CN1394591A - Menthanol and menthanol lactic acid ester composite and its preparation method and application - Google Patents

Menthanol and menthanol lactic acid ester composite and its preparation method and application Download PDF

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Publication number
CN1394591A
CN1394591A CN 02138077 CN02138077A CN1394591A CN 1394591 A CN1394591 A CN 1394591A CN 02138077 CN02138077 CN 02138077 CN 02138077 A CN02138077 A CN 02138077A CN 1394591 A CN1394591 A CN 1394591A
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China
Prior art keywords
menthol
lactic acid
acid ester
menthanol lactic
menthanol
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CN 02138077
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CN1158987C (en
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苏桂珍
汪昌国
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Nanjing Huashi New Material Co ltd
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NANJING SINO LION CHEMICAL CO Ltd
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Abstract

The present invention relates to a composite of menthol and menthol lactate, their weight ratio is 2:8-8:2 and the solidifying point of said composite is lower than 25 deg.C. Under the condition of room temp. is a liquid form, can be used as freshener, smell regualting agent and perfume in the various products of toothpaste, gargle, perfume, lotion, shave cream, shampoo, deodorant, beverage, chewing gum, tobacco product and medicine product, etc.

Description

The composition and method of making the same of menthol and menthanol lactic acid ester and application
Technical field
The present invention relates to the application of a kind of menthol and ester thereof as freshener, abnormal smells from the patient regulator, spice, the compositions of menthol and menthanol lactic acid ester specifically, this compositions freezing point is lower than room temperature, and is liquid form.
Background technology
Menthol is well-known physiological cooling agents, be applied to analgesia is arranged in skin and the oral cavity, salubrious and regulate the effect of abnormal smells from the patient.As the Herba Menthae main body of oil, menthol has been widely applied in food, beverage, toothpaste, collutory, cosmetics, detergent, confection, tobacco product and the medicinal product.But menthol exists intensive mint flavored and coarse sensation has limited its use.
Therefore, it has long lasting cooling effect to need a kind of freshener, and does not have the coarse and offending abnormal smells from the patient of similar menthol.
For improving these shortcomings of menthol, people have prepared the ester of a variety of menthols, but most ester has bad abnormal smells from the patient, and can not be employed.Menthanol lactic acid ester is successful one, and it is German Haarman ﹠amp; The freshener that Reimer GmBH company releases, commodity are called Frescolat ML.Manufacturer's data shows that Frescolat ML is an effective active component and being used in cosmetics and the food, and it is the oil-soluble product, and is very stable in the scope of pH value 4-8, adds in the prescription and needs to maintain the temperature at 40-45 ℃.For this reason, Frescolat ML must perhaps be dissolved in it perfumery oil, cosmetic oil, alcohols solvent as 1, in 2-propylene glycol, the dipropylene glycol 50-60 ℃ of fusing.When menthanol lactic acid ester is used for shampoo, gel, foam bath, it is not suitable for being dissolved in these materials.
Menthanol lactic acid ester, its general structure is as follows:
Compare with menthol, it is of a specified duration that menthanol lactic acid ester has little, the refrigerant persistent period of stimulation, and therefore not volatile advantage obtains the market approval.But, there be refrigerant effect of the moment shortcoming low than menthol in it, and the field of its application still is restricted, particularly for oral cavity, skin articles for use, user uses the back to wish that very strong refrigerant impression is just arranged immediately, and menthanol lactic acid ester can not be accomplished this point.
The report that menthol and menthanol lactic acid ester is added, is used in jointly some product is respectively also arranged in some technical literatures.Be to mention a kind of cosmetics that contain menthol and menthanol lactic acid ester in the patent of WO00/42983 as the patent No., its zest and abnormal smells from the patient are all very little.Contain the menthol of 0.01-2% and the menthanol lactic acid ester of 0.1-10% in the patent report prescription, the application percentage of menthol and menthanol lactic acid ester is 1: 1-1: 10 scopes, the abnormal smells from the patient and the zest of menthol is very little in the prescription like this, and the effect of menthol is retained again simultaneously.Also having the patent No. is also to mention menthol and menthanol lactic acid ester in the patent of JP06329528 and JP10231238 to separate the application example that makes an addition to product with the ratio of 1: 1 and 2: 1.In patent JP06329528 embodiment, the concentration of menthol and menthanol lactic acid ester from 0.1%: 0.1% (1: 1) to 0.2%: 0.2% (1: 1), the working concentration of menthol is 0.001%-10% (w/w) in its claim, and the working concentration of menthanol lactic acid ester is 0.001%-10% (w/w).In patent JP10231238, menthol and menthanol lactic acid ester are applied in the same prescription with 0.2% and 0.1% concentration respectively.
