US1848658A

US1848658A - Manufacture of papeb

Info

Publication number: US1848658A
Authority: US
Publication date: 1932-03-08
Anticipated expiration: 1949-03-08

Description

Patented Mar. 8, 1932 UNITED STATES PATENT OFFICE HAROLD R. RAF'I'ON', OF "LAWREN CE, MASSACHUSETTS, ASSIGNOB TO RAFFOLD PROCESS coarom'rron. A conronn'rron or mssncnusnr'rs MANUFACTURE OF PAPER No Drawing. Application filed April 8, 1929, Serial No. 353,687. Renewed July 28, 1981.

' 13 wet end soft lumps, which tend to cause breaks on the machine.

A further object is the production of paper of a higher quality. A further object is the production of paper 2 of a more uniform quality.

A further object is the introduction of a small amount of breakable parafiin emulsion which may be precipitated if desired in the beater.

Other objects and advantages of iny invention will become'apparent during the course of the following description. 1

In my copending applications Serial Nos. 304,171 and"304,174 filed September 5, 1928,

- and N6. 321,7 53, filed November 24, 1928, I

have disclosed methods for the prevention of foam in substantially unsized paper filled with alkaline filler. Likewise in my copending application Serial No. 321,7 54,-fil'ed November 24, 1928, I have disclosed amethod for the prevention of foam in eithersized or substantially unsized paper; and in my copending applications Serial Nos. 325,407 and 325,408 both filed December 11, 1928, I have 40 disclosed methods for the reduction or elimination of lumps in either sized or substantially unsized paper. I v

' In said applications the methods disclosed were such that intimacy and/or time of contact between the alkaline filler and the alum or the alum-sodium resinate or the like preclpitate was substantially limited; or'if the lntlmacy and/or time of contact had already resulted in deterioratin the effect of the alum or the alum precipltate, this effect was subsequently restored under conditions where the intimacy andKor time of contact with the alkaline filler was substantially limited.

In my copending application Serial No. 262,030, filed March 15, 1928, I have disclosed a method for sizing paper filled with alkaline filler in the beater wherein a paraflin emulsion is employed and flocculatedi. e. broken by alkaline filler, and wherein in one variation thereof alum is employed thereafter.

I have now discovered a modification of' that process wherein a breakable paraflin emulsion, such for instance as a saponaceous paraflin emulsion (i. e. a paraflin emulsion made with a saponaceous emulsifying agent) is thrown down-i. e. broken-by the action of an acidic precipitant such as alum instead of by alkaline filler. 1

I have found that the precipitate pro.- duced byan acidic precipitant such as alum with a breakable paraflin emulsion, which for example in the case of a saponaceous parafiin emulsion may be considered to be an aluminum soap associated with parafiin, may be used in sizing paper filled with alkaline filler as the precipltate is affected only very slowly by the action of alkaline filler, in fact so slowly that in the lengths of time ordinarily employed, it' is not ordinarily affected thereby sufficiently to interfere with its practical use. I

In my present invention, however, I am not concerned with sized paper, but with substantially unsized paper. Hence I employ in the manufacture of my paper break-' able parafiin emulsions such as saponaceous parafin emulsion, only in such an amount that, .when it is-thrown. down by an acidic precipitant such as alum, it is insuflicient to impart a substantial degree of sizing to the paper, but is nevertheless beneficial in permitting the manufacture of the resulting unsized paper with a substantial diminution of lumps and foam, it not indeed to render its manufacture substantially lump and foam free.

In the preferred practice of my invention I add to the fibrous material in the beater or like machine a'suitable amount of breakable paratfin emulsion, for example saponaceous parafiin emulsion, allow a sufficient time for mixing, and then add a quantity of alum at least sufficient to completely throw down the said emulsion, although usually considerably more will be added owing to the relatively small amount of paraffin emulsion used. I then add alkaline filler. If the alkaline filler be added prior to the addition of the saponaceous parafin emulsion and/or the alum, this will result in a prior flocculation of the emulsion by the alkaline filler as described in my above last referred to prior application. This latter procedure seems to require in certain cases a somewhat greater amount of emulsion to produce the same effect, so I preferably introduce the alkaline filler after the precipitation of the emulsion by the alum has taken place. Of course this is not always feasible especially when broke containing alkaline filler is used in the furnish, but in such case such broke may be added if desired prior to addition of the alum, and the remainder of the alkaline filler subsequent thereto. There is described below in this specification a suitable procedure which may be employed'in this case. Coloringmatter or other material may also be add: ed as is customary in the beater. 7

