JPH06500594A - Composition of natural antioxidants for stabilization of polyunsaturated oils - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Composition technology of natural antioxidants for the stabilization of polyunsaturated oils The present invention generally relates to the prevention of deterioration of foods, cosmetics, and pharmaceuticals containing polyunsaturated fatty acids. Regarding. More specifically, the present invention relates to tocopherol, ascorbic acid, citric acid and to a natural composition of antioxidants for the stabilization of polyunsaturated oils, including phospholipids. related. Phospholipids are derived from soy (commercially known as "soy lecithin") or eggs. Or it can be obtained from other sources. Rosemary extract is also added to the composition can do.

Background technology Today, cosmetic and pharmaceutical products containing polyunsaturated fatty acids are produced in plants throughout the country. Manufactured and pre-packaged for sale, shipped across the country to supermarkets and convenience stores. Delivered to Vinience Store. The nature of such products and their availability throughout the country Due to the transportation of products such as these products require a long shelf life. storage period It is necessary to prevent deterioration of product quality in order to increase the time. Degraded crude oil Also, vegetable oils containing linoleic acid and/or linuric acid are oxidized by oxygen in the air. easily generate peroxides. Peroxide decomposes into volatiles with unpleasant odors and aromas. produces volatile compounds. For example, fish oils such as menhaden oil quickly become green grass. Can produce a fishy odor and aroma. Soybean oil also oxidizes easily There are other products that can produce classic reversion odors and aromas.

Furthermore, such oxidative components can be harmful to human health.

Fish oils, such as menhaden oil, are used by Charlg et al. (U.S. Patent No. 4. No. 874.629), highly refined into odorless, fragrance-free oils, such as those taught by No. 874.629). However, the oil still turns blue and fishy when it is exposed to even trace amounts of air or oxygen. Odors and aromas can be regenerated. Fish oil packaged in gelatin capsules Even during storage, relatively high peroxide values can occur. Additionally, Tokov When gerol is added alone to fish oil, it is packaged in gelatin capsules. It was also reported that oil peroxidation cannot be effectively prevented.

Therefore, in order to use such oils in plants or as food supplements, they are Stabilizes and prevents or delays the development of unpleasant odors and aromas, as well as consumer health must be protected.

Many different antioxidants and antioxidant compositions have been developed over the years.

Many of these antioxidants, such as BHA and BIT, are synthetic. today people are more health conscious and prefer natural products that are considered safe for human consumption.

Additionally, synthetic compounds have recently come under increased scrutiny by the FDA. developed Natural antioxidant compositions also suffer from problems that limit their usefulness.

For example, EP 0326829 [Lergar L611get)] converts lipids into acids. A natural mixture of tocopherols, ascorbic acid and lecithin to protect against disclosing something. However, because the mixture is a combination of ascorbic acid and lecithin, can produce a red color in the oil.

It is therefore an object of the present invention to provide natural acids which retard the oxidation of fats and oils and thus the deterioration of food products. An object of the present invention is to provide a composition of an anti-inflammatory agent. Furthermore, it is important for oxidation and resulting food deterioration. with improved antioxidant activity over previous formulations to give better protection against . Furthermore, the present invention provides a combination of ascorbic acid and lecithin in oils or products thereof. Significantly reduces undesirable colors caused by

Disclosure of invention The present invention uses natural acids including tocopherol, ascorbic acid, citric acid and phospholipids. The present invention provides a composition of an anti-inflammatory agent. The antioxidant composition of the present invention contains about tocopherols. 10 to about 62.5% by weight, ascorbic acid about 1.5 to about 20% by weight, citric acid about 1.5 to about 20% by weight and about 26 to about 85% phospholipids.

The composition preferably contains about 29.4% tocopherol and about 5.9% ascorbic acid. , about 5.9% citric acid and 58.8% phospholipid, all by weight.

The composition further includes rosemary as described in U.S. Pat. No. 3,950,266. -extracts to the other antioxidants mentioned above. rosemary - extracts of the present invention contain about 6.5% to about 54% by weight of tocopherols, Corbic acid about 1.2 to about 16% by weight, citric acid about 1.2 to about 16% by weight, phospholipid from about 17 to about 77% by weight and from about 6.5 to about 54% by weight of rosemary extract. . Preferably the composition contains about 22.7% tocopherol and about 4.5% ascorbic acid. %, citric acid approximately 4.5%, phospholipid 45.5% and rosemary extract approximately 22% ．． 7%, all by weight.

The present invention also provides ascorbic acid, citric acid, A composition of natural antioxidants is provided that includes citric acid and phospholipids. The composition About 2% to about 27% by weight of scorbic acid, about 2% to about 27% by weight of citric acid, and about phospholipid. 56 to about 95% by weight. Preferably the composition comprises about 8.3% ascorbic acid; Contains 8.3% citric acid and 83.4% phospholipids, all % by weight. The composition is It may further include the addition of rosemary extract to the other items listed above. B The composition with Zumary extract contains about 1.8% to about 23% by weight of ascorbic acid, About 1.8 to about 23% by weight of enoic acid, about 35 to about 90% by weight of phospholipid, and rosemary. - Contains from about 5 to about 45% by weight extract. Preferably, the composition contains about ascorbic acid. 6.9%, citric acid approximately 6.9%, phospholipid 70% and rosemary extract approximately 1 7.2%, all about 0.05 to about 0.2% by weight, about 0.01 ascorbic acid ~ about 0.04% by weight, about 0.01 to about 0.04% by weight of citric acid, and deoiled soybean phosphorus 0.1 to about 0.4% by weight of lipids. The composition further includes rosemary extract. may be included in an amount of about 0.05 to about 0.2% by weight. Preferably in fish oil The composition contains about 0.1% 1. Ascorbic acid approximately 0.02%, citric acid Approximately 0.02%, deoiled soybean phospholipid 0.2% and rosemary extract approximately 0.1% , all percentages by weight.

