JPS6155889B2 - - Google Patents
Info
- Publication number
- JPS6155889B2 JPS6155889B2 JP15914080A JP15914080A JPS6155889B2 JP S6155889 B2 JPS6155889 B2 JP S6155889B2 JP 15914080 A JP15914080 A JP 15914080A JP 15914080 A JP15914080 A JP 15914080A JP S6155889 B2 JPS6155889 B2 JP S6155889B2
- Authority
- JP
- Japan
- Prior art keywords
- vanillyl
- toothpaste
- ether
- alcohol
- solution
- 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
Links
- 239000000606 toothpaste Substances 0.000 claims description 25
- 229940034610 toothpaste Drugs 0.000 claims description 25
- ZENOXNGFMSCLLL-UHFFFAOYSA-N vanillyl alcohol Chemical class COC1=CC(CO)=CC=C1O ZENOXNGFMSCLLL-UHFFFAOYSA-N 0.000 claims description 17
- 239000000551 dentifrice Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 235000019633 pungent taste Nutrition 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 7
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 7
- 229940041616 menthol Drugs 0.000 description 7
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 6
- KOCVACNWDMSLBM-UHFFFAOYSA-N 4-(Ethoxymethyl)-2-methoxyphenol Chemical compound CCOCC1=CC=C(O)C(OC)=C1 KOCVACNWDMSLBM-UHFFFAOYSA-N 0.000 description 6
- 239000000796 flavoring agent Substances 0.000 description 6
- 235000019634 flavors Nutrition 0.000 description 6
- 235000011187 glycerol Nutrition 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 230000035597 cooling sensation Effects 0.000 description 5
- 239000003205 fragrance Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 210000000214 mouth Anatomy 0.000 description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- YKPUWZUDDOIDPM-SOFGYWHQSA-N capsaicin Chemical compound COC1=CC(CNC(=O)CCCC\C=C\C(C)C)=CC=C1O YKPUWZUDDOIDPM-SOFGYWHQSA-N 0.000 description 4
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 4
- 235000019739 Dicalciumphosphate Nutrition 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000001506 calcium phosphate Substances 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- NEFBYIFKOOEVPA-UHFFFAOYSA-K dicalcium phosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])([O-])=O NEFBYIFKOOEVPA-UHFFFAOYSA-K 0.000 description 3
- 229910000390 dicalcium phosphate Inorganic materials 0.000 description 3
- 229940038472 dicalcium phosphate Drugs 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 3
- 229940081974 saccharin Drugs 0.000 description 3
- 235000019204 saccharin Nutrition 0.000 description 3
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 description 2
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 125000005233 alkylalcohol group Chemical group 0.000 description 2
- QQQCWVDPMPFUGF-ZDUSSCGKSA-N alpinetin Chemical compound C1([C@H]2OC=3C=C(O)C=C(C=3C(=O)C2)OC)=CC=CC=C1 QQQCWVDPMPFUGF-ZDUSSCGKSA-N 0.000 description 2
- 235000017663 capsaicin Nutrition 0.000 description 2
- 229960002504 capsaicin Drugs 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 235000003599 food sweetener Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000035807 sensation Effects 0.000 description 2