After suflicient treatment in the beater, the mix may be passed through the subsequent chests and treating apparatus, up to the point where it is diluted preparatory to introduction to the web-forming device of the paper machine. It is then diluted, formed into a web, and passed through the usual drying and finishing machinery of thepaper machine. The resulting paper may be further finished by the customary auxiliary machines, such as supercalenders if..desired.

The addition of this small amount of emulsion has beneficial effects on machine operation, reducing or eliminating foam, reducing or preventing the filling up of the dandy if a Fourdrinier machine. be used, reducing or preventing the formation of soft lumps,

particularly wet end soft lumps, thus reducing or eliminating breaks during machine operation. The quality and uniformity of the paper is thus improved.

While my invention may be practiced withany of the customary fibrous materials, such as mechanical and/or chemical pulps, it is particularly beneficial when used with fur-v nlshes containing old paper stock.

My invention is applicable to any grade homogenizer or the .anacidic material, such for example as alum.

One example of such an emulsion is parafin dispersed in an aqueous dispersion agent such as in a solution of sodium silicate, and made in a known manner. The precipitate produced by alum. in such case can be considered to consist susbtantially of aluminum silicate associated with paraffin, which is affected by the action of alkaline filler only very slowly, so slowly in fact that in the lengths of time ordinarily employed, it is not ordinarily af fected thereby sufliciently'to interfere with its practical use, and it is thus incorporated into the finished paper substantially unchanged. In such an emulsion as described above, it may be desirable at times to incorporate other materials in association with the paraffin as the disperse phase, such as rosin, Montan wax or the like.

Another exampe of a breakable paraffin emulsion is:.a saponaceous paraifin emulsion. As explained above the precipitate produced by alum may in this case be considered to be an aluminum soap associated with paraflin. The saponaceous paraffin emulsions which I have found suitable may be made with a variety of saponaceous emulsifying agents, e. g. sodium stearate, rosin size, or the like. However, while I do not restrict myself thereto, I prefer to use rosin size as the emulsifying agent, because it is practically the cheapest of the light colored saponifiablematerials. However at times a mixture of saponifiable materials may be used to advantage, for example rosin and Montan wax, the latter preferably in a minor percentage.

Moreover those saponaceous emulsions. in

sions in which the proportion of the emulsifying agent used is relatively large.

The saponaceous p arafiin emulsions which I'employ may be made in a varietyiof known ways, as for example in a machine suitable for intimate mixing, suchas a colloid mill,

like. A suitable method is to melt together the saponifiable material, such as the rosin, with the paraflin, and then intimately mix the fluxed mass with an aqueous solution of an alkaline material, particularly a compound or compounds of an alkali metal, such for example as sodium. One suitable compound is sodium silicate; another is sodium hydroxide. If a colloid mill is to be used, proportionate quantities of the heated melt and the referably heated alkaline solution, prefera ly in continuous streams, are directed into the orifice of the mill, from the exit of which issues the finished emulsion. The action of the alkaline material is tov s ponify or partially saponify the saponifia le material such as the rosin, and the paraffin\ is emulsified probably simultaneously. The rosin exists in the emulsion in the form ofarosin size. When sodium hydroxide is I used as, the alkaline material a suitable amount has been found to be about seven per cent. of sodium hydroxide by weight based,

on the total weight of paraffin and rosin used. Although this percentage has'been found to hold approximately correct even for a considerable variation in the. relative proportions of rosin and paraffin present, I do not restrict myself thereto as it may be widely varied. The concentration of the alkaline solution maybe such that the final emulsion issuing from the colloid mill may have as in one case found satisfactory, a concentration of per cent. solids, although this per- 30 centage may vary widely and is in no sense restrictive. The prqportion of saponifiable material such as 'lOSlIl to paraflin is subject to wide variation and I therefore do not restrict myself to any definite proportions. However I have found, for example, that a 30 parts parafiin-ZO parts, rosin emulsion works satisfactorily, as does also an 18 parts paraffin-82 parts rosin. I The above examples areillustrative only 40 and not restrictive. Nor do I restrict myself to the .above method of processing the emulsion as it will be understood by one, skilled in the art that any other known method producing a substantially equivalent emulsion will be suitable.

