U.S. patent application number 12/279762 was filed with the patent office on 2010-09-16 for water-in-oil type emulsion sunscreen cosmetics.
This patent application is currently assigned to SHISEIDO CO., LTD.. Invention is credited to Takashi Matsui, Yuki Nomura, Masayuki Shirao, Kazuhiro Yamaguchi, Norinobu Yoshikawa.
Application Number | 20100233103 12/279762 |
Document ID | / |
Family ID | 38437344 |
Filed Date | 2010-09-16 |
United States Patent
Application |
20100233103 |
Kind Code |
A1 |
Shirao; Masayuki ; et
al. |
September 16, 2010 |
Water-In-Oil Type Emulsion Sunscreen Cosmetics
Abstract
The present invention provides water-in-oil type emulsion
sunscreen cosmetics that achieve an excellent UV blocking effect,
and have excellent effects in the prevention and inhibition of
discoloration (discoloration to red). The water-in-oil emulsion
sunscreen cosmetic according to the present invention is
characterized by comprising: (a) octocrylene; (b) hydrophobized
zinc oxide; (c) cationic surfactant; and (d) silica.
Inventors: |
Shirao; Masayuki; (Kanagawa,
JP) ; Yamaguchi; Kazuhiro; ( Kanagawa, JP) ;
Matsui; Takashi; ( Kanagawa, JP) ; Yoshikawa;
Norinobu; ( Kanagawa, JP) ; Nomura; Yuki; (
Kanagawa, JP) |
Correspondence
Address: |
RANKIN, HILL & CLARK LLP
23755 Lorain Road - Suite 200
North Olmsted
OH
44070-2224
US
|
Assignee: |
SHISEIDO CO., LTD.
Chuo-ku, Tokyo
JP
|
Family ID: |
38437344 |
Appl. No.: |
12/279762 |
Filed: |
February 20, 2007 |
PCT Filed: |
February 20, 2007 |
PCT NO: |
PCT/JP2007/053043 |
371 Date: |
August 18, 2008 |
Current U.S.
Class: |
424/59 |
Current CPC
Class: |
A61K 8/585 20130101;
A61Q 17/04 20130101; A61K 8/0245 20130101; A61K 8/416 20130101;
A61K 8/25 20130101; A61K 8/40 20130101; A61K 8/27 20130101; A61K
8/738 20130101; A61K 8/06 20130101; A61K 8/064 20130101 |
Class at
Publication: |
424/59 |
International
Class: |
A61K 8/06 20060101
A61K008/06; A61Q 17/04 20060101 A61Q017/04 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 20, 2006 |
JP |
2006-043215 |
Claims
1. A water-in-oil type emulsion sunscreen cosmetic comprising: (a)
octocrylene; (b) hydrophobized zinc oxide; (c) cationic surfactant;
and (d) silica.
2. The water-in-oil type emulsion sunscreen cosmetic of claim 1,
wherein component (c), forms a surface coating on component
(b).
3. The water-in-oil type emulsion sunscreen cosmetic of claim 1,
wherein the blending amount of said component (a) is 0.2 to 15% by
mass.
4. The water-in-oil emulsion sunscreen cosmetic of claim 1, wherein
the blending amount of said component (b) is 0.2 to 30% by
mass.
5. The water-in-oil emulsion sunscreen cosmetic of claim 1, further
comprising: (e) 0.01 to 20% by mass of silicone surfactant.
6. The water-in-oil type emulsion sunscreen cosmetic of claim 2,
wherein the blending amount of said component (a) is 0.2 to 15% by
mass.
7. The water-in-oil emulsion sunscreen cosmetic according of claim
2, wherein the blending amount of said component (b) is 0.2 to 30%
by mass.
8. The water-in-oil emulsion sunscreen cosmetic according of claim
3, wherein the blending amount of said component (b) is 0.2 to 30%
by mass.
9. The water-in-oil emulsion sunscreen cosmetic of claim 2, further
comprising: (e) 0.01 to 20% by mass of silicone surfactant.
10. The water-in-oil emulsion sunscreen cosmetic of claim 3,
further comprising: (e) 0.01 to 20% by mass of silicone
surfactant.
11. The water-in-oil emulsion sunscreen cosmetic of claim 4,
further comprising: (e) 0.01 to 20% by mass of silicone
surfactant.
12. The water-in-oil type emulsion sunscreen cosmetic of claim 1,
wherein the blending amount of said component (a) is 0.5 to 10% by
mass.
13. The water-in-oil type emulsion sunscreen cosmetic of claim 2,
wherein the blending amount of said component (a) is 0.5 to 10% by
mass.
14. The water-in-oil type emulsion sunscreen cosmetic of claim 5,
wherein the blending amount of said component (a) is 0.5 to 10% by
mass.
15. The water-in-oil type emulsion sunscreen cosmetic of claim 1,
wherein the blending amount of said component (a) is 1 to 7% by
mass.
16. The water-in-oil type emulsion sunscreen cosmetic of claim 2,
wherein the blending amount of said component (a) is 1 to 7% by
mass.
17. The water-in-oil emulsion sunscreen cosmetic according of claim
1, wherein the blending amount of said component (b) is 1 to 25% by
mass.
18. The water-in-oil emulsion sunscreen cosmetic according of claim
2, wherein the blending amount of said component (b) is 1 to 25% by
mass.
19. The water-in-oil emulsion sunscreen cosmetic according of claim
1, wherein the blending amount of said component (b) is 10.1 to 25%
by mass.
20. The water-in-oil emulsion sunscreen cosmetic according of claim
2, wherein the blending amount of said component (b) is 10.1 to 25%
by mass.
Description
RELATED APPLICATIONS
[0001] This application claims the priority of Japanese Patent
Application No. 2006-043215 filed on Feb. 20, 2006, which are
incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to water-in-oil type emulsion
sunscreen cosmetics. In particular, the present invention relates
to water-in-oil type emulsion sunscreen cosmetics that have an
excellent UV protection capability and have excellent effects in
the prevention and inhibition of discoloration (discoloration to
red).
BACKGROUND OF THE INVENTION
[0003] Generally, in order to block UV radiation to the skin and
achieve high SPF (Sun Protection Factor) values, UV absorbers or UV
scattering agents (zinc oxide etc.) are blended in sunscreen
cosmetics (refer to patent literatures 1 and 2, for example).
[0004] It is generally known that the improvement in formulation
stability, improvement in removability, and the improvement in
powder dispersibility are made by blending cationic surfactants
into cosmetics.
[0005] Octocrylene is an all-purpose UV absorber. However, there is
a problem in that the appearance of the formulation turns extremely
red when a hydrophobized UV scattering agent (especially zinc
oxide) is used in combination with a cationic surfactant in
water-in-oil type sunscreen cosmetics.
[0006] Patent Literature 1: Japanese Unexamined Patent Publication
No. H10-120543 (paragraph numbers [0032], [0041], [0045], etc.)
[0007] Patent Literature 2: PCT Japanese Translation Patent
Publication No. 2002-521417 (claim section etc.)