The composition of the antioxidant of the present invention in a tocopherol-rich vegetable oil contains the following oil-related components: percentage of ascorbic acid, about 0.01 to about 0.04% by weight, citric acid about 0.01% ~0.04% by weight and 0.1 to about 0.4% by weight of deoiled soy phospholipids.

The composition further comprises about 0.025% to about 0.1% by weight rosemary extract. Can be done. Preferably, the composition in vegetable oil contains about 0.02% ascorbic acid, Approximately 0.02% phosphoric acid, 0.2% deoiled soybean phospholipid, and approximately 0.0% rosemary extract. 05%, all by weight.

The composition of the present invention is suitable for use in products containing polyunsaturated fatty acids or oils. It can be added at many different concentrations depending on the product and the economics of the product. weight of unsaturated oil The use of about 0.10 to about 0.6% by weight on a weight basis has been found to produce useful results. However, other concentrations can be used. Plants rich in tocopherols Tocopherol, ascorbic acid, citric acid, phospholipids and possibly low A composition of Zumary extract could be used.

A combination of natural antioxidants that slows down the development of blue, fishy odors and aromas caused by related. Composition comprising tocopherol, ascorbic acid, citric acid and phospholipids was found to have unexpected and effective antioxidant properties.

The tocopherols used in the antioxidant compositions of the present invention generally contain some tocopherols. Contains a mixture of erol isomers. Such compositions are commercially available.

The ascorbic acid and citric acid used in the antioxidant composition of the present invention can be Commercially available from sources.

The phospholipids used in the antioxidant compositions of the present invention can be derived from a variety of sources. can. A preferred phospholipid is deoiled soy phosphorus, commercially known as soy lecithin. phospholipids from other sources such as corn, rice, cottonseed, rapeseed, and canola. It can be obtained from canola and other oils.

The present invention utilizes compositions of the present invention to provide antioxidant compositions with improved properties. We intend to make some improvements to the phospholipids used in products. The present invention applies to aqueous organic solvents. Intended for the removal of carbohydrates in commercially available soybean lecithin by extraction. The present invention also of soybean lecithin to produce lecithin with improved light color and reduced odor. It is contemplated that a freeze-drying process will be used to dehydrate the wet gum during manufacture.

The addition of rosemary extract to the composition further enhances the antioxidant properties of the composition. Melt.

Individual natural antioxidants may be used in amounts equal to the total amount of the compositions of the present invention. It does not have the same effect of antioxidant activity as other products. Furthermore, any composition of the present invention Compositions lacking this component also do not have similar antioxidant activity as achieved with this composition. stomach.

Preferred compositions of the invention are particularly effective in deodorizing, purifying, and treating fish oils such as menhaden oil. The new embodiment is as follows by weight: Tocopherol 29.4% Ascorbic acid 5.9% Citric acid 5.9% Deoiled soybean phospholipid 58.8% The preferred amount of the above embodiment for addition to menhaden oil is 0.34%. oil The addition of 0.1% rosemary extract by weight further increases the effectiveness of antioxidant activity. It can be improved to

A particularly effective composition for soybean oil since vegetable oils are usually naturally rich in tocopherols. An example with weight is: Ascorbic acid 8.3% Citric acid 8.3% Deoiled soybean phospholipid 83.4% The preferred amount of the above composition for addition to soybean oil is 0.24%. weight of oil The addition of 0.05% rosemary extract further modifies the effectiveness of antioxidant activity. I can do it well.

The compositions of the invention also include all omega-3 fatty acid containing oils such as menhaden oil, With sardine oil, herring oil, anchovy oil, birchard oil and other such oils Can be used. Significant amounts of other possible oils with which this composition can retard oxidation Vegetable oils containing polyunsaturated fatty acids such as sunflower oil, rapeseed oil, canola oil, and corn oil Includes sardine oil, cottonseed oil and other similar oils. Many vegetable oils are already available in sufficient quantities. Naturally contains tocopherol. Therefore, it is necessary to add additional tocopherol. rather, simply combining the three components (and possibly the Simply add Zumary extract). In addition, animal fats such as lard, beef tallow and butter can be made beneficial by the use of the compositions of the present invention. Finally, many Other foods, cosmetics and pharmaceutical products containing unsaturated fatty acids also suffer from their oxidation and deterioration. can be delayed by the use of the compositions of the invention.

Examples of the invention The following examples show how to prevent the deterioration of products containing menhaden oil or vegetable oil by pre-composition. It is clearly superior to natural or synthetic antioxidants.

In all examples, the effectiveness of the antioxidant composition was determined using a recently developed instrument, Measurement of AOM time using Rancimat (Model 617) Based on the American Oil Chemistry Society an Oil Chemists'5ociety) official method, Cd 12-5 Induction using a 71° Rancimat at various temperatures and an air flow rate of 20 liters per hour. The period, time, was measured.

The materials used were: Menhaden oil: Zapata Haynie Corp Purified, multi-membrane colored menhade supplied under the trade name SPMO by Oration) The oil was further added to the Chang et al. Deodorized at 100°C and purified by passing through a silica gel column according to the teachings of Ta.

Soybean oil: Central Soya (Central 5aya Company I) Refined, bleached, deodorized soybean oil supplied by NC, ).

Tokov, o-le: by Henkel Corporation Natural mixed tocopherols supplied under the trade name Covr-0xT70.

De-oiled soybean phospholipids: Central Soya (Central 5aya Comp Centrolex powered by any Inc. Granular soybean lecithin containing 96% phospholipids under the trade name H.

Rosemary extract: Herbalox (registered trademark) 0 Standard oil supplied by Alsec Inc. under the trade name oresin extract.

