Classifications

• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
  • A23B4/00—General methods for preserving meat, sausages, fish or fish products
  • A23B4/14—Preserving with chemicals not covered by groups A23B4/02 or A23B4/12
  • A23B4/18—Preserving with chemicals not covered by groups A23B4/02 or A23B4/12 in the form of liquids or solids
  • A23B4/20—Organic compounds; Microorganisms; Enzymes
• • 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
• • 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
  • A23L3/3517—Carboxylic acid esters
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
  • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
  • Y02A40/90—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in food processing or handling, e.g. food conservation

Definitions

• the present invention relates to a preservative agent.
• preservative agents are generally known in the art. Solutions of carboxylic acids and their salts, specifically acetic acid or formic acid and potassium diformate (KDF) are known as preservatives for fish, fish products and fish by-products. The degradation processes of the fish raw material are inhibited and thus the quality of the raw material is improved. This results in a prolonged storage period of the fish products prior to further processing, as for instance fish meal production. However, it would be of interest to further inhibit the oxidation of the oil during storage of the fish products, and it would also be desirable to reduce the total volatile basic nitrogen (TVB-N) development.
• TVB-N total volatile basic nitrogen
• Addition of an antioxidant may solve the problems with oxidation and TVB-N development, but then the problem is to find an antioxidant that will not precipitate from the preservative solution over time . It could also be of interest to reduce corrosion caused by the preservative solution by adding a corrosion inhibitor.
• US 5,993,875 relates to a method for cooling and preservation of fish and products made from fish subjected to such treatment.
• the fish is cooled by means of a cooling medium in tanks, containers or other suitable facilities, and also subjected to treatment of at least one preservative agent.
• the fish is subjected to a combined treatment of a cooling medium and a preservative agent and said treatment is performed by means of a cooling medium comprising C 1 . 4 mono carboxylic acids and/or mono/di or tetra salts of alkali- and/or earth alkali salts of said acids.
• the cooling is performed by means of a cooling medium, being an aqueous solution of C ⁇ mono carboxylic salts in a concentration of 5-30 weight % salts and 97-70 weight % water, or binary ice comprising a preservative agent.
• a cooling medium being an aqueous solution of C ⁇ mono carboxylic salts in a concentration of 5-30 weight % salts and 97-70 weight % water, or binary ice comprising a preservative agent.
• the most preferred brine or binary ice comprises potassium formate and/or potassium diformate and/or formic acid.
• the pH of the brine can be adjusted by addition of an acid or disalt being the equivalent of the mono salt applied in the brine.
• the fish products have to be subjected to a combined treatment of a cooling medium and a preservative agent. It would be of interest to provide a preservative agent, which would give a prolonged storage time without a cooling medium.
• WO 01/32040 Al relates to a method of reducing oxidation in foods by selectively adding one or more antioxidants to the polar lipid fraction of a food product.
• An organic water-miscible solvent is used to dissolve the antioxidants.
• the antioxidants may be a tocopherol, carotenoid, ubiquinol, butylated hydroxyanisole, butylated hydroxytoluene, propyl gallate or t-butylhydroquinone. It is not desirable to use an organic solvent in a preservative for fish products and most of the antioxidants would not be soluble in the preservative solution. Even if it should be possible to dissolve some antioxidants without a solvent, they would precipitate when stored.
• the main object of the present invention was to arrive at a preservative agent, which would not give precipitation of the antioxidant when stored.
• Another object was to reduce the corrosion of the preservative.
• a further object was to obtain a preservative agent, which would give a prolonged storage period for fish, fish products and fish by-products, especially with regard to its lipid content, prior to fish meal production.
• an antioxidant to an aqueous solution comprising 20 - 80 weight % of - C 3 carboxylic acids in mixture with their salts. It was found that a preferable aqueous composition would be formic acid and/or acetic acid and/or lactic acid in combination with their salts, and the cation could be sodium and/or potassium and/or calcium and/or magnesium. Most preferably the cation should be potassium. At least 50 mol % of the carboxylic acids should be in undissociated form.
