JPH11246319A - Antimicrobial and antifungal agent - Google Patents
Antimicrobial and antifungal agentInfo
- Publication number
- JPH11246319A JPH11246319A JP4655698A JP4655698A JPH11246319A JP H11246319 A JPH11246319 A JP H11246319A JP 4655698 A JP4655698 A JP 4655698A JP 4655698 A JP4655698 A JP 4655698A JP H11246319 A JPH11246319 A JP H11246319A
- Authority
- JP
- Japan
- Prior art keywords
- isothiocyanate
- antibacterial
- antifungal agent
- formula
- compound
- 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.)
- Pending
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
- Cosmetics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明はω−アルキルスルフ
ィニルアルキルイソチオシアナート化合物からなる抗菌
抗かび剤に関する。本発明の抗菌抗かび剤を種々の飲食
物あるいは歯磨き、口内洗浄剤や口臭防止剤のような口
腔衛生剤(以下併せて飲食物等という)に配合すること
により各種細菌やかび等の真菌類等の微生物の発育を有
効に阻止することができる。TECHNICAL FIELD The present invention relates to an antibacterial antifungal agent comprising an ω-alkylsulfinylalkylisothiocyanate compound. By mixing the antibacterial antifungal agent of the present invention into various foods and drinks or oral hygiene agents such as toothpastes, mouthwashes and breath fresheners (hereinafter collectively referred to as foods and drinks), various fungi such as bacteria and fungi can be obtained. Etc. can be effectively inhibited.
【0002】[0002]
【従来の技術】ワサビやカラシ等のアブラナ科植物の抽
出物に微生物に対する増殖阻止・殺菌作用があることは
古くから知られている。中でも香気抽出物中の主成分で
あるアリルイソチオシアナート(CH2=CHCH2NC
S)は、食中毒の原因菌である大腸菌や黄色ブドウ球菌
に対する抗菌性を有し且つ人体に対する安全性の面か
ら、魚肉類、畜肉類の鮮度保持剤として古くから研究が
行われ実用化されている。2. Description of the Related Art It has long been known that extracts of cruciferous plants such as wasabi and mustard have a growth inhibiting and bactericidal action against microorganisms. Among them, allyl isothiocyanate (CH 2 CHCHCH 2 NC) which is a main component in an aroma extract
S) is an antibacterial agent against Escherichia coli and Staphylococcus aureus, which are the causative agents of food poisoning, and has been studied and practically used as a freshness preserving agent for fish meat and animal meat from the viewpoint of safety for the human body. I have.
【0003】しかし、アリルイソチオシアナートは揮発
性が高く、そのため適当な濃度で一定した揮散を長期間
維持させる必要がありマイクロカプセル化等の製剤化の
工夫が必要であること、また非常に強い刺激臭(検知閾
値:0.046ppm)を有していることから、添加される飲食
物等本来の味や香りを損い汎用性に乏しいことが欠点で
あった。However, allyl isothiocyanate has a high volatility, so that it is necessary to maintain a constant volatilization at an appropriate concentration for a long period of time, and it is necessary to devise a formulation such as microencapsulation. Since it has an irritating odor (detection threshold: 0.046 ppm), it has a drawback that the original taste and aroma of the added food and drink are impaired and versatility is poor.
【0004】一方、アリルイソチオシアナート以外のイ
ソチオシアナート化合物の抗菌性に関しては、Salvador
a persica L.から抽出したベンジルイソチオシアナー
トが虫歯原因菌のストレプトコッカス・ミュータンス
(Streptococcusmutans)に対して抗菌性があること、
また、Hippocratea welwitschiiの根から抽出したベン
ジルイソチオシアナートと4−メトキシベンジルイソチ
オシアナートが一般的な菌に対して抗菌性があることが
報告されているが、例えば刺激臭が改善されていないこ
と等の問題点が残されており未だ実用化されていないの
が現状である。On the other hand, regarding the antibacterial properties of isothiocyanate compounds other than allyl isothiocyanate, Salvador
a persica L. That benzyl isothiocyanate extracted from bacterium is antibacterial against Streptococcus mutans, a causative fungus,
In addition, it has been reported that benzyl isothiocyanate and 4-methoxybenzyl isothiocyanate extracted from the roots of Hippocrata welwitschii have antibacterial properties against common bacteria, but, for example, that the pungent odor is not improved At present, problems such as these remain, and they have not yet been put to practical use.
【0005】[0005]
【発明が解決しようとする課題】本発明の課題は、従来
技術における上記のような欠点を除去し、刺激臭が大幅
に緩和され安全で広く種々の飲食物等に適用でき、かつ
各種の細菌やかび類の発育抑制に優れた抗菌抗かび剤を
提供することである。特に、従来問題点を抱えながらも
広く使用されてきたアリルイソチオシアナートと抗菌抗
かび力が同程度で刺激臭が大幅に緩和された閾値の高い
優れた飲食物等用抗菌抗かび剤を提供することである。SUMMARY OF THE INVENTION An object of the present invention is to eliminate the above-mentioned drawbacks in the prior art, to greatly reduce the irritating odor, to be safe and widely applicable to various foods and drinks, and to obtain various kinds of bacteria. An object of the present invention is to provide an antibacterial antifungal agent excellent in inhibiting the growth of fungi. In particular, we provide an excellent antibacterial antifungal agent for foods and drinks with a high threshold value, which has the same antibacterial antifungal activity as allyl isothiocyanate, which has been widely used in spite of the conventional problems, and has greatly reduced irritation odor. It is to be.
