U.S. patent application number 09/504949 was filed with the patent office on 2002-06-27 for organic silicone resin powder.
Invention is credited to Miyadai, Shinji, Nakanishi, Tersuo, Ono, Ichiro.
Application Number | 20020081323 09/504949 |
Document ID | / |
Family ID | 27289680 |
Filed Date | 2002-06-27 |
United States Patent
Application |
20020081323 |
Kind Code |
A1 |
Nakanishi, Tersuo ; et
al. |
June 27, 2002 |
Organic silicone resin powder
Abstract
An organic silicone resin powder having a tabular shape the
aspect ratio of which is greater than about 1 and comprising a
copolymer produced by polymerization reaction between an
organopolysiloxane containing at least one reactive group and at
least one kind of monomer or oligomer capable of reacting to said
reactive group, which can fully achieve its excellent effects when
mixed in cosmetic materials, waxes and coating colors, especially
in cosmetic materials.
Inventors: |
Nakanishi, Tersuo;
(Gunma-ken, JP) ; Ono, Ichiro; (Gunma-ken, JP)
; Miyadai, Shinji; (Gunma-ken, JP) |
Correspondence
Address: |
Millen White Zelano And Branigan PC
Arlington Courthouse Plaza I Suite 1400
2200 Clarendon Boulevard
Arlington
VA
22201
US
|
Family ID: |
27289680 |
Appl. No.: |
09/504949 |
Filed: |
February 16, 2000 |
Current U.S.
Class: |
424/401 |
Current CPC
Class: |
A61K 8/895 20130101;
A61Q 5/02 20130101; A61Q 1/06 20130101; A61Q 19/10 20130101; A61Q
5/12 20130101; A61Q 1/10 20130101; A61Q 1/12 20130101; A61Q 19/00
20130101; A61Q 15/00 20130101; A61Q 3/02 20130101 |
Class at
Publication: |
424/401 |
International
Class: |
A61K 006/00 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 17, 1999 |
JP |
038039/99 |
Feb 18, 1999 |
JP |
039532/99 |
Feb 14, 2000 |
JP |
034875/00 |
Claims
What is claimed is:
1. An organic silicone resin powder, having a tabular shape the
aspect ratio of which is greater than about 1 and comprising a
copolymer produced by polymerization reaction between an
organopolysiloxane containing at least one reactive group and at
least one kind of monomer or oligomer capable of reacting to said
reactive group.
2. An organic silicone resin powder according to claim 1, wherein
said reacting group is a radical polymerizable group and said
monomer or oligomer is a radical polymerizable monomer or
oiligomer.
3. An organic silicone resin powder according to claim 1, further
comprising an inorganic powder.
4. An organic silicone resin powder according to claim 2, further
comprising an inorganic powder.
5. A method of producing an organic silicone resin powder having a
tabular shape the aspect ratio of which is greater than about 1;
which comprises forming a film from a copolymer produced by
polymerization reaction between an organopolysiloxane containing at
least one reactive group and at least one kind of monomer or
oligomer capable of reacting to the reactive group, grinding the
film into a powder and putting the powder through a sieve.
6. A method of producing an organic silicone resin powder in
accordance with claim 5, wherein said reacting group is a radical
polymerizable group and said monomer or oligomer is a radical
polymerizable monomer or oiligomer.
7. A method of producing an organic silicone resin powder in
accordance with claim 5, wherein said film is formed using a
biaxial extruder.
8. A method of producing an organic silicone resin powder in
accordance with claim 6, wherein said film is formed using a
biaxial extruder.
9. A cosmetic material comprising an organic silicone resin powder
according to claim 1.
10. A cosmetic material comprising an organic silicone resin powder
according to claim 2.
11. A cosmetic material comprising an organic silicone resin powder
according to claim 3.
12. A cosmetic material comprising an organic silicone resin powder
according to claim 4.
13. A cosmetic material according to claim 9, wherein the organic
silicone resin powder is comprised in a proportion of about 0.01 to
about 50% by weight.
14. A cosmetic material according to claim 13, wherein the
copolymer has a number average molecular weight of from about 2,000
to about 100,000.
15. A cosmetic material according to claim 9, further comprising at
least one ingredient selected from oils, surfactants or
powders.
16. A cosmetic material according to claim 10, further comprising
at least one ingredient selected from oils, surfactants or
powders.
17. A cosmetic material according to claim 11, further comprising
at least one ingredient selected from oils, surfactants or
powders.
18. A cosmetic material according to claim 12, further comprising
at least one ingredient selected from oils, surfactants or powders.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to an organic silicone resin
powder comprising a copolymer produced by polymerization reaction
between a reactive group-containing organopolysiloxane and at least
one kind of monomer or oligomer capable of reacting to the reactive
group, which can improve the feel of cosmetics, wax, coating color
and like materials when the powder is mixed therewith, specifically
which can elevate spreadability of such materials as cited above,
that is, enables the materials to be applied more evenly and more
thinly, and further can ensure gloss in their outward
appearance.
[0002] Further, the invention is concerned with a cosmetic material
which contains an organic silicone resin powder comprising a
copolymer produced by the polymerization reaction between an
organopolysiloxane having reactive group(s) and at least one kind
of monomer or oligomer capable of reacting to the foregoing
reactive group(s) to improve adhesiveness as well as impressions
created by the application thereof, such as a dry feel and a
feeling of refreshment, and application characteristics, such as
spreadability.
BACKGROUND OF THE INVENTION
[0003] The cosmetic materials currently in use comprise a
composition containing an inorganic powder, such as titanium oxide,
mixed with a resin of hydrocarbon type or silicone type for the
purpose of improving the characteristics required therefor and
advancing such improvements. The characteristics required for
cosmetic materials, as mentioned above, include pleasant feels upon
application, such as a dry feel and a feeling of refreshment,
spreading properties, such as even and thin application, and
texture, such as gloss and color.
[0004] For instance, the cosmetic material containing a hydrocarbon
type of synthetic resin powder, such as powder of polyethylene
resin, polyamide resin, acrylic resin, vinyl chloride resin or
epoxy resin, is disclosed in Japanese Tokkai Sho 52-99236 (the term
"Tokkai" as used herein means an "unexamined published patent
application").
[0005] As examples of a cosmetic material into which a resin of
silicone type is compounded, mention may be made of the cosmetic
material disclosed in Japanese Tokkai Hei 1-268615, which contains
a powder of polyorganosilsesquioxane as a three-dimensionally
cross-linked silicone, and the cosmetic material containing finely
pulverized silicone rubber having elasticity as disclosed in
Japanese Tokko Hei 7-53646 (the term "Tokko" as used herein means
an "examined patent publication").
[0006] As to the inorganic powder, on the other hand, red iron
oxide and titanium oxide have hitherto been used as pigment, and
tabular powders, such as mica and sericite, have so far been used
as an essential component of nail color, nail coat, face powder,
mascara or eyeliner.
[0007] Those inorganic powders have hydroxyl groups on their
surfaces, so that they are generally used after undergoing
silicone, fluoropolymer, metallic soap or activator treatment for
weakening their surface activity and the cohesiveness thereof or
making the surfaces hydrophobic.
[0008] However, the cosmetic materials containing the hydrocarbon
type of synthetic resins as recited above are generally apt to have
high hardness, and so the application thereof occasionally arises a
uncomfortable feeling, such as a hard feel, in the users.
[0009] On the other hand, the cosmetic materials containing finely
pulverized silicone rubber can wipe away a hard feel, but they are
not easy to handle because of lack in fluidity and sometimes
difficult to homogeneously mix with other ingredients because of
their strong cohesiveness and their inferiority in
compatibility.
[0010] In general those conventional fine silicone particles are
prepared by an emulsion polymerization method. As a result, such
particles have a spherical shape or a shape close thereto. While
the spherical particles are used in a cosmetic material for the
purpose of improving the sliding properties and reducing a tacky
feel at the time the cosmetic material is applied to the skin, they
lower the adhesiveness of the cosmetic material to the skin because
of their shape. Therefore, it is usually tried to improve the
adhesiveness by compounding an inorganic tabular powder, such as
mica or sericite powder, into a cosmetic material.
[0011] However, those inorganic tabular powders have their specific
gravity in the range of 2-3, and so their specific gravity is
greater than those of other ingredients to constitute a cosmetic
material. In addition, they contain impurities because of natural
materials, and so they are dull in color. Accordingly, when such
heavy inorganic tabular powders are compounded into a liquid
cosmetic material, they cause a problem of precipitation. Further,
as the color of such powders become much darker when wetted by oil,
compounding with them lowers the color saturation of the resultant
cosmetic material.
SUMMARY OF THE INVENTION
[0012] The present invention is made aiming chiefly at dissolving
the aforementioned problems. More specifically, a first object of
the invention is to provide an organic silicone powder which, when
it is compounded with other ingredients into a composition, does
not arise in users of the composition an uncomfortable feeling,
such as a hard feel or a tacky touch, which is the problem of
conventional resin powders of hydrocarbon or silicone type, and
forms no sediment because of its low specific gravity, and further
can improve the texture of the composition, including the gloss and
the touch thereof, and the impressions that the users have upon
application thereof, such as spreadability and feels.
