TECHNICAL FIELD
[0001]
The present invention relates to a high-water-content emulsion gel using an oil
10 gelling agent containing a saccharide derivative, and particularly, to a high-water-content
W /0-type emulsion gel and a method for preparing the same.
BACKGROUND ART
15 [0002]
A structure containing a fluid in a three-dimensional network structure fmmed by a
substance (hereinafter referred to as a gelator) having a gel-fmming ability is called a gel.
Generally, a gel is called a hydrogel when the fluid is water, and is called an organogel or
oil gel when the fluid is an organic liquid other than water (such as an organic solvent or
20 oil). Oil gels ( organogels) are used to adjust the fluidity of cosmetics and paints in the
field of cosmetics, pharmaceuticals, pesticides, foods, adhesives, paints, resins, and the
like. Oil gels are also widely used in the field of environmental conservation, such as,
for example, the prevention of water contamination by gelating waste oil into solid
matter.
25 Furthermore, recently, a low molecular weight gelator has recently been repm1ed
which uses a saccharide derivative and is capable of achieving gelation of a mixed
solvent of water and oil (hydrophobic solvent) (Patent Document 1).
In addition, water/oil-mixed emulsions are used in the field of cosmetics and the like.
Generally, oil-in-water-type (0/W-type) emulsions exhibit better spreadability on skin
2
and have a less oily feeling than water-in-oil-type (W/O··type) emulsions, and thus have
more applications in cosmetics. However, W/0-type emulsions also provide a
refreshing feeling when the water content in a dispersed phase (internal phase) increases.
Thus, it is known that W /0-type emulsions are applied to products that are required to
5 both provide refreshing feeling and exhibit water resistance (Non-Patent Document 1).
It is also known that W /0-type emulsions exhibit skin moistness or cosmetic effects
that last for a long time, and that silicone-based W /0-type emulsions not only give a soft
and smooth feeling, but are also less likely to cause perspiration-induced deterioration of
cosmetic effects (Non-Patent Document 2).
10 Plior-Art Documents
Patent Documents
[0003]
Patent Document 1: International Publication No. 2013-056493
Non-Patent Document
15 [0004]
Non-Patent Document 1: J. Soc. Chem. Jpn., Vol. 4, No.2, 103-117 (2010)
Non-Patent Document 2: "New Perspectives on the Molecular Chemistry of
Interfaces", March 2011, edited by The Chemical Society of Japan
20 SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
(0005]
However, in the field of cosmetics, no report has been made on the application of a
W/0-type emulsion or silicone-based W/0-type emulsion gel having a high water content
25 in a dispersed phase (internal phase), i.e., a high-water-content W/0-type emulsion or
silicone-based W/0-type emulsion gel.
In addition, Patent Document I indicates that an emulsion gel can be formed from a
mixed solvent containing water and oil (hydrophobic organic solvent), but do not disclose
a high-water-content W /0-type emulsion gel. lt is generally known that when a
3
high-water-content mixed solvent of water and oil is used as a gel, an 0/W-type emulsion
gel is easily obtained, however, a W/0-type emulsion is unstable, even if it is obtained.
Therefore, in the field of cosmetics and the like, there is a demand for a stable
high-water-content W /0-type emulsion gel which exhibits excellent spreadability on skin
5 and is remarkable in terms of both providing a refreshing feeling and exhibiting water
10
resistance.
The present invention has been made based on the above findings, and the purpose
of the present invention is to provide a stable high-water-content W/0-type emulsion gel
obtained from a mixed solvent of water and oil.
Means for Solving the Problems
[0006]
As a result of diligent research to solve the above problem, the present inventors
found that the combination of a surfactant and a low molecular weight gelator using a
15 saccharide derivative can form a W/0-type emulsion gel even in a high-water-content
mixed solvent of water and oil (hydrophobic organic solvent), and were thus able to
complete the present invention.
That is, according to a first aspect, the present invention pertains to a W /0-type
emulsion gel comprising:
20 a gel a tor composed of a compound of Formula (1) or (2) below
(wherein, R1 and R3 are each independently a linear or branched alkyl group having
a carbon atom number of 1 to 20, a cyclic alkyl group having a carbon atom number of 3
to 20, or a linear or branched alkenyl group having a carbon atom number of 2 to 20, n is
4
an integer of 0 or 1 to 4,
R2 is a hydrogen atom, a linear or branched alkyl group having a carbon atom
number of I to 10, or an aryl group optionally having a substituent, and
~and R5 are a hydroxyl group);
5 a surfactant; and
a mixed solvent of a hydrophobic organic solvent and water,
wherein the content of the gel a tor is l to 10% by mass with respect to the mass of the
mixed solvent.
According to a second aspect, the present invention pertains to a gel according to the
I 0 first aspect, wherein the surfactant is at least one surfactant selected from among a
nonionic surfactant, an anionic surfactant, or a cationic surfactant, the nonionic surfactant
being selected from the group consisting of sorbitan monolaurate, sorbitan monostearate,
sorbitan trioleate, polyoxyethylene sorbitan monolaurate, and polyoxyethylene sorbitan
monooleate, the anionic surfactant being selected from the group consisting of sodium
15 Iaury! sulfate and di(2-ethylhexyl) sodium sulfosuccinate (AOT), and the cationic
surfactant being selected from the group consisting of hexadecyltrimethylammonium
bromide and cetylpyridinium chloride.
