JP4276500B2 - Method for producing saccharide composition containing N-acetylglucosamine and method for producing food and drink using the method - Google Patents
Method for producing saccharide composition containing N-acetylglucosamine and method for producing food and drink using the method Download PDFInfo
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Description
本発明は、飲食品に利用可能なN−アセチルグルコサミンを含有する糖組成物の製造方法及び該方法を利用した飲食品の製造方法に関する。 The present invention relates to a manufacturing method and a manufacturing method for food or beverage using the method of the saccharide composition containing the available N- acetylglucosamine food or drink.
N−アセチルグルコサミンは、自然界においては、エビ、カニ等の甲殻類、カブトムシ、コオロギ等の昆虫類や真菌類の細胞壁に含まれており、キチンの構成単位として天然界に広く存在する単糖類の一種である。このN−アセチルグルコサミンは、その甘味度が砂糖の半分程度であり、生体中のムコ多糖類の合成原料として知られており、美容や関節障害改善等の生理機能性が認められたことから、近年機能性食品素材として注目されている。 N-acetylglucosamine is contained in the cell walls of crustaceans such as shrimps and crabs, insects and fungi such as beetles and crickets in nature, and is a monosaccharide widely present in nature as a structural unit of chitin. It is a kind. This N-acetylglucosamine has a sweetness that is about half that of sugar and is known as a raw material for the synthesis of mucopolysaccharides in the living body. In recent years, it has attracted attention as a functional food material.
一方、キチンオリゴ糖は、N−アセチルグルコサミンが数個結合したオリゴ糖であり、ビフィズス菌増殖作用や免疫調整機能等の生理活性が認められている機能性食品素材である。 On the other hand, chitin oligosaccharide is an oligosaccharide in which several N-acetylglucosamines are bonded, and is a functional food material that has been recognized to have physiological activities such as bifidobacteria growth action and immune regulation function.
N−アセチルグルコサミンは、キチンを塩酸で完全加水分解してグルコサミン塩酸塩を得た後、無水酢酸でアセチル化することにより製造することができるが、アセチル化合成されたN−アセチルグルコサミンは食品として利用することができなかった。 N-acetylglucosamine can be produced by completely hydrolyzing chitin with hydrochloric acid to obtain glucosamine hydrochloride, and then acetylating with acetic anhydride, but acetylated and synthesized N-acetylglucosamine is used as food. Could not be used.
そのため、飲食品に利用可能なN−アセチルグルコサミンの製造方法として、例えば、下記特許文献1には、キチンを酸により部分加水分解して得たN−アセチルキトオリゴ糖含有混合物を基質とし、N−アセチルキトオリゴ糖に対し加水分解能を有する酵素を作用させることを特徴とするN−アセチル−D−グルコサミンの製造法が開示されている。 Therefore, as a method for producing N-acetylglucosamine that can be used for foods and drinks, for example, in Patent Document 1 below, an N-acetylchitooligosaccharide-containing mixture obtained by partial hydrolysis of chitin with an acid is used as a substrate. -A method for producing N-acetyl-D-glucosamine is disclosed, wherein an enzyme having hydrolytic ability is allowed to act on acetylchitooligosaccharide.
また、下記特許文献2には、N−アセチル−D−グルコサミンとN−アセチルキトオリゴ糖の混合物であるキチンの酸加水分解物から、分離膜によりN−アセチル−D−グルコサミンを選択的に取り出すことを特徴とする天然型N−アセチル−D−グルコサミンの製造方法が開示されている。 In Patent Document 2 below, N-acetyl-D-glucosamine is selectively extracted from an acid hydrolyzate of chitin, which is a mixture of N-acetyl-D-glucosamine and N-acetylchitooligosaccharide, using a separation membrane. A method for producing natural N-acetyl-D-glucosamine is disclosed.
一方、キチンオリゴ糖(N−アセチルキトオリゴ糖)の製造方法として、下記特許文献3には、キチンの加水分解により得られた4〜5量体のN−アセチルキトオリゴ糖を基質とし、これに、ノカルデイア属の生産するキチナーゼを作用させ、その糖転移反応により、重合度の高いN−アセチルキトオリゴ糖を得ることを特徴とする、酵素によるN−アセチルキトオリゴ糖の製造法が開示されている。 On the other hand, as a method for producing chitin oligosaccharide (N-acetylchitooligosaccharide), the following Patent Document 3 discloses that a tetramer or pentamer N-acetylchitooligosaccharide obtained by hydrolysis of chitin is used as a substrate. In addition, a method for producing N-acetylchitooligosaccharide using an enzyme is disclosed, characterized in that chitinase produced by Nocardia spp. ing.
また、下記特許文献4には、キチンを酸により部分加水分解し、アルカリにより中和してN−アセチルキトオリゴ糖を生成せしめ、該中和溶液から副生塩を分離除去することからなるN−アセチルキトオリゴ糖の製造方法において、上記中和溶液からの脱塩をイオン交換膜電気透析法で行うことを特徴とするN−アセチルキトオリゴ糖の製造方法が開示されている。 In Patent Document 4 below, N is composed of partial hydrolysis of chitin with an acid, neutralization with alkali to produce N-acetylchitooligosaccharide, and separation and removal of by-product salts from the neutralized solution. -In the manufacturing method of acetylchitooligosaccharide, the manufacturing method of N-acetylchitooligosaccharide characterized by performing desalting from the said neutralization solution by an ion exchange membrane electrodialysis method is disclosed.
更に、下記特許文献5には、キチンに、ストレプトミセス属に属する微生物由来のキチン分解酵素を作用させることにより、N−アセチルグルコサミン及び/又はキトオリゴ糖を有効成分とするキチン分解物を得る方法が開示されている。
しかしながら、キチンを塩酸で加水分解した場合、グリコシド結合の分解と同時にアセトアミド基の分解も進行し、味の悪いグルコサミン塩酸塩も生成するため、N−アセチルグルコサミンの精製や品質に影響を与えてしまうという問題があった。 However, when chitin is hydrolyzed with hydrochloric acid, the degradation of the acetamide group proceeds simultaneously with the degradation of the glycosidic bond, and glucosamine hydrochloride having a bad taste is produced, which affects the purification and quality of N-acetylglucosamine. There was a problem.
また、キチンの酸加水分解物から分離膜によってN−アセチルグルコサミンを選択的に取り出した場合、スプレードライ法では収率が著しく低下してしまうことから、最終的に結晶化法や凍結乾燥法等で乾燥粉末化されるのであるが、製造コストがかかってしまうという問題があった。 In addition, when N-acetylglucosamine is selectively taken out from the chitin acid hydrolyzate by a separation membrane, the yield is significantly reduced by the spray drying method. However, there is a problem that the manufacturing cost is increased.