[0013] A second object of the invention is to provide a method of
producing the organic silicone resin powder as mentioned above.
[0014] A third object of the invention is to provide a cosmetic
material comprising a powder which can impart improved moist or dry
feel, and enhanced refreshing effect to the cosmetic material, can
elevate not only application characteristics, including
spreadability, but also adhesiveness, and further has improved
specific gravity, compatibility and dispersibility to form no
deposit.
[0015] One of the subject matters of the invention is an organic
silicone resin powder that has a tabular shape the aspect ratio of
which is greater than about 1 and comprises a copolymer produced by
polymerization reaction between an organopolysiloxane containing at
least one reactive group and at least one kind of monomer or
oligomer capable of reacting to the reactive group. Therein, the
reactive group may be a radical polymerizable group, while the
monomer or oligomer may have radical polymerizability. This organic
silicone resin powder may further comprise an inorganic powder.
[0016] Another subject matter of the invention is a method of
producing an organic silicone resin powder having a tabular shape
the aspect ratio of which is greater than about 1, with the method
comprising the steps of forming a film from a copolymer produced by
polymerization reaction between an organopolysiloxane containing at
least one reactive group and at least one kind of monomer or
oligomer capable of reacting to the reactive group, grinding the
film into a powder, and then putting the powder through a sieve.
Therein, the film may be formed using a biaxial extruder.
[0017] Still another subject matter of the invention is a cosmetic
material which contains an organic silicone resin powder having a
tabular shape the aspect ratio of which is greater about 1 and
comprising a copolymer produced by polymerization reaction between
an organopolysiloxane containing at least one reactive group and at
least one kind of monomer or oligomer capable of reacting to the
reactive group. In such a cosmetic material, the foregoing organic
silicone resin powder may be contained in a proportion of from
about 0.01 to about 50 weight %. In addition, the number average
molecular weight of the foregoing copolymer may be from about 2,000
to about 100,000. Further, the cosmetic material may further
contain at least one ingredient selected from the group consisting
of oils, surfactants and powders.
[0018] Herein, the term "aspect ratio" is defined as the b/a ratio,
when the thickness of a resin powder particle is taken as "a" and
the major axis thereof is taken as "b". Therefore, the particles
are regarded as more tabular the greater their aspect ratio is.
DETAILED DESCRIPTION OF THE INVENTION
[0019] The preferred embodiments of the present invention are
illustrated below. However, the invention should not be construed
as being limited to these embodiments.
[0020] The particles constituting the present organic silicone
resin powder have a tabular shape, and the thickness thereof is in
the range of about 0.1 .mu.m to about 2 .mu.m. Considered from the
standpoints of easiness of handling and impressions created by the
application thereof, it is desirable that their average particle
diameter on a volume equivalent basis (DP50) be from about 0.1 to
about 100 .mu.m, particularly preferably from 1 to 50 .mu.m. A
reason therefor is in that when the thickness and diameter of
particles are smaller than the foregoing range the gloss, which is
characteristic of powder, tends to be lost; while the particles
having greater thickness and diameter than the foregoing range tend
to give a rough feel.
[0021] Although the organic silicone resin powder having an aspect
ratio greater than about 1 can serve the present purpose, it is
desirable for the powder to have its aspect ratio in the range of 5
to 50 in order to further enhance its effects and make them more
certain.
[0022] The reactive group-containing organopolysiloxanes and the
monomers or oligomers capable of reacting to the reactive groups
contained in such organopolysiloxanes, which are usable in
producing copolymers according to the present invention, are
illustrated below.
[0023] The reactive group-containing organopolysiloxanes usable in
the invention are represented by the following formula;
A.sub.xR.sub.ySiO.sub.(4-x-y)/2
[0024] wherein A is a reacive group, R is a univalent hydrocarbon
group containing 1 to 10 carbon atoms, x is from 0.002 to 1.5 and y
is from 0 to 3.0, provided that 1.5.ltoreq.x+y.ltoreq.2.5.
[0025] The R groups which constitute the foregoing
organopolysiloxane molecule may be the same or different.
[0026] The reactive group represented by A is intended to include
functional groups having chemical reactivity. Suitable examples of
such a functional group include an amino group, a hydroxyl group,
an epoxy group, a carboxylic acid group, and radical polymerizable
groups, such as vinyl, styryl, .alpha.-methylstyryl, acryl and
methacryl groups.
[0027] Specifically, the reactive group-containing
organopolysiloxanes are, e.g., amino-modified silicones,
alcohol-modified silicones, epoxy-modified silicones, carboxylic
acid-modified silicones, vinyl-modified silicones, styrene-modified
silicones, bisphenol A-modified silicones, acrylic-modified
silicones, methacrylic-modified silicones, or maleic
anhydride-modified silicones.
[0028] Of the reactive group-modified silicones as recited above,
the modified silicones having acrylic reactive groups, such as
acrylate or methacrylate groups, are preferred over the others
because of their high reactivity, easiness of reaction control and
easy availability of raw materials.
[0029] As far as organopolysiloxanes have at least one reactive
group in their respective organopolysiloxane skeletons, they can
serve the present purpose. And, considering the reactivity, it is
desirable for the reactive group to be situated at a terminal
position of organopolysiloxane molecule.
[0030] Also, the organopolysiloxanes containing two or more of
reactive groups per molecule can be used in the invention, as seen
from the definition of x and y in the formula illustrated above,
and those reactive groups may be the same or different. In
addition, the organopolysiloxane used in the invention may have not
only a linear skeleton but also a branched skeleton.
[0031] Further, the organopolysiloxane used in the invention may be
a mixture of two or more of reactive group-containing
organopolysiloxanes differing in molecular weight.
[0032] As far as the reactive group-containing organopolysiloxane
selected from the aforementioned range is employed, the resultant
organic silicone resin powder can have improved spreadability and
give desirable impressions, e.g., a moist feel, to users.
[0033] The reactive monomers or oligomers usable for the production
of copolymers according to the present invention are monomers or
oligomers which each have a functional group capable of reacting to
the reactive groups contained in the organopolysiloxanes mentioned
above. More specifically, when the reactive group contained in an
organopolysiloxane used in copolymerization is an amino group, an
alcoholic group, an epoxy group, a carboxylic acid group or a
radical polymerizable group, the reactive group of the monomer or
oligomer to be selected for the copolymerization is a functional
group as a counterpart of the above-recited reactive group, namely
an epoxy group, a carboxylic acid group, an amino group, an
alcoholic group or a radical polymerizable group respectively.
[0034] In view of high reactivity, easy control of reaction and
easy availability of raw materials, similarly to the case of the
foregoing reactive group-containing organopolysiloxanes, it is
desirable for the reactive monomer or oligomer to be a monomer
containing a radical polymerizable group or an oligomer thereof.
Suitable examples of such a monomer or oligomer include a-olefins
(such as ethylene, propylene, butene, pentene, 4-methylpentene,
hexene, heptene, octene, vinylcyclohexene, styrene,
a-methylstyrene, vinyltoluene, vinylethylbenzene, vinylxylene,
p-t-butylstyrene and .alpha.-methyl-p-methylstyrene),
acrylonitrile, acrylic acid, methacrylic acid, methyl acrylate,
methyl methacrylate, butyl acrylate, 2-hydroxyethyl acrylate,
2-hydroxypropyl acrylate, 2-ethylhexyl acrylate, isobornyl
acrylate, dicyclopentenyl acrylate, 2-hydroxyethyl methacrylate,
N,N-diemthylacrylamide, N-vinylacetamide, N-vinylpyrrolidone,
N-vinylcaprolactame, acryloylmorpholine, N-vinylimidazole, maleic
anhydride, phenylimide, and oligomers of the monomers as recited
above.
[0035] Also, the reactive monomer may be a polyfunctional monomer,
such as tricyclodecanedimethanol diacrylate, pentaerythritol
triacrylate, trimethylolpropane triacrylate or
polyethylene(propylene) glycol diacrylate.
[0036] The reactive group-containing organopolysiloxane and the
reactive monomer or oligomer are properly selected from their
respective exemplifications as recited above, and subjected to
copolymerization reaction. In a special case where
organopolysiloxanes are grafted onto an organic resin by
copolymerization of a radical polymerizable monomer and a radical
polymerizable group-containing organopolysiloxane, it is
advantageous to use an organopolysiloxane having a radical
polymerizable group at one end of the siloxane chain.
[0037] The foregoing radical polymerizable monomer and radical
polymerizable group-containing organopolysiloxane can be
copolymerized in a conventional manner using a radical initiator,
such as benzoyl peroxide or azobisisobutyronitrile. As to the
method for copolymerization, any method of emulsion polymerization,
solution polymerization and block polymerization may be adopted
therein.
[0038] When the thus produced copolymer has hydroxyl groups, it may
be further reacted with a dibasic acid anhydride to convert a part
of the hydroxyl groups into carboxyl groups, thereby producing a
modified copolymer.
[0039] Further, the modified copolymer thus produced can be
neutralized with an alkali solution to be further converted into
the carboxylic acid salt.
