US3186854A - Edible oil blends - Google Patents

Description

V F f United States ate: 0 ice 85,854 g Patented June .1, 1965 with the natural salad oils or with other oils which have 3 5 been subjected to an initial Winterizing treatment. Nor EEELE 9H. ELENDS Louis H. Going, lowland, Ulric, assignor to The Procter & Gamble Company, Cincinnati, @hio, a corporation of Ghio No Drawing. Filed duly 6, 1962, Ser. No. 208,109

9' Claims. (Cl. 99-163) This invention relates to improved edible oil blends. More particularly, it relates to mixtures of triglyceride oils which can be stored at relatively low temperatures for extended periods or" time without clouding, and which are capable of being used as salad oils. 7

Many liquid triglyceride oils normally deposit stearin or otherwise become cloudy at low temperatures whereby their visual appearance and physical characteristics are impaired. It is well known that such clouded oils are considered objectionable by the housewife and other consumers. Unless these oils remain substantially clear at the temperatures ordinarily encountered, they will not be acceptable as salad oils for table use and the like. In this connection it must be remembered that the temperatures which have to be resisted are not only home refrigeration temperatures which generally run as low as 40 to 50 F. but also freezing temperatures of 32 F. and lower which may be encountered for periods of time during storage and shipment in cold climates.

The resistance of an edible triglyceride oil to clouding at low temperatures is conveniently shown by means of a well-known standardized chill test (Qiiicial Method Cc 1l-53 of the American Oil Chemists Society). If the oilis tree from clouding at 32 F. for at least 5 /2 hours when subjected to this chill test procedure, itis generally considered to be a suitable salad oil for use in mayonnaise and the like.

Certain oils, such as corn oil, soybean oil and olive oil, are natural salad oils since they contain relatively small proportions of the more saturated glycerides which tend to separate out when the oil is stored at low temperatures. But even these so-called natural salad oils frequently are subjected .to treatment of one sort or another to further improve their resistance to clouding at low temperatures,

Other oils, such as cottonseed oil or soybean oil which has been partially hydrogenated to improve its oxidative stability, exhibit poor resistance to cold temperatures and have a strong tendency to deposit stearin and other high melting solids. Although such oils generally can be used as cooking oils, they are not suitable for salad oil purposes unless they are treated in some manner whereby the said stearin or other crystal-tending constituents are either removed or inhibited.

One of the most common methods used by oil technologists for improving the resistance of triglyceride oils to clouding at low temperatures consists of subjecting the oil to a so-called Winterizing treatment whereby the stearin and other high melting constituents are removed by fractional crystallization. Another method consists of inhibiting the clouding of salad oils by adding a small amount of a crystallization inhibitor to the oil. I

Neibher of the aforesaid methods is wholly suitable to the oil trade, however, since the usual Winterizing.

treatment involves a time-consuming and costly procedure, and the known crystallization inhibitors heretofore have been significantly eiiective only when used in connection has the substitution of certain'natural salad oils such as corn oil or soybean oil for winterized cottonseed oil proved entirely suitable, since the former oils exhibit a greater tendency to revert in flavor over periods of time. A means for improving the resistance to clouding at low temperatures of poorly resistant oils, such as cottonseed oil and partially hydrogenated soybean oil, without subjecting them to the usual degree of Winterizing treatment I would be extremely useful- Accordingly, it is an object of this invention to provide novel oil blends whereby an oil blend component which normally has poor resistance to clouding at low temperablends having improved flavor characteristics and stability.

It has now been discovered that the resistance to clouding at low temperature of a summer oil having relatively poor resistance to clouding can be significantly improved and upgraded by blending it in certain proportions with a winter oil having good resistance to clouding and adding thereto a small amount of a conventional crystallization inhibitor;

As used herein, the term summer oil is intended to define a triglyceride oil which is substantially liquid at 60 F. but which has a chill test of less than 5 /2 hours according to the procedure described hereinbefore and has poor resistance to clouding in'the presence of a crystallization inhibitor.

As used herein, the term Winter oil is intended to define a liquid triglyceride oil which has good resistance to clouding and has a chill test of at least 5 /2 hours according to the procedure described hereinbefore.