In regard to the flocculation or breaking of a saponaceous paraflin emulsion by alkaline filler, I have found that the emulsions which contain only substantially sufiicient saponaceous emulsifying agent to emulsify the paraffin are in eneral more sensitive to breaking by alka ine filler than those emulsionscontaminga'large excess of saponaceous emulsifying agent. The emulsions, particularly of the latter group, although relatively less sensitive than the former, appear to have 'their sensitivity increased with increase of dilution. I have found that this sensitivity in dilute'solution can be considerably reduced on by the addition of an alkaline material, for example sodium hydroxide, and this provides a method whereby in some cases, alkaline filler or broke containing same may be added to a beater in contact with a saponaceous parafiin emuls onprior to the alum, and the flocculation of the emulsion by said alkaline filler prior to the addition of the alum may be inhibited if not entirely prevented by the presence of sufiicient alkali.

An illustrative formula suitable for practicing my invention is as follows:

' Pounds Fibrous material (e. g. half sulphite and half soda pulp, air dry basis) 1550 Breakable parafiin emulsion e. g. saponaceous paraflin emulsion (dry basis) 2O Alum r 3O Alkaline filler (e. g. calcium carbonate magnesium'hydroxide, dry basis) 450 Another illustrative formula is:

' Pounds Fibrous material (e. g. equal parts of sulphite pulp, soda pulp, and old paper stock, air dry basis) 1600 Breakable paraffin emulsion e. g. saponaceous paraflin emulsion (dry ba sis) 2O Alum 40 Alkaline filler (e. g. calcium carbonate -magnesium hydroxide, dry basis) 400 The araflin emulsion referred to in the above ormulae is a parts rosin-30 parts paraffin emulsion, and in this instance 1 per cent. on the combined weight of fibre and filler is employed. As is well known to one skilled in the art, it takes, in general, more size to size a highly filled'sheet than oneof lower filler' content. Moreover the degree of sizing obtained with any given furnish ;will depend to a considerable extent on the character of the stock,-the degree of hydration, speed of the machine, and other known variables. Furthermore machines equipped with eflicient white water recovery systems will give a sheet of higher filler content for any given filler content of the furnish than will one not so equipped, and this will effect the degree of sizing obtained. Hence it may be thatin some cases an appreciable degree of sizing would be imparted by one per cent. of paraffin emulsion, whereas in others a substantially unsized sheet wouldbe obtained.

These known variations must be taken intoconsideration in using the 1 above formulae, and if it should be found that in any given instance the conditions are such that the amount of emulsion recommended imparts .to the sheet a substantial degree of sizing, the amount used should be out down untila substantially unsized sheet is produced. Conversely in certain cases the amount of emulsion recommended may have to be increased, care being taken however not to go beyond the point where a substantially unsized paper is produced. Also in some cases it may be found that an amount of emulsion even less than that amount which is just insufiicient to produce a substantial degree of sizing in the paper will have a decidedly beneficial effect on machine operation, and in such cases it .may be uneconomical to use more. 5 There may be certain cases in the practice of my invention where conditions will be such as to cause a certain deterioration of the alum-emulsion precipitate by the alkaline filler, if the time and/or intimacy of contact with the alkaline filler were excessive. In such cases it may be desirable to use extra alum added to the mix at or subsequent to its point of dilution prior to delivery to the web-forming device of the paper machine, in other words, at the wet end of the paper machine. In some cases where coated broke is employed this practice may aid in suppression of foam.; In some cases even where no apparent deterioration of the alum-emulsion precipitate has occurred, this practice may appreciably im prove the effect of the alum-emulsion precipitate. Or it may be desirable to introduce the alkaline filler at the wet end of the paper machine, either in whole or in part, and of course both of these practices can be combined, if desired, namely the alkaline filler (either in whole or in part) and the alum (either in Whole or in part) may both be added at the wet end of the paper machine, in this latter case the alum being preferably added prior to the alkaline filler.

