U.S. patent application number 11/576705 was filed with the patent office on 2008-04-03 for surface-treating agents, surface-treated powders, and cosmetics comprising the same.
This patent application is currently assigned to SHISEIDO CO., LTD.. Invention is credited to Isamu Kaneda, Shuji Nishihama, Tomo Osawa, Atsushi Sogabe, Shin-ichi Yusa.
Application Number | 20080081029 11/576705 |
Document ID | / |
Family ID | 36142738 |
Filed Date | 2008-04-03 |
United States Patent
Application |
20080081029 |
Kind Code |
A1 |
Nishihama; Shuji ; et
al. |
April 3, 2008 |
Surface-Treating Agents, Surface-Treated Powders, And Cosmetics
Comprising The Same
Abstract
To provide surface-treating agents that can provide excellent
hydrophobicity to powder and can improve its rinsability, to
provide surface-treated powders that are treated with the
surface-treating agent, and to provide cosmetics that comprise the
surface-treated powder. A surface-treating agent consisting of a
polymer which comprises a monomer (A) represented by the general
formula (1) described below as a constituent monomer. ##STR00001##
(wherein R.sup.1 represents a hydrogen atom or an alkyl group
having 1 to 3 carbon atoms, R.sup.2 represents an alkylene group
having 4 to 22 carbon atoms, X.sup.1 represents an --NH-- group or
an oxygen atom, and M.sup.1 represents a hydrogen atom or a
monovalent inorganic or organic cation.)
Inventors: |
Nishihama; Shuji; (Kanagawa,
JP) ; Kaneda; Isamu; (Kanagawa, JP) ; Sogabe;
Atsushi; (Kanagawa, JP) ; Osawa; Tomo;
(Kanagawa, JP) ; Yusa; Shin-ichi; (Hoga,
JP) |
Correspondence
Address: |
RANKIN, HILL & CLARK LLP
925 EUCLID AVENUE, SUITE 700
CLEVELAND
OH
44115-1405
US
|
Assignee: |
SHISEIDO CO., LTD.
Chuo-ku, Tokyo
JP
|
Family ID: |
36142738 |
Appl. No.: |
11/576705 |
Filed: |
October 6, 2005 |
PCT Filed: |
October 6, 2005 |
PCT NO: |
PCT/JP05/18521 |
371 Date: |
April 12, 2007 |
Current U.S.
Class: |
424/69 ;
514/772.6 |
Current CPC
Class: |
A61K 8/11 20130101; C09C
3/10 20130101; C09C 1/3676 20130101; C09C 1/28 20130101; A61Q 1/02
20130101; A61Q 1/12 20130101; A61Q 17/04 20130101; C08F 220/28
20130101; C09C 3/12 20130101; A61K 2800/412 20130101; A61Q 1/10
20130101; A61Q 1/04 20130101; C01P 2004/10 20130101; C01P 2004/20
20130101; C09C 1/405 20130101; A61K 8/8158 20130101; C09C 1/027
20130101 |
Class at
Publication: |
424/69 ;
514/772.6 |
International
Class: |
A61K 8/84 20060101
A61K008/84; A61Q 1/12 20060101 A61Q001/12 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 7, 2004 |
JP |
2004-294618 |
Oct 7, 2004 |
JP |
2004-294619 |
Claims
1: A surface-treating agent consisting of a polymer which comprises
a monomer (A) represented by the general formula (1) described
below as a constituent monomer. ##STR00012## wherein R.sup.1
represents a hydrogen atom or an alkyl group having 1 to 3 carbon
atoms, R.sup.2 represents an alkylene group having 4 to 22 carbon
atoms, X.sup.1 represents an --NH-- group or an oxygen atom, and
M.sup.1 represents a hydrogen atom or a monovalent inorganic or
organic cation.
2: The surface-treating agent of claim 1, wherein the polymer
comprises at least 70 mole % of monomer (A).
3: The surface-treating agent of claim 1, wherein the polymer
further comprises a monomer (B) represented by any one of general
formulas (2) to (7): ##STR00013## wherein R.sup.3 represents a
hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R.sup.4
represents an alkylene group having 1 to 4 carbon atoms, X.sup.1
represents an --NH-- group or an oxygen atom, and M.sup.2
represents a hydrogen atom or a monovalent inorganic or organic
cation; ##STR00014## wherein R.sup.5 represents a hydrogen atom or
an alkyl group having 1 to 3 carbon atoms, R.sup.6 represents an
alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, an
aminoalkyl group, or a hydroxyalkyl group, and X.sup.3 represents
an --NH-- group or an oxygen atom; ##STR00015## wherein R.sup.7
represents a hydrogen atom or an alkyl group having 1 to 3 carbon
atoms, R.sup.8 represents an alkylene group having 1 to 4 carbon
atoms, R.sup.9s may be the same or different and each represents a
hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X.sup.4
represents an --NH-- group or an oxygen atom, and Y.sup.-
represents a monovalent organic or inorganic anion; ##STR00016##
wherein R.sup.10 represents a hydrogen atom or an alkyl group
having 1 to 3 carbon atoms, R.sup.11 represents an alkylene group
having 1 to 4 carbon atoms, R.sup.12 represents a hydrogen atom or
an alkyl group having 1 to 4 carbon atoms, X.sup.5 represents an
--NH-- group or an oxygen atom, and l stands for an integer of 1 to
100; ##STR00017## wherein R.sup.13 represents a hydrogen atom or an
alkyl group having 1 to 3 carbon atoms, the constituents R.sup.14
may be the same or different and each represents a hydrogen atom or
an alkyl group having 1 to 4 carbon atoms, R.sup.15 represents a
hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X.sup.6
represents an --NH-- group or an oxygen atom, and m stands for an
integer of 1 to 100; and, ##STR00018## wherein R.sup.16 represents
a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
R.sup.17 represents an alkylene group having 1 to 4 carbon atoms,
X.sup.7 represents an --NH-- group or an oxygen atom, M.sup.3
represents a hydrogen atom or a monovalent inorganic or organic
cation, and n stands for an integer of 1 to 100.
4: The surface-treating agent of claim 3, wherein the mole ratio
(A):(B) of monomer (A) to monomer (B) is from 70:30 to
99.9:0.1.
5: A surface-treated powder, including a coating comprising the
surface-treating agent of claim 1 on the powder surface.
6: The surface-treated powder of claim 5, wherein the mass ratio of
the polymer to the powder is from 3:97 to 40:60.
7: A cosmetic comprising the surface-treating agent of claim 1.
8: The surface-treating agent of claim 2, wherein the polymer
further comprises a monomer (B) represented by any one of general
formulas (2) to (7): ##STR00019## wherein R.sup.3 represents a
hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R.sup.4
represents an alkylene group having 1 to 4 carbon atoms, X.sup.2
represents an --NH-- group or an oxygen atom, and M.sup.2
represents a hydrogen atom or a monovalent inorganic or organic
cation; ##STR00020## wherein R.sup.5 represents a hydrogen atom or
an alkyl group having 1 to 3 carbon atoms, R.sup.6 represents an
alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group, an
aminoalkyl group, or a hydroxyalkyl group, and X.sup.3 represents
an --NH-- group or an oxygen atom; ##STR00021## wherein R.sup.7
represents a hydrogen atom or an alkyl group having 1 to 3 carbon
atoms, R.sup.8 represents an alkylene group having 1 to 4 carbon
atoms, R.sup.9s may be the same or different and each represents a
hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X.sup.4
represents an --NH-- group or an oxygen atom, and Y.sup.-
represents a monovalent organic or inorganic anion; ##STR00022##
wherein R.sup.10 represents a hydrogen atom or an alkyl group
having 1 to 3 carbon atoms, R.sup.11 represents an alkylene group
having 1 to 4 carbon atoms, R.sup.12 represents a hydrogen atom or
an alkyl group having 1 to 4 carbon atoms, X.sup.5 represents an
--NH-- group or an oxygen atom, and l stands for an integer of 1 to
100; ##STR00023## wherein R.sup.13 represents a hydrogen atom or an
alkyl group having 1 to 3 carbon atoms, the two constituents
R.sup.14 may be the same or different and each represents a
hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R.sup.15 represents a hydrogen atom or an alkyl group having 1 to 4
carbon atoms, X.sup.6 represents an --NH-- group or an oxygen atom,
and m stands for an integer of 1 to 100; and, ##STR00024## wherein
R.sup.16 represents a hydrogen atom or an alkyl group having 1 to 3
carbon atoms, R.sup.17 represents an alkylene group having 1 to 4
carbon atoms, X.sup.7 represents an --NH-- group or an oxygen atom,
M.sup.3 represents a hydrogen atom or a monovalent inorganic or
organic cation, and n stands for an integer of 1 to 100.
9: A surface-treated powder, including a coating comprising the
surface-treating agent of claim 3 on the powder surface.
10: A cosmetic comprising the surface-treating agent of claim
2.
11: A cosmetic comprising the surface-treating agent of claim
3.
12: A cosmetic comprising the surface-treating agent of claim
4.
13: A cosmetic comprising the surface-treating powder of claim
5.
14: A cosmetic comprising the surface-treating powder of claim 6.
Description
RELATED APPLICATIONS
[0001] This application claims the priority of Japanese Patent
Application No. 2004-294618 filed on Oct. 7, 2004 and Japanese
Patent Application No. 2004-294619 filed on Oct. 7, 2004, which are
incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to surface-treating agents,
surface-treated powders, and cosmetics comprising the same, and in
particular, relates to the improvement of hydrophobicity and
rinsability of the powder used in cosmetics.
[0004] 2. Prior Art
[0005] For cosmetics, especially for makeup cosmetics, the
beautifying effect, which makes people beautiful, is naturally
expected. In addition, the sustainability of the beautifying
effect, namely, long-lasting makeup is one of very important
required characteristics. Thus, in the development of cosmetic base
material, one of important themes has been longer-lasting makeup.
In the field of makeup cosmetics, oily bases are often used so that
the makeup does not deteriorate with moisture such as sweat, tears,
and saliva. When hydrophilic powder is blended in an oily base, the
powder easily separates from the base. In addition, the hydrophilic
powder is washed away with moisture, and it becomes a major cause
of makeup deterioration. In the past, when powder was blended into
cosmetics, the powder that had been hydrophobized in advance was
often used for blending.
[0006] There are numerous methods for the hydrophobization of
powder used in cosmetics. For example, a powder hydrophobization
method, in which higher fatty acids, higher alcohols, hydrocarbons,
triglycerides, esters, silicones such as silicone oil and silicone
resin, or fluorine compounds are used, has been practiced to cover
the surface of hydrophilic powder. In particular, the powder
hydrophobizing treatment, in which silicones are used as the
surface-treating agent, can provide excellent hydrophobicity. Thus,
numerous methods have been established so far (refer to patent
literatures 1 and 2, for example). In recent years, a method in
which a copolymer of acrylic acid and acrylic acid ester is used as
the powder surface-treating agent is also known (refer to patent
literature 3, for example).
[0007] On the other hand, the rinsability of cosmetics is also one
of the important required characteristics. When the above-described
conventional hydrophobized powder is blended, a longer-lasting
makeup can be achieved. However, the makeup cannot be easily rinsed
away with water, even when soap is used, because of the excellent
hydrophobicity. Therefore, oily cleansing agents have been widely
used, however, it also becomes necessary to wash away this oily
cleansing agent with soap. Thus, the burden to users becomes high.
When hydrophilic powder is blended to allow easy rinsing, the
makeup easily deteriorates and the makeup is short-lasting as
described above. Thus, it has been a very difficult theme to
satisfy both the characteristics: long lasting makeup in use and
easy rinsing after use.
Patent literature 1: Japanese Unexamined Patent Publication
S60-163973
Patent literature 2: Japanese Unexamined Patent Publication
S62-177070
Patent literature 3: Japanese Unexamined Patent Publication
H8-337514
SUMMARY OF THE INVENTION
[0008] The present invention was made in view of the
above-described problem, and the objects of the invention are to
provide surface-treating agents that can provide excellent
hydrophobicity to powder and can improve its rinsability, to
provide surface-treated powders that are generated with the
surface-treating agent, and to provide cosmetics that comprise the
surface-treated powder.
[0009] The present inventors have diligently researched in view of
the above-described problem and focused on the pH-responsive
hydrophobicity-hydrophilicity change. The present inventors treated
the surface of the powder with a polymer that comprised, as a
constituent monomer, an acrylic derivative of a specific structure
and found that the hydrophobicity-hydrophilicity of the
surface-treated powder dramatically changes with the pH change.
That is, the surface-treated powder with the above-described
polymer shows excellent hydrophobicity in the acidic to neutral
region, where general cosmetics are used. On the other hand, the
surface of the powder becomes hydrophilic in the moderately basic
conditions that are generated with soap water. As a result, we
found that when the surface-treated powder was blended in
cosmetics, the makeup was long-lasting; nevertheless, the makeup
could be easily rinsed away with water by using soap, thus leading
to the completion of the present invention.
[0010] The present inventors have diligently researched in view of
the above-described problem, and focused on the pH-responsive
hydrophobicity-hydrophilicity change. The present inventors used a
polymer that comprised, as a constituent monomer, an acrylic
derivative of a specific structure as the surface-treating agent of
the powder and found that the hydrophobicity-hydrophilicity of the
surface-treated powder dramatically changes with the pH change.
That is, the powder treated with the above-described
surface-treating agent shows excellent hydrophobicity in the acidic
to neutral region, where general cosmetics are used. On the other
hand, the surface of the powder becomes hydrophilic in the
moderately basic conditions that are generated with soap water. As
a result, when the treated powder is blended in cosmetics, the
makeup is long-lasting; nevertheless, the makeup can be easily
rinsed away with water by using soap. Thus, the present inventors
found that the excellent hydrophobicity could be provided to the
powder by treating the powder surface with the above-described
surface-treating agent and that the rinsability could significantly
be improved, thus leading to the completion of the present
invention.
[0011] The first subject of the present invention is a
surface-treating agent, which consists of a polymer comprising a
monomer (A) represented by the general formula (1) described below
as a constituent monomer.
##STR00002##
(wherein R.sup.1 represents a hydrogen atom or an alkyl group
having 1 to 3 carbon atoms, R.sup.2 represents an alkylene group
having 4 to 22 carbon atoms, X.sup.1 represents an --NH-- group or
an oxygen atom, and M.sup.1 represents a hydrogen atom or a
monovalent inorganic or organic cation.)
[0012] In addition, it is preferable that the polymer of the
surface-treating agent comprises the above-described monomer (A)
equal to or more than 70 mole % of the total constituent
monomers.
[0013] In addition, it is preferable that the polymer of the
above-described surface-treating agent, further comprises a monomer
(B), which is represented by any of the below-described general
formulas (2) to (7) as a constituent monomer.
##STR00003##
(wherein R.sup.3 represents a hydrogen atom or an alkyl group
having 1 to 3 carbon atoms, R.sup.4 represents an alkylene group
having 1 to 4 carbon atoms, X.sup.2 represents an --NH-- group or
an oxygen atom, and M.sup.2 represents a hydrogen atom or a
monovalent inorganic or organic cation.)
##STR00004##
(wherein R.sup.5 represents a hydrogen atom or an alkyl group
having 1 to 3 carbon atoms, R.sup.6 represents an alkyl group
having 1 to 10 carbon atoms, a fluoroalkyl group, an aminoalkyl
group, or a hydroxyalkyl group, and X.sup.3 represents an --NH--
group or an oxygen atom.)
##STR00005##
(wherein R.sup.7 represents a hydrogen atom or an alkyl group
having 1 to 3 carbon atoms, R.sup.8 represents an alkylene group
having 1 to 4 carbon atoms, R.sup.9s may be the same or different
and each represents a hydrogen atom or an alkyl group having 1 to 4
carbon atoms, X.sup.4 represents an --NH-- group or an oxygen atom,
and Y.sup.- represents a monovalent organic or inorganic
anion.)
