Note: Descriptions are shown in the official language in which they were submitted.
CA 02356474 2001-08-31
POLYETHER-POLYOL COMPOUND
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to a polyether-polyol compound and a
polyglycerol alkyl ether, an ester obtained by using the polyether-polyol
compound or the polyglycerol alkyl ether, and a composition comprising the
polyether-polyol compound, the polyglycerol alkyl ether or the ester.
Discussion of the Related Art
Conventionally, a polyether-polyol compound is prepared by carrying out
an addition reaction of an alcohol with an epoxy compound, or a condensation
reaction of a polyhydric alcohol at a high-temperature of 200°C or more
in the
presence of a catalyst. The polyether-polyol compound formed by such reactions
is mainly a linear compound. For instance, the structure of a polyglycerol, a
kind
of the polyether-polyol compound, can be generally represented as follows.
H H OH
HO 0 ~~OH
m
In the polyether-polyol compound having such a structure, as the degree
of polymerization increases, the number of secondary hydroxyl group positioned
in the inner part of the molecule increases, while the number of hydroxyl
group
positioned at a terminal of the molecule stays the time. The hydroxyl groups
other than those at a terminal of this polyether-polyol compound have a low
reactivity due to steric hindrance. Therefore, when the polyether-polyol
CA 02356474 2001-08-31
2
compound is utilized, for instance, as a crosslinking agent for the resin,
excess
energy must be applied by such means of heating, thereby causing such problems
as coloration.
In addition, the above-mentioned polyglycerol is esterified with a fatty
acid to be mainly utilized as surfactants for foods. In the esterification,
while the
reaction rapidly progresses at a terminal hydroxyl group, the reaction is
delayed
at a central hydroxyl group. Therefore, especially severe conditions are
required
to prepare a lipophilic ester by adding a large amount of a fatty acid,
thereby
undesirably making the flavor and hue poor.
Nonionic surfactants can be utilized for a wide variety of purposes such as
emulsification, solubilization, permeation, dispersion and washing. Widely
used
nonionic surfactants include glycerol fatty acid esters, sorbitan fatty acid
esters,
polyoxyethylene sorbitan fatty acid esters, polyethylene glycol fatty acid
esters,
polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers,
polyoxyethylene hardening castor oil derivatives, and the like. These nonionic
surfactants can be classified into ester-type, ether-type and ester-ether-type
by
the binding modes of the lipophilic group moiety with the hydrophilic group
moiety. Among them, ether-type surfactants are favorably utilized owing to
their
excellent stability against hydrolysis. As the hydrophilic group of the ether-
type
surfactant, polyoxyethylene is generally used. While the polyoxyethylene has
an
advantage of facilitation in the chain extension, there may arise such
problems
that harmful dioxane is formed during preparation, that formalin is generated
by
oxidation, and that the liquid becomes acidic.
In order to overcome the problems, ether-type surfactants having a
polyglycerol having high safety as a hydrophilic group have been developed.
CA 02356474 2001-08-31
For instance, Japanese Patent Laid-Open No. Sho 62-210049 discloses an ether
obtained from di-, tri-, or tetraglycerol and a higher alcohol, and Japanese
Patent
Laid-Open No. Hei 9-188755 discloses a process for preparing a polyglycerol
alkyl ether. However, conventional polyglycerols including those mentioned
above have a linear structure, and they are composed of a mixture of
polyglycerols having different degrees of polymerization. Therefore, a
polyglycerol alkyl ether having a branched structure has not yet known.
Specifically, the conventionally known polyglycerol is a polyglycerol
having a linear structure such as tetra-, hexa-, and decaglycerol, and its
degree of
polymerization is calculated on the basis of the hydroxyl value. Therefore,
each
polyglycerol does not mainly comprise tetra-, hexa-, and decamer of glycerol
as
indicated by its name, and each of them is composed of a mixture of
polyglycerol comprising monomer to deca- or more 'mers of glycerol. When an
alkyl ether is prepared by using the conventional polyglycerol, the resulting
product would undesirably be composed of a mixture of various kinds of alkyl
ethers. In addition, an alternative process for preparing a polyglycerol alkyl
ether includes a process comprising carrying out a condensation reaction of
glycidol or epichlorohydrin with an aliphatic alcohol. However, the degree of
condensation of the resulting polyglycerol is adjusted by the amount of
glycidol
or epichlorohydrin added, so that one composed of a single degree of
condensation cannot be obtained. The resulting polyglycerol alkyl ether
obtained by these processes is composed of a mixture of components having
different glycerol chain lengths, so that the compound does not exhibit the
function inherently owned by the polyglycerol alkyl ether, rendering it
necessary
to use a large amount of the polyglycerol alkyl ether to achieve its purpose.
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4
On the other hand, a polyglycerol fatty acid ester is a nonionic surfactant
having high safety which is approved as a food additive, and is widely used in
fields other than foods such as cosmetics and detergents. A polyglycerol which
is used as a raw material for the presently commercially available
polyglycerol
fatty acid ester is prepared by polymerizing a glycerol-related compound such
as
glycerol, glycidol or epichlorohydrin. The polyglycerol formed by this
reaction
is a linear polyglycerol as mentioned above, and this linear polyglycerol is
used
in the preparation of the linear fatty acid ester by means of esterification
with a
fatty acid ester, which the resulting ester is presently used as a surfactant.
Generally, the shape of the hydrophilic moiety of the hydrophilic
surfactant has a large effect on its performance. In order that the surfactant
exhibits its effects, the surfactant must be adsorbed to the interface and
cover its
entire surface. In the polyglycerol fatty acid ester having linear
polyglycerol
moiety represented by the formula mentioned above as a hydrophilic group, the
ester also takes a linear form. When the ester adsorbs to the interface, the
area
occupied by the adsorbed portion is a small value, approximating the cross-
sectional area of the ester. Therefore, in order to exhibit its surfactant
ability
sufficiently, the interface must be covered completely, thereby consuming a
large
amount of a surfactant. Consequently, lowering of product values such as
causing roughened skin when applied to cosmetics, and impairing flavors when
applied to foods.
An object of the present invention is to provide a novel polyether-polyol
compound, a polyglycerol alkyl ether and an ester having excellent
emulsification, solubilization, dispersion, detergency, foaming strength or
the
like, of a polyglycerol, and a composition comprising the polyether-polyol
CA 02356474 2001-08-31
compound, the polyglycerol alkyl ether or the ester.
These and other objects of the present invention will be apparent from the
following description.
5 SUMMARY OF THE INVENTION
According to the present invention, there are provided:
(1) a polyether-polyol compound represented by the compositional formula:
C3nH6n+2~2n+1 ~
wherein n is an integer of 4 or more,
wherein the polyether-polyol compound has a total number of 1,2-diol unit and
1,3-diol unit of [(n/2) + 1] in a case where n is an even number of 4 or more,
or a
total number of 1,2-diol unit and 1,3-diol unit of [((n - 1)/2) + 1] and one
hydroxyl group which is not involved in the units in a case where n is an odd
number of 5 or more;
(2) a polyglycerol alkyl ether, a part of hydroxyl groups in a polyglycerol
being substituted by an alkyl group, wherein the polyglycerol is the polyether
polyol compound of item (1) above;
(3) an ester prepared by the process comprising reacting the polyether-polyol
compound of item (1) above or the polyglycerol alkyl ether of item (2) above
with a fatty acid; and
(4) a composition comprising the polyether-polyol compound of item ( 1)
above, the polyglycerol alkyl ether of item (2) above, or the ester of item
(3)
above.
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DETAILED DESCRIPTION OF THE INVENTION
The polyether-polyol compound of the present invention is a compound
represented by the compositional formula:
C3nH6n+2~2n+1
wherein n is an integer of 4 or more,
wherein the polyether-polyol compound has a total number of 1,2-diol unit and
1,3-diol unit of [(n/2) + 1] in a case where n is an even number of 4 or more,
or a
total number of 1,2-diol unit and 1,3-diol unit of [((n - 1)/2) + 1] and one
hydroxyl group which is not involved in the units in a case where n is an odd
number of 5 or more. The polyether-polyol does not have a functional group
containing oxygen atom other than the alcoholic hydroxyl group and ether bond.
The compositional formula of the polyether-polyol compound of the
present invention can be confirnled by perfoming elemental analysis.
Conveniently, the present compound can be applied on high-resolution mass
spectrometer, to give its compositional formula.
In the present invention, the term "1,2-diol unit" refers to a structure in
which two carbon atoms each having one hydroxyl group are directly bonded,
and the "1,3-diol unit" refers to a structure in which two carbon atoms each
having one hydroxyl group are bonded via one carbon atom having no hydroxyl
group.
The polyether-polyol compound of the present invention has a total
number of 1,2-diol unit and 1,3-diol unit of [(n/2) + 1] in a case where n is
an
even number of 4 or more. This structure can be confirmed by subjecting the
hydroxyl group existed on the adjoining carbon atoms to a specified reaction.
For instance, 1,2-diol unit can be confirmed as follows. The present compound
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is reacted with a given amount of periodic acid, thereafter potassium iodide
is
added to the reaction mixture, and the formed iodine is titrated with a sodium
thiosulfate solution to determine the consumed periodic acid. The found value
is
then compared with the theoretical value. In addition, as a specific reaction
for
partial structures of 1,2-diol unit and 1,3-diol unit, absorption of hydroxyl
group
cannot be found when the infrared absorption spectrum of the acetal of the
polyether-polyol is determined, the acetal being obtained by reacting the
present
polyether-polyol compound with a compound having carbonyl group, such as
acetone, methyl ethyl ketone or diethyl ketone, in the presence of a catalyst.
