201225983 六、發明說明： 【發明所屬之技術領域】 尤其是具有_富貴蘭之 本發明係關於一種香料組合物， 優異香氣的類富責蘭香料組合物。 【先前技術】 富貴蘭（風蘭，Ne0finetia falcata)係蘭科風蘭屬之常綠 ^年生草本，其漂溢著濃郁之甜香，作為觀賞植物而得到 本多人之喜愛》尤其是近年來，富貴蘭與其他蘭科植物又 略有不同的濃郁且甜美之香氣受到關注，市面上開始出售 人工調和類富貴蘭之香氣而成的富貴蘭香氣之芳香劑、香 氛（fragrance)或香水等。 然而，先前之此種模仿富貴蘭之香氣的調和香料的實際 h况疋多；散發出刺鼻之氣味，並未達到實際花開時所感 覺到的具有自然之柔和感的富貴蘭香氣。 於非專利文獻1中，記载沈香醇（Linalool)為富貴蘭之主 要香料成分之一。已知沈香醇係眾多植物之精油成分，且 亦報告有自各種植物獲得不同光學純度之光學活性沈香 醇’以及藉由化學合成而製造光學活性沈香醇之方法（專 利文獻1)。 [先前技術文獻] [專利文獻] [專利文獻1]曰本專利特開平9-278號說明書 [非專利文獻] [非專利文獻 1]J. Essent. Oil Res.，12, 197-200 (2000) 160345.doc 201225983 【發明内容】 [發明所欲解決之問題] 本發明之目的在於鑒於上述情況而提供一種具有如富責 蘭化盛開時的自然之柔和感之香氣的類富貴蘭香料級合 物。 [解決問題之技術手段] 本發明者為使富貴蘭之自然香氣更忠實地苒現而進行努 力研究’結果發現’藉由使所調配的沈香醇之L體之比率 為67%以上，先前之類富貴蘭香料組合物中的刺鼻氣味得 善 了再現更自然之富貴蘭香氣，從而完成本發明。 先則之類富貴蘭香料組合物中調配有沈香醇之消旋體（[體 與〇體之等量混合物）’而完全不知沈香醇之光學異構物之 比率可對富貴蘭之香氣產生影響。 本發明之類富責蘭香料組合物之特徵在於：含有L體之 比率為67%以上之沈香醇。藉由以[體成為67%以上之方式 調配沈香醇，可改善刺鼻氣味，可提供一種具有富貴蘭之 自然之柔和感的香料組合物。L體之比率更佳為75%以 上。 本發明之類富貴蘭香料組合物通常含有甘菊花酸順_3_ 己烯酯、茉莉内酯及吲哚等作為類富貴蘭基礎香料，更佳 為進而含有選自由苯甲酸曱酯、苯甲酸順-3-己烯酯及δ-癸 内酯所組成之群中的1種以上之成分。 旦於本發明之類富貴蘭香料組合物中，沈香醇總體之調配 里相對於香料組合物總量較佳為〇 〇卜質量％。 I60345.doc 201225983 又，本發明之類S貴蘭香料組合物之製造方法之特徵在 於：於包含甘菊花酸順-3-己烯酯、茉莉内酯及吲哚之類富 貴蘭基礎香料中，以L體之比率成為67%以上之方式添加 沈香醇。類富貴蘭基礎香料更佳為進而包含選自由苯甲酸 曱酯、苯曱酸順-3-己烯酯及δ_癸内酯所組成之群中的1種 以上之成分。又，更佳為使沈香醇之L體之比率為75%以 上。 [發明之效果] 本發明之類富貴蘭香料組合物藉由以L體之比率成為 67。/。以上之方式調配沈香醇，可改善先前之類富貴蘭香料 組合物之刺鼻氣味，可提供一種更接近鮮花的自然之富貴 蘭香氣^ 【實施方式】 將沈香醇之L體（(R)沈香醇）及D體（(s)沈香醇）之結構式 示於以下》 [化1]201225983 VI. Description of the Invention: [Technical Field to Which the Invention Is Applicable] In particular, the present invention relates to a perfume composition, an excellent aroma-like fragrance-based fragrance composition. [Prior Art] Fuguilan (Ne0finetia falcata) is an evergreen herb of the genus Orchidaceae, which is rich in sweet aroma and is loved by many people as an ornamental plant, especially in recent years. Lan and other orchids have a slightly different rich and sweet aroma, and the market has begun to sell aromatic fragrances, fragrances or perfumes made from artificially blended rich aromas. However, the actual temperament of the previous blend of spices that imitated the aroma of rich blues was so much; the pungent scent did not reach the rich aroma of natural softness that was felt when the flowers were actually opened. In Non-Patent Document 1, it is described that Linalol is one of the main flavor components of Fulan. It is known that linalool is an essential oil component of many plants, and an optically active agaric alcohol having different optical purity from various plants and a method for producing an optically active linalool by chemical synthesis are also reported (Patent Document 1). [Prior Art Document] [Patent Document 1] [Patent Document 1] Japanese Patent Laid-Open No. Hei 9-278 (Non-Patent Document) [Non-Patent Document 1] J. Essent. Oil