Title of Invention

COMPOSITION OF MENTHYL LACTATE AND A MIXTURE OF MENTHOL ISOMERS

Abstract A coolant composition comprising a) menthyl lactate b) neomenthol, and c) menthol, wherein the added amount of components a), b) and c) is in the range of from 80 to 100% by weight, based on the total weight of the composition, and wherein said composition has a solidification point below +5°C.
Full Text

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the application of a mixture of menthyl lactate,
neomenthol and menthol as cooling agent or flavoring agent. In particular, this
invention relates to a coolant composition comprising menthyl lactate,
neomenthol and menthol having a solidification point below +5°C.
2. Description of the Prior Art
Menthol is a physiological cooling agent well known to the person skilled in the
art for its analgesic, freshening and flavoring effects on the skin and/or mucous
membranes.
Being a major constituent of peppermint oil, menthol has been used extensively
in foodstuff, beverages, dentifrices, mouthwashes, skin and hair care
preparations, confectionary, tobacco and pharmaceutical products.
A strong initial cooling sensation can be achieved if products containing menthol
are applied to the skin and/or mucous membrane. However, very often there is a
need for products containing a coolant composition in order to provide for a long-
lasting cooling sensation.

Menthyl lactate also is an important ingredient that is valued for its cooling
properties. Compared to menthol, one of the advantages of menthyl lactate is its
long-lasting cooling sensation as well as low volatility. However, menthyl lactate
does not produce an initial cooling sensation as strong as menthol.
The disadvantage of an addition of menthyl lactate to products is that it has to be
either melted at a temperature of 50-60°C or dissolved in perfume oils, cosmetic
oils, or glycol solvents such as 1,2-propylene glycol or dipropylene glycol. When
adding menthyl lactate to shampoos, shower gels or foam bath products, it is
advisable to first dissolve it in perfume oil or glycol solvents. The resulting
solution can then be mixed with the surfactants required.
Menthyl lactate is available from Symrise GmbH & Co. KG (Germany) in two
forms, the crystalline and the non-crystalline form:
The non-crystalline form (solidified distillate) has a congealing point of min. 40°C
and an appearance of solid, white substance, while the crystalline form has a
congealing point of min. 42°C and an appearance of white, crystalline powder
(EP 0 794 169). The non-crystalline form has the disadvantage of less
convenient handling because the product has to be melted in order to remove it
from the container, which means that the container has to be heated together
with the product.
The crystalline form has the advantage of easy handling. However, it is not
always convenient or easy to mix the powder into foodstuff, oral care or cosmetic
product bases, which may be in a liquid or a paste-like form. To solve this
problem, the crystals can be solubilized using an acceptable solvent, before
adding the solution to such a product base. However, this solubilization
constitutes an extra processing step for the formulator, making it inconvenient
and more costly to use.
There have been reports in the literature where menthol and menthyl lactate
have been used in the same formulation by adding menthol and menthyl lactate

separately. For example, WO 00/42983 describes a cosmetic composition
containing menthol and menthyl lactate, having little odor and being non-irritating.
The composition comprises 0.01% to 2% by weight menthol and 0.1% to 10% by
weight menthyl lactate, the menthol/menthyl lactate ratio lying in the range of 1/1
to 1/10, preferably 1/6 to 1/2, and being such that the odor of the menthol is
barely perceivable, said composition not being irritating, in particular for the
sensitive parts of the human body, while conserving the various beneficial effects
of menthol.
JP 06329528 and JP10231238 relate to cosmetic composition where menthol
and menthyl lactate were used in the same formulation by adding them
separately in a ratio of 1/1 and 2/1, respectively. In JP 06329528, the menthol
and menthyl lactate concentration ranged from 0.1% : 0.1 % (ratio 1:1) to 0.2% :
0.2% (ratio 1:1) in the examples, while it was claimed that the menthol
concentration can be in the range of 0.001-10.0% (w/w) and menthyl lactate can
also be added in the range of 0.001-10.0%. In JP 10231238, it was reported that
0.2% menthol and 0.1% menthyl lactate be used in the same formulation with a
ratio of 2:1.
Attempts to provide liquid mixtures of menthol and menthyl lactate mixtures that
solve the above mentioned problems have been published.
WO 2004/037764 refers to a solution consisting essentially of menthyl lactate
and menthol carboxamide dissolved in a solvent, wherein the final menthyl
lactate concentration is higher than that achievable by dissolving menthyl lactate
in a neat solvent, by a) liquefying menthyl lactate, and b) combining the liquefied
menthyl lactate with menthol carboxamide and the solvent, the solvent being
acceptable for food, oral care or cosmetic use.
US 2004/0018954 discloses mixtures containing menthol and menthyl lactate,
characterized in that it comprises menthol and menthyl lactate in a ratio by weight
in the range of 1:4 to 4:1 and the corresponding crystallization point is below
room temperature of 25°C. Such a composition which is liquid at room

temperature was produced by stirring menthol and menthyl lactate in solid form
within the mentioned ratio without heating, i.e. without melting the components.
The lowest crystallization point reported was 8.2°C for a mixture of 50% l-menthol
and 50% l-menthyl l-lactate.
Although US 2004/0018954 states that the term "menthol" and "menthyl lactate"
covers not only all such stereoisomers, but also any racemate or mixture of said
stereoisomers, the authors only investigated and used the common and widely
available commercial products l-menthol and l-menthyl l-lactate.
One main disadvantage of the liquid compositions proposed in the prior art.is that
the solidification points achievable are not low enough to enable storage at
temperatures below +5°C or lower without solidifying, especially not for a
prolonged period of time. From an industrial point of view this disadvantage is
significant since a product, once it has been solidified within a container (typically
barrel or tank), needs to be melted before removal therefrom, which means that
the container has to be heated together with the product with all the
disadvantages outlined above.