Another variation is when the emulsion preferably in dilute form may itself be added to the fibrous material at the wet end of the paper machine, either alone or together with /the alkaline filler (preferably followed thereby) and/or the alum, the alum being added preferably before the alkaline filler; or the 0 emulsion may be added in the beater and all the alum at the wet end of the paper machine, in which case the alkaline filler may be added preferably at the wet end of the paper inachine preferably after the addition of the alum. Of course any addition to the mix at the wet end of thepaper machine should be made preferably proportionately and preferably continuousfy, preferably in such a manner as to allow independent incorporation of each individual ingredient with the mix, providing more than one ingredient is added.

I have found that in place of alum as a precipitant for the emulsion, I may use with a certain measure of success certain acidic materials such as sulphuric acid (H SQQ or acid salts such as sodium bisulphate (-NaHSO or other salts of aluminum, as thechloride or the like, or the double salts which are the true alums; but because of itseconomy and of its general efficiency, 'I prefer to use the ordinary sulphate of aluminum, commonly called alum. Any of the ordinary grades of alum, such as normal or basic, may be used satisfactorily.

such for instance as would be the case to acidic and alkaline bonate magnesium basic carbonate employed in the paper disclosed in my United States Patent No. 1,595,416, issued AugustlO, 1926; calcium carbonate magnesium hydroxide disclosed in my United States Patent No.

1,415,391, issued May 9, 1922, and other substantially water insoluble normal or basic carbonates of alkaline earth metals, (which expression is herein intended to include magnesium), or compounds, double salts, or phys ically associated mixtures of these with one or more other acid soluble materials of a substantially water. insoluble nature. It should 7 be stated that any given filler of the type referred to is not necessarily of uniform particle size; nor are the average particle sizes of the fillers necessarily alike,'as some of the fillers of the type referred to have relatively coarse grain particles, whereas others are much more finely divided, and some are so finely divided that they may be said to approach or be in the colloidal condition.

By the term alkaline filler I also intend to include fibrous materialand/or other material such as paper coating constituents or the like containing one or more compounds" of the character referred to, such as old papers or similar papers, broke, or the li 'e.

By the term old paper stock, I mean to include deinked papers, either bleached or not as desired, such as are commonly used for example in book and magazine paper furnishes. This materialmay contain filler such for example as clay which of course would vary in amount with the source and kind of old papers deinked nd the particu lar modification of the deinking process used.

.By the word paraffin I mean paraffin wax, which is solid at ordinary or room temperature. I do not restrict myself only to the paraflin hydrocarbons, but mean to include in this word all the hydrocarbons of a waxy nature substantially unsaponifiahle and inert 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.

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 trated paper mix is diluted, and treated, conveyed or fed up to the point of web-formation, such as the mixing box, regulating and proportioning devices, riffles, troughs, screens, head boxes, inlets, and the like, including also instrumentalities used in the white water cycle.

When I use the word rosin, I mean to include not only the natural material, but also any synthetic resin acid or acids.

When I use the term rosin size, I mean to include any material produced by the action of an alkaline substance, generally in aqueous solution, on rosin, regardless of the exact composition of the product, or the degree of saponification, or the varying composition which different samples maypossess.

When I use the term alkali metal, I mean to include the hypothetical alkali metal ammonium.

While I have described in detail the pre ferred practice of my process it is to be understood that the details of procedure, the proportions of ingredients, and arrangement of steps may be widely varied without departing from the spirit of the invention or the scope of the subjoined claims.

I claim:

1. The method of manufacturing substanable parafiin emulsion in an amount insufficient to impart a substantial degree of sizing to the paper, an acidic precipitant for said emulsion, and alkaline filler, and thereafter making paper therefrom.

2. The method of manufacturing substan-- tially unsized paper filled with alkaline filler comprising mixing fibrous material, breakable paraflin emulsion in an amount insuflicient to impart a substantial degree of sizing to the paper, alum, and alkaline filler, and thereafter making paper therefrom.

3. The m'fimd of manufacturing substantially unsiz paper filled with alkaline filler comprising mixing fibrous material, saponaceous pa'raflin emulsion in an amount insufficient to impart a substantial degree of sizing to the paper, an acidic precipitant for said emulsion, and alkaline filler, and thereafter making paper therefrom.