DISCLOSURE OF THE INVENTION
Problem to be Solved by the Invention
[0008] The object of the present invention is to provide
water-in-oil type emulsion sunscreen cosmetics that solve the
above-described problem, achieve an excellent UV blocking effect,
and have excellent effects in the prevention and inhibition of
discoloration (discoloration to red).
Means to Solve the Problem
[0009] The present inventors have diligently studied to solve the
above-described problem. As a result, the present inventors have
found that an excellent UV blocking effect and the prevention and
inhibition effects of red discoloration could be achieved by
blending silica into a system where octocrylene, a hydrophobized UV
scattering agent (especially zinc oxide), and a cationic surfactant
are blended, thus leading to completion of the present
invention.
[0010] The present invention provides water-in-oil type emulsion
sunscreen cosmetics comprising: (a) octocrylene; (b) hydrophobized
zinc oxide; (c) cationic surfactant; and (d) silica.
[0011] The present invention provides the above-described
water-in-oil type emulsion sunscreen cosmetics comprising said
component (c), with which component (b) is surface-coated.
[0012] The present invention provides the above-described
water-in-oil type emulsion sunscreen cosmetics wherein the blending
amount of said component (a) is 0.2 to 15% by mass.
[0013] The present invention provides the above-described
water-in-oil type emulsion sunscreen cosmetics wherein the blending
amount of said component (b) is 0.2 to 30% by mass.
[0014] The present invention provides the above-described
water-in-oil type emulsion sunscreen cosmetics further comprising:
(e) 0.01 to 20% by mass of silicone surfactant.
[0015] According to the present invention, water-in-oil type
emulsion sunscreen cosmetics that can satisfactorily achieve an
excellent UV blocking effect and have excellent effects in the
prevention and inhibition of discoloration (discoloration to red)
can be provided.
[0016] Hereinafter, the water-in-oil type emulsion sunscreen
cosmetics of the present invention will be described in detail.
BEST MODE FOR CARRYING OUT THE INVENTION
[0017] Octocrylene (another name: 2-cyano-3,3-diphenyl-2-propenoic
acid 2-ethylhexyl ester), which is component (a) used in the
present invention, is a UV protection agent, and it is a publicly
known material. Octocrylene can normally be prepared by the
esterification reaction of cyanoacetic acid and 2-ethylhexanol in a
solvent (for example, cyclohexane) to 2-ethylhexyl cyanoacetate and
by the subsequent condensation reaction of the obtained
2-ethylhexyl cyanoacetate with benzophenone. In the actual
preparation, octocrylene may be produced in a state that
2-ethylhexyl cyanoacetate is not completely used in the
condensation process and 2-ethylhexyl cyanoacetate is partially
left. In the present invention, the lower the concentration of
2-ethylhexyl cyanoacetate in octocrylene, the more desirable. The
concentration is preferably 400 ppm or lower, more preferably 200
ppm or lower, and further more preferably 100 ppm or lower. The
most desirable concentration of 2-ethylhexyl cyanoacetate is zero.
If the concentration of 2-ethylhexyl cyanoacetate contained in
octocrylene is high, it tends to be more difficult to achieve the
prevention and inhibition effects of discoloration (discoloration
to red), which are the effects of the present invention.
[0018] Component (a) includes, for example, commercial products
such as "Uvinul N539" (BASF) or "Parsol 340" (DSM Nutrition Japan
K.K.), and they can be used desirably.
[0019] The blending amount of component (a) is 0.2 to 15% by mass
with respect to the cosmetics of the present invention, preferably
0.5 to 10% by mass, and more preferably 1 to 7% by mass. If the
blending amount is less than 0.2% by mass, a satisfactory UV
protection capability cannot be achieved. On the other hand, if the
blending amount exceeds 15% by mass, a high tendency of
discoloration (discoloration to red) is observed and there is a
concern with usability deterioration such as stickiness and an oily
feeling.
[0020] Hydrophobized zinc oxide, which is used as component (b), is
a UV scattering agent, and it can effectively be dispersed in the
oil phase (outer phase) after hydrophobizing treatment.
[0021] From the stand point of a UV-scattering effect, zinc oxide
is preferably prepared into fine particles. The average primary
particle size of zinc oxide fine particles can be about 1 to 50 nm.
However, the size is not limited to this size.
[0022] The method for hydrophobizing treatment is not limited in
particular, and a publicly known method can be used for treatment.
Examples of hydrophobizing agents include, but not limited in
particular, metallic soap (for example, aluminum stearate and
aluminum laurate), fatty acid dextrin, trimethylsiloxane,
fluorine-modified trimethylsiloxane, methylphenylsiloxane,
fluorine-modified methylphenylsiloxane, low-viscosity to
high-viscosity oily polysiloxanes such as dimethylpolysiloxane
(=dimethicone), methylpolysiloxane (=methicone),
diphenylpolysiloxane, and methylphenylpolysiloxane; gummy
polysiloxane, methylhydrogenpolysiloxane, fluorine-modified
methylhydrogenpolysiloxane, organic-modified silanes such as
methyltrichlorosilane, ethyltrichlorosilane, ethyltrialkoxysilane,
propyltrichlorosilane, propyltrialkoxysilane, hexyltrichlorosilane,
hexyltrialkoxysilane, methyltrialkoxysilane, hexamethyldisilane,
dimethyldichlorosilane, dimethyldialkoxysilane,
trimethylchlorosilane, trimethylalkoxysilane, long-chain
alkyltrichlorosilane, and long-chain alkyltriethoxysilane; or their
fluorine-substituted compounds, amino-modified polysiloxane,
fluorine-modified polysiloxane, and fluoroalkyl phosphate. However,
the hydrophobizing agent is not limited by these examples. In
hydrophobizing treatment, it is preferable to use 3 to 90% by mass
hydrophobizing agent, for coating, with respect to zinc oxide (base
body).
[0023] Examples of hydrophobized zinc oxide include metallic
soap-treated zinc oxide, for example by aluminum stearate; fatty
acid-dextrin treated zinc oxide, for example by cyclodextrin-fatty
acid ester; amino acid treated zinc oxide; oily polysiloxane
treated zinc oxide, for example by methylhydrogenpolysiloxane,
methylhydrogenpolysiloxane/dimethylpolysiloxane copolymer,
methicone, or dimethicone; fluorine-treated zinc oxide, for example
by perfluoroalkyl phosphate; and silane coupling agent treated zinc
oxide, for example by octyltriethoxysilane.
[0024] The blending amount of component (b) is 0.2 to 30% by mass
with respect to the cosmetics of the present invention, preferably
1 to 25% by mass, and more preferably 10.1 to 25% by mass. If the
blending amount is less than 0.2% by mass, a satisfactory UV
protective effect cannot be achieved. On the other hand, if the
blending amount exceeds 30% by mass, there is a concern with the
discoloration (discoloration to red) and usability deterioration as
typified by smoothlessness.