OBJECTS OF THE INVENTION
The main object of the present invention is to provide a composition containing
menthyl lactate and menthol that maintains its liquid state at temperatures below
+5°C, preferably without the need of adding a conventional solvent or solubilizer,
which can be added directly in liquid form into a formulation of a product without
the need of heating or melting of said coolant composition prior to addition to said
formulation, being non-irritating and of little odor.
Another object of the present invention is to provide a coolant composition that
combines both a strong initial cooling sensation and a long-lasting cooling
sensation to a product when applied on the skin and/or mucous membrane.
Accordingly, there remains a need to provide menthyl lactate in liquid form, which
is easy to use in further formulations or process operations and which remains
stable in liquid form at temperatures below +5°C, preferably at 0°C or below even
during a prolonged period of storage.
SUMMARY OF THE INVENTION
Surprisingly, it has now been found that a (coolant) composition comprising
menthyl lactate and having a solidification point of below + 5°C can be obtained
when menthyl lactate is combined, mixed or co-dissolved with a favourably
(liquid) mixture of neomenthol, menthol and optionally neoisomenthol and/or
isomenthol.
In a first aspect the present invention refers to a (coolant) composition comprising
menthyl lactate, neomenthol and menthol and optionally neoisomenthol and/or
isomenthol having a solidification point below +5°C. The composition of the
invention does not require the addition of a conventional solvent. Typically, the

coolant compositions according to the present invention are clear liquid solutions
at temperatures between +5°C and -20°C.
Within the concept of the present invention a method is provided for preparing a
clear liquid solution containing menthyl lactate and menthol, wherein the final
menthyl lactate concentration is higher than that achievable by mixing menthyl
lactate and menthol alone, by combining menthyl lactate and [a (liquid) mixture]
of neomenthol and menthol.
It was also found that a composition according to the present invention provides
both a strong initial cooling sensation and a long-lasting cooling sensation. It has
also been found that the cooling sensation of the (coolant) composition
comprising menthyl lactate, neomenthol and menthol taught herein are often not
merely additive, but a synergistic cooling sensation often were observed.
Thus, the use of the (coolant) compositions comprising menthyl lactate,
neomenthol and menthol as a cooling and/or flavoring agent is a further aspect of
the present invention.
A (coolant) composition of the present invention may be employed in a wide
variety of products for consumption by or application to the human body, e. g.,
foodstuff or oral care products such as toothpastes and mouthwashes, chewing
gums, confectionery, alcoholic and non-alcoholic beverages, cosmetic and
toiletry products such as shaving products, after-shave products, hair and
skincare products, bath and shower products, face cleansing products,
deodorants and antiperspirants, sun protection and sun tan products, after sun
products, anticellulite/slimming products, make-up products e.g. lip sticks, talcum
powders, fragrances, and other products such as detergents, fabric softeners,
soaps, tobacco products, medicaments etc.
A further aspect of the invention is a product, preferably foodstuff, oral care or
cosmetic product into which has been added an amount of a (coolant)
composition according to the present invention sufficient to provide a cooling

effect. Such foodstuff, oral care or cosmetic product may be provided with the
(coolant) composition according to the present invention by any useful method, e.
g., by simple addition to, and mixing into the (foodstuff, oral care or cosmetic)
product bases an effective amount of the coolant composition according to the
present invention.
A method of preparing a product according to the present invention particularly
relevant in practice comprises the following steps:
storing a composition according to the present invention at a temperature
(i) below +5 °C (e. g. in an outside container during wintertime) but (ii) above the
solidification point of said composition,
mixing the composition with components of the product base to form the
product,
wherein said composition is not solidified between storing and mixing.
DETAILED DESCRIPTION OF THE INVENTION
Unexpectedly, the (coolant) compositions according to the present invention
comprising menthyl lactate, neomenthol, menthol and optionally neoisomenthol
and/or isomenthol have significantly lower solidification points than those
reported in US 2004/0018954 although neomenthol and neoisomenthol and/or
isomenthol have higher melting points than the corresponding menthol-isomer
(vide infra).
Further it was found that (coolant) compositions according to the present
invention comprising menthyl lactate, neomenthol, menthol and optionally
neoisomenthol and/or isomenthol allow more variations regarding the weight
ratios of menthyl lactate and menthol-isomers than indicated in US
2004/0018954.

