US3027260A

US3027260A - Mayonnaise

Info

Publication number: US3027260A
Application number: US489A
Authority: US
Inventors: Fredric J Baur
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1960-01-05
Filing date: 1960-01-05
Publication date: 1962-03-27
Anticipated expiration: 1979-03-27

Description

United States Patent ()fiice 3,027,260 Patented Mar. 27, 1962 3,0273% MAYQNNAESE Fredric i. liaur, Cincinnati, Qhio, assignor to The Procter Gambia Company, @incinnati, Ohio, at corporation of @hio No Brewing. Filed Jan. 5, 1960, Ser. No. 489 6 Claims. (Cl. 99-144) This invention relates to mayonnaise compositions which have an outstanding degree of emulsion stability.

More particularly this invention relates to mayonnaise compositions which have been made with glyceridic oils comprising mixed esters of lower and higher molecular weight fatty acids.

This application is a continuation-in-part of applications Serial No. 500,019, filed April 7, 1955, now abandoned, and Serial No. 500,295, filed April 8, 1955, now abandoned.

Edible liquid oils are generally classified as either cooking oils or salad oils. In the United States a rather sharp differentiation is made between these two classes, the term salad oils being applied to oils which will remain substantially liquid in a refrigerator at 40 to 45 F. and which will produce a mayonnaise emulsion reasonably stable at low temperatures. A cooking oil, on the other hand, may solidify completely at temperatures of 40 to 45 F. and will not normally be capable of producing a stable mayonnaise emulsion.

Mayonnaise can readily withstand temperatures as low as about 50 F. without emulsion failure. On occasions when it is subjected to substantially lower temperatures, such as those which may be encountered when the temperature of a mechanical refrigerator is lowered for certain purposes, or in shipping and storage during the winter months, emulsion failure, as evidenced by oil separation, can readily occur. Additional difiiculties may also be encountered with mayonnaise compositions because of the susceptibility to oxidation of some of the oils commonly used in preparing such compositions.

It is an object of this invention to provide a mayonnaise composition which will have outstanding emulsion stability at low temperatures.

It is a further object of this invention to provide a mayonnaise composition which, in addition to outstanding emulsion stability, is characterized by improved oxidative stability.

Other objects and advantages will be apparent from the following detailed description.

The foregoing objects can be achieved by providing a mayonnaise composition comprising vinegar, eggs, salt and a liquid glyceridic oil which consists essentaiily of mixed triglycerides of combined low molecular weight and combined high molecular weight fatty acids. The combined low molecular Weight fatty acids are selected from the group consisting of acetic, propionic, butyric and caproic acids and mixtures thereof. Each of the combined high molecular weight fatty acids of the mixed triglycerides is derived from fats selected from the group consisting of animal fats, marine oils and their hydrogenated products and vegetable oils of the oleic-linoleic acid group and the linolenic acid group and their hydrogenated products (classifications from Industrial Oil and Fat Products, second edition, A. E. Bailey, pages 120 et seq.). Examples of such combined high molecular weight fatty acids include lauric, myristic, palmitic, stearic, arachidic, behenic and lignoceric acids, corresponding acids containing 1 or 2 carbon to carbon double bonds, and not over a minor proportion of corresponding acids having 3 or more carbon to carbon double bonds.

In the glyceridic oil constituent of the mayonnaise compositions of this invention the mixed triglycerides contain from about one-fifth to about two-thirds, on a molar basis, of combined low molecular weight fatty acids. When the said mixed triglycerides contain from about one-fifth up to, but not including two-thirds of combined low molecular weight fatty acids on a molar basis, the facts from which the combined high molecular weight fatty acids can be derived should be characterized by an iodine value in excess of 80. When, however, two-thirds of the combined fatty acids of the mixed triglycerides are of low molecular weight, i.e., where a diacetyl triglyceride is the glyceridic oil desired, the fats from which the combined high molecular weight fatty acids can be derived can be characterized by an iodine value of as low as about 55. The said glyceridic oil constituent is further characterized by crystallization of at least a part of its constituent triglycerides in less than 5.5 hours when subjected to and maintained at a temperature of 32 F.

