WO2003094630A1 - Powder composition - Google Patents
Powder composition Download PDFInfo
- Publication number
- WO2003094630A1 WO2003094630A1 PCT/JP2003/005714 JP0305714W WO03094630A1 WO 2003094630 A1 WO2003094630 A1 WO 2003094630A1 JP 0305714 W JP0305714 W JP 0305714W WO 03094630 A1 WO03094630 A1 WO 03094630A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- powder composition
- mixture
- trehalose
- carbohydrate
- mass
- 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.)
- Ceased
Links
Classifications
-
- 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
- A23L29/30—Foods or foodstuffs containing additives; Preparation or treatment thereof containing carbohydrate syrups; containing sugars; containing sugar alcohols, e.g. xylitol; containing starch hydrolysates, e.g. dextrin
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
- A23G3/00—Sweetmeats; Confectionery; Marzipan; Coated or filled products
- A23G3/34—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof
- A23G3/346—Finished or semi-finished products in the form of powders, paste or liquids
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
- A23G3/00—Sweetmeats; Confectionery; Marzipan; Coated or filled products
- A23G3/34—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof
- A23G3/36—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof characterised by the composition containing organic or inorganic compounds
- A23G3/42—Sweetmeats, confectionery or marzipan; Processes for the preparation thereof characterised by the composition containing organic or inorganic compounds characterised by the carbohydrates used, e.g. polysaccharides
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
- A23G4/00—Chewing gum
- A23G4/06—Chewing gum characterised by the composition containing organic or inorganic compounds
- A23G4/10—Chewing gum characterised by the composition containing organic or inorganic compounds characterised by the carbohydrates used, e.g. polysaccharides
-
- 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
- A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
-
- 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
- A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
- A23L27/10—Natural spices, flavouring agents or condiments; Extracts thereof
- A23L27/12—Natural spices, flavouring agents or condiments; Extracts thereof from fruit, e.g. essential oils
- A23L27/13—Natural spices, flavouring agents or condiments; Extracts thereof from fruit, e.g. essential oils from citrus fruits
-
- 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
- A23L27/00—Spices; Flavouring agents or condiments; Artificial sweetening agents; Table salts; Dietetic salt substitutes; Preparation or treatment thereof
- A23L27/30—Artificial sweetening agents
- A23L27/33—Artificial sweetening agents containing sugars or derivatives
-
- 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
- A23L29/30—Foods or foodstuffs containing additives; Preparation or treatment thereof containing carbohydrate syrups; containing sugars; containing sugar alcohols, e.g. xylitol; containing starch hydrolysates, e.g. dextrin
- A23L29/35—Degradation products of starch, e.g. hydrolysates, dextrins; Enzymatically modified starches
-
- 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
- A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
- A23P10/00—Shaping or working of foodstuffs characterised by the products
- A23P10/30—Encapsulation of particles, e.g. foodstuff additives
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23G—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF
- A23G2200/00—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF containing organic compounds, e.g. synthetic flavouring agents
- A23G2200/06—COCOA; COCOA PRODUCTS, e.g. CHOCOLATE; SUBSTITUTES FOR COCOA OR COCOA PRODUCTS; CONFECTIONERY; CHEWING GUM; ICE-CREAM; PREPARATION THEREOF containing organic compounds, e.g. synthetic flavouring agents containing beet sugar or cane sugar if specifically mentioned or containing other carbohydrates, e.g. starches, gums, alcohol sugar, polysaccharides, dextrin or containing high or low amount of carbohydrate
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
Definitions
- the present invention relates to a powder composition containing trehalose, which can be preferably used as a flavor or flavor enhancer or an enhancer for various drinks and foods, particularly powdered drinks and gums, and a food and drink containing the powder composition.
- spices, spice oils, spice oleoresins, their prepared compositions, dyes, functional substances, and other easily volatile or easily degraded additive substances can be powdered by using these substances.
- the additive substance is emulsified in a natural gum such as gum arabic, a protein solution such as gelatin, or a processed starch such as dextrin, or a sugar solution such as a monosaccharide, a disaccharide, or a polysaccharide, and spray-dried, so that the additive substance is spray-dried.
- a typical method is a method in which a core material is coated with the above-mentioned natural gum, protein, processed starch, sugar and the like to obtain a fine powder in the form of a capsule (hereinafter sometimes referred to as “microencapsulation method”).
- microencapsulation method a method in which a core material is coated with the above-mentioned natural gum, protein, processed starch, sugar and the like to obtain a fine powder in the form of a capsule.
- microencapsulation method a method in which a core material is coated with the above-mentioned natural gum, protein, processed starch, sugar and the like to obtain a fine powder in the form of a capsule.
- U.S. Pat. No. 3,704,137 discloses that oil is mixed with an antioxidant, and separately mixed with water, sucrose and DE (D extrose Equivalent, hydrolysate of 20 or less). (The percentage of direct reducing sugars converted to pudose sugar in the hydrolyzate.) Starch hydrolysates having a value are mixed, the two mixtures are emulsified together, and the resulting mixture is rod-shaped into a solvent. It is described that an essential oil composition is obtained by extruding in a shape, removing excess solvent, and finally adding an anti-caking agent.
