• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The present invention relates to a soap, in particular a soap bar, which contains as main constituents fatty acid soaps and biotensioactives. It is therefore possible to produce a soap that has exceptional foaming power, good dermatological compatibility and good skin feeling, the ingredients of which can be largely or exclusively based on renewable raw materials and which have good biodegradability.
    公开号:FR3040880A1
    申请号:FR1658400
    申请日:2016-09-09
    公开日:2017-03-17
    发明作者:Heike Schelges
    申请人:Henkel AG and Co KGaA；
    IPC主号:
    专利说明:

    The present invention relates to a soap, in particular a soap bar, which contains as main constituents fatty acid soaps and biotensioactives. It is therefore possible to produce a soap that has exceptional foaming power, good dermatological compatibility and good skin feeling, the ingredients of which can be largely or exclusively based on renewable raw materials and which have good biodegradability.
    Soaps, especially soaps, are often made from blends of beef tallow and coconut oil. This fatty mixture is hydrolysed by addition of sodium hydroxide to the base soap to which other additives are added, such as humectants, fillers and binders, superfatting agents, dyes and perfumes etc. Classic soaps contain salts of fatty acids, 10% of water and in addition to 100% of adjuvants and additives. Soaps are already in themselves natural cleaning agents and durable because they are derived from fats and oils of natural origin. However, in practice, soaps are often supplemented with frequently synthetic surfactants to improve foamability and dermatological compatibility, i.e. anionic, cationic, nonionic, amphoteric and / or zwitterionic surfactants which are not usually not obtained from natural raw materials. Such soaps are called combi bars. Soaps without fatty acid salts that contain exclusively synthetic surfactants are known as syndets.
    Said soaps (combi bars), which additionally contain salts of fatty acids, anionic, amphoteric, nonionic and cationic surfactants, have a good cleaning power and a good foaming behavior. However, most of these surfactants are totally or partially derived from petrochemicals. However, durability when using cosmetic ingredients is gaining in importance and is increasingly being demanded by consumers and manufacturers of cosmetic cleansing agents.
    Biotensioactives are surfactants of microbial origin that can be prepared from vegetable oil or sugar substrates. These substrates may consist in part of agricultural waste such as rice husks or waste water from the sugar industry so that in this case also no raw materials of food production are lost. Biotensioactives meet the requirements of sustainability because they are made from renewable raw materials. They are used both in household cleaners, laundry detergents and dishwashing detergents (eg US 5,520,839, DE 19600743 A1), as well as in various cosmetic cleansing agents (for example, WO 2014/095367 A1). , WO 2013/098066 A2).
    However, biosurfactants alone generally have low foaming power.
    An object of the present invention is to provide soaps, especially soaps which contain mainly or exclusively natural ingredients and which, despite the total or substantial absence of synthetic surfactants, have excellent foaming power and a good feeling skin.
    It has been surprisingly found that this objective can be achieved by soaps which contain biosurfactants in addition to the usual fatty acid salts. The properties in terms of washing behavior, skin sensation and foaming power were comparable to those of combi bars.
    The present invention relates to: 1. a soap which contains the following ingredients, each in percent by weight based on the total weight of the soap: a) from 0.5 to 90% by weight of sodium, potassium and / or or ammonium of fatty acids having from 6 to 30 carbon atoms, and b) from 1 to 50% by weight of one or more biosurfactants. 2. a soap according to item 1, which contains a) from 20 to 85% by weight of sodium, potassium and / or ammonium salts of fatty acids having from 6 to 30 carbon atoms, and b) from 1 to 20% by weight of one or more biosurfactants, each time relative to the total weight of the soap. 3. a soap according to item 1 or 2, which contains as component (a) sodium, potassium and / or ammonium salts, preferably sodium salts, tallow fatty acids, coconut fatty acids , olive oil fatty acids, palm oil fatty acids, lard fatty acids, palm kernel oil fatty acids or a combination thereof. 4. a soap according to one of the preceding points which comprises, as biosurfactant, a glycolipid, a lipopeptide or a combination thereof. 5. a soap according to one of the preceding points which contains, as biotensiactive agent, a rhamnolipid, a sophorolipid, a mannosylerythritol, a surfactin, a fatty acyl glutamate, a fatty acyl glycinate or a combination thereof. 6. a soap according to item 5 which contains as a biotensioactive a sophorolipid, preferably a mixture of the acid form and the lactone form, wherein 20 to 60% by weight are present in the acid form. 7. a soap according to item 6 which contains as biotensiactive a rhamnolipid, preferably a mixture of mono- and dirhamnolipid which are each derived from 3-hydroxydodecanoic acid and 3-hydroxyundecanoic acid. 8. a soap according to one of the preceding points which additionally contains from 0.1 to 10% by weight of a nonionic surfactant, in particular an alkyl polyglycoside or one or more fatty acyl glucamides or one of their combinations. 9. a soap according to one of the preceding points, containing 0.5% by weight, or less, of anionic, cationic, amphoteric and / or zwitterionic surfactants, preferably none. 10. a soap according to the preceding points which further contains one or more components selected from fillers, free fatty acids, odorants or perfumes, antioxidants, complexing agents, care agents and humectants. 11. a soap according to item 10 wherein the filler is selected from talc, starch such as corn starch or wheat starch, calcium carbonate, cellulose and combinations thereof.
