CA1083759A - Process of preparing size - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

A process for preparing size for the treatment of paper is disclosed, comprising providing a fatty acid, either saturated or unsaturated, and at least partially saponifying the fatty acid by contacting it with an alkali metal hydroxide in the presence of aluminum or zinc. In addition, methods for preparing sized paper are disclosed, including providing a fatty acid, at least partially saponifying the fatty acid by contacting with an alkali metal hydroxide in the presence of aluminum or zinc, preparing an aqueous solution of the saponified fatty acid, and applying the aqueous solution of the at least partially saponified fatty acid to fibrous materials prior to formation of a paper web therefrom.

Description

FIELD OF THE INVENTION
The present invention relates to methods for preparing size for treating paper material. More specifically, the present invention relates to the utilization of hydro-phobating agents for sizing paper. Still more particularly/
the present invention relates to processes of preparing such hydrophobating agents.

2 0 BACKGROUND OF THE INV~NTION
In the manufacturing of various paper products, it is required in most cases that the fibrous material, either prior or subsequent to the formation of a paper web therefxomr be treated in a manner to increase the resistance of the paper . . to penetration by wa~er. This is aecisively important for the use of the fibrous materials in printing paper of various types.

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~837S9 Such treatment of fibrous materials is generally called sizing, and it implies that certain agents, the so- ¦
called hydrophobating agents or sizes of various types be added to the fibrous material. Such sizing is generally divisible into two main groups, depending upon the particu-lar method of adding the size. These include stock-sizing, wherein the size is added to the fibrous material prior to formation of the paper web, i.e. in the so-called stock, and surface-sizing, wherein the paper web is surface-treated by applying surface thereon, such as by means of conventional sweeping blade methods.
The present invention is specifically directed to methods of stock-sizing ibrous materials by using a unique stock size which is described in greater detail herein.
i In such stock-sizing procedures, the added chemicals .
are employed so as to reduce the wetability of the fibers themselves. The methoas employed in this industry at present have remained substantially the same over the last one hundred years, and they include the addition of the size to the stock and its precipitation onto the fibers by means of alum. In the recent past, however, certain new sizes have been developed, but these sizes are still generally based upon resinous materials, such as fortified pine resin, .
which is usually delivered to paper mills in the form of a seventy (70%~ percent saponified resin size. -In order to obtain a good sizing, it is generally necessary that percipitation of the size take place in the form of small particles, which are preferably uniformly dis-tributed over the fibers. Thus, in the arying section of the paper making machinery, the hydrophilic shell of the .
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, sized precipitation particles is oriented toward the fiber, and at the same time the water-repellent core is turned outward. A certain outflow of the particles thus also takes place.
- The quality of the sizing obtained is influenced, in different degrees, by the conditions in the stock, on the wire, in the press section, and in the drying section.
During paper storage, certain changes in the degree of sizing can also take place at times.
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o In the early 1960~s, ortified sizes were introduced in Sweden, and the amount of resin in sized paper and card-board was thus decreased from about 1.0 down to about 0.4 percent. This was primarily due to the improved sizing tech-niques which were developed, generally based upon continuing experimental work, greater skill in those utilizing this machinery, as well as better and more uniform quality in the sizes themselves available.
! ` In addition, in very recent years, and for only limited or special purposes, some chemicals have been employed 20 which are not based upon resin acids. This has been desirous due to the increasing shortages o~ resin acids ~colop~ony) and the desire to employ a size at a neutral pH. For these reasons, efforts in developing new sizing chemicals are presently being made.
As for the resin acid materials upon which sizes have been based, these have generally fallen into a few categoxies. -Most particularly, cation ac~ive alkyl ethylene dimers have been employed~ Thus, such a produce is marketed ~ in Sweden by Kema Nora under the traaename Kenosi-f.e D54. In 30 addition~ the Hercules Company has marketed a similar product , ~qde rr~cl rk .

