Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
  • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
  • C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
  • C08B37/0084—Guluromannuronans, e.g. alginic acid, i.e. D-mannuronic acid and D-guluronic acid units linked with alternating alpha- and beta-1,4-glycosidic bonds; Derivatives thereof, e.g. alginates
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
  • A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Preparation or treatment thereof
  • A23L2/52—Adding ingredients
• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
  • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
  • A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
  • A23L29/206—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
  • A23L29/256—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin from seaweeds, e.g. alginates, agar or carrageenan

Definitions

• the present invention relates to purified alginic acid or a salt thereof, and a production method thereof.
• Alginic acid has been used as a dietary fiber of high molecular weight polyuronic acid in which ⁇ -D-mannuronic acid and ⁇ -L-guluronic acid are bound in various proportions. Furthermore, alginic acid is known to have many health benefits. In recent years, alginic acid or a salt thereof (sometimes referred to as alginic acid (salt)) due to its functions such as intestinal regulation and / or cholesterol-reducing action, is a raw material for foods for specified health use approved by the Ministry of Health, Labor and Welfare. The use as is active.
• alginic acid salt
• alginic acid (salt) has a high viscosity when dissolved in water, and therefore can only be used as a dilute solution such as an emulsion stabilizer and a thickener. Therefore, when high concentration is required, alginic acid (salt) is used as a powder as it is.
• the present invention has a weight average molecular weight of 0.040 or less, which is expressed by a difference between an absorbance at 420 nm and an absorbance at 720 nm when an aqueous solution having a concentration of 5% by weight is subjected to spectrophotometric analysis using a 1 cm cell.
• alginic acid having a reduced molecular weight of 300,000 or less or a salt thereof.
• the present invention also provides a low molecular weight alginic acid or salt thereof having a weight average molecular weight of 300,000 or less, containing 0.001 to 0.3% by weight of alginic acid having a molecular weight of 1800 or less or a salt thereof. is there.
• this invention provides the foodstuff containing said low molecular weight alginic acid or its salt.
• the present invention also includes a step of adjusting the pH of an aqueous solution of a low-molecular weight raw material alginic acid having a weight average molecular weight of 300,000 or less or a salt thereof to 1 to 3.5, and a step of separating the produced precipitate.
• a method for producing purified alginic acid or a salt thereof is provided.
• the present invention includes a step of treating an aqueous solution of a raw material alginic acid having a weight average molecular weight of 300,000 or less, or a salt thereof with an ultrafiltration membrane having a molecular weight cut off of 2,000 to 30,000.
• a method for producing purified alginic acid or a salt thereof is provided.
• the present invention relates to providing a highly purified alginic acid (salt) having a low degree of coloration.
• the present invention also relates to providing a food or drink using the highly purified alginic acid (salt).
• the present inventor has found that a low molecular weight alginic acid (salt) that has been commercially available in the prior art is colored more brown than a high molecular weight alginic acid (salt). And it is considered that these are caused by coloring in the molecular weight reduction step of converting high molecular weight alginic acid (salt) to low molecular weight alginic acid (salt). Therefore, as a generally known purification treatment, purification was attempted by activated carbon treatment or solvent washing, but a remarkable effect could not be obtained.
• a low molecular weight component is a color causative substance, and the colored component is also in an acidic condition. It was found that it exists in a dissolved state without causing precipitation. Based on this knowledge, colored low molecular weight alginic acid (salt) is dissolved in an aqueous solution, then the pH is lowered to precipitate the non-colored component in the aqueous solution, and the precipitate is separated from the water-soluble colored component, thereby coloring. It has been found that purified alginic acid or a salt thereof having a low degree can be obtained.
• the present inventor also colored an aqueous solution in which a colored low molecular weight alginic acid (salt) is dissolved with a specific ultrafiltration membrane that allows the colored component to permeate but does not allow the non-colored component to permeate. It has been found that purified alginic acid or a salt thereof having a low degree can be obtained.
• the method of adding an acid to alginic acid or a salt thereof for treatment is generally used when extracting alginic acid or a salt thereof from kelp or reducing the molecular weight of alginic acid or a salt thereof. It is known that coloring of alginic acid occurs in the molecular weight reduction using an acid. For this reason, it was expected that the acid treatment would rather result in coloration. However, surprisingly, after dissolving the already reduced molecular weight alginate in an aqueous solution, the pH is lowered by adding an acid to cause precipitation in the aqueous solution. It has been found that low purified low molecular weight alginic acid can be obtained.
