U.S. patent application number 14/122688 was filed with the patent office on 2014-07-10 for novel organopolysiloxane elastomer and use therefor.
This patent application is currently assigned to Dow Corning Toray Co. Ltd.. The applicant listed for this patent is Chiichiro Hasegawa, Seiji Hori, Kazuhiko Kojima, Tatsuo Souda, Seiki Tamura. Invention is credited to Chiichiro Hasegawa, Seiji Hori, Kazuhiko Kojima, Tatsuo Souda, Seiki Tamura.
Application Number | 20140193353 14/122688 |
Document ID | / |
Family ID | 47259089 |
Filed Date | 2014-07-10 |
United States Patent
Application |
20140193353 |
Kind Code |
A1 |
Tamura; Seiki ; et
al. |
July 10, 2014 |
Novel Organopolysiloxane Elastomer And Use Therefor
Abstract
The present invention relates to an organopolysiloxane elastomer
having a silicon-bonded sugar alcohol-modified group and having a
crosslinked three-dimensional network structure comprising a
carbon-silicon bond in the crosslinking portion. The organomodified
organopolysiloxane elastomer of the present invention has, for
example, affinity with various oil agents, has excellent
viscosity-improving characteristics, gelification characteristics,
and emulsification characteristics, imparts excellent tactile
sensation--in particular, an excellent tactile sensation
characterized by smoothness with a velvet-like thickness--and
imparts an excellent sensation during use.
Inventors: |
Tamura; Seiki;
(Ichihara-shi, JP) ; Souda; Tatsuo; (Ichihara-shi,
JP) ; Hasegawa; Chiichiro; (Awara-shi, JP) ;
Kojima; Kazuhiko; (Ichihara-shi, JP) ; Hori;
Seiji; (Sabae-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Tamura; Seiki
Souda; Tatsuo
Hasegawa; Chiichiro
Kojima; Kazuhiko
Hori; Seiji |
Ichihara-shi
Ichihara-shi
Awara-shi
Ichihara-shi
Sabae-shi |
|
JP
JP
JP
JP
JP |
|
|
Assignee: |
Dow Corning Toray Co. Ltd.
Tokyo
JP
|
Family ID: |
47259089 |
Appl. No.: |
14/122688 |
Filed: |
May 22, 2012 |
PCT Filed: |
May 22, 2012 |
PCT NO: |
PCT/JP2012/063089 |
371 Date: |
February 12, 2014 |
Current U.S.
Class: |
424/78.02 ;
428/402; 528/31 |
Current CPC
Class: |
C08G 77/50 20130101;
Y10T 428/2982 20150115; A61K 8/892 20130101; A61Q 19/007 20130101;
A61K 8/0241 20130101; C08G 77/12 20130101; C08G 77/46 20130101;
A61K 8/893 20130101; A61K 9/0014 20130101; A61K 47/34 20130101;
A61Q 19/08 20130101; C08L 83/12 20130101; A61K 8/895 20130101; A61Q
19/00 20130101; C08L 83/14 20130101; A61K 2800/10 20130101; A61Q
5/00 20130101; A61K 9/107 20130101 |
Class at
Publication: |
424/78.02 ;
528/31; 428/402 |
International
Class: |
A61K 8/892 20060101
A61K008/892; A61Q 5/00 20060101 A61Q005/00; A61Q 19/00 20060101
A61Q019/00 |
Foreign Application Data
Date |
Code |
Application Number |
May 30, 2011 |
JP |
2011-121097 |
Claims
1. An organopolysiloxane elastomer having a silicon-bonded sugar
alcohol-modified group and having a crosslinked three-dimensional
network structure comprising a carbon-silicon bond in a
crosslinking portion of the crosslinked three-dimensional network
structure.
2. The organopolysiloxane elastomer according to claim 1, wherein
the sugar alcohol-modified group is expressed by the following
general formula (4-1): ##STR00032## wherein R is a divalent organic
group, and e is 1 or 2, or the following general formula (4-2):
##STR00033## wherein R is as defined above, and e' is 0 or 1.
3. The organopolysiloxane elastomer according to claim 1, wherein
in the general formula (4-1) or (4-2), the divalent organic group
represented by R is a substituted or unsubstituted, straight-chain
or branched divalent hydrocarbon group having from 3 to 5 carbon
atoms.
4. The organopolysiloxane elastomer according to claim 1 obtained
by reacting: (A) an organohydrogenpolysiloxane; (B) a sugar alcohol
group-containing organic compound having a reactive unsaturated
group; and (C) at least one type of organic compound selected from
the group consisting of (C1) an organic compound having an average
number of reactive unsaturated groups in the molecule that is
greater than 1 and (C2) an organic compound having at least one
reactive unsaturated group and at least one epoxy group in the
molecule.
5. The organopolysiloxane elastomer according to claim 4, wherein
an average value of a number of silicon-bonded hydrogen atoms per
molecule of the component (A) reacting with the reactive
unsaturated groups of the component (C) constituting the
crosslinking portion is at least 1.5.
6. The organopolysiloxane elastomer according to claim 4, wherein
the component (A) is expressed by the average composition formula
(1): R.sup.1.sub.aH.sub.bSiO.sub.(4-a-b)/2 (1), wherein R.sup.1
moieties are each independently monovalent organic groups,
1.0.ltoreq.a.ltoreq.3.0, and 0.001.ltoreq.b.ltoreq.1.5.
7. The organopolysiloxane elastomer according to claim 4, wherein
the component (C) is at least one type of organic compound selected
from the following formulas (C1-1) to (C1-5) and (C2-1) to (C2-2):
(C1-1) an .alpha.,.omega.-diene expressed by the general formula
(2-1): CH.sub.2.dbd.CH(CH.sub.2).sub.xCH.dbd.CH.sub.2 (2-1),
wherein 1.ltoreq.x.ltoreq.20; (C1-2) an .alpha.,.omega.-diyne
expressed by the general formula (2-2):
CH.ident.C(CH.sub.2).sub.xC.ident.CH (2-2), wherein
1.ltoreq.x.ltoreq.20; (C1-3) an .alpha.,.omega.-ene-yne expressed
by the general formula (2-3):
CH.sub.2.dbd.CH(CH.sub.2).sub.xC.ident.CH (2-3), wherein
1.ltoreq.x.ltoreq.20; (C1-4) a bisalkenyl polyether compound
expressed by the general formula (2-4):
C.sub.mH.sub.2m-1O(C.sub.nH.sub.2nO).sub.yC.sub.mH.sub.2m-1 (2-4),
wherein 2.ltoreq.m.ltoreq.20, 2.ltoreq.n.ltoreq.4, y is the total
value of the number of repetitions of the oxyethylene unit, the
oxypropylene unit, or the oxybutylene unit, and
1.ltoreq.y.ltoreq.180; (C1-5) an unsaturated group-containing
silicone-compound expressed by the average composition formula
(2-5): R.sup.2.sub.pR.sup.3.sub.qSiO.sub.(4-p-q)/2 (2-5), wherein
R.sup.2 moieties may each be independent from one another but are
monovalent organic groups that are different from R.sup.3; R.sup.3
moieties are each independently monovalent unsaturated aliphatic
hydrocarbon groups having from 2 to 30 carbon atoms,
1.0.ltoreq.p.ltoreq.2.5, and 0.001.ltoreq.q.ltoreq.1.5; (C2-1) an
unsaturated epoxy compound expressed by the general formula (2-6):
##STR00034## wherein R.sup.4 is a substituted or unsubstituted,
straight-chain or branched monovalent hydrocarbon group having one
reactive unsaturated group and from 2 to 20 carbon atoms; and
(C2-2) an unsaturated group-containing cycloaliphatic epoxy
compound expressed by the general formula (2-7): ##STR00035##
wherein R.sup.5 is a substituted or unsubstituted, straight-chain
or branched monovalent hydrocarbon group having one reactive
unsaturated group and from 2 to 20 carbon atoms; R.sup.6 is a
hydrogen atom or a methyl group; and R.sup.7 is a hydrogen atom or
a methyl group.
8. The organopolysiloxane elastomer according to claim 6, wherein
in the average composition formula (1), the monovalent organic
group represented by R.sup.1 is selected from the following (D1) to
(D10): (D1) a substituted or unsubstituted, straight-chain or
branched monovalent hydrocarbon group having from 1 to 60 carbon
atoms; (D2) a polyoxyalkylene group expressed by
--R.sup.8O(AO).sub.zR.sup.9, wherein AO is an oxyalkylene group
having from 2 to 4 carbon atoms; R.sup.8 is a substituted or
unsubstituted, straight-chain or branched divalent hydrocarbon
group having from 3 to 5 carbon atoms; R.sup.9 is a hydrogen atom,
a substituted or unsubstituted, straight-chain or branched
monovalent hydrocarbon group having from 1 to 24 carbon atoms, or a
substituted or unsubstituted, straight-chain or branched acyl group
having from 2 to 24 carbon atoms; and z=1 to 100; (D3) a
substituted or unsubstituted, straight-chain or branched alkoxy
group having from 1 to 30 carbon atoms; (D4) a hydroxyl group; (D5)
an ester group expressed by --R.sup.10--COOR.sup.11, wherein
R.sup.10 is a substituted or unsubstituted, straight-chain or
branched divalent hydrocarbon group having from 2 to 20 carbon
atoms, and R.sup.11 is a substituted or unsubstituted,
straight-chain or branched monovalent hydrocarbon group having from
1 to 30 carbon atoms; (D6) an ester group expressed by
--R.sup.17--OCOR.sup.18, wherein R.sup.17 is a substituted or
unsubstituted, straight-chain or branched divalent hydrocarbon
group having from 2 to 20 carbon atoms, and R.sup.18 is a
substituted or unsubstituted, straight-chain or branched monovalent
hydrocarbon group having from 1 to 30 carbon atoms; (D7) L.sup.1
where L.sup.1 is a silylalkyl group having a siloxane dendron
structure and, when i=1, is expressed by the following general
formula (3): ##STR00036## wherein R.sup.12 is a substituted or
unsubstituted, straight-chain or branched monovalent hydrocarbon
group having from 1 to 30 carbon atoms; R.sup.13 moieties each
independently represents an alkyl group or a phenyl group having
from 1 to 6 carbon atoms; Z is a divalent organic group; i
represents a generation of the silylalkyl group represented by and
is an integer of 1 to k when k is the number of generations, which
is the number of repetitions of the silylalkyl group; the number of
generations k is an integer from 1 to 10; is the silylalkyl group
when i is less than k, and R.sup.13 when i=k; and h' is a number in
a range from 0 to 3; (D8) an alkyl group substituted by a chain
polysiloxane structure expressed by the following general formula
(4): ##STR00037## wherein R.sup.14 moieties are each independently
substituted or unsubstituted, straight-chain or branched monovalent
hydrocarbon groups having from 1 to 30 carbon atoms, hydroxyl
groups, or hydrogen atoms, and at least one of the R.sup.14
moieties is the monovalent hydrocarbon group; t is a number in a
range from 2 to 10; and r is a number in a range from 1 to 100;
(D9) an epoxy group expressed by the following general formula (5):
##STR00038## wherein R.sup.15 is a substituted or unsubstituted,
straight-chain or branched divalent hydrocarbon group having from 2
to 20 carbon atoms; and (D10) a cycloaliphatic epoxy group
expressed by the following general formula (6): ##STR00039##
wherein R.sup.16 is a substituted or unsubstituted, straight-chain
or branched divalent hydrocarbon group having from 2 to 20 carbon
atoms, and R.sup.6 and R.sup.7 are synonymous with those described
above.
9. The organopolysiloxane elastomer according to claim 1 in a
particulate form.
10. The organopolysiloxane elastomer according to claim 9 in a
particulate form having a volume average particle size in a range
from 20 to 1000 .mu.m.
11. The organopolysiloxane elastomer according to claim 1, wherein
the elastomer contains an oil agent in an amount greater than or
equal to the weight of the elastomer itself and is swellable.
12. A composition containing the organopolysiloxane elastomer
according to claim 1 and at least one type of oil agent.
13. The composition according to claim 12 in a paste form.
14. The composition according to claim 12 obtained by mixing at
least one type of oil agent after grinding the organopolysiloxane
elastomer using a mechanical force or grinding a mixture of the
organopolysiloxane elastomer and at least one type of oil agent
using a mechanical force.
15. An organopolysiloxane elastomer formed by treating the
organopolysiloxane elastomer according to claim 1 with at least one
type of acidic substance and removing volatile components by
heating or decompression.
16. The composition according to claim 12, the composition being an
emulsion composition.
17. A raw material for an external use preparation or a cosmetic
composition containing the organopolysiloxane elastomer according
to claim 11.
18. The raw material for an external use preparation or a cosmetic
composition according to claim 17, wherein the raw material is a
thickening agent, a gelling agent, a tactile sensation improver, a
surfactant, an emulsifier, or a powder dispersion stabilizer.
19. An external use preparation containing the organopolysiloxane
elastomer according to claim 11.
20. A production method for an organopolysiloxane elastomer,
comprising reacting: (A) an organohydrogenpolysiloxane; (B) a sugar
alcohol group-containing organic compound having a reactive
unsaturated group; and (C) at least one type of organic compound
selected from the group consisting of (C1) an organic compound
having an average number of reactive unsaturated groups in the
molecule that is greater than 1 and (C2) an organic compound having
at least one reactive unsaturated group and at least one epoxy
group in the molecule.
21. The production method for an organopolysiloxane elastomer
according to claim 20, wherein part or all of the reaction
requiring the component (A), the component (B) and the component
(C) is performed in the presence of at least one solvent selected
from a group indicated by (P-1) to (P-2): (P-1): organic compound;
and (P-2): compound containing silicon atoms.
22. The production method for an organopolysiloxane elastomer
according to claim 20, wherein a crosslinking reaction is performed
by adding the component (C) after first reacting the component (A)
and the component (B); and an optional component (Q) that is a
compound having one unsaturated group in the molecule, excluding
the compound of (C2), is reacted with the component (A) prior to
the reaction between the component (A) and the component (B),
further reacted after the reaction between the component (A) and
the component (B), or further reacted after crosslinking by the
component (C).
23. The production method for an organopolysiloxane elastomer
according to claim 20, wherein a reaction between the component (A)
and the component (C) is first performed to derive a crosslinked
portion, and the component (B) is then added and reacted
thereafter; and an optional component (Q) that is a compound having
one unsaturated group in the molecule, excluding the compound of
(C2), is reacted with the component (A) prior to the reaction
between the component (A) and the component (C), further reacted
after the reaction between the component (A) and the component (C),
or further reacted after the reaction with the component (B).
24. A production method for an organopolysiloxane elastomer,
wherein after an organopolysiloxane elastomer obtained by the
production method according to claim 20 or a composition containing
the same is treated with at least one type of an acidic substance,
volatile components are removed by heating or decompression.
25. The production method for an organopolysiloxane elastomer
according to claim 24, wherein after the elastomer is treated with
the acidic substance, the elastomer is neutralized by adding at
least one type of basic substance.
Description
TECHNICAL FIELD
[0001] This application claims priority rights based on Japanese
Patent Application No. 2011-121097 filed May 30, 2011 in Japan, the
content of which is incorporated herein by reference. The present
invention relates to a novel organopolysiloxane elastomer having a
crosslinked structure and uses thereof. The applications and
background art of the novel organopolysiloxane elastomer of the
present invention are common to the corresponding disclosed content
of another patent application claiming priority rights based on
Japanese Patent Application No. 2011-121097 filed on the same day
as this application (related to a modified organopolysiloxane
elastomer having a siloxane dendron structure and a
mono-diglycerin-modified organopolysiloxane elastomer).
BACKGROUND ART
[0002] As an organopolysiloxane elastomer having a hydrophilic
group, a silicone polymer which is swellable with respect to
silicone oil and a paste-like silicone composition which is
produced using the silicone polymer and can stably and uniformly
disperse water have been reported (Patent Documents 1 and 2). This
is a material provided with enhanced adaptability with respect to
formulations containing water in addition to stable
viscosity-improving characteristics for silicone oils by
introducing a polyoxyalkylene group into the gel skeleton of a
silicone gel composition (Patent Document 3) or powder, paste-like,
or grease-like silicone composition (Patent Document 4) reported
prior to these patents.
[0003] However, although the compositions proposed in Patent
Documents 1 and 2 have excellent characteristics for
emulsifying/dispersing water in silicone oils, the compositions
cannot stably emulsify/disperse water in a system containing
non-silicone oils such as a hydrocarbon oil or an ester oil,
leading to the problem that the viscosity-improving effects are
also limited. Further, there is the drawback that when the
resulting emulsion is stored for a long period of time, the pH
decreases and the emulsion develops an abnormal odor.
[0004] On the other hand, a polyoxyalkylene group-containing
organopolysiloxane elastomer having a structure differing from that
of the materials described above and a silicone paste containing
this elastomer and a solvent have also been proposed (Patent
Documents 5 and 6). These technologies are characterized in that
decamethylcyclopentasiloxane, which also has excellent
compatibility with non-silicone oil agents as a solvent, is used,
and the effect of this substance enables the stable
emulsification/dispersion of water in silicone/non-silicone mixed
oils.
[0005] However, when this organopolysiloxane elastomer uses a chain
silicone oil or non-silicone oil other than a cyclic
dimethylpolysiloxane such as decamethylcyclopentasiloxane as a
solvent, there is a problem in that it becomes difficult to stably
emulsify/disperse water in a silicone/non-silicone mixed oil or a
non-silicone oil.
[0006] Incidentally, known technologies which aim to demonstrate
stable emulsification performance with a formulation containing
organic oils by improving the compatibility of the
organopolysiloxane elastomer itself with non-silicone oils include
a technology using a composition containing a blend of a
crosslinked elastomeric silicone polyether and a crosslinked
elastomeric silicone containing an alkyl group having from 3 to 40
carbon atoms (Patent Document 7) and a technology using an
elastomer silicone terpolymer composition containing a
polyoxyalkylene group and a higher alkyl group having at least 10
carbon atoms (Patent Document 8).
[0007] Although these technologies make it possible to stably
emulsify/disperse water in not only silicone oils but also oil
phases containing large amounts of organic oils, a large amount of
the elastomer is required in order to achieve stable emulsification
with the technology of Patent Document 7, which is problematic in
that it is economically disadvantageous. In addition, with the
technology of Patent Document 8, the feel of the emulsion when
applied is heavy, which leads to the problem that the emulsion
tends to have an oily feel or a texture with strong stickiness.
[0008] In addition, a technology which uses a silicone substance
containing a polymer network structure formed by the polymerization
of a polyfunctional organosilicone compound containing an alkenyl
group and a hydride group in the same molecule (Patent Document 9),
a technology which uses a polyether siloxane elastomer compatible
with polar solvents (Patent Document 10), a technology which uses a
crosslinked silicone polymer mesh-like composition expanded by
alkyltrisiloxane (Patent Document 11), and the like have also been
reported.
[0009] However, with the technology of Patent Document 9, even if
an attempt is made to introduce allyl polyether into the molecule,
a self-polymerization reaction of the polyfunctional organosilicone
occurs preferentially due to the problem of compatibility and the
difference between the reactivities of the C.dbd.C bonding sites,
which causes the substance to gelify quickly. Therefore, the
polyether group serving as a hydrophilic portion cannot be
introduced evenly, which leads to the problem that fluctuations in
emulsification performance tend to occur. The technologies of
Patent Documents 10 and 11 have problems in that the stability of
W/O emulsions containing organic oils is insufficient. In recent
years, the use of a silicone polymer ether elastomer gel which
demonstrates improved compatibility with various organic components
and a stable viscosity-improving effect as a result of the
introduction of a polyoxypropylene group has also been proposed
(Patent Documents 12 and 13), but the function of this material as
a W/O emulsifier is small.
[0010] Further, several technologies related to emulsions or
emulsion-type cosmetic compositions using the materials described
above have also been reported (Patent Documents 14 to 17), but the
respective materials serving as a foundation have the problems
described above, so the degree of completion when used as a
cosmetic composition is low. In particular, as a problem common to
the technologies described above, the issue that the resulting
emulsion develops a strong abnormal odor when the emulsion is
stored for a long period of time remains unresolved.
[0011] On the other hand, a great deal of research into reducing
the odor of non-elastomer type polyether-modified polysiloxanes
(polyoxyalkylene group-containing organopolysiloxanes) has been
conducted. The cause of odorization over time of a
polyether-modified polysiloxane that was first reported was the
aldehyde and acid produced as a result of oxidation degradation
(rancidity) over time of the polyether moiety in the
polyether-modified polysiloxane composition. Examples of
technologies to suppress this oxidation degradation include the
methods recited in Patent Documents 18 and 19 in which tocopherol,
phytic acid, or a similar antioxidant component is added to the
polyether-modified polysiloxane composition.
[0012] However, the use of only these anti-oxidizing agent results
in the insufficient suppression of the odorization over time of a
formulation based on the polyether-modified polysiloxane and, as a
result, other causes were investigated. As a result, Patent
Document 20 recites that propionaldehyde originating from unreacted
propenyl-etherified polyoxyalkylene is a cause of the odor.
[0013] The polyether-modified polysiloxane composition is typically
synthesized via a hydrosilylation reaction of an
organohydrogenpolysiloxane having a silicon-bonded hydrogen group
and a polyoxyalkylene having an allyl ether group at a terminal.
Patent Document 20 recites that, in the production of the
polyether-modified polysiloxane composition, a double bond of the
allyl etherified polyoxyalkylene migrates inward due to the
influence of a platinum catalyst and a portion of the
allyl-etherified polyoxyalkylene becomes a propenyl-etherified
polyoxyalkylene and remains in the polyether-modified polysiloxane
composition as is without reacting with the
organohydrogenpolysiloxane. Patent Document 12 also recites that
the propenyl-etherified polyoxyalkylene degrades over time, thus
producing ketones and aldehydes which results in the odorization.
Moreover, hydrolysis in the presence of an acid is disclosed as a
useful deodorization method.
[0014] However, while this deodorization method could be thought to
be useful if all of the allyl groups of the polyoxyalkylene
remaining in the composition were replaced with propenyl groups, in
actuality, a significant proportion of the allyl-etherified
polyoxyalkylene which is not easily hydrolyzed remains. As a
result, the composition cannot be sufficiently deodorized using the
deodorization method of Patent Document 20. If a strong acid is
used that can hydrolyze the allyl-etherified polyoxyalkylene, the
carbon-oxygen bond at the polyoxyalkylene site and/or the
silicon-oxygen bond at the polysiloxane site may disconnect, so
using such an acid is inappropriate. Additionally, in order to
perform the hydrolysis reaction in a quantitative manner, excessive
amounts of water and acid are needed. These excessive amounts of
water and acid complicate post treatment processes and, therefore,
this deodorization method is not preferable.
[0015] In order to resolve this problem, methods for suppressing
the production of propionaldehyde have been disclosed (Patent
Documents 21 to 24). In these methods, a hydrogenation treatment is
performed as a deodorization method of the polyether-modified
polysiloxane composition in order to alkylate the alkenyl groups
(double bonds) included in the alkenyl group-containing
polyoxyalkylene (including both propenyl-etherified polyoxyalkylene
and allyl-etherified polyoxyalkylene) remaining in the composition.
However, even with a polyether-modified polysiloxane composition
deodorized using a hydrogenation reaction, in cases where a
formulation including water and an alcohol is compounded, it may be
difficult to achieve sufficient deodorization over time or under
elevated temperature conditions.
[0016] A cause of the odorization is acetal and similar aldehyde
condensation products that are free of unsaturated bonds that
remain in the composition. Thus, for the purpose of completely
eliminating the acetal and other aldehyde condensation products,
technology in which treatment using the acid aqueous solution and
hydrogenation treatment are combined (Patent Document 25) and
technologies in which hydrogenation treatment and treatment using a
solid acid catalyst are combined (Patent Documents 26 and 27) are
disclosed. That is, it is acknowledged that performing at least
hydrogenation treatment is preferable in the deodorization of
polyether-modified polysiloxanes as a raw material suitable for use
in cosmetic products.
[0017] Based on such a background, two technologies for reducing
the odor of an organopolysiloxane elastomer having a hydrophilic
group such as an elastomer-type polyether-modified polysiloxane
have been reported. Patent Document 28 introduces a paste-like
composition which is obtained by adding at least one type of acidic
substance selected from the group consisting of organic acids,
phosphoric acids, and phosphoric acid salts to a mixture consisting
of a crosslinked organopolysiloxane polymer having a
polyoxyalkylene chain and a liquid oil, adding a basic neutralizing
salt so that the pH is from 5 to 8, and then removing volatile
components by heating and/or decompression. The problems arising
when applying a refining method using a non-elastomer-type
polyether-modified polysiloxane to a crosslinked polymer are as
described below. Specifically, there is a drawback in that unless a
device with a glass lining is used when treating the substance with
a corrosive acidic aqueous solution such as hydrochloric acid
water, the device will be corroded. In addition, even if an effect
is recognized with regard to the reduction of odor, it is not
possible to suppress decreases in pH. Further, when performing a
hydrogenation treatment method, heavy metal catalysts such as
palladium or nickel become necessary, but it is not possible to
remove these catalysts by filtration, and the heavy metal catalysts
are left behind in the composition, which is not suitable for
applications to cosmetic compositions.
[0018] In addition, Patent Document 29 introduces a composition
obtained by adding at least one type of acidic substance selected
from the group consisting of organic acids, inorganic acids, and
inorganic acid salts to an organopolysiloxane polymer having a
glycerin derivative and containing a liquid oil in an amount equal
to or greater than its own weight so that the polymer is capable of
swelling, and a paste-like composition prepared by adding a liquid
oil agent to this polymer so that the polymer swells, adding a
basic neutralizing salt so that the pH is from 5 to 8, and then
removing volatile components by heating and/or decompression. The
problems arising when treating the polyether-modified polysiloxane
crosslinked polymer with hydrochloric acid water or the like are
described in detail as follows. Specifically, with this method, it
is not possible to suppress decreases in pH caused by the automatic
oxidation characteristic to polyoxyethylene chains, and it is not
possible to suppress decreases in viscosity or the generation of an
acidified odor due to the decomposition of the polyoxyethylene
chain. Although the problems described above can be suppressed by
adding an antioxidant, the effect of doing so is insufficient.
[0019] This organopolysiloxane elastomer containing a glycerin
derivative is assumed to have good solubility and emulsifiability
in various oil agents in comparison to conventional polyoxyalkylene
group-containing organopolysiloxane elastomers. Further, it has
been reported that when comparing the sensation during use of W/O
type creams using these substances as emulsifiers, elastomers
having glycerin derivatives demonstrate better moisture and
retention. However, this material has poor compatibility with oil
agents other than silicone oils such as hydrocarbon oils or ester
oils, for example, and there is a problem in that the
viscosity-improving effect on these organic oils is insufficient.
Further, there are cases in which the effect is also insufficient
from the perspective of the capacity to stably emulsify/disperse
water in an oil agent system containing large amounts of organic
oils.
[0020] Therefore, an organopolysiloxane elastomer characterized by
a branched structure based on a polydimethylsiloxyethyl group and
further having a hydrophilic group has been proposed by Patent
Document 30 as a material for solving these problems, and this
elastomer demonstrates a high viscosity-improving effect on
silicone oils and organic oils other than silicone oils and
provides a paste free of stickiness. However, this paste
demonstrates oily gooeyness and an unnatural warm sensation, so the
paste is not necessarily satisfactory from the perspective of the
tactile sensation. Further, in order to demonstrate an effect as an
oil viscosity-improving agent, it is necessary to add at least 10
wt. % (mass %) of an oil phase as the elastomer content, so the
paste can also be perceived as having a problem from the
perspective of the viscosity-improving efficiency.
[0021] On the other hand, non-elastomer sugar alcohol-modified
polysiloxanes and applications thereof to cosmetics and the like
have been reported in Patent Documents 31 to 38. However, these
documents are not related to organopolysiloxane elastomers having
sugar alcohol-modified groups.
BACKGROUND DOCUMENTS
Patent Documents
[0022] Patent Document 1: Japanese Unexamined Patent Application
Publication No. H04-272932A [0023] Patent Document 2: Japanese
Unexamined Patent Application Publication No. H05-104320A [0024]
Patent Document 3: Japanese Unexamined Patent Application
Publication No. H01-207354A [0025] Patent Document 4: Japanese
Unexamined Patent Application Publication No. H02-043263A [0026]
Patent Document 5: U.S. Pat. No. 5,811,487B [0027] Patent Document
6: Japanese Unexamined Patent Application Publication No.
H11-049957A [0028] Patent Document 7: Japanese Unexamined Patent
Application Publication No. 2001-187842A [0029] Patent Document 8:
Japanese Unexamined Patent Application Publication No. 2000-319515A
[0030] Patent Document 9: Japanese Unexamined Patent Application
Publication No. 2002-105318A [0031] Patent Document 10:
WO2001/014458 [0032] Patent Document 11: WO2007/061623 [0033]
Patent Document 12: WO2007/109240 [0034] Patent Document 13:
WO2009/006091 [0035] Patent Document 14: Japanese Unexamined Patent
Application Publication No. H06-040847A [0036] Patent Document 15:
Japanese Unexamined Patent Application Publication No. H06-040848A
[0037] Patent Document 16: Japanese Unexamined Patent Application
Publication No. 2001-064513A [0038] Patent Document 17: Japanese
Unexamined Patent Application Publication No. 2001-192459A [0039]
Patent Document 18: Japanese Examined Patent Application
Publication No. S55-041210A [0040] Patent Document 19: Japanese
Unexamined Patent Application Publication No. S60-018525A [0041]
Patent Document 20: Japanese Unexamined Patent Application
Publication No. H02-302438A [0042] Patent Document 21: U.S. Pat.
No. 5,225,509B [0043] Patent Document 22: Japanese Unexamined
Patent Application Publication No. H07-330907A [0044] Patent
Document 23: Japanese Unexamined Patent Application Publication No.
H09-165315A [0045] Patent Document 24: Japanese Unexamined Patent
Application Publication No. H09-165318A [0046] Patent Document 25:
WO2002/055588 [0047] Patent Document 26: WO2004/046226 [0048]
Patent Document 27: Japanese Unexamined Patent Application
Publication No. 2005-120293A [0049] Patent Document 28:
WO2003/020828 [0050] Patent Document 29: WO2004/024798 [0051]
Patent Document 30: Japanese Unexamined Patent Application
Publication No. 2008-115358A [0052] Patent Document 31: Japanese
Unexamined Patent Application Publication No. S62-068820A [0053]
Patent Document 32: Japanese Unexamined Patent Application
Publication No. S63-139106A [0054] Patent Document 33: Japanese
Unexamined Patent Application Publication No. H05-186596A [0055]
Patent Document 34: Japanese Unexamined Patent Application
Publication No. H07-041417A [0056] Patent Document 35: Japanese
Unexamined Patent Application Publication No. 2002-119840A [0057]
Patent Document 36: Japanese Unexamined Patent Application
Publication No. 2008-274241A [0058] Patent Document 37: Japanese
Unexamined Patent Application Publication No. 2002-179798A [0059]
Patent Document 38: Japanese Unexamined Patent Application
Publication No. 2003-146991A
SUMMARY OF INVENTION
Technical Problem
[0060] The present invention was conceived in order to solve the
problems described above, and a first object of the present
invention is to provide a novel organomodified organopolysiloxane
elastomer and a production method thereof, wherein the novel
organomodified organopolysiloxane elastomer has affinity with
various oil agents, has excellent viscosity-improving
characteristics, gelification characteristics, and emulsification
characteristics, imparts excellent tactile sensation--in
particular, an excellent tactile sensation characterized by
smoothness with a velvet-like thickness--and imparts an excellent
sensation during use.
[0061] A second object of the present invention is to provide a raw
material for an external use preparation or a cosmetic composition
such as a thickening agent, a gelling agent, a tactile sensation
improver, a surfactant, an emulsifier, or a powder dispersion
stabilizer containing the organomodified organopolysiloxane
elastomer, and a cosmetic composition or an external use
preparation containing the organomodified organopolysiloxane
elastomer.
[0062] A third object of the present invention is to provide an
organomodified organopolysiloxane elastomer with a reduced odor, a
raw material for an external use preparation or a cosmetic
composition containing the same, and an external use preparation or
a cosmetic composition containing the raw material.
Solution to Problem
[0063] The present inventors arrived at the present invention as a
result of conducting dedicated research in order to achieve the
objective described above. Specifically, the first object of the
present invention is achieved by an organopolysiloxane elastomer
having a silicon-bonded sugar alcohol-modified group and having a
crosslinked three-dimensional network structure comprising a
carbon-silicon bond in the crosslinking portion.
[0064] The sugar alcohol-modified group is preferably expressed by
the following general formula (4-1):
##STR00001##
(wherein R is a divalent organic group, and e is 1 or 2) or the
following general formula (4-2):
##STR00002##
(wherein R is as defined above, and e' is 0 or 1).
[0065] In the general formula (4-1) or (4-2) described above, the
divalent organic group represented by R is preferably a substituted
or unsubstituted, straight-chain or branched divalent hydrocarbon
group having from 3 to 5 carbon atoms.
[0066] The organopolysiloxane elastomer described above can be
obtained by reacting:
(A) an organohydrogenpolysiloxane; (B) a sugar alcohol
group-containing organic compound having a reactive unsaturated
group; and (C) at least one type of organic compound selected from
the group consisting of (C1) an organic compound having an average
number of reactive unsaturated groups in the molecule that is
greater than 1 and (C2) an organic compound having at least one
reactive unsaturated group and at least one epoxy group in the
molecule.
[0067] The average number of silicon-bonded hydrogen atoms per
molecule of the component (A), which reacts with reactive
unsaturated groups of the component (C) constituting the
crosslinking portion, is preferably at least 1.5.
[0068] The component (A) is preferably expressed by the average
composition formula (1):
[Formula 3]
R.sup.1.sub.aH.sub.bSiO.sub.(4-a-b)/2 (1)
(wherein R.sup.1 moieties are each independently monovalent organic
groups, 1.0.ltoreq.a.ltoreq.3.0, and
0.001.ltoreq.b.ltoreq.1.5).
[0069] The component (C) is preferably at least one organic
compound selected from the following formulas (C1-1) to (C1-5) and
(C2-1) to (C2-2):
(C1-1) an .alpha.,.omega.-diene expressed by the general formula
(2-1):
[Formula 4]
CH.sub.2.dbd.CH(CH.sub.2).sub.xCH.dbd.CH.sub.2 (2-1)
(wherein 1.ltoreq.x.ltoreq.20); (C1-2) an .alpha.,.omega.-diyne
expressed by the general formula (2-2):
[Formula 5]
CH.ident.C(CH.sub.2).sub.xC.ident.CH (2-2)
(wherein 1.ltoreq.x.ltoreq.20); (C1-3) an .alpha.,.omega.-ene-yne
expressed by the general formula (2-3):
[Formula 6]
CH.sub.2.dbd.CH(CH.sub.2).sub.xC.ident.CH (2-3)
(wherein 1.ltoreq.x.ltoreq.20); (C1-4) a bisalkenyl polyether
compound expressed by the general formula (2-4):
[Formula 7]
C.sub.mH.sub.2m-1O(C.sub.nH.sub.2nO).sub.yC.sub.mH.sub.2m-1
(2-4)
(wherein 2.ltoreq.m.ltoreq.20, 2.ltoreq.n.ltoreq.4, y is the total
value of the number of repetitions of the oxyethylene unit, the
oxypropylene unit, and the oxybutylene unit, and
1.ltoreq.y.ltoreq.180); (C1-5) an unsaturated group-containing
silicone-compound expressed by the average composition formula
(2-5):
[Formula 8]
R.sup.2.sub.pR.sup.3.sub.qSiO.sub.(4-p-q)/2 (2-5)
(wherein R.sup.2 moieties may each be independent from one another
but are monovalent organic groups that are different from R.sup.3;
R.sup.3 moieties are each independently monovalent unsaturated
aliphatic hydrocarbon groups having from 2 to 30 carbon atoms,
1.0.ltoreq.p.ltoreq.2.5, and 0.001.ltoreq.q.ltoreq.1.5); (C2-1) an
unsaturated epoxy compound expressed by the general formula
(2-6):
##STR00003##
(wherein R.sup.4 is a substituted or unsubstituted, straight-chain
or branched monovalent hydrocarbon group having one reactive
unsaturated group and from 2 to 20 carbon atoms); and (C2-2) an
unsaturated group-containing cycloaliphatic epoxy compound
expressed by the general formula (2-7): (C2-2) an unsaturated
group-containing cycloaliphatic epoxy compound expressed by the
general formula (2-7):
##STR00004##
(wherein R.sup.5 is a substituted or unsubstituted, straight-chain
or branched monovalent hydrocarbon group having one reactive
unsaturated group and from 2 to 20 carbon atoms; R.sup.6 is a
hydrogen atom or a methyl group; and R.sup.7 is a hydrogen atom or
a methyl group).
[0070] In the average composition formula (1), the monovalent
organic group represented by R.sup.1 is preferably selected from
the following (D1) to (D10):
(D1) a substituted or unsubstituted, straight-chain or branched
monovalent hydrocarbon group having from 1 to 60 carbon atoms; (D2)
a polyoxyalkylene group expressed by --R.sup.8O(AO).sub.zR.sup.9
(wherein AO is an oxyalkylene group having from 2 to 4 carbon
atoms; R.sup.8 is a substituted or unsubstituted, straight-chain or
branched divalent hydrocarbon group having from 3 to 5 carbon
atoms; R.sup.9 is a hydrogen atom, a substituted or unsubstituted,
straight-chain or branched monovalent hydrocarbon group having from
1 to 24 carbon atoms, or a substituted or unsubstituted,
straight-chain or branched acyl group having from 2 to 24 carbon
atoms; and z=1 to 100); (D3) a substituted or unsubstituted,
straight-chain or branched alkoxy group having from 1 to 30 carbon
atoms; (D4) a hydroxyl group; (D5) an ester group expressed by
--R.sup.10--COOR.sup.11 (wherein R.sup.10 is a substituted or
unsubstituted, straight-chain or branched divalent hydrocarbon
group having from 2 to 20 carbon atoms, and R.sup.11 is a
substituted or unsubstituted, straight-chain or branched monovalent
hydrocarbon group having from 1 to 30 carbon atoms); (D6) an ester
group expressed by --R.sup.17--OCOR.sup.18 (wherein R.sup.17
substituted or unsubstituted, straight-chain or branched divalent
hydrocarbon group having from 2 to 20 carbon atoms, and R.sup.18 is
a substituted or unsubstituted, straight-chain or branched
monovalent hydrocarbon group having from 1 to 30 carbon atoms);
(D7) L.sup.1 here, L.sup.1 is a silylalkyl group having a siloxane
dendron structure and, when i=1, is expressed by the following
general formula (3):
##STR00005##
(wherein R.sup.12 is a substituted or unsubstituted, straight-chain
or branched monovalent hydrocarbon group having from 1 to 30 carbon
atoms; R.sup.13 moieties each independently represents an alkyl
group or a phenyl group having from 1 to 6 carbon atoms; Z is a
divalent organic group; i represents a generation of the silylalkyl
group represented by L.sup.i and is an integer of 1 to k when k is
the number of generations, which is the number of repetitions of
the silylalkyl group; the number of generations k is an integer
from 1 to 10; L.sup.i+1 is the silylalkyl group when i is less than
k, and R.sup.13 when i=k; and h' is a number in a range from 0 to
3); (D8) an alkyl group substituted by a chain polysiloxane
structure expressed by the following general formula (4):
##STR00006##
(wherein R.sup.14 moieties are each independently substituted or
unsubstituted, straight-chain or branched monovalent hydrocarbon
groups having from 1 to 30 carbon atoms, hydroxyl groups, or
hydrogen atoms, and at least one of the R.sup.14 moieties is the
monovalent hydrocarbon group; t is a number in a range from 2 to
10; and r is a number in a range from 1 to 100); (D9) an epoxy
group expressed by the following general formula (5):
##STR00007##
(wherein R.sup.15 is a substituted or unsubstituted, straight-chain
or branched divalent hydrocarbon group having from 2 to 20 carbon
atoms); and (D10) a cycloaliphatic epoxy group expressed by the
following general formula (6):
##STR00008##
(wherein R.sup.16 is a substituted or unsubstituted, straight-chain
or branched divalent hydrocarbon group having from 2 to 20 carbon
atoms, and R.sup.6 and R.sup.7 are synonymous with those described
above).
