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BACKGROUND OF THE INVENTION
The present invention relates to basic zirconium complexes and methods of
making and using the same in antiperspirants. More particularly, the
invention is directed to the production and use of basic zirconium
carbonates and basic zirconium-amino acid compounds in highly acidic
aluminum and/or zirconium antiperspirant systems.
It has been known in the art for some time that zirconium salts provide
exceptionally effective antiperspirant properties. Such zirconium
compounds have included particularly the acidic zirconium salts, such as
zirconium oxy chloride or zirconyl chloride, zirconium hydroxy chloride,
and other halide and sulfate substitutes of the salts. However, the
zirconium salts are extremely acidic and irritating to the skin. For
example, a solution of zirconyl chloride which is effective as an
antiperspirant has a pH of only about 0.8 and a solution of zirconyl
hydroxy chloride which is effective as an antiperspirant has a pH of only
about 1.2. As a result, it is necessary to buffer these solutions up to a
pH which is suitable for application to the human skin, i.e., up to at
least about 3 to 5.
A number of prior attempts have been made in the art to buffer solutions of
zirconium salts or to form zirconium complexes which take advantage of the
effectiveness of zirconium compounds. One early attempt included the
development of sodium zirconium lactate for use in cologne-stick type
formulations. This lactate complex salt was sufficiently alkaline (pH
8.5), but was ineffective as an antiperspirant, and was repeatedly
implicated in the generation of "zirconium granulomas" in some users.
Other attempts to make use of the acidic zirconium salts involved the
buffering of solutions of these salts with urea (see U.S. Pat. No.
2,814,584 to Daley) or water soluble amino acids (see U.S. Pat. Nos.
2,814,585 to Daley and 2,854,382 to Grad) or aluminum hydroxy halides (see
U.S. Pat. No. 2,906,668 to Beekman).
More recently, various derivatives have been formed incorporating zirconium
compounds, including the amine-amide derivatives of U.S. Pat. No.
3,407,254 to Siegal et al., and the polyhydroxy derivatives of U.S. Pat.
No. 3,405,153 to Jones and Rubino.
In addition, Rubino copending application Ser. No. 418,712, now U.S. Pat.
No. 4,017,599, entitled "Aluminum-Zirconium Anti-Perspirant Systems With
Salts Of Amino Acids", and other related copending applications describe
other systems in which amino acids have been incorporated in
aluminum-zirconium complexes to offset the acidity of the zirconium and
aluminum as well as provide other advantages to the antiperspirant.
Nevertheless, still more efficient and advantageous methods are being
sought to combat the acidity of aluminum and/or zirconium while at the
same time maintaining or improving antiperspirant efficacy.
BRIEF SUMMARY OF THE INVENTION
According to the present invention, astringent complexes useful as
antiperspirant ingredients are formed by reacting acidic aluminum and/or
zirconium compounds with a freshly prepared basic zirconium compound
selected from basic zirconium-amino acid gels, zirconium hydroxide gels,
basic zirconium carbonate gels and mixtures thereof, to form a complex
having an Al/Zr mol ratio of about 10:1 to 1:10, and preferably about 3:1
to 1:6. When dissolved in an aqueous solution to the extent of about 5 to
20 weight percent (solids basis), the complexes will produce a solution pH
of at least about 3, and preferably in the range of about 3 to 5. The
complexes may be dried to a powder form and used in any of a wide variety
of conventional antiperspirant forms, including lotions, creams, roll-ons,
aerosol sprays, and powder-in-oil aerosol sprays.
The basic zirconium carbonates are preferably reacted with acidic aluminum
halides, such as aluminum chloride (AlCl.sub.3), or lower basic aluminum
halides to form complexes having an Al/Zr mole ratio of about 4:1 to 1:4
and preferably about 2:1 to 1:2. Such complexes should also have a
corresponding solution pH of about 3 to 5, and may be used in various
antiperspirant forms.
The present invention further includes an improved method for preparing
basic zirconium-amino acid gels especially for use in forming the
complexes of the present invention. According to the improved method, the
basic zirconium-amino acid gel is prepared by reacting in aqueous medium a
water soluble salt of an amino acid and a water soluble zirconium salt to
precipitate the basic zirconium gel. Preferably, the water soluble amino
acid salt is prepared by reacting the amino acid with an alkali metal or
ammonium carbonate or bicarbonate. The basic zirconium-amino acid gel is
preferably used in its wet form when preparing the antiperspirant
complexes of the present invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The astringent or acid aluminum compounds useful in forming the
antiperspirant complexes of the present invention include aluminum
halides, preferably aluminum chloride (AlCl.sub.3), and basic aluminum
compounds and complexes which are known in the antiperspirant art for
their cationicity and antiperspirant effectiveness and other properties.
