Hair cosmetics

A lower alcohol-in-oil type emulsified hair cosmetic which contains one or more types of silicone derivatives, one or more types of specific polyether modified silicone and a lower alcohol. The emulsified hair cosmetic with very good stability by using for the emulsifier a polyether modified silicone without using a surfactant or organic modified clay mineral for the emulsifier.

RELATED APPLICATION 
This application claims the priority of Japanese Patent application 
No.9-88768 filed on Mar. 24, 1997, which is incorporeted herein by 
reference. 
BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates in general to a lower alcohol in-oil type emulsified 
hair cosmetic, and more particularly to a lower alcohol-in oil type 
emulsified hair cosmetic which has extremely good emulsification 
stability, good application ease and a split ends mending effect. 
2. The Prior Art 
Silicone derivatives in the form of silicone oil are known to have superior 
water repellency, heat resistance and oxidation resistance and are 
frequently used in various industrial materials. In particular, they 
spread lightly and have a refreshing texture when used for cosmetic 
materials or quasi-drug materials and therefore they are used in various 
applications including makeup cosmetics and hair cosmetics. 
However, silicone oil has a shortcoming in that it is hard to incorporate 
it into a stable water-in-oil type emulsified composition and a solution 
for this problem has been desired. To solve this shortcoming, an 
emulsified composition comprising water, polyhydric alcohol and an oil 
phase which contains polyoxyalkylene modified organopolysiloxane, water 
swelling clay minerals, a quarternary ammonium salt type cation surfactant 
and silicone oil was proposed. Even this emulsified composition, however, 
was not adequate in terms of long term stability. 
On the other hand, for the purpose of coating split ends, dimethyl silicone 
gum, polyvinylpyrolidone-type polymer, acrylic acid type polymer, 
polysaccharide, polypeptides, etc. have been blended in hair cosmetics. 
Recently, it was reported that a hair cosmetic using both a type of 
polysiloxane-oxyalkylene copolymer and a silicone derivative had a good 
tactile sense and was superior in adhering split portions of hair 
(Japanese unexamined patent publication Tokkai Hei 6-157247). 
However, with these methods, even though they had a good tactile sense, the 
effect could not be reproduced once peeling occurred and there were many 
problems regarding the tactile sense such as creaking, dryness and 
stiffness. Furthermore, there were problems in terms of appearance such as 
flaking. 
BRIEF SUMMARY OF THE INVENTION 
The inventors conducted earnest investigation in view of the aforementioned 
problems and discovered that a stable lower alcohol-in-oil type emulsified 
composition whose oil phase contained a silicone derivative in the form of 
silicone oil could be obtained by adding for an emulsifier a polyether 
modified silicone with a specific polyoxyalkylene group content, and that 
the obtained cream-like emulsion had a unique application ease including 
spreading lightly, drying quickly and exhibiting no stickiness and also 
was superior in terms of sustained gloss of the hair and adhesion of split 
portions of hair, thus completing the present invention. 
The present invention provides a lower alcohol-in-oil type emulsified hair 
cosmetic which contains; (A) one or more types of silicone derivative; (B) 
one or more types of poly ether modified silicone represented by the 
following general formula (1): 
##STR1## 
and (C) a lower alcohol. 
In this formula, A denotes a group selected from among a methyl group, a 
phenyl group and a polyoxyalkylene group represented by the general 
formula --C.sub.3 H.sub.6 O(C.sub.2 H.sub.4 O).sub.a (C.sub.3 H.sub.6 
O).sub.b R' (where R' denotes a group selected from among a hydrogen atom, 
acyl group and alkyl group with a carbon number of 1-4, a denotes an 
integer 5-50 and b denotes an integer 5-50), and at least one of the three 
A's is a polyoxyalkylene group. R denotes a methyl group or phenyl group, 
m denotes an integer 50-1,000 and n denotes an integer 1-40. The polyether 
modified silicone contains 40 wt % or more of polyoxyalkylene groups in 
its molecules and the molecular weight of the polyether modified silicone 
is 30,000 or more. 
The present invention invention also provides the aforementioned lower 
alcohol-in-oil type emulsified hair cosmetic wherein said silicone 
derivative is a high molecular weight dimethylpolysiloxane represented by 
the following general formula (2). 
##STR2## 
In this formula, n denotes an integer 3,000 20,000. 