[0071] The organopolysiloxane elastomer of the present invention is
preferably in a particulate form and is more preferably in a
particulate form with a volume average particle size in the range
of from 20 to 1000 .mu.m.
[0072] The organopolysiloxane elastomer of the present invention is
preferably swellable with an oil agent content of at least the
weight of the elastomer itself.
[0073] Further, the first object of the present invention can be
achieved by a production method for a liquid organopolysiloxane
comprising a process of reacting:
(A) an organohydrogenpolysiloxane; (B) a sugar alcohol
group-containing organic compound having a reactive unsaturated
group; and (C) at least one type of organic compound selected from
the group consisting of (C1) an organic compound having an average
number of reactive unsaturated groups in the molecule that is
greater than 1 and (C2) an organic compound having at least one
reactive unsaturated group and at least one epoxy group in the
molecule.
[0074] In the production method for the organopolysiloxane
elastomer described above, it is preferable for part or all of the
reaction to be performed in the presence of at least one solvent
selected from the group indicated by (P-1) to (P-2) below.
(P-1): organic compound (P-2): compound containing silicon
atoms
[0075] In one aspect of the production method for the
organopolysiloxane elastomer described above, the component (A) and
the component (B) are reacted first, and a crosslinking reaction is
then performed by adding the component (C). In this case, any
component (Q) shown below may be reacted with the component (A)
prior to the reaction between the component (A) and the component
(B), further reacted after the reaction between the component (A)
and the component (B), or further reacted after crosslinking with
the component (C).
(Q): a compound having one unsaturated group in the molecule
(excluding the compound of (C2))
[0076] In another aspect of the production method for the
organopolysiloxane elastomer described above, a reaction between
the component (A) and the component (C) is first performed to
derive a crosslinked portion, and the component (B) is then added
and reacted thereafter. In this case, any component (Q) shown below
may be reacted with the component (A) prior to the reaction between
the component (A) and the component (C), further reacted after the
reaction between the component (A) and the component (C), or
further reacted after the reaction of the component (B).
(Q): a compound having one unsaturated group in the molecule
(excluding the compound of (C2))
[0077] The second object of the present invention can be achieved
by a raw material for an external use preparation, a raw material
for a cosmetic composition, an external use preparation, or a
cosmetic composition containing the organopolysiloxane elastomer; a
composition containing at least one type of oil agent in addition
to the organopolysiloxane elastomer; and a raw material for an
external use preparation or a cosmetic composition, an external use
preparation, or a cosmetic composition containing the
composition.
[0078] The composition described above can be obtained by mixing
the organopolysiloxane elastomer of the present invention with at
least one type of oil agent after grinding the elastomer using a
mechanical force or grinding a mixture of the organopolysiloxane
elastomer and at least one type of oil agent using a mechanical
force.
[0079] The composition may be in the form of an emulsion or a
paste.
[0080] The raw material for use in an external use preparation or a
cosmetic composition can be a thickening agent, a gelling agent, a
tactile sensation improver, a surfactant, an emulsifier, or a
powder dispersion stabilizer.
[0081] The third object of the present invention can be achieved by
further performing an acidizing process of treating the
organopolysiloxane elastomer obtained by the production method for
the organopolysiloxane elastomer described above with at least one
type of an acidic substance and a raw material for an external use
preparation or a cosmetic composition, an external use preparation,
or a cosmetic composition containing the composition described
above. A process of heating and/or decompressing the composition is
preferably performed after the acidizing process. Further, it is
preferable to neutralize the composition by adding at least one
type of a basic substance after the acidizing treatment
process.
Advantageous Effects of Invention
[0082] With the present invention, it is possible to provide a
novel organomodified organopolysiloxane elastomer, wherein the
novel organomodified organopolysiloxane elastomer has affinity with
various oil agents, has excellent viscosity-improving
characteristics, gelification characteristics, and emulsification
characteristics, imparts excellent tactile sensation--in
particular, an excellent tactile sensation characterized by
smoothness with a velvet-like thickness--and imparts an excellent
sensation during use.
[0083] The organomodified organopolysiloxane elastomer of the
present invention has a thickening or gelling effect on various oil
agents and can efficiently and stably thicken or gelate various oil
agents.
[0084] In addition, the organomodified organopolysiloxane elastomer
of the present invention can demonstrate excellent emulsifying
performance with respect to both nonpolar oil agents and polar oil
agents in emulsions in which both water and an oil agent are
present. The emulsion may also contain a polyhydroxy alcohol.
Accordingly, it is possible to design an external use preparation
or a cosmetic composition with various formulations by compounding
the organomodified organopolysiloxane elastomer of the present
invention in an external use preparation or a cosmetic composition.
It is unnecessary for the preparation for external use or the
cosmetic of the present invention to include a polyether-containing
compound.
[0085] In particular, a composition containing the organomodified
organopolysiloxane elastomer of the present invention has the
contradictory characteristics of having an extremely soft tactile
sensation while being in a highly viscous form capable of
guaranteeing stability. This effect is prominent when the
organomodified organopolysiloxane elastomer is in a particulate
form.
[0086] Further, the organomodified organopolysiloxane elastomer of
the present invention has an excellent effect of maintaining the
dispersion state of a powder dispersed in a medium, which makes it
possible to enhance the storage stability of a composition
containing the powder, in particular.
[0087] Due to the functionality thereof, the organomodified
organopolysiloxane elastomer of the present invention can be
advantageously used as a raw material for an external use
preparation or a cosmetic composition such as a thickening agent, a
gelling agent, a tactile sensation improver, a surfactant, an
emulsifier, or a powder dispersion stabilizer and can be compounded
in a cosmetic composition or an external use preparation as
necessary. In particular, the present invention can provide a
nonaqueous emulsion composition with excellent stability that is
usable as a drug delivery system. Similarly, the present invention
can provide a water-in-oil type or an oil-in-water type emulsion
composition having excellent stability.
[0088] Additionally, the organomodified organopolysiloxane
elastomer of the present invention can be used as a composition
with various oil agents because it can be uniformly mixed with a
wide range of types of oil agents. Furthermore, a composition
comprising an oil agent in conjunction with the organomodified
organopolysiloxane elastomer of the present invention has superior
storage stability.
[0089] With the present invention, the odor of the organomodified
organopolysiloxane elastomer can be reduced. The organomodified
organopolysiloxane elastomer of the present invention having a
reduced odor is particularly suitable as a raw material for an
external use preparation or a cosmetic composition or as a
component of an external use preparation or a cosmetic composition.
In particular, in the present invention, it is possible to provide
an organomodified organopolysiloxane elastomer or a composition
containing the same which is essentially odorless and demonstrates
suppressed odor generation at high temperatures or over time by a
simple acidizing.
[0090] The odor-reducing effect of the organomodified
organopolysiloxane elastomer of the present invention is very high,
and the odor-reducing effect achieved in the present invention
cannot be achieved even by acidizing another modified
organopolysiloxane elastomer in the same manner as in the present
invention. The present invention is advantageous in industrial
scale implementation and can provide an organomodified
organopolysiloxane elastomer or a composition containing the same
which is deodorized simply and at low cost.
[0091] In addition, the odor of the organomodified
organopolysiloxane elastomer of the present invention having a
reduced odor does not need to be masked when compounded in an
external use preparation or a cosmetic composition, and there is a
high degree of flexibility in the design of the formulations of an
external use preparation or a cosmetic composition. This is
particularly advantageous in cosmetic compositions, in which
functions that contain an odor are emphasized, and, therefore,
design of a fragrance free cosmetic composition, a faintly scented
cosmetic composition, or a cosmetic composition with a desired
fragrance is easy.
DETAILED DESCRIPTION OF THE INVENTION
Organopolysiloxane Elastomer And Production Method Thereof
[0092] A first aspect of the present invention is an
organopolysiloxane elastomer having a silicon-bonded sugar
alcohol-modified group and having a crosslinked three-dimensional
network structure comprising a carbon-silicon bond in the
crosslinking portion.
[0093] The organopolysiloxane elastomer of the present invention is
an elastic substance with a relatively high crosslinking density
and is a gel-like, rubber-like, or powder-like solid that is
insoluble in solvents or the like. The organopolysiloxane elastomer
of the present invention preferably does not have fluidity
(non-liquid form) at 25.degree. C. "Not having fluidity at
25.degree. C." means that after the organopolysiloxane elastomer is
introduced into a prescribed container and the surface thereof is
made horizontal using an instrument such as a trowel, the container
is tilted, and the surface does not become horizontal once again
after 24 hours. Here, "horizontal" means to form a plane that
intersects the direction of gravitational force at a right
angle.
[0094] In addition, the organopolysiloxane elastomer of the present
invention has a crosslinked three-dimensional network structure
having a crosslinking portion containing a carbon-silicon bond. The
crosslinked three-dimensional network structure also contains a
polysiloxane chain. However, the organopolysiloxane elastomer of
the present invention has a high crosslinking molecular structure
in which the polysiloxane chains are relatively densely crosslinked
in a three-dimensional mesh. Accordingly, the organopolysiloxane is
a gel-like, rubber-like, or powder-like solid that is insoluble in
solvents or the like.
[0095] The organopolysiloxane elastomer of the present invention is
preferably swellable with an oil agent content of at least the
weight of the elastomer itself (mass of the elastomer itself). The
organopolysiloxane elastomer of the present invention containing an
oil agent can exist in a paste form. The types and the like of the
oil agents are as described below, and silicone oils are
preferable.
[0096] The organopolysiloxane elastomer of the present invention
has a silicon-bonded sugar alcohol-modified group. The sugar
alcohol-modified group constitutes a hydrophilic site of the
organopolysiloxane elastomer of the present invention. The
structure of the sugar alcohol-modified group is not limited as
long as the structure has a sugar alcohol site, but the sugar
alcohol residue is preferably bonded to a silicon atom via a
divalent organic group.
[0097] Accordingly, the sugar alcohol-modified group is preferably
expressed by the following general formula (4-1):
##STR00009##
(wherein R is a divalent organic group, and e is 1 or 2), or the
following general formula (4-2):
##STR00010##
(wherein R is as defined above, and e' is 0 or 1).
[0098] The organopolysiloxane elastomer of the present invention is
characterized in that at least one type of a sugar alcohol-modified
group expressed by the general formula (4-1) or (4-2) above is
bonded to a silicon atom. Further, the organopolysiloxane may also
have two or more types of sugar alcohol-modified groups selected
from these sugar alcohol-modified groups in the molecule.
Similarly, a mixture of organopolysiloxanes having different sugar
alcohol-modified groups may also be used.
[0099] The divalent organic group represented by R in the general
formula (4-1) or (4-2) is not particularly limited, but examples
include substituted or unsubstituted, straight-chain or branched
divalent hydrocarbon groups having from 1 to 30 carbon atoms. A
substituted or unsubstituted, straight-chain or branched divalent
hydrocarbon group having from 3 to 5 carbon atoms is preferable.
Examples of the substituted or unsubstituted, and straight-chain or
branched divalent hydrocarbon group having from 1 to 30 carbon
atoms include: straight-chain or branched alkylene groups having
from 1 to 30 carbon atoms such as the methylene group, dimethylene
group, trimethylene group, tetramethylene group, pentamethylene
group, hexamethylene group, heptamethylene group, octamethylene
group, or the like; alkenylene groups having from 2 to 30 carbon
atoms such as the vinylene group, allylene group, butenylene group,
hexenylene group, octenylene group, or the like; arylene groups
having from 6 to 30 carbon atoms such as the phenylene group,
diphenylene group, or the like; alkylenearylene groups having from
7 to 30 carbon atoms such as the dimethylenephenylene group or the
like; and groups thereof in which hydrogen atoms bonded to carbon
atoms of the groups are at least partially substituted by a halogen
atom such as a fluorine atom or the like, or an organic group
containing the carbinol group, epoxy group, glycidyl group, acyl
group, carboxyl group, amino group, methacryl group, mercapto
group, amide group, oxyalkylene group, or the like. The divalent
hydrocarbon groups are preferably alkylene groups having from 1 to
30 carbon atoms, more preferably are alkylene groups having from 1
to 6 carbon atoms, and even more preferably alkylene groups having
from 3 to 5 carbon atoms.
[0100] In the sugar alcohol-modified group of the general formula
(4-1), it is particularly preferable for R to be a propylene group
and for e=1. Similarly, in the sugar alcohol-modified group of the
general formula (4-2), it is particularly preferable for R to be a
propylene group and for e'=0. The sugar alcohol-modified group in
this case is a xylitol residue expressed by the structural formula:
--C.sub.3H.sub.6--OCH.sub.2[CH(OH)].sub.3CH.sub.2OH or the
structural formula: --C.sub.3H.sub.6--OCH[CH(OH)CH.sub.2OH].sub.2
corresponding to the general formula (4-1) or (4-2) (hereinafter,
simply referred to as a "xylitol residue" or a "xylitol modified
group").
[0101] The bond position of the sugar alcohol-modified group may be
either the side chain or the terminal of the polysiloxane, which is
the main chain, and the organopolysiloxane of the present invention
may have two or more sugar alcohol-modified groups. Further, these
two or more sugar alcohol-modified groups may be the same or
different sugar alcohol-modified groups. These two or more sugar
alcohol-modified groups can be structured such that bonding occurs
only in a side chain of polysiloxane, which is the main chain, only
at a terminal, or in a side chain and at a terminal.
[0102] The organopolysiloxane elastomer of the present invention
can be produced by reacting:
(A) an organohydrogenpolysiloxane; (B) a sugar alcohol
group-containing organic compound having a reactive unsaturated
group; and (C) at least one type of organic compound selected from
the group consisting of (C1) an organic compound having an average
number of reactive unsaturated groups in the molecule that is
greater than 1 and (C2) an organic compound having at least one
reactive unsaturated group and at least one epoxy group in the
molecule.
[0103] The (A) organohydrogenpolysiloxane is not particularly
limited as long as it has silicon-bonded hydrogen atoms, but an
organohydrogenpolysiloxane having more than one--preferably from
1.01 to 100, more preferably from 1.1 to 50, even more preferably
from 1.2 to 25, and particularly preferably from 1.3 to
10-silicon-bonded hydrogen atoms in the molecule on average is
preferable, and a straight-chain, branched, or reticulated
organopolysiloxane may be used. The positions of the silicon-bonded
hydrogen atoms in the organohydrogenpolysiloxane are not limited,
and can be on the main chain or at the terminals. However, the
atoms are preferably positioned at the terminals from the
perspective of reducing the degree of crosslinking. One type or two
or more types of organohydrogenpolysiloxanes may be used as the
component (A).
[0104] Examples of the component (A) include
1,1,3,3-tetramethyldisiloxane,
1,3,5,7-tetramethylcyclotetrasiloxane, methylhydrogenpolysiloxane
capped at both molecular terminals with trimethylsiloxy groups,
dimethylsiloxane-methylhydrogensiloxane copolymers capped at both
molecular terminals with trimethylsiloxy groups, dimethylsiloxane
capped at both molecular terminals with dimethylhydrogensiloxy
groups, dimethylpolysiloxane capped at both molecular terminals
with dimethylhydrogensiloxy groups,
dimethylsiloxane-methylhydrogensiloxane copolymers capped at both
molecular terminals with dimethylhydrogensiloxy groups,
methylhydrogensiloxane-diphenylsiloxane copolymers capped at both
molecular terminals with trimethylsiloxy groups,
methylhydrogensiloxane-diphenylsiloxane-dimethylsiloxane copolymers
capped at both molecular terminals with trimethylsiloxy groups,
copolymers comprising (CH.sub.3).sub.2HSiO.sub.1/2 units and
SiO.sub.4/2 units, and copolymers comprising
(CH.sub.3).sub.2HSiO.sub.1/2 units, SiO.sub.4/2 units, and
(C.sub.6H.sub.5)SiO.sub.3/2 units.
[0105] The component (A) is preferably expressed by the average
composition formula (1):
[Formula 17]
R.sup.1.sub.aH.sub.bSiO.sub.(4-a-b)/2 (1)
(wherein R.sup.1 moieties are each independently monovalent organic
groups, 1.0.ltoreq.a.ltoreq.3.0, and
0.001.ltoreq.b.ltoreq.1.5).
[0106] Although the molecular structure of the (A)
organohydrogenpolysiloxane is not limited, examples include
straight-chain, partially branching straight-chain, branched-chain,
cyclic, and dentric structures, and straight-chain is preferable.
The molecular weight is not particularly limited, and products
having a low molecular weight to products having a high molecular
weight can be used. Specifically, the number-average molecular
weight is preferably in a range from 100 to 1,000,000 and more
preferably in a range from 300 to 500,000.
[0107] Examples of such organohydrogenpolysiloxanes include those
expressed by the following structural formulas:
R.sup.1.sub.3SiO(R.sup.1.sub.2SiO).sub.v(R.sup.1SiHO).sub.wSiR.sup.1.sub-
.3 (i)
HR.sup.1.sub.2SiO(R.sup.1.sub.2SiO).sub.v(R.sup.1SiHO).sub.zSiR.sup.1.su-
b.3 (ii)
HR.sup.1.sub.2SiO(R.sup.1.sub.2SiO).sub.v(R.sup.1SiHO).sub.zSiR.sup.1.su-
b.2H (iii)
(wherein R.sup.1 is as described above, v is 0 or a positive
integer, w is a positive integer, and z is 0 or a positive
integer). These organohydrogenpolysiloxanes are straight-chain
organohydrogenpolysiloxanes having a silicon-bonded hydrogen atom
on (i) only the side chain, (ii) the side chain or one molecular
terminal, or (iii) the side chain or both molecular terminals.
[0108] The monovalent organic group is not particularly limited but
is preferably selected from the following (D1) to (D10):
(D1) a substituted or unsubstituted, straight-chain or branched
monovalent hydrocarbon group having from 1 to 60 carbon atoms; (D2)
a polyoxyalkylene group expressed by --R.sup.8O(AO).sub.zR.sup.9
(wherein AO is an oxyalkylene group having from 2 to 4 carbon
atoms; R.sup.8 is a substituted or unsubstituted, straight-chain or
branched divalent hydrocarbon group having from 3 to 5 carbon
atoms; R.sup.9 is a hydrogen atom, a substituted or unsubstituted,
straight-chain or branched monovalent hydrocarbon group having from
1 to 24 carbon atoms, or a substituted or unsubstituted,
straight-chain or branched acyl group having from 2 to 24 carbon
atoms; and z=1 to 100); (D3) a substituted or unsubstituted,
straight-chain or branched alkoxy group having from 1 to 30 carbon
atoms; (D4) a hydroxyl group; (D5) an ester group expressed by
--R.sup.10--COOR.sup.11 (wherein R.sup.10 is a substituted or
unsubstituted, straight-chain or branched divalent hydrocarbon
group having from 2 to 20 carbon atoms, and R.sup.11 is a
substituted or unsubstituted, straight-chain or branched monovalent
hydrocarbon group having from 1 to 30 carbon atoms); (D6) an ester
group expressed by --R.sup.17--OCOR.sup.18 (wherein R.sup.17 is a
substituted or unsubstituted, straight-chain or branched divalent
hydrocarbon group having from 2 to 20 carbon atoms, and R.sup.18 is
a substituted or unsubstituted, straight-chain or branched
monovalent hydrocarbon group having from 1 to 30 carbon atoms);
(D7) L.sup.1
[0109] here, L.sup.1 is a silylalkyl group having a siloxane
dendron structure and, when i=1, is expressed by the following
general formula (3):
##STR00011##
(wherein R.sup.12 is a substituted or unsubstituted, straight-chain
or branched monovalent hydrocarbon group having from 1 to 30 carbon
atoms; R.sup.13 moieties each independently represents an alkyl
group or a phenyl group having from 1 to 6 carbon atoms; Z is a
divalent organic group; i represents a generation of the
aforementioned silylalkyl group represented by L.sup.i and is an
integer of 1 to k when k is the number of generations, which is the
number of repetitions of the silylalkyl group; the number of
generations k is an integer from 1 to 10; L.sup.i+1 is the
silylalkyl group when i is less than k, and R.sup.13 when i=k; and
h' is a number in a range from 0 to 3); (D8) an alkyl group
substituted by a chain polysiloxane structure expressed by the
following general formula (4):
##STR00012##
(wherein R.sup.14 moieties are each independently substituted or
unsubstituted, straight-chain or branched monovalent hydrocarbon
groups having from 1 to 30 carbon atoms, hydroxyl groups, or
hydrogen atoms, and at least one of the R.sup.14 moieties is the
monovalent hydrocarbon group; t is a number in a range from 2 to
10; and r is a number in a range from 1 to 100); (D9) an epoxy
group expressed by the following general formula (5):
##STR00013##
(wherein R.sup.15 is a substituted or unsubstituted, straight-chain
or branched divalent hydrocarbon group having from 2 to 20 carbon
atoms); and (D10) a cycloaliphatic epoxy group expressed by the
following general formula (6):
##STR00014##
(wherein R.sup.16 is a substituted or unsubstituted, straight-chain
or branched divalent hydrocarbon group having from 2 to 20 carbon
atoms, and R.sup.6 and R.sup.7 are synonymous with those described
above).
[0110] Examples of the substituted or unsubstituted, straight-chain
or branched monovalent hydrocarbon group in (D1), (D2), and (D5) to
(D8) include alkyl groups such as methyl groups, ethyl groups,
propyl groups, butyl groups, pentyl groups, hexyl groups, heptyl
groups, and octyl groups; cycloalkyl groups such as cyclopentyl
groups and cyclohexyl groups; alkenyl groups such as vinyl groups,
allyl groups, and butenyl groups; aryl groups such as phenyl groups
and tolyl groups; aralkyl groups such as benzyl groups; and groups
in which the hydrogen atoms bonded to the carbon atoms of these
groups are substituted at least partially by halogen atoms such as
fluorine atoms or organic groups such as epoxy groups, glycidyl
groups, acyl groups, carboxyl groups, amino groups, methacryl
groups, and mercapto groups. The monovalent hydrocarbon group is
preferably a group other than an alkenyl group, and is particularly
preferably a methyl group, an ethyl group, or a phenyl group.
[0111] The substituted or unsubstituted, straight-chain or branched
divalent hydrocarbon group in (D2), (D5), (D6), (D9), and (D10) is
as described above.
[0112] Examples of the substituted or unsubstituted, straight-chain
or branched alkoxy group in (D3) include lower alkoxy groups such
as methoxy groups, ethoxy groups, isopropoxy groups, and butoxy
groups and higher alkoxy groups such as lauryl alkoxy groups,
myristyl alkoxy groups, palmityl alkoxy groups, oleyl alkoxy
groups, stearyl alkoxy groups, and behenyl alkoxy groups.
[0113] Among the phenyl group or the alkyl group having from 1 to 6
carbon atoms of (D7), examples of the alkyl group having from 1 to
6 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl,
i-butyl, s-butyl, pentyl, neopentyl, cyclopentyl, hexyl, and
similar straight, branched, or cyclic alkyl groups.
[0114] In the aforementioned general formula (3), in the case of
i=k, R.sup.4 is preferably a methyl group or a phenyl group. In
particular, R.sup.4 is preferably a methyl group when i=k.
[0115] From a technical standpoint, the number of generations k is
preferably an integer from 1 to 3, and more preferably is 1 or 2.
In each of the number of generations, the group represented by
L.sup.1 is expressed as follows. In the formulae, R.sup.12,
R.sup.13, and Z are the same groups as described above.
[0116] When the number of generations is k=1, L.sup.1 is expressed
by the following general formula (3-1).
##STR00015##
[0117] When the number of generations is k=2, L.sup.1 is expressed
by the following general formula (3-2).
##STR00016##
[0118] When the number of generations is k=3, L.sup.1 is expressed
by the following general formula (3-3).
##STR00017##
[0119] In the structures expressed by the general formulae (3-1) to
(3-3) in the case of the number of generations is from 1 to 3, each
of h.sup.1, h.sup.2 and h.sup.3 moieties is independently a number
in a range from 0 to 3. These h' moieties are preferably a number
in a range from 0 to 1, and h' is, in particular, preferably 0.
[0120] In general formulae (3) and (3-1) to (3-3), Z are each
independently a divalent organic group, and specific examples
thereof include a divalent organic group formed by
addition-reacting a silicon-bonded hydrogen atom and a functional
group having an unsaturated hydrocarbon group such as an alkenyl
group, an acryloxy group, a methacryloxy group, or the like at the
terminal. Depending on the method for introducing the silylalkyl
group having a siloxane dendron structure, the functional group can
be appropriately selected and is not restricted to the functional
groups described above. Preferably, Z are each independently a
group selected from divalent organic groups expressed by the
following general formula.
--R.sup.19--
--R.sup.19--CO--
--R.sup.19--COO--R.sup.20--
--CO--R.sup.19--
--R.sup.19--COO--R.sup.20--
--R.sup.19--CONH--R.sup.20--
--R.sup.19--R.sup.20-- [Formula 25]
Of these, Z in L.sup.1 is preferably a divalent organic group
expressed by general formula --R.sup.19-- that is introduced by a
reaction between a silicon-bonded hydrogen atom and an alkenyl
group. Likewise, Z is preferably a divalent organic group expressed
by general formula --R.sup.19--COO--R.sup.20-- that is introduced
by a reaction between a silicon-bonded hydrogen atom and an
unsaturated carboxylic ester group. On the other hand, in the
silylalkyl group represented by L', in which the number of
generations k is 2 or more, and L.sup.i is L.sup.2 to L.sup.k, Z is
preferably an alkylene group having from 2 to 10 carbon atoms and,
in particular, is preferably a group selected from an ethylene
group, a propylene group, a methylethylene group, and a hexylene
group, and most preferably is an ethylene group.
[0121] In the general formula described above, R.sup.19 moieties
are each independently a substituted or unsubstituted, straight or
branched chain alkylene group or alkenylene group having from 2 to
22 carbon atoms or an arylene group having from 6 to 22 carbon
atoms. More specifically, examples of R.sup.19 include an ethylene
group, a propylene group, a butylene group, a hexylene group, and
similar straight alkylene groups; a methylmethylene group, a
methylethylene group, a 1-methylpentylene group, a
1,4-dimethylbutylene group, and similar branched alkylene groups.
R.sup.7 is preferably a group selected from an ethylene group, a
propylene group, a methylethylene group, and a hexylene group.
[0122] In the general formula described above, R.sup.2.degree. is a
group selected from divalent organic groups expressed by the
following formula.
##STR00018##
[0123] The (B) sugar alcohol-modified group-containing compound
having a reactive unsaturated group is not particularly limited as
long as the compound has at least one reactive unsaturated group
and one sugar alcohol-modified group in the molecule, but a
monounsaturated ether compound of the sugar alcohol represented by
the following general formula (4'-1):
##STR00019##
(wherein R' is an unsaturated organic group, and e is 1 or 2 and
more preferably 1) or the following general formula (4'-2):
##STR00020##
(wherein R' is an unsaturated organic group, and e' is 0 or 1 and
more preferably 0) is preferable.
[0124] The unsaturated organic groups are not particularly limited
as long as it has an unsaturated group, but a substituted or
unsubstituted, straight-chain or branched unsaturated hydrocarbon
group having from 3 to 5 carbon atoms is preferable. Examples of
the unsaturated hydrocarbon group having from 3 to 5 carbon atoms
include vinyl groups, allyl groups, butenyl groups, methallyl
groups and similar alkenyl groups. Among these, allyl groups are
preferable.
[0125] As the monounsaturated ether compound of the sugar alcohol,
a monoallyl ether of a sugar alcohol is preferable, and a xylitol
monoallyl ether expressed by the structural formula:
CH.sub.2.dbd.CH--CH.sub.2--OCH.sub.2[CH(OH)].sub.3CH.sub.2OH or the
structural formula:
CH.sub.2.dbd.CH--CH.sub.2--OCH[CH(OH)CH.sub.2OH].sub.2
(hereinafter, referred to as a "xylitol monoallyl ether") is more
preferable. The xylitol monoallyl ether can be synthesized with a
conventionally known method, and a commercially available product
may also be used.
[0126] The xylitol monoallyl ether may be only one of the compounds
represented by the structural formula:
CH.sub.2.dbd.CH--CH.sub.2--OCH.sub.2[CH(OH)].sub.3CH.sub.2OH and
the structural formula:
CH.sub.2.dbd.CH--CH.sub.2--OCH[CH(OH)CH.sub.2OH].sub.2, or mixtures
thereof can be used without any particularly restrictions. In
particular, it is preferable to refine a xylitol monoallyl ether
represented by the structural formula:
CH.sub.2.dbd.CH--CH.sub.2--OCH.sub.2[CH(OH)].sub.3CH.sub.2OH or the
structural formula:
CH.sub.2.dbd.CH--CH.sub.2--OCH[CH(OH)CH.sub.2OH].sub.2 and use the
product as a raw material or to use a xylitol monoallyl ether
containing xylitol monoallyl ethers represented by the structural
formula:
CH.sub.2.dbd.CH--CH.sub.2--OCH.sub.2[CH(OH)].sub.3CH.sub.2OH and
the structural formula:
CH.sub.2.dbd.CH--CH.sub.2--OCH[CH(OH)CH.sub.2OH].sub.2 at a
compositional ratio in a range from 5:5 to 10:0 as a raw material.
In the latter case, it is more preferable to use a xylitol
monoallyl ether containing the substances at a ratio in a range
from 8:2 to 10:0. Moreover, if the compositional ratio is 10:0, the
raw material is essentially a refined product comprising only a
xylitol monoallyl ether represented by the structural formula:
CH.sub.2.dbd.CH--CH.sub.2--OCH.sub.2[CH(OH)].sub.3CH.sub.2OH.
[0127] In order to obtain the organopolysiloxane elastomer of the
present invention, a derivative (ketal derivative) of a sugar
alcohol compound prepared by protecting a hydroxyl group of the
sugar alcohol compound corresponding to the introduced sugar
alcohol-modified group with a ketalizing agent such as
2,2-dimethoxypropane in the presence of an acid catalyst can be
used as a raw material. Specifically, a ketal derivative of a sugar
alcohol having a carbon-carbon double bond in the molecule obtained
by refining the reaction product of the ketal compound described
above and an alkenyl halide is subjected to an addition reaction
with an organohydrogenpolysiloxane instead of the monounsaturated
ether compound of the sugar alcohol described above. After the
addition reaction, the organopolysiloxane can be produced by
performing a deketalation reaction by acid hydrolysis treatment to
deprotect the hydroxyl group. Even with a production method using
the ketal derivative described above, an organopolysiloxane
elastomer having a sugar alcohol-modified group can be obtained
after deprotection, but this method is typically inefficient.
Either production method may be selected in accordance with
conditions such as the desired yield, the production equipment, and
the refinement of the raw material. Either production method may
also be selected for the purpose of improving the quality such as
the purity or the desired characteristics of the organopolysiloxane
elastomer.
[0128] There are no particularly restrictions regarding the
structure of (C1) the organic compound having an average number of
reactive unsaturated groups in the molecule that is greater than 1
serving as the component (C) as long as the compound has more than
1--preferably from 1.01 to 10, more preferably from 1.2 to 8, even
more preferably from 1.5 to 6, and particularly preferably from 2.0
to 4.5--reactive unsaturated groups and preferably carbon-carbon
double bonds on average in the molecule, and straight-chain,
branched, or reticulated organic compounds may be used. An
organopolysiloxane or an unsaturated aliphatic hydrocarbon is
preferable as an organic compound. There are also no restrictions
regarding the position of the organic compound, preferably the
organopolysiloxane, the unsaturated aliphatic hydrocarbon, or the
aforementioned reactive unsaturated group, and the component may be
positioned on the main chain or on a terminal. However, from the
perspective of the ease of controlling the crosslinking density, it
is preferable to use a compound of high purity having two
unsaturated groups in the molecule, each of which is positioned at
either terminal, for example.
[0129] A reactive unsaturated group is preferably present in an
unsaturated aliphatic hydrocarbon group. The unsaturated aliphatic
hydrocarbon group preferably has from 2 to 30 carbon atoms and more
preferably has from 2 to 20 carbon atoms. Examples of the
monovalent unsaturated aliphatic hydrocarbon group having from 2 to
30 carbon atoms include straight-chain or branched alkenyl groups
such as vinyl groups, 1-propenyl groups, allyl groups, isopropenyl
groups, 1-butenyl groups, 2-butenyl groups, pentenyl groups, and
hexenyl groups; cycloalkenyl groups such as cyclopentenyl groups
and cyclohexenyl groups; cycloalkenylalkyl groups such as
cyclopentenylethyl groups, cyclohexenylethyl groups, and
cyclohexenylpropyl groups; and alkynyl groups such as ethynyl
groups and propargyl groups. Alkenyl groups are preferred, and
vinyl groups and hexenyl groups are particularly preferred.
[0130] When the component (C1) is an organopolysiloxane, the
unsaturated aliphatic hydrocarbon group containing a reactive
unsaturated group is preferably bonded to a silicon atom. In
addition, when the component (C1) is an organopolysiloxane, the
group bonding to silicon atoms other than the unsaturated aliphatic
hydrocarbon may be a substituted or unsubstituted monovalent
hydrocarbon group or a monovalent organic group having a reactive
functional group.
[0131] Substituted or unsubstituted monovalent hydrocarbon groups
are typically substituted or unsubstituted, straight or branched
monovalent saturated hydrocarbon groups having from 1 to 30 carbon
atoms, preferably from 1 to 10 carbon atoms, and more preferably
from 1 to 4 carbon atoms, and substituted or unsubstituted
monovalent aromatic hydrocarbon groups having from 6 to 30 carbon
atoms, and more preferably from 6 to 12 carbon atoms. Moreover,
component (C1) may contain, as a monovalent organic group, a
hydroxyl group or an alkoxy group having from 1 to 12 carbon atoms,
such as a methoxy group, an ethoxy group, a propoxy group or a
butoxy group.
[0132] Examples of the monovalent saturated hydrocarbon group
having from 1 to 30 carbon atoms include straight chain or branched
chain alkyl groups such as methyl groups, ethyl groups, n-propyl
groups, isopropyl groups, n-butyl groups, isobutyl groups,
sec-butyl groups, tert-butyl groups, pentyl groups, hexyl groups,
heptyl groups, octyl groups, nonyl groups, decyl groups, and the
like; and cycloalkyl groups such as cyclopentyl groups, cyclohexyl
groups, cycloheptyl groups, cyclooctyl groups, and the like.
[0133] Examples of the monovalent aromatic hydrocarbon group having
from 6 to 30 carbon atoms include aryl groups such as phenyl
groups, tolyl groups, xylyl groups, mesityl groups, and the like.
Of these, a phenyl group is preferable. Note that, in the present
specification, "aromatic hydrocarbon group" also includes groups in
which an aromatic hydrocarbon and a saturated aliphatic hydrocarbon
are conjugated in addition to groups formed only from an aromatic
hydrocarbon. Examples of groups in which an aromatic hydrocarbon
and a saturated hydrocarbon are conjugated include aralkyl groups
such as benzyl groups, phenethyl groups, and the like.
[0134] Hydrogen atoms in the above-mentioned monovalent hydrocarbon
groups may be substituted by one or more substituted groups, and
said substituted groups may be selected from the group consisting
of, for example, a halogen atom (a fluorine atom, a chlorine atom,
a bromine atom, or an iodine atom), a hydroxyl group, an amide
group, an ester group, a carboxyl group and an isocyanate group. A
monovalent saturated or aromatic hydrocarbon group having at least
one of the above-mentioned substituted groups is preferred.
Specifically, it is possible to use a 3,3,3-trifluoropropyl group,
a 3-chloropropyl group, a 3-hydroxypropyl group, a
3-(2-hydroxyethoxy)propyl group, a 3-carboxypropyl group, a
10-carboxydecyl group, a 3-isocyanatopropyl group and the like.
[0135] Examples of monovalent organic groups having reactive
functional groups include monovalent saturated or aromatic
hydrocarbon groups having reactive functional groups selected from
the group consisting of, for example, hydroxyl groups, mercapto
groups, epoxy groups, amino groups, amide groups, ester groups,
carboxyl groups and isocyanate groups. One or a plurality of
reactive functional groups may exist in the monovalent organic
group. R.sup.1 is preferably a monosaturated or aromatic
hydrocarbon group having at least one of the reactive functional
groups described above. Specific examples of the reactive
functional group include 3-hydroxypropyl groups,
3-(2-hydroxyethoxy)propyl groups, 3-mercaptopropyl groups,
2,3-epoxypropyl groups, 3,4-epoxybutyl groups, 4,5-epoxypentyl
groups, 2-glycidoxyethyl groups, 3-glycidoxypropyl groups,
4-glycidoxybutyl groups, 2-(3,4-epoxycyclohexyl)ethyl groups,
3-(3,4-epoxycyclohexyl)propyl groups, aminopropyl groups,
N-methylaminopropyl groups, N-butylaminopropyl groups,
N,N-dibutylaminopropyl groups, 3-(2-aminoethoxy)propyl groups,
3-(2-aminoethylamino)propyl groups, 3-carboxypropyl groups,
10-carboxydecyl groups, 3-isocyanate propyl groups, and the
like.
[0136] A straight-chain or branched polysiloxane is preferable as
the component (C1). A straight-chain component (C1) is preferably a
polymer having a diorganosiloxane unit and a triorganosiloxane
unit, examples of which include dimethylpolysiloxanes capped at
both molecular terminals with dimethylvinylsiloxy groups,
copolymers of dimethylsiloxane and methylphenylsiloxane capped at
both molecular terminals with dimethylvinylsiloxy groups,
copolymers of dimethylsiloxane and methylvinylsiloxane capped at
both molecular terminals with dimethylvinylsiloxy groups,
copolymers of dimethylsiloxane and methylvinylsiloxane capped at
both molecular terminals with trimethylsiloxy groups, copolymers of
dimethylsiloxane, methylvinylsiloxane and methylphenylsiloxane
capped at both molecular terminals with trimethylsiloxy groups,
copolymers of dimethylsiloxane and methylvinylsiloxane capped at
both molecular terminals with silanol groups, polymers in which
some of the methyl groups in these polymers are substituted by
alkyl groups other than methyl groups, such as ethyl groups or
propyl groups, or halogenated alkyl groups such as
3,3,3-trifluoropropyl groups, and mixtures of two or more of these
polymers, with straight-chain diorganopolysiloxanes having
unsaturated aliphatic hydrocarbon groups, and especially alkenyl
groups, at both molecular terminals only being particularly
preferred.
