WO2009021357A1 - Cooling agent composition and preparative method thereof - Google Patents

Abstract

Cooling agent composition containing N-ethyl menthane carboxamide and preparative method thereof are provided. The said composition is composed of 30%-80%wt menthol and 20%-70%wt N-ethyl menthane carboxamide, and its freezing point is lower than 25?. The preparative method of the said composition comprises the following steps: 1) adding the menthol and N-ethyl menthane carboxamide into the vessel in proportion; 2) agitating the mixture in the vessel at the room temperature until a clarification and clearing mixture is obtained. The cooling agent composition in the invention is liquid at the common temperature, and can use with other adjuvants without heating to melt.

Description

 Cooling agent composition and preparation method thereof

Technical field

 The present invention relates to a cooling agent composition and a process for the preparation thereof, and more particularly to a amide-containing cooling agent composition and a process for the preparation thereof.

Background technique

 Menthol, menthol, also known as Menthol, is a colorless crystalline, granulated, minty solid that is readily soluble in ethanol, slightly soluble in water, melting point 40-42 ° C, boiling point 212 ° (: Menthol is a traditional cooling agent. Because it can give the product a cool, fresh feeling, menthol has been widely used in food, medicine, daily chemical, tobacco and other industries, but its shortcomings are also very obvious -

(1) The taste of mint is very obvious with bitterness and irritation:

 (2) When the dosage is low, the cooling effect is not obvious;

 (3) Because of the strong volatility, the time of action is short;

 In order to overcome the shortcomings of menthol, people have been trying to find new types of cooling substances, which are generally made in the modification of menthol. By modifying its molecular structure, it has developed menthyl lactate, menthyl acetate, menthyl succinate, menthol ketal, menthone, etc. Among the many derivatives, mentamine has better performance and can Overcome the above shortcomings of menthol.

In the 1970s, Wikirlson Sword Company of the United States first developed N-ethyl menthylformamide (commonly known as menthamide) using menthol. Its structural formula is as follows:

 L-menthol Ws - 3

Menthramide is a one that has strong impact and durability, no breath, and can improve the cooling taste of L-menthol. A cooling agent that works well with any cooling agent. The mouth-feel threshold is 200 ppb (measured by impregnating the paper strip into the inlet); when tasted at a concentration of 10-100 ppb, "there is a strong and long-term stimulation of the trigeminal nerve, and the cooling taste is slowly stabilized. Enhance, and finally until the mouth is full of cool feeling, accompanied by a slight camphor and mint taste. "Compared with menthol, menthol has the following characteristics:

 (1) There is no strong mint flavor, no bitterness;

 (2) The skin feels mild, non-irritating, no burning feeling, no volatility, and the cooling effect lasts;

(3) The cooling intensity is 5 times that of menthol, and it has a flavoring effect.

 Menthramide is mainly used in daily products such as toothpaste, air freshener, skin cream, shaving cream, shampoo, sunscreen, bath, etc.; it can be used in edible products such as chocolate, dairy products, beer, liquor, beverages, etc. In chewing gum and other products, it can also be used in tablets, throat tablets, anti-inflammatory ointments, anti-gastric acid and indigestion drugs, antipruritic agents, oils, oral painkillers, anti-heatstroke drugs, etc.; in addition, menthamide can also be used In tobacco products such as cigarettes and filters, its products are used in a wide range of applications.

Menthasamide is usually used in combination with other cooling agents. USP 5,009,893 (Cherukuri et al.) describes a confectionery containing a plurality of cooling agents, wherein the cooling agent comprises menthol and menthamide, and the content of menthamide in the cooling agent is greater than 30% due to the low content of menthamide which results in bitterness. WO 93/23005 discloses a cooling composition comprising a first cooling component ketal 00 ₂ and a second cooling component menthol amide. WO 93/25177 discloses a cooling composition comprising a first cooling component acyclic formamide and a second cooling component menthamide.

 Mentha amide is a nearly colorless/white crystal, easily soluble in ethanol, slightly soluble in water, melting point

82 ° C -84 ° C. It is solid at room temperature and has a high melting point. It needs to be heated and melted when used in a cooling agent formulation. When used in combination with other cooling agents, it needs to add solvent or solubilizing ingredients, which is difficult to reach. The ideal dispersion uniformity, and the concentration and ratio of each component are not easy to achieve the required values.