4. The method of manufacturing substantially unsized paper filled with alkaline filler comprising mixing fibrous material,

saponaceous paraflin emulsion in an amount insuflicient to impart a substantial degree of sizing to the paper, the emulsification of emulsion, and alkaline filler,

said emulsion having been effected with the aid of alkaline material, an acidic precipitant for said emulsion, and alkaline filler, and thereafter making papertherefrom.

5. The method of manufacturing substantially unsized paper filled with alkaline filler comprising mixing fibrous material,- saponaceous paraflin emulsion in an amount insufiicient to impart a substantial degree of sizing to the paper, the emulsification of said emulsion having been effected with 'the aid of an alkaline compound of an alkali metal, an acidic precipitant for said emul-Z sion, and alkaline filler,-and thereafter making paperv therefrom.

6. The method of manufacturing substantially unsized paper filled with alkaline filler comprising mixing fibrous material, saponaceous para-flin emulsion in an amount insuflicient to impart a substantial degree of sizing to the paper, the emulsification of said emulsion having been effected with the aid of an alkaline compound of sodium, an acidic precipitant for said emulsion, andalkaline filler, and thereafter making paper therefrom.

7. The method of manufacturing substantially unsized paper filled with alkaline filler comprising mixing fibrous material, saponaf ceous paraffin emulsion in an amount insufiij cient to impart a substantial degree of sizing to the paper, the emulsification of said emulsion having been eifected-withthe aid' of sodium hydroxide, an acidic precipitant for said emulsion, and alkaline filler, and thereafter making paper therefrom.

8. The method of manufacturing substantially unsized paper filled with alkaline filler tially unsized paper filled with alkaline filler comprising mixing fibrous material, breaktially unsized paper filled with alkaline filler comprising mixing fibrous material, rosin size-paraflin emulsion in an amount ins'ufli-f} ,cient to impart a substantial degree of sizing to the a er an acidic precipitant for said p p i and thereafter making paper therefrom.

10. The method of manufacturing substantially unsized paper filled with alkaline filler comprising mixing fibrous material, rosin size-parafiin emulsion in an amount insufiicient to impart a substantial degree of s1z1ng to the paper, alum, and alkaline filler, and

thereafter making paper therefrom.

11. The method of manufacturing substantially unsized paper filled with alkaline filler comprising mixing fibrous material, saponaceous rosin-Montan wax-paraffin emulslon in an amount insufficient nnpart a substantial degree of sizing to tlie paper, alum, and

alkaline filler, and thereafter making paper therefrom. i Y a i 12. The method of manufacturing substantially unsized paper filled with alkaline ficient to impart a substantial degree of sizing to the paper, alum, and alkaline filler,

. and thereafter making paper therefrom.

13. The method of manufacturing substantially unsized paper filled with alkaline filler comprising mixing fibrous material comprising sulphite pulp soda pulp and old paper stock, saponaceous paraflin emulsion in an amount insutficient to impart a substantial degree of sizing to the paper, alum, and alkaline filler, and thereafter making paper therefrom.

14. The method of manufacturing substantially unsized paper filled with alkaline filler comprising mixing fibrous material, saponaceous paraifin emulsion in, an amount insuificient to impart a substantial degree of sizing to the paper, alum, and alkaline filler comprising alkaline earth metal carbonate, and thereafter making paper therefrom.

15. The method of manufacturing substantially unsized paper filled with alkaline filler comprising mixing fibrous material,

saponaceous paraflin emulsion in an amount insuflicient to impart a substantial degree of sizing to the paper, alum, and alkaline filler camprising calcium carbonate, and thereafter makmg paper therefrom.

16. The method of manufacturing substantially unsized paper filled with alkaline filler comprising mixing fibrous material, saponaceous paraifin emulsion in an amount insufiicientto impart a substantial degree of sizing to the paper, alum, and alkaline filler comprising calcium carbonate and mague sium com ound, and thereafter making paper therefi'om.

