US1803644A - Method of sizing paper - Google Patents

Description

Patented May 5, 1931 UNITED STATES PATENT OFFICE HAROLD vROBERT RAFTON, 0F LAWRENCE, MASSACHUSETTS, ASSIGNOR TO RAFTON LABORATORIES, INC., A CORPORATION OF MASSACHUSETTS METHOD or SIZING PAPER No Drawing.

This invention relates to the manufacture of paper and more particularly to an improved sized paper and to a method of making the same.

The principal object of this invention is to provide a process of sizing paper wherein paraifin is employed as the sizing agent, the paraffin being employed in the form of a substantially nonbreakable emulsion, the disperse phase of such emulsion being concentrated by the mutual precipitation or flocculation of two suitable precipitating agents in the presence of the emulsion.

An important object of this invention is to provide an economical and elficient process of making an improved sized paper wherein the disperse phase of a substantially nonbreakable parafiin emulsion is concentrated by the mutual precipitation or flocculation of sodium resinate and alum.

Another object of this invention is to provide a process of making sized paper by employing a sizing agent which is substantially more economical than rosin which is commonly employed for such purpose and also wherein the sized paper produced by the process is whiter than the paper produced by processes wherein rosin sizing is employed.

Other objects and advantages of this invention will become apparent during the course of the following description.

Cross reference is made to my copending application Serial No. %,170, filed Septemher 5, 1928.

As will be apparent to those skilled in the art, it is substantially the universal practice in sizing paper to mix with suitable fibrous materials and filler, if such is to be employed, sodium resinate, and to precipitate the sodium resinate with alum in the presence of the fibre. While the order of addition of these ingredients may be and is varied in different processes it has been generally accepted that the addition of both sodium resinate and alum, or equivalents thereof, is necessary for imparting suitable sizing to the finished paper. As is well known the so-called sodium resinate employed in paper making processes is not always this exact compound nor when this compound is used is it always chemi- Application filed September 5, 1928. Serial No. 304,169.

cally pure, it generally containing varying amounts of uncombined rosin and sometimes uncombined alkali. However, where this term is employed herein it is to be understood that the term includes any material produced by the action of alkali, generally in aqueous solution, on rosin, or on natural or synthetic resin acid or acids, regardless of the exact composition of the product or the var ing composition which different samples 0 the product may possess.

Sized paper made substantially in accord ance with the general method outlined above is not suitable for many purposes and various other types of paper are emplo ed in numerous arts. For example, it has een proposed heretofore to make a water resistant paper by adding to suitable fibre a combination of sodium resinate and a breakable paraffin emulsion, ordinarily a saponaceous emulsion, and to precipitate the paraffin in connection with the rosin on the fibrous material by the use of alum. Paper of this class is commonly called parafi'med paper.

While parafiined papers are suitable for many uses the use of such papers is not general. For example, these papers generally have a paraifin finish which makes them substantially waterproof and are ordinarily translucent or substantially transparent. Hence such papers are not suitable for use as book, magazine, writing or printing papers.

