US2332750A - Paper manufacture - Google Patents

Description

Patented Oct. 26, 1943 I p I UNITED sures "PATENT or'rice by mesne assignments, to --Rafiold Proccss' 0017-" zporation, Andover, Mass, a corporation of 'Massachusetts NoDrawing. Application Oct6ber 5fi1938, Serial Macs-3,492

22 Claims. '(Cl. 92 -21) My invention concerns the manufacture of paper.

The principalobject of my'invention-isto prosaid process.

Anrimportant object'is to provide aprocessfor the manufacture of paper filled with alkaline filler, said paper being sized to'any 'desired de- -g-ree, and to obtainthe-paper made by saidprocess.

A further object is to provide "a process it; the manufacture of paper filled with alkalinefiller, said paper "being sized to any desired degree,

wherein-thesiz'ing effect is obtained by thefjoint useof materialscomprisinga sizing material and a copper compound'andto obtain the paper made bysaid'process. p v

A further object is'to provide a process for the manufacture of paper filled with alkaline 'filler wherein there are employed'materials comprising a sizing-material-and a copper compound, particularly a substantially water-soluble copper compound, and, to obtain the papermade by said process. I p

A iurther object is to provide a process 'for the manufacture of paper filled with alkaline filler wherein there'are employed materials comprising rosinsize and a-substantially water-soluble copper compound, for example copper sulphate, and to obtain the paper made by said process.

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

As is Well known, certain precautions must be taken in the use of certain filler substances in pape-rmakingand particularly in sizing papers in an alkaline medium asv inthe case when alkaline 'vide ajpro'cess 'of'm'anu'facturing'paper filledwith :alkaline filler, and "to obtain the papermade' by in accordance, for-exampla'with theres'ul-ts-de- My invention thus deals with an improved method of securing sizing effect in paper 'filled 'withalkalinefiller. :I' have'found thatby employing various copper salts, particularlythe sulphate, 'a' superior sizing effect-'is obtained byth'e addition of amounts of copper sulphate up to 2% "or- 3% 'on' the' weight of the fibre and filler, and as low as 1 60f 1% -on tl 1,e Weight of thefibre,

varying the rosin size emulsion "withinabout the same percentage range as the copper sulphate.

Sizing results may-be varied to any desired degree .from complete waterproofing to only slightly sized efiect by varying theamoun'ts of sizing ma terial and copper sulphate added to the papermaking materials. Thus it is apparent-that 3% of substantially water-soluble co p'per compound,

such as copper sulphate,-and/or 3% ofsizin'gm'ateri'al, such as rosin size, is not to be understood as an upper limit or as naturally, it desired, any larger-amount or amounts may V-be'use'd sired'to beobtained. p

In the application-of size'materialin'the presence of the alkaline filler, I have found that the sequence of-adding the chemicals -is of great importance. The preferred sequence, (Pl, and

one by means of, which excellent results are or tained "is as follows. the 'materi'al'being added and mixed together in the order mentioned:

filler is employed. In the past it has been 'con- 1 1 Pulp sidered impossible to size paper filled with al- 0 2 i11 I kaline filler. However comparatively recently the 1 (3. s

sizing of paper filled with alkaline filler'has been accomplished by several newly introduced. proctemporarily lowering the alkalinity by useofan acid salt and allowing the sizingagent to pre cipitate before the full chemical action between 'essesfer g. by theuse of wax emulsions, or by the acidsalt and the alkaline filler might have v taken place, and the. like. Some sizing results have beenieifected 'bythe above referred to proccases, but I have devised a process which gives improvediresults and which is wholly different.

In the manufacture of paper filled with alkaline filler, I use. conjunction with a sizing material "a substantially water-soluble copperv compound. copper compound either comp'l'etelyreplaces the alum, which is universally used in paper-making with sizing material, or is used together with-alum.