    The soap of the invention contains as essential ingredient one or more biosurfactants.
    By biotensioactives are meant substances which are produced by microorganisms and which are often also removed from the cell. Biotensioactives are like conventional surfactants surface active substances that reduce the surface tension of liquids and thus promote the mixing of aqueous phases (hydrophilic) and hydrophobic (hydrophobic). Bio-based surfactants can be manufactured under mild production conditions that require low energy consumption. They are generally easily biodegradable and is very low pollutant. They are also non-toxic and their production is also done without toxic byproducts. The raw materials used for their microbial production are carbohydrates, in particular sugars such as glucose and / or lipophilic carbon sources such as fats, oils, partial glycerides, fatty acids, fatty alcohols, hydrocarbons saturated or unsaturated long chain. According to the invention, the biotensioactives are preferably biotensioactives produced by fermentation.
    Biotensiatives include glycolipids, lipopeptides, lipoproteins, fatty acids, phospholipids, neutral lipids and polymeric surfactants (eg emulsan) which can all also be used in the present invention.
    The glycolipids that can be used in the present invention are compounds in which one or more monosaccharide units are connected to a lipid moiety by a glucosidic linkage. Examples of glycolipids used as biosurfactants according to the invention are the rhamnolipids, the sophorolipids, the lipids of mannosylerythritol and the lipids of trehalose. Among them, rhamnolipids, sophorolipids, mannosylerythrol lipids and combinations thereof are preferred.
    Rhamnolipids are obtained from bacteria of the genus Pseudomonas, in particular Pseudomonas aeruginosa, preferably during growth on hydrophobic substrates such as n-alkanes or vegetable oils. Other glycolipids, for example glucose lipids, cellobiose lipids or trehalose lipids, are produced by yet other microorganisms on various substrates. In addition, according to the invention, mannosylerythritol lipids are preferred glycolipidic biotensives; they are produced by bacteria of the genera Pseudozyma, Candida antarctica and Ustilago.
    According to the invention, rhamnolipids have the following general formula:
    in which m is equal to 2.1 or 0, n is equal to 1 or 0, R 1 and R 2 are independently identical or different organic radicals having 2 to 24, preferably 5 to 13, carbon atoms, especially an alkyl radical; substituted or unsubstituted, branched or unbranched, which may also be unsaturated, the alkyl radical being preferably a linear saturated alkyl radical having 8 to 12 carbon atoms, more preferably a nonyl or decyl radical, or a mixture thereof .
    The salts of these compounds are also included in the present invention.
    The term "di-rhamnolipid" in the present invention refers to compounds of the above formula or their salts wherein n is 1.
    Therefore, the term "mono-rhamnolipid" in the present invention refers to compounds of the general formula or their salts wherein n is 0.
    According to the invention, mixtures of mono- and dirhamnolipids are preferably used. The monorhamnolipid to dirhamnolipid ratio is preferably from about 2: 1 to 4: 1, more preferably from 2.5: 1 to 3: 1. Particularly preferred mixtures of mono- and dirhamnolipids are wherein, in the above formula, R1 and R2 are independently nonyl radical or linear decyl radical. In the latter case, it is therefore rhamnolipids which are each derived from 3-hydroxydodecanoic acid and / or 3-hydroxyundecanoic acid. Such mixtures are commercially available, for example as rhamnolipid R90, R95 or R98 from Agae Technologies, U.S.A., the number indicating in each case the degree of purity. According to the invention, rhamnolipid R90 can be used in a particularly preferred manner.
