JP2014209868A - Composition for enhancing cool feeling - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly effective and safe composition for enhancing cool feeling, and foods, medicines, perfumery, and flavoring compositions which contain the composition for enhancing cool feeling.SOLUTION: The composition for enhancing cool feeling includes one or a plurality of specific isothiocyanate compounds selected from the group consisting of an ω-alkenyl isothiocyanate compound, an ω-alkylthioalkyl isothiocyanate compound, an ω-alkylsulfonyl alkyl isothiocyanate compound, an ω-phenylalkyl isothiocyanate compound, and an alkyl isothiocyanate compound, as active ingredients. The foods, medicines, perfumery, and flavoring compositions contain the composition for enhancing cool feeling. The composition for enhancing cool feeling is useful for enhancing the cool feeling or refreshing effect of a cool sensation imparting material such as menthol and isopulegol.

Description

  The present invention relates to a cooling sensation enhancing composition containing an isothiocyanate compound as an active ingredient. Moreover, it is related with the food / beverage products, the flavor composition, the pharmaceutical, and the cosmetics containing the said cool feeling enhancement composition.

  So-called cold sensation materials that provide a refreshing sensation in the oral cavity, nose, throat, skin, and the like are used in various products such as foods, cosmetics, and haptics. Compounds such as menthol and isopulegol are also frequently used as compounds that give a cool feeling and a refreshing feeling. Further, in order to further enhance the cooling sensation effect, methods such as synthesis of a novel cooling sensation compound and combination with other cooling sensation compounds have been employed (Patent Documents 1 to 10). However, with the diversification of people's lifestyles, various products are required, and in order to meet the demands of consumers, further cooling materials and methods for enhancing the cooling sensation are required.

  The isothiocyanate compound is a component mainly contained in cruciferous plants, and is used as a spice such as horseradish, horseradish, mustard, etc. In addition to antibacterial antifungal agents (Patent Documents 11 and 12), plaque formation inhibitors ( Patent document 13), anti-periodontal disease agent (patent document 14), allergic disease inhibitory composition (patent document 15), leukemia cell growth inhibitor (patent document 16), ulcerative colitis preventive and therapeutic agent (patent document 17) ) And its use as a nerve growth factor action enhancer (Patent Document 18) has also been reported. However, as consumers improve their lives, there are various products demanded by consumers, and further expansion of applications can be expected by finding further functions in isothiocyanate compounds.

JP-A-61-194049 JP 2000-44924 A JP 2002-114649 A JP 2004-59474 A JP 2010-254622 A Special table 2010-504100 JP 2011-79953 A JP 2012-97052 JP JP 2012-131821 JP 2012-153617 A JP 11-139949 A Japanese Patent Laid-Open No. 11-246319 JP 2005-104856 A JP 2007-308378 A JP 2009-292735 A JP 2001-163775 A JP 2009-73804 A JP 2006-16362 A

  The problem to be solved by the present invention is the provision of a cooling sensation enhancing composition that improves the cooling sensation of the cooling sensation material, the sustainability and strength of the cooling sensation, and a food and drink containing the cooling sensation enhancing composition It is to provide pharmaceuticals, cosmetics, and flavoring compositions.

  As a result of intensive studies to achieve the above object, the present inventors have found that a specific isothiocyanate compound has an excellent cooling effect, and have completed the present invention.

（式中、ｑは１〜１０の整数を表し、Ｒ_３は水素あるいは水酸基を表す）
式〔５〕： Ｒ_４−ＮＣＳ
（式中、Ｒ_４は炭素数が１〜１０の直鎖又は分岐のアルキル基を表す）
（２）冷感物質及び上記の冷涼感増強組成物を含有することを特徴とする冷感物質含有組成物。
（３）上記の冷涼感増強組成物又は冷感物質含有組成物を含有することを特徴とする飲食品、香味料組成物、医薬品、又は香粧品。 That is, the present invention is as follows.
(1) ω-alkenyl isothiocyanate compound represented by the following formula [1], ω-alkylthioalkyl isothiocyanate compound represented by the following formula [2], and ω-alkyl represented by the following formula [3] One selected from the group consisting of a sulfonylalkyl isothiocyanate compound, an ω-phenylalkyl isothiocyanate compound represented by the following formula [4], and an alkyl isothiocyanate compound represented by the following formula [5] or A cooling sensation enhancing composition comprising two or more isothiocyanate compounds.
Equation _{(1): CH 2 = CH- (CH 2} ) m -NCS
(In the formula, m represents an integer of 1 to 10)
Equation _{(2): R 1 -S- (CH 2)} n -NCS
(In the formula, n represents an integer of 1 to 10, and R ₁ represents a linear or branched alkyl group having 1 to 4 carbon atoms)
The formula _{(3): R 2 -SO 2 - (CH} 2) p -NCS
(Wherein p represents an integer of 1 to 10 and R ₂ represents a linear or branched alkyl group having 1 to 4 carbon atoms)
Formula [4]:

(Wherein q represents an integer of 1 to 10, and R ₃ represents hydrogen or a hydroxyl group)
Formula [5]: R ₄ -NCS
(Wherein R ₄ represents a linear or branched alkyl group having 1 to 10 carbon atoms)
(2) A cooling sensation substance-containing composition comprising a cooling sensation substance and the cooling sensation enhancing composition described above.
(3) A food / beverage product, a flavoring composition, a pharmaceutical product, or a cosmetic product containing the cooling sensation enhancing composition or the cooling sensation substance-containing composition.