##STR00006##
(wherein R.sup.10 represents a hydrogen atom or an alkyl group
having 1 to 3 carbon atoms, R.sup.11 represents an alkylene group
having 1 to 4 carbon atoms, R.sup.12 represents a hydrogen atom or
an alkyl group having 1 to 4 carbon atoms, X.sup.5 represents an
--NH-- group or an oxygen atom, and l stands for an integer of 1 to
100.)
##STR00007##
(wherein R.sup.13 represents a hydrogen atom or an alkyl group
having 1 to 3 carbon atoms, R.sup.14s may be the same or different
and each represents a hydrogen atom or an alkyl group having 1 to 4
carbon atoms, R.sup.15 represents a hydrogen atom or an alkyl group
having 1 to 4 carbon atoms, X.sup.6 represents an --NH-- group or
an oxygen atom, and m stands for an integer of 1 to 100.)
##STR00008##
(wherein R.sup.16 represents a hydrogen atom or an alkyl group
having 1 to 3 carbon atoms, R.sup.17 represents an alkylene group
having 1 to 4 carbon atoms, X.sup.7 represents an --NH-- group or
an oxygen atom, M.sup.3 represents a hydrogen atom or a monovalent
inorganic or organic cation, and n stands for an integer of 1 to
100.)
[0014] In addition, the mole ratio (A):(B) of the monomer (A) and
the monomer (B) in the surface-treating agent is preferably within
the range from 70:30 to 99.9:0.1.
[0015] The second subject of the present invention is
surface-treated powder, which is coated with the surface-treating
agent on the powder surface. The amount of surface-treating agent
coated on the powder, expressed in the mass ratio of the polymer to
the powder, is preferably within the range from 3:97 to 40:60.
[0016] The third subject of the present invention is cosmetics,
which comprises the surface-treated powder.
EFFECT OF THE INVENTION
[0017] The excellent hydrophobicity can be provided to the powder,
and the rinsability can be significantly improved by treating the
powder surface with the surface-treating agent of the present
invention. Therefore, when the surface-treated powder treated with
the surface-treating agent of the present invention is blended into
cosmetics, the makeup can be easily rinsed away with water by using
soap although the makeup is long-lasting.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 shows a picture of pH 5 buffer solutions containing
the surface-treated powder treated with various surface-treating
agents (MAU homopolymer or MAU/AMPS copolymers) of the present
invention.
[0019] FIG. 2 shows a picture of pH 10 buffer solutions containing
the surface-treated powder treated with various surface-treating
agents (MAU homopolymer or MAU/AMPS copolymers) of the present
invention.
[0020] FIG. 3 shows the results of NMR measurement of a
surface-treating agent (MMPA homopolymer) of the present
invention.
[0021] FIG. 4 shows a picture of pH 5 and pH 10 buffer solutions
containing the surface-treated powder treated with a
surface-treating agent (MMPA homopolymer) of the present
invention.
[0022] FIG. 5 shows the results of infrared spectroscopic
measurement of a surface-treating agent (MMPA homopolymer) of the
present invention under the untreated and treated (with 1 M NaOH
solution) conditions.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0023] In the following, the preferable mode for carrying out the
present invention is described in detail.
[0024] The surface-treating agent of the present invention consists
of a polymer which comprises a monomer (A) represented by the
above-described general formula (1) as a constituent monomer.
[0025] The monomer (A) represented by the general formula (1) is a
compound in which a fatty acid is attached to acrylic acid,
alkyl-substituted acrylic acid, acrylamide, or alkyl-substituted
acrylamide. In the general formula (1), R.sup.1 represents a
hydrogen atom or an alkyl group having 1 to 3 carbon atoms. When
R.sup.1 is an alkyl group, it can be either linear or branched.
R.sup.1 is preferably a hydrogen atom or a methyl group. In the
general formula (1), R.sup.2 is an alkylene group having 4 to 22
carbon atoms. The alkylene group can be either linear or branched.
Examples of R.sup.2 include an octylene group having 8 carbon
atoms, an undecylene group having 11 carbon atoms, and a dodecylene
group having 12 atoms. In addition, R.sup.2 may include an aromatic
ring or carbon-carbon double bonds in the structure, for example,
R.sup.2 may be a vinylene group, a methylphenylene group, or a
vinylphenylene group. In the general formula (1), X.sup.1 is an
--NH-- group or an oxygen atom, and it is preferably an --NH--
group. In the general formula (1), M.sup.1 is a hydrogen atom or a
monovalent inorganic or organic cation. The monovalent inorganic or
organic cation can be any cation so far as it can form a
carboxylate salt. Examples of the monovalent inorganic cation
include sodium ion, potassium ion, and lithium ion, and examples of
the monovalent organic cation include ammonium ion,
monoethanolammonium ion, and triethanolammonium ion. In addition,
M.sup.1 can be reversibly converted, after the preparation of the
polymer, to the form of the carboxylic acid (M.sup.1=hydrogen) or
sodium salt (M.sup.1=sodium) with an appropriate amount of dilute
hydrochloric acid or dilute sodium hydroxide solution.
[0026] Examples of the monomer (A) of the present invention include
11-methacrylamidoundecanoic acid, 8-acrylamidooctanoic acid,
12-acrylamidododecanoic acid, 12-methacrylamidododecanoic acid, and
3-{4-[(methacryloxy)methyl]phenyl}acrylic acid. A polymer of the
present invention may include one or more kind of the
above-described monomer (A) as the constituent monomer.
[0027] A polymer of the present invention preferably comprises the
above-described monomer (A) in equal to or more than 70 mole % of
the total constituent monomers. If the content of the monomer (A)
is less than 70 mole %, the effectiveness in the
hydrophobicity-hydrophilicity adjustment is small, and desired
characteristics may not be provided to the powder. The content of
the monomer (A) is preferably equal to or more than 90 mole %. In
the polymer of the present invention, the above-described monomer
(A) may account for the total amount of the constituent
monomer.
[0028] In the polymer of the present invention, a monomer (B)
represented by any of the above-described general formulas (2) to
(7) can be desirably used as a constituent monomer in addition to
the above-described monomer (A).
[0029] The monomer represented by the general formula (2) is a
compound in which an alkyl sulfonic acid is attached to acrylic
acid, alkyl-substituted acrylic acid, acrylamide, or
alkyl-substituted acrylamide. In the general formula (2), R.sup.3
is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
When R.sup.3 is an alkyl group, it can be either linear or
branched. R.sup.3 is preferably a hydrogen atom or a methyl group.
In the general formula (2), R.sup.4 is an alkylene group having 1
to 4 carbon atoms. The alkylene group can be either linear or
branched. Examples of R.sup.4 include a methylene group, an
ethylene group, and a propylene group, and it is preferably an
ethylene group or a propylene group. In the general formula (2),
X.sup.2 is an --NH-- group or an oxygen atom, and it is preferably
an --NH-- group. In the general formula (2), M.sup.2 is a hydrogen
atom or a monovalent inorganic or organic cation. The monovalent
inorganic or organic cation can be any cation so far as it can form
a sulfonic acid. Examples of the monovalent inorganic cation
include sodium ion, potassium ion, and lithium ion, and examples of
the monovalent organic cation include ammonium ion,
monoethanolammonium ion, and triethanolammonium ion. In addition,
M.sup.2 can be reversibly converted, after the preparation of a
polymer, to the form of the sulfonic acid (M.sup.2=hydrogen) or
sodium salt (M.sup.2=sodium) with an appropriate amount of dilute
hydrochloric acid or dilute sodium hydroxide solution.
[0030] Examples of the monomer represented by the general formula
(2) include 2-acrylamido-2-methylpropanesulfonic acid and potassium
3-methacryloxypropanesulfonate.
[0031] The monomer represented by the general formula (3) is a
compound in which an alkyl group is attached to acrylic acid,
alkyl-substituted acrylic acid, acrylamide, or alkyl-substituted
acrylamide. In the general formula (3), R.sup.5 is a hydrogen atom
or an alkyl group having 1 to 3 carbon atoms. When R.sup.5 is an
alkyl group, it can be either linear or branched. R.sup.5 is
preferably a hydrogen atom or a methyl group. In the general
formula (3), R.sup.6 is an alkyl group having 1 to 10 carbon atoms,
a fluoroalkyl group having equal to or more than one fluorine atom,
an aminoalkyl group having equal to or more than one amino group,
or a hydroxyalkyl group having equal to or more than one hydroxyl
group. These alkyl groups can be either linear or branched. When
R.sup.6 is an alkyl group, the examples include a methyl group, an
ethyl group, a pentyl group, an octyl group, a decyl group, and a
2-ethylhexyl group, and it is preferably a 2-ethylhexyl group. When
R.sup.6 is a fluoroalkyl group, the examples include a
trifluoromethyl group, a trifluoroethyl group, and a
tetrafluoropropyl group, and it is preferably a trifluoroethyl
group or a tetrafluoropropyl group. When R.sup.6 is an aminoalkyl
group, the examples include an aminoethyl group and aminopropyl
group, and an N,N-dimethylaminoethyl group, and it is preferably an
N,N-dimethylaminoethyl group. When R.sup.6 is a hydroxyalkyl group,
the examples include a hydroxyethyl group, a hydroxypropyl group,
and a dihydroxypropyl group, and it is preferably a hydroxyethyl
group. In the general formula (3), X.sup.3 is an --NH-- group or an
oxygen atom.
[0032] Examples of the monomer represented by the general formula
(3) include 2-ethylhexyl acrylate, 2,2,2-trifluoropropyl acrylate,
2,2,3,3-tetrafluoropropyl methacrylate, 2-(N,N-dimethylamino)ethyl
acrylate, 2-dimethylaminoethyl methacrylate, N-hydroxyethyl
acrylate, and glycerol monomethacrylate.
[0033] The monomer represented by the general formula (4) is a
compound in which an alkyl ammonium salt is attached to acrylic
acid, alkyl-substituted acrylic acid, acrylamide, or
alkyl-substituted acrylamide. In the general formula (4), R.sup.7
is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
When R.sup.7 is an alkyl group, it can be either linear or
branched. R.sup.7 is preferably a hydrogen atom or a methyl group.
In the general formula (4), R.sup.8 is an alkylene group having 1
to 4 carbon atoms. The alkylene group can be either linear or
branched. Examples of R.sup.8 include a methylene group, an
ethylene group, and a propylene group, and it is preferably an
ethylene group or propylene group. R.sup.9s may be the same or
different and each represents a hydrogen atom or an alkyl group
having 1 to 4 carbon atoms. When R.sup.9 is an alkyl group, it can
be either linear or branched. R.sup.9 is preferably a hydrogen atom
or a methyl group. In the general formula (4), X.sup.4 is an --NH--
group or an oxygen atom. Y.sup.- is a monovalent organic or
inorganic anion, and it can be any anion so far as it can form a
quaternary ammonium salt. Examples of Y.sup.- include monovalent
inorganic anions such as chloride ion, fluoride ion, and iodide
ion; and monovalent organic anions such as sulfate ion, acetate
ion, benzenesulfonate ion, and phosphate ion.
[0034] Examples of the monomer represented by the general formula
(4) include N,N-dimethylaminoethyl acrylate methyl chloride and
N,N-dimethylamino acrylamide methyl chloride.
[0035] The monomer represented by the general formula (5) is a
compound, in which a (poly) alkylene oxide is attached to acrylic
acid, alkyl-substituted acrylic acid, acrylamide, or
alkyl-substituted acrylamide. In the general formula (5), R.sup.10
is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
When R.sup.10 is an alkyl group, it can be either linear or
branched. R.sup.10 is preferably a hydrogen atom or a methyl group.
In the general formula (5), R.sup.11 is an alkylene group having 1
to 4 carbon atoms, and the alkylene group can be either linear or
branched. Examples of R.sup.11 include a methylene group, an
ethylene group, and a propylene group, and it is preferably an
ethylene group or a propylene group. R.sup.12 is a hydrogen atom or
an alkyl group having 1 to 4 carbon atoms, and the examples include
a hydrogen atom, a methyl group, and an ethyl group. R.sup.12 is
preferably a methyl group. In the general formula (5), X.sup.5 is
an --NH-- group or an oxygen atom. The letter l indicates the mole
number of attached alkylene oxides, and it is an integer of 1 to
100.
[0036] Examples of the monomer represented by the general formula
(5) include methoxypolyethylene glycol methacrylate.
[0037] The monomer represented by the general formula (6) is a
compound in which polysiloxane is attached to acrylic acid,
alkyl-substituted acrylic acid, acrylamide, or alkyl-substituted
acrylamide. In the general formula (6), R.sup.13 is a hydrogen atom
or an alkyl group having 1 to 3 carbon atoms. When R.sup.13 is an
alkyl group, it can be either linear or branched. R.sup.13 is
preferably a hydrogen atom or a methyl group. In the general
formula (6), R.sup.14s may be the same or different and each
represents a hydrogen atom or an alkyl group having 1 to 4 carbon
atoms. When R.sup.14 is an alkyl group, it can be either linear or
branched. R.sup.14 is preferably a hydrogen atom or a methyl group.
R.sup.15 is a hydrogen atom or an alkyl group having 1 to 4 carbon
atoms, and the examples include a hydrogen atom, a methyl group,
and an ethyl group. R.sup.15 is preferably a hydrogen atom or a
methyl group. In the general formula (6), X.sup.6 is an --NH--
group or an oxygen atom. The letter m indicates the mole number of
attached siloxane groups, and it is an integer of 1 to 100.
[0038] Examples of the monomer represented by the general formula
(6) include methacryloxy-modified silicones.
[0039] The monomer represented by the general formula (7) is a
compound in which alkylphosphoric acid (salt) is attached to
acrylic acid, alkyl-substituted acrylic acid, acrylamide, or
alkyl-substituted acrylamide. In the general formula (7), R.sup.16
is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
When R.sup.16 is an alkyl group, it can be either linear or
branched. R.sup.16 is preferably a hydrogen atom or a methyl group.
In the general formula (7), R.sup.17 is an alkylene group having 1
to 4 carbon atoms, and the alkylene group can be either linear or
branched. Examples of R.sup.17 include a methylene group, an
ethylene group, and a propylene group, and it is preferably an
ethylene group or a propylene group. In the general formula (7),
X.sup.7 is an --NH-- group or an oxygen atom. The letter n
indicates the mole number of attached alkylene oxides, and it is an
integer of 1 to 100. In the general formula (7), M.sup.3 is a
hydrogen atom or a monovalent inorganic or organic cation. The
monovalent inorganic or organic cation can be any cation so far as
it can form a phosphate. Examples of the monovalent inorganic
cation include sodium ion, potassium ion, and lithium ion, and
examples of the monovalent organic cation include ammonium ion,
monoethanolammonium ion, and triethanolammonium ion. In addition,
M.sup.3 can be reversibly converted, after the preparation of a
polymer, to the form of the phosphoric acid (M.sup.3=hydrogen) or
sodium salt (M.sup.3=sodium) with an appropriate amount of dilute
hydrochloric acid or dilute sodium hydroxide solution.
[0040] Examples of the monomer represented by the general formula
(7) include 2-methacryloxyethyl phosphoric acid.
[0041] The polymer of the present invention may include one or more
kind of any monomer (B) represented by the above-described general
formulas (2) to (7) as the constituent monomer.
[0042] The polymer of the present invention preferably comprises
the above-described monomer (B) in 1 to 30 mole % of the total
constituent monomers. If the content of the monomer (B) is less
than 1 mole %, the blending effect cannot be achieved. If the
content of the monomer (B) is more than 30 mole %, the relative
content of monomer (A) becomes small. As a result, desired
characteristics may not be provided to the powder.