Moreover the use of emulsions particularly of the class referred to above which are employed in making parafiined papers is attended with numerous serious disadvantages as hereinafter more particularly set forth. As is well known an emulsion of parafiin is a suspension of microscopically minute particles of parafiin in a liquid, ordinarily aqueous or miscible with water, containing an emulsifying agent, i. e., a material or materials which tend to prevent the coalescence of the individual particles of paraflin. The most widely accepted work relating to emulsions points to the fact that there is actually a layer or film of the emulsifying agent one or more molecules in thickness surrounding each particle of emulsified material, which in the case of parafiin is called herein the disperse phase of the emulsion. This film or layer however in certain cases may be of very much greater thickness, for instance in the case where an insoluble emulsifying agent is used. The individual particles of the disperse phase of an emulsion act very differently from the same material in comminuted form in an aqueous medium in which no emulsifying agent is present. In such case the individual particles are not prevented from contacting with each other and in fact the particles do touch and eventually coalesce to form relatively massive lumps of the material. The same material in emulsified form however does'not have these characteristics and the individual particles of the disperse phase, such as paraffin, for example, are prevented from touching one another with the result that there is no tendency for the particles to coalesce and form lumps. Although' particles in unemulsified condition exhibit different characteristics from similar particles in emulsified condition it is to be pointed out that different emulsions differ in several respects but particularly do they differ with regard to their stability. For example, many and undoubtedly the great majority of emulsions tend to resolve or break in the well known manner. It is this characteristic that has led chiefly to the disadvantages surrounding the use of emulsions in paper making processes as heretofore employed. For example, certain emulsions commonly employed for use in paper making such for example as paraffin emulsions are broken by the addition of alum thereto. Moreover, such emulsions can usually be broken by acids and also to some extent by soluble salts such as those which occur in hard water or in incompletely washed fibrous materials. This breaking of emulsions such as a parafiin emulsion is accompanied by the rise of the individual particles such as parafiin which are released from the emulsified form, to the surface of the liquid with consequent tendency toward agglomeration and formation of relatively large particles.

When breakable emulsions of the character referred to have been employed heretofore in paper making processes the parafiin has been precipitatedin individual particles usually by alum on the fibre while the fibre was in aqueous suspension. In some cases sodium resinate has been employed in connection with such breakable emulsions and the mixture of the sodium resinate and paraffin emulsion has been mutually precipitated on the fibre by means of alum. Of course, in this case as well as in the case where no sodium resinate was employed the paraffin was deposited in individual particles, but in this instance it was commingled with the alumsodium resinate precipitate. An important factor in each of these cases resides in the direct contact of the finely divided parafiin ticularly in the screens, in the web-forming 7.

device of the paper machine, and also in various parts of the machine clothing and the press rolls.

It has also been proposed heretofore to make waterproof paper such as roofing paper by mixing an emulsion of asphalt or the like, preferably containing clay as an emulsifying agent, with suitable fibre and running this mix off on a paper machine. These emulsions, which are relatively coarse, are retained in the felted sheet by mere mechanical filtration, the proportion of the emulsion used being sufficiently great (sometimes equal to or greater than the amount of fibre present) to insure the retention of a sufficient amount of asphalt in the finished sheet. A modification of this process uses a fixing agent to attach the asphalt to the fibres. Of course, apart from other reasons, because of their color the employment of asphalt or bituminous emulsions is not feasible in making high grade book, magazine, writing or printing paper and the like. Moreover emulsions made with parafiin wherein solid emulsifying agents such as clay are employed have been found to be disadvantageous for the reason inter alia that when such emulsions are employed in small quantities in a sheet such as might be expected to be sufficient to produce a sized paper, the particle size of the parafiin is usually sufficiently large to cause waterproofing to occur in definite spots which are surrounded by areas that are substantially unsized, the finished product thereby resulting in a sheet having a combination of waterproof areas and unsized or only partially sized areas. Moreover, especially in cases where it is desired to use little or no filler in the finished sheet, such emulsions are unsuitable as the emulsifying agent being of the nature of a filler is also necessarily incorporated into the sheet. Moreover emulsions made with insoluble emulsifying agents have certain breakable characteristics as described below and have thus a tendency toward being broken during the paper making process'with consequent deposition of parafiin or like material on various parts of the paper making machine and machine clothing.

For instance, emulsions made with insoluble emulsifying agents have a tendency to the jordan. Of course in these agencies there 1 tends to be a contacting at high speed between two metal surfaces, and as is natural, this influence will tend to break down the insoluble particle, film surrounding the individual particles of emulsified material, and consequently numerous particles of the disperse phase having their protective coating ruptured or removed will tend to coalesce and produce thereby larger or smaller lumps of unemulsified material which will cause trouble in the subsequent machining of the stock. It is therefore apparent that emulsions made with an insoluble emulsifying agent are not sufliciently completely resistant to the mechanical inst-rumentalities met with in the paper making process and thus they cannot be considered as substantially nonbreakable emulsions.