【0006】[0006]
【課題を解決するための手段】発明者らは、ワサビやホ
ースラディシュ(セイヨウワサビ)に含有されるω−ア
ルキルスルフィニルアルキルイソチオシアナート化合物
が抗菌抗かび剤として優れていることを新たに見出し本
発明を完成したものである。即ち、本発明は一般式
(I) R−S(O)−(CH2)n−NCS (I) (式中、nは1〜10の整数を表し、RはC1〜C4のア
ルキル基を表す)を有するアルキルスルフィニルアルキ
ルイソチオシアナート化合物からなる抗菌抗かび剤であ
る。また本発明は、上記の抗菌抗かび剤を含有する飲食
物および口腔衛生剤である。Means for Solving the Problems The present inventors have newly found that the ω-alkylsulfinylalkylisothiocyanate compound contained in wasabi and horseradish (horseradish) is excellent as an antibacterial and antifungal agent. The invention has been completed. That is, the present invention has the general formula (I) R-S (O ) - (CH 2) n -NCS (I) ( wherein, n represents an integer of 1 to 10, R is alkyl of C 1 -C 4 Which represents an alkylsulfinylalkylisothiocyanate compound having the following formula: Further, the present invention is a food and drink and an oral hygiene agent containing the above antibacterial antifungal agent.
【0007】[0007]
【発明の実施の形態】以下、本発明をさらに詳しく説明
する。 (1)ω−アルキルスルフィニルアルキルイソチオシア
ナート化合物 一般式:R−S(O)−(CH2)n−NCS (I) においてnは1〜10の整数を表すが、2〜8、特に3
〜7、殊更3〜6の整数が好ましい。RはC1〜C4のア
ルキル基を表し、好ましい例として、メチル、エチル、
n−プロピル、イソプロピル、n−ブチル、イソブチ
ル、sec−ブチル、tert−ブチルが挙げられる。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. (1) ω-alkylsulfinylalkylisothiocyanate compound In the general formula: R—S (O) — (CH 2 ) n —NCS (I), n represents an integer of 1 to 10, but 2 to 8, especially 3
To 7, especially 3 to 6 are preferred. R represents a C 1 -C 4 alkyl group, and preferred examples include methyl, ethyl,
n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl.
【0008】式(I)を有する化合物の例としては、メチ
ルスルフィニルメチルイソチオシアナート、エチルスル
フィニルメチルイソチオシアナート、n−プロピルスル
フィニルメチルイソチオシアナート、イソプロピルスル
フィニルメチルイソチオシアナート、n−ブチルスルフ
ィニルメチルイソチオシアナート、2−メチルスルフィ
ニルエチルイソチオシアナート、2−エチルスルフィニ
ルエチルイソチオシアナート、2−n−プロピルスルフ
ィニルエチルイソチオシアナート、3−メチルスルフィ
ニルプロピルイソチオシアナート、4−メチルスルフィ
ニルブチルイソチオシアナート、5−メチルスルフィニ
ルペンチルイソチオシアナート、6−メチルスルフィニ
ルヘキシルイソチオシアナート、7−メチルスルフィニ
ルヘプチルイソチオシアナート、8−メチルスルフィニ
ルオクチルイソチオシアナート、9−メチルスルフィニ
ルノニルイソチオシアナート等が挙げられる。Examples of the compound having the formula (I) include methylsulfinylmethylisothiocyanate, ethylsulfinylmethylisothiocyanate, n-propylsulfinylmethylisothiocyanate, isopropylsulfinylmethylisothiocyanate, and n-butylsulfinylmethyl Isothiocyanate, 2-methylsulfinylethyl isothiocyanate, 2-ethylsulfinylethyl isothiocyanate, 2-n-propylsulfinylethyl isothiocyanate, 3-methylsulfinylpropyl isothiocyanate, 4-methylsulfinylbutyl isothiocyanate , 5-methylsulfinylpentylisothiocyanate, 6-methylsulfinylhexylisothiocyanate, 7-methylsulfinylheptylisothiocyanate Cyanate, 8-methylsulfinyl-octyl isothiocyanate, etc. 9 methylsulfinyl nonyl isothiocyanate and the like.
【0009】前記式(I)において、nが7以下である化
合物はワサビやホースラディシュなどの香気成分の中に
含まれていることが知られているが、その量は極めて微
量であるので工業的に得るためには合成によるのが適当
である。Rがメチルのときの前記式(I)を有する化合物
は、例えば特開平7−247497号公報に記載の方法
に従って、不活性溶媒中、下記式(II) CH3S−(CH2)n−NCS (II) (式中、nは前述したものと同一意義を有する)で表さ
れるω−メチルチオアルキルイソチオシアナートを、過
酸化物で酸化することによって製造することができる。In the above formula (I), it is known that compounds having n of 7 or less are contained in aroma components such as wasabi and horseradish. In order to obtain a target, it is appropriate to use synthesis. When R is methyl, the compound having the above formula (I) can be prepared, for example, according to the method described in JP-A-7-247497 in an inert solvent in the following formula (II): CH 3 S— (CH 2 ) n − It can be produced by oxidizing ω-methylthioalkylisothiocyanate represented by NCS (II) (wherein n has the same meaning as described above) with a peroxide.
