U.S. patent application number 10/314712 was filed with the patent office on 2004-06-10 for high efficacy, low irritation aluminum salts and related products.
Invention is credited to Chopra, Suman, Fei, Lin, Hilliard, Peter JR., Tang, Xiaozhong.
Application Number | 20040109833 10/314712 |
Document ID | / |
Family ID | 32468544 |
Filed Date | 2004-06-10 |
United States Patent
Application |
20040109833 |
Kind Code |
A1 |
Tang, Xiaozhong ; et
al. |
June 10, 2004 |
High efficacy, low irritation aluminum salts and related
products
Abstract
A zirconium-free aluminum salt which: (a) has an aluminum to
chloride molar ratio in the range of 0.5-2.5:1; (b) comprises a
nitrogen containing buffering material in an amount such that the
ratio of nitrogen containing material to aluminum is the range of
0.05-0.26:1, and which nitrogen containing material is selected
from the group consisting of a nitrogen containing buffering
material of formula 1 where n is a number in the range of 1-20, and
each of R.sup.1, R.sup.2, and R.sup.3 is independently selected
from the group consisting of hydrogen, methyl and ethyl; and (c)
the salt has a pH in the range of 2-4 at a concentration of 15%;
wherein the salt is free of any other halide scavenging material
and has a value of at least 0.50 for the ratio calculated as: area
of Peak 5/total area under Peak 2+Peak 3+Peak 4+Peak 5.
Inventors: |
Tang, Xiaozhong;
(Bridgewater, NJ) ; Fei, Lin; (Kendall Park,
NJ) ; Chopra, Suman; (Dayton, NJ) ; Hilliard,
Peter JR.; (Kendall Park, NJ) |
Correspondence
Address: |
COLGATE-PALMOLIVE COMPANY
909 River Road
P.O. Box 1343
Piscataway
NJ
08855-1343
US
|
Family ID: |
32468544 |
Appl. No.: |
10/314712 |
Filed: |
December 9, 2002 |
Current U.S.
Class: |
424/68 |
Current CPC
Class: |
A61K 8/895 20130101;
A61K 8/046 20130101; A61K 8/26 20130101; A61K 8/894 20130101; A61Q
15/00 20130101; A61K 8/0229 20130101; A61K 8/44 20130101 |
Class at
Publication: |
424/068 |
International
Class: |
A61K 007/32; A61K
007/38 |
Claims
We claim:
1. A zirconium-free aluminum salt which: (a) has an aluminum to
chloride molar ratio in the range of 0.5-2.5:1; (b) comprises a
nitrogen containing buffering material in an amount such that the
ratio of nitrogen containing material to aluminum is the range of
0.05-0.26:1 and which nitrogen containing material is selected from
the group consisting of a nitrogen containing buffering material of
formula 3where n is a number in the range of 1-20, and each of
R.sup.1, R.sup.2, and R.sup.3 is independently selected from the
group consisting of hydrogen, methyl and ethyl; and (c) the salt
has a pH in the range of 2-4 at a concentration of 15%; wherein the
salt is free of any other halide scavenging material and has a
value of at least 0.50 for the ratio calculated as: 2 area of Peak
5 total area under Peak 2 + Peak 3 + Peak 4 + Peak 5 .
2. A zirconium-free aluminum salt according to claim 1 wherein the
ratio of nitrogen containing material to aluminum is in the range
of 0.05-0.16:1.
3. A zirconium-free aluminum salt according to claim 1 wherein each
of R.sup.1, R.sup.2, and R.sup.3 is methyl.
4. A zirconium-free aluminum salt according to claim 1 wherein the
nitrogen containing material is selected from the group consisting
of glycine, alanine, serine, glutamine, threonine, valine, leucine
and betaine.
5. An antiperspirant composition made with the composition of claim
1.
6. An antiperspirant composition according to claim 5 wherein the
composition is a stick comprising a gelling agent which is stearyl
alcohol or dibenzylidene sorbitol.
7. An antiperspirant composition according to claim 6 comprising:
40-55% cyclomethicone; 20-30% stearyl alcohol; 7-15% talc; 15-22%
aluminum antiperspirant active added as a powder; optionally 1-3%
fragrance.
8. An antiperspirant composition according to claim 5 wherein the
composition is a roll-on comprising 45-65% cyclomethicone; 0.1-10%
cyclomethicone/dimethicone copolyol; 10-25% in a solution form as
25-45% actives on an anhydrous basis in water; 5-30% water; and
optionally 1-3% fragrance.
9. An antiperspirant composition according to claim 5 wherein the
composition is a soft solid comprising 40-70% elastomer in
cyclomethicone; 5-15% polyethylene; 10-20% C12-15 alkylbenzoate;
0.1-25% antiperspirant active added in powder form 1-15%
dimethicone (100 centistokes); and optionally 1-3% fragrance.
10. An antiperspirant composition according to claim 5 wherein the
composition is a gel comprising 5-50% cyclomethicone; 0.1-10%
cyclomethicone/dimethicone copolyol; 0-10% hydrogenated
polyisobutene 250; 0-10% C12-15 alkylbenzoate; 0-10% dimethicone
(100 centistokes); 0.1-25% antiperspirant active added in powder
form or 10-25% of antiperspirant active added as a solution of
25-45% actives on an anhydrous basis; 5-50% water; and optionally
1-3% fragrance.
11. An antiperspirant composition according to any one of claims
5-10 wherein the glycol content is less than 1.0 weight %.
Description
FIELD OF THE INVENTION
[0001] This invention relates to a class of high efficacy, low
irritation aluminum salts that may be used to formulate
non-aerosol, propellant-free antiperspirants and/or deodorants.
BACKGROUND OF THE INVENTION
[0002] A variety of art is available that describes various salts
and methods of making them.
[0003] U.S. Pat. No. 4,331,609 to Orr teaches an antiperspirant
active comprising aluminum and zirconium made with separate
aluminum and zirconium compounds as well as a neutral amino acid
wherein the molar ratio of neutral amino acid to total metal is
from about 0.90 to about 0.24. The total metal:chlorine ratio in
the complex that is formed is less than 1.30.
