JP3230145B2 - Deodorant material, its production method and use - Google Patents
Deodorant material, its production method and useInfo
- Publication number
- JP3230145B2 JP3230145B2 JP19520596A JP19520596A JP3230145B2 JP 3230145 B2 JP3230145 B2 JP 3230145B2 JP 19520596 A JP19520596 A JP 19520596A JP 19520596 A JP19520596 A JP 19520596A JP 3230145 B2 JP3230145 B2 JP 3230145B2
- Authority
- JP
- Japan
- Prior art keywords
- substance
- deodorant
- hop
- polyphenol
- synthetic resin
- 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.)
- Expired - Fee Related
Links
Landscapes
- Non-Alcoholic Beverages (AREA)
- Cosmetics (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
- Confectionery (AREA)
- Bakery Products And Manufacturing Methods Therefor (AREA)
- General Preparation And Processing Of Foods (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ホップ苞より得られる
ポリフェノール様物質を有効成分とする消臭用飲食品、
消臭用口腔用剤に関する。The present invention is obtained from hop bracts
Food and drink for deodorization containing a polyphenol-like substance as an active ingredient,
The present invention relates to a deodorant oral agent .
【０００２】[0002]
【従来の技術】ホップはクワ科の多年生植物であり、そ
の毬果（未受精の雌花が成熟したもの）を一般にホップ
と呼んでいる。このホップのルプリン部分（球果の内苞
の根元に形成される黄色の顆粒）は、ホップの苦味、芳
香の本体であり、ビール醸造において酵母、麦芽と並ん
で重要なビール原料である。またホップは、民間療法で
は鎮静剤や抗催淫剤として通用している。2. Description of the Related Art Hops are perennial plants of the mulberry family, and their cones (mature of unfertilized female flowers) are generally called hops. The lupulin portion of this hop (yellow granules formed at the root of the inner bract of the cone) is the main component of the bitterness and aroma of the hop, and is an important beer raw material along with yeast and malt in beer brewing. Hops are also used in folk medicine as a sedative and anti-aphrodisiac.
【０００３】一方、ホップ苞はホップ毬果よりルプリン
部分を除いたものであり、ビール醸造には有用とされ
ず、場合によってはビール醸造の際にホップ苞は取り除
かれ、副産物として生じる。その際、ホップ苞は土壌改
良用の肥料として用いられる他に特に有効な利用法は見
い出されておらず、より付加価値の高い利用法の開発が
望まれている。なお、本出願人の出願にかかる特願平07
-173931号、および特願平07-347151号公報、特願平08-7
5456号公報ではホップ、特にホップ苞由来のポリフェノ
ール様物質について抗酸化作用、発泡麦芽飲料に対する
泡安定化作用、抗う蝕作用を有することを確認してい
る。しかし、ホップ、特にホップ苞由来のポリフェノー
ル様物質について、この消臭効果を明らかにした例は見
あたらない。On the other hand, hop bracts are obtained by removing lupulin from hop cones, and are not useful for beer brewing. In some cases, hop bracts are removed during beer brewing and are produced as by-products. At that time, hop bracts have not been found to be particularly effective in use other than being used as a fertilizer for soil improvement, and it has been desired to develop a use method with higher added value. It should be noted that Japanese Patent Application No.
-173931, Japanese Patent Application No. 07-347151, Japanese Patent Application No. 08-7
Japanese Patent No. 5456 confirms that hops, especially polyphenol- like substances derived from hop bracts, have an antioxidant effect, a foam stabilizing effect on a malted beer beverage, and an anti-carious effect. However, no example has been found that reveals this deodorizing effect for hops, especially for polyphenol- like substances derived from hop bracts.
【０００４】[0004]
【発明が解決しようとする課題】タバコ臭、口臭などの
悪臭、不快臭に対する衛生意識は若年層を中心に年々高
まっており、消臭効果を持つ口腔用剤、エチケットガム
などが開発されている。しかし、これらの商品に現在主
に利用されているクロロフィル類の消臭効果は十分なも
のではなく、仮に優れた消臭効果を有する素材を提供す
る方法が開発されれば、産業的にも大いに意義のあるも
のである。The hygiene consciousness of malodor and unpleasant odor such as tobacco odor and bad breath is increasing year by year, mainly among young people, and oral agents having a deodorizing effect, etiquette gum and the like are being developed. . However, the deodorizing effect of chlorophylls currently mainly used for these products is not sufficient, and if a method for providing a material having an excellent deodorizing effect is developed, industrially, it will be greatly affected. It is significant.
【０００５】従って本発明は、ホップ苞よりポリフェノ
ール様物質を有効成分とする消臭用飲食品、消臭用口腔
用剤に関する。[0005] Accordingly, the present invention is, for the deodorant to a polyphenol-like substance as an active ingredient than hops bract food and drink, about the oral agent for deodorant.
【０００６】[0006]
【課題を解決するための手段】本発明者は、上記の課題
について鋭意検討した結果、ホップ苞に含有されるポリ
フェノール様物質で、ゲル型合成樹脂に吸着し、分画分
子量が1,000以上の限外ろ過膜により処理した際に膜を
透過しない物質、すなわちホップ苞を水または水と混和
する有機溶媒の水溶液で抽出し、ゲル型合成吸着剤また
は限外ろ過膜により処理して、それぞれ各処理工程を経
て得られる画分が、強力な消臭効果を有する物質である
こと、即ち消臭性素材として用いることのできる物質で
あることを見い出した。更にこの物質を、消臭用飲食品
や消臭用口腔用剤に利用することにより本発明を完成す
るに至った。Means for Solving the Problems As a result of diligent studies on the above-mentioned problems, the present inventors have found that polyphenol-like substances contained in hop bracts are adsorbed on gel-type synthetic resin and have a molecular weight cut-off of 1,000 or more. A substance that does not pass through the membrane when treated with an ultrafiltration membrane, that is, hop bracts, is extracted with water or an aqueous solution of an organic solvent miscible with water, and then treated with a gel-type synthetic adsorbent or an ultrafiltration membrane, and the respective treatments It has been found that the fraction obtained through the process is a substance having a strong deodorizing effect, that is, a substance that can be used as a deodorant material. In addition to this material, which resulted in the completion of the present invention by making use of the food and drink products and deodorant for oral agent for deodorant.