- Sho 61-5202656 discloses that an aqueous mixture of sugar, a starch hydrolyzate and a selected emulsifier is heated to the melting point of the aqueous mixture, and the essential oil is added to the aqueous mixture. Flavoring agents are combined and mixed to form a homogeneous melt, and the homogeneous melt is extruded into a relatively cold refrigerant to form a solid extruded material. After grinding, the material is dried to prevent coagulation. It is described that a solid essential oil flavor composition is obtained by combining the agents.
- 63-264652 discloses that edible fats and oils are converted into a saccharide mixture with a specific mass ratio of hydrolyzed starch having a DE of 5 to 12 and sucrose.
- U.S. Pat. No. 4,820,534 discloses that a minor component obtained from a water-soluble carbohydrate such as fructose and a maltodextrin having a DE of 20 or more.
- a high-molecular-weight carbohydrate base material is mixed with a volatile flavor without adding moisture, and heated at a temperature equal to or higher than the glass transition temperature of the base material in an extruder having a single screw type screw, and extruded. It describes a method of obtaining an enclosure in which volatile flavors are encapsulated in a vitreous matrix by cooling, shaping and molding.
- the amount of plasticizer such as water in the carbohydrate matrix in which unstable components serving as core substances are blended is required. It is necessary that the amount is sufficiently small, but if the amount of the plasticizer is reduced, the melt viscosity of the matrix increases, and it becomes difficult to uniformly disperse the core substance in the matrix. For this reason, various attempts have been made to obtain a powder composition that can uniformly disperse the core substance and is stable against temperature and humidity during storage.
- JP-A-8-38093 discloses that, as a carbohydrate matrix, processed starch and a hydrogen additive of a saccharide are used, and these amounts are converted to solids in terms of 15:85 to 85. A method for producing a flavor-containing capsule that can be stored for a long period of time by setting the mass ratio to: 15 is described. In addition, Japanese Patent Application Publication No.
- carbohydrate matrices include sucrose, glucose, fructose, lactose, maltose, glucovilanosyl mannitol, glucopyranosyl sorbitol, 18
- maltodextrin having the following DE value and adding 5 to 10% of water as a plasticizer, particles that have a Tg (glass transition temperature) below room temperature but are stable for a long period of time
- Tg glass transition temperature
- an object of the present invention is to provide a powder composition which does not have the above-mentioned conventional problems and also has the conventionally required properties and a method for producing the same.
- an object of the present invention is to have a low hygroscopicity, excellent storage stability, easy dispersion of the core substance, a sufficient amount of the core substance, excellent taste.
- Another object of the present invention is to provide a powder composition which does not have a feeling of sticking to teeth even after being added to gum, tableted confectionery and the like, and which can be preferably used as a flavor imparting agent or an enhancer.
- the present inventors have conducted intensive studies to solve the above-described problems, and as a result, focused on trehalose, a kind of non-reducing disaccharide in which two molecules of D-glucose were bonded in a 1,1 bond, and encapsulated a core substance.
- the present invention has been accomplished by finding that the above problem can be solved by using a specific amount of a carbohydrate mixture as a constituent material of a powder composition.
- the present invention provides a powder composition
- a powder composition comprising a carbohydrate mixture containing 30 to 70% by mass of trehalose, a plasticizer, and a core substance.
- the present invention relates to a method for heating and melting a carbohydrate mixture containing 30 to 70% by mass of trehalose and a plasticizer, adding a core substance to the melt, and mixing to obtain a homogeneous mixture, and extruding the homogeneous mixture. It is intended to provide a method for producing a powder composition, wherein the powder is cooled and solidified while cutting or pulverizing the obtained solid.
- the present invention provides a food or drink containing the powder composition.
- the powder composition of the present invention comprises a carbohydrate mixture comprising a carbohydrate mixture (a) containing 30 to 70% by mass of trehalose and a plasticizer (b) and, if necessary, further additives.
- the core material (C) is encapsulated in the material.
- Trehalose a constituent material of the carbohydrate mixture of the present invention, is a disaccharide first isolated from ergot of rye in 1832 and widely exists in nature such as mushrooms, plants, manna, shrimp, insects, and yeast. However, when it is absorbed by the human body, it is decomposed and absorbed into glucose by trehalase present in the jejunum and duodenum.
- Trehalose which can be used in the present invention includes three isomers of ⁇ , ⁇ -, ⁇ , ⁇ -, j3 and?, And naturally occurring ⁇ , Hi-trehalose is particularly preferred.
- trehalose that can be used may be any of an anhydride and a hydrate, and is not limited. Furthermore, the sweetness of trehalose is low at 45% of that of sugar, and can be preferably used for a wide range of foods and drinks.
- Trehalose can be produced, for example, by culturing yeast in a glucose solution, producing trehalose in the yeast, and isolating it from the yeast. Then, trehalose can be produced by a method of separating trehalose from the culture solution, but commercially available products (for example, “Treha” manufactured by Hayashibara Co., Ltd.) may be used.
- the blending ratio of trehalose in the carbohydrate mixture is from 30 to 70% by mass, preferably from 40 to 65% by mass, more preferably from 50 to 60% by mass. If the blending ratio of trehalose is less than 30% by mass, the effect of the present invention is not sufficient. This is not preferable because crystals may precipitate.
- the materials other than trehalose constituting the carbohydrate mixture those used when producing a powder composition by a conventional extrusion method can be used.
- Materials other than these trehalose include monosaccharides and Glucose, sugar alcohol, starch, processed starch, natural gums, cellulose derivatives, proteins and the like. More specifically, these materials other than trehalose are as follows.
