U.S. patent number 3,920,883 [Application Number 05/306,954] was granted by the patent office on 1975-11-18 for liquid cosmetic composition of a two-phase type.
This patent grant is currently assigned to Shiseido Co., Ltd.. Invention is credited to Isao Hirano, Sanae Kubo, Junichi Yamada.
United States Patent |
3,920,883 |
Yamada , et al. |
November 18, 1975 |
Liquid cosmetic composition of a two-phase type
Abstract
A two liquid-phase type liquid cosmetic composition of an
attractive appearance is provided. The cosmetic composition
comprises: (1) oil; (2) an organic liquid miscible with water; (3)
water, and; (4) finely divided solid particles insoluble in any of
the above ingredients (1), (2) and (3). The oil is dispersed in the
form of spheres in a homogeneous mixture of the organic liquid and
water. The solid particles are substantially absorbed on the
interface between the oil phase and the homogeneous mixture phase
of the organic liquid and water.
Inventors: |
Yamada; Junichi (Kamakura,
JA), Kubo; Sanae (Omiya, JA), Hirano;
Isao (Yokohama, JA) |
Assignee: |
Shiseido Co., Ltd.
(JA)
|
Family
ID: |
23187613 |
Appl.
No.: |
05/306,954 |
Filed: |
November 15, 1972 |
Current U.S.
Class: |
514/762; 514/938;
424/59; 514/939 |
Current CPC
Class: |
A61K
8/03 (20130101); A61Q 19/00 (20130101); A61K
8/0241 (20130101); A61K 8/26 (20130101); A61K
8/37 (20130101); Y10S 514/938 (20130101); Y10S
514/939 (20130101); A61Q 5/00 (20130101) |
Current International
Class: |
A61K
8/37 (20060101); A61K 8/26 (20060101); A61K
8/19 (20060101); A61K 8/30 (20060101); A61K
8/03 (20060101); A61K 8/04 (20060101); A61Q
5/00 (20060101); A61Q 19/00 (20060101); A61K
007/02 (); A61K 007/40 (); A61K 031/74 (); A61K
031/76 () |
Field of
Search: |
;424/168,63,358,78 |
References Cited
[Referenced By]
U.S. Patent Documents
|
|
|
3691270 |
September 1972 |
Charle et al. |
|
Foreign Patent Documents
Primary Examiner: Meyers; Albert T.
Assistant Examiner: Ore; Dale R.
Attorney, Agent or Firm: Burns; Robert E. Lobato; Emmanuel
J. Adams; Bruce L.
Claims
What we claim is:
1. A liquid cosmetic composition of a two phase type, which
comprises:
1. up to about 95% by weight of an aqueous phase substantially
comprised of water and at least one organic liquid selected from
the group consisting of ethyl alcohol, N-methyl pyrrolidone/and
isopropyl alcohol,
2. up to about 95% by weight of an oil phase in the form of spheres
having diameters of 0.1 mm to 1.0 cm dispersed in said aqueous
phase, said oil phase being substantially comprised of at least one
member selected from the group consisting of liquid paraffin,
squalane, 2-hexyldecyl palmitate, 2-octyldodecyl myristate,
di-2-hexyldecyl adipate, di-2- ethylhexyl sebacate, olive oil,
tsubaki oil, mink oil, isostearic acid, oleic acid, oleyl alcohol
and a polypropyleneglycol butyl ether having a polymerization
degree of approximately 40, and
3. not greater than approximately 50% by weight of finely divided
solid particles insoluble in the liquid ingredients (1) and (2) set
forth above, said solid particles having particle sizes of less
than about 100 micron and being adsorbed on the interface between
said aqueous phase (1) and said oil phase (2), said solid particle
being selected from at least one member selected from the group
consisting of talc, kaolin, iron oxide, magnesium oxide, zinc
oxide,/zinc peroxide, titanium oxide, precipitated calcium
carbonate, calcium secondary phosphate, aluminium hydroxide,
antimony oxide, alumina, barium sulfate, silicic acid anhydride,
magnesium metasilicate aluminate, silica-alumina, bismuth
oxychloride, microcrystalline cellulose, fish scale, polyvinyl
chloride and poly-.OMEGA.-lauryllactam
the proportion in the amount of water to the organic liquid in said
aqueous phase (1) being such that the difference in specific
gravity between said aqueous phase (1) and said oil phase (2) is
not greater than 0.04 and wherein a spreading coefficient S defined
as having the following formula is negative,
S=.gamma..sub.w -.gamma..sub.o -.gamma..sub.ow
wherein .gamma..sub.o and .gamma..sub.w are surface tensions of the
oil and the homogeneous mixture of water and the organic liquid
respectively, and .gamma..sub.ow is an interfacial tension between
the oil and the homogeneous mixture of water and the organic
liquid.
2. A liquid comsmetic composition according to claim 1 wherein said
oil phase is present in an amount of less than 60% by weight based
on the weight of the cosmetic composition.
