WO2012036743A1 - Stable edible fluid fats and oils and improved ascorbic acid compositions to produce same - Google Patents

Stable edible fluid fats and oils and improved ascorbic acid compositions to produce same Download PDF

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Publication number
WO2012036743A1
WO2012036743A1 PCT/US2011/001599 US2011001599W WO2012036743A1 WO 2012036743 A1 WO2012036743 A1 WO 2012036743A1 US 2011001599 W US2011001599 W US 2011001599W WO 2012036743 A1 WO2012036743 A1 WO 2012036743A1
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Prior art keywords
ascorbic acid
oil
less
micron
fatty acids
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PCT/US2011/001599
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French (fr)
Inventor
Donald Berdahl
Gregory S. Reynhout
James Barren
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Kalamazoo Holdings, Inc.
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Publication of WO2012036743A1 publication Critical patent/WO2012036743A1/en

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    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
    • A23L3/3463—Organic compounds; Microorganisms; Enzymes
    • A23L3/3481—Organic compounds containing oxygen
    • A23L3/3508—Organic compounds containing oxygen containing carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B5/00—Preserving by using additives, e.g. anti-oxidants
    • C11B5/0021—Preserving by using additives, e.g. anti-oxidants containing oxygen
    • C11B5/0028—Carboxylic acids; Their derivates
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs

Definitions

  • Ascorbic is a food additive with that serves a variety of functions in foods. It is an excellent antioxidant / stabilizer under certain circumstances. For example, it can be used to prolong the shelf life of vegetables oils, where its beneficial role appears to be in part due to its ability to reduce and thereby recycle oxidized tocopherol intermediates. As oils oxidize, peroxyl- and alkoxyl radical intermediates are formed. Tocopherols, which are natural antioxidants normally present in vegetable oils, donate a phenolic hydrogen atom to the peroxyl and / or alkoxyl radicals, effectively preventing them from carrying on the oxidation radical chain reaction. In the process, tocopherol radicals are produced.
  • Tocopherols are not naturally present in animal fats, but when added are very effective stabilizers. Ascorbic acid / tocopherol combinations in animal fats have proved to be very powerful antioxidant combinations.
  • US Patent No. 5,230,836 describes an antioxidant composition consisting essentially of solid particles of ascorbic acid which are less than about 38 microns in size on their largest dimension and their use in stabilizing fatty foods, including food oils. Additional disclosure pertains to an antioxidant composition comprising solid ascorbic acid particles in which essentially all of the particles are less than 20 microns in size on their largest dimension and, further, an
  • antioxidant composition comprising solid ascorbic acid particles in which 50% of the particles are less than 10 microns in size on their largest dimension.
  • ASCORBALOX is a registered trademark of Kalsec, Inc. This product by itself and in combination with other antioxidants, such as rosemary extract and / or tocopherols, is very useful in the stabilization of vegetable oils, animal fats and a variety of food products.
  • the utility of ASCORBALOX® in oil systems is limited by appearance and handling issues. Due to the particulate nature of ascorbic acid and its insolubility in vegetable oil, the oils treated with this product appear hazy or cloudy.
  • particulate ascorbic acid consisting essentially of solid particles of ascorbic acid which are less than about 1.0 micron in size, including less than about 0.5 micron in size, on their largest dimension that are effective stabilizers of edible fluid fats and oils.
  • ascorbic acid particles of this dimension provide treated oil with a significantly improved visual appearance over oils treated with the ascorbic acid compositions of US Patent No. 5,230,836.
  • a significant reduction in haze anjncrease in visual clarity
  • significant reduction in the amount of ascorbic acid that settles out of the oil as well as an increase in time before settling occurs can be obtained.
  • compositions of ascorbic acid consisting essentially of solid particles of ascorbic acid which are less than about one micron in size on their largest dimension, including ascorbic acid particles which are less than about 0.5 microns in size on their largest dimension, and suspended in a fluid edible carrier, which solid ascorbic acid particles are indefinitely suspendable in a fluid fat or oil, without sedimentation at 1 x g, and are transparent or nearly transparent in the fluid fat or oil which is stabilized by the ascorbic acid composition therein.
  • the stabilizing compositions of the instant invention exhibit improved performance characteristics compared to ascorbic acid compositions of US Patent No. 5,230,836 and serve as an antioxidant in foods, vegetable oils, shortenings and animal fats.
  • compositions comprising ascorbic acid consisting essentially of solid particles of ascorbic acid which are less than about one micron in size on their largest dimension in combination with other antioxidants, including, but not limited to tocopherols, Labiatae herb extracts, rosemary extracts, tea extracts, oregano extracts, BHA, BHT, propyl gallate, TBHQ, and hydrolyzed proteins, including hydrolyzed pea proteins.
  • antioxidants including, but not limited to tocopherols, Labiatae herb extracts, rosemary extracts, tea extracts, oregano extracts, BHA, BHT, propyl gallate, TBHQ, and hydrolyzed proteins, including hydrolyzed pea proteins.
  • composition of ascorbic acid consisting essentially of solid particles of ascorbic acid which are less than about 0.5 micron in size on their largest dimension and suspended in a fluid edible carrier, which solid ascorbic acid particles are indefinitely suspendable in a fluid fat or oil, without sedimentation at 1 x g and transparent or nearly transparent in the fluid fat or oil, which is stabilized by the ascorbic acid composition therein.
  • compositions comprising ascorbic acid consisting essentially of solid particles of ascorbic acid which are less than about 0.5 micron in size on their largest dimension in combination with other antioxidants, including, but not limited to tocopherols, Labiatae herb extracts, rosemary extracts, tea extracts, oregano extracts, BHA, BHT, propyl gallate, TBHQ, hydrolyzed proteins, including hydrolyzed pea proteins or Maillard reaction products or mixtures thereof.
  • antioxidants including, but not limited tocopherols, Labiatae herb extracts, rosemary extracts, tea extracts, oregano extracts, BHA, BHT, propyl gallate, TBHQ, hydrolyzed proteins, including hydrolyzed pea proteins or Maillard reaction products or mixtures thereof.
