U.S. patent application number 09/826494 was filed with the patent office on 2001-10-25 for cosmetic compositions.
This patent application is currently assigned to Unilever Home & Personal Care USA, Division of Conopco, Inc.. Invention is credited to Franklin, Kevin Ronald, Kowalski, Adam Jan, Parrott, David Terence, Rowe, Kathryn Elizabeth, White, Michael Stephen.
Application Number | 20010033851 09/826494 |
Document ID | / |
Family ID | 10851280 |
Filed Date | 2001-10-25 |
United States Patent
Application |
20010033851 |
Kind Code |
A1 |
Franklin, Kevin Ronald ; et
al. |
October 25, 2001 |
Cosmetic compositions
Abstract
A cosmetic composition preferably an antiperspirant composition,
in solid or soft-solid form has a continuous phase which contains a
water-immiscible liquid carrier and also contains a structurant
which is partially or fully esterified cellobiose of the formula 1
wherein each Z is independently hydrogen or an acyl group of the
formula 2 where R denotes a hydrocarbyl group containing from 4 to
22 carbon atoms. Not more than half of the Z groups are
hydrogen.
Inventors: |
Franklin, Kevin Ronald;
(Bebington, GB) ; Kowalski, Adam Jan; (Bebington,
GB) ; Parrott, David Terence; (Chicago, IL) ;
Rowe, Kathryn Elizabeth; (Bebington, GB) ; White,
Michael Stephen; (Bebington, GB) |
Correspondence
Address: |
UNILEVER
PATENT DEPARTMENT
45 RIVER ROAD
EDGEWATER
NJ
07020
US
|
Assignee: |
Unilever Home & Personal Care
USA, Division of Conopco, Inc.
|
Family ID: |
10851280 |
Appl. No.: |
09/826494 |
Filed: |
April 4, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09826494 |
Apr 4, 2001 |
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09548310 |
Apr 12, 2000 |
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6248312 |
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Current U.S.
Class: |
424/401 ;
424/400; 424/65 |
Current CPC
Class: |
A61K 8/042 20130101;
A61K 8/891 20130101; A61K 8/26 20130101; A61K 8/60 20130101; A61K
8/34 20130101; A61K 8/342 20130101; A61K 8/31 20130101; A61K 8/585
20130101; A61Q 15/00 20130101; A61K 8/894 20130101; A61K 8/28
20130101; A61K 8/37 20130101 |
Class at
Publication: |
424/401 ; 424/65;
424/400 |
International
Class: |
A61K 007/00; A61K
007/32 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 12, 1999 |
GB |
9908202.6 |
Claims
1. A composition of matter suitable for cosmetic use comprising a
continuous phase which contains a water-immiscible liquid carrier
and a structurant therein which is at least partially esterified
cellobiose of the formula 6wherein each Z is independently hydrogen
or an acyl group of the formula 7where R denotes a hydrocarbyl
group containing from 4 to 22 carbon atoms, with the proviso that
not more than half of the Z groups are hydrogen.
2. A composition according to claim 1 wherein at least five of
every eight groups Z are said acyl groups.
3. A composition according to claim 1 wherein at least
three-quarters of the said groups Z are said acyl groups.
4. A composition according to claim 2 or claim 3 wherein R denotes
an akyl or alkenyl group of 5 to 18 carbon atoms.
5. A composition according to claim 2 or claim 3 wherein R denotes
a linear alkyl group of 17 carbon atoms.
6. A composition according to claim 2 or claim 3 wherein R denotes
an alkyl group of 5 to 12 carbon atoms.
7. A composition according to claim 2 or claim 3 wherein R denotes
a linear alkyl group of 7 to 9 carbon atoms.
8. A composition according to claim 2 or claim 3 wherein R denotes
a linear alkyl group of 10 carbon atoms.
9. A composition according to claim 2 or claim 3 wherein
substantially all of the said groups Z are said acyl groups wherein
R is linear alkyl of 7 to 9 carbon atoms.
10. A composition according to claim 2 or claim 3 wherein
substantially all of the said groups Z are said acyl groups wherein
R is linear alkyl of 10 carbon atoms.
11. A composition according to any one of the preceding claims
characterised in that the water-immiscible liquid carrier contains
a volatile silicone and optionally a non-volatile silicone and/or a
non-silicone hydrophobic organic liquid selected from hydrocarbons,
hydrophobic aliphatic esters, aromatic esters, hydrophobic alcohols
and hydrophobic ethers.
12. A composition according to any one of the preceding claims
wherein the water-immiscible carrier liquid contains silicone oil
in an amount which is at least 10% by weight of the
composition.
13. A composition according to any one of the preceding claims
containing from 0.1 to 15% by weight of the structurant.
14. A composition according to any one of the preceding claims
which contains not more than 5% by weight of any fatty alcohol
which is solid at 20.degree. C.
15. A composition according to any one of the preceding claims
wherein the composition is an emulsion with a hydrophilic,
preferably water-miscible, disperse phase in addition to said
water-immiscible liquid continuous phase.
16. A composition according to claim 15 wherein the disperse phase
contains a diol or polyol.
17. A composition according to claim 15 or claim 16 which contains
from 0.1% to 10% by weight of a nonionic emulsifier.
18. A composition according to any one of claims 15 to 17 which
does not contain more than 8% by weight of ethanol or any
monohydric alcohol with a vapour pressure above 1.3 kPa at
22.degree. C.
19. A composition according to any one of claims 1 to 14 wherein
the composition is a suspension with a particulate solid material
dispersed in said liquid continuous phase.
20. A composition according to any one of the preceding claims
which is a deodorant or antiperspirant composition comprising a
deodorant or antiperspirant active.
21. A composition according to any one of claims 1 to 14 which is
an antiperspirant composition comprising a particulate
antiperspirant active in suspension in said water-immiscible
continuous phase.
22. A composition according to any one of claims 15 to 18 which is
an antiperspirant composition comprising an antiperspirant active
dissolved in said disperse phase.
23. A composition according to any one of claims 20 to 22 wherein
the antiperspirant active comprises an aluminium and/or zirconium
halohydrate, an activated aluminium and/or zirconium halohydrate,
or an aluminium and/or zirconium complex or an activated aluminium
and/or zirconium complex.
24. A composition according to claim 23 which is a halohydrate or
complex in which aluminium and zirconium are both present.
25. A composition according to any one of claims 20 to 24 wherein
the proportion of antiperspirant active is from 5 to 40% by weight
of the composition.
26. A composition according to any one of the preceding claims
which is a firm gel such that a penetrometer needle with a cone
angle of 9 degrees 10 minutes, drops into the gel for no more than
30 mm when allowed to drop under a total weight of 50 grams for 5
seconds.
27. A composition according to any one of the preceding claims
which is translucent or transparent.
28. A composition according to claim 27 which has at least 1%, and
preferably at least 3% light transmittance at 580 nm through a lcm
thickness of the composition at 22.degree. C.
29. An antiperspirant product comprising a dispensing container
having at least one aperture for delivery of the contents of the
container, means for urging the contents of the container to the
said aperture or apertures, and a composition according to any one
of the preceding claims accommodated within the container.
30. A product according to claim 29 wherein the composition is in
the form of a stick and the container has an open end at which an
end portion of the stick of composition is exposed for use.
31. A process for the production of a composition according to any
one of claims 1 to 28 comprising, not necessarily in any order, the
steps of incorporating into a water-immiscible liquid carrier a
structurant which is said wholly esterified or partially esterified
cellobiose, if required, mixing the liquid carrier with a solid or
a disperse liquid phase to be suspended therein, heating to an
elevated temperature at which the structurant is in solution in the
water-immiscible liquid carrier, followed by cooling or permitting
the mixture to cool to a 58 temperature at which it is thickened or
solidified.
32. A process according to claim 31 which includes a step of
pouring the mixture at elevated temperature into a dispensing
container and allowing it to cool therein so as to produce a
product according to claim 29 or claim 30.
33. A method for preventing or reducing perspiration on human skin
comprising topically applying to the skin a composition according
to any one of claims 20 to 25.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to cosmetic compositions for
application to human skin. Significant forms of the invention are
concerned with antiperspirant compositions for application to human
skin, especially the axilla. However, the invention can also be
applied to other forms of cosmetic composition.
BACKGROUND OF THE INVENTION AND SUMMARY OF PRIOR ART
[0002] A wide variety of cosmetic compositions for application to
human skin make use of a thickened or structured liquid carrier to
deliver colour or some other active material to the surface of the
skin. A significant example of such cosmetic compositions are
antiperspirant compositions which are widely used in order to
enable their users to avoid or minimise wet patches on their skin,
especially in axillary regions.
[0003] Antiperspirant formulations have been provided with a range
of different product forms. One of these is a so-called "stick"
which is usually a bar of an apparently firm solid material held
within a dispensing container and which retains its structural
integrity and shape whilst being applied. When a portion of the
stick is drawn across the skin surface a film of the stick
composition is transferred to the skin surface. Although the stick
has the appearance of a solid article capable of retaining its own
shape for a period of time, the material usually has a structured
liquid phase so that a film of the composition is readily
transferred from the stick to another surface upon contact.
[0004] Another possibility is that a stick is a softer solid
composition accommodated in a dispensing container which in use
extrudes the composition through one or more apertures.
[0005] Antiperspirant sticks can be divided into three categories.
Suspension sticks contain a particulate antiperspirant active
material suspended in a structured carrier liquid phase. Emulsion
sticks normally have a hydrophilic phase containing the
antiperspirant active in solution, this phase forming an emulsion
with a second, more hydrophobic, liquid phase. The continuous phase
of the emulsion is structured. Solution sticks typically have the
antiperspirant active dissolved in a structured liquid phase which
may be a mixture of water and a water-miscible organic solvent.
This classification into suspension, emulsion and solution types
can be applied to both firm and soft solid compositions.
[0006] Other types of cosmetic composition can also be provided in
the form of a stick and again the stick may be a structured
solution, emulsion or suspension. Examples of cosmetic compositions
which are, or can be, marketed in a stick form are lipsticks, lip
salves and eyebrow pencils.
[0007] There is substantial literature on the structuring or
thickening of cosmetic compositions.
[0008] Conventionally, many sticks have been structured using
naturally-occurring or synthetic waxy materials. Examples of these
include those fatty alcohols which are solid at room temperature,
such as stearyl alcohol, and hydrocarbon waxes or silicone waxes.
Such materials are widely available, and by suitable selection of
the materials themselves and their concentrations in the
formulation, it is possible to obtain either a soft solid or a firm
solid. Examples of these sticks are described in an article in
Cosmetics and Toiletries, 1990, Vol 105, P75-78 and in U.S. Pat.
Nos. 5,169,626 and 4,725,432. However, fatty alcohol or wax
structured sticks tend to leave visible white deposits on
application to human skin, and the deposits can also transfer onto
clothing when it comes into contact with the skin and the wearer
can, for example, find white marks at the armhole of the sleeveless
garment.
[0009] Some alternative structurants have been proposed. The term
"gellant" is often employed instead of "structurant". Where the
resulting product is liquid of increased viscosity rather than a
solid or gel, the term "thickener" can also be used. For example,
the use of dibenzylidene sorbitol (DBS) or derivatives thereof has
been proposed as gellant in a number of publications such as
EP-A-512770, WO 92/19222, U.S. Pat. No. 4,954,333, U.S. Pat. No.
4,822,602 and U.S. Pat. No. 4,725,430. Formulations containing such
gellants can suffer from a number of disadvantages, including
instability in the presence of acidic antiperspirants, and
comparatively high processing temperatures needed in the production
of sticks.
[0010] A combination of an N-acylaminoacid amide and 12-hydroxy
stearic acid to gel a non-aqueous formulation is described in, for
example, WO 93/23008 and U.S. Pat. No. 5,429,816. However, high
processing temperatures are needed to dissolve the gellants and
prevent premature gelling. When applied to skin the formulation can
be difficult to wash off, but reformulation to overcome that
problem can be made impossible by the need for a high processing
temperature.
[0011] The use of 12-hydroxy stearic acid without N-acylamino acid
amide as a secondary gellant has been disclosed in some documents
such as Japanese application 05/228915 and U.S. Pat. No.
5,744,130.
[0012] In WO 97/11678 to Helene Curtis, Inc, there is described the
use of lanosterol as a gellant to make soft gels, sometimes in
conjunction with a starch hydrolyzate derivative for antiperspirant
compositions. This document includes a brief reference to cellulose
as a possible ingredient. Cellulose is of course a polymer.