- monosaccharides include pudose, fructose, xylose, arabinose, etc.
- oligosaccharides include sucrose, maltose, rafinoinus, sucrose, cyclodextrin, etc.
- sugar alcohols include reduction.
- starches include naturally occurring starch, dextrin obtained by hydrolyzing starch, and processed starch obtained by treating and processing starch with an acid or an enzyme.
- the starch of natural origin can be of any origin, and is not particularly limited as long as it is produced from corn, wheat, potato, sweet potato, evening pio, etc., for example.
- Starch is heated to hydrolysis in the presence of water or acid in the presence of an acid or an enzyme, and then hydrolyzed into several intermediate products and finally to glucose. This intermediate product can be employed as dextrin.
- the degree of hydrolysis of dextrin can be usually represented by DE, the dextrin that can be employed in the present invention is not particularly limited by DE.
- a starch processed by a method other than the above one obtained by adding a specific functional group to a hydroxyl group of glucose constituting the starch can also be used.
- functional groups are ester-bonded, specifically, acetic esterified starch, octenyl succinic acid starch, phosphoric acid monoesterified starch, etc., and those which are ether-linked, specifically, hydroxypropyl starch, etc.
- crosslinked hydroxyl groups include phosphoric acid crosslinked starch.
- a low-viscosity starch, an oxidized starch, a pregelatinized starch, and the like can be used as needed.
- natural gums include gum arabic, mouth-to-cast bean gum, carrageenan, guar gum, karaya gum, tragacanth gum, and the like.
- Cellulose derivatives include methylcellulose and hydroxypropylcellulose.
- Proteins include: Casein, zein, gelatin, whey, isolated soy protein, etc. Can be
- a plasticizer is used to reduce the viscosity of the carbohydrate mixture at the time of melting.
- Preferred plasticizers include water, glycerin and propylene glycol. These may be used alone or in combination of two or more.
- the plasticizer is water, it is used in an amount of usually 0.5 to 50% by mass, preferably 1 to 30% by mass, based on the mass of the carbohydrate mixture.
- glycerin or propylene glycol is used as the plasticizer, it is used in an amount of usually 0.5 to 10% by mass, preferably 1 to 6% by mass, and more preferably 1.5 to 4% by mass.
- the core substance encapsulated in the carbohydrate matrix may be any substance which has been conventionally used as a core substance in an extrusion method or a microcapsule method.
- the core substance preferably used in the present invention it is necessary to prevent deterioration due to moisture absorption, caching, volatilization of components, change of components, discoloration, fading, etc.
- a substance which is desired to be released in the presence of water, such as when added may be mentioned.
- examples of such a core substance include a flavor composition, a pigment, an acidulant, a vitamin, a seasoning, a spice, a functional substance, and a mixture thereof.
- the substances preferably used as the core substance in the present invention will be more specifically described below.
- any composition that has already been used in the production of powdered fragrance can be used.
- Citrus-based flavors such as di, lemon and grapefruit, fruit-based flavors such as apple, banana, grape, peach, strawberry and pineapple, mint-based flavors such as peppermint and spearmint, spices such as pepper, cinnamon, nameg, and clove Flavors, such as vanilla, coffee, cocoa, hazelnuts, etc., tea flavors such as black tea and green tea, beef, chicken, salmon, clubs, etc. It is not limited to these.
- the above-mentioned fragrance not only a compounded fragrance but also an essential oil from which an active ingredient is extracted, oleoresin, etc. can be used depending on the kind of fragrance.
- flavors such as citral, geraniol, 1-menthol, vanillin and the like can be mentioned, and flavors in which these are mixed at an arbitrary ratio can also be used. Further, it may be a flavor component from coffee, tea such as black tea, fish knots such as bonito, natural juice, etc. obtained by steam distillation or supercritical fluid extraction.
- the pigment is not particularly limited as long as it is edible as long as the powder composition of the present invention is used in foods and drinks.
- edible pigments include natural pigments such as carotene, paprika pigment, anatoto pigment, oil-soluble pigments such as chlorophyll, and water-soluble natural pigments such as cochineal, gardenia, and grape. Examples thereof include a pericarp, a beetle, and a synthetic pigment.
- the foods are not limited to edible ones. These can be used in combination of two or more depending on the use and the like.
- the acidulant examples include citric acid, fumaric acid, dl-malic acid, and ascorbic acid. These can be used in combination of two or more depending on the use and the like.
- vitamins examples include vitamin B, vitamin A, vitamin D, lipoic acid, nicotinic acid, vitamin L, vitamins, and salts thereof such as sodium salt and hydrochloride, and derivatives such as acetate. These vitamins can be used alone or in combination of two or more.
- Seasonings include chemicals such as sodium glutamate and nucleic acid seasonings. Examples include flavorings and seasonings obtained by extraction or decomposition from natural food materials. These seasonings can be used alone or in combination of two or more.
- spices examples include spicy spices such as cloves, garlics, and cinnamon, honey spices such as basil and parsley, and spice spices such as cumin and anis. These spices can be used alone or in combination of two or more.
- Functional substances include, for example, polyphenols such as cisosex and buckwheat, chitin, chitosan, propolis, royal jelly, fish oils such as DHA and EPA, linoleic acid, linolenic acid, Powdered crude drugs such as carrots and aloe.