【０００７】すなわち、本発明の第１は、ホップ苞に含
有され、ゲル型合成樹脂に吸着するポリフェノール様物
質を有効成分とする消臭用飲食品である。本発明の第２
は、ホップ苞に含有され、分画分子量が1,000以上の限
外ろ過膜により処理した際に、膜を透過しないポリフェ
ノール様物質を有効成分とする消臭用飲食品である。本
発明の第３は、ホップ苞に含有され、ゲル型合成樹脂に
吸着し、かつ分画分子量が1,000以上の限外ろ過膜によ
り処理した際に、膜を透過しないポリフェノール様物質
を有効成分とする消臭用飲食品である。[0007] That is, the first is contained in hop bract polyphenol-like substance that adsorbs to the gel type synthetic resin of the present invention
It is a food and drink for deodorization containing quality as an active ingredient. Second embodiment of the present invention
Is contained in hop bracts and has a cut-off molecular weight of 1,000 or more.
Polyfiltration that does not pass through the membrane when treated with an ultrafiltration membrane
It is a food and drink for deodorization containing a knol-like substance as an active ingredient. Book
A third aspect of the invention is that the hop bract contains a gel-type synthetic resin.
Adsorbed and ultrafiltration membrane with molecular weight cut off of 1,000 or more
Polyphenol-like substance that does not permeate the membrane when processed
It is a food and drink for deodorization, comprising as an active ingredient .
【０００８】本発明の第４は、ホップ苞に含有され、ゲ
ル型合成樹脂に吸着するポリフェノール様物質を有効成
分とする消臭用口腔用剤である。本発明の第５は、ホッ
プ苞に含有され、分画分子量が1,000以上の限外ろ過膜
により処理した際に、膜を透過しないポリフェノール様
物質を有効成分とする消臭用口腔用剤である。本発明の
第６は、ホップ苞に含有され、ゲル型合成樹脂に吸着
し、かつ分画分子量が1,000以上の限外ろ過膜により処
理した際に、膜を透過しないポリフェノール様物質を有
効成分とする消臭用口腔用剤である。 A fourth aspect of the present invention is that the hop bract contains
Effective synthesis of polyphenol-like substance adsorbed on synthetic resin
A deodorant oral agent. The fifth aspect of the present invention is that
Ultrafiltration membrane with a molecular weight cut-off of 1,000 or more
Polyphenol-like that does not permeate the membrane when treated with
It is a deodorant oral agent containing a substance as an active ingredient . Of the present invention
Sixth, contained in hop bracts and adsorbed on gel-type synthetic resin
And an ultrafiltration membrane with a molecular weight cut-off of 1,000 or more.
Contains a polyphenol-like substance that does not permeate the membrane
It is a deodorant oral agent as an active ingredient.
【０００９】[0009]
【発明の実施の形態】本発明の原料となるホップ苞と
は、ホップ毬果よりルプリン部分を取り除いて得られる
ものであり、一般に、ホップ毬果を粉砕後、ふるい分け
によってルプリン部分を除くことによってホップ苞を得
る。しかし、最近のビール醸造において、ホップ苞をふ
るい分けして除去する手間を省くために、ビール醸造に
有用でないホップ苞を取り除かずにホップ毬果そのまま
ペレット状に成形し、ホップペレットとして、ビール醸
造に利用する傾向にある。従って、本発明の原料として
は、ホップ苞を含むものであれば特に限定せず、ホップ
苞を含むホップ毬果やホップペレットを原料としてもな
んら問題ない。BEST MODE FOR CARRYING OUT THE INVENTION The hop bract, which is a raw material of the present invention, is obtained by removing the lupulin portion from hop cones. Generally, the hop cones are pulverized and then sieved to remove the lupulin portion. Get hop bracts. However, in recent beer brewing, in order to eliminate the trouble of sieving and removing hop bracts, hop cones are formed into pellets as they are without removing hop bracts that are not useful for beer brewing. Tend to use. Therefore, the raw material of the present invention is not particularly limited as long as it contains hop bracts, and there is no problem even if hop cones or hop pellets containing hop bracts are used as raw materials.
【００１０】本発明のポリフェノール様物質の製造法と
しては、まず原料であるホップ苞またはホップ苞を含む
ホップ毬果やホップペレットなどを、水または５０V/V%
以下のアルコール、アセトン、アセトニトリルなどの水
と混和する有機溶媒の水溶液で抽出する。好適な例とし
ては、水またはエタノール５０V/V%以下の含水エタノー
ルが挙げられる。原料と抽出溶媒の割合は、１：２０〜
１００（重量比）程度が望ましく、また抽出は４〜９５
℃、攪拌下、２０〜６０分間程度行われることが望まし
い。濾過により抽出液を得るが、その際必要があればパ
ーライトなどの濾過助材を用いることもできる。In the method for producing the polyphenol-like substance of the present invention , first, a hop bract or a hop cone or a hop pellet containing a hop bract, which is a raw material, is mixed with water or 50 V / V%.
Extract with an aqueous solution of an organic solvent that is miscible with water, such as the following alcohols, acetone and acetonitrile. Preferred examples include water or aqueous ethanol at 50 V / V% or less. The ratio of the raw material and the extraction solvent is 1:20 to
About 100 (weight ratio) is desirable, and extraction is 4-95.
It is desirable to carry out the reaction for about 20 to 60 minutes under stirring at a temperature of ° C. An extract is obtained by filtration. If necessary, a filter aid such as pearlite can be used.