Preferable specific examples of the compound represented by the above formula [1] include allyl isothiocyanate, 3-butenyl isothiocyanate, 4-pentenyl isothiocyanate, 5-hexenyl isothiocyanate, and 6-heptenyl isothiocyanate. Narto etc. are mentioned. In the above formula [1], m is more preferably 2-5.
Preferable specific examples of the compound represented by the above formula [2] include methylthiomethyl isothiocyanate, ethylthiomethyl isothiocyanate, n-propylthiomethyl isothiocyanate, isopropylthiomethyl isothiocyanate, n-butylthio. Methyl isothiocyanate, isobutyl thiomethyl isothiocyanate, sec-butyl thiomethyl isothiocyanate, 2-methyl thioethyl isothiocyanate, 2-ethyl thioethyl isothiocyanate, 2-n-propyl thioethyl isothiocyanate, 3 -Methylthiopropyl isothiocyanate, 4-methylthiobutyl isothiocyanate, 5-methylthiopentyl isothiocyanate, 6-methylthiohexyl isothiocyanate, 7-methylthioheptyl isothiocyanate, 8 Methylthio octyl isothiocyanate, etc. 9-methyl-thio-nonyl isothiocyanate and the like. In the above formula [2], n is more preferably 4-7.
Preferable specific examples of the compound represented by the above formula [3] include 3-methylsulfonylpropyl isothiocyanate, 4-methylsulfonylbutyl isothiocyanate, 5-methylsulfonylpentyl isothiocyanate, 6-methylsulfonylhexyl isothiocyanate. Examples include isocyanate, 7-methylsulfonyl heptyl isothiocyanate, 8-methylsulfonyl octyl isothiocyanate, 9-methylsulfonyl nonyl isothiocyanate, and the like. In the above formula [3], p is more preferably 4-7.
Preferable specific examples of the compound represented by the formula [4] include benzyl isothiocyanate, phenethyl isothiocyanate, p-hydroxybenzyl isothiocyanate and the like. Among the compounds represented by the above formula [4], more preferred are q = 1 and R ₃ = hydroxyl compounds or q = 2-4 compounds.
Preferable specific examples of the compound represented by the above formula [5] include n-propyl isothiocyanate, isopropyl isothiocyanate, n-butyl isothiocyanate, sec-butyl isothiocyanate, isobutyl isothiocyanate, n- Examples thereof include pentyl isothiocyanate and isopentyl isothiocyanate. Among the compounds represented by the formula [5], isopropyl isothiocyanate, sec-butyl isothiocyanate, and isobutyl isothiocyanate are more preferable.

  By ingesting a combination of a cooling sensation substance and a cooling sensation enhancing composition comprising the isothiocyanate compound of the present invention as an active ingredient, for example, the sensation stimulating effect such as the enhancement of the cooling sensation or cooling effect of the sensation substance or the sustain There is expected. As a result, effects such as arousal sensation, drowsiness prevention, concentration enhancement, and refreshing feeling are brought about, and therefore, application to new foods and drinks, flavoring compositions, pharmaceuticals, cosmetics and the like is expected.

  In addition, many isothiocyanate compounds are contained in plants such as wasabi, horseradish, mustard, etc., and the isothiocyanate compounds of the present invention have abundant dietary experience and can be taken with peace of mind.

（式中、ｍ、Ｒ_３及びｑは前述したものと同一意義を有し、Ｘは臭素、塩素、ヨウ素のようなハロゲン原子を示す）
を有するω−アルケニルハライド又はω−フェニルアルキルハライドをチオシアン酸塩と反応させ、得られたω−アルケニルチオシアナート又はω−フェニルアルキルイソチオシアナート化合物を極性非プロトン溶媒中で異性化することにより得られる。
本発明で用いるω−アルキルチオアルキルイソチオシアナート化合物は、例えば特開平７−２１５９３１公報に従って、式〔１〕
式〔１〕： ＣＨ_２＝ＣＨ−(ＣＨ_２)_ｍ−ＮＣＳ
（式中、ｍは前述したものと同一意義を有し、１〜１０の整数を表す）
を有するω−アルケニルイソチオシアナート化合物にメチルメルカプタン等のアルキルメルカプタンを付加させることにより得られる。
本発明で用いるω−アルキルスルフォニルアルキルイソチオシアナート化合物は、例えば特開平７−２４７４９７公報記載の方法を改変し、式〔２〕
式〔２〕： Ｒ_１−Ｓ−(ＣＨ_２)_ｎ−ＮＣＳ
（式中、Ｒ_１及びｎは前述したものと同一意義を表す）
を有するω−アルキルチオアルキルイソチオシアナート化合物をｍ−クロロ過安息香酸で酸化することにより得られる。
本発明で用いるアルキルイソチオシアナート化合物としては、例えば市販品（東京化成(株)（東京）製の試薬）を使用できる。 (1) Isothiocyanate compound The ω-alkenyl isothiocyanate compound or the ω-phenylalkyl isothiocyanate compound used in the present invention is, for example, a compound represented by the formula [5] or [6] in an inert solvent according to Japanese Patent Publication No. 2-221255. ]
_{CH 2 = CH- (CH 2)} m -X (5)