- These functional substances can be used alone or in combination of two or more.
- tea leaves such as green tea and black tea, coffee beans, extracts obtained from fish knots such as bonito, or concentrates and powder-dried products, as well as tea leaves, coffee beans and fish knots themselves are crushed. Powders can also be used as the core material.
- a fragrance composition is particularly preferred.
- the proportion of the core substance added to the carbohydrate matrix depends on the ratio of the plasticizer contained in the core substance, the composition of the carbohydrate matrix, the state of the core substance at room temperature (liquid or solid), etc., and is usually 0.01 to 25. % By mass is preferable, and 1 to 15% by mass is more preferable. If the amount is less than 0.01% by mass, the effect of the core substance may not be obtained. On the other hand, if the amount is more than 25% by mass, a tissue cannot be formed or the structure cannot be maintained after production.
- additives such as an emulsifier and an antioxidant can be added as necessary.
- Suitable emulsifiers include, for example, sucrose fatty acid esters, polyglycerin fatty acid esters, sorbin fatty acid esters, propylene glycol fatty acid esters, lecithin, savonins and the like. If available, limited to these It is not specified.
- the emulsifier is added, the amount is not particularly limited, but may be 0.1 to 3% by mass based on the mass of the ordinary core substance.
- antioxidant examples include vitamin C, vitamin E, rosemary extract, sage extract, sodium 1-sorbate, 2,6-di-tert-butyl-4-methyl phenol, and the like.
- the antioxidant is added, there is no particular limitation on the amount of the antioxidant, but it is usually about 0.1 to 2% by mass based on the mass of the core substance.
- the method of encapsulating the core substance in a carbohydrate matrix containing trehalose may be a known method per se, and includes a batch method and a continuous method.
- the batch method for example, first, 15 to 50% by mass of water is added to the constituent materials of the carbohydrate mixture and the total weight of the constituent materials, and the mixture is dissolved while heating.
- the amount of water to be added is not particularly limited to the above range, but if the amount of water is too small, it is difficult to heat uniformly, while if the amount of water is too large, heating is performed later to reduce the water content. It takes time to lower the temperature, which is not preferable from the viewpoint of energy efficiency. Heating is carried out in a boiling pot or the like until the amount of water in the carbohydrate matrix melt becomes about 0.5 to about 0% by mass, more preferably about 1 to 6% by mass.
- the heating temperature at this time depends on the composition of the carbohydrate matrix, but is preferably in the range of about 110 to 200 ° C, more preferably in the range of about 120 to 170 ° C. If the residual moisture content in the carbohydrate matrix is too high, the resulting powder composition will have an increased moisture content, and the stability to moisture and temperature will be poor, which is not preferable. On the other hand, when the residual water content is low, the viscosity of the molten carbohydrate matrix increases, and it becomes difficult to uniformly disperse the core substance, which is not preferable. When a plasticizer other than water is used in combination as a plasticizer, the content of water can be reduced and the melt viscosity of the carbohydrate matrix can be reduced as compared with the case where only water is used as the plasticizer.
- a core substance is added to the obtained melt.
- other additives can be added as needed. This can be done while the matrix is molten.
- the obtained homogeneous mixture containing the core substance is filled in a closed container, and pressure is applied to the mixture through an injection port (die). put out.
- the shape of the solid material to be extruded can be various shapes depending on the shape of the die, but is usually a rod shape, a flat shape or a linear shape.
- a single-screw, twin-screw extruder, or a kneader which can be heated, mixed, and extruded in the same vessel, is composed of a pressure-resistant vessel with an extrusion screw or an extrusion plate, is used.
- an extruder for example, KEXP Extruder manufactured by Kurimoto Co., Ltd. can be mentioned.
- a carbohydrate mixture, a plasticizer, a core substance, and the like are introduced into the pressure vessel by a fixed-quantity supply device, and heated, mixed (kneaded) and then extruded in the pressure vessel. .
- the heating temperature depends on the composition of the carbohydrate mixture and the amount of plasticizer, but ranges from about 80 to 170 ° C.
- the core substance can also be introduced from a supply port provided between the raw material supply port and the product discharge port of the pressure-resistant container after the carbohydrate mixture and the plasticizer are heated and mixed to melt the carbohydrate mixture.
- the carbohydrate mixture containing the core substance is cooled and solidified.
- the method of solidification and cooling is not particularly limited as long as it is performed by a general method of vitrification in food.
- a cooling method for example, a liquid solvent having no harm to food hygiene such as cooled ethanol may be used, or a gas such as air or nitrogen may be used.
- a liquid solvent is used for cooling, after pulverization, the solvent can be removed using an appropriate dryer such as a conical blender-dryer.
- the solidified core substance-containing carbohydrate matrix is pulverized or cut using a suitable pulverizer such as a co-mill (manufactured by Quadro) or a ball mill to obtain the core substance-containing powder composition of the present invention.
- a suitable pulverizer such as a co-mill (manufactured by Quadro) or a ball mill to obtain the core substance-containing powder composition of the present invention.
- the particle size of the powder composition varies depending on the purpose of use, but is usually about 50 to 300 zm, preferably 100 to 100 zm.