一方、キチン分解酵素を用いた方法では、キチンが水不溶性であるため分解率が低く、実用には適さなかった。 On the other hand, the method using a chitin degrading enzyme is not suitable for practical use because chitin is insoluble in water and has a low degradation rate.
このように、従来の製造方法では、コストや品質等の面で十分に満足できる製品を得ることができなかった。 As described above, the conventional manufacturing method cannot obtain a product that is sufficiently satisfactory in terms of cost, quality, and the like.
また、N−アセチルグルコサミンは、砂糖と同等のカロリー量(4kcal/g)を有するため、近年の低甘味、低カロリー志向の飲食品に合わず、敬遠される向きもあった。 In addition, N-acetylglucosamine has a calorie content (4 kcal / g) equivalent to that of sugar, so it is not suitable for recent low-sweetness and low-calorie-oriented foods and beverages, and has been directed away.
したがって、本発明の目的は、N−アセチルグルコサミン純品に比べて低甘味、低カロリーで、飲食品に利用可能なN−アセチルグルコサミンを含有する糖組成物を安価に製造する方法、及び該糖組成物を含有する飲食品を提供することにある。 Accordingly, an object of the present invention is to provide a method for producing a sugar composition containing N-acetylglucosamine, which is less sweet and less caloric than N-acetylglucosamine pure products and can be used for food and drink, and the sugar. It is providing the food / beverage products containing a composition.
上記目的を達成するため、本発明のN−アセチルグルコサミンを含有する糖組成物の製造方法は、キチンを塩酸により部分加水分解し、この分解液を中和後、イオン交換膜電気透析法によって脱塩処理した後、共存するグルコサミン塩酸塩をイオン交換樹脂によって吸着除去して、グルコサミン塩酸塩を実質的に含有しない状態とし、酵素分解によりN−アセチルグルコサミン80〜90質量%、キチンオリゴ糖10〜20質量%で含有する糖組成物を遊離させ、スプレードライヤーによって乾燥させることを特徴とする。 In order to achieve the above object, the method for producing a saccharide composition containing N-acetylglucosamine according to the present invention comprises subjecting chitin to partial hydrolysis with hydrochloric acid, neutralizing this decomposition solution, and then removing it by ion exchange membrane electrodialysis. After the salt treatment, the coexisting glucosamine hydrochloride is adsorbed and removed by an ion exchange resin to make it substantially free of glucosamine hydrochloride, and 80-90% by mass of N-acetylglucosamine, 10-chitin oligosaccharide 10% by enzymatic decomposition The sugar composition contained at 20% by mass is liberated and dried by a spray dryer.
また、前記酵素分解した糖組成物に、デンプン、デキストリン、乳糖、トレハロースから選ばれた少なくとも一種の糖質を添加し、N−アセチルグルコサミン32〜90質量%、キチンオリゴ糖4〜20質量%、及びデンプン、デキストリン、乳糖、トレハロースから選ばれた少なくとも一種の糖質0.1〜60質量%含有する糖組成物として、スプレードライヤーによって乾燥させることが好ましい。 Further, at least one sugar selected from starch, dextrin, lactose and trehalose is added to the enzymatically decomposed sugar composition, N-acetylglucosamine 32 to 90% by mass, chitin oligosaccharide 4 to 20% by mass, and starch, dextrin, lactose, and at least one carbohydrate 0.1 to 60% by weight containing sugar composition selected from trehalose, it is preferably dried by a spray dryer.
本発明の製造方法によれば、キチンを塩酸により部分加水分解し、この分解液を中和後、イオン交換膜電気透析法によって脱塩処理した後、共存するグルコサミン塩酸塩をイオン交換樹脂によって吸着除去することにより、スプレードライ工程において褐変の原因となるグルコサミン塩酸塩を効率よく除去することができ、また、糖組成物に含まれるキチンオリゴ糖が賦型剤の役割を果たすので、スプレードライ法によって容易に乾燥粉末化することができる。また、N−アセチルグルコサミンやキチンオリゴ糖に比べて味の悪いグルコサミン塩酸塩を効率よく除去できるので、糖組成物の味を良好にすることができるだけでなく、難消化性の糖質であるキチンオリゴ糖を含むので、低甘味、低カロリーの糖組成物を得ることができる。 According to the production method of the present invention, chitin is partially hydrolyzed with hydrochloric acid, neutralized with this decomposition solution, desalted by ion exchange membrane electrodialysis, and adsorbed glucosamine hydrochloride by ion exchange resin. By removing the glucosamine hydrochloride that causes browning in the spray drying process, the chitin oligosaccharide contained in the sugar composition serves as an excipient, so the spray drying method Can easily be made into dry powder. Moreover, since glucosamine hydrochloride having a bad taste as compared with N-acetylglucosamine and chitin oligosaccharide can be efficiently removed, not only can the taste of the sugar composition be improved, but also chitin which is an indigestible carbohydrate. Since an oligosaccharide is contained, a sugar composition with low sweetness and low calories can be obtained.
また、本発明の飲食品(ただし乳飲料を除く)の製造方法は、前記糖組成物を0.01〜30質量%添加することを特徴とする。なお、本発明において、乳飲料とは、乳固形分3質量%以上の種類別乳飲料を意味する。 Moreover, the manufacturing method of the food / beverage products (except milk drink) of this invention is characterized by adding the said sugar composition 0.01-30 mass%. In addition, in this invention, a milk beverage means the milk beverage according to the type whose milk solid content is 3 mass% or more.
前記糖組成物を添加してなる飲食品は、低甘味、低カロリーである前記糖組成物を含むので、近年の低甘味、低カロリー志向に合った飲食品を提供できる。また、本飲料を摂取することにより、N−アセチルグルコサミンによる美容や関節障害改善等の生理機能、キチンオリゴ糖によるビフィズス菌増殖作用や免疫調整機能等の生理機能が期待できる。 Since the food / beverage products to which the sugar composition is added include the sugar composition having a low sweetness and a low calorie, food / beverage products suitable for the recent low sweetness and low calorie orientation can be provided. Moreover, by ingesting this beverage, physiological functions such as beauty and joint damage improvement by N-acetylglucosamine, and physiological functions such as bifidobacteria growth action and immune regulation function by chitin oligosaccharides can be expected.