I have discovered that it is possible to prepare asized paper having all the advantageous qualities of the papers prepared in accordance with the methods heretofore emcal ployed withoutany of the series disadvantages commonly attending the preparation of such papers. Moreover, I have devised'a process for effecting this result which consists broadly in adding to the fibrous materials and a filler, if a filler is employed, sodium resinate and an emulsion of parafli-n which is substantially nonbreakable by any of the chemical or mechanical agencies ordinarily used in the paper making process in the concentration or intensities in which they are normally used. This mix is then treated with a suitable precipitating agent such as alumn in the manner and for the purpose hereinafter described. It is to be understood that sodium resinate and alum are not employed primarily as sizing agents but as concentrating agents for the disperse phase of the parafiin emulsion employed, asmore particularly hereinafter set forth. For example, I may use an amount of sodium resinate which with alum would not be suflicient to size the paper but which would, in fact, produce a substantially unsized paper. However, if I desire I may use a greater quantity sodium resinate but it is to be pointed out that it is possible to secure satisfactory sizing by the employment of my process herein described where there is not sufficient sodium resinate used to impart sizing of itself.

As stated above, I have discovered that the use of emulsions which are substantially stable under normal paper making practice wholly avoids the numerous disadvantages commonlyencountered in prior processes invoLving the use of breakable emulsions. However, it will be apparent that the mere use of substantially nonbreakable emulsions doesnot alone produce the desired results since unless suitable means are provided for effecting the association of such emulsions with the fibrous material they would merely pass off with the efiluent waters and not remain associated with the fibre as desired.

I have discovered that substantially nonbreakable emulsions can be brought intothe desired association with fibres and held in such association up to the desired point sub stantially without breaking the emulsions by concentrating the disperse phase of the emulsions by means of two mutually flocculating or precipitating materials such for example as sodium resinate and alum. This concentration of the disperse phase in the concentrating precipitate however does not break the emulsion.

The fact that treatment in the manner suggested merely concentrates the dis erse phase of the emulsion and does not bre the emulsion is clearly shown by the following experiment: If a relatively dilute solution of sodium resinate is added to a breakable paraflin emulsion, such as saponaceous paraffin emulsion, and alum is then added in an amount sufiicient to completely flocculate both the sodium resinate and the parafiin emulsion, there will result a precipitate and a clear residual liquid. The precipitate will consist of an alum-sodium resinate precipitate and also of an alum-soap precipitate (that is, the soap which is used as the emulsifying agent for the paraifin), andalso individual particles of free par'aifin released from the emulsified condition. Now if some chemical is added which completely dissolves these alum-sodium resinate and alumsoap compounds, (and which has been found at the concentration used and within the time required for the experiment will not of itself break the parafiin emulsion in question) such for example as sodium hydroxide, that part of the flocculent precipitate due to the resinate and soap precipitates disappears, and the arafiin which remains undissolved rises tot e surface in more or less agglomerated form.

On the other hand, if a substantially nonbreakable emulsion of the character hereinafter described is similarly mixed with a dilute solution of sodium resinate, and suflicient alum added to completely flocculate the same, it will be found that the precipitate separates, leaving a clear residual liquid. Up to this point the result appears to be exactly the same as in the previous experiment. However, when sodium hydroxide is added in the manner suggested as above, in an amount sufficient to dissolvethe alum-sodiumresinate compound, the entire solution becomes milky, no parafiin floats to the surface, and the paraflin emulsion is thus deconcentrated, i. e., restored to its original condition substantially unbroken. A microscopic examination of the milky liquid shows that the parafiin particles are present in the emulsified condition substantially the same as they were before they were concentrated by the precipitation of the alum-sodium resinate compound. It is apparent, therefore, that the action of the mutually flocculating materials in what appears to be the breaking of this emulsion is in no sense a breaking, but is an instance of the unique concentration of the disperse phase of a substantially nonbreakable emulsion without the breaking of such emulsion. This concentration of the disperse phase is substantially completely reversible, i. e., the disperse phase can be deeoncentrated or diluted by dissolving the precipitate of the mutually fiocculating materiais.

