JP2006094856A - Method for suppressing production of milk cooked odor and application of the same - Google Patents

Method for suppressing production of milk cooked odor and application of the same Download PDF

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JP2006094856A
JP2006094856A JP2005248298A JP2005248298A JP2006094856A JP 2006094856 A JP2006094856 A JP 2006094856A JP 2005248298 A JP2005248298 A JP 2005248298A JP 2005248298 A JP2005248298 A JP 2005248298A JP 2006094856 A JP2006094856 A JP 2006094856A
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milk
trehalose
odor
mass
production
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JP4546905B2 (en
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Kazuyuki Oku
和之 奥
Michio Kubota
倫夫 久保田
Toshio Miyake
俊雄 三宅
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Hayashibara Seibutsu Kagaku Kenkyujo KK
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Hayashibara Biochemical Laboratories Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To provide an easy and efficient method for suppressing production of milk cooked odor in milk or a milk product and to provide the application of the method. <P>SOLUTION: This method for suppressing production of milk cooked odor comprises including α-glycosyltrehalose in milk or a milk product. A suppressant for production of milk cooked smell containing α-glycosyltrehalose as active ingredient is provided. The method is used for a method for producing milk or a milk product suppressed in production of milk cooked odor. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、乳加熱臭の生成抑制方法に関し、詳細には、牛乳など哺乳類由来の乳又はこれらを利用した乳製品にα−グリコシルトレハロースを含有せしめることを特徴とする乳加熱臭の生成抑制方法とその用途に関する。   TECHNICAL FIELD The present invention relates to a method for suppressing the generation of a heated odor of milk, and more specifically, a method for suppressing the generation of a heated odor of milk, characterized in that α-glycosyl trehalose is contained in milk derived from mammals such as milk or dairy products using these. And its use.

牛乳、練乳、粉末乳、乳菓、アイスクリーム、発酵乳、乳飲料などの乳又はこれを利用した乳製品の製造工程において、加熱は最も重要な工程であり、加熱によって微生物を殺菌すること及び酵素を不活性化することによって、消費者に安全で良質の乳又は乳製品を提供することができる。例えば、牛乳の場合の加熱殺菌法は、通常、72乃至85℃で15秒間以上または120乃至130℃で1乃至4秒間行なわれ、さらに、常温保存可能品の場合、140℃で4秒間の滅菌が行なわれる。しかしながら、一般に、乳清タンパク質は加熱によって熱変性し、タンパク質に含まれるSH基が活性化し、揮発性の硫化物であるジメチルスルフィドやジメチルジスルフィドが生成し、これらに起因する乳特有の加熱臭(以下、本明細書では乳加熱臭と呼称する)が発生する。乳加熱臭は、酸化臭とともに不快なものであり、乳又は乳製品にとって品質上好ましくない。   In the production process of milk such as cow's milk, condensed milk, powdered milk, confectionery, ice cream, fermented milk, milk drink, etc. or dairy products using the same, heating is the most important process, and sterilization of microorganisms by heating and By inactivating the enzyme, a safe and good quality milk or dairy product can be provided to the consumer. For example, the heat sterilization method in the case of milk is usually performed at 72 to 85 ° C. for 15 seconds or more or 120 to 130 ° C. for 1 to 4 seconds. Is done. However, in general, whey protein is thermally denatured by heating, and SH groups contained in the protein are activated to produce volatile sulfides such as dimethyl sulfide and dimethyl disulfide. Hereinafter, this is referred to as a milk heating odor. The heated odor of milk is unpleasant with the oxidized odor and is not preferable for quality of milk or dairy products.

一方、乳加熱臭を低減する方法として、低温で殺菌する方法、即ち、62乃至65℃で30分間の熱処理をする低温長時間殺菌法が知られているものの、この方法は処理時間が長く、非能率的であり多量の乳又は乳製品を処理することができないだけでなく、殺菌時間が長時間にわたり乳質の劣化も起こし易く、ごく一部にしか用いられていない。また、加熱が不十分な場合、乳又は乳製品中の病原性菌が完全に殺菌できず、安心して出荷できる製品とすることができない。また、特許文献1には、牛乳中の溶存酸素を不活性の窒素ガスと置換することにより低減させ、加熱殺菌中のジメチルスルフィドやジメチルジスルフィドの生成を抑制する方法が開示されている。しかしながら、この方法には、特殊な窒素ガス置換装置を必要とするという問題点がある。このように、乳又は乳製品においては、十分な加熱処理によって発生する乳加熱臭の生成を抑制し、乳又は乳製品本来の新鮮な香りを保つための、より簡便で新しい技術は従来存在しなかった。   On the other hand, as a method of reducing the heat odor of milk, although a method of sterilizing at low temperature, that is, a low temperature long time sterilization method of performing heat treatment at 62 to 65 ° C. for 30 minutes, this method has a long processing time, Not only is it inefficient and unable to process large quantities of milk or dairy products, it also has a long pasteurization time and is prone to deterioration of milk quality and is used only in a small part. In addition, when heating is insufficient, pathogenic bacteria in milk or dairy products cannot be completely sterilized, and a product that can be shipped with peace of mind cannot be obtained. Patent Document 1 discloses a method of reducing dissolved oxygen in milk by substituting with inert nitrogen gas to suppress the formation of dimethyl sulfide and dimethyl disulfide during heat sterilization. However, this method has a problem that a special nitrogen gas replacement device is required. As described above, in milk or dairy products, there has been a simpler and newer technology for suppressing the generation of a heated odor of milk generated by sufficient heat treatment and maintaining the original fresh scent of milk or dairy products. There wasn't.

特許第3091742号公報Japanese Patent No. 3091742

本発明は、乳又は乳製品における乳加熱臭の発生を抑制する簡便で効率的な方法とその用途を確立することを課題とする。   This invention makes it a subject to establish the simple and efficient method and its use which suppress generation | occurrence | production of the milk heating odor in milk or dairy products.