Aluminum chloride has been known for many years as one of the most
effective antiperspirant compositions available. However, the use of
aluminum chloride alone has been necessarily limited, due to the extreme
acidity of even weak aluminum chloride solutions.
However, when complexed with the basic zirconium compounds according to the
present invention, aluminum chloride is buffered to yield effective
antiperspirant solutions having an acceptable pH of at least about 3. That
is, when aluminum chloride is reacted with either basic zirconium-amino
acid compounds or basic zirconium carbonates, complexes are formed which
have a suitable buffered acidity as well as containing zirconium as an
additional antiperspirant ingredient.
The basic aluminum compounds which may be used in forming the complexes of
the present invention include many of the conventional basic aluminum
salts which have been known to the antiperspirant art for some time, and
which have a degree of antiperspirant efficacy in their own right, as a
result of the presence of the active aluminum ion. These basic aluminum
salts may be represented by the following general empirical formula:
Al.sub.2 (OH).sub.6-nx A.sub.x
wherein x may vary from greater than 0 to less than 6, 6-nx is greater than
or equal to 0, n is the valence of A, and A is selected from the group
consisting of halide, nitrate, sulfamate, sulfate and mixtures thereof.
It will of course be understood that the above formula is greatly
simplified and is intended to represent and include basic aluminum
compounds containing coordinated and/or bound molecules of water as well
as polymers, complexes and mixtures of the above basic formula.
Particularly preferred basic aluminum compounds of the above formula are
the 1/3 to 2/3 basic aluminum chlorides (also referred to as lower basic
aluminum chlorides), in which A is chloride and x is between about 2 and 4
and need not be an integer. Thus, such basic aluminum chlorides may be
represented by the formulas
Al.sub.2 (OH).sub.2 Cl.sub.4 and Al.sub.2 (OH).sub.4 Cl.sub.2
The basic aluminum chlorides are also referred to as aluminum
chlorhydroxide or aluminum chlorhydrate or aluminum hydroxy chloride, and
are readily available in the art.
In addition to the simple basic aluminum salts indicated above, complexes
or derivatives of the basic aluminum salts may also be used advantageously
in the complexes of the present invention. Examples of such derivatives or
complexes include the phenolsulfonate derivatives described in U.S. Pat.
No. 3,634,480 to Sheffield. Such complexes are formed by reacting 5/6
basic aluminum chloride with phenolsulfonic acid, zinc phenolsulfonate or
aluminum phenolsulfonate. Other suitable derivatives and complexes of
basic aluminum salts which may be used in the complexes of the present
invention will be readily apparent to those of ordinary skill in the art
in view of the present specification.
Of course, it should be understood that not all possible combinations of
aluminum chloride and basic aluminum compounds will work in accordance
with the present invention. For example, the common 5/6 basic aluminum
chloride commercially available as Chlorhydrol has been found not to react
with basic zirconium glycinate. Similarly, 2/3 basic aluminum sulfamate
does not react with basic zirconium glycinate. Also, if the basic
zirconium glycinate or basic zirconium carbonate (described below) is
dried down, it will lose its reactivity towards aluminum chloride.
However, these examples are more the exception than the rule, and one of
ordinary skill in the art can readily determine by routine experimentation
whether or not a particular species will be effective within the limits of
the present invention.
The acidic or cationic zirconium compounds which may be used in the
complexes of the present invention include both the zirconium oxy salts
and zirconium hydroxy salts, also referred to as the zirconyl salts and
zirconyl hydroxy salts. These compounds may be represented by the
following general empirical formula:
ZrO(OH).sub.2-nz B.sub.z
wherein z may vary from about 0.9 to 2 and need not be an integer, n is the
valence of B, 2-nz is greater than or equal to 0, and B may be the same as
A in the aluminum compounds, that is B may be selected from the group
consisting of halide, nitrate, sulfamate, sulfate and mixtures thereof. It
will be understood that other Group IV B metals, including hafnium could
also be used.
As with the basic aluminum compounds, it will be understood that the above
formula is greatly simplified and is intended to represent and include
compounds having coordinated and/or bound water in various quantities, as
well as polymers, mixtures and complexes of the above. For example, the
oxy group in the above general formula could instead be indicated with a
water molecule bound to the compound and written as two OH groups. Thus,
zirconyl hydroxy chloride could be written as Zr(OH).sub.3 Cl instead of
ZrO(OH)Cl. Similarly, zirconyl chloride may be written as either
ZrOCl.sub.2 or Zr(OH).sub.2 Cl.sub.2. As will be seen from the above
general formula, in which the oxy group is represented as O rather than
(OH).sub.2, the zirconium hydroxy salts actually represent a range of
compounds having various amounts of the hydroxyl group, varying from about
1.1 to only slightly greater than 0 groups per molecule.