According to a third aspect, the present invention pe1iains to a gel according to the
first or second aspect, wherein the compound of Formula (1) is a compound of Formula
20 (7)
below
(wherein, R1 is as defined in F01mula (1), and Me is a methyl group).
According to a fourth aspect, the present invention pe1iains to a gel according to any
25 one of the first to third aspects, wherein the hydrophobic organic solvent is at least one
selected from the group consisting of vegetable oils, esters, silicone oils, and
hydrocarbons.
5
According to a fifth aspect, the present invention pertains to a cosmetic or
phannacentical base material containing the gel according to any one of the first to fomth
aspects.
According to a sixth aspect, the present invention pertains to a cosmetic or
5 pharmaceutical base material containing the gel according to any one of the first to fourth
aspects and at least one polymeric compound.
10
15
According to a seventh aspect, the present invention pettains to method for
preparing a W /0-type emulsion gel, the method comprising:
a step in which
a hydrophobic organic solvent and water,
0.1-20% by mass of a gelator with respect to the total mass of the organic
solvent and the water, the gelator being composed of a compound ofFommla (1) or (2)
below
(wherein, R1 and R3 are each independently a linear or branched alkyl group
having a carbon atom number of l to 20, a cyclic alkyl group having a carbon atom
number of 3 to 20, or a linear or branched alkenyl group having a carbon atom number of
2 to 20, n is an integer of 0 or 1 to 4,
R2 is a hydrogen atom, a linear or branched alkyl group having a carbon atom
20 number of 1 to 10, or an aryl group optionally having a substituent, and
~ and R5 are a hydroxyl group), and
a surfactant are mixed, and the resultant mixture is dissolved via heating; and
a step for cooling the resultant solution.
Effects of the Invention
[0007]
6
The present invention can provide a W/0--type emulsion gel even in a water/oil
(hydrophobic organic solvent) system having a high water content. In addition, the
5 present invention uses a monosaccharide, such as glucose or a derivative thereof, as a raw
material of a gelator, and can thus provide a gel which exhibits excellent biological safety
and can be used in the field of cosmetics and the like.
Since the W/0-type emulsion gel ofthe present invention has an oily continuous
phase and an aqueous dispersed phase, the W/0-type emulsion gel is not easily washed
l 0 off with sweat or water, and can exhibit excellent spreadability on skin and provide a
refreshing feeling.
In addition, theW /0-type emulsion gel of the present invention has good storage
stability.
15 BRIEF DESCRIPTION OF THE DRAWINGS
[0008]
[FIG. 1] FIG. 1 (a) shows a photograph of the external appearance of a water/KF995
dispersion gel (water/KF995: 5/5 (vol/vol)) using glucose derivative [3] as described in
Example 3, and a confocal laser scmming microscope image of the dispersion gel. FIG.
20 1 (b) shows a photograph of the external appearance of a water/KF995 dispersion gel
(water/KF995: 8/2 (vollvol)) in which Tween 20 is added as described in Example 4, and
a confocal laser scmming microscope image of the dispersion gel.
25
[FIG. 2] FIG. 2 shows an SEM image of a 1% Tween 20-containing aqueous
solution-gel using glucose derivative [3] as described in Example 4.
MODES FOR CARRYING OUT THE INVENTION
[0009]
[Gelator]
The gelator used in the gel of the present invention is composed of a compound of
7
Formula (1) or (2) below
(wherein, R1 and R3 are each independently a linear or branched alkyl group having
a carbon atom number of 1 to 20, a cyclic alkyl group having a carbon atom number of 3
'
5 to 20, or a linear or branched alkenyl group having a carbon atom number of 2 to 20, n is
an integer of 0 or 1 to 4,
R2 is a hydrogen atom, a linear or branched alkyl group having a carbon atom
number of 1 to 10, or an aryl group optionally having a substitnent, and
~and Rs are a hydroxyl group).
10 [0010]
Examples of the linear alkyl group having a carbon atom number of 1 to 20 include
a methyl group, an ethyl group, ann-propyl group, ann-butyl group, an n-pentyl group,
an n-hexyl group, an n-heptyl group, an n-octyl group, ann-nonyl group, an n-decyl
group, an n-nndecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl
15 group, an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an
n-octadecyl group, an n-nonadecyl group, an n-eicosyl group, and the like.
Examples of the branched alkyl group having a carbon atom number of 1 to 20
include an isopropyl group, an isobutyl group, a sec-butyl group, a tett-butyl group, a
2-ethylhexyl group, and the like.
20 Examples of the cyclic alkyl group having a carbon atom number of 3 to 20 include
a group having a cyclopentyl ring structnre, a cyclohexyl ring structnre, or the like.
