EP1368362A1 - Ascorbinsäure-2-phosphat metalsalz mit geringem kalzium gehalt - Google Patents

Ascorbinsäure-2-phosphat metalsalz mit geringem kalzium gehalt

Info

Publication number
EP1368362A1
EP1368362A1 EP02701682A EP02701682A EP1368362A1 EP 1368362 A1 EP1368362 A1 EP 1368362A1 EP 02701682 A EP02701682 A EP 02701682A EP 02701682 A EP02701682 A EP 02701682A EP 1368362 A1 EP1368362 A1 EP 1368362A1
Authority
EP
European Patent Office
Prior art keywords
ascorbic acid
salt
metal salt
phosphate metal
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP02701682A
Other languages
English (en)
French (fr)
Inventor
Yoshio KAWASAKI PLANT SHOWA DENKO K.K FUJIWARA
Yuji KAWASAKI PLANT SHOWA DENKO K.K. KOBAYASHI
Makoto KAWASAKI PLANT SHOWA DENKO K.K. SAITO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Resonac Holdings Corp
Original Assignee
Showa Denko KK
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2001057982A external-priority patent/JP2002255981A/ja
Application filed by Showa Denko KK filed Critical Showa Denko KK
Publication of EP1368362A1 publication Critical patent/EP1368362A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
    • C07F9/65515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a five-membered ring
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/67—Vitamins
    • A61K8/676—Ascorbic acid, i.e. vitamin C
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin

Definitions

  • the present invention relates to L-ascorbic acid derivative reduced in the calcium content and a production process therefor. More specifically, the present invention relates to L-ascorbic acid 2-phosphate metal salt having a low calcium content, which is useful as an additive for cosmetic, medical, food and feed materials, widely applicable in various industrial fields and particularly when added to a cosmetic material containing an organic acid, causes no clouding or scarcely precipitates or deposits even in the storage of cosmetic material, and also relates to a production process therefor.
  • the L-ascorbic acid (vitamin C) has been heretofore used in various fields such as cosmetics, medical preparations, food and feed because of its various physiological and pharmacological activities such as suppression of lipoperoxide, acceleration of collagen formation, retardation of melanin formation and enhancement of immunity function.
  • L-ascorbic acid is known to be unstable to oxygen, heat, light and the like and readily undergo coloration or degradation. Therefore, L-ascorbic acid generally used in the field of cosmetic material is not L- ascorbic acid itself but a derivative improved in the stability against oxygen, heat and the like by forming the hydroxyl group at the 2-position of L-ascorbic acid into a phosphoric ester or a phosphate salt.
  • L-ascorbic acid-2-phosphate metal salts, particularly magnesium salt are widely used as a vitamin C derivative having excellent stability and being easily soluble in water.
  • L-ascorbic acid 2-phospate metal salts There are know a lot of processes for producing L-ascorbic acid 2-phospate metal salts.
  • APM L-ascorbic acid 2-phosphate magnesium salt
  • 2-AP L-ascorbic acid-2-phosphate
  • JP-B- 52-18191 the term “JP-B” as used herein means an “examined Japanese patent publication”
  • JP-A-59-51293 the term “JP- A” as used herein means an "unexamined published Japanese patent application”
  • JP-A-2-286693 the term "JP-B” as used herein means an "unexamined published Japanese patent application”
  • the thus-obtained APM has a problem in that when blended, for example, in a cosmetic material such as cosmetic lotion, it readily causes clouding, precipitation or deposition during storage. Aggregation of ingredients in the production process of APM has been considered as one of causes therefor. More specifically, in the production of APM, when APM solution is crystallized in a poor solvent such as methanol or dried in a vacuum, aggregation readily occurs and the particle size increases. If this APM increased in the particle size is blended in a cosmetic material, clouding, precipitation or the like is readily caused due to alcohols contained in the cosmetic material.
  • Blending of citrate, oxalate, gluconate or alanine in a high concentration only can attain slight retardation of the precipitation or deposition of APM and although the precipitation or deposition of APM may be slightly improved by the use of freeze-dried or spray-dried APM, the effect is not sufficiently high.
  • the present invention has been made to solve the above-described problems and one of the object of the present invention is to provide L-ascorbic acid 2-phosphate metal salt having a low calcium content, which causes no clouding and scarcely precipitates or deposits even when added to a cosmetic material or the like having blended therein an organic acid.
  • This object of the present invention includes providing a production process therefor.
  • Another object of the present invention is to provide a cosmetic material, a medical preparation, a beverage, a food and a feed, each containing L-ascorbic acid 2- phosphate metal salt and being free from generation of clouding, precipitation or deposition.
  • the present inventors have newly found this time that the clouding generated, in a cosmetic material during storage of the cosmetic material containing L-ascorbic acid 2-phosphate metal salt is caused by not only the L-ascorbic acid 2-phosphate metal salt deposited due to alcohols contained in the cosmetic material but also by salts produced in the reaction between an organic acid (for example, citric acid) present in the cosmetic material and calcium contained as an impurity in the starting material L-ascorbic acid 2-phosphate metal salt; that clouding is readily generated when this L-ascorbic acid 2- phosphate metal salt has a high calcium content; that the calcium originates in a metal compound used as a starting material; and that when the content of calcium contained as an impurity in the starting metal compound is reduced, a cosmetic lotion or the like free from generation of clouding can be obtained.
  • the present invention has been accomplished based on these findings.
  • the present invention relates to the following matters.
  • An L-ascorbic acid-2-phosphate metal salt with a low calcium content characterized in that the content of a calcium compound is 500 ppm or less in terms of calcium ion.
  • L-ascorbic acid-2-phosphate metal salt with a low calcium content as described in (1), wherein the L-ascorbic acid-2-phosphate metal salt is a salt of alkaline earth metal other than calcium, alkali metal salt, zinc salt, aluminum salt or titanium salt.
  • L-ascorbic acid-2-phosphate metal salt with a low calcium content as described in (1), wherein the L-ascorbic acid-2-phosphate metal salt is sodium salt, potassium salt, magnesium salt, zinc salt or aluminum salt.
  • L-ascorbic acid-2-phosphate metal salt with a low calcium content as described in (1), wherein the L-ascorbic acid-2-phosphate metal salt is potassium salt, magnesium salt or zinc salt.