Particularly preferred zirconium compounds for use in the complexes of the
present invention include zirconyl chloride (also referred to as basic
zirconium chloride or zirconium oxy chloride) and zirconyl hydroxy
chloride, which may be represented by the simple formulas ZrOCl.sub.2 and
ZrO(OH)Cl, respectively. These compounds are commercially available in
solution form. In the alternative, the zirconium compounds can be made by
dissolution of commercially available zirconium carbonate paste
(carbonated hydrous zirconia) in the appropriate amount of the acid of the
anion to be used, e.g. hydrochloric acid. Other useful zirconium salts
will be apparent to those of ordinary skill in the art, such as
trioxodizirconium hydroxy halides and similar salts described in U.S. Pat.
No. 2,837,400 to Blumenthal, for example.
The zirconium compounds may be incorporated in the complexes of the present
invention either alone with the basic zirconium gels or together with the
aluminum compounds and/or other metal compounds (such as zinc and
magnesium salts) having various antiperspirant effects. However, where the
zirconium compounds are incorporated without any aluminum compounds in
order to form antiperspirant systems in which zirconium is the only
significant active metal, it will usually not be possible to dry the
resulting solutions of the complexes to a solid for subsequent
reconstitution in water. Of course, the reaction solutions may be used as
is. Moreover, such all zirconium systems usually require a stabilizing
agent and buffer (see examples below) so that a stable solution of the
complex may be prepared having a pH above about 3.
Suitable magnesium compounds for incorporation into the complexes of the
present invention include magnesium halides, magnesium sulfate, and
magnesium-amino acid salts (such as magnesium glycinate), and mixtures
thereof. Suitable zinc compounds for incorporation into the complexes of
the present invention include zinc halides, zinc sulfate, zinc nitrate,
zinc sulfamate, zinc phenolsulfonate and mixtures thereof. Other magnesium
and zinc compounds having known antiperspirant advantages will be evident
to those of ordinary skill in the art.
The basic zirconium-amino acid compounds or gels useful in preparing the
complexes of the present invention may be represented by the following
general empirical formula:
Zr(OH).sub.x A.sub.4-x
wherein A is an amino acid and x is greater than 0 but less than 4 and need
not be an integer. The basic zirconium gels may be characterized by their
degree of basicity, depending upon how many hydroxyl groups they contain
out of a total theoretical possibility of 4. Thus, for example, 1/4 basic
zirconium glycinate refers to the following formula:
Zr(OH)(glycinate).sub.3 or Zr(OH)(NH.sub.2 CH.sub.2 COO).sub.3
and 1/2 basic zirconium glycinate refers to the following formula:
Zr(OH).sub.2 (glycinate).sub.2 or Zr(OH).sub.2 (NH.sub.2 CH.sub.2
COO).sub.3
actually, the above formulas have been greatly simplified for the purposes
of clarity. For example, while the gels have been shown as monomers, they
are most probably polymeric in form, and may include molecules of water in
various coordinated and/or bound forms.
Moreover, due to the unknown nature of the bonds with water molecules, the
basic zirconium gels may be shown in either their oxy or hydroxy forms;
that is, the oxygens attached to zirconium may be shown as either oxygen
alone or hydroxyl equivalents. For example, 3/4 basic zirconium glycinate
may be represented by either of the following two formulas:
ZrO(OH)(NH.sub.2 CH.sub.2 COO)
or
Zr(OH).sub.3 (NH.sub.2 CH.sub.2 COO)
among the amino acids which may be used to form the basic zirconium gels
are the so-called neutral amino acids, i.e., amino acids in which the
number of amino groups is equal to the number of carboxyl groups in the
molecule. Examples of such amino acids include glycine, DL-valine,
.beta.-alanine, arginine and L-(-)-proline and mixtures thereof. The
corresponding basic zirconium gels are the glycinates, DL-valinates,
.beta.-alaninates, argininates and L-(-)-prolinates. Other amino acids
useful in the present invention will be evident to those of ordinary skill
in the art in view of this specification. It is important to note that
insoluble derivatives as well as soluble amino acids may be used, in
contradistinction to the teachings of U.S. Pat. Nos. 2,814,585 and
2,854,382 to Daley and Grad, respectively, which indicate that only amino
acids which are sufficiently soluble in aqueous solution can be used to
buffer zirconium antiperspirant solutions.