It was further observed that certain mixtures according to the present invention of
menthyl lactate, neomenthol, menthol and optionally neoisomenthol and/or
isomenthol yield a shelf-stable liquid product with a solidification point below -
20°C. A mixture of neomenthol, menthol and optionally neoisomenthol and/or
isomenthol allows dissolution of menthyl lactate in varying amounts, the resulting
composition having a low solidification point as desribed in more detail below.
The general formula for menthyl lactate is shown as follows:

Menthyl lactate may be obtained by reacting menthol with lactic acid to form the
corresponding ester. Menthyl lactate contains 4 asymmetrical carbon atoms. It
therefore exists in 16 different stereoisomers, whereas the commonly used ones
(formula la) are made from l-menthol and l-lactic acid or d-lactic acid. L-menthyl I-
lactate (formula (lb)) has a congealing point of 40-42°C and is commercially
available.
Menthol can be obtained naturally from essential oils, e.g. peppermint oil, or can
be of synthetic origin. Menthol contains three asymmetrical carbon atoms.
Therefore exist 8 different stereoisomers comprising menthol, neomenthol,
isomenthol, and neoisomenthol. However, only the l-menthol (i. e. (-)-menthol) of
formula (IIa) has been widely used, and its melting point is 42-43°C.

Menthol and its isomers can be illustrated by the following formulas, showing one
enantiomer each of the four diastereomers.

The enantiomers (lla) to (lId) and their optical antipodes may, for example, be
obtained by hydrogenation of thymol (e.g. WO 2004/018398 and the references
cited therein) or via cyclization of citronellal to the corresponding isopulegol-
isomers and subsequent hydrogenation. The isomers can be separated via
accurate distillation (for more details on manufacturing and separation of menthol
isomers see "Common Fragrance and Flavor Materials", 4th Edition, Wiley-VCH,
Weinheim 2001, 52-55).
Racemic neomenthol (i.e. a 1:1 - mixture of formula (lIb) and its optical antipode)
has a melting point of about 53°C. It should be mentioned that neomenthol,
regardless its stereoisomeric form, does not exhibit a strong cooling sensation

when compared to menthol, in particular when compared to l-menthol. Racemic
and enantiopure neomenthol is commercially available, e.g. from Sigma-Aldrich.
The present invention provides a (coolant) composition with a solidification point
below + 5 °C, the composition comprising a) menthyl lactate, b) neomenthol and
c) menthol, wherein preferably the weight ratio of a) to the sum of b) and c) is in
the range of 6:1 to 1:15 and the weight ratio of b) to c) is in the range 20:1 to
1:10.
In a preferred embodiment the weight ratio of a) to the sum of b) and c) is in the
range of 4:1 to 1:10, more preferred in the range of 2:1 to 1:10 and particularly
preferred in the range of 1:2 to 1:8.
In a preferred embodiment the weight ratio the weight ratio of b) to c) is in the
range of 15:1 to 1:3, more preferred in the range of 10:1 to 1:1 and particularly
preferred in the range of 6:1 to 2:1.
Particularly preferred coolant compositions according to the present invention
comprise menthyl lactate, neomenthol and menthol in a total amount of 80 to
100%, preferably 85 to 100%, by weight, based on the total weight of the coolant
composition according to the present invention.
A (coolant) composition according to the present invention has a solidification
point below +5°C, preferably a solidification point of 0°C or below, more
preferably of -10°C or below.
Preferably in the (coolant) compositions according to the present invention
racemic menthol and/or racemic neomenthol are used.
In a particularly preferred embodiment a (coolant) composition according to the
present invention comprises neoisomenthol (formula (lId) and/or its enantiomer),
preferably racemic neoisomenthol, in an amount, of up to 10%, preferably 3 to
8%, by weight, based on the total weight of the coolant composition according to

the present invention. Racemic neoisomenthol has a melting point of about 52-
53°C.
The following Table 1 indicates solidification points of different mixtures. At 25-
30°C mixtures were prepared by combining and homogenizing the amounts
indicated by weight of l-menthyl l-lactate and racemic neomenthol and/or racemic
menthol. The resulting mixtures were then stored for 48 hours at temperatures of
+4°C, -10°C or -20°C respectively and their solid or liquid state determined
visually.


Table 1
In a particularly preferred embodiment a coolant composition according to the
present invention comprises or essentially consists ( i.e. the sum of menthyl
lactate, neomenthol, menthol, neoisomenthol, and isomenthol used is equal to or
greater than 96%, preferably equal to or greater than 98%, by weight) of
a) 10 - 40%, preferably 10 - 30%, more preferably 10 - 20%, of menthyl lactate,
b) 25 - 75%, preferably 40 - 75%, more preferably 50 - 70%, of neomenthol,
c) 5 - 30%, preferably 10 - 30%, more preferably 10 - 25%, of menthol,
d) 0 -10%, preferably 3 - 8%, more preferably 4 - 7%, of neoisomenthol, and
e) 0 -10%, preferably 0.5 - 3%, more preferably 0.5 - 2%, of isomenthol,
by weight, based on the total weight of the coolant composition according to the
present invention.
According to a further particularly preferred embodiment a coolant composition
according to the present invention further comprises 0.1 - 3%, more preferably
0.5 - 2%, by weight of menthone and/or isomenthone.
Solidification pointsbelow -30°C, were obtained with coolant compositions
comprising l-menthyl l-lactate, racemic neomenthol, racemic menthol and,
optionally, racemic neoisomenthol and/or racemic isomenthol.
The coolant composition of the invention exhibits excellent storage stability. It has
been observed that neither menthyl lactate nor neomenthol nor menthol nor the
optional components neoisomenthol and isomenthol precipitate from the liquid,
even at very low storage temperatures of about -20°C and even at temperatures
of about -30°C. Thus, a coolant composition comprising menthyl lactate,
neomenthol, menthol and optionally neosiomenthol or isomenthol is provided
without having the aforementioned disadvantages of a solid product.