However the us of i such a copper compound gives results wholly dif- (4) Copper-"sulphate (5) Acidic material I An illustrative example or a formula embody ing the above order (if-mixing is as followszf ,30 parts by weight of pulp H 10 parts by'weight-of alkaline filler suspended in 75o-partsby'weig'htpf water 1 1 part y Weight oi 'si ze figured as dry rosin (but actually added as a Wateremul'sion) 1 part by weight of 'copper' sulp'hate Acid toi-neut-ralize '(pheno-lplithalein as. indicator) By employingthe sequence (P referred to 7 above, I ha've'foundvthat aigreater degree (ii-sizing appears to beobtained than when Tort example the alkaline filler is fi rstftreated with 'a'c'i'd',v

then the pulp 'addediithenthe size and finally the copper sulphate. which I may term sequence (Q). When the ink float test is applied. to the paper or addition being the order in which the mater rials are mentioned:

Pulp

Filler Copper sulphate Size Neutralizing agent (acidic material) Pulp Filler Copper sulphate Neutralizing agent (acidic material) Size (C) (1) Pulp (2).. Fi1 ler (3) Size (4) Neutralizing agent (acidic material) (5) Copper sulphate The comparative sizing tests of the papers made according to these three orders of addition were as follows: i

(A) 2 5 secs.; (B) 10 mins. secs; (C) mins. 0 secs.

Obviously, I do not limit myinvention to any particular order of addition, as the above or any other order of addition of the ingredients may be used. For example,'as is apparent, the pulp, size and copper sulphate, and if desired the acidic material also, may be first mixed together, or mixed together in any sequence, prior to the addition of the filler, and then the filler added.

Also any two or more of the ingredients may be premixed, before admixture with one or more of the other ingredients. E. g. the substantially water-soluble copper compound and the siZe may be premixed prior to addition to the other ingreclients, or copper resinate, previously made, may

be added to the other ingredients, preferably in suitably dispersed form. Moreover the acidic material (neutralizing agent) may be entirely omitted, if desired. Also the entire quantity of any one ingredient need not be added all at once, but any ingredient may if desired be added in portions at more than one time, and if desired at more than one place in the papermaking process, and the addition of any ingredient may be made all at once, or in portions intermittently, or by continuous addition, as is well known in paper making.

Another example of a formula from which a paper may be made by my process is as follows:

-Per cent Sulphite pulp 3O Alkaline filler (comprising calcium carbonate) 30 Soda pulp 30 Starch (plus coloring if desired) 5 Rosin size 2 Copper sulphate 3 The above materials constitute 5% of the total of which the other 95% is water, as is also the case in the preceding formulas, that is if the formula is prepared in the beater at the usual beater proportions of solids and water. However of course I do not limit myself to a mixture of the ingredients and water in such proportions, as I may use any proportions, e. g. such as may be customary in papermaking. The above illustrated example will give a well sized sheet of book paper. terial may also be added if desired.

In practicing my invention, (e. g. as in the various sequences and formulas indicated above), the filler may be any alkaline filler, which may be untreated, or treated, e. g. as described later herein; and of course if desired other fillers may be used in addition to the alkaline filler, well known examples being clay, talc, calcium sulphate, barium sulphate and the like. Likewise the size may be any sizing material which is precipitable or affected by a substantially watersoluble copper compound; for example it may be in the form of a rosin soap containing about saponified rosin and 30% free rosin.

The acidic material employed may be sulphurous acid. Calcium acid sulphite gives highly satisfactory results. Other acid materials may be employed. but it has been found that sulphurous acid and bisulphites produce a better sizing eifect than sulphuric acid for instance. The acid material most commonly used in papermaking is alum, and in many instances I prefer to use it as my acidic material; or I may employ alum in combination with the various other acidic or other materials. Where I speak of neutralizing or neutralizing agent, of course I do not ordinarily mean that any such large amount of acidic material is added as would be suificient to react with all or with a large part or even with any substantial part of the alkaline filler, and thus destroy it or any large or substantial portion of it, as of course my invention concerns the manufacture of paper filled with alkaline filler. However if for some reason it be desired to employ an unusually large amount of acidic material, that still falls within the scope of my invention, provided that the paper made by the process still contains alkaline filler.