(Wherein m, R ₃ and q have the same meaning as described above, and X represents a halogen atom such as bromine, chlorine or iodine)
By reacting a ω-alkenyl halide or ω-phenylalkyl halide having thiocyanate with thiocyanate and isomerizing the resulting ω-alkenyl thiocyanate or ω-phenylalkyl isothiocyanate compound in a polar aprotic solvent. can get.
The ω-alkylthioalkyl isothiocyanate compound used in the present invention is represented by the formula [1] according to, for example, JP-A-7-215931.
Equation _{(1): CH 2 = CH- (CH 2} ) m -NCS
(In the formula, m has the same meaning as described above and represents an integer of 1 to 10).
It is obtained by adding an alkyl mercaptan such as methyl mercaptan to an ω-alkenyl isothiocyanate compound having the following formula.
The ω-alkylsulfonylalkyl isothiocyanate compound used in the present invention is modified by, for example, a method described in JP-A-7-247497, wherein the formula [2]
Equation _{(2): R 1 -S- (CH 2)} n -NCS
(Wherein R ₁ and n represent the same meaning as described above)
It can be obtained by oxidizing an ω-alkylthioalkylisothiocyanate compound having the following formula with m-chloroperbenzoic acid.
As the alkyl isothiocyanate compound used in the present invention, for example, a commercially available product (a reagent manufactured by Tokyo Chemical Industry Co., Ltd. (Tokyo)) can be used.

(2) Cooling sensation enhancing composition When the cooling sensation enhancing composition of the present invention is used to enhance the cooling sensation or cooling sensation effect of the cooling sensation substance, the blending ratio of the isothiocyanate compound and the sensation sensation substance such as menthol is Although it is not particularly limited, it is generally used in combination within a range of 1 to 1 / 10,000 parts by mass of an isothiocyanate compound, particularly 1/10 to 1/1000 parts by mass with respect to 1 part by mass of a cooling sensation substance such as menthol. Is preferred. The cooling sensation enhancing composition of the present invention can be mixed with a cooling sensation substance and used as a form of a cooling sensation substance-containing composition.
Examples of the cooling sensation substance include menthol, menthyl acetate, menthone, isomenton, sabinene hydrate, isopulegol, piperitol, p-menthane-3-carboxylic acid amide, p-menthanediol, menthylglucoside, menthyl-2-pyrrolidone- 5-carboxylate, menthylketoalkanoate, menthyl N-acetylglycine, menthylhydroxyalkanoate, 2-mentoxytetrahydropyran, 2-mentoxytetrahydrofuran, menthoxypropane-1,2-diol, menthyl-3- Selected from the group consisting of hydroxybutyrate, 1-alkoxy-3-mentoxypropan-2-ol, menthone ketals, 3-hydroxymethyl-p-menthane alkanoate and 2-hydroxymethylmenthol One or more that are mentioned. As the cooling sensation substance, a cooling sensation substance that activates TRPM8 which is a cooling stimulus receptor channel is preferable.

(3) Optional components to be added to the composition The cooling sensation enhancing composition of the present invention contains other optional components usually used for foods and drinks, for flavoring compositions, for cosmetics or for pharmaceuticals. May be.
Examples of optional components used include flavoring agents, sweeteners, coloring agents, preservatives, thickening stabilizers, antioxidants, bittering agents, acidulants, emulsifiers, reinforcing agents, manufacturing agents, excipients, and disintegrating agents. , Binders, lubricants, coating agents, plasticizers, preservatives, surfactants, fragrances, and the like, which can be used as various preparations and dosage forms.

(4) Formulation of the composition The cooling sensation enhancing composition of the present invention can be formulated and used in various forms such as an intact state, a diluted state, an emulsified state, and a powdered state.

(5) Flavoring composition A novel and unique flavoring composition can be prepared by appropriately adding various existing flavorings to the cooling sensation enhancing composition of the present invention.
Examples of the existing flavoring agents to be added include ethyl acetoacetate, acetophenone, anisaldehyde, α-amylcinnam aldehyde, methyl anthranilate, ionone, isoeugenol, isoamyl isovalerate, ethyl isovalerate,

Indole and its derivatives, γ-undecalactone, esters, ethyl vanillin, ethers, eugenol, octanol, octanal, ethyl octoate, isoamyl formate, geranyl formate, citronellyl formate, cinnamic acid, ethyl cinnamate, cinnamic Methyl acetate, ketones, geraniol, isoamyl acetate, ethyl acetate, geranyl acetate, cyclohexyl acetate, citronellyl acetate, cinnamyl acetate, terpinyl acetate, phenethyl acetate, butyl acetate, benzyl acetate,

Linalyl acetate, allyl cyclohexylpropionate, citral, citronellal, citronellol, 1,8-cineole, fatty acids, higher aliphatic alcohols, higher aliphatic aldehydes, higher aliphatic hydrocarbons, cinnamyl alcohol, cinnamaldehyde, thioether , Thiols, decanal, decanol, ethyl decanoate, terpineol, limonene, pinene, myrcene, tapinolen, terpene hydrocarbons, γ-nonalactone, vanillin, paramethylacetophenone, hydroxycitronellal, hydroxycitronellal dimethyl acetal , Piperonal, isoamyl phenylacetate, isobutyl phenylacetate, ethyl phenylacetate,