• the purified alginic acid or its salt of the present invention has a low degree of coloring. Since the purified alginic acid or a salt thereof of the present invention hardly changes the hue at the time of blending, the application range can be expanded to various foods, particularly foods that require colorlessness.
• the purified alginic acid or a salt thereof according to the present invention has a coloring degree represented by a difference between an absorbance at 420 nm and an absorbance at 720 nm of 0.040 or less when a 5 wt% aqueous solution is subjected to spectrophotometric analysis using a 1 cm cell.
• low molecular weight alginic acid having a weight average molecular weight of 300,000 or less or a salt thereof.
• the degree of brown to black can be determined based on the degree of coloring. When the coloring degree exceeds 0.040, it is brownish, and when it is 0.040 or less, it is almost colorless. A more preferable coloring degree is 0.03 or less (0 to 0.03).
• the purified alginic acid (salt) of the present invention has a weight average molecular weight of 300,000 or less, preferably 200,000 or less, more preferably 180,000, further 150,000 or less, particularly 100,000 or less, especially 70,000 or less. Is preferred.
• the lower limit of the weight average molecular weight is preferably 10,000 or more, more preferably 15,000 or more, particularly 20,000 or more, and particularly preferably 22,000 or more. Conventionally, there has been no such low molecular weight alginic acid (salt) having a coloring degree of 0.040 or less.
• the purified alginic acid (salt) of the present invention has a reduced content of low molecular weight components.
• Low molecular weight alginic acid (salt) is considered to be a causative component of coloring. More specifically, in the purified alginic acid (salt) of the present invention, the content of alginic acid (salt) having a molecular weight of 1800 or less is preferably 0.3% by weight or less, and more preferably 0.001 to 0.3% by weight. %, In particular 0.001 to 0.2% by weight, more preferably 0.01 to 0.2% by weight.
• the polydispersity is preferably 1 to 2.6, more preferably 1 to 2.3, and particularly preferably 1 to 2.2.
• the purified alginic acid (salt) of the present invention is a step of adjusting the pH of an aqueous solution of a raw material alginic acid having a weight average molecular weight of 300,000 or less or a salt thereof to 3.5 or less, and a step of separating a precipitate to be formed Or an aqueous solution of a low-molecular-weight raw material alginic acid having a weight average molecular weight of 300,000 or less or a salt thereof with an ultrafiltration membrane having a fractional molecular weight of 2,000 to 30,000. It is preferable to manufacture by performing the process including the process to process.
• the raw material alginic acid (salt) used in the method for producing purified alginic acid (salt) of the present invention is a low molecular weight alginic acid (salt), that is, alginic acid (salt) having a weight average molecular weight of 300,000 or less, and coloring of the above 5% by weight aqueous solution.
• the ratio and arrangement order of ⁇ -D-mannuronic acid and ⁇ -L-guluronic acid constituting alginic acid (salt) are not particularly limited.
• an alginic acid (salt) having all of a block consisting of only ⁇ -D-mannuronic acid, a block consisting of only ⁇ -L-guluronic acid, and a block in which both are mixed may be used. You may use the alginic acid which consists of 1 type, or 2 types, or its salt.
• the weight-average molecular weight of the raw material reduced molecular weight alginic acid (salt) is preferably 200,000 or less, more preferably 180,000 or less, further 150,000 or less, particularly 100,000 or less, and particularly 70,000 or less. preferable.
• the production method of the purified alginic acid (salt) of the present invention is carried out with an alginic acid (salt) aqueous solution.
• concentration is not particularly limited, but it is 50% by weight or less, more preferably 0.1 to 20% by weight, particularly 0.5 to 15% by weight, and particularly 1 to 10% by weight. It is preferable from the point of doing.
• the solvent is preferably water.
• the low molecular weight alginic acid (salt) -containing aqueous solution is adjusted to pH 3.5 or less.
• the pH is preferably from 0.5 to 3.5, more preferably from 1 to 3.5, and particularly preferably from 1 to 3, from the standpoint of efficiently separating the coloring components and hardly causing hydrolysis reaction.
• precipitation of alginic acid (salt) arises also using organic solvents, such as methanol and ethanol, it is not preferable to use an organic solvent from the point of isolate
• the pH adjuster may be any as long as the pH can be adjusted to 3.5 or less.
• acetic acid, citric acid, fumaric acid, malic acid, lactic acid, gluconic acid, tartaric acid and other organic acid salts, phosphoric acid There are no particular limitations on inorganic salts such as hydrochloric acid, sulfuric acid, and carbonic acid, and mixtures thereof.