[0004] U.S. Pat. No. 4,499,069 to Krafton describes a stable
antiperspirant emulsion comprising an aluminum salt, volatile
cyclic silicone, water, and a low pH-stable emulsifier mixture of
polyethylene glycol (21) stearyl ether and a lipophilic
co-emulsifier such that the HLB of the emulsifier mixture is
greater than 7.5 and less than 9.9.
[0005] U.S. Pat. No. 4,675,177 to Geary teaches aluminum salts
comprising particular lactate, citrate, tartrate or adipate esters
for enhanced efficacy.
[0006] U.S. Pat. No. 4,871,525 to Giovanniello et al describes a
solid powder of aluminum zirconium hydroxyl halide glycinate
complex having improved antiperspirant activity wherein the glycine
is used to prevent gel formation. The ratio of Zr to glycine is
less than 1:1.
[0007] U.S. Pat. No. 5,234,677 to Murray et al teaches a method for
making enhanced aluminum chlorides with increased efficacy.
[0008] U.S. Pat. No. 5,384,117 to Vu et al teaches a substantially
clear anhydrous antiperspirant compositions that can me made with
an aluminum chlorohydrate salt in solid particulate form suspended
in an essentially anhydrous vehicle, wherein the salt is free of
opacifying contaminants and the salt and vehicle have refractive
indices in selective ranges.
[0009] U.S. Pat. No. 5,393,518 to Kwass teaches a stable and
substantially clear antiperspirant composition comprising a stable
water-in-oil emulsion, wherein the oil phase is at lest 30% of ht e
product.
[0010] U.S. Pat. No. 5,356,612 to Curtin, et al describes an
antiperspirant comprising a basic aluminum salt mixed with
monosilicic acid in aqueous solution.
[0011] U.S. Pat. Nos. 5,718,876 and 5,908,616 to Parekh describes a
method for making enhanced aluminum halides with increased
efficacy.
[0012] U.S. Pat. No. 5,599,533 to Stepniewski et al describes a
stable water-in-oil emulsion system formed of an organopolysiloxane
elastomer, a vehicle in which the elastomer is dispersed or
dispersible, a stabilizing agent (such as a selected electrolyte),
a surfactant and an aqueous component and a process for forming the
stable water-in-oil emulsion. Possible choices for electrolytes are
alkali metal salts and alkaline earth salts, as well as aluminum
chlorohydrate, and polyelectrolytes. When the stabilizing agent is,
or includes, an electrolyte, it amounts to about 0.1 to 5 wt.-% and
more preferably 0.5 to 3 wt. % of the total composition.
[0013] U.S. Pat. No. 6,024,945 to Parekh describes aerosol products
comprising an aluminum salt, 1,1-difluoroethane in combinations
with selected additives to prevent the formation of toxic
compounds. These additives include, for example, and an amino acid
(such as glycine) selected salts thereof, or metal glycinates.
[0014] U.S. Pat. No. 6,066,314 to Tang describes the use of post
added glycine to aluminum zirconium salts in an amount in the range
of 1:1.2-1:5 of zirconium:amino acid on a weight:weight basis.
[0015] U.S. Pat. No. 6,126,928 to Swaile describes antiperspirant
compositions wherein the molar ratio of neutral amino acid to total
metal (aluminum+zirconium) is from about 0.90 to about 0.24, and
the mole ratio of (aluminum+zirconium):chlorine is less than about
1.30:1.
[0016] EP publication number 0 047 650 describes aqueous
solution-stable antiperspirant complexes comprising an aluminum
compound, a zirconium or hafnium compound, a water soluble neutral
amino acid and an inorganic acid. The molar ratio of neutral amino
acid to total metal is from about 0.90 to about 0.24 in an aqueous
system, and the molar ratio of neutral amino acid to total metal is
from about 0.90 to about 0.75 in a non-aqueous system. The total
metal:chlorine ratio in the complex that is formed is less than
1.30.
[0017] United Kingdom Patent Application GB 2,076,289 describes an
antiperspirant compositions comprising a combination of an aluminum
chloride and an aluminum zirconium hydroxychloride in a synergistic
mixture. The metal:chloride ratio is less than 0.9.
[0018] Canadian Patent 1,153,313 describes an antiperspirant
composition which contains a buffering agent such as glycine with a
synergistic mixture of aluminum chlorohydrate, aluminum chloride or
aluminum zirconium polychlorohydrate complex. The molar ratio of
aluminum to chloride is in the range of 0.78:1 to abut 1.95:1.
Various salts are described which have a metal:halide ratio of
2.1:1-0.9:1. The glycine:zirconium ratio is much less than 1:1.
[0019] None of the above cases described the combination of metal
to chloride in combination with the glycine to zirconium ratio as
found in the instant invention. Thus, it is surprising that the
antiperspirant actives described in this invention provide more
efficacious cosmetic products.
[0020] While a great deal of work has been done on Al/Zr salts,
there is still a need to have aluminum salts to use in a variety of
products (including non-aerosol sprays for antiperspirants and/or
deodorants where zirconium cannot be used) that are capable of
being formulated into products with reduced irritation and better
fragrance stability.
BRIEF SUMMARY OF THE INVENTION
[0021] This invention comprises zirconium-free aluminum salts
which:
[0022] (a) have an aluminum to chloride molar ratio in the range of
0.5-2.5:1;
[0023] (b) comprises a nitrogen containing buffering material
(particularly glycine) in an amount such that the ratio of nitrogen
containing material to aluminum is the range of 0.05-0.26:1 and
preferably in the range of 0.05-0.16:1 and which nitrogen
containing material is selected from the group consisting of a
nitrogen containing a buffering material of formula 2
[0024] where n is a number in the range of 1-20, and each of
R.sup.1, R.sup.2, and R.sup.3 is independently selected from the
group consisting of hydrogen, methyl and ethyl (preferably methyl);
and
[0025] (c) the salt has a pH in the range of 2-4 (when measured in
water at a concentration of 15%);
[0026] wherein the salt is free of any other halide scavenging
material and has a value of at least 0.50 for the ratio calculated
as: 1 area of Peak 5 total area under Peak 2 + Peak 3 + Peak 4 +
Peak 5
[0027] The salts of the invention may be made as spray dried
powders or made as solutions of up to 50 weight % based on the
weight of the final product.