- 235000019615 sensations Nutrition 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000003765 sweetening agent Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 2
- 235000012141 vanillin Nutrition 0.000 description 2
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 1
- 235000008534 Capsicum annuum var annuum Nutrition 0.000 description 1
- 235000002568 Capsicum frutescens Nutrition 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 241001247145 Sebastes goodei Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 244000290333 Vanilla fragrans Species 0.000 description 1
- 235000009499 Vanilla fragrans Nutrition 0.000 description 1
- 235000012036 Vanilla tahitensis Nutrition 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- -1 alkyl ether compound Chemical class 0.000 description 1
- 235000019658 bitter taste Nutrition 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000000546 chi-square test Methods 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 229940095079 dicalcium phosphate anhydrous Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 229940043264 dodecyl sulfate Drugs 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 210000000744 eyelid Anatomy 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000001525 mentha piperita l. herb oil Substances 0.000 description 1
- 235000019477 peppermint oil Nutrition 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- AQMNWCRSESPIJM-UHFFFAOYSA-M sodium metaphosphate Chemical compound [Na+].[O-]P(=O)=O AQMNWCRSESPIJM-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 235000019640 taste Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/34—Alcohols
- A61K8/347—Phenols
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Emergency Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Cosmetics (AREA)
Description
本発明は清涼感を増進させるワニリルアルコー
ル誘導体を配合してなる歯磨組成物に関する。更
にくわしくは、歯磨素材に次の一般式（）
（式中、Ｒは炭素数１〜６を有するアルキル基を
示す）で表わされるワニリルアルコール誘導体の
１種または２種以上を配合したことを特徴とする
歯磨組成物に関する。
一般に、歯磨は清掃研磨剤、粘稠剤、湿潤剤、
起泡剤、薬効剤、甘味料、香料、着色料、清涼剤
等から構成されている。歯磨の製品価値を定める
一つの重要な要因として、使用の際の口腔内での
清涼感があり、従来から清涼剤としてペパーミン
トオイル、メントールがひろく用いられている。
しかしながら、メントール等をもちいて強い清涼
感を得るには、この配合量を増加させる必要があ
るが、あまりに多量を使用するときは、メントー
ルの有する苦味があらわれるとか、薬効剤の効果
を損い、香気の変化をもたらす等の弊害を生ずる
という欠点があり、歯磨素材に影響を与えること
なく、強い清涼感を与える歯磨用清涼剤の開発が
望まれていた。
そこで、本発明者は、これについて鋭意研究を
行つた結果、上記一般式で表わされるワニリルア
ルコール誘導体はそれ自体強い辛味性を有するも
のであるが、これを歯磨素材に配合すると清涼感
が著しく増大されること、すなわち、歯磨用清涼
剤として極めて優れた特性を有することを見出
し、本発明を完成した。
従つて、本発明は、（）式のワニリルアルコ
ール誘導体の１種または２種以上を配合した清涼
感の優れた歯磨組成物を提供するものである。
本発明で使用されるワニリルアルコール誘導体
（）の具体例としては、例えば、ワニリルメチ
ルエーテル、ワニリル エチルエーテル、ワニリ
ル ｎ−プロピルエーテル、ワニリルイソプロピ
ルエーテル、ワニリル ｎ−ブチルエーテル、ワ
ニリル イソブチルエーテル、ワニリル ｎ−ア
ミルエーテル、ワニリルイソアミルエーテル、ワ
ニリル ｎ−ヘキシルエーテル等が挙げられる。
このうち、ワニリル メチルエーテル及びワニリ
ル エチルエーテルは、ワニラ豆の抽出液中にそ
の香気成分として存在することが知られている
〔J.Agric.Food Chem.、Vol.26.No.1、195頁
（1978）〕が、このものが歯磨用清涼剤として使用
できることを示唆する文献は未だみあたらない。
また、上記一般式（）中ＲがC3〜６のアルキ
ル基である化合物は、本発明者等が昭和55年特許
願第82530号（特開昭57−9729号公報参照）をも
つて特許出願した新規化合物である。
本発明に使用するワニリルアルコール誘導体は
公知の方法、例えばアルコール類に濃塩酸を作用
させてクロライドとなし、これにアルコール中で
ナトリウムアルコラートを反応させる方法（「香
料」、No.113、65頁、昭和50年12月発行）、ある
いはアルコール類にイオン交換樹脂を触媒として
アルコールを反応させる方法〔J.Org.Chem.