  • a stabilizing composition comprising solid particles of ascorbic acid which are less than about 1.0 micron in size on their largest dimension, wherein the solid particles are dispersed in an edible substance, such a
  • stabilizing composition wherein the solid particles of ascorbic acid are less than about 0.5 micron in size on their largest dimension, wherein the solid particles are dispersed in an edible substance, such a
  • stabilizing composition wherein the edible substance is an edible fluid fat or oil, such a
  • stabilizing composition further comprising another antioxidant, such a
  • stabilizing composition wherein the another antioxidant is selected from tocopherols, Labiatae herb extracts, rosemary extracts, tea extracts, oregano extracts, BHA, BHT, propyl gallate, TBHQ, hydrolyzed proteins, including hydrolyzed pea proteins, Maillard reaction products and mixtures thereof, such a
  • stabilizing composition further comprising a compound selected from glycerol esters; lecithin and lecithin derivatives; mono glycerides; diglycerides; mixtures of mono and diglycerides; mixtures of mono-, di- and triglycerides; capric / caprylic diglycerides; glycerol monolaurate; ethoxylated glycerol esters; ethoxylated fatty acids; propylene glycol stearate; ethoxylated fatty acids and oils; ethoxylated alcohols; sorbitan derivatives; decaglycerol tetraoleate and chemically related species; sulfosuccinates and derivatives; whey protein-based dispersants; silicone glycol copolymers; stearic acid; fatty acids; fatty alcohols; medium-chain fatty acids; medium-chain fatty alcohols; sodium stearoyl-2- lactylate; polyoxyethylene (20)
  • the invention pertains to a method of preparing solid particles of ascorbic acid which are less than about 1.0 micron in size on their largest dimension comprising, reducing the particle size of ascorbic acid solids by grinding ascorbic acid to a particle size of less than about 1.0 micron in size, and wherein the solid particles of ascorbic acid are dispersed in an edible substance, such a
  • silicone glycol copolymers stearic acid; fatty acids; fatty alcohols; medium-chain fatty acids; medium-chain fatty alcohols; sodium stearoyl-2-lactylate;
  • polyglycerol polyricinoleate decaglycerol decaoleate; and mixtures thereof, such a
  • method further comprising the step of separating the particles less than about one micron using a mechanical means including a centrifuge, filter or seive, such a
  • a mechanical means including a centrifuge, filter or seive
  • method of preparing an antioxidant composition comprising, the step of milling a mixture of ascorbic acid, rosemary extract and a food grade surfactant, wherein the ascorbic acid particles in the finished product are less than one micron on their largest dimension, such a
  • fluid fats and oils may be stabilized by the addition of compositions comprising particulate ascorbic acid of small enough dimension that the particles remain suspended by the action of Brownian motion. Moreover, if the particles of ascorbic acid are small enough, they lose the ability to scatter light and become transparent, or nearly so.
  • particulate ascorbic acid of the appropriate dimensions. This can be
  • milling or ablation is aided by the addition of ingredients with surface active properties.
  • Such components are an important component of the invention and include food grade surface active ingredients such as those found in McCutcheon's handbook of surfactants. It is important that the surface active ingredients used in the application are food grade materials, since the material will be used in food products. This presents a challenge, because food grade surface active ingredients are a limited subset of surface active ingredients and may not include the most effective structures for effecting particle size reduction.
  • the necessary food-grade surface modifying and / or aggregation-preventing substances include, but are not limited to: glycerol esters, lecithin and lecithin derivatives, mono glycerides, diglycerides, mixtures of mono and diglycerides, mixtures of mono-, di- and triglycerides, capric / caprylic diglycerides, glycerol monolaurate, ethoxylated glycerol esters, ethoxylated fatty acids, propylene glycol stearate, ethoxylated fatty acids and oils, ethoxylated alcohols, sorbitan derivatives, decaglycerol tetraoleate and chemically related species,
  • sulfosuccinates and derivatives whey protein-based dispersants, silicone glycol copolymers, stearic acid, fatty acids, fatty alcohols, medium-chain fatty acids, medium-chain fatty alcohols, sodium stearoyl-2-lactylate, polyoxyethylene (20) tritallate and maleic or succinic anhydride derivatives, polyglycerol polyricinoleate, decaglycerol decaoleate, or mixtures thereof.
  • Another important technical feature of the invention deals with preventing the agglomeration of non-sedimenting small particles, once prepared, into aggregates of larger size that form over time, creating hazy suspensions or precipitate in the form of sediment.
  • Surface active substances such as those listed above may be added to the composition to prevent or slow the
  • Particles of the appropriate size may also be obtained by separating appropriately sized "fines" from a mixture containing a range of particle sizes by using various sieving or other particle size separation techniques known in the art, including sedimentation, centrifugation, precipitation, filtration and the like.
  • Example 1 Preparation of ascorbic acid of particle size ⁇ 5 microns.
  • Dry ascorbic acid powder 25% by weight, was combined with 74% by weight of canola oil with 1% by weight of DREWPOL ® PGPR (polyglycerol polyricinoleate) and mixed using a high shear mixer at low speed for 15 minutes.
  • DREWPOL ® PGPR polyglycerol polyricinoleate
  • This mixture was introduced into a Buhler Laboratory K8 bead mill with 600 ml of 0.5 mm YTZ (yttria-stabilized zerconia) media and recirculated for 90 minutes after which a second 1% by weight of DREWPOL ® PGPR was added and recirculation continued for a total of 150 minutes.
  • the resulting milled ascorbic particle size was measured with a Horiba LA930 and was found to have a mean particle size of 0.99 microns with 100% ⁇ 5 microns.
  • DREWPOL ® is a registered trademark of the Stepan Company.
  • Example 2 Preparation of ascorbic acid of particle size ⁇ 1 microns.
  • the resulting milled ascorbic was diluted with an additional 5% canola oil and 5% DREWPOL ® 10- 10-0 and milled in a PML2-Superflow 4 mill with 0.3 mm YTZ media for 120 minutes.