• antioxidants were not very soluble in solutions of carboxylic acids and their salts. This applied to for instance butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), tochopherols and ethoxyquin.
• Other antioxidants such as ascorbic acid had no antioxidative effect.
• the gallates were soluble, but they gave precipitation over time. Since one of the objects was to reduce the corrosion of the preservative, it was desirable to find a corrosion inhibitor, which would be compatible with the antioxidant. It was then surprisingly found that when ascorbic acid (AA) was added as a corrosion inhibitor, tests showed that propyl gallate (PG) did not precipitate. The corrosion inhibitor thus had two positive effects. The corrosion inhibitor stabilised the antioxidant so that the antioxidant did not precipitate over time, and corrosion caused by the preservative was significantly reduced.
• AA ascorbic acid
• PG propyl gallate
• the present invention will in its widest scope comprise a preservative agent comprising an aqueous solution of - C 3 carboxylic acid in mixture with their salts where said solution comprises 20 - 80 weight % Ci - C 3 carboxylic acids in mixture with their salts, 0.01 - 2 weight % antioxidant being a gallate and 0.01 - 2 weight % corrosion inhibitor being ascorbic acid.
• the content of gallate is preferably 0.25 - 1.5 weight % and the content of ascorbic acid is preferably 0.25 - 1.5 weight %.
• the gallate is preferably propyl gallate.
• the carboxylic acids are formic acid and/or acetic acid and/or lactic acid.
• the cation is preferably potassium. At least 50 mol % of the carboxylic acids are in undissociated form.
• Figure 1 shows precipitation in aqueous solutions of formic acid, acetic acid and lactic acid in mixtures with potassium formate with propyl gallate and with and without addition of ascorbic acid.
• Figure 2 shows precipitation in aqueous solutions of acetic acid and lactic acid in mixtures with formic acid, potassium acetate or potassium lactate with propyl gallate and with and without addition of ascorbic acid.
• Figure 3 shows corrosion for a potassium diformate (KDF) solution with different concentrations of ascorbic acid.
• Figure 4 shows corrosion for a KDF solution comprising propyl gallate and ascorbic acid compared to a KDF solution.
• FIG. 5 shows TVB-N development in fish treated with different KDF solutions.
• Figure 6 shows TVB-N development in by-products treated with different KDF solutions.
• Figure 7 shows TVB-N development in capelin at different temperatures.
• Figure 8 shows TVB-N development in capelin at different concentrations of KDF solution.
• Example 1 was carried out to investigate the precipitation of propyl gallate in different solutions of C ⁇ - C 3 carboxylic acids in mixture with their salts exemplified with formic acid, acetic acid and lactic acid, and the salt potassium formate.
• Table 1 shows formulations of propyl gallate in solutions of formic, acetic and lactic acid in mixtures with potassium formate. Each formulation was made with and without ascorbic acid.
• the solution was left for a period of 6 months at room temperature. After the 6 months storage period the samples were filtered using a membrane filter (SS 3.0 ⁇ m).
• Fig. 1 shows precipitation in aqueous solutions of formic acid, acetic acid and lactic acid in mixtures with potassium diformate with propyl gallate and with and without addition of ascorbic acid.
• Example 2 was carried out to investigate the precipitation of propyl gallate in different solutions of Ci - C 3 carboxylic acids in mixture with their salt exemplified with formic acid, acetic acid and lactic acid, and the salts potassium lactate and potassium acetate.
• Aqueous solutions were prepared with acetic acid or lactic acid alone or in combination with formic acid, potassium acetate or potassium lactate. Each of the solutions was made in duplicate and all solutions were added 1 weight % propyl gallate. One of the parallels was added 1.25 weight % ascorbic acid. Ascorbic acid was added at the expense of water. The different formulations are shown in Table 2.
• Table 2 shows formulations of propyl gallate in solutions of acetic acid and lactic acid alone or in combination with formic acid and or potassium lactate or potassium acetate. Each formulation was made with and without ascorbic acid.
• the solution was left for a period of 2 months at room temperature. After the 2 months storage period the samples were filtered using a membrane filter (SS 3.0 ⁇ m).
• Fig. 2 shows precipitation in aqueous solutions of acetic acid and lactic acid in mixtures with formic acid, potassium acetate or potassium lactate with propyl gallate and with and without addition of ascorbic acid.