If desired, these glyceridic oils may be rendered substantially free of triglycerides the combined fatty acids of which are wholly of the group of low molecular weight fatty acids specified above.

The aforementioned glyceridic oils can be conveniently prepared by interesterifying a mixture of triglycerides the combined fatty acids of which are wholly of low molecular weight, e.g., triacetin, tripropionin, tributyrin, tricaproin, mixtures thereof, or mixed wholly low molecular Weight triglycerides, e.g., mono-butyro-di-acetin, and a high molecular weight fatty acid triglyceride selected from the group of animal fats, marine oils and vegetable oils noted hereinbefore or mixtures thereof. This interesterification is accomplished in known manner by intimately contacting the said triglyceride mixture with an interesterification catalyst, e.g., sodium methoxide, until substantial rearrangement of a'cyl groups in the triglyceride molecules has taken place. The reaction is then discontinued either by removing or inactivating the catalyst and the product is normally treated to remove substantially all of the unreacted low molecular weight triglyceride.

By way of example, a more detailed description of a preparation utilizing triacetin as the low molecular weight triglyceride is given immediately below.

To a refined and dried or deodorized oil or fat in the liquid state is added the selected quantity of triacetin. The amount of triacetin is chosen on the basis of the content of acetyl groups desired in the final interesterificarapidly becomes homogeneous as interesterification 0c The interesterifying mix is maintained at about.

curs. F., or higher if necessary to maintain homogeneity.

Within about one-half hour random interesterification is substantially complete although, while a substantial de-- gree of interesterification should be effected, it is not imperative that the reaction go to final completeness, i.e., equilibrium. The interesterification catalyst is then inactivated by acidulation or water-washing. If acidulation is employed, the excess acid is removed by an alkali refining or Water-washing step. Water-washing removes some of the triacetin present but it is sometimes desirable to remove substantially all of the triacetin from the acetin oil product. This may be accomplished by deodorization.

The rearranged mixture is complex in composition comprising triacetin, high molecular weight triglycerides, monoacyl diacetins, and diacyl monoacetins. If it is desired to obtain a wholly diacetyl triglyceride product, the unreacted triacetin and other low boiling constituents which remain in the rearranged mixture after inactivating the catalyst and washing are first removed. This is usually accomplished through distillation under a pressure of 2 or 3 mm. of mercury while passing a stream of enemas is inert gas, e.g., nitrogen or steam through the mixture. Triacetin readily distills at this pressure before a temperature of about 300 F is reached. Following this step a fraction consisting of high molecular weight diacetyl,

triglycerides is isolated. In order to do this, the temperature of the steam distillation, or other distillation, is raised and/or the pressure is reduced until diacetyl triglycerides distill. Where a substantially wholly diacetyl triglyceride product is desired conditions drastic enough to cause distillation of sustantial amounts of triglycerides containing less than two acetyl groups must obviously be avoided. The exact temperature of distillation will vary with the particular oil used and with the speed of distillation required.

The residue after distilling off the diacetyl triglycerides is largely a mixture of monoacetyl triglycerides and unreacted high molecular triglycerides and this mixture may be reworked in the process along with unreacted triacetin recovered as noted above.

It is to be understood that the foregoing description is merely illustrative and that other methods will readily suggest themselves to those skilled in the art. For example, if desired, a water-washed, dried, but unrefined oil may be used as the starting material. This oil may then be interesterified with triacetin, or one of the other low molecular weight triglycerides hereinbefore mentioned, in the presence of an interesterification catalyst. After the interesterification is complete, the catalyst may be inactivated by the addition of water to the interesterified mix and the water and soapstock may be separated by conventional means. This mix may then be hydrogenated to the desired degree in accordance with well known practice.

Other methods for introducing low molecular weight fatty acid radicals into high molecular weight fatty acid triglycerides to provide the glyceridic oils of the mayonnaise compositions of this invention, can, of course, be used as will be evident to those skilled in the art. A description of additional methods, as well as additional interesterification catalysts, which are satisfactory can be found in US. Letters Patent 2,614,937, issued October 21, 1952, columns 10, 12 and 13.