【００１１】このようにして得られた抽出液は、ゲル型
合成樹脂および／または限外ろ過膜により処理する。 ゲル型合成樹脂による処理 上記抽出工程で得られた原料の抽出液について、ゲル型
合成樹脂に消臭性物質を吸着させる吸着工程、水または
エタノール水溶液、好ましくは１〜１０V/V%のエタノー
ル水溶液によりゲル型合成吸着剤を洗浄する洗浄工程、
６０V/V%以上のエタノール水溶液またはエタノールによ
りゲル型合成吸着剤から消臭性物質を溶出する溶出工程
を行い、消臭性のポリフェノール様物質を得る。The extract thus obtained is treated with a gel-type synthetic resin and / or an ultrafiltration membrane. Treatment with gel-type synthetic resin For the extract of the raw material obtained in the above-mentioned extraction step, an adsorption step of adsorbing a deodorant substance to the gel-type synthetic resin, water or ethanol aqueous solution, preferably 1 to 10 V / V% ethanol aqueous solution Washing step for washing the gel-type synthetic adsorbent by
Perform elution eluting the deodorant material from the gel-type synthetic adsorbent by aqueous ethanol or ethanol or 60V / V%, to obtain a deodorant polyphenols like material.
【００１２】吸着工程とは、同抽出溶液を１５〜３０℃
の室温程度まで冷却した後、ゲル型合成樹脂を充填した
カラムに通液し、樹脂に消臭性物質を吸着させる工程で
ある。その際、必要があれば、吸着効率をあげるため
に、減圧濃縮などによりあらかじめ抽出液の有機溶媒濃
度を下げておくこともできる。ゲル型合成樹脂の材質と
しては、親水性ビニルポリマー、ヒドロキシプロピル化
デキストラン、スチレン−ジビニルベンゼン重合体など
を挙げることができる。通液時間は、ＳＶ値が０．５〜
１００の間となるように設定するのが好ましい。In the adsorption step, the extraction solution is heated at 15 to 30 ° C.
After cooling to about room temperature, the solution is passed through a column filled with a gel-type synthetic resin to allow the resin to adsorb deodorant substances . At that time, if necessary, the concentration of the organic solvent in the extract can be reduced in advance by concentration under reduced pressure or the like in order to increase the adsorption efficiency. Examples of the material of the gel type synthetic resin include a hydrophilic vinyl polymer, hydroxypropylated dextran, and styrene-divinylbenzene polymer. The SV value is 0.5 to
Preferably, it is set to be between 100 and 100.
【００１３】なお、ここで言うＳＶ値とは、以下の式で
定義される値である。 ＳＶ値＝（通液量(L)）／｛（樹脂量(L)）× （通液時
間(ｈ)）｝ 洗浄工程は、消臭性物質を保持したゲル型合成樹脂を洗
浄し夾雑成分を除く行程であり、消臭性物質の精製度を
よりあげることが可能となる。洗浄に用いる溶媒として
は、水ないし１〜１０V/V%のエタノール水溶液が好適で
あり、樹脂量の１〜１０倍程度の溶媒量を通液し、洗浄
することが望ましい。Note that the SV value referred to here is a value defined by the following equation. SV value = (Poured amount (L)) / {(Resin amount (L)) × (Poured time (h))} In the washing step, the gel-type synthetic resin holding the deodorant substance is washed and contaminated components are removed. This is a process excluding the above, and the degree of purification of the deodorant substance can be further increased. As a solvent used for washing, water or an aqueous solution of ethanol of 1 to 10 V / V% is suitable, and it is desirable to wash by passing a solvent amount of about 1 to 10 times the resin amount.
【００１４】溶出工程は、消臭性物質を保持したゲル型
合成樹脂より消臭性物質を脱離溶出する工程であり、溶
出に用いる溶媒としては含水アルコール、含水アセト
ン、含水アセトニトリルなどを用いることができ、特に
好適な例としては３０V/V%以上のエタノール水溶液また
はエタノールが挙げられる。溶出溶媒の通液量は樹脂量
の２〜６倍程度が望ましい。[0014] The elution step, a step of desorption eluted from deodorant materials a gel type synthetic resin which holds the deodorant material, using water-containing alcohol, aqueous acetone, and the like water-containing acetonitrile solvent used for elution Particularly preferred examples include 30 V / V% or more aqueous ethanol solution or ethanol. The flow rate of the elution solvent is desirably about 2 to 6 times the amount of the resin.
【００１５】得られた溶出溶媒を濃縮、凍結乾燥、スプ
レードライなどの通常の方法により除き、消臭性物質を
粉末として得ることができる。また減圧濃縮の際、アル
コール、アセトン、アセトニトリルなどを回収し、再利
用することもできる。このようにして得られた消臭性物
質は、かすかに苦味を呈した無臭の肌色、褐色ないし淡
黄色の粉末であり、その消臭活性本体は、ゲル型合成樹
脂に吸着し、かつ分画分子量が1,000以上の限外ろ過膜
により処理した際に膜を通過しないポリフェノール様物
質である。なお収率はホップ苞重量換算で0.5〜20.0w/w
％、ホップ毬果重量換算で0.5〜15.0w/w％である。The obtained elution solvent is removed by a conventional method such as concentration, freeze-drying, spray-drying and the like, whereby the deodorant substance can be obtained as a powder. At the time of concentration under reduced pressure, alcohol, acetone, acetonitrile, etc. can be collected and reused. Deodorant product obtained in this way
The quality is odorless flesh-colored, brown or pale yellow powder with a slightly bitter taste.The deodorant active body is adsorbed on the gel-type synthetic resin and has an ultrafiltration membrane with a molecular weight cut-off of 1,000 or more. A polyphenol-like substance that does not pass through the membrane when processed. The yield is 0.5-20.0 w / w in terms of hop bract weight.
%, And 0.5 to 15.0 w / w% in terms of hop cone weight.