- the powder composition according to the present invention has low hygroscopicity and excellent storage stability, so that it can be used in a wide range of foods and drinks, such as tea bags, powdered beverages, powdered soups, powdered desserts, candy class, gums, tableting confections, and ice cream. It can be used as a flavor enhancer or enhancer for creams, cookers and the like. Further, the powder composition of
- the amount of the powder composition according to the present invention to be added in various applications is an appropriate amount according to the purpose for which the powder composition is used, the composition of the substance to be added, the use mode of the article to be added, and the like. Thus, the amount may be in a range where the intended effect can be obtained.
- the case where the composition of the present invention is added to food and drink will be described as an example.
- the amount of addition varies greatly depending on the type of powder composition and the type of food and drink to be added.
- the amount is in the range of 0.01 to 5% by mass, preferably 0.1 to 3% by mass, based on the total amount of food and drink.
- trehalose manufactured by Hayashibara
- palatinit manufactured by Palatinit
- processed starch manufactured by National Starch and Chemical Co.
- Example 2 In the same manner as in Example 1 except that 360 g of sucrose was used instead of trehalose, 400 g of the powder composition remaining on the 60 mesh sieve was obtained.
- the solidified product was pulverized using a mill, passed through a 20-mesh sieve, and sieved so as to remain on a 60-mesh sieve, to obtain 220 g of a powder composition remaining on the 60-mesh sieve.
- the solidified product was pulverized using a mill, passed through a 20-mesh sieve, and sieved so as to remain on a 60-mesh sieve, to obtain 220 g of a powder composition remaining on the 60-mesh sieve.
- Comparative Example 4 The dextrin in Comparative Example 4 was replaced with a dextrin having a DE of 19 (Matsuya Chemical Co., Ltd.) In the same manner as in Comparative Example 4 except that the water supply rate was 4.2 g / min, 190 g of a powder composition remaining on the 60 mesh sieve was obtained.
- Trehalose manufactured by Hayashibara
- palatinit manufactured by Palatinit
- processed starch manufactured by National Starch and Chemical Co., Ltd.
- 26 g were dissolved in 250 g of ion-exchanged water. It was heated with stirring at 100 rpm by Onemo Isuzu (manufactured by HEIDON), but trehalose crystallized at 122 ° C and lost its fluidity, allowing the liquid core substance to be encapsulated in the carbohydrate matrix.
- HEIDON Onemo Isuzu
- Example 1 The powder composition of Example 1 was added to a chewing gum dough consisting of 20 parts by mass of a gum base, 66 parts by mass of powdered sugar and 14 parts by mass of corn syrup so as to be 0.4% by mass based on the chewing gum dough. After flavoring, the chewing gum dough was kneaded at about 40 ° C. for 10 minutes and spread to obtain 3 gZ sheet gum.
- Example 2 the board gum of Comparative Examples 7 to 11 was prepared in the same manner as in Example 2 except that the powder compositions of Comparative Examples 1 to 5 were used instead of the powder compositions of Example 1. Obtained.
- Example 1 and Comparative Examples 1 to 5 were stored in a thermostatic chamber at 50 ° C. and a relative humidity of 75% for 12 hours. When the state of the powder composition after storage was observed, the powder compositions of Comparative Examples 3 to 5 were caked, and the powder state could not be maintained. On the other hand, Example 1 and Comparative Examples 1 and 2 maintained sufficient powder fluidity.
- Example 2 After storing the board gum obtained in Example 2 and Comparative Examples 7 to 11 in a thermo-hygrostat at 50 ° C. and a relative humidity of 75% for 12 hours, observation of the state of the board gum and sensory evaluation Went. For sensory evaluation, expert panelists chew board gum for 5 minutes, And the chewing feeling of plate gum were evaluated.
- Trehalose (manufactured by Hayashibara) 410 g, palatinit (manufactured by Palatinite) 320 g were dissolved in 200 g of ion-exchanged water, and the boiling temperature was 140. C to obtain a carbohydrate melt. After adding 72 g of matcha powder (manufactured by Aiyasha) to the melt, the mixture was mixed for 5 minutes and uniformly dispersed. The subsequent steps were performed in the same manner as in Example 1 to obtain 390 g of the powder composition remaining on the 60 mesh sieve. The obtained powder composition had a bright green color derived from matcha. ⁇
- Board gum was prepared in the same manner as in Example 2 except that the powder composition of Example 3 was used instead of the powder composition of Example 1.
- the obtained board gum was subjected to the same preservation / sensory test of board gum as described above.
- the appearance of the plate gum of Example 4 did not change even after storage, and after chewing for 5 minutes, the aroma of matcha was sufficiently expressed and the aroma was not deteriorated. There was no feeling of adhesion to the teeth, and the chewing feeling of the plate gum was good.
- Trehalose manufactured by Hayashibara 43 0 g
- 80 g of lemon oil manufactured by Takasago International Corporation was used as the core substance, and the other conditions were the same as in Example 1 to obtain 3555 g of a powder composition remaining on the 60 mesh sieve.
- Example ⁇ The same procedure as in Example 1 was carried out except that the composition of the carbohydrate mixture in Example 1 was trehalose 365 g, raffinose (produced by Nippon Sugar Beet Co., Ltd.) 335 g, and processed starch 29 g. 450 g of the powder composition remaining on the 60 mesh sieve was obtained.
- Example ⁇ the composition of the carbohydrate mixture in Example 1 was trehalose 365 g, raffinose (produced by Nippon Sugar Beet Co., Ltd.) 335 g, and processed starch 29 g. 450 g of the powder composition remaining on the 60 mesh sieve was obtained.