本発明者等は、上記の課題を解決するために、糖質の利用に着目し、鋭意研究を続けてきた。即ち、乳の代表例として生鮮牛乳を用い、これに各種糖質を共存させ、生鮮牛乳からのジメチルスルフィド及びジメチルジスルフィドの生成に与える各種糖質の影響を調べた。その結果、意外にも、α−グリコシルトレハロースが他の糖質に比較してジメチルスルフィド及びジメチルジスルフィド自体の生成を顕著に抑制し、乳加熱臭の発生を著しく抑制することを見出し、本発明を完成した。   In order to solve the above-mentioned problems, the present inventors have focused on the use of carbohydrates and have continued intensive studies. That is, fresh milk was used as a representative example of milk, and various sugars were allowed to coexist with it, and the influence of various sugars on the production of dimethyl sulfide and dimethyl disulfide from fresh milk was examined. As a result, surprisingly, it has been found that α-glycosyl trehalose significantly suppresses the production of dimethyl sulfide and dimethyl disulfide itself, and significantly suppresses the occurrence of milk heating odor as compared with other carbohydrates. completed.

即ち、本発明は、乳又は乳製品にα−グリコシルトレハロースを含有せしめることを特徴とする乳加熱臭の生成抑制方法とα−グリコシルトレハロースを有効成分として含有する乳加熱臭生成抑制剤、及び、この方法を用いた乳加熱臭の生成が抑制された乳又は乳製品の製造方法を提供することにより上記課題を解決するものである。   That is, the present invention includes a method for inhibiting the production of a heated odor of milk, characterized by containing α-glycosyl trehalose in milk or a dairy product, a milk heated odor production inhibitor containing α-glycosyl trehalose as an active ingredient, and The above-described problems are solved by providing a method for producing milk or a dairy product in which the generation of a heated odor of milk using this method is suppressed.

本発明の乳加熱臭の生成抑制方法によれば、加熱工程を含む乳又は乳製品の製造において、乳加熱臭の生成を効果的に抑制することができる。また、本発明の方法は、牛乳のみならず、他の哺乳類の乳、更にはこれらの乳を利用した乳製品の製造においても有用である。さらに、本発明のα−グリコシルトレハロースを有効成分とする乳加熱臭の生成抑制剤及びα−グリコシルトレハロースを含有せしめることを特徴とする本発明の乳又は乳製品の製造方法によれば、乳加熱臭の生成が抑制された高品質の乳又は乳製品を製造することが可能となる。   According to the method for suppressing the production of milk heated odor of the present invention, the production of milk heated odor can be effectively inhibited in the production of milk or dairy products including a heating step. The method of the present invention is useful not only for milk but also for milk of other mammals and also for producing dairy products using these milks. Furthermore, according to the method for producing milk or dairy products of the present invention, the method further comprises the production inhibitor of milk heated odor containing the α-glycosyl trehalose of the present invention as an active ingredient and the α-glycosyl trehalose of the present invention. It becomes possible to produce high-quality milk or dairy products with suppressed odor production.

本発明でいう乳とは、最も一般的な均質化(ホモジナイズ)乳にのみ限定されず、生乳や、ビタミン及び又はミネラルを強化した加工乳、さらには、還元乳と呼称される、全粉乳、濃縮乳、脱脂粉乳又はバターなどを溶解して調製される加工乳をも含む。   Milk in the present invention is not limited to the most common homogenized milk, but raw milk, processed milk enriched with vitamins and / or minerals, and further referred to as reduced milk, whole milk powder, It also includes processed milk prepared by dissolving concentrated milk, skim milk powder or butter.

本発明でいう乳製品とは、乳を原材料とした加工品全般を意味する。例えば、バター、チーズ、クリーム、濃縮ホエイ、アイスクリーム類、濃縮乳、脱脂乳、加糖練乳、加糖脱脂練乳、全粉乳、脱脂全粉乳、クリームパウダー、バターミルクパウダー、加糖粉乳、調製粉乳、発酵乳、粉末発酵乳、乳酸菌飲料、粉末乳酸菌飲料、コーヒーミルク、フルーツミルクなどの乳飲料などが挙げられる。   The dairy product as used in the field of this invention means the whole processed goods which used milk as a raw material. For example, butter, cheese, cream, concentrated whey, ice cream, concentrated milk, skim milk, sweetened condensed milk, sweetened skim condensed milk, whole powdered milk, skimmed whole milk powder, cream powder, buttermilk powder, sweetened powdered milk, prepared powdered milk, fermented milk And milk beverages such as powdered fermented milk, lactic acid bacteria beverages, powdered lactic acid bacteria beverages, coffee milk, and fruit milk.

本発明で用いるα−グリコシルトレハロースは、乳加熱臭の生成を抑制できるものであればよく、その由来、性状は問わない。本発明でいうα−グリコシルトレハロースとは、α−グルコシルトレハロース、α−マルトシルトレハロース、α−マルトトリオシルトレハロースなどの、末端にトレハロース構造を有するトレハロースの糖質誘導体の総称であり、例えば、特開平7−143876号公報等に開示される方法で製造されるα−グルコシルトレハロース、α−マルトシルトレハロース、α−マルトトリオシルトレハロースや、特開平7−291986号公報に開示される結晶マルトシルグルコシド(α−グルコシルトレハロース)、特開平7−291987号公報に開示される結晶マルトテトラオシルグルコシド(α−マルトトリオシルトレハロース)などを適宜利用することができる。   The α-glycosyl trehalose used in the present invention is not particularly limited in its origin and properties as long as it can suppress the generation of milk heat odor. The α-glycosyl trehalose referred to in the present invention is a generic name for carbohydrate derivatives of trehalose having a trehalose structure at its terminal, such as α-glucosyl trehalose, α-maltosyl trehalose, α-maltotriosyl trehalose, and the like. Α-glucosyl trehalose, α-maltosyl trehalose, α-maltotriosyl trehalose, and crystalline maltosyl glucoside disclosed in Japanese Patent Application Laid-Open No. 7-291986, which are produced by the method disclosed in Kaihei 7-143876 (Α-glucosyl trehalose), crystalline maltotetraosyl glucoside (α-maltotriosyl trehalose) disclosed in JP-A-7-291987 can be used as appropriate.