[0028] The invention also includes antiperspirant and/or deodorant
products made with these salts. Such formulations may be made as
sticks, soft solids or creams, roll-ons or non-aerosol sprays. The
formulations are free of propellants.
[0029] This invention is limited to aluminum antiperspirant salts
that do not contain zirconium.
DETAILED DESCRIPTION OF THE INVENTION
[0030] It has been found that by adding a selected amount of a
nitrogen containing buffering agent (for example, glycine, alanine,
serine, glutamine, threonine, valine, leucine, betaine) and
lowering the aluminum:chloride ratio in aluminum chlorohydroxide
salts, the amount of smaller aluminum species is increased with an
appropriate increase in efficacy. Since the pH of such salts with
lowered aluminum:chloride ratio is low, the problems of irritancy,
fragrance compatibility, color changes, etc. must be addressed. It
has been found that by adding a nitrogen containing compound as
described above, the pH may be elevated to an acceptable range
while still maintaining or increasing the relative amount of the
smallest Peak 5 aluminum species in solution. It is also critical
to note, however, that the use of too high an amount of the
nitrogen buffering material may cause new problems such as unwanted
gellation of the active (with corresponding decrease in efficacy).
Thus, it has been found that in solutions of the salts, the amount
of nitrogen buffering material must be kept below 5 weight % ( and
preferably less than 3%) to achieve a stability of 2 weeks at room
temperature for an anhydrous aluminum dichlorohydrate in a water
solution at an anhydrous level of 25% active salt without water.
Another way of describing the amount of nitrogen containing
material that may be used is by specifying a ratio range.
[0031] In particular, the molar ratio of the nitrogen containing
material (particularly glycine) to aluminum should be in the range
of 0.05-0.26:1 and preferably in the range of 0.05-0.16:1. The
lower concentrations may be used for longer stability times such as
3 weight % for 4 weeks and 2 weight % for several months. Of course
the salt may be spray dried to create a material with much longer
stability such as on the order of years. The dried salt material
may then be added to the formulation during the manufacturing
process. Thus, efficacy may be maintained in aluminum only
systems.
[0032] The salts of this invention may be made in a variety of
ways:
[0033] Method A: An aluminum dichlorohydrate (ADCH) solution of
ADCH salt in water of suitable concentration is mixed with a
suitable concentration of a powdered form of the nitrogen
containing material such as glycine. The mixture is stirred at room
temperature to obtain the product. Aluminum sesquichlorohydrate
(ASCH may be substituted for ADCH.
[0034] Method B: Method A is repeated and the product is then spray
dried to obtain the salt in powder form.
[0035] If the product is used as a solid powder, the size of the
particles of antiperspirant active of the invention currently does
not appear to be critical and may include conventional sizes such
as greater than 2 to 100 microns, with selected grades having an
average particle size of 30-40 microns; finer sized grades having
an average particle size distribution from 2-10 microns with
average size of about 7 microns as made by a dry-grinding method;
and micronized grades of the type described in a co-pending patent
application PCT case WO 01/97,768 having an average particle size
of less than or equal to 2 microns, particularly less than or equal
to 1.5 microns.
[0036] The enhanced salts of this invention may be used to
formulate antiperspirants having improved efficacy. Such
antiperspirants include solids such as sticks and creams (creams
sometimes being included in the term "soft solid"), gels, liquids
(such as are suitable for roll-on products), and aerosols. The
forms of these products may be suspensions or emulsions.
[0037] It is preferred that the glycol content of the formulations
be kept to a minimum, preferably not exceeding 1.0 weight %.
[0038] Examples of suitable formulations include the following.
[0039] Sticks--Stick products may be made with conventional gelling
agents such as stearyl alcohol and dibenzylidene sorbitol. A sample
formulation is as follows:
[0040] 40-55% (particularly 45%) cyclomethicone (particularly D4-D6
and especially D5 cyclomethicone)
[0041] 20-30% (particularly 21%) stearyl alcohol
[0042] 7-15% (particularly 10%) talc
[0043] 15-22% (particularly 22%) aluminum antiperspirant active in
powder form
[0044] 1-3% (particularly 2%) fragrance (optional)
[0045] Roll-Ons--
[0046] 45-65% (particularly 55%) cyclomethicone (particularly D4-D6
and especially D5 cyclomethicone)
[0047] 0.1-10% (particularly 3%) cyclomethicone/dimethicone
copolyol (such as Dow Corning 2-5185 C)
[0048] 10-25% (particularly 20%) antiperspirant active in solution
form (25-45% actives on an anhydrous basis in water)
[0049] 5-30% (particularly 20%) water
[0050] 1-3% (particularly 2%) fragrance (optional)
[0051] Soft solids--Soft solids may be made with formulations
described in co-pending patent application (U.S. Ser. No. 9/273152
and PCT Publication number WO 99/51192
[0052] A sample formulation is as follows:
[0053] 40-70% (particularly 50%) elastomer in cyclomethicone
(KSG-15 from Shin-Etsu)
[0054] 5-15% (particularly 6%) polyethylene (for example, beads
having a density in the range of 0.91-0.98 g/cm.sup.3 and an
average particle size in the range of 5-40 microns)
[0055] 10-20% (particularly 15%) C12-15 alkylbenzoate (FINSOLV TN
from Finetex)
[0056] 0.1-25%% (particularly 22%) antiperspirant active in powder
form
[0057] 1-15% (particularly 5%) dimethicone (100 centistokes)
[0058] 1-3% (particularly 2%) fragrance (optional)
[0059] Gels--Gels may be made with a variety of formulations such
as
[0060] 5-50% (particularly 29%) cyclomethicone (particularly D4-D6
and particularly D5)
[0061] 0.1-10% (particularly 3%) cyclomethicone/dimethicone
copolyol (such as Dow Corning 2-5185 C)
[0062] 0-10% (particularly 5%) hydrogenated polyisobutene 250
[0063] 0-10% (particularly 5%) C12-15 alkylbenzoate (FINSOLV TN
from Finetex)
[0064] 0-10% (particularly 5%) dimethicone (100 centistokes)
[0065] 0.1-25% (particularly 20%) antiperspirant active in powder
form or 10-25% (particularly 20%) of active in solution (25-45%
actives on an anhydrous basis)
[0066] 5-50% (particularly 30%) water
[0067] 1-3% (particularly 2%) fragrance (optional)
[0068] Note that in the explanation of the invention, where water
is listed it is intended to count the contribution of the water
present in the antiperspirant solution as part of the overall water
content. Thus, water is sometimes listed as part of the actives
solution or sometimes listed separately.