[0043] The polymer of the present invention can comprise a monomer
other than the above-described monomers (A) and (B) as the
constituent monomer so far as the effect of the present invention
is not undermined. The content equal to or less than 30 mole % of
the total constituent monomers is satisfactory, and the content can
be, for example, about 1 to about 20 mole %. Examples of the
monomer include acrylamide, methacrylamide, N-vinylpyrrolidone,
.epsilon.-caprolactam, vinylalcohol, maleic anhydride,
diallyldimethylammonium chloride, and styrene.
[0044] The polymer of the present invention can be obtained by
polymerizing various monomers, including the above-described
monomers, by publicly known polymerization methods. For example,
homogeneous solution polymerization, heterogeneous solution
polymerization, emulsion polymerization, inverse emulsion
polymerization, bulk polymerization, suspension polymerization, and
precipitation polymerization can be used. For example, in the case
of homogeneous solution polymerization, the polymer of the present
invention can be obtained by dissolving various monomers in a
solvent, adding a radical polymerization initiator under a nitrogen
atmosphere, and heating the solution with stirring. In addition,
the polymer of the present invention can be obtained by the
post-modification in which functional groups are attached to
polyacrylic acid or polyacrylamide.
[0045] As the solvent for the polymerization, any solvent can be
used so far as various monomers can be dissolved or suspended and
it is an organic solvent containing no water. Examples include
alcohol solvents, such as methanol, ethanol, propyl alcohol,
isopropyl alcohol, and butyl alcohol; hydrocarbon solvents, such as
hexane, heptane, octane, isooctane, decane, and liquid paraffin;
ether solvents, such as dimethyl ether, diethyl ether, and
tetrahydrofuran; ketone solvents, such as acetone and methyl ethyl
ketone; ester solvents, such as methyl acetate, ethyl acetate, and
butyl acetate; chlorine solvents, such as methylene chloride,
chloroform, and carbon tetrachloride; dimethylformamide;
diethylformamide; dimethyl sulfoxide; and dioxane. More than one
kind of these solvents can be mixed for use. It is usually
preferable to select a solvent that has a higher boiling point than
the initiation temperature of the polymerization initiator.
[0046] The polymerization initiator is not limited in particular so
far as it can initiate radical polymerization, and examples include
peroxides such as benzoyl peroxide, azo compounds such as
azobisisobutyronitrile (AIBN) and dimethyl
2,2'-azobis(isobutyrate), and persulfate polymerization initiators
such as potassium persulfate and ammonium persulfate. The
polymerization can be conducted, without depending on a
polymerization initiator, by a photochemical reaction, radiation,
or the like. The polymerization temperature should be equal to or
more than the polymerization initiation temperature of each
polymerization initiator. For example, about 50 to about 70.degree.
C. is usually suitable for the peroxide polymerization
initiator.
[0047] The polymerization time is not limited in particular, and it
is usually about 30 minutes to about 24 hours. When a polymer with
a relatively high molecular weight is desirable, the desirable
reaction time is about 24 hours. If the reaction time is too short,
the unreacted monomer remains and the molecular weight may turn out
to be relatively small. The average molecular weight of the polymer
of the present invention is not limited in particular. If the
degree of polymerization is more than that of oligomers, the
desired effect can be achieved. However, the average molecular
weight is preferably about 3000 to about 100 thousand. In
polymerization by mixing more than one kind of monomer, a copolymer
in which various monomers are randomly added can usually be
obtained.
[0048] The surface-treated powder of the present invention is
characterized in that the above-obtained polymer is coated on the
powder surface.
[0049] The polymer used in the present invention has carboxyl
groups, which are derived from the above-described monomer (A), on
the side chains of the polymer. The carboxyl group changes to a
hydrophobic carboxylic acid (--COOH) under acidic to neutral
conditions and changes to a hydrophilic carboxylate ion
(--COO.sup.-M.sup.+) under basic conditions. Therefore, the powder
the surface of which is treated with this polymer, for example, is
considered to be hydrophobic in the acidic to neutral environment
and hydrophilic in the basic environment. As a result, the
pH-responsive hydrophobicity-hydrophilicity change is
exhibited.
[0050] When the thus obtained surface-treated powder is blended in
cosmetics, the cosmetics show hydrophobicity in the acidic to
neutral region, where cosmetics are normally used, achieving
long-lasting makeup. Nevertheless, when the surrounding becomes
moderately basic with soap, the treated powder surface becomes
hydrophilic and the makeup can be easily rinsed away.
[0051] The above-described monomer (B) is not easily affected by
pH, and the monomer shows a stable hydrophilic or hydrophobic
property in the wide range of pH. Therefore, if a polymer is
prepared by appropriately adjusting the ratio of the
above-described monomer (A) and monomer (B) as the constituent
monomers, the desirable hydrophobicity-hydrophilicity balance,
which is provided to the powder, can be achieved. For example, it
is possible to increase the hydrophilicity by combining a monomer
(B) represented by the general formula (2) with the above-described
monomer (A). On the contrary, it is possible to increase the
hydrophobicity by combining a monomer (B) represented by the
general formula (6) with the above-described monomer (A). In
addition, it is possible to increase the adsorption of powder to
the polymer by utilizing an appropriate amount of the
above-described monomer (B).
[0052] In the polymer used in the present invention, the mole ratio
(A):(B) of the monomer (A) and the monomer (B) should preferably be
adjusted within the range from 70:30 to 99.9:0.1. If the content of
the monomer (A) is less than the ratio of 70:30, the treated powder
will become hydrophilic, and satisfactory hydrophobicity may not be
achieved. On the other hand, if the content of the monomer (A) is
more than the ratio of 99.9:0.1, it will become difficult to adsorb
a polymer on the powder surface, and the stability of the powder
may be negatively affected.
[0053] The powder used in the present invention is not limited in
particular, and examples include inorganic powders, such as silicic
acid, silicic anhydride, magnesium silicate, talc, kaolin, mica,
bentonite, titanated mica, bismuth oxychloride, zirconium oxide,
magnesium oxide, zinc oxide, titanium oxide, aluminum oxide,
calcium sulfate, barium sulfate, magnesium sulfate, calcium
carbonate, magnesium carbonate, iron oxide, ultramarine blue, iron
blue, chromium oxide, chromium hydroxide, carbon black, and
composites thereof; and organic powders, such as polyamide,
polyester, polyethylene, polypropylene, polystyrene, polyurethane,
vinyl resin, epoxy resin, polycarbonate resin,
divinylbenzene/styrene copolymer, copolymers consisting of more
than one kind of monomer of the above-described compounds,
celluloid, acetylcellulose, cellulose, polysaccharides, protein, CI
pigment yellow, CI pigment orange, and CI pigment green. The shape
of powder can be any shape, for example, plate, agglomerate, scaly
shape, sphere, porous sphere, and the particle size is also not
limited in particular.
[0054] In the preparation of the surface-treated powder of the
present invention, the surface treatment of the powder can be
conducted by any normal treatment method; thus, the method is not
limited in particular. Examples of the treatment of the powder with
the above-described polymer include the method in which the polymer
is dissolved in a suitable solvent such as ethyl alcohol, the
powder is mixed into the solution and stirred, and then the solvent
is removed; and the method in which a polymer dissolved in a
non-volatile oil such as a higher alcohol is directly mixed into
the powder with stirring. When the surface-treated powder of the
present invention is blended into cosmetics, the polymer may be
directly mixed, with stirring, into the powder base during the
production process of the cosmetics.
[0055] In the present invention, when the powder is treated with
the above-described polymer, it is necessary to pay attention to
the zeta potential of the powder. Here, the zeta potential of the
powder indicates a difference between the potential of the
outermost surface (sliding surface) of the moving layer, which is
in close contact with the solid phase, and the potential in the
solution during the relative movement of the solid phase and the
liquid phase. When the solution is at near-neutral pH, the zeta
potential of titanium oxide and silica is negative; on the
contrary, the zeta potential of zinc oxide and alumina is positive.
When a powder with the positive zeta potential, such as zinc oxide
or alumina, is treated with the normal method, the carboxylic acid
site, which is important for pH response, is countered by the
positive charge of the powder surface. As a result, the obtained
surface-treated powder may not exhibit a pH response. In order to
provide pH response capability to the powder, it is necessary to
change the zeta potential of the powder surface to be negative by
treating the powder surface with an inorganic compound or an
organic compound possessing a negative charge, such as silica or
polystyrene sulfonic acid. Examples of such a treatment method
include the method in which the powder is dispersed in a water
glass solution, and silica is deposited on the surface by the
dropwise addition of an acid; and the method in which the powder is
dispersed in an aqueous solution of polystyrene sulfonic acid, and
water is evaporated.
[0056] In the surface-treated powder of the present invention, the
mass ratio of the coated polymer to the powder (polymer:powder) is
preferably 3:97 to 40:60 and more preferably 5:95 to 30:70. If the
amount of coated polymer is less than 3:97, desired characteristics
may not be provided to the powder. If the amount of coated polymer
is more than 40:60, the feeling during the use of the cosmetics may
be negatively affected.
[0057] The cosmetics of the present invention are characterized in
that the above obtained surface-treated powder is comprised in the
cosmetics. The blending amount of the surface-treated powder is
preferably equal to or more than 3 mass % of the total amount of
cosmetics and more preferably 5 to 95 mass %. If the blending
amount is less than 3 mass %, the effect of the present invention
may not be achieved.
[0058] To the cosmetics of the present invention, normally used
cosmetic ingredients, such as water, oil, powder (untreated),
surfactant, fluorine compounds, resin, thickener, preservative,
perfume, ultraviolet absorber, moisturizer, bioactive component,
salts, solvent, antioxidant, chelating agent, neutralizing agent,
and pH adjusting agent may be blended in addition to the
above-described surface-treated powder so far as the effect of the
present invention is not undermined.
[0059] The forms of cosmetics in the present invention are not
limited in particular. Their examples include makeup cosmetics such
as foundation, white face powder, lipstick, eye shadow, cheek
color, mascara, and eye liner; sunscreen; foundation cream; and
hair cream.
EXAMPLE 1
[0060] Examples of the present invention will hereinafter be
described. However, the present invention is not limited by these
examples.
[0061] Initially, the polymer synthesis methods of the present
invention will be described.
SYNTHESIS EXAMPLE 1
11-Methacrylamidoundecanoic acid (MAU) homopolymer
##STR00009##
[0063] Into a mixed solvent of 32.4 mL of methanol and 3.6 mL water
(methanol/water=9/1) were dissolved 5.244 g (18 mmol) of sodium
11-methacrylamidoundecanoate (NaMAU) and 7.4 mg (0.045 mmol) of
azobisisobutyronitrile. The solution was deaerated by bubbling
argon for 30 minutes, the container was covered with a septum, and
the polymerization was conducted by heating the solution at
60.degree. C. for 12 hours. After the completion of the
polymerization reaction, the reaction solution was dropwise added
into a large excess of ether, and the resulting precipitate was
collected by filtration under suction. This precipitate was
dissolved in water, dialyzed against pure water for 1 week, and
2.64 g of NaMAU homopolymer was obtained by freeze-drying (yield:
50.40%).
[0064] Into water was dissolved 1.10 g of the collected NaMAU
homopolymer, and the pH was adjusted to 4 with hydrochloric acid.
This solution was dialyzed against water of pH 5 for 1 week, and
0.97 g of 11-methacrylamidoundecanoic acid (MAU) homopolymer was
obtained by freeze-drying.
SYNTHESIS EXAMPLE 2
11-Methacrylamidoundecanoic acid
(MAU)/2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer
(MAU/AMPS=95/5)
##STR00010##
[0066] Into a mixed solvent of 32.4 mL of methanol and 3.6 mL water
(methanol/water=9/1) were dissolved 4.9823 g (17.1 mmol) of sodium
11-methacrylamidoundecanoate (NaMAU), 186.5 mg (0.9 mmol) of
2-acrylamido-2-methylpropanesulfonic acid (AMPS), 39.6 mg (0.99
mmol) of sodium hydroxide, and 7.4 mg (0.045 mmol) of
azobisisobutyronitrile. The solution was deaerated by bubbling
argon for 30 minutes, the container was covered with a septum, and
the polymerization was conducted by heating the solution at
60.degree. C. for 12 hours. After the completion of the
polymerization reaction, the reaction solution was dropwise added
into a large excess of ether, and the resulting precipitate was
collected by filtration under suction. This precipitate was
dissolved in water, dialyzed against pure water for 1 week, and
2.78 g of random NaMAU/AMPS copolymer (95/5) was obtained by
freeze-drying (yield: 53.71%).
[0067] Into water was dissolved 1.54 g of the collected NaMAU/AMPS
copolymer, and the pH was adjusted to 4 with hydrochloric acid.
This solution was dialyzed against water of pH 5 for 1 week, and
0.97 g of random MAU/AMPS copolymer (95/5) was obtained by
freeze-drying.
[0068] In the following section, the surface treatment method of
powder with the surface-treating agent of the present invention
will be described.
POWDER TREATMENT EXAMPLE 1
[0069] Into 500 mL of ethanol were dissolved 45 g of a polymer
prepared by the above-described Synthesis Example 1 or Synthesis
Example 2 and 15 g of stearic acid. Into this solution was blended
240 g of titanium oxide and dispersed, and the ethanol was
evaporated with an evaporator. The obtained agglomerate was
pulverized, and the surface-treated powder was obtained.
[0070] The obtained treated powder was dissolved, by mixing, into a
buffer solution of pH 5 and a buffer solution of pH 10 in a
powder-solution ratio of 1:100. This solution was centrifuged to
isolate the powder, and the residual liquid was removed by drying.
The obtained powder was analyzed by elemental analysis to measure
the degree of polymer coating, and the content of polymer was found
to be 15 mass % of the total powder, and the content of stearic
acid was 5 mass % of the total powder.
EXAMPLES 1-1 TO 1-4 AND COMPARATIVE EXAMPLES 1-1 TO 1-4
[0071] In order to investigate the properties of the powder that
has been surface-treated with the polymer of the present invention,
the present inventors prepared titanium oxide powders that were
surface-treated with various polymers according to the
above-described Synthesis Example 1, Synthesis Example 2, and
Powder Treatment Example 1. Then the present inventors evaluated
the water solubility of the treated powders under the acidic (pH 5)
and the basic (pH 10) conditions. In addition, similar tests were
conducted using silicones and acrylic acid/acrylic acid ester
copolymer, which are traditional hydrophobizing surface-treating
agents, as comparative examples. Evaluation results are shown in
Table 1 and FIGS. 1 and 2. The evaluation method was as
follows.
Water Solubility of Treated Powder
[0072] Each of 0.1 g titanium oxide powder that has been
surface-treated with various surface-treating agents and a 30 mL
aqueous buffer solution of pH 5 or pH 10 were placed in a vial,
mixed for 1 minute by stirring with a magnetic stirrer, and allowed
to stand. Then the condition of each solution was checked.
.smallcircle.: Powder evenly dissolved in water, and it formed a
white cloudy solution. x: Powder did not dissolve in water, and it
separated on the water surface.