[0011]
Examples of the linear alkenyl group having a carbon atom number of2 to 20
include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group,
8
a hepteny group, an octenyl group, a noncnyl group, a decenyl group, and the like.
Examples of the branched alkcnyl group having a carbon atom number of 2 to 20
include a 2-methyl-2-propenyl group, an isopropenyl group, a 2-methyl-1-propenyl group,
a 2-methylallyl group, and the like.
5 [0012]
Examples of the linear or branched alkyl group having a carbon atom number of 1
to 10 include those having a carbon atom number of 1 to l 0 among the linear alkyl group
having a carbon atom number of 1 to 20 and branched alkyl group having a carbon atom
number of 1 to 20 mentioned above.
10 Examples of the aryl group include a phenyl group, a benzyl group, a !-naphthyl
group, a 2-naphthy1 group, a 1-antluyl group, a 1-phenantluyl group, and the like. In
addition, the aryl group may have a substituent, and examples of such a substituent
include a halogen atom, a linear, branched, or cyclic alkyl group which may contain an
ester bond, an amide bond or an ether bond, and the like.
15 [0013]
From the viewpoint of using a gclator to achieve favorable gelation of a solvent, R2
in Formula (1) or (2) is preferably a hydrogen atom or a methyl group.
In addition, from the viewpoint of being able to form a highly transparent gel
without syneresis when used in a high-water-content mixed solvent of water and oil
20 (hydrophobic organic solvent), Rl is preferably an octyl gronp, a decyl group, or a
dodecyl group.
[00 14]
A compound of F01mula (1) or (2) is obtained by a known method, for example, by
reacting a monosaccharide with benzaldehyde dimethyl acetal having the substituent on a
25 benzene ring.
Although the use of a monosaccharide is not pmiicularly limited as long as the
monosaccharide has a pyranose ring structure, examples thereof include allose, altrose,
glucose, mannose, gulose, idose, galactose, talose, and the like.
Among these, from the viewpoint of being relatively inexpensive and being
9
expected to have especially high biocompatibility, glucose is preferable as the
monosaccharide.
[0015]
Among the compounds of Formula (1) or (2), a compound of Formula (3) below,
5 which has a glucose moiety, is particularly preferable
(wherein, R1, R2, R3, and n are as defined in Formula (1)).
[0016]
Among the compounds of Fmmula (3), a compound of Formula (5) below is
10 preferable, and a compound of Formula (7) is more preferable.
(In Formula (5), R1 and R2 are as defmed in Formula (1).)
(In Formula (7), R1 is as defined in Formula (1), and Me is a methyl group.)
15 For example, R1 in the above fmmulae is preferably an alkyl group having a carbon
atom number of8 to 12, particularly an alkyl group having a carbon atom number of 12.
[0017]
In particular, a compound of Formula (3) (glucose-type gelator) has, as its greatest
featnre, the feature of exhibiting a gel-fanning ability in both water and oil (hydrophobic
20 organic solvent), and is capable of fanning a gel in a water/oil mixed solvent. In
addition, the compound enables an alcohol-based solvent to be gelled, and forms a highly
transparent gel in water.
[00 18]
10
[Gel]
TheW /0-type emulsion gel of the present invention can be obtained by gelating the
gelator, a surfactant, and a mixed solvent of a hydrophobic organic solvent and water.
Specifically, a preparation method in which a predetermined amount of the gel a tor is
5 dissolved via heating in a mixed solvent and the resultant solution is cooled is illustrated.
Typically, it is preferable to completely dissolve the gelator during the dissolution via
heating.
In addition, the term "gelation" herein refers to a state in which a liquid having
fluidity loses the fluidity.
lO Although not particularly limited as long as the effects of the present invention are
exhibited, the amount ofthe gelator used in the present invention is 0.1-20% by mass,
and preferably 0.2-10% by mass, for example, 0.25-5% by mass, with respect to the mass
of the mixed solvent.
The aforementioned gelator may be added to a mixed solvent, dissolved via heating
15 with stirring if necessary, and then left at room temperature to obtain a gel. The gel
strength can be adjusted by varying the concentration of the gelator.
[00 19]
The surfactant may be any one that, in combination with the gelator, enables a
W/0-type emulsion gel to be obtained from a mixed solvent of a hydrophobic organic
20 solvent and water, and a surfactant having lower toxicity, particularly a non-toxic one, is
preferable. For example, a nonionic surfactant, an anionic surfactant, and a cationic
surfactant may be preferable. Examples of the nonionic smfactant include sorbitan
monolaurate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan
monolaurate, polyoxyethylene sorbitan monooleate, and the like, examples of the anionic
25 surfactant include sodium !amyl sulfate (sodium dodecyl sulfate), sodium
di(2-ethylhexyl) sulfosuccinate (sodium bis(2-ethylhexyl) sulfosnccinate) (AOT), and the
like, examples of the cationic surfactant include hexadecyltrimethylammonium bromide
(hexadecyltrimethylammonium bromide), cetylpyridinium chloride
(hexadecylpyridinium chloride-hydrate), and the like, and these may be used alone or in
II
combinations of two or more.
