US 20110081393A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2011/008 1393 A1 Komatsuki et al. (43) Pub. Date: Apr. 7, 2011 (54) COOLING SENSATION AGENT A6IP27/00 (2006.01) COMPOSITION, SENSORY STIMULATION A6IP 700 (2006.01) AGENT COMPOSITION AND USE OF THE (52) U.S. Cl. ......... 424/402:560/194: 514/548; 560/193; SAME 424/443 (75) Inventors: Yasuhiro Komatsuki, Kanagawa (57) ABSTRACT (JP); Tomoko Yamamoto, Disclosed is a cooling sensation agent composition or sensory Kanagawa (JP): Takashi Aida, stimulation agent composition which contains at least one of Tokyo (JP); Kenya Ishida, diester compounds of dicarboxylic acid represented by the Kanagawa (JP) formula (1) wherein A represents CH or CH=CH, in repre sents an integer of 0 to 4 when A is CH, or 1 when A is (73) Assignee: TAKASAGO INTERNATIONAL CH=CH, B is an alcohol residue having 10 to 18 carbon CORPORATION atoms and containing a para-menthane skeleton, which may have a substituent, and C is an alcohol residue having 6 to 18 (21) Appl. No.: 12/898,939 carbonatoms, which may have a Substituent as well as a flavor or fragrance composition, a beverage, a food product, a per (22) Filed: Oct. 6, 2010 fume or cosmetic product, a toiletry product, daily utensil products or groceries, a fiber, a fiber product, clothes, clothing (30) Foreign Application Priority Data or a medicine, wherein the cooling sensation agent composi tion or the sensory stimulation agent composition is com Oct. 7, 2009 (JP) ................................. 2009-233059 pounded. Publication Classification (1) (51) Int. Cl. A6 IK 3L/225 (2006.01) CD7C 69/40 (2006.01) 46R 9/00 (2006.01) 1. A 6LX 9/70 (2006.01) US 2011/008 1393 A1 Apr. 7, 2011 COOLING SENSATION AGENT skin (WO 94/06441 A), and the like are mentioned. In addi COMPOSITION, SENSORY STIMULATION tion to them, there are known many patents that utilize release AGENT COMPOSITION AND USE OF THE of a fragrance molecule by decomposition of a fragrance SAME precursor based on a chemical change or an enzyme reaction (JP 45-26872 B, EP 1077251 A, WO 95/04809 A, WO FIELD OF THE INVENTION 97/16523 A, JP 8-225564A, JP 2009-520701 A, and Angew. Chem. Int. Ed, 2007, 46, 5836-5863). JP 45-26872 B, for 0001. The present invention relates to novel esters of example, discloses cosmetics in which monomenthyl or dicarboxylic acid, a cooling sensation agent composition dimenthyl esters of dicarboxylic acid is contained. The esters containing the same, a sensory stimulation agent composition in the cosmetics are decomposed by an ester-hydrolyzing containing the cooling sensation agent composition as well as enzyme present in a skin or an alkali included in an alkaline a flavor or fragrance composition, a beverage, a food product, cosmetic that is already applied on the skin to release men a perfume or cosmetic product, a toiletry product, a daily thol. However, it is not known that the aforementioned dimen utensil product or grocery, fibers, fiber products, clothes, thyl esters of dicarboxylic acid themselves have an excellent clothing or a medicine, which contains the cooling sensation cooling sensation effect. In addition, when a precursor of a agent composition or the sensory stimulation agent compo flavor or fragrance compound is used, there are still some sition and a method for producing the same. The present problems that quite a long time is required till the decompo invention also relate to a method for providing long-lasting sition reaction of the precursor starts and a flavor or fragrance cooling sensation or a cool refreshment processing method compound is released after adhesion of the precursor to using the cooling sensation agent composition or the sensory clothes or a skin, the strength of cooling sensation is signifi stimulation agent composition. cantly weak, and so on. Thus, it is not a fundamental solution. 0005. Other studies on the method for providing clothes BACKGROUND OF THE INVENTION with cooling action, for example, using microcapsules or the 0002. A cooling sensation agent that endows the skin, oral like have been conducted, and many patent applications have cavity, nose and throat of a person with a refresh feeling been filed. Examples thereof include a fiber processing (refresh sensation) and cool feeling (cooling sensation), that method by use of microcapsules containing mint oil or 1-men is cooling sensation effect, is used in various products such as thol (JP 2000-96443A), a fiber processing method by use of toothpastes, confectioneries such as chewing gums and can a microcapsulated Substance which melts at a temperature not dies, tobacco, cataplasms, bath agents and cosmetics. Men higher than the body temperature, so that the substance gives thol, which is the representative cooling sensation agent persons a cooling action reversibly by latent heat when con material, has an excellent cooling sensation effect. However