The present invention invention also provides the aforementioned lower 
alcohol in-oil type emulsified hair cosmetic wherein said silicone 
derivative is an amino modified or ammonium modified silicone represented 
by the following general formula (3): 
##STR3## 
In this formula, R.sup.a denotes a methyl group or a phenyl group, and 
R.sup.b denotes the same as R.sup.c or a methyl group or hydroxyl group. 
R.sup.c denotes a substitutional group containing an amino group or 
ammonium group represented by the formula R.sup.d Z {R.sup.d denotes a 
divalent alkylene group containing 3-6 carbon atoms, Z denotes a 
monovalent group selected from among --NR.sup.e.sub.2, --N.sup.+ 
R.sup.e.sub.3 A.sup.-, --NR.sup.e (CH.sub.2).sub.n NR.sup.e.sub.n, 
NR.sup.e (CH.sub.2).sub.n N.sup.+ R.sup.e.sub.3 A.sup.- and --NR.sup.e 
(CH.sub.2).sub.n N(R.sup.e)CO(R.sup.F) (R.sup.e denotes hydrogen or an 
alkyl group containing 1-4 carbon atoms, R.sup.F denotes an alkyl group 
containing 1-4 carbon atoms, A denotes a chlorine atom, bromine atom or 
iodine atom, and n denotes an integer 2-6.)}, x and y each denotes a 
positive integer, x+y denotes an integer 3,000-20,000 and y/x is in the 
range of 1/500-1/10,000. 
The present invention invention also provides the aforementioned lower 
alcohol-in-oil type emulsified hair cosmetic wherein the content of said 
lower alcohol is 30-80 wt % of the total emulsified hair cosmetic.

DETAILED DESCRIPTION OF THE INVENTION 
The configuration of the present invention is described in detail below. 
The polyether modified silicone used for the emulsifier in the present 
invention is organopolysiloxane containing polyoxyalkylene groups 
represented by the aforementioned general formula (1). In the present 
invention, a commercial product (TS Polymer 50-IP from Toray Dow-Corning 
Silicone Co., Ltd.) can be used. The primary point of the present 
invention is that it can provide a lower alcohol-in-oil type emulsified 
hair cosmetic with very good emulsion stability by using for the 
emulsifier a specific polyether modified silicone represented by the 
aforementioned general formula (1) (lower alcohol-in-oil type emulsified 
hair cosmetics using oil containing silicone oil for the continuous phase 
has a problem in emulsification stability when conventional surfactants 
are used). In the present invention, there is no need to use a 
conventional surfactant for the emulsifier. 
At least one of the three A's in the aforementioned general formula (1) of 
the polyether modified silicone has to be a polyoxyalkylene group 
represented by the general formula --C.sub.3 H.sub.6 O(C.sub.2 H.sub.4 
O).sub.a (C.sub.3 H.sub.6 O).sub.b R' and 40 wt % or more of 
polyoxyalkylene groups has to be contained in the polyether modified 
silicone molecules. Specific examples of the acyl group for R' in the 
polyoxyalkylene group include a formyl group, acetyl group, propionyl 
group, butyroyl group, acryloyl group, benzoyl group and toluoyl group, 
and specific examples of the alkyl group with a carbon number of 1-4 
include a methyl group, ethyl group, i-propyl group, n-propyl group, 
t-butyl group and n-butyl group. In the polyoxyalkylene group, if a or b 
is less than 5, then the polyether modified silicone will not exhibit a 
sufficient emulsifying effect. If a or b is more than 50, then the 
obtained emulsified hair cosmetic will be sticky. The polyoxyalkylene 
group content is 40 wt % or more, and preferably in the range of 40-70 wt 
%. This is because the emusifying ability on nonpolar oil other than 
silicone oil decreases when the polyoxyalkylene group content is less than 
40 wt %, and the obtained emulsified hair cosmetic becomes sticky when it 
is more than 70 wt %. m is an integer 50-1,000 and preferably an integer 
15014 1,000. n is an integer 1-40. This is because the emulsifying effect 
is not sufficient if m is less than 50 and n is less than 1, and the 
obtained emulsified hair cosmetic becomes sticky if m is more than 1,000 
and n is more than 40. The ratio m:n is preferably in the range between 
200:1 and 5:1, and more preferably 60:1-15:1. 
For the polyether modified silicone, those for which every R in the 
aforementioned general formula (1) is a methyl group are preferable. 
