U.S. patent application number 16/339290 was filed with the patent office on 2020-08-13 for novel resin-linear organopolysiloxane block copolymer, use of same, and method for producing same.
The applicant listed for this patent is Dow Toray Co., Ltd. DOW SILICONES CORPORATION. Invention is credited to Haruhiko FURUKAWA, John Bernard HORSTMAN, Tomohiro IIMURA, Tadashi OKAWA, Steven SWIER.
Application Number | 20200253855 16/339290 |
Document ID | 20200253855 / US20200253855 |
Family ID | 1000004986744 |
Filed Date | 2020-08-13 |
Patent Application | download [pdf] |
United States Patent
Application |
20200253855 |
Kind Code |
A9 |
FURUKAWA; Haruhiko ; et
al. |
August 13, 2020 |
NOVEL RESIN-LINEAR ORGANOPOLYSILOXANE BLOCK COPOLYMER, USE OF SAME,
AND METHOD FOR PRODUCING SAME
Abstract
Provided is a resin-linear organopolysiloxane block copolymer
which has a high degree of freedom in formulation due to excellent
compatibility with other materials, in addition to exhibiting
excellent film forming properties and followability of a film,
while the stickiness of a film is suppressed. The resin-linear
organopolysiloxane block copolymer has: a resin structure (A1)
block that has siloxane units represented by R.sup.1SiO.sub.3/2
(wherein R.sup.1 represents a monovalent organic group, a hydroxyl
group, or an alkoxy group having 1 to 6 carbon atoms) and
SiO.sub.4/2; and a linear structure (A2) block represented by
(R.sub.2SiO.sub.2/2).sub.n (wherein n represents a number of 5 or
more while R represents an alkyl group, a fluoroalkyl group, or an
aryl group) in each molecule. The resin structure (A1) and the
linear structure (A2) are linked to each other by an Si--O--Si
bond, and an Si atom bonded to the resin structure (A1) constitutes
an RSiO.sub.3/2 unit.
Inventors: |
FURUKAWA; Haruhiko;
(Ichihara-shi, Chiba, JP) ; HORSTMAN; John Bernard;
(Midland, MI) ; IIMURA; Tomohiro; (Ichihara-shi,
Chiba, JP) ; OKAWA; Tadashi; (Ichihara-shi, Chiba,
JP) ; SWIER; Steven; (Midland, MI) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Dow Toray Co., Ltd.
DOW SILICONES CORPORATION |
Shinagawa-ku, Tokyo
Midland |
MI |
JP
US |
|
|
Prior
Publication: |
|
Document Identifier |
Publication Date |
|
US 20190231674 A1 |
August 1, 2019 |
|
|
Family ID: |
1000004986744 |
Appl. No.: |
16/339290 |
Filed: |
October 3, 2017 |
PCT Filed: |
October 3, 2017 |
PCT NO: |
PCT/JP2017/036021 PCKC 00 |
371 Date: |
April 3, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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62403951 |
Oct 4, 2016 |
|
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62403955 |
Oct 4, 2016 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
A61K 2800/10 20130101;
A61K 8/891 20130101; A61Q 19/00 20130101 |
International
Class: |
A61K 8/891 20060101
A61K008/891; A61Q 19/00 20060101 A61Q019/00 |
Claims
1. A resin-linear organopolysiloxane block copolymer comprising: a
resin structure (A1) block that has siloxane units represented by
R.sup.1SiO.sub.3/2 and SiO.sub.4/2 wherein R.sup.1 represents a
monovalent organic group, a hydroxyl group, or an alkoxy group
having 1 to 6 carbon atoms; and a linear structure (A2) block
represented by (R.sub.2SiO.sub.2/2).sub.n wherein n represents a
number of 5 or more while R represents an alkyl group, a
fluoroalkyl group, or an aryl group in each molecule; wherein the
resin structure (A1) and the linear structure (A2) are linked to
each other by an Si--O--Si bond, and an Si atom bonded to the resin
structure (A1) constitutes an RSiO.sub.3/2 unit.
2. The resin-linear organopolysiloxane block copolymer according to
claim 1, wherein a hydroxyl group (OH) content within the molecule
is 1.50 mass % or more.
3. The resin-linear organopolysiloxane block copolymer according to
claim 2, wherein the hydroxyl group (OH) content within the
molecule is 1.75 mass % or more.
4. The resin-linear organopolysiloxane block copolymer according to
claim 1, wherein 15 mol % or more of all SiO.sub.4/2 units are
SiO.sub.4/2 units having hydroxyl groups on Si atoms.
5. The resin-linear organopolysiloxane block copolymer according to
claim 1, which is soluble in cinnamic acid methyl ester.
6. The resin-linear organopolysiloxane block copolymer according to
claim 1, further comprising: one or more functional groups selected
from the group consisting of an alkyl group having 6 or more carbon
atoms, a fluoroalkyl group, an Si-macromonomer, and an Si-dendrimer
modifying group in the molecule.
7. The resin-linear organopolysiloxane block copolymer according to
claim 1, wherein the linear structure (A2) block has a silicon
atom-bonded acyloxy group, an oxime group, or an alkoxy group in
the molecule and is derived from an organopolysiloxane having a
polysiloxane structure represented by (R.sub.2SiO.sub.2/2).sub.n
wherein n represents a number of 5 or more while R represents an
alkyl group, a fluoroalkyl group, or an aryl group.
8. A composition comprising: (A) the resin-linear
organopolysiloxane block copolymer according to claim 1; and (B) a
solvent.
9. The composition according to claim 8, wherein the solvent (B) is
a volatile solvent (B1).
10. A film forming agent comprising: the resin-linear
organopolysiloxane block copolymer according to claim 1.
11. An adhesion imparting agent comprising: the resin-linear
organopolysiloxane block copolymer according to claim 1.
12. A sealant comprising: the resin-linear organopolysiloxane block
copolymer according to claim 1.
13. A composition for an electronic material comprising: the
resin-linear organopolysiloxane block copolymer according to claim
1.
14. A cosmetic composition or a preparation for external use
comprising: the resin-linear organopolysiloxane block copolymer
according to claim 1.