【００１６】使用したゲル型合成樹脂は５０V/V%以上の
アルコール水溶液、0.05Ｎ程度の水酸化ナトリウム水溶
液などで洗浄した後、繰り返し使用することが可能であ
る。 限外ろ過膜による処理 上記抽出工程で得られた原料は、ホップ苞の抽出液を、
分画分子量が1,000以上の限外ろ過膜で処理する。その
際必要があれば、抽出液を減圧濃縮し、有機溶媒濃度を
下げておくこともできる。回収された有機溶媒は再利用
することもできる。The gel type synthetic resin used can be repeatedly used after washing with an alcohol aqueous solution of 50 V / V% or more, an aqueous solution of about 0.05 N sodium hydroxide, or the like. Processing by ultrafiltration membrane The raw material obtained in the above extraction step is a hop bract extract,
Treat with an ultrafiltration membrane with a molecular weight cut-off of 1,000 or more. At that time, if necessary, the extract can be concentrated under reduced pressure to reduce the concentration of the organic solvent. The recovered organic solvent can be reused.
【００１７】膜の素材としては、セルロース、セルロー
スアセテート、ポリサルフォン、ポリプロピレン、ポリ
エステル、ポリエーテルスルホン、ＰＶＤＦなど、通常
限外ろ過膜の材質として使用するものであれば、特に制
限なく用いることができる。また分画分子量は1,000以
上であれば特に問題なく用いることができるが、あまり
分画分子量の大きい膜を用いると、収量が極端に下が
り、また分画分子量が小さい場合は、処理に要する時間
が長くなるので、分画分子量10,000〜20,000の限外ろ過
膜が好適である。また処理は、抽出溶媒の種類や抽出溶
媒とホップまたはホップ苞の割合にもよるが、およそ上
残り液の量が処理開始時の１／10〜１／100 程度になる
まで行うのが望ましい。その際の圧力は、限外ろ過膜や
ろ過装置にもよるが、およそ0.1〜10.0kg/cm2であるこ
とが望ましい。また必要があれば、一度処理した上残り
液を再び水などの適当な溶媒で薄め、同様に再処理して
精製度を高めることもできる。As the material for the membrane, any material which is usually used as a material for an ultrafiltration membrane, such as cellulose, cellulose acetate, polysulfone, polypropylene, polyester, polyethersulfone, and PVDF, can be used without any particular limitation. If the molecular weight cut-off is 1,000 or more, it can be used without any problem.However, if a membrane having a high molecular weight cut-off is used, the yield is extremely reduced. An ultrafiltration membrane having a cut-off molecular weight of 10,000 to 20,000 is preferred because of its length. The treatment is preferably performed until the amount of the remaining liquid is about 1/10 to 1/100 of the amount at the start of the treatment, depending on the type of the extraction solvent and the ratio of the extraction solvent to the hop or hop bract. The pressure at that time depends on the ultrafiltration membrane and the filtration device, but is preferably about 0.1 to 10.0 kg / cm 2 . If necessary, after the treatment, the remaining liquid can be diluted again with a suitable solvent such as water, and then re-treated in the same manner to increase the degree of purification.
【００１８】得られた上残り液の溶媒を濃縮、凍結乾
燥、スプレードライなどの通常の方法により除き、消臭
性物質を粉末として得ることができる。また減圧濃縮の
際、アルコール、アセトン、アセトニトリルなどを回収
し、再利用することもできる。このようにして得られた
消臭性物質は、かすかに苦味を呈した無臭の肌色、褐色
ないし淡緑色の粉末であり、ゲル型合成樹脂に吸着し、
分画分子量が1,000以上の限外ろ過膜により処理した際
に、膜を透過しないポリフェノール様物質である。[0018] The solvent of the obtained upper residue is removed by a conventional method such as concentration, freeze-drying, spray-drying or the like, whereby the deodorant substance can be obtained as a powder. At the time of concentration under reduced pressure, alcohol, acetone, acetonitrile, etc. can be collected and reused. The deodorant substance thus obtained is an odorless flesh color with a slightly bitter taste, a brown or pale green powder, adsorbed on the gel-type synthetic resin,
It is a polyphenol-like substance that does not pass through the membrane when treated with an ultrafiltration membrane having a molecular weight cut-off of 1,000 or more.
【００１９】なお収率は、ホップ苞重量換算で 0.5〜2
0.0 V/V％、ホップ毬果重量換算で0.5 〜15.0 V/V％で
ある。上記ゲル型合成樹脂による処理、または限外
ろ過膜による処理によって得られた消臭性物質の活性本
体は、同一のポリフェノール類であるので、ゲル型合成
樹脂による処理で得られた消臭性物質をアルコール水溶
液などの適当な溶媒に溶解し、限外ろ過膜による処理で
さらに活性本体であるポリフェノール類の精製度を高め
ることもできる。またその逆も可能であり、もちろん
またはの方法単独でも十分に有用な消臭性素材を得る
ことができる。The yield is 0.5 to 2 in terms of hop bract weight.
0.0 V / V%, 0.5-15.0 V / V% in terms of hop cone weight. Since the active substance of the deodorant obtained by the treatment with the gel-type synthetic resin or the treatment with the ultrafiltration membrane is the same polyphenol, the deodorant substance obtained by the treatment with the gel-type synthetic resin is used. Can be dissolved in a suitable solvent such as an aqueous alcohol solution, and the treatment with an ultrafiltration membrane can further enhance the degree of purification of the polyphenols that are the active substance. The reverse is also possible, and a sufficiently useful deodorant material can be obtained by or of course.
【００２０】得られた消臭性物質は、菓子類、食品類、
飲料などの飲食品、特に好ましくは、キャンディ、チョ
コレート、キャラメル、チューインガムなど、口腔滞留
時間の比較的長い飲食品に用いることができる。また、
うがい液、歯磨剤などの口腔用剤に添加して用いること
もできる。これらの飲食品、口腔用剤に消臭性物質を添
加する際には、消臭性物質を粉末のまま添加してもよい
が、好ましくは消臭性物質を１〜２％の水溶液またはア
ルコール水溶液の溶液あるいはアルコール溶液とし、飲
食品または口腔用剤に対し最終濃度が１〜500ppm、好ま
しくは10〜100ppmとなるように添加することが望まし
い。The obtained deodorant substance is used for confectionery, foods,
It can be used for foods and drinks such as beverages, particularly preferably for foods and drinks having a relatively long oral residence time, such as candy, chocolate, caramel and chewing gum. Also,
It can also be used by adding to oral preparations such as gargles and dentifrices. These food products, in addition of the deodorizing substance to the oral agent, a deodorant substance may be added as a powder, but preferably 1-2% of the aqueous or alcoholic deodorant substance It is desirable to add an aqueous solution or an alcohol solution so as to have a final concentration of 1 to 500 ppm, preferably 10 to 100 ppm, for a food or drink or an oral preparation.
