U.S. patent application number 09/934837 was filed with the patent office on 2002-02-21 for wrinkling modifiers.
This patent application is currently assigned to KAO CORPORATION. Invention is credited to Fujimura, Tsutomu, Ito, Noriko, Nagai, Minoru, Ono, Toshiya, Takema, Yoshinori, Yamamuro, Akira.
Application Number | 20020022611 09/934837 |
Document ID | / |
Family ID | 17438881 |
Filed Date | 2002-02-21 |
United States Patent
Application |
20020022611 |
Kind Code |
A1 |
Fujimura, Tsutomu ; et
al. |
February 21, 2002 |
Wrinkling modifiers
Abstract
The invention relates to wrinkling modifiers and anti-aging
cosmetic compositions which each comprise a guanidine derivative
represented by the following general formula (1): 1 wherein 2 is a
heterocyclic group selected from azetidine, pyrrolidine,
piperidine, piperazine or morpholine, and R.sup.1 and R.sup.2 are
the same or different from each other and independently a hydrogen
atom, or an alkyl, hydroxyl, hydroxyalkyl, carboxyl, carboxyalkyl
or amidino group, or a salt thereof. The cosmetic compositions are
excellent in the effects of suppressing wrinkling and of removing
wrinkles and give users a pleasant feeling upon use.
Inventors: |
Fujimura, Tsutomu; (Tochigi,
JP) ; Ito, Noriko; (Tochigi, JP) ; Nagai,
Minoru; (Tochigi, JP) ; Ono, Toshiya;
(Tochigi, JP) ; Yamamuro, Akira; (Tochigi, JP)
; Takema, Yoshinori; (Tochigi, JP) |
Correspondence
Address: |
OBLON SPIVAK MCCLELLAND MAIER & NEUSTADT PC
FOURTH FLOOR
1755 JEFFERSON DAVIS HIGHWAY
ARLINGTON
VA
22202
US
|
Assignee: |
KAO CORPORATION
Chuo-ku
JP
|
Family ID: |
17438881 |
Appl. No.: |
09/934837 |
Filed: |
August 23, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09934837 |
Aug 23, 2001 |
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09269744 |
Apr 6, 1999 |
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6306848 |
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Current U.S.
Class: |
514/210.01 ;
514/237.8; 514/252.12; 514/331; 514/408 |
Current CPC
Class: |
A61K 8/494 20130101;
A61P 17/00 20180101; A61K 8/4913 20130101; A61K 8/4926 20130101;
A61K 8/49 20130101; A61Q 19/08 20130101 |
Class at
Publication: |
514/210.01 ;
514/237.8; 514/252.12; 514/331; 514/408 |
International
Class: |
A61K 031/397; A61K
031/535; A61K 031/495 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 8, 1996 |
JP |
8-267015 |
Aug 10, 1997 |
JP |
PCT/JP97/03604 |
Claims
1. A wrinkling modifier comprising a guanidine derivative
represented by the following general formula 12wherein 13is a
heterocyclic group selected from azetidine, pyrrolidine,
piperidine, piperazine or morpholine, and R.sup.1 and R.sup.2 are
the same or different from each other and independently a hydrogen
atom, or an alkyl, hydroxyl, hydroxyalkyl, carboxyl, carboxyalkyl
or amidino group, or a salt thereof.
2. The wrinkling modifier according to claim 1, wherein the
guanidine derivative or the salt thereof is contained in an amount
of 0.001 to 50% by weight.
3. The wrinkling modifier according to claim 1 or 2, which further
comprises an organic acid, an inorganic acid or an ester
thereof.
4. The wrinkling modifier according to claim 3, wherein the organic
acid, the inorganic acid or the ester thereof is contained in an
amount of 0.001 to 30% by weight.
5. An anti-aging cosmetic composition comprising the guanidine
derivative or the salt thereof according to claim 1.
6. The anti-aging cosmetic composition according to claim 5,
wherein the guanidine derivative or the salt thereof is contained
in an amount of 0.001 to 50% by weight.
7. The anti-aging cosmetic composition according to claim 5 or 6,
which further comprises an organic acid, an inorganic acid or an
ester thereof.
8. The anti-aging cosmetic composition according to claim 7,
wherein the organic acid, the inorganic acid or the ester thereof
is contained in an amount of 0.001 to 30% by weight.
9. A cosmetic skin care composition comprising the wrinkling
modifier according to claim 1 and a synthetic sphingosine
derivative represented by the following general formula (2):
14wherein R.sup.3 is a linear, branched or cyclic, saturated or
unsaturated hydrocarbon group having 4 to 40 carbon atoms, R.sup.4,
R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are independently a hydrogen
atom or a hydrocarbon group having 1 to 10 carbon atoms, which may
be substituted by at least one hydroxyl group, and X and Y are
independently a hydrogen atom or an alkyl group having 1 to 6
carbon atoms, which may contain at least one oxygen atom in its
structure.
10. The cosmetic skin care composition according to claim 9,
wherein the wrinkling modifier and the synthetic sphingosine
derivative are contained in amounts of 0.001 to 50% by weight and
0.0001 to 10% by weight, respectively.
11. The cosmetic skin care composition according to claim 9 or 10,
which further comprises an organic acid, an inorganic acid or an
ester thereof.