Where, as in the first illustrative formula given herein, I speak of acid to neutralize (phenolphthalein as indicator) I mean that the indicator is used to make the test as soon as the acidic material has been well incorporated in the mix. The pH of the mixture may be brought belrw 7, at least temporarily, if desired, but it does not necessarily have to be brought below 7; nor even down to or near 7. Moreover in respect to the acidic material, this may, a indicated in one of the illustrative formulas given herein, even be omitted in certain cases. I do not limit myself to any definite amount of acidic material as I may use an amount necessary to neutralize according to the test indicated above, or less than that amount, or more than that amount. Where I use acidic material, I usually find from about .5% to5% (e. g. alum) calculated as dry weight on the dry weight of the ingredients of the mix to be a suitable amount to employ, butthis range is to be understood to be illustrative only and not limiting as I'may use more or less, as the occasion demands. Moreover, when used, the acidic material may be added in any order in respect to the other ingredients. It may also in certain cases, if desired, be mixed directly with the substantially water-soluble cop- As shown previously, an acidic ma-' per compound prior to the addition of the cop cipitate of the rosin size (or other sizing material) with the substantially water-soluble copper compound, the composition of which rosin size precipitat depends among other things upon the composition of the rosin size used and the conditions under which the precipitate is formed-but which for the sake of convenience herein may be assumed to be copper resinate-is unaffected by alkaline filler or at least is far more resistant to the deteriorating or destructive efiect of alkaline filler than is the precipitate produced by the action of alum on rosin size (i. e. an alum-rosin size precipitate), or other alum-size precipitate. Furthermore when the copper resinate or other substantially water-soluble copper compoundsize precipitate or th like is co-precipitated or associated with an alum-rosin size precipitate, or other size precipitate, the copper resinate or the like ma fortify or protect such size precipitate against the deteriorating or destructive action of alkaline filler. Or the substantially watersoluble copper compound may convert a forming a or already formed alum-rosin size or other size precipitate into the more resistant copper resinate or other substantially water-soluble copper compound-size precipitate. However it is to be distinctly understood that these possible explanations of the reason why a substantially watersoluble copper compound appears to be effective in my process and the resulting compound or compounds in the paper made therein are only theory, and that regardless of the correctness or incorrectness of these or of any other theories purporting to explain its action, which have or may be advanced, my invention is entirely independent-thereof, and is not to be limited or in any way restricted by these or any other theories, because the facts remain that the use of a substantially water-soluble copper compound in connection with a size in the manufacture of paper filled with alkaline filler does produce the dis-- tinctive and unique results herein described and not heretofore obtained.

The term alkaline filler has already acquired a definite meaning in the art, which may be briefiy summarized as filler which is substantially water-insoluble, and which when agitated with freshly boiled distilled water imparts thereto a pH value greater than 7. (See for example Patent 1,808,067, June 2, 1931, page 3, lines 96 et may have any desired particle size from relatively coarse, through the finer, and even down through the colloidal range, or a mixture of particle sizes, as desired.

In respect to the addition of materials in my process, I have given a preferred order (1?). I have also stated, however, that any other order may 'be used- My invention, of course, may be practiced by addition of -materials in th beater or other mixing machine, or if desired, may be practiced in connection with any of the now well known procedures for the manufacture of paper filled with alkaline filler, such for example as those mentioned in my discussion of prior processes given above, and specifically in accordance with the so-called minimizing" procedures,

I which may be briefly described without going into seq.) Examples of fillers of this type are, as is wellknown, calcium carbonate, which may come from natural sources, from the lime sludge from the causticizing process, from precipitation of lime by carbon dioxide, or from other sources; magnesium carbonate; calcium carbonate magnesium hydroxide; calcium carbonate magnesium basic carbonate and the like; or mixtures or compounds of the above. Thus when I use the expression alkaline earth metal, I mean to include magnesium within the scope of the expression. In any case, the alkaline filler may be used in the form as it occurs or is produced, or in a purified or specially prepared form, and it details as addition of one or more materials late in the' papermaking process. This addition may b made in one or more of the chests. Of the chests, it is preferable to make the addition in the machine chest (or what is substantially the equivalent, in the fiow of the mixture of pap making ingredients already added after it leav s the beater chestifa beater chest be used-and before it is delivered into the machine chestlt.