As used herein, the term crystallization inhibitor is intended to define a high molecular Weight substance having both lipophilic and lipophobic groups which is capable of substantially improving the chill test of a winter oil by retardin the formation of clouding Without adversely aiiecting its interfacial tension with respect to its normal salad oil usage.

It has been found that substantial and unexpected im-' provements in the chill test of blends of summer and,

should equal about 0.5 to about 1.0. More specifically, 1 should equal about 0.5 to about 1.0 when I is the transmitted intensity of the winter oil component and I is the transmitted intensity of the uninhibited blend of summer and winter oils when held at a temperature of 335 F. for a period of minutes and photoelectrically measured with monochromatic light having a wave length I of 600 m a The improvements obtained with the novel oil blends of this invention are completely anomalous. Thus, it is contrary to the teachings of oil technologists to blend a portion of a natural salad oil or other winter oil into a summer oil in an attempt to improve the resistance of the latter oil to clouding at low temperatures. It is well- 7 known that the practical result of such an attempt will be a substantial downgrading of the .winter oil rather than a material upgrading of the summer oil. This natural result which is obtained in practice is easily explainable on the basis of the fact that the stearin and other high melting solids of the summer oil are still present in the oil blend and, therefore, will cause clouding when the blend is subjected to low temperatures. The degree of intersolubility between such oils is usually so poor that there is negligible-improvement in the resistance to clouding of the summer oil constituent of the blend.

Moreover, it is also known that the conventional crystallization inhibitors are relatively ineffective for improving the resistance to clouding at low temperature of summer oils. The usual inhibitor materials have been found to have little or no eifeot upon the high melting solids found in a summer oil such as cottonseed oil .or partially hydrogenated soy-bean oil.

Examples of winter oils used in the compositions of this invention are the natural salad oils such assoybean oil, corn oil, olive oil, safflower oil, sunflower oil, sesame oil, and the winterized oils such as winterized cottonseed oil or winterized partially hydrogenated soybean oil.

The most common example of a summer oil which can be used in the practice of this invention is cottonseed oil. The abundant supply of cottonseed oil has led to its'wide-spread use in salad dressings. However, it has been necessary heretofore to subject cottonseed oil to a Winterizing treatment to remove its higher melting constituents in order to make it suitable as a salad oil. 7

Another usable summer oil is peanut oil. However, since peanut oil tends to deposit very difiiculty filterable crystals, it has not been common practice heretofore to winterize it for salad oil purposes. Instead, it has been used primarily as a cooking oil.

Other examples of summer oils used in this invention are the natural vegetable oils which have been partially hydrogenated in order to improve their oxidative stability.

Examples of crystallization inhibitors which can be used in the practice of this invention are lecithin and other vegetable phosphatides; certain esters of polyhydric alcohols and other hydroxycompounds with long chain .fatty acids such as those described in US. Patent 2,266,- 591, granted December 16, 1941, to Eckeyand Lutton; oxygenated and thermally modified hardened vegetable oils such as the oxystearin described hereinafter; oxidized and polymerized oils such'as described in U.S.- Patent 2,097,720, granted November 2, 1937, to Clayton et al.; certain esters of disaccharides such as sucrose, maltose and lactose with fatty acids, said disaccharide being esterified with an average of from about 15% to 85%, based on the total fatty acid inthe ester, of saturated fatty acids having from 14 to 22 carbon atoms, the balance of the fatty acids beingseleoted from the group consisting of fatty acids having from 2 tolZ carbon atoms and unsaturated fatty acids having from 14 to 22 carbon atoms, said ester having an average of not more than 5 unesterified hydroxyl groups per molecule; certain esters of dextrin with fatty acids, said dextrin being esterified with.

an average of from about /2 to 2 acyl groups of saturated fatty aoids'having from 14 to 22 carbon atoms, the bal-, ance of the fatty acids of said ester being selected from the group consisting of fatty acids having from 2 to 12 carbon atoms and unsaturated fatty acids having from 14 to 22 carbon atoms, said ester having an average of not more than 1 /2. unesterified hydroxyl groups per glucose unit; certain esters of monosaccharidic material having an oxide ring structure and selectedfrom the group consisting of aldohexose, aldohexuronolactone, aldohexuronic acid, aldohexonolactone, and methyl aldohexoside with fatty acids, said material being at least 25% esterified, based on the total hydroxyl availability, with at least 15%, based on the total fatty acid in the ester, of saturated long chain fatty acid having from about 12 to about 24 carbon atoms, the balance of the fatty acid being selected from the group consisting of short chain fatty acids having from 2 to about 6 carbon atoms and unsaturated long chain fatty acids having from about 12 to about 24 carbon atoms in such a manner that the molar proportion of said short chain fatty acids does not substantially exceed the total molar proportion of said saturated and unsaturatedlong chain fatty acids.