• inorganic salts such as hydrochloric acid, sulfuric acid, and carbonic acid, and mixtures thereof.
• the acid is preferably a food additive grade.
• the treatment temperature is not particularly limited but is preferably 0 to 80 ° C, particularly preferably 0 to 50 ° C.
• the treatment time is not particularly limited, but is generally preferably within the range of 1 minute to 100 hours, more preferably 2 minutes to 24 hours, further 3 minutes to 12 hours, particularly 5 minutes to 6 hours, particularly The time of 10 minutes to 3 hours is preferable from the viewpoint of efficiently separating the coloring components and not causing hydrolysis.
• the separation of the precipitate after the treatment and the supernatant may be performed by centrifugation or filtration.
• purification alginic acid with a still lower coloring degree can be obtained by isolate
• the precipitate obtained by the above method may be purified alginic acid by drying by freeze drying or spray drying, etc., but the purified alginic acid is neutralized with alkali metal hydroxide, alkali metal carbonate, etc.
• the purified alginate may be obtained by drying in the same manner. However, considering that the purified alginate of the present invention is mainly used in foods, it is necessary to use alginate designated as a food additive. Therefore, it is preferable to obtain sodium alginate, potassium alginate, calcium alginate, and ammonium alginate as alginate that can be used at present.
• the low molecular weight alginic acid (salt) -containing aqueous solution may be treated with an ultrafiltration membrane having a fractional molecular weight of 2,000 to 30,000. If the molecular weight cut off of the ultrafiltration membrane is 2,000 or more, the filtration rate is high, and if it is 30,000 or less, the separation of alginic acid (salt) and the coloring component is easy and the color tone is good.
• the molecular weight cut off of the ultrafiltration membrane is preferably 3,000 to 20,000, more preferably 4,000 to 10,000.
• the fractional molecular weight can be measured based on whether a substance having a known molecular weight is used as a marker and can be separated by a target membrane. Examples of the marker include Vitamin B12, cytochrome C, ⁇ globulin, and blue dextran.
• ultrafiltration membrane examples include polymer membranes such as hydrocarbons, fluorinated hydrocarbons, sulfones, and nitriles; and ceramic membranes such as membrane locks.
• polymer membranes such as hydrocarbons, fluorinated hydrocarbons, sulfones, and nitriles
• ceramic membranes such as membrane locks.
• the use of a polymer membrane is preferable in that the time required for filtration is short and the efficiency is high.
• hydrocarbon-based, fluorinated hydrocarbon-based, or sulfone-based polymer membranes include polyolefin polymer membranes such as polyethylene and polypropylene; polytetrafluoroethylene (PTFE), polyvinylidene difluoride (PVDF), etc.
• Examples include fluorinated polyolefin polymer membranes; sulfone polymer membranes such as polysulfone (PSU) and polyethersulfone (PES).
• PSU polysulfone
• PES polyethersulfone
• AIP-0013D polyacrylonitrile film: Asahi Kasei Chemicals Corporation
• SEP-0013 polysulfone film; Asahi Kasei Chemicals Corporation
• SIP-0013 polysulfone film: Asahi Kasei Chemicals Corporation
• SLP commercially available products such as -0013 (polysulfone membrane; Asahi Kasei Chemicals Corporation) and Biomax PBCC (PES membrane: Millipore) can be used.
• the form of the ultrafiltration membrane is not particularly limited, such as a sheet shape or a hollow fiber shape, but the hollow fiber shape allows the stock solution to flow in parallel with the membrane surface, so that clogging can be suppressed and the filtration capacity is stable. It is preferable from the point which is obtained automatically.
• the inner diameter of the membrane is preferably 0.5 to 2 mm, more preferably 0.6 to 1.8 mm, and particularly preferably 0.8 to 1.5 mm.
• the ultrafiltration conditions are preferably 5 to 70 ° C., more preferably 10 to 40 ° C., from the viewpoint of heat resistance of the ultrafiltration membrane.
• the pressure is preferably within the pressure resistance range of the membrane module to be used. For example, it is preferably 30 to 1,000 kPa, more preferably 50 to 800 kPa, and particularly preferably 100 to 700 kPa.
• the concentrated solution can be collected and dried by freeze drying, spray drying, or the like to obtain purified alginic acid (salt).
• the purified alginic acid (salt) of the present invention has a low degree of coloring, it can be applied to various foods and drinks.
• Examples of the product using the purified alginic acid (salt) of the present invention include foods containing purified alginic acid (salt).