    The sophorolipids are produced by fermentation with yeasts such as Candida bombicola (also known as Torulopsis bombicola), Yarrowia lipolytica, Candida apicola (Torulopsis apicola) and Candida bogoriensis by growth on sugars, hydrocarbon substances, vegetable oils or mixtures thereof
    The sophorolipids have the formulas (1) indicated below (lactone form) and (2) (free acid), both forms being generally present in the mixture.
    (0
    (2) in which R1 and R1 'are independently saturated hydrocarbon chains or monounsaturated or polyunsaturated hydrocarbon chains, in particular monounsaturated, having from 8 to 20, in particular from 12 to 18, carbon atoms, more preferably from 14 to 18 carbon atoms, which may be linear or branched and which may comprise one or more hydroxyl groups, R2 and R2 'independently represent a hydrogen atom or a saturated alkyl radical or a monounsaturated or polyunsaturated alkyl radical, in particular monounsaturated, having from 1 to 9 carbon atoms, preferably 1 to 4 carbon atoms, which may be linear or branched, and which may comprise one or more hydroxyl groups, and R3, R3 ', R4 and R4' independently represent an atom of hydrogen or an acetyl group.
    The preferred sophorolipids are those in which R1 and R1 'are a monounsaturated linear hydrocarbon chain having 15 carbon atoms. It is further preferred that R2 and R2 'are a methyl group or a hydrogen atom, preferably each a methyl group.
    According to the invention, the preferred sophorolipids are those in which the acid form and the lactone form are present in the mixture, preferably about 20% to about 60% by weight of the sophorolipid are present in the acid form and the rest of the sophorolipid is present in the lactone form.
    In particular, the preferred sophorolipids are those in which the compounds of the formulas above (1) and (2) are present in a mixture, R1 and R1, representing a monounsaturated linear hydrocarbon chain having 14 to 18 carbon atoms, preferably 15 carbon atoms, R3 and R4 representing an acetyl group, R3 'and R4' representing a hydrogen atom and R2 and R2 'representing a methyl group, and about 20% to 60% by weight of sophorolipids in the form of acid.
    These sophorolipids are commercially available, for example under the name Sopholiance S from Soliance. More specifically, the sophorolipid available under the trade name Sopholiance S from SOLIANCE is a solution of sophorolipid at 60% by weight and is obtained, for example, by fermentation of Candida bombicola on rapeseed oil methyl ester. and glucose (INCI: Candida bombicola / glucose / methyl rapeseed ferment (and) water). Sopholiance S is a preferred sophorolipid according to the invention.
    Soliance S contains the free acid form at about 20% by weight, in admixture with the lactone form.
    The lipids of mannosylerythritol are glycolipids of the following general formula:
    in which the R 1 independently represent fatty acid acyl groups having 4 to 24 carbon atoms, preferably 8 to 12 carbon atoms, the R 2 independently represent a hydrogen atom or an acetyl group and R 3 represents an atom of hydrogen or an acyl group of fatty acid having 2 to 24 carbon atoms. A suitable mannosyerythritol lipid according to the invention is commercially available under the name Ceramela-B (Toyobo) (INCI: Pseudozyma Tsukubaensis / Olive Oil / Glycerin / Soy Protein Ferment).
    The bio-surfactants also include the group of substances of lipids and lipid derivatives which include lipopeptides in particular. In general, the lipopeptides are synthesized non-ribosomally from the respective microorganisms, for example Gram-positive bacteria, in particular Bacillus and Streptomyces genera, Gram-negative bacteria, in particular of the genus Pseudomonas and myxobacteria, and filamentous fungi. Peptide chains generally consist of two to forty amino acids and can be linear, cyclic or branched. Unlike peptide chains synthesized ribosomally, they often include as monomeric components not only protein-forming L-amino acids, but also D-amino acids and carboxylic acids and / or alpha-hydroxy carboxylic acids of all kinds. . The amino acids are most often L-α- or Da-amino acids, however there may also be β-, γ- or δ-amino acids which may also be present in D or L configuration. The peptide chains may also include other chemical modifications, in particular they may be glycosylated, hydrolysed, N-methylated or N-formylated. The common structural elements are further thiazoline and / or oxazoline rings in different oxidation states. A known lipopeptide biosensitive is surfactin which has the following structure and which is generally used in the form of an alkaline or ammonium salt:
    An appropriate surfactin according to the invention is commercially available from Kaneka.