[0040] The copolymers produced using the aforementioned methods
have their individual weight average molecular weight in the range
of 2,000 to 100,000, preferably 5,000 to 60,000.
[0041] When the copolymer has a weight average molecular weight
lower than 2,000, the powder thereof is brittle, and the cosmetic
material mixed therewith tends to have a tacky feel. When the
copolymer has a weight average molecular weight higher than
100,000, on the other hand, the powder thereof is apt to have high
hardness, and so the cosmetic material mixed therewith tend to have
a rough feel. Therefore, it is desirable for the present copolymers
to have their individual molecular weight within the foregoing
limits. Additionally, the aforementioned drawbacks are certain to
be removed as far as the weight average molecular weight is from
5,000 to 60,000.
[0042] Further, it is desirable that the compounding ratio of
reactive group-containing organopolysiloxanes to reactive monomers
or oligomers be in the range of 0.1/99.9 to 50/50, particularly
from 5/95 to 30/70, by weight.
[0043] When the reactive group-containing oranopolysiloxane is
compounded in a proportion lower than 0.1 weight %, the resultant
copolymer sometimes fails to exhibit marked characteristics of
organopolysiloxanes, including slipping properties; while, when it
is compounded in a proportion higher than 50 weight %, the glass
transition temperature thereof is liable to drop, the composition
containing the resultant copolymer, such as a cosmetic material,
tends to arise an uncomfortable feeling, e.g., a stiff feel, in
users.
[0044] Then, if the foregoing compounding ratio is selected from
the range of 5/95 to 30/70 by weight, it becomes certain that the
resultant copolymer can exhibit marked characteristics of
organopolysiloxanes, such as slipping properties, and can have a
glass transition temperature of at least 40.degree. C. to arise no
uncomfortable feeling.
[0045] For raising the molecular weight of the present copolymers,
various methods can be adopted, with examples including a method of
controlling the compounding ratio upon copolymerization, a method
of carrying out copolymerization using at least two kinds of
compounds for either or both of copolymerizable monomers (namely a
reactive monomer or oligomer and a reactive group-containing
organopolysiloxane), a method of carrying out copolymerization
using a polyfunctional group-introduced compound for either of
copolymerizable monomers, and a method of carrying out the
copolymerization of a reactive monomer or oligomer and a reactive
group-containing organopolysiloxane in the presence of compounds
reactive to the monomer or the oligomer and/or the
organopolysiloxane.
[0046] More specifically, when an olefin monomer containing a
carboxylic acid group is chosen as the reactive monomer, the olefin
monomer can undergo not only the dehydration condensation reaction
with an organopolysiloxane having alcoholic group(s) reactive to
the carboxylic acid group and a polyhydric alcohol, such as glycol,
but also radical polymerization, thereby producing a copolymer.
[0047] In another case of copolymerization, the olefin monomer
containing an epoxy group instead of the carboxylic acid group in
the foregoing case is chosen as the reactive monomer, and the
addition reaction may be carried out using such an olefin monomer
in combination with an organopolysiloxane containing amino group(s)
instead of the alcoholic group(s) in the foregoing case and an
amino compound.
[0048] Instead of using polyfunctional reactive monomers in the
copolymerization reaction, the organopolysiloxane used therein
maybe chosen from polyfunctional organopolysiloxanes.
[0049] In the next place, the method of preparing the present
organic silicone resin powder having a tabular shape and an aspect
ratio greater than about 1, which can be mixed in cosmetic
materials, is illustrated below.
[0050] After the copolymer is produced in accordance with any of
the aforementioned methods, the resin component is separated by
distilling off the solvent, or it is reprecipitated as a powdery
matter with methanol or the like and then filtered off.
[0051] During, before or after the copolymerization reaction, an
inorganic matrix, such as an inorganic powder (e.g., titanium
oxide, mica or titanium mica), a pearl brightener or an inorganic
pigment, and general additives for synthetic resins, such as a
lubricant (e.g., silicone oil), an antistatic agent, an ultraviolet
absorbent and an antioxidant, can be added to the reaction
system.
[0052] Thus, the powder having the desired outward appearance,
which was impossible for conventional inorganic powders to have,
can be obtained.
[0053] The resin component thus obtained is made into a tabular
powder in a manner as described below: For instance, the resin
component is dissolved in an organic solvent, made into a thin
film, and then ground into a powder. In another manner, the resin
component may be formed into a film by means of a biaxial extruder,
and further stretched. In still another manner, the powder obtained
by reprecipitation may be dried, and then ground into a fine
powder. Anyhow, a tabular powder which can make the same impression
as mica on users can be formed by coating a solution of resin
component on a base in a filmy layer, similarly to the case of
preparing release paper, peeling the layer away from the base and
then grinding it.
[0054] In pulverizing the resin component obtained, hitherto known
grinder, such as a primary crusher (e.g., a cutter mill, a hammer
mill or a jaw crusher) or a pulverizer (e.g., a stamp mill, a jet
mill, a ball mill, a roller mill, a pin-type mill or an impeller
mill), may be employed. Additionally, the apparatus as recited
above may be used under a cooled or heated condition.
[0055] The thus obtained powder is sifted out by means of a
classifier to prepare organic silicone resin particles having a
tabular shape and the desired diameter and aspect ratio.
[0056] Further; the tabular particles thus prepared may undergo a
surface treatment using, e.g., metal soap, alumina, silica or
phosphoric acid.
[0057] The average particle diameter of tabular powder on a volume
equivalent basis (D.sub.p50) is determined by a screening method, a
laser method or a centrifugal sedimentation method. The average
thickness of tabular particles is calculated by selecting several
particles arbitrarily from the particles in the visual field of an
electron microscope, measuring their respective thicknesses, and
calculating the average value of the measured values. And the
aspect ratio is calculated from the thus measured average particle
diameter and thickness.
[0058] The organic silicone resin powder prepared in the manner as
mentioned above is mixed as one ingredient of a cosmetic material
in a proportion of, e.g., 0.01 to 50 weight %.
[0059] When the proportion of the powder mixed is smaller than 0.01
weight %, the resultant cosmetic material cannot have desirable
feels, such as a dry feel, in some cases; while the proportion
increased beyond 50 weight % tends to impair the applicability of
the resultant cosmetic material, such as smooth and even
spreadability. Therefore, it is desirable for the porportion of the
powder mixed to be in the foregoing range. The more suitable range
thereof is from 0.05 to 20 weight %, and this range is certain to
remove the foregoing drawbacks.
[0060] The cosmetic materials containing the aforementioned organic
silicone resin powder can have a remarkable reduction in specific
gravity, compared with those containing conventional inorganic
powders, so that they can successfully avoid precipitating the
powder by aging.
[0061] Further, even an uncomfortable texture, such as a rough or
tacky touch, the cosmetic materials tend to have when they contain
a conventional resin of hydrocarbon type or silicone type
respectively as an ingredient thereof, can be dissolved by adding
thereto the present organic silicone resin powder which is made up
of a copolymer having improved compatibility and dispersibility,
and further has a tabular shape having an aspect ratio greater
about 1. Moreover, the addition of the present organic silicone
resin powder makes it possible to impart only the advantageous
properties each resin has by nature, such as stability and a moist
feel, to cosmetic materials.
[0062] As mentioned above, the present powder is remarkably
improved in not only properties but also easiness of handling,
compared with hitherto employed inorganic powders, so that it can
be a highly satisfactory substitute for conventional inorganic
powders.
[0063] In the cosmetic materials according to the invention, other
ingredients can be mixed, with examples including the
following:
[0064] A wide variety of oils can be mixed depending on the
intended purpose of the cosmetic material to be prepared. The oils
mixed may be in any of solid, semisolid and liquid states.
[0065] More specifically, not only natural animal and vegetable
fats and oils but also semi-synthetic fats and oils are usable in
the present cosmetic material. Examples thereof include avocado
oil, linseed oil, almond oil, insect wax, perilla oil, olive oil,
cacao butter, kapok wax, kaya oil, carnauba wax, liver oil,
candellila wax, beef tallow, beef foot oil, beef bone fat,
hydrogenated beef tallow, apricot kernel oil, spermaceti,
hydrogenated oil, wheat germ oil, sesame oil, rice germ oil,
ricebran oil, sugarcanewax, sasanquaoil, saffloweroil, shea butter,
Chaisese tung oil, cinnamon oil, jojoba wax, shellac wax, turtle
oil, soybean oil, tea seed oil and tsubaki oil.
[0066] Other Examples of natural animal and vegetable fats and oils
and semi-synthetic fats and oils which can be used herein include
evening primrose oil, corn oil, lard, rape seed oil, Japanese tung
oil, rice-bran wax, germ oil, horse fat, persic oil, palm oil, palm
kernel oil, castor oil, hydrogenated castor oil, methyl caster oil
fatty acid, sunflower oil, grape seed oil, bayberry wax, jojoba
oil, macadamia nut oil, beeds wax, mink oil, cottonseed oil, cotton
wax, Japan wax, haze kernel oil, montan wax, coconut oil,
hydrogenated coconut oil, tricoconut oil fatty acid glyceride,
mutton-tallow, peanut oil, anhydrous lanolin, hard lanolin, lanolin
acetate, lanolin fatty acid isopropyl, hexyl laurate, POE lanolin
alcohol ether, POE lanolin alcohol acetate, polyethylene glycol
lanolin fatty acid, POE hydrogenated lanolin alcohol ether, and egg
yolk oil.