本発明で使用するα−グリコシルトレハロースは必ずしも高純度の製品に限定されず、例えば、α−グルコシルトレハロース、α−マルトシルトレハロース、α−マルトトリオシルトレハロースなど複数種のα−グリコシルトレハロースの混合物、また、乳加熱臭の生成抑制に支障がない限り、α−グリコシルトレハロースとともに他の糖質、例えば、グルコース、マルトース、マルトトリオース、マルトテトラオースなどの還元性糖質、トレハロース、ソルビトール、マルチトール、マルトトリイトール、マルトテトライトールなどの非還元性糖質を含有するα−グリコシルトレハロース含有糖組成物も乳加熱臭の生成抑制剤として有利に利用できる。さらには、α−シクロデキストリン、β−シクロデキストリン、γ−シクロデキストリン、又はそれらの糖誘導体などのシクロデキストリン類等の1種又は2種以上と併用することも随意である。市販されているα−グリコシルトレハロース含有糖組成物としては、α−マルトシルトレハロース含有水飴(登録商標「ハローデックス」、株式会社林原商事販売、固形物当たりα−マルトシルトレハロースを約53%、α−グルコシルトレハロースを約4%、α−マルトトリオシルトレハロースを約1%含有)が有利に利用できる。   The α-glycosyl trehalose used in the present invention is not necessarily limited to a high-purity product. For example, α-glycosyl trehalose, α-maltosyl trehalose, α-maltosyl trehalose, a mixture of a plurality of α-glycosyl trehaloses such as α-maltotriosyl trehalose, In addition, α-glycosyl trehalose and other saccharides, for example, reducing saccharides such as glucose, maltose, maltotriose, maltotetraose, trehalose, sorbitol, maltitol, as long as there is no hindrance to the suppression of milk odor production An α-glycosyl trehalose-containing sugar composition containing non-reducing sugars such as maltotriitol and maltotetriitol can also be advantageously used as a production inhibitor of milk odor. Furthermore, it is optional to use in combination with one or more of cyclodextrins such as α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, or sugar derivatives thereof. As a commercially available α-glycosyl trehalose-containing sugar composition, α-maltosyl trehalose-containing syrup (registered trademark “Hellodex”, sold by Hayashibara Shoji Co., Ltd., about 53% α-maltosyl trehalose per solid, α -Containing about 4% glucosyl trehalose and about 1% α-maltotriosyl trehalose).

また、α−グリコシルトレハロースとともに酸味料を併用して、乳又は乳製品のpHを酸性側に、望ましくはpH2乃至pH6附近、更に望ましくは、pH3乃至5附近に保って、乳加熱臭の生成抑制効果を高めることも有利に実施できる。酸味料としては、酢酸、乳酸、クエン酸、酒石酸、リンゴ酸、グルコン酸などの有機酸の使用が望ましく、必要ならば、無機酸を用いることもできる。更に必要に応じて、香辛料、アミノ酸系、核酸系旨味料、清酒、みりん、ワイン、ブランディー等の酒類、ペクチン、アルギン酸、プルラン等の水溶性多糖類、食塩、塩化カルシウム、塩化マグネシウム、リン酸塩等の無機塩等から選ばれる1種又は2種以上を併用して矯臭効果を発揮させることも随意である。また、上記の各種成分をα−グリコシルトレハロースとともに予め配合し、乳加熱臭の生成抑制剤とすることも有利に実施できる。   In addition, by using an acidulant together with α-glycosyl trehalose, the pH of milk or dairy products is kept on the acidic side, preferably around pH 2 to pH 6, more preferably around pH 3 to 5, to suppress generation of heated odor of milk. Increasing the effect is also advantageous. As the acidulant, it is desirable to use an organic acid such as acetic acid, lactic acid, citric acid, tartaric acid, malic acid, gluconic acid, and an inorganic acid can be used if necessary. If necessary, spices, amino acids, nucleic acid flavours, sake, mirin, wine, brandy and other alcoholic beverages, pectin, alginic acid, pullulan and other water soluble polysaccharides, salt, calcium chloride, magnesium chloride, phosphoric acid It is also optional that one or two or more selected from inorganic salts such as salts are used in combination to exert a odor-masking effect. It is also possible to advantageously implement the above-mentioned various components in advance together with α-glycosyl trehalose to form a milk heated odor production inhibitor.

本発明の乳加熱臭の生成抑制方法において、乳又は乳製品に含有せしめるα−グリコシルトレハロースの量は、通常、乳又は乳製品に含まれる乳固形分当たり、約6質量%以上約500質量%未満、望ましくは、約10質量%以上約400質量%未満、更に望ましくは、約50質量%以上約300質量%未満が良く、均一に含有せしめるのが好適である。乳製品中の乳固形分に対するα−グリコシルトレハロースの含有量が6質量%未満では、通常、ジメチルスルフィド及びジメチルジスルフィドの生成に起因する乳加熱臭の生成抑制効果が不充分で、500質量%以上では、得られる製品の甘味が強くなり過ぎる。しかし、乳又は乳製品に甘味が付いてもかまわない場合、又は甘味の付くのがむしろ好ましい場合、例えば、乳製品がアイスクリーム、スナック食品、菓子等の場合には、乳固形分当たり500質量%を越えて含有させることも有利に実施できる。   In the method for suppressing generation of heated odor of milk according to the present invention, the amount of α-glycosyl trehalose to be contained in milk or dairy product is usually about 6% by mass or more and about 500% by mass per dairy solid content in the milk or dairy product. Less, preferably about 10% by mass or more and less than about 400% by mass, and more preferably about 50% by mass or more and less than about 300% by mass, and it is preferable that they are contained uniformly. When the content of α-glycosyl trehalose relative to the milk solid content in the dairy product is less than 6% by mass, the effect of suppressing the generation of heated odor of milk due to the formation of dimethyl sulfide and dimethyl disulfide is usually insufficient, 500% by mass or more Then the sweetness of the resulting product becomes too strong. However, if the milk or dairy product may be sweetened, or if it is preferable to have a sweet taste, for example, if the dairy product is ice cream, snack food, confectionery, etc., 500 mass per milk solids It can also be advantageously implemented to contain more than%.