    Lipopeptides, which can be used as biotensioactives according to the invention, also comprise so-called fatty acyl glutamates. They have the following general formula:
    wherein R is a straight or branched alkyl chain having 5 to 21 carbon atoms, preferably 7 to 17 carbon atoms, more preferably 12 to 16 or 13 to 15 carbon atoms. Fatty acyl glutamates used as biosurfactants are usually in a mixture in which R has different chain lengths. The radical R may also be hydroxylated, preferably monohydroxylated; in this case, hydroxylation in the β position is preferred. Fatty acyl glutamates used as biosurfactants are available, for example, from Modular Genetics, Inc., USA.
    Lipopeptides, which can be used in a preferred manner according to the invention as biotensioactives, include so-called fatty acyl glycinates. They have the following general formula: RC (O) NHCH 2 CO 2 X, wherein R is a linear or branched alkyl chain having 5 to 21 carbon atoms, preferably 7 to 17 carbon atoms, preferably 12 to 15 or 15 to 15 carbon atoms and X is a cation, preferably an alkali metal or ammonium cation, more preferably a sodium or ammonium cation, or -H.
    The fatty acyl glycinates used as biotensioactives may also be present in a mixture in which R may have different chain lengths.
    The fatty acyl glycinates used as biosurfactants are available for example from Modular Genetics, Inc., USA.
    According to the invention, the preferred soaps are those containing the following biotensioactives or combinations of biotensioactives: one or more rhamnolipids, one or more sophorolipids, fatty acyl glutamates, fatty acyl glycinates, surfactin, a lipid mannosylerythritol, rhamnolipid (s) + fatty acyl glutamate (s), rhamnolipid (s) + sophorolipid (s), fatty acyl glutamate (s) + mannosylerythritol lipid (s).
    The soap of the invention contains biosurfactants in an amount of about 1 to about 50% by weight, preferably about 1 to about 20% by weight, more preferably about 1 to about 15% by weight, more preferably about 1 to about 15% by weight. 10% by weight, also preferably from 1.5 to 7.5% by weight, based on the total weight of the soap. If it is a mixture of biotensioactives, the percentages refer to the total amount of biosurfactants contained.
    The soap of the present invention contains as other important ingredients fatty acid salts or "fatty acid soaps"; they are designated by sodium, potassium or ammonium salts of fatty acids. The term "fatty acids" denotes, according to the invention, linear and / or branched, saturated and / or unsaturated carboxylic acids having from 6 to 30 carbon atoms, for example caprylic acid or 2-ethylhexaneic acid. , capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and behenic acid, erucic acid, isostearic acid, isotridecanoic acid but also elaidic acid, petroselinic acid, elaéo-stearic acid, arachinic acid, gadolinic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid and arachidonic acid. Preferred are linear and / or branched, saturated and / or unsaturated carboxylic acids having 10 to 22 carbon atoms, also preferably 12 to 18 carbon atoms.
    The technical mixtures which are preferably used are those which are obtained from vegetable and animal fats and oils, for example from tallow fatty acids, coconut fatty acids, olive oil, palm oil fatty acid, lard fatty acids, and / or palm kernel oil fatty acids.
    According to the invention, the following fatty acid salts are particularly preferably used: tallow fatty acid (INCI name: Sodium Tallowate), coconut fatty acid (INCI name: Sodium Cocoate), dicarboxylic acid fatty acids olive (INCI name: Sodium Olivate), palm oil fatty acids (INCI name: Sodium Palmate), lard fatty acids (INCI name: Sodium Lardate) and / or palm kernel oil (INCI name: Sodium palm kernelat).
    If a soap with a softer consistency, for example fluid-pasty, is desired, some of the sodium salts may be replaced by potassium salts.