Vol.27.2662（1962）〕等を利用して製造すること
もできるが、本発明者らによつて見出された、上
記方法に比較してより工業的な方法によつてつく
ることが出来る。すなわち、所望するアルキルエ
ーテル化合物を構成するところのアルキル基に相
当するアルキルアルコールに約５重量％程度の濃
塩酸を混合し、約70℃附近に加熱しておき、これ
にワニリルアルコールを徐々に加えた後、約70℃
で充分に反応させる。この際アルキルアルコール
は溶媒を兼ねさせる量、すなわちワニリルアルコ
ールに対しモル比で約10倍程度用いるのが好まし
い。反応終了後はアルカリ水溶液で塩酸を中和
し、常法により溶剤抽出、乾燥を行つた後蒸留し
て目的物を得る。また水に対する溶解度の比較的
大きいｎ−プロピルアルコールを用いるときは、
ワニリンに等モル量の５〜10％苛性ソーダ水溶液
とｎ−プロピルアルコールを混合し、これに計算
量の約２倍の水素化ホウ素ナトリウムを加える。
ｎ−プロピルアルコールは溶媒としても使用し得
る量、すなわちワニリンに対しモル比で20倍程度
を使用することが好ましい。この混合物を約35℃
に於て３〜５時間反応させる。ここにワニリルア
ルコールのホウ素化合物が生成する。次に室温で
濃塩酸を用いて反応液を酸性にしたのち、加熱
し、約70℃でエーテル化の反応を完結させる。反
応終了後、アルカリ水溶液で塩酸を中和し、溶剤
抽出、乾燥、蒸留を行つてワニリル ｎ−プロピ
ルエーテルを得る。
斯くして得られたワニリルアルコール誘導体
は、前述の如く、辛味性を有し、これを歯磨素材
に配合したときの清涼感はこの辛味性の強さに大
略比例する。ワニリルアルコール誘導体の辛味の
強さは置換基の種類によつて次のごとく異なる。
すなわち、各被検体の１％エチルアルコール了溶
液を調整し、この１ｇを秤量し、更に100mlの蒸
留水で希釈し、この溶液について検味を行い、辛
味の最も強いものを５、辛味を感じないものを０
として、０〜５段階に評価した結果は表１のとお
りである。
The present invention relates to a dentifrice composition containing a vanillyl alcohol derivative that enhances the refreshing feeling. More specifically, the toothpaste material has the following general formula () The present invention relates to a dentifrice composition containing one or more vanillyl alcohol derivatives represented by the formula (wherein R represents an alkyl group having 1 to 6 carbon atoms). Generally, toothpaste contains cleaning abrasives, thickening agents, wetting agents,
It consists of foaming agents, medicinal agents, sweeteners, fragrances, colorants, cooling agents, etc. One important factor that determines the product value of toothpaste is the cooling sensation it provides in the oral cavity upon use, and peppermint oil and menthol have traditionally been widely used as cooling agents.
However, in order to obtain a strong cooling sensation using menthol, etc., it is necessary to increase the amount of this compound, but if too much is used, the bitter taste of menthol may appear or the effectiveness of the medicinal agent may be impaired. It has the drawback of causing adverse effects such as changes in aroma, and there has been a desire to develop a refreshing agent for toothbrushing that provides a strong cooling sensation without affecting the toothpaste material. Therefore, as a result of intensive research on this subject, the present inventor found that although the vanillyl alcohol derivative represented by the above general formula itself has a strong pungency, when it is blended into toothpaste materials, it provides a significantly refreshing sensation. The present invention was completed based on the discovery that it has extremely excellent properties as a toothpaste refreshing agent. Therefore, the present invention provides a dentifrice composition with an excellent refreshing feeling, which contains one or more vanillyl alcohol derivatives of the formula (). Specific examples of vanillyl alcohol derivatives () used in the present invention include vanillyl methyl ether, vanillyl ethyl ether, vanillyl n-propyl ether, vanillyl isopropyl ether, vanillyl n-butyl ether, vanillyl isobutyl ether, vanillyl Examples include n-amyl ether, vanillyl isoamyl ether, vanillyl n-hexyl ether, and the like.
Among these, vanillyl methyl ether and vanillyl ethyl ether are known to exist as aroma components in the extract of vanilla bean [J.Agric.Food Chem., Vol.26.No.1, p. 195 (1978)], but no literature has yet been found suggesting that this product can be used as a toothpaste refreshing agent.