[0067] As examples of hydrocarbon oil which can be added, mention
may be made of ozokerite, squalane, squalene, ceresine, paraffin,
liquid paraffin, pristane, polyisobutylene, microcrystalline wax
and Vaseline.
[0068] As examples of a higher fatty acid which can be added,
mention may be made of lauric acid, myristic acid, palmitic acid,
stearic acid, behenic acid, undecylenic acid, oleic acid, linoleic
acid, linolenic acid, arachidonic acid, eicosapentaenoic acid
(EPA), docosahexaenoic acid (DHA), isostearic acid and
12-hydroxystearic acid.
[0069] As examples of a higher alcohol which can be added, mention
may be made of lauryl alcohol, myristyl alcohol, stearyl alcohol,
behenyl alcohol, hexadecyl alcohol, oleyl alcohol, isostearyl
alcohol, hexyldecanol, octyldodecanol, cetostearyl alcohol,
2-decyltetradecinol, cholesterol, phytosterol, POE cholesterol
ester, glycerin monostearyl (batyl alcohol) and monooleyl glycerin
ether (cerakyl alcohol).
[0070] As examples of ester oil which can be added, mention may be
made of diisobutyl adipate, 2-hexyldecyl adipate,
di-2-heptylundecyl adipate, N-alkylglycol monoisostearates,
isocetyl isostearate, trimethylolpropane triisostearic acid ester,
ethylene glycol di-2-ethylhexanoic acid ester, cetyl
2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoic acid
ester, pentaerythritol tetra-2-ethylhexanoic acid ester, cetyl
octanoate, octyldodecyl gum ester, oleyl oleate, octyldodecyl
oleate, decyl oleate, neopentyl glycol dicapric acid ester,
triethyl citrate, 2-ethylhexyl cinnamate, amyl acetate, ethyl
acetate, butyl acetate, isocetyl stearate and butyl stearate.
[0071] Other examples of usable esters include diisopropyl
sebacate, di-2-ethylhexyl sebacate, cetyl lactate, myristyl
lactate, isopropyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl
palmitate, 2-heptylundecyl palmitate, cholesteryl
12-hydroxystearate, dipentaerythritol fatty acid esters, isopropyl
myristate, 2-octyldodecyl myristate, 2-hexyldecyl myristate,
myristyl myristate, hexyldecyl dimethylocanoate, ethyl laurate,
hexyl laurate, N-lauroyl-L-glutaminic acid 2-octyldodecyl ester and
diisostearyl malic acid.
[0072] As examples of glyceride oil which can be added, mention may
be made of acetoglyceride, triisooctanoic acid glycride,
triisostearic acid glyceride, triisopalmitic acid glyceride,
tri-2-ethylhexanoic acid glyceride, monostearic acid glyceride,
di-2-heptylundecanoic acid glyceride and trimyristic acid
glyceride.
[0073] As examples of silicone oil which can be added, mention may
be made of dimethylpolysiloxane, methylphenylpolysiloxane,
methylhydrogenpolysiloxane, octamethylcyclotetrasiloxane,
decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane,
tetramethyltetrahydrogencyclotetrasiloxane, higher alkoxy-modified
silicones such as stearoxysilicone, and higher fatty acid-modified
silicones.
[0074] As examples of fluorine-containing oil which can be added,
mention may be made of perfluoropolyether, perfluorodecalin and
perfluorooctane.
[0075] Additionally, the oils recited above may be added alone or
as mixtures of at least two among them.
[0076] Further, the present cosmetic material can contain a
surfactant, if desired, and has no particular restriction as to the
type of surfactant used. In other words, any of anionic, cationic,
amphoteric and nonionic surfactants can be used therein.
[0077] Examples of a usable anionic surfactant include fatty acid
soap, such as sodium stearate and triethanolamine palmitate;
polyoxyethylene fatty alcohol ether carboxylic acids and salts
thereof; carboxylates, such as condensates of amino acids and fatty
acids; alkylsulfonate; alkenesulfonate; sulfonated fatty acid
ester; sulfonated fatty acid amide; alkylsulfonic acid-formaldehyde
condensate; alkylsulfate; higher secondary alcohol sulfate; alkyl
and aryl ether sulfate; fatty acid ether sulfate, fatty acid
alkylolamide sulfate; ether sulfate, such as Turkeky red oil; alkyl
phosphate; ether phosphate; alkyl aryl ether phosphate; amide
phosphate; and active agents of N-acylamino acid type.
[0078] Examples of a usable cationic surfactant include amine
salts, such as alkylamie salts, polyamines and aminoalcohol fatty
acid derivatives, quaternary alkylammonium salts, quaternary
arylammonium salts, pyridinium salts and imidazolium salts.
[0079] Examples of a usable amphoteric surfactant include betaine,
aminocarboxylate and imdazoline derivatives.
[0080] Examples of a usable nonionic surfactant include sorbitan
fatty acid esters, glycerin fatty acid esters, polyglycerin fatty
acid esters, propylene glycol fatty acid esters, polyethylene
glycol fatty acid esters, sucrose fatty acid esters,
polyoxyethylene alkyl ethers, polyoxypropylene alkyl ethers,
polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid
esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene
sorbitol fatty acid esters, polyoxyethylene glycerin fatty acid
esters, polyoxyethylene propylene glycol fatty acid esters,
polyoxyethylene castor oil, polyoxyethylene hardened castor oil,
polyoxyethylene phytostanol ehter, polyoxyethylene phytosterol
ether, polyoxyethylene cholestanol ether, polyoxyethylene
cholesteryl ether, polyoxyalkylene-modified organopolysiloxanes,
organopolysiloxanes modified with both polyoxyalkylene and alkyl
groups, alkanolamides, sugar ethers and sugar amides.
[0081] Furthermore, the following powders can be used in the
present cosmetic material.
[0082] Such powders are not particularly restricted as to their
shape, size and structure, and may have any shape, size and
structure as far as the powders used in conventional cosmetic
materials have them. Specifically, they may have any of spherical,
acicular and tabular shapes, any of haze-particle, fine-particle
and pigment-grade sizes and any of structures (e.g., a porous or
nonporous structure).
[0083] When such a powder is mixed in the present cosmetic
material, it is not limited to only one among the powders recited
below, but may be used together with another powder equivalent in
effect. In addition, the powders recited below may be used as a
mixture of two or more thereof. The suitable amount of powders
mixed is determined depending on the desired purpose.
[0084] Examples of an organic powder include polyamide powder,
polyester powder, polyethylene powder, polypropylene powder,
polystyrene powder, polyurethane powder, benzoguanamine powder,
polymethylbenzoguanamine powder, tetrafluoroethylene powder,
polymethylmethacrylate powder, cellulose powder, silk powder, nylon
powder, 12-nylon powder, 6-nylon powder, styrene-acrylic acid
copolymer powder, divinylbenzene-styrene copolymer powder, vinyl
resin powder, urea resin powder, phenol resin powder, fluororesin
powder, silicone resin powder, acrylic resin powder, melamine resin
powder, epoxy resin powder, polycarbonate resin powder,
microcrystalline fiber powder, rice starch powder and lauroyl
lysine.
[0085] Examples of a metal salt surfactant powder (metal soap
powder) include zinc stearate, aluminum stearate, calcium stearate,
magnesium stearate, zinc myristate, magensium myristate, zinc
cetylphosphate, calcium cetylphosphate and zinc sodium
cetylphosphate.
[0086] Examples of an inorganic powder include titanium oxide,
zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium
sulfate, calcium sulfate, magnesium sulfate, calcium carbonate,
magnesium carbonate, talc, mica, kaolin, sericite, synthetic mica,
muscovite, phlogopite, ruby mica, biotite, lipidolite, silicic
acid, silicic acid anhydride, aluminum silicate, magnesium
silicate, aluminum magnesium silicate, calcium silicate, barium
silicate, strontium silicate, metal salts of tungstic acid,
hydroxyapatite, vermiculite, haidilite, bentonite, montmorillonite,
hectorite, zeolite, ceramics powder, calcium secondary phosphate,
alumina, aluminum hydroxie, boron nitride, silica, titanium mica,
iron oxide red, iron oxide black, iron oxide yellow and barium
ferrite. The inorganic powder as recited above may be added in
advance to the present organic silicone resin powder, and then
mixed in a cosmetic material.
[0087] The colors include both inorganic and organic pigments. The
inorganic powders as recited above are comprised in the inorganic
pigment. More specifically, the inorganic pigment includes
inorganic red pigments, such as iron oxide iron hydroxide and iron
titanate; inorganic brown pigments, such as y-iron oxide; inorganic
yellow pigments, such as iron oxide yellow and loess; inorganic
black pigments, such as iron oxide black and carbon black;
inorganic violet pigments, such as Mango violet and cobalt violet;
inorganic green pigments, such as chromium hydroxide, chromium
oxide, cobalt oxide and cobalt titanate; inorganic blue pigments,
such as Prussian blue and ultramarine blue; lakes of tar pigments;
lakes of natural pigments; and synthetic resin powder complexes of
the inorganic pigmnents as recited above.