3. A liquid cosmetic composition of a two phase type, according to
claim 1 which consists essentially of:
1. not more than approximately 95% by weight of an aqueous phase
substantially comprised of water and at least one organic liquid
selected from the group consisting of ethyl alcohol and isopropyl
alcohol,
2. less than 60% by weight of an oil phase in the form of spheres
of 0.1 mm to 1.0 cm diameter dispersed in said aqueous phase, said
oil phase being substantially comprised of at least one member
selected from the group consisting of liquid paraffin,
di-2-hexyldecyl adipate, squalane and oleyl alcohol, and
3. not more than approximately 50% by weight of finely divided
solid particles insoluble in the liquid ingredients (1) and (2) set
forth above, said solid particles having particle sizes smaller
than approximately 100 microns and being adsorbed on the interface
between said aqueous phase (1) and said oil phase (2) and being at
least one member selected from the group consisting of precipitated
calcium carbonate, zinc oxide, zinc peroxide, talc, bentonite, iron
oxide, antimony oxide, magnesium metasilicatealuminate, bismuth
oxychloride, fish scale and poly-.OMEGA.-lauryllactam, the
proportion in the amount of water to the organic liquid in said
aqueous phase (1) being such that the difference in specific
gravity between said aqueous phase (1) and said oil phase (2) is
not greater than 0.04 and wherein a spreading coefficient S defined
as having the following formula is negative,
S=.gamma..sub.w -.gamma..sub.o -.gamma..sub.ow
wherein .gamma..sub.o and .gamma..sub.w are surface tensions of the
oil and the homogeneous mixture of water and the organic liquid,
respectively, and .gamma..sub.ow is an interfacial tension between
the oil and the homogeneous mixture of water and the organic
liquid.
4. A liquid cosmetic composition of a two phase type, according to
claim 1 which consists essentially of:
1. not more than approximately 95% by weight of an organic liquid
phase comprising at least one member selected from the group
consisting of ethyl alcohol and isopropyl alcohol,
2. not more than approximately 95% by weight of an oil phase in the
form of spheres of 0.1 mm to 1.0 cm diameter dispersed in said
organic liquid phase, said oil phase comprising at least one member
selected from the group consisting of liquid paraffin, squalane,
2-hexyldecyl palmitate, 2-octyldodecyl myristate, di-2-hexyldecyl
adipate, di-2-ethylhexyl sebacate, olive oil, tsubaki oil, mink
oil, isostearic acid, oleic acid, oleyl alcohol, and a
polypropyleneglycol butyl ether having a polymerization degree of
approximately 40, and
3. not more than approximately 50% by weight of finely divided
solid particles insoluble in the liquid ingredients (1) and (2) set
forth above, said solid particles having particle sizes of less
than 100 microns approximately and being adsorbed on the interface
between said organic liquid phase (1) and said oil phase (2), and
being at least one member selected from the group consisting of
talc, kaolin, iron oxide, magnesium oxide, zinc peroxide, titanium
oxide, precipitated calcium carbonate, calcium secondary phosphate,
aluminium hydroxide, antimony oxide, alumina, barium sulfate,
silicic acid anhydride, magnesium metasilicatealuminate,
silica-alumina, bismuth oxychloride, microcrystalline cellulose,
fish scale, pearl, polyvinyl chloride and
poly-.OMEGA.-lauryllactam,
the difference in specific gravity between said organic liquid (1)
and said oil (2) being not greater than 0.04 and wherein a
spreading coefficient S defined as having the following formula is
negative,
S=.gamma..sub.w -.gamma..sub.o -.gamma..sub.ow
wherein .gamma..sub.o and .gamma..sub.w are surface tensions of the
oil and the homogeneous mixture of water and the organic liquid,
respectively, and .gamma..sub.ow is an interfacial tension between
the oil and the homogeneous mixture of water and the organic
liquid.
Description
This invention relates to a liquid cosmetic composition of an
attractive appearance.
In general cosmetics involve both ingredients of oil and water. In
order to prepare and emulsion or other uniform dispersion from the
two ingredients immiscible with eath other, nonionic surface active
compounds and other surface active compounds have heretofore been
employed as an emulsifier or solubilizer. However, conventional
cosmetics having, incorporated therein, these surface active
compounds have some of the following disadvantages.
1. Some surface active compounds cause skin- or eyelid-irritation
or inflammation.
2. Some surface active compounds tend to decompose thereby
deteriorating the cosmetics and emitting an offensive odor.
3. When an ingredient other than oil, water and a surface active
compound is present in the cosmetic composition, the composition
becomes unstable, which leads to phase separation. This is a
frequent phenomenon in the employment of most surface active
compounds. Accordingly, it is very difficult to find a suitable
surface active compound.
4. Surface active compounds cause undesirable foaming in cosmetics
such as hair tonic and face lotion. This phenomenon is anything but
agreeable.
5. Most surfaces active compounds diminish the effects of
antiseptic, colorant and perfume components.
6. Even when a surface active compound is employed, the amount of
oil capable of being incorporated into the cosmetic is restricted,
i.e. it is difficult to obtain a liquid cosmetic composition rich
in oil.
In order to minimize these troubles, a cosmetic has been proposed
which contains a very limited amount of a surface active compound.