  • a process for producing an L-ascorbic acid-2-phosphate metal salt with a low calcium content wherein the content of a calcium compound is 500 ppm or less in terms of calcium ion said process is characterized by adding a metal compound containing a calcium compound in an amount of 2,000 ppm or less in terms of calcium ion to a solution containing an L-ascorbic acid-2-phosphoric ester.
  • a low-clouding cosmetic material characterized in that the L-ascorbic acid 2-phosphate metal salt with a low calcium content described in (1) is blended.
  • a low-clouding medical preparation characterized in that the L-ascorbic acid 2-phosphate metal salt with a low calcium content described in (1) is blended.
  • a low-clouding beverage characterized in that the L- ascorbic acid 2-phosphate metal salt with a low calcium content described in (1) is blended.
  • L-ascorbic acid 2-phosphate metal salt with a low calcium content according to the present invention and the production process therefor are described in detail below.
  • the high-purity L-ascorbic acid 2-phosphate metal salt with a low calcium content is characterized in that the content of calcium compound as an impurity is 500 ppm or less in terms of calcium ion.
  • the L-ascorbic acid-2-phosphate metal salt is a salt of metal other than calcium, preferably a salt of alkaline earth metal other than calcium, alkali metal salt, zinc salt, aluminum salt or titanium salt, more preferably sodium salt, potassium salt, magnesium salt, zinc salt or aluminum salt, still preferably potassium salt, magnesium salt or zinc salt, and most preferably magnesium salt .
  • Such the L-ascorbic acid 2-phosphate metal salt causes no clouding and scarcely precipitates or deposits even when added to a cosmetic lotion containing an organic acid such as citric acid, or ethanol . Accordingly, when such the L- ascorbic acid 2-phosphate metal salt is blended, various cosmetic, medical preparations, food and feed materials having excellent storage stability can be obtained.
  • the content of calcium compound as an impurity is suitably 500 ppm or less, preferably 300 ppm or less, in terms of calcium ion.
  • the calcium compound content exceeds 500 ppm, when the L-ascorbic acid 2- phosphate metal salt is blended in a cosmetic material or the like, a salt is formed with an organic acid (for example, a citric acid) contained in the cosmetic material or the like to readily cause clouding, precipitation or deposition.
  • an organic acid for example, a citric acid
  • a metal compound containing an impurity calcium compound in the later described amount or less is added to a solution containing an L-ascorbic acid-2-phosphoric ester (2-AP) (this solution is hereinafter sometimes called "a 2-AP- containing solution") .
  • the metal compound is a compound of a metal other than calcium, preferably a compound of alkaline earth metal other than calcium, alkali metal compound, zinc compound, aluminum compound or titanium compound, more preferably sodium compound, potassium compound, magnesium compound, zinc compound or aluminum compound, still preferably potassium compound, sodium compound, magnesium compound or zinc compound, and most preferably magnesium compound.
  • the finally obtained L-ascorbic acid 2-phosphate metal salt can be reduced in the content of calcium compound as an impurity and by using this L-ascorbic acid 2-phosphate metal salt reduced in the calcium content, a cosmetic lotion or a medical or food material can be prevented from clouding or the like.
  • the metal compound may be added to a 2-AP-containing solution and the adding method is not particularly limited insofar as the 2-AP and the metal compound can be contacted and reacted.
  • APM In producing APM by, for example, adding a metal compound to a 2-AP-containing solution and thereby reacting 2-AP with the metal compound, a commonly known method described in JP-B-52-18191, JP-A-59-51293, JP-A-2-286693 and the like may be employed.
  • the above-described reaction may be performed by adding a metal compound such as metal oxide having a calcium content in a fixed amount or less to a 2- AP-containing solution, adjusting the pH after the addition to 8.5 to 10.5, and allowing the solution to stand at a temperature of 5 to 25°C for 3 to 5 hours.
  • a metal compound such as metal oxide having a calcium content in a fixed amount or less
  • adjusting the pH after the addition to 8.5 to 10.5
  • the 2-AP-containing solution (starting material solution) for use in the present invention is not particularly limited and, for example, the following solutions may be used.
  • Examples of the 2-AP-containing solution which can be suitably used include a 2-AP-containing solution obtained by directly phosphorylating an ascorbic acid (see, JP-B-43- 9219, JP-B-45-23746 and JP-A-6-345786) and a 2-AP- containing solution obtained by phosphorylating a 5,6-0- isopropylidene-L-ascorbic acid (see, JP-B-43-9219, JP-B-45- 4497, JP-B-45-30328 and JP-B-59-4438 ) may be preferably used.
  • a 2-AP-containing solution produced from an L-ascorbic acid and a phosphoric acid donor under the action of an enzyme or a microorganism see, JP-A-2-42996 may also be used.
  • the 2-AP-containing solution can be obtained, for example, by a method where an L-ascorbic acid, an alkali metal hydroxide and a phosphorylating agent are reacted in the presence of water at a pH of 6 to 13, preferably from 6 to 8, and the obtained 2-AP alkali metal salt solution (an alkali metal salt solution of L-ascorbic acid-2-phosphoric ester) is treated with an ion exchange resin to remove metal ion.