Res., 12, 197-200 (2000) [Abstract] [Problems to be Solved by the Invention] The object of the present invention is to provide a class of rich-flavored flavors having a natural aroma of softness when blooming in full bloom, in view of the above circumstances. Things. [Technical means for solving the problem] The present inventors made an effort to study the natural aroma of Fuguilan more faithfully, and found that the ratio of the L body of the blended linalool was 67% or more. The pungent odor of the rich-rich orchid flavor composition is good enough to reproduce a more natural rich blue aroma, thereby completing the present invention. In the first class, the rich blue flavoring composition is formulated with a racemic body of linalool ([equal mixture of body and steroid]) and it is completely unknown that the ratio of optical isomer of linalool can affect the aroma of rich blue . The rich scented perfume composition of the present invention is characterized by having a linalool having a ratio of L bodies of 67% or more. By blending the linalool in a manner that the body becomes 67% or more, the pungent odor can be improved, and a flavor composition having a natural soft feeling of rich blue can be provided. The ratio of the L body is more preferably 75% or more. The rich-flavored perfume composition of the present invention usually contains cis_3_hexenyl chrysanthemum acid, jasmine lactone, hydrazine, etc. as a rich-rich orchid base perfume, and more preferably further contains decyl benzoate and benzoic acid. One or more components selected from the group consisting of -3-hexenyl ester and δ-decalactone. In the rich-flavored perfume composition of the present invention, the total amount of the linalool is preferably 〇 质量 mass% relative to the total amount of the perfume composition. Further, the method for producing a S-Fenlan perfume composition of the present invention is characterized in that, in a rich-based base spice comprising cis-3-hexenyl chrysanthemum, jasmonide and hydrazine, The linalool is added in such a manner that the ratio of the L body becomes 67% or more. More preferably, the rich-flavor-based base flavoring agent further contains one or more components selected from the group consisting of decyl benzoate, cis-3-hexenyl benzoate, and δ_caprolactone. Further, it is more preferable that the ratio of the L body of the linalool is 75% or more. [Effect of the Invention] The rich blue flavor composition of the present invention is 67 by the ratio of the L body. /. The above method of blending linalool can improve the pungent odor of the former rich orchid flavor composition, and can provide a natural rich aroma of the orchid closer to the flower ^ [Embodiment] The L body of the linalool ((R) sinks The structural formula of the fragrant alcohol) and the D body ((s) linalool) is shown below. [Chemical 1]