In addition, the compound in which R in the above general formula () is a C3-6 alkyl group was patented by the present inventors in 1982 Patent Application No. 82530 (see Japanese Patent Application Laid-Open No. 57-9729). This is a new compound for which we have applied. The vanillyl alcohol derivative used in the present invention can be obtained by a known method, for example, a method in which alcohols are reacted with concentrated hydrochloric acid to form chloride, and this is reacted with sodium alcoholate in alcohol ("Fragrance", No. 113, p. 65). , published in December 1975), or a method of reacting alcohol with alcohol using an ion exchange resin as a catalyst [J.Org.Chem.
Vol. 27.2662 (1962)], or by a more industrial method than the above-mentioned method discovered by the present inventors. That is, approximately 5% by weight of concentrated hydrochloric acid is mixed with an alkyl alcohol corresponding to the alkyl group constituting the desired alkyl ether compound, heated to approximately 70°C, and vanillyl alcohol is gradually added to the mixture. Approximately 70℃ after adding
to react sufficiently. At this time, it is preferable to use the alkyl alcohol in an amount that also serves as a solvent, that is, in a molar ratio of about 10 times that of vanillyl alcohol. After the reaction is completed, the hydrochloric acid is neutralized with an aqueous alkaline solution, followed by solvent extraction, drying, and distillation in a conventional manner to obtain the desired product. Also, when using n-propyl alcohol, which has a relatively high solubility in water,
Mix vanillin with equimolar amounts of 5-10% aqueous caustic soda and n-propyl alcohol, and add about twice the calculated amount of sodium borohydride.
It is preferable to use n-propyl alcohol in an amount that can also be used as a solvent, that is, in a molar ratio of about 20 times that of vanillin. This mixture should be heated at approximately 35°C.
Allow to react for 3 to 5 hours. Here, the boron compound of vanillyl alcohol is formed. Next, the reaction solution is made acidic using concentrated hydrochloric acid at room temperature, and then heated to complete the etherification reaction at about 70°C. After the reaction is completed, the hydrochloric acid is neutralized with an aqueous alkali solution, followed by solvent extraction, drying, and distillation to obtain vanillyl n-propyl ether. As mentioned above, the vanillyl alcohol derivative obtained in this way has a pungent taste, and the refreshing feeling when it is blended into a toothpaste material is roughly proportional to the strength of this pungent taste. The intensity of pungency of vanillyl alcohol derivatives differs depending on the type of substituent as follows.
That is, prepare a 1% ethyl alcohol solution for each test substance, weigh out 1 g, dilute it with 100 ml of distilled water, taste the solution, and choose the one with the strongest spiciness. 0 things that aren't there
Table 1 shows the results of the evaluation on a scale of 0 to 5.
【表】
ワニリル ｎ−ブチルエーテルが最も強く、ワ
ニリル メチルエーテルが最も弱い。ワニリル
メチルエーテルの場合、濃度を２倍にすれば上の
試験のワニリル エチルエーテルに相当する程度
の辛味性を有している。さらに、トウガラシの辛
味成分として著名なカプサイシンの１％エチルア