[0013] In WO 98/34588 to Lancaster Group GmbH, there is described
the use of lanosterol as a gellant for oil-based cosmetic
compositions, containing a cosmetic active material, of which one
listed material is a deodorant, though not exemplified.
[0014] EP-A-400910 discloses cosmetic compositions in which a
powdered form of cellulose is used as an absorbent for liquid
material. In one example such a powder is used to absorb volatile
silicone and the resulting material is used as a particulate
ingredient in a stick which also contains particulate
antiperspirant active and a binder polymer.
[0015] Antiperspirant emulsion sticks without any material
identified as a structurant have been disclosed in U.S. Pat. No.
4,673,570, U.S. Pat. No. 4,948,578 and U.S. Pat. No. 5,587,153.
[0016] Cosmetic compositions other than antiperspirants which take
the form of structured liquids have been disclosed, for example in
U.S. Pat. No. 3,969,087, which disclosed the use of N-acylamino
acids and derivatives thereof as gelling agents, U.S. Pat. No.
5,486,566 which utilised 12-hydroxy stearic acid.
SUMMARY OF THE INVENTION
[0017] It is an object of the present invention to provide
thickened or structured cosmetic compositions, especially but not
exclusively antiperspirant compositions, in which a liquid carrier
material is thickened or structured using a structuring agent which
is different from those mentioned above. A further object of the
invention is to provide a structurant which can have superior
properties to at least some of the structurants which have been
used previously.
[0018] A further object of at least some forms of the invention is
to provide compositions which exhibit low visible deposits.
[0019] Certain particularly preferred forms of the invention have
the objective of providing compositions which have a measure of
clarity, i.e. are translucent or even transparent.
[0020] According to a first aspect of the present invention there
is provided a composition of matter suitable for cosmetic use
having a continuous phase which comprises water-immiscible liquid
carrier and a structurant therein which is wholly esterified or
partially esterified cellobiose in which at least half the
available hydroxyl groups have been esterified to bear acyl groups
containing at least four carbon atoms. Such a compound has the
formula: 3
[0021] wherein each Z is independently hydrogen or an acyl group of
the formula 4
[0022] where R denotes a hydrocarbyl group containing from 4 to 22
carbon atoms, with the proviso that not more than half of the Z
groups are hydrogen.
[0023] The fully or partially esterified cellobiose serves as a
structuring agent or thickener for the water-immiscible liquid
carrier and when used in a sufficient amount, which is likely to be
less than 15% of the total composition, is able to structure this
liquid into a gel with sufficient rigidity to sustain its own
shape.
[0024] Without being bound to any specific theory or explanation,
it is believed that the esterified cellobiose forms a network of
fibres or strands extending throughout the liquid phase. Upon
heating the gel to the gel melting temperature, the strands of
structurant dissolve and the liquid phase becomes more mobile.
[0025] In order to promote good sensory properties at the time of
use it is preferred to include silicone oil in the water-immiscible
carrier liquid. The amount of silicone oil may be at least 10% by
weight of the composition and/or at least 40% by weight of the
water-immiscible carrier liquid.
[0026] Ethanol gives a cooling effect on application to skin,
because it is very volatile. It is preferred that the content of
ethanol or any monohydric alcohol with a vapour pressure above 1.3
kPa (10 mmHg) is not over 15% better not over 8% by weight of the
composition.
[0027] As will be explained in more detail below, the structured
water-immiscible carrier liquid may be the continuous phase of a
composition with a dispersed second phase, either an emulsion or a
suspension of particulate solid. Such a solid may be a particulate
antiperspirant active. A disperse phase may be a solution of
antiperspirant active in water or other hydrophilic solvent.
[0028] Certain preferred forms of this invention are concerned with
compositions which are translucent or transparent. As is already
known, translucent or transparent compositions can be obtained if
it is possible to match the refractive indices of the different
constituent phases present in the composition.
[0029] We have found that compositions within this invention which
are a novel transparent or translucent emulsion can be obtained by
formulating the composition to meet two criteria. Firstly the
disperse phase and the continuous phase (consisting of the
water-immiscible carrier liquid and the structurant contained
within that liquid)should be formulated so that their refractive
indices match. The refractive index of the continuous phase will be
close to the refractive index of the water-immiscible carrier
liquid in it. In order to achieve good light transmission through a
composition, the refractive index of the water-immiscible
continuous phase and the refractive index of the disperse phase
should match within 0.003 units preferably 0.002 units.
[0030] Secondly, the matched refractive indices of these two phases
should lie in a range which is an approximate match to the
refractive index of the structurant. When the structurant is a
cellobiose ester of C.sub.8 or C.sub.9, i.e. octanoic or nonanoic,
acids a range from 1.40 to 1.50 preferably from 1.41 to 1.47 has
been found suitable as will be explained below in greater
detail.
[0031] One considerable advantage of preferred structurant
materials of this invention is that they have a refractive index at
a convenient value such that it is not difficult to formulate the
rest of the composition to have a sufficiently close refractive
index, and in addition the particularly preferred structurants are
tolerant of mis-match between their refractive index and the
matched refractive indices of the continuous and disperse
phases.
[0032] Further advantages of preferred structurant materials of
this invention are that they do not require high processing
temperatures and that they are chemically stable, both during
processing and in the resultant compositions. The avoidance of high
processing temperatures can be especially valuable when the
composition contains some water or other volatile constituent.
[0033] A composition of this invention will generally be marketed
in a container by means of which it can be applied at time of use.
This container may be of conventional type.
[0034] A second aspect of the invention therefore provides a
cosmetic product comprising a dispensing container having at least
one aperture for delivery of the contents of the container, means
for urging the contents of the container to the said aperture or
apertures, and a composition of the first aspect of the invention
in the container.
[0035] The compositions of this invention can be produced by
conventional processes for making suspension or emulsion solids or
soft-solids.
[0036] Thus, according to a third aspect of the present invention
there is provided a process for the production of a cosmetic
composition comprising, not necessarily in any order, the steps
of
[0037] incorporating into a water-immiscible liquid carrier a
structurant which is said wholly esterified or partially esterified
cellobiose,
[0038] if required, mixing the liquid carrier with a solid or a
disperse liquid phase to be suspended therein,
[0039] heating the liquid carrier or a mixture containing it to an
elevated temperature at which the structurant is soluble in the
water-immiscible liquid carrier,
[0040] followed by
[0041] introducing the mixture into a mould which preferably is a
dispensing container, and then
[0042] cooling or permitting the mixture to cool to a temperature
at which it is thickened or solidified.
[0043] A suspended solid may be an antiperspirant active and a
disperse phase may be a solution of such an active in a hydrophilic
or polar solvent.
[0044] According to a fourth aspect of the present invention, there
is provided a method for preventing or reducing perspiration on
human skin comprising topically applying to the skin a composition
comprising an antiperspirant active, a water-immiscible liquid
carrier and a structurant therefor which is wholly esterified or
partially esterified cellobiose.
DETAILED DESCRIPTION AND EMBODIMENTS
[0045] As mentioned above the invention requires fully esterified
or partially esterified cellobiose as a structurant material for a
water-immiscible liquid phase. Other materials may also be present
depending on the nature of the composition. The various materials
will now be discussed by turn and preferred features and
possibilities will be indicated.
Esterified Cellobiose
[0046] The core structure of the structurant is cellobiose. This
contains two glucose residues joined through a .beta.-1,4 linkage.
The cellobiose must be esterified on many, if not all of the
available hydroxyl groups. It is convenient to utilise cellobiose
which has been fully esterified but partially esterified cellobiose
can be employed provided at least half of the hydroxyl groups have
been esterified, better a higher proportion such as at least 5 or 6
out of every 8 hydroxyl groups.
[0047] The acyl groups should contain at least 4 carbon atoms. It
is unlikely that they will contain more than 22 carbon atoms. It is
preferred that the acyl groups are aliphatic with 6 to 18 or 19
carbon atoms and more particularly preferred that each acyl group
incorporates an alkyl or alkenyl chain of 5 to 12 or 18 carbon
atoms so that the acyl group contains 6 to 13 or 19 carbon atoms.
Particularly preferred acyl groups incorporate a linear alkyl chain
of 7 to 10 carbon atoms and are thus octanoyl, nonanoyl, decanoyl
or undecanoyl.
[0048] The acyl groups may have a mixture of chain lengths but it
is preferred that they are similar in size and structure. Thus it
is preferred that all of the acyl groups are aliphatic and at least
90% of the acyl groups have a chain length within a range such that
the shorter and longer chain lengths in the range differ by no more
than two carbon atoms, i.e. length in a range from m-1 to m+1
carbon atoms where the mean acyl chain length m has a value in a
range from 7 to 10 or 11. Commercially available feedstocks for
these acyl groups are likely to include a small percentage of acyl
groups which differ from the majority and may have a branched
rather than linear chain. Thus it is likely that more than 90% but
less than 100% of the acyl groups will meet the desired criterion
of chain lengths in a range from m-1 to m+1 carbon atoms.
[0049] Linear aliphatic acyl groups may be obtained from natural
sources, in which case the number of carbon atoms in the acyl group
is likely to be an even number or may be derived synthetically from
petroleum as the raw material in which case both odd and even
numbered chain lengths are available.
[0050] Synthetic methods for the esterification of saccharides are
well known. The esterification of cellobiose has been reported by
Takada et al in Liquid Crystals, (1995) Volume 19, pages 441-448.
This article gives a procedure for the production of the alpha
anomers of cellobiose octa-alkanoates by esterification of
.beta.-cellobiose using an alkanoic acid together with
trifluoracetic anhydride. The same article also reports the
preparation of the beta anomers of cellobiose octa-alkanoates by a
synthetic route utilising the appropriate acid chloride in the
presence of pyridine. However, we have found that the alpha anomers
are more effective structurants.
[0051] The amount of esterified cellobiose structurant in a
composition of this invention is likely to be from 0.1 or 0.5 to
15% by weight of the whole composition and preferably from 0.5 up
to 8% or 10%, probably from 1 to 8%. If the composition is an
emulsion with a separate disperse phase, the amount of esterified
cellobiose structurant is likely to be from 0.5 to 20% or even 25%
by weight of the continuous phase, more likely from 1% to 15% of
this phase.
Carrier Liquid
[0052] The water-immiscible carrier liquid comprise one or a
mixture of materials which are relatively hydrophobic so as to be
immiscible in water. Some hydrophilic liquid may be included in the
carrier, provided the overall carrier liquid mixture is immiscible
with water. It will generally be desired that this carrier is
liquid (in the absence of structurant) at temperatures of
15.degree. C. and above. It may have some volatility but its vapour
pressure will generally be less than 4 kPa (30 mmHg) at 25.degree.
C. so that the material can be referred to as an oil or mixture of
oils. More specifically, it is desirable that at least 80% by
weight of the hydrophobic carrier liquid should consist of
materials with a vapour pressure not over this value of 4 kPa at
25.degree. C.
[0053] It is preferred that the hydrophobic carrier material
includes a volatile liquid silicone, i.e. liquid
polyorganosiloxane. To class as "volatile" such material should
have a measurable vapour pressure at 20 or 25.degree. C. Typically
the vapour pressure of a volatile silicone lies in a range from 1
or 10 Pa to 2 kPa at 25.degree. C.
[0054] It is desirable to include volatile silicone because it
gives a "drier" feel to the applied film after the composition is
applied to skin.
[0055] Volatile polyorganosiloxanes can be linear or cyclic or
mixtures thereof. Preferred cyclic siloxanes include
polydimethsiloxanes and particularly those containing from 3 to 9
silicon atoms and preferably not more than 7 silicon atoms and most
preferably from 4 to 6 silicon atoms, otherwise often referred to
as cyclomethicones. Preferred linear siloxanes include
polydimethylsiloxanes containing from 3 to 9 silicon atoms. The
volatile siloxanes normally by themselves exhibit viscosities of
below 10.sup.-5 m.sup.2/sec (10 centistokes), and particularly
above 10.sup.-7 m.sup.2/sec (0.1 centistokes), the linear siloxanes
normally exhibiting a viscosity of below 5.times.10.sup.-6
m.sup.2/sec (5 centistokes). The volatile silicones can also
comprise branched linear or cyclic siloxanes such as the
aforementioned linear or cyclic siloxanes substituted by one or
more pendant --O--Si(CH.sub.3).sub.3 groups. Examples of
commercially available silicone oils include oils having grade
designations 344, 345, 244, 245 and 246 from Dow Corning
Corporation; Silicone 7207 and Silicone 7158 from Union Carbide
Corporation; and SF1202 from General Electric.