~83759 under the tradename Aquapel~ These produc-ts are intended or sizing in!a pH range of fro~ about 6.9 to 9.0, and employing a recommended batching of from about 0.05 to about 0.10 percent on an absolute dry basis. Since this particular pro-duct is cation active, alum need not be added, but batching of this cation active retention agent is recommended. This pro-duct is also ra-ther expensive, generally ranging in the area of about 20 Swedish krona per kilogram, and has a dry content of - -- only about nineteen (19%) percent.

In addltion, cation active carbamoyl chloride having the following formula;

R \ O

/ N - C - Cl ' ' '' , ' ~/ ' ' ' ' ' ' ' ' '.
wherein R represents a long chain parafin, are also available for such purposes. Thls product has also been developed by Kema Nord, and is said to have certain advantages over the above alkyl ethylene dimers. This product has not, however, been employed commercially, is still being tested, and will apparently be marketed undex the tradename Kenosize D58.
The batching recommended for this product is generally the same as that with the ketene dimer, and is employed at a pH
level, for sizing, of from about 4.5 to 8Ø This material also has a dry content of abou~ twenty (20%) percent.
.
Neutral sizes based upon fatty acids from the firm of Giulini, in Ludwigshafen, Germany, under the tradename Gilutol V is also known. While the aetailed p~operties of this material are not known,since size is still being developed, it allegedly can obtain good sizing effects at a pH of about -6.5 by adding about 1.5 percent size and about 3.5 percent rad~ n~ark . . . . . ~ . . .. .

83~59 .
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aluminum sulfate.
Finally, Hercules also marke-ts a fortified emulsion size under the tradenarne "T-size 22L". This material also is apparently based upon a resin acid, and upon precipitation in a conventional manner employing aluminum sulfate, this size is claimed to be useful in a wider pH range than conventional fortlfied resin sizes. In addition, this rnaterial is marketed at a dry content of approximately forty-five (45%) percent.
Conventional sizes based upon resins, as discussed above, are generally precipitated upon the surface of the cellulose fibers in order to increase the resistance of the fibers to wettin~. In most cases, the ~uantities of size required are so great that th~yresult in adverse influences on other properties of the paper itself. In addition, this reaction is generally carried out in an acid system, which - itself has a generally unfavorable effect on the physical and optical properties of the paper produced. Therefore, in order to be useful and efficient, a paper size must meet at - least the following requirements:
- . . , The size must be water repellent (i.e. has a large .
contact angle to the penetrating liquid) in order to render the fiber surface water-repellent;
The size must be divided into small particles dis-tributed uniformly over the fiber surface, in order that the capillary walls are also water-repellent;
.. .
The size must adhere to the fiber surface by ad-hesion or chemical reaction so that it will not flow off -when water is applied to that surface; and The size must not react with or be dissolved in the penetrating liguid~ because it will then loose its water repellency capaci~y and yield a poor sizing effect.

~15 37S9 As noted above, conventional sizes do not meet all of these requirements.
SUMMARY OF THE INVENTION
According to the present invention, there is provided a process for preparing paper webs from fibrous material which comprises providing a fatty acid, at least partially saponifying said fatty acid by contacting said fatty acid with a first amount of an alkali metal hydroxide in the presence of a compound of a metal selected from the group consisting of aluminum, zinc and mixtures thereof, whereby said partially saponified fatty acid is maintained as a liquid, preparing an aqueous solution of said at least partially saponified fatty acid, adding a sufficient quantity of a second amount of an alkali metal hydroxide to said aqueous solution of said at least partially ; ;
saponified fatty acid so as to further saponify said solution, and to maintain said solution at a p~l of at least about 8, and applying said aqueous solution of said saponified fatty acid to said fibrous materials in order to size said ;
fibrous materials prior to preparation of said paper web. It has thus been discovered that paper webs prepared from fibrous materials can be sized by preparing an aqueous solution of the above-described at least partially saponified fatty acid, and applying that aqueous solution to the fibrous material prior to preparation of a paper web therefrom.
The instant invention is thus based upon the unexpected discovery that such a size must be based on fatty acids or derivatives thereof, and that the fatty acid must be partially saponified by the introduction of such a suitable metal. It has thus been found critical to achieving the effects referred to above that the saponification be carried out to the semi-saponification point, and further that the saponification employ compounds of the metals aluminum and/or zinc.
In a preferred embodiment, a solution of the alkali metal hydroxide, preferably sodium hydroxide, and the metal employed, is prepared prior to saponification of the fatty acids therewith. It is thus particularly ~ - 6 -.. . ..