12. The cosmetic skin care composition according to claim 11,
wherein the organic acid, the inorganic acid or the ester thereof
is contained in an amount of 0.001 to 30% by weight.
Description
TECHNICAL FIELD
[0001] The present invention relates to wrinkling modifiers and
anti-aging cosmetic compositions, and more particularly to
anti-aging cosmetic compositions which are excellent in the effects
of suppressing wrinkling and of removing or smoothing wrinkles.
BACKGROUND ART
[0002] It is a significant concern of, particularly, women to
maintain the healthy and beautiful skin. However, the condition of
the skin is always affected by factors such as humidity,
ultraviolet rays, cosmetic compositions, aging, diseases, stress
and eating habits. As the result thereof, various skin troubles
such as the decrement of various functions of the skin and the
aging of the skin occur. Of these, wrinkles occur due to dermal
aging by aging, light aging by exposure to sunbeam, or the like.
More specifically, cells f or producing fibers of the dermis are
made small and lessened by exposure to sunbeam or with the increase
in age. In particular, collagen fibers are lost to a great extent,
and so the skin is aged by degeneration of the dermis, reduction of
subcutaneous adipose tissue and the like, which forms the cause of
wrinkling, relaxation, and loss of resilience.
[0003] Various compositions and methods have heretofore been
proposed for preventing or treating the aging effects such as
wrinkling [Japanese Patent Application Laid-Open Nos. 185005/1987,
502546/1987, 72157/1990, 288822/1990 and 41419/1995, Japanese
Patent Application Laid-Open (KOHYO) No. 510542/1994 (through PCT
route), etc.]. However, all of these proposals have not been fully
satisfactory in the effect of modifying wrinkling (or preventing
wrinkling and removing wrinkles). There has thus been a demand for
development of cosmetic skin care compositions excellent in the
effect of modifying wrinkling.
[0004] It is an object of the present invention to provide
wrinkling modifiers and anti-aging cosmetic compositions which can
solve the above-described problems, are excellent in the effects of
suppressing wrinkling without impairing normal dermatophysiology
and removing wrinkles, and give users a pleasant feeling upon
use.
DISCLOSURE OF THE INVENTION
[0005] In view of the foregoing circumstances, the present
inventors have carried out an extensive investigation with a view
toward achieving the above object. As a result, it has been found
that guanidine derivatives having a specific structure or
acid-addition salts thereof are excellent in the effect of
modifying wrinkling and give users a pleasant feeling upon use,
thus leading to completion of the present invention.
[0006] According to the present invention, there are thus provided
a wrinkling modifier and an anti-aging cosmetic composition, each
comprising a guanidine derivative represented by the following
general formula (1): 3
[0007] wherein 4
[0008] is a heterocyclic group selected from azetidine,
pyrrolidine, piperidine, piperazine or morpholine, and R.sup.1 and
R.sup.2 are the same or different from each other and independently
a hydrogen atom, or an alkyl, hydroxyl, hydroxyalkyl, carboxyl,
carboxyalkyl or amidino group, or a salt thereof.
[0009] According to the present invention, there is also provided a
cosmetic skin care composition comprising the wrinkling modifier
(1) and a synthetic sphingosine derivative represented by the
following general formula (2): 5
[0010] wherein R.sup.3 is a linear, branched or cyclic, saturated
or unsaturated hydrocarbon group having 4 to 40 carbon atoms,
R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are independently a
hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms,
which may be substituted by at least one hydroxyl group, and X and
Y are independently a hydrogen atom or an alkyl group having 1 to 6
carbon atoms, which may contain at least one oxygen atom in its
structure.
BEST MODE FOR CARRYING OUT THE INVENTION
[0011] Among the heterocyclic groups represented by 6
[0012] in the general formula (1) which represents the guanidine
derivatives or the salts thereof used in the present invention,
pyrrolidine, piperidine, piperazine and morpholine are preferred.
The alkyl groups represented by R.sup.1 and R.sup.2 include linear
or branched alkyl groups having 1 to 6 carbon atoms. Of these,
alkyl groups having 1 to 4 carbon atoms are preferred. Specific
examples of the alkyl groups include methyl, ethyl, n-propyl and
isopropyl groups. Of these, methyl group is particularly preferred.
The hydroxyalkyl groups include hydroxyalkyl groups having 1 to 6
carbon atoms, and hydroxyalkyl groups having 1 to 4 carbon atoms
are preferred. Specific examples of the hydroxyalkyl groups include
hydroxymethyl, hydroxyethyl and hydroxypropyl groups, with the
hydroxymethyl and hydroxyethyl groups being particularly preferred.
The carboxyalkyl groups include carboxyalkyl groups having 2 to 7
carbon atoms, and carboxyalkyl groups having 2 to 5 carbon atoms
are preferred. Specific examples of the carboxyalkyl groups include
carboxymethyl, carboxyethyl, carboxypropyl and carboxybutyl groups,
with the carboxymethyl and carboxyethyl groups being particularly
preferred.
[0013] R.sup.1 and R.sup.2 may be the same or different from each
other and be an optional combination of 2 groups.
[0014] Stereoisomers exist in the guanidine derivatives (1) because
of the presence of asymmetric carbon atoms. In the present
invention, all these stereoisomers and mixtures thereof may be
used.