In addition, the surfactant is not limited to a surfactant having a low HLB value,
which used as an emulsifier for conventional W /0-type emulsions, and a surfactant
having a high HLB value, which is used an emulsifier for 0/W-type emulsions, may be
5 used.
For example, polyoxyethylene sorbitan monolaurate (Tween 20; having a HLB value
of 16.7), known as an emulsifier for 0/W-type emulsions, is preferable.
The amount ofthe surfactant used in the present invention is not particularly limited
as long as the effects of the present invention are exhibited, and can be appropriately
I 0 selected according to the types of gel a tor and surfactant used. However, for example,
the amount of the surfactant is 0.1-20% by mass, preferably 0.5 to 10% by mass, with
respect to the mass of the mixed sol vent.
In the present invention, a more uniform and stable W /0-type emulsion gel, which
has a dispersed phase (water droplet) having a small particle size, can be obtained by the
15 addition of a surfactant.
[0020]
Although the solvent is not patticularly limited as long as gelation is not prevented,
preferred specific examples of the solvent include a mixed solvent of a hydrophobic
organic solvent and water, and the like. The ratio between a hydrophobic organic
20 solvent and water may be appropriately selected according to a desired gel. For
example, the volume ratio between a hydrophobic organic solvent and water is 5:95 to
95:5, preferably 70:30 to 5:95. The term "high-water-content" herein means that the
proportion of water is highest among the components of the gel, for example, the
propmtion of water in the gel is 50 vol% or more, for example, 75 vol% or more.
25 [0021]
Prefen·ed specific examples of the hydrophobic organic solvent include vegetable
oils such as olive oil, coconut oil, castor oil, jojoba oil, or sunflower oil; esters such as
cetyl octanoatc, isopropyl myristate, or isopropyl palmitate; and hydrocarbons such as
toluene, xylene, n-hexane, cyclohexane, octane, mineral oil, silicone oil, or hydrogenated
12
polyisobutene.
Among these, olive oil, isopropyl myristate, toluene, cyclohexane, silicon oils such
as a linear silicone, a cyclic silicone, an alkyl-modified silicone, a phenyl-modified
silicone, dimethicone, or dimethiconol, and octane are preferable as the hydrophobic
5 organic solvent.
A linear silicone (trade name: 2- ll84), a cyclic silicone (trade name: SH 245), an
alkyl-modified silicone (trade name: SS-3408), a phenyl-modified silicone (trade name:
PH-1555), dimethicone (trade name: BY-11-0 series), dimethiconol (trade name:
CB-1556), and the like, which are available from Dow Coming Toray Co., Ltd., may be
10 used as the silicone oil. A cyclic silicone (trade name: KF-995) available from
Shin-Etsu Chemical Co., Ltd. may also be used.
(0022]
In a range in which the gel-forming ability of the gelator is not inhibited, various
additives (organic compounds such as ultraviolet absorbers, moisturizers, antiseptics,
15 antioxidants, perfumes, or physiologically active substances (active ingredient); inorganic
compounds such as titanium oxide, talc, mica, or water; and the like) may also be added,
as necessary, to the gel of the present invention depending on the application of the gel
and the like.
[0023]
20 [Cosmetic or phannaceutical base material]
The cosmetic or pharmaceutical base material of the present invention contains the
above mentioned gel.
The cosmetic or pharmaceutical base material of the present invention may also
contain an alcohol, a polyhydric alcohol, a hydrophilic organic solvent, or a mixed
25 solvent thereof, in addition to the gelator, the nonionic activator, the water, and the
hydrophobic organic solvent.
The hydrophilic organic solvent refers to an organic solvent which dissolves in water
to an arbitraty percentage, and examples thereof include alcohol, acetone, cyclohexanone,
acetonitrile, dioxane, glycerol, dimethylsulfoxide, and the like.
13
The alcohol is preferably a water-soluble alcohol which freely dissolves in water,
more preferably an alcohol having a carbon atom number of 1 to 9, a polyhydric alcohol,
a higher alcohol, and glycerides.
Specifically, examples of the alcohol having a carbon atom number of 1 to 9 include
5 methanol, ethanol, 2-propanol, i-butanol, pentanol, hexanol, 1-octanol, isooctanol, and
the like; examples of the polyhydric alcohol include ethylene glycol, propylene glycol,
polypropylene glycol, and the like; examples of the higher alcohol include
octyldodccanol, stearyl alcohol, oleyl alcohol, and the like; and examples of glycerides
include trioctanoin, tri( cap1yl caprylic acid) glyceryl, glyceryl stearate, and the like.
10 Among these, as the hydrophilic organic solvent, methanol, ethanol, 2-propanol,
i-butanol, pentanol, hexanol, 1-octanol, isooctanol, acetone, cyclohexanone, acetonitrile,
dioxane, glycerol, propylene glycol, ethylene glycol, and dimethylsulfoxide are
preferable, and glycerol, propylene glycol, and ethylene glycol are more preferable.