When the glyceridic oils of the mayonnaise compositions of this invention comprise mixed triglycerides of acetic and high molecular weight fatty acid radicals derived from the fat sources specified herein, and when those fat sources are characterized by an iodine value in excess of 80, it has been determined that from about to about.28% by weight of the combined fatty acids of the mixed triglycerides should be acetic if the advantages of the invention are to be fully realized.

It is to be appreciated that the amount of low molecular weight fatty acids in the mixed triglycerides will vary depending upon whether they are acetic, propionic, butyric, of. caproic acids and further, that the amount of low molecular Weight fatty acids present in the mixed triglycerides comprising the glyceridic oils of the mayonnaise compositions of this invention may also vary clepending upon the iodine value of the oils or fats from which the combined high molecular fatty acids are derived. In any case, it is advantageous that the amount of low molecular weight fatty acids in the mixed triglycerides should be sufficient so that, when the fatty materials from which the high molecular weight combined fatty acids of the mixed triglycerides are derived contain a substantial amount of polyunsaturated fatty acids, an' improvement in the oxidative stability of the oil is obtained.

Mayonnaise is produced with any of the aforementioned oils by incorporating these oils with vinegar, eggs, salt and other ingredients in the manner ordinarily employed for this purpose (e.g., in accordance with the standard for mayonnaise of the Federal Security Agency, Federal Register, August 12, 1950, pp. 5227-6232).

In the industry, the etficacy of a salad oil for mayonnaise production is based upon the results of a chill test of the salad oil itself. it is generally accepted that freedom from ciouding at 32 F. for 5.5 hours is the bare minimum standard for a salad oil which is satisfactory for use in mayonnaise (standard chill test-Official Method Cc 11-53 of the American Oil Chemists Society). It was also believed that the greater the length of time the oil remained free of clouding when subjected to this test the greater would be the resistance to freezing of the mayonnaise made with such oil. That is to say, the greater would be the emulsion stability of the mayonnaise.

Contrary to this teaching and general belief, it has now been found that mayonnaise compositions of outstanding emulsion stability can be obtained with the glyceridic oils described previously herein and which do not respond to the aforementioned ofiicial chill test. Although these oils are characterized by the crystallization of at least a portion of their constituent triglycerides in less than 5.5 hours, and in some cases only a few minutes, when maintained at a temperature of 32 F .-chill test results which would indicate that such oils were completely unsatisfactory for mayonnaise preparations-yet they can be used to prepare the mayonnaise compositions of this invention which are characterized by outstanding emulsion stability.

It is also significant that whole eggs as Well as egg yolks can be used in the mayonnaise compositions of this invention. It is generally recognized that the use of whole eggs, as opposed to egg yolks, in the preparation of mayonnaise has given rise to difliculties with regard to the low temperature emulsion stability of the mayonnaise. However, with the particular glyceridic oils specified herein, whole egg mayonnaise which is characterized by outstanding emulsion stability at low temperature can readily be made. Thus, in addition to the unpredictably outstanding emulsion stability of the mayonnaise compositions of this invention, such mayonnaise compositions offer a substantial economic advantage over those of the prior art in that they allow the substitution of whole eggs for egg yolks without affecting adversely the low tempreature emulsion stability of the mayonnaise compositions.

It is to be understood that wherever herein, or in the appended claims, the unmodified word eggs appears it is to be interpreted as including both whole eggs and egg yolks.

In the following examples, which, it is to be understood, are illustrative only, the low-temperature stability of the mayonnaise product was determined as follows unless otherwise indicated.

After preparation, the mayonnaise is first stored overnight, or from about 1624 hours, at a temperature of 50 F. Following removal from storage after this initial period it is alternately stored at 20 F. for varying lengths of time and allowed to thaw at room temperature. After thawing the mayonnaise sample is examined for possible oil separation which is indicative of the resistance of the emulsion to breaking.