[0025] The cationic surfactant, which is component (c), is not
limited in particular so far as the cationic surfactant can be
generally used in cosmetics. Examples include
stearyltrimethylammonium chloride, hexadecyltrimethylammonium
chloride, tetradecyltrimethylammonium chloride,
lauryltrimethylammonium chloride, C12 monohydroxyalkylether cation,
dihydroxyalkylether cation, dihydroxyalkylether cation,
cocodiamidopropyl cation, cocodicarboxyethyl cation, C16
dicarboxyethyl cation, C18 dicarboxyethyl cation, POP(15)
diethylmethyl cation, POP(25) diethylmethyl cation, POP(40)
diethylmethyl cation, C12 diamidopropylmethylamine, C14
diamidopropylmethylamine, C16 diamidopropylmethylamine, C18
diamidopropylmethylamine, iso-C18 diamidopropylmethylamine, di-C18
propyldimethyl cation, hydroxypropyl-bis-lauryl cation,
hydroxypropyl-bis-stearyl cation, hydroxypropyl-bis-laurylamide
cation, hydroxypropyl-bis-stearylamide cation, C18
monohydroxyalkylether cation, bis-C18 hydroxyalkylether cation, C22
trimethylammonium bromide, C22 propyldimethylamine, quaternium-91,
C22 trimethylammonium methosulfate, dicocoylamidoethylethylhydroxy
cation, di-C18 amidoethylethylhydroxy cation, di-C16
amidoethylethylhydroxy cation, di-C18 dimethylammonium salt, C18
dimethylbenzylammonium salt, perfluorotrimethylammonium salt, and
diacylamidoethylethylhydroxy cation. However, the cationic
surfactant is not limited by these examples.
[0026] The especially desirable component (c) is
distearyldimethylammonium salt, dihexadecyldimethylammonium salt,
ditetradecyldimethylammonium salt, didodecyldimethylammonium salt,
stearyltrimethylammonium chloride, hexadecyltrimethylammonium
chloride, tetradecyltrimethylammonium chloride, or
dodecyltrimethylammonium chloride. One or more of component (c) can
be used.
[0027] Silica, which is component (d), is silicon dioxide (silicic
anhydride). Treated silicas such as dimethylsilanized silicic
anhydride and trimethylsilanized silicic anhydride can also be
used. The silica can be of any shape; the shape can be spherical
and porous, plate-like and nonporous, particulate, rod-like and
porous, or spherical and nonporous, and there is no particular
restriction. However, spherical porous silica, particulate silica,
or rod-like porous silica is preferably used. Component (d)
includes, for example, commercial products such as "Sunsphere L-51"
(manufactured by Asahi Glass Co., Ltd.), "Chemiselen" (manufactured
by Sumitomo Chemical Co., Ltd.), "Aerosil 200" (manufactured by
Nippon Aerosil Co., Ltd.), "Spherical Silica P1500" (manufactured
by Catalysts & Chemicals Ind. Co., Ltd.), and "Mesoporous
Silica", and these can be used desirably.
[0028] In the present invention, the blending mode of component
(b), component (c), and component (d) is not limited in particular.
Examples include:
[0029] (i) Blending mode in which component (b), component (c), and
component (d) are individually blended.
[0030] (ii) Blending mode in which the hydrophobized and
cation-treated zinc oxide, which is obtained by treating component
(b) with component (c), is blended with component (d).
[0031] (iii) Blending mode in which the hydrophobized,
cation-treated, and silica-coated zinc oxide, which is obtained by
coating, with component (d), the hydrophobized and cation-treated
zinc oxide obtained by treating component (b) with component (c),
is blended.
[0032] (iv) Blending mode in which the hydrophobized silica-coated
zinc oxide, which is obtained by treating component (b) with
component (d), is blended with component (c).
[0033] (v) Blending mode in which untreated zinc oxide is
silica-coated with component (d), and this silica-coated zinc oxide
is hydrophobized with a hydrophobizing agent and cation-treated
with component (c). The blending mode is not limited by the
above-described examples. The blending of component (d) may be
achieved by silica-coated powders obtained by coating the surface
of powders, except for component (b), with silica.
[0034] The blending amounts of component (c) and component (d) are
as follows.
[0035] When component (c) is blended in the mode of individual
addition instead of blending the powder treated therewith, the
blending amount of component (c) in cosmetics is preferably 0.0001
to 10% by mass and more preferably 0.001 to 1% by mass. When
component (c) is used as the surface coating of component (b), the
blending amount of component (c) is preferably 0.5 to 10% by mass
with respect to zinc oxide (base body). If the blending amount of
component (c) is too small, the formulation stability,
removability, and the powder dispersibility tend to be become
lower. On the other hand, if the blending amount of component (c)
is too large, the discoloration may not be inhibited even by
blending component (d).
[0036] When component (d) is blended in the mode of individual
addition instead of blending the powder treated therewith, the
blending amount of component (d) in cosmetics is preferably 0.1 to
20% by mass and more preferably 0.5 to 10% by mass. When component
(d) is used as the surface coating of component (b) or as the
surface coating of component (b) that has been coated with
component (c), the blending amount of component (d) is preferably
0.1 to 20% by mass with respect to zinc oxide (base body). If the
blending amount of component (d) is too small, the dispersion
stability tends to become lower. On the other hand, if the blending
amount of component (d) is too large, the UV protection capability
tends to become lower. When component (d) and component (c) are
individually blended, it is desirable to blend component (d) in a
mass ratio of 0.01:6 or higher with respect to component (c). In
this case, if the blending amount of component (d) is too small,
the discoloration to red may take place.
[0037] An example of a production method when both hydrophobizing
treatment and cation treatment are performed on zinc oxide (base
body) is described below. However, the method is not limited to
this method. Into a solvent, 3 to 90% by mass of various
hydrophobizing agents and 0.5 to 10% by mass of cationic
surfactants with respect to the powder (base body) are added and
dissolved. Subsequently, the powder (base body) is added and
stirred for 1 hour at room temperature. After the completion of
stirring, the solvent removal, drying, and pulverization are
carried out to obtain the desired modified powder. As a solvent,
methyl alcohol, ethyl alcohol, and isopropyl alcohol, into which
various hydrophobizing agents and cationic surfactants can be
dissolved, may be used. In particular, isopropyl alcohol is
desirable.
[0038] The production can also be achieved by treating a commercial
hydrophobized powder with a cationic surfactant.
[0039] The amounts of coating of a hydrophobizing agent and a
cationic surfactant are preferably in the mass ratio of 1:1 to 9:1.
If the rate of the cationic surfactant is larger than the
above-described range, the water resistance may become poor. If the
rate is smaller, the dispersibility and removability may become
poor.
[0040] In the present invention, it is desirable that a (e)
silicone surfactant is further blended as an emulsifying agent. The
silicone surfactant is not limited in particular so far as it is
usable in water-in-oil emulsion systems. Examples include
poly(oxyethylene/oxypropylene) methylpolysiloxane copolymer,
polyoxyethylene methylpolysiloxane copolymer, silicone-chain
branched-type methylpolysiloxane copolymer, alkyl-chain
branched-type polyoxyethylene methylpolysiloxane copolymer,
alkyl-chain/silicone-chain branched-type polyoxyethylene
methylpolysiloxane copolymer, crosslinked-type polyoxyethylene
methylpolysiloxane, alkyl-containing crosslinked-type
polyoxyethylene methylpolysiloxane, branched-type
polyglycerin-modified silicone, crosslinked-type
polyglycerin-modified silicone, alkyl-containing crosslinked-type
polyglycerin-modified silicone, and alkyl group branched-type
polyglycerin-modified silicone. However, the silicone surfactant is
not limited to these.