The cosmetic or pharmaceutical base material of the present invention may also
15 contain, as necessary, additives such as physiologically active substances and functional
substances, which are generally incorporated in cosmetic or pharmaceutical base
materials, and examples of such additives include oily bases, humectants, feel enhancers,
surfactants, polymers, thickening/gelling agents, solvents, propellants, antioxidants,
reducing agents, oxidizing agents, preservatives, antibacterial agents, bactericides,
20 chelating agents, pH adjusting agents, acids, alkalis, powders, inorganic salts, ultraviolet
absorbers, whitening agents, vitamins and derivatives thereof, hair growth promoters,
blood circulation promoters, stimulants, hormones, anti-wrinkle agents, anti-aging agents,
tightening agents, cooling agents, warming agents, wound healing promoters, in-itation
reducing agents, analgesic agents, cell activators, planl!animal/microbial extracts,
25 antipruritic agents, desquamating/keratolytic agents, antiperspirants, fresheners,
astringents, enzymes, nucleic acids, perfumes, colorants, coloring agents, dyes, pigments,
anti-inflammatory agents, antiphlogistils, antiasthmatic agents, anti-chronic obstructive
pulmonary disease drugs, anti-allergic agents, immunomodulators, anti-infective agents,
antifungal agents, and the like.
14
[0024)
The cosmetic or phmmaceutical base material of the present invention also contains
the gelator and at least one polymeric compound.
Examples of the polymeric compound include gelatin, sodium alginate, propylene
5 glycol alginate, gum arabic, polyvinyl alcohol, polyacrylic acid, sodium polyacrylate,
carboxymethyl cellulose, gellan gum, Xanthan gum, carrageenan polystyrene, polymethyl
methacrylate, polyvinylpyrrolidone, polyethylene oxide, polylactic acid, polystyrene
sulfonic acid, polyacrylonitrile, polyethylene, polyethylene terephthalate, and the like.
[0025)
10 In addition, the gel of the present invention can be used for materials in various
fields, such as cell culture substrates, substrates for storing biomolecules such as cells and
proteins, substrates for external use, biochemical substrates, food bases, contact lenses,
disposable diapers, mtificial actuators, and arid agricultural substrates. The gel of the
present invention can also be widely used as a bioreactor canier such as an enzyme in
15 various industries such as research, healthcare, and analysis.
[0026]
[Method for preparing gelator)
The method for preparing the gelator used in the gel of the present invention is not
patticularly limited. However, for example, a step, in which a compound of Formula
20 [A) below is reacted with an acetalizing agent, and then the resultant acetal derivative is
25
subjected to a condensation reaction with glucose or a derivative thereof to prepare a
compound of Formula (1) or (2), may be performed in one-pot operation in the presence
of ethanol and p-toluenesulfonic acid,
[A]
(wherein, R1 and R3 are each independently a linear or branched alkyl group having
a carbon atom number of l to 20, a cyclic alkyl group having a carbon atom number of 3
to 20, or a linear or branched alkenyl group having a carbon atom number of 2 to 20, and
n is an integer of 0 or 1 to 4).
[Examples]
[0027]
15
Hereinafter, in order to fmiher clarify the features of the present invention, the
5 following examples are described. However, the present invention is not limited to
these examples.
[0028]
Reagents used as raw materials for synthesis in the examples are shown below.
P-(dodecyloxy) benzaldehyde was obtained from Wako Pure Chemical Industries,
10 Ltd., and methyl a-D-glucopyranoside, p-toluenesulfonic acid monohydrate, and triethyl
orthofonnate were obtained fi·om Tokyo Chemical Industry Co., Ltd.
N,N-dimethylformamide (DMF) (dehydrated, for organic synthesis) used as a
reaction solvent was obtained from Wake Pure Chemical Industries, Ltd.
Sodium bicarbonate (special grade) used in post-reaction treatment and purification
15 was obtained from Wako Pure Chemical Industries, Ltd., and hexane (special grade) was
obtained from Kanto Chemical Co., Ltd.
Deuterochlorof01m (containing 0.03% TMS (tetramethylsilane)) used for NMR
measurement was obtained from Sigma-Aldrich Japan Co., Ltd.
[0029]
20 Solvents and reagents used in gelation tests and emulsion preparation are shown
below.
Polyoxyethylene (20) sorbitan monolauratc (equivalent to Tween 20), isopropyl
myristate (first grade), octane (special grade), and sodium Iaury! sulfate (for
biochemistry) were obtained from Wako Pure Chemical Industries, hexadecylpyridinimn
25 chloride monohydrate, hexadecyltlimethylammonium bromide, sodium bis(2-ethylhexyl)
sulfosuccinate, and Span 80 (sorbitan monooleate) were obtained from Tokyo Chemical
lndustry Co., Ltd., and KF-995 was obtained from Shin-Etsu Chemical Co., Ltd. The
water used was pure water.
[0030]
5
16
The apparatus and conditions used for various measurements, analysis and
polymerization are shown below.
(!) 1H-NMR spectrum
• Apparatus: A VANCE 500, manufactured by Bruker BioS pin K.K.
JNM-ECS 400, manufactured by JEOL Ltd.