  • the particle size of this milled ascorbic reached a mean size of 0.40 microns with 98% of all particles by volume ⁇ 0.75 microns.
  • Example 3 A further example of the preparation of ascorbic acid compositions of reduced particle size.
  • Canola oil 4050 g was combined with 67.5 g DREWPOL ® 10-10-0
  • Samples of 3A, 3B and 3C were dosed separately into canola oil at levels giving 200 ppm ascorbic acid in the final dosed oil and 50 g of each dosed oil was transferred to a 55 ml clear glass centrifuge tube, stoppered and allowed to sit undisturbed at 1 x g to visually examine the appearance and settling behavior.
  • a control sample of canola oil dosed at the same level with ASCORBALOX ® the commercially available inventive composition of US Patent No. 5,230,836, was prepared coincidentally. The results after 50 days of undisturbed storage are shown in Table 2.
  • Example 4 Preparation of ascorbic acid of particle size ⁇ 0.5 microns.
  • Example 2 The milled output of Example 2 is placed in a micromedia mill with 0.05 mm media, diluted with additional vegetable oil and food grade surface active agents and milled for 120 minutes.
  • the output shows particle size distribution 100% below 0.5 microns. Further milling reduces the particle size to 0.2 microns and below.
  • the material produced by this method when dispersed in vegetable oil is clear and shows no sedimentation after 50 days of undisturbed storage.
  • Example 5 Stabilization of Vegetable oil using super-micronized ascorbic acid.
  • Sample 5A was prepared from a rosemary extract and a milled ascorbic acid suspension where 50% of ascorbic particles are less than 10 microns
  • Sample 5B was prepared from a rosemary extract and a more finely ground ascorbic acid where 98% of ascorbic particles were less than one micron on their largest dimension.
  • the preparations were formulated to provide compositions with equal levels of rosemary extract and milled ascorbic acid. These compositions were separately added to canola oil at a level of 2000 ppm and after stirring, observations on optical clarity and sedimentation rate at 1 x g were made. Initially, the oil containing Sample 5B appeared much less hazy than the oil containing Sample 5A. After 50 days of undisturbed settling at 1 x g, the oil fortified with Sample 5B showed less than 10% of the sedimentation of the oil sample treated with Sample 5A.
  • Example 6 Stabilization of Vegetable oil using super-micronized ascorbic acid from Example 4.
  • the milled ascorbic acid preparation from Example 4 is combined with a rosemary extract to provide compositions with equal levels of rosemary extract and milled ascorbic acid.
  • This composition is added to canola oil at a level of 2000 ppm to observe appearance and sedimentation rate.
  • the initial oil sample prepared from the ⁇ 0.5 micron ascorbic acid is largely transparent when compared to similar samples prepared with commercially available
  • ASCORBALOX ® - containing preparations After 50 days of undisturbed settling at 1 x g, the oil fortified with this super micronized ascorbic acid and rosemary extract shows no sedimentation of the oil sample.
  • the initial oil sample prepared from the ⁇ 0.2 micron ascorbic acid is largely transparent.
  • the oil fortified with this super micronized ascorbic acid and rosemary extract shows no sedimentation of the oil sample and has superior appearance to identical oils treated with commercially available ASCORBALOX ® - containing preparations.
  • the oil treated with the ⁇ 0.2 micron ascorbic acid shows equal or superior antioxidative stability to the samples prepared with commercially available ASCORBALOX ® - containing preparations.
  • the ascorbic acid compositions of the present invention are combined with tocopherols, Labiatae herb extracts, rosemary extracts, tea extracts, oregano extracts, BHA, BHT, propyl gallate, TBHQ, and hydrolyzed proteins, including hydrolyzed pea proteins, singly or in combination to create new antioxidant compositions suitable for use in oils, fluid fats and other foods.
  • Example 7 Demonstrating the formation of an ascorbic acid composition via a sieving process.
  • the ascorbic acid preparation resulting from Example 1 is subjected to a screening or sieving process using suitable equipment.
  • the material is placed in contact with a metallic or ceramic element having hole sizes of 0.5 microns.
  • the material is treated in a way to allow a portion of the particles less than 0.5 microns to pass through the element, together with a portion of the fluid carrier.
  • the material that passes the element contains ascorbic acid can be used as a stabilizer for vegetable oils or fluid animal without forming a sediment upon storage or presenting an unattractive hazy or cloudy appearance.
  • Example 8 Demonstrating the formation of an ascorbic acid composition via a centrifugation process.
  • Example 1 The ascorbic acid preparation of Example 1 is subjected to a
  • Centrifugation results in the formation of a pellet and a supernatant phase.
  • One skilled in the art can develop appropriate conditions for operating the centrifuge such that the supernatant phase contains particles less than 1 micron or less than 0.5 microns.
  • the supernatant can be separated from the pellet of solid ascorbic acid and used to stabilize vegetable oil as described above.
  • Example 9 Demonstrating the preparation of an antioxidant formulation prepared by the milling of a combination of ascorbic acid and rosemary extract.
  • a blend of ascorbic acid, rosemary extract, food grade surfactant and optionally vegetable oil as a thinner to control viscosity is milled using the equipment and methods described in Examples 1-4 to prepare antioxidant compositions that can be used to stabilize vegetable oil or fluid fats.

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Abstract

This invention to provides compositions of ascorbic acid consisting of solid particles of ascorbic acid which are less than about one micron in size on their largest dimension and suspended in a fluid edible carrier, which solid ascorbic acid particles are indefinitely suspendable in a fluid fat or oil, without sedimentation at 1 x g, and are transparent or nearly transparent in the fluid fat or oil which is stabilized by the ascorbic acid composition therein.