15. A method for producing the resin-linear organopolysiloxane
block copolymer according to claim 1, the method comprising: Step
(1): subjecting an organopolysiloxane having a hydroxyl group in
the molecule and having a polysiloxane structure represented by
(R.sub.2SiO.sub.2/2).sub.n wherein n represents a number of 5 or
more while R represents an alkyl group, a fluoroalkyl group, or an
aryl group to diacyloxy silanization, dioxime silanization, or
dialkoxy silanization, using one or more organotriacyloxysilanes,
organotrioximesilanes, or organotrialkoxysilanes; and Step (2):
subjecting an organopolysiloxane having a diacyloxysilyl group, a
dioximesilyl group, or a dialkoxysilyl group in the molecule
obtained by the Step (1); and a resin organopolysiloxane having a
hydroxyl group in the molecule and having a siloxane unit
represented by SiO.sub.4/2, to a decarboxylation reaction, a
deoximation reaction, or a dealcoholization reaction.
Description
TECHNICAL FIELD
[0001] The present invention provides a novel resin-linear
organopolysiloxane block copolymer, along with the use and
production method thereof.
BACKGROUND ART
[0002] Unlike organopolysiloxane having a resin or linear structure
alone, resin-linear organopolysiloxane block copolymers both having
a resin structure consisting of branched siloxane units; and a
linear (chain) structure consisting of disiloxane units in the same
molecule are used in various applications due to their unique
physical properties such as film forming properties derived from
their resin structure, along with film followability and
flexibility derived from their linear structure, in addition to
excellent curing properties and film forming properties. Examples
of such a resin-linear organopolysiloxane block copolymer include a
condensation reaction product of an organopolysiloxane having a
resin structure and an organopolysiloxane having a linear structure
and the like.
[0003] For example, Patent Documents 1 to 4 disclose a condensation
reaction product of an organopolysiloxane of a linear structure
mainly having an MQ type organopolysiloxane resin and a D unit; and
an MDQ type organopolysiloxane. While these cosmetic compositions
can be expected to improve the film forming properties and feel
derived from an organopolysiloxane condensation reaction product,
compatibility with other oleophilic cosmetic raw materials may
become insufficient, potentially causing deterioration in feel such
as precipitation of the condensation reaction product, particularly
when an organopolysiloxane condensation reaction product is blended
in large quantities. Therefore, known organopolysiloxane
condensation reaction products have a low degree of freedom in
formulation design, and it has been difficult to fully utilize the
advantages such as film forming properties based on the provision
of both resin and linear structures. In addition, known
organopolysiloxane condensation reaction products, particularly
when blended in cosmetics, have room for further improved feel,
such as the stickiness of a film derived from a resin
structure.
[0004] In contrast, Patent Documents 5 and 6 disclose resin-linear
organopolysiloxane block copolymers containing T units,
acetoxylating and reacting with the terminals of
polydimethylsiloxanes during synthesis. Unfortunately, since these
copolymers are copolymers composed of a resin structure block
primarily consisting of T units and a linear structure
organopolysiloxane, sufficient performance as a film forming agent
cannot be achieved, with room for improvement in the molecular
structure thereof.
PRIOR ART DOCUMENTS
Patent Documents
[Patent Document 1] US 2007/0196309 A
[Patent Document 2] WO 2014/151464
[0005] [Patent Document 3] U.S. Pat. No. 7,261,877
[Patent Document 4] JP 08-143426 A
[Patent Document 5] WO 2014/040367
[Patent Document 6] WO 2014/152522
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
[0006] It is an object of the present invention to provide a novel
resin-linear organopolysiloxane block copolymer, along with the use
and production method thereof, which has a high degree of freedom
in formulation due to excellent compatibility with other lipophilic
starting materials, in addition to exhibiting excellent film
forming properties and followability of a film, while the
stickiness of a film or the like is suppressed.
Means for Solving the Problems
[0007] The resin-linear organopolysiloxane block copolymer
according to the present invention includes: a resin structure (A1)
block that has siloxane units represented by R.sup.1SiO.sub.3/2
(wherein R.sup.1 represents a monovalent organic group, a hydroxyl
group, or an alkoxy group having 1 to 6 carbon atoms) and
SiO.sub.4/2; and a linear structure (A2) block represented by
(R.sub.2SiO.sub.2/2).sub.n (wherein n represents a number of 5 or
more while R represents an alkyl group, a fluoroalkyl group, or an
aryl group) in each molecule, wherein the resin structure (A1) and
the linear structure (A2) are linked to each other by an Si--O--Si
bond, and an Si atom bonded to the resin structure (A1) constitutes
an RSiO.sub.3/2 unit.
[0008] Further, the resin-linear organopolysiloxane block copolymer
(A) preferably has a hydroxyl group (OH) content in the molecule of
1.50 mass % or more, more preferably 1.75 mass % or more, and even
more preferably 2.00 mass % or more.
[0009] Further, the resin-linear organopolysiloxane block copolymer
(A) is an SiO.sub.4/2 unit in which 15 mol % or more, preferably 20
mol % or more, and more preferably 25 mol % or more of all
SiO.sub.4/2 units have hydroxyl groups on Si atoms.
[0010] The resin-linear organopolysiloxane block copolymer is
preferably soluble in cinnamic acid methyl ester.
[0011] The resin-linear organopolysiloxane block copolymer may
further have one or more functional groups selected from an alkyl
group having 6 or more carbon atoms, a fluoroalkyl group, an
Si-macromonomer, and an Si-dendrimer modifying group in the
molecule.
[0012] In the resin-linear organopolysiloxane block copolymer, the
linear structure (A2) block preferably has a silicon atom-bonded
acyloxy group, an oxime group, or an alkoxy group in the molecule
and is derived from an organopolysiloxane having a polysiloxane
structure represented by (R.sub.2SiO.sub.2/2).sub.n (wherein n
represents a number of 5 or more while R represents an alkyl group,
a fluoroalkyl group, or an aryl group). Note that a silicon
atom-bonded acyloxy group, an oxime group, or an alkoxy group is
preferably introduced as an organodiacyloxysilyl group, a
dioximesilyl group, or a dialkoxysilyl group at a terminal and
particularly preferably constitutes an RSiO.sub.3/2 unit bonded to
the resin structure (A1) block during the formation reaction of the
copolymer.
[0013] The composition according to the present invention
preferably contains the resin-linear organopolysiloxane block
copolymer and a solvent thereof. Particularly when the copolymer of
the present invention is used in the application of a film forming
agent, the solvent is preferably a volatile solvent.
[0014] The resin-linear organopolysiloxane block copolymer
according to the present invention or the composition including the
same can be suitably used in the following applications. [0015]
Film forming agent [0016] Adhesion imparting agent [0017] Sealant
[0018] Composition for an electronic material [0019] Cosmetic
composition or preparation for external use
[0020] The resin-linear organopolysiloxane block copolymer
according to the present invention can be suitably obtained by a
production method having the following Steps (1) and (2).