[0137] It is particularly preferable for a branched chain
polysiloxane of component (C1) to be a polymer that contains a
diorganosiloxane unit, an organosilsesquioxane unit and a
triorganosiloxy unit. Silicon-bonded organic groups in these units
are preferably monovalent hydrocarbon groups including alkyl groups
such as methyl groups, ethyl groups and propyl groups; alkenyl
groups such as vinyl groups, allyl groups, butenyl groups and
hexenyl groups; aryl groups such as phenyl groups and tolyl groups;
and halogenated alkyl groups such as 3,3,3-trifluoropropyl groups,
and the like, and may contain extremely small quantities of
hydroxyl groups and alkoxy groups such as methoxy groups, but at
least two silicon-bonded organic groups in this polymer must be
unsaturated aliphatic hydrocarbon groups, and especially alkenyl
groups. In addition, the proportions of these units are not
limited, but in this polymer, it is preferable for diorganosiloxane
units to account for in the range of 80.00 to 99.65 mol % and
organosilsesquioxane units to account for in the range of 0.10 to
10.00 mol %, with the balance comprising triorganosiloxy units.
[0138] Examples of the component (C1) include (C1-5) unsaturated
group-containing silicone compounds expressed by the average
composition formula (2-5):
[Formula 29]
R.sup.2.sub.pR.sup.3.sub.qSiO.sub.(4-p-q)/2 (2-5)
(wherein R.sup.2 moieties may each be independent from one another
but are monovalent organic groups that are different from
R.sup.3;
[0139] R.sup.3 moieties are each independently monovalent
unsaturated aliphatic hydrocarbon groups having from 2 to 30 carbon
atoms, 1.ltoreq.p.ltoreq.2.5, and 0.001.ltoreq.q.ltoreq.1.5). The
monovalent unsaturated aliphatic hydrocarbon group having from 2 to
30 carbon atoms is as described above.
[0140] In the average composition formula (2-5), the monovalent
organic group represented by R.sup.2 is not particularly limited,
but is preferably selected from the following (E1) to (E6):
(E1) a substituted or unsubstituted, straight-chain or branched
monovalent hydrocarbon group having from 1 to 60 carbon atoms
(excluding monovalent hydrocarbon groups having from 2 to 20 carbon
atoms and an aliphatic unsaturated group); (E2) a hydroxyl group;
(E3) an ester group expressed by --R.sup.10--COOR.sup.11 (wherein
R.sup.13 and R.sup.11 are as defined above); (E4) an ester group
expressed by --R.sup.17--OCOR.sup.18 (wherein R.sup.17 and R.sup.18
are as defined above); (E5) an amide group expressed by
--R.sup.21--NR.sup.22COR.sup.23 (wherein R.sup.21 is a substituted
or unsubstituted, straight-chain or branched divalent hydrocarbon
group having from 2 to 20 carbon atoms, R.sup.22 is a hydrogen
atom, or a substituted or unsubstituted, straight-chain or branched
monovalent hydrocarbon group having from 1 to 20 carbon atoms, and
R.sup.23 is a substituted or unsubstituted, straight-chain or
branched monovalent hydrocarbon group having from 1 to 30 carbon
atoms); and (E6) an amide group expressed by
--R.sup.24--CONR.sup.26R.sup.26 (wherein R.sup.24 is a substituted
or unsubstituted, straight-chain or branched divalent hydrocarbon
group having from 2 to 20 carbon atoms, and R.sup.25 and R.sup.26
are each independently a hydrogen atom or a substituted or
unsubstituted, straight-chain or branched monovalent hydrocarbon
group having from 1 to 20 carbon atoms). The definitions, types,
and the like of the substituted or unsubstituted, straight-chain or
branched monovalent hydrocarbon groups or divalent hydrocarbon
groups are as described above.
[0141] On the other hand, the component (C1) may be an unsaturated
aliphatic hydrocarbon. Examples of unsaturated aliphatic
hydrocarbons include various dienes, diynes, enynes and similar
products having two or more reactive unsaturated groups. In view of
crosslinking, dienes, diynes, and enynes are preferable. Dienes,
diynes, and enynes are compounds having a structure in which at
least two reactive unsaturated groups are separated by one or more,
and preferably two or more single bonds in a molecule. The
unsaturated aliphatic hydrocarbon group may be present at the
terminal of the molecular chain, or as a pendant group in the
molecular chain.
[0142] Examples of unsaturated aliphatic hydrocarbons serving as
the component (C1) include .alpha.,.omega.-unsaturated alkenes and
alkynes having from 2 to 30 carbon atoms. Examples of the component
(C1) include (C1-1) an .alpha.,.omega.-diene expressed by the
general formula (2-1):
[Formula 30]
CH.sub.2.dbd.CH(CH.sub.2).sub.xCH.dbd.CH.sub.2 (2-1)
(wherein 1.ltoreq.x.ltoreq.20); (C1-2) an .alpha.,.omega.-diyne
expressed by the general formula (2-2):
[Formula 31]
CH.ident.C(CH.sub.2).sub.xC.ident.CH (2-2)
(wherein 1.ltoreq.x.ltoreq.20); (C1-3) an .alpha.,.omega.-ene-yne
expressed by the general formula (2-3):
[Formula 32]
CH.sub.2.dbd.CH(CH.sub.2).sub.xC.ident.CH (2-3)
(wherein 1.ltoreq.x.ltoreq.20); and (C1-4) a bisalkenyl polyether
compound expressed by the general formula (2-4):
[Formula 33]
C.sub.mH.sub.2m-1O(C.sub.nH.sub.2nO).sub.yO.sub.mH.sub.2m-1
(2-4)
(wherein 2.ltoreq.m.ltoreq.20, 2.ltoreq.n.ltoreq.4, y is the total
value of the number of repetitions of the oxyethylene unit, the
oxypropylene unit, and the oxybutylene unit, and
1.ltoreq.y.ltoreq.180).
[0143] Specific examples of unsaturated aliphatic hydrocarbons
serving as the component (C1) include 1,4-pentadiene,
1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene,
1,9-decadiene, 1,11-dodecadiene, 1,13-tetradecadiene,
1,19-eicosadiene, 1,3-butadiene, 1,5-hexadiyne, and
1-hexene-5-yne.
[0144] The component (C1) may be a single component, but may also
be a mixture of two or more components having different structures.
That is, the component (C1) may be a mixture of one or more types
of organopolysiloxanes and one or more types of unsaturated
aliphatic hydrocarbons. Therefore, "having a number of reactive
unsaturated groups greater than 1 on average" means having more
than one reactive unsaturated group on average per molecule when
two or more types of organopolysiloxanes and/or unsaturated
aliphatic hydrocarbons are used.
[0145] The (C2) organic compound having at least one reactive
unsaturated group and at least one epoxy group in the molecule
serving as the component (C) is not structurally limited as long as
the compound has a total of two or more--preferably from 2 to 10,
more preferably from 2 to 7, even more preferably from 2 to 5, and
particularly preferably from 2 to 4-reactive unsaturated groups and
epoxy groups in the molecule, and straight-chain, branched, or
reticulated organic compounds can be used. An organopolysiloxane or
an unsaturated aliphatic hydrocarbon is preferable as an organic
compound. There are also no restrictions regarding the position of
the organic compound, preferably, the organopolysiloxane, the
unsaturated aliphatic hydrocarbon, or the aforementioned reactive
unsaturated group, and the component may be positioned on the main
chain or on a terminal. However, from the perspective of the ease
of controlling the crosslinking density, it is preferable to use a
compound of high purity in which the total of unsaturated groups
and epoxy groups in the molecule is two.
[0146] A reactive unsaturated group is preferably present in an
unsaturated aliphatic hydrocarbon group. Examples of unsaturated
aliphatic hydrocarbon groups are as described above.
[0147] When the component (C2) is an organopolysiloxane, the
unsaturated aliphatic hydrocarbon group containing a reactive
unsaturated group and/or the epoxy group is preferably bonded to
the silicon atom. In addition, when the component (C2) is an
organopolysiloxane, the group bonding to silicon atoms other than
the unsaturated aliphatic hydrocarbon or the epoxy group may be a
substituted or unsubstituted monovalent hydrocarbon group or a
monovalent organic group having a reactive functional group as
described above.
[0148] The component (C2) is preferably an epoxy group-containing
unsaturated aliphatic hydrocarbon having at least one epoxy group.
Examples of the unsaturated aliphatic hydrocarbon include compounds
having the unsaturated aliphatic hydrocarbon groups described
above. A compound having a monovalent unsaturated aliphatic
hydrocarbon group is preferable.
[0149] Examples of the component (C1) include: (C2-1) an
unsaturated epoxy compound expressed by the general formula
(2-6):
##STR00021##
(wherein R.sup.4 is a substituted or unsubstituted, straight-chain
or branched monovalent hydrocarbon group having one reactive
unsaturated group and from 2 to 20 carbon atoms); and (C2-2) an
unsaturated group-containing cycloaliphatic epoxy compound
expressed by the general formula (2-7):
##STR00022##
[0150] (wherein R.sup.5 is a substituted or unsubstituted,
straight-chain or branched monovalent hydrocarbon group having one
reactive unsaturated group and from 2 to 20 carbon atoms;
R.sup.6 is a hydrogen atom or a methyl group; and R.sup.7 is a
hydrogen atom or a methyl group). The definitions, types, and the
like of the reactive unsaturated groups in general formulas above
and the substituted or unsubstituted, straight-chain or branched
monovalent hydrocarbon groups are as described above.
[0151] Specific epoxy group-containing unsaturated aliphatic
hydrocarbons serving as the component (C2) include an
allylglycidylether, methallylglycidylether,
1-methyl-4-isopropenylcyclohexene oxide, 1,4-dimethylcyclohexene
oxide, 4-vinylcyclohexene oxide, vinylnorbornene monooxide,
dicyclopentadiene monooxide, butadiene monooxide,
1,2-epoxy-5-hexene, 1,2-epoxy-9-decene, and
2,6-dimethyl-2,3-epoxy-7-octene. Among these, 4-vinyl cyclohexane
oxide is preferable.
[0152] The component (C2) may be a single component, but may also
be a mixture of two or more components having different
structures.
[0153] The reaction for producing the organopolysiloxane elastomer
of the present invention may be performed in the presence or in the
absence of a reaction solvent in accordance with a known method.
The reaction between the unsaturated group and the Si--H group in
the present invention is a hydrosilylation reaction. In addition,
when crosslinking is performed using an epoxide of (C2) the organic
compound having one or more reactive unsaturated groups and one or
more epoxy groups in the molecule, bonding caused by the reaction
of the unsaturated group and the Si--H group and ether bond
generation caused by the self ring-opening polymerization of the
epoxy groups (cationic polymerization reaction that occurs in the
presence of a SiH group and a platinum catalyst) both occur,
resulting in crosslinking. In order to accelerate this reaction,
irradiation using high energy beams such as ultraviolet light can
be applied, or a common cation polymerization catalyst can be
further added.
[0154] The reaction solvent is not particularly limited as long as
the solvent is nonreactive, and examples thereof include
alcohol-based solvents such as ethanol and isopropyl alcohol;
aromatic hydrocarbon-based solvents such as toluene and xylene;
ether-based solvents such as dioxane and THF; aliphatic
hydrocarbon-based solvents such as n-hexane, cyclohexane,
n-heptane, cycloheptane, and methylcyclohexane; and chlorinated
hydrocarbon-based organic solvents such as carbon tetrachloride. An
oil agent described below may also be used as a reaction solvent.
When an oil agent is used as a reaction solvent, a composition
consisting of an organopolysiloxane elastomer and an oil agent can
be obtained directly after the crosslinking reaction, and a
composition consisting of a particulate organopolysiloxane
elastomer and an oil agent--preferably a paste-like
composition--can be easily obtained by grinding the composition
using a mechanical force.
[0155] The hydrosilylation reaction may be performed in the
presence or absence of a catalyst, but preferably is performed in
the presence of a catalyst because the reaction can be carried out
at a low temperature and in a shorter period of time. Examples of
the hydrosilylation reaction catalyst include platinum, ruthenium,
rhodium, palladium, osmium, iridium, and similar compounds, and
platinum compounds are particularly effective due to their high
catalytic activity. Examples of the platinum compound include
chloroplatinic acid; platinum metal; platinum metal supported on a
carrier such as platinum supported on alumina, platinum supported
on silica, platinum supported on carbon black, or the like; and a
platinum complex such as platinum-vinylsiloxane complex,
platinum-phosphine complex, platinum-phosphite complex, platinum
alcoholate catalyst, or the like. A usage amount of the catalyst is
about 0.5 to 1000 ppm in terms of platinum metal, when using a
platinum catalyst.
[0156] A reaction temperature of the hydrosilylation reaction is
typically from 30 to 150.degree. C., and a reaction time is
typically from 10 minutes to 24 hours and preferably from 1 to 10
hours.
[0157] The component (A) is crosslinked by the component (C) as a
result of the hydrosilylation reaction or the cationic
polymerization reaction of the epoxy groups, and the polysiloxane
chains originating from the component (A) are linked by the
crosslinking portion having a carbon-silicon bond originating from
the component (C). The component (A) also comprises a sugar
alcohol-modified group originating from the component (B). In this
way, the organopolysiloxane elastomer of the present invention can
be obtained.
[0158] Note that although the organopolysiloxane elastomer of the
present invention typically has a structure that is linked by the
crosslinking portion having a carbon-silicon bond originating from
the component (C), it may also have a portion crosslinked by the
Si--O--C bond. This is because when the structure has a
condensation-reactable functional group such as a silanol group or
an alkoxy group in the components (A) to (C), links can not only be
formed between polysiloxane chains but can also be formed
intermittently as a result of a partial reaction between the
hydroxyl groups in the sugar alcohol-modified group originating
from the component (B) and the Si--H groups of (A) when the
crosslinking conditions are severe.
[0159] In the production of the organopolysiloxane elastomer of the
present invention, the component (C) may be further reacted with
the component (A) after the reaction between the component (A) and
the component (B), or the component (B) can be further reacted with
the component (A) after the reaction between the component (A) and
the component (C).
[0160] When the component (C) is further reacted with the component
(A) after the reaction between the component (A) and the component
(B), the average value of the number of silicon-bonded hydrogen
atoms per molecule of the component (A) reacting with the reactive
unsaturated groups of the component (C) is preferably 1.5 or
greater. That is, the number of silicon-bonded hydrogen atoms per
molecule of the component (A) which constitute the crosslinking
portion and react with the unsaturated bonds of the component (C)
is, on average, at least 1.5, preferably in a range from 2.0 to
5.0, and particularly preferably in a range from 2.5 to 3.5.
[0161] Further, the organopolysiloxane elastomer may be subjected
to hydrogenation treatment for the purpose of improving the odor
after the reaction caused by the remaining unsaturated compound.
Methods of hydrogenation treatment include a method using a
pressurized hydrogen gas and a method using a hydrogenation agent
such as a metal hydride, and hydrogenation treatment may also
entail homogeneous reactions and heterogeneous reactions. One of
these methods may be performed alone, or multiple methods may be
performed in combination. However, taking into consideration the
advantage that the catalyst that is used will not remain in the
finished product, a heterogeneous catalytic hydrogenation reaction
using a solid catalyst is most preferable.
[0162] Examples of solid catalysts (hydrogenation catalyst) that
can be used include noble metal-based catalysts such as common
platinum-based catalysts and palladium-based catalysts as well as
nickel-based catalysts. More specific examples include single
substances such as nickel, palladium, platinum, rhodium, and cobalt
and catalysts combining a plurality of metals such as
platinum-palladium, nickel-copper-chromium, nickel-copper-zinc,
nickel-tungsten, and nickel-molybdenum. Examples of an optional
catalyst carrier include activated carbon, silica, silica alumina,
alumina, and zeolite. In addition, copper-containing hydrogenation
catalysts such as Cu--Cr, Cu--Zn, Cu--Si, Cu--Fe--Al, and
Cu--Zn--Ti may be used. The form of the hydrogenation catalyst
differs depending on the type of the reaction vessel and therefore
cannot be determined generally, but the form is typically selected
appropriately from forms such as a powder, granules, or pellets. In
addition, the platinum catalyst used in the synthesis process
(hydrosilylation reaction) can be used directly. These
hydrogenation catalysts may be used alone or as a combination of
two or more types of catalysts.
[0163] The hydrogenation treatment can also be used to refine a
crude product of the organopolysiloxane elastomer obtained by the
hydrosilylation reaction described above. Specifically, a crude
product can be refined by deodorization resulting from the
hydrogenation treatment in a solvent or without a solvent in the
presence of a hydrogenation catalyst, and such a refined product
can be used much more preferably when applied to an external use
preparation or a cosmetic composition in which the reduction of
odor and compatibility with other components are desired. Moreover,
the deodorizing treatment preferably has, as a pre-process or a
post-process, a stripping treatment in which nitrogen gas is
brought into contact with the crude organopolysiloxane elastomer or
the hydrogenated product to remove light matter under reduced
pressure.
[0164] In the production of the organopolysiloxane elastomer of the
present invention, (Q) an organic compound having one reactive
unsaturated group in the molecule (excluding the component (C2))
may be further reacted in addition to the components (A), (B), and
(C). One type of the component (Q) may be used, or two or more
types of the component (Q) may be used in combination. The
reactions are preferably performed sequentially in the presence of
a hydrosilylation reaction catalyst. The definitions, types, and
the like of the reactive unsaturated groups in the component (Q)
are as described above.
[0165] For example, when the component (C) is further reacted with
the component (A) after the reaction between the component (A) and
the component (B), the component (Q) may be reacted with the
component (A) prior to the reaction between the component (A) and
the component (B), the component (Q) may be reacted with the
component (A) after the reaction between the component (A) and the
component (B), or the component (Q) may be further reacted with the
component (A) after the reaction of the component (C).
[0166] For example, when the component (B) is further reacted with
the component (A) after the reaction between the component (A) and
the component (C), the component (Q) may be reacted with the
component (A) prior to the reaction between the component (A) and
the component (C), the component (Q) may be reacted with the
component (A) after the reaction between the component (A) and the
component (C), or the component (Q) may be further reacted with the
component (A) after the reaction of the component (B).
[0167] Examples of the component (Q) include (Q1) a siloxane
dendron compound having one reactive unsaturated group in the
molecule and (Q2) a hydrocarbon compound having one reactive
unsaturated group in the molecule, a chain organopolysiloxane
having one reactive unsaturated group in the molecule, or the
like.
[0168] Preferable examples of (Q1) the siloxane dendron compound
having one reactive unsaturated group in the molecule include
compounds having a siloxane dendron structure that have one
carbon-carbon double bond at a molecular terminal, the compounds
being expressed by the following general formula (3'):
##STR00023##
(wherein R.sup.12 and R.sup.13 are synonymous with those described
above; Z' is a divalent organic group; h.sup.1 is a number in a
range from 0 to 3; L'.sup.1 is the R.sup.13 moiety or, when j=1, a
silylalkyl group expressed by the general formula (3'') below:
##STR00024##
(wherein R.sup.12 and R.sup.13 are synonymous with those described
above; Z is a divalent organic group; j indicates the number of
generations of the silylalkyl group represented by L.sup.j, when
the number of generations (the number of repetitions) of the
silylalkyl group is k', j is an integer of 1 to k', and the number
of generations k' is an integer from 1 to 9; L.sup.i+1 is the
silylalkyl group when j is less than k' and is the R.sup.13 moiety
when j=k'; and h1 is a number in a range from 0 to 3). The divalent
organic groups in the general formulas (3') and (3'') are as
described above.
[0169] Preferable examples of (Q2) the hydrocarbon compound having
one reactive unsaturated group in the molecule or the chain
organopolysiloxane having one reactive unsaturated group in the
molecule include monounsaturated hydrocarbon compounds expressed by
the following general formula:
R'--R.sup.2' Formula 38
(wherein R' is synonymous with that described above; and R2' is a
substituted or unsubstituted, straight or branched monovalent
hydrocarbon group having from 7 to 58 carbon atoms, or the chain
organosiloxane group represented by the following general formula
(4-1):
##STR00025##
(wherein R.sup.14, t and r are synonymous with those described
above); or the following general formula (4-2):
##STR00026##
(wherein R.sup.14 and r are as defined above).
[0170] The hydrocarbon compound having one reactive unsaturated
group in the molecule (Q2) is preferably a monounsaturated
hydrocarbons having from 9 to 30 carbon atoms and is more
preferably a 1-alkene. Examples of the 1-alkene include 1-nonene,
1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, and
the like. Examples of the chain organopolysiloxane having one
reactive unsaturated group in the molecule include a
dimethylpolysiloxane capped at one molecular terminal with a vinyl
group, a methylphenylpolysiloxane capped at one molecular terminal
with a vinyl group, and the like.
[0171] In the production of the organopolysiloxane elastomer of the
present invention, it is preferable to further perform an acidizing
process of treating the organopolysiloxane elastomer of the present
invention obtained by the hydrosilylation reaction of the component
(A), the component (B), the component (C), and the optional
component (C) using at least one type of acidic substance. As a
result, the odor of the organopolysiloxane elastomer can be
reduced.
[0172] Odor attenuating treating may also be performed with a
method of performing an acidization process at the stage prior to
the formation of the organopolysiloxane elastomer (prior to
crosslinking), but since acid, water, and alcoholic hydroxyl groups
are present, the Si--H groups are consumed by the dehydrogenation
reaction, which makes it difficult to perform subsequent
crosslinking as designed, even if odor reduction is achieved.
Accordingly, it is more preferable to perform acidization after
forming the elastomer.
[0173] The acidic substance is not particularly limited and may be
any acid that matches the definition of a Lewis-acid, a Bronsted
acid, or an Arrhenius acid. The acidic substance used in the
present invention is preferably a water soluble acid. Therefore,
the acidic substance used in the present invention is preferably an
Arrheinius acid which releases protons in an aqueous solution. One
type of the acidic substance may be used alone, or two or more
types of acidic substances may be used in combination. In the
present invention, by using such an acidic substance, the
organopolysiloxane elastomer can be essentially deodorized and the
generation of odor over time can be completely suppressed without
severing the carbon-oxygen bonds or the silicon-oxygen bonds.
[0174] The acidic substance can be selected from the group
consisting of inorganic acids, organic acids, acidic inorganic
salts, solid acids, and acidic platinum catalysts.
[0175] The inorganic acid is not particularly limited, and examples
thereof include hydrochloric acid, sulfuric acid, nitric acid,
phosphoric acid, carbonic acid, boric acid, sulfonic acid, sulfinic
acid, and the like. Note that substances containing organic groups
such as benzene sulfonic acid are not preferable as inorganic
acids.
[0176] The organic acid is not particularly limited, and can be a
monocarboxylic acid (including monohydroxy monocarboxylic acid and
dihydroxy monocarboxylic acid), a dicarboxylic acid (including
monohydroxy dicarboxylic acid and dihydroxy dicarboxylic acid), a
polycarboxylic acid, or the like. Examples thereof include:
Straight saturated aliphatic monocarboxylic acids (alkanoic acids)
such as formic acid, acetic acid, trifluoroacetic acid, propionic
acid, butyric acid, valeric acid, caproic acid, enanthic acid,
caprylic acid, pelargonic acid, capric acid, undecanoic acid, and
the like; Branched saturated aliphatic monocarboxylic acids
(alkanoic acids) such as 2-methylpropanoic acid, 2-methylbutanoic
acid, trimethylpropanoic acid, 2-methylpentanoic acid, trimethyl
acetic acid, and the like; Unsaturated aliphatic monocarboxylic
acids (alkenoic acids) such as acrylic acid, methacrylic acid,
crotonic acid, isocrotonic acid, vinyl acetic acid, allyl acetic
acid, hexenoic acid, heptenoic acid, octenoic acid, and the like;
Unsaturated aliphatic monocarboxylic acids (alkynoic acids) such as
propiolic acid, tetrolic acid, allyl acetic acid, hexynoic acid,
octynoic acid, and the like; Polyunsaturated aliphatic
monocarboxylic acids such as pentadienoic acid, sorbic acid, and
the like; .alpha.-hydroxymonocarboxylic acids such as citric acid,
lactic acid, glycolic acid, .alpha.-oxybutyric acid, and the like;
.beta.-hydroxymonocarboxylic acids such as 2-hydroxyvaleric acid,
2-hydroxycaproic acid, 6-oxybutyric acid, and the like;
.gamma.-hydroxymonocarboxylic acids such as y-oxybutyric acid and
the like; Dihydroxymonocarboxylic acids such as glyceric acid and
the like; Other hydroxymonocarboxylic acids such as
hydroxy(meth)acrylic acid and the like; Saturated aliphatic
dicarboxylic acids such as oxalic acid, malonic acid, succinic
acid, glutaric acid, adipic acid, and the like; Monohydroxy
saturated aliphatic dicarboxylic acids such as tartronic acid,
malic acid, and the like; Dihydroxy saturated aliphatic
dicarboxylic acids such as tartaric acid and the like; Unsaturated
aliphatic dicarboxylic acids such as maleic acid, fumaric acid, and
the like; Aromatic monocarboxylic acid such as benzoic acid and the
like; Aromatic dicarboxylic acids such as phthalic acid and the
like; Amino acids such as glycine, alanine, valine, leucine,
glutamic acid, aspartic acid, PL-pyrrolidone carboxylic acid, and
the like; and Polycarboxylic acids such as gallic acid and the
like.
[0177] In addition, alkyl sulfuric acid, alkyl phosphoric acid,
phenol, and the like can be used as the organic acid. Note that
higher fatty acids or salts thereof are not preferable as organic
acids.
[0178] The acidic inorganic salt is not limited, but a water
soluble salt is preferable. Particularly preferable is a water
soluble acidic inorganic salt that is solid at 25.degree. C. and,
when 50 g thereof is dissolved in 1 L of ion exchanged water, the
solution has a pH at 25.degree. C. of not more than 4, preferably
not more than 3.5, and more preferably not more than 2.0. When the
acidic inorganic salt is solid at room temperature (25.degree. C.),
the acidic inorganic salt can be easily removed by filtration as
necessary. In addition, when the acidic inorganic salt is water
soluble, the acidic inorganic salt can be easily rinsed off with
water as necessary. Note that the pH values in the present
invention are values measured using a pH meter having a glass
electrode in a sample aqueous solution at room temperature
(25.degree. C.).
[0179] Examples that can be used as the acidic inorganic salt
include acidic inorganic salts in which at least a monovalent
hydrogen atom of the inorganic acid that is at least divalent is
neutralized by a base. Examples of the inorganic acid that is at
least divalent include sulfuric acid, sulfurous acid, and the like.
Examples of the base include an alkali metal, ammonia, and the
like.
[0180] More specifically, the acidic inorganic salt is preferably
at least one type of acidic inorganic salt comprising a
hydrogensulfate ion (HSO.sub.4.sup.-) or a hydrogensulfite ion
(HSO.sub.3.sup.-) and a monovalent cation (M.sup.+). Examples of
the monovalent cation (M.sup.+) include alkali metal ions or an
ammonium ion. Particularly, the monovalent cation is preferably at
least one type selected from the group consisting of a sodium ion,
a potassium ion, and an ammonium ion.
[0181] Specific examples of the acidic inorganic salt include
lithium hydrogensulfate, sodium hydrogensulfate, potassium
hydrogensulfate, rubidium hydrogensulfate, cesium hydrogensulfate,
ammonium hydrogensulfate, sodium hydrogensulfite, or hydrates
thereof, and Lewis-acids such as AlCl.sub.3, FeCl.sub.3,
TiCl.sub.4, and BF.sub.3-Et.sub.2O. The pH values of several
aqueous solutions in which 50 g of acidic inorganic acid is
dissolved in 1 L of ion exchanged water are as shown in the tables
below. From the perspective of the technical benefit of reducing
odor, the water soluble acidic inorganic salt having a pH of not
higher than 2.0 is most preferably at least one type of acidic
inorganic salt selected from the group consisting of sodium
hydrogensulfate, potassium hydrogensulfate, and ammonium
hydrogensulfate.
TABLE-US-00001 TABLE 1 Acidic inorganic salt pH (50 g/L) Sodium
hydrogensulfate 1.5 or lower Potassium hydrogensulfate 2.0 or lower
Ammonium hydrogensulfate 1.5 or lower Sodium hydrogensulfite
3.5
[0182] Examples of solid acids that can be used include acidic
solid substances such as activated clay, acidic clay, solid acidic
zirconium dioxide, strong acidic cation exchange resins,
fluorinated sulfonic acid resins, alumina, silica alumina, and
zeolite. Of these, a solid acidic zirconium dioxide is preferable.
Examples of the solid acidic zirconium dioxide include products
prepared at a temperature of at least 300.degree. C. after treating
zirconium hydroxide with sulfuric acid; more specifically, aluminum
hydroxides or hydrous oxides, zirconium hydroxides or hydrous
oxides, a solid acidic zirconium--specifically zirconia
sulfate--prepared by first obtaining a molded product by mixing and
molding a sulfuric acid-containing compound and then baking the
molded product at a temperature at which a tetragonal-structured
zirconia is formed--specifically at a temperature of at least
300.degree. C. A commercially available product of the solid
zirconium dioxide is SZA-60 (manufactured by Japan Energy
Corporation). The strong acidic cation exchange resin is, for
example, a cation exchange resin in which a functional group is a
sulfonic acid group (--SO.sub.3H), and examples of commercially
available products thereof include Amberlyst 15, Amberlyst 16,
Amberlyst 31, and Amberlyst 35 (manufactured by Organo
Corporation). The fluorinated sulfonic acid resin is a
perfluorinated polymer having a suspended sulfonic acid group
bonded to the polymer chain, and specific examples thereof include
the product described in Japanese Examined Patent Application
Publication No. S59-4446 and the like.
[0183] Examples of the acidic platinum catalyst include
chloroplatinic acids, alcohol-modified chloroplatinic acids, olefin
complexes of chloroplatinic acids, ketone complexes of
chloroplatinic acids, vinylsiloxane complexes of chloroplatinic
acids, and platinum tetrachlorides. Of these, chloroplatinic acid
is preferable.
[0184] The acidizing process described above can be performed by
bringing the organopolysiloxane elastomer into contact with the
acidic substance in a desired manner.
[0185] Specifically, the acidizing process can be performed by
means of operations such as adding at least one type of the acidic
substance described above and, optionally, an organic solvent such
as water or alcohol to a reaction system containing the
organopolysiloxane elastomer (for example, in a reaction vessel
such as a flask, a kneading/grinding container, an emulsifier, or
the like), mixing by stirring, kneading, and grinding or repeating
these operations. Alternatively, the process can be more
advantageously performed by first grinding the organopolysiloxane
elastomer or a composition containing the elastomer and an oil
agent in advance, adding at least one type of acidic substance and,
optionally, an organic solvent such as water or alcohol, and
performing an operation such as stirring while heating.
[0186] In particular, it is preferable to add at least one type of
the acidic substance and water to a reaction system containing the
organopolysiloxane elastomer and to then agitate or knead and
pulverize the mixture using a mechanical force while heating. In
addition, this treatment is preferably performed in the presence of
a solvent such as a lower monohydric alcohol. The acid treatment
can be carried out at any temperature and treatment time, and can
be carried out at a temperature from 0 to 200.degree. C. and more
preferably from 50 to 100.degree. C. for a reaction time of from
0.5 to 24 hours and more preferably from about 1 to 10 hours. The
amount of the acidic substance that is used can be appropriately
selected in accordance with the acid strength, the treatment
apparatus, the treatment time, and the treatment temperature.
However, when the acidic substance is one with moderate acid
strength such as sodium hydrogensulfate, potassium hydrogensulfate,
ammonium hydrogensulfate, citric acid, glycolic acid, or phosphoric
acid, the content is preferably in a range from 10 to 500 ppm and
more preferably in a range from 20 to 200 ppm in the
organopolysiloxane elastomer of the present invention. In addition,
when the acidic substance is an acidic substance with higher acid
strength such as hydrochloric acid or sulfuric acid, the content is
preferably in a range from 0.1 to 50 ppm in the organopolysiloxane
elastomer, and when the acidic substance is a substance with weak
acid strength or a solid acid exemplified by activated clay, acidic
clay, solid acidic zirconium dioxide, strong acidic cation exchange
resin, fluorinated sulfonic acid resin, zeolite, or the like, the
content is preferably in a range from 500 to 10,000 ppm in the
organopolysiloxane elastomer.
[0187] In the production method for an organopolysiloxane elastomer
of the present invention, a process of heating and/or decompressing
the composition (stripping process) is preferably included after
the acidizing process. Low-boiling-point components, which are
odor-causing substances, can be removed (stripped) by the heating
and/or decompression described above. In addition, a large amount
of the odor-causing substances can be removed by performing the
acidizing process once again after stripping. At this time, when
the acidic substance remains in the reaction system, it is
unnecessary to newly add an acidic substance, which yields the
advantage that it is sufficient to add only water. That is, the
acidizing process and the stripping process can be respectively
repeated two or more times for the purpose of increasing the degree
of reduction in odor.
[0188] The "low-boiling-point components" removed by the stripping
process include, in addition to carbonyl compounds such as
propionaldehyde, which are thought to be odor-causing substances,
volatile compounds such as the reaction solvent used in the
synthesis and the like of the organopolysiloxane elastomer.
[0189] Note that the stripping process may be performed before the
acidizing process.
[0190] Known reaction conditions may be used in the stripping
method, but stripping under normal pressure or under reduced
pressure is preferable, and stripping is preferably performed at a
temperature of 120.degree. C. or lower. In order to effectively
perform the stripping, the stripping is preferably performed under
reduced pressure or, for example, performed under a nitrogen gas or
similar inert gas stream. A specific example of the
low-boiling-point component removal operation is one in which the
organopolysiloxane elastomer or composition thereof or a
hydrogenated product thereof comprising a low boiling point
component is placed in a flask having a refluxing cooler, a
nitrogen injection port, or the like. While nitrogen gas is
supplied, the internal pressure is reduced and the temperature is
increased, and the pressure and temperature are then kept constant
so as to remove light matter. Here, typically, a pressure reduction
parameter is from 0.1 to 10.0 kPa, a heating temperature is from 50
to 170.degree. C., and a treatment time is from 10 minutes to 24
hours.
[0191] In the present invention, after the acidizing process, a
basic substance may be used to neutralize the organopolysiloxane
elastomer. One type of the basic substance may be used alone, or
two or more types of substances may be used in combination.
Examples of the basic substance include organic bases such as
sodium hydroxide, potassium hydroxide, calcium hydroxide, barium
hydroxide, ammonia water, and sodium hydrogen carbonate; basic
buffers such as trisodium phosphate, tripotassium phosphate,
trisodium citrate, and sodium acetate; and organic bases such as
basic amino acids, amines and pyridines. An amount of the basic
substance is preferably an amount needed to neutralize a reaction
system comprising the organopolysiloxane elastomer but, as
necessary, the amount of the basic substance may be adjusted to an
amount by which weak acidity or weak alkalinity is obtained.
[0192] The organopolysiloxane elastomer of the present invention is
preferably in a particulate form and is more preferably in the form
of solid particles.
[0193] The particulate organopolysiloxane can be simply obtained by
grinding the cured organopolysiloxane elastomer using a mechanical
force, and solid particles of the organopolysiloxane elastomer with
a desired particle size can be obtained by adjusting the grinding
conditions using a publicly known method. Regarding grinding, after
the organopolysiloxane elastomer prior to or following primary
grinding is mixed with an oil agent, the organopolysiloxane
elastomer in a state in which the elastomer is swelled or dispersed
in the oil agent is subjected to primary grinding or finer
secondary grinding using a mechanical force.
[0194] The mechanical means for grinding the organopolysiloxane
elastomer or the composition is not particularly limited, but the
substance is preferably ground by at least one method selected from
the group consisting of shearing, kneading, and a means of passing
the substance through an orifice under pressure.
[0195] On the other hand, it is also possible to obtain an aqueous
dispersion of organopolysiloxane elastomer particles by
emulsifying/dispersing the raw material composition of the
organopolysiloxane elastomer prior to curing in water and then
performing a crosslinking reaction and to obtain dried
organopolysiloxane elastomer particles by removing the water from
the aqueous dispersion.
[0196] The particle size of the organopolysiloxane elastomer
particles can be selected in accordance with the application or
tactile sensation and is not particularly limited, but from the
perspective of the preparation of a composition with the oil agent
described below, the volume average particle size measured by
microscopic observation or using a particle size distribution
measurement device is preferably in a range from 20 to 1000 .mu.m
and more preferably in a range from 25 to 300 .mu.m.
[0197] (Composition Containing an Organopolysiloxane Elastomer)
[0198] The present invention relates to a composition comprising
the organopolysiloxane elastomer described above. The compounded
amount of the organopolysiloxane elastomer in the composition is
not particularly limited but can be set in a range from 1 to 99 wt.
% (mass %), for example, preferably from 5 to 95 wt. % (mass %),
more preferably from 10 to 90 wt. % (mass %), even more preferably
from 20 to 80 wt. % (mass %), and even more preferably from 30 to
70 wt. % (mass %) based on the total weight (mass) of the
composition.
[0199] The composition of the present invention may contain at
least one type of oil agent in addition to the organopolysiloxane
elastomer. The oil agent is not particularly limited, and a solid,
semi-solid, or liquid oil agent may be used. Specific examples of
oil agent include one type or two or more types of oil agent
selected from the group consisting of include silicone oils,
hydrocarbon oils, ester oils, vegetable oils and fats, animal oils
and fats, fatty acids, higher alcohols, triglycerides, artificial
sebums, and fluorine-based oil agents.
[0200] Specific examples of the silicone oil include straight
organopolysiloxanes expressed by the following general formula (7),
cyclic organopolysiloxanes expressed by the general formula (8),
and branched organopolysiloxanes expressed by the general formula
(9).