【0010】上記製法において不活性溶媒は特に限定さ
れないが塩化メチレン、クロロホルム等が好ましく、ま
た過酸化物としてはm−クロロ過安息香酸、過酸化水
素、過酢酸等を使用することが好ましい。かかる過酸化
物は式(II)の化合物に対して1〜1.5当量、好適に
は1〜1.1当量の割合で使用され、反応は−10〜2
0℃、好適には−5〜5℃の温度で1〜5時間行われ
る。反応終了後、反応混合物を蒸留又はシリカゲルクロ
マトグラフィーで精製することによりω−メチルスルフ
ィニルアルキルイソチオシアナート化合物を得ることが
できる。In the above process, the inert solvent is not particularly limited, but methylene chloride, chloroform and the like are preferable, and as the peroxide, m-chloroperbenzoic acid, hydrogen peroxide, peracetic acid and the like are preferably used. Such a peroxide is used in a proportion of 1 to 1.5 equivalents, preferably 1 to 1.1 equivalents, based on the compound of the formula (II), and the reaction is carried out at -10 to 2
It is carried out at a temperature of 0 ° C, preferably -5 to 5 ° C for 1 to 5 hours. After completion of the reaction, the reaction mixture is purified by distillation or silica gel chromatography to obtain an ω-methylsulfinylalkylisothiocyanate compound.
【0011】(2)抗菌抗かび剤の適用対象 本発明の抗菌抗かび剤は、常法に従って飲食物等に好ま
しくは1〜100ppm、特に好ましくは10〜50ppmの
濃度で配合される。1ppm未満では抗菌抗かび効果が十
分発揮されず、一方100ppmを超えるとそれ自体の臭
気が飲食物等の味や香りを損なう傾向となる。(2) Application of antibacterial and antifungal agents The antibacterial and antifungal agents of the present invention are incorporated into foods and drinks at a concentration of preferably 1 to 100 ppm, particularly preferably 10 to 50 ppm, according to a conventional method. If it is less than 1 ppm, the antibacterial and antifungal effect is not sufficiently exhibited, while if it exceeds 100 ppm, its own odor tends to impair the taste and aroma of foods and drinks.
【0012】本発明の抗菌抗かび剤を配合する口腔衛生
剤の剤型としては、液剤、固形剤、半固形剤のいずれで
あってもよく、歯磨き剤、トローチ剤、液状又は粉末状
うがい薬、口腔内塗布液、口臭防止剤、チューインガム
等に適用される。また、本発明の抗菌抗かび剤を配合す
る飲食物としては、かまぼこ、ちくわ、はんぺん、魚肉
ソーセージ・ハム、すり身製品、魚介類乾燥品・燻製等
の水産製品;いか塩辛、たこ塩辛、えび塩辛、からし明
太子等の半固形水産製品;ハム、(ウィンナ)ソーセー
ジ、ベーコン、ひき肉類等の畜産肉製品;サラダ、ハン
バーグ、餃子、シュウマイ、佃煮、煮豆等の惣菜類;白
菜、胡瓜、野菜類等の浅漬けやキムチ、ザーサイ、たく
あん、からし蓮根等の漬物類;たれ、つゆ等の調味液
類;味噌、醤油等の調味料;生又はゆでたそば、うど
ん、パスタ等の麺類;カットした野菜や果物等の青果
物、これらの半調理品;その他、半加工のまま冷凍した
食品類等;果汁、炭酸飲料、茶、乳飲料、乳酸菌飲料、
コーヒー、ココア、豆乳等の各種飲料;練乳、粉乳、発
酵乳、バター、チーズ、アイスクリーム、生クリーム等
の乳製品;キャラメル、キャンデー、チューインガム、
ジャム、マーガリン等が挙げられる。The oral hygiene preparation containing the antibacterial and antifungal agent of the present invention may be in the form of a liquid, a solid, or a semi-solid, a dentifrice, a troche, a liquid or powdery mouthwash. It is applied to oral solution, bad breath inhibitor, chewing gum and the like. In addition, foods and beverages containing the antibacterial antifungal agent of the present invention include fishery products such as kamaboko, chikuwa, hampan, fish meat sausage / ham, surimi products, dried seafood / smoked products, etc .; Semi-solid marine products such as taro, mustard, etc .; livestock meat products such as ham, (winner) sausage, bacon, minced meat; salads, hamburgers, gyoza, shumai, tsukudani, boiled beans, etc .; Chinese cabbage, cucumbers, vegetables Pickles such as shallow pickles, kimchi, zasai, takuan, mustard lotus root, etc .; Seasoning liquids such as sauce and soup; Seasonings such as miso, soy sauce; Noodles such as raw or boiled soba, udon, pasta; Vegetables such as vegetables and fruits, semi-cooked products of these; other semi-processed frozen foods; fruit juice, carbonated drinks, tea, milk drinks, lactic acid drinks,
Various drinks such as coffee, cocoa, soy milk; condensed milk, powdered milk, fermented milk, butter, cheese, ice cream, fresh cream and other dairy products; caramel, candy, chewing gum,
Jam, margarine and the like.