This cosmetic comprises two different liquid phases, i.e. an oily
phase and an aqueous phase, separated above and below because of
insufficient capability of forming a homogeneous mixture.
Obviously, such an above and below separated two phase type liquid
cosmetic is inferior in capability of being readily mixed into a
homogeneous mixture by shaking. Therefore, when the cosmetic is
repeatedly used, the upper oily portion initially tends to be
consumed in an amount larger than that of the below aqueous phase.
Further, since the cosmetic contains a surface active compound,
even though only a minor amount, the troubles listed above cannot
be completely avoided.
Some conventional liquid cosmetics contain water-insoluble finely
divided solid particles. However, these also need the incorporation
of a surface active compound to impart the capability of the solid
particles being uniformly dispersed by shaking. Unless a surface
active compound is incorporated into this type of liquid cosmetic,
the solid particles inevitably form a precipitate or coagulation.
Therefore, these conventional liquid cosmetics also have the
disadvantages set forth above.
It is, therefore, an object of the present invention to provide a
liquid cosmetic composition which does not have the disadvantages
caused by a surface active compound, as set forth above.
Another object of the present invention is to provide a two-phase
type liquid cosmetic composition which exhibits improved capability
of readily forming a substantially homogeneous mixture by shaking,
although the liquid cosmetic composition contains no surface active
compound, and also exhibits an improved capability of being readily
restored to the original state after the use.
Still another object of the present invention is to provide a
liquid cosmetic composition having an attractive appearance.
A further object of the present invention is to provide a liquid
cosmetic composition which can be prepared from a great variety of
oils and oily materials.
Other objects and advantages of the present invention will be
apparent from the following description.
In accordance with the present invention, there is provided a
liquid cosmetic composition of two phase liquid type
comprising:
(1) oil; (2) an organic liquid miscible with water; (3) water and;
(4) finely divided solid particles insoluble in either of said oil,
organic liquid and water and having an average particle size of no
greater than 100.mu.. Said oil is dispersed in the form of spheres
in a homogeneous mixture of said organic liquid and water. Said
finely divided solid particles are adsorbed on the interface
between said oil and said homogeneous mixture of said organic
liquid and water.
The liquid cosmetic composition of the present invention comprises
two different liquid phases. One phase is a homogeneous mixture of
an organic liquid, and water. The organic liquid is miscible with
water but is substantially immiscible with oil. The other phase is
oil in the form of spheres dispersed in the homogeneous mixture set
forth above. The oil spheres dispersed in the homogeneous mixture
of the organic liquid and water may be transparent, opaque,
translucent or of a pearl-like appearance. The number of the oil
spheres can be voluntarily varied, and ranges from one to thousands
or more per litre of the liquid cosmetic composition. The diameter
of the oil spheres range from 0.1 mm to several centimeters.
The liquid cosmetic composition of the present invention has the
following advantages:
1. This liquid cosmetic composition contains no surface active
agent and, therefore, it is possible to avoid the troubles caused
by a surface active agent as set forth above.
2. Although this liquid cosmetic composition contains no surface
active agent, it exhibits capability over conventional liquid
cosmetics of forming a substantially homogeneous mixture when
shaken by hand at the time of use.
3. A great variety of oils can be employed for the preparation of
this liquid cosmetic composition. Therefore, an oil ingredient to
be employed can be chosen without difficulty.
4. Finely divided solid particles are adsorbed on the whole
interface between the oil phase and the aqueous phase of the
organic liquid. The solid particles are neither precipitated nor
buoyed up.
Due to the existence of such solid particles, the dispersion of oil
spheres in the aqueous phase is stable.
It has been found that the state of oil spheres dispersed in the
aqueous phase is not varied even after being in settled storage
over a period of 3 years.
This liquid cosmetic composition exhibits improved capability of
readily forming a substantially homogeneous mixture when shaken at
use, as compared to a conventional above and below separated two
phase type liquid cosmetic. Further, the liquid cosmetic
composition also exhibits improved capability of being readily
restored to the orginal state after the use.
5. The finely divided solid particles in the liquid cosmetic
composition suppress the underside glare resulting from the oil
ingredient at the time of use. Further, the solid particles exhibit
a skin-astringent effect and a sunlight-screening effect. When a
medicine is absorbed on the solid particles, the resulting
particles have a medicinal effect.
6. The liquid cosmetic composititon is of an attractive appearance.
Oil spheres dispersed in the aqueous phase may be transparent,
translucent or pearl-like in appearance. These may possess any
color. The size and the number of the oil spheres may be varied
Therefore, a great variety of cosmetic can be provided. This is
obviously advantageous from the view-point of merchandizing,
because these liquid cosmetic can be distinguished according to the
intended use. For example, liquid cosmetics containing a relatively
large number of oil spheres can be readily recognizable as being
for a dry skin use while those of a relatively small number of oil
spheres for a normal skin, and so forth.