Example 1 100 g of menhaden oil was used as a control (Sample A in Table 1). Sample B is 0, 1 g tocopherol dissolved in San, 0 dissolved in absolute ethanol, 0.02 g ascorbic acid, 0.02 g citric acid dissolved in absolute ethanol 0.2 g of soy phospholipid dissolved in acid and hexane to 100 g of menhaden oil It was produced by adding to. After thorough mixing, remove the solvent under vacuum at a temperature below 80°C. was removed using a rotary evaporator. Sample C is a mixture of absolute ethanol and exane ( 0.1 g of rosemary extract dissolved in 9:1, V/■) was first added to sample B. It was prepared by adding it to a formulation similar to that prepared by rosemary extract was added before the solvent was removed by use of a rotary evaporator. induction period for each sample was measured using Rancimat. Additionally, the synthetic antioxidants BHA and BHT The lag period was also determined relative to the mannhaden oil supplemented with mannhaden oil and the control.

A None 0.9 B Tocopherol 0.10% 25.2 Ascorbic acid 0.02% Citric acid 0.02% Soybean phospholipid 0.20% C tocopherol 0.10% 26.4 Ascorbic acid 0.02% Citric acid 0.02% Cheek rinse top 0.20% Rosemary extract 0.10% Mouth BHA (102% 2.1 E BHT 0102% 1.7 Table 18 shows that the induction period for the composition of the present invention was that of Sample A to which no antioxidant was added. clearly shows that it is much higher than that for In addition, synthetic antioxidants are F Maximum amount observed by DA, not much higher than the induction period of sample A and sample B and has a very low lag period, significantly lower than that for C. Oxidation of the composition To further demonstrate inhibitor activity, samples A% B, C and D of Example 1 were incubated at 45°C. Aged for 1 week and 2 weeks. The peroxide values of the samples after aging are shown in Table 1b.

Table 1b A None 16.8 240 B Tocopherol 0.10% 0.9 7.9 Ascorbic acid 0.02% Citric acid 0.02% Soybean phospholipid 0.20% C Tocopherol 0.10% X, 5 6.0 Ascorbic acid 0.02% Rixunr110.02% Soybean phospholipid 0.20% Rosemary extract 0.10% D BHA 0.02% 14.3 23.0 As in the sample in Table 1a, No antioxidant was added to Sample A, and the antioxidant composition of the present invention was added to Samples B and C. In addition, the synthetic antioxidant BHA was added to the sample.

Peroxide is a compound that decomposes to produce volatile compounds with unpleasant odors and aromas. , it is desirable to have a low peroxide value. Samples B and C of the present invention are different from samples A or D. Note that the peroxide value is very low. Therefore, the results of this example It is clear that the compositions of the present invention significantly retard oil oxidation and resulting deterioration and are superior to synthetic antioxidants. It clearly shows that this can be done more effectively.

Example 2 Five samples of menhaden oil with added antioxidants were prepared as in Example 1.

The composition of Sample C of Example 1 was used as the "standard" for this example. Sample 1 ~5 except that one of the five components of the composition (Sample C of Example 1) was eliminated. Manufactured from the same composition as the "standard". Then measure the induction period for each sample and Comparison was made with a composition having all the ingredients (Standard C).

Table 2 No control 0.9 Standard Sample C26,4 of Example 1 1 Elimination of rosemary extract 25.22 Elimination of tocopherol 11.8 3 Elimination of ascorbic acid 10.5 4 Elimination of citric acid 241 5 Elimination of soy phospholipids 15.6 Table 2 shows that the composition of the invention represented by the standard sample and sample 1 has one of the components excluded. It clearly shows that it has a much higher lag period than any of the other compositions. In Table 2 As shown, citric acid does not have a strong effect on antioxidant activity. But that is important in preventing the appearance of undesirable colors.

Example 3 The composition of Sample C of Example 1 with all five components was used as a standard. menhede Five samples of green oil were also prepared as in Example 1. In each sample, the composition of the invention One of the ingredients (standard) was added at a concentration of 0.44%. Measure the induction period of each sample did.

No control 0.9 Standard Sample C26,4 of Example 1 1 Tocopherol 0.44% 2.32 Ascorbic acid 0.44% 1. 43 Citric acid 0.44% 1.0 4 Deoiled soybean phospholipid 0.44% 1.35 Rosemary extract 0.44 % 6.9 Table 3 shows that when each of the five components of the composition of the present invention is added individually, the standard It has been shown that even concentrations higher than the total amount of the five components in the compound do not produce effective antioxidant activity. vinegar. Therefore, the composition of the present invention has an unusually strong antioxidant activity due to synergistic action. It clearly shows that

Example 4 The compositions of the invention have other novel advantages. The amount of phospholipid used in the present invention is determined according to the present invention. It will be sufficient to make the amount of ascorbic acid soluble in the oil. This is that Ascorbic acid, which is otherwise insoluble in oil, is dispersed more uniformly in oil, and This makes the antioxidant activity of ascorbic acid even more effective.

The surprising but obvious effect of phospholipids on the solubility of ascorbic acid in oil is This can be clearly illustrated by a simple example. 10g of ascorbic acid in anhydrous ester De-oiled soybean phospholipids (Centrolex R) 100 g were dissolved in 250 III hexane. Mix the two solutions thoroughly, The solvent was then removed using a rotary evaporator under vacuum at a temperature below 60°C. Hexa A soluble, brownish yellow powder was obtained. Ascorbic acid is originally insoluble in hexane. However, after combining it with soybean phospholipids, the resulting brownish-yellow powder is It should be noted that it was completely soluble in xane. This hexane solution It can be easily added into oils such as fish oil or vegetable oil. Ascol after removing the solvent A clear oil solution of avic acid is obtained.

Commercial product, Hoffmann La Roche Ascorbyl balmitate, manufactured by Inc.), is better than ascorbic acid. Has good oil solubility. However, ascorbyl valmitate is still directly soluble in oil. I can't figure it out. It is dissolved in a solvent such as ethanol and then the solution is dissolved in oil. I have to figure it out. Ethanol is a clear solution of ascorbyl valmitate in oil must be removed to obtain . In addition, asymmetry due to reaction with valmitic acid The loss of one hydroxyl group from the corbic acid molecule makes ascorbyl balmitate an acid. make it less effective as an inhibitor.