• Specific foods include beverages, jellies, creams, noodles, sauces, soups, rice cakes and the like.
• jelly, sauces, noodles, and the like are preferable in order to effectively exhibit the effect of the low coloring degree of the purified alginic acid (salt) of the present invention.
• beverages include beverages such as soft drinks, carbonated beverages, nutritional beverages, fruit beverages and milk beverages (including concentrated concentrates and powders for adjustment of these beverages), jelly beverages, and the like.
• beverages such as soft drinks, carbonated beverages, nutritional beverages, fruit beverages and milk beverages (including concentrated concentrates and powders for adjustment of these beverages), jelly beverages, and the like.
• a beverage such as near water that requires a low degree of coloring is preferred.
• the content of purified alginic acid (salt) in food or beverage is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight.
• the coloring degree is measured by the following method. First, water is added to alginic acid (salt) to adjust to 5.0% by weight. Next, this is filtered using a membrane filter (GL chromatodisc) having an opening diameter of 0.45 ⁇ m. The obtained filtrate is poured into a 1 cm square quartz glass cell, and the absorbance at 420 nm and 720 nm is measured with a spectrophotometer (Hitachi, Ltd .: U-2910). A value obtained by subtracting the absorbance at 720 nm from the absorbance at 420 nm is defined as the coloring degree.
• Example 1 Dissolve 10 g of potassium alginate (SKAT-K-ULV: Kimika Co., Ltd.) having a coloring degree of 0.078 and a weight average molecular weight of 45,000 in a 5 wt% aqueous solution in 90 g of water, and adjust the pH to 2.0 with hydrochloric acid. did. The mixture was stirred for 10 minutes and then centrifuged (3,000 rpm, 10 minutes) to collect the precipitate. After 90 g of water was added and sufficiently dispersed in the obtained precipitate, centrifugation (3,000 rpm, 10 minutes) was performed again to collect the precipitate. Thereafter, a potassium hydroxide solution was added to adjust the pH to 7, and it was sufficiently dried by a freeze dryer to obtain purified potassium alginate. All operations were performed at room temperature (25 ° C.).
• Example 2 Purified alginic acid in the same manner as in Example 1, except that the starting material is potassium alginate (Kalarigin K-3: Kibun Food Chemifa Co., Ltd.) having a coloring degree of 0.049 and a weight average molecular weight of 31,000 in a 5% by weight aqueous solution. (Salt) was obtained.
• potassium alginate Kalarigin K-3: Kibun Food Chemifa Co., Ltd.
• Example 3 In the same manner as in Example 1, except that the starting material is sodium alginate (Solgin: Kaigen Co., Ltd.) having a coloring degree of 0.042 and a weight average molecular weight of 54,000 in a 5% by weight aqueous solution. Purified sodium alginate was obtained using sodium hydroxide.
• sodium alginate Solgin: Kaigen Co., Ltd.
• Table 1 shows the coloration degree, weight average molecular weight, polydispersity, and content (% by weight) of a molecular weight of 1800 or less of a 5% by weight aqueous solution of alginic acid (salt) obtained.
• alginic acid (salt) having a coloring degree of 5% by weight aqueous solution of more than 0.040 is less than 0.040 by the treatment method of the present invention. It becomes purified alginic acid (salt).
• Comparative Example 1 A 5 wt% solution of potassium alginate having a weight average molecular weight of 45,000 (SKAT-K-ULV: Kimika Co., Ltd.) used in Example 1 was prepared. As a result of measuring the coloring degree of this solution, it was 0.078.
• Comparative Example 2 A 5% by weight solution of potassium alginate (Kalarigin K-3: Kibun Food Chemifa Co., Ltd.) having a weight average molecular weight of 31,000 used in Example 2 was prepared. As a result of measuring the coloring degree of this solution, it was 0.049.
• Comparative Example 3 A 5% by weight solution of sodium alginate (Solgin: Kaigen Co., Ltd.) having a weight average molecular weight of 54,000 used in Example 3 was prepared. As a result of measuring the coloring degree of this solution, it was 0.042.
• Comparative Example 4 Water was added to and dissolved in potassium alginate having a weight average molecular weight of 45,000 used in Example 1 (SKAT-K-ULV: Kimika Co., Ltd.), and then ethanol was added so that an 80% ethanol solution was obtained. And washed with stirring. Thereafter, centrifugation (3,000 rpm, 10 minutes) was performed, and the precipitate was collected and sufficiently dried by a freeze dryer to obtain purified potassium alginate.