HO CH3 HaC OH V Sf II J 1 H2C X ί X ch2 HsC CH3 HaC^ ch3 D體 乙體 沈香醇為眾多植物之精油成分，且作為各種調料或香氛 之香料原料而市售。又，可藉由自各種植物萃取而獲得不 同光學純度之光學活性沈香醇，或者如日本專利特開平9· I60345.doc 201225983 278,^說明書中所揭示般’可藉由分別化學合成[體及〇體 製以L沈香醇係由Fluka公司市售，沈香醇之消旋體 係由BASF公司市售，例如，可藉由將其等以適當 調配而製備以所期望之比率包含L體之沈香醇。 ， 於本發明之香料組合物中，沈香醇令之l體之比 67%以上’更佳為75%以上，進而更佳為㈣以上由 r尤香醇r體之比率為㈣以上，可改善刺鼻氣味：： 提供-有田貝蘭之自然之柔和感的香料組合物盆 广體之比一以上，可使自然之富貴蘭香氣= 實地再現，進而，藉由使L體之比率為9〇%以上 一種不僅其錢之制性優異，且料 2 蘭香料組合物。 慢呉的類虽責 曰^發明中，沈香醇總體之調配量相對於香料組合㈣ 為_〜㈣量％ ’更佳為質量％，進而更佳 質量％。若沈香醇之調配量未達〇〇1質量％，則有 無法充为酿出富貴蘭之香氣的情形…若高 =有香氣之平衡變差，無法再現富貴蘭所具有之甘甜 且柔和之香氣的情形。 本發明之類富貴蘭香料組合物可藉由用包含67%以上之 ⑽之沈香醇置換公知m蘭香料組合物中的沈香醇 =備，’可藉由於除去沈香醇後之類富貴蘭基礎香 製備太：體之比率成為67%以上之方式添加沈香醇，而 明之類富貴蘭香料組合物。上述之類富貴蘭基礎 公知者’較佳為至少包含甘菊花酸順-3-己烯 I60345.doc 201225983 i旨、東韌内S曰及°引D木，更佳為進而包含苯甲酸甲酷、— 1曰 本曱 酸順-3-己烯酯、δ-癸内酯等。 再者，於本發明之香料組合物中，只要不妨礙其自然 類富貴蘭香氣則可調配：聚氧乙烯月桂硫酸醚等界面=性 . 劑；二丙二醇、鄰苯二甲酸二乙酯等溶劑；突厥酮、己桂 . 皮酸、棒檬油、玫瑰油等香料物質等。 本發明之類富貴蘭香料組合物並無限定，除可應用於沐 浴劑、香水、古龍水、芳香劑以外，亦可應用於軟膏、'乳 霜、乳液、洗劑、面膜、粉底、腮紅、白粉、眼影、 紅、吸油面紙、粉紙、洗髮精、潤絲精、喷霧髮膠、止干 喷霧、身體香粉、嬰兒爽身粉等化粧料；衛生紙或紙巾: 餐巾、筆記本、記事薄等紙用品；抹布、牙粉、口罩、醫 療用紗布、柔順劑、衣料用洗滌劑、廚房用洗滌劑、芳香 劑、香薰油等曰用雜貨類或食品等。於調配於化粧料令之 情形時’其調配量並無特別限定，通常之濃度範圍例如相 對於化粧料總量可設為〇.〇〇〇〇卜30質量％，於含於雜貨等 中之情形時，可設為0.00001〜100質量〇/〇。 [實施例] ’ 卩了 ’列舉實施例對本發明進行具體的說明，但本發明 . i非限定於下述實施例者。只要無特別記載，則調配㈣、 以相對於調配該成分之系統之質量。/。而表示。 ' (1)類富貴蘭基礎香料 於以下之試驗例中，使用下述組成之類富貴蘭基礎香 料： 160345.doc 201225983 ____HO CH3 HaC OH V Sf II J 1 H2C X ί X ch2 HsC CH3 HaC^ ch3 D Body Binkyol is a essential oil component of many plants and is commercially available as a raw material for various seasonings or fragrances. Further, an optically active linalool of different optical purity can be obtained by extraction from various plants, or can be separately synthesized by chemical synthesis as disclosed in the specification of Japanese Patent Laid-Open No. Hei 9: I60345.doc 201225983 278. The oxime system is commercially available from Fluka Corporation as the L-suppleol alcohol, and the racemic system of linalool is commercially available from BASF Corporation. For example, the linalool containing L-body can be prepared in a desired ratio by appropriately blending them. In the perfume composition of the present invention, the ratio of the linalool to the body is 67% or more, more preferably 75% or more, and even more preferably (4) or more, the ratio of the r-eugenol r body is (4) or more, which can improve the thorn. Nasal scent:: Provides - the ratio of the pottery composition of the natural softness of the field of the berry to the more than one, which can make the natural rich aroma = reproduction in the field, and further, by making the ratio of the L body to 9〇% The above one is not only excellent in the system of its money, but also a material of 2 blue perfume composition. Although