[0041] Examples of the above-described
poly(oxyethylene/oxypropylene)methylpolysiloxane copolymers include
PEG/PPG-20/22 butyl ether dimethicone ("KF-6012", manufactured by
Shin-Etsu Chemical Co., Ltd.), PEG/PPG-20/20 dimethicone
("BY22-008M", manufactured by Toray Dow Corning Silicone Co.,
Ltd.), lauryl PEG/PPG-18 methicone ("5200 Formulation Aid",
manufactured by Dow Corning Toray Co., Ltd.), PEG/PPG-19/19
dimethicone ("5330 Fluid", manufactured by Dow Corning Toray Co.,
Ltd.), and PEG/PPG-15/15 dimethicone ("5330 Fluid", manufactured by
Dow Corning Toray Co., Ltd.).
[0042] Examples of polyoxyethylene methylpolysiloxane copolymers
include PEG-11 methyl ether dimethicone ("KF-6011", manufactured by
Shin-Etsu Chemical Co., Ltd.), PEG-9 dimethicone ("KF-6013",
manufactured by Shin-Etsu Chemical Co., Ltd.), PEG-3 dimethicone
("KF-6015", manufactured by Shin-Etsu Chemical Co., Ltd.), PEG-9
methyl ether dimethicone ("KF-6016", manufactured by Shin-Etsu
Chemical Co., Ltd.), PEG-10 dimethicone ("KF-6017", manufactured by
manufactured by Shin-Etsu Chemical Co., Ltd.), PEG-11 methyl ether
dimethicone ("KF-6018", manufactured by Shin-Etsu Chemical Co.,
Ltd.), PEG-9 dimethicone ("KF-6019", manufactured by Shin-Etsu
Chemical Co., Ltd.), and PEG-12 dimethicone ("SH3771M", "SH3772M",
"SH3773M", "SH3775M" etc., manufactured by Dow Corning Toray Co.,
Ltd.).
[0043] Examples of silicone-chain branched-type methylpolysiloxane
copolymers include PEG-9 polydimethylsiloxyethyl dimethicone
("KF-6028", manufactured by Shin-Etsu Chemical Co., Ltd.).
[0044] Examples of alkyl-chain branched-type polyoxyethylene
methylpolysiloxane copolymers include PEG/PPG-10/3 oleyl ether
dimethicone ("KF-6026", manufactured by Shin-Etsu Chemical Co.,
Ltd.).
[0045] Examples of alkyl-chain/silicone-chain branched-type
polyoxyethylene methylpolysiloxane copolymers include lauryl PEG-9
polydimethylsiloxyethyl dimethicone ("KF-6038", manufactured by
Shin-Etsu Chemical Co., Ltd.).
[0046] Examples of crosslinked-type polyoxyethylene
methylpolysiloxanes include dimethicone/(PEG-10/15) crosspolymer
("KSG-210", manufactured by Shin-Etsu Chemical Co., Ltd.) and
cyclomethicone/(PEG-12 dimethicone) crosspolymer ("9011 Silicone
Elastomer Blend", manufactured by Toray Dow Corning Silicone Co.,
Ltd.).
[0047] Examples of alkyl-containing crosslinked-type
polyoxyethylene methylpolysiloxanes include mineral oil/PEG-15
lauryl dimethicone crosspolymer ("KSG-310", manufactured by
Shin-Etsu Chemical Co., Ltd.), isododecane/PEG-15 lauryl
dimethicone crosspolymer ("KSG-320", manufactured by Shin-Etsu
Chemical Co., Ltd.), trioctanoin/PEG-15 lauryl dimethicone
crosspolymer ("KSG-330", manufactured by Shin-Etsu Chemical Co.,
Ltd.), and squalane/PEG-15 lauryl dimethicone crosspolymer/PEG-10
lauryl dimethicone crosspolymer ("KSG-340", manufactured by
Shin-Etsu Chemical Co., Ltd.).
[0048] Examples of branched-type polyglycerin-modified silicones
include polyglyceryl-3 disiloxane dimethicone ("KF-6100",
manufactured by Shin-Etsu Chemical Co., Ltd.) and polyglyceryl-3
polydimethylsiloxyethyl dimethicone ("KF-6104", manufactured by
Shin-Etsu Chemical Co., Ltd.).
[0049] Examples of crosslinked-type polyglycerin-modified silicones
include dimethicone/(dimethicone/polyglycerin-3) crosspolymer
("KSG-710", manufactured by Shin-Etsu Chemical Co., Ltd.).
[0050] Examples of alkyl-containing crosslinked-type
polyglycerin-modified silicones include mineral oil/(lauryl
dimethicone/polyglycerin-3) crosspolymer ("KSG-810", manufactured
by Shin-Etsu Chemical Co., Ltd.), isododecane/(lauryl
dimethicone/polyglycerin-3) crosspolymer ("KSG-820, manufactured by
Shin-Etsu Chemical Co., Ltd."), trioctanoin/(lauryl
dimethicone/polyglycerin-3) crosspolymer ("KSG-830", manufactured
by Shin-Etsu Chemical Co., Ltd.), and squalane/(lauryl
dimethicone/polyglycerin-3) crosspolymer ("KSG-840", manufactured
by Shin-Etsu Chemical Co., Ltd.).
[0051] Examples of alkyl group branched-type polyglycerin-modified
silicones include lauryl polyglyceryl-3 polydimethylsiloxyethyl
dimethicone ("KF-6105", manufactured by Shin-Etsu Chemical Co.,
Ltd.).
[0052] Among them, polyoxyethylene methylpolysiloxane copolymer,
poly(oxyethylene/oxypropylene) methylpolysiloxane copolymer,
silicone-chain branched-type methylpolysiloxane copolymer, and
alkyl-chain/silicone-chain branched-type polyoxyethylene
methylpolysiloxane copolymer are desirably used.
[0053] The blending amount of component (e) in the sunscreen
cosmetics of the present invention is preferably 0.01% by mass at
the lower limit, more preferably 0.1% by mass or higher, and
further more preferably 0.5% by mass or higher. The upper limit is
preferably 20% by mass or lower and more preferably 10% by mass or
lower. If the blending amount is less than 0.01% by mass, the
stability of cosmetics tends to become poorer. On the other hand,
if the blending amount largely exceeds 20% by mass, a sticky
feeling is generated and the feeling in use tends to become
poorer.
[0054] In the water-in-oil type emulsion sunscreen cosmetics of the
present invention, it is preferred that the oil phase (outer phase)
is 40 to 80% by mass and the water phase (inner phase) is 20 to 60%
by mass.