[0015] Specific examples of the guanidine derivatives (1) include
N-amidinoproline, 2-hydroxymethyl-1-pyrrolidine-carboxamidine,
3-hydroxy-1-pyrrolidinecarboxamidine,
N-amidinoaziridine-2-carboxylic acid,
N-amidino-2-piperidinecarboxylic acid,
N-amidino-3-piperidine-carbo- xylic acid,
N-amidino-4-piperidinecarboxylic acid, N-amidino-4-piperidinep-
ropionic acid, pyrrolidine-carboxamidine, piperidinecarboxamidine,
2-methyl-piperidinecarboxamidine, 3-methylpiperidinecarboxamidine,
4-methylpiperidinecarboxamidine, 2-methylmorpholine-carboxamidine,
3-methylmorpholinecarboxamidine, N-methyl-piperazinecarboxamidine,
N-2-hydroxyethylpiperazine-carboxamidine and
piperazinecarboxamidine.
[0016] An acid for forming salts of the guanidine derivatives (1)
may be either an organic acid or an inorganic acid. Examples
thereof include monocarboxylic acids such as formic acid, acetic
acid, propionic acid, butyric acid, isobutyric acid, hexanoic acid,
heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, lauric
acid, myristic acid, palmitic acid, stearic acid, acrylic acid,
methacrylic acid, crotonic acid, isocrotonic acid, phenylacetic
acid, cinnamic acid, benzoic acid, sorbic acid, nicotinic acid,
urocanic acid and pyrrolidone-carboxylic acid; dicarboxylic acids
such as oxalic acid, malonic acid, succinic acid, glutamic acid,
adipic acid, pimelic acid, cork acid, azelaic acid, sebacic acid,
maleic acid, fumaric acid, phthalic acid and terephthalic acid;
hydroxy acids such as glycolic acid, lactic acid, malic acid,
tartaric acid, citric acid and o-, m- or p-hydroxybenzoic acid;
amino acids such as glycine, alanine, .beta.-alanine, valine,
leucine, phenylalanine, tyrosine, serine, threonine, methionine,
cysteine, cystine, proline, hydroxyproline, pipecolic acid,
triptophan, aspartic acid, asparagin, glutamic acid, glutamine,
lysine, histidine, ornithine, arginine and aminobenzoic acid; lower
alkyl-sulfonic acids such as methanesulfonic acid and
trifluoro-methanesulfonic acid; arylsulfonic acids such as
benzene-sulfonic acid and p-toluenesulfonic acid; hydrohalogenic
acids such as hydrofluoric acid, hydrochloric acid, hydrobromic
acid and hydriodic acid; and inorganic acids such as perchloric
acid, sulfuric acid, nitric acacia, phosphoric acid and carbonic
acid.
[0017] The guanidine derivatives (1) or the salts thereof can be
obtained in accordance with, for example, a preparation process
represented by the following reaction scheme: 7
[0018] wherein 8
[0019] R.sup.1 and R.sup.2 have the same meanings defined
above.
[0020] More specifically, a cyclic amine derivative (3) is reacted
with a guanidylating reagent, whereby a guanidine derivative (1) or
a salt thereof can be obtained.
[0021] Examples of the guanidylating reagent include known
guanidylating reagents such as cyanamides, S-alkyl-isothioureas,
O-alkylisoureas, aminoiminomethanesulfonic acid,
3,5-dimethyl-1-guanylpyrazole, 1H-pyrazole-1-carbamidine.
[0022] In the case where an S-alkylisothiourea, O-alkyl-isourea,
3,5-dimethyl-1-guanylpyrazole or 1H-pyrazole-1-carbamidine is used,
the reaction may be conducted by stirring the reactants at 0 to
200.degree. C. for 1 to 72 hours in the presence or absence of a
base such as barium hydroxide, calcium hydroxide, magnesium
hydroxide, sodium hydroxide, potassium hydroxide, lithium
hydroxide, sodium hydrogen-carbonate, sodium carbonate, aqueous
ammonia, a tertiary amine such as triethylamine,
N,N-dimethylaniline, N,N'-dimethylpiperazine or N-methylpiperidine,
or pyridine. In the case where a cyanamide is used, it is only
necessary to stir the reactants at 0 to 200.degree. C. for 1 to 72
hours, or stir the reactants at 25 to 200.degree. C. for 1 to 72
hours in the presence of any one of the acids exemplified for the
formation of the salts of the guanidine derivatives.
[0023] After completion of the reaction, as needed, the acid may be
added to the reaction product in accordance with a method known per
se in the art to isolate it as an acid-addition salt.
[0024] The guanidine derivatives (1) or the salts thereof may be
used either singly or in any combination thereof. The amount of
such a compound incorporated in the wrinkling modifiers and the
cosmetic compositions is preferably 0.001 to 50% by weight. It is
particularly preferred that it be incorporated in an amount of
0.001 to 30% by weight, more preferably 0.01 to 20% by weight,
since the feeling upon use is improved, to say nothing of the
wrinkling-modifying effect.