TABLE-US-00001 TABLE1 Water solubility of powder Surface-treating
agent pH 5 pH 10 Example 1-1 MAU/AMPS copolymer (MAU/AMPS = 90/10)
X .largecircle. 1-2 MAU/AMPS copolymer (MAU/AMPS = 95/5) X
.largecircle. 1-3 MAU/AMPS copolymer (MAU/AMPS = 99/1) X
.largecircle. 1-4 MAU homopolymer (MAU/AMPS = 100/0) X
.largecircle. Comperative 1-1 Methylhydrogenpolysiloxane X X
Example 1-2 Dimethyldichlorosilane X X 1-3 Octyl acrylamide/acryl
resin copolymer *1 X X 1-4 Vinyl acetate/crotonic acid copolymer X
X *1: Darmacryl-79 (Kanebo-NSC)
[0073] As shown in Table 1 and FIGS. 1 and 2, the surface-treated
powder with MAU homopolymer or MAU/AMPS copolymer of the present
invention (Examples 1-1 to 1-4) did not dissolve in water under
acidic condition (pH 5). Thus, the powder was found to have
excellent hydrophobicity under acidic condition (pH 5). On the
other hand, under basic condition (pH 10), the treated powder
evenly dissolved in water. Thus, the powder was found to change to
hydrophilic under basic condition (pH 10). That is to say, when the
powder treated with the polymer of the present invention is blended
into cosmetics, the powder has excellent hydrophobicity in the
acidic to neutral region, in which normal cosmetics are used; as a
result, the makeup is long-lasting. Nevertheless, the powder can be
easily rinsed away with water under the moderately basic condition
that is generated with soap because the powder surface changes to
hydrophilic.
[0074] In contrast, the powder that is surface-treated with
silicones or acrylic acid/acrylic acid ester copolymer, which is
the traditionally used hydrophobizing agent in cosmetic powder
(Comparative Examples 1-1 to 1-4), dissolved in water neither under
acidic condition (pH 5) nor under basic condition (pH 10). Thus,
when the powder treated with the traditional surface-treating agent
is blended in cosmetics, long-lasting makeup could be achieved.
However, it is difficult to rinse away with soap water because
excellent hydrophobicity is maintained even under basic
conditions.
SYNTHESIS EXAMPLE 3
3-{4-[(Methacryloxy)methyl]phenyl}acrylic acid (MMPA)
homopolymer
##STR00011##
[0075] 1) Synthesis of MMPA Monomer
[0076] In 25 g of acetone were dissolved 2.46 g (15 mmol) of
4-hydroxycinnamic acid and 0.005 g of butylhydroxytoluene. To the
solution was dropwise added 1.57 g (15 mmol) of methacryloyl
chloride, and the mixture was stirred at room temperature for 3
hours. After the completion of the reaction, to the solution was
dropwise added 1.67 g of triethylamine, and then 100 g of 0.015N
dilute hydrochloric acid solution was added. The resulting
precipitate was collected by filtration under suction. The
precipitate was washed with water and dried at 30.degree. C. under
reduced pressure, whereby 2.09 g of MMPA monomer was obtained
(yield: 60%). By the NMR analysis of the product, the formation of
MMPA monomer was confirmed. The NMR analysis results are shown in
FIG. 3.
2) Polymerization of MMPA Monomer
[0077] In 100 g of tetrahydrofuran was dissolved 2.01 g (9 mmol) of
the above-obtained MMPA monomer, and nitrogen was bubbled through
the solution for 40 minutes. Subsequently, 0.038 g (0.23 mmol) of
azobisisobutyronitrile that was dissolved in 10 g of
tetrahydrofuran was dropwise added to the solution. After nitrogen
was bubbled through the solution for 10 minutes, the polymerization
was conducted by stirring at 60.degree. C. for 24 hours. After the
completion of the polymerization reaction, the reaction solution
was concentrated with an evaporator, and the precipitate was
removed by the addition of ethyl acetate. The solution was
concentrated again with an evaporator. By drying at 30.degree. C.
under reduced pressure, 1.64 g of MMPA homopolymer was obtained
(yield: 82%).
POWDER TREATMENT EXAMPLE 2
[0078] In 50 mL of tetrahydrofuran was dissolved 1 g of MMPA
homopolymer, which was prepared in the above-described Synthesis
Example 3. In this solution, 9 g of titanium oxide was blended and
dispersed, and tetrahydrofuran was evaporated with an evaporator.
The obtained agglomerate was pulverized, whereby the
surface-treated powder was obtained.
EXAMPLE 1-5
[0079] The present inventors prepared titanium oxide powder that
was surface-treated with MMPA homopolymer according to the
above-described Powder Treatment Example 2. The obtained treated
powder was blended and dispersed in buffer solutions of pH 5 and pH
10 in a powder-solution ratio of 1:100. Thus, the water solubility
of the treated powder under acidic condition (pH 5) and basic
condition (pH 10) was evaluated. The results are shown in FIG.
4.
[0080] As shown in FIG. 4, surface-treated powder with MMPA
homopolymer of the present invention (Example 1-5) did not dissolve
in water under acidic condition (pH 5). On the other hand, under
basic condition (pH 10), the treated powder evenly dissolved in
water. Thus, it was confirmed that the powder changed from
hydrophobic to hydrophilic by the change of pH.
[0081] Subsequently, the present inventors conducted infrared
spectroscopic measurement of the MMPA polymer of the
above-described Synthesis Example 3 under the condition of no
treatment and under the condition of 1 M NaOH solution treatment.
The results are shown in FIG. 5.
[0082] As shown in FIG. 5, the MMPA homopolymer of the present
invention shows peaks due to carboxylic acid (--COOH) under the
condition of no treatment. Under the condition of 1 M NaOH solution
treatment, the above-described peaks due to the carboxylic acid
disappear, and the appearance of a new carboxylate ion
(--COO.sup.-) peak was identified. According to the results, the
polymer of the present invention is in the form of hydrophobic
carboxylic acid under acidic to neutral conditions, and it changes
to the hydrophilic carboxylate ion under basic conditions. As a
result, the pH-responsive hydrophobicity-hydrophilicity change is
considered to take place.
EXAMPLE 2
[0083] The present inventors prepared cosmetics in which the
surface-treated powder with the polymer of the present invention is
blended, and the evaluation was conducted.
EXAMPLE 2-1
[0084] In 1000 mL of ethanol were dissolved 34.5 g of the MAU/AMPS
copolymer (MAU/AMPS=95/5), which was prepared according to the
above-described Synthesis Example 2, and 34.5 g of stearic acid. In
this solution, 85 g of talc, 50.8 g of sericite, 10 g of titanium
oxide, 6 g of nylon powder, 0.4 g of black iron oxide, 5.8 g of
yellow iron oxide, and 2 g of red iron oxide were blended and
dispersed, and the ethanol was evaporated with an evaporator. The
obtained agglomerate was pulverized, and the surface-treated powder
of Example 2-1 was obtained.
EXAMPLE 2-2
TABLE-US-00002 [0085] Powder type foundation Amount (mass %)
(1)Surface treated powder in Example 2-1 86.6 (2)Liquid paraffin
4.0 (3)Octyldodecyl myristate 3.0 (4)Sorbitan isostearate 3.0
(5)Octyldodecanol 3.0 (6)Preservative 0.1 (7)Disinfectant 0.1
(8)Antioxidant 0.1 (9)Perfume 0.1
(Manufacturing method) (2)-(6) are heated and dissolved, then (1),
(7)-(9) are added thereto. This was mixed with Henschel mixer, the
powder type foundation was obtained.
[0086] Above obtained powder type foundation was excellent in
long-lasting, and able to be easily rinsed away with water by using
soap.
EXECUTION EXAMPLE 2-3
TABLE-US-00003 [0087] Two-layers type W/O sunscreen Amount (mass %)
(1)Talc 10.0 (2)Surface treated titania in Example 1-1 10.0
(3)Isocetyl octate 5.0 (4)Decamethylcyclopentasiloxane 26.8
(5)Dimethylpolysiloxane 10.0 (6)POE modified dimethylpolysiloxane
2.0 (7)Ion-exchanged water 28.0 (8)1,3-Butylene glycol 8.0
(9)Preservative 0.1 (10)Perfume 0.1
(Manufacturing method) (3)-(6) were heated and mixed at 70.degree.
C. as oil phase. Separately, (8) and (9) were dissolved into (7) as
aqueous phase. The powder of (1) and (2) was added into the oil
phase, and dispersed with the homomixer. The aqueous phase was
added into this, and emulsified with the homo mixer. In addition,
(10) was mixed with them, and filled into the container.
[0088] Above obtained two-layers type W/O sunscreen was excellent
in long-lasting, and able to be easily rinsed away with water by
using soap.
EXAMPLE 2-4
TABLE-US-00004 [0089] W/O type foundation Amount (mass %) (1)
Surface treated powder in Example 2-1 20.32 (2)Liquid paraffin 5.0
(3)Decamethylcyclopentasiloxane 29.0 (4)POE modified
dimethylpolysiloxane 4.5 (5)Ion-exchanged water 36.0
(6)1,3-Butylene glycol 5.0 (7)Preservative 0.1 (8)Perfume 0.08
(Manufacturing method) (2)-(4) were heated and dissolved at
70-80.degree. C. (This was oil phase). (6) and (7) were dissolved
into (5) (This was aqueous phase). The oil phase was added into
(1), and mixed with homomixer. (8) was mixed with them, and water
was added thereto. This was filled it to the container.
[0090] Above obtained W/O type foundation was excellent in
long-lasting, and able to be easily rinsed away with water by using
soap.
EXAMPLE 2-5
TABLE-US-00005 [0091] Lipstick Amount (mass %) (1)Surface treated
titania in Example 1-3 10.0 (2)Red pigment No. 201 0.6 (3)Red
pigment No. 202 1.0 (4)Red pigment No. 223 0.2 (5)Candelilla wax
9.0 (6)Solid paraffin 8.0 (7)Beeswax 5.0 (8)Carnauba wax 5.0
(9)Lanolin 11.0 (10)Castor oil 23.2 (11)Cetyl 2-ethylhexanoate 17.0
(12)Isopropyl myristic acid ester 10.0 (13)Antioxidant q.s.
(14)Perfume q.s.
(Manufacturing method) (1)-(3) were mixed with a part of (10), and
treated with a roller (This was pigment part). (4) were dissolved
into a part of (10) (This was dye part). (5)-(13) were mixed,
heated and dissolved, then the pigment part and dye part were added
thereto. These were dispersed uniformly with homomixer. This was
poured in mold, cooled quickly, and shaped as stick.
[0092] Above obtained lipstick was excellent in long-lasting, and
able to be easily rinsed away with water by using soap.
EXAMPLE 2-6
TABLE-US-00006 [0093] Oil type stick foundation Amount (mass %)
(powder part) (1)Surface treated powder in Example 2-1 50.0 (Oil
phase) (2)Solid paraffin 3.0 (3)Microcrystalline Wax 7.0
(4)Petrolatum 15.0 (5)Dimethylpolysiloxane 3.0 (6)Squalane 5.0
(7)Isopropyl palmitate 17.0 (8)Antioxidant q.s. (9)Perfume q.s.
(Manufacturing method) (2)-(8) were dissolved at 85.degree. C., and
enough mixed powder part were added thereto with stirring. Next,
this was dispersed by grinding with colloid mill. (9) was added
thereto. After degassing, this was poured into the container at
70.degree. C. This was cooled, and the cosmetic was obtained.
[0094] Above obtained stick foundation was excellent in
long-lasting, and able to be easily rinsed away with water by using
soap.
EXAMPLE 3
[0095] The present invention will hereinafter be described in
further detail by other examples. However, the present invention is
not limited by these examples. The molecular weight was determined
with size exclusion chromatography, HLC-8220 GPC (Tosoh
Corporation). As the column, Shodex Asahipak GF-7M HQ (Showa Denko
K.K.) was used, and as the mobile phase, methanol containing 100 mM
of lithium perchlorate was used. As the standard material,
polyethylene oxide was used, and the obtained weight average
molecular weight is based on polyethylene oxide.
EXAMPLE 3-1
11-Methacrylamidoundecanoic acid (MAU) homopolymer
[0096] In 224.69 g of methanol were dissolved 75.0 g (278.49 mmol)
of 11-methacrylamidoundecanoic acid (MAU) and 0.31 g (1.89 mmol) of
azobisisobutyronitrile (Nacalai Tesque, Inc.). The solution was
deaerated by bubbling nitrogen for 60 minutes. The container was
covered with a septum, and the polymerization was conducted by
heating at 60.degree. C. for 20 hours. After the completion of the
polymerization reaction, the reaction solution was dropwise added
into a large excess of ethyl acetate, and the resulting precipitate
was collected by filtration under suction. After drying under
reduced pressure, 45.6 g of MAU homopolymer was obtained (yield:
60.8%). The weight average molecular weight was 66000.
EXAMPLE 3-2
11-Methacrylamidoundecanoic acid (MAU) homopolymer
[0097] In 224.07 g of methanol were dissolved 75.0 g (278.49 mmol)
of 11-methacrylamidoundecanoic acid (MAU) and 0.93 g (5.66 mmol) of
azobisisobutyronitrile (Nacalai Tesque, Inc.). The solution was
deaerated by bubbling nitrogen for 60 minutes. The container was
covered with a septum, and the polymerization was conducted by
heating at 60.degree. C. for 20 hours. After the completion of the
polymerization reaction, the reaction solution was dropwise added
into a large excess of ethyl acetate, and the resulting precipitate
was collected by filtration under suction. After drying under
reduced pressure, 64.9 g of MAU homopolymer was obtained (yield:
86.5%). The weight average molecular weight was 61000.
EXAMPLE 3-3
12-Methacrylamidododecanoic acid (MAD) homopolymer
[0098] In 120.0 g of methanol was dissolved 40.0 g (141.34 mmol) of
12-methacrylamidododecanoic acid (MAD) and 0.58 g (3.53 mmol) of
azobisisobutyronitrile (Nacalai Tesque, Inc.). Before use,
azobisisobutyronitrile was recrystallized from methanol in the
usual way. The solution was deaerated by bubbling argon for 60
minutes. The container was covered with a septum, and the
polymerization was conducted by heating at 60.degree. C. for 20
hours. After the completion of the polymerization reaction, the
reaction solution was dropwise added into a large excess of diethyl
ether, and the resulting precipitate was collected by filtration
under suction. After drying under reduced pressure, 124.15 g of MAD
homopolymer was obtained (yield: 60.4%). The weight average
molecular weight was 33000.
EXAMPLE 3-4
12-Acrylamidododecanoic acid (AAD) homopolymer
[0099] In 360.0 g of methanol were dissolved 40.0 g (148.70 mmol)
of 12-acrylamidododecanoic acid (AAD) and 0.61 g (3.71 mmol) of
azobisisobutyronitrile (Nacalai Tesque, Inc.). Before use,
azobisisobutyronitrile was recrystallized from methanol in the
usual way. The solution was deaerated by bubbling argon for 60
minutes. The container was covered with a septum, and the
polymerization was conducted by heating at 60.degree. C. for 20
hours. After the completion of the polymerization reaction, the
reaction solution was dropwise added into a large excess of diethyl
ether, and the resulting precipitate was collected by filtration
under suction. After drying under reduced pressure, 27.51 g of AAD
homopolymer was obtained (yield: 68.8%). The weight average
molecular weight was 44000.
EXAMPLE 3-5
11-Methacrylamidoundecanoic acid
(MAU)/2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer
(99/1)
[0100] In 223.92 g of methanol were dissolved 74.23 g (275.63 mmol)
of 11-methacrylamidoundecanoic acid (MAU), 0.77 g (3.72 mmol) of
2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich
Japan K.K.), 0.15 g (3.72 mmol) of sodium hydroxide, and 0.93 g
(5.66 mmol) of azobisisobutyronitrile (Nacalai Tesque, Inc.). The
solution was deaerated by bubbling nitrogen for 60 minutes. The
container was covered with a septum, and the polymerization was
conducted by heating at 60.degree. C. for 20 hours. After the
completion of the polymerization reaction, the reaction solution
was dropwise added into a large excess of diethyl ether, and the
resulting precipitate was collected by filtration under suction.
After drying under reduced pressure, 52.0 g of random MAU/AMPS
copolymer (99/1) was obtained (yield: 69.2%). The weight average
molecular weight was 56000.