Oils used in the present invention are those which are liquid at
room temperatures, immiscible with water, and have a specific
gravity smaller than that of water. For example, oils include
preferably high-molecular weight hydrocarbons such as liquid
paraffin (a hydrocarbon oil consisting mainly of alkyl naphthene),
squalane (2, 6, 10, 15, 19, 23-hexamethyltetracosane) and the like;
mono- or di-esters of fatty acid such as 2-hexyldecyl palmitate,
2-octyldodecyl myristate, di-2-hexyldecyl adipate, di-2-ethylhexyl
sebacate and the like; vegetable and animal oils, i.e.
triglycerides of fatty acid, such as olive oil, tsubaki oil, mink
oil and the like; higher fatty acids having 10 to 25 carbon atoms
such as isostearic acid, oleic acid and the like; fatty alcohols
having 10 to 25 carbon atoms such as oleyl alcohol; and synthetic
oils such as silicone oil, polyalkylene glycol derivatives and the
like. The polyalkylene glycol derivatives include, for example,
Unilube MB-370 (Bu--O--CH(CH.sub.3)--CH.sub.2 --O--.sub.n H,
n.apprxeq.40, trade name made by NIHON YUSHI K. K., Japan). These
oils can be used either alone or in a combination of at least two.
Oily solid substances such as wax, i.e. an ester of a
high-molecular weight fatty acid with a high-molecular weight fatty
alcohol, and fat, i.e. a triglyceride of a high-molecular weight
fatty acids, may be dissolved in the oil used in the present
invention.
The amount of oil present in the liquid cosmetic composition may be
varied within the range of lower than approximately 95% by weight,
preferably lower than 60% by weight.
Finely divided solid particles used in the present invention are
those which have an average particle size of below approximately
100.mu., are pharmaceutically non-toxic to the skin, and insoluble
in both oil and the homogeneous mixture of water and the organic
liquid. Preferable finely divided solid particles include those of,
for example, natural inorganic substances such as talc, kaolin, and
the like; artificial inorganic substances such as iron oxide,
magnesium oxide, zinc oxide, zinc peroxide, titanium oxide, calcium
carbonate (prepared and precipitated), calcium secondary phosphate,
aluminum hydroxide, antimony oxide, alumina, barium sulfate;
inorganic pearl-like substances (bismuth oxychloride, titania),
silicic acid anhydride, magnesium metasilicate aluminate (MgO.sup..
Al.sub.2 O.sub.3.sup.. 2SiO.sub.2), silica-alumina, and the like;
natural organic substances such as protein, microcrystalline
cellulose, fish scale, pearl and the like; and artificial organic
substances such as high polymeric substances, e.g. polyvinyl
chloride, nylon-12 (poly--.OMEGA.--lauryllactam
H--NH--(CH.sub.2).sub.11 --CO--.sub.n OH), and the like; organic
pigments and lakes, e.g. Permanent Orange (see Colour Index,
Pigment Orange 5, 12075) and Lithol Rubine BCA (Trade name, made by
BASF, Germany). These finely divided solid particles may be coated
with suitable substances such as, for example, metal soaps,
surfactants and polymers. These solid particles may be used either
alone or in combination.
The amount of the finely divided solid particles present in the
liquid cosmetic composition may be varied within the range of lower
than approximately 50% by weight.
Organic liquids used in the present invention are pharmaceutically
non-toxic to the skin, and miscible with water, but substantially
immiscible with the oil set forth above. The organic liquids may be
either completely immiscible, or slightly miscible with the oil if
the homogeneous mixture of the organic liquid with water is
immiscible with the oil. Further, the organic liquid has in usual a
specific gravity of lower than 1.0.
The organic liquid include, for example, monohydric alcohols having
carbon atoms of no greater than 5 such as ethyl alcohol, isopropyl
alcohol and tetrahydrofurfuryl alcohol; polyhydric alcohols such as
those having carbon atoms of no greater than 6, for example,
propylene glycol, glycerin, sorbitol, dipropylene glycol,
1,3-butylene glycol and mannitol, and polyethylene glycol having
carbon atoms of no greater than 50; ethers having carbon atoms of
no greater than 6 such as diethylene glycol ethyl ether, ethyl
ether, dioxane and tetrahydrofuran; ketones having carbon atoms of
no greater than 6 such as acetone and N-methylpyrrolidone. Of these
organic liquids, ethyl alcohol, isopropyl alcohol and
N-methylpyrrolidone are most preferable.
The homogeneous mixture of water and the organic liquid present in
the liquid cosmetic composition may be varied within the range of
lower than approximately 95% by weight.
In the liquid cosmetic composition of the present invention, oil
ingredient, in the form of small spheres, are dispersed in a
homogeneous mixture of water and the organic liquid. In order to
prepare the stable dispersion of the oil spheres in the homogeneous
mixture of water and the organic solvent, the following
prerequisites should be satisfied.
1. The difference in specific gravity between the oil ingredient
(d.sub.o) and the homogeneous mixture (d.sub.w) of water and the
organic liquid is zero or nearly zero.
d.sub.o -d.sub.w .apprxeq.0
A permissible range of the difference varies depending upon the
temperature. However, in general, the absolute value of the
difference may be not greater than 0.04.