tacting with skin (JP 2006-161226 A), or the like. However, as menthol is highly volatile, the cooling sensation effect they have also problems. That is, in the former method, pro thereof does not last so long. Therefore, studies have been cessed clothes, of course, loses its action after releasing of all carried out to maintain a cooling sensation action for a long cooling sensation agent by destruction of the microcapsules, period of time. Examples of the compounds having been and it is actually impossible to re-process the clothes at home. developed to maintain the cooling sensation for a prolonged Further, because the stage of releasing the cooling sensation period of time include menthoxypropanediol that is glycerin agent by destruction of the microcapsules is the rate-deter ether of menthol, lacticester of menthol, ethylene glycol ether mining step in this method, similar to a chemical reaction, it of menthol and the like. is not currently at the technological level where the cooling 0003. However, under influence of recent global warming, action can be provided to persons just after wearing of the there has been a demand for cool feeling processing of cloth clothes. In the latter method which relies on phase transition ing Such as clothes and the like to make people feel more between solid and liquid, the cooling action cannot be pro comfortable even in hot Summer. Most cooling sensation vided to persons in constantly hot areas where the microcap agents including menthol, however, are highly volatile and sulated substance does not return to the solid state after melt also highly water-soluble, and thus, the cool feeling process ing. ing of clothes and the like by use of the cooling sensation 0006 An object of the present invention is to provide a agents often results in loss of the action within a short period cooling sensation agent composition by which the conven of time. For example, even if a cooling sensation agent is tional problems described above are solved, i.e., to provide a compounded with a detergent or a softener, the cooling sen cooling sensation agent composition which shows the long sation agent hardly remains on the clothing fiber after wash lasting cooling action for an extended period of time. ing because of its water Solubility and further, no cooling 0007 Another object of the present invention is to provide sensation agent remains after drying because of its high Vola a sensory stimulation agent composition which contains the tility. cooling sensation agent composition. 0004 To solve these problems, sustained-release cooling 0008 Still another object of the present invention is to sensation agents utilizing a chemical change has been devel provide a flavor or fragrance composition, a beverage, a food oped. For example, a method for giving a refresh feeling to product, a perfume or cosmetic product, a toiletry product, gas to be breathed at Smoking by releasing a cooling sensation daily utensil products and groceries, and a medicine, which agent, menthol due to thermal decomposition of chlorocar contain the cooling sensation agent composition or the sen bonic esters or carbonic esters contained in tobacco on com sory stimulation agent composition, and also a production bustion of tobacco (U.S. Pat. No. 3,312.226), a method for method of the same. releasing a fragrance component by decomposition of car 0009 Further, still another object of the present invention bonic esters on the skinto elongate the diffusion period of the is to provide a method for providing a prolonged cooling fragrance (JP 10-95752A), a method for releasing a fragrance action by applying one of the aforementioned products con due to decomposition of orthoesters by perspiration on the taining the cooling sensation agent composition or the sen US 2011/008 1393 A1 Apr. 7, 2011 sory stimulation agent composition directly onto a skin or a 2 The cooling sensation agent composition described in Scalp, administering it into an oral cavity, or applying it on above item 1, wherein C in the formula (1) is an alcohol fibers, a fiber product, clothes or clothing; or a cool refresh residue having a para-menthane skeleton, which may have a ment processing method of fibers, a fiber product, clothes or substituent. clothing by compounding a cooling sensation agent compo 3 The cooling sensation agent composition described in sition or the sensory stimulation agent composition with above item 2, wherein Band C in the formula (1) are not the those or processing those with a cooling sensation agent same residue. composition or the sensory stimulation agent composition. 4The cooling sensation agent composition described in any one of above items 1 to 3, wherein the alcohol residue for 0010 Furthermore, another object of the present invention B or B and C in the formula (1) having a para-menthane is to provide novel diesters of dicarboxylic acid.