Phenol ethers, phenols, furfural and derivatives thereof, propionic acid, isoamyl propionate, ethyl propionate, benzyl propionate, hexanoic acid, allyl hexanoate, ethyl hexanoate, ethyl heptanoate, l-perilaldehyde, benzyl alcohol, Benzaldehyde, aromatic alcohols, aromatic aldehydes, d-borneol, maltol, methyl N-methylanthranylate, methyl β-naphthyl ketone, butyric acid, isoamyl butyrate, ethyl butyrate, cyclohexyl butyrate, butyl butyrate, lactones, linalool, etc. Citrus essential oils such as orange, lemon, lime, grapefruit, apple, banana, grape, melon, peach, pineapple, strawberry, etc. Essential oils or recovered flavor of the system,

Milk-based extract flavors such as milk, cream, butter, cheese, yogurt, green tea, oolong tea, tea, coffee, cocoa, etc.Recovery flavor, asanomi, asafetida, ajowan, anise, angelica, fennel, turmeric, oregano, allspice , Orange nope, pepper, cassia, chamomile, mustard, cardamom, curry leaf, licorice, caraway, gardenia, cumin, watercress, clove, poppy flea, caper, pepper, sesame, coriander, sassafras, saffron, savory, salvia, sun show,

Cinnamon, shallot, juniper berry, ginger, star anise, horseradish, celery, sorrel, thyme, onion, tamarind, tarragon, chives, dill, pepper, nutmeg, sagebrush, nigera, carrot, garlic, basil, parsley, vanilla, paprika , Hyssop, Fenegreek, Horseradish, Marjoram, Myoga, Lavender, Linden, Lemongrass, Lemon Balm, Rose, Rosemary, Laurel, Wasabi, etc.

Asafetida, Asian Tam, Ajowan, Azuki, Asparagus Linea Alice, Apple Mint, Artichoke, Anise, Avocado, Achacha, Amazazuru, Amiga Sayuri, Amiris, Almond, Aritasou, Alcanna, Artemisia, Arnica, Alfalfa, Aloe, Angoslaan , Chanterelles, angelica, amber, ambergris, amblet, squid, licorice, rush, yeast, itadori, strawberries, figs, ginkgo, mushrooms, ylang ylang, sardine, impeller tria, immortel, winter green, watercress, sea cucumber, turmeric , Usbasaishin, Woodruff, Sea Urchin, Ume, Oolongcha, Egoma, Enokidake, Shrimp, Shrimp, Eligeron, Elda , Eleutherococcus, Erekanpen, elemi, Corydalis, Sophora, endive, Europe thistle, Coptis,

Psyllium, casserole, krill, oak, oak moss, okera, osmanthus, opoponax, omienae, omodaka, holland sennici, origanum, oris, olibanum, olive, allspice, orange, orange flower, kai, kaininso, cacao, oyster, kasai, Cashew nut, Cascara, Cascarilla, Castrium, Katakuri, Cutlet obsi, Cassie, Cassia fistula, catechu, crab, carnation, valerian, camomil,

Kayapute, mustard, crow uri, crow birch, guarana, calamus, galanga, currant, carissa, karin, cardamom, galvanum, curry, kawamidori, licorice, ganbia, kanran, kiwifruit, kikaigaratake, kyoto, chrysanthemum, chrysanthemum, scallop , Kina, Yellowfin, Hosta, Gymnema Sylvestre, Catnip, Caraway, Carop, Cucumber, Kiraya, Kinkihizuki, Guava, Guayak, Kuko, Kusasagi Kazura, Kuboke, Kuzu, Kusunoki, Kusunohagasiwa, Gooseberry,

Gardenia, Kubeba, Bearberry, Gummy, Cumin, Ground Ivy, Clara, Clarisage, Cranberry, Chestnut, Walnut, Cream, Grain of Paradise, Cretadi Tanny, Grapefruit, Clover, Clove, Black Moji, Chlorella, Mulberry, Quasher, Caper, Ghetto , Cade, Kebraco, Germander, Kentur, Kemponashi, Gennoshouko, Kouji, Kodatake, Koucha, Kohone, Coca, Koganebana, Kokuto, Kokului, Coconut, Goshuyu, Pepper, Costas, Costmary, Copaipa, Coffee, Kobushi, Burdock, Sesame, cola, coriander, coltsfoot, golden rod, colombo, consai, conzulango, confrey, cypress,

Fish, Sakura, Cherry, Pomegranate, Salmon Cass, Sasa, Sasakusa, Search, Sassafras, Saffron, Sapodilla, Cactus, Sarasinashouma, Salsaparilla, Salsify, Sarnosica, Hawthorn, Sanshuyu, Salamander, Santa Herb, Sandalak, Sandalwood, Sandal Red, Shiitake, Gene, Cedar, Citrus, Citronella, Cinus, Civet, Shimaruba, Shimji, Peonies, Jasmine, Janohige, Jaborangi, Shallot, Shukusha, Juniper Berry, Ginger, Shoyu, Shoyukas, Zhouryusshu, Shoro, Shirotamogi Ginseng, cinnamon, vinegar, watermelon, narcissus, cedar, star anise, star fruit, stylax, suppon, suptake bamboo, zudravets, snake crew , Spikenard, spruce,

