US2462664A

US2462664A - Stabilization of oleaginous materials

Info

Publication number: US2462664A
Application number: US566244A
Authority: US
Inventors: Frank A Norris
Original assignee: General Mills Inc
Current assignee: General Mills Inc
Priority date: 1944-12-01
Filing date: 1944-12-01
Publication date: 1949-02-22
Anticipated expiration: 1966-02-22

Description

Patented Feb. 22, 1949 STABELEZA'EHGN F OLEAGINUUS IVMi'EERHALS Frank A. Norris, Minneapolis, Minn, assignor to General Miiis, line, a corporation of Delaware No Drawing. Application December 1, 19%, Serial No. 566.2%

18 (Ciairns. i

The present invention relates to a process of stabilizing oleaginous materials against the development of rancidity, and to the resultant product. rhe invention is directed particularly to oleaginous materials composed of or containing animal fats or oils, such as oils, shortening, salad dressings, spreads, and the like,

The present invention involves a synergistic anti-oxidant effect resulting from the combined use of a plurality of substances. It has been found that combinations of certain antioxidants produce a resultant stability far in excess of the sum of the stabilities obtained by the use of the compounds singly. i

It is therefore a primary object of the present invention to provide a process of stabilizing fatty or oleaginous materials against oxidation and the development of rancldity.

It is another object of the invention to provide products containing fats or oils which are stabilized against oxidation and the development oi rancidity.

A further object of the invention is to provide a process of stabilizing fatty or oleaginous products of animal origin by means of antioxidants which exhibit synergistic effects.

These and other objects of the invention will be apparent from the following description of the invention with particular reference to specific examples which are to be understood as illustrative only and not as limiting the invention.

It has been found that a synergistic antioxidant effect is obtained by the conjoint use of galllc acid and compounds containing the ene-dioi group (HO-(i=(3-0n) such as l-a-scorbic acid. While ascorbic acid, which is water-soluble, has been known to have antioxidant effect in aqueous media, it has not been particularly effective in fats probably because of its extremely low solubility. Gallic acid on the other hand has a considerable antioxidant etlect in fatty media. It has been found, however, that when these two compounds are used together, they exhibit a pronounced synergistic efl'ect which gives the oleaginous material a stability far in excess of that of the untreated material andjar in excess of the sum of the individual stabilities contributed when each or these cbm- 2 pounds is used alone. This is demonstrated by theiollowing table showing the effect on prime steam lard.

Table I Swl Protective Sampliigggg Factor 1 Prime stoum Iard 3. 5 2 (l)+0.02% gullic acid 107 30. 6 3 Prime steam lord... 2.5 l 4 (3)+0.05% l-ascorhic ll. 5 l G 5 Prime steam lard 3.8 6 (5) +0.02% gallic midi-0.05% l-ascorbic acid 207. 5 5i. 7

In place of l-ascorbic acid other compounds havsynergistic action of these compounds is demonstrated by the following table showing the effectiveness of gallic acid, l-ascorbic acid. and pamino-benzoic acid.

Table 1! "Swift" Pl'OtGCLlYl' Sample stnaglllligy Fucmrs 1 Prime steam lord 3.5 2 (l)+0.02% gallic acid 107 3|), l; 3 Prime steam lard 2.5 4 (3)+0.05% l-oscorbic acid-loss than... ll. 5 4. G 5 Prime stcnm lard 3.8 l l 6 (5) +0.02% galiic ncki +0.05% i-ascorbic acid 207.5 A. 7 7 (3)+0.03% p-amino-bonzoic acid-loss than 2 3 i 8 (l)+0.05% l-ascorhic nclrl+0.0i% pnminobcnzoic acid.. 22 I (i. 7 9 (1)+0.05% l-ascorbic ocid+0.03% n- I amino-bonzolc acid+0.02% izallic 5 acid 318 1 to. 9

The prime steam lard employed was the article the amount of antioxidant added.

Instead of the amounts of antioxidants shown above, it is possible to employ decidedly lower. concentration where such a high stability is not cent of each of a compound containing an enediol group, and a compound selected from the group consisting of gallic acid and its lower aliphatic esters.

3. A process 01 stabilizing an oleaginous material of animal origin which comprises incorporating therein, not substantially in excess oi' one-tenth per cent of each of l-ascorbic acid,

and a compound selected from the group consisting of gallic acid and its lower aliphatic esters.

4. A process oi stabilizing an oleaginous material oi animal origin which comprises incorporating therein, not substantially in excess oi one-tenth per cent of each or l-ascorbic acid and gallic acid.

necessary or desirable. The lower limit of antirial of animal origin which comprises incorporatoxidant to be added appears to be dictated by the resultant stability desired. There does not ap-.

pear to be any upper limit to the amount of antioxidant which may be employed. However, the cost of the antioxidant constituents usually dictates that they should not be employed in much greater concentration than 0.1 percent.

In addition to its effect on the antioxidant.

properties or the product, p-amino-benzoic acid has decided preservative action and represses microbiological growth. The common materials employed to inhibit oxidative rancidity have no effect on microbiological growth. Consequently yeast, molds, and the like, continue to grow and produce hydrolytic or other enzymic changes which result in rancidity. Thus, while the rancidity so .produced is a distinct disadvantage in itself, the presence of large numbers of micro organisms is an even greater disadvantage in view of the possible ill effect on those who consume such a product.