Description

STABLE EDIBLE FLUID FATS AND OILS AND IMPROVED ASCORBIC ACID COMPOSITIONS TO PRODUCE SAME
BACKGROUND OF THE INVENTION
[0001] Ascorbic is a food additive with that serves a variety of functions in foods. It is an excellent antioxidant / stabilizer under certain circumstances. For example, it can be used to prolong the shelf life of vegetables oils, where its beneficial role appears to be in part due to its ability to reduce and thereby recycle oxidized tocopherol intermediates. As oils oxidize, peroxyl- and alkoxyl radical intermediates are formed. Tocopherols, which are natural antioxidants normally present in vegetable oils, donate a phenolic hydrogen atom to the peroxyl and / or alkoxyl radicals, effectively preventing them from carrying on the oxidation radical chain reaction. In the process, tocopherol radicals are produced. These can be converted back into active tocopherols by the reducing action of ascorbic acid. Tocopherols are not naturally present in animal fats, but when added are very effective stabilizers. Ascorbic acid / tocopherol combinations in animal fats have proved to be very powerful antioxidant combinations.
[0002] US Patent No. 5,230,836 describes an antioxidant composition consisting essentially of solid particles of ascorbic acid which are less than about 38 microns in size on their largest dimension and their use in stabilizing fatty foods, including food oils. Additional disclosure pertains to an antioxidant composition comprising solid ascorbic acid particles in which essentially all of the particles are less than 20 microns in size on their largest dimension and, further, an
antioxidant composition comprising solid ascorbic acid particles in which 50% of the particles are less than 10 microns in size on their largest dimension. Such a product is now available on the market under the brand name ASCORBALOX®. ASCORBALOX is a registered trademark of Kalsec, Inc. This product by itself and in combination with other antioxidants, such as rosemary extract and / or tocopherols, is very useful in the stabilization of vegetable oils, animal fats and a variety of food products. Unfortunately, the utility of ASCORBALOX® in oil systems is limited by appearance and handling issues. Due to the particulate nature of ascorbic acid and its insolubility in vegetable oil, the oils treated with this product appear hazy or cloudy. Over time, the ascorbic acid composition described in US Patent No. 5,230,836 settles out of the oil and an unattractive sediment layer appears in the product. This settling phenomenon can present handling issues in the case of bulk transport and storage of oils, where, for example, a sludgy solid must be removed from a tanker truck after an oil delivery. Moreover, for oils packaged for retail sale, the cloudiness and/or sediment layer present an unattractive appearance which is unacceptable to consumers who select the ASCORBALOX® protected oil.
[0003] There is a need to provide oxidative stability to edible fluid fats and oils that is similar to or improved over that provided by the ascorbic acid
compositions of US Patent No. 5,230,836, which are about 10-38 microns in size on their largest dimension. There is a further need to stabilize edible fluid fats and oils with ascorbic acid in a manner in which the treated oil is more
transparent and sediment-free than when the ascorbic acid compositions of US Patent No. 5,230,836.
[0004] One approach to providing stabilized clear / non-sediment-forming stabilizing formulations for edible oils has been to chemically modify ascorbic acid, providing compounds such as ascorbyl palmitate. This and similar ester derivatives, though soluble in oils and fats, are not as effective as ascorbic acid at stabilizing the oils. They are also seen by some consumers as synthetic chemical compounds and are not preferred. [0005] Another approach to providing clear, stabilized, non-sediment-forming oils is to use the technology described in Australian Application No. 2003204456, in which ascorbic acid is solubilized in an excess of emulsifier with an HLB value of about 9 to 18, for example a polysorbate. In our hands, this technology has not provided oil with the stability one can achieve with particulate ascorbic acid and is therefore not preferred.
BRIEF SUMMARY OF THE INVENTION
[0006] We have discovered that particulate ascorbic acid consisting essentially of solid particles of ascorbic acid which are less than about 1.0 micron in size, including less than about 0.5 micron in size, on their largest dimension that are effective stabilizers of edible fluid fats and oils. We have unexpectedly found that ascorbic acid particles of this dimension provide treated oil with a significantly improved visual appearance over oils treated with the ascorbic acid compositions of US Patent No. 5,230,836. Depending upon the particle size of the ascorbic acid and the characteristics of the oil being treated, a significant reduction in haze (anjncrease in visual clarity) and significant reduction in the amount of ascorbic acid that settles out of the oil as well as an increase in time before settling occurs can be obtained. There is a particle size level below which, for a given oil, the treated oil remains indefinitely clear and transparent and sediment- free.
DETAILED DESCRIPTION OF THE INVENTION
[0007] It is the purpose of this invention to provide stabilizing compositions of ascorbic acid consisting essentially of solid particles of ascorbic acid which are less than about one micron in size on their largest dimension, including ascorbic acid particles which are less than about 0.5 microns in size on their largest dimension, and suspended in a fluid edible carrier, which solid ascorbic acid particles are indefinitely suspendable in a fluid fat or oil, without sedimentation at 1 x g, and are transparent or nearly transparent in the fluid fat or oil which is stabilized by the ascorbic acid composition therein.
[0008] The stabilizing compositions of the instant invention exhibit improved performance characteristics compared to ascorbic acid compositions of US Patent No. 5,230,836 and serve as an antioxidant in foods, vegetable oils, shortenings and animal fats.
[0009] It is a further purpose of this invention to provide compositions comprising ascorbic acid consisting essentially of solid particles of ascorbic acid which are less than about one micron in size on their largest dimension in combination with other antioxidants, including, but not limited to tocopherols, Labiatae herb extracts, rosemary extracts, tea extracts, oregano extracts, BHA, BHT, propyl gallate, TBHQ, and hydrolyzed proteins, including hydrolyzed pea proteins.
[0010] It is a further object of this invention to describe methods for preparing the inventive micronized ascorbic acid compositions, and stabilizing those
compositions by limiting aggregation (agglomeration) through the use of food grade emulsifiers (surfactants).
[001 ] It is a further object of this invention to provide methods for preparing the micronized ascorbic acid compositions which may aggregate upon storage and exhibit increased particle sizes over those observed immediately after the particle size reduction steps are completed, but in which the aggregation is readily reversed when the ascorbic acid composition is dispersed in an oil or fluid fat and stirred. These treated oils show similar levels of haze and sedimentation as those prepared from freshly micronized ascorbic acid which has not had sufficient time to aggregate. [0012] It is a further purpose of this invention to provide methods of stabilizing foods, including vegetable oils, shortenings and animal fats using the improved compositions.