More than invention is mentioned is that interpolation respectively with menthol and menthanol lactic acid ester is used in same prescription, and uses concentration less than 15%, does not also mention mixture.The shortcoming of doing like this is: menthol and menthanol lactic acid ester must be heated to 50-60 ℃ of fusing earlier, or it is dissolved in perfumery oil, cosmetic oil, alcohols solvent, could add in the prescription easily.Above-mentioned Haarman ﹠amp; The menthanol lactic acid ester of Reimer GmBH company has two kinds of forms, crystallization and non-crystalline types.Non-crystalline type product, freezing point are solid-state at 40 ℃, do not have other additives; Crystal type product freezing point is at 42 ℃, and white powder contains 0.1% sodium bicarbonate simultaneously.The shortcoming of non-crystalline type product is that inconvenience is handled, because product will be poured out from pail pack, must be heated to the product fusing together with pail pack.And the crystal type product though good the processing wherein has other additive, and may cause consistency problem with formula material.
It is inconvenient that above-mentioned menthol and menthanol lactic acid ester add under solid-state situation, is very disadvantageous for industrialized great production particularly, need provide Special Equipment and heating equipment to come heat fused menthol and menthanol lactic acid ester on the one hand; Can only use cold treatment process for some product, also be inappropriate, and this technology is a kind of development trend, and it can be saved the energy, enhance productivity.On the other hand, menthol volatile, very strong pungent taste of when heating has negative effect to operator ' s health.
Summary of the invention
The purpose of this invention is to provide under a kind of room temperature liquid state, can directly use, lowly stimulate, low flavor, low volatilization the compositions that combines by menthol and menthanol lactic acid ester, and do not contain solvent and solubilising composition.
Another object of the present invention provides a kind of this menthol and menthanol lactic acid ester preparation of compositions method.
The present invention also aims to provide a kind of said composition is made moment refrigerant sensation and all well application of the application of freshener and abnormal smells from the patient regulator, spice of refrigerant persistency.
Purpose of the present invention can reach by following measure:
Menthol is to extract or synthetic chemical compound from Oleum menthae.Exist three chiral carbon atoies in the menthol molecular structure, 12 kinds of optical isomers are arranged in theory, but widely used have only the L-menthol, its fusing point is 42-43 ℃, menthanol lactic acid ester is by menthol and lactic acid esterification and obtain, have 4 chiral carbon atoies in its molecular structure, have 16 kinds of optical isomers in theory, what application was arranged at present is L-menthol and L or D-lactic acid derivative.The market extensive use then be L-menthol-L-lactate, its fusing point is 43-45 ℃.
The menthol component of mentioning in the compositions provided by the invention has comprised all optical isomers of menthol, and the menthanol lactic acid ester component of mentioning has comprised all optical isomers of menthanol lactic acid ester.And for convenience, below will be with widely used L-menthol and L-menthol-L-lactate as description object.
The inventor considers, menthol is a kind ofly knownly can form the chemical compound that melts system altogether, and the fusing point that forms the mixture that melts altogether will be lower than single component, but the fusing point of the fused matter of having reported is generally in room temperature or be higher than room temperature.Menthol and menthanol lactic acid ester form mixture and yet there are no report.The present invention has disclosed menthol and menthanol lactic acid ester for the first time and has formed and melt system altogether, and the fusing point of its fused matter can subambient phenomenon.For reaching menthol and menthanol lactic acid ester fused matter freezing point is reduced to below the room temperature, in addition lower, and it is important controlling both suitable ratios.
Menthol provided by the invention and menthanol lactic acid ester compositions are characterized in: the weight ratio of menthol and menthanol lactic acid ester is in 2: 8~8: 2 scope, and its freezing point is lower than 25 ℃ of room temperatures;
Menthol provided by the invention and menthanol lactic acid ester compositions, more suitably ratio be the weight ratio of menthol and menthanol lactic acid ester in 3.5: 6.5~6.5: 3.5 scopes, its freezing point is lower than 15 ℃;
Menthol provided by the invention and menthanol lactic acid ester compositions, best component is: the part by weight of menthol and menthanol lactic acid ester is 1: 1, its freezing point is not higher than 8.5 ℃.
According to the present invention, menthol and menthanol lactic acid ester compositions at room temperature are in a liquid state.