- Example ⁇ The same procedure as in Example 1 was carried out except that the composition of the carbohydrate mixture in Example 1 was trehalose 365 g, raffinose (produced by Nippon Sugar Beet Co., Ltd.) 335 g, and processed starch 29 g. 450 g of the powder composition remaining on the 60 mesh sieve was
- Example 2 The same procedures as in Example 1 were carried out except that the composition of the carbohydrate mixture in Example 1 was trehalose 365 g, palatinose (manufactured by Mitsui Sugar Co.) 335 g, and processed starch 29 g. 470 g of the powder composition remaining on the 60 mesh sieve was obtained.
- the composition of the carbohydrate mixture in Example 1 was trehalose 365 g, multitoll (manufactured by Towa Kasei Kogyo Co., Ltd.) 335 g, and processed starch 29 g, and the boiling temperature was set at 140 ° C. Except that in the same manner as in Example 1, 470 g of the powder composition remaining on the 60 mesh sieve was obtained.
- the powder compositions obtained in Examples 5 to 9 were subjected to a storage test at room temperature (20 to 30 ° C) for 30 days. All of them had sufficient powder fluidity after storage. . Further, when the powder composition after storage was chewed, it had organoleptically sufficient flavor intensity. (Oil content measurement test)
- the oil content of the powder compositions obtained in Examples 6 to 9 was quantified by an essential oil determination method (Japanese Pharmacopoeia 13; Crude Drug Test Method B—223 to 224), and the results are shown in Table 1 below. The results were as follows, and all contained a sufficient amount of core material.
- a powder composition containing a core substance when a powder composition containing a core substance is formed, by using a specific amount of trehalose as a constituent material of the carbohydrate mixture, the hygroscopic property is low, the storage stability is excellent, and the core substance is excellent. It is easy to disperse evenly, contains a sufficient amount of core substance, has excellent taste, and does not have a feeling of sticking to teeth even after being added to gum, tableted confectionery, etc.
- a powder composition that can be preferably used as an enhancer or the like can be obtained.
- the effect is the same when the powder composition of the present invention is added to various products.
- the added product does not deteriorate in appearance and quality even after long-term storage, and has excellent storage stability. Even after long-term storage, the core substance can sufficiently exhibit the desired properties originally possessed.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Food Science & Technology (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Nutrition Science (AREA)
- Molecular Biology (AREA)
- Inorganic Chemistry (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Confectionery (AREA)
- Seasonings (AREA)
- Non-Alcoholic Beverages (AREA)
- Cosmetics (AREA)
- Grain Derivatives (AREA)
- General Preparation And Processing Of Foods (AREA)
- Jellies, Jams, And Syrups (AREA)
Description
Claims
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP03749991A EP1504675B1 (en) | 2002-05-08 | 2003-05-07 | Powder composition |
| KR1020047017891A KR100886097B1 (ko) | 2002-05-08 | 2003-05-07 | 분말 조성물 |
| BR0309852-4A BR0309852A (pt) | 2002-05-08 | 2003-05-07 | Composição em pó |
| MXPA04011076A MXPA04011076A (es) | 2002-05-08 | 2003-05-07 | Composicion en polvo. |
| AU2003234909A AU2003234909A1 (en) | 2002-05-08 | 2003-05-07 | Powder composition |
| DE60310914T DE60310914T2 (de) | 2002-05-08 | 2003-05-07 | Pulverzusammensetzung |
| US10/982,773 US20050069628A1 (en) | 2002-05-08 | 2004-11-08 | Powder composition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002132666A JP3662550B2 (ja) | 2002-05-08 | 2002-05-08 | 粉末組成物 |
| JP2002-132666 | 2002-05-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2003094630A1 true WO2003094630A1 (en) | 2003-11-20 |
Family
ID=29416647
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2003/005714 Ceased WO2003094630A1 (en) | 2002-05-08 | 2003-05-07 | Powder composition |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US20050069628A1 (ja) |
| EP (1) | EP1504675B1 (ja) |
| JP (1) | JP3662550B2 (ja) |
| KR (1) | KR100886097B1 (ja) |
| CN (1) | CN100384342C (ja) |
| AU (1) | AU2003234909A1 (ja) |