[0055] In the cosmetics of the present invention, in addition to
the above-described components, other components normally be used
in cosmetics can be blended as necessary so far as the objectives
and effects of the present invention are not undermined. Examples
of these components include water-soluble polymers, oil-soluble
polymers, polymer powders, emulsifying agents (other than the
above-described component (e)), waxes, alcohols, liquid fats, ester
oils, hydrocarbon oils, silicone oils, fatty acids, higher
alcohols, fatty acid esters, drugs, UV absorbers (other than the
above-described component (a)), UV scattering agents (other than
the above-described component (b)), and organic-modified clay
minerals. However, the components are not limited by these
examples.
[0056] Examples of water-soluble polymers include a homopolymer and
copolymers of 2-acrylamido-2-methyl propane sulfonic acid
(hereinafter abbreviated as "AMPS"). The copolymer comprises
comonomers such as vinylpyrrolidone, acrylamide, sodium acrylate,
and hydroxyethyl acrylate. Examples include AMPS homopolymer,
vinylpyrrolidone/AMPS copolymer, dimethylacrylamide/AMPS copolymer,
acrylamide/AMPS copolymer, and sodium acrylate/AMPS copolymer.
[0057] Further examples include carboxyvinyl polymer, ammonium
polyacrylate, sodium polyacrylate, sodium acrylate/alkyl
acrylate/sodium methacrylate/alkyl methacrylate copolymer,
carrageenan, pectin, mannan, curdlan, chondroitin sulfate, starch,
glycogen, gum arabic, sodium hyaluronate, tragacanth gum, xanthan
gum, mucoitin sulfate, hydroxyethyl guar gum, carboxymethyl guar
gum, guar gum, dextran, kerato sulfate, locust bean gum,
succinoglucan, chitin, chitosan, carboxymethyl chitin, and
agar.
[0058] Examples of oil-soluble polymers include
trimethylsiloxysilicate, alkyl-modified silicone, and
polyamide-modified silicone.
[0059] Examples of polymer powders include dimethicone
crosspolymer, (dimethicone/vinyldimethicone) crosspolymer,
polymethylsilsesquioxane, polyethylene, and
polymethylmethacrylate.
[0060] Examples of waxes include beeswax, candelilla wax, carnauba
wax, lanolin, lanolin oil, and jojoba wax.
[0061] Examples of emulsifying agents (other than the
above-described component (e)) include glycerin fatty acid ester,
polyglycerin fatty acid ester, polyoxyethylene glycerin fatty acid
ester, sorbitan fatty acid ester, and polyoxyethylene sorbitan
fatty acid ester.
[0062] Examples of alcohols include lower alcohols such as ethanol
and isopropanol; higher alcohols such as isostearyl alcohol,
octyldodecanol, and hexyldecanol; and polyhydric alcohols such as
ethylene glycol, propylene glycol, 1,3-butylene glycol, dipropylene
glycol, and polybutylene glycol.
[0063] Examples of liquid fats include avocado oil, camellia oil,
turtle oil, macadamia nut oil, corn oil, mink oil, olive oil,
rapeseed oil, egg oil, sesame oil, persic oil, wheat germ oil,
sasanqua oil, castor oil, linseed oil, safflower oil, cottonseed
oil, perilla oil, soybean oil, peanut oil, tea seed oil, kaya oil,
rice bran oil, paulownia oil, Japanese tung oil, jojoba oil, germ
oil, and triglycerin.
[0064] Examples of ester oils include isopropyl myristate, cetyl
octanoate, octyldodecyl myristate, isopropyl palmitate, butyl
stearate, hexyl laurate, myristyl myristate, decyl oleate,
hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate,
acetylated lanolin, isocetyl stearate, isocetyl isostearate,
isononyl isononate, cholesteryl 12-hydroxystearate, ethylene glycol
di-2-ethylhexanoate, dipentaerythritol fatty acid ester,
N-alkylglycol monoisostearate, neopentyl glycol dicaprylate,
diisostearyl malate, glyceryl di-2-heptylundecanoate,
trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane
triisostearate, pentaerythritol tetra-2-ethylhexanoate, glyceryl
tri-2-ethylhexanoate, glyceryl trioctanoate, glyceryl
triisopalmitate, trimethylolpropane triisostearate, cetyl
2-ethylhexanoate, 2-ethylhexyl palmitate, glyceryl trimyristate,
glyceride tri-2-heptylundecanoate, castor oil fatty acid methyl
ester, oleyl oleate, acetoglyceride, 2-heptylundecyl palmitate,
diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester,
di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl
sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate,
2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate,
and triethyl citrate.
[0065] Examples of hydrocarbon oils include liquid paraffin,
ozokerite, squalane, pristane, paraffin, ceresin, squalene,
petrolatum, microcrystalline wax, polyethylene wax, and
Fischer-Tropsch wax.
[0066] Examples of silicon oils include dimethylpolysiloxane,
octamethylsiloxane, decamethyltetrasiloxane,
methylhydrogenpolysiloxane, methylphenylpolysiloxane,
hexamethylcyclotrisiloxane, octamethylcyciotetrasiloxane, and
decamethylcyclopentasiloxane.
[0067] Examples of fatty acids include lauric acid, myristic acid,
palmitic acid, stearic acid, behenic acid, and arachidonic
acid.
[0068] Examples of higher alcohols include lauryl alcohol, myristyl
alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, arachyl
alcohol, batyl alcohol, chimyl alcohol, carnaubyl alcohol, ceryl
alcohol, koryanyl alcohol, myricyl alcohol, lacceryl alcohol,
elaidyl alcohol, isostearyl glyceryl ether, octyl alcohol,
triacontyl alcohol, cerakyl alcohol, cetostearyl alcohol, oleyl
alcohol, lanolin alcohol, hydrogenated lanolin alcohol,
hexyldecanol, and octyldecanol.
[0069] Examples of fatty acid esters include myristyl myristate,
cetyl palmitate, cholesteryl stearate, and 2-octyldodecyl beeswax
fatty acid.
[0070] Examples of drugs include L-ascorbic acid and its salt
derivatives, glycyrrhizic acid and its derivatives such as
dipotassium glycyrrhizate and monoammonium glycyrrhizate,
glycyrrhetinic acid and its derivatives such as stearyl
glycyrrhetinate, allantoin, tranexamic acid and its salt
derivatives, alkoxysalicylic acid and its salt derivatives,
glutathione and its salt derivatives, allantoin, and azulene.