The concrete operations technology that realizes the object of the invention is as follows:
Menthol and menthanol lactic acid ester compositions can make by following steps as freshener, abnormal smells from the patient regulator, spice:
A. menthol and menthanol lactic acid ester part by weight are set in 1: 4-4: 1, and both add in the container,
B. stirring at low speed under the room temperature,
C. mixture stops to stir to transparent clarification,
D. the said mixture suitable containers of packing into can be used as freshener, abnormal smells from the patient regulator, spice,
E. repeat the a-c step as required.
Menthol provided by the present invention and menthanol lactic acid ester compositions, its advantage is: said composition at room temperature promptly is in a liquid state, and makes freshener with it and uses very conveniently in product, does not need heat fused, both save the cost that equipment drops into, saved the energy again.And simplified production technology, saved the operating time, can be used at room temperature, cold technology manufacture process, thereby make produce convenient and economical.
Menthol provided by the invention and menthanol lactic acid ester compositions are done the application of freshener, abnormal smells from the patient regulator, spice, also can be made of said composition and other adjuvant.Adjuvant can be liquids such as the water dispersant of menthol and menthanol lactic acid ester, pure system, oils and fats, silicone oil, esters or quintessence oil; These liquids can not satisfy the requirement of product to activity concentration to the dissolubility deficiency of menthol and menthanol lactic acid ester, but can be used as the liquid dispersion carrier of compositions.The dispersion form of this compositions can provide freshener, abnormal smells from the patient regulator, the spice of the high concentration of other form for practical application, has expanded the range of application of compositions greatly.In prescription, because the fused matter of menthol and menthanol lactic acid ester exists, can be prescription provides than the higher concentration of other possibility modes as freshener, abnormal smells from the patient regulator, fragrance applications for menthol provided by the invention and menthanol lactic acid ester compositions.
The concrete operations that the compositions of above-mentioned dispersion form realizes are as follows: the compositions of menthol and menthanol lactic acid ester is added suitable surfactant, mix with above-mentioned materials of mentioning such as water, oil, fat, carry out homogenizing.Can obtain the said composition dispersion.
Compositions provided by the invention and dispersion thereof can be used in the multiple product that influences mucosa and skin, as toothpaste, collut, perfume, lotion, shaving cream, back preparation, shampoo, antiperspirant, deodorizer, beverage, chewing gum, tobacco product and medicinal product etc. shave.
Compositions provided by the invention is as freshener, has moment refrigerant sensation and refrigerant persistency good advantage all.
Description of drawings
Fig. 1 is in the present invention's the compositions, the graph of a relation of menthol content and said composition freezing point.
The specific embodiment
Embodiment 1:
Be under 23 ℃ the condition, 50g solid menthol and 50g solid menthanol lactic acid ester to be dropped in the beaker in indoor temperature, with agitator stirring at low speed 20 minutes, compositions became complete clarifying liquid.Freezing point to said composition detects, and measuring its freezing point is 8.2 ℃.
Embodiment 2:
Be under 23 ℃ the condition, 25g solid menthol and 75g solid menthanol lactic acid ester to be dropped in the flask in indoor temperature, use the agitator stirring at low speed, after 20 minutes, compositions becomes complete clarifying liquid.The freezing point of measuring said composition is 20.5 ℃.
Embodiment 3:
Be under 23 ℃ the condition, 75g solid menthol and 25g solid menthanol lactic acid ester to be dropped in the flask in indoor temperature, use the agitator stirring at low speed, after 20 minutes, compositions becomes complete clarifying liquid.The freezing point of measuring said composition is 21.1 ℃.
Embodiment 4:
With the compositions 10g among the embodiment 1, add 3g polysorbate60 and 87g water, homogenizing at room temperature, the homogenizer rotating speed is 5000rpm, makes 10% stable menthol of milky and menthanol lactic acid ester water dispersant.
Embodiment 5:
With the compositions 10g among the embodiment 1, add 3.6g Phospholipid SV (hard ester acyl ammonium propyl group propylene glycol list phospholipid base alkyl dimethyl ammonium chloride), 3.6g Brij72 (polyoxyethylene-2-monostearate), and add entry to total amount 100g, at room temperature use common homogenizer homogenizing, at high pressure high-shear emulsion machine homogenizing, make milky stable 10% nanometer menthol and menthanol lactic acid ester water dispersant again.
Embodiment 6:
With the compositions 20g among the embodiment 1, add 5g department classes 80 and 75g diformazan silicone, homogenizing at room temperature, the homogenizer rotating speed is 5000rpm, makes the 20% stable menthol of milky and the oil dispersant of menthanol lactic acid ester.