本発明によれば、低甘味、低カロリーで飲食品に利用可能なN−アセチルグルコサミンを含有する糖組成物を安価に提供することができる。また、この糖組成物を飲食品に添加することにより、低甘味、低カロリーで、N−アセチルグルコサミンやキチンオリゴ糖の生理機能を付与した飲食品を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the sugar composition containing N-acetylglucosamine which can be utilized for food-drinks with a low sweetness and a low calorie can be provided at low cost. Moreover, the food / beverage products which provided the physiological function of N-acetylglucosamine and chitin oligosaccharide by low sweetness and a low calorie can be provided by adding this saccharide | sugar composition to food / beverage products.
本発明において原料として用いられるキチンは、エビ、カニ、オキアミ等、甲殻類の甲皮を塩酸処理してカルシウム分を除去し、更に水酸化ナトリウム処理により蛋白質を除去することなどにより調製されるが、その他の入手経路、調製手段などで得られるキチンを用いることもできる。 The chitin used as a raw material in the present invention is prepared by removing the calcium content by treating the crustacean crust, such as shrimp, crab, krill, etc., with hydrochloric acid, and further removing the protein by sodium hydroxide treatment. Further, chitin obtained by other acquisition routes, preparation means, and the like can also be used.
本発明において、キチンの塩酸による部分加水分解は、キチン質量の2〜20倍量の塩酸を添加して、撹拌しながら30〜60℃、2〜8時間反応させることにより行われる。より好ましくはキチン質量の3〜10倍量の濃塩酸を添加して、撹拌しながら40〜50℃、3〜5時間反応させる。塩酸の添加量が上記範囲外であると、分解効率が悪くなったり、中和塩の量が多くなり脱塩に時間がかかるため好ましくない。また、反応温度及び反応時間が上記範囲外であると、分解効率が悪くなったり、グルコサミン塩酸塩の生成量が多くなるため好ましくない。 In the present invention, partial hydrolysis of chitin with hydrochloric acid is carried out by adding 2 to 20 times the amount of chitin mass and reacting at 30 to 60 ° C. for 2 to 8 hours with stirring. More preferably, 3 to 10 times the amount of chitin mass of concentrated hydrochloric acid is added, and the mixture is reacted at 40 to 50 ° C. for 3 to 5 hours with stirring. If the amount of hydrochloric acid added is outside the above range, the decomposition efficiency is deteriorated or the amount of neutralized salt is increased, which takes time for desalting. Moreover, it is not preferable that the reaction temperature and the reaction time are out of the above ranges because the decomposition efficiency deteriorates and the amount of glucosamine hydrochloride produced increases.
次に、加水分解反応を終了させるために、部分加水分解溶液と同容量程度の水で希釈し、さらに温度が上昇しないように、例えば25〜50%水酸化ナトリウム溶液等のアルカリ剤を用いてpH3〜7になるように中和を行う。 Next, in order to complete the hydrolysis reaction, it is diluted with about the same volume of water as the partially hydrolyzed solution, and an alkaline agent such as 25-50% sodium hydroxide solution is used so that the temperature does not rise. Neutralize to pH 3-7.
中和した部分加水分解溶液には、N−アセチルグルコサミン、キチンオリゴ糖、グルコサミン塩酸等の他、未分解の不溶性キチンも含まれており、糖の分解により多少褐色みを呈しているが、未分解の不溶性キチンや着色は少量の活性炭及びフィルターを用いて濾過することにより除去することができる。 The neutralized partially hydrolyzed solution contains N-acetylglucosamine, chitin oligosaccharides, glucosamine hydrochloride and the like, as well as undegraded insoluble chitin, which is somewhat brownish due to the decomposition of sugar. Decomposed insoluble chitin and coloring can be removed by filtration using a small amount of activated carbon and a filter.
そして、中和した部分加水分解溶液を特許第2134244号(特公平5−86399号)に記載された方法(イオン交換膜電気透析法)で脱塩処理を行う。イオン交換膜電気透析に用いられるイオン交換膜は特に限定されないが、例えば、ネオセプタCL−25T、CM−1〜2、AM−1〜3(徳山曹達株式会社製)、セレミオンCMV/AMV(旭硝子株式会社製)等が挙げられる。 The neutralized partially hydrolyzed solution is then desalted by the method (ion exchange membrane electrodialysis method) described in Japanese Patent No. 2134244 (Japanese Patent Publication No. 5-86399). The ion exchange membrane used for the ion exchange membrane electrodialysis is not particularly limited. For example, Neocepta CL-25T, CM-1 to 2, AM-1 to 3 (manufactured by Tokuyama Soda Co., Ltd.), Selemion CMV / AMV (Asahi Glass Co., Ltd.) Company-made).
次に、脱塩処理した部分加水分解溶液をイオン交換樹脂で処理し、溶液中のグルコサミン塩酸塩を吸着除去する。イオン交換樹脂処理は、強酸性イオン交換樹脂と弱塩基性イオン交換樹脂の組み合わせによって行われる。これにより、N−アセチルグルコサミンやキチンオリゴ糖と比べて味が悪く、スプレードライ工程においても粉末の褐変化の原因となるグルコサミン塩酸塩を非常に効率よく除去することができる。 Next, the desalted partial hydrolysis solution is treated with an ion exchange resin to adsorb and remove glucosamine hydrochloride in the solution. The ion exchange resin treatment is performed by a combination of a strongly acidic ion exchange resin and a weakly basic ion exchange resin. Thereby, compared with N-acetyl glucosamine and chitin oligosaccharide, taste is bad and the glucosamine hydrochloride which causes the browning of a powder also in a spray drying process can be removed very efficiently.
具体的には、脱塩処理した部分加水分解溶液を強酸性イオン交換樹脂で処理した後、続いて弱塩基性イオン交換樹脂で処理する。処理の方法は、カラム式でもよく、バッチ式でもよい。上記強酸性イオン交換樹脂としては、例えば、商品名「ダイヤイオンSK1−B」(三菱化学製)等が使用でき、上記弱塩基性イオン交換樹脂としては商品名「ダイヤイオンWA−30」(三菱化学製)等が使用できる。 Specifically, the desalted partially hydrolyzed solution is treated with a strongly acidic ion exchange resin and subsequently treated with a weakly basic ion exchange resin. The processing method may be a column type or a batch type. As the strong acid ion exchange resin, for example, trade name “Diaion SK1-B” (manufactured by Mitsubishi Chemical) can be used, and as the weakly basic ion exchange resin, trade name “Diaion WA-30” (Mitsubishi). Chemical) etc. can be used.