本発明でいう含有せしめるとは、共存させることをいい、乳又は乳製品にα−グリコシルトレハロースを含有せしめることによって、加熱により生成するジメチルスルフィド及びジメチルジスルフィドに起因する乳加熱臭の生成が抑制された乳又は乳製品を製造できればよく、含有せしめる方法は問わない。望ましくは、乳又は乳製品に対して、α−グリコシルトレハロースを水性媒体でできるだけ均一に含有せしめるのがよい。例えば、目的とする乳製品が、液状乃至ペースト状物のような多汁状態である場合には、これにα−グリコシルトレハロースを粉末、結晶等の固状状態で、できるだけ均一に混合溶解して含有せしめるか、又は、シラップ状状態で、できるだけ均一に混合して含有せしめればよい。   Inclusion in the present invention means coexistence, and by containing α-glycosyl trehalose in milk or dairy products, the production of heated odor of milk due to dimethyl sulfide and dimethyl disulfide generated by heating is suppressed. Any method can be used as long as milk or dairy products can be produced. Desirably, α-glycosyl trehalose should be contained as uniformly as possible in an aqueous medium for milk or dairy products. For example, when the target dairy product is in a succulent state such as a liquid or pasty product, α-glycosyl trehalose is mixed and dissolved in a solid state such as a powder or a crystal as uniformly as possible. It may be contained, or mixed as uniformly as possible in a syrup state.

また、乳製品が固状である場合には、これを水で液状乃至ペースト状物のような多汁状態にした後、含有せしめるか、又はα−グリコシルトレハロースをシラップ状態とし、これに乳製品を、分散、溶解乃至懸濁し、できるだけ均一になるように含有せしめればよい。   Further, when the dairy product is in a solid state, it is made into a succulent state such as a liquid or pasty product with water and then contained, or α-glycosyl trehalose is made into a syrup state, and this is added to the dairy product. May be dispersed, dissolved or suspended, and contained as uniformly as possible.

乳又は乳製品を製造するに際し、原料乳又は乳製品にα−グリコシルトレハロースを含有せしめ、次いで、常法に従って加熱処理又は噴霧乾燥など加熱を含む処理を施すことにより、目的とする乳加熱臭の生成が抑制された乳又は乳製品を製造することができる。また、乳又は乳製品を保存する際にも、乳又は乳製品にα−グリコシルトレハロースを含有させることにより、乳加熱臭の生成を抑制することができ、その鮮度を長期間安定に保持できる。さらに、α−グリコシルトレハロースには蛋白質の変性や脂質の変敗を抑制する作用があり、乳製品の製造時における乳成分の加熱処理による変性や変敗、保存時における変性や変敗を著しく抑制する作用がある。一方、乳の酸化臭は、乳に含まれる脂質の変敗が原因であり、乳加熱臭とともに生乳や加工乳にとって品質上好ましくない臭気であるところ、本発明で用いるα−グリコシルトレハロースは、乳製品の脂質の変敗を抑制し、酸化臭の生成を抑制することができる。   In producing milk or dairy products, the raw milk or dairy product is mixed with α-glycosyl trehalose, and then subjected to a treatment including heating such as heat treatment or spray drying in accordance with a conventional method, so that the desired milk odor can be obtained. Milk or dairy products with suppressed production can be produced. In addition, when storing milk or dairy products, the production of heated odor of milk can be suppressed by containing α-glycosyl trehalose in the milk or dairy products, and the freshness can be stably maintained for a long period of time. In addition, α-glycosyl trehalose has the effect of suppressing protein denaturation and lipid degradation, and remarkably inhibits denaturation and degradation due to heat treatment of milk components during dairy production, and denaturation and degradation during storage. Has the effect of On the other hand, the oxidized odor of milk is caused by deterioration of lipids contained in milk, and it is an unpleasant odor in terms of quality for raw milk and processed milk together with the heated odor of milk. It can suppress the deterioration of the lipid of the product and suppress the generation of oxidized odor.

以上述べてきたように、本発明の方法により、乳又は乳製品にα−グリコシルトレハロースを含有せしめて調製した乳製品は、殺菌・滅菌、濃縮、粉末化などの熱加工処理を加えた場合、又は、製品を流通又は保存する場合においても、乳加熱臭が抑制されており、良好な風味を長時間維持することができる。   As described above, a dairy product prepared by adding α-glycosyl trehalose to milk or a dairy product according to the method of the present invention is subjected to heat treatment such as sterilization / sterilization, concentration, and powdering. Alternatively, even when the product is distributed or stored, the heated odor of milk is suppressed, and a good flavor can be maintained for a long time.

以下、実験により本発明を詳細に説明する。   Hereinafter, the present invention will be described in detail by experiments.

<実験:牛乳におけるジメチルスルフィド及びジメチルジスルフィドの生成に及ぼす各種糖質共存の影響>
生鮮牛乳に各種糖質を、生鮮牛乳中の乳固形分を10質量%として、乳固形分当たり無水物換算で終濃度10、20、50又は100質量%になるよう添加・溶解し、糖質含有牛乳を調製した。それぞれの2mlを20ml容バイアル瓶にそれぞれ採取し、ブチルゴム栓で密栓後、130℃で1分間加熱した。糖質としては、α−グルコシルトレハロース、α−マルトシルトレハロース、α−マルトシルトレハロース含有水飴(登録商標『ハローデックス』、株式会社林原商事販売、固形物当たりα−マルトシルトレハロースを約53%、α−グルコシルトレハロースを約4%、α−マルトトリオシルトレハロースを約1%含有)、スクロース、マルトース、マルトトリオース、又はマルトテトラオースを用いた。バイアル瓶を流水中で冷却した後、予熱したヒートブロック装置で80℃、5分間加温し、そのヘッドスペースガス(HSG)1mlをガスシリンジにて採取し、ガスクロマトグラフィー(以下、GCと略称する。)によりHSG中のジメチルスルフィド及びジメチルジスルフィド濃度を測定した。なお、本実験では、HSG中のジメチルスルフィド濃度とジメチルジスルフィド濃度の合計を総揮発性硫化物濃度とした。GCは、水素炎イオン化検出器を装着したガスクロマトグラフ(島津製GC−14A)に、カラムとしてGLサイエンス社製DB−1キャピラリーカラムを用い、キャリアーガスとしてヘリウムガスを流速1ml/分で流し、50℃で定温分析した。結果を表1に示した。
<Experiment: Effects of various carbohydrates on the production of dimethyl sulfide and dimethyl disulfide in milk>
Various sugars are added to fresh milk, and 10% by mass of milk solids in fresh milk is added and dissolved to a final concentration of 10, 20, 50 or 100% by mass in terms of anhydride per milk solids. Containing milk was prepared. 2 ml of each was collected in a 20 ml vial, sealed with a butyl rubber stopper, and heated at 130 ° C. for 1 minute. As the saccharide, α-glucosyl trehalose, α-maltosyl trehalose, α-maltosyl trehalose-containing syrup (registered trademark “Hellodex”, sold by Hayashibara Corporation, about 53% α-maltosyl trehalose per solid matter, α-glucosyl trehalose was contained in about 4% and α-maltotriosyl trehalose was contained in about 1%), sucrose, maltose, maltotriose, or maltotetraose. After cooling the vial in running water, it was heated at 80 ° C. for 5 minutes with a preheated heat block device, 1 ml of its headspace gas (HSG) was collected with a gas syringe, and gas chromatography (hereinafter abbreviated as GC) The concentration of dimethyl sulfide and dimethyl disulfide in HSG was measured. In this experiment, the total of dimethyl sulfide concentration and dimethyl disulfide concentration in HSG was defined as the total volatile sulfide concentration. The GC is a gas chromatograph (GC-14A manufactured by Shimadzu) equipped with a flame ionization detector, and a DB-1 capillary column manufactured by GL Science Co., Ltd. is used as the column. Was subjected to constant temperature analysis. The results are shown in Table 1.

Figure 2006094856
Figure 2006094856

表1の結果から明らかなように、牛乳の加熱時に乳固形分当たり10、20、50又は100質量%のα−グルコシルトレハロース、α−マルトシルトレハロース又はα−マルトシルトレハロース含有水飴を共存させた試験系における総揮発性硫化物濃度は、対照(糖質無添加系)のそれぞれ約75%以下、約60%以下、約40%以下又は約20%以下となり、用量依存的にジメチルスルフィド及びジメチルジスルフィドなど揮発性硫化物の生成を抑制した。とりわけ、α−マルトシルトレハロース含有水飴は、固形分当たりのα−グリコシルトレハロース含量が約60%と少ないため、乳固形当たりα−マルトシルトレハロース含有水飴を10質量%用いた試験系では、乳固形分当たりのα−グリコシルトレハロース量は約6質量%となるにもかかわらず、揮発性硫化物の生成抑制効果はα−グルコシルトレハロース又はα−マルトシルトレハロースを単独で使用した場合と同等であった。この理由としては、α−マルトシルトレハロース含有水飴中に含まれる他の糖質による何らかの相乗効果が考えられた。これに対して、スクロース、マルトース、マルトトリオース又はマルトテトラオースを共存させた試験系では、その抑制効果は全く認められなかった。また、実際に各試料のHSGの臭いを嗅いで、乳加熱臭を対照と比較したところ、α−グルコシルトレハロース、α−マルトシルトレハロース又はα−マルトシルトレハロース含有水飴を共存させた試験系では、明らかに不快臭が低減していた。   As is apparent from the results in Table 1, 10, 20, 50, or 100% by mass of α-glucosyl trehalose, α-maltosyl trehalose or α-maltosyl trehalose-containing starch syrup was allowed to coexist when milk was heated. The total volatile sulfide concentration in the test system is about 75% or less, about 60% or less, about 40% or less, or about 20% or less of the control (no sugar added system), respectively. Generation of volatile sulfides such as disulfide was suppressed. In particular, α-maltosyl trehalose-containing starch syrup has a low α-glycosyl trehalose content of about 60% per solid content. Therefore, in the test system using 10% by mass of α-maltosyl trehalose-containing starch syrup, Although the amount of α-glycosyl trehalose per minute was about 6% by mass, the effect of suppressing the formation of volatile sulfides was the same as when α-glucosyl trehalose or α-maltosyl trehalose was used alone. . The reason for this was considered to be some synergistic effect due to other carbohydrates contained in the α-maltosyltrehalose-containing water tank. On the other hand, in the test system in which sucrose, maltose, maltotriose or maltotetraose coexisted, no inhibitory effect was observed. In addition, when actually smelling the HSG odor of each sample and comparing the milk heating odor with the control, in the test system in which α-glucosyl trehalose, α-maltosyl trehalose or α-maltosyl trehalose-containing chickenpox coexisted, Obviously, unpleasant odor was reduced.

以下、実施例により本発明をさらに具体的に説明する。   Hereinafter, the present invention will be described more specifically with reference to examples.

<乳加熱臭の生成抑制剤>
濃度20質量%のとうもろこし澱粉乳に最終濃度0.1質量%となるように炭酸カルシウムを加えた後、pH6.5に調製し、これにα−アミラーゼ(ノボ社製造、商品名「ターマミール60L」)を澱粉グラム当たり0.2%になるように加え、95℃で15分間作用させた。その反応液を、120℃で10分間オートクレーブした後、50℃に冷却し、pHを5.8に調製後、特開昭63−240784号公報に開示されたマルトテトラオース生成アミラーゼ(株式会社林原生物化学研究所製造)を澱粉グラム当たり5単位と、イソアミラーゼ(株式会社林原生物化学研究所製造)を澱粉グラム当たり500単位となるように加え、48時間反応させ、これにα−アミラーゼ(上田化学株式会社製造、商品名「α−アミラーゼ2A」)を澱粉グラム当たり30単位加え、更に65℃で4時間反応させた。その反応液を120℃で10分間オートクレーブし、次いで、45℃に冷却し、特開平7−143876号公報に開示されたアルスロバクター・スピーシーズQ36(FERM BP−4316)由来の非還元性糖質生成酵素を澱粉グラム当たり2単位の割合になるように加え、48時間反応させた。その反応液を95℃で10分間保った後、冷却し、濾過して得られる濾液を、常法に従って活性炭で脱色し、H型及びOH型イオン交換樹脂により脱塩して精製した糖化液を更に濃縮して、濃度約70質量%のシラップを、無水物換算で、収率約90%で得た。本品は無水物換算で、α−グリコシルトレハロースとして、α−マルトシルトレハロースを52.5%含有しており、他に、α−グルコシルトレハロースを4.1%、α−マルトトリオシルトレハロースを1.1%、それ以外のα−グリコシルトレハロースを0.4%含有していた。本品は、乳加熱臭の生成抑制剤として各種乳又は乳製品の製造に有利に利用できる。
<Production inhibitor of heated odor of milk>
Calcium carbonate was added to corn starch milk having a concentration of 20% by mass to a final concentration of 0.1% by mass, and then adjusted to pH 6.5, and α-amylase (manufactured by Novo, trade name “Termamir 60L”) was prepared. ) Was added at 0.2% per gram starch and allowed to act at 95 ° C for 15 minutes. The reaction solution was autoclaved at 120 ° C. for 10 minutes, cooled to 50 ° C., adjusted to pH 5.8, and then maltotetraose-producing amylase (Hayashibara Co., Ltd.) disclosed in JP-A-63-240784. Biochemical Laboratories) was added to 5 units per gram of starch and Isoamylase (produced by Hayashibara Biochemical Laboratories Co., Ltd.) was added to 500 units per gram of starch, reacted for 48 hours, and α-amylase (Ueda) Chemical Co., Ltd., trade name “α-amylase 2A”) was added at 30 units per gram of starch, and further reacted at 65 ° C. for 4 hours. The reaction solution was autoclaved at 120 ° C. for 10 minutes, then cooled to 45 ° C., and non-reducing saccharide derived from Arthrobacter species Q36 (FERM BP-4316) disclosed in Japanese Patent Application Laid-Open No. 7-143876. The produced enzyme was added at a rate of 2 units per gram starch and allowed to react for 48 hours. The reaction solution is kept at 95 ° C. for 10 minutes, then cooled, filtered, and the filtrate obtained is decolorized with activated carbon according to a conventional method, and desalted with H-type and OH-type ion exchange resins to obtain a purified saccharified solution. Further concentration was performed to obtain syrup having a concentration of about 70% by mass in terms of anhydride in a yield of about 90%. This product contains 52.5% α-maltosyl trehalose as α-glycosyl trehalose in terms of anhydride, and in addition, 4.1% α-glucosyl trehalose and 1 α-maltotriosyl trehalose. .1% and 0.4% other α-glycosyl trehalose. This product can be advantageously used in the production of various types of milk or dairy products as an inhibitor of the generation of milk heated odor.

<乳加熱臭の生成抑制剤>
実施例1の方法で脱塩・精製し調製した糖化液を、塩型強酸性カチオン交換樹脂(ダウケミカル社販売、商品名「ダウエックス50W−X4」、Mg2+型)を用いたカラムクロマトグラフィーに供した。樹脂を内径5.4cmのジャケット付ステンレスカラム4本に充填し、直列につなぎ樹脂層全長20mとした。カラム内温度を55℃に維持しつつ、上記糖化液を樹脂に対して5v/v%加え、これに55℃の温水をSV0.13で流して分画し、グルコース及びマルトース高含有画分を除去し、α−グリコシルトレハロース高含有画分を回収し、更に精製、濃縮後、噴霧乾燥して非晶出のα−グリコシルトレハロース高含有糖質粉末を調製した。本品は、無水物換算で、α−マルトシルトレハロース70.2%を含有しており、他に、α−グルコシルトレハロース6.1%、α−マルトトリオシルトレハロース2.1%、それ以外のα−グリコシルトレハロース4.1%を含有していた。本品は、乳加熱臭の生成抑制剤として各種乳又は乳製品の製造に有利に利用できる。
<Production inhibitor of heated odor of milk>
The saccharified solution prepared by desalting and purifying by the method of Example 1 was subjected to column chromatography using a salt-type strongly acidic cation exchange resin (sold by Dow Chemical Co., Ltd., trade name “Dowex 50W-X4”, Mg 2+ type). It was used for. The resin was packed into four jacketed stainless steel columns with an inner diameter of 5.4 cm and connected in series to a total resin layer length of 20 m. While maintaining the internal temperature of the column at 55 ° C., the above saccharified solution was added to the resin at 5 v / v%, and this was fractionated by flowing warm water at 55 ° C. with SV0.13 to obtain a fraction containing high glucose and maltose. The α-glycosyl trehalose-rich fraction was recovered, and the fraction containing α-glycosyltrehalose-rich content was further purified, concentrated, and spray-dried to prepare an amorphous α-glycosyltrehalose-rich saccharide powder. This product contains 70.2% of α-maltosyl trehalose in terms of anhydride. Besides, α-glucosyl trehalose 6.1%, α-maltotriosyl trehalose 2.1%, other It contained 4.1% α-glycosyl trehalose. This product can be advantageously used in the production of various types of milk or dairy products as an inhibitor of the generation of milk heated odor.

<乳加熱臭の生成抑制剤>
実施例1の方法で得た濃度約70質量α−グリコシルトレハロース含有シラップを固形分濃度約60質量%に水で希釈した。次いで、これをオートクレーブに入れ、触媒としてラネーニッケルを固形分に対し約9質量%添加し、攪拌しながら温度を130℃に上げ、水素圧を75kg/cmに上げて水素添加して、α−グリコシルトレハロース含有シラップに含まれるグルコース、マルトースなどの還元性糖質を、それらの糖アルコールに変換した。この反応液からラネーニッケルを除去し、常法により脱色、脱塩して精製し、濃縮して濃度約70質量%のシラップを得た。本品は無水物換算で、α−グリコシルトレハロースとして、α−マルトシルトレハロースを53.5%含有しており、他に、α−グルコシルトレハロースを3.8%、α−マルトトリオシルトレハロースを1.0%、それ以外のα−グリコシルトレハロースを0.4%、糖アルコールを41.3%含有していた。本品は、乳加熱臭の生成抑制剤として各種乳又は乳製品の製造に有利に利用できる。
<Production inhibitor of heated odor of milk>
The syrup containing about 70 mass α-glycosyl trehalose obtained by the method of Example 1 was diluted with water to a solid concentration of about 60 mass%. Next, this was put into an autoclave, Raney nickel as a catalyst was added at about 9% by mass with respect to the solid content, the temperature was raised to 130 ° C. while stirring, the hydrogen pressure was raised to 75 kg / cm 2 , and hydrogenation was performed. Reducing sugars such as glucose and maltose contained in the glycosyl trehalose-containing syrup were converted to their sugar alcohols. Raney nickel was removed from the reaction solution, and it was purified by decoloring, desalting by a conventional method, and concentrated to obtain syrup having a concentration of about 70% by mass. This product contains 53.5% of α-maltosyl trehalose as α-glycosyl trehalose in terms of anhydride, 3.8% of α-glucosyl trehalose, and 1 of α-maltotriosyl trehalose. 0.0%, other α-glycosyl trehalose 0.4%, sugar alcohol 41.3%. This product can be advantageously used in the production of various types of milk or dairy products as an inhibitor of the generation of milk heated odor.

<加糖練乳>
生鮮牛乳100質量部に実施例1の方法で得た乳加熱臭の生成抑制剤25質量部、無水結晶マルチトール(登録商標『マビット』、株式会社林原商事販売)5質量部を加え、この混合物を、湯煎で適宜かきまぜながら当初の容量の4割になるまで煮詰め、次いで、氷水で冷却して加糖練乳を調製した。本品は、従来の加糖練乳とは異なり、砂糖に替えて乳加熱臭の生成抑制剤としてのα−グリコシルトレハロース含有シラップを用いていることから、加熱による乳加熱臭の生成が抑制された高品質の加糖練乳である。本品は各種乳飲料やアイスクリームの原料として有利に利用できる。
<Sweetened condensed milk>
A mixture of 25 parts by mass of a milk heated odor production inhibitor obtained by the method of Example 1 and 5 parts by mass of anhydrous crystalline maltitol (registered trademark “Mabit”, Hayashibara Shoji Co., Ltd.) was added to 100 parts by mass of fresh milk, and this mixture The mixture was boiled until it reached 40% of the original volume while being properly stirred in a hot water bath, and then cooled with ice water to prepare a sweetened condensed milk. Unlike conventional sweetened condensed milk, this product uses α-glycosyl trehalose-containing syrup as a milk heated odor production inhibitor in place of sugar, which prevents the production of milk heated odor by heating. Quality sweetened condensed milk. This product can be advantageously used as a raw material for various milk drinks and ice creams.

<加糖粉乳>
生鮮牛乳100質量部に対して実施例2の方法で調製した乳加熱臭の生成抑制剤2質量部、含水結晶トレハロース(登録商標『トレハ』、株式会社林原商事販売)4質量部を溶解後、約50℃に加温して原料牛乳の容量が1/3になるまで減圧濃縮し、常法により噴霧乾燥して加糖粉乳を調製した。本品は、固形分当たり約18質量%のα−グルコシルトレハロースを含有しており、加熱処理を含む噴霧乾燥工程を経ているにもかかわらず乳加熱臭の生成が抑制された高品質の加糖粉乳である。本品は各種飲食物の原料やコーヒー用の粉乳として有利に利用できる。
<Sweetened powdered milk>
After dissolving 2 parts by mass of a milk heating odor production inhibitor prepared by the method of Example 2 and 4 parts by mass of hydrated crystal trehalose (registered trademark “Treha”, sold by Hayashibara Corporation) with respect to 100 parts by mass of fresh milk, The mixture was heated to about 50 ° C., concentrated under reduced pressure until the volume of raw milk became 1/3, and spray-dried by a conventional method to prepare sweetened milk powder. This product contains about 18% by mass of α-glucosyl trehalose per solid content, and high-quality sweetened powdered milk with suppressed generation of heated milk odor despite undergoing a spray drying process including heat treatment It is. This product can be advantageously used as a raw material for various foods and drinks and as a milk powder for coffee.

<乳含有果汁飲料>
実施例2の方法で調製した乳加熱臭の生成抑制剤100質量部及び砂糖30質量部を水265質量部に溶解した後、アスコルビン酸2−グルコシド(株式会社林原生物化学研究所販売、商品名「AA2G」)1質量部、無水結晶マルチトール(登録商標『マビット』、株式会社林原商事販売)20質量部、0.5%コレカルシフェロール粉末0.005質量部を加え、これに牛乳100質量部、濃縮ミカン果汁(3倍濃縮品)170質量部、クエン酸15質量部、オレンジ香料1質量部を加え、80℃で5分間殺菌し、濃縮タイプの乳含有果汁飲料を調製した。本品は、加熱殺菌工程を経ているにもかかわらず乳加熱臭の生成が抑制された高品質の乳含有果汁飲料である。
<Milk-containing fruit juice beverage>
After dissolving 100 parts by mass of the milk heated odor production inhibitor and 30 parts by mass of sugar prepared in the method of Example 2 in 265 parts by mass of water, ascorbic acid 2-glucoside (sales by Hayashibara Biochemicals, Inc., trade name) "AA2G") 1 part by weight, anhydrous crystalline maltitol (registered trademark "Mabit", Hayashibara Shoji Sales) 20 parts by weight, 0.5% cholecalciferol powder 0.005 parts by weight, and milk 100 parts by weight Part, concentrated mandarin orange juice (3-fold concentrated product) 170 parts by weight, citric acid 15 parts by weight, orange flavor 1 part by weight, sterilized at 80 ° C. for 5 minutes to prepare a concentrated type milk-containing juice drink. This product is a high-quality milk-containing fruit juice beverage in which the generation of a heated odor of milk is suppressed despite the heat sterilization process.

<ラクトアイス>
ヤシ油3質量部、脱脂粉乳4質量部、実施例3の方法で得た乳加熱臭の生成抑制剤20質量部、スクラロース0.05質量部、安定剤0.3質量部、乳化剤0.3質量部、水75質量部を約70℃で混合し、均質化(12,000rpmで10分間ホモジナイズ)した後、70℃で30分間殺菌した。これを冷却し、5℃で一晩エージングした。次いで、これにバニラエッセンス0.3質量部を混合し、フリージングした。オーバーラン50%の操作を行い、カップ取りの後、−40℃の冷凍庫で24時間保持して硬化させ、ラクトアイスを調製した。本品は、加熱による乳加熱臭の生成が抑制された高品質のラクトアイスである。
<Lact ice>
3 parts by mass of coconut oil, 4 parts by mass of skim milk powder, 20 parts by mass of a generation inhibitor of milk odor obtained by the method of Example 3, 0.05 parts by mass of sucralose, 0.3 parts by mass of stabilizer, 0.3 parts of emulsifier Part by mass and 75 parts by mass of water were mixed at about 70 ° C. and homogenized (homogenized at 12,000 rpm for 10 minutes), and then sterilized at 70 ° C. for 30 minutes. This was cooled and aged at 5 ° C. overnight. Subsequently, 0.3 mass part of vanilla essence was mixed with this, and it freezed. The operation of overrun 50% was performed, and after taking the cup, it was kept in a freezer at −40 ° C. for 24 hours to be cured to prepare lacto ice. This product is a high-quality lacto ice that suppresses the production of heated odors from heating.

<缶コーヒー>
焙煎したコーヒー豆約100質量部を粉砕し、これを沸騰水約1,000質量部で抽出し、コーヒー抽出液約860質量部を得た。本液約450質量部と牛乳50質量部、グラニュー糖20質量部、実施例3の方法で得た乳加熱臭の生成抑制剤100質量部、及び適量の重曹を含む水約380質量部を均一に混合してpH約6.5のミルクコーヒーを調製した。次いで、これを常法に従って缶に充填した後、123℃で20分間加熱滅菌し、水冷して缶コーヒーを製造した。本品は香り、味とも良好であり、また、加熱による乳加熱臭の生成が抑制された高品質のコーヒーである。
<Canned coffee>
About 100 parts by mass of roasted coffee beans were pulverized and extracted with about 1,000 parts by mass of boiling water to obtain about 860 parts by mass of a coffee extract. About 450 parts by mass of this solution, 50 parts by mass of milk, 20 parts by mass of granulated sugar, 100 parts by mass of a production inhibitor of heated odor of milk obtained by the method of Example 3, and about 380 parts by mass of water containing an appropriate amount of baking soda To prepare milk coffee having a pH of about 6.5. Subsequently, this was filled in a can according to a conventional method, then heat sterilized at 123 ° C. for 20 minutes, and water-cooled to produce a can coffee. This product is a high-quality coffee that has good aroma and taste, and that suppresses the generation of heated odor of milk by heating.

<ヨーグルト>
牛乳80質量部にグラニュー糖6質量部及び安定剤(商品名「NEWGELIN X−04086Y」、中央フーズマテリアル株式会社販売)0.3質量部を添加し、加温しつつ混合した。次いで、これに実施例1の方法で得た乳加熱臭の生成抑制剤9質量部を加え、ホモミキサーにて5,000rpm、5分間攪拌・溶解した後、90℃で10分間保持して殺菌した。冷却後、スターターとしてのヨーグルト5質量部、及びヨーグルトフレーバー0.1質量部をさらに加え、ホモミキサーにて5,000rpm、5分間攪拌・混合した。これを容器に充填し、35℃で一晩発酵させた後、冷蔵し、ヨーグルトを調製した。本品は、加熱による乳加熱臭の生成が抑制されており、また、控えめな甘さとほのかな酸味が調和した高品質のヨーグルトである。
<Yogurt>
To 80 parts by mass of milk, 6 parts by mass of granulated sugar and a stabilizer (trade name “NEWGELIN X-04086Y”, sold by Chuo Foods Materials Co., Ltd.) 0.3 parts by mass were added and mixed while heating. Next, 9 parts by mass of a milk heating odor production inhibitor obtained by the method of Example 1 was added thereto, and the mixture was stirred and dissolved at 5,000 rpm for 5 minutes with a homomixer, and then sterilized by maintaining at 90 ° C. for 10 minutes. did. After cooling, 5 parts by weight of yogurt as a starter and 0.1 part by weight of yogurt flavor were further added, and the mixture was stirred and mixed with a homomixer at 5,000 rpm for 5 minutes. This was filled in a container, fermented overnight at 35 ° C., and then refrigerated to prepare yogurt. This product is a high-quality yogurt that suppresses the generation of heated odor of milk due to heating and harmonizes its modest sweetness with a faint acidity.

上記したように、本発明は、乳又は乳製品製造時に、乳又は乳製品にα−グリコシルトレハロースを含有せしめることにより、ジメチルスルフィドやジメチルジスルフィドに起因する乳加熱臭の生成を抑制する方法を提供するものである。この方法によれば、乳加熱臭の生成が抑制された風味の良い乳又は乳製品を製造することが可能となり、乳製品、飲食品などの分野に与える産業的意義は極めて高い。   As described above, the present invention provides a method for suppressing the generation of heated odor caused by dimethyl sulfide or dimethyl disulfide by incorporating α-glycosyl trehalose in milk or dairy products during the production of milk or dairy products. To do. According to this method, it is possible to produce savory milk or dairy products in which the generation of heated odors of milk is suppressed, and the industrial significance given to fields such as dairy products and foods and drinks is extremely high.

Claims (7)

乳又は乳製品にα−グリコシルトレハロースを含有せしめることを特徴とする乳加熱臭の生成抑制方法。   The production | generation suppression method of the milk heat odor characterized by making alpha-glycosyl trehalose contain milk or dairy products. α−グリコシルトレハロースが、α−グルコシルトレハロース、α−マルトシルトレハロース及び/又はα−マルトトリオシルトレハロースである請求項1記載の乳加熱臭の生成抑制方法。   The method for suppressing the formation of a heated odor of milk according to claim 1, wherein the α-glycosyl trehalose is α-glucosyl trehalose, α-maltosyl trehalose and / or α-maltotriosyl trehalose. 乳加熱臭の成分が、ジメチルスルフィド及び/又はジメチルジスルフィドである請求項1又は2記載の乳加熱臭の生成抑制方法。   The method for suppressing the production of a milk heat odor according to claim 1 or 2, wherein the component of the milk heat odor is dimethyl sulfide and / or dimethyl disulfide. 乳又は乳製品を、α−グリコシルトレハロースの共存下で加熱及び/又は乾燥処理又は保存することを特徴とする乳加熱臭の生成抑制方法。   A method for suppressing the formation of a heated odor of milk, characterized in that milk or a dairy product is heated and / or dried or stored in the presence of α-glycosyl trehalose. 乳固形分当たり、α−グリコシルトレハロースを合計で約6質量%以上含有せしめることを特徴とする請求項1乃至4記載のいずれかに乳加熱臭の生成抑制方法。   The method for suppressing the formation of a heated odor of milk according to any one of claims 1 to 4, wherein the total amount of α-glycosyl trehalose is about 6% by mass or more per milk solid content. α−グリコシルトレハロースを有効成分とする乳加熱臭の生成抑制剤。   An inhibitor of the generation of heated odor of milk comprising α-glycosyl trehalose as an active ingredient 原料乳又は乳製品にα−グリコシルトレハロースを含有せしめ加熱処理工程を経て製造することを特徴とする乳加熱臭の生成が抑制された乳又は乳製品の製造方法。
A method for producing milk or dairy products in which the production of heated odor of milk is suppressed, wherein the raw milk or dairy product is produced through a heat treatment step by adding α-glycosyl trehalose.
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WO2020085517A1 (en) * 2018-10-26 2020-04-30 株式会社明治 Method for producing high-protein milk raw material
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