• Formulations of propyl gallate in solutions of acetic and lactic acid alone or in combination with formic acid and/or potassium lactate or potassium acetate (weight / weight %)
• a dose-response experiment was carried out to determine the relationship between dosage of ascorbic acid and corrosion inhibition in a KDF solution.
• Three plates of unalloyed steel (40 x 30 x 2 mm) were submersed in solutions containing 1.4 weight % KDF (30 weight % solution in water) with different concentrations of ascorbic acid and a control solution of 1.4 weight % KDF (30 weight % solution in water).
• the test was performed at room temperature for 7 days. The pH during the test period was 3.7.
• the specimens were mounted to glass racks with glass hooks and placed in beakers containing the test solutions. Magnetic stirrers were used to circulate the solutions. After exposure the specimens were ultrasonically cleaned in inhibited hydrochloric acid, soapy water, tap water and acetone. The corrosion rates were calculated from weight loss.
• the ascorbic acid concentration is given as the percentage ascorbic acid in the stock solution (30 weight % KDF in water).
• addition of ascorbic acid decreased the corrosion rate by 40-42 %.
• Three plates of unalloyed steel (40 x 30 x 2 mm) were submersed in solutions containing 1.4 % KDF (30 weight % solution in water) with 0.5 weight % propyl gallate and 0.5 weight % ascorbic acid and a control solution of 1.4 % KDF.
• the test was performed at 3 and 22 °C for 7 days at a pH of 6.0.
• the specimens were mounted to a glass rack with glass hooks and placed in beakers containing the test solutions. Magnetic stirrers were used to circulate the solutions. After exposure the specimens were ultrasonically cleaned in inhibited hydrochloric acid, soapy water, tap water and acetone. The corrosion rates were calculated from weight loss.
• Fig. 4 The result of the test is shown in Fig. 4. As can be seen from the Figure, reduced corrosion rates were observed at the lower temperature for both the control and the solution with propyl gallate and ascorbic acid. At 3 °C the corrosion rate decreased by 54 % in the solution containing propyl gallate and ascorbic acid and at 22 °C the corrosion rate decreased by 26 %.
• the capelin had been frozen prior to the experiment and was of good quality (TVB-N - 7.7 mg/100 g fish).
• the raw material was added 1.4 weight % KDF (30 weight % solution in water) with 0.5 weight % propyl gallate and 0.5 weight % ascorbic acid or 1.4 weight % KDF (30 weight % solution in water) without antioxidant and corrosion inhibitor.
• the treatments were prepared with a parallel and compared with a control without addition of KDF.
• the temperature and pH were registered during the experiment and the TVB-N analysed.
• the results from the TVB-N analyses were subjected to non-linear regression analyses.
• Fig. 5 shows the TVB- N development in capelin during storage.
• the KDF solution comprising propyl gallate and ascorbic acid decreased the TVB-N development and thus increased the storage period of the fish.
• the TVB-N value was slightly over 40 mg/100 g fish for fish treated with the KDF solution comprising propyl gallate and ascorbic acid, while fish treated with just KDF solution reached this TVB-N value after about 11 days, and the control without addition reached the same value after about 6.5 days storage.
• Propyl gallate was found to increase the storage period 6 days compared to KDF solution without antioxidant.
• Cut of herring was added 1.5 weight % KDF (30 weight % solution in water) with or without addition of antioxidants and ascorbic acid. The addition was done as weight-to- weight percentage. The cut was divided in 6 containers (1 litre), 600 g in each. Two of the containers were kept as a control without KDF addition, two containers were added KDF (30 weight % solution in water) and two of the containers a mix of KDF (30 weight % solution in water) and 0.5 weight % propyl gallate and 0.5 weight % ascorbic acid. The fish was stored at 5°C and TVB-N analysed.
• the TVB-N development in the different treatments is shown in Fig. 6.
• addition of antioxidants was found to decrease the TVB-N development.
• the TVB-N increased fast and reached a TVB-N value of 40 after approximately 3.5 days.
• the TVB-N development was lower and the storage period was 6 and 8 days, respectively.
• Addition of propyl gallate was found to increase the storage period by 2 days compared to KDF solution without antioxidant.
• TVB-N total volatile basic nitrogen
• the capelin had been frozen prior to the experiment and was of good quality (TVB-N - 7.7 mg/100 g fish).
• the fish containers were stored at three different temperatures, 1.5, 5.6 and 7.8 °C.