[0088] As examples of a pearl pigment, mention may be made of
titanium oxide-coated mica, bismuth oxychloride, titanium
oxide-coated bismuth oxychloride, titanium oxide-coated talc, fish
scales, and titanium oxide-coated colored mica.
[0089] As examples of a metallic powder pigment, mention may be
made of aluminum powder, copper powder and stainless powder.
[0090] The foregoing tar pigments include Red No. 3, Red No.104,
Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205,
Red No. 220, Red No. 226, Red No. 227, Red No. 228, Red No. 230,
Red No. 401, Red No. 505, Yellow No. 4, Yellow No. 5, Yellow No.
202, Yellow No. 203, Yellow No. 204, Yellow No. 401, Blue No. 1,
Blue No. 2, Blue No. 201, Blue No. 404, Green No. 3, Green No. 201,
Green No. 204, Green No. 205, Orange No. 201, Orange No. 203,
Orange No. 204, Orange No. 206 and Orange No. 207 (according to the
pigment nomenclature method in JIS).
[0091] The foregoing natural pigments include carminic acid,
laccaic acid, carthamin, bradilin and crocin.
[0092] Additionally, complexes of the powders as recited above or
those obtained by treating the aforementioned powders with general
oil, silicone oil or fluorine-containing compound may be used. Of
course, the powders as recited above may be used as a mixture of
two or more thereof.
[0093] To the present cosmetic material, the ingredients used in
general cosmetic materials, such as water, alcohols, water-soluble
polymers, film-forming agents, oil-soluble gelling agents, clay
minerals modified with organic compounds, resin, ultraviolet
absorbents, moisture-holding agents, antiseptics, antibacterial
agents, perfume, salts, antioxidants, pH regulators, chelating
agents, tonic, skin beautifying components, vitamins, amino acids,
nucleic acids, hormones and clathrate compounds, can be added so
far as they have no adverse influence on the effects of the present
invention.
[0094] Examples of usable alcohols include lower alcohols, such as
ethanol and isopropanol; sugar alcohols, such as sorbitol and
maltose; and sterols, such as cholesterol, phytosterol and
lanosterol.
[0095] Examples of usable water-soluble polymers include vegetable
polymers, such as gum arabic, tragacanth, arabine galactan, carob
gum, guar gum, karaya gum, carrageenan, pectin, agar, quince seed,
starch (rice, corn, potato, wheat), alge colloid, tranto gum and
locust bean gum; microbial polymers, such as xanthan gum, dextran,
succinoglucan and pullulan; animal polymers, such as collagen,
casein, albumin and gelatin; starch polymers, such as carboxymethyl
starch and methylhydroxypropyl starch; and cellulose polymers, such
as methyl cellulose, ethyl cellulose, methylhydroxypropyl
cellulose, carboxymethyl cellulose, hydroxymethyl cellulose,
hydroxypropyl cellulose, nitrocellulose, sodium cellulose sulfate,
sodium carboxymethylcellulose, microcrystalline cellulose and
powdery cellulose.
[0096] As other examples of usable water-soluble polymers, mention
may be made of alginic acid polymers, such as sodium alginate and
propylene glycol ester of alginic acid; vinyl polymers, such as
polyvinyl methyl ether and carboxyvinyl polymer; polyoxyethylene
polymers; polyoxyethylene-polyoxypropylene copolymers; acrylic
polymers, such as sodium salts of polyacrylic acid,
polyethylacrylate and polyacrylamide; polyethyleneimines; cationic
polymers; and inorganic water-soluble polymers, such as bentonite,
aluminum magnesium silicate, laponite, hectorite and silicic acid
anhydride.
[0097] Therein, film-forming agents, such as polyvinyl alcohol and
polyvinyl pyrrolidine, may be included.
[0098] Examples of an oil-soluble gelling agent which can be used
herein include metal soaps, such as aluminum stearate, magnesium
stearate and zinc myristate; amino acid derivatives, such as
N-lauroyl-L-glutamic acid and .alpha.,.gamma.-di-n-butylamine;
dextrin fatty acid esters, such as dextrin palmitic acid ester,
dextrin stearic acid ester and dextrin 2-ethylhexaminic acid
palmitic acid ester; sucrose fatty acid esters, such as sucrose
palmitic acid ester and sucrose stearic acid ester; benzylidene
derivatives of sorbitol, such as monobenzylidene sorbitol and
dibenzylidene sorbitol; and clay minerals modified with organic
compounds, such as dimethylbenzyldodecyl ammonium montmorillonite
clay and dimethyldioctadecyl ammonium montmorillonite clay.
[0099] Examples of an ultraviolet absorbent which can be used
herein include those of benzoic acid type, uch as p-aminobenzoic
acid; hose of anthranilic acid type, uch as methyl anthrarilate;
hose of salicylic acid type,such as methyl salicylate; those of
succinic acid type, such as octyl p-methoxysuccinate; those of
benzophenone type, such as 2,4-dihydroxybenzophenone; and those of
urocanic acid type, such as ethyl urocanate.
[0100] Examples of a moisture-holding agent which can be used
herein include sorbitol, xylitol, polyethylene glycol, hyaluromic
acid, chondroitin sulfuric acid and pyrrolidone carboxylic
acid.
[0101] Examples of an antiseptic which can be used herein include
alkyl p-hydroxybenzoates, benzoic acid, sodium benzoate, sorbic
acid, potassium sorbate and phenoxyethanol.
[0102] Examples of an antimacrobial agent which can be used herein
include benzoic acid, salicylic acid, carbolic acid, sorbic acid,
alkyl p-hydroxybenzoates, p-chlorometacresol, hexachlorophene,
benzalkonium chloride, chlorhexidine chloride,
trichlorocarbanilide, photosensitizer and phenoxyethanol.
[0103] Examples of an antioxidant which can be used herein include
tocopherol, butylhydroxyanisole, dibutylhydroxy-toluene and
.gamma.-oryzanol.
[0104] Examples of a pH regulator which can be used herein include
lactic acid, citric acid, glycolic acid, succinic acid, tartaric
acid, dl-malic acid, potassium carbonate, sodium hydrogen carbonate
and ammonium hydrogen carbonate.
[0105] Examples of a chelating agent which can be used herein
include alanine, sodium ethylenediaminetetraacetate, sodium
polyphosphate, sodium metaphosphate and phosphoric acid. Examples
of a tonic which can be used herein include L-menthol and
camphor.
[0106] Examples of an anti-inflammatory agent which can be used
herein include allantoin, glycyrrhetinic acid, tranexamic acid and
azulene.
[0107] Examples of a skin-beautifying component which can be used
herein include whitening agents, such as placenta extract, arbutin,
glutathione and Ykinoshita extract; cell activators, such as royal
jelly, photosensitizer, cholesterol derivatives and calf blood
extract; and rough dry skin improvers, including blood circulation
improvers such as nonylic acid vanillyl amide, benzyl nicotinate,
.beta.-butoxyethyl nicotinate, zingerone, cantharis tincture,
ichtammol, caffeine, tannic acid, .alpha.-borneol, tocopheryl
nicotinate, inositol hexanicotinate, cyclandelate, cinnarizine,
tolazoline, acetyl choline, verapamil, cepharanthin and
.gamma.-oryzanol, skin astringents such as zinc oxide and tannic
acid, and anti-seborrheic agents such as sulfur and thianthol.
[0108] Examples of vitamins which can be used herein include
vitamin A, such as vitamin A oil, retinol, retinyl acetate and
retinyl palmitate; vitamin B.sub.2, such as riboflavin, riboflavin
buyrate and flavin adenine nucleotide; vitamin B.sub.6, such as
pyridoxine hydrochloride and pyridoxine dioctanoate; vitamin C,
such as L-ascorbic acid, L-ascorbic acid dipalmitic ester, disodium
(L-ascorbic acid)-2-sulfate and dipotassium
dl-(-tocopherol-L-ascorbic acid phosphoric diester; vitamin D,
pantothenic acids, such as calcium pantothenate, D-pantothenyl
alcohol, pantothenyl ethyl ether and acetylpantothenyl ethyl ether,
ergocalciferol and cholecarciferol; vitamin E, including nicotinic
acids such as nicotinic acid, benzyl nicotinate and nicotinic acid
amide, dl-.alpha.-tocopherol, dl-.alpha.-tocopheryl acetate,
dl-.alpha.-tocopheryl nicotinate and dl-.alpha.-tocopheryl
succinate; vitamin P; and biotin.
[0109] Examples of an amino acid which can be used herein include
alginine, aspartic acid, cystine, cysteine, methionine, serine,
leucine and tryptopphan; an example of usable nucleic acids is
deoxyribonucleic aicd; and examples of usable hormone are estradiol
and ethenyl estradiol.