In order to demonstrate the above novel advantages of the present invention, another set of samples was prepared as described in Example 1. Manufactured in the same way. Samples A, B, C and D are exactly as described in Example I. It was. However, an additional sample B-FA was added. This sample (B-FA) Same as sample B except that phosphoric acid was replaced with ascorbyl balmitate. It was. As ascorbyl valmitate has a larger molecular weight than ascorbic acid. , to make it equal to 0.02% of γ-scorbic acid in the molecule, Scolbyl 0.04% was used.

As shown in Table 4, the induction period results of the above samples show that ascorbic acid is A shown to be more effective than ascorbyl valmitate in antioxidant compositions None 0.9 B Ascorbic acid 0.02% 25.2 Tocopherol 0.10% Citric acid 0.02% Soybean phospholipid 0.20% B-AP Ascorbyl Valmitate 0.04% 18.8 Tocopherol 0.10% Citric acid 0.02% Soy phosphorus 1! VitO, 20% CBHA 0.02% 2.1 D BHT 0.02% 1.7 Example 5 The present invention is equally effective when applied to vegetable oils such as refined, bleached, and deodorized soybean oil.

No additional tocopherols were added as vegetable oils are generally rich in tocopherols. .

Samples were prepared with the exception that menhaden oil was replaced with purified, bleached, and deodorized soybean oil. Manufactured similarly to that in Example 1.

Table 5 A None 6.50 8 Ascorbic acid 0.02% 13.15 Citric acid 0.02% Cheek rinse 0.20% CBHA O, 20% 6.50 D BHT 0.20% 6.60 Table 5 shows the induction period of these samples. A sample of the composition of the present invention (sample B) is a synthetic acid much greater than the antioxidant (sample C and D) or the sample without antioxidant (sample A). It has a long induction period.

Example 6 The extraordinary antioxidant activity of the compositions of the present invention when used in soybean oil shows that menhaden The following results, similar to those used for oil (in Example 2), demonstrate:

Hayashi Composition of the present invention Example 7 This example demonstrates the advantages of the composition of the present invention over prior art three-component compositions. intended. Lallger's patented three-component composition contains tocopherol- M, 1%, ascorbic acid 0.02% and lecithin 0.2%. Each composition Antioxidants were added to purified, decolorized menhaden oil. The four-component composition of the present invention On the citric side, 02% by weight was added to Lallger's three-component system. added.

Table 7 Menhaden oil (refined/decolorized) has no Lovibond color 0.6 10.4 Lergar's patented three-component system of tocopherol 0.10% 3.7 27.7 T Scorbin l! 0.02% lecithin 0.20% Tocopherol 0.10% 11 17.74 component composition of the present invention Asco Rubic acid 0.02% Lecithin 0.20% Citric acid 0.02% Book (based on oil weight %) Table 7 shows Lallger's patented three-component composition and the four-component composition of the present invention. Showing the difference in color between objects. The composition of Lergar (LSI Iget) is based on the present invention. gives an undesirable red color, which is much greater than the color that would result from the use of avoid red is considered to be very important for oil quality. 1 unit difference in Lovibond color is significant. Therefore, the composition of the present invention contains citric acid (and rose in the five-component composition). The addition of M. mari extract) has at least three advantages compared to the prior art: (1) Significantly reduces the undesirable color caused by the combination of ascorbic acid and lecithin descend; (2) Has improved antioxidant activity as shown in Table 2 of Example 2, and has citric acid Exclusion of acid reduces the induction period of the four-component system from 26.4 hours to 2t1 hours: (3) Use of very small amounts of "lecithin". All about Lallger's patents In the example 1% "lecithin" was used. Such a high level of "lecithin" Too much will give the product an unpleasant odor and aroma.

improved phospholipid Commercially available plant phospholipids such as plasticized soy lecithin contain free and bound carbohydrates, essentially Plant sugars (dextrose, raffinose, galactose and stachyose) 5 %including. The color of oils containing soybean lecithin when heated to temperatures above 80°C turns dark. This includes amine-containing phospholipids such as phosphatidylethanolamide. This may be due to the non-enzymatic browning reaction between phosphatidylserine and carbohydrates. .

Such commercially available plant phospholipids, when used in the antioxidant compositions of the present invention, The inhibitor composition can cause a darkening of the oil to which it is added. Oil is an antioxidant + 1. Silicate, antioxidant composition, which can make the color darker than oil without silk acid The amount of soybean I nocytin or phospholipids from other sources used in Therefore, the effect of the color of the oil is probably negligible. But high color when heated It is desirable to use a stable plant phospholipid such as soybean lecithin.

The present invention produces improved phospholipids from crude plant phospholipids such as soybean lecithin. Two methods are contemplated. The products produced by these methods are referred to below as "improved products". is designated as lipid J.

The first method for producing improved phospholipids is to dissolve crude phospholipids in an organic solvent and The quality solution is extracted with an aqueous solution of lower alkanol and then extracted under vacuum at a relatively low temperature. including removing the solvent. This method also provides improved color stability when added to oils. produces two phospholipids. This method is illustrated by Examples 8 and 9.

A second method to produce improved phospholipids is to extract the crude phospholipids with water and then freeze-dry them. including removing moisture. This method has improved odor, aroma and color. Produces phospholipids. The amount of water used for water extraction in this method is It will be 2-5 times (w/v), preferably about 3-5 times (w/v). This person The method is illustrated by Examples 10-14.

Example 8 Dissolve 100 g of plastic soybean lecithin in 300 ml of dimethyl ether and add It was extracted three times with 300 ml of a 30% aqueous solution of Ropatool. Extraction is done by separating 2 liters of liquid. Shake vigorously in the funnel. After extraction, separate the ether layer and rotate the solvent Removed under vacuum using an evaporator. The product was coded soy lecithin A.