[0025] The synthetic sphingosine derivative is represented by the
formula (2). Examples of the linear, branched or cyclic, saturated
or unsaturated hydrocarbon group having 4 to 40 carbon atoms
represented by R.sup.3 in the general formula (2) include alkyl
groups such as n-butyl, sec-butyl, pentyl, hexyl, octyl,
2-ethylhexyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl,
octadecyl, 5,7,7-trimethyl-2-(1,3,3-trimethylbutyl- )octyl,
2-heptylundecyl and methyl-branched isostearyl groups; alkenyl
groups such as butenyl, hexenyl, oleyl, 9-octadecenyl,
9,12-octadeca-dienyl, 3,7-dimethylocta-2,6-dienyl and
3,7,11-trimethyl-2,6,10-dodecatrienyl groups; cycloalkyl groups
such as cyclopentyl and cyclohexyl groups; and aryl groups such as
phenyl, tolyl and naphthyl groups.
[0026] In the present invention, the linear or branched, saturated
hydrocarbon groups having 4 to 40 carbon atoms are preferred. Of
these, tetradecyl, octadecyl and methyl-branched isostearyl groups
are particularly preferred.
[0027] The hydrocarbon groups having 1 to 10 carbon atoms
represented by R.sup.4 to R.sup.8, which may be substituted by at
least one hydroxyl group, include alkyl groups and mono-,di- or
tri-hydroxyalkyl groups such as methyl, ethyl, n-propyl, isopropyl,
hydroxymethyl, hydroxyethyl, 2-hydroxy-ethyl and
3,3,3-trihydroxypropyl groups. However, a hydrogen atom or methyl
group is preferred as each of R.sup.4 to R.sup.8.
[0028] Examples of the alkyl groups having 1 to 6 carbon atoms
represented by X and Y, which may contain at least one oxygen atom
in their structures, include glucosyl, fructosyl, galactosyl,
mannosyl, methyl, ethyl, propyl, hexyl, 2-hydroxyethyl,
3-hydroxyethyl, 4-hydroxypropyl, 5-hydroxy-6-hydroxybutyl,
2,3-dihydroxypropyl, 2-(1,2,3-trihydroxypropyl)- methyl and
3-(2,3-dihydroxypropyloxy)-2-hydroxyethyl groups. However, a
hydrogen atom or 2-hydroxyethyl group is particularly preferred as
each of X and Y.
[0029] These sphingosine derivatives may be used either singly or
in any combination thereof. The amount of such a derivative
incorporated in the cosmetic compositions is preferably 0.0001 to
10% by weight. It is particularly preferred that it be incorporated
in an amount of 0.001 to 2% by weight, since the feeling upon use
is improved, to say nothing of the wrinkling-modifying effect.
[0030] Into the wrinkling modifiers and the cosmetic compositions
according to the present invention, may be further incorporated an
organic acid, an inorganic acid such as phosphoric acid, sulfuric
acid or hydrochloric acid, or an ester thereof. The incorporation
of such a compound is preferred because the wrinkling-modifying
effect can be more enhanced.
[0031] No particular limitation is imposed on the organic acid or
the ester thereof so far as it is not included in the guanidine
derivatives (1). For example, .alpha.- or .beta.-hydroxycarboxylic
acids, dicarboxylic acids, fatty acids and esters thereof may be
mentioned. One or more of these compounds may be incorporated.
Examples of these organic acids include those represented by the
following formulae (4) to (6), and esters thereof. 9
R.sup.9(CR.sup.10OH).sub.q(CH.sub.2).sub.rCOOH (5)
[0032] In the formula (4), Y.sup.1 is a hydrogen atom or
CH.sub.3(C.sub.1H.sub.m).sub.n (l being an integer of 1 to 27, m
being an integer of 2 to 54, and n being 0 or 1). In the formula
(5), R.sup.9 and R.sup.10 are independently a hydrogen atom, a
saturated or unsaturated, branched, linear or cyclic alkyl group
having 1 to 25 carbon atoms, an aralkyl group or an aryl group, q
is an integer of 1 to 9, and r is an integer of 0 to 23. In the
formula (6), s is an integer of 0 to 9, and t is an integer of 0 to
23. More specific examples of the organic acids include ascorbic
acid, .epsilon.-aminocaproic acid, erythorbic acid, citric acid,
succinic acid, tartaric acid, sorbic acid, dehydroacetic acid,
lactic acid, urocanic acid, edetic acid, hydroxybenzonesulfonic
acid, orotic acid, capric acid, glycolic acid, cerotic acid,
nicotinic acid, hydroxyethanediphosphonic acid, phytic acid,
fumaric acid, malic acid, levulinic acid, acrylic acid and
oligomers or polymers thereof, and esters thereof.
[0033] Examples of the fatty acids include linolic acid,
.gamma.-linolenic acid, columbinic acid,
icosa-(.eta.-6,9,13)-trienoic acid, arachidonic acid,
.alpha.-linolenic acid, thymunodonic acid, hexanoic acid,
isostearic acid, undecylenic acid, stearic acid, palmitic acid,
behenic acid, myristic acid, coconut oil fatty acid, lauric acid,
lanolinic acid and DHA, and besides hydroxy fatty acids such as
12-hydroxystearic acid. The inorganic acids or the esters thereof
include monoalkylphosphoric acids such as cetylphosphoric acid, and
dialkylphosphoric acids.