the slow-drying class is responsible for the invention, the total amount of the linalool is _~(four)%%' is more preferably the mass%, and further preferably the mass%. If the blending amount of linalool is less than 质量1% by mass, there is a situation in which the aroma of rich orchids cannot be filled. If the balance of aroma is worse, the sweet and soft aroma of rich orchids cannot be reproduced. The situation. The rich blue flavor composition of the present invention can be prepared by replacing the linalool in the known m-blue perfume composition with 67% or more of the (10) linalool, which can be obtained by removing the rich fragrant base such as linalool. The preparation of too much: the ratio of the body is 67% or more, and the linalool is added, and the rich fragrant flavor composition such as Ming. Preferably, the above-mentioned rich base of the rich orchids is preferably at least comprising glycerol chrysanthemum acid cis-3-hexene I60345.doc 201225983 i, east tough inner S曰 and ° lead D wood, more preferably further comprising benzoic acid methyl cool , - 1 曰 cis-3-hexenyl decanoate, δ-decalactone and the like. Furthermore, in the perfume composition of the present invention, it can be blended as long as it does not interfere with the natural rich-rich blue aroma; the interface of the polyoxyethylene lauryl sulfate or the like; the agent; the solvent such as dipropylene glycol or diethyl phthalate; ; Turkic ketone, hexagui. Spices such as citric acid, lemon oil, rose oil, etc. The rich blue flavoring composition of the present invention is not limited, and can be applied to an ointment, a cream, an emulsion, a lotion, a mask, a foundation, and a blush, in addition to a bathing agent, a perfume, a cologne, and a fragrance. , white powder, eye shadow, red, oil-absorbing facial tissue, powder paper, shampoo, moisturizing essence, spray hair spray, dry spray, body powder, baby powder and other cosmetics; toilet paper or paper towels: napkins, notebooks, Paper products such as notepads; rags, tooth powders, masks, medical gauze, softeners, detergents for clothing, kitchen detergents, fragrances, aromatherapy oils, etc. When it is formulated in the case of a cosmetic material, the amount of the compounding is not particularly limited, and the usual concentration range is, for example, 30% by mass based on the total amount of the cosmetic material, and is contained in the groceries, etc. In the case, it can be set to 0.00001 to 100 mass 〇 / 〇. [Examples] The present invention will be specifically described by way of examples, but the present invention is not limited to the following examples. Unless otherwise stated, (4) is formulated to the quality of the system in which the component is formulated. /. And said. ' (1) Rich Royal Basic Flavor In the following test examples, the rich base of the following ingredients is used: 160345.doc 201225983 ____