Furthermore, due to its liquid form, it is considerably easier to manufacture
products containing the (coolant) compositions according to the present
invention, particularly foodstuff, oral care and cosmetic products, rather than
using a powder or an other solid mass which has to be melted prior to use.
The sensory properties of the different menthol-isomers are described in Rivista
Italiana EPPOS 1995 Special edition, 31.08. - 02.09.1995, 111-115. It is well
known that menthol, most particularly l-menthol, exhibits the strongest and
freshest sensory profile among menthol and its isomers.
The presence of menthol (and the isomers neomenthol and/or neoisomenthol
and/or isomenthol to a smaller extent) in the coolant composition according to the
present invention provides a strong initial cooling sensation, and the menthyl
lactate portion provides the long-lasting cooling sensation. Furthermore,
surprisingly it has been found that the cooling sensation of the coolant
composition according to the present invention comprising menthyl lactate,
neomenthol, menthol and optionally neoisomenthol and/or isomenthol often not
merely reflects the additive effects of the ingredients. Unexpectedly, when
coolant compositions of the present invention were tested by trained panelists in
sensory evaluations against menthyl lactate, neomenthol or menthol individually,
a synergistic cooling sensation was often observed. This surprising synergistic
effect is described in more detail in the examples presented below.
A coolant composition according to the present invention, as a cooling and/or
flavoring agent, has the advantage of providing both a strong initial cooling
sensation as well as a long-lasting cooling sensation.
Coolant compositions according to the present invention are therefore eminently
suitable for incorporation into foodstuff, oral care and cosmetic products in order
to deliver the desired cooling sensation by consumption or application to the
human body.

The presence of (racemic) neomenthol in a coolant composition according to the
present invention reduces or even eliminates the harshness caused by menthol,
in particular when using l-menthol, without reducing the overall cooling sensation
when compared to the use of l-menthol alone.
In view of the teaching of the present invention the skilled formulator in the art is
able to adjust an appropriate ratio of menthyl lactate to neomenthol, menthol and
optionally neoisomenthol and/or isomenthol in order to achieve any desired
sensory effect as a matter of routine or by a few routine experiments.
A coolant composition of the present invention may be prepared according to the
following procedure: under stirring solid menthyl lactate is either directly
dissolved in a liquid mixture comprising or consisting of neomenthol, menthol and
optionally neoisomenthol and/or isomenthol or alternatively first liquefied or
melted, typically at a temperature of about 40°C to 50°C, prior to addition to the
liquid mixture of neomenthol, menthol and optionally neoisomenthol and/or
isomenthol. The procedure results in a shelf-stable coolant composition of the
present invention.
Alternatively, the coolant composition of the present invention may be formed by
liquefying or melting menthyl lactate, typically at a temperature of about 40°C to
50°C, and adding neomenthol, menthol and optionally neoisomenthol and/or
isomenthol, preferably in form of a (liquid) mixture, under stirring. The procedure
results in a shelf-stable coolant composition of the present invention.
As stated hereinabove, the (coolant) compositions of the present invention are
provided in a liquid form even below + 5°C that exhibits excellent shelf life with no
precipitation. This major advantage allows storage of the coolant composition
under conditions of varied humidity and temperature e. g. in the range of -20 °C
to 40 °C, makes it easy to handle and to add directly into formulations without
heating, thereby saving time, energy and money. Additionally, the liquid coolant
composition of the present invention can be used for manufacturing products
without heating.Examples of other cooling substances which advantageously can