次に、上記イオン交換樹脂処理した部分加水分解溶液中に含まれるキチンオリゴ糖を分解してN−アセチル−グルコサミンを更に遊離させるために、キチンオリゴ糖に対して加水分解能を有する酵素を作用させる。このような酵素としては、キチンオリゴ糖を単糖のN−アセチルグルコサミンにまで分解してしまう酵素であればいずれの酵素を用いてもよく、例えば、リゾチーム、キチナーゼ、キトビアーゼ(β−N−アセチルヘキソサミニダーゼ)等が挙げられる。なお、リゾチームやキチナーゼの中にはキチンオリゴ糖の二糖や三糖に対して加水分解能が低いものがあるため、キトビアーゼ等の低分子オリゴ糖に対して高い加水分解能を有する酵素を併用することが好ましい。 Next, an enzyme having hydrolytic ability is allowed to act on the chitin oligosaccharide to decompose the chitin oligosaccharide contained in the partially hydrolyzed solution treated with the ion exchange resin to further release N-acetyl-glucosamine. . As such an enzyme, any enzyme capable of degrading chitin oligosaccharide to monosaccharide N-acetylglucosamine may be used. For example, lysozyme, chitinase, chitobiase (β-N-acetyl) Hexosaminidase) and the like. In addition, some lysozyme and chitinase have low hydrolytic ability for disaccharides and trisaccharides of chitin oligosaccharides, so use an enzyme with high hydrolytic ability for low molecular weight oligosaccharides such as chitobiase. Is preferred.
上記酵素は、市販の酵素を利用することができ、例えば、リゾチームは、ニワトリの卵白リゾチームが一般的である。キチナーゼは、ストレプトマイセス・グリセウス、セラチア・マルツセンス(シグマ社)、アエロモナス・ハイドロフイラ(合同酒精)、ストレプトマイセス・アンティビオテイカス(カルビオケム社)等の微生物起源の酵素が挙げられる。なお、キチナーゼやキトビアーゼ等のキチンあるいはキチンオリゴ糖分解酵素を産生する微生物を培養し、この培養物から酵素を抽出した粗酵素を使用することもできる。 Commercially available enzymes can be used as the enzyme. For example, lysozyme is generally chicken egg white lysozyme. Examples of the chitinase include enzymes derived from microorganisms such as Streptomyces griseus, Serratia martzens (Sigma), Aeromonas hydrophila (joint sake spirit), Streptomyces antibiotecus (Calbiochem). It is also possible to use a crude enzyme obtained by culturing a microorganism producing chitin or chitin oligosaccharide-degrading enzyme such as chitinase or chitobiase and extracting the enzyme from this culture.
また、市販の酵素製剤(セルラーゼ製剤、ペクチナーゼ製剤、アミラーゼ製剤、プロテアーゼ製剤等)の中には、キチナーゼやキトビアーゼ等を含む製剤が多く、これらの市販酵素製剤を使用することもできる。 In addition, among commercially available enzyme preparations (cellulase preparations, pectinase preparations, amylase preparations, protease preparations, etc.), there are many preparations containing chitinase, chitobiase, etc., and these commercially available enzyme preparations can also be used.
本発明において、上記イオン交換樹脂処理した部分加水分解溶液中に含まれるキチンオリゴ糖の酵素分解反応の条件は、酵素の種類や酵素量に応じて適宜設定すればよいが、最終的に得られる糖組成物が、N−アセチルグルコサミン80〜90質量%、キチンオリゴ糖10〜20質量%含有するように設定する。また、好ましくはN−アセチルグルコサミン80〜85質量%、キチンオリゴ糖15〜20質量%含有するように設定する。N−アセチルグルコサミンの比率が上記範囲より高くなると、スプレードライ法での乾燥が難しくなり、キチンオリゴ糖の比率が上記範囲より高くなると、糖組成物の水への溶解性が低下し、飲料等への使用に支障をきたすため好ましくない。 In the present invention, the conditions for the enzymatic degradation reaction of the chitin oligosaccharide contained in the partially hydrolyzed solution treated with the ion exchange resin may be appropriately set according to the type of enzyme and the amount of the enzyme, but finally obtained. The sugar composition is set to contain 80 to 90% by mass of N -acetylglucosamine and 10 to 20% by mass of chitin oligosaccharide . Also, good Mashiku is set so as to contain 15 to 20 wt% N-acetylglucosamine 80-85 wt%, chitin oligosaccharides. When the ratio of N-acetylglucosamine is higher than the above range, drying by a spray drying method becomes difficult, and when the ratio of chitin oligosaccharide is higher than the above range, the solubility of the sugar composition in water is reduced, and beverages and the like This is not preferable because it interferes with the use of the product.
そして、酵素反応終了後、酵素分解溶液を加熱して酵素を失活させた後、スプレードライ法により乾燥粉末化する。スプレードライの条件は、通常、イン120〜200℃、アウト50〜120℃で行えばよい。本発明においては、上記酵素分解溶液に含まれるキチンオリゴ糖がちょうど賦型材のような役割を果たすので、スプレードライ法で容易に乾燥粉末化することができる。また、グルコサミン塩酸塩を含まないので、スプレードライ工程で問題となる褐変を防止することができる。 Then, after the enzyme reaction is completed, the enzyme decomposition solution is heated to inactivate the enzyme, and then dried by spray drying. The conditions of spray drying may be normally performed at 120 to 200 ° C. in and 50 to 120 ° C. out. In the present invention, the chitin oligosaccharide contained in the enzyme decomposition solution plays a role just as a shaping material, so that it can be easily powdered by spray drying. Moreover, since glucosamine hydrochloride is not included, browning which becomes a problem in a spray-drying process can be prevented.
本発明においては、上記の酵素を失活させた後の溶液に、デンプン、デキストリン、乳糖、トレハロースから選ばれた少なくとも一種の糖質を添加してもよい。これにより、スプレードライ法でより容易に粉末乾燥化することができ、効率的な製造が可能となる。 In the present invention, at least one carbohydrate selected from starch, dextrin, lactose, and trehalose may be added to the solution after the enzyme is deactivated. As a result, the powder can be more easily dried by a spray drying method, and efficient production becomes possible.