.vertline.d.sub.o -d.sub.w .vertline..ltoreq.0.04
2. Spreading coefficient (S) defined by the following equation is
negative.
S=.gamma..sub.w -.gamma..sub.o -.gamma..sub.ow <0
wherein .gamma..sub.o is a surface tension of the oil ingredient,
.gamma..sub.w is a surface tension of a homogeneous mixture of
water and the organic liquid, and .gamma..sub.ow is an interfacial
tension between the oil ingredient and the homogeneous mixture of
water and the organic liquid.
If spreading coefficient is zero or positive, oil spheres break,
when buoyed up to the surface, to form an above and below separated
two-phase type liquid. This two-phase liquid is not restored to the
original state.
3. Oil and the homogeneous mixture are immiscible with each
other.
In order to balance the specific gravity between the oil and the
homogeneous mixture of water and the organic liquid, the particular
organic solvent to be mixed with water and the proportion of the
amount thereof to the amount of water should be suitably determined
depending upon the specific gravity of the particular oil used. For
example, when a liquid paraffin having a specific gravity of
d.sub.30.sup.30 0.8470 is employed as an oil ingredient, a
homogeneous mixture of the same specific gravity can be prepared by
blending 25% by weight of water and 75% by weight of ethyl alcohol
having a specific gravity of d.sub.4.sup.30 0.7808.
When finely divided solid particles having a relatively large
particle size, i.e. 10.mu.-100.mu., are employed, the specific
gravity should preferably be completely balanced between the oil
and the homogeneous mixture of water and the organic liquid.
However, the smaller the particle size of the solid particles, the
greater the warrantable difference in specific gravity between the
oil and the homogeneous mixture.
In one modified embodiment of the liquid cosmetic composition of
the present invention, the liquid cosmetic composition is composed
of oil, an organic liquid miscible with water and finely divided
solid particles, i.e. water can be omitted from the cosmetic
composition, if the prerequisites set forth above are satisfied, as
exemplified in Example 1 below.
Further, the following factors should preferably be taken into
consideration for ensuring good dispersibility when shaken, good
reproducibility of the dispersion after shaking is stopped and a
reasonably high reproduction speed of the dispersion after shaking
is stopped.
The dispersibility when shaken depends upon the interfacial tension
between the oil and the aqueous mixture, the viscosity of the oil
and the shaking force. Reproducibility of the dispersion after
shaking is stopped depends upon the joining speed of oil spheres
dispersed, the polarity of oil, the miscibility between oil and the
aqueous mixture, and the solubility between oils when two or more
oils are employed. Reproduction speed of the dispersion after
shaking is stopped depends upon the joining speed of oil spheres,
the difference in specific gravity between oil and the aqueous
mixture, the temperature, and the viscosity of the aqueous
mixture.
The relationship between physical characteristics of finely divided
solid particles and the shape of the oil spheres dispersed in the
homogeneous mixture of water and organic liquid will be illustrated
with reference to the accompanying drawings.
FIGS. 1A and 1B show model pictures of the microscopic photograph
of the interfacial portion between the oil phase and the aqueous
phase consisting of a homogeneous mixture of water and the organic
liquid, and the appearance of the waterorganic liquid-solid
particles-oil system, respectively, when hydrophilic, finally
divided solid particles are employed.
FIGS. 2A and 2B, 3A and 3B, and 4A and 4B, show similar model
pictures when slightly hydrophilic, slightly oleophilic and
oleophilic, finely divided solid particles are employed,
respectively.
As shown in FIGS. 1A and 1B, when the finely divided solid
particles employed are hydrophilic, the particles 1 are dispersed
in an aqueous liquid phase 2, but not in an oil phase 3, and
gradually settle to the bottom of the aqueous liquid phase 2 to
form a sediment 4. Therefore, hydrophilic solid particles are
unsuitable for the provision of the cosmetic composition of the
present invention.
When the solid particles are slightly hydrophilic, these solid
particles 1 are adsorbed on the interface of oil spheres 3 and
thereby the oil spheres 3 are stably dispersed in an aqueous phase
2, as shown in FIGS. 2A and 2B. The number and the size of the oils
sphere 2 may be varied depending upon the amount of the solid
particles employed.
When the solid particles are slightly oleophilic, the solid
particles 1 are adsorbed on an inside of the surface of oil spheres
3, and the oil spheres 3 are unstable and tend to unite with each
other, as shown in FIGS. 3A and 3B. The united oil sphere 3'
exhibits an intricate shape and a creased surface with wrinkles.
Therefore, finely divided solid particles should preferably possess
a hydrophilic property slightly stronger than or well-balanced with
an oleophilic property.
When the solid particles are oleophilic, these particles 1 are
dispersed within an oil sphere 3, as shwon in FIGS. 4A and 4B.
Hydrophilic characteristics of the solid particles may be expressed
in terms of a sedimentation volume per unit of apparent specific
volume (hereinafter referred to as fw for brevity) of the solid
particles in water, or a hydrophilic coefficient of the solid
particles.