Example 1 One part of refined cottonseed oil was hydrogenated to an iodine value of 81 and then interesterified by mixing one part of triacetin and 0.3% sodium methoxide catalyst and holding at F. for 15 minutes. The catalyst was inactivated with water and the soap formed was separated by filtration. Unreacted triacetin was substantially completely removed by steam distillation at reduced pressure.

The resulting oil had an iodine value of 59.6 and 21.5% by weight of its combined fatty acids were determined to be acetic.

This oil was subsequently used in the preparation of both whole egg and egg yolk mayonnaise and, although the oil itself had a chill test of about 10 minutes, ac-

cording to the aforementioned AOCS test, both'the whole egg and egg yolk mayonnaise showed no oil separation upon thawing after storage at 20 F. for 11 days.

A comparable whole egg mayonnaise prepared with a grained cottonseed oil containing added crystallization inhibitor to inhibit the crystallization of the higher melting triglycerides remained stable, i.e., exhibited no oil separation, for only two days under the test conditions.

For purposes of this application, in this and some of the following examples, this grained cottonseed oil containing added crystallization inhibitor is referred to as standard salad oil.

Example 11 Four parts of refined and bleached cottonseed oil having an iodine value of 110 was interesterified with one part of triacetin in accordance with the procedure of Example I.

The resulting oil had an iodine value of 89.8 and it was determined that 12.2% by weight of the combined fatty acids of this oil were acetic.

Whole egg and egg yolk mayonnaise prepared from this oil still exhibited satisfactory emulsion stability (no oil separation) according to the foregoing test after 11 daysthis in spite of the fact that the oil per se had a chill test performance according to the aforementioned AOCS test of only four hours.

A comparable whole egg mayonnaise prepared with the aforementioned standard salad oil exhibited satisfactory emulsion stability for only two days under the test conditions.

Example III One part of refined and bleached soybean oil was hydrogenated to a 97 iodine value and was then treated as in Example I using one part of triacetin.

The resulting oil, 20.5% by weight of the combined fatty acids of which were acetic, had an iodine value of 71.5 and exhibited a chill test performance according to the aforementioned AOCS method of-less than minutes.

Although the chill test performance of this oil, according to the accepted criterion, indicated that the oil would be completely unsuitable for use in mayonnaise, a whole egg mayonnaise made with the oil still exhibited satisfactory emulsion stability according to the aforedescribed test after 11 days.

A comparable whole egg mayonnaise made with the above standard salad oil exhibited satisfactory emulsion stability.

Example IV 9 parts of refined and bleached cottonseed oil having an iodine value of 106 was interesterified with 1 part of triacetin in accordance with the procedure of Example I.

The resulting oil, which exhibited a chill test performanee according to the aforementioned AOCS method of less than 1 hour, had an iodine value of 96.7 and 7.1% by weight of the combined fatty acids of this oil were acetic.

A whole egg mayonnaise prepared with this oil still exhibited satisfactory emulsion stability according to the aforedescribed test after nine days.

A comparable whole egg mayonnaise emulsion prepared with the aforementioned standard salad oil was observed to remain stable for two days but to have separated after five days.

Example V 350 gms. of refined, bleached and dried cottonseed oil was mixed with 172 gms. of tributyrin, and 0.5% sodium methoxide interesterification catalyst in xylene was added to this mixture. The interesterification was carried out in accordance with the procedure of Example 4 including the steam deodorization step to free the product of tributyrin.

The resulting oil exhibited a chill test performance in accordance with the above AOCS test to less than 4 hours.

This oil was subsequently used in the preparation of egg yolk mayonnaise which still exhibited satisfactory emulsion stability after being subjected to storage overnight at 20 F. followed by warming to room temperature.

A comparable mayonnaise made with the aforementioned standard salad oil had separated after being subjected to the same treatment.

Example VI One part of a mixture of oils consisting of by weight of refined soybean oil and 15% by weight of refined cottonseed oil hydrogenated to an iodine value of 59 was interesterified by mixing with one part of triacetin and 0.3 sodium methoxide catalyst and holding at 140 F. for 20 minutes. The catalyst was inactivated with water and remaining triacetin was removed by steam distillation at 2 to 3 mm. of mercury. Removal of the triacetin was substantially complete at 320 F. The temperature of the mix was then raised and the diacetin portion of the oil was separated in the range from 390 to 465 F. at a pressure of 1-3 mm. of mercury.