The yield was 92.5%.

Example 9 Dissolve 100g of plasticized soybean lecithin in 400sl of pentane and dilute the solution with 60% ester. Extraction was performed three times with 500 ml of an aqueous solution of tanol. Extraction is done in a 2 liter separatory funnel. I stirred it vigorously. In case of emulsion formed during extraction, sodium chloride A few grams of lium can be used to break the emulsion. Separate the pentane layer Removed and then freed of solvent under vacuum. The product was coded lecithin B.

The yield was 87.2%.

The products obtained in Examples 8 and 9 were analyzed by thin layer chromatography, and commercially available soybean The effectiveness of carbohydrate removal from plastic lecithin was detected. The conditions used are as follows. It's a cage Plate: Plate silica gel 60TLC plate, thickness 0.255w*solvent :CHCl5:CHsOH:HJ=65:25:4, v/v color development : Spray 2% Ce5O in 50% H, S, and heat the plate at 120°C for 5 minutes. Heated.

The presence of carbohydrates in lecithin is indicated by the appearance of black spots at R,=O. It was done. Commercially available plastic lecithin shows a dark spot at R,=0, lecithin A and Lecithin B showed a very faint spot at R,=0. This is an embodiment of the invention Both showed effective input removal of carbohydrates.

Commercially available soybean plastic lecithin prepared by the above novel method described in Examples 8 and 9 To improve color stability, commercially available plastic lecithin, lecithin A, and lecithin 82g were used. This is illustrated by dissolving it in 100 g of purified, decolorized and deodorized soybean oil. That's it Three oils, including one of the three samples, were heated to 180°C and then cooled.

The color of the heated oil samples was measured using a Lovibond colorimeter and a UV spectrophotometer.

The results are shown in Table 8. Produced by the novel method described in Examples 8 and 9 Two samples of soybean lecithin are shown to have clearly improved color stability. .

once blue Color stability of soybean oil containing soybean lecithin Commercially available soybean lecithin usually has a so-called "wet" texture obtained from the refining and processing of crude soybean oil. Therefore, the dehydration process can always induce undesirable colors and odors in the final product. Ru. The present invention uses freeze-drying to produce an unexpected fluff-like solid with a light color and little odor. Dehydrate this.

The present invention also cleans the wet gum prior to freeze drying to produce an even less odoriferous material. intend to. A small amount of soy lecithin is used in the antioxidant composition of the present invention. However, commercially available soy lecithin, which has a unique and unpleasant odor, has a poor oil quality. You can influence it. Phospholipids produced by this new method! Ma Highly suitable for use in antioxidant compositions of the present invention.

Even though the examples are limited to soybean phospholipids, commonly referred to as soybean lecithin, the present invention phospholipids from other sources such as corn oil, rice bran oil, cottonseed, and canola oil. It can be applied to phospholipids.

The present invention also provides a process modification that allows rigid products to be manufactured by the novel method of the present invention. starch or ultrafine silica such as commercially available (abo-Si+).

Example 10 A mixture of 50 g of soybean wet gum (water content 33%) and 250 sl of distilled water was Blend for 3-5 minutes until a homogeneous emulsion is obtained. .

Commercial soybean plastic resin produced by freeze-drying an emulsion and thermal dehydration under vacuum. 33 g of a fluffy pale solid was obtained which had a significantly less odor than Cytin. Freeze-dried raw The moisture content of the product was 0.70%.

The amount of water used for water extraction should be 2 to 5 times the wet gum (W/V). twice Using less water may not result in a less satisfactory product. Approximately 3 It is preferred to use ~5 times as much water.

Example 11 As in Example 10, but 10% of the weight of the wet gum starch was added before freeze drying. was added to the emulsion. The starch used was soluble according to Sigma. It was potato starch. The resulting product was firmer.

Example 12 Similar to Example 11 but manufactured by Cahot 15% o-Si (by weight of wet gum) was added. The product uses 5% starch similar to that manufactured.

Example 13 Similar to Example 11, but using 5% starch.

Example 14 5% solution of IJum (chloride of 50 g of soybean wet gum (water content 33%) in water) 1 50In+. Waring the mixture into a homogeneous emulsion in Brengu blended into. The emulsion was then centrifuged and the separated aqueous layer was discarded.

The gum was then washed four times with 100 ml each time of a 2.5% sodium chloride solution in water. . Finally, the thick gum was made into an emulsion with 100 sl of distilled water and 2 g of starch. engineering Lyophilized J. lechon produces a pale yellow, fluffy solid with virtually no objectionable odor. I got it.

The moisture content of the final lyophilized product was 1.10%.

The appearance of the freeze-dried soybean lecithin produced by the above new method is a fluffy solid; The virtually colorless, odorless solid is a commercially available product prepared by conventional methods of dehydration under vacuum with heat. It is completely different from the viscous dark brown liquid of soy lecithin.

Rather, the scope of the invention described is to be considered as exemplary only. many changes Those skilled in the art will know what can be done without departing from the spirit of the invention or the scope of the claims. It would be obvious.

international search report Continuation of front page (81) Designated countries EP (AT, BE, CH, DE.

DK, ES, FR, GB, GR, IT, LU, MC, NL, SE), AU, CA, FX, JP, N.