The molecular weight of the polyether modified silicone is 30,000 or more, 
and preferably 50,000 or more. This is because the emulsifying ability of 
silicone derivatives decreases when the molecular weight of the polyether 
modified silicone is less than 30,000. 
The viscosity of the polyether modified silicone is not limited in 
particular, but it is desirable that the viscosity of a 50 wt % solution 
of the polyether modified silicone in octamethylsiloxane or isoparaffin is 
in the range of 1,000-100,000 cps for the sake of formation of a stable 
emulsion and smooth feeling. 
The content of the polyether modified silicone is not limited in 
particular, but a preferable range is 1-50 wt % of the total emulsified 
hair cosmetic and a more preferable range is 3-30 wt %. If the content of 
the polyether modified silicone is less than 1 wt %, then stable 
emulsification becomes difficult and if it is more than 50 wt % then the 
emulsified hair cosmetic will be sticky. 
In the present invention, a lower alcohol-in-oil type (hereafter referred 
to as simply "alcohol-in-oil type" or "A/O type" as well) emulsified hair 
cosmetic means that the discontinuous phase is a lower alcohol or a mixed 
solution of water and a lower alcohol. 
The type of the lower alcohol used in the present invention (hereafter 
referred to as simply "alcohol" as well) is not limited in particular, but 
methanol or ethanol is preferable. Considering safety, ethanol is 
particularly preferable. When using i-propanol, n-propanol, t- butanol, 
s-butanol, etc., they should be used with ethyl alcohol because they are 
too hydrophobic and are therefore hard to emulsify. 
While it was difficult to obtain a stable water-in-oil type emulsified 
composition with a high alcohol concentration, the present invention makes 
it possible to obtain a stable emulsified composition even when the 
alcohol content in the emulsified composition is 30 wt % or more. This 
fact illustrates the importance of the present invention. 
The content of the alcohol used in the present invention is preferably 6-80 
wt % of the total emulsified hair cosmetic, and more preferably in the 
range of 10-80 wt %. In particular, a characteristic of the present 
invention is the fact that the emulsification stability is high even with 
a high alcohol concentration where the alcohol content is 30-80 wt %. If 
the alcohol content is less than 6 wt %, then oil separation may occur 
over time and emulsification stability deteriorates. If it is more than 80 
wt % then alcohol separates from the emulsified hair cosmetic and a stable 
emulsified composition may not be obtained. 
The present invention includes cases where the lower alcohol phase, which 
is the discontinuous phase, is a mixed solution with water. In these 
cases, the weight ratio of the lower alcohol to water should preferably be 
1/5 or more. If the ratio of the lower alcohol to water is less than 1/5 
then the polyether modified silicone may cause gelation of the whole 
system to increase the viscosity excessively and the emulsification 
becomes difficult. 
The silicon derivative used in the present invention is organo 
polysiloxanes containing a siloxane bond(s) including dimethyl 
polysiloxane, methylphenyl polysiloxane, polyether modified silicone, 
epoxy modified silicone, fluorine modified silicone, alcohol modified 
silicone, alkyl modified silicone, alkoxy modified silicone and organic 
silicone resin. The silicon derivative constitutes the oil phase, which is 
the continuous phase in the emulsified hair cosmetic of the present 
invention. For the silicone derivative, those represented by the 
aforementioned general formula (2) or (3) is preferable. Also, those 
represented by the following general formulas (4)-(17) with a general 
formula of R.sub.n SiO .sub.(4-n)/2 are preferably used as well. The 
polyether modified silicone represented by the aforementioned general 
formula (1) which is used for the emulsifying agent is also a silicone 
derivative as defined in the present invention, and if the amount of it is 
sufficient to form the oil phase then other silicone derivatives do not 
have to be contained. 
(1) Dimethyl polysiloxane 
##STR4## 
In this formula, n denotes an integer 3-20,000. (2) Methylphenyl 
polysiloxane 
##STR5## 
e denotes an integer 1-20,000 and f+g denotes an integer 1-500. (3) 
Polyether modified silicone 
##STR6## 
R.sup.1 denotes a hydrogen atom or an alkyl group with a carbon number of 
1-12, h denotes an integer 1-100 (preferably 3-30), i denotes an integer 
1-50 (preferably 1-30), j denotes an integer 1-50 (preferably 3-30), k 
denotes an integer 0 50 (preferably 0-30). The total of h and i is an 
integer of 15 or larger, and the total of j and k is an integer of 5 or 
larger. 