The basic zirconium-amino acid gels are themselves insoluble in water.
However, with moderate heating or stirring, the insoluble basic zirconium
gels react with the aluminum antiperspirant compounds to form water
soluble antiperspirant complexes. The dissolution of the basic zirconium
gels in the aqueous medium is an indication that a reaction has taken
place with the aluminum compound to form a water soluble complex.
It is also important that the gels used in forming the complexes of the
present invention be freshly prepared. Thus, it has been found that upon
aging for as little as a week or two, the gels begin to lose their
capacity to react with acidic aluminum compounds to form antiperspirant
complexes. This is manifested by a failure to obtain a clear solution
after the reaction process. It is difficult to set a definite time limit
for using the gels. However, as used herein "freshly prepared" will be
understood to refer to a gel which has been prepared sufficiently recently
that a substantially clear solution is obtained when the gel is reacted
with an acidic aluminum compound in the appropriate amount.
In general, the relative amounts of the aluminum compound and basic
zirconium compound to be reacted together should be such as to yield an
Al/Zr mole ratio of between about 10:1 to 1:10, and preferably 3:1 to 1:6.
Although relatively high ratios of zirconium are desirable from the
standpoint of antiperspirant efficacy, such ratios are sometimes
contraindicated due to the greater cost of zirconium. In addition, large
amounts of zirconium usually increase the possibilities of skin
irritation, but these are greatly mitigated by the buffering action of the
hydroxyl and amino acid groups which accompany the zirconium.
In addition to basic zirconium-amino acid gels, basic zirconium carbonate
(BZC) gels may also be used to form suitable antiperspirant complexes, by
reacting with acidic aluminum halides and lower basic aluminum halides,
such as 1/3 or 2/3 basic aluminum chlorides.
The basic zirconium carbonates may be represented by the following general
empirical formula:
Zr(OH).sub.4-2x (CO.sub.3).sub.x
wherein x is greater than 0 but less than 2 and need not be an integer. As
with the basic zirconium-amino acid gels, this formula is greatly
simplified, and various polymeric and water containing forms are more
probable. Also, two OH groups may be represented instead as an equivalent
oxide or oxy group. Thus, an example of the above may be represented as
Zr(O)CO.sub.3 instead of Zr(OH).sub.2 CO.sub.3. Moreover, it should be
understood that these gels may also include bicarbonate groups (HCO.sub.3)
in addition to or in place of the carbonate groups.
The basic zirconium carbonate gels can be prepared by standard
precipitation techniques using sodium carbonate and most any of the usual
zirconium oxy or zirconium hydroxy salts previously referred to, such as
zirconyl chloride or zirconyl hydroxy chloride. The impurity levels of
various undesired ions (e.g. sodium, chloride, etc.) can be controlled in
the precipitate by adjusting the pH of the final slurry before filtration
and washing.
The acidic aluminum compound and basic zirconium carbonate should be
reacted in such proportions as to yield in the final complex an Al/Zr mole
ratio of about 4:1 to 1:4, and preferably about 2:1 to 1:2. Such complexes
when dissolved in an aqueous solution to the extent of about 5 to 20
weight percent (solids basis) yield a solution pH of at least about 3 and
preferably about 3 to 5.
The basic zirconium gels useful in forming the complexes of the present
invention also include zirconium hydroxide (Zr(OH).sub.4) gels. It will be
observed that these gels are simply the extension of the above general
formulas where x=4 in Zr(OH).sub.x A.sub.4-x and x=0 in Zr(OH).sub.4-2x
(CO.sub.3).sub.x. However, in general due to the higher basicity of the
all hydroxide gels, they are less reactive than the amino acid and
carbonate analogs, but still react with acidic aluminum solutions.
With the complexes formed with any of the basic zirconium gels, it may be
necessary to also include a stabilizing agent or buffer to yield a stable
solution and desirable solution pH of at least about 3. Many suitable
buffers are known in the art (see for example the Grad and Daley patents
referred to above), and others (described in copending applications) have
been recently developed. Suitable buffers, which may simply be added to
the reaction solution, include urea, amino acids, alkaline and hydroxy
salts of amino acids (see copending application Ser. No. 418,712 of
Rubino), alkaline earth salts, such as magnesium carbonate, etc. Also, the
basic zirconium carbonates can be dissolved first in a glycine solution,
for example, to yield water soluble zirconium glycinates. It is preferable
that any added buffer be kept to a minimum and preferably less than about
15 weight percent of the complex.