Purslane, slow berry, savory, buffalo, sage, zedary, senega, geranium, celery, nematode, centauria, sengen, st jones wort, senna, sauce, diau, soy, thyme, bamboo shoot, octopus, tade, dabana, egg, tamagotake , Onion, tamarind, Damiana, tamogitake, tarragon, taranoki, tansy, tangerine, dandelion, cherimola, cherry laurel, cherry wild, chigaya, chicory, cheese, chichitake, chives, chervil, champaca, tuberose, datura, chillata, tsukushi, Tsukumono, ivy, camellia, camellia, crimson carrot, tsurugokudami, diatang, thistle, ditany, dill, dates,

Ladybug, Tenma, Capsicum, Toki, Dokushokutsu Protein Sat, Dokushokutsuyu, Tomitsu, Corn, Dokudami, Tochu, Doggrass, Tomato, Dragon Blood, Dorian, Truffle, Truval Sam, Tonka, Naginata Koju, Pear, Naster Siam, Nuts , Natto, jujube, nutmeg, radish, sea cucumber, larvae, niari, nuisance, garlic, garlic, rat peach, nettle, leeks, knotgrass, violet, pineapple, hibiscus, malt, pepper, basil, lotus, lotus cup, perth Cup, parsley, butter, butter oil, buttermilk, birch, honey, patchouli, buck bean, hakushu, hakkounyu, hakkoumieki, passion Roots, Hatsutake, buffalo berry, pearl barley, Anemarrhenae asphodeloides, banana, vanilla, Hanesakkuru,

Papaya, barberry, clam, hamasuge, hamanasu, hamabofu, hamamelis, rose, palmarosa, panda, van lychee, toad, cypress, pistachio, hyssop, hickory, peanuts, cypress, hiba, pipsiwa, himehagi, hyacinth, hiratake, hiratake, hirabin, hinata Feijoa, Fenegreek, Fennel, Fujibakama, Fujimodoki, Fusuma, Fuselyu, Petit Grain, Buchu, Grapes, Grape Salmon Cass, Peach, Beech, Beech Haritake, Black Caraway, Blackberry, Plum, Briononia, Prickly Ash, Primrose, Prunella, Blueberries, breadfruit,

Hay, bay, hazelnut, vetiver, betel, safflower, penny royal, snake, pepino, peptone, bergamot, bergamot mint, peruvian balsam, velvena, veronica, benzoin, boadrose, hoahound, hoe, broomtake, scallop, bowfish, whey, hoonoki , Horseradish, button, hop, poppy, poplar, poppo, jojoba, squirt, bordeaux, bologna, maitake, mawwalt, marshmallow, marjoram, mastic, masui, matabobi, machiko, pine, pine mushroom, mushroom, matsutake, matsubusa, Matsuhodo, matecha, bean, marigold, marubadao, quince, malein, mallow, mango, mangosteen, mandarin orange, mishima psycho, miso, mitsumata, beeswax, mi Door, mimosa, Zingiber mioga, milk, myrtle, Mirufoiru, myrrh, Mirobaran, barley tea, musk, purple, Mesquite, Meadow sweet, Mehajiki, maple, Melissa, MERIROTTO,

Melon, Mosengoke, Moniria Bayoueki, Mominoki, Peach, Moroheiya, Yakuchi, Yamabomo, Eucalyptus, Yukinoshita, Yuzu, Yucca, Lily, Yosai, Yorusa, Lions Foot, Lychee, Life Everlasting Flower, Lime, Lilac, Lacanka, Lacan Show, raspberry, latania, radish, lovedanum, lavender, langwald, langmoth,

Rambutan, Liqueur, Leak, Lyzea, Linaroe, Longan, Ryofunsou, Ryokucha, apple, linden, gentian, roux, borage, reseda, lemon, lemongrass, forsythia, lotus, renbu, rosemary, lobe, laurel, longosa, wasabi Natural fragrances obtained from cotton bud, wormwood, worm seed, bracken, bracken, etc. are exemplified, and are selected and used as appropriate.

(6) Food / beverage products In order to produce a food / beverage product containing the cooling sensation enhancing composition according to the present invention, the component produced by the above method or a preparation thereof can be used, and edible using conventional means. A suitable state, for example, granules, granules, tablets, capsules, soft capsules, pastes and the like can be used.
This food and drink may be used for food as it is as a spice, refreshing confectionery, and a variety of foods (for example, ham, sausage, kamaboko, chikuwa, bread, butter, powdered milk, chewing gum, biscuits, candy, etc.) Etc.) or may be used by adding to beverages such as water, alcoholic beverages, fruit juice, milk, soft drinks and the like.

(7) Pharmaceutical Product A pharmaceutical product containing the cooling sensation enhancing composition of the present invention can be produced by mixing the cooling sensation enhancing composition of the present invention with an appropriate medicinal component according to a conventional method. The medicament containing the cooling sensation enhancing composition of the present invention can be used as it is or in various dosage forms, but when used as an internal medicine, it is preferably a tablet, pill, powder, syrup, emulsion, liquid, capsule. In the case of use as an external preparation, it is preferably formulated into a cream, a poultice, a bath preparation or the like.

(8) Cosmetics Cosmetics containing the coolness enhancing composition of the present invention can be produced by blending into known cosmetics according to a conventional method.
Examples of cosmetics containing the cooling sensation enhancing composition of the present invention include cosmetic compositions and bath agent compositions, which are liquid, emulsion, basto, gel, powder (powder), respectively. It may be provided in any form such as a granular form, a pellet form, a stick form, and a solid form.