【0013】さらに、本発明の抗菌抗かび剤は、いわゆ
る抗菌グッズ(商品)と呼ばれる種々の商品、例えば、
まな板等の台所用品;歯ブラシ等の洗面具;筆記具、消
しゴムやノート等の文房具;肌着等の衣料品;ハンド
ル、シート等の自動車内装品;ワープロ、冷蔵庫等の家
電製品;畳、壁紙等の建築内装材等に広く適用すること
ができる。即ち、本抗菌抗かび剤を上記商品の製造段階
で原材料に練り込んで混合し、又は本剤を溶媒を用い必
要に応じて界面活性剤等の補助剤を添加して液剤化して
商品表面に塗布するか或いはスプレー剤にして噴霧して
適用する。また、液剤化又はスプレー剤化した本剤は、
台所の流し下、トイレの便座、浴室ダイルの除菌剤や防
かび剤として適用することができる。さらに、液剤化し
た本剤を紙・布類等の吸液性支持体に含浸させて除菌ク
リーナーやウェットティッシュ等の衛生用品として適用
することもできる。Further, the antibacterial antifungal agent of the present invention can be used for various products called so-called antibacterial goods (products), for example,
Kitchen utensils such as cutting boards; toiletries such as toothbrushes; stationery such as writing utensils, erasers and notebooks; clothing such as underwear; car interiors such as handles and sheets; home appliances such as word processors and refrigerators; It can be widely applied to interior materials and the like. That is, the antibacterial and antifungal agent is kneaded and mixed with the raw materials in the production stage of the product, or the agent is liquefied by adding an auxiliary agent such as a surfactant as necessary using a solvent to the surface of the product. It is applied by spraying or spraying. In addition, the liquid or sprayed this agent,
It can be applied as a disinfectant or fungicide for kitchen toilets, toilet seats and bathroom dill. In addition, the liquid preparation of the present invention can be impregnated into a liquid-absorbing support such as paper or cloth to be applied as sanitary cleaners or hygiene articles such as wet tissues.
【0014】なお、本発明の抗菌抗かび剤は他の抗菌
剤、例えばアルコール;セージ、ローズマリー等の香辛
料成分;クエン酸、乳酸、酢酸等の有機酸と併用するこ
ともできる。The antibacterial and antifungal agent of the present invention can be used in combination with other antibacterial agents such as alcohol; spice components such as sage and rosemary; and organic acids such as citric acid, lactic acid and acetic acid.
【0015】次に各種の菌に対する最小阻止濃度(MI
C)を測定することにより本発明の抗菌抗かび剤の効果
を示す。 (1)黄色ブドウ球菌(Staphylococcus aureus IFO 12
732)に対する抗菌性試験 菌培養に際して以下に示す組成の培地Aを使用した。 (培地A) ペプトン 5.0g 酵母エキス 1.5g 肉エキス 1.5g 塩化ナトリウム 3.5g グルコース 1.0g リン酸水素二ナトリウム 3.0g リン酸二水素カリウム 1.32g 蒸留水 1000mlNext, the minimum inhibitory concentrations (MI
The effect of the antibacterial antifungal agent of the present invention is shown by measuring C). (1) Staphylococcus aureus IFO 12
Antimicrobial test against 732) During culture of the bacterium, a medium A having the following composition was used. (Medium A) Peptone 5.0 g Yeast extract 1.5 g Meat extract 1.5 g Sodium chloride 3.5 g Glucose 1.0 g Disodium hydrogen phosphate 3.0 g Potassium dihydrogen phosphate 1.32 g Distilled water 1000 ml
【0016】検定菌を培地Aに接種し35℃の温度下で
12時間振とう培養した。次いでこの菌液を1×106c
ells/mlとなるように調整した。菌液を96穴マイクロ
プレートの第1列に324μl、第2〜11列に180
μl入れ、表1に記載の各種イソチオシアナート溶液3
6μlを第1列に添加した。撹拌後、第1列の溶液18
0mlを第2列に移し、連続2倍希釈系列を作成し、35
℃の温度下で6時間静置培養した。各穴における菌の生
育はマイクロプレートリーダー(波長630nmで吸光度
(光学濃度)が0.05以下の時)と肉眼で判定した。
各種イソチオシアナートの最小阻止濃度は表1のとおり
であった。The test bacteria were inoculated into the medium A and cultured with shaking at 35 ° C. for 12 hours. Then, 1 × 10 6 c
It was adjusted to be ells / ml. 324 μl of the bacterial solution was placed in the first row of a 96-well microplate, and 180 µl was placed in the second to 11th rows.
μl of each of the isothiocyanate solutions 3 shown in Table 1.
6 μl was added to the first row. After stirring, the first row of solution 18
Transfer 0 ml to the second row and make a serial two-fold dilution series,
The culture was allowed to stand at a temperature of 6 ° C. for 6 hours. The growth of the bacteria in each well was determined with a microplate reader (when the absorbance (optical density) at a wavelength of 630 nm was 0.05 or less) and the naked eye.