(2) Vortex mixer
• Apparatus: Voltex Genie 2, manufactured by Scientific Industries, Inc.
(3) Confocal laser scanning microscope
• Apparatus: LSM 700, manufactured by Carl Zeiss AG
10 (4) Scanning electron microscope (SEM)
· Apparatus: Inspect S50, manufactured by FEI Company
[0031]
[Example 1: Synthesis of saccharide derivative]

15 Scheme I
RCHO
methyl-a-D..gluoopyranoside
p-TsOH•H20, HC(OEt)3
DMF
[2), [31
R---\"0~ ~0
OH
OMe
Synthesis of compound [3]: Triethyl orthofotmate (5.0 mL, 30 mmo1) was added to
a DMF (100 mL) suspension ofmethyl-u-D-glucopyranoside (8.74 g, 45 mmol),
p-(dodecyloxy) benzaldehyde [2] (8.71 g, 30 mmol) and p-toluenesulfonic acid
20 monohydrate (143 mg, 0.75 mmol) at room temperature. The reaction solution was
heated to 50°C and depressurized. After 6 hours, the reaction solution was allowed to
cool to room temperature, 200 mL of saturated aqueous sodium hydrogen carbonate
solution was added, and the mixture was filtered. The residue on the filter paper was
washed with 400 mL of pure water, and to the obtained solid was added pure water and
25 heated at 90°C for 30 minutes. The resulting suspension solution was filtered and
17
washed with 400 mL of pure water. The obtained solid was dried under reduced
pressure, finely pulverized, and then subjected to solid-liquid separation and washing
with 300 mL of hexane at room temperature. The suspension was filtered and washed
with 400 mL of hexane, and then the white powder was dried under reduced pressure to
5 obtain the target compound.
Yield: 83% (11.7 g) 1H NMR (400MHz, CDC13): {j 7.39 (2H, d, J= 8.7 Hz), 6.88
(2H, d, J = 8.7 Hz), 5.48 (lH, s), 4.80 (IH, d, J = 4.1 Hz), 4.27 (lH, dd, J = 4.6, 9.6 Hz),
3.98-3.88 (3H, m), 3.84-3.68 (2H, m), 3.63 (1H, dt, J= 4.1, 9.2 Hz), 3.52-3.41 (4H, m),
2.72 (IH, s), 2.27 (lH, d,J= 9.6 Hz), 1.76 (2H, quintet,]= 6.9 Hz), 1.50-1.16 (18H, m),
10 0.88 (3H, t, J = 6.9 Hz).
[0032]
Example 2: [Gelation test]

If a gel can be formed even when a surfactant is added, it follows that a water/oil
15 dispersion gel can be easily prepared. Therefore, the gel-forming ability when Tween
20 (HLB= 16. 7) having a high HLB value was added was investigated.
[0033]
The gelation test performed adding a surfactant was carried out as follows. 0.5 wt%
surfactant-containing aqueous solutions were prepared, in which various surfactants
20 (polyoxyethylene (20) sorbitan monolaurate (Tween 20) which is a nonionic surfactant,
hexadecylpyridinium chloride monohydrate (CPC) and hexadecyltrimethylamrnonium
bromide (CTAB), which are cationic surfactants, and sodium dodecyl sulfate (SDS) and
sodium bis(2-ethylhexyl) sulfosuccinate (AOT), which are anionic surfactants) were
dissolved in water. Subsequently, a gelator (glucose derivative [3]) was added, to a
25 predetermined concentration, to a 4 mL screw tube, and the prepared
surfactant-containing aqueous solution was added thereto and heated at 100°C for 30
minutes. The obtained solution was cooled to room temperature and left for one day.
The formation of gel was checked by turning the screw tube upside down. The results
are shown in Table 1.
18
[0034]
Table 1 Results of the gelation test for 0.5 wt% surfactant-containing aqueous
solutions
Gelator [3]
0.5 wt% Tween 20-containing
0.25TL
aqueous solution
0.5 wt% CPC-containing
0.25TL
aqueous solution
0.5 wt% CTAB-containing
0.25TL
aqueous solution
0.5 wt% SDS-containing
0.1 TP
aqueous solution
0.5 wt% AOT-containing
0.25TL
aqueous solution
Water Not dissolved
*The numerical values in the table indicate the minimum concentration (wt%) of the
5 gel a tor (compound) required to gelate each solvent.
* TL: translucent gel. TP: transparent gel.
[0035]
As shown in Table 1, the obtained results indicate that a hydrogel can be formed by
adding glucose derivative [3] and Tween 20 as a surfactant, etc. to water. On the other
10 hand, the glucose derivative [3] alone cannot form a hydrogel. The feature in which a
hydrogel can be formed by the addition of an oil gelling agent and a surfactant (in
patticular, the hydrogel can be formed regardless of the type of surfactant) is a very
distinct example.
In addition, by the same method, a hydrogel having self-sustainable hardness
15 (self-suppotting property) was obtained from an aqueous solution containing 2 wt% of
glucose derivative (3] and 1 wt% of Tween 20.