Further, this acetal is applied on high-resolution mass spectrometer, whereby
the
resulting compound can be confirmed to be the polyether-polyol compound of
the present invention by comparing the resulting compositional formula with
the
theoretical compositional formula.
In addition, the polyether-polyol compound of the present invention has a
total number of 1,2-diol unit and 1,3-diol unit of [((n - 1)/2) + 1] and one
hydroxyl group which is not involved in any of the units in a case where n is
an
odd number of 5 or more. The structure can be confirmed by the following
method. Specifically, the present polyether-polyol compound is reacted with
acetone in the presence of a catalyst, and the molecular weight of the
resulting
acetal of the polyether-polyol compound is determined, whereby the total
number of 1,2-diol unit and 1,3-diol unit can be confirmed. Next, when the
acetal is acetylated with acetic acid anhydride and pyridine to determine its
molecular weight, the molecular weight increased by 42 as compared to that
before acetylation. Each of the acetal and the resulting acetylated product is
applied on high-resolution mass spectrometer, whereby the structure of the
CA 02356474 2001-08-31
compound of the present invention can be confirmed more accurately by
comparing the resulting compositional formula with the theoretical
compositional formula.
The structure of the polyether-polyol of the present invention are
exemplified as follows, without being limited to those exemplified.
H OH
OH HQ
OH HQ )
O ~O
0 '- OH HO ~ HO
~,...o off ~o ~ off
Ho off off
Ho ~ off '~° off
C12H26~9 ~ 12H26~9 C 12H26~9
~(n=4~ (n=~) (n=~)
N
OH H H
OH H
OH
Q O
~O OH ~pH HO
H ~ ~ pH OH ON
CrsH3zW 1 ~laH~s~l3
(n=5) (n=6~
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9
H
OH
~OH HO 1
OH OH OH OH
CmH4aW s C24HsoW 7
(n= 7) (n= 8)
rr~
G~o~~~z~ ~~zH$b~z~
~~-xo) (rx=~4)
The process for synthesizing the compound of the present invention is not
particularly limited. For instance, the compound can be prepared by
polymerizing a raw material polyhydric alcohol such as glycerol or a
corresponding epoxide compound thereof with heating in the presence of a
catalyst, thereafter reacting the product with a carbonyl group-containing
compound such as acetone to give an acetal, purifying the desired product by
separation distillation, and decomposing the acetal. Concretely, the compound
of the present invention can be prepared by carrying out an addition reaction
of
epichlorohydrin to a glycerol or a polyglycerol having a degree of
CA 02356474 2001-08-31
polymerization of 2 or more, such as diglycerol, to give an epoxide, and
subjecting the epoxide to a ring-opening reaction. Alternatively, the compound
of the present invention can be prepared by the steps of carrying out an
addition
reaction of an allyl halide with glycerol or a polyglycerol having a degree of
5 polymerization of two or more to give an allyl ether compound, and carrying
out
a reaction for converting a double bond contained in allyl group of the allyl
ether
compound to a single bond to introduce two hydroxyl groups. Among the above
processes, the latter process is more preferable. In addition, by repeating
this
reaction, the polyether-polyol compound having an even larger molecular weight
l0 can also be prepared.
In the present invention, a first step for preparation of the polyether-polyol
compound comprises etherifying glycerol or a glycerol derivative with an allyl
halide. The etherification can be carried out by a known method, and is not
limited to a particular method. In this step, since all of hydroxyl groups of
the
glycerol or glycerol derivative are subjected to allyl-etherification, it is
desired
that the allyl halide is used in an amount equimolar to the glycerol or
glycerol
derivative. It is preferable that the amount of the allyl halide is from 1.5-
to
5-folds by mol, preferably from 2- to 3-folds by mol, to the number of
hydroxyl
groups of the raw material glycerol or glycerol derivative.
As the allyl halide, allyl chloride, allyl bromide, allyl iodide, or the like
can be utilized, and the allyl chloride and the allyl bromide are desired from
the
economic viewpoint.
The reaction can proceed at room temperature, and heating can be applied
to the reaction in order to further increase efficiency. In this case, the
upper limit
of the heating temperature is determined by the boiling point of the allyl
halide
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used. In addition, since the efficiency is markedly lowered in any of the
allyl
halide because the reactivity is lowered when the reaction temperature is low,
it
is preferable that the reaction temperature is from 10° to 45°C,
preferably from
30° to 45°C in a case of the allyl chloride, that the reaction
temperature is from
10° to 71°C, preferably from 30° to 71°C in a case
of the allyl bromide, and that
the reaction temperature is from 10° to 103°C, preferably from
30° to 103°C in a
case of the allyl iodide.
In this reaction, the reaction rate can be increased by adding a base or a
catalyst. The base or catalyst includes alkali metals and allcaline earth
metals;
oxides, hydrides, hydroxides, and carbonates of these metals; organic basic
compounds such as triethylamine; metals or metal oxides such as silver oxide
and copper powder, without being limited thereto. Especially when the alkali
metal hydroxide is used, the alkali metal hydroxide may be mixed with a
glycerol derivative and thermally dehydrated to give an alkoxide, and the
alkoxide is then reacted with the allyl halide.
Further, in order to efficiently progress the reaction, a solvent can be used.
The solvent includes water, dimethyl sulfoxide, dimethyl formamide, dimethyl
ether, tetrahydrofuran, dioxane, and the like, without being limited thereto.
The
amount of the solvent is not particularly limited, and it is preferably from
about
equivolume to about 5-folds the amount of the other raw materials.
In order to increase the purity of the final product, it is desired that a
purification procedure is carried out after the termination of the allyl
etherification reaction. For instance, the unreacted raw material glycerol or
glycerol derivative, an unnecessary product having a low degree of
etherification,
an excess base or catalyst, a salt formed by the reaction or the like can be
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removed by washing the allyl ether compound with water. In addition, an excess
allyl halide can be removed by heating the reaction mixture to a temperature
equal to or higher than the boiling point of the allyl halide used, and the
allyl
halide can be even more efficiently removed under reduced pressure. Further,
in
order to improve the purity of the desired ether compound, the allyl ether
compound itself can be purified by distillation with heating under normal
pressure or reduced pressure. In addition, the desired ether compound can be
purified by utilizing column chromatography using an adsorbent such as silica
gel or alumina or a separating agent such as ion-exchanged resin, or
distribution
using an organic solvent.
In this allyl etherification reaction, it is desired that all of the hydroxyl
groups of the raw material glycerol or glycerol derivative disappear at the
termination point of the reaction. Since the allyl-etherified glycerol
derivative
has a dramatically lowered polarity, it can be readily confirmed by thin layer
chromatography. In addition, the disappearance of the absorbance of hydroxyl
group can be confirmed by infrared absorption spectrum. In a case where
unreacted hydroxyl group exists in the resulting allyl ether compound obtained
after the reaction and its subsequent purification, the resulting allyl ether
compound can be reacted again with the allyl halide.
Hydroxyl group can be introduced into the allyl etherified derivative by a
known process, and this process is not particularly limited. Examples of the
process includes, for instance, a process comprising introducing a halogen
such
as chlorine or bromine, or a halohydrin, and hydrolyzing the product, thereby
introducing hydroxyl group; or a process of introducing hydroxyl group via an
epoxide. In general, a double bond is formed into an epoxide, and thereafter
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13
subjecting the epoxide to a ring-opening reaction with an acid or alkali to
introduce hydroxyl group. In this epoxidation, a peracid is generally
employed.
The peracid includes peracetic acid, performic acid, pertrifluoroacetic acid
and
the like, which are usually prepared by adding an aqueous hydrogen peroxide to
a corresponding acid. Besides, an organic peracid such as
metachloroperbenzoic acid, orthosulfoperbenzoic acid, peroxyphthalic acid,
monoperoxysuccinic acid or disuccinoyl peroxide can be utilized. Further, an
oxidizing agent such as potassium permanganate or osmium tetraoxide can be
utilized.
In the epoxidation step, the reaction can be carried out at 10° to
100°C.
When the temperature is low, the reactivity is low, and when the temperature
is
high, the formed epoxide compounds are polymerized with each other, so that
the purity of the reaction product is lowered. The reaction can be preferably
achieved at a temperature of from 30° to 50°C.
This epoxide compound is subsequently hydrolyzed, and hydroxyl group
is introduced, to give a polyglycerol or polyglycerol derivative. The epoxide
compound is hydrolyzed with an acid or aqueous alkali solution, desirably with
an aqueous sodium hydroxide or an aqueous potassium hydroxide. The reaction
can be preferably achieved at a temperature of from 20° to 60°C,
preferably from
40° to 50°C. During the process, when the reaction temperature
is low, the
reactivity is low, and when the temperature is high, the formed epoxide
compounds are polymerized with each other, so that the purity of the reaction
product is lowered. After a major part of the epoxide compound is decomposed,
the reaction mixture can be finally heated to a temperature of 100°C or
higher,
and refluxed with heating in order to complete the reaction.
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In addition, this epoxide compound can be reacted with hydroxyl group of
glycerol or a glycerol derivative, to give a polyglycerol or polyglycerol
derivative. In this case, the reaction proceeds without a catalyst, but a
catalyst
can be used. The basic catalyst includes hydroxides and alcholates of alkali
metals and alkaline earth metals, and organic basic compounds. The acidic
catalyst includes protonic acids such as hydrochloric acid, sulfuric acid,
nitric
acid, and phosphoric acid; Lewis acids such as boron trifluoride and aluminum
chloride; and organic acids such as formic acid and acetic acid, without being
limited thereto. It is preferable that the reaction temperature is from
40° to
250°C, preferably from 70° to 150°C. When the reaction
temperature is less than
40°C, too much time is consumed before the termination of the reaction,
thereby
making its efficiency poor, and when the reaction temperature exceeds
250°C,
the decomposition of the epoxide undesirably takes place.