##STR7## 
l denotes a number 1-2,000 and m denotes a number 1-1,000. R.sup.2 denotes 
a methyl group or phenyl group, R.sup.3 denotes an alkylene group with a 
carbon number of 1-3. A denotes a hydrogen atom or an alkyl group with a 
carbon number of 1-12. D and E each denotes an integer 0-50, and 
D+E.gtoreq.1. 
(4) Epoxy modified silicone 
##STR8## 
p denotes an integer 1-500 (preferably 1-250), q denotes an integer 1-50 
(preferably 1-30) and R.sup.3 denotes an alkylene group with a carbon 
number of 1-3. 
(5) Fluorine modified silicone 
##STR9## 
r denotes an integer 1-400 (preferably 1-250). (6) Alcohol modified 
silicone 
##STR10## 
s and t each denotes an integer 1-500 (preferably 1-200) and R.sup.4 
denotes C.sub.F H.sub.2F (F denotes an integer 0-4). 
(7) Alkyl modified silicone 
##STR11## 
u and v each denotes an integer 1-500 (preferably 1-200). R.sup.5 denotes 
an alkyl group with a carbon number of 2-18, R.sup.6 denotes C.sub.G 
H.sub.2G (G denotes an integer 0-4 ) and R.sup.7 denotes an alkyl group 
with a carbon number of 10-16. 
(8) Alkoxy modified silicone 
##STR12## 
R.sup.6 denotes a methyl group and phenyl group, R.sup.0 denotes an alkyl 
group with a carbon number of 1-28 (preferably 12-22), w denotes an 
integer 0-6, l denotes an integer 1-3,000 and m and n denote integers for 
which m+n=1-500. 
(9) Organic silicone resin 
General formula: R.sub.n SiO.sub.(4-n)/2 It comprises an appropriate 
combination of R.sub.3 SiO.sub.1/2 units, R.sub.2 SiO unites, RSiO.sub.3/2 
unites and SiO.sub.1/2 units. The ratio is such that the average unit is 
represented by the general formula R.sub.n SiO.sub.(4-n)/2 (where R 
denotes a hydrocarbon group with a carbon number of 1-6 or phenyl group 
and n denotes a value of 1.0-1.8). 
In the present invention, one or more types of silicon derivative form the 
oil phase. The oil phase may contain oil components other than the silicon 
derivative. Depending on the purpose, oil components listed below 
including hydrocarbon oils, higher fatty acids, higher alcohols, synthetic 
ester oils, liquid oils/fats, solid oils fats and waxes can be blended in. 
Examples of the hydrocarbon oils include liquid paraffin, ozokerite, 
squalene, pristane, paraffin, ceresin, squalene, vaseline and 
microcrystalline wax. 
Examples of the higher fatty acids include lauric acid, myristic acid, 
palmitic acid, stearic acid, behenic acid, oleic acid, 12-hydroxystearic 
acid, undecylenic acid, toll oil, isostearic acid, linoleic acid, 
linolenic acid, eicosapentaenoic acid (EPA) and docosahexaenoic acid 
(DHA). 
Examples of the higher alcohols include linear chain alcohols such as 
lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl 
alcohol, oleyl alcohol and cetostearyl alcohol as well as branched chain 
alcohols such as monostearyl glycerine ether (batyl alcohol), 
2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, 
hexyldodecanol, isostearyl alcohol and octyl dodecanol. 
Examples of the synthetic ester oils include isopropyl myristate, cetyl 
octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, 
hexyl laurate, myristyl myristate, decyl oleate, hexyldecyl 
dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, 
isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, 
ethylene glycol di-2-ethylhexylate, dipentaerythritol fatty acid ester, 
N-alkyl glycol monoisostearate, neopentyl glycol dicaprate, diisostearyl 
malate, glyceryl di-2-heptylundecanoate, trimethylolpropane tri-2- 
ethylhexylate, trimethylolpropane triisostearate, pentaneerythritol 
tetra-2-ethylhexylate, glyceryl tri-2-ethylhexylate, trimethylolpropane 
triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glyceryl 
trimyristate, tri-2-heptylundecanoic glyceride, castor oil fatty acid 
methyl ester, oleyl oleate, cetostearyl alcohol, acetoglyceride, 
2-heptylundecyl palmitate, diisopropyl adipate, N-lauroyl-L-glutamic 
acid-2-octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, 
di-2-ethylhexyl cebatate. 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 
2-hexyldecyl adipate, diisopropyl cebatate, 2-ethylhexyl succinate, ethyl 
acetate, butyl acetate, amyl acetate and triethyl |citrate. 