| BR (1) | BR0309852A (ja) |
| DE (1) | DE60310914T2 (ja) |
| MX (1) | MXPA04011076A (ja) |
| WO (1) | WO2003094630A1 (ja) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110248559A (zh) * | 2017-03-03 | 2019-09-17 | 布朗国际有限责任公司 | 柑橘类水果油提取器的高架输送和清洗系统 |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004056216A1 (ja) * | 2002-12-19 | 2004-07-08 | Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo | 組成物における水分の変動を抑制する方法とその用途 |
| DE102004052800B4 (de) * | 2004-10-30 | 2017-02-23 | Südzucker Aktiengesellschaft Mannheim/Ochsenfurt | Verbesserte Trägerformulierungen |
| EP1903887A1 (en) * | 2005-07-20 | 2008-04-02 | DSMIP Assets B.V. | Novel stabilized carotenoid compositions |
| JP2007254339A (ja) * | 2006-03-22 | 2007-10-04 | Takasago Internatl Corp | ロックイン型粉末 |
| KR100933263B1 (ko) * | 2007-01-19 | 2009-12-22 | 주식회사 삼양제넥스 | 흡습성 물질의 분말 조성물 및 이의 제조 방법 |
| WO2008088196A1 (en) * | 2007-01-19 | 2008-07-24 | Samyang Genex Corporation | Powder composition of hygroscopic substances and manufacturing metho thereof |
| US20110236557A1 (en) * | 2008-12-16 | 2011-09-29 | T. Hasegawa Co., Ltd | Manufacturing method of flavor-containing particle composition |
| JP5088889B2 (ja) * | 2008-12-16 | 2012-12-05 | 長谷川香料株式会社 | クリスピー感のある香料含有顆粒状組成物の製造方法 |
| JP5088890B2 (ja) * | 2008-12-16 | 2012-12-05 | 長谷川香料株式会社 | 香料含有粉末状組成物の製造方法 |
| US9687010B2 (en) * | 2012-03-14 | 2017-06-27 | Mccormick & Company, Incorporated | Extrusion encapsulation of actives at an increased load, using surface active plant extracts |
| WO2014180827A1 (en) * | 2013-05-06 | 2014-11-13 | Dsm Ip Assets B. V. | Powderous vitamin e formulation |
| JP5904677B2 (ja) * | 2014-03-14 | 2016-04-20 | 長谷川香料株式会社 | 香料含有顆粒状組成物の製造方法 |
| WO2016031651A1 (ja) | 2014-08-29 | 2016-03-03 | 花王株式会社 | 難溶解性ポリフェノール類を含有する固体分散体の製造方法 |
| JP6688736B2 (ja) * | 2014-10-03 | 2020-04-28 | 株式会社明治 | オリゴ糖製剤及びその製造方法 |
| WO2016164774A1 (en) * | 2015-04-10 | 2016-10-13 | Wild Flavors | Processes of dispersing a flavor in a confection and products produced therefrom |
| LU100332B1 (en) * | 2017-07-06 | 2019-01-08 | Soremartec Sa | Process for producing a chewing-gum pellet |
| CN107373663B (zh) * | 2017-07-07 | 2020-12-25 | 江西清源汉本生物科技有限公司 | 速溶菊花提取物及其制备方法 |
| CN107334819B (zh) * | 2017-07-07 | 2021-04-06 | 江西清源汉本生物科技有限公司 | 速溶荷叶提取物及其制备方法 |
| CN107319510B (zh) * | 2017-07-07 | 2020-12-22 | 江西清源汉本生物科技有限公司 | 速溶产品及其制备方法 |
| CN107373662B (zh) * | 2017-07-07 | 2020-12-22 | 江西清源汉本生物科技有限公司 | 速溶金银花提取物及其制备方法 |
| CN107307422B (zh) * | 2017-07-07 | 2018-09-18 | 许辉良 | 速溶石斛提取物及其制备方法 |
| KR102583693B1 (ko) * | 2017-12-22 | 2023-09-27 | 롯데정밀화학 주식회사 | 바 형태의 고체 식품용 결착제 조성물 및 이로부터 제조된 바 형태의 고체 식품 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1023842A2 (en) * | 1999-01-27 | 2000-08-02 | T. Hasegawa Co., Ltd. | Edible powder material having excellent shelf stability |
| EP1159882A2 (en) * | 2000-05-30 | 2001-12-05 | Takasago International Corporation | Coating material and coated powder |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3704137A (en) * | 1970-06-11 | 1972-11-28 | Eugene E Beck | Essential oil composition and method of preparing the same |
| FR2540136A1 (fr) * | 1983-01-28 | 1984-08-03 | Roussel Uclaf | Nouveau procede de preparation d'acylglycoproteines immunostimulantes extraites de klebsiella pneumoniae, compositions pharmaceutiques et procede de lutte contre les maladies allergiques |
| US4820534A (en) * | 1984-03-19 | 1989-04-11 | General Foods Corporation | Fixation of volatiles in extruded glass substrates |
| EP0693884A4 (en) * | 1993-04-16 | 1996-03-27 | Mccormick & Co Inc | ENCLOSURE COMPOSITIONS |
| US5510137A (en) * | 1993-04-28 | 1996-04-23 | Ajinomoto Co., Inc. | Sweet ice stuffs and jellied foods |
| US5709895A (en) * | 1994-05-31 | 1998-01-20 | Takasago International Corporation Usa | Process for producing flavor-containing capsule |
| JP3469694B2 (ja) * | 1995-10-13 | 2003-11-25 | 長谷川香料株式会社 | 粉末香料の製造方法 |
| JP3452713B2 (ja) * | 1996-01-12 | 2003-09-29 | 長谷川香料株式会社 | 乳化又は粉末機能性物質の製造方法 |
| US5972395A (en) * | 1997-04-25 | 1999-10-26 | Kraft Foods, Inc. | Method of preparing glass stabilized material |
| CA2310503A1 (en) | 1997-11-21 | 1999-06-03 | Wm. Wrigley Jr. Company | Chewing gum containing trehalose |
| GB2362555A (en) | 2000-05-26 | 2001-11-28 | British Sugar Plc | Amorphous sugar coatings |