EXAMPLE 3-6
11-Methacrylamidoundecanoic acid
(MAU)/2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer
(99/1)
[0101] In 223.30 g of methanol were dissolved 74.23 g (275.63 mmol)
of 11-methacrylamidoundecanoic acid (MAU), 0.77 g (3.72 mmol) of
2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich
Japan K.K.), 0.15 g (3.72 mmol) of sodium hydroxide, and 1.55 g
(9.44 mmol) of azobisisobutyronitrile (Nacalai Tesque, Inc.). The
solution was deaerated by bubbling nitrogen for 60 minutes. The
container was covered with a septum, and the polymerization was
conducted by heating at 60.degree. C. for 20 hours. After the
completion of the polymerization reaction, the reaction solution
was dropwise added into a large excess of ethyl acetate, and the
resulting precipitate was collected by filtration under suction.
After drying under reduced pressure, 52.3 g of random MAU/AMPS
copolymer (99/1) was obtained (yield: 69.6%). The weight average
molecular weight was 36000.
EXAMPLE 3-7
11-Methacrylamidoundecanoic acid
(MAU)/2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer
(99/1)
[0102] In 236.75 g of methanol were dissolved 74.23 g (275.63 mmol)
of 11-methacrylamidoundecanoic acid (MAU), 0.77 g (3.72 mmol) of
2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich
Japan K.K.), 0.15 g (3.72 mmol) of sodium hydroxide, and 3.10 g
(18.88 mmol) of azobisisobutyronitrile (Nacalai Tesque, Inc.). The
solution was deaerated by bubbling nitrogen for 60 minutes. The
container was covered with a septum, and the polymerization was
conducted by heating at 60.degree. C. for 20 hours. After the
completion of the polymerization reaction, the reaction solution
was dropwise added into a large excess of ethyl acetate, and the
resulting precipitate was collected by filtration under suction.
After drying under reduced pressure, 60.1 g of random MAU/AMPS
copolymer (99/1) was obtained (yield: 80.0%). The weight average
molecular weight was 21000.
EXAMPLE 3-8
11-Methacrylamidoundecanoic acid
(MAU)/2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer
(90/10)
[0103] In 59.4 g of methanol were dissolved 18.42 g (68.41 mmol) of
11-methacrylamidoundecanoic acid (MAU), 1.58 g (7.60 mmol) of
2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich
Japan K.K.), 0.31 g (7.60 mmol) of sodium hydroxide, and 0.31 g
(1.89 mmol) of azobisisobutyronitrile (Nacalai Tesque, Inc.). The
solution was deaerated by bubbling nitrogen for 60 minutes. The
container was covered with a septum, and the polymerization was
conducted by heating at 60.degree. C. for 20 hours. After the
completion of the polymerization reaction, the reaction solution
was dropwise added into a large excess of ethyl acetate, and the
resulting precipitate was collected by filtration under suction.
After drying under reduced pressure, 17.8 g of random MAU/AMPS
copolymer (90/10) was obtained (yield: 87.9%). The weight average
molecular weight was 92000.
EXAMPLE 3-9
11-Methacrylamidoundecanoic acid
(MAU)/2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer
(99/1)
[0104] A polymerization inhibitor comprised in MAU was removed by
dissolving 11-methacrylamidoundecanoic acid (MAU) in chloroform and
passing the solution through an inhibitor remover disposable column
(Aldrich Chemical). In 59.91 g of methanol were dissolved 19.85 g
(73.69 mmol) of MAU without the polymerization inhibitor, 0.15 g
(0.74 mmol) of 2-acrylamido-2-methylpropanesulfonic acid (AMPS:
Sigma-Aldrich Japan K.K.), 0.03 g (0.74 mmol) of sodium hydroxide,
and 0.06 g (0.37 mmol) of azobisisobutyronitrile (Nacalai Tesque,
Inc.). The solution was deaerated by bubbling nitrogen for 60
minutes. The container was covered with a septum, and the
polymerization was conducted by heating at 60.degree. C. for 20
hours. After the completion of the polymerization reaction, the
reaction solution was dropwise added into a large excess of ethyl
acetate, and the resulting precipitate was collected by filtration
under suction. After drying under reduced pressure, 17.33 g of
random MAU/AMPS copolymer (99/1) was obtained (yield: 86.6%). The
weight average molecular weight was 740000.
EXAMPLE 3-10
11-Methacrylamidoundecanoic acid (MAU)/potassium
3-methacryloxypropanesulfonate copolymer (90/10)
[0105] In 59.69 g of methanol were dissolved 18.15 g (67.41 mmol)
of 11-methacrylamidoundecanoic acid (MAU), 1.85 g (7.49 mmol) of
potassium 3-methacryloxypropanesulfonate (Tokyo Chemical industry
Co.), and 0.31 g (1.89 mmol) of azobisisobutyronitrile (Nacalai
Tesque, Inc.). The solution was deaerated by bubbling nitrogen for
60 minutes. The container was covered with a septum, and the
polymerization was conducted by heating at 60.degree. C. for 20
hours. After the completion of the polymerization reaction, the
reaction solution was dropwise added into a large excess of ethyl
acetate, and the resulting precipitate was collected by filtration
under suction. After drying under reduced pressure, 18.47 g of
random MAU/potassium 3-methacryloxypropanesulfonate copolymer
(90/10) was obtained (yield: 92.4%). The weight average molecular
weight was 240000.
EXAMPLE 3-11
12-Methacrylamidododecanoic acid
(MAD)/2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer
(99/1)
[0106] In 60.0 g of methanol were dissolved 19.85 g (70.14 mmol) of
12-methacrylamidododecanoic acid (MAD), 0.15 g (0.72 mmol) of
2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich
Japan K.K.), 0.028 g (0.70 mmol) of sodium hydroxide, and 0.29 g
(1.77 mmol) of azobisisobutyronitrile (Nacalai Tesque, Inc.).
Before use, azobisisobutyronitrile was recrystallized from methanol
in the usual way. The solution was deaerated by bubbling argon for
60 minutes. The container was covered with a septum, and the
polymerization was conducted by heating at 60.degree. C. for 20
hours. After the completion of the polymerization reaction, the
reaction solution was dropwise added into a large excess of diethyl
ether, and the resulting precipitate was collected by filtration
under suction. After drying under reduced pressure, 13.5 g of
random MAD/AMPS copolymer (99/1) was obtained (yield: 67.5%). The
weight average molecular weight was 49000.
EXAMPLE 3-12
12-Methacrylamidododecanoic acid
(MAD)/2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer
(90/10)
[0107] In 60.0 g of methanol were dissolved 18.50 g (65.37 mmol) of
12-methacrylamidododecanoic acid (MAD), 1.50 g (7.24 mmol) of
2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich
Japan K.K.), 0.29 g (7.25 mmol) of sodium hydroxide, and 0.30 g
(1.83 mmol) of azobisisobutyronitrile (Nacalai Tesque, Inc.).
Before use, azobisisobutyronitrile was recrystallized from methanol
in the usual way. The solution was deaerated by bubbling argon for
60 minutes. The container was covered with a septum, and the
polymerization was conducted by heating at 60.degree. C. for 20
hours. After the completion of the polymerization reaction, the
reaction solution was dropwise added into a large excess of diethyl
ether, and the resulting precipitate was collected by filtration
under suction. After drying under reduced pressure, 15.2 g of
random MAD/AMPS copolymer (90/10) was obtained (yield: 75.1%). The
weight average molecular weight was 50000.
EXAMPLE 3-13
12-Methacrylamidododecanoic acid
(MAD)/2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer
(80/20)
[0108] In 60.0 g of methanol were dissolved 16.90 g (59.72 mmol) of
12-methacrylamidododecanoic acid (MAD), 3.10 g (14.96 mmol) of
2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich
Japan K.K.), 0.60 g (1.50 mmol) of sodium hydroxide, and 0.31 g
(1.89 mmol) of azobisisobutyronitrile (Nacalai Tesque, Inc.).
Before use, azobisisobutyronitrile was recrystallized from methanol
in the usual way. The solution was deaerated by bubbling argon for
60 minutes. The container was covered with a septum, and the
polymerization was conducted by heating at 60.degree. C. for 20
hours. After the completion of the polymerization reaction, the
reaction solution was dropwise added into a large excess of ethyl
acetate, and the resulting precipitate was collected by filtration
under suction. After drying under reduced pressure, 16.1 g of
random MAD/AMPS copolymer (80/20) was obtained (yield: 78.6%). The
weight average molecular weight was 95000.
EXAMPLE 3-14
12-Methacrylamidododecanoic acid
(MAD)/2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer
(70/30)
[0109] In 60.0 g of methanol were dissolved 15.22 g (53.78 mmol) of
12-methacrylamidododecanoic acid (MAD), 4.78 g (23.06 mmol) of
2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich
Japan K.K.), 0.92 g (23.0 mmol) of sodium hydroxide, and 0.32 g
(1.95 mmol) of azobisisobutyronitrile (Nacalai Tesque, Inc.).
Before use, azobisisobutyronitrile was recrystallized from methanol
in the usual way. The solution was deaerated by bubbling argon for
60 minutes. The container was covered with a septum, and the
polymerization was conducted by heating at 60.degree. C. for 20
hours. After the completion of the polymerization reaction, the
reaction solution was dropwise added into a large excess of ethyl
acetate, and the resulting precipitate was collected by filtration
under suction. After drying under reduced pressure, 19.0 g of
random MAD/AMPS copolymer (70/30) was obtained (yield: 91.6%). The
weight average molecular weight was 108000.
EXAMPLE 3-15
12-Methacrylamidododecanoic acid
(MAD)/2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer
(60/40)
[0110] In 60.0 g of methanol were dissolved 13.44 g (47.49 mmol) of
12-methacrylamidododecanoic acid (MAD), 6.56 g (31.65 mmol) of
2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich
Japan K.K.), 1.27 g (31.75 mmol) of sodium hydroxide, and 0.32 g
(1.95 mmol) of azobisisobutyronitrile (Nacalai Tesque, Inc.).
Before use, azobisisobutyronitrile was recrystallized from methanol
in the usual way. The solution was deaerated by bubbling argon for
60 minutes. The container was covered with a septum, and the
polymerization was conducted by heating at 60.degree. C. for 20
hours. After the completion of the polymerization reaction, the
reaction solution was drop wise added into a large excess of ethyl
acetate, and the resulting precipitate was collected by filtration
under suction. After drying under reduced pressure, 20.05 g of
random MAD/AMPS copolymer (60/40) was obtained (yield: 95.4%). The
weight average molecular weight was 129000.
EXAMPLE 3-16
12-Methacrylamidododecanoic acid
(MAD)/2-acrylamido-2-methylpropanesulfonic acid (AMPS) copolymer
(50/50)
[0111] In 60.0 g of methanol were dissolved 11.55 g (40.81 mmol) of
12-methacrylamidododecanoic acid (MAD), 8.45 g (40.77 mmol) of
2-acrylamido-2-methylpropanesulfonic acid (AMPS: Sigma-Aldrich
Japan K.K.), 1.63 g (40.75 mmol) of sodium hydroxide, and 0.33 g
(1.97 mmol) of azobisisobutyronitrile (Nacalai Tesque, Inc.).
Before use, azobisisobutyronitrile was recrystallized from methanol
in the usual way. The solution was deaerated by bubbling argon for
60 minutes. The container was covered with a septum, and the
polymerization was conducted by heating at 60.degree. C. for 20
hours. After the completion of the polymerization reaction, the
reaction solution was dropwise added into a large excess of ethyl
acetate, and the resulting precipitate was collected by filtration
under suction. After drying under reduced pressure, 20.95 g of
random MAD/AMPS copolymer (50/50) was obtained (yield: 98.4%). The
weight average molecular weight was 176000.
EXAMPLE 3-17
11-Methacrylamidoundecanoic acid (MAU)/2-ethylhexyl acrylate
copolymer (90/10)
[0112] In 59.69 g of methanol were dissolved 18.59 g (69.02 mmol)
of 11-methacrylamidoundecanoic acid (MAU), 1.41 g (7.67 mmol) of
2-ethylhexyl acrylate (Sigma-Aldrich Japan K.K.), and 0.31 g (1.89
mmol) of azobisisobutyronitrile (Nacalai Tesque, Inc.). The
solution was deaerated by bubbling nitrogen for 60 minutes. The
container was covered with a septum, and the polymerization was
conducted by heating at 60.degree. C. for 20 hours. After the
completion of the polymerization reaction, yellow candy-like
material was obtained. To this was added 80 g of methanol, and the
material was dissolved. The obtained solution was dropwise added
into a large excess of ethyl acetate, and the resulting precipitate
was collected by filtration under suction. After drying under
reduced pressure, 13.01 g of random MAU/2-ethylhexyl acrylate
copolymer (90/10) was obtained (yield: 65.0%). The weight average
molecular weight was 560000.
EXAMPLE 3-18
11-Methacrylamidoundecanoic acid (MAU)/2,2,2-trifluoroethyl
acrylate copolymer (90/10)
[0113] In 59.68 g of methanol were dissolved 18.80 g (69.82 mmol)
of 11-methacrylamidoundecanoic acid (MAU), 1.20 g (7.76 mmol) of
2,2,2-trifluoroethyl acrylate (Tokyo Chemical industry Co.), and
0.32 g (1.95 mmol) of azobisisobutyronitrile (Nacalai Tesque,
Inc.). The solution was deaerated by bubbling nitrogen for 60
minutes. The container was covered with a septum, and the
polymerization was conducted by heating at 60.degree. C. for 20
hours. After the completion of the polymerization reaction, the
reaction solution was dropwise added into a large excess of ethyl
acetate, and the resulting precipitate was collected by filtration
under suction. After drying under reduced pressure, 9.02 g of
random MAU/2,2,2-trifluoroethyl acrylate copolymer (90/10) was
obtained (yield: 45.1%). The weight average molecular weight was
35000.
EXAMPLE 3-19
11-Methacrylamidoundecanoic acid (MAU)/2,2,3,3-tetrafluoropropyl
methacrylate copolymer (90/10)
[0114] In 59.69 g of methanol were dissolved 18.47 g (68.60 mmol)
of 11-methacrylamidoundecanoic acid (MAU), 1.53 g (7.62 mmol) of
2,2,3,3-tetrafluoropropyl methacrylate (Tokyo Chemical industry
Co.), and 0.31 g (1.89 mmol) of azobisisobutyronitrile (Nacalai
Tesque, Inc.). The solution was deaerated by bubbling nitrogen for
60 minutes. The container was covered with a septum, and the
polymerization was conducted by heating at 60.degree. C. for 20
hours. After the completion of the polymerization reaction, the
reaction solution was dropwise added into a large excess of diethyl
ether, and the resulting precipitate was collected by filtration
under suction. After drying under reduced pressure, 16.15 g of
random MAU/2,2,3,3-tetrafluoropropyl methacrylate copolymer (90/10)
was obtained (yield: 80.8%). The weight average molecular weight
was 220000.
EXAMPLE 3-20
11-Methacrylamidoundecanoic acid (MAU)/2-(N,N-dimethylamino)ethyl
acrylate copolymer (90/10)
[0115] In 59.68 g of methanol were dissolved 18.88 g (70.12 mmol)
of 11-methacrylamidoundecanoic acid (MAU), 1.12 g (7.79 mmol) of
2-(N,N-dimethylamino)ethyl acrylate (Tokyo Chemical industry Co.),
and 0.32 g (1.95 mmol) of azobisisobutyronitrile (Nacalai Tesque,
Inc.). The solution was deaerated by bubbling nitrogen for 60
minutes. The container was covered with a septum, and the
polymerization was conducted by heating at 60.degree. C. for 20
hours. After the completion of the polymerization reaction, the
solution was concentrated to dryness under reduced pressure, and
the solid was dissolved in 60 g of dimethylformamide. The obtained
solution was dropwise added into a large excess of diethyl ether,
and the resulting precipitate was collected by filtration under
suction. After drying under reduced pressure, 5.22 g of random
MAU/2-(N,N-dimethylamino)ethyl acrylate copolymer (90/10) was
obtained (yield: 26.1%). The weight average molecular weight was
130000.