- 1~)83759 preferred that the saponification be carried out in a plurality of steps.
Furthermore, it is also particularly preferred that an aliphatic hydrocarbon be added to the at least partially saponified fatty acid in order to minimize micelle formation therefrom, prior to use in sizing paper products therewith.

- 6a -."~' , DETA:[LED DESCRIPTION
It has thus been discovered that by preparing size in this way, subs-tantial advantages over conven-tional sizes may be realizea. The product obtainecl in accordance with the present inven-tion is thus fluid at room temperatures-, as well as at much lower temperatures. This facili-tates the handling, storage and transport of ~his size, and in particular ~acili-tates the batching required for preparation of the size, since this size can be easily pumped, and flow meters ana other :feed means can be used wlth efflciency and easy of operatlon.
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The fluidity oE this size thus renders it possible to design speclfic batching means particularly suited for such purposes.
It is also now possible in accordance with this in-vention to employ a size which can be utilized within a wide pH-interval, and in particular at a neutral pH. This is of great significance for avoiding the detrimental effects which .
sizing and acid environments have had on the strength properties -~ of paper and the like. In accordance with this invention, and - as can be seen in the working examples reviewed below~ it is now possible to add size in considerably smaller amounts as ¦
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compared to a conventional sizlng procedure, which itself implies an improvement in the economy of paper sizing~ Of even greater interest, however, is the fact that deterioration of the optical properties of the paper can now also be avoided.
Xt has also been found that by employing the size of the present invention, an optimum Cobb-value for various types of paper can be obtained, as can also be seen from the working examples reviewed below.
The fatty acids which can be utilized in accordance with the present invention include both the saturated and ., .,.".'. . . .
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unsaturated fatty acids. In particular, it is preferred that a fatty acid having from 12 to 24 carbon atoms be employed.
~ither a single fluid fatty acid, a mi~ture of fatt~ acids, or a mixture of fatty acids and/or their derivatives may be employed in accordance with the present inventlon. In particu-lar, it is preferred that the fatty acid be saponified to the semi-saponification point by addition of an aluminum or zinc compound in accordance with the present invention in conjunc-tion with alkali metal hydroxide to the stirred fatty acid.
Preferably a solution of the aluminum or zinc compound and alkali metal hydroxide are previously prepared prior to their addition to the stireed fatty acid. In addition, it is pre-ferred that saponification be carried out successively, prefer-ably in which'the above-noted solution is added to the fatt~
acid in two or more steps.
The aluminum compounds which may be utilized thus in-clude the aluminum sulfates and chlorides, while when zinc com-pounds are utilized; they may include the zinc chlorides, sulfates and oxides.
It is also preferred that the fatt~ acid be heated, pref-'erably to above about 100DC., prior to saponification thereof The present invention may be further understood by reference to the following examples thereof.
In order to saponify a fatty acid, a saponification solution was first prepared by mixing 75 kilogr~s of a forty (40~) percent solution of NaOH corresponding to 752 e~uivalents with 13 kilograms of aluminum sulfate having the formula A12(SO4)3 1~ H2O, corresponding to 117 equivalents thereof.
The reaction products thereof were heated to about 60C , 30 'while being stirred, at which time the temperature was held_constant and water was added in proportions until a clear solution was obtained. About 59 kilograms of water '`
were added in toto, and the solution thus obtained consisted 375~

of an aqueous solution of sodium hydroxide~ sodium alumina~e and sodium sulphate.
As a starting material for the preparation of a size in accordance with the present invention, a fatty acid fraction was utilizea which is marketed by Bergviks Hartspro-dukter AB under the notation "TO 2". Thi$ fatty acid fraction had the following composition;
- Oleic acid 32%
.
Linoleic acid 62%