In other words in the concentrating precipitate, in this instance the alum-sodium resinate compound, the paraffin of a substantially nonbreakable emulsion does not exist as deposited particles released from emulsified form, and when the reaction is carried out in the presence of fibre the paraffin is not deposited jointly with the alum-sodium resinate precipitate upon the fibre, and does not therefore cause the difficulties experienced in the paper making process, as is the case when breakable emulsions are broken with alum, either alone or in the presence of alum-sodium resinate precipitate in the paper making process.

Moreover when the disperse phase of a substantially nonbreakable parafiin emulsion, concentrated in an alum-sodium resinate precipitate on fibre, is subjected to the beating and jordaning operations in regular papermaking practice, although of course the concentrating precipitate may be mechanically subdivided by these agencies, there is no evidence that any paraflin has been released from the emulsified condition. the concentrated disperse phase thus being apparently nonbreakable by the mechanical agencies to which it is subjected in the papermaking operation.

The alum-sodium resinate precipitate in the present instance, therefore, merely serves as a means for concentrating the disperse phase of an emulsion without breaking the emulsion, the disperse phase in the meantime being maintained in emulsified condition and substantially nonbreakable by mechanical means. This concentration of the disperse phase appears to produce a complex which experiments indicate to be an intermediate be tween a true emulsion and a resolved or broken emulsion. For example, the complex can be temporarily dispersed by mechanical means as indicated above but not diluted in the true sense as in the case of true emulsions. However, the complex can in a sense he diluted by dissolving the mutually flocculating agents therein and reconverting to a true emulsion. Thus while it is clear that the complex is not a true emulsion it is on the other hand, not a resolved emulsion. For example, the paraflin is not present in the concentrate as individual unitary deposited particles of parafiin, but rather in emulsified form, each particle being surrounded by a layer or film of emulsifying agent which prevents the individual particles from having contact not only with other particles of parafiin but also from having contact with either the alumsodium resinate precipitate, or the fibres, or other constituents of the fibrous mix. The existence of the parafiin in emulsified form is thus continued throughout the entire wet end of the paper making proces. It is associatedwith the solids in the paper mix but is not deposited as paraffin thereon,'and thus, as heretofore stated, completely eliminates the difficulties which are present when emulsions are broken with alum, alone or in conjunction with sodium resinate, or by mechanical agencies in the paper making process. This is a very great advance in the art of sizing paper with paraflin emulsions as will be readily appreciated by those skilled in the art.

The emulsions which I have found to be substantially unaffected by ordinary materials in the concentration in which they exist in the paper making process may be made in a variety of ways, for instance. with gums such as gum ghatti or gum arabic. While dextrin of itself does not appear to be suitable as an emulsifying agent, particularly if the emulsion is to be stored for any appreciable time, it does however appear to be useful in connection with the gums mentioned above. As the gums are normally much more expensive than dextrin, the dextrin may thus be used in conjunction with the gums to produce in general a lower cost emulsion. I have tested several formulae involving the use of gums and dextrin which give emulsions of essentially the nature desired, and which appear to work satisfactorily for the purpose. However, the one which I prefer to use in practice and which I have found to work well on a practical scale, is an emulsion made of paraffin with gum ghatti and dextrin as emulsifying agents. In one such emulsion, for example, which proved satisfactory, I used by weight as follows:

parts paraffin, I part gum ghatti, 1 part dextrin, 83 parts water.