The method of forming the complexes of the present invention is not
particularly critical. However, various parameters and properties of the
complex such as viscosity and reactivity will be affected by certain
variables, including the particular reactants used, the source of the
amino acid compound, the order of addition of the reactants and the pH of
the final slurry when the product has been precipitated.
The various components are preferably added one at a time, and stirring
and/or moderate heating or even refluxing may be advantageous or even
necessary to complete reaction of certain ingredients, particularly during
and after addition of the insoluble basic zirconium compounds.
Although the basic zirconium compounds may be added as either wet or dry
gels, it is greatly preferred to use a wet gel which has never been dried
down to a powder form. Thus, it has been found that wet gels are far more
reactive with respect to aluminum compounds. That is, drying of the basic
zirconium gels appears to reduce the potential reactivity of the gels.
The drying of the finished prepared antiperspirant complexes of the
invention is not particularly critical and may be carried out in a number
of different ways, including vacuum drying, oven drying, spray drying or
freeze drying. It will be understood that drying does not mean that all of
the water is removed, since a certain amount of water should remain in the
complex as coordinated and/or bound water. Thus, drying to just past the
point where the solution becomes a friable solid should be sufficient. If
the complex is over dried, so that some of the coordinated and/or bound
water is removed, the stability and/or activity of the complex may be
interfered with, and the complex may not be readily redissolvable in
solvents, particularly hydroalcoholic solvents.
While it has been indicated that the reaction process is not considered
particularly critical, it will be understood that sufficient time, heat
and agitation are needed to allow reaction of the compounds to form the
new complexes of the present invention. This is particularly so in the
case of the insoluble basic zirconium compounds used to form complexes of
this invention.
As indicated previously, a further feature of the present invention is an
improved method for the preparation of the basic zirconium-amino acid gels
used in forming the complexes of the present invention. Various zirconium
glycinates have been previously reported in the literature. However, these
compounds are usually formed by the reaction of zirconyl chloride or
zirconyl hydroxy chloride with glycine.
According to the present invention, it has been found that highly reactive
basic zirconium-amino acid gels may be formed by reacting in aqueous
medium a water soluble salt of an amino acid and a water soluble zirconium
salt, which results in the precipitation of a basic zirconium-amino acid
gel.
For example, sodium glycinate may be reacted with zirconyl chloride or
zirconyl hydroxy chloride to precipitate out a basic zirconium glycinate
(BZG) gel. Only trace impurities will remain in the precipitate since
sodium chloride can be readily washed out of the gel.
However, the reaction is not limited to chloride zirconium salts, nor is
the amino acid limited to glycine. Instead, virtually any cationic
zirconium compounds referred to previously (as extra antiperspirant
ingredients) may be used in forming the basic zirconium-amino acid
compounds.
The water soluble amino acid salts include particularly the alkali metal
salts and ammonium salts of amino acids in which the number of amino
groups is equal to the number of carboxyl groups in the acid molecule.
Sodium glycinate is particularly preferred of these salts.
The water soluble amino acid salts are preferably prepared by reaction of
the alkali metal or ammonium carbonate or bicarbonate with the particular
amino acid desired. For example, sodium glycinate is preferably formed by
reaction of sodium carbonate or sodium bicarbonate with glycine.
Alternatively, the water soluble amino acid salt could be formed with the
corresponding hydroxide instead of carbonate. For example, sodium
glycinate could be formed by reacting sodium hydroxide with glycine.
However, the amino acid salts formed in this manner are less reactive than
those prepared with sodium carbonate. By less reactive is meant reactivity
toward active antiperspirant ingredients, such as aluminum chloride, 1/3
basic aluminum chloride, etc., used in forming the final antiperspirant
complexes of the present invention. Although applicants do not wish to be
bound by any particular theory, it is believed that the greater reactivity
of salts formed from the carbonate or bicarbonate is due to incomplete
neutralization with the amino acid. Hence, the final basic zirconium
compound will contain carbonate and/or bicarbonate groups, whose presence
makes the insoluble zirconium gels more reactive to aluminum.
The preparation of the basic zirconium-amino acid compounds according to
the present invention will now be illustrated with reference to the
following specific, non-limiting examples:
EXAMPLE A
A sodium glycinate solution was prepared by diluting 336.5 grams of
16.degree. Baume sodium carbonate (Na.sub.2 CO.sub.3) solution (12% w/w
Na.sub.2 CO.sub.3) with 3 liters of water and dissolving into this
solution 52.5 grams of glycine. The above clear solution was titrated into
450 grams of 33% zirconyl hydroxy chloride solution with overhead
agitation. The precipitate which formed was filtered and washed. The
washed gel analyzed: 5.7% Zr and 0.92% glycine.