Or addition may be made, and this is preferable;

in the dilute stageof the paperrnaking process such as at the mixing box, rifflers or headboxof the machine. t I

Thus, for example, the alkaline'filler, the size, the substantially water-soluble copper 'com-' pound, and the acidic material, if used, or any of them, or any part of any of them, (or fibrous material associated therewith, e. gfbroke or-old paper stock), may be added at any point in the,

papermaking process either in thefbeater or 1 other mixing or treating device, or subsequent thereto up to the point of web formation. Moreover addition of such material may be made on the web itself, either while it is o'n the webforming device, or subsequently. This, as well as the above procedures, are all now well known. If the addition is subsequent to the beater, such addition is preferably made continuously rather than intermittently. One illustrative example of practicing my invention in connection with a minimizing procedure is to add the pulp, size and substantially water soluble copper .com-

pound in the beater, then add the alkaline filler in the beater, and then add alum later in the process, e. g. at the dilute stage. Another illustrative example is toadd the pulp, size and substantially water soluble copper compound in the beater, and then add alkaline filler and alum later in the process, e. g. at the dilute stage.

Also, of course, any other procedures well known for use in the manufacture of paper'filled with alkaline filler may be used in connection with the practice of my invention.

In respect to the cases where the substantially water-soluble copper compound is added prior to the addition of the sizing material and where the alkaline filler may also be present'prior thereto, there will be more or less reaction between the copper compound and the alkaline filler, but because that is a-reaction between a.

copper compound with the rosin' size is rapid, if not in'most cases practically instantaneous, because the rosin size is either in solution or in substantially colloidal solution. Therefore although there may be more or less reaction of the copper compound with the alkaline filler, depending on the time ofcontact of the two before the sizing material is present, nevertheless the preponderant part of the substantially water-soluble copper compound present if not substantially the entire amount, will "react with thesizing materiaL'espec'iaHy if the sizing material in suitable aimount' be added with, or shortly aftenth'e alkaline filler. However in all these cases the alkaline filler may-have some joint or 1 be, as suggested above, that the substantially water-'solublecopp'er compoundmay'additionally 'act upo'n the fibrous matcrialin agreater or less degree, or prepare the fibre in some way to 'rec'eive'the size. It should be'understoodho'weVer, "that these are merely theories, and that my invention is independento'f their correctness or incorrectne'ss.

-'It' is well known touse allt'ypes of 'pulp with alkaline "fillers, (for "example, see Patent No.

1,595,416 -of-'Aug.= 10, 1926). For instance there "maybe used *mechanical (i.e.- groundwood pulp) or'chemi'cal wood pulp, rag pulp, straw pulp, espa'rto pulp, jute-hemp or'asbestos or the like,

"or mixtures of one or more of these may be used. Of course my invention maybe practiced with'any of these or any other pulps used in the paperin'du'stry, all of'which arewell known. Of the well known chemical pulps there may be mentioned,as examples, sodapulpfsulphite pulp,

sulphate or so-called 'k'raft pul'p, Kecbra pulps,

as well as semi-chemical lpulps, and the like. These or any of them'may be used as produced, or maybe highlyp'urified if desired such as in the case of;"alplia" pulp, 'i. e., afpulp high in alpha'cellulose content. Additionallyof course reworked pulps such'as old papers, either'without deinkingor after deinkin'g may be, used. Such old Ipaper s'to'ek'isco'rnmonly used. The waste paper of the'papermaking process'the' socalled broke,-' may of course also be used as'is customatyin papermaking. -Any ofthe pulps mentioned may be used either in unbleached, partly bleached Orin-bleached condition. The pulps 'may'of'coursebe-used alone or admixed in anyproportions as-desired.