[0034] In the present invention, among these organic acids and
inorganic acids, the organic acids represented by the formulae (4),
(5) and (6) are preferred. The dicarboxylic acids represented by
the formula (6) are more preferred, with succinic acid being
particularly preferred because the wrinkling-modifying effect can
be more enhanced. The organic acid, inorganic acids and the like
may be used either singly or in any combination thereof. The amount
of such an acid incorporated in the wrinkling modifiers and the
cosmetic compositions is preferably 0.001 to 30% by weight. It is
particularly preferred that it be incorporated in an amount of
0.005 to 20% by weight, more preferably 0.01 to 10% by weight,
since the feeling upon use is improved, to say nothing of the
wrinkling-modifying effect. An incorporating ratio of the organic
acid, inorganic acid or the like to the guanidine derivative or the
acid-addition salt thereof is preferably 0.5:99.5 to 99.5:0.5 in
terms of weight ratio. It is particularly preferred that the ratio
be 5:95 to 95:5, since the wrinkling-modifying effect can be more
enhanced.
[0035] Into the wrinkling modifiers and the cosmetic compositions
according to the present invention, may be further incorporated an
oily substance. No particular limitation is imposed on the oily
substance, and examples thereof include hydrocarbons such as solid
and liquid paraffins, crystal oil, ceresin, ozocerite, montan wax,
squalane and squalene; ester oils such as olive oil, carnauba wax,
lanolin, jojoba oil, glyceryl monostearate, glyceryl distearate,
glyceryl monooleate, isopropyl stearate, neopentylglycol dicaprate
and glycerol isostearate; higher alcohol such as cetanol and
stearyl alcohol; and naturally extracted sphingosine derivatives
and synthetic ceramide derivatives represented by the following
general formula (7): 10
[0036] wherein R.sup.11 is a linear or branched, saturated or
unsaturated hydrocarbon group having 10 to 26 carbon atoms,
R.sup.12 is a linear or branched, saturated or unsaturated
hydrocarbon group having 9 to 25 carbon atoms, and A and B are
independently a hydrogen atom or a sugar residue. One or more of
these oily substances may be used.
[0037] When these oily substances are incorporated, they are
preferably incorporated in a proportion of 0.001 to 50% by weight,
particularly preferably 0.005 to 30% by weight into the wrinkling
modifiers and the cosmetic compositions.
[0038] Into the wrinkling modifiers and the cosmetic compositions
according to the present invention, may be further incorporated a
sterol. Examples of the sterol include cholesterol, provitamin
D.sub.3, campesterol, stegmastanol, stegmasterol,
5-dihydrocholesterol, .alpha.-spinasterol, palysterol,
clionasterol, .gamma.-sitosterol, stegmastenol, sargasterol,
apenasterol, ergostanol, sitosterol, colubisterol,
chondrillasterol, polyphellasterol, haliclonasterol,
neospongosterol, fucosterol, aptostanol, ergostadienol, ergosterol,
22-dihydroergosterol, brassicasterol, 24-methylene-cholesterol,
5-dihydroergosterol, dehydroergosterol, fungisterol, cholestenol,
coprostenol, zymosterol, 7-hetocholesterol, lathosterol,
22-dehydrocholesterol, .beta.-sitosterol, cholestatrien-3.beta.-ol,
coprostanol, cholestanol, ergostenol, 7-dehydrocholesterol,
24-dehydrocholestadion-3.beta.-ol, equilenine, equilin, estrone,
17.beta.-estradiol, androst-4-ene-3 .beta.,17.beta.-diol and
dehydroepiandrosterone. One or more of these sterols may be
used.
[0039] When these sterols are incorporated, they are preferably
incorporated in a proportion of 0.001 to 50% by weight,
particularly preferably 0.005 to 30% by weight into the cosmetic
skin care compositions.
[0040] Into the wrinkling modifiers and the cosmetic compositions
according to the present invention, may be further incorporated a
surfactant. Examples of the surfactant include polyoxyethylene
alkyl ethers, polyoxyethylene fatty acid esters, polyoxyethylene
sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid
esters, glycerol fatty acid esters, polyoxyethylene hardened castor
oil alkylsulfates, polyoxyethylene alkylsulfates, alkylphosphates,
polyoxyethylene alkylphosphates, alkali metal salts of fatty acids,
sorbitan fatty acid esters, glycerol fatty acid esters and alkyl
glyceryl ethers. One or more of these surfactants may be used.
[0041] When these surfactants are incorporated, they are preferably
incorporated in a proportion of 0.001 to 50% by weight,
particularly preferably 0.005 to 30% by weight into the wrinkling
modifiers and the cosmetic compositions.
[0042] Into the wrinkling modifiers and the cosmetic compositions
according to the present invention, may be further incorporated a
water-soluble polyhydric alcohol. Examples of the water-soluble
polyhydric alcohol include alcohols having two or more hydroxyl
groups in their molecules, for example, ethylene glycol, propylene
glycol, 1,3-butylene glycol, 1,4-butylene glycol, dipropylene
glycol, glycerol and polyglycerols such as diglycerol, triglycerol
and tetraglycerol, glucose, maltose, maltitol, sucrose, fructose,
xylitol, sorbitol, maltotriose, threitol, erythritol, and alcohols
obtained by reduction of amylolytic sugar. One or more of these
alcohols may be used.
[0043] When these water-soluble polyhydric alcohols are
incorporated, their proportion in the wrinkling modifiers and the
cosmetic compositions may be suitably determined according to the
preparation forms of the modifiers and the cosmetic compositions.