##STR00027##
[0201] In the formulas (7) to (9) above, R.sup.27 is a hydrogen
atom, hydroxyl group or a group selected from a monovalent
unsubstituted or fluorine substituted alkyl group having from 2 to
30 carbon atoms, an aryl group, an amino substituted alkyl group,
an alkoxy group, and a group expressed by
(CH.sub.3).sub.3SiO[(CH.sub.3).sub.2SiO].sub.uSi(CH.sub.3).sub.2CH.sub.2C-
H.sub.2--. Specific examples thereof include saturated aliphatic
hydrocarbon groups such as ethyl groups, propyl groups, butyl
groups, pentyl groups, hexyl groups, heptyl groups, octyl groups,
decyl groups, and dodecyl groups; unsaturated aliphatic hydrocarbon
groups such as vinyl groups, allyl groups, and hexenyl groups;
saturated cycloaliphatic hydrocarbon groups such as cyclopentyl
groups and cyclohexyl groups; aromatic hydrocarbon groups such as
phenyl groups, tolyl groups, and naphthyl groups; and groups in
which the hydrogen atoms bonded to the carbon atoms of these groups
are substituted partially by an organic group having a halogen
atom, an epoxy group, a carboxyl group, an amino group, a methacryl
group, a mercapto group, or the like or a group substituted by a
trimethylsiloxy group bonded via a divalent hydrocarbon group
and/or a chain polydimethyl siloxane bond. Here, c is an integer
from 0 to 1,000; d is an integer from 0 to 1,000; c+d is an integer
from 1 to 2,000; f and g are each independently 0, 1, 2, or 3; l
and o are each independently an integer from 0 to 8, provided that
3.ltoreq.l+o.ltoreq.8; s is an integer from 1 to 4.
[0202] Examples of silicone oils having the structure described
above include cyclic organopolysiloxanes such as hexamethyl
cyclotrisiloxane (D3), octamethyl cyclotetrasiloxane (D4),
decamethyl cyclopentasiloxane (D5), dodecamethyl-cyclohexasiloxane
(D6), 1,1-diethylhexamethyl cyclotetrasiloxane, phenylheptamethyl
cyclotetrasiloxane, 1,1-diphenylhexamethyl cyclotetrasiloxane,
1,3,5,7-tetravinyltetramethyl cyclotetrasiloxane,
1,3,5,7-tetramethyl cyclotetrasiloxane,
1,3,5,7-tetracyclohexyltetramethyl cyclotetrasiloxane,
tris(3,3,3-trifluoropropyl) trimethylcyclotrisiloxane,
1,3,5,7-tetra(3-methacryloxypropyl) tetramethyl cyclotetrasiloxane,
1,3,5,7-tetra(3-acryloxypropyl) tetramethyl cyclotetrasiloxane,
1,3,5,7-tetra(3-carboxypropyl) tetramethyl cyclotetrasiloxane,
1,3,5,7-tetra(3-vinyloxypropyl) tetramethyl cyclotetrasiloxane,
1,3,5,7-tetra(p-vinylphenyl) tetramethyl cyclotetrasiloxane,
1,3,5,7-tetra[3-(p-vinylphenyl) propyl]tetramethyl
cyclotetrasiloxane,
1,3,5,7-tetra(N-acryloyl-N-methyl-3-aminopropyl) tetramethyl
cyclotetrasiloxane, 1,3,5,7-tetra(N,N-bis(lauroyl)-3-aminopropyl)
tetramethyl cyclotetrasiloxane, and the like. Examples of straight
organopolysiloxanes include dimethylpolysiloxane in which both
molecular terminals are capped with trimethylsiloxy groups
(dimethylsilicone with a low viscosity such as 2 cst or 6 cst to
dimethylsilicone with a high viscosity such as 1,000,000 cst),
organohydrogenpolysiloxane, methylphenylpolysiloxane in which both
molecular terminals are capped with trimethylsiloxy groups, a
copolymer of methylphenylsiloxane and dimethylsiloxane in which
both molecular terminals are capped with trimethylsiloxy groups,
diphenylpolysiloxane in which both molecular terminals are capped
with trimethylsiloxy groups, a copolymer of diphenylsiloxane and
dimethylsiloxane in which both molecular terminals are capped with
trimethylsiloxy groups, trimethylpentaphenyltrisiloxane, phenyl
(trimethylsiloxy) siloxane, methylalkylpolysiloxane in which both
molecular terminals are capped with trimethylsiloxy groups, a
copolymer of methylalkylsiloxane and dimethylpolysiloxane in which
both molecular terminals are capped with trimethylsiloxy groups, a
copolymer of methyl (3,3,3-trifluoropropyl) siloxane and
dimethylsiloxane in which both molecular terminals are capped with
trimethylsiloxy groups,
.alpha.,.omega.-dihydroxypolydimethylsiloxane,
.alpha.,.omega.-diethoxypolydimethylsiloxane,
1,1,1,3,5,5,5-heptamethyl-3-octyltrisiloxane,
1,1,1,3,5,5,5-heptamethyl-3-dodecyltrisiloxane,
1,1,1,3,5,5,5-heptamethyl-3-hexadecyltrisiloxane,
tristrimethylsiloxymethylsilane, tristrimethylsiloxyalkylsilane,
tetrakistrimethylsiloxysilane, tetramethyl-1,3-dihydroxydisiloxane,
octamethyl-1,7-dihydroxytetrasiloxane,
hexamethyl-1,5-diethoxytrisiloxane, hexamethyldisiloxane,
octamethyltrisiloxane, a higher alkoxy-modified silicone, a higher
fatty acid-modified silicone, a carbinol-modified silicone
(hydrocarbyl functional siloxane), long-chain alkyl-modified
silicone, amino-modified silicone, amide-modified silicone,
quaternary ammonium salt-modified silicone, and the like. The
organopolysiloxane elastomer of the present invention is able to
stably maintain various powders dispersed in an oil phase
containing these silicone oils and to stably emulsify/disperse an
aqueous phase in an oil phase containing these silicone oils.
[0203] Examples of the hydrocarbon oil include liquid paraffin,
light liquid isoparaffin, heavy liquid isoparaffin, vaseline,
n-paraffin, isoparaffin, isododecane, isohexadecane,
polyisobutylene, hydrogenated polyisobutylene, polybutene,
ozokerite, ceresin, microcrystalline wax, paraffin wax,
polyethylene wax, polyethylene/polypropylene wax, squalane,
squalene, pristane, polyisoprene, wax, and the like. The
organopolysiloxane elastomer of the present invention is able to
stably maintain various powders dispersed in an oil phase
containing these hydrocarbon oils and to stably emulsify/disperse
an aqueous phase in an oil phase containing these hydrocarbon
oils.
[0204] Examples of the ester oil include hexyldecyl octanoate,
cetyl octanoate, isopropyl myristate, isopropyl palmitate, butyl
stearate, hexyl laurate, myristyl myristate, oleyl oleate, decyl
oleate, octyldodecyl myristate, hexyldecyl dimethyloctanoate, cetyl
lactate, myristyl lactate, diethyl phthalate, dibutyl phthalate,
lanolin acetate, ethylene glycol monostearate, propylene glycol
monostearate, propylene glycol dioleate, glyceryl monostearate,
glyceryl monooleate, glyceryl tri(2-ethylhexanoate),
trimethylolpropane tri(2-ethylhexanoate), ditrimethylolpropane
triethylhexanoate, ditrimethylolpropane isostearate/sebacate,
trimethylolpropane trioctanoate, trimethylolpropane triisostearate,
diisopropyl adipate, diisobutyl adipate, 2-hexyldecyl adipate,
di-2-heptylundecyl adipate, diisostearyl malate, hydrogenated
castor oil monoisostearate, N-alkylglycol monoisostearate,
octyldodecyl isostearate, isopropyl isostearate, isocetyl
isostearate, ethylene glycol di-2-ethylhexanoate, cetyl
2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate,
octyldodecyl gum ester, ethyl oleate, octyldodecyl oleate,
neopentylglycol dicaprate, triethyl citrate, 2-ethylhexyl
succinate, dioctyl succinate, isocetyl stearate, diisopropyl
sebacate, di-2-ethylhexyl sebacate, diethyl sebacate, dioctyl
sebacate, dibutyloctyl sebacate, cetyl palmitate, octyldodecyl
palmitate, octyl palmitate, 2-ethylhexyl palmitate, 2-hexyldecyl
palmitate, 2-heptylundecyl palmitate, cholesteryl
12-hydroxystearate, dipentaerythritol fatty acid ester,
2-hexyldecyl myristate, ethyl laurate, 2-octyldodecylester
N-lauroyl-L-glutamate, di(cholesteryl/behenyl/octyldodecyl)
N-lauroyl-L-glutamate, di(cholesteryl/octyldodecyl)
N-lauroyl-L-glutamate, di(phytosteryl/behenyl/octyldodecyl)
N-lauroyl-L-glutamate, di(phytosteryl/octyldodecyl)
N-lauroyl-L-glutamate, isopropyl N-lauroylsarcosinate, diisostearyl
malate, neopentylglycol dioctanoate, isodecyl neopentanoate,
isotridecyl neopentanoate, isostearyl neopentanoate, isononyl
isononanoate, isotridecyl isononanoate, octyl isononanoate,
isotridecyl isononanoate, diethylpentanediol dineopentanoate,
methylpentanediol dineopentanoate, octyldodecyl neodecanoate,
2-butyl-2-ethyl-1,3-propanediol dioctanoate, pentaerythrityl
tetraoctanoate, pentaerythrityl hydrogenated rosin, pentaerythrityl
triethylhexanoate, dipentaerythrityl
(hydroxystearate/stearate/rosinate), polyglyceryl tetraisostearate,
polyglyceryl-10 nonaisostearate, polyglyceryl-8
deca(erucate/isostearate/ricinoleate), (hexyldecanoic acid/sebacic
acid) diglyceryl oligoester, glycol distearate (ethylene glycol
distearate), diisopropyl dimer dilinoleate, diisostearyl dimer
dilinoleate, di(isostearyl/phytosteryl) dimer dilinoleate,
(phytosteryl/behenyl) dimer dilinoleate,
(phytosteryl/isostearyl/cetyl/stearyl/behenyl) dimer dilinoleate,
dimer dilinoleyl dimer dilinoleate, dimer dilinoleyl diisostearate,
dimer dilinoleyl hydrogenated rosin condensate, dimer dilinoleic
acid hydrogenated castor oil, hydroxyalkyl dimer dilinoleyl ether,
glyceryl triisooctanoate, glyceryl triisostearate, glyceryl
trimyristate, glyceryl triisopalmitate, glyceryl trioctanoate,
glyceryl trioleate, glyceryl diisostearate, glyceryl
tri(caprylate/caprate), glyceryl
tri(caprylate/caprate/myristate/stearate), hydrogenated rosin
triglyceride (hydrogenated ester gum), rosin triglyceride (ester
gum), glyceryl behenate eicosane dioate, glyceryl
di-2-heptylundecanoate, diglyceryl myristate isostearate,
cholesteryl acetate, cholesteryl nonanoate, cholesteryl stearate,
cholesteryl isostearate, cholesteryl oleate, cholesteryl
12-hydroxystearate, cholesteryl ester of macadamia nut oil fatty
acid, phytosteryl ester of macadamia nut oil fatty acid,
phytosteryl isostearate, cholesteryl ester of soft lanolin fatty
acid, cholesteryl ester of hard lanolin fatty acid, cholesteryl
ester of long-chain branched fatty acid, cholesteryl ester of
long-chain .alpha.-hydroxy fatty acid, octyldodecyl ricinoleate,
octyldodecyl ester of lanolin fatty acid, octyldodecyl erucate,
isostearic acid hydrogenated castor oil, ethyl ester of avocado
fatty acid, isopropyl ester of lanolin fatty acid, and the like.
The organopolysiloxane elastomer of the present invention is able
to stably maintain various powders dispersed in an oil phase
containing these ester oils and to stably emulsify/disperse an
aqueous phase in an oil phase containing these ester oils.
[0205] Examples of natural animal or vegetable oils and fats and
semi-synthetic oils and fats include oils and fats such as avocado
oil, linseed oil, almond oil, ibota wax, perilla oil, olive oil,
cacao butter, kapok wax, kaya oil, carnauba wax, liver oil,
candelilla wax, beef tallow, neatsfoot oil, beef bone fat,
hydrogenated beef tallow, apricot kernel oil, spermaceti wax,
hydrogenated oil, wheat germ oil, sesame oil, rice germ oil, rice
bran oil, sugar cane wax, sasanqua oil, safflower oil, shea butter,
Chinese tung oil, cinnamon oil, jojoba wax, olive squalane, shellac
wax, turtle oil, soybean oil, tea seed oil, camellia oil, evening
primrose oil, corn oil, lard, rapeseed oil, Japanese tung oil, rice
bran wax, germ oil, horse fat, persic oil, palm oil, palm kernel
oil, castor oil, hydrogenated castor oil, castor oil fatty acid
methyl ester, sunflower oil, grape oil, bayberry wax, jojoba oil,
hydrogenated jojoba ester, macadamia nut oil, beeswax, mink oil,
cottonseed oil, cotton wax, Japanese wax, Japanese wax kernel oil,
montan wax, coconut oil, hydrogenated coconut oil, tri-coconut oil
fatty acid glyceride, mutton tallow, peanut oil, lanolin, liquid
lanolin, reduced lanolin, lanolin alcohol, hard lanolin, lanolin
acetate, lanolin fatty acid isopropyl ester, POE lanolin alcohol
ether, POE lanolin alcohol acetate, lanolin fatty acid polyethylene
glycol, POE hydrogenated lanolin alcohol ether, egg yolk oil, and
the like. Herein, "POE" means "polyoxyethylene".
[0206] Examples of higher fatty acids include lauric acid, myristic
acid, palmitic acid, stearic acid, behenic acid, undecylenic acid,
oleic acid, linolic acid, linolenic acid, arachidonic acid,
eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), isostearic
acid, 12-hydroxystearic acid, and the like.
[0207] Examples of higher alcohols include lauryl alcohol, myristyl
alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol,
hexadecyl alcohol, oleyl alcohol, isostearyl alcohol,
hexyldodecanol, octyldodecanol, cetostearyl alcohol,
2-decyltetradecinol, cholesterol, sitosterol, phytosterol,
lanosterol, POE cholesterol ether, monostearyl glycerol ether
(batyl alcohol), monooleyl glycerol ether (selachyl alcohol), and
the like.
[0208] Examples of the fluorine-based oil agent include
perfluoropolyether, perfluorodecalin, perfluorooctane, and the
like, and one or two or more types of these oil agents can be used
as necessary.
[0209] The compounded amount of the oil agent in the composition of
the present invention is not particularly limited but can be set in
a range from 0.1 to 95 wt. % (mass %), for example, preferably from
1 to 90 wt. % (mass %), more preferably from 2 to 80 wt. % (mass
%), even more preferably from 3 to 70 wt. % (mass %), and even more
preferably from 5 to 60 wt. % (mass %) based on the total weight
(mass) of the composition.
[0210] The composition of the present invention containing at least
one type of oil agent in addition to the organopolysiloxane
elastomer may be in the form of a paste.
[0211] The organopolysiloxane elastomer compounded in the
composition of the present invention is preferably in a particulate
form. The mixing ratio with the oil agent (weight (mass) ratio) is
arbitrary, but from the perspective of obtaining a paste-like
composition consisting of uniform, fine particles without a foreign
body sensation, the ratio is preferably in a range from 5/95 to
95/5, particularly preferably from 20/80 to 80/20, and most
preferably from 25/75 to 50/50. In particular, when the
organopolysiloxane elastomer can be swelled with an oil agent in an
amount equal to or greater than the weight (mass) of the elastomer
itself, a composition which is swelled using an oil agent in an
amount equal to or greater than the weight of the elastomer
itself--preferably a paste-like composition--can be easily
prepared.
[0212] The composition containing the particulate
organopolysiloxane elastomer and an oil agent can be obtained by
mixing the organopolysiloxane elastomer with an oil agent after
grinding the elastomer using a mechanical force or grinding a
mixture of the organopolysiloxane elastomer and an oil agent using
a mechanical force.
[0213] The composition of the present invention can contain water.
The compounded amount of the water in the composition of the
present invention is not particularly limited but can be set in a
range from 1 to 90 wt. % (mass %), for example, preferably from 5
to 80 wt. % (mass %), more preferably from 10 to 70 wt. % (mass %),
even more preferably from 20 to 60 wt. % (mass %), and even more
preferably from 30 to 50 wt. % (mass %) based on the total weight
(mass) of the composition.
[0214] In particular, since the organopolysiloxane elastomer of the
present invention has a hydrophobic silicone chain and a
hydrophilic sugar alcohol-modified group, the organopolysiloxane
elastomer functions as a surfactant or an emulsifier. That is, by
mixing the organopolysiloxane elastomer of the present invention
and water (or water and a hydrophilic medium), each component can
be uniformly dispersed, so the present invention can be
advantageously used as a hydrous composition.
[0215] The hydrous composition described above is a composition
containing the organopolysiloxane elastomer of the present
invention and water and can be in the form of a hydrous gel
composition or an emulsion composition. The emulsion form is not
particularly limited and can be a water-based-oil-based oil
composition such as an oil-in-water emulsion or a water-in-oil
emulsion; or an arbitrary form of emulsion such as an
oil-in-alcohol (polyol, for example) emulsion or an alcohol(polyol,
for example)-in-oil emulsion. In particular, a water-in-oil
emulsion composition or an alcohol(polyol, for example)-in-oil
emulsion is preferable.
[0216] The average particle size of the emulsion particle formed by
emulsification using the organopolysiloxane elastomer of the
present invention can be measured by a conventional measurement
device using a laser diffraction/scattering method or the like. The
emulsion composition according to the present invention is
preferably a polar solvent-in-oil emulsion but may also be an
oil-in-polar solvent emulsion. In addition, the emulsion
composition of the present invention may be a transparent
micro-emulsion in which the measured average particle size is not
more than 0.1 .mu.m or may be a large particulate white turbid
emulsion in which the average particle size is more than 10.0
.mu.m. Furthermore, the emulsion particles may be micronized for
the purpose of improving the stability and transparency of the
appearance of the emulsion. An emulsion having a particle diameter
from 0.5 to 20 .mu.m can be selected for the purpose of improving
sensation during use and adhesion characteristics to hair and
skin.
[0217] The emulsion and the like described above may be produced by
blending the organopolysiloxane elastomer of the present invention
or composition comprising the same and water by means of a
mechanical force using an apparatus such as a homomixer, a paddle
mixer, a Henschel mixer, a homo-disper, a colloid mill, a propeller
stirrer, a homogenizer, an in-line continuous emulsifier, an
ultrasonic emulsifier, or a vacuum kneader. In addition, in the
production method of the emulsion composition, the content and
compounding ratio of the water is as described above and is
preferably appropriately selected within a range from 1 to 99 wt. %
(mass %) of the entire emulsion composition in accordance with the
form and use of the emulsion.
[0218] The composition of the present invention can contain at
least one type of alcohol. The alcohol preferably has water
miscibility and more preferably is a lower alcohol or a polyhydric
alcohol.
[0219] Examples of lower alcohols include ethanol, isopropanol,
n-propanol, t-butanol, s-butanol, and the like. Examples of
polyhydric alcohols include divalent alcohols such as 1,3-butylene
glycol, 1,2-butylene glycol, propylene glycol, trimethylene glycol,
tetramethylene glycol, 2,3-butylene glycol, pentamethylene glycol,
2-buten-1,4-diol, dibutylene glycol, pentyl glycol, hexylene
glycol, octylene glycol, and the like; trivalent alcohols such as
glycerol, trimethylol propane, 1,2,6-hexanetriol, and the like;
polyhydric alcohols having 4 or more valences such as
pentaerythritol, xylitol, and the like; and sugar alcohols such as
sorbitol, mannitol, maltitol, maltotriose, sucrose, erythritol,
glucose, fructose, a starch-decomposed product, maltose, xylitose,
starch-decomposed sugar-reduced alcohol, and the like. Furthermore,
examples other than these low-molecule polyhydric alcohols include
polyhydric alcohol polymers such as diethylene glycol, dipropylene
glycol, triethylene glycol, polypropylene glycol, tetraethylene
glycol, diglycerol, polyethylene glycol, triglycerol,
tetraglycerol, polyglycerol, and the like.
[0220] The compounded amount of the alcohol in the composition of
the present invention is not particularly limited but can be set in
a range from 0.1 to 50 wt. % (mass %), for example, preferably from
1 to 40 wt. % (mass %), more preferably from 2 to 30 wt. % (mass
%), even more preferably from 3 to 20 wt. % (mass %), and even more
preferably from 4 to 10 wt. % (mass %) based on the total weight
(mass) of the composition.
[0221] (Carbonyl Value Measurement Method)
[0222] The degree of odor of the organopolysiloxane elastomer of
the present invention or the composition containing the same can be
determined by the carbonyl value measured from the absorbance of a
reaction solution obtained by reacting the organopolysiloxane
elastomer or the composition containing the same and
2,4-dinitrophenylhydrazine (2,4-DNPH) in a reaction medium
containing at least one type of monovalent lower alcohol having
from 1 to 4 carbon atoms. Furthermore, in addition to a compound
having a carbonyl group such as an aldehyde or a ketone, the
"carbonyl compound" also includes a potential carbonyl compound
such as an acetal, propenyl ether, or a similar compound that does
not comprise a carbonyl group but generates a carbonyl group by
decomposing under certain conditions.
[0223] Accordingly, in order to assay the degree of odor of the
organopolysiloxane elastomer of the present invention or the
composition containing the same, it is possible to measure the
carbonyl value of the organopolysiloxane elastomer or the
composition containing the same from the absorbance of a reaction
solution obtained by reacting the organopolysiloxane elastomer
containing a carbonyl compound or the composition containing the
same and 2,4-dinitrophenylhydrazine in a reaction medium containing
at least one type of monovalent lower alcohol having from 1 to 4
carbon atoms.
[0224] The carbonyl value measured with the method described above
for the organopolysiloxane elastomer of the present invention,
which is a sugar alcohol-modified silicone, or the composition
containing the same is preferably not more than 4.0 Abs/g, more
preferably not more than 3.0 Abs/g, and even more preferably not
more than 2.0 Abs/g.
[0225] In the measurement method described above, carbonyl value of
an organopolysiloxane elastomer or a composition comprising the
same is determined based on the absorbance of the reaction solution
obtained by reacting 2,4-DNPH and a carbonyl compound in the
organopolysiloxane elastomer or the composition comprising the
same, and from this carbonyl value, it is possible to measure the
total amount of carbonyl (calculated on a propanal basis) in the
organopolysiloxane elastomer or in the composition by using a
pre-plotted calibration curve.
[0226] The "carbonyl value" is the carbonyl content index value,
and is a value obtained by converting the absorbance (absorbance at
430 nm or 460 nm) of the reaction solution, obtained by reacting
2,4-DNPH with the sample, to per 1 g of sample.
[0227] Measurement of the carbonyl value uses the property of
hydrazone, produced by reacting a carbonyl and 2,4-DNPH in the
presence of an acid, that the hydrazone becomes quinoid ions in a
base and gives color. The carbonyl value is determined based on the
absorbance, which indicates the degree of coloring at 430 nm (a
maximum wavelength attributable to saturated carbonyl exists in the
vicinity thereof) and at 460 nm (a maximum wavelength attributable
to unsaturated carbonyl exists in the vicinity thereof).
[0228] The "total amount of carbonyl" is the total amount of
carbonyl compound for an organopolysiloxane elastomer or a
composition comprising the same. The concentration of carbonyl
compounds (total amount of carbonyl) of various samples (an
organopolysiloxane elastomer or a composition comprising the same)
can be measured by obtaining a calibration curve by measuring
carbonyl values of standard samples having known concentrations of
the carbonyl compound (concentration of propionaldehyde).
[0229] In the measurement method described above, at least a
monovalent lower alcohol having from 1 to 4 carbon atoms is used as
the reaction solvent in the reaction between a carbonyl compound
and 2,4-DNPH, but it is preferable to use water at the same
time.
[0230] By using water together with a monovalent lower alcohol
having from 1 to 4 carbon atoms as the reaction solvent, it is
possible to reliably determine the carbonyl value with high
precision, even for a sample containing an aldehyde condensation
product (potential carbonyl compound) such as an acetal. Thus, it
is possible to quantitate the total amount of carbonyls, while
taking into consideration carbonyl compounds attributable to these
odor-causing substances. Although the reason is unclear, it is
inferred that, because water is present in the reaction system, an
aldehyde condensation product is decomposed, and the reaction with
2,4-DNPH is reliably performed. In the reaction solvent comprising
a monovalent lower alcohol having from 1 to 4 carbon atoms and
water, the mixing ratio (mass ratio) of the monovalent lower
alcohol having from 1 to 4 carbon atoms to water is preferably from
99.9:0.1 to 50:50, and more preferably from 99:1 to 75:25.
[0231] In the measurement method described above, "reaction
solvent" indicates a solvent that is present in the reaction system
containing 2,4-DNPH and a carbonyl compound in a sample. A reaction
solvent is formed by using, in addition to (a) a solvent used to
prepare a sample solution, (b) a solvent used to prepare the added
acid solution, (c) a solvent used to prepare a solution of
2,4-DNPH, and the like.
[0232] Each of (a) an alcohol that forms a sample solution, (b) an
alcohol that forms an acid solution, and (c) an alcohol that forms
a 2,4-DNPH solution need not be a monovalent lower alcohol having
from 1 to 4 carbon atoms, provided that the alcohol in the reaction
solvent resulting from mixture thereof contains a monovalent lower
alcohol having from 1 to 4 carbon atoms.
[0233] In the measurement method described above, it is preferable
to use an alcohol as the solvent (hereinafter, also referred to as
"diluent solvent") added to make the volume of a reaction solution
to be a prescribed amount when measuring the absorbance of a
reaction solution, and it is preferable to use a monovalent lower
alcohol having from 1 to 4 carbon atoms. Furthermore, all of the
diluent solvent need not be an alcohol. Water and/or an organic
solvent (organic solvent not having a carbonyl group in its
structure, and having low toxicity) can be used as a part of the
diluent solvent.
[0234] The monovalent lower alcohol having from 1 to 4 carbon atoms
is preferably a saturated alcohol. Examples thereof include
methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol,
and sec-butanol. Of these, n-butanol is preferable. As the
monovalent lower alcohol having from 1 to 4 carbon atoms, one type
can be used independently, or two or more types can be mixed and
used.
[0235] These alcohols lack toxicity (toxicity such as the toxicity
that benzene has), and the alcohols are capable of dissolving
various substances having different polarities and molecular
weights. Consequently, by using these alcohols as the reaction
solvent and diluent solvent, it is possible to safely and easily
perform each operation for determining the carbonyl value.
[0236] As a monovalent lower alcohol having from 1 to 4 carbon
atoms, it is preferable to use a monovalent lower alcohol having a
total aldehyde/ketone content of not more than 3 ppm, preferably
not more than 2 ppm, and more preferably not more than 1 ppm
(hereinafter, also referred to as "ultrapure alcohol"). When the
total aldehyde/ketone content exceeds 3 ppm, the baseline increases
when measuring the absorbance for the resulting reaction solution,
and it may not be possible to obtain proper (highly precise) index
values due to the absorbance measured for a reaction solution
containing a sample with a low carbonyl content being smaller than
the absorbance measured for a solution for a blank test (solution
not containing the sample). By using an ultrapure alcohol having a
total aldehyde/ketone content of not more than 3 ppm as a reaction
solvent, it is possible to properly and easily determine the
carbonyl value for a sample with a low carbonyl content (for
example, a carbonyl value of less than 3).
[0237] As a method of preparing (refining) an ultrapure alcohol, a
method that distills an alcohol under normal pressure or under
reduced pressure after adding proper quantities of 2,4-DNPH and an
acid lacking oxidative action (e.g., hydrochloric acid or
trichloroacetic acid) to the alcohol to be refined and heating and
stirring this system over several hours, can be used. Furthermore,
it is preferable to perform these refining treatments within 24
hours before measuring the absorbance of the reaction solution.
[0238] Additionally, as the ultrapure alcohol, it is preferable to
use a commercially available highly pure reagent that has been
refined so that a total amount of aldehydes and ketones is 3 ppm or
less. Examples of commercially available highly pure reagents that
can be used as an ultrapure alcohol include ethanol (99.8%)
Infinity Pure; ethanol (99.8%) for precise analysis; ethanol
(99.5%) for high-performance liquid chromatography; ethanol (99.5%)
for spectrometry; 2-propanol (99.9%) Infinity Pure, 2-propanol
(99.9%) for precise analysis; 2-propanol (99.5%) for
high-performance liquid chromatography; 2-propanol (99.5%) for
spectrometry; 1-propanol (99.8%) Infinity Pure, 1-propanol (99.5%)
for high-performance liquid chromatography; methanol (99.8%)
Infinity Pure, methanol (99.8%) for precise analysis; methanol
(99.5%) for high-performance liquid chromatography; methanol
(99.5%) for spectrometry, n-butyl alcohol for high-performance
liquid chromatography; n-butyl alcohol for spectrometry (all
manufactured by Wako Pure Chemical Industries, Ltd.), and the
like.
[0239] Furthermore, even for such highly pure reagents, the total
amount of aldehydes and ketones increases over time, and sometimes
exceeds 3 ppm. In addition, the total amount of aldehydes and
ketones exceeds 3 ppm in a relatively short time period after
opening (e.g. within 24 hours). Therefore, from the perspective of
satisfying the essential requirement for ultrapure alcohols (that
is, the total aldehyde/ketone content is not more than 3 ppm), the
following commercially available highly pure reagents are
preferable:
(a) a reagent produced within 6 months before use, and (b) a
reagent opened within 24 hours before use.
[0240] In the measurement method described above, the solvent used
as the reaction solvent need not be composed solely of a monovalent
lower alcohol having from 1 to 4 carbon atoms, or a mixed solvent
of water and a monovalent lower alcohol having from 1 to 4 carbon
atoms. A low toxicity organic solvent also may be used as a part of
the reaction solvent as long as it does not have a carbonyl group
in the structure thereof. However, when an organic solvent other
than a monovalent lower alcohol having from 1 to 4 carbon atoms is
used as a part of the reaction solvent, the total amount of
aldehydes and ketones contained in the reaction solvent (total
excluding water), which is formed by mixing the organic solvent
(part) and a monovalent lower alcohol having from 1 to 4 carbon
atoms (remaining part), is preferably not more than 3 ppm.
[0241] In the measurement method described above, a basic reaction
solution (the reaction solution for absorbance measurement) can be
prepared by adding an acid and 2,4-DNPH to a sample solution
prepared by uniformly dispersing a sample in a solvent, reacting
the carbonyl compound in the sample and 2,4-DNPH by heat treating
this system, adding an alkali in the system after cooling, and then
adjusting the volume of to a prescribed volume with a diluent
solvent. Here, it is preferable to use a volumetric flask with a
volume of 10 to 100 mL as the container for preparing a basic
reaction solution.
[0242] (1) Sample Solution
[0243] The solvent used to prepare the sample solution also
constitutes the reaction solvent as is, so such a solvent is
preferably a mixed solvent of an ultrapure alcohol and water. The
mass of the sample solution (sample and solvent) used to measure
absorbance is normally about 2 to 6 g, and preferably about 5 g.
The mass of the sample contained in a sample solution differs
according to the carbonyl content of the sample (i.e., the carbonyl
value) and the prepared quantity of reaction solution for
absorbance measurement (i.e., the volume of the used volumetric
flask). However, when, for example, a 50 mL volumetric flask is
used to prepare a reaction solution (i.e., the reaction solution
for absorbance measurement), the mass of the sample contained in a
sample solution is preferably from 5 to 250 mg, and more preferably
from 10 to 150 mg.
[0244] (2) Acids
[0245] Examples of acids added to the sample solution include
mineral acids such as dilute sulfuric acid, hydrochloric acid,
dilute nitric acid, phosphoric acid, and the like; organic acids
such as trichloroacetic acid, trifluoroacetic acid, formic acid,
acetic acid, sulfonic acid, phenolic acid, and the like; and Lewis
acids such as AlCl.sub.3, FeCl.sub.3, TiCl.sub.4, and the like; and
the like. These acids can be used alone or in combinations of two
or more. Of these, from the standpoint of accurately quantitating
the total amount of carbonyl in a highly refined organopolysiloxane
elastomer or a composition comprising the same, trichloroacetic
acid, dilute sulfuric acid (particularly, the dilute sulfuric acid
with a concentration of 20% or less), and hydrochloric acid
(particularly, the hydrochloric acid with a concentration of 37% or
less) are preferable. In addition, the acid used in the measurement
method described above is preferably an acid with the highest
purity (reagent-grade or higher purity).
[0246] These acids may be added as is to a sample solution.
However, from the perspective of performing accurate measurement or
the like, it is preferable to add the acids in a solution state
obtained by dissolving in an appropriate solvent. Furthermore, the
solvent used to prepare an acid solution also constitutes the
reaction solvent as is, thus, as such the solvent, it is preferable
to use a monovalent lower alcohol having from 1 to 4 carbon atoms
or a mixed solvent of monovalent lower alcohol having from 1 to 4
carbon atoms and water. When preparing a reaction solution (a
reaction solution that contains from 5 to 250 mg of sample) in a 50
mL volumetric flask, the added amount of acid is preferably from
0.03 to 5.0 g.
[0247] (3) 2,4-DNPH
[0248] The 2,4-DNPH added to the sample solutions is preferably a
2,4-DNPH having a purity of at least a reagent-grade and containing
an equal amount of water. Also, the purity can be further raised by
recrystallization or a similar refining operation. 2,4-DNPH can be
added as is to a sample solution. However, from the standpoint of
performing an accurate measurement, it is preferable to add the
2,4-DNPH in a solution state obtained by dissolving in an
appropriate solvent. Furthermore, the solvent used to prepare the
2,4-DNPH solution also constitutes the reaction solvent as is.
Thus, as such the solvent, it is preferable to use a monovalent
lower alcohol having from 1 to 4 carbon atoms, or a mixed solvent
of water and a monovalent lower alcohol having from 1 to 4 carbon
atoms. When preparing a reaction solution (reaction solution that
contains from 5 to 250 mg of sample) in a 50 mL volumetric flask,
it is preferable to add 0.5 to 100 mg of 2,4-DNPH.
[0249] (4) Heat Treatment
[0250] A condition for the heat treatment of a mixed solution
containing a sample, acid, and 2,4-DNPH is 20 to 180 minutes at 30
to 120.degree. C. (however, the temperature is lower than the
boiling point of the reaction solvent). At a treatment temperature
below 30.degree. C., it takes a long time to react the 2,4-DNPH and
the carbonyl compound in a sample, which is inefficient. On the
other hand, when heating at a temperature above 120.degree. C.,
there is a risk that the generated hydrazone will decompose. When
the treatment time is less than 20 minutes, it becomes difficult to
complete the reaction with 2,4-DNPH. On the other hand, if the
treatment time exceeds 180 minutes, there is a risk that the
generated hydrazone will decompose.
[0251] (5) Alkali
[0252] It is preferable to use an inorganic strong base such as
potassium hydroxide, sodium hydroxide, and the like as the alkali
added to the reaction solution resulting from the reaction between
the 2,4-DNPH and carbonyl compound in a sample. These alkalis can
be added as is to a sample solution. However, from the perspective
of performing accurate measurement or the like, it is preferable to
add these alkalis in a solution state obtained by dissolving in an
appropriate solvent. As such solvents, one or two or more solvents
can be selected from among solvents that can dissolve an alkali, do
not have a carbonyl group in the structure thereof, are compatible
with the solvent used as the reaction solvent, and that have low
toxicity. Specific examples thereof include monovalent saturated
lower alcohols such as methanol, ethanol, 2-propanol, 1-propanol,
1-butanol, 2-butanol, and the like, or mixed solvents prepared by
mixing a proper quantity of water and/or other organic solvent (the
organic solvent without a carbonyl group in their structure and
having low toxicity) in these solvents. It is preferable to use an
ultrapure alcohol or a mixed solvent of water and ultrapure
alcohol. When a reaction solution (reaction solution that contains
from 5 to 250 mg of sample) is prepared in a 50 mL volumetric
flask, the added amount of alkali is preferably from 0.05 to 5.0
g.
[0253] (6) Diluent Solvent
[0254] The reaction solution to which alkali was added is adjusted
to a specific volume (for example, 50 mL) with a diluent solvent
having an alcohol as a main constituent. The alcohol forming the
diluent solvent is preferably an ultrapure alcohol.
[0255] (7) Specific Preparation Method
[0256] An example of a method of preparing a reaction solution for
absorbance measurement is as follows. In a 50 mL volumetric flask,
5 g of a sample solution is placed, prepared by uniformly
dispersing from 5 to 250 mg of a sample in a mixed solvent of water
and a monovalent lower alcohol having from 1 to 4 carbon atoms.
Next, a solution prepared by dissolving from 0.03 to 5.0 g of acid
in a monovalent lower alcohol having from 1 to 4 carbon atoms and a
solution prepared by dissolving from 0.5 to 500 mg of 2,4-DNPH in a
monovalent lower alcohol having from 1 to 4 carbon atoms are added
to the flask. This solution is then mixed well and homogenized, and
heat treatment is performed for 20 to 180 minutes at 30 to
120.degree. C., thereby reacting the 2,4-DNPH and the carbonyl
compound in the sample, while the volumetric flask is capped. After
this mixture is cooled to room temperature, a solution prepared by
dissolving from 0.05 to 5.0 g of an alkali in an alcohol is added.
A diluent solvent composed of an alcohol is then added, mixed well,
and homogenized to adjust the volume of the mixture to 50 mL.
[0257] In the measurement method described above, the absorbance at
430 nm or 460 nm is measured for the basic reaction solution
obtained as described above. Here, when the carbonyl compound
contained in a sample is estimated to be mainly a saturated
carbonyl compound, the absorbance at 430 nm is measured for the
reaction solution, and when the carbonyl compound contained in a
sample is estimated to be mainly an unsaturated carbonyl compound,
the absorbance at 460 nm is measured for the reaction solution.
When absorbance is measured, it is preferable that the absorbance
cell that contains the reaction solution is made of quartz. Also,
the length (thickness) of the liquid layer specified by the
absorption cell is preferably 1 cm.
[0258] It is preferable to measure the absorbance within 10 to 20
minutes after the addition of an alkali to the reaction solution
resulting from the reaction of the 2,4-DNPH and the carbonyl
compound in a sample. Absorbance measured before 10 minutes after
the addition of an alkali sometimes lacks stability. Also, more
than 20 minutes after the addition of an alkali, the absorbance
tends to drop as a result of the discoloration of the reaction
solution. Based on experience with various samples, if the
absorbance is measured 15 minutes after the addition of an alkali,
the value with best reproducibility is obtained.
[0259] In the measurement method described above, the carbonyl
value of a sample (an organopolysiloxane elastomer or a composition
comprising the same) is determined based on the absorbance measured
as described above. It is possible to measure the total amount of
carbonyl in the sample, by using a premeasured calibration curve
based on this carbonyl value. Here, the calibration curve is
obtained by measuring, according to the method (carbonyl value
measurement method) described above, the carbonyl values of a
plurality of standard samples whose total amount of carbonyl
(propionaldehyde concentration) is known.
[0260] For example, a calibration curve is obtained by measuring
the carbonyl values of standard samples, for which total amounts of
carbonyl (propionaldehyde concentrations) are known, by a method
that determines the carbonyl value (CV) by substituting the
absorbance (A.sub.1) and the absorbance (A.sub.2), which are
measured by the following processes (1) to (9), into the formula
CV=(A.sub.1-A.sub.2)/B (where B is the mass (g) of the sample
contained in 5.000 g of sample solution). The same method as
aforementioned, which was adopted to obtain this calibration curve,
is used to measure the carbonyl value of a sample (an
organopolysiloxane elastomer or a composition comprising the same)
for which the total amount of carbonyl is unknown. Based on this
carbonyl value and the calibration curve, it is possible to measure
the total amount of carbonyl in the sample. Furthermore, it is
preferable that the solvent described below for use in the
following processes (1) and (9) contains an ultrapure alcohol and
water, and that the solvent described below for use in the
following process (7) contains an ultrapure alcohol.