Saturated fatty acids 2.5%
Resin acids 1.5%
Unsaponified 2%
Five Hundred kilograms r corresponding to 1,738 equivalents of this material, were then charged into a jacketed steam-heated reactor, and the material was heated to about 100C. The aforementioned sodium hydroxide- -aluminate solution was then added in portions to obtain a successive saponification thereof. This reaction was per-mitted to proceed until the foam formation ceased, and a uniform consistency was obtained. Heating oE this solution was then interrupted, and the reaction proaucts were per-mitted to cool to about 70~C., whereafter 5 kilograms of:
~2,~,4-trimethyl pentane was adeed while stirring continued.
The reaction was permitted to continue for a short perioa of time while slowly cooling. The product thus obtained was fluid at ro~m temperature, and was maintained in a fluid state as it was cooled to a temperature of about -10C.
By this method, all water was removed, and the praduct was thus 100~ size. ;~

In accordance with the present invention, zinc ~- ~0l337S9 compounds can be substituted for the aforementioned aluminum compounds~ In such a case, substantially the same method of preparation will be applied, however, employing certain modi-fications which will be understood to be necessary to those skilled in this art in vièw of the ~enerally known properties of such zinc compounds.
While a mixture of the unsaturated fatty acids oleic acid and linoleic acid are employed in this example, other such unsatura-~ed fatty acids, or combinations thereof, can also be employed as a starting material herein~ As an ' , " ,.
example, other unsaturated fatty acids which may be employed in accordance with this invention include linolenic acid, eleostearic acid and pinolenic acid.
Furthermore, saturated fatty acids may also be em-ployed, either alone or in admixture with other saturated or unsaturated fatty acids, in accordance with this invention.
Examples of such saturated fatty acids include laurinic acid, myristinic acid, palmitinic acid, stearic acid, arachinic acid, behenic acid, and lignocerinic acid.
As discussed above, it is also preferred to add an aliphatic hydrocarbon to the reaction mixture after saponification to the semi-saponification point, in order to prevent possible micelle formation thereof. In place of . .
the 2,2,4-trimethyl pentane noted above, other such aliphatic -hydrocarbons can also be employed, either having straight or branched carbon chains, and preferably including from about 5 to 12 carbon atoms. Examples of such hydrocarbons include pentane, hexane, heptane, octane, nonane, decane r undecane or dodecane, and isoheptane, isobutyl isoamyl, or 2,2,5-trimethyl hexane. It is most preferred that when such ',' ' ' ' " .
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hydrocarbons are added to the reaction mixture, the mixture itself is cooled prior to such mixture, preferably to a temperature below the boiling point of the particular hydro-carbon thus employed. I-t is thus preferred that micelle formation is prevented either entirely or at least partially, by the addition of such hydrocarbons, which are thus prefer-ably added in amounts ranging from about 0.1 to about 10 ~
percent by weight-, preferably about 0.1 to about 1 percent by weight, calculated on the amount of fatty acid present.
i lt is further noted that in the preparation of the solution of alkali metal hydroxide and a compound including either aluminum and/or ~inc, that the amount of each compound employed, with respect to the other, comprise a mixture of , alkali metal hydroxide to the metal compound, preferably an .
- aluminum compound, in an equivalence ratio of from about 30 to l to about 1 to 10, preferably from about 6 to 1 to about 7 to l. -~

In accordance with the example specifically reviewed .. . .. .
- above, in order to prepare a size solution for stock-sizing according to this in~ention, the 100 percent size prepared : - :, .
in accordance with that example was dissolved in water, in a conventional manner. Such dissolution was carried out in order to dissolve the size directly in an amount correspond-ing to the concentration which was to be batched fox use in the fiber suspension, i.e. the so-called stock. For a series of experiments reviewed below, the concentration of the stock was varied within the range from about 2 to 5 percent by weight. The water temperature was about 50C., and in a . preferred method o~ operation, concentrated sodium hydroxide (about 40~) was aaded to the solution in an amount such that :