Step (1): subjecting an organopolysiloxane having a hydroxyl group
in the molecule and having a polysiloxane structure represented by
(R.sub.2SiO.sub.2/2).sub.n (wherein n represents a number of 5 or
more, while R represents an alkyl group, a fluoroalkyl group, or an
aryl group) to diacyloxy silanization, dioxime silanization, or
dialkoxy silanization, using one or more organotriacyloxysilanes,
organotrioximesilanes, or organotrialkoxysilanes; and Step (2):
subjecting an organopolysiloxane having a diacyloxysilyl group, a
dioximesilyl group, or a dialkoxysilyl group in the molecule
obtained by the Step (1); and a resin organopolysiloxane having a
hydroxyl group in the molecule and having a siloxane unit
represented by SiO.sub.4/2 to a decarboxylation reaction, a
deoximation reaction, or a dealcoholization reaction.
Effects of the Invention
[0021] The present invention can provide a novel resin-linear
organopolysiloxane block copolymer, along with the use and
production method thereof, and can particularly provide a copolymer
having a structure or functional group content suitable for various
applications including a film forming agent, along with a method
for producing the same.
MODE FOR CARRYING OUT THE INVENTION
[0022] [Resin-Linear Organopolysiloxane Block Copolymer (A)]
[0023] The resin-linear organopolysiloxane block copolymer of the
present invention has a structure in which a resin structure (A1)
block that has siloxane units represented by R.sup.1SiO.sub.3/2
(wherein R.sup.1 represents a monovalent organic group, a hydroxyl
group or an alkoxy group having 1-6 carbon atoms) and SiO.sub.4/2;
and a linear structure (A2) block represented by
(R.sub.2SiO.sub.2/2).sub.n (wherein n represents a number of 5 or
more while R represents an alkyl group, a fluoroalkyl group or an
aryl group) are connected by an Si--O--Si bond in each molecule,
wherein in an Si--O--Si bond which links the resin structure (A1)
block and the linear structure (A2) block to each other, an Si atom
bonded to the resin structure (A1) constitutes an
R.sup.1SiO.sub.3/2 unit. Hereinafter, the resin-linear
organopolysiloxane block copolymer (A) may be simply referred to as
"copolymer (A)" when the component is described.
[0024] The copolymer (A) has a resin structure (A1) block and a
linear structure (A2) block. The resin structure (A1) block is a
resinous (resin) organopolysiloxane structure, contains T units or
Q units represented by R.sup.1SiO.sub.3/2 (R.sup.1 is a monovalent
organic group, a hydroxyl group, or an alkoxy group having 1 to 6
carbon atoms) and by SiO.sub.4/2 as essential siloxane units, and
forms partial structures consisting of resinous organopolysiloxanes
in which a large number of Q units are primarily bonded. Such a
resin structure is a partial structure which imparts film forming
properties when the copolymer (A) of the present invention is
incorporated into a cosmetic composition or a preparation for
external use.
[0025] Examples of such resin structures (A1) include an MQ resin,
an MDQ resin, an MTQ resin, an MDTQ resin, a TQ resin, and a TDQ
resin, which consist of any combination including a triorganosiloxy
unit (M unit) represented by R.sup.1.sub.3SiO.sub.1/2 (R.sup.1 is a
monovalent organic group, a hydroxyl group, or an alkoxy group
having 1 to 6 carbon atoms); and a diorganosiloxy unit (D unit)
represented by R.sup.1.sub.2SiO.sub.2/2 (R.sup.1 is a monovalent
organic group, a hydroxyl group, or an alkoxy group having 1 to 6
carbon atoms), in addition to the abovementioned T unit and Q unit.
In particular, the MQ resin is preferable, and in the Si--O--Si
bond connecting the resin structure (A1) block and the linear
structure (A2) block, the T units may be preferably included only
in the portion in which the Si atom bonded to the resin structure
(A1) constitutes an R.sup.1SiO.sub.3/2 unit. Note that in relation
to the linear structure (A2) described later, the resin structure
(A1) does not include a partial structure in which 5 or more D
units are consecutively included.
[0026] The functional groups R.sup.1 on the siloxane unit
constituting the resin structures (A1) are each independently a
monovalent organic group, a hydroxyl group, or an alkoxy group
having 1 to 6 carbon atoms. In particular, the functional groups
R.sup.1 include an alkyl group having 1 to 20 carbon atoms, a
halogen-substituted alkyl group having 1 to 20 carbon atoms, an
aryl group having 6 to 20 carbon atoms, a halogen-substituted aryl
group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20
carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an
acryl-containing group, a methacryl-containing group, an alkoxy
group having 1 to 6 carbon atoms, and a hydroxyl group.
[0027] Specifically, the functional groups R.sup.1 include alkyl
groups such as a methyl group, an ethyl group, a propyl group, a
butyl group, a pentyl group, a hexyl group, a heptyl group, an
octyl group, a nonyl group, a decyl group, an undecyl group, and a
dodecyl group; aryl groups such as a phenyl group, a tolyl group, a
xylyl group, a naphthyl group, an anthracenyl group, a phenanthryl
group, and a pyrenyl group; aralkyl groups such as a phenethyl
group and a phenylpropyl group; groups in which some or all of the
hydrogen atoms bonded to these groups are replaced with a halogen
atom such as a fluorine atom, a chlorine atom, a bromine atom, or
the like; alkoxy groups such as a methoxy group, an ethoxy group,
or a propoxy group; alkenyl groups having 2 to 20 carbon atoms such
as a vinyl group, an allyl group, a butenyl group, a pentenyl
group, a hexenyl group, a heptenyl group, an octenyl group, a
nonenyl group, a decenyl group, an undecenyl group, and a dodecenyl
group; acrylic-containing groups such as a 3-acryloxypropyl group
and a 4-acryloxybutyl group; methacryl-containing groups such as a
3-methacryloxypropyl group and a 4-methacryloxybutyl group; and
hydroxyl groups.
[0028] From an industrial point of view, the functional group
R.sup.1 on the siloxane unit constituting the resin structure (A1)
is preferably an alkyl group, a fluorine-substituted alkyl group,
an aryl group, an alkenyl group, an alkoxy group, or a hydroxyl
group and is preferably a group selected from a methyl group, an
ethyl group, a propyl group, a phenyl group, a vinyl group, a
hexenyl group, a methoxy group, an ethoxy group, and a hydroxyl
group. In particular, when a large number of aryl groups such as
phenyl groups are contained in the molecule, the refractive index
of the polymer (A) is improved, while a highly transparent
appearance is provided at the time of film forming, which is
particularly preferable.