[0013] It is a further purpose of this invention to provide methods for stabilizing foods containing the stabilized vegetable oils, shortenings and animal fats obtained through use of the ascorbic acid compositions.
[0014] It is a purpose of the present invention to provide ascorbic acid containing, stabilized fluid fats and oils of improved appearance which are transparent or nearly transparent and which are free from sediment over the course of at least two months or greater.
[0015] It is the purpose of this invention to provide a composition of ascorbic acid consisting essentially of solid particles of ascorbic acid which are less than about 0.5 micron in size on their largest dimension and suspended in a fluid edible carrier, which solid ascorbic acid particles are indefinitely suspendable in a fluid fat or oil, without sedimentation at 1 x g and transparent or nearly transparent in the fluid fat or oil, which is stabilized by the ascorbic acid composition therein.
[0016] It is a further purpose of this invention to provide compositions comprising ascorbic acid consisting essentially of solid particles of ascorbic acid which are less than about 0.5 micron in size on their largest dimension in combination with other antioxidants, including, but not limited to tocopherols, Labiatae herb extracts, rosemary extracts, tea extracts, oregano extracts, BHA, BHT, propyl gallate, TBHQ, hydrolyzed proteins, including hydrolyzed pea proteins or Maillard reaction products or mixtures thereof.
[0017] What we therefore believe to be comprised by our invention may be summarized inter alia in the following words: [0018] A stabilizing composition comprising solid particles of ascorbic acid which are less than about 1.0 micron in size on their largest dimension, wherein the solid particles are dispersed in an edible substance, such a
[0019] stabilizing composition wherein the solid particles of ascorbic acid are less than about 0.5 micron in size on their largest dimension, wherein the solid particles are dispersed in an edible substance, such a
[0020] stabilizing composition wherein the edible substance is an edible fluid fat or oil, such a
[0021] stabilizing composition further comprising another antioxidant, such a
[0022] stabilizing composition, wherein the another antioxidant is selected from tocopherols, Labiatae herb extracts, rosemary extracts, tea extracts, oregano extracts, BHA, BHT, propyl gallate, TBHQ, hydrolyzed proteins, including hydrolyzed pea proteins, Maillard reaction products and mixtures thereof, such a
[0023] stabilizing composition further comprising a compound selected from glycerol esters; lecithin and lecithin derivatives; mono glycerides; diglycerides; mixtures of mono and diglycerides; mixtures of mono-, di- and triglycerides; capric / caprylic diglycerides; glycerol monolaurate; ethoxylated glycerol esters; ethoxylated fatty acids; propylene glycol stearate; ethoxylated fatty acids and oils; ethoxylated alcohols; sorbitan derivatives; decaglycerol tetraoleate and chemically related species; sulfosuccinates and derivatives; whey protein-based dispersants; silicone glycol copolymers; stearic acid; fatty acids; fatty alcohols; medium-chain fatty acids; medium-chain fatty alcohols; sodium stearoyl-2- lactylate; polyoxyethylene (20) tritallate and maleic or succinic anhydride derivatives; polyglycerol polyricinoleate; decaglycerol decaoleate; and mixtures thereof, such a [0024] stabilized edible fluid fat or oil comprising a stabilizing composition comprising solid particles of ascorbic acid which are less than about 1.0 micron in size on their largest dimension and dispersed in an edible substance, and optionally comprising additional antioxidants.
[0025] Moreover, the invention pertains to a method of preparing solid particles of ascorbic acid which are less than about 1.0 micron in size on their largest dimension comprising, reducing the particle size of ascorbic acid solids by grinding ascorbic acid to a particle size of less than about 1.0 micron in size, and wherein the solid particles of ascorbic acid are dispersed in an edible substance, such a
[0026] method wherein the edible substance is an edible fluid fat or oil, such a
[0027] method wherein the grinding is performed in the presence of glycerol esters; lecithin and lecithin derivatives; mono glycerides; diglycerides; mixtures of mono and diglycerides; mixtures of mono-, di- and triglycerides; capric / caprylic diglycerides; glycerol monolaurate; ethoxylated glycerol esters; ethoxylated fatty acids; propylene glycol stearate; ethoxylated fatty acids and oils; ethoxylated alcohols; sorbitan derivatives; decaglycerol tetraoleate and chemically related species; sulfosuccinates and derivatives; whey protein-based dispersants;
silicone glycol copolymers; stearic acid; fatty acids; fatty alcohols; medium-chain fatty acids; medium-chain fatty alcohols; sodium stearoyl-2-lactylate;
polyoxyethylene (20) tritallate and maleic or succinic anhydride derivatives;
polyglycerol polyricinoleate; decaglycerol decaoleate; and mixtures thereof, such a
[0028] method further comprising the step of separating the particles less than about one micron using a mechanical means including a centrifuge, filter or seive, such a [0030] method of preparing an antioxidant composition comprising, the step of milling a mixture of ascorbic acid, rosemary extract and a food grade surfactant, wherein the ascorbic acid particles in the finished product are less than one micron on their largest dimension, such a
[0031] method, wherein the ascorbic acid particles in the finished product are less than 0.5 microns on their largest dimension, such a
[0032] method of treating an edible fluid fat or oil comprising, admixing the stabilizing composition with an edible fluid fat or oil, wherein after admixing, the edible fluid fat or oil is transparent and free from sediments after 50 days at 1 x g.
[0033] We have found that fluid fats and oils may be stabilized by the addition of compositions comprising particulate ascorbic acid of small enough dimension that the particles remain suspended by the action of Brownian motion. Moreover, if the particles of ascorbic acid are small enough, they lose the ability to scatter light and become transparent, or nearly so.