• Table 1 shows the coloring degree, weight average molecular weight, polydispersity, and content (wt%) of a molecular weight of 1800 or less of a 5 wt% aqueous solution of alginic acid (salt) obtained. As can be seen from the results shown in Table 1, the coloring degree of the 5 wt% aqueous solution was 0.066. From this, it was shown by this method that the coloring component contained in alginic acid (salt) cannot fully be removed.
• Example 4 1.0 g of potassium alginate (SKAT-K-ULV: Kimika Co., Ltd.) having a coloring degree of 0.078 and a weight average molecular weight of 45,000 was dissolved in 99.0 g of water.
• a stirring cell (stirring cell Model 8050: manufactured by Millipore) equipped with an ultrafiltration filter (Biomax PBCC 5,000 NMWL: manufactured by Millipore) with a molecular weight cut off of 5,000 was filled with the aqueous solution and concentrated at 400 kPa. This concentrated solution was sufficiently dried by lyophilization to obtain 0.86 g of purified potassium alginate. All operations were performed at room temperature (25 ° C.).
• Example 5 1.0 g of potassium alginate (SKAT-K-ULV: Kimika Co., Ltd.) having a coloring degree of 0.078 and a weight average molecular weight of 45,000 was dissolved in 99.0 g of water.
• a stirring cell (stirring cell Model 8050: manufactured by Millipore) equipped with an ultrafiltration filter (Biomax PBCC 10,000 NMWL: manufactured by Millipore) with a molecular weight cut-off of 10,000 was filled with the aqueous solution and concentrated at 400 kPa. This concentrated solution was sufficiently dried by lyophilization to obtain 0.75 g of purified potassium alginate. All operations were performed at room temperature (25 ° C.).
• Table 2 shows the coloration degree, weight average molecular weight, polydispersity, and content (wt%) of a molecular weight of 1800 or less of a 5 wt% aqueous solution of alginic acid (salt) obtained.
• alginic acid (salt) having a coloring degree of 5% by weight aqueous solution of more than 0.040 is less than 0.040 by the treatment method of the present invention. It becomes purified alginic acid (salt).
• Example 6 Using the purified potassium alginate obtained in Example 1, a potassium alginate-containing jelly having the following Formula 1 and Formula 2 was prepared.
• the preparation method was as follows: 250.0 g of water was put in a pan and boiled with pure potassium alginate 6.0 g obtained in Example 1 and powdered agar immediately before boiling. Stir further and turn off the fire. When the pot was removed, it was poured into a mold. Lemon juice was poured, stirred, placed in a refrigerator and cooled for 20-30 minutes to obtain a potassium alginate-containing jelly.
• Formulation 2 Purified potassium alginate (Example 1) 10.0 g Powdered agar 2.0g 15.0g of sugar Lemon juice 30.0g 250.0 g of water
• the obtained purified potassium alginate-containing jelly was a highly transparent jelly with a low degree of coloration, despite containing a high concentration of potassium alginate.
• Example 7 Using the purified potassium alginate obtained in Example 1, a potassium alginate-containing beverage of the following formulation 3 was prepared. In the adjustment method, 2.0 g of purified potassium alginate of Example 1 was dissolved in 198.0 g of water. The pH was adjusted to 4.0 using citric acid. Further, 0.080 g of lemon flavor was added and dissolved by stirring to obtain a potassium alginate-containing beverage.
• the obtained purified potassium alginate-containing beverage was a beverage having a small coloring degree and excellent transparency, despite containing a high concentration of potassium alginate.
• Comparative Example 5 A potassium alginate-containing jelly was prepared by the same adjustment method as in Example 4.
• the potassium alginate (SKAT-K-ULV: Kimika Co., Ltd.) having a weight average molecular weight of 45,000 of Comparative Example 1 was used.
• the obtained potassium alginate-containing jelly was a jelly whose appearance was known to be colored.
• Comparative Example 6 A potassium alginate-containing beverage was prepared in the same manner as in Example 5.
• the potassium alginate (SKAT-K-ULV: Kimika Co., Ltd.) having a weight average molecular weight of 45,000 of Comparative Example 1 was used.
• the obtained potassium alginate-containing beverage was a beverage whose appearance was clearly colored.

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• Dispersion Chemistry (AREA)
• Coloring Foods And Improving Nutritive Qualities (AREA)
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• Jellies, Jams, And Syrups (AREA)
• Non-Alcoholic Beverages (AREA)

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• 2009
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