[0029] The organopolysiloxane resin raw material providing the
resin structure (A1) block of the copolymer (A) preferably has a
weight-average molecular weight in the range of from 500 to 20,000,
more preferably in the range of from 1,000 to 15,000, and more
preferably in the range of from 1,500 to 12,000. The
organopolysiloxane resin raw material providing the resin structure
(A1) block may be two or more kinds having different weight-average
molecular weights, hydroxyl group contents, ratios of siloxane
units (M, D, T, Q units), and the like. The weight-average
molecular weight (weight-average molecular weight based on styrene
polymer) of the resin structure (A1) block in the molecule of the
copolymer (A) varies depending on the organopolysiloxane resin as a
raw material and the degree of condensation reaction between the
hydroxyl groups in the organopolysiloxane resin.
[0030] The linear structure (A2) is an unreactive block represented
by (R.sub.2SiO.sub.2/2).sub.n (n is a number of 5 or more, R is an
alkyl group, a fluoroalkyl group, or an aryl group) and has a
structure in which diorganosiloxy units represented by
R.sub.2SiO.sub.2/2 are connected in a chain form by at least 5
units or more. Such a linear structural (A2) block is a partial
structure that gives flexibility and followability to the film
formed by the copolymer (A). In the formula, n is the degree of
polymerization of the diorganosiloxy unit constituting the partial
structure, preferably in the range of from 5 to 1000 and more
preferably in the range of from 5 to 500, 10 to 300, and 15 to 200.
When n in the partial structure exceeds the above upper limit, the
properties as a linear molecule derived from the linear structure
are strongly expressed and the film forming properties or the like
may be deteriorated in some cases. On the other hand, when n is
less than the abovementioned lower limit, the properties as a
linear molecule are not sufficient, preventing the characteristic
physical properties of the copolymer (A) from being realized in
some cases.
[0031] The functional group R on the diorganosiloxy unit
constituting the linear structure (A2) is an alkyl group, a
fluoroalkyl group, or an aryl group, which is unreactive with
respect to the resin structure (A1) and the functional group in the
same molecule, making it necessary to maintain the linear structure
(A2) without causing a polymerization reaction such as a
condensation reaction within the molecule. The alkyl group and the
aryl group are the same groups as described above, with a methyl
group or a phenyl group preferable from an industrial point of
view.
[0032] The diorganopolysiloxane providing the linear structure (A2)
block of the copolymer (A) is a chain organopolysiloxane in which
the degree of polymerization of the diorganosiloxy unit having a
hydroxyl group or a hydrolyzable functional group at the molecular
chain end is within the above range (such as within the range of
from 5 to 1000) and is preferably a diorganopolysiloxane in which
the degree of polymerization of the diorganosiloxy unit is from 15
to 200 and has, at the molecular chain end, the hydroxyl group
(silanol group); or a siloxysilyl end, a dioximesilyl end, or a
dialkoxy silyl end derived from the silanol group described
later.
[0033] [Resin/linear structure connecting portion of the copolymer
(A)]
[0034] The copolymer (A) is characterized by having a structure in
which the resin structure (A1) and the linear structure (A2) are
connected by an Si--O--Si bond while an Si atom bonded to the resin
structure (A1) constitutes an RSiO.sub.3/2 unit. A plurality of
partial structures connected by these Si--O--Si bonds may be
included in the molecules, and all resin structure (A1) blocks
preferably have R.sup.1SiO.sub.3/2 units at the bonding sites
thereof. The functional group R.sup.1 is the same group as above
and preferably a group selected from a methyl group, an ethyl
group, a propyl group, a phenyl group, a vinyl group, a hexenyl
group, a methoxy group, an ethoxy group, and a hydroxyl group. The
Si--O--Si bonds connecting the structures are siloxane bonds
between silicon atoms constituting the resin structure (A1) or the
linear structure (A2), the silicon atoms on the T unit or the Q
unit represented by R.sup.1SiO.sub.3/2 or SiO.sub.4/2 constituting
the resin structure (A1) respectively, and the silicon atoms of the
linear structure (A2) represented by (R.sub.2SiO.sub.2/2).sub.n (n
is a number of 5 or more, and R is an alkyl group, a fluoroalkyl
group, or an aryl group) form a partial structure (T-Dn) or (Q-Dn)
as follows. In the copolymer (A), the Si atom bonded to the resin
structure (A1) is required to constitute an RSiO.sub.3/2 unit and
always has the following partial structure (T-Dn) in the
molecule.
[0035] Partial structure (T-Dn)
##STR00001##
[0036] Partial structure (Q-Dn)
##STR00002##
[0037] In the above partial structure, the end of the left
Si--O-bond constituting the T unit or the Q unit is bonded to a
hydrogen atom or another siloxane unit constituting the resin
structure (A1), respectively. However, at least one of Si--O-bonds
is bonded to another siloxane unit constituting the resin structure
(A1). On the other hand, the end of the right Si--O-bond is bonded
to another siloxane unit, triorganosiloxy unit (M unit), or
hydrogen atom that forms a linear structure (A2) or a resin
structure (A1). Needless to say, a silanol group (Si--OH) is formed
when a hydrogen atom is bonded to the end of the Si--O-bond.
[0038] While there must be at least one of the above partial
structures in the molecule, it may have two or more of the above
partial structures. A resin-linear organopolysiloxane block
copolymer having at least one of the partial structures (T-Dn) in
the molecule thereof is required from the viewpoint of
compatibility and affinity with lipophilic raw materials.
[0039] Such partial structures (T-Dn) may suitably be constituted
by condensation reacting an organopolysiloxane having a linear
structure with a diacyloxysilyl end, a dioxime silyl end, or a
dialkoxysilyl end with an organopolysiloxane having a resin
structure. More specifically, a resin-linear organopolysiloxane
block copolymer can be obtained by the production method thereof
having:
[0040] Step (I): condensation reacting an organopolysiloxane having
a silanol end (--OH) with an organotriacyloxysilane, an
organotrioximesisilane, or an organotrialkoxysilane to form a
linear structure organopolysiloxane having a siloxysilyl end, a
dioximesilyl end, or a dialkoxy silyl; and Step (II): after Step
(I), subjecting a linear structure organopolysiloxane having a
diacyloxysilyl end, a dioximesilyl end, or a dialkoxysilyl end; and
a resin structure organopolysiloxane having a hydroxyl group in the
molecule and having a siloxane unit represented by SiO.sub.4/2 to a
decarboxylation reaction, a deoximation reaction, or a
dealcoholization reaction to obtain a resin-linear
organopolysiloxane block copolymer having an Si--O--Si bond,
wherein an Si atom bonded to the resin structure constitutes an
RSiO.sub.3/2 unit.