Although specific summer and winter oils and specific crystallization inhibitors are mentioned herein, the invention is not'lirnited to these particular materials.

It will be understood that certain combinations of summer and winter oils are particularly desirable for.

purposes of this invention, although the invention is not limited to these particular combinations. Specific combinations that are particularly good include, for example, the following blends: from 15% to 30% soybean oil blended with from 70% to 85% cottonseed oil; from 10% to 30% soybean oil blended with from to 50% cottonsed .oil and from 35% 'to 50%. winterized cottonseed oil, the preceding blend with up to 50% partially hydrogenated soybean oil (iodine value 105-:

v 110) substituted for an equal amount of cottonseed impurities for salad oil purposes.

to 50% corn oil (either winterized or unwinterized) sub I stituted for an equal amount of winter oil; any of the preceding blends with up to 25 satllower seed oil or sunfiower seed oil substituted for an equal amount of the highest iodine value component; and any of the preceding blends with up to 15 peanut oil substituted for an equal amount of the lowest iodine value component. All of the aforesaid blends are stated in percent by weight of the total composition and include therein from about 0.005% to about 0.5% crystallization inhibitor. Amounts of crystallization inhibitor in excess of about 0.5%, by weight, are generally unnecessary as affording no significant added improvemcntin chill test of the blend. These blends have excellent chill tests, show good flavor stability, and are usable for normal salad oil: purposes.

The components of the oil blends of this invention can include oils formed by random or directed low temperature interesterification of animal and vegetable-fatty materials, followed by removal of higher melting solids formed during the reaction. They can also include other materials, such as the acetin fats having one or two short chain acyl groups such as acetyl, which. are dissolved in the oil blends and which are not deleterious to the normal usage of salad oils.

The following examples will further illustrate the oil blends of this invention. The oils used in these examples were subjected to the usual bleaching and deodorizingv treatment in addition to caustic refining to remove undesirablegums and similar materials which occur naturally in crude vegetable oil, but are generally considered These refined 'oils were not subjected to a Winterizing treatment, however,

unless otherwise specifically mentioned. Table A, below,

indicatesv the approximate fatty acid composition of the oils used in'the'se examples; and Table B shows other pertinent analytical values obtained therefor. All chill test results shown were obtained by the A.O.C.S. method described hereinbefore.

Table A FATTY ACID CONTENT 011 Myristie Palmitic lzalrni- Stearic Oleic Linoleic Linolenic Gadolele Erucie Behenic Lignoeeric o ere Cottonseed oil 2 17 54 Peanut oil 3 48 30 4 4 Partially hydrogen oil 12 5 49 32 2 Soybean oil 11 5 29 49 6 Safllower oil 8 3 74 Corn oil 13 2 30 55 winterized cottonseed oil 1 2 19 57 winterized partially hydrogenated soybean oil 11 4 48 35 2 Rapeseed oil 8 2 20 27 6 6 31 Percent by weight determined by gas chromatography.

A batch of refined cottonseed oil having a chill test of /3 hour was divided into 3 parts. To one part of the oil was added 0.1% by weight of the total blend, of acetyl palmitoyl dextrin; to a second part'was added 30%, by weight of the total blend, of refined soybean oil; and to the third part was added the combination of 0.1%, by weight of the total blend, of acetyl palmitoyl dextrin and 30%, by weight of the total blend, of refined soy.- bean oil. The chill test. results obtained with these blends are shown in the following table. All percentages shown in this example are stated in percent by weight of the total blend.