【００２１】更に悪臭を取る目的で、トイレッタリー製
品やウエットティッシュ等に使用することも可能であ
る。Further, it can be used for toiletry products, wet tissues and the like for the purpose of removing bad smell.
【００２２】[0022]
【実施例】以下、実施例を示すが本発明はこれに限定さ
れるものではない。 実施例１ （ゲル型合成樹脂によるホップ毬果からの消
臭性物質の調製） ホップ毬果20gを乳鉢で粉砕し、2Lの水で攪拌下、95
℃、40分間抽出した。ろ過後、放冷し、抽出液を親水性
ビニルポリマー樹脂（東ソー社製、商品名トヨパールHW
40）80mlを充填したカラムに2時間かけて通液し（ＳＶ
＝12.5）、次いで400mlの5％エタノール水溶液で洗浄し
た。さらに同カラムに80％エタノール水溶液400mlを通
液し、同溶出液を回収し、凍結乾燥して、消臭性物質80
0mgを無臭のかすかに苦味を呈した淡黄色の粉末として
得た。ホップからの収率は4％であった。The present invention is not limited to the following examples. Example 1 (Preparation of deodorant substance from hop cones using gel-type synthetic resin) 20 g of hop cones was ground in a mortar, and stirred with 2 L of water.
Extracted at 40 ° C for 40 minutes. After filtration, the mixture is allowed to cool, and the extract is subjected to hydrophilic vinyl polymer resin (manufactured by Tosoh Corporation, trade name: Toyopearl HW
40) Pass the solution through a column filled with 80 ml for 2 hours (SV
= 12.5) and then washed with 400 ml of 5% aqueous ethanol. Further, 400 ml of an 80% aqueous ethanol solution was passed through the same column, and the eluate was recovered, freeze-dried, and deodorized substance 80
0 mg was obtained as an odorless, slightly bitter, pale yellow powder. The yield from hops was 4%.
【００２３】実施例２ （ゲル型合成樹脂によるホップ
苞からの消臭性物質の調製） ホップ苞20gを600mlの50％エタノール水溶液で攪拌下、
80℃、40分間抽出した。ろ過後、容積が300mlになるま
で減圧濃縮し、その濃縮液をスチレン−ジビニルベンゼ
ン樹脂（三菱化学社製、商品名セパビーズ825）80mlを
充填したカラムに1時間かけて通液し（ＳＶ＝3.75）、
次いで400mlの水で洗浄した。さらに同カラムに80％エ
タノール水溶液400mlを通液し、同溶出液を回収し、凍
結乾燥して、消臭性物質1.6gを無臭のかすかに苦味を呈
した淡黄色の粉末として得た。ホップ苞からの収率は8
％であった。Example 2 (Preparation of a deodorant substance from hop bracts using a gel-type synthetic resin) 20 g of hop bracts were stirred with 600 ml of a 50% aqueous ethanol solution.
Extraction was performed at 80 ° C. for 40 minutes. After filtration, the solution was concentrated under reduced pressure until the volume reached 300 ml, and the concentrated solution was passed through a column filled with 80 ml of styrene-divinylbenzene resin (manufactured by Mitsubishi Chemical Corporation, trade name Sepabeads 825) over 1 hour (SV = 3.75). ),
Then it was washed with 400 ml of water. Further, 400 ml of an 80% aqueous ethanol solution was passed through the same column, and the eluate was collected and freeze-dried to obtain 1.6 g of a deodorant substance as an odorless, slightly bitter, pale yellow powder. 8 from hop bracts
%Met.
【００２４】実施例３ （限外ろ過膜によるホップ毬果
からの消臭性物質の調製） ホップ毬果20gを乳鉢で粉砕し、2Lの水で攪拌下、95
℃、40分間抽出した。ろ過後、放冷し、抽出液を分画分
子量が50,000の限外ろ過膜（アミコン社製、商品名XM5
0）により、1.0kg/cm2、室温下、20mlになるまで処理し
た。得られた上残り液を減圧乾固し、消臭性物質200mg
を無臭のかすかに苦味を呈した淡黄色の粉末として得
た。ホップからの収率は1％であった。Example 3 (Preparation of deodorant substance from hop cones using an ultrafiltration membrane) 20 g of hop cones were ground in a mortar and stirred with 2 L of water under agitation.
Extracted at 40 ° C for 40 minutes. After filtration, the mixture was allowed to cool, and the extract was subjected to ultrafiltration with a molecular weight cutoff of 50,000 (trade name: XM5, manufactured by Amicon)
0) at 1.0 kg / cm 2 at room temperature until the volume reached 20 ml. The obtained upper residue was dried under reduced pressure, and 200 mg of deodorant substance
Was obtained as a pale yellow powder having an odorless and slightly bitter taste. The yield from hops was 1%.
【００２５】実施例４ （限外ろ過膜によるホップ苞か
らの消臭性物質の調製） ホップ苞20gを600mlの50％エタノール水溶液で攪拌下、
80℃、40分間抽出した。ろ過後、抽出液を分画分子量が
1,000の限外ろ過膜（アミコン社製、商品名YM10）によ
り、3.0kg/cm2、室温下、60mlになるまで処理した。得
られた上残り液を凍結乾燥して、消臭性物質0.8gを無臭
のかすかに苦味を呈した淡黄色の粉末として得た。ホッ
プ苞からの収率は4％であった。Example 4 (Preparation of a deodorant substance from hop bracts by an ultrafiltration membrane) 20 g of hop bracts were stirred with 600 ml of a 50% aqueous ethanol solution.