Likewise I may employ in my paper any desired proportion of 'alkalinefiller'to pulp, as is well known in the a'rt,"to obtain-any percentage of'filler in the resulting, paper that I'rnay desire. However in r'nany "cases I prefer to use the amount that will give me from -5-"40% oi'alk'aline filler iri 'the resulting paper, generally '15 30% being-a conv nient amount.

As to sizin'gm'at'eri'al, I prefer-rosin size, andin the substantially wholly saponified sizes, such as the wellk-n'own Delthirna size, orthe like,

through the resin: sizes containin i'more or less "free,- i.' e.,"unsaponified rosin, but which are predomi'n'antlysaponified rosin, down to the sizes which may be 'preponderatingly or substantially completely in unsaponified condition, such :as Bewoid size or the like. The rosin sizes used may be the ones made 'by'treating rosin or the like 'with a'nysuitable'saponifyin'g or emulsifying agent, such as an alkali, ofwhich the alkaline sodiumcompou'nds are the commonest ones; or they maybe made with alkaline potassium *or ammonium compounds or ammonia "or with an amine, all of which are well known for makin r'osin sizes.

or treating agents such as casein, solubleolls,

Or other well known emulsifying sulphonated higher fatty'acids, or "other 5111- phated '01 sulphon'ated 'productsmay *be :used with therosin or the like, aloha-or inconjunction with, or following, the "agents previously mentioned. If desired the melting point 'of the rosin used-may be lowered, asby'fluxing'witha material which'will lower its melting p'oint, suchas an oil,"e. g, mineral 'oil,'o'r anim'al'or vegetable oil, or by parafiin or the like.

of rosin or synthetic rosin"acid"or a'cids.

In the place of rosin size, l may use any other suitable well known sizing "materialswhic'h are used with alkaline filler, for examplathe'wa'x or parafiin emulsions'mentioned previously herein, or'oil emulsions, suchas mineral'oil-emulsions,

or petroleum jelly emulsions, all of whichma'yif desired be conveniently made with rosin size as an'emulsifyin g agent; or I may use org'anic'material reactive 'with alkali such as a fatty'acld, e. g. stearic, oleic, palmitic, linoleic, o'r the 'like,

which may be hardened or hydrogenated ifde-- sired, in my size instead of rosin," which"may be emulsified or treated if desired e. g. with any of the emulsifying or treating agents mentioned above in connection with rosin, and particularly if desired with an alkaline materialsuch as an alkaline sodium,'potassium, orammonium compound, or ammonia, or an amine-or the-like.

Moreover certain pulps-usedin the papermak-' ing process may contain more or less mat'erial as an integral part thereof "which :may impart a certain degree'of sizing to ordinary paper-made therewith (i. e., paper "not containing alkaline filler) without the actual addition of sizing: ma-

terial itself in the papermaking process; or whichmay impart a degree of sizing to such "paper which may be enhanced by the 'addition of other 'sizing material in the paperrnaking "process r pulps are somewhat undercooked--'where-thev krait pulp may have a certain so-calledself sizlng "quality, that is to say, may impart a certain 'eflect of the pulp itself. -My inven'tion .may be used in connection withany such pulp containing. s zing material as an integral part thereoL tO' obtain sizing effect-or improve'sizin'gefiecfiwhen Where I use the word r esinate" herein, it refers to a derivative :alka'line :filler ;is used "therewith, the .situation being the same in all respects as described in detail herein for the gpractice .of my invention,

.except in this instance some :or -.all of :the pulp of ,pulps thavingsizing=material as an integral "part thereof falls within the scope of my invention.