Table 1 shows the minimum inhibitory concentrations of various isothiocyanates.
【0017】(2)大腸菌(Esherichia coli IFO 330
1)に対する抗菌性試験 上記の黄色ブドウ球菌と同様の手法で行った。各種イソ
チオシアナートの最小阻止濃度は表1のとおりであっ
た。(2) Escherichia coli IFO 330
Antibacterial test for 1) The test was performed in the same manner as that for Staphylococcus aureus described above. Table 1 shows the minimum inhibitory concentrations of various isothiocyanates.
【0018】(3)緑膿菌(Pseudomonas aeruginosa I
FO 3080)に対する抗菌性試験 上記の黄色ブドウ球菌と同様の手法で行った。各種イソ
チオシアナートの最小阻止濃度は表1のとおりであっ
た。(3) Pseudomonas aeruginosa I
FO 3080) An antibacterial test was performed in the same manner as described above for Staphylococcus aureus. Table 1 shows the minimum inhibitory concentrations of various isothiocyanates.
【0019】(4)枯草菌(Bacillus subtilis IFO 31
34)に対する抗菌性試験 検定菌を培地Aに接種し35℃の温度下で12時間振と
う培養した。次いでこの菌液中の芽胞を1×106cells
/mlとなるように調整した。菌液を96穴マイクロプレ
ートの第1列に324μl、第2〜11列に180μl入
れ、表1に記載の各種イソチオシアナート溶液36μl
を第1列に添加した。撹拌後、第1列の溶液180mlを
第2列に移し、連続2倍希釈系列を作成し、35℃の温
度下で6時間静置培養した。各穴における菌の生育はマ
イクロプレートリーダー(波長630nmで吸光度(光学
濃度)が0.05以下の時)と肉眼で判定した。各種イ
ソチオシアナートの最小阻止濃度は表1のとおりであっ
た。(4) Bacillus subtilis IFO 31
Antibacterial test against 34) The test bacteria were inoculated into medium A and cultured with shaking at 35 ° C for 12 hours. Then, the spores in this bacterial solution were 1 × 10 6 cells
/ Ml. 324 μl of the bacterial solution was placed in the first row of the 96-well microplate, and 180 μl was placed in the second to eleventh rows, and 36 μl of the various isothiocyanate solutions shown in Table 1
Was added to the first row. After agitation, 180 ml of the solution in the first row was transferred to the second row to form a serial two-fold dilution series, which was incubated at 35 ° C for 6 hours. The growth of the bacteria in each well was determined with a microplate reader (when the absorbance (optical density) at a wavelength of 630 nm was 0.05 or less) and the naked eye. Table 1 shows the minimum inhibitory concentrations of various isothiocyanates.
【0020】(5)クロカビ(Aspergillus niger IFO
4414)に対する抗かび性試験 培養に際して以下に示す組成の培地Bを使用した。 (培地B) ペプトン 10.0g グルコース 40.0g 蒸留水 1000ml(5) Black mold (Aspergillus niger IFO)
Antifungal test against 4414) During culture, a medium B having the following composition was used. (Medium B) Peptone 10.0 g Glucose 40.0 g Distilled water 1000 ml
【0021】検定菌を培地Bに接種し25℃の温度下で
24時間振とう培養した。次いでこの菌液中の胞子を1
×104cells/mlとなるように調整した。菌液を96穴
マイクロプレートの第1列に324μl、第2〜11列
に180μl入れ、表1に記載の各種イソチオシアナー
ト溶液36μlを第1列に添加した。撹拌後、第1列の
溶液180mlを第2列に移し、連続2倍希釈系列を作成
し、25℃の温度下で15時間静置培養した。各穴にお
ける胞子の発芽を顕微鏡で判定した。各種イソチオシア
ナートの最小阻止濃度は表1のとおりであった。The test bacteria were inoculated into the medium B and cultured with shaking at a temperature of 25 ° C. for 24 hours. Then the spores in this bacterial solution were
It was adjusted to be × 10 4 cells / ml. 324 μl of the bacterial solution was added to the first row of the 96-well microplate, and 180 μl to the second to eleventh rows, and 36 μl of the various isothiocyanate solutions shown in Table 1 were added to the first row. After agitation, 180 ml of the solution in the first row was transferred to the second row to form a serial two-fold dilution series, which was incubated at 25 ° C. for 15 hours. Germination of spores in each well was determined microscopically. Table 1 shows the minimum inhibitory concentrations of various isothiocyanates.
【0022】(6)カンジダ菌(Candida albicans IFO
1835)に対する抗菌性試験 検定菌を前記培地Bに接種し25℃の温度下で24時間
振とう培養した。次いでこの菌液を1×105cells/ml
となるように調整した。菌液を96穴マイクロプレート
の第1列に324μl、第2〜11列に180μl入れ、
表1に記載の各種イソチオシアナート溶液36μlを第
1列に添加した。撹拌後、第1列の溶液180mlを第2
列に移し、連続2倍希釈系列を作成し、25℃の温度下
で22時間静置培養した。各穴における菌の生育はマイ
クロプレートリーダー(波長630nmで吸光度(光学濃
度)が0.05以下の時)と肉眼で判定した。各種イソ
チオシアナートの最小阻止濃度は表1のとおりであっ
た。(6) Candida albicans IFO
Antibacterial test against 1835) A test bacterium was inoculated into the above-mentioned medium B and cultured with shaking at a temperature of 25 ° C. for 24 hours. Then, this bacterial solution was added to 1 × 10 5 cells / ml.