[0041] Here, the organopolysiloxane having a resin structure having
a siloxane unit represented by SiO.sub.4/2 used in Step (II) is
particularly preferably an MQ resin.
[0042] In Step (I) above, since the RSiO.sub.3/2 units of the
connecting moiety are derived from triacyloxysilane, trioxymylane,
or trialkoxysilane, the functional groups on the RSiO.sub.3/2 units
bonded to the resin structures (A1) in the polymer can be designed
by selecting triacyloxysilane, trioxymylane, or trialkoxysilane
having particular functional groups. Specifically, the functional
group R bonded to silicon atoms constituting an
organotriacetoxysilane represented by R(CH.sub.3COO).sub.3Si is
introduced on the RSiO.sub.3/2 units of the connecting portion.
Therefore, by using phenyltriacetoxysilane represented by
(Ph)(CH.sub.3COO).sub.3Si or alkyltriacetoxysilane represented by
R.sup.2(CH.sub.3COO).sub.3Si (R.sup.2 is an alkyl group having 3 to
20 carbon atoms), a resin-linear organopolysiloxane block copolymer
containing a PhSiO.sub.3/2 (Ph is a phenyl group) unit or an
R.sup.2Si.sub.3/2 (R.sup.2 is an alkyl group having 3 to 20 carbon
atoms) unit can be easily obtained.
[0043] The copolymer (A) may have an aryl group such as a phenyl
group in the molecule, and in particular, a triorganosiloxy group
constituting the end of a resin structure or a linear structure may
have at least one or more aryl groups. The high content of aryl
groups in the copolymer (A) of the present invention tends to
increase the refractive index of the polymer as a whole, in
addition to improving the optical transparency.
[0044] The copolymer (A) may further have one or more functional
groups selected from an alkyl group having 6 or more carbon atoms,
a fluoroalkyl group, an Si-macromonomer, and an Si-dendrimer
modifying group in the molecule. Since these functional groups have
high hydrophobicity or water repellency, along with affinity for
specific components, the film formed by the copolymer (A) may be
further improved in functionality in some cases.
[0045] The copolymer (A) may have a triorganosiloxy group having at
least two aryl groups in the molecule and may contain
R.sup.4R.sup.5R.sup.6SiO.sub.1/2 units (R.sup.4 to R.sup.6 are each
independently a monovalent organic group, with at least two of
these being aryl groups). Such triorganosiloxy groups may be
triorganosiloxy groups having at least two phenyl groups or
triorganosiloxy groups having three phenyl groups. Moreover, a
triorganosiloxy group having aryl groups other than at least two
phenyl groups may be used. Such a triorganosiloxy group is
introduced by condensation reactions using an organosilane
represented by R.sup.4R.sup.5R.sup.6SiX (R.sup.4 to R.sup.6 are
each independently monovalent organic groups, at least two of which
are aryl groups, and X is a hydroxyl group or a hydrolyzable group)
as a raw material.
[0046] [Hydroxyl Group Content of Copolymer (A)]
[0047] From the viewpoint of compatibility and affinity with other
cosmetic raw materials, the copolymer (A) preferably has a hydroxyl
group in the molecule and preferably has a hydroxyl group (OH)
content in the molecule of 1.50 mass % or more, more preferably
1.75 mass % or more, more preferably 2.0 mass % or more, and
particularly preferably 2.25 mass % or more. Most preferably, the
hydroxyl group (OH) content of the copolymer is in the range of
from 2.25 to 3.50 mass %. While the copolymer may be a single type
or a mixture of copolymers having two different hydroxyl group (OH)
contents, the average value of the hydroxyl group (OH) contents of
these copolymers is preferably in the above range.
[0048] In particular, the copolymer (A) can preferably be obtained
by condensation reacting an organopolysiloxane having a linear
structure with a diacyloxysilyl end, a dioxime silyl end, or a
dialkoxysilyl end and an organopolysiloxane having a resin
structure having a siloxane unit represented by SiO.sub.4/2. Since
the reaction at the siloxysilyl end, the dioximesilyl end, or the
dialkoxysilyl end proceeds selectively with respect to the hydroxyl
group on the organopolysiloxane having the resin structure, many
hydroxyl groups react between the organopolysiloxanes having the
resin structure and it is possible to synthesize a resin-linear
organopolysiloxane block copolymer in which a competitive reaction
which lowers the hydroxyl group (OH) content of the copolymer
hardly occurs and a large number of hydroxyl groups (OH) on the
resin structure are maintained. Therefore, the copolymer (A) of the
present invention can be designed to have a regular structure and a
high hydroxyl group (OH) content on the resin structure as compared
with the conventional resin/linear organopolysiloxane condensation
product. For example, in the case of a reaction product of a
polysiloxane resin of the MQ type having a known hydroxyl group and
a chain polysiloxane having a hydrolyzable terminal such as a
hydroxyl group, the condensation reaction between the resins and
the condensation reaction of the chain polysiloxane proceed
competitively, the hydroxyl group is consumed in the reaction
between the resins, and a random intermolecular bond tends to be
formed, such that the affinity with other lipophilic raw materials
and the film forming ability may be lowered as compared with the
copolymer (A) of the present invention.
[0049] More specifically, the copolymer (A) has SiO.sub.4/2 units
and 15 mol % or more of all SiO.sub.4/2 units preferably have
hydroxyl groups on Si atoms. The SiO.sub.4/2 unit (Q) unit is a
siloxane unit mainly constituting a resin structure and the high
proportion of Q units having a hydroxyl group on the Si atom means
that a large number of hydrophilic functional groups are included
in the resin portion of the polymer (A) and the affinity with other
cosmetic raw materials is improved along with the film forming
properties. In this respect, preferably 20 mol % or more, more
preferably 25 mol % or more, and most preferably 27.5 to 40.0 mol %
of all SiO.sub.4/2 units of the copolymer (A) have hydroxyl groups
on Si atoms. Even when a polysiloxane resin having a large number
of hydroxyl groups is used as a raw material, the amount of
hydroxyl groups decreases and the molecular structure of the
copolymer randomizes when a large number of condensation reactions
between resin raw materials proceed when forming the copolymer (A),
such that the copolymer (A) has the partial structure (T-Dn)
described above, and it is particularly preferable that the
copolymer (A) has a regular resin-linear structure.