*In respect ito {the substantially water-soluble .coppercompound, 'I may use substantially waterscluble coppercompoundsuch-as iorexample the sulphate,nitrate,chloride orxacetate, all of which are well :known, :as wellasother well known substantially water-soluble copper compounds :such

' filler'may be used untreated.v

as the chloratesilicofluoride or the 'like,.or douand, in such cases, this is to be understood to be the equivalent .of the substantially water-soluble copper compoundspI employ. I can sometimes :accomplishthisby ithe -useof a substantially watar-insoluble copper'compound, such as copper carbonate ior example, which in certain in-' "stances whenin contactwith acidic material in the papermaking mix :may 'produce a substantially water-soluble copper-compound.

Also alkaline copper-compounds e. g. copperammonia compounds may be used. Alkaline copper compounds-maybe used as such withgood results, ,or their -:alkalinity may be reduced, if .not completely neutralized, or the compound may acidic material such gas alum :may be conjunction itherewith if desired.

The substantially water soluble copper com- ?poundsare ,in the main :cuprimnearly all of the cuprous' compounds, zat' l'ast those commercially available, *being water insoluble or, only very used in slightly soluble; "However .the cuprous 'compounds may be use'd'if rdisso'lvedin a uitable solvent, such as an acid, but in suchcases there is usually considerable oxidationlto the cupric compound, so that the cuprous compound alone is not being used, but a mixture of the cuprous and cupric compounds. As'most-of the cuprous compounds tried do not appear tobe as efflcient as the cupriccompounds, the'cupric compounds are preferred. Y

My invention may .be practiced if desired in connection with the treatment of alkaline filler with a substantially water-soluble copper compound, such as is described and claimed in my copending application .Serial No. 679,994, filed July 11, 1933, now patent numbered 2,178,606, granted,Nov.u'7,1939. In such case it is convenient to pretreat the alkaline filler, for example onederived' from dolomitic material, with substantially wateresoluble copper compound before adding to'thepaperm'a'king mix, but this .is not necessary. -.Although$-I do not restrict myself to the amount of "substantially water-soluble copper compound-used in such case, one percent on the weight of the alkaline'ifiller is usually enough, but more or Jessmay -beused-ifadesired. It will be noted 111:3. discussion given previously herein,

veven be acidified, with :acidic materials. Or

that when asubstantially water-soluble copp r a compound is in the presence of alkaline I'fille'r before the'copper compound 'has reacted with;

the size, the alkaline fillermay also be acted;

upon by the copper compound without such pretreatment as is indicated above. ,Asis wellaknown in the art, the alkaline filler maybe pretreated with an .acidic material such as alum, and/or with a soap or oil emulsion or the like prior to addition to the paper mix, together with alum if .desired, .and such treatment of the alkaline filler may be employed .in the practice zof my invention, or as stated previously, the. alkaline While it is convenient to usethesizeI employ,

such as rosin size, in rather a diluteemulsion or solution such-as for example one 'containing'about 2% of rosin, I do not confine myself-totheuse of any definite concentration, but may use any :concentration .up to where the'size is in thick paste form, or even in dry form. It will be seen from the illustrative formulas given herein that I use in certain cases ansamount of substantially water soluble copper compound, e. g. copper ulphate, calculated as (311894551120, in weight equal to the weight (dry basis) ofthe sizing material, e. g. rosin size, employed, and in other cases equal to one and a half times the weight of the sizing material employed. It is .to be understood, however, that I do not limit myself to these proportions but may vary them widely, and without being limited thereby Icanpstate that for most purposes I employ a range from about onefifth to five parts of copper sulphate to one part by weight of rosin size, accordingto conditions, with the range of proportions shown in the illustrative formulas usually giving the optimum results.