When finely divided hydrophilic solid particles are dispersed in
water, these particles form a relatively uniform dispersion. In
contrast, when finely divided oleophilic solid particles are
dispersed in water, these particles do not form a uniform
dispersion but partially coagulate. In other words, in water the
hydrophilic solid particles exhibit a small sedimentation volume,
but the oleophilic solid particles exhibit a large sedimentation
volume. Therefore, fw may be one of the yardsticks for determining
the hydrophilic property. The fw in water is represented by the
formula:
fw=sedimentation volume in water (in cc/g)/apparent specific volume
(in cc/g)
The sedimentation volume in water and the apparent specific volume
are determined as follows.
1. Sedimentation volume
A finely divided solid particle specimen is heated at 105.degree.C
for 2 hours, cooled, and then weighed. The specimen is dispersed in
an aqueous 20% ethyl alcohol solution. After the dispersion is
deaired by vacuuming at a pressure of 4 to 5 mmHg, the dispersion
is settled in a settling tube over a period of one month. Then, the
sedimentation volume is measured.
2. Apparent specific volume
A finely divided solid particle specimen is heated, cooled and
weighed in the same manner as described above. A slender glass tube
is then filled with approximately 20 g of the specimen. After that,
the glass tube is repeatedly dropped 400 times from a height of 4
cm. Then, the apparent specific volume is measured.
Sedimentation volume, apparent specific volume and fw of some
finely divided solid particles are exemplified in Table I.
Table I ______________________________________ Sedimenta- Apparent
Specific Solid particle tion volume specific No. in H.sub.2 O
volume fw gravity* (cc/g) (cc/g)
______________________________________ 1 Anhydrous silicic A 4.33
12.20 0.35 2.441 acid 2 " B 15.37 15.90 0.97 2.774 3 " C 3.51 -- --
3.576 4 Calcium aluminate 1.09 3.49 0.31 2.431 5 Calcium carbonate,
3.11 1.94 1.60 2.432 precipitated 6 Calcium carbonate, 1.26 1.22
1.03 2.676 prepared 7 Titanium dioxide, 1.71 1.19 1.44 4.080 rutile
8 Titanium dioxide, 1.90 1.27 1.50 3.783 anatase 9 Titanium dioxide
(particle size 5.21 6.80 0.77 3.430 30 m.mu.) 10 Zinc 2.59 1.17
2.21 5.715 flower A 11 Zinc 2.70 1.17 2.31 5.528 flower B 12 Zinc
peroxide 2.41 0.90 2.68 4.444 13 Talc A 3.80 1.79 2.12 2.612 14
Talc B 3.30 2.08 1.57 2.779 15 Talc C 3.51 0.25 3.69 2.599 16
Colloidal 1.14 1.77 0.64 2.503 kaolin 17 Inorganic 1.84 1.54 1.19
2.801 pearl agent 18 Bentonite 1.70 0.95 1.79 2.235 19 Alumina 0.31
1.02 0.30 1.826 20 Pearl calc 2.37 1.72 1.38 2.618 21 Antimony
oxide 1.69 0.74 2.28 5.520 22 Magnesium 2.54 2.51 1.01 2.648 oxide
23 Mica 2.17 1.83 1.19 2.789 24 Magnesium silicate- 5.26 2.67 1.97
2.719 aluminate 25 Yellow 12.28 4.70 2.61 3.539 iron oxide 26 Black
4.99 1.00 4.99 4.887 iron oxide 27 Bismuth 2.37 1.05 2.26 3.618
oxychloride 28 Zinc laurate 7.73 3.99 1.94 1.123 coated silica 29
Cellulose, micro- 5.72 1.90 3.01 1.412 crystalline 30 Nylon-12 2.94
2.04 1.44 1.018 31 Permant -- 4.00 -- 1.566 Orange 32 Carbon black
10.32 5.40 1.91 -- 33 Lithol 3.76 1.64 2.29 1.782 Rubine BCA 34
Polyvinyl 1.37 -- -- 1.460 chloride
______________________________________ Note: Determined on specimen
after heating at 105.degree.C for 2 hours.
Alternatively, hydrophilic characteristics of the solid particles
may be expressed in terms of hydrophilic coefficient. The
hydrophilic coefficient is represented by the ratio of
S.sub.H.sbsb.2O /S.sub.N.sbsb.2, wherein S.sub.H.sbsb.20 and
S.sub.N.sbsb.2 are the surface areas determined from adsorption
isotherms of water and gaseous nitrogen on the solid particles,
respectively, plotted according to Brunauer-Emmett-Teller equation.
The larger the hydrophilic coefficient, the greater the hydrophilic
property of the solid particles.
Hydrophilic coefficient of some finely divided solid particles are
exemplified in Table II.