[0056] The hydrophobic carrier employed in compositions herein can
alternatively or additionally comprise non-volatile silicone oils,
which include polyalkyl siloxanes, polyalkylaryl siloxanes and
polyethersiloxane copolymers. These can suitably be selected from
dimethicone and dimethicone copolyols. Commercially available
non-volatile silicone oils include Dow Corning 556 and Dow Corning
200 series.
[0057] The water-immiscible liquid carrier may contain from 0 to
100% by weight of one or more liquid silicones. Preferably, there
is sufficient liquid silicone to provide at least 10%, better at
least 15%, by weight of the whole composition. If silicone oil is
used, volatile silicone preferably constitutes from 20 to 100% of
the weight of the carrier liquid. In many instances, when a
non-volatile silicone oil is present, its weight ratio to volatile
silicone oil is chosen in the range of from 1:3 to 1:40.
[0058] Silicon-free hydrophobic liquids can be used instead of, or
more preferably in addition to liquid silicones. Silicon-free
hydrophobic organic liquids which can be incorporated include
liquid aliphatic hydrocarbons such as mineral oils or hydrogenated
polyisobutene, often selected to exhibit a low viscosity. Further
examples of liquid hydrocarbons are polydecene and paraffins and
isoparaffins of at least 10 carbon atoms.
[0059] Other hydrophobic carriers are liquid aliphatic or aromatic
esters, but these can be used as only part of the liquid carrier,
desirably not above 20%, and possibly less than 10% by weight of
the water-immiscible liquid carrier.
[0060] Suitable aliphatic esters contain at least one long chain
alkyl group, such as esters derived from C.sub.1 to C.sub.20
alkanols esterified with a C.sub.8 to C.sub.22 alkanoic acid or
C.sub.6 to C.sub.10 alkanedioic acid. The alkanol and acid moieties
or mixtures thereof are preferably selected such that they each
have a melting point of below 20.degree. C. These esters include
isopropyl myristate, lauryl myristate, isopropyl palmitate,
diisopropyl sebacate and diisopropyl adipate.
[0061] Suitable liquid aromatic esters, preferably having a melting
point of below 20.degree. C., include fatty alkyl benzoates.
Examples of such esters include suitable C.sub.8 to C.sub.18 alkyl
benzoates or mixtures thereof.
[0062] Further instances of suitable hydrophobic carriers comprise
liquid aliphatic ethers derived from at least one fatty alcohol,
such as myristyl ether derivatives e.g. PPG-3 myristyl ether or
lower alkyl ethers of polyglycols such as PPG-14 butyl ether.
[0063] Aliphatic alcohols which are solid at 20.degree. C., such as
stearyl alcohol are preferably absent or present in low
concentration such as less than 5% by weight of the whole
composition since these lead to visible white deposits when a
composition is used.
[0064] However, aliphatic alcohols which are liquid at 20.degree.
C. may be employed. These include branched chain alcohols of at
least 10 carbon atoms such as isostearyl alcohol and octyl
dodecanol.
[0065] Silicon-free liquids can constitute from 0-100% of the
water-immiscible liquid carrier, but it is preferred that silicone
oil is present and that the amount of silicon-free constituents
preferably constitutes up to 50 or 60% and in many instances from
20 to 60% by weight of the carrier liquid.
Liquid Disperse Phase
[0066] If the composition is an emulsion in which the esterified
cellobiose acts as a structurant in the continuous phase, the
emulsion will contain a more polar disperse phase. The disperse
phase may be a solution of an active ingredient.
[0067] The hydrophilic disperse phase in an emulsion normally
comprises water as solvent and can comprise one or more water
soluble or water miscible liquids in addition to or replacement for
water. The proportion of water in an emulsion according to the
present invention is often selected in the range of up to 60%, and
particularly from 10% up to 40% or 50% of the whole
formulation.
[0068] One class of water soluble or water-miscible liquids
comprises short chain monohydric alcohols, e.g. C.sub.1 to C.sub.4
and especially ethanol or isopropanol, which can impart a
deodorising capability to the formulation. A further class of
hydrophilic liquids comprises diols or polyols preferably having a
melting point of below 40.degree. C., or which are water miscible.
Examples of water-soluble or water-miscible liquids with at least
one free hydroxy group include ethylene glycol, 1,2-propylene
glycol, 1,3-butylene glycol, hexylene glycol, diethylene glycol,
dipropylene glycol, 2-ethoxyethanol, diethylene glycol
monomethylether, triethyleneglycol monomethylether and sorbitol.
Especially preferred are propylene glycol and glycerol.
[0069] In an emulsion the disperse phase is likely to constitute
from 5 to 80 or 85% of the weight of the composition preferably
from 5 to 50 or 65% more preferably from 25 or 35% up to 50 or 65%,
while the continuous phase with the structurant therein provides
the balance from 15 or 35% up to 95% of the weight of the
composition. Compositions with high proportion of disperse phase,
i.e. from 65 to 85% disperse phase, may also be advantageous. They
can give good hardness even though the concentration of esterified
cellobiose structurant may be only a small percentage of the total
composition.
[0070] An emulsion composition will generally include one or more
emulsifying surfactants which may be anionic, cationic,
zwitterionic and/or nonionic surfactants. The proportion of
emulsifier in the composition is often selected in the range up to
10% by weight and in many instances from 0.1 or 0.25 up to 5% by
weight of the composition. Most preferred is an amount from 0.1 or
0.25 up to 3% by weight. Nonionic emulsifiers are frequently
classified by HLB value. It is desirable to use an emulsifier or a
mixture of emulsifiers with an overall HLB value in a range from 2
to 10 preferably from 3 to 8.
[0071] It may be convenient to use a combination of two or more
emulsifiers which have different HLB values above and below the
desired value. By employing the two emulsifiers together in
appropriate ratio, it is readily feasible to attain a weighted
average HLB value that promotes the formation of an emulsion.
[0072] Many suitable emulsifiers of high HLB are nonionic ester or
ether emulsifiers comprising a polyoxyalkylene moiety, especially a
polyoxyethylene moiety, often containing from about 2 to 80, and
especially 5 to 60 oxyethylene units, and/or contain a polyhydroxy
compound such as glycerol or sorbitol or other alditol as
hydrophilic moiety. The hydrophilic moiety can contain
polyoxypropylene. The emulsifiers additionally contain a
hydrophobic alkyl, alkenyl or aralkyl moiety, normally containing
from about 8 to 50 carbons and particularly from 10 to 30 carbons.
The hydrophobic moiety can be either linear or branched and is
often saturated, though it can be unsaturated, and is optionally
fluorinated. The hydrophobic moiety can comprise a mixture of chain
lengths, for example those deriving from tallow, lard, palm oil,
sunflower seed oil or soya bean oil. Such nonionic surfactants can
also be derived from a polyhydroxy compound such as glycerol or
sorbitol or other alditols. Examples of emulsifiers include
ceteareth-10 to -25, ceteth-10-25, steareth-10-25 (i.e. C.sub.16 to
C.sub.18 alcohols ethoxylated with 10 to 25 ethylene oxide
residues) and PEG-15-25 stearate or distearate. Other suitable
examples include C.sub.10-C.sub.20 fatty acid mono, di or
triglycerides. Further examples include C.sub.18-C.sub.22 fatty
alcohol ethers of polyethylene oxides (8 to 12 EO).
[0073] Examples of emulsifiers, which typically have a low HLB
value, often a value from 2 to 6 are fatty acid mono or possibly
diesters of polyhydric alcohols such as glycerol, sorbitol,
erythritol or trimethylolpropane. The fatty acyl moiety is often
from C.sub.14 to C.sub.22 and is saturated in many instances,
including cetyl, stearyl, arachidyl and behenyl. Examples include
monoglycerides of palmitic or stearic acid, sorbitol mono or
diesters of myristic, palmitic or stearic acid, and
trimethylolpropane monoesters of stearic acid.
[0074] A particularly desirable class of emulsifiers comprises
dimethicone copolymers, namely polyoxyalkylene modified
dimethylpolysiloxanes. The polyoxyalkylene group is often a
polyoxyethylene (POE) or polyoxypropylene (POP) or a copolymer of
POE and POP. The copolymers often terminate in C.sub.1 to C.sub.12
alkyl groups.
[0075] Suitable emulsifiers and co-emulsifiers are widely available
under many trade names and designations including Abil.TM.,
Arlacel.TM., Brij.TM., Cremophor.TM., Dehydrol.TM., Dehymuls.TM.,
Emerest.TM., Lameform.TM., Pluronic.TM., Prisorine.TM., Quest
PGPR.TM., Span.TM., Tween.TM., SF1228, DC3225C and Q2-5200.
Antiperspirant Actives
[0076] If the composition is an antiperspirant, it will contain an
antiperspirant active. Antiperspirant actives, are preferably
incorporated in an amount of from 0.5-60%, particularly from 5 to
30% or 40% and especially from 5 or 10% to 30 or 35% of the weight
of the composition.
[0077] Antiperspirant actives for use herein are often selected
from astringent active salts, including in particular aluminium,
zirconium and mixed aluminium/zirconium salts, including both
inorganic salts, salts with organic anions and complexes. Preferred
astringent salts include aluminium, zirconium and
aluminium/zirconium halides and halohydrate salts, such as
chlorohydrates.
[0078] Aluminium halohydrates are usually defined by the general
formula Al.sub.2(OH).sub.xQ.sub.y.wH.sub.2O in which Q represents
chlorine, bromine or iodine, x is variable from 2 to 5 and x+y=6
while wH.sub.2O represents a variable amount of hydration.
Especially effective aluminium halohydrate salts, known as
activated aluminium chlorohydrates, are described in EP-A-6739
(Unilever NV et al), the contents of which specification is
incorporated herein by reference. Some activated salts do not
retain their enhanced activity in the presence of water but are
useful in substantially anhydrous formulations, i.e. formulations
which do not contain a distinct aqueous phase.
[0079] Zirconium actives can usually be represented by the
empirical general formula: ZrO(OH).sub.2-n-nzB.sub.z.wH.sub.2O in
which z is a variable in the range of from 0.9 to 2.0 so that the
value 2n-nz is zero or positive, n is the valency of B, and B is
selected from the group consisting of chloride, other halide,
sulphamate, sulphate and mixtures thereof. Possible hydration to a
variable extent is represented by wH2O. Preferable is that B
represents chloride and the variable z lies in the range from 1.5
to 1.87. In practice, such zirconium salts are usually not employed
by themselves, but as a component of a combined aluminium and
zirconium-based antiperspirant.
[0080] The above aluminium and zirconium salts may have coordinated
and/or bound water in various quantities and/or may be present as
polymeric species, mixtures or complexes. In particular, zirconium
hydroxy salts often represent a range of salts having various
amounts of the hydroxy group. Zirconium aluminium chlorohydrate may
be particularly preferred.
[0081] Antiperspirant complexes based on the above-mentioned
astringent aluminium and/or zirconium salts can be employed. The
complex often employs a compound with a carboxylate group, and
advantageously this is an amino acid. Examples of suitable amino
acids include dl-tryptophan, dl-.beta.-phenylalanine, dl-valine,
dl-methionine and .beta.-alanine, and preferably glycine which has
the formula CH.sub.2(NH.sub.2)COOH.
[0082] It is highly desirable to employ complexes of a combination
of aluminium halohydrates and zirconium chlorohydrates together
with amino acids such as glycine, which are disclosed in U.S. Pat.
No. 3,792,068 (Luedders et al). Certain of those Al/Zr complexes
are commonly called ZAG in the literature. ZAG actives generally
contain aluminium, zirconium and chloride with an Al/Zr ratio in a
range from 2 to 10, especially 2 to 6, an Al/Cl ratio from 2.1 to
0.9 and a variable amount of glycine. Actives of this preferred
type are available from Westwood, from Summit and from Reheis.
[0083] Other actives which may be utilised include astringent
titanium salts, for example those described in GB 2299506A.
[0084] The proportion of solid antiperspirant salt in a composition
normally includes the weight of any water of hydration and any
complexing agent that may also be present in the solid active.
However, when the active salt is in solution, its weight excludes
any water present.
[0085] If the composition is in the form of an emulsion the
antiperspirant active will be dissolved in the disperse phase. In
this case, the antiperspirant active will often provide from 3 to
60% by weight of the aqueous disperse phase, particularly from 10%
or 20% up to 55% or 60% of that phase.