[0034] An important part of the invention deals with methods for forming
particulate ascorbic acid of the appropriate dimensions. This can be
accomplished by a process of reducing the particle size of commercially available, solid ascorbic acid using a variety of grinding or particle size reduction processes such as milling or ablation that are known in the art by way of various mills, grinders and particle size reducing equipment as known in the art. It is well known in the art that milling or ablation is aided by the addition of ingredients with surface active properties. Such components are an important component of the invention and include food grade surface active ingredients such as those found in McCutcheon's handbook of surfactants. It is important that the surface active ingredients used in the application are food grade materials, since the material will be used in food products. This presents a challenge, because food grade surface active ingredients are a limited subset of surface active ingredients and may not include the most effective structures for effecting particle size reduction. The necessary food-grade surface modifying and / or aggregation-preventing substances include, but are not limited to: glycerol esters, lecithin and lecithin derivatives, mono glycerides, diglycerides, mixtures of mono and diglycerides, mixtures of mono-, di- and triglycerides, capric / caprylic diglycerides, glycerol monolaurate, ethoxylated glycerol esters, ethoxylated fatty acids, propylene glycol stearate, ethoxylated fatty acids and oils, ethoxylated alcohols, sorbitan derivatives, decaglycerol tetraoleate and chemically related species,
sulfosuccinates and derivatives, whey protein-based dispersants, silicone glycol copolymers, stearic acid, fatty acids, fatty alcohols, medium-chain fatty acids, medium-chain fatty alcohols, sodium stearoyl-2-lactylate, polyoxyethylene (20) tritallate and maleic or succinic anhydride derivatives, polyglycerol polyricinoleate, decaglycerol decaoleate, or mixtures thereof.
[0035] Another important technical feature of the invention deals with preventing the agglomeration of non-sedimenting small particles, once prepared, into aggregates of larger size that form over time, creating hazy suspensions or precipitate in the form of sediment. Surface active substances such as those listed above may be added to the composition to prevent or slow the
agglomeration of smaller into larger particles.
[0036] We have found that freshly prepared ascorbic acid particles of the inventive composition re-agglomerate upon standing, and grow to particle sizes greater than 1 micron (See Example 3). Surprisingly, these agglomerated materials perform as well as freshly prepared non-agglomerated samples in terms of reduced haze and sedimentation when they are added to oils or fluid fats and incorporated or blended by simple low-shear stirring. Apparently the agglomerates that are formed are only loosely held together and easily break apart into their smaller constituents. [0037] Micro-particulate ascorbic acid of the appropriate size can also be formed by particle synthesis steps using a variety of precipitation or solid forming processes known in the art. These may involve crystallization, precipitation, evaporation, solvent / non solvent processes, chemical vapor deposition, supercritical fluid expansion or other techniques.
[0038] Particles of the appropriate size may also be obtained by separating appropriately sized "fines" from a mixture containing a range of particle sizes by using various sieving or other particle size separation techniques known in the art, including sedimentation, centrifugation, precipitation, filtration and the like.
Representative Examples
Example 1. Preparation of ascorbic acid of particle size <5 microns.
[0039] Dry ascorbic acid powder, 25% by weight, was combined with 74% by weight of canola oil with 1% by weight of DREWPOL® PGPR (polyglycerol polyricinoleate) and mixed using a high shear mixer at low speed for 15 minutes. This mixture was introduced into a Buhler Laboratory K8 bead mill with 600 ml of 0.5 mm YTZ (yttria-stabilized zerconia) media and recirculated for 90 minutes after which a second 1% by weight of DREWPOL® PGPR was added and recirculation continued for a total of 150 minutes. The resulting milled ascorbic particle size was measured with a Horiba LA930 and was found to have a mean particle size of 0.99 microns with 100% <5 microns. DREWPOL® is a registered trademark of the Stepan Company.
Example 2. Preparation of ascorbic acid of particle size <1 microns.
[0040] 3.6 Kg of canola oil was combined with 36 gm DREWPOL® 10-10-0
(Decaglycerol decaoleate), this was recirculated at a rate of 60kg/hr in a Buhler Laboratory K8 bead mill with 1.0 mm Zirconia TZP media as 720 gm of dry ascorbic acid powder was slowly added. This mixture was milled for 180 minutes. The particle size of this milled ascorbic reached a mean size of 0.92 microns with 98% of all particles by volume < 4.19 microns. The Buhler K8 media was replaced with 0.5 mm YTZ media the mixture thinned with an additional 5% canola oil and milling continued for an additional 50 minutes. The resulting milled ascorbic was diluted with an additional 5% canola oil and 5% DREWPOL® 10- 10-0 and milled in a PML2-Superflow 4 mill with 0.3 mm YTZ media for 120 minutes. The particle size of this milled ascorbic reached a mean size of 0.40 microns with 98% of all particles by volume < 0.75 microns.
Example 3. A further example of the preparation of ascorbic acid compositions of reduced particle size.
[0041] Canola oil, 4050 g, was combined with 67.5 g DREWPOL® 10-10-0
(decaglycerol decaoleate) with stirring and 1350 g of ascorbic acid was added slowly using a Silverson high shear rotor/stator. The material was mixed at 80% power for 15 minutes at which time it had reached a temperature of 50° C. The mixture was fed to a Buhler K8 mill where it was processed for 90 minutes using 0.65 mm YTZ media. 4270 g of milled product was recovered and split into two portions of 2914 g and 1455 g, respectively. The 2914 g lot was fed back into the K-8 mill and processed for another 45 minutes (total of 135 minutes). The mill was stopped and 2274 g of product was recovered. This material was labeled Sample 3A. The 1455 g lot from above was fed into a Buhler PML2 mill containing 0.2 mm YTZ media. This material was run in the MicroMedia configuration on the PML2 for 90 minutes. 460 g of the resultant product was retained and labeled Sample 3B. The additional product was added back into the hopper for a final run of 30 minutes in the PML2 with the same MicroMedia attachment. For this final step however, an industrial surfactant (Lubrizol 16000) was added to the mixture. After 30 minutes, a sample of 376g of product was retained and labeled as Sample 3C. Each of the samples was analyzed for particle size and the results are shown in Table 1.