Table 1 Chill test Oil blend: in hours Cottonseed oil /3 Cottonseed oil+0.1% acetyl palmitoyl dextrin 2%. Cottonseed oil+30% soybean oil /2 Cottonseed oil}0.1% acetyl palrnitoyl dextrin and 30% soybean oil 12 When dioleoyl hexapalmitoyl sucrose was substituted for the acetyl palmitoyl dextrin in the above example, sub-' stantially similar chill test results were obtained. The above results show that, although neither the crystallization inhibitor nor the soybean oil (winter oil) alone significantly improved the chill test of the cottonseed oil (summer oil), the combination of the inhibitor and soybean oil in the given proportions substantially up graded the chill test of cottonseed oil.

EXAMPLE 2 A batch of refined peanut oil having a chill test of hour was divided into 7 parts. To each part was added a portion of refined and winterized cottonseed oil and/or 0.1%, by weight of the total blend, of an oxygenated and thermally modified hardened vegetable oil herein referred to as oxystearin. The said oxystearin was prepared from hydrogenated cottonseed oil having aniodine'value of about 6 to 8 and a butyro refractive index of about 39:1 at 48 C. The said hydrogenated oil was bodied with heat at about 225 -250 C. and air blown at the rate of about 20 cubic feet per-minute per 1000 pounds of oil until the final product met the following specifications:

Acid number 14.

Iodine value 14. Saponification number 225-240. I-lydroxyl value 30-45. Unsaponifiable matter 0.8%.

Butyro refractive index :1 at 48 C. Molecular weight 925975.

The chill test results obtained with these blends are shown in the following table. All percentages shown in this When refined and partially hydrogenated soybean oil :WBS substituted for the refined peanut oil in the above example, substantially similar chill test resultswere obtained; and when refined safiiower oil was substituted for the winterized cottonseed oil, substantially similar chill test results were again obtained.

. Several blends of the above peanut and winterized cottonseed oils were prepared. Each blend was trans- -ferred to a separate 250 ml. beaker and heated to 130 C. to remove moisture. The blends were then cooled to about 80100 C., transferred to Coleman .6-300A cu vettes (25 mm. x 105 mm.), corked, and placed in an ice bath which was held at 33.5 F. for a period of minutes. The transparency of each blend and a similarly treated sample of unblended winterized cottonseed oil were photo'- electrically measured with monochromatic light having a wave length of 600 m in a Coleman Junior Spectrophotometer. The results showed an increase in relative transparency, defined as wherein I is the transmitted intensity of the winterized cottonseed oil and I is the transmitted intensity. of the V blend, from about 0.5 to about 1.0 when theconcentraarsena s an accurately reproducible approximation of the percent inhibitor to either cottonseed oil or partially hydroby weight of winter oil required to be blended with summer oil and crystallization-inhibitor to provide a substantial improvement in the chill testof the blend.

EXAMPLE 3 A batch of refined cottonseed oil having a chill test of /3 hour wasdivided into 5 parts. 'To each part was blended a portion of refined corn oil and/or 0.1%, by weight of the total blend, of the oxystearin described in Example 2. The chill test results obtained with these blends is shown in the following table. All percentages shown in this example are stated in percent by weight of the total blend.

Table III Chill test Oil blend: in hours I Cottonseed oil /s Cottonseed oil+0.1% oxystearin 2 /2 Cottonseed oil+% corn oi-l /2 Cottonseed oil+30% corn oil /2 Cottonseed oi1+10% corn oil and 0.1% oxystearin I I Cottonseed oil+30% corn oil and 0.1% oxystearin When refined safflower oil, refined and winterized cot-- Several blends of refined rapeseed oil, refined and partially hydrogenated soybean oil, and one or more materials from the group consisting of refined cottonseed oil, refined soybean oil and acetyl palmitoyl dextrin were prepared in the proportions shown in the following table and produced the chill test results described therein. The amounts of all components of the blends shown in this example are stated in parts by weight.