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~83~5~39 the pH-value was adjusted to about 10.5. Thereafter, continued saponification of the size occurred, and ~e saponification proceeded relatively rapidly so that during the short treat-ment time involved saponification was almost complete. The diluted size was then continuously batched to the stock utiliz-ing flow meters. In order to fully evaluate the applicability - of this product as a stock size, paper was actually sized carryed out both on a pilot-plant and on a mill scale. The pilot-plant experiments were thus carried out in an experi-mental paper making machine manufactured under the name SICMA. The machine had a width of approximately 0.5 meters, and a noxmal machine speed from about 30 to 40 meters per minute. Such sizing experirqents were carried out utilizing , two different qualities of paper. These included sackpaper (unbleached sulphate) having a suhstance of about 70 grams/meters2. In addition, a writing paper (50% bleached pine sulphate plus 50% bleached birch sulphate) was employed both with and without the addition of fillers. The fillers employed in this case were clay or chalk, and the experiments were carried out with various size additions at different pH values. This material also had a substance of about 70 grams/meters2 For purposes of a compaxison, a commercial resin size prepared by Kema Nord under the tradename Kenosize FL 70 was also tested. -These experiments, i.e. utilizing Kenosize FL 70, were carried out so that the stock was mixed with a suitable amount of size in a machine chest at a pH of about 6.5. The size was then precipitated with alum7 and the resulting pH
after the addition of alum was about 4.7. The pH of the backwater duxing operation with this size was about 5.5.

In those experiments utilizing a size solu~ion in accordance with the present invention, the stock was first .

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, adjusted to a pH of about 7. Alum was thereafter added, and the size solutio~ was batched in a substance box. The pH of the backwater during operation was varied bètween about 6 and 7. The results of these experiments ,are reported in Table 1.

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For each of the experiments as sh~wn in Table I, .
the Cobb-values are shown, that is the amount of water absorbed during a given period of time according to the TAPPI standard T441. In order to realize the true impact of these experiments, comparisons must be made with pre-viously employed sizes employing amounts of size of approxi-mately equal amounts, for example comparing experiments 4 and 7 thereof. By doing so, su~stantial improvements in . .
employing the size o the present invention can be seen.

Subsequent experiments were also carried out on a .
mill scale, and the results of these expeximents are shown in Table II.
;, TABLE II
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- Experiments - f ~ ` 19 20 21 22 23 24 25 ;

Sizihg ~ata:~ ~ -1. Kenosize, % 0,24 :

2. Acc. to inven- :
tion, % 0,15 0,20 0,20 0,20 Oj30 0,50

3. "Alum", % 1,2 0,8 0,8 0,8 0,8 1,2 1,2 Stock data:

Unbleached sulphate X X X X X X X

pH in stock - 5,5 5,51) 6,5 6,5 6,5 6,5 6,5 pH in backwater 5,5 5,51) 6,5 6,5 6,5 6,5 6,5 Paper data:

Sack paper X X X X X X X

Substance, g/m2 go 70 85 80 80 90 90 Testing- ~

Cobb45, g/m2 28 26 28 27 27 27 22 1) Sizing at this H was conditioned by change-over from the size solution in accordance with the present: in~ention to that of the Kenosize size.

337S~

In these experiments, a comparison can also be made with.the commercial Kenosize product~ These experiments thus again show that favorable results are obtainable on a mill scale which are comparable to -those obtained in the experimental machine as shown in the exarnples of Table I.
:The present invention is not restricted to any of the above-noted examples,.but can be varied within the scope of.the inventive concept.

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Claims (25)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY OR
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for preparing paper webs from fibrous material which comprises providing a fatty acid, at least partially saponifying said fatty acid by contacting said fatty acid with a first amount of an alkali metal hydroxide in the presence of a compound of a metal selected from the group consisting of aluminum, zinc and mixtures thereof, whereby said partially saponified fatty acid is maintained as a liquid, preparing an aqueous solution of said at least partially saponified fatty acid, adding a sufficient quantity of a second amount of an alkali metal hydroxide to said aqueous solution of said at least partially saponified fatty acid so as to further saponify said solution, and to maintain said solution at a pH of at least about 8, and applying said aqueous solution of said saponified fatty acid to said fibrous materials in order to size said fibrous materials prior to preparation of said paper web.