| JP2002119245A (ja) * | 2000-10-16 | 2002-04-23 | Toyo Shinyaku:Kk | ケール乾燥粉末の製造方法 |
| WO2002071857A1 (en) * | 2001-03-12 | 2002-09-19 | Bristol-Myers Squibb Company | Confectionery compositions containing fiber |
-
2002
- 2002-05-08 JP JP2002132666A patent/JP3662550B2/ja not_active Expired - Lifetime
-
2003
- 2003-05-07 EP EP03749991A patent/EP1504675B1/en not_active Expired - Lifetime
- 2003-05-07 BR BR0309852-4A patent/BR0309852A/pt not_active Application Discontinuation
- 2003-05-07 CN CNB038102609A patent/CN100384342C/zh not_active Expired - Fee Related
- 2003-05-07 AU AU2003234909A patent/AU2003234909A1/en not_active Abandoned
- 2003-05-07 WO PCT/JP2003/005714 patent/WO2003094630A1/ja not_active Ceased
- 2003-05-07 KR KR1020047017891A patent/KR100886097B1/ko not_active Expired - Fee Related
- 2003-05-07 DE DE60310914T patent/DE60310914T2/de not_active Expired - Lifetime
- 2003-05-07 MX MXPA04011076A patent/MXPA04011076A/es active IP Right Grant
-
2004
- 2004-11-08 US US10/982,773 patent/US20050069628A1/en not_active Abandoned
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1023842A2 (en) * | 1999-01-27 | 2000-08-02 | T. Hasegawa Co., Ltd. | Edible powder material having excellent shelf stability |
| EP1159882A2 (en) * | 2000-05-30 | 2001-12-05 | Takasago International Corporation | Coating material and coated powder |
Non-Patent Citations (1)
| Title |
|---|
| See also references of EP1504675A4 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110248559A (zh) * | 2017-03-03 | 2019-09-17 | 布朗国际有限责任公司 | 柑橘类水果油提取器的高架输送和清洗系统 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20050069628A1 (en) | 2005-03-31 |
| KR100886097B1 (ko) | 2009-02-27 |
| DE60310914D1 (de) | 2007-02-15 |
| JP3662550B2 (ja) | 2005-06-22 |
| BR0309852A (pt) | 2005-03-15 |
| MXPA04011076A (es) | 2005-02-14 |
| CN100384342C (zh) | 2008-04-30 |
| EP1504675A4 (en) | 2005-08-10 |
| EP1504675B1 (en) | 2007-01-03 |
| KR20040106488A (ko) | 2004-12-17 |
| AU2003234909A1 (en) | 2003-11-11 |
| DE60310914T2 (de) | 2007-10-11 |
| EP1504675A1 (en) | 2005-02-09 |
| CN1652699A (zh) | 2005-08-10 |
| JP2003325127A (ja) | 2003-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3662550B2 (ja) | 粉末組成物 | |
| CN100548151C (zh) | 玻璃状大珠粒 | |
| EP1361803B1 (en) | Encapsulated flavor and/or fragrance composition | |
| JP3190229B2 (ja) | 香味料含有シュガーフリーカプセルの製造法 | |
| CA2470351C (en) | Microcapsule and oral compositions containing the same | |
| US6607778B2 (en) | Solid delivery systems for aroma ingredients | |
| US4981698A (en) | Multiple encapsulated sweetener delivery system and method of preparation | |
| EP1567021B1 (en) | Granulated flavor and method for producing the same | |
| JPH06504448A (ja) | 疎水性液体用の水溶性送出系 | |
| WO2010071026A1 (ja) | 香料含有粒子組成物の製造方法 | |
| JP3611652B2 (ja) | コーティング粉末の製造方法 | |
| CN112292040A (zh) | 低血糖组合物及其制备和使用方法 | |
| WO2004084650A1 (ja) | 非糖質成分の粉末化方法及び粉末化基剤 | |
| CA2316207A1 (en) | Saccharide-based matrix comprising a maltodextrin, a gelling agent and a sugar | |
| CN100506081C (zh) | 美味食品及其制备方法 | |
| US20140127361A1 (en) | Extruded delivery system | |
| JPH0965850A (ja) | コーテイング粉末の製造方法 | |
| JP3122307B2 (ja) | コーテイング香料粉末の製造方法 | |
| JP5004198B2 (ja) | 粉末組成物の製造方法 | |
| JP3157379B2 (ja) | 外観、食感の改善された粉末食品素材 | |
| JP2005211024A (ja) | 耐圧性香料製剤を添加した打錠製品 | |
| JP3308092B2 (ja) | 食用の顆粒状材料およびこれが添加されている食品 | |
| JP2010035430A (ja) | 香気成分を含有するミネラル塩構造物とその製造方法 | |
| JP2018164447A (ja) | キャンディー用親水性高分子粒子 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PH PL PT RO RU SC SD SE SG SK SL TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
| DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
| WWE | Wipo information: entry into national phase |
Ref document number: 1020047017891 Country of ref document: KR |
|
| WWE | Wipo information: entry into national phase |
Ref document number: PA/a/2004/011076 Country of ref document: MX Ref document number: 20038102609 Country of ref document: CN |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2003749991 Country of ref document: EP |
|
| WWP | Wipo information: published in national office |
Ref document number: 1020047017891 Country of ref document: KR |
|
| WWP | Wipo information: published in national office |
Ref document number: 2003749991 Country of ref document: EP |
|
| WWG | Wipo information: grant in national office |
Ref document number: 2003749991 Country of ref document: EP |