Claims (10)

1, menthol and menthanol lactic acid ester compositions is characterized in that: the weight ratio of menthol and menthanol lactic acid ester is in 2: 8~8: 2 scope, and its freezing point is lower than 25 ℃ of room temperatures.
2, menthol according to claim 1 and menthanol lactic acid ester compositions, more suitably ratio be the weight ratio of menthol and menthanol lactic acid ester in 3.5: 6.5~6.5: 3.5 scopes, its freezing point is lower than 15 ℃.
3, menthol according to claim 1 and menthanol lactic acid ester compositions, best component is: the part by weight of menthol and menthanol lactic acid ester is 1: 1, its freezing point is not higher than 8.5 ℃.
4, menthol according to claim 1 and menthanol lactic acid ester compositions, the menthol component comprises all optical isomers of menthol, the menthanol lactic acid ester component comprises all optical isomers of menthanol lactic acid ester.
5, make freshener according to claim 3 and 4 described compositionss, be applied in the prescription, the fused matter of menthol and menthanol lactic acid ester exists, and can be prescription provides than the higher concentration of other possibility modes.
6, make the abnormal smells from the patient regulator according to claim 3 and 4 described compositionss, be applied in the prescription, the fused matter of menthol and menthanol lactic acid ester exists, and can be prescription provides than the higher concentration of other possibility modes.
7, make spice according to claim 3 and 4 described compositionss, the fused matter of menthol and menthanol lactic acid ester exists, and can be prescription provides than the higher concentration of other possibility modes.
8, menthol and menthanol lactic acid ester compositions can make by following steps as freshener, abnormal smells from the patient regulator, spice:
A. menthol and menthanol lactic acid ester part by weight are set in 1: 4-4: 1, and both add in the container;
B. stirring at low speed under the room temperature;
C. mixture stops to stir to transparent clarification;
D. the said mixture suitable containers of packing into can be used as freshener, abnormal smells from the patient regulator, spice;
E. repeat the a-c step as required.
9, preparation method according to claim 8, menthol and menthanol lactic acid ester weight ratio preferably are 3.5: 6.5-6.5: 3.5.
10, preparation method according to claim 8, the best weight ratio of menthol and menthanol lactic acid ester is 1: 1.
CNB021380775A 2002-08-07 2002-08-07 Menthanol and menthanol lactic acid ester composite and its preparation method and application Expired - Lifetime CN1158987C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104491092A (en) * 2014-12-12 2015-04-08 湖南天龙制药有限公司 Composition for refreshing brain and regaining consciousness and preparation method thereof
CN108360256A (en) * 2017-09-29 2018-08-03 上海大学 A kind of interim curable type material of liquid and its preparation method and application
CN112245317A (en) * 2020-09-07 2021-01-22 广州雨晓生物制品有限公司 Mouthwash

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104491092A (en) * 2014-12-12 2015-04-08 湖南天龙制药有限公司 Composition for refreshing brain and regaining consciousness and preparation method thereof
CN108360256A (en) * 2017-09-29 2018-08-03 上海大学 A kind of interim curable type material of liquid and its preparation method and application
WO2019062216A1 (en) * 2017-09-29 2019-04-04 上海大学 Liquid-state temporary reinforcing material, preparation method therefor and application thereof
US11873605B2 (en) 2017-09-29 2024-01-16 Shanghai University Liquid-state temporary reinforcing material, preparation method therefor and application thereof
CN112245317A (en) * 2020-09-07 2021-01-22 广州雨晓生物制品有限公司 Mouthwash

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