Examples of liquid oils/fats include avocado oil, tsubaki oil, turtle oil, 
macademia nut oil, corn oil, mink oil, olive oil, rape seed oil, egg yolk 
oil, sesame seed oil, persic oil, wheat germ oil, sasanqua oil, castor 
oil, linseed oil, safflower oil, cotton seed oil, perilla oil, soybean 
oil, peanut oil, tea seed oil, kaya oil, rice bran oil, chinese wood oil, 
Japanese wood oil, jojoba oil, germ oil, triglycerol, glyceryl 
trioctanoate and glyceryl triisopalmitate. 
Examples of the solid oils/fats include cacao butter, coconut oil, horse 
tallow, hardened coconut oil, palm oil, beef tallow, sheep tallow, 
hardened beef tallow, palm kernel oil, pork tallow, beef bone tallow, 
Japanese core wax, hardened oil, neatsfoot tallow, Japanese wax and 
hydrogenated castor oil. 
Examples of the waxes include honeybee wax, candelilla wax, cotton wax, 
carnauba wax, bayberry wax, tree wax, whale wax, montan wax, bran wax, 
lanolin, kapok wax, lanolin acetate, liquid lanolin, sugar cane wax, 
lanolin fatty acid isopropyl ester, hexyl laurate, reduced lanolin, jojoba 
wax, hard lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin 
alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene 
glycol and POE hydrogenated lanolin alcohol ether. 
In the present invention, the silicone derivative content should preferably 
be 1-85 wt %, more preferably 3-70 wt %, of the total emulsified hair 
cosmetic. This content is the total amount including the polyether 
modified silicone represented by the general formula (1) which is used as 
the aforementioned emulsifying agent. When oil components other than the 
silicone derivative are blended in, the total of the silicone derivative 
and other oil which form the oil phase should preferably be 5-90 wt % of 
the total emulsified hair cosmetic. 
In addition to the aforementioned essential ingredients, depending on the 
purpose, other ingredients which are usually blended into cosmetics can be 
blended in as necessary within the quantitative and qualitative range 
which does not affect the effect of the present invention. Examples of 
these ingredients include water soluble polyhydric alcohols such as 
ethylene glycol, propylene glycol, 1,3 butylene glycol, glycerine, 
sorbitol and polyethylene glycol, humectants such as hyaluronic acid, 
chondroitin sulfuric acid and pyrolidonecarboxylate, ultraviolet light 
absorbents, ultraviolet light scattering agents, resins such as acrylic 
type resins and polyvinylpyrolidone, proteins or decomposed proteins such 
as soybean protein, gelatin, collagen, silk fibroin and elastin, 
preservatives such as ethyl paraben and butyl paraben, various amino 
acids, activating agents such as biotin and pantothenic acid, blood flow 
promoting agents such as .tau.-oryzanol, sodium dextran sulfate, vitamin E 
derivatives and nicotine derivatives, anti-seborrhea agents such as sulfur 
and thiantol, thickeners such as carboxyvinyl polymer, drugs, perfumes and 
coloring agents. 
The water-in-oil and/or alcohol-in-oil type emulsified hair cosmetic of the 
present invention can be used as various hair cosmetics including general 
hairdressings, split ends coating agents, shampoos, rinse agents, 
treatment agents, setting agents, permanent wave liquid and mascara. 
According to the present invention, a lower alcohol-in-oil type emulsified 
hair cosmetic with very good emulsification stability which uses a silicon 
derivative for the oil phase can be obtained. The emulsified hair cosmetic 
of the present invention gives excellent gloss and smooth tactile sense to 
the hair, has an excellent application ease because it spreads easily and 
is not sticky, and it can also adhere and mend split ends. 
EXAMPLES 
Further details of the present invention are described below by referring 
to examples. The present invention is not limited to these examples. The 
units of the blended amounts are weight percent. 
First, the emulsification stability of the lower alcohol-in-oil type 
emulsified hair cosmetic of the present invention with a high alcohol 
concentration was investigated in comparison with the following 
conventional typical water-in-oil type emulsified hair cosmetic. 