[0069] In a preferred embodiment the refractive indices of the
external and internal phases are matched within 0.005 to obtain a
clear product.
[0070] Particular formulations of interest include:
[0071] Formulation A:
[0072] 0.5-2.5% dimethicone copolyol (for example, Dow Corning
2-5185C (48%))
[0073] 55-65% elastomer in cyclomethicone (for example, DC-9040
from Dow Corning Corporation (Midland, Mich.) or KSG-15 from
Shin-Etsu Silicones of America (Akron, Ohio))
[0074] 1-10% PPG-3 myristyl ether
[0075] 10-25% antiperspirant active of the invention
[0076] 10-25% water
[0077] 0.5-1.5% fragrance
[0078] Formulation B
[0079] 1.0-3.0% dimethicone copolyol (for example, Dow Corning
2-5185C (48%))
[0080] 40-60% elastomer in cyclomethicone (for example, DC-9040
from Dow Corning Corporation (Midland, Mich.) or KSG-15 from
Shin-Etsu Silicones of America (Akron, Ohio))
[0081] 1-5% cyclomethicone (in addition to that found in the
elastomer)
[0082] 4-12% PPG-3 myristyl ether
[0083] 15-30% antiperspirant active of the invention
[0084] 15-35% water
[0085] 0.5-1.5% fragrance
[0086] Formulation C
[0087] 1.0-3.0% dimethicone copolyol (for example, Dow Corning
2-5185C (48%))
[0088] 1-10% hydrogenated polyisobutene (for example, Fancol.TM.
Polyiso 250)
[0089] 40-55% elastomer in cyclomethicone (for example, DC-9040
from Dow Corning Corporation (Midland, Mich.) or KSG-15 from
Shin-Etsu Silicones of America (Akron, Ohio))
[0090] 3-8% PPG-3 myristyl ether
[0091] 15-20% antiperspirant active of the invention 20-30%
water
[0092] 1.0-3.0% fragrance
[0093] Formulation D
[0094] 1.0-3.0% dimethicone copolyol (for example, Dow Corning
2-5185C (48%))
[0095] 40-60% elastomer in cyclomethicone (for example, DC-9040
from Dow Corning Corporation (Midland, Mich.) or KSG-15 from
Shin-Etsu Silicones of America (Akron, Ohio))
[0096] 3-8% PPG-3 myristyl ether
[0097] 15-30% antiperspirant active of the invention
[0098] 15-30% water
[0099] 0.5-1.5% fragrance
[0100] 1-10% diethylhexyl naphthalate
[0101] Formulation E
[0102] 0.5-2.5% dimethicone copolyol (for example, Dow Corning
2-5185C (48%))
[0103] 60-70% elastomer in cyclomethicone (for example, DC-9040
from Dow Corning Corporation (Midland, Mich.) or KSG-15 from
Shin-Etsu Silicones of America (Akron, Ohio))
[0104] 7-10% antiperspirant active of the invention
[0105] 25-35% water
[0106] 1-10% methylpropylene diol (MP Diol)
[0107] 0.5-1.5% fragrance
[0108] Formulation F
[0109] 1.0-3.0% dimethicone copolyol (for example, Dow Corning
2-5185C (48%))
[0110] 6-10% hydrogenated polyisobutene (for example, Fancol.TM.
Polyiso 250)
[0111] 35-45% elastomer in cyclomethicone (for example, DC-9040
from Dow Corning Corporation (Midland, Mich.) or KSG-15 from
Shin-Etsu Silicones of America (Akron, Ohio))
[0112] 6-10% PPG-3 myristyl ether
[0113] 40-50% antiperspirant active of the invention as 43% active
in water
[0114] no additional water
[0115] 0.5-1.0% fragrance
[0116] Formulation G
[0117] 0.1-0.6% dimethicone copolyol (for example, Dow Corning
2-5185C (48%))
[0118] 4-7% hydrogenated polyisobutene (for example, Fancol.TM.
Polyiso 250)
[0119] 40-50% elastomer in cyclomethicone (for example, DC-9040
from Dow Corning Corporation (Midland, Mich.) or KSG-15 from
Shin-Etsu Silicones of America (Akron, Ohio))
[0120] 4-7% PPG-3 myristyl ether
[0121] 40-50% antiperspirant active of the invention as 43% active
in water
[0122] no additional water
[0123] 0.5-1.0% fragrance
[0124] Formulation H
[0125] 0.5-2.0% dimethicone copolyol (for example, Dow Corning
2-5185C (48%))
[0126] 1-7% hydrogenated polyisobutene (for example, Fancol.TM.
Polyiso 250)
[0127] 40-50% elastomer in cyclomethicone (for example, DC-9040
from Dow Corning Corporation (Midland, Mich.) or KSG-15 from
Shin-Etsu Silicones of America (Akron, Ohio))
[0128] 45-55% antiperspirant active as 43% active of the invention
in water
[0129] no additional water
[0130] 0.5-1.5% fragrance
[0131] Formulation I
[0132] 2-7% dimethicone copolyol (for example, Dow Corning 2-5185C
(48%))
[0133] 0.1-1% Oleath-20
[0134] 1-5% C12-15 alkyl benzoate (FINSOLV TN)
[0135] 15-25% elastomer in cyclomethicone (for example, DC-9040
from Dow Corning Corporation (Midland, Mich.) or KSG-15 from
Shin-Etsu Silicones of America (Akron, Ohio))
[0136] 15-25% antiperspirant active
[0137] 15-30% water
[0138] 0.5-1.5% fragrance
[0139] The cosmetic composition according to the present invention
can be packaged in conventional containers, using conventional
techniques. Where a gel, cream or soft-solid cosmetic composition
is produced, the composition can be introduced into a dispensing
package (for example, conventional packages for gels with glide on
applicators, jars where the gel or cream is applied by hand, and
newer style packages having a top surface with pores) as
conventionally done in the art. Thereafter, the product can be
dispensed from the dispensing package as conventionally done in the
art, to deposit the active material, for example, on the skin. For
sticks, sprays, aerosols and roll-ons the compositions can be
placed in a conventional types of container (with the inclusion of
propellants in aerosols). This provides good deposition of the
active material on the skin.