[0071] Examples of UV absorbers (other than the above-described
component (a)) include cinnamic acid derivatives such as ethylhexyl
methoxycinnamate, isopropyl methoxycinnamate, and isoamyl
methoxycinnamate; PABA derivatives such as para-aminobenzoic acid
(hereinafter abbreviated as "PABA"), ethyl PABA, ethyl
dihydroxypropyl PABA, ethylhexyl dimethyl PABA, and glyceryl PABA;
salicylic acid derivatives such as homosalate, ethylhexyl
salicylate, dipropylene glycol salicylate, and TEA salicylate;
benzophenone derivatives such as benzophenone-1, benzophenone-2,
benzophenone-3 or oxybenzone, benzophenone-4, benzophenone-5,
benzophenone-6, benzophenone-8, benzophenone-9, and
benzophenone-12; benzylidene camphor derivatives such as
3-benzylidene camphor, 4-methylbenzylidene camphor, benzylidene
camphor sulfonic acid, camphor benzalkonium methosulfate,
terephthalylidene dicamphor sulfonic acid, and polyacrylamidomethyl
benzylidene camphor; triazine derivatives such as anisotriazine,
ethylhexyl triazone, diethylhexyl butamido triazone, and
2,4,6-tris(diisobutyl 4'-aminobenzalmalonate)-s-triazine;
phenylbenzimidazole derivatives such as disodium
phenyldibenzimidazole tetrasulfonate; phenylbenzotriazol
derivatives such as drometrizole trisiloxane and methylene
bis-benzotriazolyl tetramethylbutylphenol; anthranilic derivatives
such as menthyl anthranilate; imidazoline derivatives such as
ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate;
benzalmalonate derivatives such as polyorganosiloxanes with
benzalmalonate functional groups; and 4,4-diarylbutadiene
derivatives such as
1,1-dicarboxy(2,2'-dimethylpropyl)-4,4-diphenylbutadiene.
[0072] Examples of UV scattering agents (other than the
above-described component (b)) include hydrophobized inorganic
pigments such as titanium dioxide, kaolin, and calcium
carbonate.
[0073] Examples of organic-modified clay minerals include
quaternary ammonium cation modified clay minerals.
[0074] The water-in-oil type emulsion sunscreen cosmetics of the
present invention include products such as emulsion type and cream
type. These products can be prepared by the conventional method by
mixing the above-described essential components and the components
that are normally blended in cosmetics.
[0075] Hereinafter, the present invention will be described in
further detail with reference to examples. However, the present
invention is not limited by the following examples. All the
blending amounts are shown in % by mass.
EXAMPLES
[0076] Before the examples are described, test methods and
evaluation methods used in the present invention will be
described.
[Prevention and Inhibition Effects of Red Discoloration]
[0077] After each sample was allowed to stand at 70.degree. C. for
3 days, the appearance was visually evaluated.
(Evaluation)
[0078] .largecircle.: No discoloration (discoloration to red) was
observed. .largecircle..DELTA.: A slight discoloration
(discoloration to red) was observed. .DELTA.: Some discoloration
(discoloration to red) was observed. .DELTA.X: Appreciable
discoloration (discoloration to red) was observed. X: Discoloration
(discoloration to red) was observed. XX: Significant discoloration
(discoloration to red) was observed.
Example 1
[0079] In a simple oil phase system, the prevention and inhibition
effects of red discoloration were evaluated according to the
above-described evaluation criteria. The evaluation was conducted,
with the use of samples A to K of the below-described compositions,
in relation to the blending/non-blending of respective components
(a) to (d), system discoloration to red, and the prevention and
inhibition effects of red discoloration. The results are shown in
Table 1.
[0080] In Table 1, "octocrylene".sup.(*.sup.1), in which the amount
of 2-ethylhexyl cyanoacetate is about 1000 ppm, and
"octocrylene".sup.(*.sup.2), in which the amount of 2-ethylhexyl
cyanoacetate is about 100 ppm, were used. They were the same in
examples in Table 2 and examples in tables below Table 2.
[0081] In Table 1, the percentages (mass ratio) of component (b)
and component (c) in "(6) hydrophobized (silane
treatment)/cation-treated zinc oxide [component (b)+component (c)]"
were about 98% by mass and about 2% by mass, respectively.
[0082] The percentages (mass ratio) of component (b) and component
(d) in "(7) hydrophobized (silane treatment)/silica-coated zinc
oxide [component (b)+component (d)]" were about 80% by mass and
about 20% by mass, respectively.
[0083] The percentage (mass ratio) of component (d) in "(8)
hydrophobized (silane treatment)/silica-coated titanium dioxide
[component (d)]" was about 10% by mass. That is, the blending
amount of component (d) in sample I was 1.5% by mass.
TABLE-US-00001 TABLE 1 Sam- ple A Sam- Sam- Sam- Sam- Sam- Sam-
Sam- Sam- (control) ple B ple C, D, E ple F, G, H ple I ple J ple K
ple L ple M (1) Decamethylcyclopentasiloxane 65 50 Balance Balance
35 35 65 50 50 (2) Methylphenylpolysiloxane 20 20 20 20 20 20 20 20
20 (3) Octocrylene (*1) [component (a)] 15 15 15 15 15 15 -- -- --
(4) Octocrylene (*2) [component (a)] -- -- -- -- -- -- -- 15 15 (5)
Hydrophobized (silane treatment) zinc oxide -- 15 -- -- -- -- -- --
-- [component (b)] (6) Hydrophobized (silane treatment)/cation- --
-- 5, 10, 15 15 15 15 15 15 15 treated zinc oxide [component (b) +
component (c)] (7) Hydrophobized (silane treatment)/silica- -- --
-- -- -- 15 -- -- -- coated zinc oxide [component (b) + component
(d)] (8) Hydrophobized (silane treatment)/silica- -- -- -- -- 15 --
-- -- -- coated titanium dioxide [component (d)] (9) Silica powder
[component (d)] -- -- -- 1, 3, 6 -- -- -- -- 1 Prevention and
inhibition, effects of red .largecircle. .largecircle. X, XX, XX
.largecircle., .largecircle., .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle..DELTA. .largecircle.
discoloration (at 70.degree. C. for 3 days, visual evaluation)
[0084] As is clear from the results in Table 1, sample A (control)
containing component (a) but not containing components (b) and (c)
did not discolor to red even without blending component (d). Sample
B containing components (a) and (b) but not containing component
(c) did not discolor to red even without component (d). Samples C
to E containing components (a) to (c) but not containing component
(d) discolored to red. However, samples F to H, in which component
(d) was added to components (a) to (c), and samples I and J, in
which component (d) was added by coating the powder therewith, did
not discolor to red. As shown in sample K, when component (a) was
not blended, the discoloration to red did not take place even when
components (b) and (c) were blended. When octocrylene containing
100 ppm of 2-ethylhexyl cyanoacetate was used as component (a), the
prevention and inhibition effects of red discoloration were better
than when octocrylene containing 1000 ppm of 2-ethylhexyl
cyanoacetate was used (comparison between sample E and sample
L).
Example 2
[0085] For the case in that component (c) and component (d) are
individually blended instead of blending the powder coated
therewith, the blending amounts and the prevention effect of red
discoloration were evaluated according to the above-described
evaluation criteria. The results are shown in Tables 2 and 3.
[0086] In Table 2, the percentages (mass ratio) of component (b)
and component (c) in "(5) hydrophobized (silane
treatment)/cation-treated zinc oxide [component (b)+component (c)]"
were about 98% by mass and about 2% by mass, respectively.