17. The method of manufacturing substan-' tially unsized paper filled with alkaline filler comprising mixlng fibrous material, saponaceous paraffin emulsion in an amount insufficient to import a substantial degree of sizing to the paper, alum, and alkaline filler comprising calcium carbonate magnesium hydroxide, and thereafter making paper therefrom. v

18. The method of manufacturing substantially unsized paper filled with alkaline filler comprising mixing in the beater fibrous ma terial, saponaceous paraflin emulsion in an amount insuflicient to impart a substantial degree of sizing to the paper, alum, and alkaline filler, and thereafter making paper therefrom. i

19. The method of manufacturing s'ubstantially unsized paper filled with alkaline filler comprising mixing in the beater fibrous material, fsaponaceous paraflin emulsion in an amount insuflicient to impart a substantial degree ofsizing to the paper, alum, and a1- degree of sizing to said paper.

emulsion, said precipitate being present in an amount insuflicient to impart a substantial degree of sizing to said paper.

22. A paper comprising fibrous material, alkaline by the action of acidic material on saponaceous paraflin emulsion, said precipitate being present in an amount insuflicient to impart a substantial degree of sizing to said paper.

23. A paper comprising fibrous material, alkaline filler, and the precipitate produced by the action of acidic material on rosin sizeparaffin emulsion, said precipitate being present in an amount insufiicient to impart a substantial degree of sizing to said paper.

24. A paper comprising fibrous material, alkaline filler, and the precipitate produced by the action of alum on rosin size-paraflin emulsion, said precipitate being present in an amount insutficient to impart a substantial 25. A paper comprising fibrous material, alkaline filler, and the precipitate produced by the action of alum on saponaceous rosin- Montan wax-paraffin emulsion, said preeipitate being present in an amount insuflicient to impart a substantial degree of sizing to said paper.

26'. A substantially unsized paper comprismg fibrous material, alkaline filler, parafiin.

and the precipitate produced by the action of alum on rosin size said parafin and-said precipitate being present in insuflicient amount to impart a substantial degree of sizing to said paper.

27. A magazine paper comprising fibrous material including old paper stock, alkaline filler, paraflinand the precipitate produced by. the action of alum on rosin size, said paraflin and said precipitate being present in insufiicient amount to impart a substantial degi'ee of sizing to said paper.

28. A supercalendered magazine paper comprising fibrous material including old paper stock, alkaline filler, paraflinand the precipitate produced by the action of alum on rosin size, said paraflin and said precipitate being present in insuflicient amount to impart a substantial degree of sizing to said paper.

29. The method of manufacturing substantially unsized paper filled with alkaline filler, and the precipitate produced filler comprising mixing fibrous material,

breakable paraffin emulsion in an amount insufficient to impart a substanital' degree of sizing to the paper, and an acidic precipitant for said emulsion, subsequently adding alkaline filler to the mix, and thereafter making'paper therefrom;

30. The method of manufacturing substantially unsized paper filled with alkaline filler comprising mixing fibrous material, breakable parafiin emulsion in an amount insuflicient to impart asubstantial degree of sizing to the paper, and alum, subsequently adding alkaline filler to the mix, and thereafter making paper therefrom.

31. The method of manufacturing substantially unsized paper filled with alkaline filler comprising mixing fibrous material, saponaceous paraffin emulsion-in an amount insufiicient to impart a substantial degree of sizing to the paper, and an acidic precipitant for said emulsion, subsequently adding alkaline filler to the mig, and thereafter making paper therefrom.

32. The method of manufacturing substantially unsized paper filled with alkaline filler comprising mixing fibrous material, saponaceous paraffin emulsion in an amount insufficient to impart a substantial degree of sizing to the paper, the emulsification of the said emulsion having been effected with the aid of alkaline material, and an acidic precipitant for said emulsion, subsequently adding alkaline filler to the mix, and thereafter making paper therefrom.

33. The method of manufacturing substantLJlymnsized paper filled with alkaline filler c ggprising mixing fibrous material, saponaceous parafiin emulsion in an amount insuflicient to impart a substantial degree of sizing to the paper, the emulsification of said emulsion having been effected with the aid of an j alkaline compound of an alkali metal, and an acidic precipitant for said emulsion, subsequently adding alkaline filler to the mix, and thereafter making paper therefrom.

34. The method of manufacturing substantially unsized paper filled with alkaline filler Y comprising mixing fibrous material, saponaceous paraflin emulsion in an amount insuflicient to impart a substantial degree of sizing to the paper, the emulsification of said emulsion having been effected with the aid of an alkaline compound of sodium, and an acidic precipitant for said emulsion, subsequently adding alkaline filler to the mix, and thereafter making paper therefrom.