The separated diacetin oil had a chill test of less than one hour according to the AOCS test referred to hereinbefore. Yet, when utilized in the preparation of a whole egg mayonnaise it resulted in a mayonnaise which still exhibited satisfactory emulsion stability, in accordance with the emulsion stability test outlined above, after nine days.

A comparable whole egg mayonnaise prepared from the standard salad oil above was observed to remain stable for two days but had separated aft-er five days.

Example VII Two part of refined and bleached cottonseed oil having an iodine value of was interesterified with one part of triacetin in accordance with the procedure of Example VI.

The diacetin fraction of the product of the interesterification reaction was separated in the range from 390 F. to 465 F. by distillation at l to 3 mm. of mercury.

The separated diacetin oil, which had a. chill test performance of less than 2 hours according to the above standard chill test, was subsequently used in the preparation of egg yolk mayonnaise.

This egg yolk mayonnaise still exhibited satisfactory emulsion stability according to the foregoing test after 7 days. A comparable egg yolk mayonnaise emulsion prepared with the standard salad oil broke after one day.

The following example will serve to illustrate the oxidative stability of the glyceridic oils hereinbefore described. This oxidative stability is reflected in the mayonnaise compositions of this invention since the said glyceridic oils are used in their preparation. The oxidative stability was determined by the oxygen-absorption method outlined by E. W. Eckey in the February 1946 issue of Oil and Soap (now the Journal of the American Oil Chemists Society), volume 23, No. 2, pages 38-40.

Example VIII Using the above method with no sand, a determination was made of the amount of time required in hours for 1 gram of the following oils to absorb 3 ml. of oxygen from air.

Time in hours Cottonseed oil, refined, bleached and dried 10 Cottonseed oil, random rearranged 15% Cottonseed oil interesterified with a 1:1 ratio by weight with triacetin 39 A The greatly increased length of time required for the acetin-containing cottonseed oil to absorb a given amount of oxygen under the accelerated conditions of the test acct/gee 6 indicates the much greater resistance. to the development of oxidative rancidity of the oils utilized in the mayonnaise compositions of this invention.

The sample of random rearranged cottonseed oil was included to show that the increased oxidative stability was obtained from the incorporation of the acetyl radical and not from the rearrangement per se of the cottonseed oil.

It is to be appreciated that although the maximum benefits are derived from the mayonnaise compositions of this invention when glyceridic oils as hereinbefore defined are used in their preparation as the oil oil constituent, such oils may also, if desired, be used in combination with other edible oils. Moreover, if further increased oxidative stability or further increased low tern perature emulsion stability over and above that which is exhibited by the mayonnaise compositions of this invention is desired for certain purposes, various antioxidants such as tocopherols, butylated hydroxy anisole and propyl gallate, or various crystallization inhibitors such as. lecithin and oxidized (blown) oils may be added in the preparation of the mayonnaise compositions.

What is claimed is:

1. A mayonnaise characterized by outstanding low temperature stability comprising vinegar, eggs, salt and aliquid glyceridic oil which consists essentially of mixed triglycerides of combined low molecular and combined high molecular weight fatty acids, the said combined low molecular weight fatty acids being selected from the group consisting of acetic, propionic, butyric and caproic acids and mixtures thereof, and each or" the said combined high molecular Weight fatty acids being derived from fats selected from the group consisting of (1) animal fats, (2) marine oils and their hydrogenated products and (3) vegetable oils of the oleiclinoleic acid group and the linolenic acid group and their hydrogenated products, the said fats being characterized by an iodine value in excess of 80 when the said mixed triglycerides contain from about one-fifth up to, but not including, two-thirds of the said low molecular weight combined fatty acids on a molar basis, and by an iodine value in excess of about 55 when the said mixed triglycerides contain two-thirds of the said low molecular Weight combined fatty acids on a molar basis, and the said liquid glyceridic oil being substantially free of'trigly-cerides wholly of low molecular weightfatty acids and being characterized by the crystallization of at least part of its constituent triglycerides in less than 5.5 hours when maintained at. a temperature of 32 F.