  Cosmetic compositions include lotion, milky lotion, cream, oil, ointment, pack, lip, lipstick, foundation, eyeliner, blusher, mascara, eye shadow, nail polish / pedicure, nail coating, nail coating removal Agent, shaving agent, shampoo, rinse, hair treatment, hair tonic, hair spray, hair cream, hair lotion, hair conditioner, hair restorer, permanent liquid, hair dye, hand soap / body soap, toothpaste, mouthwash And facial cleansers and soaps.

  The bath agent composition is used by bathing in bath water at the time of bathing, and the form may be any of liquid, powder, granule, solid, gel and the like.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is further demonstrated, this invention is not limited to these. The isothiocyanate compound was synthesize | combined as the following manufacture examples 1-6.

[Production Example 1] Synthesis of 4 -pentenyl isothiocyanate 32 g of 4-pentenyl iodide is dissolved in 40 g of 1,3-dimethyl-2-imidazolidinone, 16 g of potassium thiocyanate and 5.5 g of calcium carbonate are added and mixed. The liquid was heated and stirred at 75 ° C. for 1 hour.
Next, the temperature was raised to an internal temperature of 155 ° C. and stirred for 6 hours. After removing insolubles, extraction with methylene chloride yielded a crude oil. The crude oil was distilled under reduced pressure to obtain 4.2 g of 4-pentenyl isothiocyanate. The yield was 20% and the boiling point was 83 ° C./96 mmHg.

[Production Example 2] Synthesis of 3-butenyl isothiocyanate, 5-hexenyl isothiocyanate, and 6-heptenyl isothiocyanate were synthesized in the same manner as in Production Example 1.

[Production Example 3] Synthesis of 6-methylthiohexyl isothiocyanate To a mixture of 28 g of 5-hexenyl isothiocyanate and 50 g of a methanol solution of methyl mercaptan (30%), 0.4 g of t-butyl hydroperoxide (TBHP) was added, and For 2 hours. Ethyl acetate was added, washed with water, and distilled to obtain 32 g of 6-methylthiohexyl isothiocyanate. The yield was 82% and the boiling point was 119 ° C./0.5 mmHg.

[Production Example 4] Synthesis of 3-methylthiopropyl isothiocyanate, 4-methylthiobutyl isothiocyanate, 5-methylthiopentyl isothiocyanate, and 7-methylthioheptyl isothiocyanate were synthesized in the same manner as in Production Example 3.

[Production Example 5] Synthesis of 6-methylsulfonylhexyl isothiocyanate 10 g of 6-methylsulfonylhexyl isothiocyanate is dissolved in 200 g of methylene chloride and cooled to -5 ° C. Methylene chloride (340 g) of m-chlorobenzoic acid (17 g) was added dropwise and stirred for 3 hours, followed by washing with saturated aqueous sodium hydrogen carbonate and saturated brine. The methylene chloride layer was concentrated under reduced pressure and recrystallized to obtain 14 g (yield 83.5%) of 6-methylsulfonylhexyl isothiocyanate.

[Production Example 6] Synthesis of 3-methylsulfonylpropyl isothiocyanate, 4-methylsulfonylbutyl isothiocyanate, and 5-methylsulfonylpentyl isothiocyanate were synthesized in the same manner as in Production Example 5.

  ω-Phenylalkyl isothiocyanate and alkyl isothiocyanate were purchased from Tokyo Chemical Industry Co., Ltd. (Tokyo) and Sigma-Aldrich Co., Ltd. (St. Louis, USA).

<Sensory evaluation example 1>
Thirty-nine expert panels evaluated the two-point preference method. Two types of samples were prepared: a 0.001% menthol aqueous solution (no additive) and an aqueous solution (added product) obtained by adding 4-pentenyl isothiocyanate (25 ppb) to a 0.001% menthol aqueous solution. Each panel contained each aqueous solution in its mouth and the coolness was compared.

  As a result, the number of people who felt that the cool feeling was strong was 8 for the additive-free product and 31 for the additive product. As a result of statistical analysis in the two-point preference method, the additive product was significant at a risk rate of 5% compared to the additive-free product. Therefore, it was revealed that when 4-pentenyl isothiocyanate (25 ppb) was added to a 0.001% menthol aqueous solution, the cooling sensation was increased as compared to a 0.001% menthol aqueous solution.

<Sensory evaluation example 2>
Thirty-one expert panels evaluated by a 7-step scale method. Two types of samples were prepared: a 0.001% menthol aqueous solution (no additive) and an aqueous solution (added product) obtained by adding 4-pentenyl isothiocyanate (25 ppb) to a 0.001% menthol aqueous solution. Each panel contained each aqueous solution in its mouth, and the coolness was compared. The cooling feeling is divided into 1 to 7 points, and the cooling feeling of the additive-free product is 4 points, 3 points, 2 points, 1 point if weaker than the additive-free product, 5 points, 6 points if strong. , 7 points were selected.

  As a result, the additive product was 5.1 points compared to the additive-free product, and a significant difference was observed at p <0.05 as a result of Student's t-test, and the 4-pentenylisothiol was added to 0.001% menthol aqueous solution. It has been clarified that the addition of the isocyanate (25 ppb) increases the cool feeling compared to 0.001% aqueous menthol solution.