 Summary of the invention

 The invention overcomes the disadvantages of the heat of melting or adding solvent or solubilizing component when the menthamide is used as a cooling agent formulation, has poor dispersion uniformity and low concentration, and provides a desiccant composition containing menthamide, which has strong impact, freshness and durability. The aroma and cooling sensation, the composition is liquid at normal temperature and can be used directly; and the composition can achieve a higher concentration of menthamide than other possible ways.

 Another object of the present invention is to provide a process for preparing the menthamide-containing cooling agent composition.

 The technical scheme adopted by the present invention is as follows - a menthamide-containing cooling agent composition consisting of menthol and N-ethyl menthylformamide, containing 30% to 80% by weight of menthol and 20% to 70% by weight N-ethylmenthylformamide having a freezing point below 25 °C.

 Menthol can form a co-melt with other compounds, forming a co-melt having a lower melting point than a single component. The formation of a eutectic mixture of menthol with N-ethyl menthylformamide has not been reported. The present invention combines menthol with N-ethyl menthylformamide and studies the relationship between the freezing point of the eutectic and its composition, as shown in Table 1 and Figure 1.

 Composition melting point and composition

4 30 70 24.5

4 30 70 24.5

5 40 60 15

 6 50 50 9

 7 60 40 12

 8 70 30 14.5

 9 80 20 27

 10 90 10 29

 11 100 0 42 In order to obtain a menthamide-containing composition having a freezing point lower than normal temperature, according to the present invention, the content of menthol is 30% to 80% by weight, N-ethyl menthylcarboxamide. The content is from 20% to 70% by weight, and the resulting composition has a freezing point of less than 25 °C.

 There are three chiral carbon atoms in the menthol structure, theoretically eight optical isomers, and the natural menthol is L-menthol with a melting point of 40-42 °C. N-ethyl menthylformamide is a menthol derivative which can be obtained by chemical synthesis, has a melting point of 82-83 ° C, and has the same chirality as menthol, so that it has a good cold feeling. A combination of menthol and menthamide that has a strong, fresh, long-lasting aroma and a refreshing sensation.

 In the composition of the present invention, the menthol component comprises all optical isomers of menthol molecules; the menthamide component is a left-handed or mixed-rotation structure.

In order to further reduce the freezing point of the menthamide-containing cooling agent composition, in the composition of the present invention, the menthol content is preferably 40% to 70% by weight, and the content of N-ethyl menthylcarboxamide is From 30% to 60% by weight, the resulting composition has a freezing point of less than 15 °C. More preferably, the content of menthol and N-ethyl menthylformamide is 50% by weight each, and the freezing point of the composition is lower than 9 ° C. The menthol and menthamide compositions provided by the present invention can be used directly as a cooling agent, odor conditioner or perfume, or can be used in the formulation from the composition and other adjuvants. The auxiliary agent may be a liquid substance such as an aqueous dispersant, an alcohol system, a grease, a silicone oil, an ester or an essential oil of the composition; although the solubility of the liquid substance to menthol and menthamide is insufficient to satisfy the requirement of the active substance concentration of the product, It can be used as a liquid dispersion carrier for the composition. The composition of the composition is obtained by adding a composition of menthol and menthamide to a suitable surfactant and mixing with water, oil, fat or the like to carry out a homogenization operation. The formation of a dispersion of such a composition can provide a high concentration of a cooling agent, an odor modifier or a fragrance which cannot be achieved in other forms for practical use, and can greatly expand its application range. In summary, the compositions provided by the present invention can be used as a cooling agent, an odor modifier, and a fragrance in a formulation. Due to the presence of a co-melt of menthol and menthamide, the formulation can be provided with a higher yield of menthamide than other methods. concentration.

 The compositions and dispersions thereof provided by the present invention can be used in various products affecting mucous membranes and skin, such as toothpastes, mouthwashes, perfumes, lotions, shaving creams, post-shave preparations, shampoos, antiperspirants , deodorants, beverages, chewing gum, tobacco products, and pharmaceutical products.

 The composition provided by the present invention is useful as a cooling agent, and has the advantage of producing explosive, instant cooling and durability.

 The present invention also provides a process for preparing the menthamide-containing cooling agent composition.