Table II ______________________________________ No. Solid Particle
S.sub.N.sbsb.2 S.sub.H.sbsb.2 O S.sub.H.sbsb.2 O/S.sub.N.sbsb.2
(m.sup.2 /g) (m.sup.2 /g) ______________________________________ 1
Colloidal kaolin 11.3 17.0 1.50 2 Mica 8.6 12.0 1.40 3 Calcium
carbonate, precipitated 3.2 4.3 1.34 4 Titanium dioxide, rutile
11.3 15.4 1.36 5 Titanium dioxide, anatase 8.9 9.0 1.01 6 Yellow
iron oxide 25.3 25.1 0.99 7 Zinc flower A 4.8 4.5 0.94 8 Zinc
flower B 4.4 3.0 0.68 9 Zinc laurate 3.6 2.8 0.78 10 Talc A 4.1 2.3
0.56 11 Carbon black 215.8 97.7 0.45
______________________________________
The relationship between hydrophilic coefficient (S.sub.H.sbsb.20
/S.sub.N.sbsb.2) and sedimentation volume in water per unit of
apparent specific volume (fw) is shown in FIG. 5. Numerical
references indicated in FIG. 5 correspond to those of specimens
shown in Table II. As apparent from FIG. 5, S.sub.H.sbsb.20
/S.sub.N.sbsb.2 and fw exhibit a negative interrelationship.
The relationship between specific gravity and fw is shown in FIG.
6. Finely divided solid particles having a specific gravity and an
fw, both falling within the area expressed with hatching in FIG. 6
are preferably employed for the preparation of the liquid
composition of the present invention. FIG. 6 has been drawn on
various solid particle specimens in the case where a
di-2-hexyldecyl adipate-water-ethyl alcohol combination was
employed. However, a similar tendency has been observed in the case
where other combinations were employed.
With reference to the above considerations, finely divided solid
particles suitably employed in the present invention will be easily
chosen. Preferable solid particles depend upon the particular oil
and the particular liquid miscible with water. For example, finely
divided solid particles having an fw falling within the range of
0.5 to 3.5 are suitable for the combination of liquid paraffin and
an aqueous ethyl alcohol solution of a 78% concentration. When
finely divided solid particles do not have an fw falling within the
above range, a stable liquid composition wherein oil spheres are
dispersed is not obtainable. That is, the solid particles settle
down, and the oil phase and the aqueous phase separate from each
other above and below. Otherwise, the liquid composition becomes
cloudy, or oil spheres dispersed in the aqueous phase tend to be
incorporated with each other.
The number and size of oil spheres dispersed in the aqueous phase
can be easily varied by controlling the amount of finely divided
solid particles and oil employed. The size of oil spheres may be
varied within the range of 0.1 mm to 1.0 cm or more, preferably 1.0
mm to 5.0 mm, as expressed in diameter.
The manner of preparation of the two-phase type liquid cosmetic
composition of the present invention is not critical. Four
ingredients, oil, water, the organic liquid and finely divided
solid particles may be blended with each other concurrently or
sequentially in any order, by using a conventional blending device.
However, the liquid cosmetic composition is preferably prepared in
the following manner. First, water and the organic liquid miscible
with water are mixed with each other to prepare the homogeneous
mixture, followed by the addition of finely divided solid
particles. Then, oil is added to the mixture followed by agitation.
The resulting mixture is left to settle over a stated period, e.g.
one day.
The two-phase type liquid cosmetic composition of the present
invention may contain additives such as, for example, colorant,
perfume, antioxidant, ultraviolet ray absorber, antiseptic, wetting
agent, astringent, or other cosmetic base. The liquid cosmetic
composition has a wide variety of uses as hair or skin cosmetics
such as hair tonic or lotion, skin lotion or toilet water.
The invention will now be illustrated with reference to Examples.
In the Examples, all parts are parts by weight.
EXAMPLE 1
0.03 part of talc powder having an fw of 2.12 (made by NIHON
BIRYUSHI KOGYO, Japan) was incorporated into 90.0 parts of ethyl
alcohol. To the mixture, 10.0 parts of squalane (C.sub.30 H.sub.62,
made by NIKKO CHEMICALS CO., Japan) was added followed by
agitation. The mixture was settled over a period of one day. A
liquid composition of attractive appearance was obtained wherein
small translucent spheres of squalane were dispersed.
EXAMPLE 2
55.51 parts of ethyl alcohol and 7.41 parts of polyethylene glycol
having a molecular weight of approximately 300 were mixed with
18.55 parts of water. To the mixture, 0.01 part of magnesium
metasilicate aluminate powder, MgO . Al.sub.2 O.sub.3. 2SiO.sub.2
(trade name, Neusilin made by FUJI KAGAKU KOGYO, CO., Japan) and
18.52 parts of di-2-hexadecyl adipate (trade name, Eshelan 201 made
by Nihon Shono Co., Japan) were added in order followed by
agitation. The mixture was settled over a period of one day. A
liquid composition of attractive appearance was obtained wherein
small transparent spheres of di-2-hexadecyl adipate were
dispersed.
EXAMPLE 3
A liquid composition was prepared in the manner similar to that
described in Example 2 from the following ingredients.
______________________________________ Liquid paraffin (viscosity
150 sec/30.degree.C, trade name, Union SHP-280 made by Union Yushi
Co., Japan) 9.90 parts Ethyl alcohol 67.16 " Water 23.73 " Antimony
oxide (fw 2.28) 0.02 " ______________________________________
The liquid composition so prepared was of attractive appearance
wherein relatively small white spheres of liquid paraffin were
dispersed.