<Sensory evaluation example 3>
14 expert panels evaluated by a 7-step scale method. Two types of samples were prepared: a 0.001% menthol aqueous solution (additive-free product) and an aqueous solution (added product) obtained by adding 6-methylthiohexyl isothiocyanate (25 ppb) to a 0.001% menthol aqueous solution. Each panel contained each aqueous solution in its mouth, and the coolness was compared. The cooling feeling is divided into 1 to 7 points, and the cooling feeling of the additive-free product is 4 points, 3 points, 2 points, 1 point if weaker than the additive-free product, 5 points, 6 points if strong. , 7 points were selected.

  As a result, the additive product was 4.8 points compared to the additive-free product, and as a result of Student's t-test, a significant difference was found at p <0.05, and 6-methylthiohexyl was added to 0.001% menthol aqueous solution. It was found that the addition of isothiocyanate (25 ppb) increased the cool feeling compared to 0.001% aqueous menthol solution.

<Sensory evaluation example 4>
Twenty-one specialist panels evaluated using a seven-level scale method. The sample is a total of 0.001% menthol aqueous solution (additive-free product) and aqueous solution (additional product) obtained by adding sec-butylisothiocyanate (50ppb) (Tokyo Kasei Co., Ltd., Tokyo) to 0.001% menthol aqueous solution. Two types were produced. Each panel contained each aqueous solution in its mouth, and the coolness was compared. The cooling feeling is divided into 1 to 7 points, and the cooling feeling of the additive-free product is 4 points, 3 points, 2 points, 1 point if weaker than the additive-free product, 5 points, 6 points if strong. , 7 points were selected.

  As a result, compared with 4 additive-free products, the additive product was 4.5 points, and as a result of Student's t-test, a significant difference was recognized at p <0.05. It has been clarified that the addition of an isocyanate (50 ppb) increases the coolness compared to 0.001% aqueous menthol solution.

<Sensory evaluation example 5>
Thirty-two special panels evaluated by the 2-point preference method. Two types of samples were prepared: a 0.003% aqueous solution of isopulegol (additive-free product) and an aqueous solution (added product) obtained by adding 6-methylthiohexyl isothiocyanate (25 ppb) to a 0.003% aqueous solution of isopulegol. Each panel contained each aqueous solution in its mouth, and the coolness was compared.

  As a result, the number of people who felt that the cool feeling was strong was 7 for the additive-free product and 25 for the additive product. As a result of statistical analysis in the two-point preference method, the additive product was significant at a risk rate of 5% compared to the additive-free product. Therefore, it was revealed that when 6-methylthiohexyl isothiocyanate (25 ppb) was added to 0.003% isopulegol aqueous solution, the cooling sensation was increased compared to 0.003% isopulegol aqueous solution.

<Sensory evaluation example 6>
Twenty-one specialist panels evaluated using a seven-level scale method. Two types of samples were prepared: a 0.003% aqueous solution of isopulegol (additive-free product) and an aqueous solution (added product) obtained by adding sec-butylisothiocyanate (50 ppb) to a 0.003% aqueous solution of isopulegol. Each panel contained each aqueous solution in its mouth, and the coolness was compared. The cooling feeling is divided into 1 to 7 points, and the cooling feeling of the additive-free product is 4 points, 3 points, 2 points, 1 point if weaker than the additive-free product, 5 points, 6 points if strong. , 7 points were selected.

  As a result, the additive product was 4.7 points compared to the additive-free product, and as a result of Student's t-test, a significant difference was found at p <0.05, and the 0.003% isopulegol aqueous solution was added to the sec-butylisothiol aqueous solution. It was found that the addition of isocyanate (50 ppb) increased the cool feeling compared to 0.003% aqueous isopulegol solution.

[Example 1] (plate gum)
Gum base, sugar, glucose and corn syrup are mixed and added to 0.5% by weight of menthol and 0.0001% by weight of 4-pentenyl isothiocyanate, and about 50 using a high shear mixer according to a conventional method. The mixture was mixed at 0 ° C., cooled, and compression-molded with a roller to prepare a plate gum.

[Example 2] (Candy)
Bx. 70 maltitol syrup was cooked to 185 ° C., rapidly cooled to 155 ° C., added with menthol and 6-methylthiohexyl isothiocyanate, homogenized and molded to prepare the candy of the present invention. Menthol was added at 0.5% by mass when finished, and 6-methylthiohexyl isothiocyanate was added at 0.0001% by mass when finished.

[Example 3] (Biscuits)
100 g of strong powder, 100 g of shortening, 40 g of white sucrose, 30 g of weak flour, 20 g of water, 4 g of whole milk powder, and 0.6 g of baking soda were mixed, molded and baked to obtain biscuits. Menthol was added before molding so that the final amount was 0.5% by mass, and 5-methylthiopentyl isothiocyanate was 0.0001% by mass when finished.

[Example 4] (Tablet confectionery)
30 parts by weight of gum arabic and 50 parts by weight of DE10 dextrin are heated and dissolved in 150 parts by weight of water, and after cooling, added to 20 parts by weight of menthol and 0.0001% by weight of 5-hexenyl isothiocyanate, emulsified, The menthol powder flavor of the present invention was prepared by spray drying with a spray dryer. A menthol tablet was prepared by adding 1.0% by mass of sucrose fatty acid ester as a lubricant and the menthol powder flavor to sorbitol, and tableting at 1 t of tableting pressure.