EXAMPLE 3-21
11-Methacrylamidoundecanoic acid (MAU)/2-dimethylaminoethyl
methacrylate copolymer (90/10)
[0116] In 59.68 g of methanol were dissolved 18.78 g (69.74 mmol)
of 11-methacrylamidoundecanoic acid (MAU), 1.22 g (7.75 mmol) of
2-dimethylaminoethyl methacrylate (Tokyo Chemical industry Co.),
and 0.32 g (1.95 mmol) of azobisisobutyronitrile (Nacalai Tesque,
Inc.). The solution was deaerated by bubbling nitrogen for 60
minutes. The container was covered with a septum, and the
polymerization was conducted by heating at 60.degree. C. for 20
hours. After the completion of the polymerization reaction, the
solution was concentrated to dryness under reduced pressure, and
the solid was dissolved in 60 g of dimethylformamide. The obtained
solution was dropwise added into a large excess of diethyl ether,
and the resulting precipitate was collected by filtration under
suction. After drying under reduced pressure, 7.78 g of random
MAU/2-dimethylaminoethyl methacrylate copolymer (90/10) was
obtained (yield: 38.9%). The weight average molecular weight was
250000.
EXAMPLE 3-22
12-Methacrylamidododecanoic acid (MAD)/N-hydroxyethylacrylamide
(HEAA) copolymer (90/10)
[0117] In 60.0 g of methanol were dissolved 19.14 g (67.63 mmol) of
12-methacrylamidododecanoic acid (MAD), 0.86 g (7.51 mmol) of
N-hydroxyethylacrylamide (HEAA: Kohjin Co., Ltd.), and 0.33 g (1.97
mmol) of azobisisobutyronitrile (Nacalai Tesque, Inc.). Before use,
azobisisobutyronitrile was recrystallized from methanol in the
usual way. The solution was deaerated by bubbling argon for 60
minutes. The container was covered with a septum, and the
polymerization was conducted by heating at 60.degree. C. for 20
hours. After the completion of the polymerization reaction, the
reaction solution was dropwise added into a large excess of diethyl
ether, and the resulting precipitate was collected by filtration
under suction. After drying under reduced pressure, 16.90 g of
MAD/HEAA copolymer (90/10) was obtained (yield: 84.5%).
EXAMPLE 3-23
11-Methacrylamidoundecanoic acid (MAU)/N,N-dimethylaminoethyl
acrylate methyl chloride copolymer (90/10)
[0118] In 59.69 g of methanol were dissolved 18.52 g (68.77 mmol)
of 11-methacrylamidoundecanoic acid (MAU), 1.48 g (7.64 mmol) of
N,N-dimethylaminoethyl acrylate methyl chloride (Kohjin Co., Ltd.),
and 0.31 g (1.89 mmol) of azobisisobutyronitrile (Nacalai Tesque,
Inc.). The solution was deaerated by bubbling nitrogen for 60
minutes. The container was covered with a septum, and the
polymerization was conducted by heating at 60.degree. C. for 20
hours. After the completion of the polymerization reaction, the
obtained solution was dropwise added into a large excess of
acetone, and the resulting precipitate was collected by filtration
under suction. After drying under reduced pressure, 9.43 g of
random MAU/N,N-dimethylaminoethyl acrylate methyl chloride
copolymer (90/10) was obtained (yield: 47.2%). The weight average
molecular weight was 68000.
EXAMPLE 3-24
11-Methacrylamidoundecanoic acid
(MAU)/N,N-dimethylaminopropylacrylamide methyl chloride copolymer
(90/10)
[0119] In 59.69 g of methanol were dissolved 18.43 g (68.43 mmol)
of 11-methacrylamidoundecanoic acid (MAU), 1.57 g (7.60 mmol) of
N,N-dimethylaminopropylacrylamide methyl chloride (Kohjin Co.,
Ltd.), and 0.31 g (1.89 mmol) of azobisisobutyronitrile (Nacalai
Tesque, Inc.). The solution was deaerated by bubbling nitrogen for
60 minutes. The container was covered with a septum, and the
polymerization was conducted by heating at 60.degree. C. for 20
hours. After the completion of the polymerization reaction, the
obtained solution was dropwise added into a large excess of
acetone, and the resulting precipitate was collected by filtration
under suction. After drying under reduced pressure, 9.60 g of
random MAU/N,N-dimethylaminopropylacrylamide methyl chloride
copolymer (90/10) was obtained (yield: 48.0%). The weight average
molecular weight was 42000.
EXAMPLE 3-25
11-Methacrylamidoundecanoic acid (MAU)/methoxypolyethylene glycol
monomethacrylate copolymer (90/10)
[0120] In 59.70 g of methanol were dissolved 17.96 g (66.67 mmol)
of 11-methacrylamidoundecanoic acid (MAU), 2.04 g (7.41 mmol) of
methoxypolyethylene glycol monomethacrylate (Blenmer PME-200:
Nippon Oil & Fats Co.), and 0.30 g (1.83 mmol) of
azobisisobutyronitrile (Nacalai Tesque, Inc.). The solution was
deaerated by bubbling nitrogen for 60 minutes. The container was
covered with a septum, and the polymerization was conducted by
heating at 60.degree. C. for 20 hours. After the completion of the
polymerization reaction, the obtained solution was dropwise added
into a large excess of ethyl acetate, and the resulting precipitate
was collected by filtration under suction. After drying under
reduced pressure, 9.69 g of random MAU/methoxypolyethylene
glycol-monomethacrylate copolymer (90/10) was obtained (yield:
48.5%). The weight average molecular weight was 110000.
EXAMPLE 3-26
11-methacrylamidoundecanoic acid (MAU)/methoxypolyethylene glycol
monomethacrylate copolymer (99/1)
[0121] In 59.70 g of methanol were dissolved 19.80 g (73.50 mmol)
of 11-methacrylamidoundecanoic acid (MAU), 0.20 g (0.74 mmol) of
methoxypolyethylene glycol monomethacrylate (Blenmer PME-200:
Nippon Oil & Fats Co.), and 0.30 g (1.83 mmol) of
azobisisobutyronitrile (Nacalai Tesque, Inc.). The solution was
deaerated by bubbling nitrogen for 60 minutes. The container was
covered with a septum, and the polymerization was conducted by
heating at 60.degree. C. for 20 hours. After the completion of the
polymerization reaction, the obtained solution was dropwise added
into a large excess of ethyl acetate, and the resulting precipitate
was collected by filtration under suction. After drying under
reduced pressure, 10.28 g of random MAU/methoxypolyethylene glycol
monomethacrylate copolymer (99/1) was obtained (yield: 51.4%). The
weight average molecular weight was 34000.
EXAMPLE 3-27
11-Methacrylamidoundecanoic acid (MAU)/methacryloxy-modified
silicone copolymer (90/10)
[0122] In a mixed solution of 30 g of methanol and 30 g of
chloroform were dissolved 14.16 g (52.57 mmol) of
11-methacrylamidoundecanoic acid (MAU), 5.84 g (5.84 mmol) of
methacryloxy-modified silicone (FM-0711: Chisso Corporation), and
0.24 g (1.46 mmol) of azobisisobutyronitrile (Nacalai Tesque,
Inc.). The solution was deaerated by bubbling nitrogen for 60
minutes. The container was covered with a septum, and the
polymerization was conducted by heating at 60.degree. C. for 20
hours. After the completion of the polymerization reaction, the
solution was concentrated to dryness under reduced pressure, and
the solid was dissolved in 100 g of tetrahydrofuran. The obtained
solution was dropwise added into a large excess of n-hexane, and
the resulting precipitate was collected by filtration under
suction. After drying under reduced pressure, 12.15 g of random
MAU/methacryloxy-modified silicone copolymer (90/10) was obtained
(yield: 60.8%). The weight average molecular weight was 53000.
EXAMPLE 3-28
11-Methacrylamidoundecanoic acid (MAU)/2-methacryloxyethyl
phosphoric acid copolymer (90/10)
[0123] In a mixed solvent of 75 g of methanol and 25 g of
ion-exchanged water were dissolved 18.40 g (68.32 mmol) of
11-methacrylamidoundecanoic acid (MAU), 1.60 g (7.59 mmol) of
2-methacryloxyethyl phosphoric acid (Phosmer-M: Uni-Chemical Co.),
0.30 g (7.59 mmol) of sodium hydroxide, and 0.31 g (1.89 mmol) of
azobisisobutyronitrile (Nacalai Tesque, Inc.). The solution was
deaerated by bubbling nitrogen for 60 minutes. The container was
covered with a septum, and the polymerization was conducted by
heating at 60.degree. C. for 20 hours. After the completion of the
polymerization reaction, a gelatinous product was obtained. This
product was dried under reduced pressure, and 6.0 g of the dried
material was added to 200 g of methanol. After sufficient stirring,
insoluble material was removed by filtration. The obtained solution
was dropwise added into a large excess of ethyl acetate, and the
resulting precipitate was collected by filtration under suction.
After drying under reduced pressure, 2.01 g of random
MAU/2-methacryloxyethyl phosphoric acid copolymer (90/10) was
obtained. The weight average molecular weight was 190000.
EXAMPLE 4
[0124] In the following section are shown formulation examples of
cosmetics in which the powders treated with various
surface-treating agents described in the above examples are
blended.
TABLE-US-00007 EXAMPLE 4-1 Powder solid foundation mass %
Dimethylpolysiloxane 5 Isostearic acid 0.5 Diisostearyl malate 1
Glyceryl tri2-ethylhexanoate 3 Sorbitan sesquiisostearate 1
Spherical PMMA coated mica 4 Fineparticle zinc oxide 1 Fineparticle
titanium oxide 3 Synthetic phlogopite 1 Metallic soap treated talc
Balance Spheric silica 3 Red iron oxide coated titanated mica 1
Anhydrous silicic acid coated mica 6 DL-alpha-tocopherol acetate
0.1 D-sigma-tocopherol 0.1 Ethylparaben q.s. Methyl
bis(trimethylsiloxy)silylisopentyl trimethoxycinnamate 0.1
2-Ethylhexyl p-methoxycinnamate 3 Spheric polyalkylacrylate powder
2 Polyalkylacrylate powder including liquid paraffin 4 Treated talc
with Example 3-13 *1 20 Treated sericite with Example 3-13 *2 15
Treated titania with Example 3-13 *1 10 Treated yellow iron oxide
(coloring material) 4.2 with Example 3-13 *1 Treated red iron oxide
(coloring material) 0.7 with Example 3-13 *1 Treated black iron
oxide (coloring material) 0.1 with Example 3-13 *1 *1
Powder:Polymer = 80:20(mass %) *2 Powder:Polymer = 75:25(mass
%)
TABLE-US-00008 EXAMPLE 4-2 Powder solid foundation mass %
Alpha-olefine oligomer 3 Petrolatum 2 Synthetic hydrocarbon wax
powder 2 Dimethylpolysiloxane 3 Isostearic acid 1 Glyceryl
tri2-ethylhexanoate 3 Sorbitan sesquiisostearate 1 Glycerol
modified silicone resin coated talc 5 Treated synthetic phlogopite
with Example 3-18 *3 27 Treated titania with Example 3-18 *4 5
Boron nitride 1 Treated sericite with Example 3-18 *3 20 Treated
talc with Example 3-18 *3 Balance Treated mica with Example 3-18 *4
5 Treated barium sulfate with Example 3-18 *4 1 Red iron oxide
coated titanated mica 0.1 DL-alpha-tocopherol acetate 0.1
D-delta-tocopherol 0.1 Parahydroxybenzoic acid ester q.s Red iron
oxide coated titanated mica q.s Treated yellow iron oxide with
Example 3-18 *3 q.s Treated black iron oxide with Example 3-18 *3
q.s Nylon powder 2 Silicic anhydride 2 Spheric polyalkylacrylate
powder 6 *3 Powder:Polymer = 80:20(mass %) *4 Powder:Polymer =
75:25(mass %)
TABLE-US-00009 EXAMPLE 4-3 Powder solid foundation mass % Synthetic
hydrocarbon wax particle 2 Dimethylpolysiloxane 6 Purified lanolin
5 Glyceryl tri2-ethyl hexanoate 2 Sorbitan sesquiisostearate 0.5
Treated needle-shape fineparticle titania with Example 3-12 *5 5
Treated fineparticle zinc oxide with Example 3-12 *5 1 Treated iron
oxide/titania sintered material 7 with Example 3-12 *6 Treated
barium sulfate with Example 3-12 *5 8 Treated sericite carcined
material with Example 3-12 *6 Balance Titanium-deoxided titanated
mica pearl pigments 2 Treated synthetic phlogopite with Example
3-18 *6 5 Treated talc with Example 3-12 *6 2 Spheric silica 3
Treated mica with Example 3-12 *6 15 Stearyl glycyrrhetate 0.1
Ascorbyl dipalmitate 0.1 DL-alpha-tocopherol acetate 0.1
D-delta-tocopherol 0.1 Parahydroxybenzoic acid ester q.s.
Ethylhexyl methoxycinnamate 3 Treated red iron oxide with Example
3-12 *6 1 Treated yellow iron oxide in Example 3-12 *6 1 Treated
black iron oxide in Example 3-12 *6 1 Spheric polyalkyl acrylate 3
Perfume q.s. *5 Powder:Polymer = 85:15(mass %) *6 Powder:Polymer =
75:25(mass %)
TABLE-US-00010 EXAMPLE 4-4 Powder solid foundation mass %
Alpha-olefine oligomer 10 Microcrystalline wax 0.5 Ceresin 5
Dimethylpolysiloxane 15 Methylphenyl polysiloxane 10 Macadamia nuts
oil 0.1 Carnauba wax 0.1 Glyceryl tri2-ethylhexanoate 7 Cetyl
2-ethylhexanoate 10 Sorbitan sesquiisostearate 1.5 Treated mica
with Example 3-1 0.5 Aluminum stearate 1 Cross-linked silicone
powder (Trefil E-506) 8 N-Lauroyl-L-lisine 0.1 D-delta-tocopherol
q.s. Treated red iron oxide with Example 3-2 + behenyl alcohol q.s.
Treated yellow iron oxide with Example 3-2 + behenyl alcohol q.s.