TABLE-US-00002 TABLE 2 Sample X Sample Y (1)
Decamethylcyclopentasiloxane Balance Balance (2)
Methylphenylpolysiloxane 20 20 (3) Octocrylene (*2) [component (a)]
15 15 (4) Hydrophobized (silane treatment) zinc oxide -- 15
[component (b)] (5) Hydrophobized (silane treatment)/cation- 15 --
treated zinc oxide [component (b) + component (c)] (6)
Distearyldimethylammonium chloride -- Table 3 [component (c)] (7)
Silica powder [component (d)] -- Table 3 Prevention and inhibition
effects of red X Table 3 discoloration (at 70.degree. C. for 3
days, visual evaluation)
TABLE-US-00003 TABLE 3 Distearyldimethylammonium chloride
[component (c)] (blending amounts in sample Y, in % by mass) 0 0.01
0.1 0.5 1 3 6 Prevention and inhibition effects of red
discoloration (at 70.degree. C. for 3 days, visual evaluation)
Silica powder [component (d)] 0 .largecircle. X X XX XX XX XX
(blending amounts in sample Y, 1 -- .DELTA.X X XX XX XX XX in % by
mass) 3 -- .DELTA.X X XX XX XX XX 6 -- .largecircle..DELTA.
.DELTA.X XX XX XX XX 10 -- .largecircle..DELTA. -- -- -- -- --
[0087] As shown in the results of Tables 2 and 3, the improvement
in discoloration was observed by blending 6% by mass or higher
component (d) to 0.01% by mass component (c).
Example 3
[0088] The discoloration of a system (sample Z) in which other
powder components are blended instead of silica was evaluated
according to the above-described evaluation criteria. The results
are shown in Tables 4 and 5.
[0089] In Table 4, the percentages (mass ratio) of component (b)
and component (c) in "(5) hydrophobized (silane
treatment)/cation-treated zinc oxide [component (b)+component (c)]"
were about 98% by mass and about 2% by mass, respectively.
TABLE-US-00004 TABLE 4 Sample Z (1) Decamethylcyclopentasiloxane
Balance (2) Methylphenylpolysiloxane 20 (3) Octocrylene (*1)
[component (a)] 15 (4) Hydrophobized (silane treatment) zinc oxide
-- [component (b)] (5) Hydrophobized (silane
treatment)/cation-treated zinc oxide 15 [component (b) + component
(c)] (6) Distearyldimethylammonium chloride [component (c)] -- (7)
Powder component shown in table 5 6 Prevention and inhibition
effects of red discoloration Table 5 (at 70.degree. C. for 3 days,
visual evaluation)
TABLE-US-00005 TABLE 5 Prevention and inhibition effects of red
discoloration (at 70.degree. C. for 3 days, Powder component visual
evaluation) Silicone resin powder X Cellulose powder X Starch
powder X talc powder X Cross linked-type silicone powder X PMMA
powder X Barium sulfate powder X Cross linked-type silicone powder
X
[0090] As is clear from the results in Tables 4 and 5, the
prevention and inhibition effects of red discoloration could not be
achieved by powder components other than silica.
Example 4
[0091] Water-in-oil type emulsion sunscreen cosmetics of the
compositions shown in Tables 6 and 7 were prepared according to the
normal method. The prevention and inhibition effects of
discoloration were evaluated for these samples according to the
above-described evaluation criteria. The results are shown in
Tables 6 and 7.
[0092] In Tables 6 and 7, "(13) hydrophobized (silane
treatment)/cation-treated zinc oxide".sup.(*.sup.3) with a specific
surface area of about 50 m.sup.2/g, "(14) hydrophobized (silane
treatment)/cation-treated zinc oxide".sup.(*.sup.4) with a specific
surface area of about 50 to 70 m.sup.2/g, and "(15) hydrophobized
(silane treatment)/cation-treated zinc oxide".sup.(*.sup.5) with a
specific surface area of about 70 m.sup.2/g were used,
respectively. The percentages (mass ratio) of component (b) and
component (c) contained in components (13), (14), and (15) were
about 98% by mass and about 2% by mass, respectively.
[0093] The percentages (mass ratio) of component (b) and component
(d) in "(17) hydrophobized (silane treatment)/silica-coated zinc
oxide [component (b)+component (d)]" were about 80% by mass and
about 20% by mass, respectively.
[0094] The percentage (mass ratio) of component (d) in "(18)
hydrophobized (silane treatment)/titanium dioxide [component (d)]"
was about 10% by mass. That is, the blending amount of component
(d) contained in sample 7, shown in Table 7, was 1.5% by mass, and
the blending amount of component (d) contained in sample 11 was
0.5% by mass.
TABLE-US-00006 TABLE 6 Control Sample 1 Sample 2 Sample 3 Sample 4
Sample 5 (1) Ion-exchanged water Balance Balance Balance Balance
Balance Balance (2) Organic-modified clay minerals 0.1 0.1 0.1 0.1
0.1 0.1 (3) Dynamite glycerol 3.0 3.0 3.0 3.0 3.0 3.0 (4)
Polyoxyethylene methylpolysiloxane copolymer [component (e)] 2.0
2.0 2.0 2.0 2.0 2.0 (5) Distearyldimethylammonium chloride
[component (c)] -- -- -- -- -- -- (6) Decamethylcyclopentasiloxane
20.0 20.0 15.0 20.0 20.0 20.0 (7) Dimethylpolysiloxane 10.0 10.0
10.0 10.0 10.0 10.0 (8) Olefin oligomer 5.0 5.0 5.0 5.0 5.0 5.0 (9)
Trimethylsiloxysilicate 5.0 5.0 5.0 5.0 5.0 5.0 (10) Octyl
methoxycinnamate 10.0 10.0 10.0 10.0 10.0 10.0 (11) Octocrylene
(*1) [component (a)] 5.0 5.0 5.0 5.0 5.0 5.0 (12) Hydrophobized
(silane treatment) zinc oxide [component (b)] 15.0 -- -- -- -- --
(13) Hydrophobized (silane treatment)/cation-treated zinc oxide
(*3) -- 15.0 15.0 -- -- -- [component (b) + component (c)] (14)
Hydrophobized (silane treatment)/cation-treated zinc oxide (*4) --
-- 15.0 15.0 -- [component (b) + component (c)] (15) Hydrophobized
(silane treatment)/cation-treated zinc oxide (*5) -- -- -- -- 15.0
[component (b) + component (c)] (16) Hydrophobized (fatty acid
dextrin treatment) zinc oxide -- -- 3.0 -- -- -- [component (b)]
(17) Hydrophobized (silane treatment)/silica-coated zinc oxide --
-- -- -- -- [component (b) + component (d)] (18) Hydrophobized
(silane treatment)/silica-coated titanium dioxide -- -- -- -- --
[component (d)] (19) Silica powder [component (d)] -- -- 4.0 -- 4.0
-- (20) Edetate Appro- Appro- Appro- Appro- Appro- Appro- priate
priate priate priate priate priate amount amount amount amount
amount amount (21) Phenoxyethanol 0.5 0.5 0.5 0.5 0.5 0.5
Prevention and inhibition effects of red discoloration
.largecircle. X .largecircle. .DELTA.X .largecircle. X (at