It was adjusted to be. 324 μl of the bacterial solution was placed in the first row of a 96-well microplate, and 180 μl was placed in the second to 11th rows.
36 μl of the various isothiocyanate solutions described in Table 1 were added to the first row. After stirring, add 180 ml of the solution in the first row to the second
The cells were transferred to a column, and a serial two-fold dilution series was prepared, followed by stationary culture at a temperature of 25 ° C. for 22 hours. The growth of the bacteria in each well was determined with a microplate reader (when the absorbance (optical density) at a wavelength of 630 nm was 0.05 or less) and the naked eye. Table 1 shows the minimum inhibitory concentrations of various isothiocyanates.
【0023】[0023]
【表1】 [Table 1]
【0024】次に各種イソチオシアナートの閾値を次の
とおり測定した。閾値測定は、次のようなAmooreの方法
に従い2:5点法を用いた。5個の褐色ガラス製コップ
に水20mlを入れ、そのうち2個には評価者が試料のイ
ソチオシアナートを検知できる濃度に希釈した水溶液2
0mlを入れる。 水は活性炭を装着したフィルター(オ
ルガノ社製「D−4型」)を通すことにより残留塩素を
除去して用いる。水溶液の温度は20±1℃、室温は2
0±5℃、湿度は60〜80%にそれぞれ設定し、測定
は午前中に行う。評価者は20歳代の男性10名からな
り、各評価者は5個のコップ中の水又は試料溶液を少し
ずつ口に含み試料が含まれていると感じる2個のコップ
を選択する。この選択が正解である場合には、さらに試
料濃度を10-0.5倍低くして同様の官能評価を行い誤答
が出るまで繰り返す。各評価者が最後に正解を出したと
きの試料濃度の相乗平均値を閾値とする。閾値試験の結
果は図1に記載のとおりであった。Next, the threshold values of various isothiocyanates were measured as follows. For the threshold measurement, the 2: 5 point method was used according to the following Amoore's method. 20 ml of water was placed in five brown glass cups, two of which were diluted with an aqueous solution 2 diluted to a concentration at which the evaluator could detect isothiocyanate in the sample.
Add 0 ml. Water is used after removing residual chlorine by passing through a filter ("D-4" manufactured by Organo) equipped with activated carbon. The temperature of the aqueous solution is 20 ± 1 ° C, the room temperature is 2
The temperature is set at 0 ± 5 ° C. and the humidity is set at 60 to 80%, and the measurement is performed in the morning. The evaluators consisted of 10 males in their twenties, and each evaluator selected two cups that contained the water or sample solution in the five cups little by mouth and felt that the sample was contained. If this selection is correct, the same sensory evaluation is performed with the sample concentration further reduced by 10 -0.5 times, and the process is repeated until a wrong answer is given. The geometric mean value of the sample concentration at the time when each evaluator finally gives the correct answer is set as the threshold. The results of the threshold test were as shown in FIG.
【0025】上記の抗菌性試験並びに閾値試験の結果か
ら次のように総括される。前記式(I)においてRがメチ
ルである場合の本発明のω−メチルスルフィニルアルキ
ルイソチオシアナートは、黄色ブドウ球菌、枯草菌、大
腸菌および黒かびに対して強い抗菌効果を奏することが
判明した。特に4−メチルスルフィニルブチルイソチオ
シアナートは、黄色ブドウ球菌、枯草菌および大腸菌に
ついてアリルイソチオシアナートの抗菌力を上回ること
が明らかとなった。また、ω−メチルスルフィニルアル
キルイソチオシアナートは、他のイソチオシアナート系
化合物であるアリルイソチオシアナート等のω−アルケ
ニルイソチオシアナート、ω−メチルチオイソチオシア
ナートに比べ閾値も高いことから飲食物等に同量添加し
た場合に飲食物等の本来の香味を損なうことがないこと
も明らかとなった。The results of the above antibacterial test and threshold test are summarized as follows. It has been found that the ω-methylsulfinylalkylisothiocyanate of the present invention wherein R is methyl in the formula (I) has a strong antibacterial effect against Staphylococcus aureus, Bacillus subtilis, Escherichia coli and black mold. In particular, 4-methylsulfinylbutyl isothiocyanate was found to outperform allyl isothiocyanate's antibacterial activity against Staphylococcus aureus, Bacillus subtilis and Escherichia coli. Further, ω-methylsulfinylalkyl isothiocyanate has a higher threshold value than ω-alkenyl isothiocyanate such as allyl isothiocyanate, which is another isothiocyanate compound, and ω-methylthioisothiocyanate. It was also found that when the same amount was added, the original flavor of food and drink was not impaired.