[0140] Compositions of the present invention can be formulated as
clear, translucent or opaque products, although clear products are
preferred. A desired feature of the present invention is that a
clear, or transparent, cosmetic composition, (for example, a clear
or transparent deodorant or antiperspirant composition) can be
provided. The term clear or transparent according to the present
invention is intended to connote its usual dictionary definition;
thus, a clear liquid or gel antiperspirant composition of the
present invention allows ready viewing of objects behind it. By
contrast, a translucent composition, although allowing light to
pass through, causes the light to be scattered so that it will be
impossible to see clearly objects behind the translucent
composition. An opaque composition does not allow light to pass
therethrough. Within the context of the present invention, a gel or
stick is deemed to be transparent or clear if the maximum
transmittance of light of any wavelength in the range 400-800 nm
through a sample 1 cm thick is at least 35%, preferably at least
50%. The gel or liquid is deemed translucent if the maximum
transmittance of such light through the sample is between 2% and
less than 35%. A gel or liquid is deemed opaque if the maximum
transmittance of light is less than 2%. The transmittance can be
measured by placing a sample of the aforementioned thickness into a
light beam of a spectrophotometer whose working range includes the
visible spectrum, such as a Bausch & Lomb Spectronic 88
Spectrophotometer. As to this definition of clear, see European
Patent Application Publication No. 291,334 A2. Thus, according to
the present invention, there are differences between transparent
(clear), translucent and opaque compositions.
[0141] It is believed that the more homogeneous the composition is
and the more uniform the particle size, the better properties of
the composition.
[0142] Throughout the present specification, where compositions are
described as including or comprising specific components or
materials, or where methods are described as including or
comprising specific steps, it is contemplated by the inventors that
the compositions of the present invention also consist essentially
of, or consist of, the recited components or materials, and also
consist essentially of, or consist of, the recited steps.
Accordingly, throughout the present disclosure any described
composition of the present invention can consist essentially of, or
consist of, the recited components or materials, and any described
method of the present invention can consist essentially of, or
consist of, the recited steps.
EXAMPLES
[0143] The following Examples are offered as illustrative of the
invention and are not to be construed as limitations thereon. In
the Examples and elsewhere in the description of the invention,
chemical symbols and terminology have their usual and customary
meanings. In the Examples as elsewhere in this application values
for n, m, etc. in formulas, molecular weights and degree of
ethoxylation or propoxylation are averages. Temperatures are in
degrees C. unless otherwise indicated. If alcohol is used, it is
95% unless otherwise indicated. Unless otherwise indicated, "water"
or "D.I. water" means deionized water. As is true throughout the
application, the amounts of the components are in weight percents
based on the standard described; if no other standard is described
then the total weight of the composition is to be inferred. Various
names of chemical components include those listed in the CTFA
International Cosmetic Ingredient Dictionary (Cosmetics, Toiletry
and Fragrance Association, Inc., 7.sup.th ed. 1997). While specific
amounts of particular elastomers have been described, there are
chemical differences in the variety of elastomers that are
available. The use of different elastomers may result in the need
to increase or decrease the amount of elastomer used in a
particular formulation, especially if a clear product is
desired.
[0144] In the Examples, as elsewhere in the description of the
invention, reference is made to using the antiperspirant active
either as a powder or in some type of solution such as dissolved in
water at a concentration or 25-45% actives on an anhydrous
basis.
Examples 1-4
Antiperspirant Salts
[0145] Improved aluminum di-chlorohydrate salts (10.0% anhydrous)
can be made with glycine as follows using the amounts of
ingredients listed in Table A. Glycine powder (at the level listed
in Table A) and distilled water are added into an aluminum
dichlorohydrate solution (Westchlor 100, 38% anhydrous excluding
waters of hydration) and stirred for 5 minutes to make six Examples
as shown in Table A. The concentration for all the Examples 1-6 is
10% by weight. Table A also contains the pH values as measured with
a Corning pH meter 430. Finally, a profile was run on each of the
solutions listed in Table A and the areas under each peak were
calculated. The method used is the same one described in U.S. Pat.
No. 6,066,314. The Size exclusion chromatography ("SEC") column
separates the species by molecular size, using a refractive index
(RI) detector connected to the column outlet. The % of each peak of
the whole was also calculated and the values are listed in Table A.
All concentrations are in % by weight based on the entire weight of
the solution. The increase in Peak 5 species is supportive of
improved efficacy. (Also see U.S. Pat. No. 6,375,937.)
[0146] Size exclusion chromatography method is frequently used for
obtaining information on polymer distribution in antiperspirant
salt solutions. With appropriate chromatographic columns, at least
5 distinctive groups of polymer species can be detected in an
aluminum salt, appearing in a chromatogram as peaks 1, 2, 3, 4, and
a peak referred to here as "5". Peaks 2 and 3 are larger aluminum
species. Peak 4 is smaller aluminum species (aluminum oligomers)
and has been correlated with enhanced efficacy for ACH salts. Peak
5 is the smallest aluminum species. The relative retention time
("Kd") for each of these peaks varies depending on the experimental
conditions. Data for Table A was obtained using the SEC method
described in an issued patent owned by the same company as this
case, U.S. Pat. No. 6,066,314, incorporated by reference as to the
test method described therein.
1TABLE A Concentration of % Example glycine (anhydrous) pH Peak 3 %
Peak 4 % Peak 5 1 0 2.67 24.58 25.61 49.81 2 1 2.79 19.93 17.15
62.92 3 2 2.84 18.85 13.85 67.30 4 3 2.94 18.75 13.92 67.34 5 4
3.10 17.87 14.31 67.81 6 5 3.50 18.01 14.63 67.36
Examples 7-12
Analytical Data
[0147] Using the concentration listed in Table B, betaine powder
and distilled water are added into an aluminum di chlorohydrate
solution (Westchlor 100, 48% anhydrous) and stirred for five
minutes to make Examples 7-12 with a concentration of 10 weight %
ADCH. The same analytical method described for Examples 1-6 was
used to obtain the data listed in Table B.