70.degree. C. for 3 days, visual evaluation)
TABLE-US-00007 TABLE 7 Sample 6 Sample 7 Sample 8 Sample 9 Sample
10 Sample 11 (1) Ion-exchanged water Balance Balance Balance
Balance Balance Balance (2) Organic-modified clay minerals 0.1 0.1
0.1 0.1 0.1 0.1 (3) Dynamite glycerol 3.0 3.0 3.0 3.0 3.0 3.0 (4)
Polyoxyethylene methylpolysiloxane copolymer [component (e)] 2.0
2.0 2.0 2.0 2.0 2.0 (5) Distearyldimethylammonium chloride
[component (c)] -- -- 0.001 0.001 -- -- (6)
Decamethylcyclopentasiloxane 20.0 20.0 20.0 20.0 20.0 20.0 (7)
Dimethylpolysiloxane 10.0 10.0 10.0 10.0 10.0 10.0 (8) Olefin
oligomer 5.0 5.0 5.0 5.0 5.0 5.0 (9) Trimethylsiloxysilicate 5.0
5.0 5.0 5.0 5.0 5.0 (10) Octyl methoxycinnamate 10.0 10.0 10.0 10.0
10.0 10.0 (11) Octocrylene (*1) [component (a)] 5.0 5.0 5.0 5.0 5.0
5.0 (12) Hydrophobized (silane treatment) zinc oxide [component
(b)] -- -- 15.0 15.0 -- -- (13) Hydrophobized (silane
treatment)/cation-treated zinc oxide (*3) -- -- -- -- 15.0 15.0
[component (b) + component (c)] (14) Hydrophobized (silane
treatment)/cation-treated zinc oxide (*4) -- -- -- -- -- [component
(b) + component (c)] (15) Hydrophobized (silane
treatment)/cation-treated zinc oxide (*5) -- -- -- -- -- [component
(b) + component (c)] (16) Hydrophobized (fatty acid dextrin
treatment) zinc oxide 15.0 -- -- -- -- -- [component (b)] (17)
Hydrophobized (silane treatment)/silica-coated zinc oxide -- -- --
5.0 -- [component (b) + component (d)] (18) Hydrophobized (silane
treatment)/silica-coated titanium dioxide -- 15.0 -- -- -- 5.0
[component (d)] (19) Silica powder [component (d)] -- -- -- 6.0 --
-- (20) Edetate Appro- Appro- Appro- Appro- Appro- Appro- priate
priate priate priate priate priate amount amount amount amount
amount amount (21) Phenoxyethanol 0.5 0.5 0.5 0.5 0.5 0.5
Prevention and inhibition effects of red discoloration
.largecircle. .largecircle. X .largecircle. .largecircle.
.largecircle. (at 70.degree. C. for 3 days, visual evaluation)
[0095] As is clear from the results in Tables 6 and 7 for
water-in-oil type emulsion sunscreen cosmetics containing component
(a), if component (d) is not blended in the system where component
(b) and component (c) are contained, the sample changed into red
(samples 1, 3, 5, and 8). If component (d) is blended, however, the
discoloration to red could be inhibited (samples 2, 4, 9, 10, and
11). When at least one of component (b) and component (c) was
missing, the discoloration to red did not take place either with or
without component (d) (samples 6 and 7).
[0096] More formulation examples are shown below.
Example 5
Water-in-Oil Type Emulsion Sunscreen Milky Lotion
TABLE-US-00008 [0097] (Blending components) (% by mass) (1)
Decamethylcyclopentasiloxane 15 (2)
Polyoxyethylene/methylpolysiloxane copolymer 1 (3) Olefin oligomer
10 (4) Dimethylpolysiloxane 10 (5) Octyl methoxycinnamate 10 (6)
Octocrylene 5 (7) Diethylamino hydroxybenzoyl hexyl benzoate 2 (8)
Phenoxyethanol 0.5 (9) Fragrance 0.5 (10) Organic-modified clay
minerals 0.1 (11) Hydrophobized (silane treatment)/cation- 15
treated zinc oxide (12) Silica powder 5 (13) Crosslinked-type
silicone/network-type 5 silicone block copolymer (KSP 100) (14)
Ion-exchanged water Balance (15) Glycerin 3 (16) Edetate
Appropriate amount
(Production Method)
[0098] Components (1) to (9) were mixed and dissolved at room
temperature to prepare an oil phase in advance. Subsequently,
components (10) to (13) were added, and the mixture was
dispersively mixed with a disper. Components (14) to (16) were
mixed, dissolved, and gradually added to the oil phase by stirring
with a disper. The desired sunscreen milky lotion was obtained by
mixing and dissolving to a sufficiently homogeneous state.
Example 6
Water-in-Oil Type Emulsion Sunscreen Milky Lotion
TABLE-US-00009 [0099] (Blending components) (% by mass) (1)
Decamethylcyclopentasiloxane 20 (2)
Polyoxyethylene/methylpolysiloxane copolymer 1 (3) Olefin oligomer
10 (4) Dimethylpolysiloxane 10 (5) Octyl methoxycinnamate 10 (6)
Octocrylene 5 (7) Paraben 0.5 (8) Fragrance 0.5 (9)
Organic-modified clay minerals 0.1 (10) Hydrophobized (silane
treatment)/cation-treated 15 zinc oxide (11) Hydrophobized (silane
treatment)/silica-coated 5 titanium dioxide (12) Crosslinked-type
silicone/network-type 5 silicone block copolymer (KSP 105) (13)
Ion-exchanged water Balance (14) Glycerin 3 (15) Edetate
Appropriate amount
(Production Method)
[0100] Components (1) to (8) were mixed and dissolved at room
temperature to prepare an oil phase in advance. Subsequently,
components (9) to (12) were added, and the mixture was dispersively
mixed with a disper. Components (13) to (15) were mixed, dissolved,
and gradually added to the oil phase by stirring with a disper. The
desired sunscreen milky lotion was obtained by mixing and
dissolving to a sufficiently homogeneous state.
Example 7
Water-in-Oil Type Emulsion Sunscreen Cream
TABLE-US-00010 [0101] (Blending components) (% by mass) (1)
Decamethylcyclopentasiloxane 20 (2)
Polyoxyethylene/methylpolysiloxane copolymer 3 (3) Cetyl
isooctanoate 10 (4) Dimethylpolysiloxane 5 (5) Octocrylene 10 (6)
2,4-bis{[4-(2-ethylhexyloxy)-2-hydroxy]- 0.5
phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine (7)
Distearyldimethylammonium chloride 0.001 (8) Phenoxyethanol 0.5 (9)
Fragrance 0.5 (10) Organic-modified clay minerals 2.5 (11)
Hydrophobized (silane treatment) zinc oxide 10 (12) Silica powder 6
(13) Crosslinked-type silicone/network-type 5 silicone block
copolymer (KSP 101) (14) Ion-exchanged water Balance (15)
1,3-butylene glycol 2 (16) Edetate Appropriate amount
(Production Method)
[0102] Components (1) to (9) were mixed and dissolved at 70.degree.
C. to prepare an oil phase in advance. Subsequently, components
(10) to (13) were added, and the mixture was dispersively mixed
with a disper. Components (14) to (16) were mixed, dissolved, and
gradually added to the oil phase by stirring with a disper. The
desired sunscreen cream was obtained by mixing and dissolving to a
sufficiently homogeneous state.
* * * * *