EXAMPLE B
A sodium glycinate solution was prepared by diluting 300 grams of
16.degree. Baume sodium carbonate solution with 3 liters of water and then
dissolving into this solution 51 grams of glycine. The above clear
solution was titrated into 535 grams of zirconyl chloride (5.74% Zr). The
precipitate which formed was filtered and washed, and the resulting gel
analyzed: 9.1% Zr and 2.7% glycine.
EXAMPLE C
A sodium .beta.-alaninate solution was prepared by diluting 336.5 grams of
16.degree. Baume sodium carbonate with 3 liters of water and dissolving
into this solution 62.5 grams of .beta.-alanine. The above clear solution
was then titrated into 450 grams of 33% zirconyl hydroxy chloride solution
with agitation. The precipitate which formed was filtered and washed, and
the resulting gel analyzed: 4.37% Zr and 1.2% .beta.-alanine.
The antiperspirant complexes according to the present invention will now be
illustrated in more detail, with reference to the following specific,
non-limiting examples. Examples I-III illustrate complexes wherein the
sodium glycinate was prepared with sodium hydroxide rather than sodium
carbonate. As indicated previously, sodium glycinate prepared in this
manner is not as reactive with the active antiperspirant ingredients, and
hence the glycine content in all of the complexes of these examples is
relatively low, namely less than about 1 percent by weight.
Example IV illustrates a preparation using a zirconium hydroxide gel.
Sodium carbonate was not used in the preparation of the gel, and the
overall reactivity with the basic aluminum and zirconium compounds was
correspondingly low.
Examples V-XVI show preparations in which the sodium glycinate or
corresponding amino acid salt, used to prepare the basic zirconium-amino
compound, was prepared from sodium carbonate and the amino acid. The basic
zirconium carbonates used in Examples XVII and XVIII were also prepared
without the presence of sodium hydroxide.
Except where otherwise indicated, all of the following and foregoing
examples were performed in aqueous media, and all percents are on a weight
basis.
EXAMPLE I
Forty grams of zirconyl hydroxybromide solution (13.6% Zr) was reacted with
70 g. of 24.degree. Baume AlCl.sub.3 solution at 80.degree. C. Into this
hot solution was dissolved 20 g. of a basic zirconium glycinate (BZG) gel
(4.14% Zr, 1.4% glycine). The above mixture was added slowly to a 25%
solution of 5/6 basic aluminum bromide (4.1% Al) while undergoing reflux.
The product was oven-dried at 55.degree. C. under a vacuum of 35 cm. of
Hg. The material analyzed: 13.2% Al, 7.57% Zr, and 0.84% glycine.
EXAMPLE II
One hundred grams of an aluminum chloride solution (2.1% Al) was heated to
85.degree. C. prior to the addition of 10 g. of a BZG gel (4.74% Zr, 0.91%
glycine). After thirty minutes of agitation, the solution cleared. Fifty
grams of a 50% solution of aluminum chlorhydrate (5/6 basic aluminum
chloride) was added to the cooled solution. The product was oven-dried at
50.degree. C. under a vacuum of 40 cm. of Hg. The material analyzed: 18.0%
Al, 1.1% Zr, and 0.46% glycine.
EXAMPLE III
Ten grams of zirconyl chloride solution (14.4% Zr) was mixed in with 40 g.
of AlCl.sub.3 solution (2.1% Al) and heated to 75.degree. C. prior to
reacting with 10 g. of BZG gel (4.14% Zr, 1.4% glycine).
Sixty grams of a 5/6 basic aluminum iodide solution (5.6% Al) was heated to
85.degree. C. prior to the slow addition of the Al-Zr solution described
above. On cooling, the pH was 3.6. The product was oven-dried under a
vacuum of 38 cm. of Hg at 60.degree. C. The material analyzed: 6.46% Zr,
12.99% Al, and 0.45% glycine.
EXAMPLE IV
Ten grams of a compressed Zr(OH).sub.4 gel (5.1% Zr) was suspended in 90
grams of water to form a 10% suspension containing 0.51% Zr. The
suspension was reacted with 2 g. of glycine at 75.degree. C. for one half
hour. The slurry was then dissolved in 190 g. of zirconyl hydroxychloride
solution (14.1% Zr) plus 20 g. of aluminum chloride solution (4.2% Al)
while heating at 85.degree. C. The above was added to 500 g. of aluminum
chlorhydrate solution (6.2% Al), which was under reflux. After cooling, 2
g. ZnCl.sub.2 and 2 g. MgCl.sub.2.6H.sub.2 O were dissolved in the
solution, to yield a pH of 3.2. The product was oven-dried at 55.degree.