上記糖質の添加量は、最終的に得られる糖組成物が、N−アセチルグルコサミン32〜90質量%、キチンオリゴ糖4〜20質量%、及びデンプン、デキストリン、乳糖、トレハロースから選ばれた少なくとも一種の糖質0.1〜60質量%含有するように設定することが好ましい。上記糖質の添加量が多過ぎると、糖質自体の味が強く出てしまい、デンプン、デキストリンの場合は水に溶解した後に粘性が上昇する等の不具合を生じるため好ましくない。 The amount of the saccharide added is such that the finally obtained saccharide composition is selected from N-acetylglucosamine 32-90 mass%, chitin oligosaccharide 4-20 mass%, and starch, dextrin, lactose, trehalose. It is preferable to set so as to contain 0.1 to 60% by mass of one kind of carbohydrate. If the amount of the saccharide added is too large, the taste of the saccharide itself will be strong, and starch and dextrin are not preferred because they cause problems such as an increase in viscosity after dissolution in water.
上記のようにして得られる糖組成物は、N−アセチルグルコサミン及びキチンオリゴ糖を含むので、N−アセチルグルコサミン純品に比べると甘味度が低く、また、キチンオリゴ糖は難消化性の糖質であるので、N−アセチルグルコサミン純品に比べて低カロリーである。したがって、上記糖組成物を飲食品に配合することにより、該飲食品の甘味及びカロリーを抑えつつ、N−アセチルグルコサミンやキチンオリゴ糖の生理機能を付与することができる。 Since the sugar composition obtained as described above contains N-acetylglucosamine and chitin oligosaccharide, the sweetness is lower than that of pure N-acetylglucosamine, and chitin oligosaccharide is an indigestible carbohydrate. Therefore, the calorie content is lower than that of pure N-acetylglucosamine. Therefore, the physiological function of N-acetylglucosamine or chitin oligosaccharide can be imparted by suppressing the sweetness and calories of the food and drink by adding the sugar composition to the food and drink.
本発明の糖組成物は、様々な飲食品に配合することができる。本発明の糖組成物を添加するのに好適な飲料としては、例えば、清涼飲料、炭酸飲料、果実飲料、野菜ジュース、乳酸菌飲料、豆乳、ミネラルウォーター、茶系飲料、コーヒー飲料、スポーツ飲料、アルコール飲料、ゼリー飲料等が例示でき、中でも、炭酸飲料、果実飲料、野菜ジュース、コーヒー飲料、茶飲料、ゼリー飲料、豆乳又はアルコール飲料などが挙げられる。 The sugar composition of this invention can be mix | blended with various food-drinks. Beverages suitable for adding the sugar composition of the present invention include, for example, soft drinks, carbonated drinks, fruit drinks, vegetable juices, lactic acid bacteria drinks, soy milk, mineral water, tea-based drinks, coffee drinks, sports drinks, alcohol Beverages, jelly drinks and the like can be exemplified, and among them, carbonated drinks, fruit drinks, vegetable juices, coffee drinks, tea drinks, jelly drinks, soy milk, alcoholic drinks and the like can be mentioned.
また、本発明の糖組成物を添加するのに好適な食品としては、(1)農産加工食品…例えば、トマトピューレ、キノコ缶詰、乾燥野菜(キノコ、紫蘇等)、漬物等の野菜加工品や、乾燥果実、ジャム、フルーツピューレ、果実缶詰等の果実加工品や、カレー粉、わさび、ショウガ、スパイスブレンド、シーズニング粉等の香辛料や、パスタ、うどん、ソバ、ラーメン、マカロニ等の麺(生麺・乾燥麺含む)や、食パン、菓子パン、調理パン、ドーナッツ等のパン類や、アルファー化米、オートミール、麩、バッター粉等や、焼菓子、ビスケット、米菓子、キャンデー、チョコレート、チューイングガム、スナック菓子、冷菓、砂糖漬け菓子、和生菓子、洋生菓子、半生菓子、プリン、アイスクリーム等の菓子類や、小豆、豆腐、納豆、きな粉、湯葉、煮豆、ピーナッツ製品等の豆類や、蜂蜜、ローヤルゼリー加工食品など、(2)畜産加工食品…例えば、ハム、ソーセージ、ベーコン等の肉製品や、ヨーグルト、プリン、練乳、チーズ、発酵乳、バター、アイスクリーム等の酪農製品や、加工卵製品など、(3)水産加工食品…例えば、干物、蒲鉾、ちくわ、魚肉ソーセージ等の加工魚や、乾燥ワカメ、昆布、佃煮等の加工海藻や、タラコ、数の子、イクラ、からすみ等の加工魚卵など、(4)その他の食料品…例えばだしの素、醤油、酢、ミリン、コンソメベース、中華ベース、濃縮出汁、ドレッシング、マヨネーズ、ケチャップ、味噌等の調味料や、サラダ油、ゴマ油、リノール油、ジアシルグリセロール、べに花油等の食用油脂や、スープ(粉末、液体含む)等の調理・半調理食品や、惣菜、レトルト食品、チルド食品、半調理食品(炊き込みご飯の素、カニ玉の素等)などが挙げられる。 In addition, foods suitable for adding the sugar composition of the present invention include (1) processed agricultural foods such as tomato puree, canned mushrooms, dried vegetables (mushrooms, shiso, etc.), processed vegetables such as pickles, Processed fruits such as dried fruit, jam, fruit puree, canned fruit, spices such as curry powder, wasabi, ginger, spice blend, seasoning powder, noodles such as pasta, udon, buckwheat, ramen, macaroni (raw noodles) (Including dry noodles), bread such as bread, confectionery bread, cooking bread, donuts, alpha rice, oatmeal, rice cake, batter flour, baked confectionery, biscuits, rice confectionery, candy, chocolate, chewing gum, snack confectionery, Confectionery such as frozen confectionery, candied confectionery, Japanese confectionery, Western confectionery, half confectionery, pudding, ice cream, red beans, tofu, natto, kinako Beans such as yuba, boiled beans, peanut products, honey, royal jelly processed foods, etc. (2) livestock processed foods ... meat products such as ham, sausage, bacon, yogurt, pudding, condensed milk, cheese, fermented milk, butter Dairy products such as ice cream, processed egg products, etc. (3) Seafood processed foods ... For example, processed fish such as dried fish, salmon, chikuwa, fish sausage, processed seaweed such as dried wakame, kelp, boiled fish, tarako, (4) Other food products such as dashi-no-moto, soy sauce, vinegar, mirin, consommé base, Chinese base, concentrated soup stock, dressing, mayonnaise, ketchup, miso Cooking / semitones for cooking oils, salad oils, sesame oils, linoleic oils, diacylglycerols, edible oils such as beni flower oil, soups (including powders and liquids) Food and, prepared foods, retort food, chilled food, semi-cooked food (cooked rice Moto, arsenide crab balls), and the like.