【0026】[0026]
【実施例】次に参考例および実施例を示して本発明をさ
らに具体的に説明する。ω−アルキルスルフィニルアル
キルイソチオシアナートの合成例 参考例1 3−メチルスルフィニルプロピルイソチオシ
アナートの製造 3−メチルチオプロピルイソチオシアナート12.8g
を塩化メチレン200gに溶解し、−5℃に冷却する。
m−クロロ過安息香酸15.6gの塩化メチレン(32
0g)溶液を滴下し、そのまま1時間撹拌する。反応液
を飽和重曹水および飽和食塩水で洗浄後、分液し有機層
を得る。次いで、減圧濃縮した後、シリカゲルクロマト
グラフィーで精製すると、3−メチルスルフィニルプロ
ピルイソチオシアナート12.1g(収率85%)が得
られた。EXAMPLES Next, the present invention will be described more specifically with reference to Reference Examples and Examples. Synthesis Example of ω-alkylsulfinylalkylisothiocyanate Reference Example 1 Production of 3-methylsulfinylpropylisothiocyanate 12.8 g of 3-methylthiopropylisothiocyanate
Is dissolved in 200 g of methylene chloride and cooled to -5 ° C.
15.6 g of m-chloroperbenzoic acid in methylene chloride (32
0 g) The solution is added dropwise and stirred for 1 hour. The reaction solution is washed with a saturated aqueous solution of sodium bicarbonate and a saturated saline solution and then separated to obtain an organic layer. Then, after concentration under reduced pressure, purification by silica gel chromatography gave 12.1 g (yield 85%) of 3-methylsulfinylpropyl isothiocyanate.
【0027】参考例2 6−メチルスルフィニルヘキシ
ルイソチオシアナートの製造 6−メチルチオヘキシルイソチオシアナート14.4g
を塩化メチレン225gに溶解し、−5℃に冷却する。
m−クロロ過安息香酸14.8gの塩化メチレン(34
0g)溶液を滴下し、そのまま3時間撹拌する。反応液
を飽和重曹水および飽和食塩水で洗浄後、分液し有機層
を得る。次いで、減圧濃縮した後、シリカゲルクロマト
グラフィーで精製すると、6−メチルスルフィニルヘキ
シルイソチオシアナート13.8g(収率88%)が得
られた。Reference Example 2 Production of 6-methylsulfinylhexyl isothiocyanate 14.4 g of 6-methylthiohexyl isothiocyanate
Is dissolved in 225 g of methylene chloride and cooled to -5 ° C.
14.8 g of m-chloroperbenzoic acid in methylene chloride (34
0 g) The solution is added dropwise and stirred for 3 hours. The reaction solution is washed with a saturated aqueous solution of sodium bicarbonate and a saturated saline solution and then separated to obtain an organic layer. Then, after concentration under reduced pressure, purification by silica gel chromatography gave 13.8 g (88% yield) of 6-methylsulfinylhexylisothiocyanate.
【0028】実施例1 キャンデーの調製 下記の成分からなるキャンデー組成物を用いて常法によ
り本発明の抗菌抗かび剤を配合したキャンデーを調製し
た。 砂糖 50 水飴 33 有機酸 2 香料 0.2 水 残部 6−メチルスルフィニルヘキシルイソチオシアナート 0.002 合 計 100gExample 1 Preparation of candy A candy containing the antibacterial antifungal agent of the present invention was prepared by a conventional method using a candy composition comprising the following components. Sugar 50 starch syrup 33 organic acid 2 flavor 0.2 water balance 6-methylsulfinylhexyl isothiocyanate 0.002 total 100g
【0029】実施例2 チューインガムの調製 下記の成分からなるチューインガム組成物を用いて常法
により本発明の抗菌抗かび剤を配合したチューインガム
を調製した。 ガムベース 20.09 砂糖 53 グルコース 10 水飴 16.4 香料 0.5 5−メチルスルフィニルペンチルイソチオシアナート 0.01 合 計 100gExample 2 Preparation of chewing gum Chewing gum containing the antibacterial antifungal agent of the present invention was prepared by a conventional method using a chewing gum composition comprising the following components. Gum base 20.09 sugar 53 glucose 10 starch syrup 16.4 fragrance 0.5 5-methylsulfinylpentyl isothiocyanate 0.01 total 100g
【0030】実施例3 練り歯磨き 下記の成分からなる練り歯磨き組成物を用いて常法によ
り本発明の抗菌抗かび剤を配合した練り歯磨きを調製し
た。 リン酸水素カルシウム 20 無水ケイ酸 10 ソルビット液 40 グリセリン 10 塩化ベンザルコニウム 0.01 増粘剤 0.6 香料 0.8 水 残部 6−メチルスルフィニルヘキシルイソチオシアナート 0.002 合 計 100gExample 3 Toothpaste A toothpaste containing the antibacterial antifungal agent of the present invention was prepared by a conventional method using a toothpaste composition comprising the following components. Calcium hydrogen phosphate 20 Silicic anhydride 10 Sorbit liquid 40 Glycerin 10 Benzalkonium chloride 0.01 Thickener 0.6 Fragrance 0.8 Water Remainder 6-methylsulfinylhexyl isothiocyanate 0.002 Total 100 g
【0031】実施例4 マウスウォッシュ(口内洗浄
剤) 下記の成分からなるマウスウォッシュ組成物を用いて常
法により本発明の抗菌抗かび剤を配合したマウスウォッ