[0050] [weight-average molecular weight of the total copolymer
(A)]
[0051] The copolymer (A) is preferably composed of a resin
structure (A1) block and a linear structure (A2) block bonded by
the abovementioned connecting structure, wherein the molecular
weight distribution thereof can be controlled to some extent by the
organopolysiloxane resin as a raw material, the chain
diorganopolysiloxane, and the degree of condensation reaction;
however, from the viewpoint of the function as a film forming agent
and compatibility with other raw materials, the weight-average
molecular weight specified from the molecular weight distribution
using styrene polymer as a standard is preferably within the range
of from 5,000 to 100,000, particularly preferably within the range
of from 10,000 to 50,000, and within the range of from 12,000 to
40,000. The cosmetic composition or preparation for external use of
the present invention may be combined with the two or more
copolymers (A) having different structures or molecular weight
distributions.
[0052] [Mass Ratio of Resin/Linear Structure Block of Copolymer
(A)]
[0053] The copolymer (A) is composed of a resin structure (A1)
block and a linear structure (A2) block bonded by the
abovementioned connecting structure, wherein the mass ratio of both
blocks in the molecule can be controlled by the amount of the
organopolysiloxane resin and the chain diorganopolysiloxane used as
raw materials. Suitably, the organopolysiloxane resin constituting
the resin structure (A1) block and the chain diorganopolysiloxane
constituting the linear structure (A2) block can be reacted at a
mass ratio of from 10:90 to 95:5, and from the viewpoint of film
forming properties of the obtained copolymer (A), an excess of the
resin, that is, a mass ratio of from 50:50 to 95:5 is preferable,
with a mass ratio of from 60:40 to 90:10 particularly preferable.
When the mass ratio of the resin structure (A1) block in the
molecule is within the abovementioned range as derived from the raw
material, the film forming properties with little stickiness which
are hard and excellent in sensation during use is realized while
maintaining followability and flexibility of the film derived from
the linear structure (A2) block. Incidentally, in the case of a
resin-linear organopolysiloxane block copolymer having no
R.sup.1SiO.sub.3/2 units in molecules thereof, even within the
abovementioned mass ratio, the film forming properties are
insufficient and stickiness of the film, lowering of the affinity
with other cosmetic raw material components, and the like may
occur.
[0054] [Compatibility of the Copolymer (A)]
[0055] The copolymer (A) is excellent in compatibility with other
lipophilic raw materials and when used in combination with a
solvent (B) described later, it has a feature of being compatible
with lipophilic raw materials of 1/2 or more the mass of the
copolymer (A), and the film forming performance thereof does not
deteriorate. For example, for cinnamic acid methyl ester, in
particular, octyl methoxycinnamate (p-methoxycinnamate ethylhexyl
cinnamate) as a representative and general purpose lipophilic raw
material, the copolymer (A) exhibits solubility in the presence of
the solvent (B) described below. For a 20 mass % solution of the
solvent (B), the copolymer (A) uniformly dissolves with cinnamic
acid methyl ester having the same, preferably 1.2-fold, and more
preferably 1.5-fold or more mass as that of the copolymer (A) in
the solution, and the separation and precipitation of cinnamic acid
methyl ester preferably do not occur over time. With such
properties, the copolymer (A) is advantageously usable in a wide
range of dosage forms and formulations as a film forming agent
because of the high degree of freedom of formulation design as a
lipophilic raw material and the excellent compounding stability
compared with copolymers having a known resin-linear structure
within the same molecule in the related art.
[0056] [Solvent (B)]
[0057] The cosmetic composition or preparation for external use is
characterized by containing the copolymer (A) described above, and
since the copolymer (A) is in a solid to viscous semi-solid state
at room temperature, it is preferable to blend the copolymer (A) in
a form dissolved in the solvent (B) from the viewpoint of handling
workability. Since the copolymer (A) is excellent in affinity with
other cosmetic raw materials and has high solubility, the solvent
(B) can utilize a physiologically acceptable oil agent without any
particular limitation, and in particular, the solvent (B) is
preferably at least one kind in a liquid state at from 5 to
100.degree. C. selected from the group consisting of silicone oil,
non-polar organic compound, and low polarity organic compound and
may be a combination of two or more kinds. Moreover, from the
viewpoint of the sensation during the use of the cosmetic
composition or the preparation for external use of the present
invention and the workability when the copolymer (A) is handled as
a film forming agent, the solvent (B) is preferably a volatile
solvent (B1), and a solvent containing a volatile silicone oil is
particularly preferable.
[0058] Silicone oils are hydrophobic and their molecular structure
may be any of cyclic, linear, or branched. The viscosities of
silicone oils at 25.degree. C. are usually within the range of from
0.65 to 100,000 mm.sup.2/s and preferably within the range of from
0.65 to 10,000 mm.sup.2/s.
[0059] Silicone oils include, for example, linear
organopolysiloxanes, cyclic organopolysiloxanes, and branched
organopolysiloxanes. Among these, volatile linear
organopolysiloxanes, cyclic organopolysiloxanes, and branched
organopolysiloxanes are preferable, with
octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane
(D5), or chain dimethylpolysiloxane having viscosities ranging from
0.65 to 10 mm.sup.2/s at 25.degree. C. particularly preferable as
initial dispersing solvents of the present polymer (A).
[0060] The solvent (B) may be added to the composition of the
present invention as the initial dispersion solvent of the
copolymer (A) or may be added to other components or as independent
components, with the type/combination thereof not particularly
limited.
[0061] From the viewpoint of handling workability as a film forming
agent, while it is suitable to include a volatile solvent (B1) as
an initial dispersion solvent of the copolymer (A), a non-volatile
solvent (B) may be added as another oil agent. The compounding
amount is not particularly limited, but is preferably from 3 to 60
mass %, more preferably from 4 to 50 mass %, and still more
preferably from 5 to 40 mass %, based on the total mass of the
cosmetic composition or the preparation for external use.
[0062] In addition to silicone oils, non-polar organic compounds
and low-polarity organic compounds (for example, hydrocarbon oils
and fatty acid ester oil oils and fats), higher alcohols, higher
fatty acids, fluorine-based oils, etc. may be used as solvents, or
two or more of these may be used in combination.
[0063] [Film Forming Agent]
[0064] The resin-linear organopolysiloxane block copolymer
according to the present invention forms a uniform and hard film
having little stickiness on a substrate by removing a solvent.
Further, since the film has flexibility and followability to
substrates derived from a linear structure, problems such as
cracking and peeling are less likely to occur compared with known
resin based film forming agents, leading to excellent durability.