[0110] The term "cosmetic material" as used herein are intended to
include preparation products in all fields where the feel is
regarded as important when they are put on the skin, including not
only cosmetics but also medicines for external application, and
further enamel for manicure and hairdressing products.
[0111] More specifically, the present cosmetic material includes
skin care products, such as face lotion, milky lotion, cream,
facial pack, massage articles, lip cream, hand cream and cleaning
articles; makeup products, such as face powder, foundation, rouge,
eye shadow, mascara, eyeliner, eyebrow articles, overcoat articles
and lipstick; nail-beautifying articles, such as enamel for
manicure; and hairdressing products, such as shampoo, rinse,
rinse-in-shampoo, treatment, conditioner, hair cream, hair oil,
brushing articles, hair-set articles and hair tonic.
[0112] Additionally, the present cosmetic material may have any of
forms, including liquid, emulsion, solid, cream, paste,
multi-layer, mousse, gel and spray forms, if desired.
[0113] Besides the cosmetics, the present organic silicone resin
powder can be used in the field of coating, e.g., for a releasable
coating agent, a protective coating agent, a water-repellant
coating agent, printing ink, coating color or wax.
[0114] The present invention will now be illustrated in greater
detail by reference to the following examples and comparative
examples.
[0115] Additionally, the entire disclosure of all applications,
patents and publications, cited above and below, and of
corresponding Japanese applications No. 11-038039 and 11-039532,
filed on February. 17 and February 18 respectively in 1998, is
hereby incorporated by reference.
EXAMPLE 1
[0116] Preparation of Tabular Powder of Organic Silicone Resin:
[0117] Toluene in an amount of 100 parts was placed in a glass-made
reaction vessel equipped with a stirrer, a reflux condenser, a
thermometer and a nitrogen introduction tube, and thereinto
nitrogen gas was blown to remove the dissolved oxygen from the
toluene. Thereto, 70 parts by weight of styrene and 30 parts by
weight of Organopolysiloxane (1) represented by the following
formula (i) were added, and then 0.2 parts by weight of
azobisisobutyronitrile was added as the reaction vessel was kept at
a temperature of 80.degree. C. 1
[0118] Further, 0.2 parts by weight portions of
azobisisobutyronitrile were added at intervals of two hours till
the non-volatile component concentration in the reaction solution
was increased beyond 50%. After the reaction was completed, the
resulting solution was cooled to room temperature, and poured into
300 parts by weight of methanol to deposit a colorless powdery
resin. The thus deposited resin was filtered off, dried, and
examined for molecular weight and glass transition point by GPC
measurement and differential scanning calorimetry (DSC),
respectively. Thus, it was found that the weight average molecular
weight of the resin obtained was 43, 000 on a polystyrene basis and
the glass transition point thereof was 62.degree. C.
[0119] The thus synthesized resin was dissolved in toluene, applied
to an aluminum plate, and then dried to form a film. The film thus
formed was ground into a powder by a jet mill, and put through a
325-mesh sieve. Thus, a tabular powder of organic silicone resin
having an average particle size of 30 .mu.m was obtained. The
particles constituting the thus obtained tabular powder had an
average aspect ratio of 32, determined from electron micrographs
thereof.
EXAMPLE 2
[0120] Preparation of Tabular Powder of Organic Silicone Resin:
[0121] Toluene in an amount of 40 parts was placed in a glass-made
reaction vessel equipped with a stirrer, a reflux condenser, a
thermometer and a nitrogen introduction tube, and thereinto
nitrogen gas was blown to remove the dissolved oxygen from the
toluene. Thereto was added dropwise a mixture of 24 parts by weight
of methyl methacrylate, 6 parts by weight of butyl methacrylate, 4
parts by weight of 2-hydroxyethyl acrylate and 6 parts by weight of
Organopolysiloxane (2) represented by the following formula
together with 0.6 parts by weight of azobisisobutyronitrile while
keeping the reaction vessel temperature at 90.degree. C. 2
[0122] After 2-hour lapse, the reaction solution was further mixed
with 0.2 parts by weight of azobisisobutyronitrile, and ripened for
five hours to complete the reaction. After the completion of the
reaction, the resultant solution was cooled to room temperature,
and thereto methyl ethyl ketone was added to thoroughly dissolve
the resin component, followed by filtration.
[0123] The thus obtained synthetic resin solution was processed in
the same manner as in Example 1, thereby preparing a tabular powder
of organic silicone resin having a weight average molecular weight
of 28,000 and a glass transition point of 80.degree. C. And the
organic silicone resin powder obtained herein had an powder of
organic silicone resin having a weight average molecular weight of
28,000 and a glass transition point of 80.degree. C. And the
organic silicone resin powder obtained herein had an average
particle size of 24 gm and an average aspect ratio of 28.
EXAMPLE 3
[0124] Preparation of Tabular Powder of Organic Silicone Resin:
[0125] The foregoing Organopolysiloxane (2) in an amount of 10
parts by weight and methyl ethyl ketone in an amount of 60 parts
were placed in a glass-made reaction vessel equipped with a
stirrer, a reflux condenser, a thermometer and a nitrogen
introduction tube, and thereinto nitrogen gas was blown to remove
the dissolved oxygen. Thereto were added dropwise a mixture of 26
parts by weight of methyl methacrylate with 4 parts by weight of
methacrylic acid and 0.2 parts by weight of azobisisobutyronitrile
while keeping the reaction vessel temperature at 80.degree. C.
After 7-hour lapse, 0.2 parts by weight of azobisisobutyronitrile
was further added to the reaction solution, and the ripening was
carried out for four hours to complete the reaction. After the
completion of the reaction, the resultant solution was cooled to
room temperature, and poured into 300 parts by weight of methanol
to precipitate a colorless powdery resin.
[0126] The powdery resin obtained was dissolved in methyl ethyl
ketone, and the resultant resin solution was processed in the same
manner as in Example 1, thereby preparing a tabular powder of
organic silicone resin having a weight average molecular weight of
32,000 and a glass transition point of 110.degree. C. And the
organic silicone resin powder obtained herein had an average
particle size of 15 .mu.m and an average aspect ratio of 19 .
EXAMPLE 4
[0127] Preparation of Tabular Powder of Organic Silicone Resin:
[0128] Toluene in an amount of 100 parts was placed in a glass-made
reaction vessel equipped with a stirrer, a reflux condenser, a
thermometer and a nitrogen introduction tube, and thereinto
nitrogen gas was blown to remove the dissolved oxygen from the
toluene. Thereto, 70 parts by weight of styrene, 30 parts by weight
of Organopolysiloxane (1) illustrated above and 0.5 parts by weight
of trimethoxymethacryloylpropyl- silane were added, and then 0.2
parts by weight of azobisisobutyronitrile was added as the reaction
vessel was kept at a temperature of 80.degree. C. Further, 0.2
parts by weight portions of azobisisobutyronitrile were added at
intervals of two hours till the non-volatile component
concentration in the reaction solution was increased beyond 50%.
After the reaction was completed, a small portion of the reaction
solution was taken out, dried, and subjected to molecular weight
measurement by GPC. The thus determined weight average molecular
weight of the reaction product was 45,000 on a polystyrene basis.
Then, the reaction solution was mixed with 2 parts by weight of
fine grain titanium oxide, and the stirring thereof was further
continued under heating. The thus treated reaction solution was
cooled to room temperature, and poured into 300 parts by weight of
methanol to deposit a colorless powdery resin. The thus deposited
resin was examined for glass transition point by DSC. And the glass
transition point thereof was found to be 64.degree. C.
[0129] The thus synthesized resin was dissolved in toluene, applied
to an aluminum plate, and then dried to form a film. The film thus
formed was ground into a powder by a jet mill, and put through a
325-mesh sieve. Thus, a tabular powder of organic silicone resin
having an average particle size of 28 .mu.m was obtained. The
particles constituting the thus obtained tabular powder had an
average aspect ratio of 25, determined from electron micrographs
thereof.
EXAMPLE 5
[0130] The tabular powder of organic silicone resin prepared in
Example 1 was mixed with the following ingredients, and made into
milky lotion in the process described below:
1 Amount Ingredients mixed (%) 1. Microcrystalline wax 1.0 2.
Lanolin 1.0 3. Dimethylpolysiloxane (6 cs) 40.0 4.
Dimethylpolysiloxane (> 1,000,000 cs) 2.0 5. Tabular powder of
organic silicone resin 2.0 6. Sorbitan sesquioleic acid ester 4.0
7. Polyoxyethylene(20) sorbitan monooleic acid ester 1.0 8.
1,3-Butylene glycol 5.0 9. Antiseptic proper 10. Perfume proper 11.
Purified water the rest
[0131] [Making Process]
[0132] A: The ingredients 1 to 7 were mixed together under heating
to prepare a mixture A.
[0133] B: The ingredients 8, 9 and 11 were mixed together, added to
the mixture A, and made into an emulsion B.
[0134] C: The emulsion B was cooled, and thereto the ingredient 10
was added.
[0135] The thus prepared milky lotion had no tackiness and went on
quite well when applied to the skin, caused dry and refreshed feels
in the applied skin, and had a very smooth texture.