(72) Inventor Steven Chan Niss New Chassis, USA -state 08816 East Brunswick Gloucester Court 29 (72) Inventor Wu Keian United States of America Illinois 60514 Clarendon Hills Tennessee Drive 7368 Apartment 8-106

Claims (1)

[Claims] 1. A natural antioxidant composition for the stabilization of polyunsaturated oils, characterized in that it comprises tocopherol, ascorbic acid, citric acid and phospholipids. 2. Additionally, about 10 to about 62.5% tocopherol, about 1.5 to about 20% by weight; % ascorbic acid, citric acid in an amount of about 1.5 to about 20% by weight, and phospholipid in an amount of about 26 to about 85% by weight. Inhibitor composition. 3. Further, the amount of tocopherol is about 29.4% by weight, the amount of ascorpivic acid is about 5.9% by weight, the amount of citric acid is about 5.9% by weight, and the amount of phospholipid is about 58% by weight. Antioxidant set according to claim 2, characterized in that: .8% by weight. A product. 4. The acid according to claim 1, further comprising rosemary extract. Antioxidant composition. 5. Further, tocopherol in an amount of about 6.5 to about 54% by weight, ascorbic acid in an amount of about 1.2 to about 16% by weight, citric acid in an amount of about 1.2 to about 16% by weight, about 17 to about 5. The antioxidant composition of claim 4, characterized in that it has phospholipids in an amount of 77% by weight and rosemary extract in an amount of about 6.5 to about 54% by weight. 6. Furthermore, the amount of tocopherol is about 22.7% by weight, the amount of ascorbic acid is about 4.5% by weight, the amount of citric acid is about 4.5% by weight, and the amount of phospholipid is about 45% by weight. .5% by weight, and the amount of rosemary extract is about 27.7% by weight. The antioxidant composition according to claim 5, characterized in that: 7. Tocopherol, ascorbic acid, citric acid, soy phospholipid and rosemary A natural antioxidant composition for the stabilization of polyunsaturated oils, characterized in that it contains a - extract. 8. Further, tocopherol in an amount of about 6.5 to about 54% by weight, ascorbic acid in an amount of about 1.2 to about 16% by weight, citric acid in an amount of about 1.2 to about 16% by weight, about 17 to about soy phospholipids in an amount of 77% by weight and rosema in an amount of about 6.5 to about 54% by weight. Antioxidant composition according to claim 7, characterized in that it has Leigh extract. 9. Further, the amount of tocopherol is about 22.7% by weight, the amount of ascorbic acid is about 4.5% by weight, the amount of citric acid is about 4.5% by weight, and the amount of soybean phosphorus is about 4.5% by weight. Antioxidant composition according to claim 8, characterized in that the amount of rosemary extract is about 45.5% by weight and the amount of rosemary extract is about 22.7% by weight. 10. Tocoff, characterized in that it contains ascorbic acid, citric acid and phospholipids Natural antioxidant composition for the stabilization of erol-rich oils. 11. further characterized by having ascorbic acid in an amount of about 2 to about 27% by weight, citric acid in an amount of about 2 to about 27% by weight, and phospholipids in an amount of about 56 to about 95% by weight. The antioxidant composition according to claim 10. 12. Further characterized in that the amount of ascorbic acid is about 8.3% by weight, the amount of citric acid is about 8.3% by weight, and the amount of phospholipid is about 83.4% by weight. Item 12. The antioxidant composition according to Item 11. 13. The antioxidant composition according to claim 10, further comprising rosemary extract. 14. Additionally, ascorbic acid in an amount of about 1.8 to about 23%, citric acid in an amount of about 1.8 to about 23%, phospholipids in an amount of about 35 to about 90%, and about 5 to about Antioxidant composition according to claim 13, characterized in that it has rosemary extract in an amount of 45% by weight. 15. Furthermore, the amount of ascorbic acid is about 6.9% by weight, the amount of citric acid is about 6.9% by weight, the amount of phospholipid is about 70% by weight, and the amount of rosemary extract is about 17% by weight. 13. Antioxidant composition according to claim 12, characterized in that: .2% by weight. 16. A set of natural antioxidants for the stabilization of tocopherol-rich oils, characterized by containing ascorbic acid, citric acid, soybean fat and rosemary extract. A product. 17. Additionally, ascorbic acid in an amount of about 8 to about 23% by weight, citric acid in an amount of about 1.8 to about 23% by weight, soy phospholipid in an amount of about 35 to about 70% by weight, and about 5 to about 45% by weight. as claimed in claim 16, characterized in that it has rosemary extract in an amount of % by weight. Antioxidant composition. 18. Further, the amount of ascorbic acid is about 6.9% by weight, the amount of citric acid is about 6.9% by weight, the amount of soybean phospholipid is about 83.4% by weight, and the amount of rosemary is about 6.9% by weight. -Antioxidant composition according to claim 17, characterized in that the amount of extract is about 17.2% by weight. 19. Tocofe in an amount of about 0.05 to about 0.2% by weight, all based on the weight of the fish oil. roll, ascorbic acid in an amount of about 0.01 to about 0.04% by weight, citric acid in an amount of about 0.01 to about 0.04% by weight, and citric acid in an amount of about 0.1 to about 0.4% by weight. A fish oil comprising an antioxidant composition characterized in that it comprises deoiled soybean phospholipids. 20. 20. A fish oil comprising the antioxidant composition of claim 19, further comprising rosemary extract in an amount of about 0.05 to about 0.2% by weight of the fish oil. 21. In addition, tocopherols in an amount of approximately 0.1% by weight based on the weight of all fish oils. ascorbic acid in an amount of about 0.02% by weight, citric acid in an amount of about 0.02% by weight and deoiled soybean phospholipids in an amount of about 0.2% by weight and about 0.1% by weight. Fish oil comprising an antioxidant composition according to claim 20, characterized in that it has a rosemary extract of: 22. Asbestos in an amount of about 0.01 to about 0.04% by weight, all based on the weight of the vegetable oil. corbic acid, citric acid in an amount of about 0.01% to about 0.04% by weight, and about 0.1% to about 0.0% by weight. A tomato containing antioxidant characterized in that it contains deoiled soybean phospholipids in an amount of 4% by weight. Vegetable oil rich in copherol. 