be combined with a coolant composition according to the present invention and
incorporated into products, such as products for direct consumption by or
application to the human body, are, for example, substances having a
physiologically cooling action, that is to say substances which cause an
impression of cold on human skin and/or in the mucous membranes. Suitable
substances having a cooling action are, for example, 1-isopulegol, menthone
glycerol acetal, substituted menthane-3-carboxamides (for example N-
ethylmenthane-3-carboxamide), 2-isopropyl-N,2,3-trimethylbutanamide,
substituted cyclohexanecarboxamides, 3-menthoxy-1,2-propanediol, 2-
hydroxyethylmenthyl carbonate, 2-hydroxypropylmenthyl carbonate, N-
acetylglycine menthyl ester, menthylhydroxycarboxylic esters (for example
menthyl 3-hydroxybutyrate), menthyl monosuccinate, 2-mercaptocyclodecanone,
and menthyl 2-pyrrolidin-5-one carboxylate, l-menthyl methyl ether.
For use in food and oral care products, a coolant composition of the present
invention are favorably employed at levels of 0.01% to 5% by weight, preferably
from 0.05% to 3%, more preferably from 0.1% to 2% by weight, based on the
total weight of the food or oral care product.
For use in cosmetic products, the coolant compositions of the present invention
are favorably employed at levels of 0.01% to 10% by weight, preferably from
0.05% to 5%, more preferably from 0.1% to 2% by weight, based on the total
weight of the cosmetic product. However, it is understood that the skilled person
may employ the inventive coolant compositions in amounts outside the
aforementioned ranges to achieve sensorial effects as desired.
Products in which the coolant composition of the present invention
advantageously may be incorporated are many and varied. These products
include a wide variety of products for consumption by or application to the human
body. The following illustrate the range of products into which coolant
compositions of the present invention can be incorporated: edible or potable
products including alcoholic and non-alcoholic beverages, confectionery, chewing
gum, ice cream, jellies, cosmetics and toiletries including after shave lotions,

shaving soaps, creams and foams; toilet water, deodorants and antiperspirants,
„solid colognes", toilet soaps, bath foams, oils and salts; shower gels, body wash,
hair shampoos, oils, conditioners, tonics, creams, gels and antidandruff
shampoos; talcum powders, face creams, lotions, tonics and gels; hand creams,
hand and boby lotions, anticellulite/slimming creams and lotions, sunscreen
lotions, balms, gels, sprays and creams; after sun lotions, sprays and gels; lip
sticks, cleansing tissues, dentifrices, toothpicks, mouthwashes. Other products
are pharmaceutical products such as antiseptic ointments, liniments and lotions,
cough mixtures, oral analgesic, tobacco preparations, detergents, fabric
softeners, water soluble adhesive products for envelopes, postage stamps,
adhesive labels etc.
The coolant compositions according to the present invention are essentially
insoluble in water. It is therefore preferred to incorporate them into products in a
way so that they remain stably distributed throughout the products. This can be
done by forming a dispersion, emulsion, or microemulsion, with the=compositions
solubilized in a suitable solvent that then becomes part of the dispersion or
emulsion (including microemulsions). Emulsion systems include oil-in-water,
water-in-oil, water-in-oil-in-water, and oil-in-water-in-silicone emulsions. The
emulsions can cover a broad range of consistencies including thin lotions (which
can also be suitable for spray or aerosol delivery), creamy lotions, light creams,
heavy creams, and the like. Suitable solvents for the compositions according to
the present invention include lipophilic or nonpolar solvents such as diethylene
glycol, dipropylene glycol, C1-C6 alcohols, acetone, and other organic solvents,
many of which are also suitable for use as perfume solvents.
Products comprising coolant compositions according to the present invention
can, depending on their formulation, be used, for example, as creams, gels,
lotions, alcoholic and aqueous/alcoholic solutions, emulsions or stick
preparations. These products may also comprise, as further auxiliaries and
additives, mild surfactants, co-emulsifiers, superfafting agents, pearlescent
waxes, bodying agents, thickeners, polymers, silicone compounds, fats, waxes,
stabilizers, biogenic active ingredients, deodorant active ingredients, antidandruff

agents, film formers, swelling agents, hydrotropic agents, preservatives, insect
repellants, tanning agents, artificial self-tanning agents (e.g. dihydroxyacetone),
stabilizers, antioxidants, perfume oils, dyes, antimicrobial agents and the like.
The amounts of cosmetic or dermatological auxiliaries and carrier and perfume
which can be used in each case can be determined easily by the person skilled in
the art by simple trial and error, depending on the nature of the product in
question.
A lipid phase of products comprising a coolant composition of the present
invention can advantageously be chosen from the following group of substances:
mineral oils, mineral waxes; oils, such as triglycerides of capric or of caprylic acid,
and also natural oils, such as, for example, castor oil; fats, waxes and other
natural and synthetic fatty substances, preferably esters of fatty acids with
alcohols of low carbon number, e.g. with isopropanol, propylene glycol or
glycerol, or esters of fatty alcohols with alkanoic acids of low carbon number or
with fatty acids; alkyl benzoate; silicone oils, such as dimethylpolysiloxane,
diethylpolysiloxane, diphenylpolysiloxane, and mixed forms thereof.
The aqueous phase of products comprising a coolant composition according to
the present invention advantageously comprises one or more of the following
substances: alcohols, diols or polyols (lower alkyl), and ethers thereof, preferably
ethanol, isopropanol, propylene glycol, glycerol, ethylene glycol-monoethyl or
monobutyl ether, propylene glycol monomethyl, -monoethyl or monobutyl ether,
diethylene glycol monomethyl or -monoethyl ether and analogous products, and
also alcohols (lower alkyl), e.g. ethanol, 1,2-propanediol, glycerol, and, in
particular, one or more thickeners which can advantageously be chosen from the
group of silicon dioxide, aluminum silicates, polysaccharides and derivatives
thereof, e.g. hyaluronic acid, xanthan gum, hydroxypropylmethylcellulose,
particularly advantageously from the group of polyacrylates, preferably a
polyacrylate from the group of so-called Carbopols, for example, Carbopol
grades 980, 981, 1382, 2984, 5984, in each case individually or in combination.