As stated above so far as I have been able to discover by experiment, the emulsions which I employ are not affected in any way by any of the chemicals with which they come in contact at the concentrations at which they are used in the paper making process, nor are they affected by any of the mechanical agencies with which they come in contact at the intensities at which they are normally employed in the paper making process.

The reason for this latter characteristic is probably that the particles in my emulsions are surrounded with a film as set forth previously which is one or more molecules in thickness and hence entirely of negligible thickness compared with any solid particle film. Hence such films cannot be knocked off or ruptured by ordinary mechanical means, as the thickness of this film is of entirely different order of magnitude (smaller) than are the clearances which obtain in the paper making machinery. This of course is not the case with emulsifiers of the insoluble type which possess much thicker films, whether the films so produced be made up of individual particles of materials like clay, or whether they be of jelly-like character such as is thecase where certain insoluble materials are employed which are of that character, whether introduced as one material or produced in situ by the reaction of two or more materials.

Of course it is not necessary that the emulsifier I use be water soluble in the sense that sodium chloride, for instance, is soluble, as materials which are known in the art as being colloidally soluble, are also suitable. For example gum ghatti which is suitable for my use may be considered to be in a measure colloidally soluble. With emulsifiers of the type I employ the condition of the layer surrounding the disperse phase is such that by mechanical action in the paper making process, this layer is not disrupted, and therefore, the emulsion remains substantially nonbreakable as heretofore indicated.

It is to be understood that I do not confine myself to the materials indicated above as being suitable for my emulsion since now that the principle of the use of a substantially nonbreakable paraffin emulsion which is capable of having its disperse phase concentrated has been established in the paper industry, other similar emulsions undoubtedly will be evolved. Nor do I confine myself to the definite concentration of the parafiin in the emulsion nor to definite proportions of emulsifying agents to each other or to the paraflin, as these may be varied in considerable degree without affecting the desirable qualities of the emulsion.

Emulsions of the character referred to may be made in a variety of ways, as for example, in a dispersion machine such as one of a number of colloid mills or homogenizers. A suitable way is to melt the paraffin, dissolve the emulsifying agent or agents in water, heat the emulsifying agent solution above the melting point of the paraffin and then feed the melted parafiin and the heated solution of emulsifying agents jointly to the emulsifying machine.

In regard to the paraffin used, of course,

either low or high melting point material can be employed. The so-called fully refined paraflin is entirely satisfactory because it does not impart objectionable color to White sheets. However, for purposes of economy, it is often desirable to use a less pure material. For example, such material as is known to the trade as semi-refined parafiin scale, containing approximately 12% of oil and water as impurities, gives satisfactory results. Such material will perhaps in certain cases have varying melting points, but one. particular sample used has a melting point of approximately 115 F. (46 (3.). Other even more impure parafiins may be used, especially if the color (whiteness) requirements of the finished paper are not too exacting, or if papers, other than white, are to be made.

In the preferred practice of my invention I place suitable fibrous pulp in the beater or other similar or compounding or mixing or disintegrating or treating machine, then add sodium resinate, and thereafter a substantially nonbreakable paraffin emulsion, a convenient way being in dilute form. Thereafter these materials are thoroughly incorporated with the pulp. If ordinary filler, such for instance, as clay or talc, is to be used, this may be added, and followed by the alum. I do not confine myself strictly to this order of addition. I have found that a suitable way is to allow sufficient time for the sodium resinate and the substantially nonbreakable paraffin emulsion to be thoroughly incorporated with the fibres prior to the addition of the alum. The mix is then subjected to the usual beating treatment and passed through the regular paper making apparatus onto the paper machine as inthe case ofordinary rosin sized paper.

An illustrative furnish which advantageously may be used in practicing my invention is as follows:

Pounds Fibrous furnish, (e. g. suipliite and soda pulps) 1800 Ciay 200 Rosin (added in the form of sodium resinate) 10 Parafiin (added in the form of substantially nonbreakable pziratiin emulsion) Alum (Al (SO.,) .18i-I O) Another illustrative furnish is as follows:

Pounds Fibrous furnish (e, g. approximately equal parts of suiphite and soda and old paper stocks) 1530 Broke (machine broke) above formulae. The resultant paper may be used for such purposes as those to which sized papers are normally put, including that as a raw stock for further conversion as for example for coating.