2. The mayonnaise of claim 1 wherein the combined low molecular weight fatty acids of the liquid glyceridic oil are acetic.

3. The mayonnaise of claim 1 wherein the combined low molecular weight fatty acids of the liquid glyceridic oil are propionic.

4. The mayonnaise of claim 1 wherein the combined '4. low molecular weight fatty acids of the liquid glyceridic oil are butyric.

5. The mayonnaise of claim 1 wherein the combined high molecular weight fatty acids of the liquid glyceridic oil are derived from cottonseed oil.

6. The mayonnaise of claim 1 wherein the combined high molecular weight fatty acids of the liquid glyceridic oil are derived from peanut oil.

References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Vicknair et al.: J. Physical Chem, vol. 58, pp. 6'4-66, January 1954.

Ward et al.: J. Physical Chem., vol. 58, pp. 4-6, January 1955.

Feuge et al.: J.A.O.C.S.,"vol. 30, No. 8, pp. 320- 325, (August 1953).

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION "Pi-tent N0. 3 O27 26O March 27 U 1962 Fredric J. Baur It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 3 line 55, for "of'H first occurrence read or column 6 line 1 for "to" read of column 7, line 12 for "soil" read sole Signed and sealed this 28th day of August 1962,

(SEAL) Attest:

ESTON G. JOHNSON DAVID L LADD Attesting Officer Commissioner of Patents

Claims

1. A MAYONNAISE CHARACTERIZED BY OUTSTANDING LOW TEMPERATURE STABILITY COMPRISING VINEGAR, EGGS, SALT AND A LIQUID GLYCERIDIC OIL WHICH CONTAINS ESSENTIALLY OF MIXED TRIGLYCERIDES OF COMBINED LOW MOLECULAR AND COMBINED HIGH MOLECULAR WEIGHT FATTY ACIDS, THE SAID COMBNINED LOW MOLECULAR WEIGHT FATTY ACIDS BEING SELECTED FROM THE GROUP CONSISTING OF ACETIC, PROPIONIC, BUTYRIC AND CAPROIC ACIDS AND MIXTURES THEREOF, AND EACH OF THE SAID COMBINED HIGH MOLECULAR WEIGHT FATTY ACIDS BEING DERIVED FROM FATS SELECTED FROM THE GROUP CONSISTING OF (1) ANIMAL FATS, (2) MARINE OILS AND THEIR HYDROGENATED PRODUCTS AND (3) VEGATABLE OIL OF THE OLEICLINOLEIC ACID GROUP AND THE LINOLENIC ACID GROUP AND THEIR HYDROGENATED PRODUCTS, THE SAID FATS BEING CHARACTERIZED BY AN IODINE VALUE IN EXCESS OF 80 WHEN THE SAID MIXED TRIGLYCERIDES CONTAIN FROM ABOUT ONE-FIFTH UP TO, BUT NOT INCLUDING, TWO-THIRDS OF THE SAID LOW MOLECULAR WEIGHT COMBINED FATTY ACIDS ON A MOLAR BASIS, AND BY AN IODINE VALUE IN EXCESS OF ABOUT 55 WHEN THE SAID MIXED TRIGLYCERIDES CONTAIN TWO-THIRDS OF THE SAID LOW MOLECULAR WEIGHT COMBINED FATTY ACIDS ON A MOLAR BASIS, AND THE SAID LIQUID GLYERIDIC OIL BEING SUBSTANTIALLY FREE OF TRIGLYCERIDESWHOLLY OF LOW MOLECULAR WEIGHT FATTY ACIDS AND BEING CHARACTERIZED BY THE CRYSTALLIZATION OF AT LEAST PART OF ITS CONSTITUENT TRIGLYCERIDES IN LESS THAN 5.5 HOURS WHEN MAINTAINED AT A TEMPERATURE OF 32* F.