______________________________________ 
(Comparative example 1) 
(wt%) 
______________________________________ 
(1) Isoparaffin 15.0 
(2) Dimethyl polysiloxane 
10.0 
(n = 3,000 in the general formula (2)) 
(3) Distearyldimethyl ammonium chloride 
0.8 
(4) Diglyceryl diisostearate 
2.0 
(5) Dextrin fatty acid ester 
1.2 
(6) Hectorite treated withe 
1.5 
dimethylstearylammonium chlorid 
(7) Ion exchanged water 30.0 
(8) Ethanol 35.0 
(9) Glycerine 4.0 
(10) Polyethylene glycol 6000 
0.5 
______________________________________ 
(Preparation method) 
The components (1)-(6) were heated up to 70.degree. C. and mixed and 
dissolved to prepare the oil phase. The components (7)-(10) were then 
dispersed and mixed at 70.degree. C. and gradually added to the oil phase 
using a disper for agitation. After a thorough and homogeneous mixing and 
agitation, the system was cooled to obtain the target alcohol-in-oil type 
emulsified hair cosmetic with a viscosity of 65,000 cps. 
______________________________________ 
(Comparative example 2) 
(wt%) 
______________________________________ 
(1) Isoparaffin 15.0 
(2) Dimethyl polysiloxane 10.0 
(n = 3,000 in the general formula (2)) 
(3) Polyether modified silicone 
10.0 
(m = 35, n = 7, a = 20 and b = 0 in the general 
formula (18)) 
(4) Ion exchanged water 25.0 
(5) Ethanol 35.0 
(6) Glycerine 4.0 
(7) Sodium glutamate 0.5 
(8) Polyethylene glycol 6000 
0.5 
______________________________________ 
(Preparation method) 
An alcohol-in-oil type emulsified hair cosmetic was obtained in the same 
manner as in Comparative example 1. 
______________________________________ 
(Example 1) 
(wt%) 
______________________________________ 
(1) Isoparaffin 15.0 
(2) Dimethyl polysiloxane 10.0 
(n = 3,000 in the general formula (2)) 
(3) Polyether modified silicone 10.0 
(50% solution of the general formula (18) with 
m = 400, n = 10, a = 19 and b = 19 in isoparaffin) 
(4) Ion exchanged water 25.0 
(5) Ethanol 35.0 
(6) Glycerine 4.0 
(7) Sodium glutamate 0.5 
(8) Polyethylene glycol 6000 0.5 
______________________________________ 
##STR13## 
(Preparation method) 
The components (1)-(3) were mixed at room temperature to prepare the oil 
phase. The components (4)-(8) were then mixed and agitated and gradually 
added to the oil phase using a disper for agitation. After a thorough 
agitation, the target alcohol-in-oil type emulsified hair cosmetic with a 
viscosity of 50,000 cps was obtained. 
The results of the emulsification stability are shown in Table 1. 
TABLE 1 
______________________________________ 
Emulsification stability 
______________________________________ 
Comparative example 1 
Demulsification occurred after a week at room 
temperature. 
Comparative example 2 
Creaming occurred after a month at room 
temperature. 
Example 1 Stable with no changes after three months 
at 50.degree. C. 
______________________________________ 
Table 1 indicates that Comparative examples 1 and 2 did not produce a 
stable alcohol-in-oil type emulsified hair cosmetic with a high alcohol 
concentration but that Example 1 of the present invention produced a very 
stable alcohol-in-oil type emulsified hair cosmetic with a high alcohol 
concentration. 
The emulsification stability was investigated by comparing the polyether 
modified silicone used in the present invention and other polyether 
modified silicones when they were used in alcohol-in-oil type emulsified 
hair cosmetics with a high alcohol concentration. 
Tables 3 to 5 show the emulsification stability and stickiness for various 
combinations of a, b, m and n of the polyether modified silicone 
represented by the general formula (18) used in emulsified hair cosmetics 
with the basic recipe shown in Table 2. 
TABLE 2 
______________________________________ 
Basic recipe Weight (%) 
______________________________________ 
(1) Dimethyl polysiloxane 6CS 
15.0 
(2) Dimethyl polysiloxane 15.0 
(n = 3,000 in the general formula (2)) 
(3) Polyether modified silicone 
10.0 
(50% solution of the general formula (18) in 
isoparaffin) 
(4) Sodium glutamate 1.0 
(5) Polyethylene glycol 6000 1.0 
(6) Ion exchanged water 23.0 
(7) Ethanol 35.0 
______________________________________ 
(Preparation method) 
The components (1), (2) and (3) were mixed together and then the components 
(4), (5), (6) and (7) were gradually added to this mixture while agitation 
with a disper was carried out to emulsify it. 