0.1 0.5 0.1 0.5 12.0 3〇.〇 3.0 0.2 0.5 6.0 4.0 1.0 0.5 0.5 !〇〇.〇 醋酸順-3-己烯酯 甲基庚烯酮 順-3-己烯醇 異戊酸順-3-己稀酯 苯甲酸甲酯 甘菊花酸順-3-己烯龜 苄醇 大茴香醛 巴豆酸苄酯 苯曱酸順-3-己烯酯 δ-癸内酯 茉莉内醋 吲哚 香蘭素 —丙二醇(DPG) ------- 合計 (2)香料組合物之製備 、^之類富責蘭基礎香料中，如 不同比率添知砵4 1 τ迷表1所示般，0.1 0.5 0.1 0.5 12.0 3〇.〇3.0 0.2 0.5 6.0 4.0 1.0 0.5 0.5 !〇〇.〇 cis-3-hexenyl acetate methylheptenone cis-3-hexenol isovaleric acid cis-3-hexyl Dilute ester methyl benzoate, chrysanthemum acid, cis-3-hexene, benzyl alcohol, anisaldehyde, crotonate, benzyl benzoate, cis-3-hexenyl ester, δ-decalactone, jasmine, vinegar, vanillin, propylene glycol DPG) ------- Total (2) preparation of the fragrance composition, and the like, and the like, as in the case of different ratios, as shown in Table 1,
午添加沈香醇之消旋體（L L_沈香醇，製備以5。〜画之間之::比之_蝴 料組合―例卜8)。 Π之各㈣率包含L體之 (3)香氣評價試驗 據以下之s平價基準對各香料 及塗佈2小時後之香氣（保香 由專業官能檢查員7名，根 組合物之剛塗佈後之香氣，以 性）進行評價： .具有非常優異之類富貴蘭之自然香氣 4:具有優異之類富貴蘭之自然香氣 3 ··具有類富貴蘭之自然香氣 160345.doc 201225983 2:具有類富貴蘭之香氣 1:幾乎不具有類富貴蘭之香氣。 將結果以平均值示於下述表1以及圖1。 [表1] 成分 試驗例 1 2 3 4 5 6 7 8 類富貴蘭基礎香料 85 85 85 85 85 85 85 85 沈香醇(消旋體） 15 12 10 8 7 5 3 0 L-沈香醇 0 3 5 Ί 7 8 ίο-1 12 15 合計 100 100 100 100 100 100 , 100 100 沈香醇中之L體之比率(〇/〇) 50 60 67 73 77 83 90 100 ______ 香氣評價 剛塗佈後(平均分） 2.0 2.0 2.29 2.86 3.43 3.57 3.86 4.57 2小時後(平均分） 2.0 2.0 2.0 2.0 2.0 2.0 [2.71 3.86 所調配之沈香醇中之L體的比率為67%〜100%之試驗例 3〜8中’於剛塗佈後之香氣之評價中，獲得顯著高於先前 技術之L·體之比率為5〇。/。的試驗例！之評價。尤其是藉由使 沈香醇之L體之比率為75%以上，獲得3 〇以上之較高平均 評分’表示可製備更忠實地再現自然之ft蘭香氣之香料 組合物。進而，若L體之比率為9〇%以上，則塗佈2小時後 之af·分亦顯著較咼，表示保香性亦優異。 以下述配方製備本發明之類富貴蘭香料組合物（實施们 及2 )以及比較組合物（比較例1)。 實施例1 : 30.0 30.0 0.2 1.0 0.5 沈香醇(L體之比率為90%) 甘菊花酸順-3-己烯酯 丁酸順-3-己烯酯 茉莉内酯 吲哚 160345.doc 201225983 苯甲酸甲酯 10.0 苯甲酸順-3-己烯酯 5.0 δ-癸内酯 3.0 香蘭素 0.5 1%茉莉精油 5.0 二丙二醇 14.8 本香料具有自然之富貴蘭香氣。 比較例1 : 沈香醇(L體之比率為50%) 30.0 甘菊花酸順-3-己烯酯 30.0 丁酸順-3-己烯酯 0.2 茉莉内酯 1.0 吲哚 0.5 苯甲酸曱酯 10.0 苯曱酸順-3-己烯酯 5.0 δ-癸内酯 3.0 香蘭素 0.5 1%茉莉精油 5.0 二丙二醇 14.8 本香料為普通之富貴蘭香氣 0 實施例2 : 沈香醇(L體之比率為100%) 1.0 甘菊花酸順-3-己烯酯 30.0 已酸順-3-己烯酯 0.1 苯曱酸丁酯 0.1 苯曱酸己酯 0.1 茉莉内酯 1.0 吲哚 0.5 苯曱酸曱酯 10.0 苯曱酸順-3-己烯酯 5.0 δ-癸内酯 3.0 160345.doc - 10- 201225983 香蘭素 0.5 二丙二醇 48.7 本香料具有自然之富貴蘭香氣。 【圖式簡單說明】 圖1係表示研究沈香醇之L體之比率對類富貴蘭香料組合 物之香氣之影響的香氣評價試驗的結果之圖。 160345.docIn the afternoon, add the aroma of linalool (L L_ linalol, prepared by 5. ~ between the painting:: than the combination of the butterfly - example 8). Each of the four (4) rates includes the L body (3) aroma evaluation test. According to the following s parity benchmark, the fragrance and the aroma after 2 hours of application (the fragrance is 7 by the professional inspector, the root composition is just coated. After the aroma, evaluation by sex: . Has a very good natural rich aroma of rich blue 4: has a natural aroma of rich and rich orchids 3 · · has