Moreover, due to the excellent affinity and compatibility thereof
with lipophilic industrial raw materials such as dyes or
ultraviolet light protecting components, functional films on which
these components are supported in films can be formed.
[0065] In addition, when used in cosmetics or preparations for
external use, various tissues such as hair, skin, and the body can
be protected by film formation on the human body while various
active components can be supported on various tissues. In
particular, since the copolymer has flexibility and followability
derived from a linear structure, the copolymer has flexibility
while being a hard and strong film derived from a resin, along with
high compatibility and affinity with various lipophilic raw
materials. Therefore, it may be used in a form in which a package
or capsule is formed by coating an active ingredient.
[0066] [Adhesion Imparting Agent]
[0067] The resin-linear organopolysiloxane block copolymer
according to the present invention has excellent adhesion to
substrates and therefore functions as an adhesion imparting agent
when used in combination with other curable compositions or film
forming components. For example, when blended in a paint, coating
agent, etc., due to the excellent compatibility thereof with other
cured film forming components, the film properties and flexibility
derived from the copolymer (A) are imparted to a cured film such as
paint, improving adhesion with the substrate.
[0068] [Sealant]
[0069] The resin-linear organopolysiloxane block copolymer
according to the present invention is active to condensation
reactions because it has a large number of hydroxyl groups in the
resin structure block in the molecule. Therefore, the addition
thereof to a known condensation reaction curing system enables its
use as a sealant with excellent transparency. In particular, by
containing a main agent or an additive in a curable composition
having a condensation reaction catalyst, it is possible to form a
flexible and strong cured product having excellent affinity with
other curable components.
[0070] [Composition for Electronic Materials]
[0071] The resin-linear organopolysiloxane block copolymer
according to the present invention can be used as a film forming
agent, an adhesion imparting agent, and a sealant for forming a
cured product; and as a composition for use in electronic materials
such as semiconductor circuits, optical semiconductors, and solar
cells. For example, a semiconductor circuit or an optical
semiconductor element can be sealed or cure coated by a cured
product containing the resin-linear organopolysiloxane block
copolymer according to the present invention.
[0072] [Cosmetic Composition or Preparation for External Use]
[0073] The resin-linear organopolysiloxane block copolymer
according to the present invention is particularly useful in a film
forming agent as a cosmetic raw material and can be blended into
various cosmetic compositions or preparations for external use. In
particular, since the copolymer has excellent compatibility with
other cosmetic raw materials, the composition or the preparation
has a high degree of freedom of formulation design. It is possible
to provide a cosmetic composition or a preparation for external use
containing a resin-linear organopolysiloxane block copolymer that
has excellent film forming properties and film followability, with
the stickiness of the film being suppressed, etc.
EXAMPLES
[0074] The cosmetic composition or the preparation for external use
and the cosmetic raw material composition of the present invention
will be explained in detail with reference to examples and
comparative examples. In the formula, Me represents a methyl group
and Et represents an ethyl group. In addition, unless otherwise
specified, in the examples, the M unit is a siloxane unit
represented by the Me.sub.3SiO.sub.1/2, the Q unit is a siloxane
unit represented by the SiO.sub.4/2, and the MQ resin means a
resinous organopolysiloxane (resin) having a hydroxyl group bonded
on the M unit, the Q unit, and silicon atoms of the
[0075] Q unit. The average degree of polymerisation of the
dimethylsiloxane units of polydimethylsiloxane was calculated from
the ratio of the intensities of the peaks to the Si atoms
constituting both ends using .sup.29Si-NMR. The weight-average
molecular weight was determined as a value converted to standard
polystyrene by GPC.
Example 1: Copolymer a1
[0076] An equimolar mixture of 0.8 grams (3.53 mmol) of
methyltriacetoxysilane and ethyltriacetoxysilane was added to a
solution of 6 grams (1.68 mmol) of polydimethylsiloxane capped with
silanol (--SiMe.sub.2(OH)) groups at both ends (an average degree
of polymerization of 48); and 10 grams of n-heptane and then
stirred at room temperature for 30 minutes. Upon .sup.29SiNMR
analysis, it was found that the SiOH group completely disappeared
and diacetoxysilylated. The solution was then added to a mixed
solution of 34 grams of trimethyl siloxysilicate having a molar
ratio of M units (Me.sub.3SiO.sub.1/2) to Q units (SiO.sub.4/2) of
54:46, an OH group content derived from silanol groups of 3.13 wt
%, a ratio of Q units bound to OH groups to total Q units of 26.5%,
and a weight-average molecular weight of 2970; and 50 grams of
n-heptane and then heated and stirred for 2 hours while removing a
by-product aqueous acetic acid aqueous solution by azeotropic
dehydration. Water was added and heated to stir for 1 hour and
allowed to stand to remove the lower layer. This operation was
further repeated to completely remove the acetic acid. After
azeotropic dehydration, the low boiling point substances were
removed by heating to give the MQ resin-polydimethylsiloxane
copolymer (copolymer a1).
[0077] The copolymer a1 is designed to have a mass ratio of MQ
resin as a raw material to chain polydimethylsiloxane of 85:15 and
contains T units represented by MeSiO.sub.3/2 and EtSiO.sub.3/2
which are bonded to Si atoms constituting a resin structure at a
connecting site (Si--O--Si) of a resin structure and a linear
structure by way of diacetoxysilylation in a condensation
reaction.
[0078] Partial Structure of the Copolymer a1:
[0079] MQ resin block (Si)-T unit (Si)--O--(Si)
polydimethylsiloxane block
[0080] The residual OH group content in the copolymer a1 was 2.28
mass %, the ratio of Q units bound to OH groups to total Q units
was 20.5 mol %, and the weight-average molecular weight thereof was
18500.
Example 2: Copolymer a2
[0081] An equimolar mixture of 1.07 grams (4.71 mmol) of
methyltriacetoxysilane and ethyltriacetoxysilane was added to a
solution of 8 grams (2.24 mmol) of polydimethylsiloxane capped with
silanol (--SiMe.sub.2(OH)) groups at both ends (an average degree
of polymerization of 48); and 10 grams of n-heptane and then
stirred at room temperature for 30 minutes. Upon .sup.29SiNMR
analysis, it was found that the SiOH group completely disappeared
and diacetoxysilylated. The solution was then added to a mixed
solution of 25.6 grams of trimethyl siloxysilicate having a molar
ratio of M units (Me.sub.3SiO.sub.1/2) to Q units (SiO.sub.4/2) of
54:46, an OH group content derived from silanol groups of 3.13 wt
%, a ratio of Q units bound to OH groups to total Q units of 26.5%,
and a weight-average molecular weight of 2970; 6.4 grams of
trimethyl siloxysilicate having a molar ratio of M units
(Me.sub.3SiO.sub.1/2) to Q units (SiO.sub.4/2) of 51:49, an OH
group content derived from silanol groups of 2.74 wt %, a ratio of
Q units bound to OH groups to total Q units of 23.9%, and a
weight-average molecular weight of 7400; and 50 grams of n-heptane
and then heated and stirred for 2 hours while removing a by-product
aqueous acetic acid aqueous solution by azeotropic dehydration. 5
grams of water was added and heated to stir for 1 hour and allowed
to stand to remove the lower layer. This operation was repeated to
completely remove the acetic acid. After azeotropic dehydration,
the low boiling point substances were removed by heating to give
the MQ resin-polydimethylsiloxane copolymer (copolymer a2).