    The soap of the invention contains the fatty acid salts in an amount of about 0.5 to 90% by weight, preferably about 10 to 85% by weight, more preferably about 20 to 85% by weight. % by weight, still more preferably 40 to 80% by weight, also preferably 50 to 80% by weight, based on the total weight of the soap. If they are mixtures of fatty acid salts, percentages refer to the total amount of fatty acid salts contained.
    The soap of the invention is preferably a bar of soap, that is to say a soap having a solid consistency. If desired, the soap of the invention may also be present in liquid pasty form or in liquid form.
    In preferred embodiments, the soap of the invention contains, in addition to the biotensioactives and fatty acid salts, 0.5% by weight or less of other surfactants, still more preferably no other surfactants, therefore no other nonionic, anionic, cationic, amphoteric and / or zwitterionic surfactants.
    In other preferred embodiments, the soap of the invention contains 0.5% by weight, or less, of anionic, cationic, amphoteric and / or zwitterionic surfactants, preferably none. In these cases, the nonionic surfactants may be contained in amounts ranging from 0.1% to 10% by weight. In addition, in these cases, the nonionic surfactants are preferably sugar-based nonionic surfactants, such as alkylpolyglycosides and / or N-alkylglucamides of fatty acids which are also referred to as fatty acyl glucamides.
    The soap of the invention preferably further contains one or more components such as additives selected from fillers, free fatty acids, odorants and fragrances, antioxidants, complexing agents, care agents and agents. humectants. However, other additives may also be included in the present invention.
    Fatty acid salts, biosurfactants and additives are added to preferably about 85 to 98% by weight, more preferably about 88 to 95% by weight and water is added to reach 100%.
    In particular, the fillers are natural fillers, possibly soluble in water, for example talc, starch, such as corn starch or wheat starch, calcium carbonate, cellulose and their combinations.
    The free fatty acids, which may be used for regreasing the skin, may be fatty acids comprising a linear or branched aliphatic acyl radical containing from 6 to 30, preferably from 10 to 22, more preferably from 12 to 18, carbon atoms. carbon and 0 and / or 1, 2 or 3 double bonds. Typical examples are caproic acid, 2-ethylhexanic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and the like. behenic acid, erucic acid, isostearic acid, isotridecanoic acid also elaidic acid, elaéo-stearic acid, petroselinic acid, gadoleic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid and arachidonic acid. Preferred are the technical fatty acids having from 12 to 18 carbon atoms, such as coconut, palm, palm kernel or tallow fatty acids, which correspond to the corresponding salts of component (a).
    The free fatty acids may be contained in the soap for example in amounts ranging from 0.1% to 10% by weight, preferably from 1% to 7% by weight; this is the total amount of free fatty acids in the soap.
    The preferred odorous substances or perfumes, which may be contained in the soap, according to the invention are in particular natural odorous substances. If an odorant substance is present, it is preferably present in an amount of 0.05% to 3% by weight, preferably 0.1% and 2% by weight, more preferably 0.2% by weight. and 1% by weight, and also preferably from 0.5 to 1% by weight, in each case based on the total weight of the cleaner. If several odorous substances are present, the percentages refer to the total quantity of odorants or perfumes.
    Typical antioxidants that can be used according to the invention are t-butylhydroxytoluene or a vitamin (tocopheryl acetate). Typical complexing agents that may be used according to the invention are salts of 1-hydroxyethane-1,1-diphosphonic acid (INCI: Tetrasodium Etidronate) or ethylenediaminetetraacetic acid (INCI: Tetrasodium EDTA).
    The soap may contain as a care substance, for example, oily substances, preferably oily substances such as vegetable oils and fats, plant extracts, as well as mono- or oligosaccharides and / or lipids. Examples include aloe vera extract (INCI), lanolin, niacinamide, avocado oil or olive oil.
    The soap may contain as humectant for example glycerol and / or lactates.
    The soap manufacture of the invention can be carried out in the usual manner for such products. Conventional processes for mixing or homogenizing, kneading, optionally grinding, spinning, optionally pelletizing, extruding, cutting and pressing are known to those skilled in the art and can be used for the manufacture of soap bars of the invention. The manufacture is preferably carried out in the temperature range of 40 to 90 ° C; the fusible ingredients are placed in a mixer or a heated mixer and the non-fusible components are introduced with stirring. To homogenize, the mixture can then be passed through a sieve before shaping.