EXAMPLE 6
[0136] The tabular powder of organic silicone resin prepared in
Example 2 was mixed with the following ingredients, and made into a
skin cleaning agent in the process described below:
2 Ingredients Amount mixed (%) 1. Myristic acid 15.0 2. Palmitic
acid 5.0 3. Stearic acid 3.0 4. Beeds wax 3.0 5. Polyethylene
glycol 6000 2.0 6. Ethylene glycol distearate 2.0 7. Coconut oil
fatty acid diethanolamide 3.0 8. Glycerin 15.0 9. Antiseptic proper
10. Potassium hydroxide 5.5 11. Purified water the rest 12. Sodium
N-lauroylsarcosine 10.0 13. Tabular powder of organic silicone 2.0
resin (aspect ratio: 28)
[0137] [Making Process]
[0138] A: The ingredients 1 to 9 were mixed together under heating
to prepare a mixture A.
[0139] B: The ingredients 10 and 11 were mixed together under
heating to prepare a mixture B.
[0140] C: The mixture B was added to the mixture A to prepare a
homogeneous solution. To this solution, the ingredients 12 and 13
were further added, and made into a homogeneous matter. This matter
was cooled with stirring to prepare a skin cleaning lotion.
[0141] The thus prepared skin cleaning lotion went on quite well
and produced massage effect when applied to the skin, and brought
about dry and refreshed feelings without attended by a stiff
feeling after it was washed away.
EXAMPLE 7
[0142] The tabular powder of organic silicone resin prepared in
Example 3 was mixed with the following ingredients, and made into
compressed face powder (such as the so-called Pan-Cake) in the
process described below:
3 Ingredients Amount mixed (%) 1. Titanium oxide 5.0 2. Kaolin 5.0
3. Talc the rest 4. Zinc myristate 5.0 5. Iron oxide red 0.7 6.
Iron oxide yellow 2.1 7. Iron oxide black 0.2 8. Tabular powder off
organic silicone resin (aspect ratio: 19) 9. Porous globular silica
10.0 10. Squalane 3.0 11. Glyceryl trioctanoate 2.0 12. Antiseptic
proper 13. Perfume proper
[0143] [Making Process]
[0144] A: The ingredients 1 to 9 were mixed together to prepare a
mixture A.
[0145] B: The ingredients 10 to 12 were mixed together, and then
added to the mixture A to prepare a mixture B.
[0146] C: The ingredient 13 was added to the mixture B and mixed
therein homogeneously. The resultant matter was compressed tightly
into a metal pan, thereby obtaining face powder according to the
invention.
[0147] The face powder thus compressed had a dry and smooth
texture, spread smoothly, and stayed well due to its good
adhesiveness. Thus, the present face powder can produce a beautiful
makeup result and the result wears well.
EXAMPLE 8
[0148] The tabular powder of organic silicone resin prepared in
Example 2 was mixed with the following ingredients, and made into
face powder in the process described below:
4 Ingredients Amount mixed (%) 1. Titanium oxide 12.0 2. Zinc oxide
10.0 3. Kaolin 10.0 4. Talc the rest 5. Iron oxide red 0.8 6. Iron
oxide yellow 2.5 7. Iron oxide black 0.2 8. Tabular powder of
organic silicone 18.0 resin (aspect ratio: 28) 9. Cured silicone
rubber powder (*1) 5.0 10. Liquid parrafin 4.0 11.
Octamethylcyclotetrasiloxane 5.0 12. Dimethylpolysiloxane 5.0 13.
Isopropyl palmitate 3.0 14. Glycerin 3.0 15. Antiseptic proper 16.
Perfume proper *1:KSP-100 (globular particles having anaverage size
of 5 .mu.m, produced by Shin-Etsu Chemical Co., Ltd.)
[0149] [Making Process]
[0150] A: The ingredients 1 to 9 were mixed together to prepare a
homogeneous mixture A.
[0151] B: The ingredients 10 to 15 were mixed together, and then
added to the mixture A to obtain a mixture B.
[0152] C: The ingredient 16 was added to the mixture B, and the
resultant matter was compressed tightly into a metal pan.
[0153] The thus prepared face powder according to the invention had
a quite dry and smooth texture, spread smoothly, and stayed well
due to its good adhesiveness. Thus, the present face powder can
produce a beautiful makeup result, and the result wears well.
EXAMPLE 9
[0154] The tabular powder of organic silicone resin prepared in
Example 3 was mixed with the following ingredients, and made into
foundation in the process described below:
5 Ingredients Amount mixed (%) 1. Silicone-treated titanium oxide
7.0 2. Tabular powder of organic silicone 6.0 resin (aspect ratio:
19) 3. Silicone-treated iron oxide red 0.5 4. Silicone-treated iron
oxide yellow 1.3 5. silicone-treated iron oxide black 0.2 6. Liquid
parrafin 5.0 7. Dimethylpolysiloxane 8.0 8.
Octamethylcyclotetrasiloxane 12.0 9. Perfluoropolyether 2.0 10.
Octyl paramethoxysuccinate 2.0 11. Dextrin palmitic acid ester 2.0
12. Sorbitan sesquioleic acid ester 1.5 13. Polyether-modified
silicone (*2) 3.0 14. 1,3-Butylene glycol 1.5 15. Glycerin 7.0 16.
Antiseptic proper 17. Perfume proper 18. Purified water the rest
*2:KF-6017 (produced by Shin-Etsu Chemical Co. Ltd.)
[0155] [Making Process]
[0156] A: The ingredients 6 to 13 were mixed together under
heating. Thereto, the ingredients 1 to 5 were added and mixed
homogeneously to prepare a mixture A.
[0157] B: The ingredients 14, 15, 16 and 18 were mixed together
under heating to obtain a mixture B.
[0158] C: The mixture B was added to the mixture A, and made into
an emulsion. The emulsion was cooled, and then the ingredient 17
was added thereto.
[0159] The thus prepared foundation according to the invention was
fluent and smooth, spread smoothly, and stayed well due to its good
adhesiveness. Thus, the present foundation can produce a beautiful
makeup result, and its effect lasts well.
EXAMPLE 10
[0160] The tabular powder of organic silicone resin prepared in
Example 4 was mixed with the following ingredients, and made into
eye shadow sticks in the process described below:
6 Ingredients Amount mixed (%) 1. Gypsum 35.0 2. Talc 17.5 3.
Pigment 10.0 4. Nylon powder 15.0 5. Tabular powder of organic
silicone resin (aspect ratio: 25) 15.0 6. Squalane 3.0 7.
Polyoxyethylene sorbitan monooleic 0.5 acid ester 8. Glycerin 4.0
9. Antiseptic proper 10. Perfume proper 11. Purified water (100)
12. Ethanol (50)
[0161] [Making Process]
[0162] A: The ingredients 1 to 5 were mixed together to prepare a
mixture A.
[0163] B: The ingredients 6 to 12 were mixed together to prepare a
mixture B.
[0164] C: The mixture A was added to the mixture B, and the
resultant mixture was charged in a container, allowed to stand for
hardening, and then dried.
[0165] Additionally, the ingredients 11 and 12 were used for
hardening the ingredient 1 (gypsum), but they vaporized during the
drying treatment; as a result, the mixture obtained were free of
them. Therefore, the amounts of these ingredients used are given
above in parentheses.
[0166] The thus obtained eye shadow sticks according to the
invention had a good appearance and a dry and smooth texture,
spread lightly and smoothly, stayed well due to their good
adhesiveness. Thus, the present eye shadow stick can produce a
beautiful makeup result, and the result wears well. In addition,
the present eye shadow stick gave no powdery impression and was
easily shaded off when put on eyelid.
EXAMPLE 11
[0167] The tabular powder of organic silicone resin prepared in
Example 3 was mixed with the following ingredients, and made into
lipstick in the process described below:
7 Ingredients Amount mixed (%) 1. Paraffin wax 12.0 2. Lanolin wax
12.0 3. Candelilla wax 3.0 4. Kaolin 10.0 5. Castor oil the rest 6.
Dimethylpolysiloxane 10.0 7. Trioctanoic ester of glycerin 2.5 8.
Tabular powder of organic silicone 6.0 resin(aspect ratio: 19) 9.
Titanium oxide 1.0 10. Red No. 201 1.0 11. Red No. 202 2.0 12. Blue
No. 1 aluminum lake 0.5 13. Perfume proper
[0168] [Making Process]
[0169] A: The ingredients 1 to 12 were mixed together under heating
to prepare a mixture A.
[0170] B: The ingredient 13 was added to the mixture A, and mixed
homogeneously therein to prepare a mixture B.
[0171] C: The mixture B was filled in capsules to prepare
lipstick.
[0172] The thus prepared lipstick according to the invention had a
lustrous and smooth texture, spread lightly and smoothly, and
stayed well due to its good adhesiveness. Thus, the present
lipstick can produce a beautiful makeup result, and the result
wears well.