[0261] [Processes]
(1) Process of preparing a sample solution by uniformly dispersing
a sample in a solvent (2) Process of adding 3 mL of an alcohol
solution of 4.3% (wt/vol) trichloroacetic acid to 5.000 g of the
sample solution and homogenizing by mixing well (3) Process of
adding 5 mL of an alcohol solution of 2,4-DNPH ([0.025% (wt/vol)]
to the mixed solution obtained in the aforementioned process (2)
and homogenizing by mixing well (4) Process that reacts the
carbonyl compound in a sample and 2,4-DNPH by heating the mixed
solution obtained in the aforementioned process (3) for 30 minutes
at 60.degree. C. (5) Process that lets stand the reaction solution
obtained in the aforementioned process (4) for 30 to 70 minutes at
room temperature (6) Process of adding 10 mL of an alcohol solution
of potassium hydroxide [4.0% (wt/vol)] to the reaction solution
after being left to stand in the aforementioned process (5) and
homogenizing by mixing well (7) Process of preparing a reaction
solution with a total volume of 50 mL by adding a solvent to the
reaction solution and homogenizing by mixing well, 5 to 10 minutes
after the aforementioned process (6) (8) Process that measures the
absorbance (A.sub.1) at 430 nm or 460 nm, of the reaction solution
obtained in the aforementioned process (7), 10 to 20 minutes after
the aforementioned process (6) (9) Process that, as a blank
measurement, measures the absorbance (A.sub.2) at 430 nm or 460 nm
of a solution obtained by using 5.000 g of solvent instead of using
the sample solution and performing the same operations as those in
the aforementioned processes (2) to (7)
[0262] Furthermore, either the calibration curve measurements
(measurements of carbonyl value of standard samples) or the
measurements of carbonyl values of unknown samples can be performed
before the other measurements.
[0263] Next, each process will be described below. Furthermore, the
processes (2) to (7) for the preparation of the reaction solution
are normally performed using a 50 mL volumetric flask.
[0264] Process (1) is a process of preparing a sample solution by
uniformly dispersing a sample in a solvent containing a monovalent
lower alcohol (and preferably, water) having from 1 to 4 carbon
atoms. The proportion of the sample in a sample solution is
modified in accordance with the carbonyl value estimated for the
sample. For example, the following settings are preferable: if the
carbonyl value is estimated to be less than 6 in the sample, from 2
to 3 wt. % (mass %) (from 100 to 150 mg per 5.000 g of sample
solution); if the carbonyl value is estimated to be in a range from
6 to 15 in the sample, from 0.8 to 2 wt. % (mass %) (from 40 to 100
mg per 5.000 g of sample solution); if the carbonyl value is
estimated to be in a range from 15 to 30 in the sample, from 0.4 to
0.8 wt. % (mass %) (from 20 to 40 mg per 5.000 g of sample
solution); if the carbonyl value is estimated to be in a range from
30 to 60 in the sample, from 0.2 to 0.4 wt. % (mass %) (from 10 to
20 mg per 5.000 g of sample solution); and if the carbonyl value is
estimated to be greater than 60 in the sample, less than 0.2 wt. %
(mass %) (less than 10 mg per 5.000 g of sample solution).
[0265] Additionally, when preparing a sample solution, it is
preferable to dilute the sample stepwise. For example, as a method
of preparing 5.000 g of a 2 wt. % (mass %) sample solution, 25.00 g
of an 8 wt. % (mass %) dispersion is first prepared by uniformly
dispersing 2.00 g of a sample in 21.00 g of a monovalent lower
alcohol having from 1 to 4 carbon atoms and 2.00 g of water. Next,
1.250 g of the 8 wt. % (mass %) dispersion and 3.750 g of a
monovalent lower alcohol having from 1 to 4 carbon atoms are
accurately added to a 50 mL volumetric flask and mixed well to
dilute the solution four-fold.
[0266] Process (2) is a process of adding 3 mL of an alcohol
solution of 4.3% (wt/vol) of trichloroacetic acid to 5.000 g
(sample: 0.100 g) of the 2 wt. % (mass %) sample obtained in the
aforementioned process (1) using a volumetric pipette or the like
and homogenizing the solution by mixing well. The solvent (a
monovalent lower alcohol having from 1 to 4 carbon atoms) of this
alcohol solution is preferably an ultrapure alcohol. It is
preferable to prepare the alcohol solution of trichloroacetic acid
by opening a bottle containing 100 mL of ultrapure alcohol,
directly adding 4.3 g of trichloroacetic acid to this bottle,
covering the bottle, and then shaking the bottle to uniformly mix
the contents in the bottle. Also, alcohol solution of
trichloroacetic acid is preferably prepared within 24 hours before
measuring the absorbance of the reaction solution.
[0267] Process (3) is a process of adding 5 mL of an alcohol
solution [0.025% (wt/vol)] of 2,4-DNPH to the mixed solution
obtained in the aforementioned process (2) using a volumetric
pipette or the like and homogenizing the solution by mixing well.
The solvent (a monovalent lower alcohol having from 1 to 4 carbon
atoms) of this alcohol solution of 2,4-DNPH is preferably an
ultrapure alcohol. The alcohol solution of 2,4-DNPH is preferably
prepared by opening a bottle containing 100 mL of ultrapure
alcohol, directly adding 50 mg of 2,4-DNPH (reagent-grade product
containing an equal amount of water) to this bottle, covering the
bottle, and then putting the bottle into an ultrasonic bath for
about 5 minutes to completely dissolve the 2,4-DNPH in the bottle.
In addition, the alcohol solution of 2,4-DNPH is preferably
prepared within 24 hours before measuring the absorbance of the
reaction solution. It is preferable to add more water to hydrolyze
the precursors of the carbonyl compound of acetal and the like
present in the sample, to detect the precursors as carbonyl
compounds.
[0268] In process (4), the mixed solution obtained in the
aforementioned process (3) is heated for 30 minutes at 60.degree.
C. to react the 2,4-DNPH and the carbonyls in the sample, thereby
yielding a reaction solution containing hydrazone.
[0269] In process (5), the reaction solution obtained in the
process (4) is cooled by letting the reaction solution stand for 30
to 70 minutes at room temperature.
[0270] In process (6), 10 mL of alcohol solution of potassium
hydroxide (4.0% (wt/vol)) was added and mixed to the reaction
solution after letting it stand, using a volumetric pipette or the
like. As a result, the reaction solution exhibits basicity, and the
generated hydrazone becomes quinoid ions and gives color. The
solvent (a monovalent lower alcohol having from 1 to 4 carbon
atoms) of this alcohol solution of potassium hydroxide is
preferably an ultrapure alcohol. The alcohol solution of potassium
hydroxide is preferably prepared by opening a bottle containing 100
mL of ultrapure alcohol, directly adding 4.0 g of potassium
hydroxide (pellet shaped reagent-grade product) to this bottle, and
covering the bottle, and after shaking until the pellets disappear,
this bottle is placed in an ultrasonic bath for about 5 to 10
minutes, to completely dissolve the potassium hydroxide in the
bottle. Also, it is preferable to prepare the alcohol solution of
potassium hydroxide within 24 hours before measuring the absorbance
of the reaction solution.
[0271] Process (7) is a process of preparing a reaction solution
(basic reaction solution) with a total volume of 50 mL by adding a
diluent solvent consisting of a monovalent lower alcohol having
from 1 to 4 carbon atoms (preferably, an ultrapure alcohol) to the
reaction solution and homogenizing the solution by mixing well, 5
to 10 minutes after the aforementioned process (6).
[0272] In process (8), for the reaction solution obtained in the
aforementioned process (7), the absorbance (A.sub.1) is measured at
430 nm (when the carbonyl in the sample is estimated to be mainly a
saturated carbonyl) or at 460 nm (when the carbonyl in the sample
is estimated to be mainly an unsaturated carbonyl). The absorbance
must be measured 10 to 20 minutes after addition of the alcohol
solution of potassium hydroxide of the aforementioned process (6),
and it is most preferable to measure the absorbance 15 minutes
after the addition of the alcohol solution of potassium
hydroxide.
[0273] Process (9) is a process of measuring the absorption
(A.sub.2) at 430 nm and 460 nm for a solution obtained by
performing the same operations as in the aforementioned processes
(2) to (7) (addition of an alcohol solution of trichloroacetic
acid; addition of an alcohol solution of 2,4-DNPH; heating and
cooling of the obtained mixed solution; addition of an alcohol
solution of potassium hydroxide; and addition of a diluent solvent
consisting of a monovalent lower alcohol having from 1 to 4 carbon
atoms) using 5.000 g of a monovalent lower alcohol having from 1 to
4 carbon atoms (preferably, a mixed solution with monovalent lower
alcohol water having from 1 to 4 carbon atoms) instead of the
sample solution described above as a blank test.
[0274] It is possible to determine the carbonyl value (CV) by
substituting the absorbance (A.sub.1) obtained by the
aforementioned processes (1) to (8) and the absorbance (A.sub.2)
obtained by the aforementioned process (9), respectively, into the
formula: CV=(A.sub.1-A.sub.2)/B.) In the above formula, B is the
mass (g) of the sample contained in 5.000 g of sample solution, and
in a 2 wt. % (mass %) sample solution, B is 0.1
(5.000.times.0.02).
[0275] The organopolysiloxane elastomer of the present invention or
the composition containing the same has, in essence, a small
tendency to deteriorate due to oxidation caused by the oxygen in
the air. Thus, it is not necessary to add a phenol, a hydroquinone,
a benzoquinone, an aromatic amine, a vitamin, or similar
antioxidant in order to prevent oxidation deterioration; or take
steps to increase oxidation stability. However, adding such an
antioxidant, for example, BHT(2,6-di-t-butyl-p-cresol), vitamin C,
vitamin E, or the like, will result in a further increase in
stability. In this case, an added amount of the antioxidant that is
used is in a range (by weight (mass)) from 10 to 1,000 ppm, and
preferably from 50 to 500 ppm, of the organopolysiloxane
elastomer.
[0276] (Raw Material for External Use Preparation and Raw Material
for Cosmetic Composition)
[0277] The organopolysiloxane elastomer of the present invention or
the composition comprising the same can be advantageously used as a
raw material for an external use preparation and a raw material for
a cosmetic composition for use on a human body. In particular, a
paste-like composition containing the particulate
organopolysiloxane elastomer of the present invention and an oil
agent can be used directly as a raw material for an external use
preparation and a raw material for a cosmetic composition.
[0278] A proportion of the organopolysiloxane elastomer or the
composition comprising the same in the raw material for an external
use preparation and the raw material for a cosmetic composition is
preferably from 50 to 100 wt. % (mass %), more preferably from 80
to 100 wt. % (mass %), and even more preferably from 90 to 100 wt.
% (mass %) based on the total weight (mass) of the raw material. A
proportion of the raw material compounded in the external use
preparation or the cosmetic composition is not particularly limited
but, for example, can be from 0.1 to 90 wt. % (mass %), and is
preferably from 1 to 80 wt. % (mass %), more preferably from 2 to
70 wt. % (mass %), and even more preferably from 5 to 50 wt. %
(mass %) based on the total weight (mass) of the external use
preparation or the cosmetic composition.
[0279] Examples of the raw material for an external use preparation
and the raw material for a cosmetic composition of the present
invention include a thickening agent, a gelling agent, a tactile
sensation improver, a surfactant, an emulsifier, and a powder
dispersion stabilizer.
[0280] External Use Preparation and Cosmetic Composition
[0281] The organopolysiloxane elastomer of the present invention or
the composition comprising the same, or the raw material for use in
an external use preparation and a cosmetic composition comprising
the organopolysiloxane elastomer or the composition comprising the
same, can be advantageously compounded in an external use
preparation or a cosmetic composition and can constitute the
external use preparation or the cosmetic composition of the present
invention. The external use preparation or the cosmetic composition
of the present invention is preferably stored in a container formed
from a thermoplastic material or a container formed from a
non-thermoplastic material. In addition, at least one compartment
can be defined in the container so as to constitute a cosmetic
product unit or external use preparation unit consisting of the
container and the cosmetic composition or the external use
preparation according to the present invention. The external use
preparation or the cosmetic composition of the present invention
can be primarily applied to and used on keratinous substances such
as skin or hair as a non-therapeutic beauty technique for the
purpose of doing applying cosmetics (makeup) or performing care
(that is, dry skin care).
[0282] The external use preparation is a product to be applied to
human skin, nails, hair, and the like and, for example, medicament
active components can be compounded therein and used in the
treatment of various disorders. The cosmetic composition is also a
product to be applied to human skin, nails, hair, and the like, and
is used for beauty purposes. The external use preparation or the
cosmetic composition is preferably a skin external use preparation
or a skin cosmetic composition, skin care cosmetic composition, sun
care cosmetic composition, antiperspirant, foundation, color
cosmetic, or a hair external use preparation or a hair cosmetic
composition product.
[0283] The skin external use preparation or the skin cosmetic
composition product of the present invention comprises the
organopolysiloxane elastomer of the present invention or the
composition comprising the same and, although the form thereof is
not particularly limited, the product may be in the form of a
solution, cream-like, solid, semi-solid, paste-like, gel-like,
powder-like, multi-layer, mousse-like, or spray-like form. Specific
examples of the skin external use preparation or the skin cosmetic
composition product according to the present invention include skin
lotions, emulsions, creams, sunscreen emulsions, sunscreen creams,
hand creams, cleansing compositions, massage lotions, cleansing
agents, anti-perspirants, deodorants, and similar basic cosmetic
products; foundations, make-up bases, blushers, rouges, eye
shadows, eye liners, mascaras, nail enamels, and similar make-up
cosmetic products; and the like.
[0284] Similarly, the hair external use preparation or the hair
cosmetic composition product according to the present invention
comprises the organopolysiloxane elastomer of the present invention
or the composition comprising the same and can be used in various
forms. For example, the hair external use preparation or the hair
cosmetic composition product according to the present invention may
be dissolved or dispersed in an alcohol, a hydrocarbon, a volatile
cyclic silicone, or the like and used, or the product may also be
used in the form of an emulsion by dispersing the
organopolysiloxane elastomer of the present invention and a desired
emulsifier in water. Additionally, the hair external use
preparation or the hair cosmetic composition product according to
the present invention can be used as a spray by using propane,
butane, trichloromonofluormethane, dichlorodifluoromethane,
dichlorotetrafluoroethane, carbonic acid gas, nitrogen gas, or a
similar propellant. Examples of other forms include milk-like,
cream-like, solid, semi-solid, paste-like, gel-like, powder-like,
multi-layer, mousse-like, and similar forms. There various forms
can be used as shampooing agents, rinsing agents, conditioning
agents, setting lotions, hair sprays, permanent wave agents,
mousses, hair colorants, and the like.
[0285] The following other components generally used in external
use preparations or cosmetic compositions may be added to the
external use preparation or the cosmetic composition of the present
invention, provided that such components do not inhibit the
effectiveness of the present invention: water, powders or coloring
agents, alcohols, water-soluble polymers, film-forming agents, oil
agents, oil-soluble gelling agents, organomodified clay minerals,
surfactants, resins, mediums allowable in cosmetic products,
adipose phases, film-forming polymers, fibers, light protection
systems capable of blocking UV rays, UV absorbers, moisturizing
agents, preservatives, antimicrobial agents, perfumes, salts,
antioxidants, pH adjusting agents, chelating agents, refreshing
agents, anti-inflammatory agents, skin beautifying components
(skin-lightening agents, cell activating agents, agents for
ameliorating skin roughness, circulation promoters, skin
astringents, antiseborrheic agents, and the like), vitamins, amino
acids, nucleic acids, hormones, clathrates, and the like; bioactive
substances, medicament active ingredients, and perfumes. However,
the additives are not particularly limited thereto.
[0286] The water must be free of components that are harmful to the
human body and to be clean, and examples thereof include tap water,
purified water, mineral water, and deep sea water. When the
external use preparation or the cosmetic composition of the present
invention is water-based, water soluble additives can be compounded
as needed, provided that such components do not inhibit the
effectiveness of the present invention. Examples of components that
can be compound to constitute the aqueous phase include water
soluble active materials such as vitamin Bs (described below),
vitamin C and derivatives thereof, pantothenic acid and derivatives
thereof, vitamins such as biotins; antiperspiration active
components, water soluble UV absorbers, and various water soluble
pigments, but the components are not limited thereto. In addition,
a known pH adjusting agent, preservative, antimicrobial agent, or
antioxidant can be compounded as needed for the purpose of
improving the storage stability of the external use preparation or
the cosmetic composition.
[0287] The powder and/or coloring agent can be any powder provided
that it is normally used in external use preparations and cosmetic
compositions, and is not limited to form (sphere, bar, needle,
plate, amorphous, spindle, or the like), particle diameter
(aerosol, micro-particle, pigment-grade particle, or the like), or
particle structure (porous, nonporous, or the like) thereof. When
compounding the powder and/or coloring agent as a pigment,
preferably, one or two or more selected from an inorganic pigment
powder, an organic pigment powder, and a resin powder having an
average particle diameter in a range from 1 nm to 20 .mu.m is
compounded. In addition, when a pigment is used, a coated pigment
is more preferable. Note that recessed fine particles formed from a
silicone material, and particularly recessed fine particles with a
structure that is partially spherical and hollow having an average
particle size of less than 5 .mu.m (having an arch shape or a horse
hoof-shaped cross section), can also be advantageously used for the
purpose of thickening the oil phase, improving tactile sensation,
or the like.
[0288] Examples of the powder or coloring agent include flakes,
inorganic powders, organic powders, surfactant metal salt powders
(metallic soaps), colored pigments, pearl pigments, organo-modified
clay minerals, and metal powder pigments. Further, compounded
products of these pigments can also be used. Specific examples of
inorganic powders include titanium oxide, zirconium oxide, zinc
oxide, cerium oxide, magnesium oxide, barium sulfate, calcium
sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate,
talc, mica, kaolin, sericite, white mica, synthetic mica,
phlogopite, lepidolite, black mica, lithia mica, silicic acid,
silicic acid anhydride, aluminum silicate, sodium silicate,
magnesium sodium silicate, magnesium silicate, aluminum magnesium
silicate, calcium silicate, barium silicate, strontium silicate,
metal salts of tungstic acid, hydroxyapatite, vermiculite,
higilite, bentonite, montmorillonite, hectorite, zeolite, ceramic
powder, dicalcium phosphate, alumina, aluminum hydroxide, boron
nitride, and the like. Examples of organic powders include
polyamide powder, polyester powder, polyethylene powder,
polypropylene powder, polystyrene powder, polyurethane powder,
benzoguanamine powder, polymethylbenzoguanamine powder,
polytetrafluoroethylene powder, poly (methyl methacrylate) powder,
cellulose, silk powder, nylon powder, nylon 12, nylon 6, silicone
powder, silicone rubber spherical powder, silicone rubber spherical
powder that is surface-coated with polymethylsilsesquioxane,
polymethylsilsesquioxane spherical powder, copolymers of styrene
and acrylic acid, copolymers of divinylbenzene and styrene, vinyl
resin, urea resin, phenol resin, fluorine resin, silicone resin,
acrylic resin, melamine resin, epoxy resin, polycarbonate resin,
macrocrystalline fiber powder, starch powder, lauroyl lysine, and
the like. Examples of surfactant metal salt powders include zinc
stearate, aluminum stearate, calcium stearate, magnesium stearate,
zinc myristate, magnesium myristate, zinc palmitate, zinc laurate,
zinc cetylphosphate, calcium cetylphosphate, sodium zinc
cetylphosphate, and the like. Examples of colored pigments include
inorganic red pigments such as red iron oxide, iron oxide, iron
hydroxide, iron titanate, and the like; inorganic brown pigments
such as gamma-iron oxide and the like; inorganic yellow pigments
such as yellow iron oxide, ocher, and the like; inorganic black
pigments such as black iron oxide, carbon black and the like;
inorganic purple pigments such as manganese violet, cobalt violet,
and the like; inorganic green pigments such as chromium hydroxide,
chromium oxide, cobalt oxide, cobalt titanate, and the like;
inorganic blue pigments such as Prussian blue, ultramarine blue,
and the like; laked pigments of tar pigments such as Red No. 3, Red
No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red
No. 205, Red No. 220, Red No. 226, Red No. 227, Red No. 228, Red
No. 230, Red No. 401, Red No. 505, Yellow No. 4, Yellow No. 5,
Yellow No. 202, Yellow No. 203, Yellow No. 204, Yellow No. 401,
Blue No. 1, Blue No. 2, Blue No. 201, Blue No. 404, Green No. 3,
Green No. 201, Green No. 204, Green No. 205, Orange No. 201, Orange
No. 203, Orange No. 204, Orange No. 206, Orange No. 207, and the
like, laked pigments of natural pigments such as carminic acid,
laccaic acid, carthamin, brazilin, crocin, and the like. Examples
of pearl pigments include a pearl essence agent, titanium
oxide-coated mica, titanium mica, iron oxide-coated titanium mica,
titanium oxide-coated mica, bismuth oxychloride, titanium
oxide-coated bismuth oxychloride, titanium oxide-coated talc, fish
scale foil, titanium oxide-coated colored mica, and the like.
Examples of the metal powder pigment include powders of metals such
as aluminum, gold, silver, copper, platinum, stainless steel, and
the like.
[0289] In particular, a powder that absorbs and scatters
ultraviolet light, such as microparticulate titanium oxide,
microparticulate iron-containing titanium oxide, microparticulate
zinc oxide, microparticulate cerium oxide, compound products
thereof, and the like may be used as the inorganic powder. More
specifically, an inorganic ultraviolet light blocking component may
be compounded as an ultraviolet light scattering agent such as the
inorganic powder pigments and metal powder pigments described
above, and examples thereof include metal oxides such as titanium
oxide, zinc oxide, cerium oxide, titanium suboxide, and iron-doped
titanium oxides; metal hydroxides such as iron hydroxides; metal
flakes such as platy iron oxide and aluminum flakes; and ceramics
such as silicon carbide. Of these, at least one type of a material
selected from fine particulate metal oxides and fine particulate
metal hydroxides with an average particle size in a range from 1 to
100 nm is particularly preferable.
[0290] Examples of the organo-modified clay mineral include
dimethylbenzyl dodecylammonium montmorillonite clay,
dimethyldioctadecylammonium montmorillonite clay,
dimethylalkylammonium hectorite, benzyldimethylstearylammonium
hectorite, distearyldimethylammonium chloride-treated aluminum
magnesium silicate, and the like. Examples of commercially
available products include Benton 27 (benzyldimethylstearylammonium
chloride-treated hectorite, manufactured by Nationalred Co.),
Benton 38 (distearyldimethylammonium chloride-treated hectorite,
manufactured by Nationalred Co.), and the like.
[0291] The silicone rubber spherical powder (also known as a
silicone elastomer spherical powder) preferably has a primary
particle size in a range from 0.1 to 50 .mu.m. Examples of
commercially available products of the silicone rubber spherical
powder include Trefil E-506S, Trefil E-508, 9701 Cosmetic Powder,
9702 Powder, EP-9215 Cosmetic Powder, EP-9261 TI Cosmetic Powder,
EP-9293 AL Cosmetic Powder, EP-9289 LL Cosmetic Powder (all
manufactured by Dow Corning Toray Co., Ltd.). In addition, the
silicone rubber spherical powder can also be used in the external
use preparation or cosmetic composition of the present invention in
the form of an aqueous dispersion liquid. Examples of such
commercially available aqueous dispersion liquids include BY29-129,
and PF-2001 PIF Emulsion manufactured by Dow Corning Toray Co.,
Ltd.
[0292] Furthermore, the powder or coloring agent is preferably
subjected to a water-repellent treatment. Additionally, a product
can be used in which these powders and/or coloring agents are
compounded together; or subjected to surface treatment using a
general oil agent, a silicone compound other than the
organopolysiloxane elastomer according to the present invention, a
fluorine compound, a surfactant, or the like. One type thereof or
two or more types thereof can be used, as necessary.
[0293] Examples of these water-repellent treatments include various
treatments in which the powder and/or coloring agent is surface
treated with a water repellency agent. Specific examples thereof
include organosiloxane treatments such as a
methylhydrogenpolysiloxane treatment, a silicone resin treatment, a
silicone gum treatment, an acryl silicone treatment, a fluorinated
silicone treatment, a glycerin-modified silicone treatment, and the
like; metallic soap treatments such as a zinc stearate treatment
and the like; silane treatments such as a silane coupling agent
treatment, an alkylsilane treatment, and the like; fluorine
compound treatments such as a perfluoroalkylsilane treatment, a
perfluoroalkyl phosphate treatment, a perfluoro polyether
treatment, and the like; amino acid treatments such as an
N-lauroyl-L-lysine treatment and the like; oil agent treatments
such as a squalane treatment and the like; and acryl treatments
such as an alkyl acrylate treatment and the like. A combination of
one or more of the treatments described above can be used.
[0294] Particularly preferable examples of these powders or
coloring agents include at least one type of powder or coloring
agent selected from the group consisting of a silicone resin
powder, a silicone rubber powder, an organic resin powder
(excluding silicone resin powders), an organo-modified clay
mineral, titanium oxide, zinc oxide, a titanated mica, a metal
soap, an inorganic body pigment, an inorganic coloration pigment
and a coated pigment.
[0295] Examples of alcohols include at least one type selected from
a lower alcohol, a sugar alcohol, and a higher alcohol. Specific
examples include lower alcohols such as ethanol and isopropanol;
sugar alcohols such as sorbitol and maltose; and higher alcohols
such as lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl
alcohol, behenyl alcohol, hexadecyl alcohol, oleyl alcohol,
isostearyl alcohol, hexyldodecanol, octyldodecanol, cetostearyl
alcohol, 2-decyltetradecinol, cholesterol, sitosterol, phytosterol,
lanosterol, POE cholesterol ether, monostearyl glycerol ether
(batyl alcohol), and monooleyl glycerol ether (selachyl
alcohol).
[0296] The water-soluble polymer can be compounded for the purpose
of enhancing sensation during use of the external use preparation
or the cosmetic composition or as a water soluble moisturizing
agent or film-forming polymer. Any of amphoteric, cationic,
anionic, and nonionic polymers, and water-swellable clay minerals
can be used, provided that the water-soluble polymer is one that is
commonly used in external use preparations or cosmetic products,
and it is possible to use one or two or more types of these
water-soluble polymers. These water-soluble polymers have an effect
of thickening the hydrous component, so the polymers are
particularly useful for stabilizing the system when obtaining a
gel-like hydrous external use preparation or cosmetic composition,
a water-in-oil emulsion external use preparation or cosmetic
composition, and an oil-in-water emulsion external use preparation
or cosmetic composition.
[0297] Examples of amphoteric water-soluble polymers include
amphoteric starches, dimethyldiallylammonium chloride derivatives
(for example, acrylamide-acrylic acid-dimethyldiallylammonium
chloride copolymers and acrylic acid-dimethyldiallylammonium
chloride copolymers), and methacrylic acid derivatives (for
example, polymethacryloylethyldimethylbetaines,
N-methacryloyloxyethyl-N,N-dimethylammonium-.alpha.-methylcarboxybetaine--
alkyl methacrylate copolymers, and the like).
[0298] Examples of cationic water-soluble polymers include
quaternary nitrogen-modified polysaccharides (for example,
cation-modified cellulose, cation-modified hydroxyethylcellulose,
cation-modified guar gum, cation-modified locust bean gum,
cation-modified starch, and the like); dimethyldiallylammonium
chloride derivatives (for example, copolymers of
dimethyldiallylammonium chloride and acrylamide,
poly(dimethylmethylene piperidinium chloride), and the like);
vinylpyrrolidone derivatives (for example, copolymers of
vinylpyrrolidone and dimethylaminoethyl methacrylic acid,
copolymers of vinylpyrrolidone and methacrylamide
propyltrimethylammonium chloride, copolymers of vinylpyrrolidone
and methylvinylimidazolium chloride, and the like); and methacrylic
acid derivatives (for example,
methacryloylethyldimethylbetaine-methacryloylethyltrimethyl
ammonium chloride-2-hydroxyethyl methacrylate copolymers,
methacryloylethyldimethylbetaine-methacryloylethyltrimethyl
ammonium chloride-methoxy polyethylene glycol methacrylate
copolymers, and the like).
[0299] Examples of anionic water-soluble polymers include
poly(acrylic acid) and alkali metal salts thereof, poly(methacrylic
acid) and alkali metal salts thereof, hyaluronic acid and alkali
metal salts thereof, acetylated hyaluronic acid and alkali metal
salts thereof, water-soluble polymers of aliphatic carboxylic acids
or metal salts thereof, such as hydrolysates of methyl vinyl
ether-maleic anhydride copolymers, carboxymethyl cellulose and
alkali metal salts thereof, methyl vinyl ether-maleic acid half
ester copolymers, alkanolamine solutions of acrylic resins,
carboxyvinyl polymers, 2-acrylamide-2-methylpropane sulfonate
polymers, or the like.
[0300] Examples of nonionic water-soluble polymers include
poly(vinyl pyrrolidone), highly polymerized polyethylene glycols,
PEG/PPG-36/41 dimethyl ethers, PEG/PPG-14/7 dimethyl ethers, vinyl
pyrrolidone-vinyl acetate copolymers, vinyl
pyrrolidone-dimethylaminoethyl methacrylate copolymers, vinyl
caprolactam-vinyl pyrrolidone-dimethylaminoethyl methacrylate
copolymers, cellulose and derivatives thereof (for example, methyl
cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl
cellulose, and carboxymethyl cellulose), keratin and collagen and
derivatives thereof, calcium alginate, pullulan, agar, gelatin,
tamarind seed polysaccharides, xanthan gum, carrageenan,
high-methoxylpectin, low-methoxylpectin, guar gum, pectin, gum
arabic, crystalline cellulose, arabinogalactan, karaya gum, gum
tragacanth, alginic acid, albumin, casein, curdlan, gellan gum,
dextran, pyrus cydonia seed gum, gum tragacanth, chitin/chitosan
derivatives, starches (rice, corn, potato, wheat and the like),
keratin and collagen and derivatives thereof, and similar natural
polymer compounds.
[0301] The water-swellable clay mineral is an inorganic
water-soluble polymer and is a type of colloid-containing aluminum
silicate having a three-layer structure. Typical examples thereof
are expressed by the following formula (A).
(X,Y).sub.2-3(Si,Al).sub.4O.sub.10(OH).sub.2Z.sub.1/3.nH.sub.2O
(A)
(Wherein X is Al, Fe(III), Mn(III), or Cr(III), Y is Mg, Fe(II),
Ni, Zn, or Li, and Z is K, Na, or Ca). Specific examples of such
inorganic water-soluble polymers include bentonite,
montmorillonite, beidellite, nontronite, saponite, hectorite,
magnesium aluminum silicate, and silicic anhydride, and these may
be natural or synthetic products.
[0302] An oil agent described above can be used, and one type or
two or more types thereof can be used as necessary.
[0303] Examples of the oil-soluble gelling agent include metal
soaps such as aluminum stearate, magnesium stearate, and zinc
myristate; amino acid derivatives such as N-lauroyl-L-glutamic
acid, and .alpha.,.gamma.-di-n-butylamine; dextrin fatty acid
esters such as dextrin palmitate esters, dextrin stearate esters,
and dextrin 2-ethylhexanoate palmitate esters; sucrose fatty acid
esters such as sucrose palmitate esters and sucrose stearate
esters; fructooligosaccharide fatty acid esters such as inulin
stearate esters and fructooligosaccharide 2-ethylhexanoate esters;
semi-crystalline homopolymers or copolymers obtained by the
polymerization of a monomer comprising a long chain alkyl acrylate
and/or a long chain alkyl methacrylate having from 14 to 24 carbon
atoms or the like; benzylidene derivatives of sorbitol such as
monobenzylidene sorbitol and dibenzylidene sorbitol; and
organo-modified clay minerals such as dimethylbenzyl
dodecylammonium montmorillonite clay and
dimethyldioctadecylammonium montmorillonite clay. One type or two
or more types thereof can be used as necessary.
[0304] Surfactants other than the components described above can be
compounded in the external use preparation or the cosmetic
composition of the present invention. In particular, one type or
two or more types of surfactants selected from the group consisting
of a silicone-based surfactant other than the organopolysiloxane
elastomer according to the present invention, an anionic
surfactant, a cationic surfactant, a nonionic surfactant, an
amphoteric surfactant, and a semipolar surfactant can be used in
combination as the surfactant.
[0305] The silicone-based surfactant is a silicone-based surfactant
other than the organopolysiloxane elastomer according to the
present invention. This silicone-based surfactant is often used as
a component for the emulsification or washing of an oil agent, and
the dispersion or surface treatment of a powder, and representative
examples include polyglyceryl-modified silicones, glyceryl-modified
silicones, sugar-modified silicones, fluoropolyether-modified
silicones, polyether-modified silicones, carboxylic acid-modified
silicones, sugar-modified silicones, block copolymers of
straight-chain silicones and polyethers (polysilicone-13 and the
like), and long-chain alkyl-polyether comodified silicones. Since
the organopolysiloxane elastomer according to the present invention
consists of elastomer particles having a hydrophilic portion and a
hydrophobic portion, the elastomer functions as a stabilizer for a
powder dispersed in an oil. Thus, in cases where used in
combination with a silicone-based nonionic surfactant, the
organopolysiloxane also functions as an aid to enhance the
compounding stability of the nonionic surfactant and may improve
overall stability of the formulation. In particular, the
organopolysiloxane elastomer according to the present invention can
be advantageously used in combination with a glycerin
derivative-modified silicone, a sugar-modified silicone, a sugar
alcohol-modified silicone, a carboxylic acid-modified silicone, and
a polyglycerin-modified silicone elastomer (otherwise known as a
polyglycerated silicone elastomer), and a silicone-based nonionic
surfactant in which alkyl branching, straight-chain silicone
branching, siloxane dendrimer branching or the like is performed
along with the hydrophilic group as necessary can be advantageously
used. Note that it is also possible to use the substance in
combination with a polyoxyalkylene-modified silicone (a
polyether-modified silicone, a fluorine polyether-modified
silicone, or the like), a polyether-modified silicone elastomer
(otherwise known as a polyoxyalkylated silicone elastomer), or an
organopolyoxyalkylene group-containing surfactant.
[0306] Examples of the anionic surfactants include those in which
carboxylic acid-modified silicone is neutralized using an alkaline
substance; saturated or unsaturated fatty acid salts (for example,
sodium laurate, sodium stearate, sodium oleate, sodium linolenate,
and the like); alkylsulfuric acid salts; alkylbenzene sulfonic
acids (for example, hexylbenzenesulfonic acid, octylbenzenesulfonic
acid, dodecylbenzenesulfonic acid, and the like) and salts thereof;
polyoxyalkylene alkyl ether sulfuric acid salts; polyoxyalkylene
alkenyl ether sulfuric acid salts; polyoxyethylene alkylsulfuric
ester salts; sulfosuccinic acid alkyl ester salts; polyoxyalkylene
sulfosuccinic acid alkyl ester salts; polyoxyalkylene alkylphenyl
ether sulfuric acid salts; alkanesulfonic acid salts;
octyltrimethylammonium hydroxide; dodecyltrimethylammonium
hydroxide; alkyl sulfonates; polyoxyethylene alkylphenyl ether
sulfuric acid salts; polyoxyalkylene alkyl ether acetic acid salts;
alkyl phosphoric acid salts; polyoxyalkylene alkyl ether phosphoric
acid salts; acylglutamic acid salts; .alpha.-acylsulfonic acid
salts; alkylsulfonic acid salts; alkylallylsulfonic acid salts;
.alpha.-olefinsulfonic acid salts; alkylnaphthalene sulfonic acid
salts; alkanesulfonic acid salts; alkyl- or alkenylsulfuric acid
salts; alkylamide sulfuric acid salts; alkyl- or alkenyl phosphoric
acid salts; alkylamide phosphoric acid salts; alkyloylalkyl taurine
salts; N-acylamino acid salts; sulfosuccinic acid salts; alkyl
ether carboxylic acid salts; amide ether carboxylic acid salts;
.alpha.-sulfofatty acid ester salts; alanine derivatives; glycine
derivatives; and arginine derivatives. Examples of salts include
alkali metal salts such as sodium salts and the like, alkaline
earth metal salts such as magnesium salts and the like,
alkanolamine salts such as triethanolamine salts and the like, and
ammonium salts.
[0307] Examples of cationic surfactants include
alkyltrimethylammonium chloride, stearyltrimethylammonium chloride,
lauryltrimethylammonium chloride, cetyltrimethylammonium chloride,
beef tallow alkyltrimethylammonium chloride,
behenyltrimethylammonium chloride, stearyltrimethylammonium
bromide, behenyltrimethylammonium bromide,
distearyldimethylammonium chloride, dicocoyldimethylammonium
chloride, dioctyldimethylammonium chloride,
di(POE)oleylmethylammonium (2 EO) chloride, benzalkonium chloride,
alkyl benzalkonium chloride, alkyl dimethylbenzalkonium chloride,
benzethonium chloride, stearyl dimethylbenzylammonium chloride,
lanolin derivative quaternary ammonium salt, diethylaminoethylamide
stearate, dimethylaminopropylamide stearate, behenic acid amide
propyldimethyl hydroxypropylammonium chloride, stearoyl
colaminoformyl methylpyridinium chloride, cetylpyridinium chloride,
tall oil alkylbenzyl hydroxyethylimidazolinium chloride, and
benzylammonium salt.
[0308] Examples of nonionic surfactants include polyglyceryl
diisostearate and polyhydroxy diglyceryl stearate, isostearyl
glyceryl ethers, polyoxyalkylene ethers, polyoxyalkylene alkyl
ethers, polyoxyalkylene fatty acid esters, polyoxyalkylene fatty
acid diesters, polyoxyalkylene resin acid esters, polyoxyalkylene
(cured) castor oils, polyoxyalkylene alkyl phenols, polyoxyalkylene
alkyl phenyl ethers, polyoxyalkylene phenyl ethers, polyoxyalkylene
alkyl esters, polyoxyalkylene alkyl esters, sorbitan fatty acid
esters, polyoxyalkylene sorbitan alkyl esters, polyoxyalkylene
sorbitan fatty acid esters, polyoxyalkylene sorbitol fatty acid
esters, polyoxyalkylene glycerol fatty acid esters, polyglycerol
alkyl ethers, polyglycerol fatty acid esters, sucrose fatty acid
esters, fatty acid alkanolamides, alkylglucosides, polyoxyalkylene
fatty acid bisphenyl ethers, polypropylene glycol,
diethyleneglycol, polyoxyethylene-polyoxypropylene block polymers,
alkylpolyoxyethylene-polyoxypropylene block polymer ethers, and
fluorine-based surfactants.