Extraction was performed at 80 ° C. for 40 minutes. After filtration, the extract has a molecular weight cut off.
The solution was treated with 1,000 ultrafiltration membranes (trade name: YM10, manufactured by Amicon) at 3.0 kg / cm 2 at room temperature until the volume became 60 ml. The resulting upper residue was freeze-dried to obtain 0.8 g of a deodorant substance as a pale yellow powder having an odorless and slightly bitter taste. The yield from hop bracts was 4%.
【００２６】実施例５ （消臭性活性物質のさらなる精
製および定性分析） 実施例２で得た消臭性物質0.8gを、500mlの10％エタノ
ール水溶液に溶解し、分画分子量が1,000の限外ろ過膜
（アミコン社製、商品名YM10）により、1.0kg/cm2、室
温下、20mlになるまで処理した。得られた上残り液を凍
結乾燥して、消臭性素材0.4gを無臭のかすかに苦味を呈
した肌色の粉末として得た。この粉末を下記に示すよう
な条件でＨＰＬＣ分析すると、特徴的なクロマトグラム
となり、また一般的なポリフェノール類の定量法のひと
つであるカテキン定量（食品公定分析法）を行ったとこ
ろカテキン含量に換算して40.6％の値を得た。Example 5 (Further purification and qualitative analysis of deodorant active substance) 0.8 g of the deodorant substance obtained in Example 2 was dissolved in 500 ml of a 10% aqueous ethanol solution, and the molecular weight cut off was 1,000. The solution was treated with an external filtration membrane (trade name: YM10, manufactured by Amicon) at 1.0 kg / cm 2 at room temperature until the volume became 20 ml. The obtained upper residue was freeze-dried to obtain 0.4 g of a deodorant material as an odorless, slightly bitter, flesh-colored powder. When analyzed by HPLC under the conditions shown the powder below, catechin content was carried out becomes FEATURES chromatogram and catechin quantification is one of determination of general polyphenols (Food official analysis method) Converted to a value of 40.6%.
【００２７】（ＨＰＬＣ条件）装置：島津ＬＣ−10Ａシ
ステム、カラム：ODS-80TM(東ソー、4.6mmI.D.×25c
m)、移動相：（Ａ液：Ｂ液）＝（100:0）から同（50:5
0）まで30分間の直線グラディエント、Ａ液：5％アセト
ニトリル（0.1% HCl含有）、Ｂ液：アセトニトリル、サ
ンプル注入量：20μｇ、検出：200〜300nmでの多波長検
出。(HPLC conditions) Apparatus: Shimadzu LC-10A system, column: ODS-80TM (Tosoh, 4.6 mm ID × 25c)
m), mobile phase: (solution A: solution B) = (100: 0) to (50: 5
0) linear gradient for 30 minutes, solution A: 5% acetonitrile (containing 0.1% HCl), solution B: acetonitrile, sample injection amount: 20 μg, detection: multi-wavelength detection at 200 to 300 nm.
【００２８】実施例６ （ゲルろ過による実施例５の分
子量の推定） 下記のＨＰＬＣ条件にてゲルろ過を行い、実施例５で得
られた消臭性物質の分子量を推定した。保持時間を検量
線と比較して、分子量はおよそ36,000〜40,000であると
思われた。 （ＨＰＬＣ条件）装置：島津ＬＣ−８Ａシステム、カラ
ム：東ソーTSK-GEL G4000PWXL, G5000PWXL、移動相：
0.1M Tris-HCl 緩衝液(pH10.0)：2-プロパノール=1:1
、検出：UV220nm、マーカー：LMW GEL FILTRATION KIT
(ファルマシアバイオテク製、商品名)、流速：0.3ml/m
in． 実施例７ （歯磨剤） 上記の各重量部の各成分を用い、常法に従って歯磨剤と
した。なお実施例１で得られた物質の代わりに、それぞ
れ実施例２、３、４、５で得られた物質を添加した歯磨
剤も同様に得た。Example 6 (Estimation of Molecular Weight of Example 5 by Gel Filtration) Gel filtration was carried out under the following HPLC conditions, and the molecular weight of the deodorant substance obtained in Example 5 was estimated. Comparing the retention time with the calibration curve, the molecular weight appeared to be approximately 36,000-40,000. (HPLC conditions) Apparatus: Shimadzu LC-8A system, column: Tosoh TSK-GEL G4000PWXL, G5000PWXL, mobile phase:
0.1 M Tris-HCl buffer (pH 10.0): 2-propanol = 1: 1
, Detection: UV220nm, Marker: LMW GEL FILTRATION KIT
(Pharmacia Biotech, trade name), flow rate: 0.3ml / m
in. Example 7 (Dentifrice) A dentifrice was prepared according to a conventional method using the above components in each part by weight. Note that, instead of the substance obtained in Example 1, dentifrices to which the substances obtained in Examples 2, 3, 4, and 5, respectively, were added were similarly obtained.
【００２９】実施例８ （洗口液） 上記の各重量部の各成分を用い、常法に従って洗口液と
した。なお実施例１で得られた物質の代わりに、それぞ
れ実施例２、３、４、５で得られた物質を添加した洗口
剤も同様に得た。Example 8 (Mouthwash) A mouthwash was prepared according to a conventional method using the above components in each part by weight. Note that, instead of the substance obtained in Example 1, mouthwashes to which the substances obtained in Examples 2, 3, 4, and 5 were added were also obtained in the same manner.