However, it is generally preferred to incorporate them in a
proportion of 0.001 to 75% by weight, particularly preferably 0.1
to 25% by weight.
[0044] Into the wrinkling modifiers and the cosmetic compositions
according to the present invention, may be further incorporated
powder. Examples of the powder include extenders such as mica,
talc, sericite, kaolin, nylon powder and polymethylsil sesquioxane;
inorganic pigments such as pearl; organic pigments such as Red
Color No. 202, Red Color No. 226, Yellow Color No. 4 and aluminum
lake; and inorganic powders for ultraviolet screening, such as zinc
oxide, titanium oxide, zirconium oxide and iron oxide. These
powders may be subjected to a silicone treatment with methyl
hydrogenmethylpolysiloxane, trimethylsiloxysilicic acid,
methylpolysiloxane or the like, a fluorine treatment with a
perfluoroalkyl phosphate, perfluoroalcohol or the like, an amino
acid treatment with N-acylglutamic acid or the like, a lecithin
treatment, a metal soap treatment, a fatty acid treatment, an
alkylphosphate treatment, or the like before their use.
[0045] When these powders are incorporated, their proportion in the
wrinkling modifiers and cosmetic compositions may be suitably
determined according to the preparation forms of the modifiers and
the cosmetic compositions. However, it is generally preferred to
incorporate them in a proportion of 0.001 to 50% by weight,
particularly preferably 0.005 to 30% by weight.
[0046] Into the wrinkling modifiers and the cosmetic compositions
according to the present invention, may be further incorporated a
silicone. No particular limitation is imposed on the silicone so
far as it is that commonly incorporated into the classical cosmetic
compositions. Examples thereof include octamethylpolysiloxane,
tetradecamethylpolysiloxane, methylpolysiloxane, high-polymeric
methylpolysiloxane and methylphenylpolysiloxane, and besides
methylpolycyclosiloxanes such as octamethylcyclotetrasiloxane and
decamethylcyclopenta-siloxane, trimethylsiloxysilicic acid, and
modified silicones such as polyether alkyl-modified silicone and
alkyl glyceryl ether-modified silicone.
[0047] When these silicones are incorporated, their proportion in
the wrinkling modifiers and the cosmetic compositions may be
suitably determined according to the preparation forms of the
modifiers and the cosmetic compositions. However, it is generally
preferred to incorporate them in a proportion of 0.001 to 50% by
weight, particularly preferably 0.005 to 30% by weight.
[0048] Into the wrinkling modifiers and the cosmetic compositions
according to the present invention, various ingredients commonly
incorporated into the classical cosmetics, quasi-drugs, drugs and
the like may be incorporated so far as no detrimental influence is
thereby imposed on the objects of the present invention. Examples
of such ingredients include inorganic salts such as magnesium
sulfate, potassium sulfate, sodium sulfate, magnesium chloride and
sodium chloride; viscosity modifiers such as polyvinyl alcohol,
carboxyvinyl polymers, carboxymethyl cellulose, gelatin, tragacanth
gum, xanthan gum, hyaluronic acid, tuberose extract, agarose and
sodium alginate; and besides antiseptics such as parabens, pH
adjusters, wetting agents, ultraviolet absorbents, coloring matter,
medicinally-effective ingredients and perfume bases.
[0049] The wrinkling modifiers and the cosmetic compositions
according to the present invention are preferably at a pH of 2 to
11. It is particularly preferred that the pH be at 3 to 10, since
the normal physiological function of the skin can be retained. The
wrinkling modifiers and the cosmetic compositions according to the
present invention can be prepared in accordance with a method known
per se in the art, formulated into any desired forms such as
emulsions, dispersions, two-layer compositions, solutions and gel,
and provided as toilet waters, milky lotions, creams, packs, paps,
foundations and the like.
EXAMPLES
[0050] The present invention will hereinafter be described in more
detail by the following examples. However, the present invention is
not limited by these examples.
[0051] The following Compounds (1) to (16) were used as the
guanidine derivatives or the salts thereof to evaluate them as to
the wrinkling-modifying effect. 11
Effect of the Guanidine Derivatives (1) to (16) on Wrinkles Formed
on Hairless Mice by Exposure to UVB
[0052] (1) Hairless mice (HR/ICR, aged 6 weeks at the beginning of
the experiment) were,exposed to UVB 3 times a week by using 6
Toshiba healthy lamps, 20SE. The amount of energy was measured by
means of a UV-Radiometer, UVR-305/365D manufactured by TOKYO
OPTICAL K.K. The dose upon one exposure was determined to be 1 MED
or less, i.e., 65 mJ in an amount of energy of 0.28 mW/cm.sup.2.
The exposure was effected for 20 weeks. After confirming that the
hairless mice had got wrinkles at their backs, they were divided
into groups each consisting of 8 mice. Aqueous ethanol
(water/ethanol=50/50 vol. %) solutions separately containing
Compounds (1) to (16) at a concentration of 4% were applied 5 times
a week to their corresponding groups of mice over 6 weeks in a dose
of 100 .mu.l. As a control, aqueous ethanol (water/ethanol=50/50
vol. %) was applied in a dose of 100 .mu.l like the samples. After
completion of the application, the degree of wrinkles was visually
observed to evaluate the samples in accordance with the following
standard (wrinkle index). The results are shown in Table 1.
