparin@z the'dry sizing compound consists in pulverizino, or o,rinding @n I@n the natural rosin with t selective protective @st,,tbilizer, both,silbstances being iii the iaormally. dry stage, that is, in the presence of "O only so 1,,trge a quantity of water as may be present as hygroscopic moisture upon the surf aces of the dry substance, which quantity will be conditioned by the humidity of the surrounding atmosphere. For I eftectively producing filiely divided and intimate@y inter.-dispersed mixtures, the grindinv is e:ffected at temperatures considerably. below the fusion poilit or softening pcint of the constituents of the mixture that is to say, below: about seventy dearees centig@,,,de., In tlle practictl,wa,.y of rli ing, I cm, I)Ioy a ball mill or pebble mill, ai).d 1, rind ihe constitLieni4 which I desire to incorporate iii my finished dry sizing mixture siintiltaneously, for reasons set fortli hereinabove. I prefer to chtrge lumps or chunks of the raw materials, which are preferablv larler than a quartet inch in size. During the grinding and pulv I erizing of these particles, 85 90 95 100
[2]2 1,908,716 air films surrouriding them are elimiliated and -tn intimate imprealiition of one into th,e otlier is effected. By employing a b,,tll mill, pebble mill, rod mill or disc mill the co.ltinuous impact and rubbin,@,, action of the harder fliiit.IT pebbles, rods or discs upon the rosin ana the protectlive stabilizer with ivliieh it is bein ground, insure intimate contact of the 10 fi nished a-nd finely ground m,,tterial. By th'e use of such t mill, I inay work the process aclvantageously as a contiriuous one, but where condit;-ons reqliire, it cati iiatur,,illy be an intermittent process as well. I li-,tve discovered that it is possible to mtke a rosin soap by intimately grinding, rubbing, and ci@ushino, together pirticles of rosiii, and ,,t saponitying ao,-ent. Wheii ihese substances are in a normally dry condition, or siibst,,in@- 20 tially dry, no cheniical reaction occurs when the solid ingredients are mixed tooetlier. ?@, However, the finely divide(I and intim@,ttely interdispersed products of the saponifying agent and rosin, is to be disti-ngiiis]-ied from t 25 inei-e inixttire of tliege subst,,tnees. Diirinth,e crusliing and u@inding actioti the attrition of one part, -icl@upon @nother, the criishiiig shegrin,,- ,ictiou I)roduced iiitliiii t,h6 orinding mill not only mix these vtri ous so ingreclients, but prodiiee an iiitimate impreanation of one particle within tl-ie other. m Tb.is friction and attrition pro(I-Lice sufiqcient local h6ating to insure t substantialllr con-lplete chemicil reaction bet-ween o-.i(,, molecule 35 -Lipon an adjacent molecule, yet, without heati-n- the mass. Such a result could not pos1, i ere mixin- of the ,,ibly be obtained b i-n pulverized materials at room temperatiir(,. I, believe that I also eltect anotb.er im40 port,,i.nt resiilt by means of this grindidg a,ncl attrition, that is to say, -where ,i gaseoiis env;el(pe surrounds the various p,,ti-ticles in the i,eacting mixture, the said envelope tend,,3 to 45 prevent ell-emical retetion of tlle contigtious 1),,trticles. During tlie, crus'@in(r and grinaing action, howe@er, the (r-,iseo@@s film'is de-,itcl disi-)(,rs,--i or t,@lie IL-e-.qac;,tv with -\Tl-iieli ill-j ter@ds to ziirroiincl tl-io, plirticle. so 50, materi,,illy lessened, thit chemical re,'LctiOn will ocetir between tlie fipely divicled materials. Tn one wav of working, I grotincl to.(,retber in the drv @iate one biinclred ptrts of COIO55 phony resin of light vello-w color witli fifteen parts of dry soditim'hydroxide. Tbe resiilti,ng material was -a clry powder cotisisting. e -Drep,-tred ssentially of soclium re-qlT,.a,te. withotit recoiirse to hiyl-i temt)eratures o-r c ' alk,,iline sollition. When diqsolve,-l in water C, 0,: to form a five per cent soliition, tliere w,,ts obtained a clear tea colored li(i-Liid, which coulcl be clarified and decolorizecl'bv tlae acld;-tion of alum. In another wiy of -worli:ing, T groiincl, toffetl-ier in the drv state one hundred pirtg of rosin with forty parts of sodium carbonate tc, produce a dry powdered substance. Upon shaking the material -Lip with water, I found that there was produced a turbid colored liquid producii-ig a lather upcn shaking, and 70 containing no lumps or nodules of rosin. This dispersion looked very much like an ord@na)ry soap solution. The dispersion coulcl be clarified by the addition of an excess of @.r, alum solution.. I prepared material iii the sime w-'a@y using eighteen parts of sodiiiiii carboiiate to one hundred parts of rosin and obtained an aqueous dispersion of rosin forming.a lather on shaking and from which the disper@ed rosiii and stponi-fied rosih couicl be 10 precipitated bv the liddition of alum. It may,,be, noted that when working with carboiiate in this f asliiori, the addition of altim causes the liberation of notice,,tble quantities of carbon dioxid I e. 85 In aiiother way of working, I grouiid together in the dry st,@tte one liundred parts of rcsin with five parts of caustic alkali, and obtainecl from tl-ie roduct -,t water-dispersible p sizin- composition whiell -vvas opaque and 90 white i:n color. From this it Wll be appreciated that@l, because 0 the method ei-nployed, I may prevet-it the -nattiral reaction of soap formation, while converting the normally in95 scrluble rosin into a I dispersible conclition. This proced-Lire is advantageotis i-n sizing paper, as it permits of the admixture of the size and the piilp -witho-Lit the use of laroe amoiints of coagtil@iting agents, such ,ts ,tliiin. whiel). ub when carried into the finished paper, are s - 100 sequentl y extractecl by water or moistlire to render the paper more permeable ind less water repellent. In still n,nother way of I)racticino- the in1 105 vention I gro-Lind together in the CT'ry condition one5 h-Lindred parts of rosin and ten partq of "soliible@7 starch. The resulting product was tran-qferred into a water-soluble material, ind, wlien a sli,-ht ',Imount of 110 wav, added, the dispersion could be clarified with alum solution. From the forep,,oinz illtistrative examples, it -will be appreciated by tt-iose sIKilled in t-lic' art, that it is not necessary to resort to chem - 1115 ical reactions invol-vin(,@ the use of soliitions or high temperatures in the conversion of a normally insoluble sizing n-laterial into t dispersed and Lisable form. - Sotisf actory @esults mav be obtained by applying, to the surf ace.9 of - hnely divided , particles of the solid materi--gl ,t colloidal film of some substance 120 which serves as a surface tension reducing ,iuent or peptizer so that, when the dry material is talren up in water, a dispersion of 12,1 the minute sizing particles can be obtqined. If d.esired, rosin soap of high quality m,,iy b(-. made acecrrding to the method by employina saponifving agent in such proportions @Lq. to effect the desired chemical reaction. 130