シュを調製した。 エチルアルコール 10.0 ポリオキシエチレン硬化ひまし油 2.0 サッカリンナトリウム 0.2 安息香酸ナトリウム 0.1 グリセリン 5.0 香料 0.2 クエン酸ナトリウム(pH調整剤) 適量 水 残部 4−メチルスルフィニルブチルイソチオシアナート 0.002 合 計 100gExample 4 Mouthwash (Mouthwash) A mouthwash containing the antibacterial antifungal agent of the present invention was prepared by a conventional method using a mouthwash composition comprising the following components. Ethyl alcohol 10.0 Polyoxyethylene hydrogenated castor oil 2.0 Saccharin sodium 0.2 Sodium benzoate 0.1 Glycerin 5.0 Fragrance 0.2 Sodium citrate (pH adjuster) Water Water balance 4-Methylsulfinylbutyl isothiocyanate 0.002 total 100g
【0032】[0032]
【発明の効果】本発明の抗菌抗かび剤は、日常頻繁に接
することの多い各種細菌やかび等真菌類の発育を有効に
阻止することができ、しかもワサビ、カラシ等の食用植
物由来の成分であるため人体に対する安全性も高く飲食
物や口腔衛生剤への添加に好適である。また、従来使用
されてきたアリルイソチオシアナート等の他のイソチオ
シアナート系化合物に比し、刺激臭が格段に緩和されて
閾値が高いので高濃度で添加しても飲食物等の本来の味
や臭いを損なうことがない。従って、対処する菌の種類
に応じて低〜高濃度の広範囲で添加でき実用性に優れ
る。さらに、揮発性が低いので配合にあたって取り扱い
性に優れる。Industrial Applicability The antibacterial antifungal agent of the present invention can effectively inhibit the growth of fungi such as various kinds of bacteria and mold which are frequently in contact with daily life, and is a component derived from edible plants such as wasabi and mustard. Therefore, it has high safety to the human body and is suitable for addition to foods and drinks and oral hygiene agents. Also, compared to other isothiocyanate compounds such as allyl isothiocyanate which have been conventionally used, the irritating odor is remarkably reduced and the threshold value is high, so even if added at a high concentration, the original taste of food and drink etc. No odor or smell. Therefore, it can be added in a wide range of low to high concentrations depending on the type of the bacterium to be treated, and is excellent in practicality. Furthermore, since it has low volatility, it is excellent in handleability in compounding.
【図1】一般式:R−S(O)−(CH2)n−NCSにおい
てRがメチル基である場合の本発明のω−メチルスルフ
ィニルアルキルイソチオシアナートの閾値と他のイソチ
オシアナート系化合物の閾値との比較を示したグラフで
ある。他の比較したイソチオシアナート系化合物は、一
般式CH3−S−(CH2)n−NCSで表されるω−メチ
ルチオアルキルイソチオシアナート、一般式CH2=C
H−(CH2)n-2−NCSで表されるω−アルケニルイソ
チオシアナートである。縦軸は閾値(単位ppb)を、横
軸は上記各式中のnを表す。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1: The threshold value of the ω-methylsulfinylalkyl isothiocyanate of the present invention when R is a methyl group in the general formula: RS (O) — (CH 2 ) n -NCS and other isothiocyanate systems 3 is a graph showing a comparison with a threshold value of a compound. Other compared isothiocyanate compounds are ω-methylthioalkylisothiocyanates represented by the general formula CH 3 —S— (CH 2 ) n —NCS, and the general formula CH 2 CC
Ω-Alkenyl isothiocyanate represented by H- (CH 2 ) n-2- NCS. The vertical axis represents the threshold value (unit: ppb), and the horizontal axis represents n in each of the above equations.
Claims (3)
ルキル基を表す)を有するω−アルキルスルフィニルア
ルキルイソチオシアナート化合物からなることを特徴と
する抗菌抗かび剤。1. A compound represented by the general formula (I): RS (O)-(CH 2 ) n -NCS (I) wherein n is an integer of 1 to 10, and R is a C 1 to C 4 alkyl. Which represents an ω-alkylsulfinylalkylisothiocyanate compound having the formula:
る飲食物。2. A food or drink comprising the antibacterial antifungal agent according to claim 1.
る口腔衛生剤。3. An oral hygiene agent comprising the antibacterial antifungal agent according to claim 1.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4655698A JPH11246319A (en) | 1998-02-27 | 1998-02-27 | Antimicrobial and antifungal agent |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4655698A JPH11246319A (en) | 1998-02-27 | 1998-02-27 | Antimicrobial and antifungal agent |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH11246319A true JPH11246319A (en) | 1999-09-14 |
Family
ID=12750609
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP4655698A Pending JPH11246319A (en) | 1998-02-27 | 1998-02-27 | Antimicrobial and antifungal agent |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH11246319A (en) |
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JP2001288072A (en) * | 2000-02-04 | 2001-10-16 | Akira Sasaki | Bathing agent |
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