In the polyglycerol or polyglycerol derivative (hereinafter simply referred
to as "reaction product") obtained by these processes, the raw materials used
in
epoxidation and hydrolysis and by-product salts formed during the process can
be contained. These raw materials and by-product salts can be removed by
distilling off low-molecular compounds under normal pressure or reduced
pressure, or by using an ion-exchanging resin. Further, the reaction product
can
be purified by a known means utilizing molecular distillation or
chromatographic
apparatus. The purity of the polyglycerol or polyglycerol derivative thus
obtained can be determined by an analytical means such as gas chromatography
or liquid chromatography described above.
In the process described above, a polyglycerol comprising a glycerol
polymer having a single degree of polymerization in a high purity can be
CA 02356474 2001-08-31
efficiently prepared. The high-purity polyglycerol in the present invention is
not
particularly limited. For instance, when subjected to previously mentioned gas
chromatography or liquid chromatography, it is desired that the purity of the
single component is 60% by area or more, preferably 70% by area or more, more
5 preferably 80% by area or more.
In addition, as the glycerol derivative, the glycerol bone structure can be
extended by following the same procedures as above. The polyglycerol
derivative consequently obtained can be used as a polyglycerol by removing the
introduced substituent, or the polyglycerol derivative per se can be utilized
with
10 the substituent. For instance, the polyglycerol alkyl ether per se obtained
from a
raw material glycerol alkyl ether can be utilized as a hydrophilic surfactant.
In
this case, not only the hydrophilic moiety has an evenly sized degree of
polymerization of glycerol, but also the monoalkyl ether only can be
efficiently
obtained.
15 Alternatively, the polyether-polyol compound can also be synthesized by
carrying out an addition polymerization of a commercially available linear
polyglycerol obtained by polymerizing glycerol or an epoxide compound, with
the allyl halide, to give an allyl ether compound; and carrying out a reaction
for
converting a double bond contained in allyl group of the allyl ether compound
to
a single bond to introduce two hydroxyl groups. In this case, since the
resulting
product is composed of a mixture of the polyether-polyol having different
degrees of polymerization, the gas chromatography mass spectrometer (GC-MS)
or the liquid chromatography mass spectrometer (LC-MS) is preferred as its
analysis or structural confirmation. Specifically, the polyether-polyol
compound
can be identified by forming the compound into an acetal, acetylating the
acetal,
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16
and applying the acetylated compound on GC-MS or LC-MS to determine its
molecular weight at each peak, and comparing the found values with those of
the
theoretical values. Further, if the composition is determined by subjecting
each
peak to a higher resolution mass spectroscopy, its determination can be made
more accurately. A part of the molecular weights of the branched polyglycerol
with its degree of polymerization and compositional formula, the branched
polyglycerol formed into an acetal with acetone, and those acetylated products
after acetal formation is shown in Table 1.
Table 1
Degree Compositional Molecular ght
of Wei
Polymeri-Formula Before Acetal Acetylated
zation Treatment Formation After Acetal
Formation
4 C12Ha6O9 314 434 434
S C15H32~11 388 508 550
6 C18H38013 462 622 622
7 C21H4aW s 536 696 738
C24H50~17 610 810 810
9 C2~H56O19 684 884 926
1O C3oH62Oai 758 998 998
11 C33H68O23 832 1072 1114
12 C36H~4O25 906 1186 1186
13 C39HgpO2~ 980 1260 1302
14 C42Hg6Oa9 1054 1374 1374
IS Cq5H92~31 1128 1448 1490
In the polyglycerol alkyl ether of the present invention, a part of hydroxyl
groups in a polyglycerol is substituted by an alkyl group, wherein the
CA 02356474 2001-08-31
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polyglycerol is the polyether polyol compound of the present invention.
The term "polyglycerol" used herein refers to a compound which is
regarded to be prepared by dehydrating glycerol molecules and polymerizing
them, namely a compound comprising four or more consecutive units, and is
represented by the compositional formula:
C3nH6n+2~2n+1 ~
wherein n is an integer of 4 or more.
The structures which are taken by the polyglycerol alkyl ether of the
present invention are exemplified as follows, without being limited thereto.
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RO
~O R
OH OH
OH
HO
HO
O~O~OH
RO
HO OH
Y HO
RO O~ HO OH O OH
~o o~
H ~OH
HO
HO
RO
O HO
OR O~.O~OH
O HO
OOH
OH
OH
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The process for synthesizing the polyglycerol alkyl ether of the present
invention is not particularly limited. The polyglycerol alkyl ether can be
similarly obtained as the polyether-polyol compound except for using an alkyl
ether of the glycerol or polyglycerol as a starting substance in place of the
glycerol or polyglycerol during the preparation of the polyether-polyol
compound of the present invention.
The process for preparing a raw material alkyl ether of the glycerol or
polyglycerol is not particularly limited, and any of commercially available
natural products and synthetic products can be utilized. The chain length of
the
alkyl moiety is not particularly limited, and can be properly selected in
accordance with its purposes. For instance, those in a linear or branched form
having preferably 6 to 30 carbon atoms, more preferably 8 to 22 carbon atoms
can be utilized.
The HLB of the polyglycerol alkyl ether of the present invention is not
particularly limited, and those in accordance with their purposes can be
utilized.
Those esters having an HLB of 5 or more, preferably an HLB of 8 or more, more
preferably an HLB of 10 or more, are recommendable, from the viewpoint of
dispersibility in water. This HLB can be determined by using a known
lipophilic
surfactant and a fat or oil. In addition, the HLB can be calculated from the
following equation:
HLB = 7 + 11.7 log (MW/MO),
wherein MW is a molecular weight of the hydrophilic group moiety of the ether,
and MO is a molecular weight of the lipophilic group moiety of the ether.
Further, the present invention provides an ester prepared by the process
comprising reacting the polyether-polyol compound or polyglycerol alkyl ether
CA 02356474 2001-08-31
described above with a fatty acid.
The ester of the present invention is obtained by esterifying the polyether-
polyol compound or polyglycerol alkyl ether with a fatty acid by an
appropriate
method. The kinds of the fatty acid and the degree of esterification are not
5 particularly limited. The fatty acid, such as a saturated or unsaturated,
linear or
branched fatty acid, or a fatty acid containing hydroxyl group in its
molecule,
each preferably having 6 to 30 carbon atoms, more preferably having 8 to
22 carbon atoms, and a mixture thereof in a given molar ratio in accordance
with
its purposes can be used in accordance with its purposes. The polyether-polyol
10 compound or polyglycerol alkyl ether can be usually esterified with the
fatty acid
by heating the reaction mixture to a temperature of 200°C or more with
removing water in the presence of an acidic or alkali catalyst, or in the
absence
of the catalyst. In addition, in place of the fatty acid, a derivative of the
fatty
acid, such as a corresponding acid chloride, acid hydride and methyl ester of
the
15 fatty acid can be utilized. Also, when an appropriate organic solvent such
as
pyridine is used, the reaction can be achieved at an even lower temperature.
The
ester thus obtained can be purified in accordance with its purposes. The
purification can be carned out by distillation techniques such as distillation
under
reduced pressure, molecular distillation, or vapor distillation. Besides the
20 distillation techniques, extraction with an organic solvent, fractionation,
or
chromatography separation on a column packed with a synthetic adsorbent or gel
filtration agent can be utilized. In addition, a selective esterification can
be
carried out by using an enzyme in a system containing very small amount of
water.
The HLB of the ester of the present invention is not particularly limited,
CA 02356474 2001-08-31
21
and those in accordance with their purposes can be utilized. Those esters
having
an HLB of 5 or more, preferably 8 or more, more preferably 10 or more are
recommendable, from the viewpoint of dispersibility in water. This HLB can be
determined by using a known lipophilic surfactant and a fat or oil. In
addition,
the HLB can be calculated from the following equation:
HLB = 20 x ( 1 - S/A),
wherein S is a saponification value of the ester, and A is a neutralization
value of
the fatty acid used.
Each of the polyether-polyol compound, the polyglycerol alkyl ether and
the ester of the present invention can be used alone. In addition, each of
these
can be utilized in the form of a composition by adding and mixing each of them
with other substances in accordance with its purposes. The composition can be
favorably used as foods, cosmetics and the like for the purposes of
emulsification,
solubilization, dispersion, washing, foaming, defoaming, permeation,
antibacterial action, and the like. For instance, the composition can be
utilized as
follows. In the field of foods, the composition can be applied to instant
foods
such as instant noodles, retort pouch foods, canned foods, microwave-cooking
foods, instant soups and miso soups, and freeze-dried foods; beverages such as
soft drinks, fruits juices, vegetable juices, soya milk beverages, coffee
beverages,
2o tea beverages, powdered drinks, concentrate beverages, nutritious
beverages, and
alcoholic beverages; flour products such as bread, pastas, noodles, cake mix,
deep flying powder, and bread crumbs; confectioneries such as caramel,
candies,
chewing gums, chocolate, cookies, biscuits, cakes, pies, snacks, crackers,
Japanese sweets, and desert confectioneries; seasonings such as sauces, tomato-
based seasonings, flavor seasonings, culinary mix, gravy sauces, dressings,
clear
CA 02356474 2001-08-31
22
soups, and roux for curry sauce and stew; fats and oils such as processed fats
and
oils, butter, margarine, and mayonnaise; milk products such as milk beverages,
yogurts, lactobacilli beverages, ice creams, and creams; marine processed
products such as frozen foods, hams and sausages made of fish, and marine
pastes (chikuwa and kamaboko); livestock processed products such as livestock
ham and sausages; agricultural processed products such as agricultural canned
foods, jams and marmalades, pickles, cooked beans, and cereals; nutritional
foods; emulsifiers for foods; and the like. Especially when utilized in foods,
in
addition to those applications, the composition can be used in the
modifications
of starches, proteins and fats and oils. In addition, in the field of the
cosmetics,
the composition can be applied to detergents such as soaps, cleansing lotions,
shampoos, rinses, raw materials for surfactants; basic cosmetics such as
lotions,
milky lotions, moisturizers, skin creams, facial packs, hair tonics, and hair
creams; finishing cosmetics such as lipsticks, eye shadows, set lotions, and
hairdressings; fragrances such as perfumes and lotions; oral use cosmetics
such
dentifrice and mouthwash; and the like. Further, the composition can be
applied
to pharmaceuticals and industrial purposes. In the field of industry, the
composition can be used for applications of dispersion of a filler, a pigment,
or a
paint in a resin, a cross-linking agent for a resin, a swelling agent, a
surfactant, a
dyeing aid, a paper modifier, a preventive for ti-iboelectric charging, and a
plasticizer. In the field of food industry, the composition can be used as
cleaning
agents for equipments, processing aids, detergents for vegetables and fruits;
and
the like. The applications of the composition are not limited to those listed
above.
Further, the polyether-polyol compound, the polyglycerol allcyl ether, and
CA 02356474 2001-08-31
23
the ester of the present invention can be, for instance, used as a surfactant
preparation by mixing with other surfactants. Other surfactants which can be
used for this purpose include natural occurring surfactants such as lecithin,
saponin, proteins, and polysaccharides; those modified by acting the
surfactant
with an enzyme; and those chemically synthesized. The chemically synthesized
surfactants can be roughly classified into ionic surfactants and nonionic
surfactants. The ionic surfactants can be further classified into anionic
surfactants, cationic surfactants and amphoteric surfactants. Examples of the
anionic surfactants include aliphatic monocarboxylates, polyoxyethylene alkyl
ether carboxylates, N-acyl sarcosine salts, N-acyl glutamate,
dialkylsulfosuccinates, alkanesulfonates, alpha-olefinsulfonates, linear or
branched alkylbenzenesulfonates, formaldehyde condensates of
naphthalenesulfonates, alkylnaphthalenesulfonates, N-methyl-N-acyltaurine
salts,
alkylsulfates, polyoxyethylene alkyl ether sulfates, salts of fat and oil
sulfuric
acid esters, alkylphosphates, polyoxyethylene alkyl ether phosphates,
polyoxyethylene alkylphenyl ether phosphates, and the like. Examples of the
cationic surfactants include alkylamine salts, alkyltrimethylammonium
chlorides,
bromides or iodides, dialkyldimethylammonium chlorides, bromides or iodides,
alkyl benzalkonium chloride. Examples of amphoteric surfactants include alkyl
betaines, fatty acid amide propyl betaines, 2-alkyl-N-carboxymethyl-N-
hydroxyethylimidazolinium betaines, alkyl- or dialkyldiethylenetriaminoacetic
acids, alkylamine oxides. Examples of the nonionic surfactants include
glycerol
fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters,
propylene
glycol fatty acid esters, polyoxyedrylene alkyl ethers, polyoxyethylene
alkylphenyl ethers, polyoxyethylene polyoxypropylene glycols, fatty acid
CA 02356474 2001-08-31
24
polyethylene glycols, fatty acid polyoxyethylene sorbitans, fatty acid
alkanolamides, and the like. The surfactants are not limited to those listed
above.
Especially in the field of foods, surfactants which are included in the
glycerol
fatty acid esters include conventional linear polyglycerol fatty acid esters,
glycerol fatty acid esters, glycerol acetic acid ester, lactic acid esters of
monoglyceride, citric acid esters of monoglyceride, succinic acid esters of
monoglyceride, diacetyl tartaric acid esters of monoglyceride, polyglycerol
poly-recinoleates, without being limited thereto. Also, other components can
be
added to each of the polyether-polyol compound, the polyglycerol alkyl ether,
and the ester of the present invention, so that the handling of the mixture
can be
facilitated. For instance, in order to lower the viscosity of the product, one
or
more solvents selected from the group consisting of water, ethanol, propylene
glycol, glycerol, linear polyglycerols, liquid sugars, and fats and oils can
be
added to the composition of the present invention. In addition, a
polysaccharide
such as lactose or dextrin or a protein such as caseinate can be added to the
composition, and then powderized. Further, other components constituting a
final product can be added to each of the polyether-polyol compound, the
polyglycerol alkyl ether, and the ester of the present invention to give an
intermediary product. For instance, each of the polyether-polyol compound, the
polyglycerol alkyl ether, and the ester of the present invention can be mixed
with
an oil-soluble vitamin such as vitamin E, an oil-soluble pigment such as (3-
carotene, an oil-soluble bioactive substance such as a higher unsaturated
fatty
acid and an oil-soluble perfume, to give each product of a water-dispersible
oil-
soluble vitamin, a water-dispersible oil-soluble pigment, a water-dispersible
bioactive substance, or a water-dispersible oil-soluble perfume.
CA 02356474 2001-08-31
EXAMPLES
Next, the present invention will be described in detail by means of the
following Examples, without intending to limit the present invention thereto.
5
Example A 1
A one-liter four-necked flask equipped with a stirrer, a reflux condenser
and a thermometer was charged with 100 g of glycerol, 310 g of a 50% by
weight aqueous sodium hydroxide and 310 ml of allyl chloride, and the mixture
l0 was stirred at 40°C for 10 hours. Water was added to the product,
with stirring,
and thereafter the mixture was allowed to stand to separate into aqueous and
organic layers. After removing the aqueous layer, the organic layer was
concentrated with heating under reduced pressure, to give 196 g of a residue.
Separately, a 3-liter flask was charged with one liter of formic acid and 500
ml of
15 a 35% by weight aqueous hydrogen peroxide, and to this flask was gradually
added the previous reaction mixture, and the mixture was allowed to react at
45°C for 8 hours. Subsequently, formic acid and water were distilled
off with
heating under reduced pressure, and thereafter 500 ml of a 10% by weight
aqueous sodium hydroxide was added to the resulting residue, and the mixture
20 was stirred at 40°C for 5 hours. The reaction mixriwe was
neutralized with a
10% by weight hydrochloric acid, and thereafter thermally dehydrated under
reduced pressure. Water was added to the resulting residue, and the mixture
was
desalted through a cationic exchange resin and an anionic exchange resin. The
desalted product was dehydrated under reduced pressure, to give 205 g of
25 tetraglycerol.
CA 02356474 2001-08-31
26
A part of this compound was analyzed by mass spectrometer. As a result,
the compound was found to have a molecular weight of 314 and a compositional
formula of C12H2609, which was perfectly identical with the theoretical value
of
the tetraglycerol. The infrared absorption spectroscopy of this compound was
determined. As a result, absorptions of ether bonds and hydroxyl groups were
detected. Also, a 100-ml four-necked flask equipped with a stirrer, a reflux
condenser and a thermometer was charged with 1 g of the resulting
tetraglycerol,
40 ml of dry acetone and 0.4 g of ferric chloride, and the mixture was stirred
at
40°C for 8 hours. After removing acetone under reduced pressure, 50 ml
of
diethyl ether was added to the residue and then rinsed with water. A diethyl
ether layer was dried over anhydrous sodium sulfate, and thereafter the
solvent
was removed under reduced pressure, to give 1.3 g of a residue. The infrared
absorption spectroscopy of the resulting compound was determined. As a result,
no absorption by hydroxyl group was found. In addition, this acetal was
analyzed by mass spectrometer. The compound was found to have a molecular
weight of 434 and a compositional formula C21H3gO9, which was perfectly
identical to theoretical value. It was confirmed from these results that the
tetraglycerol has three partial structures of 1,2-diol.
Example A2
A one-liter four-necked flask equipped with a stirrer, a reflux condenser
and a thermometer was charged with 100 g of diglycerol (manufactured by
Solway, purity: 94%), 240 g of a 50% by weight aqueous sodium hydroxide and
245 ml of allyl chloride, and the mixture was stirred at 40°C for 10
hours. Water
was added to the product, with stirring, and thereafter the mixture was
allowed to
CA 02356474 2001-08-31
27
stand to separate into aqueous and organic layers. After removing the aqueous
layer, the organic layer was concentrated with heating under reduced pressure,
to
give 165 g of a residue. Separately, a 3-liter flask was charged with 800 ml
of
formic acid and 400 ml of a 35% by weight aqueous hydrogen peroxide, and to
this flask was gradually added the previous reaction mixture. The temperature
of
the mixture was raised to 45°C, and the mixture was allowed to react at
45°C for
8 hours. Subsequently, formic acid and water were distilled off with heating
under reduced pressure, and thereafter 500 ml of a 10% by weight aqueous
sodium hydroxide was added to the resulting residue, and the mixture was
stirred
at 40°C for 5 hours. The reaction mixture was neutralized with a 10% by
weight
hydrochloric acid, and thereafter thermally dehydrated under reduced pressure.
Water was added to the resulting residue, and the mixture was desalted through
a
cationic exchange resin and an anionic exchange resin. The desalted product
was dehydrated under reduced pressure, to give 183 g of hexaglycerol.
A part of this compound was analyzed by mass spectrometer. As a result,
the compound was found to have a molecular weight of 462 and a compositional
formula of ClgH3g013, which was perfectly identical with the theoretical value
of
the hexaglycerol. The infrared absorption spectroscopy of this compound was
determined. As a result, absorptions of ether bonds and hydroxyl groups were
detected. Also, a 100-ml four-necked flask equipped with a stirrer, a reflux
condenser and a thermometer was charged with 1 g of the resulting
hexaglycerol,
40 ml of dry acetone and 0.4 g of ferric chloride, and the mixture was stirred
at
40°C for 8 hours. After removing acetone under reduced pressure, 50 ml
of
diethyl ether was added to the residue and then rinsed with water. A diethyl
ether layer was dried over anhydrous sodium sulfate, and thereafter the
solvent
CA 02356474 2001-08-31
28
was removed under reduced pressure, to give 1.3 g of a residue. The infrared
absorption spectroscopy of the resulting compound was determined. As a result,
no absorption by hydroxyl group was found. In addition, this acetal was
analyzed by mass spectrometer. The compound was found to have a molecular
weight of 622 and a compositional formula C3pH54013~ which was perfectly
identical to theoretical value. It was confirmed from these results that the
hexaglycerol has four partial structures of 1,2-diol.
Example A3
A 500 ml four-necked flask equipped with a stirrer, a reflux condenser
and a thermometer was charged with 50 g of tetraglycerol obtained in Example
A1, 100 g of a 50% by weight aqueous sodium hydroxide and 100 ml of allyl
chloride, and the mixture was stirred at 40°C for 15 hours. Water was
added to
the product, with stirring, and thereafter the mixture was allowed to stand to
separate into aqueous and organic layers. After removing the aqueous layer,
the
organic layer was concentrated with heating under reduced pressure, to give 69
g
of a residue. Separately, a one-liter flask was charged with 400 ml of formic
acid and 200 ml of a 35% by weight aqueous hydrogen peroxide, and to this
flask was gradually added the previous reaction mixture. The temperature of
the
mixture was raised to 45°C, and the mixture was allowed to react at
45°C for
10 hours. Subsequently, formic acid and water were distilled off with heating
under reduced pressure, and thereafter 200 ml of a 10% by weight aqueous
sodium hydroxide was added to the resulting residue, and the mixture was
stirred
at 40°C for 10 hours. The reaction mixture was neutralized with a 10%
by
weight hydrochloric acid, and thereafter thermally dehydrated under reduced
CA 02356474 2001-08-31
29
pressure. Water was added to the resulting residue, and the mixture was
desalted
through a cationic exchange resin and an anionic exchange resin. The desalted
product was dehydrated under reduced pressure, to give 71 g of decaglycerol.
A part of this compound was analyzed by mass spectrometer. As a result,
the compound was found to have a molecular weight of 758 and a compositional
formula of C3oH62421, which was perfectly identical with the theoretical value
of
the decaglycerol. The infrared absorption spectroscopy of this compound was
determined. As a result, absorptions of ether bonds and hydroxyl groups were
detected. Also, a 100-ml four-necked flask equipped with a stirrer, a reflux
condenser and a thermometer was charged with 1 g of the resulting
decaglycerol,
40 ml of dry acetone and 0.4 g of ferric chloride, and the mixture was stirred
at
40°C for 8 hours. After removing acetone under reduced pressure, 50 ml
of
diethyl ether was added to the residue and then rinsed with water. A diethyl
ether layer was dried over anhydrous sodium sulfate, and thereafter the
solvent
was removed under reduced pressure, to give 1.3 g of a residue. The infrared
absorption spectroscopy of the resulting compound was determined. As a result,
no absorption by hydroxyl group was found. In addition, this acetal was
analyzed by mass spectrometer. The compound was found to have a molecular
weight of 998 and a compositional formula C48Hg6O21, which was perfectly
identical to theoretical value. It was confirmed from these results that the
decaglycerol has six partial structures of 1,2-diol.
Exam 1p a A4
A 500 ml four-necked flask equipped with a stirrer, a reflex condenser
and a thermometer was charged with 50 g of the polyglycerol obtained in
CA 02356474 2001-08-31
Comparative Example A2, 120 g of a 50% by weight aqueous sodium hydroxide
and 150 ml of allyl chloride, and the mixture was stirred at 40°C for
15 hours.
Water was added to the product, with stirring, and thereafter the mixture was
allowed to stand to separate into aqueous and organic layers. After removing
the
5 aqueous layer, the organic layer was concentrated with heating under reduced
pressure, to give 71 g of a residue. Separately, a one-liter flask was charged
with
400 ml of formic acid and 200 ml of a 35% by weight aqueous hydrogen
peroxide, and to this flask was gradually added the previous reaction mixture.
The temperature of the mixture was raised to 45°C, and the mixture was
allowed
10 to react at 45°C for 10 hours. Subsequently, formic acid and water
were distilled
off with heating under reduced pressure, and thereafter 200 ml of a 10% by
weight aqueous sodium hydroxide was added to the resulting residue, and the
mixture was stirred at 40°C for 10 hours. The reaction mixture was
neutralized
with a 10% by weight hydrochloric acid, and thereafter thermally dehydrated
15 under reduced pressure. Water was added to the resulting residue, and the
mixture was desalted through a cationic exchange resin and an anionic exchange
resin. The desalted product was dehydrated under reduced pressure, to give 73
g
of a polyglycerol.
Also, a 100-ml four-necked flask equipped with a stirrer, a reflux
20 condenser and a thermometer was charged with 1 g of the resulting
polyglycerol,
ml of dry acetone and 0.4 g of ferric chloride, and the mixture was stirred at
40°C for 8 hours. After removing acetone under reduced pressure, 50 ml
of
diethyl ether was added to the residue and then rinsed with water. A diethyl
ether layer was dried over anhydrous sodium sulfate, and thereafter the
solvent
25 was removed under reduced pressure, to give 1.2 g of a residue. This acetal
was
CA 02356474 2001-08-31
31
acetylated with acetic anhydride and pyridine, and thereafter analyzed by gas
chromatographic mass spectrometer. As a result, it was found that the compound
was composed of the plural kinds of polyglycerol components in branched forms
and their compositional ratio is as shown in the following table.
Table A1
Degree of Content (%) Molecular WeightMolecular Weight
Polymerization (found value) (theoretical
value)
4 22.7 434 434
5 0 - 550
6 28.6 622 622
7 0 - 738
8 16.2 810 810
9 0 - 926
18.7 998 998
11 0 - 1114
12 13.9 1186 1186
Comparative Example A 1
A five-liter four-necked flask equipped with a stirrer, a gas-discharging
10 tube and a thermometer was charged with 4000 g of a glycerol and 40 g of a
50%
by weight aqueous sodium hydroxide. The mixture was heated to 240°C
with
removing water from the system at a pressure of 100 Torr under nitrogen gas
stream, and the mixture was kept at 240°C for 13 hours, to give 2460 g
of a
polyglycerol reaction mixture. The reaction mixture was decolorized with
activated charcoal, and thereafter the mixture was purified with an ion
exchange
CA 02356474 2001-08-31
32
resin. Water was removed under reduced pressure, to give 2430 g of a
polyglycerol. A part of the resulting polyglycerol was taken, and its hydroxyl
value thereof was determined. As a result, the hydroxyl value was found to be
1080, which corresponded to a tetraglycerol in a linear form. Also, a 100-ml
four-necked flask equipped with a stirrer, a reflux condenser and a
thermometer
was charged with 1 g of the resulting polyglycerol, 40 ml of dry acetone and
0.4 g of ferric chloride, and the mixture was stirred at 40°C for 8
hours. After
removing acetone under reduced pressure, 50 ml of diethyl ether was added to
the residue and then rinsed with water. A diethyl ether layer was dried over
anhydrous sodium sulfate, and thereafter the solvent was removed under reduced
pressure, to give 0.8 g of a residue. The infrared absorption spectroscopy of
the
resulting compound was determined. As a result, absorptions by hydroxyl
groups were detected. In addition, this acetal was acetylated with acetic
anhydride and pyridine, and thereafter analyzed by gas chromatographic mass
spectrometer. As a result, the polyglycerol component in a branched form was
not detected.
Comparative Exam 1p a AZ
A five-liter four-necked flask equipped with a stirrer, a gas-discharging
tube and a thermometer was charged with 4000 g of a glycerol and 40 g of a 50%
by weight aqueous sodium hydroxide. The mixture was heated to 240°C
with
removing water from the system at a pressure of 100 Torr under nitrogen gas
stream, and the mixture was kept at 240°C for 48 hours, to give 2315 g
of a
polyglycerol reaction mixture. The reaction mixture was decolorized with
activated charcoal, and thereafter the mixture was purified with an ion
exchange
CA 02356474 2001-08-31
33
resin. Water was removed under reduced pressure, to give 2282 g of a
polyglycerol. A part of the resulting polyglycerol was taken, and its hydroxyl
value thereof was determined. As a result, the hydroxyl value was found to be
896, which corresponded to a decaglycerol in a linear form. Also, a 100-ml
four-
s necked flask equipped with a stirrer, a reflux condenser and a thermometer
was
charged with 1 g of the resulting polyglycerol, 40 ml of dry acetone and 0.4 g
of
ferric chloride, and the mixture was stirred at 40°C for 8 hours. After
removing
acetone under reduced pressure, 50 ml of diethyl ether was added to the
residue
and then rinsed with water. A diethyl ether layer was dried over anhydrous
sodium sulfate, and thereafter the solvent was removed under reduced pressure,
to give 0.7 g of a residue. The infrared absorption spectroscopy of the
resulting
compound was determined. As a result, absorptions by hydroxyl groups were
detected. In addition, this acetal was acetylated with acetic anhydride and
pyridine, and thereafter analyzed by gas chromatographic mass spectrometer. As
a result, the polyglycerol component in a branched form was not detected.
Example B 1
A 3-liter four-necked flask equipped with a stirrer, a nitrogen inlet tube
and a thermometer was charged with 760 g of glycerol and 4 g of sodium
hydroxide, and the mixture was dehydrated at 120°C under reduced
pressure for
1 hour. Having changed the pressure back to normal pressure, 400 g of glycidyl
dodecyl ether was added dropwise over a period of 2 hours to the dehydrated
mixture at 160°C under nitrogen stream, and thereafter the mixture was
stirred
for 8 hours. The resulting reaction mixture was purified by molecular
distillation,
to give 212 g of diglycerol dodecyl ether. A one-liter four-necked flask
equipped
CA 02356474 2001-08-31
34
with a stirrer, a nitrogen inlet tube and a thermometer was charged with 200 g
of
the diglycerol dodecyl ether, 84 g of sodium hydroxide and 230 g of allyl
chloride, and the mixture was stirred at 40°C under nitrogen gas stream
for
hours. Water was added to the product, with stirring, and thereafter the
S mixture was allowed to stand to separate into aqueous and organic layers.
After
removing the aqueous layer, the organic layer was concentrated with heating
under reduced pressure, to give 196 g of a residue. Separately, a 3-liter
flask was
charged with 900 ml of formic acid and 450 ml of a 35% by weight aqueous
hydrogen peroxide, and to this flask was gradually added the previous reaction
10 mixture, and the mixture was allowed to react at 45°C for 8 hours.
Subsequently,
formic acid and water were distilled off with heating under reduced pressure,
and
500 ml of a 10% by weight aqueous sodium hydroxide was added to the resulting
residue, and the mixture was stirred at 40°C for 5 hours. The reaction
mixture
was neutralized with a 10% by weight hydrochloric acid, and thereafter
thermally dehydrated under reduced pressure. Water was added to the resulting
residue, and the mixture was desalted through a cationic exchange resin and an
anionic exchange resin. The desalted product was dehydrated under reduced
pressure, to give 216 g of pentaglycerol dodecyl ether.
A part of this compound was analyzed by mass spectrometer. As a result,
the compound was found to have a molecular weight of 556 and a compositional
formula of C2~H56011, which was perfectly identical with the theoretical value
of
the pentaglycerol dodecyl ether. Also, a 100-ml four-necked flask equipped
with
a stirrer, a reflex condenser and a thermometer was charged with 1 g of the
resulting pentaglycerol dodecyl ether, 40 ml of dry acetone and 0.4 g of
ferric
chloride, and the mixture was stirred at 40°C for 8 hours. After
removing
CA 02356474 2001-08-31
acetone under reduced pressure, 50 ml of diethyl ether was added to the
residue
and then rinsed with water. A diethyl ether layer was dried over anhydrous
sodium sulfate, and thereafter the solvent was removed under reduced pressure,
to give 1.3 g of a residue. The infrared absorption spectroscopy of the
resulting
5 compound was determined. As a result, no absorption by hydroxyl group was
found. In addition, this acetal was analyzed by mass spectrometer. The
compound was found to have a molecular weight of 676 and a compositional
formula C36H6gO11, which was perfectly identical to theoretical value. It was
confirmed from these results that the tetraglycerol has three partial
structures of
10 1,2-diol. The HLB of the pentaglycerol dodecyl ether is 10.7.
Example B2
A 3-liter four-necked flask equipped with a stirrer, a nitrogen inlet tube
and a thermometer was charged with 600 g of glycerol and 3 g of sodium
15 hydroxide, and the mixture was dehydrated at 120°C under reduced
pressure for
1 hour. Having changed the pressure back to normal pressure, 400 g of glycidyl
octadecanoyl ether was added dropwise to the dehydrated mixture over a period
of 2 hours at 160°C under nitrogen stream, and thereafter the mixture
was stirred
for 8 hours. The resulting reaction mixture was purified by molecular
distillation,
20 to give 192 g of diglycerol octadecanoyl ether. A one-liter four-necked
flask
equipped with a stirrer, a nitrogen inlet tube and a thermometer was charged
with
180 g of the diglycerol octadecanoyl ether, 60 g of sodium hydroxide and 165 g
of allyl chloride, and the mixture was stirred at 40°C under nitrogen
gas stream
for 10 hours. Water was added to the product, with stirring, and thereafter
the
25 mixture was allowed to stand to separate into aqueous and organic layers.
After
CA 02356474 2001-08-31
36
removing the aqueous layer, the organic layer was concentrated with heating
under reduced pressure, to give 208 g of a residue. Separately, a 3-liter
flask was
charged with 900 ml of formic acid and 450 ml of a 35% by weight aqueous
hydrogen peroxide, and to this flask was gradually added the previous reaction
mixture, and the mixture was allowed to react at 45°C for 8 hours.
Subsequently,
formic acid and water were distilled off with heating under reduced pressure,
and
500 ml of a 10% by weight aqueous sodium hydroxide was added to the resulting
residue, and the mixture was stirred at 40°C for 5 hours. The reaction
mixture
was neutralized with a 10% by weight hydrochloric acid, and thereafter
thermally dehydrated under reduced pressure. Water was added to the resulting
residue, and the mixture was desalted through a cationic exchange resin and an
anionic exchange resin. The desalted product was dehydrated under reduced
pressure, to give 220 g of pentaglycerol octadecanoyl ether. A part of this
compound was analyzed by mass spectrometer. As a result, the compound was
found to have a molecular weight of 640 and a compositional formula of
C33H68011~ which was perfectly identical with the theoretical value of the
pentaglycerol octadecanoyl ether. Also, a 100-ml four-necked flask equipped
with a stirrer, a reflux condenser and a thermometer was charged with 1 g of
the
resulting pentaglycerol octadecanoyl ether, 40 ml of dry acetone and 0.4 g of
ferric chloride, and the mixture was stirred at 40°C for 8 hours. After
removing
acetone under reduced pressure, 50 ml of diethyl ether was added to the
residue
and then rinsed with water. A diethyl ether layer was dried over anhydrous
sodium sulfate, and thereafter the solvent was removed under reduced pressure,
to give 1.2 g of a residue. The infrared absorption spectroscopy of the
resulting
compound was determined. As a result, no absorption by hydroxyl group was
CA 02356474 2001-08-31
37
found. In addition, this acetal was analyzed by mass spectrometer. The
compound was found to have a molecular weight of 760 and a compositional
formula Cq2HgpO1l, which was perfectly identical to theoretical value. It was
confirmed from these results that the tetraglycerol has three partial
structures of
1,2-diol. The HLB of the pentaglycerol octadecanoyl ether is 8.8.
Exam 1p a B3
A one-liter four-necked flask equipped with a stirrer, a nitrogen inlet tube
and a thermometer was charged with 200 g of glycerol dodecyl ether, 77 g of
sodium hydroxide and 294 g of allyl chloride, and the mixture was stirred at
40°C under nitrogen gas stream for 10 hours. Water was added to the
product,
with stirring, and thereafter the mixture was allowed to stand to separate
into
aqueous and organic layers. After removing the aqueous layer, the organic
layer
was concentrated with heating under reduced pressure, to give 235 g of a
residue.
Separately, a 3-liter flask was charged with one liter of formic acid and 500
ml of
a 35% by weight aqueous hydrogen peroxide, and to this flask was gradually
added the previous reaction mixture, and the mixture was allowed to react at
45°C for 8 hours. Subsequently, formic acid and water were distilled
off with
heating under reduced pressure, and thereafter 500 ml of a 10% by weight
aqueous sodium hydroxide was added to the resulting residue, and the mixture
was stirred at 40°C for 5 hours. The reaction mixture was neutralized
with a
10% by weight hydrochloric acid, and thereafter thermally dehydrated under
reduced pressure. Water was added to the resulting residue, and the mixture
was
desalted through a cationic exchange resin and an anionic exchange resin. The
desalted product was dehydrated under reduced pressure, to give 251 g of
CA 02356474 2001-08-31
38
triglycerol dodecyl ether.
A one-liter four-necked flask equipped with a stirrer, a nitrogen inlet tube
and a thermometer was charged with 200 g of the resulting triglycerol dodecyl
ether, 88 g of sodium hydroxide and 300 g of allyl chloride, and the mixture
was
stirred at 40°C under nitrogen gas stream for 10 hours. Water was added
to the
product, with stirring, and thereafter the mixture was allowed to stand to
separate
into aqueous and organic layers. After removing the aqueous layer, the organic
layer was concentrated with heating under reduced pressure, to give 248 g of a
residue. Separately, a 3-liter flask was charged with one liter of formic acid
and
l0 500 ml of a 35% by weight aqueous hydrogen peroxide, and to this flask was
gradually added the previous reaction mixture, and the mixture was allowed to
react at 45°C for 8 hours. Subsequently, formic acid and water were
distilled off
with heating under reduced pressure, and thereafter 500 ml of a 10% by weight
aqueous sodium hydroxide was added to the resulting residue, and the mixture
was stirred at 40°C for 5 hours. The reaction mixture was neutralized
with a
10% by weight hydrochloric acid, and thereafter thermally dehydrated under
reduced pressure. Water was added to the resulting residue, and the mixture
was
desalted through a cationic exchange resin and an anionic exchange resin. The
desalted product was dehydrated under reduced pressure, to give 261 g of
heptaglycerol dodecyl ether. A part of this compound was analyzed by mass
spectrometer. As a result, the compound was found to have a molecular weight
of 705 and a compositional formula of C33H6901s, which was perfectly identical
with the theoretical value of the heptaglycerol dodecyl ether. Also, a 100-ml
four-necked flask equipped with a stirrer, a reflux condenser and a
thermometer
was charged with 1 g of the resulting heptaglycerol dodecyl ether, 40 ml of
dry
CA 02356474 2001-08-31
39
acetone and 0.4 g of ferric chloride, and the mixture was stirred at
40°C for
8 hours. After removing acetone under reduced pressure, 50 ml of diethyl ether
was added to the residue and then rinsed with water. A diethyl ether layer was
dried over anhydrous sodium sulfate, and thereafter the solvent was removed
under reduced pressure, to give 1.3 g of a residue. The infrared absorption
spectroscopy of the resulting compound was determined. As a result, no
absorption by hydroxyl group was found. In addition, this acetal was analyzed
by mass spectrometer. The compound was found to have a molecular weight of
865 and a compositional formula C45Hg5O15, which was perfectly identical to
theoretical value. It was confirmed from these results that the heptaglycerol
dodecyl ether has four partial structures of 1,2-diol. The HLB of the
heptaglycerol dodecyl ether is 12.4.
Comparative Example B 1
A one-liter four-necked flask equipped with a stirrer, a nitrogen inlet tube
and a thermometer was charged with 186 g of dodecyl alcohol and 9 g of sodium
hydroxide. The mixture was then dehydrated with heating to 120°C under
reduced pressure. Next, 370 g of glycidol (5 times by mol against the dodecyl
alcohol) was added dropwise at 120°C over a period of 1 hour, and the
mixture
was stirred for additional 2 hours. Water was added to the resulting product,
and
the product was desalted through a cationic exchange resin and an anionic
exchange resin. The desalted product was dehydrated under reduced pressure, to
give 523 g of pentaglycerol dodecyl ether. A 1 g sample of the resulting
product
was taken, and subjected to acetal formation in the same manner as in Example
B 1. The infrared absorption spectroscopy of the resulting product was
CA 02356474 2001-08-31
determined. As a result, an absorption by hydroxyl group was detected. It was
confirmed from these results that the pentaglycerol dodecyl ether has hydroxyl
group other than the structure of 1,2-diol or 1,3-diol.
5 Comparative Example B2
Two-hundred and seventy grams of octadecanoyl alcohol, 370 g of
glycidol (5 times by mol against the octadecanoyl alcohol) and 9 g of sodium
hydroxide were reacted and purified in the same manner as in Comparative
Example B 1, to give 598 g of pentaglycerol octadecanoyl ether. A 1 g sample
of
10 the resulting product was taken, and subjected to acetal formation in the
same
manner as in Example B 1. The infrared absorption spectroscopy of the
resulting
product was determined. As a result, an absorption by hydroxyl group was
detected. It was confirmed from these results that the pentaglycerol
octadecanoyl ether has hydroxyl group other than the structure of 1,2-diol or
1,3-
15 diol.
Comparative Example B3
One-hundred and eighty-six grams of dodecyl alcohol, 518 g of glycidol
(7 times by mol against the dodecyl alcohol) and 9 g of sodium hydroxide were
20 reacted and purified in the same manner as in Comparative Example B 1, to
give
633 g of heptaglycerol dodecyl ether. A 1 g sample of the resulting product
was
taken, and subjected to acetal formation in the same manner as in Example B 1.
The infrared absorption spectroscopy of the resulting product was determined.
As a result, an absorption by hydroxyl group was detected. It was confirmed
25 from these results that the heptaglycerol dodecyl ether has hydroxyl group
other
CA 02356474 2001-08-31
41
than the structure of 1,2-diol or 1,3-diol.
Test Example B 1
The detergency was determined for each of surfactants, the pentaglycerol
dodecyl ether obtained in Example B 1 and the pentaglycerol dodecyl ether
obtained in Comparative Example B 1, in accordance with Gosei Senzai
Shikenhou (Testing Method for Synthetic Detergent) (published by Japanese
Industrial Standards Committee, JIS K3362, revised February l, 1990) by a
detergency tester. Here, the test was carried out at a temperature of
25°C with a
l0 concentration of each surfactant of 0.03% by weight. The results, which are
expressed by the removal percentage of the model fat and oil stains, are shown
in
Table B 1.
Table B 1
Surfactant Removal
Percentage
(%)
Pentaglycerol Dodecyl Ether 99
Obtained in Example B 1
Pentaglycerol Dodecyl Ether 61
Obtained in Comparative
Example B 1
It is clear from the results in Table B 1 that the pentaglycerol dodecyl ether
obtained in Example B 1 has more excellent detergency as compared to the
pentaglycerol dodecyl ether obtained in Comparative Example B 1.
CA 02356474 2001-08-31
42
Test Example B2
The emulsion stability was determined for each of surfactants, the
pentaglycerol octadecanoyl ether obtained in Example B2 and the pentaglycerol
octadecanoyl ether obtained in Comparative Example B2, in accordance with the
following procedures. Specifically, 2.5 g of each surfactant was added to 250
g
of water, and the mixture was heated to 60°C. With stirnng with a
homomixer at
3000 rpm, 250 g of rapeseed oil separately heated to 60°C was gradually
added
to the resulting mixture, and thereafter the mixture was stirred at 10000 rpm
for
3 minutes, to give an emulsion. This emulsion was stored at 60°C for 24
hours.
l0 The emulsion state of the pentaglycerol octadecanoyl ether obtained in
Example
B2 was compared with that of the pentaglycerol octadecanoyl ether obtained in
Comparative Example B2. As a result, while no separated water was found for
the one containing the pentaglycerol octadecanoyl ether obtained in Example
B2,
23% separated water was found for the one containing the pentaglycerol
octadecanoyl ether obtained in Comparative Example B2. It is clear from the
above results that the pentaglycerol octadecanoyl ether obtained in Example B2
has more excellent emulsion stability as compared to the pentaglycerol
octadecanoyl ether obtained in Comparative Example B2.
Test Example B3
The solubilizing capacity was determined for each of surfactants, the
heptaglycerol dodecyl ether obtained in Example B3 and the heptaglycerol
dodecyl ether obtained in Comparative Example B3, in accordance with the
following procedures. Each of ten test tubes was charged with dl-a-tocopherol
with varying its amount in the range of 0 to 50 mg, and 10 ml of 1% by weight
CA 02356474 2001-08-31
43
solution of the heptaglycerol dodecyl ether obtained in Example B3 was added
thereto. The mixture was stirred with a homogenizer for 10 seconds, and
thereafter the transmittance at 650 nm was determined. The results are plotted
in
a graph, taking the amount of the tocopherol as the abscissa, and the
transmittance as the ordinate. The amount of the tocopherol which corresponds
to the transmittance of 90% was determined. Similarly, a test was carried out
with the heptaglycerol dodecyl ether obtained in Comparative Example B3. It is
found from the comparison of the results that in contrast to the fact that 45
mg of
the heptaglycerol dodecyl ether obtained in Example B3 can be solubilized for
the transmittance to be lowered to 90%, only 5 mg or less of the heptaglycerol
dodecyl ether obtained in Comparative Example B3 can be solubilized, whereby
showing that the heptaglycerol dodecyl ether obtained in Example B3 is more
excellent in the solubilizing capacity as compared to that of the
heptaglycerol
dodecyl ether obtained in Comparative Example B3.
Test Exam 1p a B4
Each of cleansing creams, inventive product A and comparative product B,
was prepared in accordance with the composition as shown in Table B2.
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44
Table B2
A B
Liquid Paraffin 55 55
Glycerol 37 37
1,3-Butylene Glycol 2 2
Purified Water 2 2
Pentaglycerol Dodecyl 2
Ether
Obtained in Example B
1
Pentaglycerol Dodecyl 2
Ether
Obtained in Comparative
Example B 1
Units: % by weight
The liquid paraffin was added dropwise with mixing each surfactant,
glycerol, 1,3-butylene glycol and purified water at 60°C. The resulting
composition was stored at 60°C for 10 days. As a result, the mixture
was
separated into two layers in the composition B, in contrast to no property
changes
in the composition A. It is clear from above that the pentaglycerol dodecyl
ether
obtained in Example B 1 is more excellent in properties, as compared to that
of the
pentaglycerol dodecyl ether obtained in Comparative Example B 1, when applied
to cleansing cream.
As verified above, since the polyglycerol alkyl ether of the present
invention is contained in the composition, the resulting composition can
exhibit
higher detergency, emulsion stability, and solubilizing capacity.
Example C 1
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A 200-ml four-necked flask equipped with a stirrer, a thermometer, a
nitrogen inlet tube and a gas-discharging tube was charged with 60.0 g of the
tetraglycerol obtained in Example A1, 38.2 g of lauric acid and 0.4 g of
sodium
hydroxide, and the mixture was reacted at 230°C for 2 hours under
nitrogen gas
5 stream, to give 93.3 g of tetraglycerol laurate (HLB = 11.9). In addition,
similarly, the esterification reaction was carried out by using 54.3 g of
stearic
acid in place of lauric acid, to give 106.3 g of tetraglycerol stearate (HLB =
10.2).
Exam 1p a C2
10 A 100-ml four-necked flask equipped with a stirrer, a thermometer, a
nitrogen inlet tube and a gas-discharging tube was charged with 30.0 g of the
decaglycerol obtained in Example A3, 8.0 g of lauric acid and 0.04 g of sodium
hydroxide, and the mixture was reacted at 230°C for 2 hours under
nitrogen gas
stream, to give 36.0 g of decaglycerol laurate (HLB = 15.7). In addition,
15 similarly, the esterification reaction was carned out by using 11.5 g of
stearic
acid in place of lauric acid, to give 39.5 g of decaglycerol stearate (HLB =
14.4).
Example C3
A 200-ml four-necked flask equipped with a stirrer, a thermometer, a
20 nitrogen inlet tube and a gas-discharging tube was charged with 60.0 g of
the
polyglycerol obtained in Example A4, 22.5 g of stearic acid and 0.1 g of
sodium
hydroxide, and the mixture was reacted at 230°C for 2 hours under
nitrogen gas
stream, to give 78.0 g of a mixture of plural kinds of polyglycerol stearate
in
branched form (HLB = 14.0).
CA 02356474 2001-08-31
46
Comparative Example C 1
A one-liter four-necked flask equipped with a stirrer, a thermometer, a
nitrogen inlet tube and a gas-discharging tube was charged with 400.0 g of the
tetraglycerol obtained in Comparative Example A 1, 255.0 g of lauric acid and
0.7 g of sodium hydroxide, and the mixture was reacted at 230°C for 2
hours
under nitrogen gas stream, to give 628.8 g of tetraglycerol laurate (HLB =
11.9).
In addition, similarly, the esterification reaction was carned out by using
362 g
of stearic acid in place of lauric acid, to give 723.9 g of tetraglycerol
stearate
(HLB = 10.2).
Comparative Example C2
A one-liter four-necked flask equipped with a stirrer, a thermometer, a
nitrogen inlet tube and a gas-discharging tube was charged with 400.0 g of the
decaglycerol obtained in Comparative Example A2, 105.5 g of lauric acid and
0.5 g of sodium hydroxide, and the mixture was reacted at 230°C for 2
hours
under nitrogen gas stream, to give 470.1 g of decaglycerol laurate (HLB =
15.7).
In addition, similarly, the esterification reaction was carried out by using
150.0 g
of stearic acid in place of lauric acid, to give 522.5 g of decaglycerol
stearate
(HLB = 14.4).
Test Example C 1
The interfacial tension of a 0.1% aqueous surfactant solution and corn oil
at 40°C was determined by a Wilhemy's method, for the tetraglycerol
laurate and
the tetraglycerol stearate each obtained in Example C 1, and the tetraglycerol
laurate and the tetraglycerol stearate obtained in Comparative Example C 1.
The
CA 02356474 2001-08-31
47
results are shown in Table C1.
Table C 1
Name of Surfactant Surface Tension
(mN/m)
No Addition 24.5
Tetraglycerol Laurate Obtained2.1
in
Example C 1
Tetraglycerol Stearate Obtained1.5
in
Example C 1
Tetraglycerol Laurate Obtained15.4
in
Comparative Example C 1
Tetraglycerol Stearate Obtained11.3
in
Comparative Example C 1
It is clear from the results in Table C 1 that the tetraglycerol laurate and
stearate in branched forms are more excellent in lowering the surface tension
than the tetraglycerol laurate and stearate in linear forms.
Test Example C2
The emulsion ability was determined for each of surfactants, the
tetraglycerol stearate obtained in Example C 1, the decaglycerol stearate
obtained
in Example C2, the polyglycerol stearate obtained in Example C3, the
tetraglycerol stearate obtained in Comparative Example C 1 and the
decaglycerol
stearate obtained in Comparative Example C2, by the following procedures.
Specifically, 2.5 g of each surfactant was added to 250 g of water, and the
mixture was heated to 60°C. With stirring the mixture with a homomixer
at
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48
3000 rpm, 250 g of rapeseed oil separately heated to 60°C was gradually
added
to the mixture, and thereafter the mixture was stirred at 10000 rpm for 3
minutes
to give an emulsion. The emulsion state was compared after storing the
emulsion at 60°C for 24 hours. The emulsion state was evaluated by the
S following criteria:
[Criteria]
O: amount of water separated being 1% or less;
O: amount of water separated being 10% or less and exceeding 1%;
o: amount of water separated being 30% or less and exceeding 10%; and
x : emulsion corrupting (separation of oil droplets)
The results are shown in Table C2.
Table C2
Name of Surfactant Evaluation of
Emulsion State
Tetraglycerol Stearate Obtained in O
Example C 1
Decaglycerol Stearate Obtained in O
Example C2
Polyglycerol Stearate Obtained in O
Example C3
Tetraglycerol Stearate Obtained in x
Comparative Example C 1
Decaglycerol Stearate Obtained in o
Comparative Example C2
It is clear from the results in Table C2 that the tetra- and decaglycerol
CA 02356474 2001-08-31
49
stearate in branched forms and the mixture of plural kinds of polyglycerol
stearates in branched forms are more excellent in the emulsion ability than
the
tetra- and decaglycerol stearates in linear forms.
Test Example C3
The detergency was determined for each of surfactants, the decaglycerol
laurate obtained in Example C2 and the decaglycerol laurate obtained in
Comparative Example C2, in accordance with Gosei Senzai Shikenhou (Testing
Method for Synthetic Detergent) (published by Japanese Industrial Standards
Committee, JIS K3362, revised February 1, 1990) by a detergency tester. Here,
the test was carried out at a temperature of 25°C with a concentration
of each
surfactant of 0.03% by weight. The results, which are expressed by the removal
percentage of the model fat arid oil stains, are shown in Table C3.
Table C3
Surfactant Removal
Percentage
(%)
Decaglycerol Laurate Obtained 99
in Example C2
Decaglycerol Laurate Obtained 55
in Comparative Example C2
It is clear from the results in Table C3 that the decaglycerol laurate in a
branched form has more excellent detergency as compared to the decaglycerol
laurate in a linear form.
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Test Example C4
Three kinds of emulsion dressings, the inventive product A and the
comparative products B and C were prepared in accordance with the composition
shown in Table C4.
5
Table C4
A B C
Corn Oil 65 65 65
Acetic Acid 15 15 15
Table Salt 2 2 2
Water 17 17 17
Decaglycerol Stearate Obtained in 1
Example C2
Polyglycerol Stearate Obtained in 1
Example C3
Decaglycerol Stearate Obtained in 1
Comparative Example C2
Unit: % by weight
Acetic acid, table salt a:nd an emulsifying agent were added to water, and
10 the mixture was heated to 60°C with stirring with a homomixer at
5000 rpm, and
corn oil separately heated to 60°C was gradually added thereto.
Thereafter, the
mixture was emulsified at 10000 rpm for 5 minutes. Each of the emulsions A to
C was stored at 40°C for 5 days, and as a result, 34% by volume of the
corn oil
was separated in the composition C, in contrast to having completely no oil
layer
15 separation in the compositions A and B.
CA 02356474 2001-08-31
51
It is clear from the above results in Table C4 that the decaglycerol stearate
in a branched form and the mixture of the plural kinds of polyglycerol
stearates
in branched forms are more excellent in lowering the oil-layer reparability as
compared with that of the decaglycerol stearate in a linear form.
Test Example CS
The cocoa beverages, the inventive product A and the comparative
product B were prepared in accordance with the composition shown in Table C5.
1 o Table CS
A B
Cocoa Powder 25 25
Sugar 60 60
Lactose 10 10
Water 4 4
Decaglycerol Laurate Obtained in 1
Example C2
Decaglycerol Laiu~ate Obtained in 1
Comparative Example CZ
Unit: % by weight
Each of the compositions A and B was mixed and thereafter granulated
with a granulator. A 10 g sample of each composition was gently added to 40 ml
of water, and the mixture was allowed to stand for 4 hours. Thereafter, the
liquid
was gently decanted, and the amount of the granules sedimented at the bottom
of
the granulator without dispersing the liquid mixture was determined. As a
result,
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52
the amount of the granules was 0.2 g for the composition A and 1.8 g for the
composition B.
It is clear from the above that the decaglycerol laurate in a branched form
is more excellent in the emulsion stability as compared to the decaglycerol
laurate in a linear form.
Test Example C6
Each of cleansing creams, inventive product A and comparative product B,
was prepared in accordance with the composition as shown in Table C6.
Table C6
A B
Liquid Paraffin 55 55
Glycerol 37 37
1,3-Butylene Glycol 2 2
Purified Water 2 2
Tetraglycerol Laurate Obtained in 2
Example C 1
Tetraglycerol Laurate Obtained in 2
Comparative Example C 1
Units: % by weight
The liquid paraffin was added dropwise with mixing each emulsifying
agent, glycerol, 1,3-butylene glycol and purified water at 60°C. The
resulting
composition was stored at 60°C for 10 days. As a result, the mixture
was
separated into two layers in the composition B, in contrast to no property
changes
CA 02356474 2001-08-31
53
in the composition A.
It is clear from above that the tetraglycerol laurate in a branched form is
more excellent in lowering the two-layer separability, as compared to that of
the
tetraglycerol laurate in a linear form, when applied to cleansing cream.