2TABLE B Concentration of % Example betaine (anhydrous) pH Peak 3 %
Peak 4 % Peak 5 7 0 2.67 24.58 25.61 49.81 8 1 2.72 24.10 23.63
52.27 9 2 2.80 22.76 22.7 54.54 10 3 2.82 20.83 21.37 57.80 11 4
2.90 20.83 21.37 57.80 12 5 3.03 18.20 18.33 63.47
Examples 13-18
Efficacy Screening
[0148] A clinical evaluation with forearm screening using the
procedure described below was done with liquid gel formulae
containing antiperspirant salt solution made with aluminum
dichlorohydrate, water and glycine so that the concentration of the
antiperspirant on an anhydrous basis is 25 weight % and the
concentration of glycine is the amount listed in Table C. It will
be noted that the % sweat reduction of the salt in stored solution
(8 days at about 40 degrees C. (105 degrees F.) decreases after the
amount of glycine exceeds 3%. The sweat reduction for the Examples
with 1% and 2% glycine is similar to the one without glycine. This
means that the use of glycine does not negatively impact efficacy.
The drop in efficacy at the addition levels of 3% and 5% glycine is
due to the gellation of the aluminum salt in the internal phase.
Thus, if a solution of the salt is to be used, the concentration
should be kept less than 3%. Table C shows that the use of a 1% or
2% salt material of the invention as a solution to achieve the low
irritancy and fragrance favorable properties in a clear,
non-yellowing solution can be done without sacrificing efficacy.
Note that spray drying the salt product can keep this gellation
from happening and allow the use of higher concentrations of
glycine.
3TABLE C Concentration Forearm rating Example of glycine (% sweat
reduction) 13 0% 60% 14 1% 70% 15 2% 60% 16 3% 25% 17 4% NA 18 5%
15%
Examples 19-36
Powder Forms
[0149] Each of the Examples 1-18 can be formed into a powder using
conventional spray drying or freeze drying techniques known to
those skilled in the art. Examples of such methods may be found in
U.S. Pat. No. 5,589,196. Note that in spray drying the material,
the maximum amount of water left in the spray dried product should
not exceed 25 weight %.
Example 37
General Method for Making Antiperspirant Products
[0150] In general, the external and internal phases are formed
separately either at room temperature or with heating as described
below. The internal phase is added to the external phase very
slowly while stirring at to form an emulsion. After the addition
has been completed, the mixture is stirred at higher speed to
achieve a homogeneous mixture. The final formula viscosity is then
achieved by homogenizing the emulsion under either batch or
continuous process conditions as described below. The fragrance may
be added at any time during the process prior to final
homogenization.
[0151] Preparation of the External Phase:
[0152] The ingredients to be used in the external phase (including
the elastomer) are weighed out at room temperature and combined in
a suitable vessel such as a 2 liter glass beaker. The mixture is
stirred at about 500 rpm for 15-20 minutes using an overhead mixer
such as a Lightnin Mixer Model L1003. If a waxy or solid emollient
is to be added to the external (also called "continuous") phase,
the mixture may be heated to facilitate dissolution while stirring
then cooled to room temperature prior to combination with the
internal phase as described below. The elastomer component is
obtained as a suspension of elastomer in cyclomethicone (for
example at a concentration of 6% active in D5 cyclomethicone). The
elastomer component is added to the external phase with stirring at
high speed (500-700 rpm for a 0.5 kilogram batch) until no
particles of elastomer are visible to the eye.
[0153] Preparation of the Internal Phase:
[0154] The internal dispersed phase is prepared as described below.
Ingredients are mixed for a time sufficient to achieve homogeneity.
The antiperspirant active used is weighed into a large beaker
equipped with an overhead stirrer. Other internal phase ingredients
are then added while stirring.
[0155] The fragrance (if any is used) is added last and may be
added either to the internal phase or the external phase or the
final formula prior to homogenization. For many of the examples
described here, one could add the fragrance to the internal
phase.
[0156] If an optional non-ionic emulsifier such as Oleath-20 is
used, the emulsifier and propylene glycol are combined in a
separate beaker and heated to 40 degrees C. with stirring until the
non-ionic emulsifier completely dissolved. The heat is turned off
and the remaining ingredients to be used in the internal phase,
including the antiperspirant active are weighed out and added to
the mixture of propylene glycol and non-ionic emulsifier.
[0157] If water or a salt solution are used, the internal phase is
prepared as follows. The solution containing antiperspirant active
salt as received from supplier is weighed into a large beaker
equipped with a magnetic stirrer. Additional ingredients such as
propylene glycol, ethanol and water are added while stirring. If a
salt water solution is used (such as for NaCl, etc.), the salt
water solution is prepared by dissolving the crystalline salt in
water in a separate beaker and stirring until dissolved. The salt
water solution is then added to the rest of the internal phase and
the mixture is stirred until homogeneous.
[0158] Preparation of the Emulsion:
[0159] The internal phase made as described above is then added to
the external phase over the course of 15-30 minutes while stirring
at a speed of 500-700 rpm. After the addition is complete, the
mixture is stirred at 500-700 rpm for 20 minutes using a Lightnin
Mixer Model L1003. The mixture is then homogenized for 2-4 minutes
(especially 3 minutes) using a homogenizer from Greerco Corp.,
Hudson, N.H. at a reading of about 60 on a Powerstat Variable
Autotransformer from Superior Electric Co., Bristol, Conn.
[0160] Further Processing:
[0161] The product is then further processed by homogenization to
achieve the desired final viscosity. This can be done by using a
Gilford-Wood Model 1-L (Greerco Corp., Hudson, N.H.) homogenizer.
The homogenizer speed is controlled by a Powerstat Variable
Autotransformer Type 3PN116B (Superior Electronic. Co., Bristol,
Conn.). Typical voltage setting and processing time are chosen to
give a desired final formula viscosity.