【００３０】実施例９ （トローチ剤） アラビアゴム ６．０ ステアリン酸マグネシウム ３．０ ブドウ糖 ７３．０ 乳 糖 １７．６ リン酸第２カリウム ０．２ リン酸第１カリウム ０．１ 香 料 ０．０９５ 実施例１の物質 ０．００５ 合 計 １００．０ 上記の各重量部の各成分を用い、常法に従ってトローチ
剤とした。なお、実施例１で得られた物質の代わりに、
それぞれ実施例２、３、４、５で得られた物質を添加し
たトローチ剤も同様に得た。Example 9 (troche) Gum arabic 6.0 Magnesium stearate 3.0 Glucose 73.0 Lactose 17.6 Dipotassium phosphate 0.2 Potassium potassium phosphate 0.1 Flavor 0 095 Substance of Example 1 0.005 Total 100.0 Using the above components in each part by weight, a troche was prepared according to a conventional method. In addition, instead of the substance obtained in Example 1,
Lozenges to which the substances obtained in Examples 2, 3, 4, and 5 were added were obtained in the same manner.
【００３１】実施例１０ （飴） 上記の各重量部の各成分を用い、常法に従って飴とし
た。なお実施例１で得られた物質の代わりに、それぞれ
実施例２、３、４、５で得られた物質を添加した飴も同
様に得た。Example 10 (candy) A candy was prepared according to a conventional method using the above components in each part by weight. Note that, instead of the substance obtained in Example 1, candy to which the substances obtained in Examples 2, 3, 4, and 5 were respectively added was obtained in the same manner.
【００３２】実施例１１ （チューインガム） ガムベース ２０．０ 炭酸カルシウム ２．０ 乳 糖 ７７．０ ステビオサイド ０．０９５ 実施例１の物質 ０．００５ 香 料 ０．９ 合 計 １００．０ 上記の各重量部の各成分を用い、常法に従ってチューイ
ンガムとした。なお実施例１で得られた物質の代わり
に、それぞれ実施例２、３、４、５で得られた物質を添
加したチューインガムも同様に得た。Example 11 (Chewing gum) Gum base 20.0 Calcium carbonate 2.0 Lactose 77.0 Stevioside 0.095 Substance of Example 1 Perfume 0.9 Total 100.0 Each of the above parts by weight Was used as a chewing gum according to a conventional method. Note that, instead of the substance obtained in Example 1, chewing gums to which the substances obtained in Examples 2, 3, 4, and 5 were added were also obtained in the same manner.
【００３３】実施例１２ （ジュース） 上記の各重量部の各成分を用い、常法に従ってジュース
とした。なお実施例１で得られた物質の代わりに、それ
ぞれ実施例２、３、４、５で得られた物質を添加したジ
ュースも同様に得た。Example 12 (juice) A juice was prepared according to a conventional method using each of the above components by weight. Note that, instead of the substance obtained in Example 1, juices to which the substances obtained in Examples 2, 3, 4, and 5 were added were obtained in the same manner.
【００３４】実施例１３ （クッキー） 上記の各重量部の各成分を用い、常法に従ってクッキー
とした。なお実施例１で得られた物質の代わりに、それ
ぞれ実施例２、３、４、５で得られた物質を添加したク
ッキーも同様に得た。Example 13 (Cookie) Cookies were prepared according to a conventional method using each of the above components by weight. In addition, instead of the substance obtained in Example 1, cookies to which the substances obtained in Examples 2, 3, 4, and 5 were added were obtained in the same manner.
【００３５】実施例１４（キャラメル） 上記の各重量部の各成分を用い、常法に従ってキャラメ
ルとした。なお実施例１で得られた物質の代わりに、そ
れぞれ実施例２、３、４、５で得られた物質を添加した
キャラメルも同様に得た。Example 14 (caramel) Using the above-mentioned respective parts by weight of each component, caramel was prepared according to a conventional method. Note that, instead of the substance obtained in Example 1, caramels to which the substances obtained in Examples 2, 3, 4, and 5 were respectively added were obtained in the same manner.
【００３６】実施例１５ （消臭活性：ガスクロマトグ
ラフを用いたヘッドスペース法） 実施例１、２、３、４、５で得られた消臭性物質、およ
び消臭性を持つ代表的な化合物である銅クロロフィリン
ナトリウム（和光純薬工業）について、ガスクロマトグ
ラフ（ＧＣ）を用いたヘッドスペース法にて、消臭効果
を測定した。具体的には、30mLのバイアルに0.05％の悪
臭物質（酪酸、メチルメルカプタン、スカトール）と1%
の試験物質の水溶液10mLを入れ、密栓し、攪拌下、37℃
に保温した。5分後、バイアル上部の空気3mLを気密を損
なわないよう注射筒にて採取し、HEWLETT-PACKARD社ガ
スクロマトグラフ装置にて下記条件で悪臭物質の定量を
行った。コントロール（試験物質なし）に対する悪臭物
質のピーク面積の減少率を消臭効果の強さとした。結果
を表１に示す。実施例１、２、３、４、５で得られた消
臭性物質は、銅クロロフィリンナトリウムに比べると、
強い消臭活性を示した。Example 15 (Deodorizing Activity: Headspace Method Using Gas Chromatograph) Deodorant Substances Obtained in Examples 1, 2, 3, 4, 5 and Representative Compounds Having Deodorant Properties Of copper chlorophyllin sodium (Wako Pure Chemical Industries, Ltd.) was measured for its deodorizing effect by a head space method using a gas chromatograph (GC). Specifically, 0.05 mL of malodorous substances (butyric acid, methyl mercaptan, skatole) and 1%
Add 10 mL of an aqueous solution of the test substance in
Was kept warm. Five minutes later, 3 mL of air above the vial was collected with a syringe so as not to impair airtightness, and odorous substances were quantified using a gas chromatograph manufactured by HEWLETT-PACKARD under the following conditions. The reduction rate of the peak area of the malodorous substance relative to the control (no test substance) was defined as the strength of the deodorizing effect. Table 1 shows the results. Deodorant material obtained in Example 1, 2, 3, 4, as compared to sodium copper chlorophyllin,
It showed strong deodorant activity.