飲料における上記糖組成物の配合量は、N−アセチルグルコサミン換算で0.01〜30質量%が好ましく、0.1〜10質量%がより好ましい。N−アセチルグルコサミンの配合量が少な過ぎると、N−アセチルグルコサミンの生理活性を得るために1回当りの摂取量を大幅に増やす必要があるため、継続的に摂取することが困難となり、多すぎると製品中での結晶化による沈殿発生や、過剰摂取による軟便等の症状がでる可能性がある。 The amount of the sugar composition in the beverage is preferably 0.01 to 30% by weight N- acetylglucosamine terms, more preferably from 0.1 to 10% by weight. If the amount of N-acetylglucosamine is too small, it is necessary to greatly increase the amount of each intake in order to obtain the physiological activity of N-acetylglucosamine. May cause precipitation due to crystallization in the product, or loose stool due to excessive intake.
なお、N−アセチルグルコサミンの安全性については、ラットを用いた急性毒性試験の結果から、ラットに対する50%致死量(LD50)は、5,000mg/体重kg以上であることが分かっており、非常に安全な成分である。 Note that the safety of N- acetylglucosamine, the results of acute toxicity test using rats, LD50 rat (LD 50) is found to be 5,000 mg / kg body weight or more, It is a very safe ingredient.
上記糖組成物を添加してなる飲食品は、他の成分として、コラーゲンペプチド、サメ軟骨抽出物、ビタミンB群、MS.M(メチル・スルフォニル・メタン)、ショウガエキス等を含むことができる。例えば、コラーゲンペプチドやサメ軟骨抽出物を含むことにより、生体内でのコラーゲンやムコ多糖の生合成が促進され、N−アセチルグルコサミンとの相乗効果が期待できる。飲食品中のコラーゲンペプチドやサメ軟骨抽出物の含有量は、通常、0.01〜10質量%が好ましく、0.1〜10質量%がより好ましい。 The food and drink obtained by adding the sugar composition may contain collagen peptide, shark cartilage extract, vitamin B group, MS.M (methyl sulfonyl methane), ginger extract and the like as other components. For example, by including a collagen peptide or shark cartilage extract, biosynthesis of collagen or mucopolysaccharide in vivo is promoted, and a synergistic effect with N-acetylglucosamine can be expected. The content of collagen peptide and shark cartilage extract in food and drink is usually preferably 0.01 to 10% by mass, more preferably 0.1 to 10% by mass.
上記糖組成物を添加してなる飲食品は、各飲食品を製造する際に採用される常法に従って製造することができ、例えば、上記糖組成物及び必要に応じて上記他の成分を、他の飲食品原料と一緒に、液体原料(水、発酵乳、茶、コーヒー、果汁、野菜搾汁、ピューレ等)に添加して混合、溶解させた後、加熱殺菌等を行うことにより製造することができる。 The food and drink obtained by adding the sugar composition can be produced according to a conventional method employed when producing each food and drink. For example, the sugar composition and the other ingredients as necessary, Manufactured by adding to liquid ingredients (water, fermented milk, tea, coffee, fruit juice, vegetable juice, puree, etc.), mixing and dissolving together with other food and drink ingredients, followed by heat sterilization, etc. be able to.
上記糖組成物を添加してなる飲食品の摂取量は、成人1日当たり、N−アセチルグルコサミン換算で0.1〜15gであり、より好ましくは0.5〜1.5gである。N−アセチルグルコサミンの摂取量が0.1g未満では十分な生理活性が期待できず、15gを超えると体質により軟便、下痢等の症状が出る可能性があるため好ましくない。 The intake of foods and drinks to which the sugar composition is added is 0.1 to 15 g, more preferably 0.5 to 1.5 g in terms of N-acetylglucosamine per adult day. If the intake amount of N-acetylglucosamine is less than 0.1 g, sufficient physiological activity cannot be expected, and if it exceeds 15 g, symptoms such as loose stool and diarrhea may occur depending on the constitution.
<実施例1>
10Lのガラス容器中で濃塩酸4Lにキチン1kgを撹拌しながら投入した。容器を外部から温水加熱して40℃に保ちながら加水分解反応を行った。4時間後、水2.5Lをゆっくりと投入し、反応を停止した。ソーダ灰でpH3〜7に中和し、活性炭100gを投入後60分間撹拌、脱色を行った。ろ紙ろ過により活性炭を除去後、ろ液を電気透析脱塩装置(商品名「セレミオンCMV/AMV」、旭硝子株式会社製)により脱塩した。
<Example 1>
1 kg of chitin was added to 4 L of concentrated hydrochloric acid in a 10 L glass container while stirring. The hydrolysis reaction was carried out while heating the container from the outside with warm water and maintaining the temperature at 40 ° C. After 4 hours, 2.5 L of water was slowly added to stop the reaction. The mixture was neutralized with soda ash to pH 3 to 7, and 100 g of activated carbon was added, followed by stirring and decolorization for 60 minutes. After removing the activated carbon by filtration with a filter paper, the filtrate was desalted with an electrodialysis desalting apparatus (trade name “Celemion CMV / AMV”, manufactured by Asahi Glass Co., Ltd.).
次いで脱塩液を、強酸性イオン交換樹脂(商品名「ダイヤイオンSK1−B」、三菱化学製)を充填した500ml容カラム、また弱塩基性イオン交換樹脂(商品名「ダイヤイオンWA−30」、三菱化学製)を充填した500ml容カラムに順番に通液し(SV=2)、共存するグルコサミン塩酸塩を除去した。 Next, the desalted solution was added to a 500 ml column packed with a strongly acidic ion exchange resin (trade name “Diaion SK1-B”, manufactured by Mitsubishi Chemical), or a weakly basic ion exchange resin (trade name “Diaion WA-30”). , Manufactured by Mitsubishi Chemical Co., Ltd.), and sequentially passed through a 500 ml column (SV = 2) to remove coexisting glucosamine hydrochloride.