 A method for preparing a mentholamide-containing cooling agent composition, comprising the steps of:

1) adding menthol and menthamide to the container in proportion to the composition,

2) Stir the mixture in the vessel at room temperature until the mixture is clear and transparent. The mentholamide-containing refresher composition provided by the present invention is liquid at normal temperature, and is not required It is heated and melted, and can be used directly or in combination with an adjuvant, and is convenient to use as a cooling agent; and the composition can achieve a higher concentration of menthamide than other methods. As a cooling agent, the application of the composition saves energy, saves costs, and simplifies the process. The preparation method of the composition is simple.

 The present invention will be described in detail below in conjunction with the specific embodiments. The scope of protection of the present invention is not limited to the specific embodiments, but is defined by the claims. DRAWINGS

 Figure 1 is a graph showing the relationship between the freezing point and the menthol content of the composition of the present invention.

DETAILED DESCRIPTION OF THE INVENTION Example 1

 30 g of solid menthol and 70 g of N-ethyl-L-menthylformamide were placed in a beaker at room temperature, stirred at low speed for 30 min, and the composition slowly turned from solid to viscous and gradually clarified to obtain the desired oil. Things. The composition was subjected to a freezing point test with a freezing point of 24.5 °C. Example 2

 40 g of solid menthol and 60 g of N-ethyl-L-menthylformamide were placed in a beaker at room temperature, stirred at low speed for 30 min, and the composition slowly turned from solid to viscous and gradually clarified to obtain the desired oil. Things. The composition was subjected to a freezing point test with a freezing point of 15 °C. Example 3

50 g of solid menthol and 50 g of N-ethyl-L-menthylformamide were placed in a beaker at room temperature, stirred at low speed for 30 min, and the composition slowly turned from solid to viscous and gradually clarified to obtain the desired oil. Things. The composition was subjected to a freezing point test with a freezing point of: 9. C. Example 4 60 g of solid menthol and 40 g of N-ethyl-L-menthylformamide were placed in a beaker at room temperature, stirred at low speed for 30 min, and the composition slowly turned from solid to viscous and gradually clarified to obtain the desired oil. Things. The composition was subjected to a freezing point test with a freezing point of 12 °C. Example 5

 70 g of solid menthol and 30 g of N-ethyl menthylformamide were placed in a beaker at room temperature and stirred at low speed for 30 min. The composition was slowly turned from solid to viscous and gradually clarified to give the desired oil. The composition was subjected to a freezing point test with a freezing point of 14.5 °C. Example 6

 20 g of the composition of Example 3, 6 g of Tween 120 and 174 g of water were added, homogenized at room temperature, and the homogenizer speed was 5000 rpm to prepare a milky white stable 10% menthol and N-ethyl menthyl formamide. Water dispersant. Example Ί

 20 g of the composition of Example 3, adding 7.2 g of Phospholipid sv (stearamidopropyl propylene glycol monophospholipid dimethyl ammonium chloride), 7.2 g of Brij72 (polyoxyethylene-2-monostearate) and Add water to a total amount of 200g, homogenize at room temperature with a homogenizer, and homogenize in a high-pressure high-shear emulsifier to form a milky white stable 10% nanomenthol and N-ethyl-L-menthol Amide water dispersant. Example 8

 40 g of the composition of Example 3 was added to 10 g of Siban 160 and 150 g of dimethicone, homogenized at room temperature, and the homogenizer was rotated at 5000 rpm to prepare a milky white stable 20% menthol and N-ethyl- An oil dispersant for L-menthylformamide.

Claims

Rights request  A mentholamide-containing cooling agent composition comprising menthol and N-ethyl menthylformamide, comprising 30% to 80% by weight of menthol and 20% to 70% of N-ethylmenthyl Formamide, which has a freezing point below 25 °C.  The cooling agent composition according to claim 1, wherein the composition is a co-melt of menthol and N-ethyl menthylformamide.  The freshener composition according to claim 1 or 2, wherein: the menthol comprises all optical isomers of a menthol molecule; and the N-ethyl menthylcarboxamide is Its left-handed or mixed-rotation structure.  The freshener composition according to claim 1 or 2, wherein the menthol content is 40% to 70% by weight, and the N-ethyl menthylformamide is 30% by weight. ~ 60%, the freezing point of the composition is below 15 °C.  The freshener composition according to claim 4, wherein the content of the menthol and N-ethyl menthylformamide is 50% by weight, and the freezing point of the composition is lower than 9 °C. .  6. A method of preparing a cooling agent composition according to claim 1, comprising the steps of: 1) adding menthol and N-ethyl menthylformamide to the container in a composition ratio;  2) Stir the mixture in the vessel at room temperature until the mixture is clear and transparent.