[0036]
[Example 3: Water/oil dispersion test using glucose derivative]

20 An emulsion preparation technology for unifonnly dispersing and stabilizing an oil
agent and water is required for various applications, such as cosmetics, pharmaceuticals,
foods, functional materials, and the like.
19
Suppressing the coalescence of droplets by gelating a continuous phase is an
impmiant factor in the stabilization of an emulsion. In tllis experimental result, the
W/0-type emulsion gel of the present invention has the potential to stabilize an emulsion
by inducing gelation of a continuous phase in W/0-type and 0/W-typc emulsions.
5 Therefore, in Example 3, a water/oil dispersion test was conducted in order to verifY
whether the W/0-type emulsion gel of the present invention can uniformly disperse both
sol vents of water and an oil agent.
[0037]
The water/oil dispersion test was carried out as follows. A gelator (glucose
10 derivative [3]), an oil agent (KF-995), and water were added, to predetermined
concentrations, to a 4 mL screw-capped sample tube. When Tween 20 was used in the
addition of a surfactant, a 1 wt% Tween 20-containing aqueous solution was used instead
of water. The sample tube, which contains a mixed solvent containing the gelator and
the like, was dissolved via heating for 30 minutes. Subsequently, the sample was
15 sheared off using a vottex mixer, and then left for 1 hour at room temperature to observe
the dispersed state. A state in which the solution lost fluidity after cooling so that the
solution did not flow down even when the sample tube was turned upside down, and in
which water and oil were unifonnly dispersed, was detetmined to be a "water/oil
dispersion gel". The obtained results are shown in Table 2.
20 [0038]
Table 2 Preparation test ofwater/KF-995 dispersion gel using glucose derivative
[3]
Glucose derivative [3]
Additive None Tween20
7/3 1 (100,3min.) ----------- KF-995/water
5/5 0.25 (100°C, 3 min.) ~
(vol/vol) 3/7 2 (1 oooc, 3 min.) 1 (100°C, 2 min.)
2/8 ~ 2 (100°C, 3 min.)
20
*The numerical values in the table indicate the concentration (wt%) of the gelator
(compound) required to gelate each solvent.
*The numerical values in parentheses in the table indicate heating temperature (0 C) and
shearing time (min.) by vortex mixer.
5 * Diagonal lines indicate that the test was not conducted.
[0039]
As shown in Table 2, even when the gelator (glucose derivative [3]) was used alone
in the preparation of a water/KF-995 dispersion gel, the dispersion gel could be prepared
at a ratio ofwater/KF-995 in which the fraction of water was larger than that ofKF-995,
10 as well as a ratio ofwater/KF-995 in which the fraction ofKF-995 (oil agent) was larger
than that of water. In addition, the dispersion gel could be prepared even when a
surfactant wad added.
Here, it was found tl1at when 0.05 wt% of the gelator (glucose derivative [3]) was
added and the ratio between 1 wt% Tween 20-containing aqueous solution and KF995
15 was 30/70 (vol/vol), the test conducted under the same preparation conditions as above
produced an 0/W-type emulsion instead of a gel.
[0040]

20 Based on the water/KF-995 dispersion gel preparation conditions, the preparation of
a dispersion gel was investigated using an aqueous solution containing 2 wt% of glucose
derivative [3] and 1 wt% of Tween 20 when the ratio of water/octane and the ratio of
water/IPM were 80/20 (val/val). The results are shown in Table 3.
Table 3 Preparation test of water/octane and water/IPM dispersion gels using
25 glucose derivative [3]
Solvent
Gelation
Water/octane Water!IPM
Yes (1 00°C, 5 min.) Yes (100°C, 5 min.)
* The numerical values in parentheses in the table indicate heating temperature (°C) and
shearing time (min.) by vmiex mixer.
[0041]
21
ln addition, based on the water/KF-995 dispersion gel preparation conditions, the
preparation of a dispersion gel was investigated using 0.5 wt% or 1.0 wt% of glucose
derivative (3] and 0.5 wt% of Span 80 when the ratio of water/octane was 80/20, 85/15,
90/10 and 95/5 (vol/vol). The results are shown in Table 4.
5 Table 4 Preparation test of water-octane dispersion gel using glucose derivative [3]
Water-octane
ratio 80/20 85/15 90/10 95/5
(vollvol)
Gelator 1.0 0.5 0.5 0.5
concentration
(100°C, 2 min.) (1 00°C, 5min.) (1 00°C, 5min.) (1 00°C, Smin.)
(wt%)
* The numerical values in parentheses in the table indicate heating temperature (0 C) and
shearing time (min.) by vortex mixer.
[0042]
From the results in tables 2, 3, and 4, it was revealed that a gel emulsion having a
10 high intemal phase ratio in various solvents can be prepared with a gel a tor concentration
of 2 wt% or less.
(0043]

15 An emulsion gel was prepared in the same manner as above using an aqueous
solution of 5 f!M uraninc, which is a fluorescent dye, instead of water, and confocal laser
scanning microscope was used to identify whether water is locally present in a dispersed
phase or locally present in a continuous phase. A photograph of the obtained sample
tube and a microscope image of the emulsion gel are shown in FIG. 1.