While I have described herein the effect of sodium resinate and alum as mutually precipitating agents to produce a concentrating effect on the disperse phase of a substantially nonbreakable parafiin emulsion, other materials maybe used, as for instance, soaps other than sodium resinate or any partially or comletely saponified material, such as saponified Beeswax. Moreover, in place of alum as one of the mutually precipitating agents I may employ salts of other trivalent metals, such as ferric iron. Also, I may employ in place of ordinary alum other salts of aluminum, such as the chloride, or the like. In addition, sodium bisulphate may be employed with a certain measure of success.

When I employ the term paraffin herein, I mean paratlin wax, which is solid at ordinary or room temperature. I do not mean to restrict myself only to the paraffin hydrocarbons, but mean to include in this term all the hydrocarbons of a waxy nature substantially unsaponifiable and inert to acidic and alkaline materials under ordinary conditions of temperature and pressure, whether derived from petroleum, shale, lignite, earth wax, or other natural or artificial sources. I do not, however, mean to include in this term material of a pitchy nature, such as bitumen or asphalt.

When I use the word paper herein, I use it in the broad sense to include products of manufacture of all types and of all weights and thicknesses, which contain as an essential constituent a considerable amount of prepared fibre and which are capable of being roduced on a Fourdrinier, cylinder, or other orming, or felting, or shaping, or molding machine.

Altho I have described in detail several illustrative furnishes I do not intend to be limited thereby, nor to the proportions of ingredients given therein, as my invention may be practiced with a broad variety of formulae, using the various materials customarily employed for the various grades of paper in any suitable proportions. Moreover, various changes in tprocedure, ingredients, and arrangement steps may be resorted to in the practice of my invention without departing from the spirit of my invention or the scope of the subjoined claims.

I claim:

1. The method of sizing paper comprising adding to fibrous material a substantially nonbreakable paraffin emulsion and a substance capable of reacting with a second substance subsequently added to form a precipitate, said precipitation serving to concentrate the disperse phase of said paraflin emulsion,

but not to break said emulsion, and thereafter makin paper therefrom.

2. T e method of sizing paper comprising adding to fibrous materlal a substantially nonbreakable paraifin emulsion and a substance capable of reacting with a second substance subsequently added to form a precipitate, said reaction serving to concentrate in association with said preclpitate the disperse phase of said paraflin emulsion, but not to break said emulsion said precipitate being substantially incapable of havin the paraflin associated therewith released rom emulsified condition by mechanical means, and

thereafter making paper therefrom.

3; The method of sizing paper comprising adding to fibrous material a substantially nonbreakable paraiiin emulsion and a substance capable of reacting with a. second substance subsequently added to form a precipitate upon the fibrous material, said precipitation serving to concentrate the disperse phase of the said paraflin emulsion upon the fibrous material, but not to break said emulsion, and thereafter making paper therefrom.

4. The method of sizing paper comprising adding to fibrous material a substantially nonbreakable paraffin emulsion and a substance capable of reacting with a second substance subsequently added to form a precipitate upon the fibrous material, said reaction serving to concentrate in association with said precipitate the disperse phase of said paraflin emulsion, but not to break said emulsion, said precipitate being substantially incapable of having the paraifin associated therewith released from emulsified condition by mechanical means, and thereafter making paper therefrom.

5. The method of sizing paper comprising mixing with fibrous material a saponified material, a substantially nonbreakable paraffin emulsion, and a precipitant for said saponified material, and thereafter making paper therefrom.

6. The method of sizing paper comprising mixing with fibrous material a soap, a substantially nonbreakable paraflin emulsion, and a salt of a trivalent metal, and thereafter making paper therefrom.