35. The method of manufacturing substantially unsized paper filled with alkaline filler comprising mixing fibrous material,-saponaceous paraflin emulsion in an amount-insuflicient to impart asubstantial degree of sizing to the paper, the emulsification of said emulsion having been effected with the aid of sodium' hydroxide, and an acidic precipitant for. said emulsion, subsequently adding al-,

tially unsized paper filled with alkaline filler comprising mixing fibrous material, saponaceous parafiin emulsion in an amount insufiicient to impart a substantial degree of sizing to the paper, and alum, subsequently adding alkaline filler to the mix, and thereafter making paper therefrom.

37. The method of manufacturing substantially unsized paperfilled with alkaline filler comprising mlxing fibrous material, rosin size-paraflin emulsion in an amount insufficient to impart a substantial degree of sizing to the paper, and an acidic precipitant for said emulsion, subsequently adding alkaline filler to the mix, and thereafter making paper therefrom. I

38. The method of manufacturing substantially unsized paper filled with alkaline filler comprising mixing fibrous material, rosin alkaline filler to the mix, and thereafter mak-- ing paper therefrom.

39. The method of manufacturing substantially unsized paper filled with alkaline filler comprising mixing fibrous material, saponaceous rosin-Montan wax-paraffin emulsion in an amount insufiicient to impart a substantial degree of sizing to the paper, and alum, subsequently adding alkaline filler to the mix, and thereafter making paper therefrom.

40. The method of manufacturing substantially unsized paper filled with alkaline filler comprising mixing fibrous material comprising sulphite and soda pulps, saponaceous parafiin emulsion in an amoimt insufficient to impart a substantial degree of sizing to. the paper, and alum, subsequently adding alkaline filler to the mix, and thereafter making paper therefrom. 1

41. The method of manufactu 'ng substantially unsized paper filled with alkaline filler comprising mixing fibrous material comprising sulphite pulp, soda pulp and old paper stock, saponaceous parafiin emulsion in an amount insufficient to impart aisubstantial degree of sizing to the paper, and'illum, sub sequently adding alkaline filler to the mix, and thereafter making paper therefrom.

42. The method of manufacturing substantially unsized paper filled with alkaline filler comprising mixing fibrous material, saponaceous paraffin emulsion in an amount insufiicient to impart a substantial degree of sizing to the paper, and alum, subsequently adding to the mix alkaline filler comprising alkaline earth metal carbonate, and thereafter making paper therefrom.

43. The method of manufacturing substantially unsized paper filled with alkaline filler comprising mixing fibrous material, saponaceous paraffin emulsion m an amount msufiicient to impart a substantial degree of sizing to the paper, and alum, subsequently adding 5 to the mix alkaline filler'comprising calcium carbonate, and thereafter making paper therefrom. 44. The method of manufacturing substantially unsized paper filled with alkaline filler m comprising mixing fibrous material, saponaceous paraflin emulsion in an'amount insufli-- cient to impart a substantial degree of sizing to the paper, an alum, subsequently addsing to the mix alkaline filler comprising calci- 11 um carbonate and magnesium compound, and

thereafter making paper therefrom.

45. The method of manufacturing substantially unsized paper filled with alkaline filler comprising mixing fibrous material, sapona- 20 ceous paraifin emulsionin an amount insuflicient to impart a substantial degree of sizing to the paper, and alum, subsequently adding .tothe mix alkaline filler comprising calcium carbonate magnesium hydroxide, and there- 223 after making paper therefrom.

46. The method of manufacturing substantially unsized paper filled with alkaline filler comprising mixing in the beater fibrous material, saponaceous paraflin emulsion in an amount insufficient to impart a substantial degree of sizing to the paper, and alum, sub-.

sequently adding alkaline filler to the mix,

and thereafter making paper therefrom.

47 The method of manufacturing substantially unsized paper filled with alkaline fillercomprising mixing in the beater fibrous'material, saponaceous' paraffin emulsion inan amount insuificient to impart a substantial H J degree of sizing to the paper, and alum, subao sequently adding alkaline filler to the mix, adding a subsequent quantity of alum at the wet end of the paper machine, and thereafter making paper therefrom.

In testimony whereof I afiix my signature.

HAROLD ROBERT RAFTON.