20 [0044]
From FIG. 1 (a), it was found that the water/KF-995 dispersion gel (water/KF-995:
5/5 (vol/vol)) using the glucose derivative [3] is a W/0-type emulsion gel (having an
aqueous dispersed phase and a continuous phase of KF-995). From FIG. 1 (b), it was
found that the high-water-content water/KF-995 dispersion gel (water/KF-995: 8/2
25 (vol/vol)) prepared using the 1 wt% Tween 20-containing aqueous solution instead of
22
water is a W /0-typc emulsion gel (having an aqueous dispersed phase and a continuous
phase of KF995).
Generally, Tween 20 is a surfactant used for forming an 0/W-type emulsion.
Meanwhile, in this experimental result, a W /0-type emulsion gel was formed. From the
5 results in Example 2, it was found that the glucose derivative [3], which does not have a
gel-forming ability in water, can be made to form a hydrogel by adding Tween 20 to
water. From these facts, it is suggested that a complex of glucose derivative [3] and
Tween 20 is involved in the formation of an emulsion gel.
In addition, in cosmetic applications, high-water-content W/0-type emulsions are
10 not easily washed off with sweat or water, exhibit excellent spreadability on skin, and arc
expected to be applied to products that are required to both feel refreshing and exhibit
water resistance. However, high-water-content W/0-type emulsions are known to be
generally unstable. By using the method according to the present invention, it was
shown that a high-water-content W /0-type emulsion, which is considered to be difficult
15 to prepare, can be prepared as a gel.
[0045]
[Example 4: SEM observation of gel]

20 SEM observation of 1% Tween 20-containing aqueous solution-gel (hydrogel) was
carried out as follows. A 1% Tween 20-containing aqueous solution-gel, in which 2
wt% of glucose derivative [3] was added, was prepared, and then was placed on a carbon
tape and observed using SEM under a reduced pressure of 80 Pa. The obtained result is
shown in FIG. 2.
25 As shown in the SEM image in FIG. 2, a phase in which fibrous stmctures were
30
bundled was obtained from the 1% Tween20-containing aqueous solution-gel (hydrogel)
using glucose derivative [3]. From this fact, it was revealed that the hydrogel composed
of glucose derivative [3] and surfactant Tween 20 formed a gel based on a fibrous
structure.

CLAIMS
1. A W /0-type emulsion gel comprising:
a gelator composed of a compound of Fmmula (I) or (2) below
(wherein, R1 and R3 are each independently a linear or branched alkyl group
having a carbon atom number of 1 to 20, a cyclic alkyl group having a carbon atom
number of 3 to 20, or a linear or branched alkenyl group having a carbon atom number of
2 to 20, n is an integer of 0 or 1 to 4,
R2 is a hydrogen atom, a linear or branched alkyl group having a carbon atom
number of 1 to 10, or an aryl group optionally having a substituent, and
R! and Rs are a hydroxyl group);
a surfactant; and
a mixed solvent of a hydrophobic organic solvent and water,
wherein the content of the gelator is 0.1-20% by mass with respect to the mass of
the mixed solvent.
2. The gel according to claim 1, wherein the surfactant is at least one surfactant
selected from among a nonionic surfactant, an anionic surfactant, or a cationic surfactant,
20 the nonionic surfactant being selected from the group consisting of sorbitan monolaurate,
sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, and
polyoxyethylene sorbitan monooleate, the anionic surfactant being selected from the
group consisting of sodium Iaury! sulfate and di(2-ethylhexyl) sodium sulfosuccinate
(AOT), and the cationic surfactant being selected from the group consisting of
5
24
hexadecyltrimethylammonium bromide and cetylpyridinium chloride.
3. The gel according to claim I or 2, wherein the compound of Formula (1) is a
compound ofFonnula (7) below
(wherein, R1 is as defined in Formula (1 ), and Me is a methyl group).
4. The gel according to any one of claims 1 to 3, wherein the hydrophobic organic
solvent is at least one selected from the group consisting of vegetable oils, esters, silicone
10 oils, and hydrocarbons.
15
20
5. A cosmetic or phatmaceutical base material containing the gel according to any
one of claims 1 to 4.
6. A cosmetic or phatmaceutical base material containing the gel according to any
one of claims l to 4, and at least one polymeric compound.
7. A method for preparing a W/0-type emulsion gel, the method comprising:
a step in which
a hydrophobic organic solvent and water,
0.1-20% by mass of a gel a tor with respect to the total mass of the
hydrophobic organic solvent and the water, the gel a tor being composed of a compound of
Formula ( 1) or (2) below
25
(wherein, R1 and R3 are each independently a linear or branched alkyl group
having a carbon atom number of I to 20, a cyclic alkyl group having a carbon atom
number of 3 to 20, or a linear or branched alkenyl group having a carbon atom number of
5 2 to 20, n is an integer of 0 or 1 to 4,
10
R2 is a hydrogen atom, a linear or branched alkyl group having a carbon atom
number of 1 to 10, or an aryl group optionally having a substituent, and
R