[0309] Examples of amphoteric surfactants include imidazoline-type,
amidobetaine-type, alkylbetaine-type, alkylamidobetaine-type,
alkylsulfobetaine-type, amidosulfobetaine-type,
hydroxysulfobetaine-type, carbobetaine-type, phosphobetaine-type,
aminocarboxylic acid-type, and amidoamino acid-type amphoteric
surfactants. Specifically, examples include imidazoline-type
amphoteric surfactants such as
2-undecyl-N,N,N-(hydroxyethylcarboxymethyl)-2-imidazoline sodium,
2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt,
and the like; alkylbetaine-type amphoteric surfactants such as
lauryl dimethylaminoacetic betaine, myristyl betaine, and the like;
amidobetaine-type amphoteric surfactants such as coconut oil fatty
acid amidopropyl dimethylamino acetic acid betaine, palm kernel oil
fatty acid amidopropyl dimethylamino acetic acid betaine, beef
tallow fatty acid amidopropyl dimethylamino acetic acid betaine,
hardened beef tallow fatty acid amidopropyl dimethylamino acetic
acid betaine, lauric acid amidopropyl dimethylamino acetic acid
betaine, myristic acid amidopropyl dimethylamino acetic acid
betaine, palmitic acid amidopropyl dimethylamino acetic acid
betaine, stearic acid amidopropyl dimethylamino acetic acid
betaine, oleic acid amidopropyl dimethylamino acetic acid betaine,
and the like; alkylsulfobetaine-type amphoteric surfactants such as
coconut oil fatty acid dimethyl sulfopropyl betaine and the like;
alkyl hydroxy sulfobetaine-type amphoteric surfactants such as
lauryl dimethylaminohydroxy sulfobetaine and the like;
phosphobetaine-type amphoteric surfactants such as laurylhydroxy
phosphobetaine and the like; and amidoamino acid-type amphoteric
surfactants such as sodium
N-lauroyl-N'-hydroxyethyl-N'-carboxymethyl ethylenediamine, sodium
N-oleoyl-N'-hydroxyethyl-N'-carboxymethyl ethylenediamine, sodium
N-cocoyl-N'-hydroxyethyl-N'-carboxymethyl ethylenediamine,
potassium N-lauroyl-N'-hydroxyethyl-N'-carboxymethyl
ethylenediamine, potassium
N-oleoyl-N'-hydroxyethyl-N'-carboxymethyl ethylenediamine, sodium
N-lauroyl-N-hydroxyethyl-N'-carboxymethyl ethylenediamine, sodium
N-oleoyl-N-hydroxyethyl-N'-carboxymethyl ethylenediamine, sodium
N-cocoyl-N-hydroxyethyl-N'-carboxymethyl ethylenediamine,
monosodium N-lauroyl-N-hydroxyethyl-N',N'-dicarboxymethyl
ethylenediamine, monosodium
N-oleoyl-N-hydroxyethyl-N',N'-dicarboxymethyl ethylenediamine,
monosodium N-cocoyl-N-hydroxyethyl-N',N'-dicarboxymethyl
ethylenediamine, disodium
N-lauroyl-N-hydroxyethyl-N',N'-dicarboxymethyl ethylenediamine,
disodium N-oleoyl-N-hydroxyethyl-N',N'-dicarboxymethyl
ethylenediamine, disodium
N-cocoyl-N-hydroxyethyl-N',N'-dicarboxymethyl ethylenediamine, and
the like.
[0310] Examples of semipolar surfactants include alkylamine
oxide-type surfactants, alkylamine oxides, alkylamide amine oxides,
alkylhydroxyamine oxides, and the like. Alkyldimethylamine oxides
having from 10 to 18 carbon atoms, alkoxyethyl dihydroxyethylamine
oxides having from 8 to 18 carbon atoms, and the like are
preferably used. Specific examples thereof include
dodecyldimethylamine oxide, dimethyloctylamine oxide,
diethyldecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide,
dipropyltetradecylamine oxide, methylethylhexadecylamine oxide,
dodecylamidopropyldimethylamine oxide, cetyldimethylamine oxide,
stearyldimethylamine oxide, tallow dimethylamine oxide,
dimethyl-2-hydroxyoctadecylamine oxide, lauryldimethylamine oxide,
myristyldimethylamine oxide, stearyldimethylamine oxide,
isostearyldimethylamine oxide, coconut fatty acid
alkyldimethylamine oxide, caprylic amide propyldimethylamine oxide,
capric amide propyldimethylamine oxide, lauric amide
propyldimethylamine oxide, myristic amide propyldimethylamine
oxide, palmitic amide propyldimethylamine oxide, stearic amide
propyldimethylamine oxide, isostearic amide propyldimethylamine
oxide, oleic amide propyldimethylamine oxide, ricinoleic amide
propyldimethylamine oxide, 12-hydroxystearic amide
propyldimethylamine oxide, coconut fatty acid amide
propyldimethylamine oxide, palm kernel oil fatty acid amide
propyldimethylamine oxide, castor oil fatty acid amide
propyldimethylamine oxide, lauric amide ethyldimethylamine oxide,
myristic amide ethyldimethylamine oxide, coconut fatty acid amide
ethyldimethylamine oxide, lauric amide ethyldiethylamine oxide,
myristic amide ethyldiethylamine oxide, coconut fatty acid amide
ethyldiethylamine oxide, lauric amide ethyldihydroxyethylamine
oxide, myristic amide ethyldihydroxyethylamine oxide, and coconut
fatty acid amide ethyldihydroxyethylamine oxide.
[0311] The ultraviolet light blocking agent can be an inorganic
ultraviolet light blocking agent or an organic ultraviolet light
blocking agent. When the external use preparation or the cosmetic
composition of the present invention is to be used for sunblocking,
it is preferable for the composition to contain at least one type
of organic ultraviolet light blocking agent. In particular, using
both inorganic and organic ultraviolet light blocking agents in
combination is preferable, and using a UV-A blocking agent in
combination with a UV-B blocking agent is more preferable.
[0312] The inorganic ultraviolet light blocking agent may be
compounded as an ultraviolet light scattering agent such as the
inorganic pigment powders and metal powder pigments mentioned
above. Examples thereof include metal oxides such as titanium
oxide, zinc oxide, cerium oxide, titanium suboxide, iron-doped
titanium oxides, and the like; metal hydroxides such as iron
hydroxides and the like; metal flakes such as platy iron oxide,
aluminum flake, and the like; and ceramics such as silicon carbide,
and the like. Of these, at least one type of a material selected
from fine particulate metal oxides and fine particulate metal
hydroxides with an average particle diameter in a range from 1 to
100 nm and a particulate, plate-like, needle-like, or fiber form is
particularly preferable. These powders are preferably subjected to
conventionally known surface treatment such as, for example,
fluorine compound treatment (of which perfluoroalkyl phosphate
treatment, perfluoroalkylsilane treatment, perfluoropolyether
treatment, fluorosilicone treatment, and fluorinated silicone resin
treatment are preferable), silicone treatment (of which
methylhydrogen polysiloxane treatment, dimethylpolysiloxane
treatment, vapor-phase tetramethyltetrahydrogen cyclotetrasiloxane
treatment, and glycerin-modified silicone treatment are
preferable), silicone resin treatment (of which
trimethylsiloxysilicic acid treatment is preferable), pendant
treatment (which is a method of adding alkyl chains after
vapor-phase silicone treatment), silane coupling agent treatment,
titanium coupling agent treatment, silane treatment (of which
alkylsilane or alkylsilazane treatment is preferable), oil agent
treatment, N-acylated lysine treatment, polyacrylic acid treatment,
metal soap treatment (of which a stearic acid or myristic acid salt
is preferable), acrylic resin treatment, metal oxide treatment, or
the like, and the powders are preferably treated with a plurality
of these treatments. For example, the surface of the fine
particulate titanium oxide can be coated with a metal oxide such as
silicon oxide and alumina, and, thereafter, surface treating using
an alkylsilane can be carried out. A total amount of the surface
treatment agent is preferably in a range from 0.1 to 50 wt. % (mass
%) of the powder.
[0313] The organic ultraviolet light blocking agent is a lipophilic
ultraviolet light blocking agent, and examples thereof include
benzoic acid-based UV absorbers such as paraminobenzoic acid
(hereinafter abbreviated as "PABA"), PABA monoglycerol ester,
N,N-dipropoxy-PABA ethyl ester, N,N-diethoxy-PABA ethyl ester,
N,N-dimethyl-PABA ethyl ester, N,N-dimethyl-PABA butyl ester, and
2-[4-(diethylamino)-2-hydroxybenzoyl]hexylester benzoate (trade
name: Uvinul A plus); anthranilic acid-based UV absorbers such as
homomethyl-N-acetylanthranilate; salicylic acid-based UV absorbers
such as amyl salicylate, menthyl salicylate, homomethyl salicylate,
octyl salicylate, phenyl salicylate, benzyl salicylate, and
p-isopropanolphenyl salicylate; cinnamic acid-based UV absorbers
such as octyl cinnamate, ethyl-4-isopropylcinnamate,
methyl-2,5-diisopropylcinnamate, ethyl-2,4-diisopropylcinnamate,
methyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate,
isopropyl p-methoxycinnamate, isoamyl-p-methoxycinnamate,
octyl-p-methoxycinnamate (2-ethylhexyl-p-methoxycinnamate),
2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxy cinnamate,
ethyl-.alpha.-cyano-.beta.-phenylcinnamate,
2-ethylhexyl-.alpha.-cyano-.beta.-phenylcinnamate, glyceryl
mono-2-ethylhexanoyl-diparamethoxycinnamate,
3-methyl-4-[methylbis(trimethylsiloxy) silyl]butyl
3,4,5-trimethoxycinnamate, and dimethicodiethyl benzalmalonate
(trade name: Parsol SLX (INCI name: Polysilicone-15));
benzophenone-based UV absorbers such as 2,4-dihydroxybenzophenone,
2,2'-dihydroxy-4-methoxybenzophenone,
2,2'-dihydroxy-4,4'-dimethoxybenzophenone,
2,2',4,4'-tetrahydroxybenzophenone,
2-hydroxy-4-methoxybenzophenone,
2-hydroxy-4-methoxy-4'-methylbenzophenone,
2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenylbenzophenone,
2-ethylhexyl-4'-phenylbenzophenone-2-carboxylate,
hydroxy-4-n-octoxybenzophenone, and
4-hydroxy-3-carboxybenzophenone; benzotriazole-based UV absorbers
such as 3-(4'-methylbenzylidene)-d,l-camphor,
3-benzylidene-d,l-camphor, urocanic acid, urocanic acid ethyl
ester, 2-phenyl-5-methylbenzoxazole, 2,2'-hydroxy-5-methylphenyl
benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole,
2-(2'-hydroxy-5'-methylphenyl)benzotriazole, dibenzaladine,
dianisoylmethane, 4-methoxy-4'-t-butyldibenzoylmethane,
5-(3,3-dimethyl-2-norbornylidene)-3-pentan-2-one, 2,2'-methylene
bis(6-(2H-benzotriazole-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol)
(trade name: Tinosorb.RTM. M),
2-[4-(2-ethylhexyloxy)-2-hydroxyphenyl]-2H-benzotriazole, and
2-(2-hydroxy-4-isobutoxyphenyl)-2H-benzotriazole; triazine-based UV
absorbers such as
2,4,6-tris[4-(2-ethylhexyloxycarbonyl)anilino]1,3,5-triazine (INCI:
octyltriazone) and 2,4-bis-6-(4-methoxyphenyl)-1,3,5-triazine
(INCI: bis-ethylhexyloxyphenol methoxyphenyl triazine, trade name:
Tinosorb.RTM. S); and
2-cyano-3,3-diphenylprop-2-enoate-2-ethylhexyl ester (INCI:
octocrylene).
[0314] Generally, the organic-based UV absorber has high polarity
and does not readily dissolve. Therefore, conventionally, it has
been difficult to stably compound a desired (high) amount of the
organic-based UV absorber in water-in-oil (W/O) emulsion cosmetic
compositions. However, when the organopolysiloxane elastomer of the
present invention is used as an emulsifier and a medium polarity
oil such as an ester oil or the like is combined therewith as a
binding agent, a stable UV absorber-containing W/O emulsion
cosmetic composition can be obtained even when the oil phase
contains a low polarity oil such as a silicone oil, a hydrocarbon
oil, or the like. At this time, it is preferable to use a
xylitol-modified silicone having a siloxane dendron structure and a
long-chain alkyl group or a diglycerin-modified silicone having a
siloxane dendron structure and a long-chain alkyl group as a second
emulsifying agent and to use this agent in combination with the
organopolysiloxane elastomer of the present invention. In this
case, the compounded amount of the organic-based UV absorber is
preferably in a range from 0.1 to 10 mass % and the compounded
amount of the binding agent is preferably in a range from 0.005 to
5 mass %.
[0315] Additionally, it is possible to use a product in which the
organo-ultraviolet light blocking agent is comprised in a
hydrophobic polymer powder. The polymer powder may be or may not be
hollow, and preferably has an average primary particle size in a
range from 0.1 to 50 .mu.m. Particle size distribution may be broad
or sharp. Types of polymer include acrylic resins, methacrylic
resins, styrene resins, polyurethane resins, polyethylene,
polypropylene, polyethylene terephthalate, silicone resins, nylons,
acrylamide resins, and silylated polypeptide resins. A polymer
powder comprising from 0.1 to 30 wt. % (mass %) of an organic
ultraviolet light blocking agent is preferable, and a polymer
powder comprising 4-tert-butyl-4'-methoxydibenzoylmethane, which is
a UV-A absorber, is particularly preferable.
[0316] The ultraviolet light blocking agent that can be preferably
used is at least one selected from the group consisting of fine
particulate titanium oxide, fine particle zinc oxide, paramethoxy
cinnamic acid 2-ethylhexyl,
4-tert-butyl-4'-methoxydibenzoylmethane, a benzotriazole-based UV
absorber, and a triazine-based UV absorber. These ultraviolet light
blocking agents are generally used, are easy to acquire, and have
high ultraviolet light blocking effects and, thus can be
beneficially used.
[0317] Examples of salts include inorganic salts, organic salts,
amine salts, and amino acid salts. Examples of inorganic salts
include sodium salts, potassium salts, magnesium salts, calcium
salts, aluminum salts, zirconium salts, and zinc salts of inorganic
acids such as hydrochloric acid, sulfuric acid, carbonic acid, and
nitric acid. Examples of organic acid salts include salts of
organic acids such as acetic acid, dehydroacetic acid, citric acid,
malic acid, succinic acid, ascorbic acid, and stearic acid.
Examples of amine salts and amino acid salts include salts of
amines such as triethanolamine and salts of amino acids such as
glutamic acid. In addition, salts of hyaluronic acid, chondroitin
sulfuric acid, and the like, aluminum zirconium glycine complexes
and the like, and acid-alkali neutralization salts and the like
used in cosmetic product formulations can be used.
[0318] Examples of moisturizing agents include polyhydric alcohols
such as glycerin, sorbitol, propylene glycol, dipropylene glycol,
1,3-butylene glycol, glucose, xylitol, maltitol, and
polyethyleneglycol; hyaluronic acid, chondroitin sulfuric acid,
pyrrolidone carboxylic acid salts, polyoxyethylene methylglucoside,
polyoxypropylene methylglucoside, PEG/PPG dimethylether, polyols,
glycols, glycol esters, and the like.
[0319] Examples of preservatives include alkyl paraoxybenzoates,
benzoic acid, sodium benzoate, sorbic acid, potassium sorbate,
phenoxyethanol, and the like. Examples of antimicrobial agents
include benzoic acid, salicylic acid, carbolic acid, sorbic acid,
alkyl paraoxybenzoates, parachloromethacresol, hexachlorophene,
benzalkonium chloride, chlorhexidine chloride,
trichlorocarbanilide, triclosan, photosensitizers, phenoxy ethanol
and the like. However, in cases where the cosmetic composition is a
rouge, it is preferable that these are not included.
[0320] Examples of the antioxidants include tocopherol,
butylhydroxyanisole, dibutylhydroxytoluene, phytic acid, and the
like.
[0321] Examples of pH adjusting agents include lactic acid, citric
acid, glycolic acid, succinic acid, tartaric acid, dl-malic acid,
potassium carbonate, sodium hydrogen carbonate, ammonium hydrogen
carbonate, and the like.
[0322] Examples of the chelating agent include alanine, sodium salt
of edetic acid, sodium polyphosphate, sodium metaphosphate,
phosphoric acid, and the like.
[0323] Examples of the refreshing agents include L-menthol and
camphor, and examples of the anti-inflammatory agents include
allantoin, glycyrrhetic acid, glycyrrhizinic acid, tranexamic acid,
and azulene.
[0324] Moreover, examples of skin beautifying components include
skin-lightening agents such as placenta extracts, arbutin,
glutathione, saxifrageous extracts, and the like; cell activating
agents such as royal jelly and the like; agents for ameliorating
skin roughness; circulation promoters such as nonylic acid
vanillylamide, benzyl nicotinate, beta-butoxyethyl nicotinate,
capsaicin, zingerone, cantharide tincture, ichthammol, caffeine,
tannic acid, .alpha.-borneol, tocopherol nicotinate, inositol
hexanicotinate, cyclandelate, cinnarizine, tolazoline,
acetylcholine, verapamil, cepharanthine, .gamma.-oryzanol, and the
like; astringents such as zinc oxide, tannic acid, and the like;
antiseborrheic agents such as sulfur, thianthol, and the like; and
the like. Examples of vitamins include vitamin As such as vitamin A
oil, retinol, retinol acetate, retinol palmitate, and the like;
vitamin Bs such as vitamin B2s such as riboflavin, riboflavin
butyrate, flavin adenine dinucleotide, and the like; vitamin B6s
such as pyridoxine hydrochloride, pyridoxine dioctanoate,
pyridoxine tripalmitate, and the like; vitamin B12 and derivatives
thereof; vitamin B15 and derivatives thereof, and the like; vitamin
Cs such as L-ascorbic acid, L-ascorbyl dipalmitic acid esters,
sodium L-ascorbyl 2-sulfate, dipotassium L-ascorbyl phosphoric acid
diester, and the like; vitamin Ds such as ergocalciferol,
cholecalciferol, and the like; vitamin Es such as
.alpha.-tocopherol, 13-tocopherol, y-tocopherol,
dl-.alpha.-tocopherol acetate, dl-.alpha.-tocopherol nicotinate,
dl-.alpha.-tocopherol succinate, and the like; vitamin H; vitamin
P; nicotinic acids such as nicotinic acid, benzyl nicotinate, and
the like; pantothenic acids such as calcium pantothenate,
D-pantothenyl alcohol, pantothenyl ethyl ether, acetyl pantothenyl
ethyl ether, and the like; and the like.
[0325] Examples of amino acids include amino acids such as glycine,
valine, leucine, isoleucine, serine, threonine, phenylalanine,
arginine, lysine, aspartic acid, glutamic acid, cysteine, cysteine,
methionine, tryptophan, and the like, and/or salts thereof.
[0326] Examples of nucleic acids include deoxyribonucleic acid, and
examples of hormones include estradiol and ethenyl estradiol.
[0327] The bioactive component is a substance that imparts some
sort of bioactivity to the skin or the hair when applied to the
skin or the hair, and examples thereof are lipophilic substances.
Examples thereof include anti-inflammatory agents, anti-aging
agents, tightening agents, hair regrowth agents, hair growth
promoters, moisturizing agents, circulation promoters, drying
agents, warming agents, vitamins, wound healing accelerators,
irritation mitigation agents, analgesics, cell activating agents,
enzyme components, and the like. Similarly, natural vegetable
extract components, seaweed extract components and herbal medicine
components can be preferably blended.
[0328] The medicament active component is a substance having a
disease-treating effect, and examples thereof include proteins,
peptides, and low molecular weight compounds.
[0329] The perfume is not particularly limited as long as it is a
lipophilic perfume, and examples thereof include perfumes that are
extracted from a variety of plant flowers, seeds, leaves, roots,
and the like, perfumes extracted from seaweed, perfumes extracted
from a variety of animal parts and secretions (for example, musk or
sperm oil), and artificially synthesized perfumes (for example,
menthol, musk, acetic acid esters, and vanilla). The perfume is
compounded for the purpose of imparting a fragrance or scent to the
external use preparation or the cosmetic composition. Examples of
the pigment include oil-soluble dyes, water-soluble dyes, extender
pigments, inorganic pigments, organic pigments, and lipophilic
optical brighteners.
[0330] [Combinations with Other Silicone-Based Cosmetic Raw
Materials]
[0331] Depending on the dosage form and formulation thereof, the
external use preparation or the cosmetic composition according to
the present invention may further contain a solid silicone resin or
crosslinking organopolysiloxane (excluding the organopolysiloxane
elastomer of the present invention), an acryl silicone dendrimer
copolymer, a silicone raw rubber (silicone gum), a
polyamide-modified silicone, an alkyl-modified silicone wax, or an
alkyl-modified silicone resin wax. The main chain of the
organopolysiloxane elastomer of the present invention comprises a
polysiloxane chain, and the organopolysiloxane elastomer has a
hydrophilic sugar alcohol modified group as a modifying group. This
is advantageous in that it is possible to design a cosmetic
composition that has excellent compounding stability with these
silicone-based compounds and that takes advantage of the tactile
sensation that is characteristic to these silicone-based cosmetic
raw materials.
[0332] Solid Silicone Resin or Crosslinking Organopolysiloxane
[0333] The external use preparation or cosmetic composition of the
present invention may further contain a solid silicone resin or
crosslinking organopolysiloxane. The solid silicone resin or
crosslinking organopolysiloxane preferably is hydrophobic, having
absolutely no solubility in water at room temperature, or a
solubility of less than 1 wt. % (mass %) per 100 g of water.
[0334] The solid silicone resin is an organopolysiloxane having a
highly branched structure, a net-like structure, or a cage
structure, and is solid at room temperature. Any type of product
may be used, provided that it is a silicone resin that is commonly
used in cosmetic compositions and does not oppose the object of the
present invention. The solid silicone resin may be a spherical
powder, a flaky powder, a needle like powder, a plate-like flaky
powder (including plate-like powders having appearances and
particle aspect ratios commonly identified with plate-like forms),
or a similar particulate. Particularly, a silicone resin powder
having monoorganosiloxy units (T units) and/or siloxy units (Q
units), described below, can be preferably used.
[0335] Compounding the organopolysiloxane elastomer of the present
invention along with the solid silicone resin is useful because the
compatibility with the oil agent and uniform dispersibility are
improved, improvement effects in sensation during use can be
obtained, namely uniform adhesion to the applied area due to the
compounding of the solid silicone resin, and improvement effects in
cosmetic retainability such as moisture resistance and sebum
resistance can be obtained. Note that solid silicone resins are
often used as film-forming polymers that can be compounded in an
oil-based system.
[0336] Examples of the solid silicone resin include MQ resins, MDQ
resins, MTQ resins, MDTQ resins, TD resins, TQ resins, and TDQ
resins formed from arbitrary combinations of triorganosiloxy units
(M units) (where the organo groups are only methyl groups, or are
methyl groups and vinyl groups or phenyl groups), diorganosiloxy
units (D units) (where the organo groups are only methyl groups, or
are methyl groups and vinyl groups or phenyl groups),
monoorganosiloxy units (T units) (where the organo groups are
methyl groups, vinyl groups, or phenyl groups), and siloxy units (Q
units). Furthermore, other examples include
trimethylsiloxysilicate, polyalkylsiloxysilicate, dimethylsiloxy
unit-containing trimethylsiloxysilicate, and
alkyl(perfluoroalkyl)siloxysilicate. These silicone resins are
preferably oil soluble and can be dissolved in volatile
silicone.
[0337] Particularly, a phenyl silicone resin having a high
refractive index and a high content of phenyl groups (e.g. 217
Flake resin and the like, manufactured by Dow Corning Toray Co.,
Ltd.) can be easily used as a flaky silicone resin powder and, when
compounded in a cosmetic composition, in particular, can impart a
radiant feeling of sheerness to the skin or hair.
[0338] Types of crosslinking organopolysiloxanes (excluding the
organopolysiloxane elastomer of the present invention) include
non-emulsifiable crosslinking organopolysiloxanes and emulsifiable
crosslinking organopolysiloxanes, but the organopolysiloxane chain
preferably has a structure which is three-dimensionally crosslinked
by a reaction between a crosslinking component consisting of a
polyether unit, an alkylene unit having from 4 to 20 carbon atoms,
or an organopolysiloxane unit and other optional modifying agents
or the like.
[0339] Specifically, the crosslinking organopolysiloxane (excluding
the organopolysiloxane elastomer of the present invention) can be
obtained by performing an addition reaction on an
organohydrogenpolysiloxane having a silicon-bonded hydrogen atom, a
polyether compound or glycerin derivative having reactive
unsaturated groups at both terminals of the molecular chain, an
unsaturated hydrocarbon having more than one double bond in the
molecule, and an organopolysiloxane having more than one double
bond in the molecule. Here, the crosslinking organopolysiloxane may
have or may be free of unreacted silicon-bonded hydrogen atoms,
phenyl groups, and similar aromatic hydrocarbon groups; octyl
groups and similar long chain alkyl groups having from 6 to 30
carbon atoms; polyether groups, carboxyl groups, and similar
modifying functional groups. In other words, any crosslinking
organopolysiloxane can be used without limitations to physical
modes or preparation methods such as dilution, properties, and the
like.
[0340] As an example, the crosslinking organopolysiloxane can be
obtained via an addition reaction of crosslinking components
selected from an organohydrogenpolysiloxane formed from a
structural unit selected from the group consisting of an SiO.sub.2
unit, an HSiO.sub.15 unit, a R.sup.bSiO.sub.1.5 unit, a R.sup.bHSiO
unit, a R.sup.b.sub.2SiO unit, a R.sup.b.sub.3SiO.sub.0.5 unit, and
a R.sup.b.sub.2HSiO.sub.0.5 unit (where R.sup.b is a substituted or
unsubstituted monovalent hydrocarbon group having from 1 to 30
carbon atoms, with the exception of aliphatic unsaturated groups;
and a portion of R.sup.b is a monovalent hydrocarbon group having
from 8 to 30 carbon atoms), the organohydrogenpolysiloxane having
an average of 1.5 or more silicon-bonded hydrogen atoms in the
molecule; a polyoxyalkylene compound having unsaturated hydrocarbon
groups at both molecular terminals; a polyglycerine compound, a
polyglycidylether compound, or similar polyether compound; an
.alpha.,.omega.-diene unsaturated hydrocarbon expressed by the
general formula: CH.sub.2.dbd.CH--C.sub.rH.sub.2, CH.dbd.CH.sub.2
(where r is an integer from 0 to 26); and an organopolysiloxane
formed from a structural unit selected from the group consisting of
an SiO.sub.2 unit, a (CH.sub.2.dbd.CH)SiO.sub.15 unit, a
R.sup.cSiO.sub.1.5 unit, a R.sup.c(CH.sub.2.dbd.CH)SiO unit, a
R.sup.c.sub.2SiO unit, a R.sup.c.sub.3SiO.sub.0.5 unit, and a
R.sup.c.sub.2(CH.sub.2.dbd.CH)SiO.sub.0.5 unit (where R.sup.c is a
substituted or unsubstituted monovalent hydrocarbon group having
from 1 to 30 carbon atoms, with the exception of aliphatic
unsaturated groups), the organopolysiloxane having an average of
1.5 or more silicon-bonded vinyl groups in the molecule. Note that
by addition reacting the unreacted silicon-bonded hydrogen atoms,
the modifying functional groups described above can be introduced.
For example, by reacting 1-hexene with a crosslinking
organopolysiloxane having unreacted silicon-bonded hydrogen atoms,
hexyl groups (C6 alkyl groups) are introduced.
[0341] Such a crosslinking organopolysiloxane can be used without
limitations, regardless of the physical modes or preparation
methods such as dilution, properties, and the like, but
particularly preferable examples thereof include
.alpha.,.omega.-diene crosslinking silicone elastomers
(commercially available products include DC 9040 Silicone Elastomer
Blend, DC 9041 Silicone Elastomer Blend, DC 9045 Silicone Elastomer
Blend, DC 9046 Silicone Elastomer Blend, EL-9140 DM Silicone
Elastomer Blend, 9546 Silicone Elastomer Blend, 9027 Silicone
Elastomer Blend, FB-9586 Silicone Elastomer Blend, and EL-8040 ID
Silicone Organic Blend manufactured by Dow Corning USA) described
in U.S. Pat. No. 5,654,362. Additional examples of partially
crosslinked organopolysiloxane polymers include a
(dimethicone/vinyldimethicone) crosspolymer, a
(dimethicone/phenylvinyldimethicone) crosspolymer, a (PEG-8 to
30/C.sub.6 to C.sub.30 alkyldimethicone) crosspolymer, a
(vinylmethicone/C.sub.6 to C.sub.30 alkyldimethicone) crosspolymer,
and a (dimethicone/polyglycerin) crosspolymer according to the INCI
names (International Nomenclature Cosmetic Ingredient Labeling
Names).
[0342] Other preferable examples of crosslinkable
organopolysiloxanes include a silicone polyester elastomer gel
disclosed in WO2007/109240 and WO2009/006091 in which compatibility
with various organic components is enhanced and stable thickening
effects are displayed as a result of introducing a polyoxypropylene
group; commercially available Dow Corning EL-8050 ID SILICONE
ORGANIC ELASTOMER BLEND, Dow Corning EL-8051 IN SILICONE ORGANIC
ELASTOMER BLEND, and Dow Corning EL-7040 HYDRO ELASTOMER BLEND; and
PITUITOUS SILICONE FLUIDS disclosed in WO2011/028765 and
WO2011/028770.
[0343] When compounded in an external use preparation or a cosmetic
composition as an emulsifiable crosslinking organopolysiloxane that
is crosslinked by a polyether compound, the organopolysiloxane
elastomer of the present invention functions as a dispersion
stabilizer, which yields the advantage that a uniform
emulsification system (dosage form) can be formed.
[0344] On the other hand, when a non-emulsifiable crosslinking
organopolysiloxane (also called a non-emulsifiable silicone
elastomer) which is crosslinked by an unsaturated group-containing
organopolysiloxane or an unsaturated hydrocarbon group such as a
diene, a polyoxypropylene having reactive unsaturated groups at
both molecular terminals of the molecular chain, or the like is
compounded as a component in an external use preparation or a
cosmetic composition, a thick, smooth tactile sensation can be
imparted to the skin or the hair, and a matte finish and effects of
concealing wrinkles, pigmented spots, and the like can be obtained.
Further, this configuration is advantageous in that the feel of
adhesion to the skin of the cosmetic composition is improved and
cosmetic retainability is enhanced because the effects of retaining
various oil agents and increasing the viscosity are high.
[0345] One type or two or more types of the solid silicone resin or
crosslinking organopolysiloxane (excluding the organopolysiloxane
elastomer of the present invention) can be compounded in accordance
with the purpose thereof and are preferably compounded in a range
from 0.05 to 25 wt. % (mass %) and more preferably in a range from
0.1 to 15 wt. % (mass %) of the entire cosmetic composition or the
external use preparation, depending on the purpose and the
intention of compounding.
[0346] Acryl Silicone Dendrimer Copolymer
[0347] The external use preparation or the cosmetic composition of
the present invention may further contain an acryl silicone
dendrimer copolymer. The acryl silicone dendrimer copolymer is a
vinyl polymer having a carbosiloxane dendrimer structure on the
sidechain, and particularly preferable examples thereof include the
vinyl polymer described in Japanese Patent No. 4009382 (Japanese
Unexamined Patent Application Publication No. 2000-063225).
Examples of commercially available products include FA 4001 CM
Silicone Acrylate, FA 4002 ID Silicone Acrylate, and the like
manufactured by Dow Corning Toray Co., Ltd. and acryl silicone
dendrimer copolymers having a long chain alkyl group on the
sidechain or the like having from 8 to 30 carbon atoms and
preferably from 14 to 22 carbon atoms. When compounding the acryl
silicone dendrimer copolymer alone, superior film formability can
be obtained. Therefore, by compounding the acryl silicone dendrimer
copolymer in the external use preparation or cosmetic composition
according to the present invention, a strong coating film can be
formed on the applied part, and cosmetic durability such as sebum
resistance, rubbing resistance, and the like can be significantly
improved.
[0348] Using the organopolysiloxane elastomer of the present
invention in combination with the acryl silicone dendrimer
copolymer yields advantages in that the surface protective
properties such as sebum resistance can be improved due to strong
water repellency provided by the carbosiloxane dendrimer structure,
and irregularities such as pores can also be effectively concealed.
In addition, the organopolysiloxane elastomer of the present
invention causes the acryl silicone dendrimer copolymer to blend
well with the other oil agents and has excellent compatibility with
the skin and surface of the hair, so the hardness of the acryl
silicone dendrimer copolymer can be reduced, and a film with an
excellent adhesive sensation and a lasting feel of moisture can be
achieved. In addition, cosmetic retainability is improved, which
has the advantage that degradation of the skin surface or hair can
be suppressed for an extended period of time.
[0349] A compounded amount of the acryl silicone dendrimer
copolymer can be suitably selected based on the purpose and
compounding intent thereof, but is preferably in a range from 1 to
99 wt. % (mass %) and more preferably in a range from 30 to 70 wt.
% (mass %) of the entire external use preparation or cosmetic
composition.
[0350] [Silicone Raw Rubber (Silicone Gum)]
[0351] In the external use preparation or the cosmetic composition
of the present invention, an ultra-high viscous yet fluid component
having a viscosity at room temperature of 1,000,000 mm.sup.2/s or
higher, which is referred to as a silicone raw rubber (silicone
gum), can be suitably used as the silicone oil. Silicone rubber is
a straight-chained diorganopolysiloxane with an ultra-high degree
of polymerization and is also called silicone raw rubber or
organopolysiloxane rubber. Silicone rubber is differentiated from
the oily silicones described above because the degree of
polymerization of silicone rubber is high and, as a result, it has
a degree of plasticity that is measurable. These silicone gums can
be compounded directly in the external use preparation or the
cosmetic composition of the present invention--in a hair cosmetic
composition for the purpose of imparting a tactile sensation--or
can be compounded as liquid gum dispersions in which an oil-like
silicone is dispersed (oil dispersions of silicone gums).
[0352] Examples of such a silicone raw rubber include substituted
or unsubstituted organopolysiloxanes having a dialkylsiloxy unit (D
unit) such as a dimethylpolysiloxane, a methylphenylpolysiloxane,
an aminopolysiloxane, or a methylfluoroalkylpolysiloxane, or
products having micro-crosslinked structures thereof, and typical
examples thereof include products expressed by the general formula:
R.sup.10(CH.sub.3).sub.2SiO[(CH.sub.3).sub.2SiO].sub.s[(CH.sub.3)R.sup.12-
SiO].sub.tSi(CH.sub.3).sub.2R.sup.10 (wherein R.sup.12 moieties are
each independently a group selected from vinyl groups, phenyl
groups, alkyl groups having from 6 to 20 carbon atoms, aminoalkyl
groups having from 3 to 15 carbon atoms, perfluoroalkyl groups
having from 3 to 15 carbon atoms, and quaternary ammonium salt
group-containing alkyl groups having from 3 to 15 carbon atoms; the
terminal group R.sup.10 moieties are each independently a group
selected from alkyl groups having from 1 to 8 carbon atoms, phenyl
groups, vinyl groups, aminoalkyl groups having from 3 to 15 carbon
atoms, hydroxyl groups, and alkoxy groups having from 1 to 8 carbon
atoms; s=2,000 to 6,000; t=0 to 1,000; and s+t=2,000 to 6,000). Of
these, a dimethylpolysiloxane raw rubber having a degree of
polymerization of 3,000 to 20,000 is preferable. Additionally, an
amino-modified methylpolysiloxane raw rubber having a 3-aminopropyl
group, an N-(2-aminoethyl)-3-aminopropyl group, or the like on the
molecular sidechain or terminal is preferable. Moreover, in the
present invention, one or two or more types of silicone gums can be
used as necessary.
[0353] Silicone gum has an ultra-high degree of polymerization and,
therefore forms a protective film with superior breathability and
retention on hair. Therefore, the silicone gum is a component which
can particularly provide glossiness and luster to hair and can
impart a texture of firmness and body to the entire hair during use
and after use. A silicone gum with a high degree of polymerization
can also be compounded in the external use preparation or the
cosmetic composition in a form that is diluted with a silicone oil
to reduce the viscosity. Further, the use of the organopolysiloxane
elastomer of the present invention imparts a smooth, sliding
feeling to wet hair at the time of rinsing or the like, and the
substance is effectively absorbed by the surface of the hair, which
yields a sustained moisturizing effect to the hair after drying and
a protective effect to the hair surface and makes it possible to
suppress flyaway.
[0354] A compounded amount of the silicone gum is, for example,
from 0.05 to 30 wt. % (mass %) and preferably from 1 to 15 wt. %
(mass %) of the entire external use preparation or cosmetic
composition. When the silicone gum is used as an emulsion
composition prepared via a process of pre-emulsifying (including
emulsion polymerization), the silicone gum can easily be
compounded, and can be stably compounded in the hair cosmetic
composition of the present invention. An effect of imparting a
specific feeling to touch or glossiness of the hair may be
insufficient if the compounded amount of the silicone gum is less
than the lower limit described above.
[0355] [Polyamide-Modified Silicone]
[0356] Examples of polyamide-modified silicones that can be
preferably compounded in the external use preparation or the
cosmetic composition of the present invention include
siloxane-based polyamide compounds described in U.S. Pat. No.
5,981,680 (Japanese Unexamined Patent Application Publication No.
2000-038450) and Japanese Unexamined Patent Application Publication
(Translation of PCT Application) No. 2001-512164, and examples of
commercially available products include 2-8178 Gellant, 2-8179
Gellant and the like (manufactured by Dow Corning USA). This
polyamide-modified silicone also functions as an oil-based raw
material, specifically as a thickening/gelling agent of a silicone
oil.
[0357] When the polyamide-modified silicone is used in combination
with the organopolysiloxane elastomer of the present invention, the
external use preparation or the cosmetic composition of the present
invention has good spreading and setting as well as an excellent
sense of stability and adhesion when applied to the skin, the hair,
or the like. Additionally, there are advantages from a quality
standpoint such that a glossy feeling of sheerness and superior
luster can be provided, the viscosity or hardness (softness) of the
entire cosmetic composition containing the oil-based raw material
can be appropriately adjusted, and an oily sensation (oily and
sticky feeling to touch) can be totally suppressed. Furthermore, by
using the organopolysiloxane elastomer, the dispersion stability of
perfumes, powders, and the like will be improved. Therefore, the
obtained cosmetic composition will be characterized by being able
to maintain a uniform and fine cosmetic sensation for an extended
period of time.