7. The method of sizing paper comprising mixing with fibrous material a soap, a substantially nonbreakable paraflinemulsion, and alum, and thereafter making paper therefrom.

8. The method of sizing paper comprising mixing with fibrous material sodium resinate, a substantially nonbreakable paraffin emulsion, and alum,- and thereafter making paper therefrom.

9. The method of sizing paper comprising mixing with fibrous material, sodium resinate, parafiin emulsion made with gum ghatti as emulsifying agent, and alum, and thereafter making paper therefrom.

alum, and thereafter making paper therefrom.

11. The method of sizing paper comprising mixing with fibrous material, filler, a saponifiedmaterial, a substantially nonbreakable I paraflin emulsion, and a precipitant for said saponified material, and thereafter making paper therefrom.

12. The method of sizing paper comprising mixing with fibrous material, filler, sodium resinate, a substantially nonbreakable paraffin emulsion, and alum, and thereafter making paper therefrom.

13. The method of sizing paper comprising mixing with fibrous material, filler, sodium resinate, paraffin emulsion made with gum ghatti as emulsifying agent, and alum, and thereafter making paper therefrom.

14. The method of sizing paper comprising mixing with fibrous material, filler, sodium resinate, paraflin emulsion made with gum ghatti and dextrin as emulsifying agents, and alum, and thereafter making paper therefrom.

15. The method of sizing paper comprising mixing with fibrous material, clay, sodium resinate, a substantially nonbreakable paraffin emulsion, and alum, and thereafter making paper therefrom.

16. The method of sizing pap'er comprising mixing with fibrous material, sodium resinate in an amount which of itself would be substantially insufficient to produce a sized paper, a substantially nonbreakable paraffin emulsion, and alum, and thereafter making paper therefrom.

17. The method of sizing paper comprising mixing with fibrous material, filler, sodium resinate in an amount which of itself would be substantially insufficient to produce a sized paper, a substantially nonbreakable paraffin emulsion, and alum, and thereafter making paper therefrom.

8. The method of sizing paper comprising mixing with fibrous material, clay, sodium resinate in an amount which of itself would be substantially insufficient to produce a sized paper, a substantially nonbreakable paraffin emulsion, and alum, and thereafter mak= ing paper therefrom.

19. The method of concentrating the disperse phase of a substantially nonbreakable emulsion without breaking said emulsion, comprising effecting the precipitation of a saponified material and a precipitant thereof in the presence of said emulsion.

20. The method of concentrating the disperse phase of a substantially nonbreakable emulsion without breaking said emulsion, comprising causing sodium resinate and alum to precipitate in the presence of said emul- S1011.

21. The method of concentrating the disperse phase of a substantially nonbreakable paraflin emulsion on fibrous material comprising causing sodium resinate and alum to precipitate in the presence of said emulsion and said fibrous material.

22. As a new composition of matter, the concentrate comprising the disperse phase of a substantially nonbreakable emulsion associated with the precipitate produced by two mutually precipitating materials.

23. As a new composition of matter, the concentrate comprising the disperse phase of a substantially nonbreakable paraflin emulsion associated with the precipitate produced by two mutually precipitating materials.

24. As a new composition of matter, fibrous material on which has been precipitated a compound resulting from the interaction of two mutually reacting substances, said compound being associated with the concentrated disperse phase of a substantially nonbreakable paraffin emulsion.

25. As a new composition of matter, fibrous material upon which has been precipitated a compound resulting from the interaction of sodium resinate and alum having associated therewith the concentrated disperse phase 0 a substantially nonbreakable paraffin emulsion.

26. A sized paper having precipitated on the fibres thereof the resultant compound of two mutually reacting materials, said compound being associated with the concentrated disperse phase of a substantially nonbreakable paraflin emulsion.

In testimony whereof I affix my signature.

HAROLD ROBERT RAFTON.