Cosmetic and/or dermatological products comprising a coolant composition
according to the present invention can have the customary constitution and can
be used to convey a refreshing / cooling sensation to the human body, and also
for the treatment, care and cleansing of the skin and/or of the hair and as a
make-up product in decorative cosmetics. Preference is given to those cosmetic
and dermatological products in the form of a cosmetic product which are used to
convey a refreshing / cooling sensation to the human body, in particular the
human skin.
The following examples illustrate the various aspects of the present invention.
Unless indicated otherwise all parts, amounts and percentages are by weight.
EXAMPLE 1
A mixture of 76.9 g racemic neomenthol, 14.8 g racemic menthol, 6.6 g racemic
neoisomenthol and 1.7 g racemic isomenthol were stirred resulting in a liquid
mixture (Mix A). Alternatively such a liquid mixture can be obtained via
hydrogenation of thymol (see WO 2004/018398) and subsequent distillation.
25 g of l-menthyl l-lactate were warmed to 45-50°C to liquefy the l-menthyl I-
lactate and added with stirring to 75 g of Mix A.
The resulting clear solution was allowed to cool and then stored at -20°C for 48 h.
No precipitation or solidification was observed.
EXAMPLE 2
A mixture of 67.8 g racemic neomenthol, 25.6 g racemic menthol, 5.6 g racemic
neoisomenthol and 1 g racemic isomenthol were stirred resulting in a liquid
mixture (Mix B). Alternatively such a liquid mixture can be obtained via
hydrogenation of thymol (see WO 2004/018398) and subsequent distillation.

15 g of l-menthyl l-lactate were warmed to 45-50°C to liquefy the l-menthyl I-
lactate and added with stirring to 85 g of Mix B.
The resulting clear solution was allowed to cool and then stored at -20°C for 48 h.
No precipitation or solidification was observed.
EXAMPLE 3
A mixture of 50 g racemic neomenthol and 50 g racemic menthol were stirred
resulting in a liquid mixture (Mix C).
25 g of l-menthyl l-lactate were warmed to 45-50°C to liquefy the l-menthyl I-
lactate and added with stirring to 75 g of Mix C.
The resulting clear solution was allowed to cool and then stored at -20°C for 48 h.
No precipitation or solidification was observed.
Comparative Example
To illustrate the solidification / precipitation of l-menthyl l-lactate in racemic
menthol alone, 25 g of l-menthyl l-lactate were liquefied by heating to 45-50°C
and mixed at 45-50°C with 75 g racemic menthol. Upon cooling and storage at
0°C for 8 h the mixture had completely solidified.
According to US 2004/0018954 a mixture consisting of 25 g l-menthyl l-lactate
and 75 g l-menthol has a solidification point of 21.1 °C.

EXAMPLE 4
A sensory test was carried out with a group of 19 trained panelists in order to
evaluate the performance of the coolant composition according to the present
invention of Example 2 consisting of 15% l-menthyl l-lactate, 57.6% racemic
neomenthol, 21.8% racemic menthol, 4.8% racemic neoisomenthol and 0.8%
racemic isomenthol) for topical applications.
The cooling sensation of the coolant composition of Example 2 was tested in
direct comparison to l-menthyl l-lactate. The mixture according to Example 2 and
l-menthyl l-lactate were separately incorporated into samples of an alcohol-free
face lotion at a level of 0.3%, based on the total weight of the face lotion.
Although neomenthol does not have a strong cooling sensation (vide supra) the
panelists found a significantly higher overall cooling sensation and preferred the
cooling sensation of the coolant composition of Example 2 according to the
present invention.
The presented data are average values. The overall cooling sensation was rated
on a scale of 1 to 5 (1 = very weak; 5 = very strong).



EXAMPLE 5
A sensory test was carried out with a group of 10 trained panelists in order to
evaluate the performance of the liquid coolant compositions of Examples 1 and 2.
Panelists were asked to assess the intensity of cooling sensation at certain time
periods on a line scale of zero to one hundred. Panelists held toothpaste
containing formulations of Example 1 (0.6% by weight based on total weight of
the toothpaste) and Example 2 (0.6% by weight based on the total weight of the
toothpaste) in their mouths for 90 seconds before spitting and rinsing. Panelists
recorded the cooling sensation at rinse (time zero), 30s, 60s, 90s, 2min, 3min, 4,
min, 5 min, 10 min, 15 min, 20 min, 25 min and 30 min.
Toothpastes containing a coolant composition produced according to Example 1
or Example 2 both outperformed toothpastes containing only menthyl lactate or
containing only racemic neomenthol and/or racemic menthol.
In the following examples reference is made to "Fresc 36-07" or "Fresc 36-37",
both being compositions according to the present invention.
"Fresc 36-07" is a mixture of 15% of l-menthyl l-lactate and 85% of a mixture of
menthol isomers consisting of 67.6% racemic neomenthol, 25.6% racemic
menthol, 5.5% racemic neoisomenthol, 0.7% racemic isomenthol, 0.4% racemic
menthone and 0.2% racemic isomenthone.