It is apparent that these various objections of the prior art are overcome by the present inven- 5. A process of stabilizing an oleaginous mateing therein, not substantially in excess of .1 per cent of each of a compound containing an enediol group, and a compound selected from the group consisting of gallic acid and its lower aliphatic esters.

6. A composition of matter comprising an oleaginous material of animal oringin containing, and being stabilized against the development of rancidity by, not substantially in excess of onetenth per cent of each of l-ascorbic acid, p-aminobenzoic acid, and gallic acid.

7. A" composition of matter comprising an oleaginous material of animal origin containing, and being stabilized against the development of rancidity by, not substantially in excess of .1 per cent oi. each of a compound containing an enediol group. D-amino-benzoic acid, and a compound selected from the group consisting of gallic acid and its lower aliphatic esters.

8. A process of stabilizing an oleaginous mation in that it inhibits ibOth oxidative rancidity and microbiological growth. Hydrolytic and enzymic rancidity are likewise inhibited in view of the inhibition of microbological growth. Moreover all of the substances are non-toxic and the p-amino-benzoic acid and l-ascorbic acid are recognlzed vitamins which perform additional functions when consumed.

While particular reference has been made to the use of l-ascorbic acid as a compound of the ene-diol group in the multiple synergy, it is to 7 be understood that other compounds having this group, such as those specifically enumerated with respect to the single synergy, may also be employed in the multiple synergy. Likewise the lower aliphatic esters of gallic acid previously mentioned may be used in place of free gallic acid in the multiple synergy.

'-It is also to be understood that the invention may be applied to animal oils or fats or any nature whether edible or not, all of which products are contemplated by the term "oleaginous material of animal origin as used in the appended claims.

I claim as my invention:

1. A composition of matter comprising an oleaginous material of animal origin containing, and being stabilized against the development of rancidity by, not substantially in excess of onetenth per cent of each of l-ascorbic acid and gallic acid.

2. A composition of matter comprising an oleaginous material of animal origin containing, and being stabilized against the development of rancidity by, not substantially in excess of .1 per porating therein, not substantially in excess of one-tenth per cent of each of l-ascorbic acid, p-amino-benzoic acid,'and a compound selected from the group consisting of gallic acid and its lower aliphatic esters.

9. A process of stabilizing an oleaginous material of animal origin which comprises incorporating therein, not substantially in excess 01' one-tenth per cent of each of l-ascorbic acid, p-amino-benzoic acid, and gallic acid.,

10. A process of stabilizing an oleaginous material of animal origin which comprises incorporating therein, not substantially in excess of .1 per cent of each of a compound containing an ene-diol group, p-amino-benzoic acid, and a compound selected from the group consisting of gallic acid and its lower aliphatic esters.

11. An edible shortening containing an oleaginous material of animal origin, and being stabilized against the development of' rancidity by, not substantially in excess of .1 per cent of each of l-ascorbic acid and a compound selected from the group consisting of gallic acid and its lower aliphatic esters.

12. An edible shortening containing an oleaginous material oi animal origin, and being stabilized against'the development 01' rancidity by, not substantially in excess oi .1 per cent of each of l-ascorbic acid, p-amino-benzoic acid, and a compound selected from the group consisting of gallic acid and its lower aliphatic esters.

13. A composition of matter comprising an oleaginous material of animal origin containing, and being stabilized against the development of acid and its lower aliphatic esters and 0.05% of a compound containg an ene-diol group.

14. A composition of matter comprising an oleaginous material of animal origin containing. and being stabilized against the development of rancidity by, approximately 0.02% of a compound selected from the group consisting of gallic acid and its lower aliphatic esters, 0.05% of a compound containing an ene-diol group, and 0.03% p-amino-benzoic acid.

15. A composition of matter comprising an oleaginous material of animal origin containing, and being stabilized against the development of rancidity by, approximately 0.02% gallic acid and 0.05% l-ascorbic acid.

16. A composition of matter comprising an oleaginous material of animal origin containing, and being stabilized against the development of rancidity by, approximately 0.02% gallic acid, 0.05% l-ascorbic acid, and 0.03% p-aminobenzoic acid.

17. A process of stabilizing an oleaginous material of animal origin which porating therein approximately 0.02% of a compound selected from the group consisting of gallic acid and its lower aliphatic esters, and 0.05% of a compound containing an ene-diol group.

comprises incor- 18. A process of stabilizing an oleagin'ous ma.- terial or animal origin which comprises incorporating therein approximately 0.02% of a' compound selected from the group consisting of gallic. acid and its lower aliphatic esters, 0.05% of a compound containing an ene-diol group, and

The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,763,326 Reed June 10, 1930 1,970,339 Rogers et a1 Aug. 14, 1934 1,975,755 Hoyt et a1. Oct. 2, 1934 2,159,986 Gray et a1 May 30, 1939 2,255,191 Sabalitschka et al. Sept. 9, 1941 2,279,973 ,Dietrich Apr. 14, 1942 OTHER REFERENCES Filer et. al., "Antioxidant L'osses During the Induction Period of Fat Oxidation," Oil and Soap," Oct. 1944, pages 289 to 292.