  • the 2-AP-containing solution can be obtained, for example, by a method where an L- ascorbic acid is dissolved in a mixed solvent of pyridine and water, reacted with a phosphorylating agent such as phosphorus oxychloride while adjusting the pH to 6 to 13, preferably 6 to 8, using an aqueous alkali metal hydroxide solution (for example, an aqueous solution of sodium hydroxide, potassium hydroxide or lithium hydroxide) and at the same time, with the alkali metal hydroxide, and the obtained 2-AP alkali metal salt solution is treated with an ion exchange resin to remove metal ion.
  • a aqueous alkali metal hydroxide solution for example, an aqueous solution of sodium hydroxide, potassium hydroxide or lithium hydroxide
  • a 2-AP alkali metal salt solution or a 2-AP alkaline earth metal salt solution may be used in place of the 2-AP- containing solution.
  • these solutions aqueous solution
  • these solutions are preferably subjected to a metal ion-removing treatment (hereinafter sometimes referred to as decation- ization) before use.
  • decation- ization a metal ion-removing treatment
  • Examples of the decationization method include a method of treating a 2-AP metal salt solution with an appropriate ion exchange resin.
  • a 2-AP metal salt solution such as L-ascorbic acid 2-phosphate magnesium salt (APM) is passed through a strongly acidic cation exchange resin and then water is eluted, whereby the cation portion (metal ion) of the 2-AP metal salt solution is exchanged with hydrogen ion, and the metal ion remains on the exchange resin, as a result, a decationized 2-AP solution is obtained.
  • APM L-ascorbic acid 2-phosphate magnesium salt
  • the 2-AP-containing solution can also be obtained by a general method, for example, where a 2-AP metal salt solution (aqueous solution) is passed through a weakly or moderately basic anion-exchange resin to adsorb 2-AP to the ion exchange resin and at the same time, allow metal ion (cation) such as alkali metal ion or alkaline earth metal ion to flow out, and the adsorbed 2-AP is eluted with an acid such as 0.1 to 2 N dilute hydrochloric acid.
  • a 2-AP metal salt solution aqueous solution
  • a weakly or moderately basic anion-exchange resin to adsorb 2-AP to the ion exchange resin and at the same time, allow metal ion (cation) such as alkali metal ion or alkaline earth metal ion to flow out, and the adsorbed 2-AP is eluted with an acid such as 0.1 to 2 N dilute hydrochloric acid.
  • the thus-obtained high- purity 2-AP extremely reduced in the metal ion content may be used, where the content of alkali metal ion or alkaline earth metal ion, such as Na ion or Ca ion, is usually 10 ppm or less, preferably 1 ppm or less in terms of the L- ascorbic acid-2-phosphoric ester.
  • the metal compound which is used as a starting material in the production process of the L-ascorbic acid 2-phosphate metal salt according to the present invention is, as mentioned above, a compound of a metal other than calcium, preferably a compound of alkaline earth metal other than calcium, alkali metal compound, zinc compound, aluminum compound or titanium compound, more preferably sodium compound, potassium compound, magnesium compound, zinc compound or aluminum compound, still preferably potassium compound, sodium compound, magnesium compound or zinc compound, and most preferably magnesium compound.
  • the metal compound is, for instance, metal oxide, metal hydroxide or metal carbonate, and preferably metal oxide or metal hydroxide.
  • examples of magnesium compound include, for instance, magnesium oxide, magnesium hydroxide and magnesium carbonate. Among these, magnesium oxide and magnesium hydroxide are preferred.
  • the content of calcium compounds as an impurity contained in the metal compound for use in the present invention is suitably 2,000 ppm or less, preferably 1,500 ppm or less, more preferably 750 ppm or less, in terms of calcium ion. If the calcium content in the starting material metal salt exceeds 2,000 ppm, the L- ascorbic acid 2-phosphate metal salt produced using the metal compound has a high calcium concentration and when blended in a cosmetic material or the like, an organic acid (e.g., citric acid) contained in the base material of the cosmetic material reacts with the calcium compound to form a salt, as a result, clouding, precipitation or deposition is readily caused and this is not preferred.
  • an organic acid e.g., citric acid
  • the obtained L-ascorbic acid 2-phosphate metal salt can have a low calcium content of 500 ppm or less, preferably 300 ppm or less, in terms of calcium ion.
  • the L-ascorbic acid 2-phosphate metal salt with a low calcium content according to the present invention does not cause clouding, precipitation or deposition even when added to a cosmetic material having blended therein particularly an organic acid (e.g., citric acid, succinic acid, malic acid, tartaric acid) and stored for a long period of time, and therefore, can be suitably used in various cosmetic materials .
  • an organic acid e.g., citric acid, succinic acid, malic acid, tartaric acid
  • Examples of the cosmetic material to which the L- ascorbic acid 2-phosphate metal salt with low calcium content obtained by the present invention can be added include : a lotion where citric acid, sodium citrate, g- aminocaproic acid, 1,3-butylene glycol, ethanol, glycerol, polyoxyethylene hydrogenated castor oil, purified water, perfume and the like are blended; a cream where stearic acid, cetanol, 1,3-butylene glycol, parahydroxybenzoic ester, dipentaerythritol fatty ester, purified water, perfume and the like are blended; a milky lotion where stearic acid, cetanol, octyldodecyl erucate, polyoxyethylene tetraoleate and the like are blended; and a pack where dipropylene glycol, sodium pyrrolidone- carboxylate, polyvinyl alcohol, tetrasodium edetate and the like are blended.