[0358] [Silicone Wax]
[0359] Silicone waxes that can be preferably compounded in the
external use preparation or the cosmetic composition of the present
invention are higher alkyl-modified silicones and alkyl-modified
silicone resins. The higher alkyl-modified silicone is a wax at
room temperature and is a component that is useful as a portion of
the base material of a solid cosmetic composition (for example, an
oil-based solid skin cosmetic composition or a solid hair cosmetic
composition). Therefore, the higher alkyl-modified silicone can be
preferably used in the external use preparation or the cosmetic
composition of the present invention. Examples of the higher
alkyl-modified silicone wax include methyl (long chain alkyl)
polysiloxanes having both molecular terminals capped with
trimethylsiloxy groups, copolymers of a dimethylpolysiloxane having
both molecular terminals capped with trimethylsiloxy groups and a
methyl (long chain alkyl) siloxane, dimethylpolysiloxane modified
with long chain alkyls at both molecular terminals, and the like.
Examples of commercially available products include AMS-C30
Cosmetic Wax, 2503 Cosmetic Wax, and the like (manufactured by Dow
Corning Corporation, in the USA).
[0360] The organopolysiloxane elastomer of the present invention
has good affinity with the higher alkyl-modified silicone wax and
has excellent dispersibility properties in wax, so an external use
preparation or a cosmetic composition having excellent storage
stability over time can be obtained. In addition, the moldability
of the external use preparation or the cosmetic composition, and
particularly of a solid cosmetic composition, is excellent. In
particular, in a system comprising a powder, an effect of uniformly
and stably dispersing the powder in the base material containing
the higher alkyl-modified silicone wax is obtained, and the
hardness of the base material after molding can be moderately
mitigated, which makes it possible to provide an external use
preparation or a cosmetic composition that spreads smoothly and
uniformly when applied.
[0361] In the external use preparation or cosmetic composition of
the present invention, the higher alkyl-modified silicone wax
preferably has a melting point of not lower than 60.degree. C.
because such will lead to cosmetic retainability effects and
stability at high temperatures.
[0362] The alkyl-modified silicone resin is a type of film-forming
polymer that is compoundable in an oil phase and is a component
that imparts sebum durability, moisturizing properties, and a fine
tactile sensation of the skin to the external use preparation or
the cosmetic composition. An alkyl-modified silicone resin that is
in the form of a wax at room temperature can be suitably used.
Preferred examples thereof include the silsesquioxane resin wax
described in Japanese Unexamined Patent Application Publication
(Translation of PCT Application) No. 2007-532754. Examples of
commercially available products include SW-8005 C30 RESIN WAX
(manufactured by Dow Corning Corporation, in the USA), and the
like.
[0363] As in the case of a higher alkyl-modified silicone wax, the
organopolysiloxane elastomer of the present invention has good
affinity with the alkyl-modified silicone resin wax and has
excellent dispersion properties in wax, so an external use
preparation or a cosmetic composition having superior storage
stability over time can be obtained. Further, an aqueous phase can
be stably emulsified along with other optional surfactants in the
oil phase containing the alkyl-modified silicone resin wax, which
makes it possible to impart a luxurious tactile sensation,
moisturizing effects, and effects of improving cosmetic
retainability exemplified by moisture resistance and sebum
resistance to the skin or the hair.
[0364] [Antiperspiration Active Component and Deodorant Agent]
[0365] Additionally, in cases where the external use preparation or
the cosmetic composition according to the present invention is an
anti-perspirant, or depending on the purpose thereof, the external
use preparation or the cosmetic composition can contain an
anti-perspiration active component and/or a deodorant agent.
[0366] Examples of the anti-perspiration active component include
astringent salts such as aluminum chlorohydrate, aluminum-zirconium
tetrachlorohydrex glycine (ZAG), and the like; but aluminum,
hafnium, zinc, and zirconium salts (e.g. aluminum halide, aluminum
hydroxy halide, zirconium halide, zirconium oxyhalide, zirconium
hydroxy halide, zirconyl hydroxide halide, aluminum chloride
zirconium, zirconium lactate-aluminum, and basic aluminum halide)
can be used. Examples thereof include Al.sub.2(OH).sub.5Cl,
aluminum bromide, buffer aluminum sulphate, alum, dried alum,
various aqueous, alcohol, or glycine complexes thereof (e.g. a
complex of an aluminum-zirconium chlorohydrate and glycine
comprising aluminum, zirconium, and glycine (a ZAG complex), and
the like. A single anti-perspiration active component may be used
or a combination of two or more may be used. In cases where the
anti-perspirant composition according to the present invention is a
water-in-oil emulsion-type anti-perspirant composition, these
anti-perspiration active components are an aqueous phase component.
On the other hand, soybean extracts and isoflavones are known for
their anti-perspirant effects; and, because they have low water
solubility, are preferably used by dissolving them in the oil
phase.
[0367] In the present invention, a compounded amount of the
anti-perspiration active component is an amount sufficient to
reduce perspiration, and suppressing the compounded amount to a
small amount can be beneficial in personal care compositions.
Specifically, from the standpoints of anti-perspirant effects and
feeling to touch, the compounded amount of the anti-perspiration
active component in an anti-perspirant composition is preferably
from 5 to 25 wt. % (mass %) of the entire cosmetic composition.
When using a water soluble anti-perspiration active component, from
the standpoint of cost effectiveness, it is preferable to increase
the proportion of water in the composition to a maximum limit,
while maintaining anti-perspirant effects, but the
anti-perspiration active component can also be added to the aqueous
phase at amount near the saturation amount.
[0368] A deodorant agent can be compounded together with or instead
of the anti-perspiration active component in the external use
preparation or the cosmetic composition of the present invention,
and particularly an antiperspiration composition. Examples of the
deodorant agent include deodorizers, perfumes, and substances that
prevent or remove odors caused by perspiration. Such deodorant
agents are antimicrobial agents (germicides or fungicides),
bacteriostatic agents, odor absorbing substances, deodorizers,
perfumes, or the like, and are compounded for the purpose of
preventing underarm odor, odor from perspiration, foot odor, and
other bodily odors. Note that these deodorant agents are useful in
cosmetic compositions or external use preparations other than
anti-perspirants and it goes without saying that they can be
beneficially compounded in the external use preparation or cosmetic
composition of the present invention.
[0369] Examples of antimicrobial agents include
alkyltrimethylammonium bromide, cetylpyridinium chloride,
benzethonium chloride, benzalkonium chloride, chlorhexidine
hydrochloride, chlorhexidine gluconate,
[[(diisobutylphenoxy)ethoxy]ethyl] dimethylbenzylammonium chloride,
N-lauroyl sarcosine sodium, N-palmitoyl sarcosine sodium,
N-myristoyl glycine, N-lauroyl sarcosine potassium, trimethyl
ammonium chloride, aluminum chlorohydroxy sodium lactate, triethyl
citrate, tricetyl methyl ammonium chloride, 1,5-pentanediol,
1,6-hexanediol, 2,4,4'-trichloro-2'-hydroxy diphenylether
(triclosan), and 3,4,4'-trichlorocarbanilide(triclocarban);
L-lysine hexadecylamide and similar diaminoalkylamidos; citric
acid, salicylic acid, piroctose, and other heavy metal salts,
preferably zinc salts and acids thereof; pyrithione heavy metal
salts, preferably pyrithione zinc, phenol zinc sulfate,
ethylparaben, butylparaben, hinokitiol, farnesol, phenoxyethanol,
isopropyl methylphenol, propolis, lysozyme, lysozyme chloride,
combinations of lysozyme and vitamin E or derivatives thereof,
combinations of organic acids such as lysozyme and
.alpha.-hydroxyacid and the like; and the like.
[0370] Examples of bacteriostatic agents include 1-heptyl glyceryl
ether, 1-(2-ethylhexyl)glyceryl ether, 1-octyl glyceryl ether,
1-decyl glyceryl ether, 1-dodecyl glyceryl ether, and similar
glyceryl monoalkyl ethers.
[0371] The odor absorbing substance is not particularly limited,
provided that it absorbs odor causing substances and reduces odor,
is constituted by a portion of the inorganic powders and organic
polymers described above, and displays the same
characteristics.
[0372] Examples of the odor absorbing substance include zinc oxide,
magnesium oxide, zeolite, aluminometasilicate, silicic anhydride,
colloidal silica, talc, mica, hydroxyapatite, cellulose, corn
starch, silk, nylon powder, crosslinking organopolysiloxane powder,
organopolysiloxane elastomer spherical powder, and the like.
Likewise, carbonates such as alkali metal carbonates, alkali metal
bicarbonate salts, and the like and hydrogen carbonates, ammonium
salts, tetraalkylammonium salts, and the like can be used. Of these
odor absorbing substances, sodium salts and potassium salts are
more preferable. Additionally, organic or inorganic porous
particles carrying silver, copper, zinc, cerium, or similar metal
ions (e.g. silver ion-carrying zeolite, silver ion/zinc
ion/ammonium ion-carrying zeolite), or aggregates of needle-like
crystals including silver cancrinite can be used. Because these
function as antimicrobial agents and odor absorbing substances,
they can be used beneficially as the deodorant agent.
[0373] Furthermore, hydroxyalkylated cyclodextrin, sake cake
extract containing rice fermenting liquid, and various extracts
derived from animals, vegetables, microorganisms, fungi, and the
like such as brown seaweed extract, cinnamon bark, clove, fennel,
ginger, mentha, citron, gentiana lutea, apricot, eucalyptus,
Sophora flavescens, mulberry, althea, sage, Anthemis nobilis,
Scutellaria root, nutgall, gardenia, hamamelis, herbs, and the like
can be used as the deodorant agent. A part of these components
overlaps with a bioactive component described above, but selecting
these extracts as the deodorant agent for the purpose of the
functional effects thereof is both beneficial and preferable from
the standpoint of the composition design of the cosmetic
composition.
[0374] Preferably from 0.001 to 60 wt. % (mass %), more preferably
from 0.01 to 30 wt. % (mass %), and yet more preferably from 0.01
to 3 wt. % (mass %) of the odor absorbing substance is included in
the entire composition. Provided that the compounded amount of the
odor absorbing substance is within this range, there is an
advantage that deodorizing performance can be improved while not
negatively affecting the strength and feeling to touch of the
formulation.
[0375] Suitable perfumes include known topical use substances,
topical use substances that are effective in masking malodor
accompanied by perspiration, and various topical use substances
that provide a composition having a desired aroma. Examples thereof
include the whole of perfumes and perfume chemicals such as perfume
precursors, deodorizing fragrances, and the like that are suitable
for topical application to the skin and, as necessary, may be a
blended perfume component.
Technical Field
[0376] The organopolysiloxane elastomer of the present invention or
the composition containing the same can be suitably used as a raw
material for an external use preparation or a raw material for a
cosmetic composition. In particular, the organopolysiloxane
elastomer of the present invention produced via an acidizing
process and the composition of the present invention containing the
organopolysiloxane elastomer of the present invention and at least
one type of acid have a reduced odor and can therefore be suitably
compounded in an external use preparation or a cosmetic
composition.
[0377] Note that the carbonyl value measurement method described
above is capable of accurately and simply assaying a carbonyl
compound, so the method can be preferably used for the evaluation
of the odor of a product of an external use preparation or a
cosmetic composition.
PRACTICAL EXAMPLES
[0378] The present invention is described below using examples, but
the present invention is not limited thereto. In the following
composition formulas, an Me.sub.3SiO group (or an Me.sub.3Si group)
is represented by "M", an Me.sub.3SiO group is represented by "D",
an Me.sub.2HSiO group (or an Me.sub.2HSi group) is represented by
"M.sup.H", an MeHSiO group is represented by "D.sup.H", an
Me.sub.2(CH.sub.2.dbd.CH)SiO group [or an
Me.sub.2(CH.sub.2.dbd.CH)Si group] is represented by "M.sup.Vi",
and an Me(CH.sub.2.dbd.CH)SiO group is represented by "D.sup.Vi".
An Me.sub.2[CH.sub.2.dbd.CH--(CH.sub.2).sub.4]SiO group [or an
Me.sub.2[CH.sub.2.dbd.CH--(CH.sub.2).sub.4]Si group] is represented
by "M.sup.Hex", an Me[CH.sub.2.dbd.CH--(CH.sub.2).sub.4]SiO group
is represented by "D.sup.Hex" an MeSiO.sub.3/2 group is represented
by "T", and an MeSiO.sub.4/2 group is represented by "Q". Units in
which the methyl groups in M and D are modified by one of the
substituents are represented by M.sup.R and D.sup.R.
[0379] In addition, the xylitol monoallyl ether and xylitol residue
described below are a raw material and functional groups as
described in this specification. More specifically, the xylitol
monoallyl ether is a raw material containing a xylitol monoallyl
ether expressed by the structural formula:
CH.sub.2.dbd.CH--CH.sub.2--OCH.sub.2[CH(OH)].sub.3CH.sub.2OH and
the structural formula:
CH.sub.2.dbd.CH--CH.sub.2--OCH[CH(OH)CH.sub.2OH].sub.2 at a
composition ratio of approximately 9:1, and a xylitol residue
represented by the corresponding formula
--C.sub.3H.sub.6--OCH.sub.2[CH(OH)].sub.3CH.sub.2OH or
--C.sub.3H.sub.6--OCH[CH(OH)CH.sub.2OH].sub.2 is introduced to the
co-modified silicone of the present invention at the same
composition ratio.
[0380] Note that in the practical examples and comparative examples
below, "Production of Silicone Compound No. X" and the like is
included for the sake of convenience, and the obtained products are
in the form of mixtures containing a small amount of unreacted raw
material and the like in addition to the main components.
Practical Example 1
Production of Silicone Compound No. 1
[0381] First, 59.8 g of a methylhydrogenpolysiloxane expressed by
the average composition formula: MD.sub.42.9D.sup.H.sub.6.7M and
2.2 g of a 3-methacryloxypropyl(tris(trimethylsiloxy)silyl ethyl
dimethylsiloxy)silane expressed by the following average
composition formula:
##STR00028##
were placed in a reaction vessel and heated to 80.degree. C. while
agitating under a nitrogen stream. Next, 0.12 mL of an isopropyl
alcohol solution of a
platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt
concentration: 0.45 wt. %) was added and the mixture was reacted
for 2 hours at 80.degree. C. A small amount of the reaction liquid
was then sampled, and it was confirmed that the target reaction
rate was reached by an alkali decomposition gas generation method
(the remaining Si--H groups were decomposed using a KOH
ethanol/aqueous solution, and the reaction rate was calculated from
the volume of the generated hydrogen gas). Next, 6.3 g of
hexadecene (.alpha.-olefin purity: 91.7%) was added to the reaction
mixture, and after the mixture was reacted for 6 hours at
80.degree. C., it was confirmed via the same method that the target
reaction rate was reached. Next, 6.2 g of xylitol monoallyl ether
(purity: 91.2%) and 138 g of isopropyl alcohol (IPA) were added to
the reaction mixture, and 0.13 ml of the platinum catalyst
described above was added. After reacting for 3 hours at 80.degree.
C., the mixture was sampled. As a result of calculating the
reaction rate, it was found that a modified silicone intermediate
expressed by the average composition formula:
MD.sub.42.9D.sup.R*.sup.31.sub.0.1D.sup.R*.sup.21.sub.2.4D.sup.R-
*.sup.11.sub.1.6D.sup.H.sub.2.6M had been produced. Here,
R*.sup.11, R*.sup.21, and R*.sup.31 are as described below.
R*.sup.11=-C.sub.16H.sub.33
R*.sup.21=xylitol residue
##STR00029##
[0382] Here, 155.6 g of a methylvinylpolysiloxane expressed by the
average composition formula:
.sup.ViMD.sub.136D.sup.Vi.sub.2.25M.sup.Vi, 0.025 g of natural
vitamin E, and 0.14 ml of the platinum catalyst described above
were added to the mixture. When a reaction was performed for 2.5
hours at 70 to 80.degree. C., elastomerization occurred and the
reaction mixture assumed a soft ricecake or jam-like consistency
with a feeling of sheerness. In this case, the Vi/H molar ratio
when crosslinking was 1.2. As a result of continuing the reaction
for 2 more hours in this state in order to advance crosslinking,
the hardness increased and the mixture became a dry, collapsible
grease. Here, 450 g of a dimethylpolysiloxane (6 cst) serving as a
diluent was added and mixed well.
[0383] Next, 3.5 g of a 0.12% phosphoric acid aqueous solution and
3.5 g of purified water were added, and after the mixture was
treated for 1.5 hours at 60 to 80.degree. C., the mixture was
neutralized by adding 0.1 g of 2.5% ammonia water. A composition
containing a novel organopolysiloxane elastomer modified by a
xylitol group was then obtained by heating under reduced pressure
to distill out low-boiling-point matter. The composition was then
transferred to a Hobart mixture and subjected to kneading and
grinding for 3 hours to obtain a homogenized, translucent or white,
soft paste-like composition (elastomer concentration: 33%).
[0384] The average structural formula (schematic illustration) of
the organopolysiloxane elastomer obtained in Practical Example 1 is
illustrated below.
##STR00030##
(wherein Me is a methyl group, Z in [ ]n is --CH.sub.2CH.sub.2--, Z
outside of [ ]n is --C.sub.3H.sub.6--COO--C.sub.3H.sub.6--, R is
--C.sub.16H.sub.33, Y is a linking group derived from
.sup.ViMD.sub.136D.sup.Vi.sub.2.25M.sup.Vi, a is 42.9, b is 2.4, c
is 2.6, d is 0.1, e is 1.6, m is 3, and n is 3.)
Practical Example 2
Production of Silicone Compound No. 2
[0385] First, 119.2 g of a methylhydrogenpolysiloxane expressed by
the average composition formula: MD.sub.43.4D.sup.H.sub.74M and
23.1 g of hexadecene (.alpha.-olefin purity: 91.7%) were placed in
a reaction vessel, and when 0.10 ml of a hexamethyldisiloxane
solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane
complex (Pt concentration: 0.45 wt. %) was added at 30.degree. C.
while agitating under a nitrogen stream, heat was generated
immediately, and the mixture heated to 60.degree. C. after three
minutes. The temperature was then maintained at 30 to 60.degree.
C., and a small amount of the reaction solution was sampled after
one hour. When the sample was confirmed using an alkali
decomposition gas generation method, the reaction rate had reached
the target rate. Next, 14.1 g of a xylitol monoallyl ether (purity:
85.3%), 138 g of isopropyl alcohol (IPA), and 0.03 g of natural
vitamin E were added to the reaction mixture, and 0.03 ml of the
platinum catalyst described above was then added. After a reaction
was performed for 6 hours at 65 to 70.degree. C., a small amount of
the reaction solution was sampled. As a result of calculating the
reaction rate with the same method, it was found that a modified
silicone intermediate expressed by the average composition formula:
MD.sub.43.4D.sup.R*.sup.11.sub.3.30D.sup.R*.sup.21.sub.1.98D.sup.H.sub.2.-
12M had been produced. Here, R*.sup.11 and R*.sup.21 are as defined
above.
[0386] Here, 73.9 g of a methylhexenylpolysiloxane expressed by the
average composition formula:
.sup.HexMD.sub.56.7D.sup.Hex.sub.3.3M.sup.Hex was added to the
mixture. When a reaction was performed at 70 to 80.degree. C.,
elastomerization occurred after approximately 33 minutes, and the
reaction mixture turned into a soft, greasy mass with a feeling of
sheerness. In this case, the Vi/H molar ratio when crosslinking was
1.2. As a result of continuing the reaction for 2 more hours in
this state in order to advance crosslinking, the hardness increased
and the mixture became a dry, collapsible grease or powdered
mass.
[0387] Next, 6.9 g of a 0.12% phosphoric acid aqueous solution and
3.5 g of purified water were added, and after the mixture was
treated for 6 hours at 80 to 85.degree. C., the mixture was
neutralized by adding 0.20 g of 2.5% ammonia water. Next, 221 g of
a novel organopolysiloxane elastomer modified by a xylitol group
was obtained by heating under reduced pressure to distill out
low-boiling-point matter. The aforementioned elastomer was then
transferred to a Hobart mixer, and after the elastomer was
subjected to kneading and grinding for one hour, the elastomer was
subjected to kneading and grinding while slowly adding 409 g of a
dimethylpolysiloxane (6 cst) serving as a diluent over the course
of 8.5 hours to obtain a translucent or white, soft paste-like
composition (elastomer concentration: 33%).
Practical Example 3
Production of Silicone Compound No. 3
[0388] First, 171.8 g of a methylhydrogenpolysiloxane expressed by
the average composition formula: MD.sub.43.4D.sup.H.sub.7.4M and
32.4 g of hexadecene (.alpha.-olefin purity: 91.7%) were placed in
a reaction vessel, and when 0.10 ml of a hexamethyldisiloxane
solution of a platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane
complex (Pt concentration: 0.45 wt. %) was added at 25.degree. C.
while agitating under a nitrogen stream, heat was generated, and
the mixture heated to 57.degree. C. after four minutes. The
temperature was then maintained at 55 to 70.degree. C., and a
reaction was performed for two hours. A small amount of the
reaction solution was sampled, and when the sample was confirmed
using an alkali decomposition gas generation method, the reaction
rate had reached the target rate. Next, 6.0 g of
3-methacryloxypropyl(tris(trimethylsiloxy)silylethyldimethylsiloxy)silane
was added to the reaction mixture and reacted for 1.5 hours at 55
to 75.degree. C., and it was confirmed by the same method that the
reaction rate had reached the target rate. Next, 15.2 g of xylitol
monoallyl ether (purity: 91.2%), 138 g of isopropyl alcohol (IPA),
and 0.023 g of natural vitamin E were added to the reaction
mixture, and after reacting for 2 hours at 60 to 75.degree. C., a
small amount of the reaction solution was sampled. As a result of
calculating the reaction rate, it was found that a modified
silicone intermediate expressed by the average composition formula:
MD.sub.43.4D.sup.R*.sup.31.sub.0.10D.sup.R*.sup.21.sub.1.60D.sup-
.R*.sup.H.sub.3.20D.sup.H.sub.2.60M had been produced. Here,
R*.sup.11, R*.sup.21, and R*.sup.31 are as described above.
[0389] The mixture was temporarily cooled to 50.degree. C., and 5.5
g of 5-hexadiene and 0.15 ml of the platinum catalyst described
above were added to the mixture. When a reaction was performed for
2.5 hours at 50 to 60.degree. C., elastomerization occurred, and
the reaction mixture turned to a collapsible grease-like or
paste-like substance. In this case, the Vi/H molar ratio when
crosslinking was 1.2. As a result of continuing the reaction for 2
more hours in this state in order to advance crosslinking, the
hardness increased and the mixture became a dry grease in large
drops.
[0390] Next, 6.9 g of a 0.12% phosphoric acid aqueous solution and
3.5 g of purified water were added, and after the mixture was
treated for 3.5 hours at 80.degree. C., the low-boiling-point
matter was removed by distillation while heating under reduced
pressure to obtain 223 g of a novel organopolysiloxane elastomer
modified by a xylitol group. The elastomer was then transferred to
a Hobart mixer, and when the mixture was kneaded for 15 minutes,
the mixture assumed the form of a white, light soft ricecake rolled
up in the shape of a ball. The elastomer was then subjected to
kneading while slowly adding 446 g of a dimethylpolysiloxane (6
cst) serving as a diluent over the course of 7 hours to obtain a
translucent or transparent, homogeneous, soft ricecake-like
composition (elastomer concentration: 33%).
Practical Example 4
Production of Silicone Compound No. 4
[0391] First, 168.9 g of a methylhydrogenpolysiloxane represented
by the average composition formula: MD.sub.42.9D.sup.H.sub.6.7M and
6.1 g of
3-methacryloxypropyl(tris(trimethylsiloxy)silylethyldimethylsiloxy)silane
were placed in a reaction vessel, and 0.12 ml of an isopropyl
alcohol solution of a platinum
divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt concentration:
0.45 wt. %) was added while agitating under a nitrogen stream.
After reacting for 2 hours at 80.degree. C., a small amount of the
reaction liquid was sampled, and it was confirmed by an alkali
decomposition gas generation method that the target reaction rate
was reached. Next, 30.9 g of hexadecene (.alpha.-olefin purity:
91.7%) was added to the reaction mixture, and after the mixture was
reacted for 3 hours at 90.degree. C., it was confirmed via the same
method that the target reaction rate was reached. Next, 9.5 g of a
xylitol monoallyl ether (purity: 91.2%), 138 g of isopropyl alcohol
(IPA), and 0.025 g of natural vitamin E were added to the reaction
mixture, and 0.13 ml of the platinum catalyst described above was
then added. After reacting for 3 hours at 80.degree. C., the
mixture was sampled. As a result of calculating the reaction rate,
it was found that a modified silicone intermediate expressed by the
average composition formula:
MD.sub.42.9D.sup.R*.sup.31.sub.0.1D.sup.R*.sup.21.sub.1.2D.sup.R*.sup.11.-
sub.2.8D.sup.H.sub.2.6M had been produced. Here, R*.sup.11,
R*.sup.21 and R*.sub.31 are as described above.
[0392] Here, 14.6 g of a vinylcyclohexene monooxide expressed by
the following structural formula:
##STR00031##
and 0.20 ml of the platinum catalyst described above were added to
the mixture. When a reaction was performed for 3 hours at
80.degree. C., elastomerization occurred, and the reaction mixture
assumed a soft ricecake or jam-like consistency with a feeling of
sheerness. In this case, the Vi/H molar ratio when crosslinking was
1.0. As a result of continuing the reaction for 2 more hours in
this state in order to advance crosslinking, the hardness increased
and the mixture became a dry, collapsible grease.
[0393] Next, 6.9 g of a 0.12% phosphoric acid aqueous solution and
3.5 g of purified water were added, and after the mixture was
treated for 1 hour at 60 to 80.degree. C., the low-boiling-point
matter was removed by distillation while heating under reduced
pressure to obtain a novel organopolysiloxane elastomer modified by
a xylitol group. The composition was then transferred to a Hobart
mixture and subjected to kneading and grinding for 3 hours to
obtain a homogenized, white grease-like composition. The elastomer
was then subjected to kneading while slowly adding 450 g of a
dimethylpolysiloxane (6 cst) serving as a diluent over the course
of 3 hours to obtain a translucent or white, soft paste-like
composition (elastomer concentration: 33%).
Practical Example 5
Production of Silicone Compound No. 5
[0394] First, 140.4 g of a methylhydrogenpolysiloxane represented
by the average composition formula: MD.sub.43.4D.sup.H.sub.7.4M and
5.0 g of
3-methacryloxypropyl(tris(trimethylsiloxy)silylethyldimethylsiloxy)silane
were placed in a reaction vessel, and 0.10 ml of a
hexamethyldisiloxane solution of a
platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt
concentration: 0.45 wt. %) was added while agitating under a
nitrogen stream. After reacting for 2 hours at 60 to 65.degree. C.,
a small amount of the reaction liquid was sampled, and it was
confirmed by an alkali decomposition gas generation method that the
target reaction rate was reached. Next, when 32.8 g of hexadecene
(.alpha.-olefin purity: 91.7%) was added to the reaction mixture,
heat was generated immediately, and the mixture heated to
95.degree. C. after two minutes. The mixture was then maintained at
60 to 80.degree. C., and when a reaction was performed for 8.5
hours (0.10 ml of the aforementioned catalyst was added at an
intermediate stage), it was found that the reaction rate had
reached the target rate and that an intermediate expressed by the
average composition formula:
MD.sub.43.4D.sup.R*.sup.31.sub.0.1D.sup.R*.sup.11.sub.4.0D.sup.H-
.sub.2.98D.sup.OR.sub.0.32M had been produced. Next, 2.3 g of
xylitol monoallyl ether (purity: 91.2%), 138 g of isopropyl alcohol
(IPA), and 0.03 g of natural vitamin E were added to the reaction
mixture, and after a reaction was performed for 2 hours at
70.degree. C., the mixture was sampled. As a result of calculating
the reaction rate, it was found that a modified silicone
intermediate expressed by the average composition formula:
MD.sub.43.4D.sup.R*.sup.31.sub.0.1D.sup.R*.sup.11.sub.4.0D.sup.R-
*.sup.21.sub.0.31D.sup.H.sub.2.67D.sup.OR.sub.0.32M had been
produced. Here, R*.sup.11, R*.sup.21, and R*.sup.31 are as
described above. In addition, D.sup.OR is a structural unit
produced by the dehydrogenation of D.sup.H and an alcoholic
hydroxyl group, the unit being an Me(OR)SiO group containing a
Si--O--C bond or a Si--O--H bond. In this example,
OR.dbd.O--CH(CH.sub.3).sub.2 or OH.
[0395] Here, 44.7 g of a bisallylpolyether expressed by the average
composition formula:
CH.sub.2.dbd.CH--CH.sub.2--(OCH.sub.2CH.sub.2).sub.15--O--CH.sub.2--CH.db-
d.CH.sub.2 and 0.10 ml of the platinum catalyst described above
were added to the mixture. When a reaction was performed for 32
minutes at 75 to 80.degree. C., elastomerization occurred, and the
reaction mixture turned to a soft, grease-like composition that
could be easily cut into thin strips. In this case, the Vi/H molar
ratio when crosslinking was 1.2. As a result of continuing the
reaction for 2 more hours in this state in order to advance
crosslinking, the hardness increased slightly, and the composition
assumed the form of a paste with a powdery appearance (and a
tactile sensation similar to that of grains of boiled rice).
[0396] Next, 6.9 g of a 0.12% phosphoric acid aqueous solution and
3.5 g of purified water were added, and after the mixture was
treated for 3 hours at 80 to 85.degree. C., the low-boiling-point
matter was removed by distillation while heating under reduced
pressure to obtain 219 g of a novel organopolysiloxane elastomer
modified by a xylitol group. The elastomer was then transferred to
a Hobart mixer, and when the mixture was kneaded for 20 minutes,
the mixture assumed the form of a white, light soft ricecake rolled
up in the shape of a ball. The elastomer was then subjected to
kneading while slowly adding 438 g of a dimethylpolysiloxane (6
cst) serving as a diluent over the course of 8 hours to obtain a
white, homogeneous, soft paste-like composition (elastomer
concentration: 33%).
Practical Example 6
Production of Silicone Compound No. 6
[0397] First, 13.1 g of a methylhydrogenpolysiloxane expressed by
the average composition formula: MD.sub.42.9D.sup.H.sub.6.7M, 5.4 g
of a methylhydrogenpolysiloxane expressed by the average
composition formula: MD.sub.7D.sup.H.sub.12T.sub.1M, and 1.2 g of a
methylhydrogenpolysiloxane expressed by the average composition
formula: M.sup.H.sub.4Q were placed in a reaction vessel (the
average composition formula of the mixture was
M.sub.1.33M.sup.H.sub.1.33D.sub.16.63D.sup.H.sub.6.23T.sub.0.33Q.sub.0.33-
M). Next, 1.4 g of
3-methacryloxypropyl(tris(trimethylsiloxy)silylethyldimethylsiloxy)silane
was added, and 0.12 g of an isopropyl alcohol solution of a
platinum-1-3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Pt
concentration: 0.45 wt. %) was added while agitating under a
nitrogen stream. After reacting for 2 hours at 90.degree. C., a
small amount of the reaction liquid was sampled, and it was
confirmed by an alkali decomposition gas generation method that the
target reaction rate was reached. Next, 6.8 g of hexadecene
(.alpha.-olefin purity: 91.7%) was added to the reaction mixture,
and after the mixture was reacted for 2 hours at 90.degree. C., it
was confirmed via the same method that the target reaction rate was
reached. Next, 4.4 g of a xylitol monoallyl ether (purity: 91.2%),
138 g of isopropyl alcohol (IPA), and 0.025 g of natural vitamin E
were added to the reaction mixture, and 0.13 g of the platinum
catalyst described above was then added. After reacting for 1 hour
at 80.degree. C., the mixture was sampled, and the reaction rate
was calculated. As a result, it was found that of the 1.33 M.sup.H
units and the 6.23 D'' units in the average molecular composition
of methylhydrogenpolysiloxane, 0.1 equivalents were subjected to
the addition of
3-methacryloxypropyl(tris(trimethylsiloxy)silylethyldimethylsiloxy)silane-
, 2.66 equivalents were subjected to the addition of 1-hexadecene,
2.0 equivalents were subjected to the addition of xylitol monoallyl
ether, and the remaining M.sup.H units and D'' units were
equivalent to a total of 2.8 units.
[0398] Here, 197.7 g of a methylvinylpolysiloxane expressed by the
average composition formula: .sup.ViMD.sub.149M.sup.Vi and 0.14 g
of the platinum catalyst described above were added to the mixture.
When a reaction was performed for 2 hours at 80.degree. C.,
elastomerization occurred, and the reaction mixture assumed a soft
ricecake or jam-like consistency with a feeling of sheerness. In
this case, the Vi/H molar ratio when crosslinking was 1.2. As a
result of continuing the reaction for 2 more hours in this state in
order to advance crosslinking, the hardness increased and the
mixture became a dry, collapsible grease.
[0399] Next, 6.9 g of a 0.12% phosphoric acid aqueous solution and
3.5 g of purified water were added, and after the mixture was
treated for 1 hour at 80.degree. C., the low-boiling-point matter
was removed by distillation while heating under reduced pressure to
obtain a novel organopolysiloxane elastomer modified by a xylitol
group. The composition was then transferred to a Hobart mixture and
subjected to kneading and grinding for 3 hours to obtain a
homogenized, white grease-like composition. The elastomer was then
subjected to kneading while slowly adding 450 g of a
dimethylpolysiloxane (6 cst) serving as a diluent over the course
of 3 hours to obtain a translucent or white, soft paste-like
composition (elastomer concentration: 33%).
Comparative Example 1
Production of Silicone Compound No. RE-1
[0400] First, 110.1 g of a methylhydrogenpolysiloxane represented
by the average composition formula: MD.sub.40D.sup.H.sub.15M and
12.1 g of 1-dodecene (equivalent to 1/4 the total amount of
1-dodecene added) were placed in a reaction vessel and heated to
50.0.degree. C. while agitating under a nitrogen air flow, and 0.10
g of an ethanol solution of chloroplatinic acid (Pt concentration:
3 wt. %) was then added. The temperature increased to 80.degree. C.
due to the reaction heat, and after it was confirmed that the
temperature dropped naturally thereafter, a second batch of 12.1 g
of 1-dodecene was added and reacted. Third and fourth batches of
1-dodecene were further added and reacted with the same method.
After reacting for 1 hour at 90 to 100.degree. C., a small amount
of the reaction liquid was sampled, and it was confirmed by an
alkali decomposition gas generation method that the target reaction
rate was reached. Next, low-boiling-point matter such as unreacted
dodecene was removed by heating under reduced pressure.
[0401] Next, 25.4 g of a vinylmethylpolysiloxane expressed by the
average composition formula: .sup.ViMD.sub.6M and 0.10 g of the
platinum catalyst described above were added to the reaction
mixture, and after a reaction was performed for 2 hours at 90 to
100.degree. C., it was confirmed that the reaction rate had reached
the target rate with the same method. As a result of calculating
the reaction rate, it was found that a modified silicone
intermediate expressed by the average composition formula:
MD.sub.40D.sup.R*.sup.41.sub.1.5D.sup.R*.sup.12.sub.10D.sup.H.sub.3.5M
had been produced. Here, R*12 and R*41 are as described below.
R*.sup.12=--C.sub.12H.sub.25
R*.sup.41=--C.sub.2H.sub.4SiMe.sub.2(OSiMe.sub.2).sub.6OSiMe.sub.3
[0402] Here, 46.4 g of bisallylpolyether expressed by the average
composition formula:
CH.sub.2.dbd.CH--CH.sub.2--(OCH.sub.2CH.sub.2).sub.15--O--CH.sub.2--CH.db-
d.CH.sub.2, 0.025 g of natural vitamin E, 138 g of toluene, and
0.10 g of the platinum catalyst described above were added to the
mixture. When a reaction was performed for 2 hours at 90.degree.
C., elastomerization occurred, and the reaction mixture assumed a
translucent, soft ricecake or jam-like consistency. In this case,
the Vi/H molar ratio when crosslinking was 1.2. As a result of
continuing the reaction for 2 more hours in this state in order to
advance crosslinking, the hardness increased and the mixture became
a dry, collapsible grease. Next, toluene was removed by heating
under reduced pressure.
[0403] Next, 25.3 g of a 2% citric acid aqueous solution was added,
and after the mixture was treated for 2 hours at 80.degree. C., 2%
baking soda water was added to neutralize the mixture for 1 hour.
By distilling out low-boiling-point matter while heating under
reduced pressure, an organopolysiloxane elastomer modified by
polyether group, a C12 alkyl group, and a group having a linear
polysiloxane structure was obtained. The composition was then
transferred to a Hobart mixture and subjected to kneading and
grinding for 3 hours to obtain a homogenized, white grease-like
composition. The elastomer was then subjected to kneading while
slowly adding 450 g of a dimethylpolysiloxane (6 cst) serving as a
diluent over the course of 3 hours to obtain a translucent or
white, soft paste-like composition (elastomer concentration:
33%).
Comparative Example 2
Production of Silicone Compound No. RE-2
[0404] First, 125.3 g of a methylhydrogenpolysiloxane represented
by the average composition formula: MD.sub.40D.sup.H.sub.15M and
13.7 g of 1-dodecene (equivalent to 1/4 the total amount of
1-dodecene added) were placed in a reaction vessel and heated to
50.0.degree. C. while agitating under a nitrogen air flow, and 0.10
g of an ethanol solution of chloroplatinic acid (Pt concentration:
3 wt. %) was then added. The temperature increased to 85.degree. C.
due to the reaction heat, and after it was confirmed that the
temperature dropped naturally thereafter, a second batch of 13.7 g
of 1-dodecene was added and reacted. Third and fourth batches of
1-dodecene were further added and reacted with the same method.
After reacting for 1 hour at 90 to 100.degree. C., a small amount
of the reaction liquid was sampled, and it was confirmed by an
alkali decomposition gas generation method that the target reaction
rate was reached. Next, low-boiling-point matter such as unreacted
dodecene was removed by heating under reduced pressure.
[0405] Next, 28.9 g of a vinylmethylpolysiloxane expressed by the
average composition formula: .sup.ViMD.sub.6M and 0.10 g of the
platinum catalyst described above were added to the reaction
mixture, and after a reaction was performed for 2 hours at 90 to
100.degree. C., it was confirmed that the reaction rate had reached
the target rate with the same method. As a result of calculating
the reaction rate, it was found that a modified silicone
intermediate expressed by the average composition formula:
MD.sub.40D.sup.R*.sup.41.sub.1.5D.sup.R*.sup.12.sub.10D.sup.H.sub.3.5M
had been produced. Here, R*.sup.12 and R*.sup.41 are as defined
above.
[0406] Here, 20.9 g of bisallyltriglycerine (or triglycerine allyl
ether) expressed by the average composition formula:
CH.sub.2.dbd.CH--CH.sub.2O--(C.sub.3H.sub.6O.sub.2).sub.3--CH.sub.2--CH.d-
bd.CH.sub.2, 0.025 g of natural vitamin E, 138 g of toluene, and
0.10 g of the platinum catalyst described above were added to the
mixture. When a reaction was performed for 2 hours at 80.degree.