Table IV Chill test in hours Oil blend:

Cottonseed oil 100 parts cottonseed ,oil-0i1001 part acetyl palmitoyl dextrin 2 /2 Partially hydrogenated soybean oil A 100 parts partially hydrogenated soy-beanoil 0,1001 part acetyl palmitoyl dextrin A 10 parts rapeseed oil-70 parts cottonseed oil- 20 parts partially hydrogenated soybean oil..- V2 10 parts rapeseed oil-20 parts partially hydrogenated soybean oil-70 parts soybean oil 1 /2 10 parts rapeseed oil-70 parts cottonseed oil- 20 parts partially hydrogenated soybean oil-- 0.1001 part acetyl palmitoyl dextrin 2 10 parts rapeseed oil-20 parts partially hydrogenated soybean oil-70 parts soybean oil- 0.1001- part acetyl palmitoyl dextrin 25 The above blend of 10 parts rapeseed oil, 70 parts cottonseed oil and 20 parts partially hydrogenated soygenated soybean oil (summer oils) had negligible effect upon the chill test of the summer oil. The addition of various amounts of winter oils, such as soybean oil and/or irapeseed oil, tothe summer oils also gave no significant It was 1 also found that the blendsof summer and winter oils improvement in the chill test of the latter oils.

were substantially improved by the addition of a crystallization inhibitor only when the summer and winter oil components were blended in such proportions that the relative transparency (determined according to the procedure of Example 2) was between 0.5 and 1.0.

EXAMPLE 5 The addition of about 0.1%, by weight of the total blend, of the oxystearin described in Example 2 to a blend of 15% peanut oil, 25% winterized cottonseed oil, 25% partially hydrogenated soybean oil and 35% safflower oil lengthened the chill test from one hour to about 12 hours. Substantial improvements in chill test results are also obtained by using either 0.005% or 0.5% oxystearin in the above example in place of 0.1% ,oxystearin.

EXAMPLE 6 The addition of about 0.1%, by weight of the total blend, of the oxystearin described in Example'2 to a blend of 15% soybean oil, 35% cottonseed oiland winterized cottonseed oil lengthened the chill test from less than 5 /2 hours to greater than 24 hours. The improved blend also had excellent flavor characteristics.

Each blend in Examples 1-6 which has a chill test in excess of 5 /2 hours is suitable for normal salad oil purposes.

The above examples clearly show that substantial improvement in chill test is obtained when from about 15 to about 85% summer oil .is blended with the combination of from about 15 to about 85% winter oil and from about 0.005% to about 0.5% crystallization inhibitor, compared to the chill test obtained when'the summer oilis blended with material independently selected from the group consisting of said winter oil and said crystal-.

be substantially upgraded in chilltest performance by bean oil had a relative transparency of less than 0.1.

relative transparency of about 1.0.

la the above example, the addition of a crystallization the addition of from about 0.005 to about 0.5% crystallization inhibitor whereas blends which do not have such transparency are not significantly improved by said crystallization inhibitor.

What is claimed is:

V f 1. A clear liquid glyceride oil composition characterized by substantial stability against clouding and stearin deposition whereby it has a chill test of at least 5 /2 hours at 32 P. which comprises the blend of at least two fatty triglycerideoils at least one of which is a summer oil normally having poor stability against clouding and stearin deposition and at least another of which is a winter oil normally having good stability against clouding and stearin deposition with a crystallization inhibitor in an amount of from about 0.005 to about 0.5%, by weight of the total composition, the blend containing from about 15 to about by weight of the total composition, of summer oil and having such proportions of summer oil to winter oil as to satisfy the condition that the relative transparency, defined as wherein I is the transmitted intensity of the winter oil component and I is the transmitted intensity of the uninhibited blend of summer and winter oils, should equal.

9 measured with monochromatic light having a wave length of 600 mg.

2. The composition of claim 1 wherein the crystallization inhibitor is selected from the group consisting of acetyl palmitoyl dextrin, dioleoyl hexapalmitoyl sucrose, and oxystearin.

3. The method of substantially improving the chill test of a summer oil normally having poor stability against clouding and stearin deposition which comprises blending it with a winter oil normally having good stability against clouding and stearin deposition and with a crystallization inhibitor in an amount of from about 0.005% to about 0.5%, by weight of the total composition, the blend containing from about 15% to about 85% summer oil, by weight of the total composition, and having such proportions of summer oil to winter oil as to satisfy the condition that the relative transparency, defined as wherein I is the transmitted intensity of the winter oil component and I is the transmitted intensity of the uninhibited blend of summer and winter oils, should equal about 0.5 to about 1.0 when held at a temperature of 33.5 F. for a period of 90 minutes and photoelectrioally measured with monochromatic light having a Wave length of 600 my.