. As stated in the early part of this .specifica- I tion, I may use in the practice of my invention as little as 1 6 of one percent of thesubstantially' claims I employ the expression 'copper-compound, I means that there should-'be used'not less than that much as a minimumlin' the proc- .esses claimed, and also in the processes :fro

which resulted the produotsclaimed, i

The word "paper is used herein in a broad. sense to include products of all types, weights and thicknesses which contain fibrousmaterial as a necessary constituent and which can he produced on a Fourdrinier, cylinder, or other forming, felting, or the like single or multi-ply paperv or board machine. While in one of the illustrative formulas shown above I refer to the product as being suitable for book paper, his to be understood that I am not in any way restricted to the manufacture of book paper, as the paper of my invention maybe used for any of the variety of uses for which paper is used such as for printing paper of any kind including news, writing paper, wrapping paper, or the like, or for conversion, as to bags, coated paper, corrugated board, or infact for any ,other use to which paper can be put which may possess as desired from only a slightly sized efieotto complete waterproofing.

It is to be noted thatrin paper-filled wit-halkaline filler wherein sizing material is employed, the :use-of a substantially water-soluble copper compound for reaction withthe sizing material produces the unique, distinct, and wholly unexresinate.

pected result of yielding a sizing effect, as tested by ink flotation, greatly superior to that obtained in either unfilled or clay filled paper, where only very poor sizing effect is obtained when such copper compound is employed for reaction with the sizing material.

This application is a continuation in part of my copending application Serial No. 679,994, filed July 11, 1933, now patent numbered 2,178,606, granted Nov. 7, 1939, and also a continuation in part of my copending' application Serial No. 679,993, filed July 11, 1933, now patent numbered 2,186,040, granted Jan. 9, 1940, both of which as filed contained substantially identical disclosure in respect to the invention herein claimed, but which disclosure in application Ser. No. 679,993 has been cancelled because said disclosure and claims to diflerent phases thereof are contained herein and in my copending application Ser. No. 679,994, now Patent No. 2,178,606.

While I have described in detail the preferred embodiments of my invention, it is to beunderstood that the details of procedure, the proportions of ingredients, and the arrangement of 1 steps may be widely varied without departin from the spirit of my invention or the scope of the subjoined claims,

I claim:

'1. Filled paper comprising fibrous materlaL a filler comprising alkaline earth metal carbonate,

and the product derived from the bringing topresence 'of water.

2. Filled paper comprising fibrous material, a

I filler comprising calcium carbonate, and the product derived from the bringing together of materials comprisingrosin size and a substanproduct derived from the bringing together of materials comprising, rosin size and copper sul phate in the presence 01' water.

4. Filled paper comprising fibrous material, a filler comprising calcium carbonate, and copper 5. Filled paper comprising a filler which cornprises calcium carbonate, and a substantially water-insoluble copper compound, said paper begether of materials comprising rosin size and a substantially water-soluble copper salt the bonate, rosin size, and copper sulphate, and thereafter making paper therefrom.

9. The process of manufacturing paper filled with a filler which comprises calcium carbonate,

comprising mixing materials which comprise fibrous material, a filler comprising calcium carbonate: rosin size, co per sulphate, and. aim,

and thereafter makin paper therefrom.

10. In a process for the manufacture-of paper filled with a filler comprising calcium carbonate, wherein materials are employed comprising fibrous material, a filler comprising calcium car-- bonate, and rosin size, the steps which consist in providing a substantially water-soluble copper compound and eil'ecting a reaction between saidv copper compound and said size.

11. The process for the manufacture of paper water-soluble copper salt, and thereafter drying said web.

12. The process for the manufacture of paper filled with alkaline filler which comprises providing a wet paper web' made from materials comprising fibrous material, a filler which comprises calcium carbonate, rosin size, substantially water-soluble copper salt, and alum, and thereafter drying said web.

l3. Filled paper comprising fibrous material,

alkaline filler in intimate association therewith,

and a substantially water-insoluble copper compound resulting from the bringing together and interaction, in the presence of water, of a substantially water-soluble copper compound.and

ing derived from the bringing together, in the 7 presence of water, of materials comprising .fibrous material, a filler which comprises calcium carbonate, .a substantially water-soluble copper compound, and a size selected from the group consisting of rosin sizes and fatty acid sizes, said substantially water-insoluble copper compound resulting from the interaction of said substantially water-soluble copper compoundand said size, said filler in said paperv being in intimate I association with said fibrous material.

ing derived from the bringing together of mate- I rials comprising fibrous material, a filler comprising calcium carbonate, rosin size, copper sulphate, and alum,'in the presence oi. water.

soluble copper compound, and alum, and there-.

after making paper therefrom.