• Two containers were stored at each temperature, one added 1.4 weight % KDF (30 weight % solution in water) with 0.5 weight % propyl gallate and 0.5 weight % ascorbic acid and the other without addition of KDF solution. The temperature was registered during the experiment and the TVB-N analysed.
• the TVB-N development is shown in Fig. 7. As can be seen from the Figure, higher temperatures increased the TVB-N development in both the containers added KDF solution comprising propyl gallate and ascorbic acid and the control. At all temperatures the TVB-N development in the containers added KDF solution with antioxidant and corrosion inhibitor was lower than the TVB-N development in the control samples.
• the TVB-N value in the samples comprising KDF solution with propyl gallate and ascorbic acid was only about 40 mg/lOOg after 30 days of storage, whereas the corresponding storage period for the control was 9 days. At 7.8 °C the storage period was 16 days and 5.5 days respectively.
• a pilot scale experiment was carried out to test the effect of different concentrations of KDF-solutions comprising propyl gallate and ascorbic acid on the storage stability of industrial fish.
• the storage stability on fish was determined by analysing the development of total volatile basic nitrogen (TVB-N).
• the capelin had been frozen prior to the experiment and was of good quality (TVB-N - 7.7 mg/100 g fish).
• the fish in the containers was added three different concentrations, 1.0, 1.4 and 1.8 weight % of KDF-solution (30 weight solution % in water) with propyl gallate (0.5 weight %) and ascorbic acid (0.5 weight %).
• One container was kept as a control and not added KDF solution comprising propyl gallate and ascorbic acid.
• the containers were stored at 5.6 °C.
• the TVB-N development is shown in Fig. 8.
• Addition of KDF solution comprising propyl gallate and ascorbic acid was found to decrease the TVB-N development compared to the control sample without addition of KDF solution comprising propyl gallate and ascorbic acid. Without addition of propyl gallate to the KDF solution, there was a rapid increase in the TVB-N development after 4 days.
• a concentration of 1 weight % KDF solution (30 weight % solution in water) with propyl gallate and ascorbic acid was added to the fish, there was a rapid increase in the TVB-N development after about 9 days storage.
• a concentration of 1.4 weight % the fish could be stored for 14 days before there was a significant increase in the TVB-N development. With 1.8 weight % added, the fish could be stored for over 20 days without significant increase in the TVB-N development.
• Fig. 9 A positive effect of adding propyl gallate and ascorbic acid was observed at all samplings. After 9 days, the totox for the oil from fish treated with 1.5 weight % of a 30 weight % KDF solution comprising 0.5 weight % propyl gallate and 0.5 weight % ascorbic acid was slightly over 3 compared to above 9 in the sample without antioxidant, and after 12 days the totox was 3.6 in the group added antioxidant.
• the preservative agent according to the present invention gives a prolonged storage period for products treated with said preservative.
• the added corrosion inhibitor prevents that the antioxidant precipitates over time and also reduces the corrosion of the preservative.
• the product according to the invention is particularly suitable for preserving fish, fish products and fish by-products.
• the antioxidant reduces the TVB-N development and prevents oxidation in the oil during storage of the fish products.

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• Life Sciences & Earth Sciences (AREA)
• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Food Science & Technology (AREA)
• General Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Microbiology (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Nutrition Science (AREA)
• Wood Science & Technology (AREA)
• Zoology (AREA)
• Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
• Meat, Egg Or Seafood Products (AREA)
• Anti-Oxidant Or Stabilizer Compositions (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)

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Cited By (3)

Citations (3)

• 2002
  • 2002-11-15 NO NO20025472A patent/NO317162B1/no not_active IP Right Cessation
• 2003
  • 2003-10-22 AU AU2003282633A patent/AU2003282633A1/en not_active Abandoned
  • 2003-10-22 WO PCT/NO2003/000349 patent/WO2004045317A1/en not_active Application Discontinuation
  • 2003-10-22 GB GB0508679A patent/GB2409623B/en not_active Expired - Fee Related
  • 2003-11-07 PE PE2003001130A patent/PE20040546A1/es active IP Right Grant
• 2005
  • 2005-05-11 DK DK200500683A patent/DK178350B1/da not_active IP Right Cessation
  • 2005-05-25 IS IS7865A patent/IS2316B/is unknown

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