Table 1. Particle size data from Example 3.
Figure imgf000013_0001
[0042] Samples of 3A, 3B and 3C were dosed separately into canola oil at levels giving 200 ppm ascorbic acid in the final dosed oil and 50 g of each dosed oil was transferred to a 55 ml clear glass centrifuge tube, stoppered and allowed to sit undisturbed at 1 x g to visually examine the appearance and settling behavior. A control sample of canola oil dosed at the same level with ASCORBALOX®, the commercially available inventive composition of US Patent No. 5,230,836, was prepared coincidentally. The results after 50 days of undisturbed storage are shown in Table 2.
Table 2. Appearance and settling data on samples dispersed in canola oil from Example 3 (Day 50).
Figure imgf000013_0002
[0043] An evaluation of the originally milled samples (3A, 3B and 3C) at 150 days after milling showed that particle size growth was occurring in samples 3A and 3B (particles up to 30 microns in diameter being observed). Sample 3C did not show appreciable particle growth - possibly due to the more effective industrial surfactant which was used. The aged samples (150 days after milling) were again dispersed in canola oil at 200 ppm ascorbic acid and subjected to the same appearance and settling test as described in Example 3. The results were identical to those shown in Table 2, indicating that the aggregation or
agglomeration which occurred in samples 3A and 3B did not affect their performance when dispersed in oil.
Example 4. Preparation of ascorbic acid of particle size <0.5 microns.
[0044] The milled output of Example 2 is placed in a micromedia mill with 0.05 mm media, diluted with additional vegetable oil and food grade surface active agents and milled for 120 minutes. The output shows particle size distribution 100% below 0.5 microns. Further milling reduces the particle size to 0.2 microns and below. The material produced by this method when dispersed in vegetable oil is clear and shows no sedimentation after 50 days of undisturbed storage.
Example 5. Stabilization of Vegetable oil using super-micronized ascorbic acid.
[0045] Two blends of ascorbic acid and rosemary extract were prepared. Sample 5A was prepared from a rosemary extract and a milled ascorbic acid suspension where 50% of ascorbic particles are less than 10 microns, and Sample 5B was prepared from a rosemary extract and a more finely ground ascorbic acid where 98% of ascorbic particles were less than one micron on their largest dimension. The preparations were formulated to provide compositions with equal levels of rosemary extract and milled ascorbic acid. These compositions were separately added to canola oil at a level of 2000 ppm and after stirring, observations on optical clarity and sedimentation rate at 1 x g were made. Initially, the oil containing Sample 5B appeared much less hazy than the oil containing Sample 5A. After 50 days of undisturbed settling at 1 x g, the oil fortified with Sample 5B showed less than 10% of the sedimentation of the oil sample treated with Sample 5A.
Example 6. Stabilization of Vegetable oil using super-micronized ascorbic acid from Example 4.
[0046] The milled ascorbic acid preparation from Example 4 is combined with a rosemary extract to provide compositions with equal levels of rosemary extract and milled ascorbic acid. This composition is added to canola oil at a level of 2000 ppm to observe appearance and sedimentation rate. The initial oil sample prepared from the <0.5 micron ascorbic acid is largely transparent when compared to similar samples prepared with commercially available
ASCORBALOX® - containing preparations. After 50 days of undisturbed settling at 1 x g, the oil fortified with this super micronized ascorbic acid and rosemary extract shows no sedimentation of the oil sample. The initial oil sample prepared from the <0.2 micron ascorbic acid is largely transparent. After 50 days of undisturbed settling the oil fortified with this super micronized ascorbic acid and rosemary extract shows no sedimentation of the oil sample and has superior appearance to identical oils treated with commercially available ASCORBALOX® - containing preparations. The oil treated with the <0.2 micron ascorbic acid shows equal or superior antioxidative stability to the samples prepared with commercially available ASCORBALOX® - containing preparations. In a similar manner, the ascorbic acid compositions of the present invention are combined with tocopherols, Labiatae herb extracts, rosemary extracts, tea extracts, oregano extracts, BHA, BHT, propyl gallate, TBHQ, and hydrolyzed proteins, including hydrolyzed pea proteins, singly or in combination to create new antioxidant compositions suitable for use in oils, fluid fats and other foods.
Example 7. Demonstrating the formation of an ascorbic acid composition via a sieving process. [0047] The ascorbic acid preparation resulting from Example 1 is subjected to a screening or sieving process using suitable equipment. In one case, the material is placed in contact with a metallic or ceramic element having hole sizes of 0.5 microns. The material is treated in a way to allow a portion of the particles less than 0.5 microns to pass through the element, together with a portion of the fluid carrier. The material that passes the element contains ascorbic acid can be used as a stabilizer for vegetable oils or fluid animal without forming a sediment upon storage or presenting an unattractive hazy or cloudy appearance.
Example 8. Demonstrating the formation of an ascorbic acid composition via a centrifugation process.
[0048] The ascorbic acid preparation of Example 1 is subjected to a
centrifugation process using suitable equipment (batch or continuous).
Centrifugation results in the formation of a pellet and a supernatant phase. One skilled in the art can develop appropriate conditions for operating the centrifuge such that the supernatant phase contains particles less than 1 micron or less than 0.5 microns. The supernatant can be separated from the pellet of solid ascorbic acid and used to stabilize vegetable oil as described above.
Example 9. Demonstrating the preparation of an antioxidant formulation prepared by the milling of a combination of ascorbic acid and rosemary extract.
[0049] A blend of ascorbic acid, rosemary extract, food grade surfactant and optionally vegetable oil as a thinner to control viscosity is milled using the equipment and methods described in Examples 1-4 to prepare antioxidant compositions that can be used to stabilize vegetable oil or fluid fats.

Claims

1. A stabilizing composition comprising solid particles of ascorbic acid which are less than about 1.0 micron in size on their largest dimension, wherein the solid particles are dispersed in an edible substance.