  • the present invention is not
  • the ratio of L-ascorbic acid 2-phosphate metal salt with low calcium content blended to these cosmetic materials varies depending on the amount of organic acid blended, the preparation form and the like but assuming that the entire amount of the cosmetic material is 100 wt%, the ratio is generally from 0.01 to 30 wt%, preferably from 0.1 to 20 wt% in a lotion; generally from 0.01 to 30 wt%, preferably from 0.1 to 15 wt% in a cream; generally from 0.01 to 30 wt%, preferably from 0.1 to 20 wt% in a milky lotion; and generally from 0.01 to 30 wt%, preferably from 0.1 to 15 wt% in a pack.
  • the amount of the organic acid contained in the cosmetic material varies depending on the kind of the cosmetic material but is generally from 0.1 to 10 wt%.
  • This L-ascorbic acid 2-phosphate metal salt reduced in the calcium content can be suitably used also for medical preparations (e.g., preparation for oral cavity, ophthalmic solution, bath preparation), beverages, feed for animals, food and the like containing particularly an organic acid (e.g., citric acid, succinic acid, malic acid, tartaric acid) and the same effect as in the cosmetic material can be obtained.
  • medical preparations e.g., preparation for oral cavity, ophthalmic solution, bath preparation
  • beverages feed for animals, food and the like containing particularly an organic acid (e.g., citric acid, succinic acid, malic acid, tartaric acid) and the same effect as in the cosmetic material can be obtained.
  • an organic acid e.g., citric acid, succinic acid, malic acid, tartaric acid
  • the present invention is described in greater detail below by referring to examples, however, the present invention is not limited to these Examples.
  • the invention is described in accordance with the production of L-ascorbic acid 2- phosphate magnesium salt.
  • the invention is not limited to magnesium salt, but include the various metal salts of L-ascorbic acid 2-phosphate metal.
  • the concentration of calcium compound as an impurity in the starting material magnesium hydroxide and in the final product L-ascorbic acid 2-phosphate magnesium salt was measured by ICP (manufactured by Seiko Instruments K.K.) (similarly measured in Example 2 and Comparative Examples 1 to 2 below) .
  • An L-ascorbic acid 2-phosphate magnesium salt as a white dry product was obtained in the same manner as in Example 1 except that magnesium hydroxide having an impurity calcium compound content of 2,500 ppm in terms of calcium ion was used in place of the magnesium hydroxide having an impurity calcium compound content of 500 ppm in terms of calcium ion in Example 1.
  • the calcium compound content in this white dry product was 580 ppm.
  • in-solution stability tests 1 and 2 described later were performed. In both in-solution stability tests 1 and 2, clouding was observed at room temperature (20°C) and more distinguished clouding was observed at 50°C.
  • reaction solution after such adjustment of pH was diluted by adding 6,500 ml of pure water, passed through a column packed with 2,000 ml of a moderately basic anion exchange resin (Amberlite IRA-68, produced by Organo) and then developed with 23,500 ml of 0.05N hydrochloric acid and further with 11,000 ml of 0.2N hydrochloric acid to obtain a fraction containing 2-AP.
  • An aqueous solution of this fraction was dialyzed using an electrodialyser (Model DU-Ob, manufactured by Asahi Glass K.K.) until chlorine ion was reduced to 500 ppm.
  • An L-ascorbic acid 2-phosphate magnesium salt as a white dry product was obtained in the same manner as in Example 2 except that magnesium oxide having an impurity calcium compound content of 3,000 ppm in terms of calcium ion was used in place of the magnesium oxide having an impurity calcium compound content of 1,000 ppm in terms of calcium ion in Example 2.
  • the calcium compound content in this white dry product was 750 ppm in terms of calcium ion.
  • in-liquid stability tests described later were performed. As a result, in the in-solution stability test 1, clouding was observed when the dry product was allowed to stand at room temperature, and more distinguished clouding was observed when allowed to stand at 50°C. In the in-liquid stability test 2, distinguished clouding was observed under both conditions of room temperature and 50°C.
  • L-ascorbic acid 2-phosphate metal salt with a low calcium content can be produced, where the content of calcium compound as an impurity contained in the L-ascorbic acid 2-phosphate metal salt, giving rise to clouding, precipitation or deposition, is reduced to 500 ppm or less in terms of calcium ion.
  • the L-ascorbic acid 2-phosphate metal salt with a low calcium content according to the present invention can be free of clouding, precipitation or deposition during storage either at room temperature or at a high temperature (for example, 50°C) when the L-ascorbic acid 2-phosphate metal salt is blended in a cosmetic material containing particularly an organic acid, and therefore, can be suitably used for this usage.
  • this L-ascorbic acid 2-phosphate metal salt can exhibit stability during the same storage as above even when blended in a medical, feed or food material containing particularly an organic acid, and therefore, can be widely used in various industrial fields .