    Summary table:
    In the following, the preferred cosmetic cleaning agents are given for the cleaning agent system of the invention. The figures are expressed as percentage by weight and refer to the concentration of active substance. Particularly preferred soaps are those having the compositions of formulas 9, 10, 14, 15, 19, 20, 24, 25, 29, 30, 34, 35, 39, 40, 44, 45, 49 and 50.
    "Miscellaneous" means according to the invention water and the usual ingredients of soaps such as fillers, free fatty acids, odorants or perfumes, antioxidants, complexing agents, care agents and humectants.
    The biosurfactants and the fatty acid salts preferably add up to about 85-98% by weight, more preferably about 88-95% by weight, and the balance of 100% is preferably water.
    Examples
    The soap bars shown in the following tables were manufactured. The percentages must be in percentages by weight, each time relative to the total weight of the detergent.
    Table 1
    Table 2
    Soaps have a very good washing behavior, a very good skin sensation and a very good foaming power, similar to the properties of combi bars.
    权利要求:
    Claims (10)
    [1" id="c-fr-0001]
    claims
    1. Soap which contains the following ingredients, each in percent by weight based on the total weight of the soap: (a) 0.5 and 90% by weight of sodium, potassium and / or ammonium salts fatty acids having from 6 to 30 carbon atoms, and (b) from 1 to 50% by weight of one or more biosurfactants.
    [2" id="c-fr-0002]
    2. Soap according to claim 1, which contains (a) from 20 to 85% by weight of sodium, potassium and / or ammonium salts of fatty acids having from 6 to 30 carbon atoms, and (b) from 1 to 20% by weight of one or more biosurfactants, in each case based on the total weight of the soap.
    [3" id="c-fr-0003]
    3. Soap according to claim 1 or 2, which contains as component (a) sodium, potassium and / or ammonium salts, preferably sodium salts, tallow fatty acids, coconut fatty acids, olive oil fatty acids, palm oil fatty acids, lard fatty acids, palm kernel oil fatty acids or a combination thereof.
    [4" id="c-fr-0004]
    4. Soap according to one of the preceding claims which contains as biosensitive a glycolipid, a lipopeptide or a combination thereof.
    [5" id="c-fr-0005]
    5. Soap according to one of the preceding claims which contains as biotensiactive a rhamnolipid, a sophorolipid, a mannosylerythritol, a surfactin, a fatty acyl glutamate, fatty acyl glycinate or a combination thereof.
    [6" id="c-fr-0006]
    6. Soap according to claim 5 which contains as a biosurfactant a sophorolipid, preferably a mixture of the acid form and the lactone form, wherein 20 to 60% by weight are present in the acid form.
    [7" id="c-fr-0007]
    7. Soap according to claim 5 which contains as biotensiactive a rhamnolipid, preferably a mixture of mono- and dirhamnolipid which are each derived from 3-hydroxydodecanoic acid and 3-hydroxyundecanoic acid.
    [8" id="c-fr-0008]
    8. Soap according to one of the preceding claims which additionally contains from 0.1 to 10% by weight of a nonionic surfactant, in particular alkyl polyglycoside (s), fatty acyl gluconamide (s) or of their combinations.
    [9" id="c-fr-0009]
    9. Soap according to one of the preceding claims, containing 0.5% by weight, or less, of anionic surfactants, cationic, amphoteric and / or zwitterionic, preferably none.
    [10" id="c-fr-0010]
    10. Soap according to the preceding claims which further contains one or more components selected from fillers, free fatty acids, odorants or fragrances, antioxidants, complexing agents, care agents and humectants.
    类似技术:
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    同族专利:
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    EP3940049A1|2020-07-13|2022-01-19|Dalli-Werke GmbH & Co. KG|Mannosylerythritol lipid comprising liquid rinse aids|
    法律状态:
    2017-09-28| PLFP| Fee payment|Year of fee payment: 2 |
    优先权:
    申请号 | 申请日 | 专利标题
    DE102015217506.5A|DE102015217506A1|2015-09-14|2015-09-14|Soap with biosurfactants|
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