a natural aroma of rich green orchids 160345.doc 201225983 2: with class The aroma of Fuguilan 1: It has almost no aroma of rich greens. The results are shown as the average values in Table 1 below and FIG. [Table 1] Ingredient test example 1 2 3 4 5 6 7 8 class rich orchid base perfume 85 85 85 85 85 85 85 85 scented alcohol (racemate) 15 12 10 8 7 5 3 0 L-saling alcohol 0 3 5 Ί 7 8 ίο-1 12 15 Total 100 100 100 100 100 100 , 100 100 Ratio of L body in linalool (〇/〇) 50 60 67 73 77 83 90 100 ______ Aroma evaluation just after application (average score) 2.0 2.0 2.29 2.86 3.43 3.57 3.86 4.57 2 hours later (average score) 2.0 2.0 2.0 2.0 2.0 2.0 [2.71 3.86 The ratio of the L body in the blended linalool is 67%~100% in Test Examples 3~8 In the evaluation of the aroma immediately after coating, a ratio of L 体 which was significantly higher than that of the prior art was obtained as 5 〇. /. Test case! Evaluation. In particular, by setting the ratio of the L body of the linalool to 75% or more, a higher average score of 3 Å or more is obtained, indicating that a perfume composition which more faithfully reproduces the natural scent of FF can be prepared. Further, when the ratio of the L body is 9% by weight or more, the af·min after 2 hours of application is also remarkably fine, and the fragrance retention property is also excellent. The rich blue flavor compositions (activators and 2) of the present invention and the comparative compositions (Comparative Example 1) were prepared in the following formulations. Example 1: 30.0 30.0 0.2 1.0 0.5 linalool (L ratio of L body is 90%) cis-3-hexenyl phthalate cis-3-hexene jasperide 吲哚160345.doc 201225983 Benzoic acid Methyl ester 10.0 cis-3-hexene benzoate 5.0 δ-decalactone 3.0 vanillin 0.5 1% jasmine essential oil 5.0 Dipropylene glycol 14.8 This fragrance has a natural rich aroma. Comparative Example 1: linalool (L ratio of L body is 50%) 30.0 cis-3-hexenyl chrysanthemum acid 30.0 cis-3-hexenyl butyrate 0.2 jasmonide 1.0 吲哚0.5 decyl benzoate 10.0 benzene Cis-3-hexenyl decanoate 5.0 δ-decalactone 3.0 vanillin 0.5 1% jasmine essential oil 5.0 dipropylene glycol 14.8 This fragrance is a common rich blue aroma 0 Example 2: linalol (L ratio of L body is 100% 1.0 Chamomile cis-3-hexenyl ester 30.0 Acid cis-3-hexene ester 0.1 Butyl benzoate 0.1 Benzoyl benzoate 0.1 Jasmine lactone 1.0 吲哚 0.5 Benzoyl benzoate 10.0 Benzoquinone Acid cis-3-hexenyl ester 5.0 δ-decalactone 3.0 160345.doc - 10- 201225983 Vanillin 0.5 Dipropylene glycol 48.7 This fragrance has a natural rich aroma. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the results of an aroma evaluation test for examining the effect of the ratio of the L body of the linalool on the aroma of the rich-flavored perfume composition. 160345.doc