2. The process of Claim 1 wherein said fatty acid comprises a mixture of fatty acids and derivatives thereof.

3. The process of Claim 1 wherein a solution of said alkali metal hydroxide and said metal selected from the group consisting of aluminum and zinc is prepared prior to contacting said fatty acid with said alkali metal hydroxide and said metal.

4. The process of Claim 1 wherein said at least partial saponification is carried out in a plurality of steps.

5. The process of Claim 1 including the addition of an aliphatic hydrocarbon to said at least partially saponified fatty acid in order to minimize micelle formation therein.

6. The process of Claim 5 wherein said aliphatic hydrocarbon comprises a hydrocarbon selected from the group consisting of straight chain hydrocarbons and branch chain hydrocarbons.

7. The process of Claim 6 wherein said straight chain hydrocarbons are selected from the group consisting of pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, and mixtures thereof.

8. The process of Claim 1 wherein said fatty acid comprises from about 12 to 14 carbon atoms.

9. The process of Claim 8 wherein said fatty acid is selected from the group consisting of saturated fatty acids and unsaturated fatty acids.

10. The process of Claim 9 wherein said unsaturated fatty acids are selected from the group consisting of oleic acid, linoleic acid, linolenic acid, eleostearic acid, pinolenic acid, and mixtures thereof.

11. The process of Claim 9 wherein said saturated fatty acid is selected from the group consisting of laurinic acid, myristinic acid, palmitinic acid, stearic acid, arachinic acid, behenic acid, lignocerinic acid, and mixtures thereof.

12. A process for preparing paper webs from fibrous material which comprises providing a fatty acid, at least partially saponifying said fatty acid by contacting said fatty acid with an alkali metal hydroxide in the presence of a metal selected from the group consisting of aluminum, zinc and mixtures thereof, preparing an aqueous solution of said at least partially saponified fatty acid, and applying said aqueous solution of said at least partially saponified fatty acid to said fibrous materials in order to size said fibrous materials prior to preparation of said paper web.

13. The process of Claim 12 wherein said fatty acid is selected from the group consisting of saturated fatty acids, unsaturated fatty acids, and mixtures thereof.

14. The process of Claim 13 wherein said saturated fatty acid is selected from the group consisting of laurinic acid, myristinic acid, palmitinic acid, stearic acid, arachinic acid, behenic acid, lignocerinic acid, and mixtures thereof.

15. The process of Claim 13 wherein said unsaturated fatty acids is selected from the group consisting of oleic acid, linoleic acid, linolenic acid, eleostearic acid, pinolenic acid, and mixtures thereof.

16. The process of Claim 12 wherein an aliphatic hydrocarbon is added to said at least partially saponified fatty acid in order to prevent micelle formation therein.

17. The process of Claim 16 wherein from between about .1 to 10 weight percent of said aliphatic hydrocarbon is added to said at least partially saponified fatty acid.

18. The process of Claim 16 wherein from about 0.1 to 1 weight percent of said aliphatic hydrocarbon is added to said at least partially saponified fatty acid, calculated based on the amount of said fatty acid.

19. The process of Claim 16 wherein said at least partially saponified fatty acid is cooled to a tempera-ture below the boiling point of said aliphatic hydrocarbon prior to the addition of said aliphatic hydrocarbon thereto.

20. The process of Claim 16 wherein said aliphatic hydrocarbon is selected from the group consisting of straight chain aliphatic hydrocarbons, branched chain aliphatic hydro-carbons, and mixtures thereof.

21. The process of Claim 12 wherein alkali metal hydroxide is added to said aqueous solution of said at least partially saponified fatty acid in order to maintain said solution at a pH of at least about 8Ø

22. The process of Claim 12 wherein said solution of said at least partially saponified fatty acid is maintained at a pH of between about 9.8 and 10.8 by the addition of said alkaki metal hydroxide.

23. The process of Claim 12 wherein said alkali metal hydroxide comprises sodium hydroxide.

24. The process of Claim 12 wherein said fatty acid, prior to the at least partial saponification thereof, is heated to a temperature of about 100°C.

25. The process of Claim 12 wherein said metal comprises aluminum, and further wherein the ratio of said alkali metal hydroxide to said aluminum ranges from about 30 to l to 1 to 10.