【００３７】ＧＣ条件； カラム：Fused Silica Capil
lary Column (HEWLETT-PACKARD社,0.53mm ID, 30m)、流
速：10ml/min、キャリアガス：ヘリウム、注入口温度：
200℃、検出口温度：200℃、検出器：ＦＩＤ．GC conditions; Column: Fused Silica Capil
lary Column (HEWLETT-PACKARD, 0.53mm ID, 30m), flow rate: 10ml / min, carrier gas: helium, inlet temperature:
200 ° C, detection port temperature: 200 ° C, detector: FID.
【００３８】[0038]
【表１】 [Table 1]
【００３９】[0039]
【発明の効果】本発明によれば、ホップ苞及びホップ苞
を含むホップ毬果等を原料として、市販の消臭性物質よ
りも極めて活性の強い消臭性物質を得ることができた。
更に植物由来の消臭性物質として、飲食品や口腔用剤と
して容易に利用することができた。According to the present invention, it is possible to obtain a deodorant substance which is extremely active compared to a commercially available deodorant substance , using hop bracts and hop cones including the hop bracts as raw materials . Was completed.
Further, it could be easily used as a plant-derived deodorant substance, as a food or drink or an oral agent.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ａ２３Ｌ 2/02 Ａ２３Ｌ 2/02 Ｂ Ａ６１Ｋ 7/00 Ａ６１Ｋ 7/00 Ｋ Ｗ Ａ６１Ｌ 9/01 Ａ６１Ｌ 9/01 Ｒ (58)調査した分野(Int.Cl.7，ＤＢ名) A61K 7/00 - 7/50 A61L 9/01 - 9/014 A21D 13/08 A23G 3/00 - 3/30 A23L 1/015 A23L 2/02 - 2/36 ────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. 7 Identification code FI A23L 2/02 A23L 2/02 B A61K 7/00 A61K 7/00 KW A61L 9/01 A61L 9/01 R (58) Survey Field (Int.Cl. 7 , DB name) A61K 7 /00-7/50 A61L 9/01-9/014 A21D 13/08 A23G 3/00-3/30 A23L 1/015 A23L 2/02-2 / 36
Claims (6)
吸着するポリフェノール様物質を有効成分とする消臭用
飲食品。1. A contained in hop bract, deodorant as an active ingredient polyphenol-like substance which adsorbs the gel type synthetic resin
Food and drink .
0以上の限外ろ過膜により処理した際に、膜を透過しな
いポリフェノール様物質を有効成分とする消臭用飲食
品。2. A contained in hop bract, fractional molecular weight 1,00
Deodorant food and beverage containing as active ingredient a polyphenol-like substance that does not pass through the membrane when treated with 0 or more ultrafiltration membranes
Goods .
吸着し、かつ分画分子量が1,000以上の限外ろ過膜によ
り処理した際に、膜を透過しないポリフェノール様物質
を有効成分とする消臭用飲食品。3. A contained in hop bract, when adsorbed to the gel type synthetic resin, either One fractional molecular weight was treated with 1,000 ultrafiltration membrane, polyphenols like material that does not pass through the membrane
A deodorant food or beverage comprising, as an active ingredient .
吸着するポリフェノール様物質を有効成分とする消臭用
口腔用剤。 4. A gel type synthetic resin contained in hop bracts
For deodorization using adsorbed polyphenol-like substance as active ingredient
Oral preparations.
0以上の限外ろ過膜により処理した際に、膜を透過しな
いポリフェノール様物質を有効成分とする消臭用口腔用
剤。5. A hop bract having a molecular weight cut off of 1,00.
When treated with zero or more ultrafiltration membranes,
Oral for deodorization, which contains a polyphenol-like substance as active ingredient
Agent .
吸着し、かつ分画分子量が1,000以上の限外ろ過膜によ
り処理した際に、膜を透過しないポリフェノール様物質
を有効成分とする消臭用口腔用剤。 6. A gel synthetic resin contained in hop bracts.
Adsorbed and ultrafiltration membrane with molecular weight cut off of 1,000 or more
Polyphenol-like substance that does not permeate the membrane when processed
A deodorant oral agent comprising, as an active ingredient.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19520596A JP3230145B2 (en) | 1996-07-08 | 1996-07-08 | Deodorant material, its production method and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19520596A JP3230145B2 (en) | 1996-07-08 | 1996-07-08 | Deodorant material, its production method and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1025232A JPH1025232A (en) | 1998-01-27 |
| JP3230145B2 true JP3230145B2 (en) | 2001-11-19 |
Family
ID=16337213
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19520596A Expired - Fee Related JP3230145B2 (en) | 1996-07-08 | 1996-07-08 | Deodorant material, its production method and use |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3230145B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001039886A (en) * | 1999-05-24 | 2001-02-13 | Asahi Breweries Ltd | Hop polyphenol having topoisomerase inhibitory activity |
| JP4521703B2 (en) * | 2000-05-17 | 2010-08-11 | アサヒビール株式会社 | Lipase inhibitor obtained from hops |
| CA2427661C (en) * | 2000-11-03 | 2013-05-28 | Proteotech, Inc. | Methods of isolating amyloid-inhibiting compounds and use of compounds isolated from uncaria tomentosa and related plants |
| JP2003160459A (en) * | 2001-11-22 | 2003-06-03 | Kansai Koso Kk | Methionase activity inhibitor and composition for oral cavity |
| JP2007051096A (en) * | 2005-08-18 | 2007-03-01 | Asahi Breweries Ltd | Composition for oral cavity |
| US8071136B2 (en) | 2006-04-21 | 2011-12-06 | Bioactives, Inc. | Water-soluble pharmaceutical compositions of hops resins |
| WO2008026473A1 (en) | 2006-08-31 | 2008-03-06 | Asahi Breweries, Ltd. | Method for production of hop preparation, hop preparation, antiinflammatory agent, food/beverage, and oral product |
| WO2008065875A1 (en) * | 2006-11-30 | 2008-06-05 | Sapporo Breweries Limited | Mouth refreshing agent and drink and food containing the same |
-
1996
- 1996-07-08 JP JP19520596A patent/JP3230145B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH1025232A (en) | 1998-01-27 |
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