Calcium alginate powder 1 Nylon powder Balance Treated spherical
anhydrous silicic acid 1 with Example 3-2 + behenyl alcohol Treated
titania with Example 3-2 + behenyl alcohol 1
*Powder:Polymer:Behenyl alcohol = 75:20:5(mass %)
TABLE-US-00011 EXAMPLE 4-5 Powder solid foundation mass %
Microcrystalline wax 5 Dimethylpolysiloxane 10
Decamethylcyclopentasiloxane 30 Polyoxyethylene/methylPolysiloxane
copolymer 2 Dipropylene glycol 3 Palmitic acid 0.5 Sorbitan
sesquiisostearate 1 Treated yellow iron oxide with Example 3-9 +
isostearic acid *7 3 Treated red iron oxide Example 3-9 +
isostearic acid *7 1 Treated black iron oxide with Example 3-9 +
isostearic acid *7 q.s. Treated anhydrous silicic acid 2 with
Example 3-9 + isostearic acid *8 Treated titania with Example 3-9 +
isostearic acid *7 15 Treated sericite with Example 3-9 +
isostearic acid *8 10 Treated titania/red iron oxide coated mica 3
with Example 3-9 + isostearic acid *8 Cross-linked silicone powder
(Trefil E-506) 3 N-Lauroyl-L-lisine 0.1 Tocopheryl acetate 0.1
Delta-tocopherol 0.1 Parahydroxybenzoic acid ester q.s. Melilot
extract 2 Purified water Balance *7 Powder:Polymer:Isostearic acid
= 75:20:5(mass %) *8 Powder:Polymer:Isostearic acid = 75:45:10(mass
%)
TABLE-US-00012 EXAMPLE 4-6 Powder solid foundation mass %
Microcrystalline Wax 1 Dimethylpolysiloxane 15
Decamethylcyclopentasiloxane 2 1,3-Butylene glycol 6 Candelilla wax
3 Isostearic acid 1 Ethylene glycol fatty acid ester 0.1
Octyldodecyl lanolate 0.5
2-alkyl-N-carboxymethy-N-hydroxyethylimidazolinium betaine 4
Treated pigment class titania with Example 3-21 7.5 Treated barium
sulfate with Example 3-21 5 Treated fineparticle titania with
Example 3-21 7 Treated talc with Example 3-21 3 Treated silicic
anhydrid with Example 3-21 4 Cross-linked silicone powder (Trefil
E-506) 0.1 Sodium metaphosphate 0.1 Hydroxypropyl cyclodextrin 0.1
DL-alpha-tocopherol acetate 0.1 Hamamelis extract 0.1 Peony root
extract 0.1 Sodium chondroitin sulphate 0.1 Sodium hyaluronate 0.1
Parahydroxybenzoic acid ester q.s. Treated red iron oxide with
Example 3-21 q.s. Treated yellow iron oxide with Example 3-21 q.s.
Treated black iron oxide with Example 3-21 q.s. Xanthan gum 0.2
Carboxymethyl cellulose sodium 0.2 Melilot extract 2 Purified water
Balance *Powder:Polymer = 75:25(mass %)
TABLE-US-00013 EXAMPLE 4-7 Powder solid foundation mass % Ceresin 5
Dimethylpolysiloxane 10 Decamethylcyclopentasiloxane 10
Dodecamethylcyclohexasiloxane 20 Carnauba wax 0.5 Candelilla wax
0.5 Glyceryl tri2-ethylhexanoate Balance Sorbitan sesquiisostearate
1.5 Treated titania with Example 3-3 8 Treated kaolin with Example
3-3 10 Treated mica with Example 3-3 12 Titanated mica/polyalkyl
acrylatecomposite powder 1 Polyalkylacrylate coated titanated mica
1 Treated titania MT-014TV with Example 3-3 5 Treated black iron
oxide coated titanated mica 0.5 with Example 3-3 Tocopheryl acetate
0.1 Delta-tocopherol 0.1 Treated red iron oxide with Example 3-3
q.s. Treated yellow iron oxide with Example 3-3 q.s. Treated iron
blue with zinc oxide q.s. Treated black iron oxide with Example 3-3
q.s. Perfume q.s. *Powder:Polymer = 75:25(mass %)
TABLE-US-00014 EXAMPLE 4-8 Powder solid foundation mass %
Dimethylpolysiloxane 15 Decamethylcyclopentasiloxane 20
Polyoxyethylene/methylpolysiloxane copolymer 5 High moleculer
weight amino modified silicone 0.1 Glycerin 5 1,3-Butylene glycol
10 Palmitic acid 0.5 Cholesteryl macadamiate 0.1
Distearyldimethylammonium chloride 0.2 Treated yellow iron oxide
with Example 3-19 2 Treated red iron oxide with Example 3-19 1
Treated black iron oxide with Example 3-19 0.3 Treated titania with
Example 3-19 10 Treated talc with Example 3-19 1.5 Treated
spindle-shape titania with Example 3-19 3 L-sodium glutamate 0.5
DL-alpha-tocopherol acetate 0.1 Parahydroxybenzoic acid ester q.s.
Methyl bis(trimethylsiloxy)sirylisopentil 0.1 trimethoxycinnamate
Dimethyldistearylammonium hectorite 1.5 Spheric nylon powder 1
Purified water Balance Perfume q.s. *Powder:Polymer = 75:25(mass
%)
TABLE-US-00015 EXAMPLE 4-9 Powder solid foundation mass %
Dimethylpolysiloxane 3 Decamethylcyclopentasiloxane 15
Polyoxyethylene/methylpolysiloxane copolymer 3 Glycerin 3
1,3-Butylene glycol 5 Palmitic acid 0.5 Distearyldimethylammonium
chloride 0.2 Glycerol modified silicone resin coated sericite 0.5
Treated yellow iron oxide coated titanated mica 0.5 with Example
3-11 *9 Treated titania with Example 3-11 *9 2 Treated iron
oxide/titania sintered material (PK) 12 with Example 3-11 *10
Treated talc with Example 3-11 *9 10 Treated titania coated
sericite with Example 3-11 *10 0.5 Boron nitride 0.5 Fineparticle
titanium oxide 0.5 Treated red iron oxide coated titanated mica 0.5
with Example 3-11 *10 Phytosterol 0.1 L-sodium glutamate 1.5
Ascorbyl dipalmitate 0.1 DL-alpha-tocopherol acetate 0.1 Acetylated
sodium hyaluronate 0.1 Parahydroxybenzoic acid ester q.s.
Phenoxyethanol q.s. Red iron oxide coated titanated mica 0.5
Treated yellow iron oxide with Example 3-11 *9 2 Treated black iron
oxide with Example 3-11 *9 0.2 Spheric nylon powder 1 Purified
water Balance Perfume q.s. *9 Powder:Polymer = 80:20(mass %) *10
Powder:Polymer = 75:25(mass %)
TABLE-US-00016 EXAMPLE 4-10 Powder solid foundation mass % Behenyl
alcohol 0.5 Dipropylene glycol 6 Stearic acid 1 Glyceryl
monostearate 1 Potassium hydroxide 0.2 Triethanolamine 0.8
DL-alpha-tocopherol acetate 0.1 Parahydroxybenzoic acid ester q.s.
Treated yellow iron oxide with Example 3-4 1 Alpha-olefine oligomer
3 Dimethylpolysiloxane (6 mPa s) 2 Dimethylpolysiloxane (100 mPa s)
5 Batylalcohol 0.5 Isostearic acid 1 Behenic acid 0.5 Cetyl
2-ethylhexanoate 10 Polyoxyethylene glycerin monostearate 1 Treated
titania with Example 3-4 3 Titanated mica/polyalkyl acrylate
composite powder 0.5 Treated fineparticle titania with Example 3-4
10 Polyalkylacrylate coated titanated mica 0.5 Treated black iron
oxide coated titanated mica in Example 3-4 0.5 Treated silicic
anhydride with Example 3-4 6 2-Ethylhexyl p-methoxycinnamate 2
Treated red iron oxide with Example 3-4 q.s. Treated iron blue with
Example 3-4 q.s. Treated black iron oxide with Example 3-4 q.s.
Legal coloring pigment q.s. Xanthan gum 0.1 Bentonite 1 Sodium
carboxymethylcellulose 0.1 Purified water Balance Perfume q.s.
*Powder:Polymer = 85:15(mass %)
TABLE-US-00017 EXAMPLE 4-11 Powder solid foundation mass %
Dodecamethylcyclohexasiloxane 15 Decamethylcyclopentasiloxane
Balance 3-Tris(trimethylsiloxy) silylpropyl carbamoyl pullulan 3
Ethanol 10 Isostearic acid 0.5 Treated zinc oxide with Example 3-11
0.5 Treated titania with Example 3-12 10 Treated talc with Example
3-12 7 Treated fineparticle titania with Example 3-12 5
Cross-linked silicone powder 1 Spheric silicic anhydride 2
Magnesium ascorbyl phosphate 0.2 DL-alpha-tocopherol acetate 0.1
D-delta-tocopherol 0.1 Glutathione 0.1 Sophora Extract 0.1
2-Ethylhexyl p-methoxycinnamate 5 Treated red iron oxide with
Example 3-11 q.s. Treated yellow iron oxide with Example 3-11 q.s.
Treated black iron oxide with Example 3-11 q.s. Perfume q.s.
*Powder: Polymer (execution example 3-11) = 85:15 (mass %) Powder:
Polymer (execution example 3-12) = 90:10 (mass %)
TABLE-US-00018 EXAMPLE 4-12 Powder solid foundation mass %
Decamethylcyclopentasiloxane 10 Dodecamethylcyclohexasiloxane 20
Trimethylsiloxysilicate 1 Poly (oxyethylene/oxypropylene)
methylpolysiloxane copolymer 3 Ethanol 10 Isostearic acid 0.5
Treated titania with Example 3-16 10 Treated fineparticle zinc
oxide with Example 3-16 5 Dextrin palmitate coated talc 5 Treated
needle-shape fineparticle titania with Example 3-16 1 Treated
spherical anhydrous silicic acid with Example 3-16 5 Anhydrous
silicic acid coated mica q.s. Sodium citrate q.s.
N-Lauroyl-L-lisine 0.5 DL-alpha-tocopherol acetate 0.1
D-delta-tocopherol 0.1 Sophora extract 1 Treated red iron oxide
with Example 3-16 q.s. Treated yellow iron oxide with Example 3-16
q.s. Treated black iron oxide with Example 3-16 q.s. Melilot
extract 2 Purified water Balance *Powder:Polymer = 80:20(mass
%)
TABLE-US-00019 EXAMPLE 4-13 Powder solid foundation mass % Ethyl
alcohol 2 Glycerin 2 1,3-Butylene glycol 6 Treated titania (30
.mu.m) with Example 3-20 4 Treated titania (ultrafineparticle 20
nm) with Example 3-20 2 Treated zinc oxide with Example 3-20 2
Treated plate-shape barium sulfate with Example 3-20 5 Treated talc
with Example 3-20 1 Treated kaolin with Example 3-20 2 Treated mica
with Example 3-20 0.5 Treated spheric silica in Example 3-20 0.5
Salt 0.3 L-Arginine hydrochloride 0.1 Creeping thyme extract 0.1
Hamamelis 0.1 Phellodendron extract 0.1 Peppermint extract BG 0.1
Phenoxyethanol 0.5 Red iron oxide 0.5 Ocre 1 Treated iron oxide
black with Example 3-20 0.7 Magnesium aluminometasilicate 0.1
Ion-exchanged water Balance *Powder:Polymer = 95:5(mass %)
TABLE-US-00020 EXAMPLE 4-14 Powder solid foundation mass % Ethanol
2.0 Glycerin 10.0 1,3-Butylene glycol 15.0 Silica coated titania
8.0 Treated synthetic phlogopite with Example 3-10 3.0 Spheric
silicic anhydride 5.0 Treated red iron oxide coated titanated mica
2.0 (color rendering pearl G) with Example 3-10 Sodium chloride 0.3
Hydroxypropyl beta-cyclodextrin 0.1 Mukurossi Extract 0.1 Sweet tea
extract 0.1 Lily extract 0.1 Red iron oxide 0.1 Gellan gum 0.1
Porous spheric cellulose 0.1 Lavender extract 0.1 Purified water
Balance *Powder:Polymer = 95:5(mass %)
TABLE-US-00021 EXAMPLE 4-15 POW oil-in-water emulsified milky
foundation mass % (1) Treated titania with Example 3-13 9.0 (2)
Treated ultrafine particle titania(40 nm) with Example 3-13 5.0 (3)
Treated iron oxide(red) with Example 3-13 0.5 (4) Treated iron
oxide(yellow) with Example 3-13 1.5 (5) Treated iron oxide(black)
with Example 3-13 0.2 (6) Polyoxyalkylene modified
organopolysiloxane 0.5 (7) Decamethylpentacycrosiloxane 5.0 (8)
Octyl p-methoxycinnamate 5.0 (9) Acrylic silicone 4.0 (10) PEG-100
hydrogenated castor oil 2.0 (11) Dynamite glycerin 6.0 (12) Xanthan
Gum 0.1 (13) Carboxymethylcellulose 0.3 (14) Sodium
acryloyldimethyltaurate/ 1.5 hydroxy ethyl acrylate copolymer
(content: 35-40 mass %) (SIMULGEL NSTM: Seppic) (15)Ethanol 3.0
(16) Ion-exchanged water Balance *Powder:Polymer = 80:20(mass %)
(Manufacturing method) (1)-(9) were mixed and dispersed, then this
was added into an aqueous phase dissolving (10)-(16) with
homomixer.
TABLE-US-00022 EXAMPLE 4-16 O/W type mascara mass %
Microcrystalline wax 6 Methylpolysiloxane emulsion q.s. Isopropanol
3 Batylalcohol 1 Dipropylene glycol 5 Isostearic acid 3 Stearic
acid 1 Di(phytostearyl/2-octyldodecyl) N-lauroyl-L-glutamate 0.1
Sorbitan monostearate 1 Polyoxyethylene (20EO) solbitan
monostearate 1 Sucrose fatty acid ester 15 Isobutylene/sodium
maleate copolymer solution 0.1 Titanated mica 1 Potassium hydroxide
0.5 Sodium hydrogen carbonate 0.1 DL-alpha-tocopherol acetate 0.1
Parahydroxybenzoic acid ester q.s. Sodium dehydroacetate q.s.
Phenoxyethanol q.s. Treated black iron oxide (coloring material)
with Example 3-13 10 Seaweed extract 0.1 Magnesium aluminum
silicate 0.1 Polyalkylacrylate emulsion 5 Polyvinyl alcohol 0.5
Polyvinyl acetate emulsion 7 Purified water Balance Silicic
anhydride 0.5 Treated titania with Example 3-13 0.1
TABLE-US-00023 EXAMPLE 4-17 O/W type mascara mass % Light
isoparaffin 6 Dimethylpolysiloxane 1 Decamethylcyclopentasiloxane 5
Trimethylsiloxy silicate 5 Methylpolysiloxane emulsion q.s.
Isopropanol 3 1,3-Butylene glycol 6 Polyoxyethylene hydrogenated
castor oil 1 Sucrose fatty acid ester 0.6 Diglyceryl diisostearate
1 Sodium hydrogen carbonate 0.01 DL-alpha-tocopherol acetate 0.1
Acetylated sodium hyaluronnate 0.1 Parahydroxybenzoic acid ester
q.s. Phenoxyethanol 0.3 Treated black iron oxide with Example 3-13
8 Bentonite 1 Dimethyldistearylammonium hectorite 4 Polyvinyl
alcohol 4 Alkylacrylate copolymer emulsion 12 Polyvinyl acetate
emulsion 12 Nylon fiber (1-2 mm) 6 Purified water Balance Silicic
anhydride 0.5 Treated titania with Example 3-13 1 Perfume q.s.
TABLE-US-00024 EXAMPLE 4-18 O/W type eyeliner mass % Liquid
paraffin 5 Methylpolysiloxane emulsion q.s. Glycerin 3 1,3-Butylene
glycol 6 Polyoxyethylene (20EO) solbitan monolaurate 2
Isobutylene/sodium maleate copolymer 1 Treated titania with Example
3-13 q.s. Plate-shape barium sulfate q.s. Treated kaolin with
Example 3-13 8 Black iron oxide coated titanated mica (pearl
ingredient) 3 Treated black iron oxide with Example 3-13 9
DL-alpha-tocopherol acetate 0.1 Parahydroxybenzoic acid ester q.s.