[0162] An other method of homogenization of the final product is to
pass the emulsion through a colloid mill such as a Sonic Tri-Homo
Colloid Mill or a process sonolator such Sonic Production Sonolator
200-30 both available from Sonic Corporation of Stratford, Conn.
Process conditions are chosen to give the desired final product
viscosity.
Examples 38-58
Compositions
[0163] The method described in Example 37 may be used to make the
compositions listed in Tables D and E with the types and amounts of
ingredients listed in the Tables. Amounts are in percent by weight
based on the total weight of the composition. For the
antiperspirant active, any of the solutions of actives described in
Examples 1-18 may be used.
4TABLE D Ingredient Ex. 38 Ex. 39 Ex. 40 Ex. 41 Ex. 42 Ex. 43 Ex.
44 Ex. 45 Ex. 46 Ex. 47 External Phase Elastomer (KSG-15, 6%
active) 62 50 48 40 41.5 42.0 46.5 35 32.17 25 Dimethicone copolyol
2 2 1.5 4 1.5 0.5 1.0 1.0 2.48 1.0 (Dow Corning 2-5185, 48% active
in cyclomethicone) Hydrogenated 0 0 5 8 5 5 5 5 4.95 0
polyisobutene (Polyiso 250) PPG-3 Myristyl Ether 5 5 4.5 0 4.5 5.0
0 0 0 5 C12-l5 alkyl benzoate 0 0 0 2.0 0 0 0 0 0 0 (FINSOLV TN)
Cyclomethicone (Dow Corning 245) 0 2 0 0 0 0 0 0 0 0 Fragrance 1 1
1 1 1 1 1 1 1 0 Internal Phase 0 Antiperspirant Active.sup.a 15 20
17.5 19.5 46.5 46.5 46.5 58 59.40 48.45 Water (deionized).sup.b 15
20 22.5 25 0 0 0 0 0 0 Oleath-20 (HLB > 8) 0 0 0 0.5 0 0 0 0 0
19.55 Total 100 100 100 100 100 100 100 100 100 100 .sup.a= Any of
the actives described in Examples 1-18 may be used. .sup.b= Note
that in the examples, sometimes the antiperspirant active is listed
as a solution (which will include a water component) under the
"active"designation with little or no water and sometimes the
active and water are listed separately.
[0164]
5TABLE E Ingredient Ex. 48 Ex. 49 Ex. 50 Ex. 51 Ex. 52 Ex. 53 Ex.
54 Ex. 55 Ex. 56 Ex. 57 Ex. 58 External Phase Elastomer (DC 9040)
12% 55 62 62 40 41.5 25 31.5 21 17 17 50 active) Dimethicone
copolyol 1 2 2 4 1 1 2.5 1 1 1 2 (Dow Corning 2-5185, 48% active in
cyclomethicone) Hydrogenated 5 -- -- 8 5 -- 5 1.5 1.5 1.5 --
polyisobutene (Polyiso 250) PPG-3 Myristyl Ether 3 4.5 5 -- 5 5 --
0.5 0.5 0.5 5.0 C12-15 alkyl benzoate -- -- -- 2 -- -- -- -- -- --
-- (FINSOLV TN) Cyclomethicone -- -- -- -- -- -- -- 5 9.0 9.0 2.0
(Dow Corning 245) Fragrance 1 1 1 1 1 1 1 1 1 1 1 Internal Phase
Antiperspirant Active.sup.a 15 15.5 30 19.5 46.5 48.45 60.0 60.5
63.68 60.13 20 Water (deionized).sup.b 20 15 25 19.55 9.5 6.32 9.87
20 Oleath-20 (HLB > 8) -- -- -- 0.5 -- -- -- -- -- -- -- Total
100 100 100 100 100 100 100 100 100 100 100 .sup.a= See explanation
of actives used. Actives according to Examples 1-18 may be used.
.sup.b= Note that in the examples, sometimes the antiperspirant
active is listed as a solution (which will include a water
component) under the "active"designation with little or no water
and sometimes the active and water are listed separately.
Example 59
ForearmTest
[0165] A forearm starch/iodine test may be used as a rapid
screening tool for underarm formulations prior to underarm clinical
testing. The following procedure may be used for all tests
discussed in this patent document. Panelists should be chosen who
had not placed any antiperspirant products on their interior
forearms for at least 14 days prior to the start of the test. Test
formulations are applied on the inner forearms in preselected
amounts. A control product such as a commercial product (Lady Speed
Stick AP) is applied to one site on the panelists' arms as a
positive control. After application of the formulations, the sites
are occluded with covering chambers for one hour under conditions
of about 40 degrees C. and 30% relative humidity. Panelists then
remove the covering chambers. One hour after removal of the
covering chambers, the forearms are each washed with a mild soap.
This is repeated for the first two days of the study. On the third
day of product application, the sites are occluded for one (1)
hour, but are not washed with soap. The panelists perform their
normal cleansing regimen using a mild soap during the course of the
study. Approximately 20 hours after the last application of the
products, the panelists are equilibrated in a room at 40 degrees C.
(105.degree. F.) and 40% relative humidity for 15 minutes. The
panelists arms are then patted dry with a paper towel followed by
application of paper strips impregnated with iodine to the test
sites. Exposure to sweat causes the paper to turn purple at sites
of hydration, generating a spatial map of the firing sweat glands.
The papers are removed once the purple spots begin to appear on the
backside or after five minutes, whichever comes first. Images of
the papers may be digitized to quantify the amount of purple spot
coverage. Once images are digitized, the area for measurement is
identified using the same area as occluded by the chambers. A
comparison of the total area of hydration for treated skin versus
untreated sites is used to calculate a % Sweat Reduction (Eq:1).
The area of sweat from untreated sites used in Equation 1 is
calculated as the mean sweat areas of all the untreated sites
directly adjacent to the treated site of interest. Since the number
of firing sweat glands varies along the surface of the volar
forearm, the mean sweat area of the adjacent untreated sites is
used to approximate the area of sweat which would have been
produced if a formula had not been applied to the treatment
site.