The judgment criteria of emulsification stability and stickiness in each 
table are as follows. 
"Emulsification stability" 
.circleincircle.: Stable with no changes after three months at 50.degree. 
C. 
.largecircle.: Stable with no changes after one month at 50.degree. C. 
.DELTA.: Stable with no changes after two weeks at 50.degree. C. 
X: Separated within one week at 50.degree. C. 
"Stickiness" 
.largecircle.: Eight or more members of a specialist panel of ten women 
judged the sample to be not sticky and having a good usability. 
.DELTA.: Eight or more members of a specialist panel of ten women judged 
the sample to be slightly sticky. 
X: Eight or more members of a specialist panel of ten women judged the 
sample to be sticky. 
Table 3 shows the results of testing the emulsification stability and 
stickiness with various values of a and fixed values of m=400. n=10 and 
b=20 in the basic recipe shown in Table 2. 
TABLE 3 
______________________________________ 
Com- 
parative 
Exam- Exam- Exam- Comparative 
example 3 
ple 2 ple 3 ple 4 example 4 
______________________________________ 
Polyether 
m 400 400 400 400 400 
modified 
n 10 10 10 10 10 
silicone 
a 3 5 20 47 60 
(the general 
b 20 20 20 20 20 
formula (2)) 
Emulsification 
x .circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
stability 
Stickiness 
.smallcircle. 
.smallcircle. 
.smallcircle. 
.smallcircle. 
.DELTA. 
______________________________________ 
Table 3 indicates the following: when a is 3, the emulsification stability 
is poor; when a is from 5 to approximately 50 both the emulsification 
stability and stickiness are good; and it is not preferable when a is 60 
because stickiness arises while there is no significant effect on the 
emulsification stability. These results indicate that the preferable range 
of a is 5-50. Similar test results were obtained for values of b. 
Table 4 shows the results of testing the emulsification stability and 
stickiness with various values of m and fixed values of n=10 and a=b=20 in 
the basic recipe shown in Table 2. 
TABLE 4 
__________________________________________________________________________ 
Comparative 
Example 
Example 
Example 
Example 
Example 
Example 
Example 
Comparative 
example 5 
5 6 7 8 9 10 11 example 
__________________________________________________________________________ 
8 
Polyether 
m 30 50 120 150 220 400 800 1000 2000 
modified 
n 10 10 10 10 10 10 10 10 10 
silicone 
a 20 20 20 20 20 20 20 20 20 
(the general 
b 20 20 20 20 20 20 20 20 20 
formula (2)) 
Emulsification 
x .smallcircle. 
.smallcircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
stability 
Stickiness 
.smallcircle. 
.smallcircle. 
.smallcircle. 
.smallcircle. 
.smallcircle. 
.smallcircle. 
.smallcircle. 
.smallcircle. 
.DELTA. 
__________________________________________________________________________ 
Table 4 indicates the following: the emulsification stability is 
significantly poor when m is 30 and it is improved when m is 50 while the 
high temperature stability is somewhat poor; when m is 200 or larger, the 
emulsification stability, including the high temperature stability, is 
significantly improved; it is not preferable to increase m above 1,000 
because then stickiness arises although the emulsification stability is 
guaranteed; therefore, the preferable range of m is 50-1,000 and the more 
preferable range is 150-1,000. 
Table 5 shows the results of testing the emulsification stability and 
stickiness with various values of n and fixed values of m=400, n=10 and 
b=24 in the basic recipe shown in Table 2. 
TABLE 5 
__________________________________________________________________________ 
Comparative 
Example 
Example 
Example 
Example 
Example 
Comparative 
example 7 
12 13 14 15 16 example 8 
__________________________________________________________________________ 
Polyether 
m 400 400 400 400 400 400 400 
modified 
n 0 1 3 10 30 40 50 
silicone 
a 20 20 20 20 20 20 20 
(the general 
b 20 20 20 20 20 20 20 
formula (2)) 
Emulsification 
x .smallcircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
stability 
Stickiness 
.smallcircle. 
.smallcircle. 