2. The stabilizing composition of Claim 1, wherein the solid particles of ascorbic acid are less than about 0.5 micron in size on their largest dimension, wherein the solid particles are dispersed in an edible substance.
3. The stabilizing composition of Claim 1 , wherein the edible substance is an edible fluid fat or oil.
4. The stabilizing composition of Claim 1 , further comprising one or more additional antioxidants.
5. The stabilizing composition of Claim 4, wherein the additional
antioxidant is selected from tocopherols, Labiatae herb extracts, rosemary extracts, tea extracts, oregano extracts, BHA, BHT, propyl gailate, TBHQ, hydrolyzed proteins, including hydrolyzed pea proteins, Mail lard reaction products and mixtures thereof.
6. The stabilizing composition of Claim 1 , further comprising a compound selected from glycerol esters; lecithin and lecithin derivatives; mono glycerides; diglycerides; mixtures of mono and diglycerides; mixtures of mono-, di- and triglycerides; capric / caprylic diglycerides; glycerol monoiaurate; ethoxylated glycerol esters; ethoxylated fatty acids;
propylene glycol stearate; ethoxylated fatty acids and oils; ethoxylated alcohols; sorbitan derivatives; decaglycerol tetraoleate and chemically related species; sulfosuccinates and derivatives; whey protein-based dispersants; silicone glycol copolymers; stearic acid; fatty acids; fatty alcohols; medium-chain fatty acids; medium-chain fatty alcohols;
sodium stearoyi-2-lactylate; polyoxyethylene (20) tritallate and maleic or succinic anhydride derivatives; polyglycerol polyricinoleate;
decaglycerol decaoleate; and mixtures thereof.
7. A stabilized edible fluid fat or oil comprising a stabilizing composition comprising solid particles of ascorbic acid which are less than about 1.0 micron in size on their largest dimension and dispersed in an edible substance, and optionally comprising additional antioxidants.
8. A method of preparing solid particles of ascorbic acid which are less than about 1.0 micron in size on their largest dimension comprising, reducing the particle size of ascorbic acid solids by grinding ascorbic acid to a particle size of less than about 1.0 micron in size, and wherein the solid particles of ascorbic acid are dispersed in an edible substance.
9. The method of Claim 8, wherein the edible substance is an edible fluid fat or oil.
10. The method of Claim 8, wherein the grinding is performed In the
presence of glycerol esters; lecithin and lecithin derivatives; mono glycerides; diglycerides; mixtures of mono and diglycerides; mixtures of mono-, di- and triglycerides; capric / caprylic diglycerides; glycerol monolaurate; ethoxylated glycerol esters; ethoxylated fatty acids;
propylene glycol stearate; ethoxylated fatty acids and oils; ethoxylated alcohols; sorbitan derivatives; decaglycerol tetraoleate and chemically related species; sulfosuccinates and derivatives; whey protein-based dispersants; silicone glycol copolymers; stearic acid; fatty acids; fatty alcohols; medium-chain fatty acids; medium-chain fatty alcohols; sodium stearoyI-2-lactylate; polyoxyethylene (20) tritallate and maleic or succinic anhydride derivatives; polyglycerol polyricinoleate;
decaglycerol decaoleate; and mixtures thereof.
11. The method of Claim 8, further comprising the step of separating the particles less than about one micron using a mechanical means.
12. The method of Claim 11, wherein the mechanical means is selected from a centrifuge, filter and sieve.
13. A method of preparing an antioxidant composition comprising, the step of miliing a mixture of ascorbic acid, rosemary extract and a food grade surfactant, wherein the ascorbic acid particles in the finished product are less than one micron on their largest dimension.
14. The method of Claim 13, wherein the ascorbic acid particles in the finished product are less than O.S microns on their largest dimension.
15. A method of treating an edible fluid fat or oil comprising, admixing the stabilizing composition of Claim 1 with an edible fluid fat or oil, wherein after admixing, the edible fluid fat or oil is transparent and free from sediments after 50 days at 1 x g.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5230836A (en) 1991-06-20 1993-07-27 Kalamazoo Holdings, Inc. Low micron-sized ascorbic acid particles, especially a suspension thereof in a medium in which they are insoluble, and the use thereof as an antioxidant for mediums in which the particles remain insoluble
WO2000006155A1 (en) * 1998-07-27 2000-02-10 Sunsmart, Inc. Stabilized ascorbic acid, composition, and method of use
WO2001003664A1 (en) * 1999-07-08 2001-01-18 International Flora Technologies, Ltd. Stabilized ascorbic acid, composition, and method of use
AU2003204456A1 (en) 2002-11-23 2004-06-10 Aquanova German Solubilisate Technologies (Agt) Gmbh Aqueous solution of ascorbic acid and method for producing same
US7101563B1 (en) * 2000-03-03 2006-09-05 Australian Importers, Ltd. Micronized vitamin C formulation

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5230836A (en) 1991-06-20 1993-07-27 Kalamazoo Holdings, Inc. Low micron-sized ascorbic acid particles, especially a suspension thereof in a medium in which they are insoluble, and the use thereof as an antioxidant for mediums in which the particles remain insoluble
US5290481A (en) * 1991-06-20 1994-03-01 Kalamazoo Holdings, Inc. Low micron-sized ascorbic acid particles, especially a suspension thereof in a medium in which they are insoluble, and the use thereof as an antioxidant for mediums in which the particles remain insoluble
WO2000006155A1 (en) * 1998-07-27 2000-02-10 Sunsmart, Inc. Stabilized ascorbic acid, composition, and method of use
WO2001003664A1 (en) * 1999-07-08 2001-01-18 International Flora Technologies, Ltd. Stabilized ascorbic acid, composition, and method of use
US7101563B1 (en) * 2000-03-03 2006-09-05 Australian Importers, Ltd. Micronized vitamin C formulation
AU2003204456A1 (en) 2002-11-23 2004-06-10 Aquanova German Solubilisate Technologies (Agt) Gmbh Aqueous solution of ascorbic acid and method for producing same

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