"Fresc 36-37" is a mixture of 15% of l-menthyl l-lactate and 85% of a mixture of
menthol isomers consisting of 78.0% racemic neomenthol, 13.7% racemic
menthol, 5.7% racemic neoisomenthol, 1.0% racemic isomenthol, 1.1% racemic
menthone and 0.5% racemic isomenthone.


Manufacturing Process
Part A:
Dissolve all ingredients in the water.
Part B:
Dissolve Cetiol SB 45 with heating to max. 35°C in Tegosoft TN. Add the other
ingredients of part B at ambient temperature. Disperse Pemulen evenly with high
shear stirring. Add part B with stirring to part A and homogenize.
Part C:
Add with stirring to part A/B and homogenize.
The pH value of the finished product should be approx. 6.0 and has to be
checked.
EXAMPLE 7
Face Cream (O/W) with Fresc 36-07


Manufacturing Process
Part A:
Heat to approx. 80°C.
Part B and C:
Swell Carbopol and Keltrol in water. Heat to approx. 80°C. Add part A to part B
using an Ultra-Turrax and emulsify, add part C while emulsifying. Allow to cool
while stirring.
Part D:
Mix the ingredients and add at approx. 30°C to the emulsion and homogenise.

The pH value of the finished product should be approx. 5.7 and has to be
checked.
EXAMPLE 8
Manufacturing Process
Transparent Hair Shampoo with Fresc 36-37


Part A:
Mix all ingredients.
Part B:
Mix Fresc 36-07 with Arlatone G and the fragrance. Then add to part A.
Part C:
Dissolve Polymer JR 400 in the water. Add the other ingredients and add part C
to part A/B. Stir until homogeneous.
The pH value of the finished product should be approx. 6.0 and has to be
checked.
EXAMPLE 9
Body Wash with Fresc 36-07


Manufacturing Process
Dissolve phase A by warming up slightly. Add ingredients of phase B in listed
order and dissolve.
The pH value of the finished product should be approx. 5.5 and has to be
checked.
EXAMPLE 10
Hair Tonic with Fresc 36-37


Manufacturing Process
Part A:
Dissolve Crinipan® AD and Fresc 36-07 in the other ingredients of part A.
Part B:
Mix all ingredients and add to part A.
The pH value of the finished product should be approx. 6.5 and has to be
checked.
EXAMPLE 11
Sunscreen Lotion with Fresc 36-07


Manufacturing Process
Part A:
Heat up to 85°C (without Keltrol and carbopol) until all ingredients completely
dissolved. Disperse Keltrol and Carbopol in part A.

Part B:
Heat part B to 85°C. Add part B to part A while stirring.
Part C:
Add directly. Homogenise the product for 5 minutes. Cool down to ambient
temperature.
Part D:
At ambient temperature add part D and homogenise.
The pH value of the finished product should be approx. 7.2 to 7.5 and has to be
checked.
EXAMPLE 12
Shower Gel with Fresc 36-07


Manufacturing Process
Part A:
Mix all ingredients.
Part B:
Mix the ingredients. The add part B to part A.
Part C:
Dissolve Polymer JR 400 under stirring in the water. Add the other ingredients of
part C and add to part A/B. Stir until homogeneous.
The pH value of the finished product should be approx. 6 and has to be checked.

EXAMPLE 13
Shaving Foam with Fresc 36-37

Manufacturing Process
Part A:
Dissolve Solbrol M in Sorbitol A, add the water. With mixing slowly add Myvatex
Texture Lite until well dispersed. Heat up to 40°C ( do not exceed 45°C).
Part B:
Combine and heat up to 60°C. Mix until uniform. Cool down to 50°C and add part
A to part B while stirring.
Part C:
Add part C to part A/B and continue mixing for approx. 20 minutes.

Part D:
Add to part A/B/C. Fill into aerosol containers.
Filling instructions:
95.30 % filling composition
4.70 % Propan/butan 2,7 bar
Remark on the can: Shake before use !
The pH value of the finished product should be approx. 7.0 and has to be
checked.



Manufacturing Process
Heat Phases A and B separately to approx. 80°C. Then add phase B to phase A
and emulsify (Ultra-Turrax). Allow the emulsion to cool while stirring using a vane
stirrer. Reduce stirring speed while the base is cooling. Add phase C at approx.
30°C.

The invention disclosed and claimed in the application, did not use any biological material, originating from india or outsourced from india.