% Sweat Reduction=100[1-(Area-Treated/Mean(Area-Untreated))]
Eq:1
Example 60
Soft Solid with Powdered Salt
[0166] An antiperspirant product can be made using the following
ingredients:
[0167] Part 1
[0168] 51% Cyclomethicone (D5); 3% PPG-3 myristyl ether; 6% C12-15
alkyl benzoate (FINSOLV TN from Finetex Inc., Elmwood Park, N.J.);
1% fragrance; 10% vinyl polydimethyl siloxane elastomer 10% in D5
cyclomethicone (USG-103 from Shin-Etsu Silicones of America, Inc.,
Akron, Ohio);
[0169] Part 2
[0170] 5% fumed silica (Cab-O-Sil from Cabot Corp.); 24% of an
active made as for Example 32
[0171] All ingredients in Part 1 are added into a beaker, and
stirred at about 400 rpm using an overhead mixer such as a
Lightnin' Mixer Model L1003 until it becomes visually homogeneous.
The mixture is then transferred into the container of a Hobart
Mixer (Model N-50), where the ingredients in Part 2 have been
placed. The Hobart Mixer is then turned on and running at "low"
speed for 30 minutes or until a uniform creamy product is
formed.
Example 61
Stick with Powdered Salt
[0172] An antiperspirant product can be made using the following
ingredients:
[0173] Part 1
[0174] 10% Cyclomethicone (DC 345 from Dow Corning); 20% stearyl
alcohol; 12% C12-15 alkyl benzoate (FINSOLV TN); 4% hydrogenated
castor oil (MP80); 4% PEG-8 distearate
[0175] Part 2
[0176] 20.80% Cyclomethicone (DC 345); 3% dimethicone copolyol (DC
5225C from Dow Corning, 10%); 25% of an active as described in
Example 33
[0177] Part 3
[0178] 1% fragrance
[0179] Formation of Part 1
[0180] Mix cyclomethicone and FINSOLV TN at 300 rpm using an
overhead mixer such as a Lightnin' Mixer Model L1003. Heat the
mixture to 70.degree. C. and add stearyl alcohol with continuous
stirring. After stearyl alcohol is melted, the temperature is
increased to 75.degree. C. Melt PEG-8 distearate by adding it to
the mixture. Increase temperature further to 80.degree. C. Add
hydrogenated castor oil. Stir it in the solution until it is
dissolved.
[0181] Formation of Part 2
[0182] Put all ingredients in Part 2 in a separate beaker. Heat it
to 70.degree. C. with stirring.
[0183] Formation of Stick
[0184] Add Part 2 to Part 1 at 70-75.degree. C., and mix at 450 rpm
for 15 min. Turn the heater off and let it cool to 65.degree. C.,
and add fragrance. Pour the sample out into barrels at 58.degree.
C. Form sticks by placing the barrels into refrigerator for 15
minutes.
Example 62
Roll-On with ADCH Solution
[0185] An antiperspirant product can be made using the following
ingredients:
[0186] Part 1
[0187] 3% dimethicone copolyol (DC 5225C); 13.5% dimethicone (2 cst
viscosity, DC 200 from Dow Corning); 2.5% PPG-3 myristyl ether;
0.80% fragrance
[0188] Part 2
[0189] 72% of the composition described in Example 14; 8.2%
propylene glycol
[0190] Mix the ingredients in Part 1 to form a clear solution with
an overhead mixture. Mix the ingredients in Part 2 in a separate
beaker to form an aqueous solution. Add Part 2 to Part 1 slowly
with continuous mixing at 600 rpm using a Lightnin' Mixer (Model
L1003). Keep stirring for another 20 minutes after addition of Part
2 is finished or until a visually uniform emulsion is formed.
Homogenize the emulsion for 2-4 minutes using a homogenizer
(Greerco Corp., Hudson, N.H.) at a reading of about 30 on a
Powerstat Variable Autotransformer (Superior Electric Co., Bristol,
Conn.).
Example 63
Non-Aerosol Spray with ADCH Solution
[0191] An antiperspirant product can be made using the following
ingredients:
[0192] Part 1:
[0193] 36% Phase inversion temperature concentrate ("PIT
Concentrate" such as Emulgade.RTM. CM from (from Cognis Co.,
Ambler, Pa.)
[0194] Part 2:
[0195] 1% fragrance; 1% nonionic surfactant (Emulgen L from Cognis
Co., Ambler, Pa.)
[0196] Part 3:
[0197] 62% of a composition as described in Example 15
[0198] Mix the fragrance and surfactant in a separate beaker to
form a clear solution. Add Part 3 and the above solution into Part
1 one after the other at room temperature with continuous stirring
until a uniform translucent liquid is formed.
Example 64
Two-Phase Roll-On with ADCH Solution
[0199] An antiperspirant product can be made using the following
ingredients:
[0200] Part 1:
[0201] 16.30% Cyclomethicone (DC 245 from Dow Corning); 2.80% PPG-3
myristyl ether; 0.80% fragrance
[0202] Part 2:
[0203] 69.99% of a composition from Example 14; 9.70% propylene
glycol; 0.40% Polyquaternium-10 (Polymer JR, from Amerchol, Edison,
N.J.); 0.010% Oleath-10 (Volpo 10 from Croda, Inc., New Jersey)
[0204] All of the ingredients for Part 1 are combined in a beaker
and the mixture is stirred at 300-400 rpm using a Lightnin' Mixer
Model L 1003 until a homogeneous solution is obtained.
[0205] Add all the ingredients in Part 2 in a separate beaker
together and heat it to 40-50.degree. C. with agitation until a
clear solution is obtained.
[0206] Add Part 2 to Part 1.
Example 65
Two-Phase Spray with Salt Solution
[0207] An antiperspirant product can be made using the following
ingredients:
[0208] Part 1:
[0209] 24.00% Cyclomethicone (D5); 5.00% PPG-3 myristyl ether;
1.00% fragrance
[0210] Part 2:
[0211] 65.00% of a composition of Example 15; 5.00% ethanol
(Alcohol SD-200 proof (100%))
[0212] Mix the ingredients in Part 1 to form a clear solution by
using an overhead mixer. Mix the ingredients in Part 2 to form an
aqueous solution. Add Part 2 to Part 1.
* * * * *