EXAMPLE 12
[0173] The tabular powder of organic silicone resin prepared in
Example 2 was mixed with the following ingredients, and made into a
hair rinse in the process described below:
8 Ingredients Amount mixed (%) 1. Ethylene glycol distearate 3.0 2.
Cetanol 2.0 3. Propylene glycol inonostearate 3.0 4.
dimethylpolysiloxane (100 cs) 3.0 5. Monostearic ester of glycerin
4.0 6. Polyoxyethylene(3) stearate 4.0 7.
Chioroacetyltrimethylammonium 5.0 8. Polyoxyethylene(20) cetyl
ether 2.0 9. Tabular powder of organic silicone 2.0 resin(aspect
ratio: 28) 10. 1,3-Butylene glycol 5.0 11. Antiseptic proper 12.
Perfume proper 13. Purified water the rest
[0174] [Making Process]
[0175] A: The ingredients 1 to 9 were mixed with stirring to
prepare a mixture A.
[0176] B: The ingredients 10, 11 and 13 were mixed together under
heating to prepare a mixture B.
[0177] C: The mixture B was added to the mixture A, mixed, cooled,
and then mixed with the ingredient 12 to prepare a hair rinse.
[0178] The hair rinse thus prepared according to the invention was
neither tacky nor heavy, gave fine luster, dry and smooth touch and
puff to the hair treated therewith, and made it easy to pass a comb
through the hair treated therewith. And these effects lasted a long
time.
EXAMPLE 13
[0179] The tabular powder of organic silicone resin prepared in
Example 3 was mixed with the following ingredients, and made into a
hair conditioner in the process described below:
9 Ingredients Amount mixed (%) 1. Ethylene glycol distearate 1.0 2.
Liquid paraffin 10.0 3. Squalane 5.0 4. Stearyl alcohol 1.5 5.
Dimethylpolysiloxane 3.0 6. Stearic acid 6.0 7. Polyoxyethylene(3)
stearyl alcohol 4.5 8. Polyoxyethylene(150) cetyl ether 2.0 9.
Tabular powder of organic silicone 1.5 resin (aspect ratio: 19) 10.
1,3-butylene glycol 6.0 11. Antiseptic proper 12. Perfume proper
13. Purified water the rest
[0180] [Making Process]
[0181] A: The ingredients 1 to 9 were mixed under heating to
prepare a mixture A.
[0182] B: The ingredients 10, 11 and 13 were mixed together to
prepare a dispersion B.
[0183] C: The dispersion B was added to the mixture A, mixed,
cooled, and then mixed with the ingredient 12, thereby obtaining a
treatment.
[0184] The treatment thus prepared according to the invention had
neither tacky nor heavy tough, gave fine luster, dry and smooth
touch and puff to the hair treated therewith, and made it easy to
pass a comb through the hair treated therewith. And these effects
lasted a long time.
EXAMPLE 14
[0185] The tabular powder of organic silicone resin prepared in
Example 3 was mixed with the following ingredients, and made into
water-based enamel for manicure in the process described below:
10 Ingredients Amount mixed (%) 1. Styrene-acrylic acid copolymer
40.0 2. Ethanol 10.0 3. Neutralizer proper 4. carbitol proper 5.
Plasticizer proper 6. Antifoaming agent proper 7. Antiseptic proper
8. Perfume proper 9. Purified water the rest 10. Tabular powder of
organic silicone 1.0 resin (aspect ratio: 19) 11. Colored pigment
for coloring 3.0
[0186] [Making Process]
[0187] All ingredients set forth above were mixed homogeneously,
and filled in vials.
[0188] The thus prepared water-base enamel for manicure was
convenient to apply, spread well, had smooth texture and gave a
fine luster to nails. The enamel applied kept well. Further, the
present water-base enamel hardly caused in its viscosity upon
storage, namely it had excellent storage stability.
EXAMPLE 15
[0189] The tabular powder of organic silicone resin prepared in
Example 2 was mixed with the following ingredients, and made into
an aerosol composition in the process described below:
11 Amount Ingredients mixed (%) 1. Tabular powder of organic
silicone resin (aspect ratio: 3.0 28) 2. Chloro-hydroxo-aluminum
complex 2.0 3. Isopropylmethylphenol 0.3 4. Sorbitan sesquioleic
acid ester 0.2 5. Isopropyl myristate 5.0 6. Perfume proper 7.
Jetting agent the rest
[0190] [Making Process]
[0191] A: The ingredients 1 to 6 were mixed together to prepare a
mixture A.
[0192] B. The mixture A was charged in an aerosol can. Then, the
can was filled with the ingredient 7.
[0193] The aerosol composition thus prepared according to the
invention produced a high deodorization effect. The composition was
coated in a very thin layer, and the composition coated had neither
tacky nor heavy tough, and gave a dry and smooth feel. In addition,
the present aerosol composition had high re-dispersibility, so it
was very usable.
EXAMPLE 16
[0194] The milky lotion was prepared using the same ingredients
under the same compounding condition as in Example 5, except that
the titanium oxide-incorporated tabular powder of organic silicone
resin having an aspect ratio greater than about 1, which was
prepared in Example 4, was used in place of the tabular powder of
organic silicone resin having an aspect ratio of 32 (which was free
of titanium oxide).
[0195] The milky lotion obtained had fine appearance similarly to
that obtained in Example 5, arouse no uncomfortable feelings, such
as rough and tacky feels, in the users when applied to their skin,
spread smoothly, caused dry and refreshed feels in the applied
skin, and had a very smooth texture.
[0196] Further, this milky lotion was stored in a reagent bottle
for aging test. Even after 3-month lapse, the lotion had no deposit
although it contained the inorganic powder.
COMPARATIVE EXAMPLE 1
[0197] The white resin powder prepared by copolymerization reaction
according to the same method as in Example 1 was dried, ground with
a jet mill, and then put through a sieve. Thus, the organic
silicone resin powder having an average particle size of 20 .mu.m
was obtained. As to the powder shape, the resin powder obtained was
a mixture of globular, columnar, stick-like, tabular and acicular
particles.
[0198] Another milky lotion was prepared under the same compounding
condition as in Example 5, except that the organic silicone resin
powder obtained above was used in place of the tabular powder of
organic silicone resin having an aspect ratio of 32. The lotion
thus obtained had a dusty gloss and arouse an uncomfortable feeling
in users when applied to their skin.
COMPARATIVE EXAMPLE 2
[0199] Still another milky lotion was prepared under the same
compounding condition as in Example 5, except that untreated mica
was used in place of the tabular powder of organic silicone resin
having an aspect ratio of 32.
[0200] The thus obtained lotion had a fine appearance, but the
aging test by the storage in a reagent bottle showed that it formed
a little deposit after the lapse of one week.
[0201] Additionally, the foregoing examples are some embodiments of
the invention, so that the present invention should not be
construed as being limited to those examples. Therefore, any
materials are included in the technical scope of the invention if
they have in a substantial sense the same constitutions as the
technological ideas described in the present claims and the same
functions and effects as the present materials.
[0202] For instance, although the organic silicone resin powder
used as one ingredient of a cosmetic material in each of Examples 5
to 16 is the tabular (aspect ratio: greater than about 1) powder of
a copolymer prepared from a radical polymerizable group-containing
dimethylorganopolysiloxane and radical polymerizable monomer(s),
the same effects are produced even when the copolymer used is a
copolymer prepared from compounds having reactive groups other than
radical polymerizable groups, e.g., a copolymer of
organopolysiloxane(s) and monomer(s) whose reactive groups are
different from each other, such as carboxylic acid group and
alcoholic group.
[0203] In accordance with the invention, the organic silicone resin
is a copolymer prepared by polymerization reaction between an
organopolysiloxane containing one or more of a reactive group and
at least one kind of monomer or oligomer capable of reacting to the
reactive group, and the powder of such a copolymer is a tabular
powder having an aspect ratio greater than about 1. The cosmetic
materials containing the present tabular powder as one essential
ingredient are non-viscous, arise neither tacky nor heavy feelings
in the persons who put them on the skin or the like, spread lightly
and smoothly, have good adhesiveness. The skin to which the
cosmetic material according to the invention is applied has a dry
and smooth texture and acquires a refreshed feel, and these effects
last a long time. In other words, the cosmetic materials according
to the invention produce a comfortable feeling and excellent
results when applied to skin, hair, or so on.
[0204] Further, the present organic silicone resin powder has a
markedly small specific gravity, compared with inorganic powders so
far been used, so that it causes no conventional precipitation
trouble.
[0205] Furthermore, as the present organic silicone resin powder
has excellent compatibility with base substances of cosmetics and
high dispersibility therein, mixing it as an essential ingredient
in cosmetics not only dissolves uncomfortable feels, such as a
rough feel which is liable to be caused when conventional organic
resin powders are mixed therein and a tacky feel which is liable to
be caused when conventional silicone resin powders are mixed
therein, but also confer excellent characteristics those
conventional resins have by nature, such as stability and a moist
texture, on the cosmetics.
[0206] Therefore, the combined use of the present organic silicone
resin powder and conventional inorganic powders in cosmetics can
remarkably improve the characteristics and handling easiness of the
resultant cosmetics, compared with the independent use of inorganic
powders in cosmetics, and enables the inexpensive and easy
preparation of cosmetics.
* * * * *