さらに処理液に、市販の酵素製剤(商品名「ヘミセルラーゼアマノ90」、アマノエンザイム製)8gを添加し、50℃にて12時間処理した後、85℃まで昇温して酵素を失活させてからスプレードライ法(ニロ社製スプレードライヤー)にて乾燥(乾燥温度:イン160℃、アウト95℃)し、白色粉末430gを得た。得られた粉末をHPLCにより分析した結果、質量組成比はN−アセチルグルコサミン82%、キチンオリゴ糖18%であり、グルコサミン塩酸塩は検出されなかった。 Further, 8 g of a commercially available enzyme preparation (trade name “Hemicellulase Amano 90”, manufactured by Amano Enzyme) was added to the treatment liquid, treated at 50 ° C. for 12 hours, and then heated to 85 ° C. to deactivate the enzyme. Then, it was dried (drying temperature: in 160 ° C., out 95 ° C.) by a spray drying method (spray dryer manufactured by Niro Co., Ltd.) to obtain 430 g of a white powder. As a result of analyzing the obtained powder by HPLC, the mass composition ratio was N-acetylglucosamine 82%, chitin oligosaccharide 18%, and glucosamine hydrochloride was not detected.
<実施例2>
10Lのガラス容器中で濃塩酸4Lにキチン1kgを撹拌しながら投入した。容器を外部から温水加熱して40℃に保ちながら加水分解反応を行った。6時間後、水2.5Lをゆっくりと投入し、反応を停止した。ソーダ灰でpH3〜7に中和し、活性炭100gを投入して60分間撹拌し、脱色を行った。ろ紙ろ過により活性炭を除去後、ろ液を電気透析脱塩装置(商品名「セレミオンCMV/AMV」、旭硝子株式会社製)により脱塩した。
<Example 2>
1 kg of chitin was added to 4 L of concentrated hydrochloric acid in a 10 L glass container while stirring. The hydrolysis reaction was carried out while heating the container from the outside with warm water and maintaining the temperature at 40 ° C. After 6 hours, 2.5 L of water was slowly added to stop the reaction. Neutralized with soda ash to pH 3-7, charged with 100 g of activated carbon and stirred for 60 minutes for decolorization. After removing the activated carbon by filtration with a filter paper, the filtrate was desalted with an electrodialysis desalting apparatus (trade name “Celemion CMV / AMV”, manufactured by Asahi Glass Co., Ltd.).
次いで脱塩液を強酸性イオン交換樹脂(商品名「ダイヤイオンSK1−B」、三菱化学製)を充填した500ml容カラム、また弱塩基性イオン交換樹脂(商品名「ダイヤイオンWA−30」、三菱化学製)を充填した500ml容カラムに順番に通液し(SV=2)、共存するグルコサミン塩酸塩を除去した。 Subsequently, the desalted solution is a 500 ml column packed with a strongly acidic ion exchange resin (trade name “Diaion SK1-B”, manufactured by Mitsubishi Chemical), or a weakly basic ion exchange resin (trade name “Diaion WA-30”, The solution was sequentially passed through a 500 ml column packed with Mitsubishi Chemical (SV = 2) to remove coexisting glucosamine hydrochloride.
さらに処理液に対し、市販の酵素製剤(商品名「ヘミセルラーゼアマノ90」、アマノエンザイム製)10gを添加し、50℃にて12時間処理した後、85℃まで昇温して酵素を失活させ、デキストリン(商品名「パインデックスNO.2」、松谷化学製)480gを添加溶解し、スプレードライ法(ニロ社製スプレードライヤー)にて乾燥(乾燥温度:イン160℃、アウト95℃)し、白色粉末910gを得た。得られた粉末をHPLCにより分析した結果、粉末中に含まれる糖の質量組成比はN−アセチルグルコサミン44%、キチンオリゴ糖6%、デキストリン50%であり、グルコサミン塩酸塩は検出されなかった。 Furthermore, 10 g of a commercially available enzyme preparation (trade name “Hemicellulase Amano 90”, manufactured by Amano Enzyme) was added to the treatment liquid, treated at 50 ° C. for 12 hours, and then heated to 85 ° C. to deactivate the enzyme. 480 g of dextrin (trade name “Paindex NO. 2”, made by Matsutani Chemical Co., Ltd.) is added and dissolved, and dried (drying temperature: 160 ° C. in, 95 ° C. out) by spray drying (spray dryer manufactured by Niro Co., Ltd.). 910 g of white powder was obtained. As a result of analyzing the obtained powder by HPLC, the mass composition ratio of the saccharide contained in the powder was 44% for N-acetylglucosamine, 6% for chitin oligosaccharide, and 50% for dextrin, and glucosamine hydrochloride was not detected.
<実施例3>
下記に示す配合で常法に従って清涼飲料を作った。この清涼飲料は、加熱殺菌による褐変等も生じることがなく、また、適度な甘味を有しており、非常に飲みやすかった。この清涼飲料は1日1本(50g)を目安に摂取することが好ましい。
<Example 3>
A soft drink was prepared according to a conventional method with the following composition. This soft drink did not cause browning due to heat sterilization, had an appropriate sweetness, and was very easy to drink. This soft drink is preferably taken on a daily basis (50 g).
(配合:50g/本当たり)
エリスリトール 7g
フィッシュコラーゲンペプチド 1g
実施例1で得られた糖組成物 1g
ビタミンC 0.5g
ビタミンB2 5mg
酸味料 適量
甘味料 適量
香料 適量
保存料 適量
水 残り
(Formulation: 50g / per bottle)
Erythritol 7g
Fish collagen peptide 1g
1 g of the sugar composition obtained in Example 1
Vitamin C 0.5g
Vitamin B2 5mg
Acidulant appropriate amount Sweetener appropriate amount Fragrance appropriate amount Preservative appropriate amount Water remaining
<実施例4>
下記に示す配合で常法に従ってゼリー飲料を作った。このゼリー飲料は、ゲル化も良好で非常に飲みやすかった。このゼリー飲料は1日1本(100g)を目安に摂取することが好ましい。
<Example 4>
A jelly drink was prepared according to a conventional method with the following composition. This jelly beverage had good gelation and was very easy to drink. This jelly drink is preferably taken on a daily basis (100 g).
(配合:100g/本当たり)
砂糖 10g
フィッシュコラーゲンペプチド 5g
濃縮果汁 5g
実施例1で得られた糖組成物 1.5g
ビタミンB2 4mg
酸味料 適量
ゲル化剤 適量
香料 適量
保存料 適量
水 残り
(Formulation: 100g / per bottle)
10g sugar
Fish collagen peptide 5g
Concentrated fruit juice 5g
1.5 g of the sugar composition obtained in Example 1
Vitamin B2 4mg
Acidulant appropriate amount Gelling agent appropriate amount Fragrance appropriate amount Preservative appropriate amount Water remaining
<実施例5>
下記に示す配合で常法に従って野菜飲料を作った。この野菜飲料は、粘度も低く、果汁感があり、非常に飲みやすかった。この野菜飲料は1日1缶(200g)を目安に摂取することが好ましい。
<Example 5>
A vegetable drink was prepared according to a conventional method with the following composition. This vegetable drink had a low viscosity, a fruit juice feeling, and was very easy to drink. It is preferable to take this vegetable drink with 1 can (200 g) per day as a guide.
(配合:200g/缶)
人参ピューレ 20g
セロリピューレ 1g
リンゴピューレ 5g
オレンジ果汁 5g
レモン果汁 5g
砂糖 5g
実施例2で得られた糖組成物 2g
ビタミンC 0.3g
ショウガエキス 0.3g
酸味料 適量
結晶セルロース 適量
水 残り
(Composition: 200g / can)
Carrot puree 20g
Celery puree 1g
Apple puree 5g
5g orange juice
Lemon juice 5g
5g sugar
2 g of the sugar composition obtained in Example 2
Vitamin C 0.3g
Ginger extract 0.3g
Acidulant appropriate amount crystalline cellulose appropriate amount water remaining
<実施例6>
下記に示す配合で常法に従って果実飲料を作った。この果実飲料は、外観も色鮮やかで香り良く、非常に飲食意欲をそそり、実際に試飲すると非常に美味しかった。この果実飲料は1日1パック(200g)を目安に摂取することが好ましい。
<Example 6>
A fruit drink was prepared according to a conventional method with the following composition. This fruit drink was colorful and fragrant in appearance, very inspiring to eat and drink, and was very tasty when actually tasting. This fruit drink is preferably ingested in 1 pack (200 g) per day.
(配合:200g/パック当たり)
濃縮アセロラ果汁 50g
濃縮ラズベリー果汁 50g
実施例2で得られた糖組成物 3g
キチンオリゴ糖 0.2g
ローヤルゼリー 0.1g
水 残り
(Formulation: 200g / pack)
Concentrated acerola juice 50g
Concentrated raspberry juice 50g
3 g of the sugar composition obtained in Example 2
Chitin oligosaccharide 0.2g
Royal Jelly 0.1g
Water rest
<実施例7>
下記に示す配合で常法に従って豆乳飲料を作った。この豆乳飲料は、配合成分とNAGの相性が良く、褐変・沈殿等もなく、味もシンプルかつマイルドで非常に飲みやすかった。この豆乳飲料は1日1パック(125g)を目安に摂取することが好ましい。
<Example 7>
A soy milk drink was prepared according to a conventional method with the following composition. This soymilk drink had good compatibility between the compounding ingredients and NAG, no browning / precipitation, etc. The taste was simple and mild, and it was very easy to drink. It is preferable to take this soymilk drink with 1 pack (125 g) per day as a guide.
(配合:125g/パック当たり)
豆乳 100g
大豆イソフラボン 0.5g
実施例1で得られた糖組成物 0.5g
砂糖 4g
水 残り
(Formulation: 125g / pack)
100g soy milk
Soy isoflavone 0.5g
0.5 g of the sugar composition obtained in Example 1
4g sugar
Water rest
<実施例8>
下記に示す配合で常法に従って炭酸飲料を作った。この炭酸飲料は、適度な発泡感があり、のど越しが良く、沈殿物等もなく、非常に飲みやすかった。この炭酸飲料は1日1本(150g)を目安に摂取することが好ましい。
<Example 8>
A carbonated beverage was prepared according to a conventional method with the following composition. This carbonated beverage had a moderate foaming feeling, had a good throat, no precipitates, etc., and was very easy to drink. This carbonated beverage is preferably taken on a daily basis (150 g).
(配合:150g/本当たり)
果糖液糖 25g
実施例1で得られた糖組成物 0.2g
水溶性食物繊維 1g
ショウガエキス 0.1g
酒精 1g
酸味料 適量
香料 適量
炭酸水 残り
(Formulation: 150g / per bottle)
Fructose liquid sugar 25g
0.2 g of the sugar composition obtained in Example 1
1g water-soluble dietary fiber
Ginger extract 0.1g
Alcohol 1g
Acidulant appropriate amount Fragrance appropriate amount carbonated water remaining
低甘味、低カロリーで飲食品に利用可能なN−アセチルグルコサミンを含有する糖組成物を安価に得ることができるので、機能性食品素材として広く飲食品に利用することができる。また、この糖組成物を添加した飲食品は、N−アセチルグルコサミンによる美容や関節障害改善等の生理機能、及びキチンオリゴ糖によるビフィズス菌増殖作用や免疫調整機能等の生理機能が期待できるので、美容・健康飲食品として利用できる。 Since a sugar composition containing N-acetylglucosamine that is low in sweetness and low in calories and can be used in foods and drinks can be obtained at low cost, it can be widely used in foods and drinks as functional food materials. In addition, foods and drinks to which this sugar composition is added can be expected to have physiological functions such as beauty and joint damage improvement by N-acetylglucosamine, and physiological functions such as bifidobacteria growth and immune regulation functions by chitin oligosaccharides. Can be used as beauty and health food.
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JP2006327979A (en) * | 2005-05-25 | 2006-12-07 | Yaizu Suisankagaku Industry Co Ltd | Articular cartilage injury healing promoter, tendon injury healing promoter, and food and drink containing them |
JP5256509B2 (en) * | 2008-01-18 | 2013-08-07 | 甲陽ケミカル株式会社 | Method for producing N-acetylglucosamine and use thereof |
JP2011193819A (en) * | 2010-03-19 | 2011-10-06 | Cosmo Plus:Kk | Raw royal jelly food |
JP5714963B2 (en) * | 2011-04-11 | 2015-05-07 | 甲陽ケミカル株式会社 | Method for producing chitin degradation product |
JP5578384B1 (en) * | 2013-11-15 | 2014-08-27 | 株式会社東洋新薬 | Flavor improving method and flavor improving composition containing N-acetylglucosamine |
JP6173262B2 (en) * | 2014-06-24 | 2017-08-02 | 株式会社東洋新薬 | Flavor improving method and flavor improving composition containing N-acetylglucosamine |
CN113180159B (en) * | 2017-04-14 | 2022-09-27 | 浙江艾杰斯生物科技有限公司 | A kind of lysozyme feed additive prepared by fermentation process |
JP2017163999A (en) * | 2017-06-29 | 2017-09-21 | 株式会社東洋新薬 | Flavor improving method and flavor improving composition comprising n-acetylglucosamine |
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