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  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Organic Chemistry (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Molecular Biology (AREA)
  • Birds (AREA)
  • Epidemiology (AREA)
  • Biochemistry (AREA)
  • Dermatology (AREA)
  • Cosmetics (AREA)
EP02701682A 2001-03-02 2002-03-01 Ascorbinsäure-2-phosphat metalsalz mit geringem kalzium gehalt Withdrawn EP1368362A1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2001057982 2001-03-02
JP2001057982A JP2002255981A (ja) 2001-03-02 2001-03-02 カルシウム含量が低減されたアスコルビン酸−２−リン酸エステルマグネシウム塩
US27503301P 2001-03-13 2001-03-13
US275033P 2001-03-13
PCT/JP2002/001926 WO2002070531A1 (en) 2001-03-02 2002-03-01 Ascorbic acid 2-phosphate metal salt with low calcium content

Publications (1)

Publication Number Publication Date
EP1368362A1 true EP1368362A1 (de) 2003-12-10

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EP02701682A Withdrawn EP1368362A1 (de) 2001-03-02 2002-03-01 Ascorbinsäure-2-phosphat metalsalz mit geringem kalzium gehalt

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Country Link
EP (1) EP1368362A1 (de)
CN (1) CN1216061C (de)
WO (1) WO2002070531A1 (de)

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CN101247834B (zh) * 2005-06-17 2013-10-30 生命健康科学公司 包含一种或多种二-和/或单-（电子转移剂）磷酸酯衍生物或其络合物的载体
CN101550163B (zh) * 2008-10-06 2011-09-07 北京贝丽莱斯生物化学有限公司 从维生素c-2-磷酸盐粗品制备维生素c-2-磷酸镁的生产工艺
CN101735274A (zh) * 2008-11-18 2010-06-16 高锦秋 维生素c磷酸酯镁加工工艺
CN101735275A (zh) * 2008-11-18 2010-06-16 高锦秋 维生素c磷酸酯镁的生产方法
CN101747376B (zh) * 2010-01-15 2012-05-23 北京化工大学 一种应用双极膜电渗析提取抗坏血酸-2-磷酸酯的方法
CN108690076A (zh) * 2018-04-19 2018-10-23 安徽顺利生物有限公司 无有机溶剂残留的l-抗坏血酸磷酸酯镁的制备方法

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JP2694947B2 (ja) * 1987-03-31 1997-12-24 ポーラ化成工業株式会社 美白化粧料
JP2877366B2 (ja) * 1988-08-25 1999-03-31 協和醗酵工業株式会社 結晶状ｌ−アスコルビン酸−２−リン酸ナトリウム塩の製造法
DE3909198A1 (de) * 1989-03-21 1990-09-27 Basf Ag Verfahren zur herstellung von ascorbinsaeure-2-phosphat sowie von 5,6-isorpropyliden-ascorbinsaeure als ausgangsprodukt
CA2230774C (en) * 1997-03-18 2007-06-26 F. Hoffmann-La Roche Ag Manufacture of ascorbyl monophosphates
JP3772468B2 (ja) * 1997-06-11 2006-05-10 昭和電工株式会社 Ｌ−アスコルビン酸−２−リン酸亜鉛塩及びその製造方法
DE19831056A1 (de) * 1998-07-13 2000-01-20 Basf Ag Verfahren zur Herstellung von Salzen von Ascorbyl-2-phosphorsäureestern

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CN1216061C (zh) 2005-08-24
CN1494547A (zh) 2004-05-05
WO2002070531A1 (en) 2002-09-12

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