8. The process of manufacturing paper filled with a filler which comprises calcium carbonate, comprising mixing material which comprise fibrous material, a filler comprising calcium car- 1'5. Filled paper comprising a filler which comprises calcium carbonate, and a substantially water-insoluble copper compound, said paper being derived from the bringing together, in the presence of water, of materials comprising fibrous material, a filler which comprises calcium carbonate, a substantially water-soluble coppersalt, acidic material, and a size selected from the group consisting of rosin sizes and fatty acid sizes, said substantially water-insoluble copper compound resulting from the interaction of said substantially water-soluble copper salt and said size.

. 16. Filled paper comprising a filler which comprises calcium carbonate, and a substantially water-insoluble copper compound, said paper being derived from the bringing together, in the presence of water, of materials. comprising fibrous material, a filler .which comprises calcium carbonate, a substantially water-soluble copper compound, alum, and a size selected from the group consisting of rosin'sizes and fatty acid sizes, said substantially water-insoluble copper compound resulting from the interaction of said substantially water-solublecopper compound and said size.

17. Filled paper comprising a filler which comprises calcium carbonate, and a substantially water-insoluble copper compound, said paper being derived from the bringing together, in the presence of water, of materials comprising a filler which comprises calcium carbonate, pulp having as an integral part thereof a size selected from the group consisting of rosin sizes and fatty acid sizes, and a substantially water-solublecopper compound, said substantially water-insoluble copper compound resulting from the interaction of said substantially water-soluble copper compound and said size.

18. The process for the manufacture of paper filled with alkaline filler, comprising mixing materials which comprise fibrous material, alkaline filler, a size selected from the group consisting of rosin sizes and fatty acid sizes, and a substantially water-soluble copper compound, and thereafter making paper therefrom, said size being reactive with said substantially water-soluble copper compound in the presenceof water.

19. The process for'the manufacture of paper filled with alkaline filler, comprising mixing materials which comprise fibrous material, alkaline filler, a size selected from the group consisting of rosin sizes and fatty acid sizes, a substantially water-soluble copper compound, and acidic material, and thereafter making paper therefrom, said size being reactive with said substantially water-soluble copper compound in the presence of water.

20. The process for the manufacture of paper filled with a filler which comprises alkaline earth metal carbonate, comprising mixing materials which comprise fibrous material, a filler comprising alkaline earth metal carbonate,- a size selected from the group consisting of rosin sizes and fatty acid sizes, and copper sulphate, and thereafter making paper therefrom, said size being reactive with said copper sulphate in the presence of water.

21. The process for the manufacture of paper filled with a filler which comprises alkaline earth metal carbonate, comprising mixing materials which comprise fibrous material, a filler comprising alkaline earth metalcarbonate, a size selected from the group consisting of rosin sizes and fatty acid sizes, a substantially watersoluble copper compound, and alum, and thereafter making paper therefrom, said size being reactive with said substantially water-soluble copper compound in the presence of water.

22. In a process for the manufacture of paper filled with alkaline flller wherein papermaking materials are employed comprising alkaline filler, fibrous material having sizing material as an in tegral part thereof, and a size selected from the group consisting of rosin sizes and fatty acid sizes, said size being reactive with a substantially water-soluble copper compound in the presence of water, the steps of introducing into said papermaking materials comprising said alkaline filler and said fibrous material and said size, a substantially water-soluble copper compound, and effecting a reaction between said copper compound and said size, thereby forming in the papermaking material a substantially water-insoluble copper compound having a sizing effect which is resistant to the deteriorating action of said alkaline filler in an aqueous medium.

JOSEPH E. PLUMSTEAD.