[0082] The copolymer a2 is designed to have a mass ratio of MQ
resin as a raw material to chain polydimethylsiloxane of 80:20 and
contains T units represented by MeSiO.sub.3/2 or EtSiO.sub.3/2
which are bonded to Si atoms constituting a resin structure at a
connecting site (Si--O--Si) of a resin structure and a linear
structure by way of diacetoxysilylation in a condensation reaction.
Since methyltriacetoxysilane and ethyltriacetoxysilane used for
diacetoxysilylation are equimolar, the ratio of the abovementioned
T units is 1:1.
[0083] Partial Structure of the Copolymer a2:
[0084] MQ resin block (Si)-T unit (Si)--O--(Si)
polydimethylsiloxane block
[0085] The residual OH group content in copolymer a2 was 2.07 mass
%, the ratio of Q units bound to OH groups to total Q units was
19.3 mol %, and the weight-average molecular weight thereof was
28800.
Comparative Example: Copolymer c without T Unit
[0086] 1 gram of 28 wt % ammonia water was then added to a mixed
solution of 6 grams (1.68 mmol) of silanol (--SiMe.sub.2(OH))
polydimethylsiloxane at both ends (an average degree of
polymerization of 48); 34 grams of trimethyl siloxysilicate having
a molar ratio of M units (Me.sub.3SiO.sub.1/2) to Q units (SiO4/2)
of 54:46, an OH group content derived from silanol groups of 3.13
wt %, a ratio of Q units bound to OH groups to total Q units of
26.5%, and a weight-average molecular weight of 2970; and 60 grams
of n-heptane and then heated and stirred at 40.degree. C. for 6
hours. Subsequently, the by-product water was heated and stirred
for 1 hour while removing a by-product water by azeotropic
dehydration. The low boiling point substances were removed by
heating to give the MQ resin-polydimethylsiloxane condensation
product (copolymer c).
[0087] The copolymer c does not contain a component constituting a
T unit and has a partial structure in which a resin structure and a
linear structure are simply bonded via a siloxane bond. The
residual OH group content in copolymer c was 1.42 mass %, the ratio
of Q units bound to OH groups to total Q units was 13.2 mol %, and
the weight-average molecular weight thereof was 23200.
Example 1, 2 and Comparative Example 1, 2
[0088] The compositions according to the examples using the
copolymer a1 and the copolymer a2 described above and the
comparative examples using the copolymer c described above and
conventional MQ silicone resins (MQ1600 manufactured by Dow Corning
Corporation) were prepared and evaluated in the following manner.
[0089] Solubility evaluation: Polymers (the respective copolymers
or MQ-silicone resins) and dimethylpolysiloxane (viscosity: 2
mPass, volatile) were dissolved beforehand in the parts by mass
shown in Table 1, and then other components were added and stirred
to confirm the appearance thereof. [0090] Film followability: A 20%
dimethylpolysiloxane (viscosity: 2 mPass, volatile) solution of the
respective polymers was applied to a commercially available latex
film, and then the solution was dried to form a film of about 50
.mu.m on the latex film. Latex membranes were subsequently
repeatedly stretched and the appearance of the films examined.
[0091] Stickiness: Solutions of 20% dimethylpolysiloxane
(viscosities: 2 mPass, volatile) of the respective polymers were
coated on a glass plate and dried to form a film, and then the
stickiness was evaluated by contacting the glass plate. [0092]
Contact angle (water): 20% dimethylpolysiloxane (viscosities: 2
mPass, volatile) solutions of the respective polymers were coated
on a glass plate and dried to form a film, and then the contact
angle of water was measured by an automated contact angle meter
(manufactured by Kyowa Interface Science Co., Ltd). [0093] Contact
angle (artificial sebum): 20% dimethylpolysiloxane (viscosities: 2
mPass, volatile) solutions of the respective polymers were coated
on a glass plate and dried to form a film, and then the contact
angle of artificial sebum was measured by an automated contact
angle meter (manufactured by Kyowa Interface Science Co., Ltd).
[0094] In Examples 1, 2 and Comparative Example 1, copolymers
prepared in Examples 1 and 2 and Comparative Example 1,
respectively, were blended. In Comparative Example 2, an MQ1600
manufactured by Dow Corning Corporation was blended.
TABLE-US-00001 TABLE 1 Compar- Compar- Experiment ative ative
Example Example 1 Example 2 Example 1 Example 2 Polymer 3 3 3 3
Uvinul A 2 Octyl 5 methoxycinnamate Octocrylene 3 Isotridecyl 9
isononanoate Dimethyl 12 polysiloxane (viscosity: 2 mPa s)
Solubility Disso- Disso- Separated Disso- lution lution lution Film
followability Not Not Not Cracks changed changed changed Stickiness
No cracks No cracks Cracks Cracks generated generated Contact angle
102 100 101 96 (water) Contact angle 57 49 61 31 (artificial
sebum)
[0095] As described in the above examples, the copolymers a1 and a2
having T units at the bonding sites were uniformly dissolved with
other cosmetic raw material components, were excellent in sensation
during use, and were able to realize film forming properties having
high skin followability. On the other hand, in the copolymer c
obtained in the comparative example, the other cosmetic raw
material components were separated and not only was the compounding
stability inferior, but also only a solid adhesive film was
obtained. Moreover, in the evaluations using MQ1600, since it was a
hard film derived from a resin, there was no skin followability,
resulting in cracks. In addition, the contact angle evaluation of
the Examples was comparable and equivalent to that of the
Comparative Examples in both water and artificial sebum. From the
above, it is possible to confirm the usefulness of a film forming
agent (and various compositions containing it) excellent in
compounding stability, sensation during use, and skin followability
using the copolymers a1 and a2 of the present invention, unlike the
known film forming agents.
* * * * *