[Example 5] (Patching agent)
According to Formulation Example 1, a patch containing 0.0002% by mass of 4-pentenyl isothiocyanate was prepared.

[Example 6] (Body soap)
According to Formulation Example 2, 0.0001% by mass of 3-butenyl isothiocyanate was blended to prepare a body soap of the present invention.

  The cooling sensation enhancing composition of the present invention can be used for enhancing the effect of cooling sensation and cooling sensation of, for example, foods and drinks, pharmaceuticals, cosmetics, and flavoring compositions.

Claims (10)

Ω-alkenyl isothiocyanate compound represented by the following formula [1], ω-alkylthioalkyl isothiocyanate compound represented by the following formula [2], ω-alkylsulfonylalkyl isothiocyanate represented by the following formula [3] One or more selected from the group consisting of an isocyanate compound, an ω-phenylalkyl isothiocyanate compound represented by the following formula [4], and an alkyl isothiocyanate compound represented by the following formula [5] A cooling sensation enhancing composition comprising the following isothiocyanate compound.
Equation _{(1): CH 2 = CH- (CH 2} ) m -NCS
(In the formula, m represents an integer of 1 to 10)
Equation _{(2): R 1 S- (CH 2)} n -NCS
(In the formula, n represents an integer of 1 to 10, and R ₁ represents a linear or branched alkyl group having 1 to 4 carbon atoms)
The formula _{(3): R 2 -SO 2 - (CH} 2) p -NCS
(Wherein p represents an integer of 1 to 10 and R ₂ represents a linear or branched alkyl group having 1 to 4 carbon atoms)
Formula [4]:

(In the formula, q represents an integer of 1 to 10, and R ₃ represents hydrogen or a hydroxyl group)
Formula [5]: R ₄ -NCS
(Wherein R ₄ represents a linear or branched alkyl group having 1 to 10 carbon atoms)   Allyl isothiocyanate, 3-butenyl isothiocyanate, 4-pentenyl isothiocyanate, 5-hexenyl isothiocyanate, 6-heptenyl isothiocyanate, methyl thiomethyl isothiocyanate, ethyl thiomethyl isothiocyanate, n- Propylthiomethyl isothiocyanate, isopropyl thiomethyl isothiocyanate, n-butyl thiomethyl isothiocyanate, isobutyl thiomethyl isothiocyanate, sec-butyl thiomethyl isothiocyanate, 2-methyl thioethyl isothiocyanate, 2-ethyl Thioethyl isothiocyanate, 2-n-propylthioethyl isothiocyanate, 3-methylthiopropyl isothiocyanate, 4-methylthiobutyl isothiocyanate, 5-methylthiopentyl Sothiocyanate, 6-methylthiohexyl isothiocyanate, 7-methylthioheptyl isothiocyanate, 8-methylthiooctyl isothiocyanate, 9-methylthiononyl isothiocyanate, 3-methylsulfonylpropyl isothiocyanate, 4-methylsulfonylbutyl isothiocyanate Nate, 5-methylsulfonylpentyl isothiocyanate, 6-methylsulfonylhexyl isothiocyanate, 7-methylsulfonyl heptyl isothiocyanate, 8-methylsulfonyl octyl isothiocyanate, 9-methylsulfonyl nonyl isothiocyanate, benzyl isothiocyanate Narate, phenethyl isothiocyanate, p-hydroxybenzyl isothiocyanate, n-propyl isothiocyanate, iso One or two selected from the group consisting of propyl isothiocyanate, n-butyl isothiocyanate, sec-butyl isothiocyanate, isobutyl isothiocyanate, n-pentyl isothiocyanate, and isopentyl isothiocyanate A cooling sensation enhancing composition comprising the above compound.   The cooling sensation enhancing composition according to claim 1 or 2, which enhances the cooling sensation or cooling sensation effect of the cooling sensation substance.   The cooling sensation substance is menthol, menthyl acetate, menthone, isomentone, sabinene hydrate, isopulegol, piperitol, p-menthane-3-carboxylic acid amide, p-menthanediol, menthylglucoside, menthyl-2-pyrrolidone-5 Carboxylate, menthylketoalkanoate, menthyl N-acetylglycine, menthylhydroxyalkanoate, 2-mentoxytetrahydropyran, 2-mentoxytetrahydrofuran, menthoxypropane-1,2-diol, menthyl-3-hydroxybuty 1 type selected from the group consisting of a rate, 1-alkoxy-3-mentoxypropan-2-ol, menthone ketals, 3-hydroxymethyl-p-menthane alkanoate and 2-hydroxymethylmenthol It is 2 or more, according to claim 3 cool feel enhancing composition.   The cooling sensation enhancing composition according to claim 1 or 2, which enhances a cooling sensation or a cooling sensation effect of a cooling sensation substance that activates TRPM8 which is a cooling stimulus receptor channel.   A cooling sensation substance-containing composition comprising the cooling sensation substance and the cooling sensation enhancing composition according to any one of claims 1 to 5.   Food / beverage products containing the composition of any one of Claims 1-6.   A flavoring composition comprising the composition according to any one of claims 1 to 6.   A pharmaceutical comprising the composition according to any one of claims 1 to 6.   Cosmetics comprising the composition according to any one of claims 1 to 6.