WE CLAIM :
1. A coolant composition comprising
a) menthyl lactate
b) neomenthol, and
c) menthol,
wherein the added amount of components a), b) and c) is in the range of from
80 to 100% by weight, based on the total weight of the composition, and
wherein said composition has a solidification point below +5°C.
2. Composition as claimed in claim 1, further comprising
d) neoisomenthol and/or
e) isomenthol.
3. Composition as claimed in claim 1 or 2, wherein the weight ratio of component
a) to the sum of components b) and c) is in the range of from 6:1 to 1:15, and
the weight ratio of components b) to c) is in the range of from 20:1 to 1:10.
4. Composition as claimed in any preceding claim, comprising 10 - 40%,
preferably 10 - 30%, more preferably 10 - 20%, of menthyl lactate, 25 - 75%,
preferably 40 - 75%, more preferably 50 - 70%, of neomenthol, 5 - 30%, pref-
erably 10 - 30%, more preferably 10 - 25%, of menthol, 0 -10%, preferably 3 -
8%, more preferably 4 - 7%, of neoisomenthol, and 0 - 10%, preferably 0.5 -
3%, more preferably 0.5 - 2%, of isomenthol, by weight, based on the total
weight of the composition.
5. Composition as claimed in any preceding claim, wherein component a)
comprises or consists of 1-menthyl 1-lactate and/or component c) consists of 1-
menthol.

6. Product for consumption or application to the human body, wherein the product
is a food product, an oral care product, a cosmetic product or a pharmaceutical
product, comprising a coolant composition as claimed in any of claims 1 to 5 in
an amount sufficient to provide a cooling effect.
7. Method of preparing a product as claimed in claim 6, comprising the steps:
Storing a composition according to any of claims 1-5 at a temperature (i)
below +5 °C but (ii) above the solidification point of said composition,
Mixing the composition with components of the product base to form the
product,
wherein said composition is not solidified between storing and mixing.




ABSTRACT


COMPOSITION OF MENTHYL LACTATE AND A MIXTURE OF MENTHOL
ISOMERS
A coolant composition comprising a) menthyl lactate b) neomenthol, and
c) menthol, wherein the added amount of components a), b) and c) is in the
range of from 80 to 100% by weight, based on the total weight of the
composition, and wherein said composition has a solidification point
below +5°C.

Documents:

00933-kolnp-2007-correspondence-1.1.pdf

00933-kolnp-2007-form-3-1.1.pdf

0933-kolnp-2007 abstract.pdf

0933-kolnp-2007 assignment.pdf

0933-kolnp-2007 claims.pdf

0933-kolnp-2007 correspondence others.pdf

0933-kolnp-2007 description(complete).pdf

0933-kolnp-2007 form-1.pdf

0933-kolnp-2007 form-3.pdf

0933-kolnp-2007 form-5.pdf

0933-kolnp-2007 international publication.pdf

0933-kolnp-2007 international search authority report.pdf

0933-kolnp-2007 pct other.pdf

933-KOLNP-2007-(05-09-2011)-ABSTRACT.pdf

933-KOLNP-2007-(05-09-2011)-CLAIMS.pdf

933-KOLNP-2007-(05-09-2011)-CORRESPONDENCE.pdf

933-KOLNP-2007-(05-09-2011)-DESCRIPTION (COMPLETE).pdf

933-KOLNP-2007-(05-09-2011)-FORM 1.pdf

933-KOLNP-2007-(05-09-2011)-FORM 2.pdf

933-KOLNP-2007-(05-09-2011)-FORM 3.pdf

933-KOLNP-2007-(05-09-2011)-OTHERS.pdf

933-KOLNP-2007-(05-09-2011)-PETITION UNDER RULE 137.pdf

933-KOLNP-2007-(17-02-2012)-CORRESPONDENCE.pdf

933-KOLNP-2007-ASSIGNMENT.pdf

933-KOLNP-2007-CANCELLED PAGES.pdf

933-KOLNP-2007-CORRESPONDENCE 1.2.pdf

933-KOLNP-2007-CORRESPONDENCE-1.1.pdf

933-KOLNP-2007-EXAMINATION REPORT.pdf

933-KOLNP-2007-FORM 18.pdf

933-KOLNP-2007-FORM 3.pdf

933-KOLNP-2007-FORM 5.pdf

933-KOLNP-2007-GPA.pdf

933-KOLNP-2007-GRANTED-ABSTRACT.pdf

933-KOLNP-2007-GRANTED-CLAIMS.pdf

933-KOLNP-2007-GRANTED-DESCRIPTION (COMPLETE).pdf

933-KOLNP-2007-GRANTED-FORM 1.pdf

933-KOLNP-2007-GRANTED-FORM 2.pdf

933-KOLNP-2007-GRANTED-SPECIFICATION.pdf

933-KOLNP-2007-OTHERS.pdf

933-KOLNP-2007-REPLY TO EXAMINATION REPORT.pdf


Patent Number 255769
Indian Patent Application Number 933/KOLNP/2007
PG Journal Number 13/2013
Publication Date 29-Mar-2013
Grant Date 21-Mar-2013
Date of Filing 15-Mar-2007
Name of Patentee SYMRISE GMBH & CO. KG
Applicant Address MUHLENFELDSTRASSE 1, 37603 HOLZMINDEN
Inventors:
# Inventor's Name Inventor's Address
1 LANGNER, ROLAND. JAHNSTRASSE 9, 37639 BEVERN
2 NOWAK, REINHARD. 1607 WILLOWWICK CT., MT.PLEASANT, 29466 SOUTH CAROLINA, UNITED STATES OF AMERICA
PCT International Classification Number A61K 7/16
PCT International Application Number PCT/EP2004/052529
PCT International Filing date 2004-10-13
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA