U.S. patent application number 09/185742 was filed with the patent office on 2001-12-27 for cleansing composition.
Invention is credited to HONDA, SHINKICHI, TSUBOI, MIKIO.
Application Number | 20010055576 09/185742 |
Document ID | / |
Family ID | 16012824 |
Filed Date | 2001-12-27 |
United States Patent
Application |
20010055576 |
Kind Code |
A1 |
HONDA, SHINKICHI ; et
al. |
December 27, 2001 |
CLEANSING COMPOSITION
Abstract
The present invention relates to a cleansing composition
comprising at least one compound selected from N-long chain
acylamino acids represented by formula (I): 1 (wherein n represents
1 or 2; and R represents a saturated or unsaturated hydrocarbon
group having 5 to 23 carbon atoms), and salts thereof.
Inventors: |
HONDA, SHINKICHI;
(NAGAREYAMA-SHI, JP) ; TSUBOI, MIKIO;
(KOMATSU-SHI, JP) |
Correspondence
Address: |
ANTONELLI TERRY STOUT AND KRAUS
SUITE 1800
1300 NORTH SEVENTEENTH STREET
ARLINGTON
VA
22209
|
Family ID: |
16012824 |
Appl. No.: |
09/185742 |
Filed: |
November 4, 1998 |
Current U.S.
Class: |
424/70.1 ;
424/405; 424/70.19; 424/70.21; 424/70.22; 424/70.23; 424/70.24;
424/70.27; 424/70.28; 424/70.31; 424/74 |
Current CPC
Class: |
C11D 1/10 20130101; A61K
8/44 20130101; A61Q 5/02 20130101; A61Q 19/10 20130101; Y10S
514/975 20130101 |
Class at
Publication: |
424/70.1 ;
424/70.19; 424/70.21; 424/70.22; 424/70.23; 424/70.24; 424/70.27;
424/70.28; 424/70.31; 424/74; 424/405 |
International
Class: |
A01N 025/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 12, 1995 |
JP |
176390/95 |
Claims
What is claimed is:
1. A composition comprising N-long chain acylamino acids or salts
thereof, selected from the group consisting of N-coconut oil fatty
acid acylglutamine or a salt thereof, N-coconut oil fatty acid
acylasparagine or a salt thereof, N-palm kernel oil fatty acid
acylglutamine or a salt thereof, and N-palm kernel oil fatty acid
acylasparagine or a salt thereof.
2. A composition according to claim 1, wherein said N-long chain
acylamino acids are producible by reacting coconut oil fatty acid
or palm kernel oil fatty acid with glutamine or asparagine or a
salt thereof.
3. A composition according to claim 1, wherein said N-long chain
acylamino acid consists essentially of 1-8 mol % N-octanoyl
glutamine or a salt thereof, 3-10 mol % N-decanoyl glutamine or a
salt thereof, 45-53 mol % N-dodecanoyl glutamine or a salt thereof,
16-25 mol % N-tetradecanoyl glutamine or a salt thereof, 5-10 mol %
N-hexadecanoyl glutamine or a salt thereof, 2-10 mol %
N-octadecanoyl glutamine or a salt thereof, 4-17 mol %
N-octadecenoyl glutamine or a salt thereof, and 0-2 mol %
N-octadecadienoyl glutamine or a salt thereof; or 1-8 mol %
N-octanoyl asparagine or a salt thereof, 3-10 mol % N-decanoyl
asparagine or a salt thereof, 45-33 mol % N-dodecanoyl asparagine
or a salt thereof, 16-25 mol % N-tetradecanoyl asparagine or a salt
thereof, 5-10 mol % N-hexadecanoyl asparagine or a salt thereof,
2-10 mol % N-octadecanoyl asparagine or a salt thereof, 4-17 mol %
N-octadecenoyl asparagine or a salt thereof, and 0-2 mol %
N-octadecadienoyl asparagine or a salt thereof.
4. The composition according to claim 3, containing a further
compound which is a surfactant.
5. The composition according to claim 4, wherein said N-long chain
acylamino acids or salts thereof are contained in the composition
in an amount of 1 to 90 wt %.
6. A composition according to claim 1, wherein said N-long chain
acylamino acids or salts thereof are included in the composition in
an amount of 3 to 80 wt %.
7. A composition according to claim 1, wherein said N-long chain
acylamino acids or salts thereof is N-coconut oil fatty acid
acylglutamine or a salt thereof.
8. A composition according to claim 1, wherein said N-long chain
acylamino acids or salts thereof are selected from the group
consisting of N-coconut oil fatty acid acylasparagine or a salt
thereof and N-palm kernel oil fatty acid acylasparagine or a salt
thereof.
9. A composition according to claim 1, wherein said composition is
a cleansing composition, said N-long chain acylamino acids or salts
thereof being active cleaning agents in said cleansing
composition.
10. The composition according to claim 2, containing a further
compound which is a surfactant.
11. The composition according to claim 10, wherein said N-long
chain acylamino acids or salts thereof are contained in the
composition in an amount of 1 to 90 wt %.
12. The composition according to claim 1, containing a further
compound which is a surfactant.
13. The composition according to claim 12, wherein said N-long
chain acylamino acids or salts thereof are contained in the
composition in an amount of 1 to 90 wt %.
Description
[0001] This application is a Continuation application of
application Ser. No. 08/793,888, filed Mar. 12, 1997.
TECHNICAL FIELD
[0002] The present invention relates to a cleansing composition
comprising an N-long chain acylamino acid or a salt thereof which
composition is excellent in foaming power, foam breakage and
feeling after its use.
BACKGROUND ART
[0003] Inorganic salts and organic salts of N-long chain acylamino
acids have bactericidal activity in addition to surface activity.
Cleansing agents comprising these salts are mild to skin and have
an excellent detergency, and thus are widely used as a main
component of cleansing compositions (Japanese Published Examined
Patent Application No. 38604/79, Japanese Published Examined Patent
Application No. 83538/93 and Japanese Published Examined Patent
Application No. 27720/85).
[0004] Among the salts of N-long chain acylamino acids used as
cleansing agents, salts of N-long chain acylamino acids of tertiary
amide type are excellent in water-solubility, but are known to have
the defects that much rinse is necessary for breaking the foam
generated and that they give a slimy feeling. Salts of N-long chain
acylamino acids of secondary amide type are known to be
disadvantageous in that the foam is not stable enough for cleansing
and that they give a poor feeling after their use. To solve these
problems, it is known to use an N-long chain acyldipeptide in
combination with an N-long chain acylamino acid (Japanese Published
Unexamined Patent Application No. 78693/93).
[0005] N-acylglutamine is known to have hair-growing activity
(Japanese Published Unexamined Patent Application No. 32726/94) and
melanin formation inhibiting activity (Japanese Published
Unexamined Patent Application No. 157284/94), but its use as a
cleansing agent is not known.
DISCLOSURE OF THE INVENTION
[0006] The present invention provides a cleansing composition
comprising at least one compound selected from N-long chain
acylamino acids represented by formula (I): 2
[0007] (wherein n represents 1 or 2; and R represents a saturated
or unsaturated hydrocarbon group having 5 to 23 carbon atoms), and
salts thereof [hereinafter referred to as Compound (I)].
[0008] Examples of the saturated hydrocarbon group having 5 to 23
carbon atoms in the definition of Compound (I) are straight-chain
or branched-chain ones such as pentyl, isopentyl, hexyl, heptyl,
octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,
pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl,
heneicosyl, docosyl, and tricosyl. Examples of the unsaturated
hydrocarbon group having 5 to 23 carbon atoms are straight-chain or
branched-chain ones such as pentenyl, 3-methyl-1-butenyl, hexenyl,
heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl,
tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl,
octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl,
tricosenyl, 1,3-pentadienyl, 8,11-heptadecadienyl,
8,11,14-heptadecatrienyl, and 4,7,10,13-nonadecatetraenyl.
[0009] Preferred examples of the saturated hydrocarbon group are
saturated straight-chain or branched-chain hydrocarbon groups
having 11 to 17 carbon atoms such as undecyl, dodecyl, tridecyl,
tetradecyl, pentadecyl, hexadecyl, and heptadecyl. Preferred
examples of the unsaturated hydrocarbon group are unsaturated
straight-chain or branched-chain hydrocarbon groups having 11 to 17
carbon atoms such as undecenyl, dodecenyl, tridecenyl,
tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl,
1,3-pentadienyl, 8,11-heptadecadienyl, and
8,11,14-heptadecatrienyl.
[0010] Examples of the salts in Compound (I) are alkali metal salts
such as sodium salt, potassium salt, and lithium salt, alkaline
earth metal salts such as calcium salt and magnesium salt, ammonium
salt, amine addition salts such as salts with monoethanolamine,
diethanolamine, triethanolamine, and triisopropanolamine, and basic
amino acid addition salts such as salts with arginine and
lysine.
[0011] Compound (I) can be prepared by converting a straight-chain
or branched-chain fatty acid having 6 to 24 carbon atoms which is
saturated or unsaturated (hereinafter referred to as a long chain
fatty acid) into halides such as chloride and bromide by the use of
halogenating agents such as thionyl chloride and phosgene, and then
condensing the halide with an amino acid selected from glutamine
and asparagine (hereinafter referred to simply as an amino acid).
Alternatively, Compound (I) can be prepared by converting a long
chain fatty acid into an acid anhydride, and then reacting the acid
anhydride with an amino acid.
[0012] Examples of the long chain fatty acid are fatty acids
composed of single fatty acids such as caproic acid, enanthic acid,
caprylic acid, pelargonic acid, capric acid, undecylic acid, lauric
acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic
acid, stearic acid, isostearic acid, nonadecanoic acid, arachic
acid, behenic acid, lignoceric acid, oleic acid, sorbic acid,
linolic acid, linolenic acid, and arachidonic acid. Fatty acids
composed of these single fatty acids such as coconut oil fatty acid
and palm kernel oil fatty acid can also be used.
[0013] A representative process for preparing Compound (I) via an
acid halide is described below.
[0014] A long chain fatty acid is dispersed in a solvent such as
methylene chloride, chloroform, carbon tetrachloride, benzene,
toluene, xylene or n-hexane, and 1 to 5 equivalents of a
halogenating agent is added thereto based on the long chain fatty
acid to obtain a long chain fatty acid halide as a reaction
product. Then, an amino acid is dissolved or dispersed in a
solvent, and the above-mentioned long chain fatty acid halide is
added thereto in an amount of 0.3 to 1.0 equivalent based on the
amino acid, while maintaining the reaction solution at a
temperature of 5 to 70.degree. C. and thus acylation is carried out
to obtain Compound (I).
[0015] Examples of the solvent used for acylation are water,
methanol, ethanol, isopropanol, isobutanol, acetone, toluene,
tetrahydrofuran, ethyl acetate, N,N-dimethylformamide and
dimethylsulfoxide, which may be used singly or in combination. In
the step where an amino acid is dissolved or dispersed in a
solvent, an alkaline substance such as sodium hydroxide or
potassium hydroxide in an amount of 0.8 to 2.0 equivalents based on
the amino acid may also be dissolved or dispersed in the solvent as
may be appropriate.
[0016] In the case where a salt of Compound (I) is desired and it
is produced in the form of the desired salt, it can be subjected to
purification as such. In the case where Compound (I) is produced in
the free state and its salt is desired, Compound (I) is dissolved
or suspended in a suitable solvent, followed by addition of a base
to form a salt.
[0017] Compound (I) is usually employed in the cleansing
composition of the present invention in an amount of 1 to 90 wt %,
preferably 3 to 80 wt %.
[0018] The cleansing compositions of the present invention may be
formulated to contain adjuvants such as pigments, fragrances,
solubilizing agents and builders, and also surfactants such as
anionic surfactants, cationic surfactants, amphoteric surfactants
and nonionic surfactants to adjust foaming and detergency.
[0019] Examples of the surfactants are fatty acid soap, higher
alcohol ester sulfate, polyoxyethylene higher alcohol ester
sulfate, higher alcohol ester phosphate, polyoxyethylene higher
fatty acid ester phosphate, salt of sulfonated higher fatty acid,
salt of sulfonated higher fatty acid ester, higher fatty acid ester
isethionate, salt of .alpha.-sulfo higher fatter acid ester, higher
alkyldimethyl benzyl ammonium salt, higher alkylamine, higher
alkyl-trimethyl ammonium salt, higher fatty acid diethanolamide and
its ethylene oxide or propylene oxide addition product, higher
fatty acid monoethanolamide and its ethylene oxide or propylene
oxide addition product, polyoxyethylene higher fatty acid
monoethanol amide ester phosphate, salt of N-long chain acylamino
acid such as salt of N-long chain acyl acidic amino acid, N-long
chain acyl sarcosinate and salt of N-long chain
acyl-.beta.-alanine, higher alkylamino propinonate such as
laurylamino propionate, higher alkylimino diacetate such as
laurylimino diacetate, and amine or amide compounds such as higher
alkyldimethyl betaine, higher alkyl dihydroxyethyl betaine,
N-alkanoyl-N'-(2-hydroxyethyl)-N'-carboxyme- thylethylenediamine,
and N-alkanoyl-N-(2-hydroxyethyl)-N',N'-biscarboxymet-
hylethylenediamine.
[0020] The cleansing compositions of the present invention are
useful as shampoo, facial washing compositions, bath soap, kitchen
detergents, etc.
[0021] Test Examples are shown below in which the cleansing
compositions of the present invention were evaluated in respect of
foaming and foam breaking and also by sensory test.
TEST EXAMPLE 1
[0022] Sodium salt of N-lauroylglutamine obtained in Reference
Example 1 and sodium salt of N-coconut oil fatty acid acylglutamine
obtained in Reference Example 2 were respectively dissolved in
water to prepare 30 wt % aqueous solutions (hereinafter referred to
as Compositions of Invention 1 and 2, respectively). Compositions
of Invention 1 and 2, and aqueous solutions respectively containing
N-coconut oil fatty acid acyl-L-sodium glutamate, sodium salt of
N-coconut oil fatty acid-N-methyl-.beta.-alanin- e and potassium
salt of N-coconut oil fatty acid acylglycin (hereinafter referred
to as Comparison Compositions 1, 2 and 3, respectively) were
adjusted to the concentration of 1.2 wt %. Each of the obtained
aqueous solutions (100 ml) (temperature of solution: 30.degree. C.)
was poured into a graduated cylinder. Then, a stirrer bar was set
therein, followed by stirring at 1500 rpm for one minute. After the
end of stirring, the volume (ml) of the foam generated was
measured, and also 2 minutes after the end of stirring, the volume
of the foam remaining was measured.
[0023] The results are shown in Table 1.
1 TABLE 1 Composition No. Composition No. (Invention) (Comparison)
1 2 1 2 3 Foam I 213 224 190 173 152 volume II 202 212 180 158 125
(ml) I: immediately after the end of stirring II: 2 minutes after
the end of stirring
TEST EXAMPLE 2
[0024] Sensory evaluation was made on the 1.2 wt % aqueous
solutions prepared in Test Example 1 by panelists consisting of 10
men and 10 women. The test solutions were used for cleansing their
skin and hair, and were evaluated according to the following
criteria. The average of the scores was calculated for each
evaluation item and graded as follows.
[0025] A) Slimy feel in washing and E) unsmoothness feel in
drying
[0026] 5: very little
[0027] 4: a little
[0028] 3: average
[0029] 2: considerable
[0030] 1: very much
[0031] B) Foam breakage in rinsing
[0032] 5: excellent
[0033] 4: good
[0034] 3: average
[0035] 2: poor
[0036] 1: unsatisfactory
[0037] C) Smoothness in rinsing, D) smoothness after rinsing and F)
smoothness after drying
[0038] 5: excellent
[0039] 4: good
[0040] 3: average
[0041] 2: poor
[0042] 1: unsatisfactory,
[0043] The results are shown in Table 2.
2 Average .gtoreq. 4.5 Excellent +++ = 3.5-4.4 Good ++ = 2.5-3.4
Average + .ltoreq. 2.4 Poor -
[0044] As apparent from Tables 1 and 2, the cleansing compositions
of the present invention are excellent in foaming power and foam
breakage and show excellent results in sensory evaluation.
[0045] Examples of the present invention are shown below.
BEST MODE FOR CARRYING OUT THE INVENTION
Example 1
A Cleansing Cream
[0046] A cleansing cream having the following composition was
prepared.
3TABLE 3 Ingredient Composition (wt %) (1) Sodium salt of N-coconut
oil 10.0 fatty acid acylglutamine (30 wt % aqueous solution) (2)
Sodium lauryl sulfate 25.0 (3) Ethylene glycol distearate 4.0 (4)
Myristic acid 8.0 (5) Stearic acid 10.0 (6) Cetanol 3.0 (7) Butyl
paraben 0.1 (8) Potassium hydroxide 2.0 (9) Triethanolamine 4.0
(10) Glycerin 3.0 (11) Fragrance 0.1 (12) Purified water 30.8
Method for Preparation
[0047] A mixture of the ingredients (8) through (10) and (12) was
heated at 80 to 90.degree. C. to make a solution, and immediately
thereafter, a solution prepared by heating a mixture of the
ingredients (1) through (7) at 80 to 90.degree. C. was added
thereto gradually with stirring. Then, the ingredient (11) was
added to the mixture at 60.degree. C., followed by cooling to room
temperature with stirring to obtain the product.
Example 2
A Shampoo (Liquid)
[0048]
4TABLE 4 Ingredient Composition (wt %) (1) Sodium salt of N-coconut
oil fatty 28.0 acid acylglutamine (30 wt % aqueous solution) (2)
Ammonium lauryl sulfate (30 wt % 20.0 aqueous solution) (3)
Monoethanolamide lauryl sulfate 2.0 (4) Preservative 0.1 (5)
Fragrance 0.1 (6) Purified water 49.8
Method for Preparation
[0049] A mixture of the ingredients (1) through (4) and (6) was
heated at 80 to 90.degree. C., and the resulting solution was
cooled gradually. Then, rise ingredient (5) was added to the
solution at 60.degree. C., follower by cooling to room temperature
with stirring to obtain the product.
Example 3
Liquid Bath Soap
[0050]
5TABLE 5 Ingredient Composition (wt %) (1) Sodium salt of N-coconut
oil 9.0 fatty acid acylglutamine (30 wt % aqueous solution) (2)
2-Alkyl-N-carboxymethyl-N-hydro- 25.0 xyethylimidazolinium betaine
(40 wt % aqueous solution) (3) Coconut oil fatty acid 5.0
diethanolamide (4) Polyoxyethylene alkyl ether 10.0 sodium sulfate
(25 wt aqueous solution) (5) Propylene glycol 6.0 (6) Sodium
chloride 1.0 (7) Preservative 0.1 (8) Phosphoric acid 0.1 (9)
Fragrance 0.1 (10) Purified water 43.7
Method for Preparation
[0051] A mixture of the ingredients (1) through (8) and (10) was
heated at 80 to 90.degree. C., and the resulting solution was
cooled gradually. Then, the ingredient (9) was added to the
solution at 60.degree. C., followed by cooling to room temperature
with stirring to obtain the product.
Reference Example 1
Process for Producing N-lauroyl-glutamine
[0052] (1) Halogenation reaction
[0053] In 300 ml of methylene chloride was dispersed 100 g of
lauric acid, and 35.5 g of thionyl chloride was added thereto with
stirring over 30 minutes, followed by further stirring for 3 hours.
The temperature of the solution was maintained at 20.degree. C.
during this reaction. After the reaction was completed, the
infrared absorption spectrum of the reaction mixture was measured.
It was confirmed that lauroyl chloride was formed by the fact that
the peak at 1695 cm.sup.-1 derived from carboxylic acid (--COOH)
was not observed, whereas the peak at 1785 cm.sup.-1 derived from
an acid chloride (--COCl) was observed. After methylene chloride,
thionyl chloride and hydrogen chloride were distilled off under
reduced pressure, with nitrogen gas being passed through the
reaction mixture, the fraction distilled at 150.degree. C. under
reduced pressure (22 mHg) was recovered to give 96 g of lauroyl
chloride.
[0054] (2) Acylation reaction
[0055] In a solution of 19.5 g of potassium hydroxide in 75 ml of
water was dispersed 50 g of glutamine. To the obtained solution
were added dropwise with stirring a solution of 72 g of lauroyl
chloride obtained in (1) in 145 ml of tetrahydrofuran and 73.9 g of
a 25% aqueous solution of potassium hydroxide over one hour, during
which the solution was kept at 20.degree. C. The resulting mixture
was stirred at the same temperature for 4 hours. Then, 6 N
hydrochloric acid was added to the mixture with stirring until the
pH of the mixture reached 1.0, followed by further stirring for one
hour. After the reaction was completed, the precipitated crystals
were collected by filtration and dried to give 101.4 g of crystals.
The measurement of the infrared absorption spectrum and the
elementary analysis were carried out on the obtained crystals.
[0056] Infrared absorption spectrum (KBr tablet) (cm.sup.-1): 1735,
1650, 1565 Elementary analysis (.) C H.sub.32O.sub.4N.sub.2 Calcd:
C, 62.17; H, 9.82; N, 8.53 Found: C, 62.42; H, 9.69; N, 8.43
[0057] The above results confirmed that the crystals were N-lauroyl
glutamine.
Reference Example 2
Process for Producing N-coconut Oil Fatty Acid Acylglutamine
[0058] (1) Halogenation reaction
[0059] In 300 ml of methylene chloride was dispersed 100 g of
coconut oil fatty acid, and 30.2 g of thionyl chloride was added
thereto with stirring over 30 minutes, followed by further stirring
for 3 hours. The temperature of the solution was maintained at
20.degree. C. during this reaction. After the reaction was
completed, the infrared absorption spectrum of the reaction mixture
was measured. It was confirmed that lauroyl chloride was formed bus
the fact that the peak at 1695 cm.sup.-1 derived from carboxylic
acid (--COOH) was not observed, whereas the peak at 1785 cm.sup.-1
derived from an acid chloride (--COCl) was observed. After
methylene chloride and thionyl chloride, as well as sulfur dioxide
and hydrogen chloride formed as by-products, were distilled off
under reduced pressure, the fraction distilled at 105 to
200.degree. C. under reduced pressure (5 mmHg) was recovered to
give 92.8 g of coconut oil fatty acid chloride.
[0060] (2) Acylation reaction
[0061] In a solution of 19.5 g of potassium hydroxide in 75 ml of
water was dispersed 50 g of glutamine. To the obtained solution
were added dropwise with stirring a solution of 82.2 g of coconut
oil fatty acid chloride obtained in (1) in 145 ml of
tetrahydrofuran and 73 g of a 25% aqueous solution potassium
hydroxide, during which the solution was kept at 35 to 40.degree.
C. and at pH 8.5 to 9.5 over one hour. The resulting mixture was
stirred at the same temperature for 4 hours. Then, 6 N hydrochloric
acid was added to the mixture with stirring until the pH of the
mixture reached 1.0, followed by further stirring for one hour.
After the reaction was completed, the precipitated crystals were
collected by filtration and dried to give 104.9 g of crystals. The
measurement of the infrared absorption spectrum and the elementary
analysis were carried out on the obtained crystals.
[0062] Infrared absorption spectrum (KBr tablet) (cm.sup.-1): 1740,
1640, 1550
[0063] Elementary analysis:
[0064] Coconut oil fatty acid chloride obtained in (1) was
decomposed with water, and analyzed by gas chromatography for
constituent fatty acids of the coconut oil fatty acid. The average
molecular weight calculated based on the fatty acid composition was
234.58. The elementary analysis values calculated based on the
average molecular weight of N-coconut oil fatty acid acylglutamine
and those found on the compound obtained in (2) are shown
below.
[0065] Calcd: C, 63.91; H, 10.73; N, 7.72 Found: C, 64.02; H,
10.70; N, 7.59
[0066] The above results confirmed that the obtained compound was
N-coconut oil fatty acid acylglutamine represented by formula (II):
3
[0067] (wherein X represents an acyl group derived from coconut oil
fatty acid).
Industrial Applicability
[0068] The present invention provides a cleansing composition which
is excellent in foaming power, foam breakage and feeling after its
use. The composition is useful as a shampoo, a facial washing
composition, bath soap, and a kitchen detergent, etc.
* * * * *