[0086] Alternatively, the composition may take the form of a
suspension in which antiperspirant active in particulate form is
suspended in the water-immiscible liquid carrier. Such a
composition will probably not have any separate aqueous phase
present and may conveniently be referred to as "substantially
anhydrous" although it should be understood that some water may be
present bound to the antiperspirant active or as a small amount of
solute within the water-immiscible liquid phase. In such
compositions, the particle size of the antiperspirant salts often
falls within the range of 0.1 to 200 .mu.m with a mean particle
size often from 3 to 20.mu.m. Both larger and smaller mean particle
sizes can also be contemplated such as from 20 to 50 .mu.m or 0.1
to 1 .mu.m.
Optional Ingredients
[0087] Optional ingredients in compositions of this invention can
include deodorants, for example at a concentration of up to about
10% w/w. Suitable deodorant actives can comprise deodorant
effective concentrations of antiperspirant metal salts,
deoperfumes, and/or microbicides, including particularly
bactericides, such as chlorinated aromatics, including biguanide
derivatives, of which materials known as Irgasan DP300.TM.
(Triclosan), Tricloban.TM., and Chlorhexidine warrant specific
mention. A yet another class comprises biguanide salts such as
available under the trade mark Cosmosil.TM..
[0088] Other optional ingredients include wash-off agents, often
present in an amount of up to 10% w/w to assist in the removal of
the formulation from skin or clothing. Such wash-off agents are
typically nonionic surfactants such as esters or ethers containing
a C.sub.8 to C.sub.22 alkyl moiety and a hydrophilic moiety which
can comprise a polyoxyalkylene group (POE or POP) and/or a
polyol.
[0089] A further optional constituent of the formulation comprises
one or more secondary structurants which can be employed in
addition to the esterified cellobiose which is the primary
structurant. The amount of such secondary structurants in the
formulation is often zero, and usually not more than 15% of the
formulation. It is normally not greater than the amount of the
primary structurant.
[0090] The secondary structurants employable herein can be
non-polymeric or polymeric. Solid linear fatty alcohol and/or a wax
may be included but are not preferred. Non-polymeric structurants,
sometimes referred to as gellants, can be selected from fatty acids
or salts thereof, such as stearic acid or sodium stearate or
12-hydroxy stearic acid. Other suitable gellants can comprise
dibenzylidene alditols, e.g. dibenzylidene sorbitol. Further
suitable gellants can comprise lanosterol, selected N-acyl amino
acid derivatives, including ester and amide derivatives, such as
N-lauroyl glutamic acid dibutylamide, which gellants can be
contemplated in conjunction with 12-hydroxy stearic acid or an
ester or amide derivative thereof. Still further gellants include
amide derivatives of di or tribasic carboxylic acids, such as alkyl
N,N'-dialkylsuccinamides, e.g. dodecyl N,N'-dibutylsuccinamide.
[0091] Polymeric structurants which can be employed can comprise
organo polysiloxane elastomers such as reaction products of a vinyl
terminated polysiloxane and a cross linking agent or alkyl or alkyl
polyoxyalkylene-terminated poly (methyl substituted) or poly
(phenyl substituted) siloxanes. A number of polyamides have also
been disclosed as structurants for hydrophobic liquids. Polymers
containing both siloxane and hydrogen bonding groups, which might
be used as secondary structurants, have been disclosed in WO
97/36572 and WO 99/06473. If an aqueous disperse phase is present,
polyacrylamides, polyacrylates or polyalkylene oxides may be used
to structure or thicken this aqueous phase.
[0092] The compositions herein can incorporate one or more cosmetic
adjuncts conventionally contemplatable for antiperspirant solids or
soft solids. Such cosmetic adjuncts can include skin feel
improvers, such as talc or finely divided polyethylene, for example
in an amount of up to about 10%; skin benefit agents such as
allantoin or lipids, for example in an amount of up to 5%; colours;
skin cooling agents other than the already mentioned alcohols, such
a menthol and menthol derivatives, often in an amount of up to 2%,
all of these percentages being by weight of the composition. A
commonly employed adjunct is a perfume, which is normally present
at a concentration of from 0 to 4% and in many formulations from
0.25 to 2% by weight of the composition.
Translucent/Transparent Compositions
[0093] If a composition of this invention is formulated as an
emulsion it is possible to construct the formulation such that the
emulsion is translucent or transparent. In order to do this the
refractive indices of the water-immiscible continuous phase and the
polar or aqueous disperse phase must be matched to each other and
the value of refractive index at which they are matched must also
approximately match the refractive index of the structurant.
[0094] The refractive index of a fibrous network of a structurant
can be determined by using that structurant to gel a number of oils
or oil mixtures of differing refractive index. When the resulting
gel is transparent, the refractive index of the oil or oil
mixture(which can be determined by conventional measurement) is a
good approximation to the refractive index of the structurant. The
oils or mixtures or oils should be chosen from these which are
gelled well by the structurant to avoid interfering effects.
[0095] Using this method we have determined the refractive index of
a preferred esterified cellobiose, namely cellobiose
octa-nonanoate, to fall in a range between 1.45 and 1.50, being
approximately 1.48 at 22.degree. C.
[0096] When the structurants are cellobiose esters of C.sub.9 or
shorter fatty acids, we have found that the value at which the
refractive indices of the continuous and disperse phases are
matched can be somewhat below the refractive index of the
structurant, down to a value of 1.42 or even down as far as 1.41 or
1.40. A value slightly above 1.48 would be useable also, but is
inconvenient to achieve.
[0097] When the structurants are esters of C.sub.10 or longer
acids, the matched refractive indices of the two phases have to be
closer to 1.48. For cellobiose octa-decanoate the refractive index
of the two phases needs to be above 1.44 and preferably above 1.45
in order to obtain a high level of translucency.
[0098] For the continuous phase, silicon-free water-immiscible
liquid oils generally have refractive indices in a range from 1.43
to 1.49 at 22.degree. C. and can be used alone or mixed together to
give a silicon-free carrier liquid with refractive index in this
range. Volatile silicone oils generally have a refractive index
slightly below 1.40 at 22.degree. C., but carrier liquid mixtures
with refractive indices in the range from 1.41 to 1.46 can be
obtained by mixing volatile silicone with other oils. Non-volatile
silicone oils generally have refractive indices in a range from
1.45 to 1.48 at 22.degree. C. and so can be included when
desired.
[0099] The refractive index of the continuous phase will be very
close to the refractive index of the carrier liquid (usually a
carrier liquid mixture) which is its principal component.
[0100] For the disperse phase, a solution of an antiperspirant
active salt in water alone will generally display a refractive
index below 1.425. The refractive index can be raised by
incorporating a diol or polyol into the aqueous solution. It is
believed to be novel to match the refractive index of a polar
disperse phase to that of a structurant network within a continuous
phase. Moreover, it can be achieved without using so much diol or
polyol as will make the composition excessively sticky.
[0101] If composition of this invention is a gelled continuous
phase without any disperse phase, it can be made transparent or
translucent by approximating the refractive index of the liquid
carrier to that of the esterified cellobiose structurant in the
manner discussed above.
[0102] For a composition which is a suspension the route to a
transparent or translucent composition is to match the refractive
indices of the liquid carrier and the suspended solid to that of
the esterified cellobiose. Particulate antiperspirant actives which
are anhydrous solids generally have a refractive index
substantially above 1.50 which is brought down by hydration, but we
have found that it is not easy to obtain an antiperspirant active
with a refractive index of 1.48 or below even if the active is
partially hydrated to lower its refractive index.
[0103] For this reason, a feature within this invention is to
prefer the emulsion form of antiperspirant stick when seeking to
achieve a transparent or translucent product.
[0104] For the regular production of compositions with optimum
transparency it may prove desirable to monitor the refractive
indices of the raw materials to detect any batch to batch
variation. If necessary the composition of a liquid phase can be
adjusted by variations in the quantity of a constituent
material.
Mechanical Properties and Product Packages
[0105] The compositions of this invention are structured liquids
and may be firm or soft in appearance. Even a soft solid has an
ability to sustain its own shape, for instance if it is removed
from a mould without being subjected to shear it will retain its
shape for at least 30 seconds, usually longer.
[0106] A composition of this invention will usually be marketed as
a product comprising a container with a quantity of the composition
therein, where the container has at least one aperture for the
delivery of composition, and means for urging the composition in
the container towards the delivery aperture. Conventional
containers take the form of a barrel of oval cross section with the
delivery aperture(s) at one end of the barrel.
[0107] A composition of this invention may be sufficiently rigid
that it is not apparently deformable by hand pressure and is
suitable for use as a stick product in which a quantity of the
composition in the form of a stick is accommodated within a
container barrel having an open end at which an end portion of the
stick of composition is exposed for use. The opposite end of the
barrel is closed.
[0108] Generally the container will include a cap for its open end
and a component part which is sometimes referred to as an elevator
or piston fitting within the barrel and capable of relative axial
movement along it. The stick of composition is accommodated in the
barrel between the piston and the open end of the barrel. The
piston is used to urge the stick of composition along the barrel.
The piston and stick of composition may be moved axially along the
barrel by manual pressure on the underside of the piston using a
finger or rod inserted within the barrel. Another possibility is
that a rod attached to the piston projects through a slot or slots
in the barrel and is used to move the piston and stick. Preferably
the container also includes a transport mechanism for moving the
piston comprising a threaded rod which extends axially into the
stick through a correspondingly threaded aperture in the piston,
and means mounted on the barrel for rotating the rod. Conveniently
the rod is rotated by means of a handwheel mounted on the barrel at
its closed end, i.e. the opposite end to the delivery opening.
[0109] If a composition of this invention is softer, but still
capable of sustaining its own shape it will be more suited for
dispensing from a barrel with a closure instead of an open end,
where the closure has one or more apertures through which
composition from the barrel can be extruded. The number and design
of such apertures is at the discretion of the designer of the
package.
[0110] The component parts of such containers are often made from
thermoplastic materials, for example polypropylene or polyethylene.
Descriptions of suitable containers, some of which include further
features, are found in U.S. Pat. Nos. 4,865,231, 5,000,356 and
5,573,341.
Measurement of Properties
[0111] i) Penetrometer
[0112] The hardness and rigidity of a composition which is a firm
solid can be determined by penetrometry. If the composition is a
softer solid, this will be observed as a substantial lack of any
resistance to the penetrometer probe.
[0113] A suitable procedure is to utilises a lab plant PNT
penetrometer equipped with a Seta wax needle (weight 2.5 grams)
which has a cone angle at the point of the needle specified to be
9.degree.10'.+-.15'. A sample of the composition with a flat upper
surface is used. The needle is lowered onto the surface of the
composition and then a penetration hardness measurement is
conducted by allowing the needle with its holder to drop under a
total weight, (i.e. the combined weight of needle and holder) of 50
grams for a period of five seconds after which the depth of
penetration is noted. Desirably the test is carried out at a number
of points on each sample and the results are averaged. Utilising a
test of this nature, an appropriate hardness for use in an
open-ended dispensing container is a penetration of less than 30 mm
in this test, for example in a range from 2 to 30 mm. Preferably
the penetration is in a range from 5 mm to 20 mm.
[0114] In a specific protocol for this test measurements on a stick
were performed in the stick barrel. The stick was wound up to
project from the open end of the barrel, and then cut off to leave
a flat, uniform surface. The needle was carefully lowered to the
stick surface, and then a penetration hardness measurement was
conducted. This process was carried out at six different points on
the stick surface. The hardness reading quoted is the average value
of the 6 measurements.
[0115] ii) Texture analyser
[0116] The hardness of a softer solid can be measured by using a
texture analyser. This test apparatus can move a blunt probe into
or out from a sample at a controlled speed and at the same time
measure the applied force. The parameter which is determined as
hardness is a function of the peak force and the projected area of
indentation.
[0117] A specific test protocol used a Stable Micro systems TA.XT2i
Texture Analyser. A metal sphere, of diameter 9.5 mm, was attached
to the underside of the Texture Analyser's 5 kg load cell such that
it could be used for indenting a sample placed beneath it on the
base plate of the instrument. After positioning the sample, the
sphere position was adjusted until it was just above the sample
surface. Texture Expert Exceed software was used to generate the
subsequent motion profile used in the test method. This profile
initially indented the sphere into the sample at an indentation
speed of 0.05 mm/s until a designated force was reached, which was
chosen such that the distance of penetration into the sample was
less than the radius of the sphere. At this load the direction of
motion of the sphere was immediately reversed to withdraw the
sphere from the sample at the same speed of 0.05 mm/s. During the
course of the test, the data acquired were time(s), distance (mm)
and force (N) and the data acquisition rate was 25 Hz.
[0118] Suitable samples for measurement were either contained in
stick barrels, which had a screw mechanism, or in 15 ml glass jars.
For the barrel samples, the stick was wound up until it protruded
above the edges of the barrel and then a knife was used to skim the
top of the barrel in such a way as to leave a flat uniform surface.
The stick was then pushed back into the barrel as far as possible
to minimise any mechanical interference resulting from the
compliance of the screw mechanism in the pack. Two indents were
generally made either side of the screw. The samples in the 15 ml
jars needed no surface preparation but only had enough surface area
for a single indentation test to be performed.
[0119] The data associated with each test were manipulated using
standard spreadsheet software and used to calculate the hardness,
H, using the following equation: 1 H [ N / mm 2 ] = F max [ N ] A p
[ mm 2 ]
[0120] where F.sub.max is the peak load and A.sub.p is the
projected area of the indentation remaining on unloading. This area
can be calculated geometrically from the plastic indentation depth.
This is slightly less than the total penetration depth measured
under load because of elastic deformation of the sample. The
plastic indentation depth is calculated from a graph of the
unloading-force-versus-total-penetration-depth. The initial slope
of this unloading data depends on the initial elastic recovery of
the sample. The plastic indentation depth is estimated from an
intercept between the zero force axis and a straight line drawn at
a tangent to the initial part of the unloading slope.
[0121] Similar hardness measurements were also done using a desktop
Instron Universal Testing Machine (Model 5566) fitted with a 10 N
load cell, and the data analysis performed in the same way.
[0122] iii) Deposition and whiteness of deposit
[0123] Another test of the properties of a composition is the
amount of the composition which is delivered onto a surface when
the composition is drawn across that surface (representing the
application of a stick product to human skin). To carry out this
test of deposition, a sample of the composition with standardised
shape and size is fitted to apparatus which draws the sample across
a test surface under standardised conditions. The amount
transferred to the surface is determined as an increase in the
weight of the substrate to which it is applied. If desired the
colour, opacity or clarity of the deposit may subsequently be
determined.
[0124] A specific procedure for such tests used apparatus to apply
a deposit from a stick onto a substrate under standardised
conditions and then measures the mean level of white deposits using
image analysis.
[0125] The substrates used were
[0126] a: 12.times.28 cm strip of grey abrasive paper (3M.TM. P800
WetorDry.TM. Carborundum paper)
[0127] b: 12.times.28 cm strip of black Worsted wool fabric.
[0128] The substrates were weighed before use. The sticks were
previously unused and with domed top surface unaltered.
[0129] The apparatus comprised a flat base to which a flat
substrate was attached by a clip at each end. A pillar having a
mounting to receive a standard size stick barrel was mounted on an
arm that was moveable horizontally across the substrate by means of
a pneumatic piston.
[0130] Each stick was kept at ambient laboratory temperature
overnight before the measurement was made. The stick was advanced
to project a measured amount from the barrel. The barrel was then
placed in the apparatus and a spring was positioned to biassed the
stick against the substrate with a standardised force. The
apparatus was operated to pass the stick laterally across the
substrate eight times. The substrate was carefully removed from the
rig and reweighed.
Whiteness of Deposit
[0131] The deposits from the previous test were assessed for their
whiteness after an interval of 24 hours approximately.
[0132] This was done using a Sony XC77 monochrome video camera with
a Cosmicar 16mm focal length lens positioned vertically above a
black table illuminated from a high angle using fluorescent tubes
to remove shadowing. The apparatus was initially calibrated using a
reference grey card, after the fluorescent tubes had been turned on
for long enough to give a steady light output. A cloth or
Carborundum paper with a deposit thereon from the previous test was
placed on the table and the camera was used to capture an image. An
area of the image of the deposit was selected and analysed using a
Kontron IBAS image analyser. This notionally divided the image into
a large array of pixels and measured the grey level of each pixel
on a scale of 0 (black) to 255 (white). The average of the grey
intensity was calculated. This was a measure of the whiteness of
the deposit, with higher numbers indicating a whiter deposit. It
was assumed that low numbers show a clear deposit allowing the
substrate colour to be seen.
[0133] It has been found desirable to carry out deposition of a
standard stick composition in the manner specified above, and
determine the whiteness of the deposit, as a control.
[0134] iv) Light transmission
[0135] The translucency of a composition may be measured by placing
a sample of standardised thickness in the light path of a
spectrophotometer and measuring transmittance, as a percentage of
light transmitted in the absence of the gel.
[0136] We have carried out this test using a dual-beam
spectrophotometer. The sample of composition was poured hot into a
4.5 ml cuvette made of polymethylmethacrylate (PMMA) and allowed to
cool to an ambient temperature of 20-25.degree. C. Such a cuvette
gives a 1 cm thickness of composition. Measurement was carried out
at 580 nm, with an identical but empty cuvette in the reference
beam of the spectrophotometer, after the sample in the cuvette had
been held for 24 hours. We have observed that a composition which
gives a transmittance of as little as 1% in this test is perceived
by eye as "translucent". If a stick is made from a composition with
3% transmittance, it is possible to see cavities made by boring
beneath the surface of the sample. By contrast, a conventional
stick structure with stearyl alcohol is so opaque that it is
impossible to see beneath its surface. A transmittance measured at
any temperature in the range from 20-25.degree. C. is usually
adequately accurate, but measurement is made at 22.degree. C. if
more precision is required. In a number of preferred examples we
have achieved a transmittance of 20% or above.
Preparation
[0137] Compositions of this invention can be produced by
conventional processes for making suspension or emulsion solids or
soft-solids. Such processes involve forming a heated mixture of the
composition at a temperature which is sufficiently elevated that
all the esterified cellobiose structurant dissolves, pouring that
mixture into a mould, which may take the form of a dispensing
container, and then cooling the mixture whereupon the structurant
solidifies into a network of fibres extending through the
water-immiscible liquid phase.
[0138] A convenient process sequence for a composition which is a
suspension comprises first forming a solution of the esterified
cellobiose structurant in the water-immiscible liquid. This is
normally carried out by agitating the mixture at a temperature
sufficiently high that all the structurant dissolves (the
dissolution temperature) such as a temperature in a range from 50
to 120.degree. C. Thereafter the particulate constituent, for
example particulate antiperspirant active, is blended with the hot
mixture. This must be done slowly, or the particulate solid must be
preheated, in order to avoid premature gelation. The resulting
blend is then introduced into a dispensing container such as a
stick barrel. This is usually carried out at a temperature 5 to
30.degree. C. above the setting temperature of the composition. The
container and contents are then cooled to ambient temperature.
Cooling may be brought about by nothing more than allowing the
container and contents to cool. Cooling may be assisted by blowing
ambient or even refrigerated air over the containers and their
contents.
[0139] In a suitable procedure for making emulsion formulations, a
solution of the esterified structurant in the water-immiscible
liquid phase is prepared at an elevated temperature just as for
suspension sticks. If any emulsifier is being used, this is
conveniently mixed into this liquid phase. Separately an aqueous or
hydrophilic disperse phase is prepared by introduction of
antiperspirant active into the liquid part of that phase (if this
is necessary; antiperspirant actives can sometime be supplied in
aqueous solution which can be utilised as is). This solution of
antiperspirant active which will become the disperse phase is
preferably heated to a temperature similar to that of the
continuous phase with structurant therein, but without exceeding
the boiling point of the solution, and then mixed with the
continuous phase. Alternatively, the solution is introduced at a
rate which maintains the temperature of the mixture. If necessary a
pressurised apparatus could be used to allow a higher temperature
to be reached, but with the structurant materials of this invention
this is usually unnecessary. After two phases are mixed, the
resulting mixture is filled into dispensing containers, typically
at a temperature 5 to 30.degree. C. above the setting temperature
of the composition, and allowed to cool as described above for
suspension sticks.
EXAMPLES
[0140] The examples below were prepared using a number of materials
set out with their proprietary names in the following list. All
temperature are in degrees Celsius. Refractive indices were
measured at 22.degree. C.
[0141] 1 & 2) Volatile cyclic silicones (cyclomethicones) DC
245 and DC 345 (Dow Corning)
[0142] 3 & 4) Non-volatile silicone fluids DC 556 and DC 710
(Dow Corning)
[0143] 5) Polydecene (Silkflo 364NF from Albemarle)
[0144] 6) Isostearyl Alcohol (abbreviated to ISA--Prisorine 3515
from Unichema)
[0145] 7) C12-15 alkyl benzoate (Finsolv TN from Fintex) 8) Mineral
Oil (Sirius M70 from Dalton)
[0146] 9) Polypropyleneglycol 14 butylether (Fluid AP from
Amercol)
[0147] 10) Isopropyl myristate (abbreviated to IPM from
Unichema)
[0148] 11) Cetyl dimethicone copolyol (Abil EM90 emulsifier from
Th. Goldschmidt)
[0149] 12) Al/Zr Tetrachlorohydrex glycine complex (AZAG-7167 from
Summit)
[0150] 13) 50% aqueous solution of Al/Zr pentachlorohydrate
(Zirkonal 50 from Giulini)
[0151] 14) Superfino talc (particle size about 5 .mu. from Cyprus
Minerals)
[0152] 15) Glycerol (from Aldrich)
[0153] 16) Propylene glycol (from Fisons)
[0154] 17) Al/Zr Tetrachlorohydrex glycine complex 30% in propylene
glycol (WA2Z 8106 from Westwood)
[0155] 18) Al/Zr tetrachlorohydrex glycine complex (AZG-375 from
Summit)
[0156] 19) Isohexadecane (Permethyl 101A from Presperse Inc)
[0157] 20) Isoeicosane (Permethyl 102A from Presperse Inc).
[0158] 21) Bis-phenylpropyldimethicone, a non-volatile silicone
fluid (SF 1555 from G E Silicones)
[0159] 22) Polyglyceryl polyricinolate (Quest PGPR)
[0160] 23) 1-octyldodecanol (Eutanol G from Henkel/Cognis)
[0161] 24) Hydrogenated polyisobutene (Panalene-L-14E from
Amoco)
[0162] 25) Hydrogenated polyisobutene (Fancol 800 from Fanning
Corp)
[0163] 26) Polyglyceryl-3-diisostearate (Lameform TGI from
Henkel/Cognis)
[0164] 27) Polyglyceryl-2-dipolyhydroxystearate (Dehymuls PGPH from
Henkel/Cognis)
[0165] 28) Polyalpha olefins (Puresyn 4 from Mobil Chemical)
[0166] 29) Ceteareth 20 (Eumulgin B2 from Henkel)
[0167] 30) C20-C40 alcohols (Unilin 425 from Petrolite)
Example 1
[0168] Cellobiose was esterified with nonanoic acid to yield the
fully esterified product in the form of its .alpha.-anomer
following a procedure generally as described in Takada et al,
Liquid Crystals, Volume 19, page 441 (1995).
[0169] The following materials were used:
[0170] .beta.-D-cellobiose, 20 grams, 0.058 moles
[0171] Nonanoic acid, 591.6 grams, 3.74 moles
[0172] Trifluoroacetic anhydride, 297.6 grams, 1.42 moles.
[0173] These materials were obtained from Acros Organics--Fisher
Scientific.
[0174] Into a 2 liter flange pot equipped with an overhead stirrer,
water condenser and addition inlet was placed the nonanoic acid
together with the trifluoroacetic anhydride. The resultant clear
mixture was stirred up and heated to 100.degree. C. using a
silicone oil bath and temperature probe. During heating it was
noted that the colour of the reaction mixture darkened and
developed a dark brown tinge. After allowing the mixture to stir
for one hour at 100.degree. C., the cellobiose was slowly added via
a solid powder funnel to the dark activated solution, and a dirty
brown suspension was formed which re-dissolved forming a clear
black solution within 10-20 minutes.
[0175] The reaction flask was then maintained at 100.degree. C. for
a total of 6 hours then cooled down to ambient laboratory
temperature. Next the contents of the flask were transferred into 2
liters of methanol containing 10% de-ionised water in an ice-cooled
5 liter beaker. Immediately an off-white solid precipitate came out
of solution, this was filtered off and collected. The crude solid
was recrystallised a total of 4 times from a
tetrahydrofuran/methanol solution producing a white solid
product.
[0176] The product was obtained in a quantity of 31.5 g which was a
37% yield. It had a melting point of 110.degree. C. The infra-red
spectrum showed an absorption peak at 1739 cm.sup.-1 for the ester
carbonyl group. The amount of free acid could be determined from
its absorption peak at 1705 cm.sup.31 1.
[0177] The n.m.r. spectrum showed the amount of cellobiose which
was fully esterified and the proportions of product which were the
.alpha.- and .beta.-anomers.
[0178] The same procedure was followed using acids of different
chain lengths. The acids used and details of the products are set
out in the following table.
1 Properties of product % fully Mpt % of esteri- Acid used
(.degree. C.) .alpha.-anomer fied Comments Hexanoic 104.9 95% 86%
no free acid white solid Heptanoic 110 100% 100% white needles
Octanoic 110 98% 100% no free acid white fluffy powder Nonanonic
101 93.5% 93.5% 0.3% free acid off white powder Decanoic 97 87%
85.4% no free acid off white powder Undeca- 101- 98.9% 100% white
powder noic 104 trace of free acid Dodeca- 60- 80% 70% 2% free acid
noic 61* off white powder Octadeca- 92 83% 74% no free acid noic
white powder Nonanonic 90 86% 90% 1-4% free C.sub.9 acid and deca-
1-3% free C.sub.10 noic in acid equimolar off white powder ratio
*Melting point reduced by methyldodecanoate impurity.
Example 2
[0179] Samples of esterified cellobiose prepared in accordance with
Example 1 were used to gel various water-immiscible liquids and
mixtures of liquids. The procedure was as follows:
[0180] 0.5 grams esterified cellobiose and 9.5 grams of the liquid
(or other proportions to give a total of 10 grams) were weighed
directly into a 15 gram or 30 gram glass jar. A small magnetic
follower was placed in the jar which was then placed on a hot
plate. It was stirred and heated until all of the esterified
cellobiose had dissolved in the liquid. This "dissolution
temperature" was noted. The jar was then removed from the hot
plate, the stirrer was removed from the hot liquid in the jar. A
thermometer was placed in the liquid and the contents of the jar
were then left undisturbed to cool. The gelling temperature, i.e.
the temperature at which the contents gelled, was noted. The jar
was left to stand for 24 hours and then the contents of the jar
were inspected visually, pressed with a probe and classified
qualitatively according to their appearance as a soft, medium or
hard gel. The clarity or otherwise of the gel was noted. In most
instances the gel was remelted, the remelting temperature was
noted, and some of the melt was poured into a plastic
(polymethylmethacrylate) cuvette and allowed to cool back to
ambient laboratory temperature so that the gel reformed in the
cuvette. The transmittance of light through the lcm thickness of
gel in the cuvette was determined at a wave length of 580 nm using
an ultraviolet/visible spectrophotometer.
[0181] The following tables show the water-immiscible liquids which
were used, the percentage of esterified cellobiose structurant used
to gel the liquid, and some or all of the dissolution temperature,
the gelling temperature, the visual appearance of the gel the
remelt temperature and the percentage light transmittance (denoted
as %T) through lcm of the gel at 580 nm. In a few instances
gel-formation was carried out as a test on a smaller scale, and
less data could be recorded.
2 Diss Gel Remelt Visual appearance Liquid Temp Temp Temp % T of
gel Gelling with .alpha.-cellobiose octa-hexanoate ("CB6" R =
--COC.sub.5H.sub.11) % CB6 ISA (6) 5 53 26 45 76 Soft &
transparent DC 345 (2) 5 90 59 70 0.03 Medium & opaque DC 556
(3) 5 58 30 50 78 V. soft & transparent Silkflo 364 NF 5 80 65
70 27 v. soft & transparent (5) Fluid AP (9) 5 65 30 53 46 Soft
& transparent DC 345: Fluid AP 5 72 30 55 56 Medium/hard &
80:20 wt ratio transparent Gelling with .alpha.-cellobiose
octa-heptanoate ("CB7" R = --COC.sub.6H.sub.13) % CB7 ISA (6) 5 41
25 41 Very soft & transparent gel -> crystal growth occurs
DC 345 (2) 5 51 38 51 Medium & transparent -> crystal growth
Silkflo 364 NF 5 57 48 57 Very soft & opaque (5) Fluid AP (9) 5
55 35 55 Very soft & opaque -> crystal growth Gelling with
.alpha.-cellobiose octa-octanoate("CB8" R = COC.sub.7H.sub.15) %
CB8 ISA (6) 5 41 30 41 Hard & transparent -> crystal growth
10 41 35 Hard & translucent -> crystal growth DC 345 (2) 5
48 41 50 17 Hard & transparent/ translucent 10 53 50 Hard &
opaque DC 556 (3) 5 48 30 45 49 Hard & transparent 10 49 35
Hard & transparent Silkflo 5 53 45 51 22 Hard & transparent
364 NF (5) 10 55 50 Hard & opaque Gelling with
.alpha.-cellobiose octa-nonanoate ("CB9" R = COC.sub.8H.sub.17) %
CB9 ISA (6) 5 57 25 46 78 Medium/hard & transparent DC 345 (2)
5 62 42 60 15 Hard & transparent/ translucent DC 566 (3) 5 69
29 52 81 Hard & transparent Silkflo 364NF (5) 5 71 40 55 78
Hard & transparent Fluid AP (9) 5 82 38 55 37 Soft/medium &
transparent DC 345:Fluid AP 5 68 28 54 39 Soft/medium & 80:20
wt ratio transparent DC 710(4) 5 82 48 62 11 Medium &
translucent DC 710:DC 345 5 74 33 60 4 Hard & translucent 60:40
wt ratio Gelling with .alpha.-cellobiose octa-decanoate ("CB10" R =
COC.sub.9H.sub.19) % CB10 Finsolv TN (7) 5 72 25 38 Very soft &
transparent gel ISA (6) 5 72 25 47 46 Medium & transparent 7 68
25 52 Hard & translucent 10 76 30 Medium & transparent DC
345 (2) 5 85 62 71 0.02 Hard & translucent/ opaque 7 84 65 59
Hard & opaque DC 556 (3) 3 79 46 59 Medium & transparent 5
n/d 50 52 2 Medium/hard & translucent 7 74 40 67 Hard &
translucent Fluid AP (9) 3 85 35 60 Medium & transparent 5 82
33 51 Medium & transparent 7 78 51 53 3 Medium &
translucent 10 84 45 Medium & translucent/opaque DC 345:Fluid
AP 5 73 25 55 <0.01 Medium & 80:20 wt ratio
translucent/opaque 7 82 36 49 Hard & opaque 10 83 41 Hard &
opaque DC 710(4) 5 100 80 80 0.15 Medium & opaque DC 710:DC 345
5 92 65 65 1 Medium & 60:40 wt ratio translucent/opaque Gelling
with .alpha.-cellobiose octa-undecanoate ("CB11" R =
COC.sub.10H.sub.21) % Liquid CB11 % T Visual appearance of gel ISA
(6) 5 -- Opaque gel DC 245 (1) 5 0.4 Opaque gel DC 556 (3) 5 34
Transparent gel 10 22 Transparent gel 15 18 Almost transparent gel
Silkflo 364NF (5) 5 58 Transparent gel 10 45 Transparent gel 15 37
Transparent gel Mineral oil (8) 5 -- Opaque soft gel 10 -- Opaque
gel Fluid AP (9) 5 -- Opaque gel DC 245:Finsolv TN 5 3 Transparent
gel 80:20 wt ratio 15 0.3 Opaque gel DC 245:Silkflo 364NF 5 5.2
Translucent gel 40:60 wt ratio 10 1.0 Translucent gel 15 1.3
Translucent gel DC 245:Silkflo 364NF 5 28 Transparent gel 20:80 wt
ratio 10 21 Transparent gel 15 11 Translucent gel DC 710 (4):DC 245
5 13 Almost transparent gel 60:40 wt ratio 10 7 Translucent gel
Diss Gel Remelt Visual appearance Liquid Temp Temp Temp % T of gel
Gelling with .alpha.-cellobiose octa-dodecanoate ("CB12" R =
COC.sub.11H.sub.23) % CB12 ISA(6) 5 54 30 48 12 Soft &
transparent/trans- lucent DC 345(2) 5 50 48 50 0.17 Soft &
opaque DC 556(3) 5 60 35 48 17 Medium & transparent/trans-
lucent Silkflo 364 NF 5 53 45 55 3 Medium & (5) transparent
Fluid AP (9) 5 63 43 55 4 Soft & transparent/ translucent DC
345:Finsolv 5 65 29 42 3 soft & translucent TN 80:20 wt ratio
DC 345:Fluid AP 5 63 42 50 0.25 Soft/medium & 80:20 wt ratio
opaque DC 710 (4) 5 65 57 65 1 Medium & opaque DC 710:DC 345 5
65 48 55 39 Soft & transparent 60:40 wt ratio Gelling with
.alpha.-cellobiose octa-octadecanoate ("CB18" R =
COC.sub.17H.sub.35) % CB18 Finsolv TN (7) 5 68 47 60 0.12 very soft
& opaque 7 68 47 IPM (10) 5 68 50 59 0.01 very soft &
opaque 7 72 50 very soft& opaque ISA (6) 5 68 58 62 0.03 very
soft & opaque 7 70 61 soft & opaque DC 345 (2) 5 85 82 80
<0.01 soft & opaque 7 87 86 soft & opaque 10 85 84
medium & opaque DC 556 (3) 5 77 76 75 0.08 soft & opaque 7
83 79 soft & opaque 10 83 79 medium & opaque Silkflo 364 NF
5 72 66 75 0.11 medium & opaque (5) 7 72 68 medium & opaque
10 79 69 medium & opaque Fluid AP (9) 5 78 76 78 0.01 soft
& opaque 7 82 77 medium & opaque 10 82 81 soft &
opaque
Example 3
[0182] Cellobiose was esterified with a less than stoichiometric
quantity of nonanoic acid to yield a partially esterified product,
following a procedure generally similar to that of Example 1.
[0183] The following materials were used:
[0184] .beta.-D-cellobiose, 2.5 grams, 7.3.times.10.sup.-3
moles
[0185] Nonanoic acid, 5.78 grams, 3.65.times.10.sup.-2 moles
[0186] Trifluoroacetic anhydride, 2.91 grams, 1.38.times.10.sup.-2
moles.
[0187] Into a 3-neck round bottomed flask equipped with an overhead
stirrer, water condenser and addition inlet was placed the nonanoic
acid together with the trifluoroacetic anhydride. The resultant
clear mixture was stirred and heated to 100.degree. C. The colour
of the reaction mixture darkened. The cellobiose was slowly added
and a grey suspension was formed. The reaction mixture was kept at
100.degree. C. for 6 hours then allowed to cool to ambient
laboratory temperature. 100 ml of ice-cold methanol containing 10%
water was mixed with the contents of the reaction flask. A fine
white product was formed. This was filtered off and washed with
further portions of methanol/water before drying in a vacuum oven.
The yield was 2.5 grams.
[0188] The infra-red spectrum showed absorption peaks at 1744 and
3340 cm.sup.-1 corresponding to the ester carbonyl group and free
hydroxyl groups respectively. Mass spectrometer showed the presence
of unacylated cellobiose and the penta-, hexa-, hepta- and
octa-nonanoate esters of the cellobiose. The mono- di- and tri-
esters could not be observed.
[0189] The ability of this partially esterified cellobiose to gel
water-immiscible liquids was tested using the following procedure
in which fully acylated cellobiose was included for comparison. In
this procedure a large number of gels can be prepared
simultaneously.
[0190] Gels were prepared in a 96 well (8 by 12 row) glass
micro-titre plate. Each well had a volume of about 1 ml. About 0.01
g of each esterified cellobiose material was placed into 8
consecutive wells in a single row. Approximately 0.2 g of the
required liquid was added to each well. A glass lid was placed on
top of the plate. The plate was carefully placed in a
thermostatically controlled fan assisted box oven at 150.degree. C.
for 2.5 hours. The plate was then removed from the oven and allowed
to cool naturally to ambient laboratory temperature. The contents
of each well were evaluated after 18 hours. Evaluation was carried
out by visual inspection and by poking the contents of each well
with a micro-spatula.
[0191] The results obtained were:
3 Fully Partially Fully acylated .alpha.C9 acylated .alpha.C9
acylated .alpha.C10 Liquid Cellobiose Cellobiose Cellobiose Mineral
oil (8) hard gel no gel hard gel Fluid AP (9) medium hard soft gel
hard gel gel Polydecene (5) hard gel soft gel hard gel DC 556 (3)
hard gel soft gel hard gel Isostearyl alcohol hard gel no gel hard
gel (6)
[0192] This demonstrates that partially esterified cellobiose can
be used, but the fully esterified compound is superior.
Example 4
[0193] Antiperspirant suspension sticks were prepared using a
water-immiscible liquid or a mixture of water-immiscible liquids,
an antiperspirant active and an esterified cellobiose. In all cases
the procedure was as follows: the liquid or mixture of liquids was
heated to a temperature 5 to 10.degree. C. above a temperature at
which the esterified cellobiose had been observed to dissolve in a
preliminary test. During this heating the liquid was mixed gently
using a Silverson mixer. The esterified cellobiose was added and
allowed to dissolve. Next, the particulate antiperspirant active
was added to this solution. The resulting mixture was then allowed
to cool (or, if necessary, heated) whilst mixing gently until it
reached a temperature of about 5 to 10.degree. above the gelling
point. At this stage the mixture was poured into antiperspirant
stick barrels and left to cool without further disturbance until
the formulation had solidified.
[0194] The resulting sticks were evaluated after at least 24 hours
at ambient laboratory temperature. In all cases the appearance of
the stick was noted, the hardness was determined by penetrometer
and texture analyser, and tests of deposition and whiteness of the
resulting deposit were carried out using the procedures described
earlier.
[0195] The formulations which were prepared and the properties of
the resulting sticks are set out in the table below. The testing of
hardness and whiteness of deposit was also carried out with a
commercial white solid stick (CWS) structured with 15% stearyl
alcohol and 3% castor wax, these percentages being by weight of its
whole composition.
[0196] "Esterified cellobiose C.sub.12" denotes cellobiose
esterified with dodecanoic acid, as in Example 1.
[0197] "Esterified cellobiose Chd 9/C.sub.10" denotes cellobiose
esterified with an equimolar mixture of nonanoic and decanoic
acids, as in Example 1.
4 Example CWS 4.1 4.2 4.3 4.4 4.5 4.6 4.7 % by Weight
Cyclomethicone, DC 245 (1) 68.50 54.80 52.80 66.00 51.05 52.80
66.00 Polydecene (5) -- 13.70 13.20 -- 9.95 13.20 -- Esterified
cellobiose C.sub.12 7.50 7.50 10.00 10.00 15.00 -- -- Esterified
cellobiose C.sub.9/C.sub.10 -- -- -- -- -- 10.00 10.00 AZAG 7167
(12) 24.00 24.00 24.00 24.00 24.00 24.00 24.00 penetration depth
(mm) 9.40 -- 11.2 13.5 12.6 -- 16.2 12.0 Hardness by texture
analyser -- -- 0.26 0.18 0.21 0.50 0.11 0.24 (N/mm.sup.2) Whiteness
on grey paper 24 118 80 26 25 50 -- 25 37 hours after deposition
Whiteness on black wool 24 186 102 18.5 27 90 -- 28 92 hours after
deposition
Example 5
[0198] Two soft solid products were prepared with the following
formulations:
5 Ingredient % by weight Cyclomethicone DC 245 (1) 55.0 55.45
Polydecene (5) 13.0 13.86 Esterified cellobiose (fully esterified
4.0 -- with C18 fatty acid) Esterified cellobiose (fully esterified
-- 2.97 with C9 and C10 fatty acids) Talc (14) 4.0 3.96 AZAG 7.167
(12) 24.0 23.76
[0199] The liquids and esterified cellobiose structurant were mixed
together and heated with gentle stirring from a Silverson mixer to
reach a temperature about 20-30.degree. C. above the minimum
temperature at which the esterified cellobiose would dissolve. The
particulate antiperspirant active and talc were both added with
more vigorous mixing. The mixture was then cooled further with
continued mixing until the temperature had fallen to somewhat below
a gelation temperature measured during a preliminary test. Then the
mixture (which was still mobile) was poured into stick barrels and
left to cool to ambient laboratory temperature.
[0200] Both formulations were spreadable and extrudable soft solids
which was nevertheless capable of sustaining their own shape during
storage for a period of 24 hours at 50.degree. C.
Example 6
[0201] Opaque emulsion sticks were prepared with formulations as
set out in tables below.
[0202] To prepare these sticks, the cyclomethicone was mixed with
the other organic liquids (if any) including the cetyl dimethicone
copolyol which functioned as an emulsifier (silicone surfactant)
and the mixture was heated with gentle stirring to a temperature 5
to 10.degree. C. above the temperature at which the structurant had
been found to dissolve. The esterified cellobiose was then added
and allowed to dissolve.
[0203] The disperse phase (also referred to as internal phase) was
an aluminium zirconium active dissolved in water or in a mixture of
a polyol and water. This disperse phase was pre-heated to the same
temperature as the organic oils containing the esterified
cellobiose and added slowly to them over a period of one minute
while mixing with a Silverson mixer. After addition was complete
the formulation was mixed at higher speed for five minutes.
Stirring speed was then reduced for a further one minute after
which the mixture was poured into stick barrels and allowed to cool
undisturbed to ambient laboratory temperature. The sticks were
tested by penetrometer, by texture analyser and for whiteness of
deposits, in each instance by the test procedures given earlier.
All of the sticks were opaque although without the chalky white
appearance of a commercial white stick structured with stearyl
alcohol and castor wax.
6 Examples 6.1 6.2 6.3 6.4 6.5 6.6 % by weight Cyclomethicone 18
22.25 21.7 45.5 -- -- DC 245 (1) Cyclomethicone -- -- -- -- 23.8
24.4 DC 345 (2) Mineral Oil (8) -- -- -- -- 22.9 23.4 Polydecene
(5) 22.75 27.5 27.4 -- -- -- PPG-14 Butyl Ether (9) 4.5 5.5 5.4 --
-- -- Esterified cellobiose --C.sub.9 3.75 3.75 4.5 -- -- --
Esterifled cellobiose --C.sub.10 -- -- -- 2.5 4.8 2.4 Cetyl
Dimethicone 1 1 1 2 1 1 Copolyol (11) Zirkonal 50 (13) 40 40 40 40
38 38 Glycerol (15) -- -- -- -- 9.5 10.8 Water 10 -- -- 10 -- --
Properties penetration depth (mm) 16.8 17.5 15.7 40 12.5 --
Hardness by texture 0.11 0.10 0.12 -- -- -- analyser (N/mm.sup.2)
Whiteness on grey paper 19 16 16 31 -- -- 24 hours after deposition
Whiteness on black wool 28 29 27 11 -- -- 24 hours after deposition
N.B. 40% of Zirkonal 50 provides 20% of antiperspirant active and
20% of water.
[0204]
7 Examples 6.7 6.8 6.9 6.10 6.11 6.12 % by weight Cyclomethicone DC
245 -- 23.5 20.95 19.8 20.95 22.3 (1) Cyclomethicone DC 345 23.3 --
-- -- -- -- (2) Mineral Oil (8) 23.3 22.2 21.0 Polydecene (5) 25.9
PPG-14 Butyl Ether (9) -- DC 556 (3) 24.75 Isostearyl alcohol (6)
-- -- -- -- 24.8 -- Esterified cellobiose --C.sub.9 -- -- -- -- --
Esterified cellobiose --C.sub.10 2.4 2.5 2.5 2.5 2.5 5 Cetyl
Dimethicone 1 1.8 1.8 1.8 1.75 1.7 Copolyol (11) Zirkonal 50 (13)
40 40 40 40 40 40 Glycerol (15) 10 10 10 10 10 10 Water -- -- -- --
-- -- Properties penetration depth (mm) 22.7 25.6 25.0 29.0 17.8
Hardness by texture -- analyser (N/mm.sup.2) Whiteness on grey
paper 27 25 22 23 28 24 hours after deposition Whiteness on black
wool 17 13 15 11 16 24 hours after deposition
Example 7
[0205] A number of oils, with various values of refractive index,
were gelled with cellobiose octa-ester, or with another structurant
as stated in the table below. The clarity of the gels was assessed
by measuring light transmission at 580 nm, when a 1cm thickness of
gel in a cuvette was placed in a spectrophotometer light beam at
20-25.degree. C.
[0206] Results are given in the following table, where Refractive
index mismatch=Refractive index of liquid--Refractive index of
structurant. Refractive index mismatch
8 Refractive index mismatch Structurant and its -0.08 -0.04 -0.02
0.0 +0.06 Refractive index 5% cellobiose octa- 16% 40% 63%
.about.100% 13% nonanoate (.about.1.48) 5% cellobiose <0.2% 2%
16% 40% 3% octa-dodecanoate (.about.1.48) 5% cellobiose <0.01%
<0.01% <0.1% 6% <0.05% octa-octadecanoate (.about.1.48) 4%
N-lauroyl glutamic <0.01% <0.01% 6% 63% 25% acid
di-n-butylamide (GP1) (.about.1.48) 2.5% 12-hydroxy stearic 16% 40%
63% .about.100% no data acid (.about.1.52)
[0207] It can be seen that mis-match of refractive index reduces
light transmittance. Cellobiose octa-nonanoate is much more
tolerant of mismatch than are esters of cellobiose with longer
acids and the N-acylaminoacid amide gellants. 12-hydroxy stearic
acid is also tolerant of mis-match but requires the liquids to be
matched to its higher refractive index.
Example 8
[0208] The procedure of Example 6 was repeated to prepare a number
of emulsion sticks with formulations set out in the following
tables. The continuous and disperse phases were formulated to have
refractive indices which matched closely at the value given in the
tables. These sticks were tested as before and the properties are
also given in these tables.
9 Examples 8.1 8.2 8.3 8.4 8.5 8.6 % by weight Cyclomethicone
22.625 18.75 25.5 19 26 17.75 DC245 (1) Mineral Oil (8) 22.625 --
-- -- -- -- Polydecene (5) -- 22.5 15.75 22 15 22 PPG-14 Butyl
Ether -- 4 4 -- -- 4.25 (9) Isostearyl Alcohol (6) -- -- -- 4.25
4.25 -- Esterified Cellobiose 3.75 3.75 3.75 3.75 3.75 5 C.sub.9
Cetyl Dimethicone 1 1 1 1 1 1 Copolyol (11) Zirkonal 50 (13) 40 40
40 40 40 40 Glycerol (15) 10 10 7.5 10 7.5 10 Water -- -- 2.5 --
2.5 -- PG(16) -- -- -- -- -- -- AZG 375(18) -- -- -- -- -- --
Properties Matched Refractive 1.43 1.43 1.425 1.435 1.425 1.43
index of phases penetration depth 19.3 18.5 17.3 24.7 23.6 12.4
(mm) Hardness by texture 0.11 0.12 0.08 0.07 0.06 0.17 analyser
(N/mm.sup.2) Whiteness on grey -- 15 16 18 19 16 paper 24 hours
after deposition Whiteness on black -- 24 28 25 30 26 wool 24 hours
after deposition Transmittance at -- 38% 33% 41% 35% 51% 580 nm
Examples 8.7 8.8 8.9 8.10 8.11 8.12 % by weight Cyclomethicone
DC245 (1) 16.75 18 14.02 28.4 4.5 Cyclomethicone DC345 (2) 4.4
Mineral Oil (8) -- -- -- -- 43.4 Polydecene (5) 20.75 22.75 17.72
13.1 50.75 PPG-14 Butyl Ether (9) 4 4.5 3.51 3.75 -- Isostearyl
Alcohol (6) -- -- -- -- -- Esterified Cellobiose C.sub.9 7.5 3.75
3.75 3.75 3.75 Esterified Cellobiose C.sub.10 2.4 Cetyl Dimethicone
1 1 1 1 1 1 Copolyol (11) Zirkonal 50 (13) 40 -- 40 40 -- Westwood
Active (17) 48.8 Glycerol (15) 10 4 17.5 6.25 12 Water -- 14 2.5
3.75 8 PG(16) -- 12 -- -- -- AZG 375 (18) -- 20 -- -- 20 Properties
Matched Refractive index 1.43 1.43 1.43 1.42 1.45 1.46 of phases
penetration depth (mm) 11 14.5 14.9 15.1 14.8 -- Hardness by
texture 0.29 0.11 0.14 0.13 0.11 -- analyser (N/mm.sup.2) Whiteness
on grey paper 17 20 18 21 16 -- 24 hours after deposition Whiteness
on black wool 25 28 25 31 19 -- 24 hours after deposition
Transmittance at 580 nm 48% 82% 65% 30% 72% 74% Examples 8.13 8.14
8.15 8.16 8.17 % by weight Cyclomethicone DC245 (1) 41.85 35.4
10.04 10.64 6.96 Permethyl 101A (19) 2.15 Permethyl 102A (20) --
8.6 Polydecene (5) 12.7 13.45 8.8 PPG-14 Butyl Ether (9) 2.51 2.66
1.74 Esterified Cellobiose C.sub.9 5 5 3.75 2.25 1.5 Cetyl
Dimethicone 1 1 1 1 1 Copolyol (11) Zirkonal 50 (13) 40 40 52.71
52.71 60.24 Glycerol (15) 0.75 4.5 17.29 17.29 19.76 Water 9.25 5.5
-- -- -- Properties Matched refractive index of 1.40 1.41 1.43 1.43
phases penetration depth (mm) 13.5 13.2 12.0 16.8 Hardness by
texture 0.16 0.15 0.13 0.07 analyser (N/mm.sup.2) Whiteness on grey
paper 24 59 61 24 24 hours after deposition Whiteness on black wool
122 24 15 16 24 hours after deposition Transmittance at 580 nm 2.7%
5% 33% 73%
[0209] In the above table Example 8.17 is a stick with a high
percentage of internal phase. It was observed to have good clarity,
but was not very hard (although capable of sustaining its own
shape).
Example 9
[0210] .alpha.-cellobiose octanoate was deacylated at the anomeric
carbon atom by reaction with a mixture of acetic acid and ethylene
diamine, in an adaptation of a procedure given at J. Carb. Chem 18
pages 461-469 (1999).
[0211] The procedure was as follows: Glacial acetic acid (0.6 g)
was added slowly dropwise with stirring to a solution of ethylene
diamine (1.2 G) in THF (250 cm.sup.3). A white precipitate formed
which remained during the reaction. Cellobiose Octanonanoate (14.6
g) was then added and the whole reaction mixture stirred at room
temperature for a total of 48 hours. After this time the contents
of the flask were transferred to a one liter separating funnel,
100cm.sup.3 of water was then added and the mixture extracted with
dichloromethane (250 cm.sup.3). The organic layer was collected and
further washed with 100 cm.sup.3 portions of dilute HCl (0.1M),
aqueous sodium bicarbonate (1M) and water. The resultant organic
phase was then dried over anhydrous magnesium sulphate, filtered
and the remaining solvent removed by rotary evaporation. A slightly
sticky off-white crude solid was obtained, this was dissolved in
THF (20 cm.sup.3) in a 500 cm.sup.3 conical flask, heated on a
steam bath then methanol (about 150 cm.sup.3) added slowly, the
resultant solution was kept on the steam bath for 3-4 minutes then
removed and allowed to cool down to room temperature overnight.
Next morning the white solid precipitate was filtered off, dried
and collected.
[0212] The product was obtained in a quantity of 6.8 g (51% yield).
It had a melting point of 100.degree. C and purity determined by
high performance liquid chromatography was 98.5%.
[0213] Its structure was checked by mass spectrometer (molecular
ion of mass 1341) proton n.m.r. and infra red (peaks at 3446, 2923,
2853 and 1742 cm.sup.-1). The material was found to be the
.beta.-anomer of cellobiose heptanonanoate. The reaction can thus
be represented as: 5
[0214] The material was used to gel some water-immiscible liquids
as in Example 2. The results are given in the following table.
10 Gelling with .beta.-cellobiose hepta-nonanoate "CB-HN" Diss Gel
Liquid % CB Temp Temp Visual appearance of gel DC 345 (2) 5 82 67
Opaque gel DC 556 (3) 5 -- -- Opaque gel Silkflo 364NF (5) 10 -- --
Very soft opaque gel DC 345:Silkflo 364NF 5 76 71 Opaque soft gel
80:20 wt ratio DC 345:Silkflo 364NF 5 73 69 Opaque soft gel 50:50
wt ratio
Example 10
[0215] Sticks were prepared and tested in accordance with the
procedure given in Example 6. The sticks were tested for hardness
by texture analyser and/or by penetrometer. They were observed to
give deposits of low whiteness, but numerical data were not
recorded.
[0216] For some sticks in this example the refractive indices of
the water-immiscible continuous phase and the polar anti-perspirant
active solution were matched sufficiently to give translucent
sticks. Some values of transmittance are shown.
11 Examples 10.1 10.2 10.3 10.4 10.5 % by weight DC245 (1) 44
21.625 21.625 21.625 18 Silkflo 364 (5) -- -- -- 21.625 4 Permethyl
102A (20) -- 21.625 -- -- -- SF1555 (21) -- -- 21.625 -- 22 Abil
EM90 (11) 1 -- -- -- 1 Quest PGPR (22) -- 1.75 1.75 1.75 --
Esterified Cellobiose - C9 5 5 5 5 5 Zirkonal 50 (13) 39 40 40 40
40 Glycerol (15) -- 8 9 8.75 10 Water 11 2 1 1.25 -- Properties
Penetration depth (mm) 9.3 12 11.3 13 Hardness by texture analyser
0.10 0.12 0.12 0.21 0.13 (N/mm.sup.2) Examples 10.6 10.7 10.8 10.9
10.10 % by weight Cyclomethicone 7.6 6.8 36.5 1.7 1.25 DC245 (1)
isostearyl alcohol (6) -- -- -- 23.3 -- octyldodecanol (23) -- --
-- -- 23.1 SF1555 (21) 37.43 37.7 7 -- -- Silkflo 364 (5) -- -- --
16.8 17.65 Esterified Cellobiose - C10 8.12 7.3 7.8 7 7 Cetyl
Dimethicone Copolyol 1.1 1 1 1 1 (Abil EM90) (11) Westwood active
(17) 43.54 41 42 40 40 Glycerol (15) -- 4.7 5.2 6.8 6.5 Water 2.21
1.5 0.5 3.4 3.5 Properties Matched RI of phases 1.45 1.45 1.46 1.45
1.45 penetration depth (mm) 9.1 6.9 8.7 8.8 9.1 Hardness by texture
analyser 0.37 0.03 0.08 0.04 0.19 (N/mm.sup.2) Transmittance at 580
nm 8 3 5 6 5 (%) Examples 10.11 10.12 10.13 10.14 % by weight DC245
(1) 12 11.32 -- -- Silkflo 364 (5) 32.5 30.68 39 41.5 Abil EM90
(11) 0.5 0.5 1 1 Esterified Cellobiose - C10 5 7.5 10 7.5 Zirkonal
50 (13) 33 33 -- -- Westwood active (17) -- -- 48.06 48.06 Glycerol
(15) 17 17 -- -- water -- -- 1.94 1.94 Properties penetration depth
(mm) 19 14 7.3 9.6 Hardness by texture analyser 0.44 0.07 0.47 0.15
(N/mm.sup.2)
Example 11
[0217] The procedure of Example 6 was repeated to prepare a number
of emulsion sticks with formulations set out in the following
tables. As in Example 8, the continuous and disperse phases were
formulated to have refractive indices which matched closely at the
value given in the tables. The sticks were tested for hardness by
texture analyser and/or by penetrometer. They were observed to give
deposits of low whiteness, consistent with their good clarity, but
numerical data were not recorded.
[0218] The refractive indices of sample quantities of the
water-immiscible liquid mixture and the antiperspirant active
solutions were checked before making the sticks. If necessary their
formulations were modified very slightly to optimise the refractive
index match.
12 Examples 11.1 11.2 11.3 11.4 11.5 11.6 % by weight Permethyl
102A (20) 41.36 -- -- -- -- -- Panalene L-14E (24) -- -- 22 -- --
-- Fancol 800 (25) -- -- -- 22 22 -- Puresyn 4 (28) -- -- -- -- --
22 DC245 (1) 2.64 11.4 22 22 22 22 SF1555 (21) -- 34.1 -- -- -- --
Esterified cellobiose C9 5 4.9 5 5 5 5 Abil EM90 (11) 1 1 1 1 1 1
Zirkonal 50 (13) -- -- 40 40 36.6 40 Westwood active (17) 50 48.6
-- -- -- -- Glycerol (15) -- -- 9.35 7.5 13.4 8.75 Water -- -- 0.65
2.5 -- 1.25 Properties Matched refractive index 1.46 1.45 1.431
1.425 1.437 1.429 of phases (at 25.degree. C.) penetration depth
(mm) 9 11 10.5 12.1 7.9 8.8 Hardness by texture analyser 0.11 0.11
0.13 0.12 0.11 0.10 (N/mm.sup.2) Transmittance at 580 nm (%) 68 70
40 6 70 37 Examples 11.7 11.8 11.9 11.10 11.11 % by weight DC245
(1) 22 22.25 22.25 21.625 -- DC556 (3) 22 -- -- -- -- Silkflo 364
(5) -- -- -- -- 44 Permethyl 102A (20) -- 22.25 -- -- --
Panalene-L-14E (24) -- -- -- 21.625 -- SF1555 (21) -- -- 22.25 --
-- Abil EM90 (11) 1 0.5 0.5 -- 1 Lameform TGI (26) -- -- -- 0.875
-- Dehymuls PGPH (27) -- -- -- 0.875 -- Esterified cellobiose C9 5
5 5 5 5 Zirkonal 50 (13) 40 40 40 40 50 Glycerol (15) 9 8 9 9.8 --
Water 1 2 1 0.2 Properties Matched refractive index 1.428 1.43 1.43
1.43 1.46 of phases (at 25.degree. C.) penetration depth (mm) 9.0
11 11 10.5 9 Hardness by texture analyser 0.10 0.09 0.16 0.13 0.13
(N/mm.sup.2) Transmittance at 580 nm (%) 40 22 33 36 24 Examples
11.12 11.13 11.14 11.15 11.16 11.17 % by weight DC245 (1) -- -- --
22 22 18 Silkflo 364 (5) 44 -- -- -- 5.3 Permethyl 102A (20) -- 44
-- 22 -- -- Panalene-L-14E (24) -- -- 44 -- -- -- SF1555 (21) -- --
-- -- 22 -- Octyldodecanol (23) -- -- -- -- -- 21.9 Abil EM90 (11)
1 1 1 1 1 1 Esterified Cellobiose C9 5 5 5 5 5 5 Zirkonal 50 (13)
18 21.5 12 -- -- 37.8 AZG-375 (18) -- -- -- 25 25 -- Glycerol (15)
32 28.5 38 0.6 2.5 11 Water -- -- -- 24.4 22.5 -- Properties
Matched refractive index 1.45 1.45 1.46 1.43 1.43 1.43 of phases
(at 25.degree. C.) penetration depth (mm) 9 9 7 9 8 -- Hardness by
texture analyser 0.13 0.15 0.20 -- 0.21 0.12 (N/mm.sup.2)
Transmittance at 580 nm (%) 74 46 82 53 41 24
Example 12
[0219] The procedure of Example 6 was used to prepare a number of
emulsion sticks with formulations set out in the following table.
These sticks did not contain antiperspirant active. They would be
useful as moisturizing stick or lip salve and their compositions
could be used as the basis for other, probably opaque, cosmetic
stick products. The continuous and disperse phases were formulated
to have refractive indices which matched closely at the values
given in the table, but evaporative losses during processing
interfered with this. The sticks were tested for hardness by
texture analyser and/or by penetrometer.
13 Examples 12.1 12.2 12.3 12.4 % by weight DC45 (1) 22 22 16.72
19.36 Silkflo364 (5) 22 -- 27.28 -- SF1555 (21) -- 22 -- 24.64 Abil
EM90 (11) 1 1 1 1 Esterified Cellobiose C9 5 5 5 5 Glycerol (15)
33.5 37.5 -- -- Water 16.5 12.5 -- -- Propylene Glycol (16) -- --
50 50 Properties Matched refractive index of 1.42 1.43 1.43 1.43
phases (at 25.degree. C.) penetration depth (mm) 9 9 -- 10 Hardness
by texture analyser 0.13 0.15 0.15 -- (N/mm.sup.2)
Example 13
[0220] The procedure of Example 6 was used to prepare translucent
emulsion sticks with the formulation below in which the structurant
is .alpha.-cellobiose octa-undecanoate ("CB11"). As in Example 8,
the continuous and disperse phases were formulated to have
refractive indices which matched closely at the value given. The
sticks were tested for hardness by texture analyser and/or by
penetrometer. They were observed to give deposits of low
whiteness.
14 percent by weight Ingredients DC245 (1) 11 Silkflo 364 (5) 33
Abil EM90 (11) 1 Esterified Cellobiose C11 5 Zirkonal 50 (13) 33
Glycerol (15) 17 Properties Matched refractive index of phases 1.44
(at 25.degree. C.) penetration depth (mm) 16 Hardness by texture
analyser 0.05 (N/mm.sup.2) Transmittance at 580 nm (%) 6
Example 14
[0221] The procedure of Example 6 was used to prepare an opaque
emulsion stick of the following formulation, which included agents
to assist wash-off.
15 Ingredients percent by weight DC245 (1) 16.4 Silkflo 364 (5)
24.6 Abil EM90 (11) 1 Esterified cellobiose C9 5 Zirkonal 50 (13)
40 Glycerol (15) 10 Ceteareth 20 (29) 2.5 C.sub.20-40 alcohols (30)
0.5
* * * * *