[0053] (Wrinkle index)
[0054] 1: Wrinkles were completely removed or smoothed;
[0055] 2: Wrinkles were scarcely observed;
[0056] 3: Wrinkles were somewhat observed;
[0057] 4: Wrinkles were observed to a great extent.
[0058] (2) In order to further analyze the particulars of wrinkles,
skin replicas of the size of 14 mm in diameter were gathered from a
portion of the back in each of the mice using a Hydrophilic Exaflex
hydrophilic vinylsilicone impression material. Each of these
replicas was held horizontally and illuminated at an angle of 30
degrees from the horizontal direction, thereby finding a proportion
of shadows of the wrinkles as an area percent by means of an image
analyzer. The results are shown in Table 1.
1 TABLE 1 Area percent by image Compound Wrinkle index analysis (%)
Control 3.73 10.6 Compound (1) 2.0 3.21 Compound (2) 2.125 2.48
Compound (3) 2.50 4.32 Compound (4) 2.50 5.37 Compound (5) 2.75
4.76 Compound (6) 2.75 3.51 Compound (7) 2.75 4.28 Compound (8)
2.25 3.26 Compound (9) 2.375 4.00 Compound (10) 2.50 3.41 Compound
(11) 2.75 4.02 Compound (12) 2.50 3.62 Compound (13) 2.375 4.30
Compound (14) 2.125 3.62 Compound (15) 2.50 4.48 Compound (16) 2.25
4.25
[0059] As apparent from Table 1, the wrinkles formed on the backs
of the hairless mice can be removed by applying any of the
guanidine derivatives (1) to (16) thereto.
EXAMPLE 2
[0060] Compounds (17) to (21) in which the definitions of the
respective symbols in the general formula (2) are as shown in Table
2 were used as the synthetic sphingosine derivatives to evaluate
them as to the wrinkling-modifying effect in accordance with the
same process as in Example 1. The experiment was conducted at
concentrations of 5% for the guanidine derivatives and 0.5% for the
synthetic sphingosine derivatives.
2TABLE 2 Compound R.sup.3 R.sup.4 R.sup.5--R.sup.8 X Y Compound
(17) Methyl- H H H H branched isostearyl Compound (18) Methyl-
CH.sub.3 H H H branched isostearyl Compound (19) Tetradecyl H H H H
Compound (20) Octadecyl CH.sub.3 H H H Compound (21) Methyl- H H
--CH.sub.2--CH.sub.2--OH H branched isostearyl
[0061]
3TABLE 3 Guanidine Sphingosine Wrinkle Area percent by derivative
derivative index image analysis (%) Not used Not used 3.75 10.2
Compound (1) Compound (17) 2.25 3.73 Compound (2) Compound (17)
2.75 4.03 Compound (4) Compound (17) 2.75 3.88 Compound (5)
Compound (17) 1.75 2.40 Compound (6) Compound (17) 2.125 2.39
Compound (1) Compound (18) 2.5 3.60 Compound (1) Compound (18) 2.75
3.97 Compound (2) Compound (19) 2.375 3.45 Compound (2) Compound
(19) 2.125 3.26 Compound (8) Compound (20) 2.25 4.14 Compound (9)
Compound (21) 2.0 2.78
[0062] As apparent from Table 3, the wrinkles formed on the backs
of the hairless mice can be removed by the cosmetic skin care
compositions comprising the guanidine derivative and the
sphingosine derivative.
[0063] The following wrinkling-modifying cosmetic compositions were
prepared.
4 (Components) (% by weight) Example 3: Cream Stearic acid 2.00
Squalane 2.00 Cholesterol 3.00 Olive oil 1.00 Cetanol 7.00 Jojoba
oil 2.00 Arginine 2-hexadecylphosphate 2.00 Polyoxyethylene (40 EO)
hardened castor oil 0.50 Glycerol 10.00 1,3-Butylene glycol 5.00
Compound (1) 5.00 Succinic acid 1.00 Purified water Balance Total
100.00 Example 4: Gel Polyoxyethylene (20 EO) isocetyl ether 1.00
Sodium polyoxyethylene (10 EO) trialkyl- 1.00 phosphate Sorbitol
0.50 1,3-Propanediol 0.50 Xanthan gum 0.50 Tuberose polysaccharide
3.00 Carboxyvinyl polymer (Carbopol 940, product 0.20 of Goodrich
Co.) Allantoin 0.10 Zinc sulfocarbolate 0.20 Compound (1) 10.00
Ethanol 20.00 Antiseptic Proper amount Perfume base Proper amount
Purified water Balance Total 100.00 Example 5: Gel Silicone
composition (XSG-16, product of 5.00 Shin-Etsu Chemical Co., Ltd.)
Methylpolysiloxane (KF96A-6cs, product of 15.00 Shin-Etsu Chemical
Co., Ltd.) Methylpolysiloxane (SH244, product of 5.00 Dow Corning
Toray Silicone Co., Ltd.)
Methylpolysiloxane.methyl(polyoxyethylene)- 2.00 siloxane copolymer
(SH3771C, product of Dow Corning Toray Silicone Co., Ltd.)
Methylpolysiloxane.methyl(polyoxyethylene)- 1.00 siloxane copolymer
(SH3775C, product of Dow Corning Toray Silicone Co., Ltd.) Methyl
cellulose 0.20 Hydroxyethyl cellulose hydroxypropyltrimethyl- 0.02
ammonium chloride ether (Caticelo H-60, product of Kao Corporation)
dl-.alpha.-Tocopherol acetate 0.05 Isostearyl glycyrrhetinate 0.10
Isopropylmethylphenol 0.10 Zinc white 1.50 Compound (1) 7.00
Compound (17) 0.50 Ethanol 5.00 Antiseptic Proper amount Perfume
base Proper amount Purified water Balance Total 100.00 Example 6:
Toilet water Arginine 0.40 Lysine 0.40 Polyoxyethylene (40 EO)
hardened castor oil 1.50
Methylpolysiloxane.multidot.methyl(polyoxyethylene- )- 0.60
siloxane copolymer (SH3775C, product of Dow Corning Toray Silicone
Co., Ltd.) Glycerol 5.00 Glycinebetaine 0.20 Trisodium citrate 0.90
Citric acid 0.40 Urea 0.50 .epsilon.-Aminocaproic acid 0.10
Compound (1) 5.00 Compound (17) 0.50 Ethanol 5.00 Antiseptic Proper
amount Perfume base Proper amount Purified water Balance Total
100.00 Example 7: Toilet water Triethanolamine 0.40 Potassium
hydroxide 0.20 Polyoxyethylene (20 EO) isocetyl ether 0.30 Sodium
polyoxyethylene (8 EO) oleyl ether 0.30 phosphate Sodium
polyoxyethylene (10 EO) dialkyl- 0.10 phosphate Polyethylene glycol
1500 2.00 Polyoxyethylene (10 EO) methylglycoside 1.50 Dipropylene
glycol 0.50 Disodium hydrogenphosphate 0.50 Succinic acid 0.30
Compound (1) 7.00 Ethanol 10.00 Antiseptic Proper amount Perfume
base Proper amount Purified water Balance Total 100.00 Example 8:
Pack Polyvinyl alcohol (Gohsenol EG-30, product 15.00 of The Nippon
Synthetic Chemical Industry Co., Ltd.) Aqueous solution of
carboxymethylchitin 5.00 (Chitin Liquid HV-10, product of Ichimaru
Pharcos Co., Ltd.) Triglucopolysaccharide (Pullulan PI-20, 0.50
product of Hayashibara Company, Ltd.) Xanthan gum 0.50 Sodium
carboxymethyl cellulose 0.50 Titanium oxide 15.00 Aluminum
magnesium silicate 1.00 1-Isostearoyl-3-myristoylglycerol 1.00
Diglycerol 1.50 Polyoxyethylene (20 EO) isocetyl ether 1.00
Compound (1) 7.00 Compound (14) 0.70 Ethanol 5.00 Antiseptic Proper
amount Perfume base Proper amount Purified water Balance Total
100.00 Example 9: Milky lotion Palmitic acid 0.50 Olive oil 2.00
Cetanol 1.00 Jojoba oil 5.00 Sodium monohexadecylphosphate 2.00
Sorbitan monostearate 0.50 Glycerol 15.00 Ethanol 5.00 Compound (2)
10.00 Compound (17) 0.30 Lactic acid 2.00 Purified water Balance
Total 100.00 Example 10: Milky lotion
N-(3-Hexadecyloxy-2-hydroxypropyl)-N-2- 0.50 hydroxyethyldecanamide
N-(3-Hexadecyloxy-2-hydroxypropyl)-N-2- 1.00
hydroxyethylhexadecanamide N-(3-Tetradecyloxy-2-hydrox-
ypropyl)-N-2- 0.50 hydroxyethyldecanamide Polyoxyethylene (10 EO)
hardened castor oil 1.00 Methylpolysiloxane.methyl(polyoxy-
ethylene)- 1.00 siloxane copolymer (SH3775C, product of Dow Corning
Toray Silicone Co., Ltd.) Sorbitan monostearate 0.20 Sodium
stearoylmethyltaurine 0.50 Cholesterol 0.80 Cholesterol isostearate
0.20 Stearic acid 0.20 Palmitic acid 0.30 Myristic acid 0.10 Pentyl
glycol dicaprate 4.00 Methylpolysiloxane (KF96A-500cs, product of
2.00 Shin-Etsu Chemical Co., Ltd.) Isostearyl alcohol 1.20 Cetyl
alcohol 1.00 Glycerol 3.50 Lactic acid 0.20 Sodium lactate 0.30
Compound (2) 5.00 Antiseptic Proper amount Perfume base Proper
amount Purified water Balance Total 100.00 Example 11: Pap
.alpha.-Monoisostearyl glyceryl ether 1.00 Pentyl glycol neocaprate
methylpolysiloxane 4.00 Glycerol 35.00 Purified water 15.80 Sodium
polyacrylate 5.50 Aluminum potassium sulfate 1.00 Aqueous solution
(10%) of polyacrylic acid 15.00 Precipitated silicic acid anhydride
2.00 Compound (1) 10.00 Compound (17) 0.20 Purified water Balance
Total 100.00
Industrial Applicability
[0064] The wrinkling modifiers and the cosmetic compositions
according to the present invention are excellent in the effects of
suppressing wrinkling and of removing wrinkles and give users a
pleasant feeling upon use.
* * * * *