23. 23. The vegetable oil comprising the antioxidant composition of claim 22, further comprising rosemary extract in an amount of about 0.25 to about 0.1% by weight of the vegetable oil. 24. Additionally, an amount of Ascor in an amount of about 0.02% by weight, all based on the weight of the vegetable oil. citric acid in an amount of about 0.02% by weight, deoiled soybean phospholipids in an amount of about 0.2% by weight, and rosemary extract in an amount of about 0.05% by weight; A vegetable oil comprising the antioxidant composition of claim 23. 25. Specially contains tocopherol, ascorbic acid, citric acid and phospholipids. A vegetable oil antioxidant composition. 26. Tocof in an amount effective in stabilizing polyunsaturated oils with low odor and color. Natural antioxidant composition for the stabilization of polyunsaturated oils, characterized in that it contains erol, ascorbic acid, citric acid and modified vegetable phospholipids. 27. Additionally, tocopherol in an amount of about 10 to about 62.5%, ascorbic acid in an amount of about 1.5 to about 20%, citric acid in an amount of about 1.5 to about 20%, and about 26 to about 20% by weight. Antioxidant composition according to claim 26, characterized in that it has an amount of improved plant phospholipids of 85% by weight. 28. Furthermore, the amount of tocopherol is about 29.4% by weight, the amount of ascorbic acid is about 5.9% by weight, the amount of citric acid is about 5.9% by weight, and the amount of improved plant phospholipids is about 5.9% by weight. Antioxidant composition according to claim 27, characterized in that it is about 58.8% by weight. 29. Additionally, it contains an effective amount of rosemary extract to further stabilize polyunsaturated oils. The antioxidant composition according to claim 26, characterized in that: 30. Additionally, tocopherol in an amount of about 6.5 to about 54% by weight, phosphoscorbic acid in an amount of about 1.2 to about 16% by weight, citric acid in an amount of about 1.2 to about 16% by weight, about 1 30. The antioxidant set of claim 29, characterized in that the antioxidant set has an amount of improved plant phospholipids of 7 to about 77% by weight and rosemary extract in an amount of about 6.5 to about 54% by weight. A product. 31. Furthermore, the amount of tocopherol is about 22.7% by weight, the amount of ascorbic acid is about 4.5% by weight, the amount of citric acid is about 4.5% by weight, and the amount of improved plant phospholipid is about 4.5% by weight. 31. The antioxidant composition of claim 30, wherein the antioxidant composition is about 45.5% by weight and the amount of rosemary extract is about 22.7% by weight. 32. A natural antioxidant for the stabilization of polyunsaturated oils, characterized in that it contains tocopherol, ascorbic acid, citric acid, modified soybean phospholipids and rosemary extract in amounts effective for stabilizing polyunsaturated oils. Composition. 33. and about 6.5% to about 54% tocopherol, about 1.2% to about 16% by weight. ascorbic acid in an amount of % by weight, citric acid in an amount of about 1.2 to about 16% by weight, modified soy phospholipid in an amount of about 17 to about 77% by weight, and an amount of about 6.5 to about 54% by weight. Antioxidant composition according to claim 32, characterized in that it comprises rosemary extract. 34. Furthermore, the amount of tocopherol is about 22.7% by weight, the amount of ascorbic acid is about 4.5% by weight, the amount of citric acid is about 4.5% by weight, and the amount of improved soybean phospholipid is about 4.5% by weight. 34. The antioxidant composition of claim 33, wherein the antioxidant composition is about 45.5% by weight and the amount of rosemary extract is about 22.7% by weight. 35. Ascorbic acid, quenchant, in an amount effective to stabilize tocopherol-rich oils. A natural antioxidant composition for the stabilization of tocopherol-rich oils, characterized in that it comprises phosphoric acid and modified soybean phospholipids. 36. further characterized by having ascorbic acid in an amount of about 2 to about 27% by weight, citric acid in an amount of about 2 to about 27% by weight, and an improved plant phospholipid in an amount of about 56 to about 95% by weight; The antioxidant composition according to claim 35. 37. Furthermore, the amount of ascorbic acid is about 8.3% by weight, the amount of citric acid is about 8.3% by weight, and the amount of plant phospholipid is about 83.4% by weight. 37. The antioxidant composition of claim 36, wherein the antioxidant composition has the following characteristics. 38. Antioxidant composition according to claim 35, characterized in that it has an amount of rosemary extract effective for further stabilizing the tocopherol-rich oil. 39. Additionally, ascorbic acid in an amount of about 1.8 to about 23% by weight, citric acid in an amount of about 1.8 to about 23% by weight, modified phospholipids in an amount of about 35 to about 90% by weight, and Antioxidant composition according to claim 38, characterized in that it has rosemary extract in an amount of about 45% by weight. 40. Further, the amount of ascorbic acid is about 6.9% by weight, the amount of citric acid is about 6.9% by weight, the amount of improved plant phospholipid is about 70% by weight, and the amount of rosemary is about 70% by weight. -Antioxidant composition according to claim 37, characterized in that the amount of extract is about 17.2% by weight. 41. Ascorbic acid, quenchant, in an amount effective to stabilize tocopherol-rich oils. toco acid, improved soybean phospholipid and rosemary extract. Natural antioxidant composition for stabilization of ferol-rich oils. 42. Additionally, ascorbic acid in an amount of about 1.8 to about 23% by weight, citric acid in an amount of about 1.8 to about 23% by weight, modified soy phospholipid in an amount of about 35 to about 70% by weight, and about 5% by weight. 42. The antioxidant composition of claim 41, characterized in that it has rosemary extract in an amount of ~45% by weight. 43. Further, the amount of ascorbic acid is about 6.9% by weight, the amount of citric acid is about 6.9% by weight, the amount of improved soybean phospholipid is about 83.4% by weight, and the amount of rosemary extract is about 6.9% by weight. Claim 42, characterized in that the amount is about 17.2% by weight. Antioxidant composition. 44. Tocofe in an amount of about 0.05 to about 0.2% by weight, all based on the weight of the fish oil. roll, ascorbic acid in an amount of about 0.01 to about 0.04% by weight, citric acid in an amount of about 0.01 to about 0.04% by weight, and about 0.1 to about 0.4% by weight. Improved oil removal large A fish oil comprising an antioxidant composition, characterized in that it comprises bean phospholipids. 45. 45. A fish oil comprising the antioxidant composition of claim 44, further comprising rosemary extract in an amount of about 0.05 to about 0.2% by weight of the fish oil. 46. In addition, tocopherols in an amount of about 0.1% by weight, all based on the weight of the fish oil. ascorbic acid in an amount of about 0.02% by weight, citric acid in an amount of about 0.02% by weight, modified deoiled soybean phospholipid in an amount of about 0.2% by weight, and an amount of 0.1% by weight. Rosema 46. The antioxidant composition according to claim 45, characterized in that it has Mu fish oil. 47. Asbestos in an amount of about 0.01 to about 0.04% by weight, all based on the weight of the vegetable oil. corbic acid, citric acid in an amount of about 0.01% to about 0.04% by weight, and about 0.1% to about 0.0% by weight. An antioxidant set comprising modified deoiled soybean phospholipids in an amount of 4% by weight. Vegetable oils rich in tocopherols. 48. 48. A vegetable oil comprising the antioxidant composition of claim 47, further comprising rosemary extract in an amount of about 0.25 to about 0.1% by weight of the vegetable oil. 49. Additionally, an amount of Ascor in an amount of about 0.02% by weight, all based on the weight of the vegetable oil. citric acid in an amount of about 0.02% by weight; modified deoiled soybeans in an amount of about 0.2% by weight; phospholipids; and rosemary extract in an amount of about 0.05% by weight. 49. A vegetable oil comprising the antioxidant composition of claim 48. 50. Tocopherol, ascorbic acid, and quenchant in amounts effective to stabilize vegetable oils. 1. A vegetable oil antioxidant composition comprising phosphoric acid and an improved vegetable phospholipid. 51. Crude vegetable lecithin is extracted with water and then freeze-dried to remove water. An improved plant characterized by a lighter color and lower odor and aroma properties. Things lecithin. 52. Improved vegetable lecithin according to claim 51, further characterized in that the starting material is soybean wet gum. 53. 53. The improved soy lecithin of claim 52, further characterized in that the water comprises about 2 to about 5 times the wet gum (w/v). 54. 53. The improved soy lecithin of claim 52, further characterized in that the water comprises about 3 to about 5 times the wet gum (w/v). 55. Characterized by a low carbohydrate concentration and thus improved color stability during heating, produced by extracting crude plant phospholipids with an aqueous alkanol solvent and then freeze-drying the extracted phospholipids under vacuum. Improved phospholipids. 56. The improved phospholipid according to claim 55, further comprising crude lecithin or soybean lecithin. 57. Furthermore, the aqueous alkanol solvents are isopropanol, ethanol and methane. Improved phospholipid according to claim 55, characterized in that it is selected from the group consisting of phospholipids. 58. Form a solution of crude vegetable lecithin in an organic solvent and dilute the lecithin solution with an aqueous alkanosol. The modified phospholipids were recovered by extraction with a solvent and removing the solvent under vacuum. A method for producing an improved plant phospholipid characterized by: 59. Dissolving ascorbic acid in a polar solvent to form a solution; phospholipid mixing a solution of ascorbic acid with a solution of phospholipids; and removing the solvent from said mixture to form a product that is soluble in the nonpolar solvent. 1. A method for producing an oil-soluble antioxidant composition, comprising: producing an oil-soluble antioxidant composition. 60. Ascorbic acid can be added to a lower alkyl group having up to 3 carbon atoms in the alkyl group. Dissolving the phospholipid in a paraffin series hydrocarbon having 5 to 8 carbon atoms in the molecule to form a solution. and; mixing a solution of ascorbic acid with a solution of phospholipids; removing the solvent from said mixture; and ascorbic acid-phospholipid antioxidant with increased oil solubility. A method for producing an oil-soluble antioxidant, comprising: recovering an inhibitor composition. 61. Further characterized in that the phospholipids are derived from a plant material selected from the group consisting of soybean, rice, corn, cottonseed, rapeseed, canola and compositions thereof. 61. The method of claim 60. 62. 61. The method of claim 60, further characterized in that the phospholipid is a deoiled soybean phospholipid. 63. Furthermore, the lower alkyl alcohol is anhydrous ethanol. 61. The method of claim 60. 64. 61. A method according to claim 60, further characterized in that the second organic solvent is hexane. 65. 61. The method according to claim 60, further characterized in that the weight ratio of ascorbic acid to phospholipid is 1:1.5 to 1:60. 66. Additionally, the ascorbic acid-phospholipid composition may be combined with other antioxidant components. 61. The method according to claim 60, characterized in that: 67. Additionally, the ascorbic acid-phospholipid composition is combined with an antioxidant selected from the group consisting of citric acid, tocopherol, rosemary extract, and mixtures thereof. 61. The method according to claim 60, characterized in that: 68. 61. Process according to claim 60, characterized in that the solvent is completely removed from the mixture and the dry ascorbic acid-phospholipid composition is recovered. 69. Dissolving ascorbic acid in a polar solvent to form a solution; phospholipid dissolving the substance in a non-polar solvent to form a solution thereof; mixing a solution of ascorbic acid with a solution of phospholipid; and removing the solvent from said mixture to form a product that is soluble in the non-polar solvent. to generate An oil-soluble antioxidant composition produced by a method characterized by: 70. Ascorbic acid can be added to a lower alkyl group having up to 3 carbon atoms in the alkyl group. Dissolving the phospholipid in a paraffin series hydrocarbon having 5 to 8 carbon atoms in the molecule to form a solution. and; mixing a solution of ascorbic acid with a solution of phospholipids; removing the solvent from said mixture; and ascorbic acid-phospholipid antioxidant with increased oil solubility. An oil-soluble antioxidant composition with increased oil solubility produced by a method comprising: recovering an inhibitor.