ルコール溶液１ｇを秤取し、これを100ml蒸留水
で希釈して基準溶液とし、この基準溶液を蒸留水
で希釈してゆき、被検溶液と同じ辛味を呈する希
釈度を測定して調べたところ、ワニリル ｎ−ブ
チルエーテルはカプサイシンの約1/20の辛味を示
した。
本発明において、ワニリルアルコール誘導体
は、その辛味性の強さに応じて歯磨組成物中に配
合する量が選定される。普通は歯磨組成物に対し
１〜20ppm、好ましくは２〜15ppmが用いられ
る。本発明の歯磨組成物は煉歯磨、潤製歯磨、粉
歯磨、水歯磨等のいずれ製品形態にも構成するこ
とが出来る。また、通常一般に用いられる歯磨素
材と、本発明に使用するワニリルアルコール誘導
体は製造上何ら支障なく配合出来る。すなわち一
般的に使用されている不溶性メタリン酸ソーダ、
軽質炭酸カルシウム、重質炭酸カルシウム、第二
リン酸カルシウム等の清掃研磨剤、サツカリン等
の甘味剤、グリセリン等の湿潤剤、ソジウム、カ
ルボキシメチルセルロース等の粘稠剤、ソジウ
ム、ラウリル、サルフエート等の起泡剤、薬効
剤、香料、着色料等と配合しても、それらの性質
及び使用目的に何らの影響もあたえない。また、
従来から使用されているメントールと併用すると
きは、清涼感を増大または増強せしめることがで
きるか、あるいはその使用量を低減させることが
できる。
叙上の如く、本発明の歯磨組成物は、従来の歯
磨にくらべてメントールの使用量を多くすること
なく、清涼感を著しく増大せしめ、口腔内に爽快
な感触とさわやかさをあたえることのできる極め
て優れたものである。
次に試験例及び実施例を挙げて説明する。
試験例（清涼感の官能試験）
次に示す実施例１の歯磨組成物(A)と、実施例１
からワニリル ｎ−ブチルエーテルを除いた歯磨
組成物(B)を比較した。
(i) 試験方法
パネルの口中を洗浄した後、パネルを２組に
わけ、１組は先づ歯磨(A)を使用した後、口中を
洗浄し、次に歯磨(B)を使用してその清涼感を比
較した。他の組は先づ歯磨(B)を使用した後、口
中を洗浄し、次に歯磨(A)を使用して清涼感を比
較した。
(ii) 試験結果
パネル数 40名
「(A)の方が清涼感が強い」とした者 23名
「(A)の方が清涼感が弱い」とした者 ９名
「どちらとも云えない」とした者 ８名
この結果、２点比較法でカイニ乗検定におい
て５％の危険率をもち有意差を認めた。
実施例 １
練歯磨
（重量％）
第二リン酸カルシウム 50
ソジウムカルボキシメチルセルローズ １
ソジウムラウリルサルフエート 1.5
グリセリン 25
サツカリン 0.15
薬効剤 適量
「ツース ペースト フレーバー Ｘ−9135」（高
砂香料工業株式会社製香料） 0.8
メントール 0.2
ワニリル ｎ−ブチルエーテル（エチルアルコー
ル１％溶液） 0.06
水 適量
100
実施例 ２
練歯磨
（重量％）
第二燐酸カルシウム 50
アイリツシユ モス 1.1
ソジウムラウリルサルフエート 1.5
グリセリン 25
サツカリン 0.2
薬効剤 適量
「ツース ペースト フレーバー Ｘ−9135」（高
砂香料工業株式会社製香料） 0.8
メントール 0.2
ワニリル ｎ−ブチルエーテル（エチルアルコー
ル１％溶液） 0.03
水 適量
100
実施例 ３
練歯磨
（重量％）
重質炭酸カルシウム 33
軽質炭酸カルシウム 22
ソジウムカルボキシメチルセルローズ １
ソジウムラウリルサルフエート 1.4
グリセリン 25
サツカリン 0.15
薬効剤 適量
「ツース ペースト フレーバー Ｘ−9135」（高
砂香料工業株式会社製香料） 0.8
メントール 0.2
ワニリル ｎ−ブチルエーテル（エチルアルコー
ル１％溶液） 0.03
ワニリル ｎ−エチルエーテル（エチルアルコー
ル１％溶液） 0.04
ワニリル ｎ−メチルエーテル（エチルアルコー
ル１％溶液） 0.05
水 適量
100
実施例 ４
潤製歯磨
（重量％）
第二リン酸カルシウム 50
炭酸カルシウム 30
グリセリン ９
ソジウムラウリルサルフエート 1.4
サツカリン 0.1
薬効剤 適量
「ツース ペースト フレーバー Ｘ−9135」（高
砂香料工業株式会社製香料） 0.8
メントール 0.2
ワニリル ｎ−ブチルエーテル（エチルアルコー
ル１％溶液） 0.03
ワニリル ｎ−ヘキシルエーテル（エチルアルコ
ール１％溶液） 0.01
水 適量
100
実施例 ５
粉歯磨
（重量％）
軽質炭酸カルシウム 49
重質炭酸カルシウム 33
グリセリン ５
ソジウムラウリルサルフエート １
サツカリン 0.15
薬効剤 適量
「ツース ペースト フレーバー Ｘ−9135」（高
砂香料工業株式会社製香料） 0.8
メントール 0.2
ワニリル ｎ−ブチルエーテル（エチルアルコー
ル１％溶液） 0.02
ワニリル ｎ−アミルエーテル（エチルアルコー
ル１％溶液） 0.02
水 適量
100[Table] Vanillyl n-butyl ether is the strongest, and vanillyl methyl ether is the weakest. Wanirill
In the case of methyl ether, if the concentration is doubled, it has a pungency equivalent to that of vanillyl ethyl ether in the above test. Furthermore, we weighed out 1 g of a 1% ethyl alcohol solution of capsaicin, which is well-known as the pungent component of chili peppers, diluted it with 100 ml of distilled water to obtain a standard solution, diluted this standard solution with distilled water, and then added the test solution. When the dilution level at which the same pungent taste was measured was determined, vanillyl n-butyl ether had a spiciness about 1/20 that of capsaicin. In the present invention, the amount of the vanillyl alcohol derivative to be blended into the dentifrice composition is selected depending on the strength of its pungent taste. Usually 1 to 20 ppm, preferably 2 to 15 ppm of the dentifrice composition is used. The dentifrice composition of the present invention can be formed into any product form such as dentifrice, moisturized dentifrice, powdered dentifrice, and water dentifrice. Furthermore, the commonly used toothpaste materials and the vanillyl alcohol derivative used in the present invention can be blended without any problems in production. i.e. the commonly used insoluble sodium metaphosphate,