EXAMPLE 4
A liquid composition was prepared in the manner similar to that
described in Example 2 from the following ingredients.
______________________________________ di-2-Hexadecyl adipate 10.0
parts Ethyl alcohol 57.79 " Water 32.21 " Sodium chloride 0.1 "
Bismuth oxychloride (indicated in Table I as sample No. 27) 0.02
part ______________________________________
The liquid composition so prepared was of attractive appearance
wherein small pearl-like spheres of di-2-hexadecyl adipate were
dispersed, as shown in FIG. 7.
EXAMPLE 5
A liquid composition was prepared in the manner similar to that
described in Example 2 from the following ingredients.
______________________________________ Liquid paraffin 50.0 parts
Ethyl alcohol 41.32 " Water 8.68 " Sodium chloride 0.1 " Fish scale
powder 0.08 " ______________________________________
The liquid composition so prepared was of attractive appearance
wherein small pearl-like spheres of liquid paraffin were
dispersed.
EXAMPLE 6
A liquid composition was prepared in the manner similar to that
described in Example 2 from the following ingredients.
______________________________________ di-2-Hexadecyl adipate 47.61
parts Ethyl alcohol 35.68 " Water 11.93 " Polyethylene glycol
(molecular weight approximately 300) 4.76 " Magnesium metasilicate
aluminate 0.03 " ______________________________________
The liquid composition so prepared was of attractive appearance
wherein small transparent spheres of di-2-hexadecyl adipate were
dispersed, as shown in FIG. 8.
EXAMPLE 7
A liquid composition was prepared in the manner similar to that
described in Example 2 from the following ingredients.
______________________________________ Liquid paraffin 24.02 parts
Ethyl alcohol 59.17 " Water 1.593 " Bismuth oxychloride 0.07 "
______________________________________
The liquid composition so prepared was of attractive appearance
wherein relatively small pearl-like spheres of liquid paraffin were
dispersed, as shown in FIG. 9.
EXAMPLE 8
A liquid composition was prepared in the manner similar to that
described in Example 1 from the following ingredients.
______________________________________ Squalane 10.0 parts Ethyl
alcohol 90.0 " Bismuth oxychloride 0.01 "
______________________________________
The liquid composition so prepared was of attractive appearance
wherein relatively large pearl-like spheres of squalane were
dispersed, as shown in FIG. 10.
EXAMPLE 9
A liquid composition was prepared in the manner similar to that
described in Example 2 from the following ingredients.
______________________________________ Liquid paraffin 12.5 parts
di-2-Hexadecyl adipate 12.5 " Ethyl alcohol 54.87 " Water 20.13 "
Bismuth oxychloride 0.04 "
______________________________________
The liquid composition so prepared was of attractive appearance
wherein small pearl-like spheres of liquid paraffin and
di-2-hexadecyl adipate were dispersed, as shown in FIG. 11.
EXAMPLE 10
A liquid composition was prepared in the manner similar to that
described in Example 2 from the following ingredients.
______________________________________ di-2-Hexadecyl adipate 25.0
parts Liquid paraffin 25.0 " Ethyl alcohol 36.58 " Water 13.42 "
Nylon 12 (made by Toray Industries Inc., Japan) 0.06 "
______________________________________
The liquid composition so prepared was attractive appearance
wherein relatively small translucent spheres of di-2-hexadecyl
adipate and liquid paraffin were dispersed, as shown in FIG.
12.
EXAMPLE 11
A liquid composition was prepared in the manner similar to that
described in Example 2 from the following ingredients.
______________________________________ di-2-Hexadecyl adipate 25.0
parts Ethyl alcohol 48.16 " Water 26.84 " Sodium chloride 0.1 "
Titanium dioxide powder (particle size, approximately 30 m.mu.)
0.01 " ______________________________________
The liquid composition so prepared was of attractive appearance
wherein small translucent spheres of di-2-hexadecyl adipate were
dispersed.
EXAMPLE 12
A liquid composition was prepared in the manner similar to that
described in Example 2 from the following ingredients.
______________________________________ Liquid paraffin 5.0 parts
Oleyl alcohol 5.0 " Ethyl alcohol 79.58 " Water 10.42 " Talc
(indicated in Table I as sample No. 13) 0.02 "
______________________________________
The liquid composition so prepared was of attractive appearance
wherein very small translucent spheres of liquid paraffin and oleyl
alcohol were dispersed, as shown in FIG. 13.
EXAMPLE 13
A liquid composition was prepared in the manner similar to that
described in Example 2 from the following ingredients.
______________________________________ di-2-Hexadecyl adipate 18.52
parts Isopropyl alcohol 55.60 " Water 18.64 " Polyethylene glycol
(molecular weight, approximately 300) 7.41 " Magnesium metasilicate
aluminate 0.01 " ______________________________________
The liquid composition so prepared was of attractive appearance
wherein small transparent spheres of di-2-hexadecyl adipate were
dispersed.
* * * * *