Bentonite 1 Sodium carboxymethylcellulose 2 Alkyl acrylate
copolymer emulsion 7 Purified water Balance
TABLE-US-00025 EXAMPLE 4-19 Pencil-type eyeliner mass % Liquid
paraffin Balance Microcrystalline wax 20 Macadamia nuts oil 0.1
Candelilla wax 2 Sorbitan sesquiisostearate 1 Treated titania with
Example 3-13 1 Treated mica with Example 3-13 5 Treated titanated
mica with Example 3-13 15 Treated synthetic micas with Example 3-13
0.1 Treated iron blue coated titanated mica with Example 3-13 2
Treated red iron oxide coated titanated mica with Example 3-13 2
Treated mica with Example 3-13 10 DL-alpha-tocopherol acetate 0.02
D-delta-Tocopherol 0.02 Glyceryl di(p-methoxy cinnamate)
mono(2-ethylhexanoate) 0.1 Treated zinc oxide with iron blue 2 Iron
blue 5 Heavy liquid isoparaffin 1 Polyalkyl acrylate powder 2
Cross-linked silicone powder 5
TABLE-US-00026 EXAMPLE 4-20 Solid type eyeliner mass % Petrolatum 3
Hardened oil 30 Japan wax 10 Stearic acid 12 Trimethylolpropane
triethyloctanoate 5 Treated titania with Example 3-13 2 Treated
titanated mica with Example 3-13 10 Treated red iron oxide with
Example 3-13 2 Treated yellow iron oxide with Example 3-13 0.5
Treated iron blue with Example 3-13 5 Treated black iron oxide with
Example 3-13 1 Treated mica with Example 3-13 Balance
TABLE-US-00027 EXAMPLE 4-21 Pencil-type eyebrow mass % Hardened oil
10 Macadamia nuts oil 0.1 Soybean oil 0.1 Japan wax 10 Behenic acid
Balance Diisostearyl malate 1 Glyceryl tri2-ethylhexanoate 2
Sucrose fatty acid ester 5 Treated titania with Example 3-13 4
Treated mica with Example 3-13 2 Delta-tocopherol 0.05 Treated red
iron oxide with Example 3-13 8 Treated yellow iron oxide with
Example 3-13 13 Treated black iron oxide with Example 3-13 14
Adsorption purified lanolin 5 Spheric nylon powder 3
TABLE-US-00028 EXAMPLE 4-22 Pencil-type eyebrow mass %
Decamethylcyclopentasiloxane 10 Polyoxyethylene/methylpolysiloxane
copolymer 0.5 Methylphenylpolysiloxane q.s. Behenyl alcohol 14
Macadamia nuts oil 0.1 Carnauba wax 2 Candelilla wax 13 Sorbitan
sesquiisostearate 0.5 Treated titania with Example 3-13 1 Treated
red iron oxide coated titanated mica with Example 3-13 0.1 Treated
sericite with Example 3-13 Balance Silicic anhydride 0.5 Mica 6
Delta-tocopherol 0.05 Treated red iron oxide with Example 3-13 2
Treated yellow iron oxide with Example 3-13 3 Treated black iron
oxide with Example 3-13 8 Trimethylsiloxysilicate 8 Polyethylene
wax 2
TABLE-US-00029 EXAMPLE 4-23 Pencil-type lipliner mass % Herdened
oil 20 Macadamia nuts oil 2 Japan wax 6 Behenic acid 10 Glyceryl
tri2-ethylhexanoate Balance Sucrose fatty acid ester 5 Treated
titania with Example 3-13 10 Treated mica with Example 3-13 10
D-delta-tocopherol 0.04 Treated red iron oxide with Example 3-13 13
Treated yellow iron oxide with Example 3-13 5 Treated black iron
oxide with Example 3-13 2 Sorbitan sesquiisostearate 1
TABLE-US-00030 EXAMPLE 4-24 Pencil-type lipliner mass %
Polyethylene wax 8 Ceresin 4 Macadamia nuts oil 0.1 Liquid lanolin
0.1 Carnauba wax 1 Candelilla wax 10 Phytosteryl hydroxystearate
0.1 Glyceryl triisostearate 15 Diisostearyl malate 0.1 Glyceryl
diisostearate Balance Trimethylolpropane trioctanoate 5 Glyceryl
tri2-ethylhexanoate 13 Treated yellow iron oxide with Example 3-13
5 Treated red iron oxide with Example 3-13 7 Treated black iron
oxide with Example 3-13 0.5 Treated titania with Example 3-13 0.1
Barium sulfate 1.5 Silicic anhydride 0.5 Tocopherol acetate 0.02
Delta-tocopherol 0.02 4-tert-butyl-4'-methoxydibenzoylmethane 0.1
Glyceryl di(p-methoxy cinnamate) mono(2-ethylhexanoate) 0.1 Pigment
1 Heavy liquid isoparaffin 15
TABLE-US-00031 EXAMPLE 4-25 Stick-type lip rouge mass % Ceresin 6
Decamethylcyclopentasiloxane Balance
Polyoxyethylene/methylpolysiloxane copolymer (MW = 6000) 5
Non-aqueous dispersion 30 (Dispersion of alkyl
acrylate/tris(trimethylsiloxy)silylpropyl methacrylate in
decamethylcycropentasiloxane) Dimethylsiloxane/diphenylsiloxane/ 20
methyl(Perfluoroalkyl)siloxane Methylphenyl polysiloxane 5
Stearoxymethyl polysiloxane 2 Candelilla wax 4 Silylated silicic
anhydride 1 Treated silicone coated pigments 7 (titania, iron oxide
red etc.)with Example 3-13 Treated red iron oxide coated titanated
mica with Example 3-13 5 Treated mica with Example 3-13 1 Dye q.s.
Silicic anhydride 2 Treated titania with Example 3-13 3
Poly(oxyethylene/oxypropylene)/methylpolysiloxane copolymer 2 (MW =
50000) Perfume q.s.
TABLE-US-00032 EXAMPLE 4-26 Emulsion-type lip rouge mass %
Microcrystalline wax 3 Ceresin 2 Polyoxyethylene/methylpolysiloxane
copolymer 0.5 Methylphenyl polysiloxane Balance Glycerin 0.5
Xylitol 0.1 Liquid lanolin 2 Squalane 1 Glycerine triisostearate 1
Cholesteryl macadamiate 2 Gryceryl tri(2-ethylhexanoate) 15
Glyceryl tri(hydrogenated rosinate/isostearate) 10 Treated silicon
resin coated titania with Example 3-13 1 Treated calmine coated
mica titanium with Example 3-13 2 Treated titanated mica with
Example 3-13 5 Dye q.s. Citric acid 0.1 Potassium hydroxide 0.05
Hydroxypropyl cyclodextrin 0.3 Pantothenyl ethyl ether 0.05
Arginine hydrochloride 0.01 DL-alpha-tocopherol acetate 0.05 Sodium
hyaluronnate 0.05 2-Ethylhexyl p-methoxycinnamate 5 Spheric
cellulose powdere 2 Heavy liquid isoparaffin 20 Purified water 0.5
Perfume q.s.
TABLE-US-00033 EXAMPLE 4-27 Middle plate-type lip rouge mass %
Liquid paraffin 11 Carnauba wax 2 Glyceryl tri2-ethylhexanoate
Balance Sorbitan sesquioleate 1 treated titania with Example 3-13 5
Treated titanated mica with Example 3-13 12 Treated mica with
Example 3-13 17 Treated iron blue with Example 3-13 5 Treated black
iron oxide in Example 3-13 1
TABLE-US-00034 EXAMPLE 4-28 Liquid tip-type lip rouge mass % Liquid
paraffin Balance Ceresin 5 Heavy liquid isoparaffin 30 Methylphenyl
polysiloxane 5 Liquid lanolin 3 Diisostearyl malate 15 Polyethylene
terephtalate/polymethyl metacrylate 3 laminated film powder Treated
silicone coated pigments with Example 3-13 3 (Bengala, iron oxide
and titania, etc.) Treated red iron oxide coated titanated mica
with Example 3-13 2 Polyoxyethylene/methylpolysiloxane copolymer
0.5 1,3-Butylene glycol 3 Hydrogenated lecithin 0.1 Calcium
chloride 0.1 Sodium hyaluronnate 0.02 Parabene q.s. Laponite 1.5
Purified water 1
TABLE-US-00035 EXAMPLE 4-29 Powder solid eye shadow mass % Liquid
paraffin 0.5 Petrolatum 1 Methylphenyl polysiloxane 2 Sorbitan
sesquiisostearate 1 Treated titania with Example 3-13 0.1 Treated
mica with Example 3-13 10 Treated synthetic mica with Example 3-13
2 Treated sericite with Example 3-13 30 Treated talc with Example
3-13 Balance Zinc myristate 2 D-delta-Tocopherol 0.02
Parahydroxybenzoic acid ester q.s. Treated yellow iron oxide with
Example 3-13 2 Treated black iron oxide with Example 3-13 20
Pigment q.s. Diisostearyl malate 3
TABLE-US-00036 EXAMPLE 4-30 Oily stick-type eye shadow mass %
Paraffin 11 Carnauba wax 1.5 Glyceryl tri2-ethylhexanoate balance
Sorbitan sesquioleate 2 Treated titania with Example 3-13 3 Treated
titanated mica with Example 3-13 15 Treated mica with Example 3-13
20 Treated iron blue with Example 3-13 2 Treated black iron oxide
with Example 3-13 5 Perfume q.s.
TABLE-US-00037 EXAMPLE 4-31 Oily middle plate-type eye shadow mass
% Alpha-olefine oligomer 2 Microcrystalline wax 1.5 Ceresin 6
Dimethylpolysiloxane 5 Methylphenyl polysiloxane 5 Carnauba wax 2
Gryceryl tri2-ethylhexanoate 20 Cetyl 2-ethylhexanoate Balance
Sorbitan sesquiisostearate 1 Treated titania with Example 3-13 3
Treated boron nitride with Example 3-13 5 Treated titanated mica
with Example 3-13 10 Treated sericite with Example 3-13 8
Cross-linked silicone powder 5 DL-alpha-tocopherol acetate 0.02
D-delta-tocopherol 0.02 Treated red iron oxide with Example 3-13
0.1 Treated yellow iron oxide with Example 3-13 0.2 Polyalkyl
acrylate powder 15 Perfume q.s. 12-Hydroxystearic acid 3
TABLE-US-00038 EXAMPLE 4-32 W/O type sunscreen mass %
Decamethylcyclopentasiloxane 20 Trimethylsiloxysilicate 1
Polyoxyethylene/methylpolysiloxane copolymer 2 Dipropylene glycol 4
Squalane 5 Treated silicone coated microprticle titania (20 nm) 10
with Example 3-13 Treated talc(hydophobing material) with Example
3-13 6 Parabene q.s. Phenoxyethanol q.s. Trisodium edetate 0.02
4-t-butyl-4'-methoxydibenzoylmethane 0.1 2-Ethylhexyl
p-methoxycinnamate 7 Glyceryl di(p-methoxycinnamate)
mono(2-ethylhexanoate) 0.5 Spheric polyethylene powder 5
Dimethyldistearylammonium hectorite 1 Purified water Balance
Perfume q.s.
TABLE-US-00039 EXAMPLE 4-33 W/O type sunscreen mass %
Dimethylpolysiloxane 5 Decamethylcyclopentasiloxane 20
Trimethylsiloxysilicate 3 Polyoxyethylene/methylpolysiloxane
copolymer 3 Dipropylene glycol 3 Cetyl 2-ethylhexanoate 1 Treated
silicone coating fineparticle zinc oxide (60 nm) 10 with Example
3-13 Treated talc with Example 3-13 1 Treated Silicone coated
fineparticle titania(40 nm) 7 with Example 3-13 Parabene q.s.
Phenoxyethanol q.s. Trisodium edetate 0.2 Dimethyldistearylammonium
hectorite 1 Polymethyl methacrylate copolymer spherical powder 3
Purified water Balance Perfume q.s.
TABLE-US-00040 EXAMPLE 4-34 W/O type sunscreen mass %
Decamethylcyclopentasiloxane 20 Ethanol 5 Isostearyl alcohol 2
Dipropylene glycol 3 Isostearic acid 2 Glyceryl tri2-ethylhexanoate
5 Cetyl 2-ethylhexanoate 2 Treated dextrin fatty acid ester coated
2 fineparticle titanium oxide(40 nm) with Example 3-13 Sodium
chloride 2 Trisodium edetate q.s. Yubinal T-150 (BASF) 1
4-t-butyl-4'-methoxydibenzoylmethane 1 Ethylhexyl methoxycinnamate
7.5 Sodium carboxymethylcellulose 0.5 Ethyl cellulose 1 Spheric
acrylic resin powder 5 Purified water Balance Perfume q.s.
TABLE-US-00041 EXAMPLE 4-35 O/W type sunscreen mass %
Dimethylpolysiloxane 5 Decamethylcyclopentasiloxane 25
Trimethylsiloxysilicate 5 Polyoxyethylene/methylpolysiloxane
copolymer 2 Dipropylene glycol 5 Treated fineparticle zinc oxide
(Hydrophobic treated material 15 60 nm) with Example 3-13 Parabene
q.s. Phenoxyethanol q.s. Trisodium edetate q.s. 2-Ethylhexyl
p-methoxycinnamate 7.5 Dimethyldistearylammonium hectorite 0.5
Spheric polyalkyl acrylate powder 5 Purified water Balance Perfume
q.s.
TABLE-US-00042 EXAMPLE 4-36 O/W type sunscreen mass % Dipropylene
glycol 5 Stearic acid 1 Palmitic acid 1 Glyceryl
tri2-ethylhexanoate 3 Cetyl 2-ethylhexanoate 2 Polyoxyethylene
glyceryl isostearate 1 Glyceryl monostearate 1 Polyoxyethylene
glyceryl monostearate 1 Treated fineparticle titania (30 nm) with
Example 3-13 2 Sodium hexametaphosphate 0.1 Phenoxyethanol q.s.
Trisodium edetate q.s. 4-t-butyl-4'-methoxydibenzoylmethane 1
2-Ethylhexyl p-methoxycinnamate 7 Bentonite 1
Eicosene/vinylpyrrolidone copolymer 2 Purified water q.s. Perfume
q.s.
TABLE-US-00043 EXAMPLE 4-37 W/O type sunscreen mass %
Dimethylpolysiloxane 5 Decamethylcyclopentasiloxane 25
Trimethylsiloxysilicate 5 Polyoxyethylene/methylpolysiloxane
copolymer 2 Dipropylene glycol 5 Treated dextrin palmitate coated
fineparticle zinc oxide(60 nm) 15 with Example 3-13 Dipotassium
glycyrrhizinate 0.02 Glutathione 1 Thiotaurine 0.05 Sophora Extract
1 Parabene q.s. Phenoxyethanol q.s. Trisodium edetate q.s.
2-Ethylhexyl p-methoxycinnamate 7.5 Dimethyldistearylammonium
hectorite 0.5 Spheric polyalkyl acrylate powder 5
Butylethylpropanediol 0.5 Purified water Balance Perfume q.s.
TABLE-US-00044 EXAMPLE 4-37 W/O type protector mass %
Dimethylpolysiloxane 2 Decamethylcyclopentasiloxane 25
Dodecamethylcyclohexasiloxane 10 Polyoxyethylene/methylpolysiloxane
copolymer 1.5 Trimethylsiloxysilicate 1 1,3-Butylene glycol 5
Squalane 0.5 Talc 5 Dipotassium glycyrrhizinate 0.1 Tocopheryl
acetate 0.1 Trisodium edetate 0.05
4-t-butyl-4'-methoxydibenzoylmethane 1 2-Ethylhexyl
p-methoxycinnamate 5 Glyceryl di(p-methoxycinnamate)
mono(2-ethylhexanoate) 1 Treated silicone coated fineparticle
titania(40 nm) 4 with Example 3-13 Dimethyldistearylammonium
hectorite 0.5 Spheric polyethylene powder 3 Phenoxyethanol q.s.
Purified water Balance Perfume q.s.
* * * * *