C. under a vacuum of 45 cm. of Hg and found to contain: 16.5% Al, 11.8%
Zr, 1.01% glycine, 0.37% Zn, and 0.11% Mg.
EXAMPLE V
One hundred grams of aluminum chloride solution (0.84% Al) was heated to
85.degree. C. prior to the addition of 52 g. of a BZG gel (9.1% Zr, 2.7%
glycine). After 30 minutes of agitation, the solution cleared, to yield a
product with a pH of 3.3. The material was dried in an oven at 55.degree.
C. under a vacuum of 45 cm. of Hg, and was found to contain: 35.7% Zr,
5.4% Al and 12.1% glycine.
EXAMPLE VI
Fifty grams of a 1/3 basic aluminum chloride solution [Al(OH)Cl.sub.2 ;
5.8% Al] was heated to 80.degree. C. prior to the addition of 120 g. of a
BZG gel (5.7% Zr, 0.92% glycine). The solution cleared on agitation to
yield a solution pH of 3.2. The product was oven-dried at 55.degree. C.
under a vacuum of 40 cm. of Hg and was found to contain: 8.98% Al, 16.3%
Zr and 3.7% glycine.
EXAMPLE VII
Fifty grams of a 2/3 basic aluminum chloride solution [Al(OH).sub.2 Cl;
8.81% Al] was heated to 80.degree. C. prior to the addition of 86 g. of
BZG gel (5.7% Zr, 0.92% glycine). After 30 minutes of agitation, the
solution cleared to yield a solution pH of 3.1. The product was oven-dried
under a vacuum of 40 cm. of Hg at 60.degree. C. The material analyzed:
14.3% Al, 13.5% Zr and 3.14% glycine.
EXAMPLE VIII
Twenty grams of 3/4 basic aluminum bromide solution [Al.sub.4 (OH).sub.9
Br.sub.3 ; 9.0% Al] was heated to 80.degree. C. prior to the addition of
15 g. of a BZG gel (5.7% Zr, 0.92% glycine). After 30 minutes of
agitation, the solution cleared to yield a solution pH of 3.97. The
product was oven-dried at 55.degree. C. under a vacuum of 42 cm. of Hg.
The material analyzed: 15.7% Al, 7.2% Zr and 1.71% glycine.
EXAMPLE IX
Thirty-four grams of a BZG gel (5.7% Zr, 0.92% glycine) was dissolved in 40
g. of a zirconyl iodide solution (1.21% Zr). This product was then added
to 20 g. of a 25% solution of 5/6 basic aluminum phenolsulfonate (4.2%
Al), to yield a product with a pH of 3.85. The solution was evaporated
under a vacuum of 45 cm. of Hg at 45.degree. C., and analyzed: 9.2% Al,
19.6% Zr, and 2.63% glycine.
EXAMPLE X
Eighty-six grams of a BZG gel (5.7% Zr, 0.92% glycine) was dissolved in 60
g. of a zirconyl nitrate solution [ZrO(NO.sub.3).sub.2 ; 4.5% Zr]. The
above was added to 103 g. of 1/3 basic aluminum sulfate (3.1% Al). The
product was oven-dried at 50.degree. C. under a vacuum of 35 cm. of Hg and
was found to contain: 12.4% Al, 26.4% Zr, and 3.14% glycine.
EXAMPLE XI
Fifty-one grams of a BZG gel (4.6% Zr, 0.66% glycine) was dissolved in 40
g. of AlCl.sub.3 solution (2.1% Al) which was being heated under reflux.
On cooling, the above solution was added to 20 g. of 2/3 basic aluminum
sulfamate (4.8% Al). The product was oven-dried at 55.degree. C. under a
vacuum of 43 cm. of Hg. The material analyzed: 16.3% Al, 21.3% Zr, and
3.06% glycine.
EXAMPLE XII
Forty grams of a BZG gel (4.6% Zr, 0.66% glycine) was dissolved in 40 g. of
AlCl.sub.3 solution (2.1% Al) which was being heated under reflux. After
the solution cleared, 1 g. of Mg (glycinate).sub.2 (obtained from J. H.
Walker and Co.; 13.0% Mg) was added under the same conditions. The
resulting clear solution was dried in an oven at 60.degree. C. under a
vacuum of 40 cm. of Hg. The product analyzed: 9.33% Al, 20.7% Zr, 1.44% Mg
and 2.96% glycine.