4. A clear liquid glyceride oil composition characterized by substantial stability against clouding and stearin separation whereby it has a chill test of at least hours at 32 F. comprising, by weight of the composition,

(a) from about to about winter oil selected from the group consisting of soybean oil, corn oil, safiiower oil, sunflower seed oil, sesame oil, winterized cottonseed oil, winterized partially hydrogenated soybean oil having an I.V. of from about 105 to about 115, and mixtures thereof,

(b) from about 0.005% to about 0.5% crystallization inhibitor and (c) from about 70% to about 85% cottonseed oil.

5. The composition of claim 4 wherein the crystallization inhibitor is selected from the group consisting of acetyl palmitoyl dextrin, dioleoyl hexapalmitoyl sucrose, and oxystearin.

6. A clear liquid glyceride oil composition characterized by substantial stability against clouding and stearin separation whereby it has a chill test of at least 5 /2 hours at 32 F. comprising, by Weight of the composition,

(a) from about 25% to about summer oil selected 5 from the group consisting of peanut oil, partially hydrogenated soybean oil having an I.V. of from about 105 to about 115, and mixtures thereof,

(b) from about 0.005% to about 0.5 crystallization inhibitor and (c) from about to about winter oil selected from the group consisting of soybean oil, corn oil, safflower oil, sunflower seed oil, sesame oil, winterized cottonseed oil, winterized partially hydrogenated soybean oil having an I.V. of from about to about 115, and mixtures thereof.

7. The composition of claim 6 wherein the crystallization inhibitor is selected from the group consisting of acetyl palmitoyl dextrin, dioleoyl hexapalmitoyl sucrose, and oxystearin.

h. A clear liquid glyceride oil composition having excellent flavor and characterized by substantial stability against clouding and stearin separation whereby it has a chill test of at least 5 /2 hours at 32 F. comprising, by weight of the composition,

(a) from about 10% to about 30% soybean oil,

(b) from about 0.005% to about 0.5 crystallization inhibitor,

(c) from about 35% to about 50% winterized cottonseed oil and (d) from about 35% to about 50% cottonseed oil.

9. The composition of claim 8 wherein the crystallization inhibitor is selected from the group consisting of acetyl palmitoyl dextrin, dioleoyl hexapalmitoyl sucrose, and oxystearin.

References Cited by the Examiner UNITED STATES PATENTS 40 2,554,872 5/51 Musher 99-118 OTHER REFERENCES Bailey: Industrial Oil and Fat Products, 1951, Interscience Pub. Inc., N.Y., page 199.

A. LOUIS MONACELL, Primary Examiner.

Claims (1)

1. A CLEAR LIQUID GLYCERIDE OIL COMPOSITION CHARACTERIZED BY SUBSTANTIAL STABILITY AGAINST CLOUDING AND STEARIN DEPOSITION WHEREBY IT HAS A CHILL TEST OF AT LEAST 5 1/2 HOURS AT 32*F. WHICH COMPRISES THE BLEND OF A T LEAST TWO FATTY TRIGLYCERIDE OILS AT LEAST ONE OF WHICH IS A SUMMER OIL NORMALLY HAVING POOR STABILITY AGAINST CLOUDING AND STEARIN DEPOSITION AND AT LEAST ANOTHER OF WHICH IS A WINTER OIL NORMALLY HAVING GOOD STABILITY AGAINST CLOUDING AND STEARIN DEPOSTION WITH A CRYSTALLIZATION INHIBITOR IN AN AMOUNT OF FROM ABOUT 0.005% TO ABOUT 0.5%, BY WEIGHT OF THE TOTAL COMPOSITION, THE BLEND CONTAINING FROM ABOUT 15% TO ABOUT 85%, BY WEIGHT OF THE TOTAL COMPOSITION, OF SUMMER OIL AND HAVING SUCH PROPORTIONS OF SUMMER OIL TO WINTER OIL AS TO SATISFY THE CONDITION THAT THE RELATIVE TRANSPARENCY, DEFINED AS