C., elastomerization occurred, and the reaction mixture assumed a
translucent, soft ricecake or jam-like consistency. In this case,
the Vi/H molar ratio when crosslinking was 1.2. As a result of
continuing the reaction for 2 more hours in this state in order to
advance crosslinking, the hardness increased and the mixture became
a dry, collapsible grease. Next, toluene was removed by heating
under reduced pressure.
[0407] Next, 25.3 g of a 2% citric acid aqueous solution was added,
and after the mixture was treated for 2 hours at 80.degree. C., 2%
baking soda water was added to neutralize the mixture for 1 hour.
By distilling out low-boiling-point matter while heating under
reduced pressure, an organopolysiloxane elastomer modified by
triglycerine group, a C1-2 alkyl group, and a group having a linear
polysiloxane structure was obtained. The composition was then
transferred to a Hobart mixture and subjected to kneading and
grinding for 3 hours to obtain a homogenized, white grease-like
composition. The elastomer was then subjected to kneading while
slowly adding 450 g of a dimethylpolysiloxane (6 cst) serving as a
diluent over the course of 3 hours to obtain a translucent or
white, soft paste-like composition (elastomer concentration:
33%).
Practical Examples 7 to 12 and Comparative Examples 3 and 4
[0408] The sensation during use was evaluated for the paste-like
compositions obtained in Practical Examples 1 to 6 and Comparative
Examples 1 and 2 (elastomer concentration: 33%) in accordance with
the following procedure and evaluation criteria. The results are
shown in Table 2. In the table, "parts" indicates "parts by weight
(mass)".
[0409] [Method of Functional Evaluation (Sensation During Use)]
1. 0.20 g of the paste-like composition was placed on a finger and
spread over the back of the hand. 2. At this time, the tactile
sensation at the time of application and during application and the
sensation on the skin after application were evaluated.
[0410] [Functional Evaluation Criteria]
"Tactile Sensation: At the Time of Application and During
Application"
[0411] .circleincircle.: The composition has excellent elastomeric,
soft elasticity and spreads smoothly. The composition is
characterized by a smoothness with a velvet-like thickness.
.smallcircle.: The composition has elastomeric, soft elasticity,
spreads smoothly, and has a unique thick feel. .DELTA.: The
spreadability is good and the sensation during use is smooth and
natural when first applied, but there is a conspicuous stickiness
and gooeyness while applied to the skin. The thick feel unique to
elastomers is also minimal. x: There is no problem with
spreadability, but there is a strong, oily stickiness and gooeyness
from when the composition is first applied until the end of the
test. The thick feel unique to elastomers is also minimal.
[0412] "Sensation on the Skin: After Application"
.circleincircle.: Skin compatibility is good, and a favorable
moisturizing feel is also achieved. In addition, the oiliness is
suppressed, so an extremely natural sensation on the skin with no
discomfort in terms of appearance can be obtained. .smallcircle.:
Skin compatibility is good, and a favorable moisturizing feel is
also achieved. In addition, the oiliness is suppressed, and there
is practically no discomfort. .DELTA.: The moisturizing feel is
reduced, and there is a slightly stronger oily tactile sensation.
x: Oily gooeyness is strong, and there is a feeling of warmth,
which is disagreeable.
TABLE-US-00002 TABLE 2 Table 2: Formulations and evaluation results
of the mixtures (compositions) with oil agents (Practical Examples
7 to 12 and Comparative Examples 3 and 4) Comparative Practical
Examples Examples Name of raw material 7 8 9 10 11 12 3 4
Paste-like composition of 100 -- -- -- -- -- -- -- Practical
Example 1 Paste-like composition of -- 100 -- -- -- -- -- --
Practical Example 2 Paste-like composition of -- -- 100 -- -- -- --
-- Practical Example 3 Paste-like composition of -- -- -- 100 -- --
-- -- Practical Example 4 Paste-like composition of -- -- -- -- 100
-- -- -- Practical Example 5 Paste-like composition of -- -- -- --
-- 100 -- -- Practical Example 6 Paste-like composition of -- -- --
-- -- -- 100 -- Comparative Example 1 Paste-like composition of --
-- -- -- -- -- -- 100 Comparative Example 2 Tactile sensation (at
the time .circleincircle. .circleincircle. .circleincircle.
.largecircle. .circleincircle. .largecircle. X .DELTA. of
application and during application) Sensation on the skin (after
.circleincircle. .circleincircle. .circleincircle. .largecircle.
.largecircle. .largecircle. X X application)
Practical Examples 13 to 18 and Comparative Examples 5 and 6
[0413] In accordance with the following procedure, the paste-like
compositions and mixtures with oil agents obtained in Practical
Examples 1 to 6 and Comparative Examples 1 and 2 were prepared as
prescribed by the formulations shown in Table 3 (elastomer
concentration: 10%) and Table 4 (elastomer concentration: 5%). In
addition, the viscosities of the resulting compositions were
measured, and the thickening/gelling effect of the oil agent of the
organopolysiloxane elastomer having a sugar alcohol-modified group
of the present invention was confirmed. The results are shown in
Tables 3 and 4. In the table, "parts" indicates "parts by weight
(mass)".
[0414] [Preparation Method for Mixture with Oil Agent]
1. The paste-like composition was placed in a Hobart mixer, and an
oil agent was dripped into the composition while mixing over the
course of 5 minutes to form a uniform composition. 2. The viscosity
of the mixture was measured under conditions at 25.degree. C.
TABLE-US-00003 TABLE 3 Table 3: Formulations and evaluation results
of mixtures (compositions) with oil agents (Practical Examples 13
to 18 and Comparative Examples 5 and 6) Comparative Practical
Examples Examples Name of raw material 13 14 15 16 17 18 5 6
Paste-like composition of 30 -- -- -- -- -- -- -- Practical Example
1 Paste-like composition of -- 30 -- -- -- -- -- -- Practical
Example 2 Paste-like composition of -- -- 30 -- -- -- -- --
Practical Example 3 Paste-like composition of -- -- -- 30 -- -- --
-- Practical Example 4 Paste-like composition of -- -- -- -- 30 --
-- -- Practical Example 5 Paste-like composition of -- -- -- -- --
30 -- -- Practical Example 6 Paste-like composition of -- -- -- --
-- -- 30 -- Comparative Example 1 Paste-like composition of -- --
-- -- -- -- -- 30 Comparative Example 2 Oil agent (6 cs, MO, ID,
IOTG)* 70 70 70 70 70 70 70 70 Viscosity (Pa s) oil agent = 6 cs
450 750 400 380 650 520 250 270 Viscosity (Pa s) oil agent = MO 230
660 380 400 610 220 190 190 Viscosity (Pa s) oil agent = ID 220 430
210 250 380 190 130 160 Viscosity (Pa s) oil agent = IOTG 680
>1,000 850 760 >1,000 710 520 550 Note* 6 cst:
dimethylpolysiloxane (6 cst) MO: mineral oil 50 SUS (37.8.degree.
C.) ID: Isododecane IOTG: Trioctanoin
TABLE-US-00004 TABLE 4 Table 4: Formulations and evaluation results
of mixtures (compositions) with oil agents (Practical Examples 19
to 24 and Comparative Examples 7 and 8) Comparative Practical
Examples Examples Name of raw material 19 20 21 22 23 24 7 8
Paste-like composition of 15 -- -- -- -- -- -- -- Practical Example
1 Paste-like composition of -- 15 -- -- -- -- -- -- Practical
Example 2 Paste-like composition of -- -- 15 -- -- -- -- --
Practical Example 3 Paste-like composition of -- -- -- 15 -- -- --
-- Practical Example 4 Paste-like composition of -- -- -- -- 15 --
-- -- Practical Example 5 Paste-like composition of -- -- -- -- --
15 -- -- Practical Example 6 Paste-like composition of -- -- -- --
-- -- 15 -- Comparative Example 1 Paste-like composition of -- --
-- -- -- -- -- 15 Comparative Example 2 Oil agent (6 cs, MO, ID,
IOTG)* 85 85 85 85 85 85 85 85 Viscosity ( Pa s) oil agent = 6 cs
250 410 220 210 360 290 120 130 Viscosity ( Pa s) oil agent = MO
130 360 210 220 340 130 90 95 Viscosity ( Pa s) oil agent = ID 120
240 120 140 210 110 60 75 Viscosity ( Pa s) oil agent = 370 830 450
430 730 360 260 280 IOTG Note* 6 cst: dimethylpolysiloxane (6 cst)
MO: mineral oil 50 SUS (37.8.degree. C.) ID: Isododecane IOTG:
Trioctanoin
[0415] It was found from the above results that the
organopolysiloxane elastomer having a sugar alcohol-modified group
of the present invention has excellent affinity with various oil
agents and that the elastomer can efficiently and stably thicken or
gelify various oil agents. In contrast, although also depending on
the type of oil agent used, the conventional hydrophilic
organopolysiloxane elastomers used in the comparative examples
required that a large amount of the elastomer be compounded in
order to demonstrate clear effects as an oil thickening agent, and
there was a problem from the perspective of the efficiency of
thickening or gelification.
Practical Examples 25 to 60 and Comparative Examples 9 to 20
[0416] Using the paste-like compositions obtained in Practical
Examples 1 to 6 and Comparative Examples 1 and 2, water-in-oil
emulsion compositions having the formulations shown in Tables 5 to
9 were prepared in accordance with the following procedure. These
compositions were evaluated in terms of the functionality (tactile
sensation and sensation during use), aesthetic appearance and form
stability, emulsified particle size stability, and odor over time
according to the evaluation criteria below. The results are shown
in Tables 5 to 9. In the table, "parts" indicates "parts by weight
(mass)".
[0417] Preparation Method for Water-in-Oil Emulsion Composition
1. The paste-like composition was placed in the pot of a Hobart
mixer. 2. An oil agent was dropped into the mixture while agitating
over the course of 5 minutes to obtain a uniform mixture (oil phase
A). 3. Table salt and ion exchanged water were placed in a separate
container. The salt was dissolved by mixing using a spatula.
Furthermore, 1,3-butylene glycol was mixed and dissolved therein
(aqueous phase B). 4. An aqueous phase B was dropped into the oil
phase A over the course of 10 minutes while agitating the oil phase
A with the Hobart mixer. 5. Agitation was halted after agitating
for two more minutes. The oily component and water droplets
adhering to the inner wall of the container were then scraped off
using a spatula and mixed with the produced emulsion. 6. The
mixture was further agitated for 3 minutes with the Hobart
mixer.
[0418] Functionality Evaluation (Tactile Sensation and Sensation
During Use)
[0419] The sensation during use at the time of application, during
application, and after application when using each water-in-oil
emulsion composition as a cosmetic composition was evaluated. Here,
all of the samples were at a level that was not problematic in
terms of spreadability and pure smoothness, so evaluations were
performed with focus on the following points. Also, relative
comparisons were carried out within groups that used a common oil
agent. Specifically:
1. 0.20 g of the water-in-oil emulsion composition was placed on a
finger and spread on the back of the hand. 2. At this time, the
watery tactile sensation and the thick smoothness unique to
elastomers at the time of application and during application were
evaluated, and the imparting of a moisturizing feeling and the
suppression of oiliness after application were evaluated in
accordance with the following criteria.
[0420] "Watery Tactile Sensation and Thick Smoothness Unique to
Elastomers: At the Time of Application and During Application"
.circleincircle.: The composition has an extremely watery tactile
sensation, and the unique thick and smooth tactile sensation is
ongoing. .smallcircle.: A watery tactile sensation is achieved, and
the unique thick and smooth tactile sensation is ongoing. .DELTA.:
A watery tactile sensation is achieved, but smoothness and
thickness are not perceived strongly. x: A slightly thick
smoothness is perceived, but the composition otherwise has the feel
of a common cream when applied, and practically no watery tactile
sensation is perceived. (Cases where the Emulsifying Itself was not
Possible are Also Indicated as "x")
[0421] "Imparting of a Moisturizing Feel and Suppression of
Oiliness after Application: Sensation on the Skin after
Application"
.circleincircle.: Skin compatibility is good, and a favorable
moisturizing feel is also achieved. In addition, the oiliness is
suppressed, so an extremely natural sensation during use with no
discomfort in terms of appearance can be obtained. .smallcircle.:
Skin compatibility is good, and a natural sensation on the skin is
achieved due to a favorable moisturizing feel, but there is a
slight degree of oily shininess. .DELTA.: Although the composition
has a moisturizing feeling, the oiliness and shininess are
troubling, and there is some discomfort with regard to the
sensation on the skin. x: The composition has no moisturizing
feeling and has strong oily gooeyness and shininess. (Cases where
the emulsifying itself was not possible are also indicated as
"x")
[0422] [Evaluation of emulsion appearance and form] The appearance
and form were observed and evaluated in accordance with the
following criteria on the day that each water-in-oil emulsion
composition was prepared and after the emulsion composition (28 g
allocated into a 35 ml glass vial and hermetically sealed) was left
to stand for 2 weeks at 50.degree. C.
.circleincircle.: The entire mixture is uniform and has a cream or
gel-like form with a matte texture. .smallcircle.: Most of the
mixture is uniform and has a cream or gel-like form with a matte
texture. Slight deposits may be present. .DELTA.: The surface
roughness of the emulsion can be easily seen, and there is a
somewhat large amount of unevenness and deposits. x: Emulsification
itself is not complete, and phase separation is observed or the
surface is clearly uneven.
[0423] Measurement of Emulsified Particle Size and Evaluation of
Stability
[0424] One day after preparing the water-in-oil emulsion
compositions, and after allowing the emulsion compositions (the
capped 35 mL glass bottles containing 28 g of each water-in-oil
emulsion composition, as described above) to sit at rest at
50.degree. C. for two weeks, the compositions were observed
(1.000.times.) and photographed using an optical microscope, and
the distribution range of the particle sizes was visually
determined. Thereby, stability was evaluated by examining the
initial emulsified particle size and the emulsified particle size
over time.
[0425] Note that notes were made in the tables when particle
coalescence was observed.
.circleincircle.: Change in emulsified particle size was small, and
signs of coalescence were absent. .smallcircle.: The emulsified
particle size potentially increased slightly but definite
coalescence was not observed. Alternatively, the emulsified
particle size increased, but the overall particle size was small
and the emulsion system was maintained. .DELTA.: It is thought that
partial coalescence of the particles occurred. Definite increase in
the emulsified particle size. x: Many particles were coalesced and
emulsion was in the state of breaking down. (Cases where the
emulsifying itself was not possible are also indicated as "x")
[0426] [Evaluation of Emulsion Odor Over Time]
[0427] After allowing the emulsion compositions (the capped 35 mL
glass bottles containing 28 g of each water-in-oil emulsion
composition, as described above) to sit at rest at 50.degree. C.
for two weeks, the compositions were removed and returned to room
temperature. The bottles were opened on the next day, and the odor
produced was evaluated in accordance with the following criteria.
Note that relative comparisons were carried out within groups that
used a common oil agent.
.circleincircle.: Level with practically no noticeable odor.
.smallcircle.: Slight odor (sweet solution-like specific odor) is
perceived. .DELTA.: Moderate odor (sweet solution-like specific
odor) is perceived. x: Strong odor (sweet solution-like specific
odor) is perceived.
TABLE-US-00005 TABLE 5 Table 5: Formulations and evaluation results
of the water-in-oil emulsion compositions (Practical Examples 25 to
30 and Comparative Examples 9 and 10) Comparative Practical
Examples Examples Name of raw material 25 26 27 28 29 30 9 10
Paste-like composition of Practical 6.7 -- -- -- -- -- -- --
Example 1 Paste-like composition of Practical -- 6.7 -- -- -- -- --
-- Example 2 Paste-like composition of Practical -- -- 6.7 -- -- --
-- -- Example 3 Paste-like composition of Practical -- -- -- 6.7 --
-- -- -- Example 4 Paste-like composition of Practical -- -- -- --
6.7 -- -- -- Example 5 Paste-like composition of Practical -- -- --
-- -- 6.7 -- -- Example 6 Paste-like composition of -- -- -- -- --
-- 6.7 -- Comparative Example 1 Paste-like composition of -- -- --
-- -- -- -- 6.7 Comparative Example 2 Dimethylpolysiloxane (6 cst)
18.3 18.3 18.3 18.3 18.3 18.3 18.3 18.3 Sodium chloride 0.5 0.5 0.5
0.5 0.5 0.5 0.5 0.5 Purified water 68.5 68.5 68.5 68.5 68.5 68.5
68.5 68.5 1,3-butylene glycol 6 6 6 6 6 6 6 6 Sensation during use
(at the time .circleincircle. .circleincircle. .circleincircle.
.circleincircle. .circleincircle. .circleincircle. X .DELTA. of
application until after application) Sensation during use (senation
on .circleincircle. .circleincircle. .circleincircle.
.circleincircle. .largecircle. .circleincircle. X .largecircle. the
skin) Appearance and form (initial) .circleincircle.
.circleincircle. .circleincircle. .circleincircle. .circleincircle.
.largecircle. .circleincircle. .circleincircle. Appearance and form
(over time) .circleincircle. .circleincircle. .circleincircle.
.circleincircle. .circleincircle. .largecircle. .circleincircle.
.largecircle. Initial particle size distribution (.mu.m) 3-11 3-15
3-12 3-10 1-7 3-10 1-5.2 2-11 Pass Particle size distribution over
time 3-11 3-14 3-12 3-11 1-8 3-11 1-8 2-20 (.mu.m) Pass Stability
of emulsified particles .circleincircle. .circleincircle.
.circleincircle. .circleincircle. .circleincircle. .circleincircle.
.largecircle. .DELTA. Odor of emulsion over time .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle.
TABLE-US-00006 TABLE 6 Table 6: Formulations and evaluation results
of the water-in-oil emulsion compositions (Practical Examples 31 to
36 and Comparative Examples 11 and 12) Comparative Practical
Examples Examples Name of raw material 31 32 33 34 35 36 11 12
Paste-like composition of 6.7 -- -- -- -- -- -- -- Practical
Example 1 Paste-like composition of -- 6.7 -- -- -- -- -- --
Practical Example 2 Paste-like composition of -- -- 6.7 -- -- -- --
-- Practical Example 3 Paste-like composition of -- -- -- 6.7 -- --
-- -- Practical Example 4 Paste-like composition of -- -- -- -- 6.7
-- -- -- Practical Example 5 Paste-like composition of -- -- -- --
-- 6.7 -- -- Practical Example 6 Paste-like composition of -- -- --
-- -- -- 6.7 -- Comparative Example 1 Paste-like composition of --
-- -- -- -- -- -- 6.7 Comparative Example 2 Mineral oil 50SUS
(37.8.degree. C.) 18.3 18.3 18.3 18.3 18.3 18.3 18.3 18.3 Sodium
chloride 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Purified water 68.5 68.5
68.5 68.5 68.5 68.5 68.5 68.5 1,3-butylene glycol 6 6 6 6 6 6 6 6
Sensation during use (at the .circleincircle. .circleincircle.
.circleincircle. .circleincircle. .circleincircle. .circleincircle.
X .DELTA. time of application until after application) Sensation
during use (senation .circleincircle. .circleincircle.
.circleincircle. .circleincircle. .largecircle. .circleincircle. X
.largecircle. on the skin) Appearance and form (initial)
.circleincircle. .circleincircle. .circleincircle. .circleincircle.
.circleincircle. .largecircle. .circleincircle. .circleincircle.
Appearance and form (over .circleincircle. .circleincircle.
.circleincircle. .circleincircle. .circleincircle. .largecircle.
.circleincircle. .largecircle. time) Initial particle size
distribution 2-8 2-11 2-10 2-10 1-6 2-9 2-7 2-30 (.mu.m) Pass
Particle size distribution over 2-10 2-10 2-11 2-10 1-6 2-11 2-10
4-30 time (.mu.m) Pass Stability of emulsified particles
.largecircle. .circleincircle. .circleincircle. .circleincircle.
.circleincircle. .largecircle. .largecircle. .DELTA. Odor of
emulsion over time .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle.
TABLE-US-00007 TABLE 7 Table 7: Formulations and evaluation results
of the water-in-oil emulsion compositions (Practical Examples 37 to
42 and Comparative Examples 13 and 14) Comparative Practical
Examples Examples Name of raw material 37 38 39 40 41 42 13 14
Paste-like composition of 6.7 -- -- -- -- -- -- -- Practical
Example 1 Paste-like composition of -- 6.7 -- -- -- -- -- --
Practical Example 2 Paste-like composition of -- -- 6.7 -- -- -- --
-- Practical Example 3 Paste-like composition of -- -- -- 6.7 -- --
-- -- Practical Example 4 Paste-like composition of -- -- -- -- 6.7
-- -- -- Practical Example 5 Paste-like composition of -- -- -- --
-- 6.7 -- -- Practical Example 6 Paste-like composition of -- -- --
-- -- -- 6.7 -- Comparative Example 1 Paste-like composition of --
-- -- -- -- -- -- 6.7 Comparative Example 2 Isododecane 18.3 18.3
18.3 18.3 18.3 18.3 18.3 18.3 Sodium chloride 0.5 0.5 0.5 0.5 0.5
0.5 0.5 0.5 Purified water 68.5 68.5 68.5 68.5 68.5 68.5 68.5 68.5
1,3-butylene glycol 6 6 6 6 6 6 6 6 Sensation during use (at the
.circleincircle. .circleincircle. .circleincircle. .circleincircle.
.circleincircle. .circleincircle. X X time of application until
after application) Sensation during use (senation .circleincircle.
.circleincircle. .circleincircle. .circleincircle. .circleincircle.
.circleincircle. X X on the skin) Appearance and form (initial)
.circleincircle. .circleincircle. .circleincircle. .circleincircle.
.circleincircle. .largecircle. .circleincircle. X Appearance and
form (over .circleincircle. .circleincircle. .circleincircle.
.circleincircle. .circleincircle. .largecircle. .circleincircle. X
time) Initial particle size distribution 2-10 3-13 3-13 3-11 2-9
3-12 2-9 -- (.mu.m) Particle size distribution over 2-10 3-12 3-13
3-11 2-7 3-13 2-10 -- time (.mu.m) Stability of emulsified
particles .circleincircle. .circleincircle. .circleincircle.
.circleincircle. .circleincircle. .largecircle. .largecircle. X
Odor of emulsion over time .circleincircle. .circleincircle.
.circleincircle. .circleincircle. .circleincircle. .circleincircle.
.circleincircle. --
TABLE-US-00008 TABLE 8 Table 8: Formulations and evaluation results
of the water-in-oil emulsion compositions (Practical Examples 43 to
48 and Comparative Examples 15 and 16) Comparative Practical
Examples Examples Name of raw material 43 44 45 46 47 48 15 16
Paste-like composition of 6.7 -- -- -- -- -- -- -- Practical
Example 1 Paste-like composition of -- 6.7 -- -- -- -- -- --
Practical Example 2 Paste-like composition of -- -- 6.7 -- -- -- --
-- Practical Example 3 Paste-like composition of -- -- -- 6.7 -- --
-- -- Practical Example 4 Paste-like composition of -- -- -- -- 6.7
-- -- -- Practical Example 5 Paste-like composition of -- -- -- --
-- 6.7 -- -- Practical Example 6 Paste-like composition of -- -- --
-- -- -- 6.7 -- Comparative Example 1 Paste-like composition of --
-- -- -- -- -- -- 6.7 Comparative Example 2 Trioctanoin 18.3 18.3
18.3 18.3 18.3 18.3 18.3 18.3 Sodium chloride 0.5 0.5 0.5 0.5 0.5
0.5 0.5 0.5 Purified water 68.5 68.5 68.5 68.5 68.5 68.5 68.5 68.5
1,3-butylene glycol 6 6 6 6 6 6 6 6 Sensation during use (at the
.circleincircle. .circleincircle. .circleincircle. .circleincircle.
.circleincircle. .circleincircle. X X time of application until
after application) Sensation during use .circleincircle.
.circleincircle. .circleincircle. .circleincircle. .circleincircle.
.circleincircle. X X (senation on the skin) Appearance and form
(initial) .largecircle. .circleincircle. .circleincircle.
.circleincircle. .circleincircle. .largecircle. .circleincircle.
.circleincircle. Appearance and form (over .largecircle.
.circleincircle. .circleincircle. .circleincircle. .circleincircle.
.largecircle. .circleincircle. .largecircle. time) Initial particle
size distribution 1-6 1-5 1-4 1-4 1-4 1-6 1-5 3-30 (.mu.m) Pass
Particle size distribution over 1-8 1-5 1-4 1-4 1-4 1-8 1-7 3-30
time (.mu.m) Pass Stability of emulsified particles
.circleincircle. .circleincircle. .circleincircle. .circleincircle.
.circleincircle. .largecircle. .largecircle. .DELTA. Odor of
emulsion over time .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle.
TABLE-US-00009 TABLE 9 Table 9: Formulations and evaluation results
of the water-in-oil emulsion compositions (Practical Examples 49 to
52 and Comparative Examples 17 and 18) Comparative Practical
Examples Examples Name of raw material 49 50 51 52 17 18 Paste-like
composition of Practical Example 2 6.7 -- -- -- -- -- Paste-like
composition of Practical Example 3 -- 6.7 -- -- -- -- Paste-like
composition of Practical Example 4 -- -- 6.7 -- -- -- Paste-like
composition of Practical Example 5 -- -- -- 6.7 -- -- Paste-like
composition of Comparative Example 1 -- -- -- -- 6.7 -- Paste-like
composition of Comparative Example 2 -- -- -- -- -- 6.7 Sunflower
oil 9.15 9.15 9.15 9.15 9.15 9.15 Mineral oil 50SUS (37.8.degree.
C.) 9.15 9.15 9.15 9.15 9.15 9.15 Sodium chloride 0.5 0.5 0.5 0.5
0.5 0.5 Purified water 68.5 68.5 68.5 68.5 68.5 68.5 1,3-butylene
glycol 6 6 6 6 6 6 Sensation during use (at the time of application
.circleincircle. .circleincircle. .circleincircle. .circleincircle.
X X until after application) Sensation during use (senation on the
skin) .circleincircle. .circleincircle. .circleincircle.
.circleincircle. X X Appearance and form (initial) .circleincircle.
.circleincircle. .circleincircle. .circleincircle. .circleincircle.
X Appearance and form (over time) .circleincircle. .circleincircle.
.circleincircle. .circleincircle. .largecircle. X Initial particle
size distribution (.mu.m) 1-5 1-5 1-5 1-6 1-6 -- Particle size
distribution over time (.mu.m) 1-5 1-5 1-5 1-5 2-9 -- Stability of
emulsified particles .circleincircle. .circleincircle.
.circleincircle. .circleincircle. .DELTA. X Odor of emulsion over
time .largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. --
[0428] Based on the above results, it was found that by using
ground particles of the sugar alcohol-modified organopolysiloxane
elastomer of the present invention as an emulsifier for a
water-in-oil emulsion composition, it is possible to stably
emulsify/disperse an aqueous phase in various oil agents having
various characteristics such as polar ester oils (trioctanoin,
sunflower oil), mineral oils with relatively high molecular
weights, and non-polar isododecane having a low molecular weight in
addition to silicone oils, and that an emulsion having the
contradictory characteristics of an extremely soft structure and
tactile sensation while having high viscosity capable of
guaranteeing stability can be obtained.
[0429] In particular, since conventional emulsifiers have a limited
effect of improving the tactile sensation of oil agents, only hard
emulsions with a heavy tactile sensation were obtained with
formulations containing large amounts of ester oils such as
triglycerides. However, by using the organopolysiloxane elastomer
of the present invention, an extremely watery tactile sensation and
a smooth, velvet-like sensation during use with a unique thick
feeling can be imparted even with formulations containing large
amounts of such heavy oil agents, and the emulsification stability
can be secured. That is, the ground partiesl of the sugar
alcohol-modified organopolysiloxane elastomer of the present
invention can be used with much more versatility than the
conventional hydrophilic silicone elastomers used in the
comparative examples, and it was confirmed that the elastomer
dramatically increases the overall value of the external use
preparation or cosmetic composition.
[0430] Further, the emulsion obtained here has the excellent
feature that there is very little odor generation due to the
passage of time or temperature, which verifies that the emulsion is
extremely useful as a raw material for an external use preparation
or a cosmetic composition.
Practical Example 53
[0431] The polyol (non-water)-in oil emulsion composition with the
formulation shown in Table 10 was prepared using the paste-like
composition obtained in Practical Example 1. In the table, "parts"
indicates "parts by weight (mass)".
TABLE-US-00010 TABLE 10 Table 10: Formulation of non-water-in-oil
emulsion composition (Practical Example 53) Name of raw material
Practical Example 53 Paste-like composition of 6.7 Practical
Example 1 Oil agent: dimethylpolysiloxane 13.3 (2 cst) Sodium
chloride 1.0 Ascorbic acid 1.0 Propylene glycol 78.0
[0432] [Preparation Method for Non-Water-in-Oil Emulsion
Composition] [0433] 1. The paste-like composition was placed in the
pot of a Hobart mixer. [0434] 2. An oil agent was dropped into the
mixture while agitating over the course of 5 minutes to obtain a
uniform mixture (oil phase A). [0435] 3. Table salt, ascorbic acid,
and propylene glycol were placed in a separate container, mixed
well with a spatula, and dissolved (polyol phase B). [0436] 4. The
polyol phase B was dropped into the oil phase A over the course of
5 minutes while agitating the oil phase A with the Hobart mixer.
[0437] 5. Agitation was halted after agitating for two more
minutes. The oily component and polyol phase adhering to the inner
wall of the container were then scraped off using a spatula and
mixed with the produced emulsion. [0438] 6. The mixture was further
agitated for 3 minutes with the Hobart mixer.
[0439] The cream or gel-like emulsion composition obtained here was
stable without any noticeable changes in appearance or form even
after being stored for 2 weeks at 50.degree. C.
Practical Example 54
[0440] Using the paste-like composition obtained in Practical
Example 1, a water-in-oil emulsion clear gel-type antiperspirant
composition with the formulation shown in Table 11 was prepared in
accordance with the following procedure. In the table, "parts"
indicates "parts by weight (mass)".
[0441] Preparation procedure [0442] 1. Components 1 to 3 were mixed
and dissolved uniformly (oil agent). [0443] 2. Component 4 was
placed in the pot of the Hobart mixer. [0444] 3. An oil agent was
dropped into the mixture while agitating with the Hobart mixer over
the course of 5 minutes to obtain a uniform mixture (oil phase A).
[0445] 4. Specified amounts of the aqueous phase components
(excluding the ion exchange water No. 10 shown last) were placed in
a separate container and mixed and dissolved using a spatula
(aqueous phase B). [0446] 5. Two or three drops of each of these
two phases were sampled, and refractive indices (RI) of each at
25.degree. C. were measured. [0447] 6. The up to 1.0 parts of ion
exchange water (No. 10) shown last was added in small portions so
that the RI value of the aqueous phase was within 0.0001 units and
matched the RI of the oil phase. This process was repeated until
the desired matching of the RI values was achieved. [0448] 7. The
aqueous phase B was poured into the oil phase A little by little
over the course of approximately 10 minutes while agitating the oil
phase A with the Hobart mixer. [0449] 8. Agitation was halted after
agitating for two more minutes, oil component and aqueous component
adhered to the inner wall of the container was scraped off by using
a spatula and mixed with the produced W/O transparent emulsion
composition. [0450] 9. The mixture was further agitated for 3
minutes with the Hobart mixer.
TABLE-US-00011 [0450] TABLE 11 Table 11: Formulation of a
water-in-oil transparent gel- like antiperspirant composition
(Practical Example 54) Practical No. Component Example 54 Portion
A: Oil phase -- 1 Dimethylpolysiloxane (2 cst) 13.0 2
Dimethylpolysiloxane (20 cst) 3.3 3 Isopropyl palmitate 1.0 4
Paste-like composition of Practical 6.7 Example 1 Portion B:
Aqueous phase -- 5 Ion exchange water 14.5 6 Propylene glycol 10.0
7 POE (20) sorbitan monooleate 0.66 8 50% aluminum chlorohydrate
aqueous 40.0 solution 9 70% sorbitol aqueous solution 13.6 10 Ion
exchange water (for balancing with 0.05 the RI of Portion A) Total
~103 Measurement RI of portion A (at 25.degree. C.) 1.4025 RI of
portion B (at 25.degree. C.) 1.4025 Final RI (at 25.degree. C.)
1.4027
[0451] The water-in-oil emulsion transparent gel-like
antiperspirant composition obtained here was stable with no
noticeable changes in appearance or form even after being stored
for 2 weeks at 50.degree. C.
Practical Example 55 and Comparative Examples 21 and 22
[0452] In accordance with the following procedure, oil-based
foundations containing the paste-like compositions obtained in
Practical Example 1 and Comparative Examples 1 and 2 were prepared
as prescribed by the formulations in Table 12. In addition, an
artificial leather surface was coated with each obtained foundation
using a Meyer bar, and the cosmetic retention was evaluated in
accordance with the following evaluation criteria for films
obtained after the foundations dried. The storage stability of the
obtained foundations was also evaluated. The results are shown in
Table 12. In the table, "parts" indicates "parts by weight
(mass)".
[0453] [Oil-Based Foundation Preparation Method]
1. Components other than an inorganic powder were dissolved or
uniformly dispersed while agitating at 70 to 80.degree. C. 2. An
inorganic powder (silicone-treated kaolin, silicone-treated
titanium dioxide, and silicone-treated red iron oxide) was added to
this, mixed well, and uniformly dispersed. 3. After being degassed,
a container was filled with the mixture, and the mixture was
returned to room temperature.
[0454] [Cosmetic Retention Test Method]
1. After an artificial leather surface was coated with an oil-based
foundation using a Meyer bar, the foundation was left to stand
overnight and dried in a constant-temperature bath at 40.degree. C.
Three of these samples were prepared for each foundation. 2. A
filter paper soaked with water, a filter paper soaked with
squalane, and a filter paper not soaked with anything were
prepared. 3. The artificial leather surfaces coated with the
foundation in 1 were pressed into the filter papers of 2 and moved
forward and backward ten times. 4. The amount of transfer of the
sample from the artificial leather to the filter paper after the
completion of the forward and backward movements was determined
visually based on the darkness of the color.
[0455] [Cosmetic Retention Evaluation Criteria]
.circleincircle.: No transfer whatsoever. .smallcircle.: Very
little transfer. .DELTA.: Some transfer. x: Severe transfer.
[0456] [Storage Stability Test Method]
1. First, 28 g of each oil-based foundation was measured in a 35 mL
glass bottle. The bottles were capped and allowed to sit at rest in
a 50.degree. C. constant temperature bath for two weeks. 2. The
bottles were removed and allowed to return to room temperature, and
the presence or absence of changes in appearance relative to the
initial appearance was confirmed.
[0457] [Storage Stability Evaluation Criteria]
.circleincircle.: No changes in appearance are observed.
.smallcircle.: Practically no abnormalities in appearance are
observed. .DELTA.: Slight powder precipitation or slight separation
of the oil phase is observed on the surface. x: Powder
precipitation or phase separation are clearly observed.
TABLE-US-00012 TABLE 12 Table 12: Formulations and evaluation
results of the oil-based foundations (Practical Example 55 and
Comparative Examples 21 and 22) Practical Comparative Examples
Examples Name of raw material 55 21 22 Paste-like composition of
Practical Example 1 8 -- -- Paste-like composition of Comparative
-- 8 -- Example 1 Paste-like composition of Comparative -- -- 8
Example 2 Microcrystalline wax 4 4 4 Mineral oil 3 3 3 Sorbitan
sesquioleate 1 1 1 Decamethyl cyclopentasiloxane 39 39 39 Isopropyl
myristate 2 2 2 Silicone-treated kaolin 25 25 25 Silicone-treated
titanium dioxide 15 15 15 Silicone-treated red Iron oxide 3 3 3
Cosmetic retention (not applied) .circleincircle. .largecircle.
.circleincircle. Cosmetic retention (water application)
.circleincircle. .largecircle. .circleincircle. Cosmetic retention
(squalane application) .circleincircle. .DELTA. .largecircle.
Storage stability .circleincircle. .circleincircle. .DELTA.
[0458] As described above, it was confirmed that when the sugar
alcohol-modified organopolysiloxane elastomer of the present
invention is used, the moisture resistance and sebum resistance of
a cosmetic composition containing the powder improve in comparison
to cases in which the conventional hydrophilic group-containing
organopolysiloxane elastomers used in the comparative examples are
used, and there is little secondary adhesion. In addition, the
oil-based foundations using the organopolysiloxane elastomer of the
present invention demonstrated good storage stability. These
results indicate that the organopolysiloxane elastomer of the
present invention is an excellent powder dispersion stabilizer.
[0459] Further, the organopolysiloxane elastomer of the present
invention can be used in formulations 1 to 47 of the specific
cosmetic compositions shown in the table below.
TABLE-US-00013 TABLE 13 Formulation example 1: W/O cream foundation
Formulation example 2: W/O Liquid foundation Formulation example 3:
W/O compact foundation Formulation example 4: O/W/O liquid
foundation Formulation example 5: W/O makeup foundation Formulation
example 6: Rouge Formulation example 7: Powder foundation
Formulation example 8: W/O compact foundation Formulation example
10: Eye shadow Formulation example 10: W/O UV cutting cream
Formulation example 11: W/O UV cutting emulsion Formulation example
12: O/W UV cutting cream Formulation example 13: W/O/W cream
Formulation example 14: O/W/O emulsion Formulation example 15: Skin
care emulsion Formulation example 16: Skin care cream Formulation
example 17: Foundation Formulation example 18: O/W sunscreen
Formulation example 19: Powder eye shadow Formulation example 20:
Rouge Formulation example 21: Mascara Formulation example 22: O/W
cream Formulation example 23: O/W cream Formulation example 24:
Stick-type antiperspirant Formulation example 25: Anhydrous roll-on
antiperspirant Formulation example 26: Nonaqueous anti- perspirant
deodorant stick composition Formulation example 27: W/O solid anti-
perspirant stick composition Formulation example 28: W/O emulsion
type anti-perspirant cream composition Formulation example 29:
Water-in-oil emulsion transparent antiperspirant composition
Formulation example 30: Non-aqueous stick-type antiperspirant
composition Formulation example 31: Hair conditioner Formulation
example 32: Shampoo Formulation example 33: Hair cream (set type)
Formulation example 34: Shampoo Formulation example 35: Hair
conditioner Formulation example 36: Hair treatment rinse type
Formulation example 37: Hair treatment leave-on type Formulation
example 38: Hair mist Formulation example 39: Hair foam Formulation
example 40: Hair spray Formulation example 41: Hair wax Formulation
example 42: Hair cream Formulation example 43: Hair lotion
Formulation example 44: Hair oil Formulation example 45: Hair color
oxidation type Formulation example 46: Hair manicure Formulation
example 47: Perm
[0460] The specific content of these formulation examples has been
disclosed in detail and in entirety in the patent application
corresponding to this application (Japanese Patent Application
involving a priority claim based on Japanese Patent Application No.
2011-121097) and the Japanese patent application serving as a basis
for the priority claim (Japanese Patent Application No.
2011-121097) filed in Japan by the present patent applicant on the
same day as this application, and the content thereof is
incorporated herein by reference.
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