EXAMPLE XIII
Forty grams of an aluminum chloride solution (2.1% Al) was heated to
85.degree. C. prior to the addition of 81 g. of BZG gel (4.6% Zr, 0.66%
glycine). After 30 minutes of heating with agitation, the solution
cleared. Two grams of zinc phenolsulfonate were then dissolved in the
cooled solution. The product was oven-dried at 55.degree. C. under a
vacuum of 45 cm. of Hg and was found to contain: 5.9% Al, 2.2% Zn and 3.8%
glycine.
EXAMPLE XIV
Eighty grams of a zirconyl chloride solution (7.7% Zr) was heated to
80.degree. C. prior to the addition of 108 g. of BZG gel (4.6% Zr, 0.66%
glycine). After 15 minutes of agitation, the solution cleared. The cooled
solution was then added to 100 g. of a 5% w/w suspension of magnesium
glycinate (0.51% Mg. 3.11% glycine) and stirred for 10 minutes until the
solution cleared prior to the addition of 12.5 g. of 50% aluminum
chlorhydrate (12.5% Al). The product was oven-dried under a vacuum of 45
cm. of Hg at 60.degree. C. The material analyzed: 31.9% Zr, 16.5% Al,
10.6% glycine and 1.38% Mg.
EXAMPLE XV
One hundred five grams of a basic Zr .beta.-alaninate gel (4.37% Zr, 1.2%
.beta.-alanine) was reacted with 40 g. of refluxing AlCl.sub.3 solution
(2.1% Al). The mixture was refluxed for one hour when the solution turned
clear. On cooling, 2 g. of ZnCl.sub.2 and 2 g. of MgCl.sub.2.6H.sub.2 O
were dissolved in the clear solution. The product was oven-dried at
55.degree. C. under a vacuum of 45 cm. of Hg. The material analyzed: 5.25%
Al, 28.6% Zr, 1.5% Mg, 1.18% Zn and 7.9% .beta.-alanine.
EXAMPLE XVI
Forty grams of an AlCl.sub.3 solution (2.1% Al) was heated to 80.degree. C.
prior to dissolving in 105 g. of a basic Zr .beta.-alaninate gel (4.37%
Zr, 1.2% .beta.-alanine). The pH of the solution after cooling was 3.6.
The product was oven-dried at 58.degree. C. under a vacuum of 50 cm. of
Hg. The material analyzed: 5.8% Al, 19.6% Zr, and 3.3% .beta.-alanine.
EXAMPLE XVII
Five grams of glycine was dissolved in 80 g. of AlCl.sub.3 solution (2.1%
Al). The solution was heated to 75.degree. C. before dissolving in 90 g.
of a basic zirconium carbonate(BZC) gel (7.37% Zr). After 15 minutes of
stirring and heating, the solution cleared to yield a pH of 3.52. The
product was oven-dried at 60.degree. C. under a vacuum of 45 cm. of Hg.
The material analyzed: 5.24% Al, 19.3% Zr and 13.3% glycine.
EXAMPLE XVIII
Thirty-six grams of a basic zirconium carbonate (BZC) gel (5.67%) was
dissolved in 40 g. of refluxing AlCl.sub.3 solution (2.1% Al). The cooled
solution had a pH of 3.2. The product was oven-dried at 60.degree. C.
under a vacuum of 40 cm. of Hg. The material analyzed: 7.19% Al, 19.6% Zr.
Among the advantages of the complexes of the present invention is that
highly acidic aluminum or aluminum-zirconium antiperspirant systems may be
effectively buffered with a complex which also provides an additional
source of zirconium, a metal which is known for its antiperspirant
efficacy. Moreover, due to the presence of the additional basicity
(hydroxyl groups) in the buffering complex, smaller amounts of amino acid
are required in the final complex than have been required in many prior
art antiperspirant systems using amino acids as buffers.
As indicated previously, the complexes of the present invention may be used
in a variety of conventional antiperspirant forms which are applied to the
human axilla for effective perspiration inhibition. In such formulations,
the complex should be present in amounts of about 1.5 to 20 weight percent
(depending on the type of formulation employed).
For example, aqueous solutions of the complexes may be used in lotions,
oil/water creams, and co-dispensing aerosols. The complexes of the present
invention are not as a rule soluble in pure alcoholic solvent systems.
However, the complexes may be considered for use in hydro-alcoholic mixed
solvents, such as 50 percent ethanol and 50 percent water. In | | |