Cleaning abrasives such as light calcium carbonate, heavy calcium carbonate, and dicalcium phosphate, sweeteners such as saccharin, wetting agents such as glycerin, thickening agents such as sodium, carboxymethylcellulose, and foaming agents such as sodium, lauryl, and sulfate. Even if it is mixed with medicinal agents, fragrances, coloring agents, etc., there will be no effect on their properties or intended use. Also,
When used in combination with conventionally used menthol, the cooling sensation can be increased or enhanced, or the amount used can be reduced. As mentioned above, the dentifrice composition of the present invention is an extremely effective toothpaste that can significantly increase the cooling sensation and give a refreshing feel and freshness to the oral cavity without using a large amount of menthol compared to conventional dentifrices. It is excellent. Next, a description will be given with reference to test examples and examples. Test Example (Sensory Test of Cool Feeling) The toothpaste composition (A) of Example 1 shown below and Example 1
A dentifrice composition (B) obtained by removing vanillyl n-butyl ether was compared. (i) Test method After washing the inside of the mouth of the panel, the panel was divided into two groups, and one group first used toothpaste (A), then washed the inside of the mouth, and then used toothpaste (B). We compared the coolness. The other group first used toothpaste (B), then washed their mouths, and then used toothpaste (A) to compare the refreshing sensation. (ii) Number of test results panels 40 people said ``(A) has a stronger refreshing feeling'' 23 people said ``(A) has a weaker refreshing feeling'' 9 people said ``I can't say either way'' As a result, a significant difference was found in the chi-square test using the two-point comparison method with a risk rate of 5%. Example 1 Toothpaste (% by weight) Dicalcium phosphate 50 Sodium carboxymethyl cellulose 1 Sodium lauryl sulfate 1.5 Glycerin 25 Saccharin 0.15 Medicinal agent Appropriate amount "Tooth Paste Flavor X-9135" (Flavor manufactured by Takasago International Co., Ltd.) 0.8 Menthol 0.2 Vanillyl n-butyl ether (1% ethyl alcohol solution) 0.06 Water appropriate amount 100 Example 2 Toothpaste (weight%) Dicalcium phosphate 50 Eyelid moss 1.1 Sodium lauryl sulfate 1.5 Glycerin 25 Satucalin 0.2 Medicinal agent Appropriate amount Tooth paste Flavor Sodium carboxymethyl cellulose 1 Sodium lauryl sulfate 1.4 Glycerin 25 Saccharin 0.15 Medicinal agent Appropriate amount "Tooth Paste Flavor 0.03 Vanillyl n-ethyl ether (1% ethyl alcohol solution) 0.04 Vanillyl n-methyl ether (1% ethyl alcohol solution) 0.05 Appropriate amount of water 100 Example 4 Junsei toothpaste (% by weight) Dibasic calcium phosphate 50 Calcium carbonate 30 Glycerin 9 Dium lauryl sulfate 1.4 Satucalin 0.1 Medicinal agent Appropriate amount "Tooth Paste Flavor 1% solution) 0.01 Water appropriate amount 100 Example 5 Powdered toothpaste (wt%) Light calcium carbonate 49 Heavy calcium carbonate 33 Glycerin 5 Sodium lauryl sulfate 1 Satucalin 0.15 Medicinal agent Appropriate amount "Tooth Paste Flavor X-9135" (Takasago Fragrance Fragrance manufactured by Kogyo Co., Ltd.) 0.8 Menthol 0.2 Vanillyl n-butyl ether (1% ethyl alcohol solution) 0.02 Vanillyl n-amyl ether (1% ethyl alcohol solution) 0.02 Water appropriate amount 100
Claims (1)
示す）で表わされるワニリルアルコール誘導体の
１種または２種以上を配合したことを特徴とする
歯磨組成物。[Claims] 1. The toothpaste material has the following general formula () A dentifrice composition comprising one or more vanillyl alcohol derivatives represented by the formula (wherein R represents an alkyl group having 1 to 6 carbon atoms).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15914080A JPS5782308A (en) | 1980-11-12 | 1980-11-12 | Tooth paste composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15914080A JPS5782308A (en) | 1980-11-12 | 1980-11-12 | Tooth paste composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5782308A JPS5782308A (en) | 1982-05-22 |
| JPS6155889B2 true JPS6155889B2 (en) | 1986-11-29 |
Family
ID=15687119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15914080A Granted JPS5782308A (en) | 1980-11-12 | 1980-11-12 | Tooth paste composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5782308A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005004635A1 (en) | 2003-07-10 | 2005-01-20 | Takasago International Corporation | Flavor enhancer, food or beverage containing the flavor enhancer, and method of flavor enhancement |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4657700A (en) * | 1983-10-07 | 1987-04-14 | Givaudan Corporation | Fragrance compositions containing benzyl ethers |
| JP2692101B2 (en) * | 1988-02-05 | 1997-12-17 | ライオン株式会社 | Oral composition |
| FR2721508B1 (en) * | 1994-06-24 | 1996-08-09 | Rhone Poulenc Chimie | Process for obtaining perfume compositions and perfumed products and products thus obtained. |
| US6042812A (en) * | 1996-11-26 | 2000-03-28 | The Procter & Gamble Company | Flavor systems for oral care products |
| JP4017758B2 (en) * | 1998-08-04 | 2007-12-05 | 高砂香料工業株式会社 | Cooling agent composition |
| JP4675457B2 (en) * | 2000-06-20 | 2011-04-20 | 高砂香料工業株式会社 | Cyclodextrin inclusion compound of vanillyl alcohol derivative and composition containing the same |
| JP2002114649A (en) * | 2000-10-10 | 2002-04-16 | Takasago Internatl Corp | Composition for improving cool feeling effect |
| JP4996834B2 (en) | 2005-07-06 | 2012-08-08 | 高砂香料工業株式会社 | Vanillin acetals and sensory stimulant compositions containing the same |
| US8962057B2 (en) | 2009-04-29 | 2015-02-24 | The Procter & Gamble Company | Methods for improving taste and oral care compositions with improved taste |
-
1980
- 1980-11-12 JP JP15914080A patent/JPS5782308A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005004635A1 (en) | 2003-07-10 | 2005-01-20 | Takasago International Corporation | Flavor enhancer, food or beverage containing the flavor enhancer, and method of flavor enhancement |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5782308A (en) | 1982-05-22 |
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