.smallcircle. 
.smallcircle. 
.smallcircle. 
.DELTA. 
x 
__________________________________________________________________________ 
Table 5 indicates the following: when n is 0, there is hardly any 
emulsification stabilizing effect; when n is 1, there is a noticeable 
emulsification stabilizing effect; when n is 3 or more, there is a 
distinctive emulsification stabilizing effect; however, when n is over 40, 
stickiness tends to arise; therefore, the preferable range of n is 1-40 
and the more preferable range is 3-30. 
Emulsified hair cosmetics of the following examples and comparative 
examples were evaluated for their application ease (spreadability on the 
hair, stickiness, smoothness), gloss and split end mending effect. The 
evaluation results are shown in Table 6. 
______________________________________ 
EXAMPLE 17 
A/O type hair cream (treatment type) 
(wt %) 
______________________________________ 
(1) Dimethyl polysiloxane 5 
(n = 3,000 in the general formula (2)) 
(2) Light type liquid isoparaffin 
30 
(3) Polyether modified silicone 
15 
(50% solution of the general formula (18) 
with m = 400, n = 10, a = 24 and b = 24 in 
isoparaffin) 
(4) Ethanol 30 
(5) Ion exchanged water 19 
(6) Perfume Appropriate amount 
(7) Paraben Appropriate amount 
(8) Antioxidant Appropriate amount 
(9) Sodium glutamate 1 
______________________________________ 
(Preparation method) 
A mixture of the components (4)-(9) was added to a mixture of the 
components (1), (2) and (3) using a disper for agitation to obtain an A/O 
type hair cream. 
______________________________________ 
EXAMPLE 18 
A/O type hair cream (treatment type) 
(wt %) 
______________________________________ 
(1) Decamethylcyclopentasiloxane 
15 
(2) Amino modified polymer silicone 
10 
(R.sup.a and R.sup.b are methyl groups, R.sup.c is 
-(CH.sub.2).sub.3 N(CH.sub.3)(CH.sub.2).sub.2 N(CH.sub.3).sub.2, x = 
10,000 
and y = 5 in the general formula (3)) 
(3) Polyether modified silicone 
15 
(50% solution of the general formula (18) 
with m = 500, n = 20, a = 20 and b = 20 in 
Isoparaffin) 
(4) Ethanol 40 
(5) Ion exchanged water 3.6 
(6) Hyaluronic acid 0.1 
(7) Phosphatidyl choline 0.1 
(8) Hydrolyzed collagen 0.1 
(9) 2-hydroxy-4-methoxybenzophenone 
0.1 
(10) Perfume Appropriate amount 
(11) Polyethylene glycol 1 
(molecular weight 6,000) 
______________________________________ 
(Preparation method) 
The component (2) was dissolved in the component (1) and then mixed with 
the component (3). This oil phase was agitated with a homomixer at room 
temperature while a solution prepared by mixing the components (4)-(11) 
was added to obtain an A/O type hair cream. 
______________________________________ 
COMATIVE EXAMPLE 9 
A/O type hair cream (treatment type) 
(wt %) 
______________________________________ 
(1) Isoparaffin 15.0 
(2) Dimethyl polysiloxane 
10.0 
(n = 1,000 in the general formula (2)) 
(3) Diglyceryl diisostearate 
2 
(4) Dextrine fatty acid ester 
1.5 
(5) Ion exchanged water 67 
(6) Glycerine 4.0 
(7) Polyethylene glycol 6000 
0.5 
______________________________________ 
(Preparation method) 
The components (1)-(4) were heated up to 70.degree. C. and mixed to prepare 
the oil phase. A mixture of the components (5)-(7) was then added to the 
oil phase using a disper for agitation to obtain an A/O type hair cream. 
______________________________________ 
COMATIVE EXAMPLE 10 
A/O type hair cream (styling type) 
(wt %) 
______________________________________ 
(1) Isoparaffin 15 
(2) Amino modified polymer silicone 
10 
R.sup.a and R.sup.b are methyl groups, R.sup.c is 
--(CH.sub.2).sub.3 N(CH.sub.3)(CH.sub.2).sub.2 N(CH.sub.3).sub.2 
, 
x = 10,000 
and y - 5 in the general formula (3)) 
(3) Diglyceryl diisostearate 
2 
(4) Dextrine fatty acid ester 
1.5 
(5) Hectorite treated withe 
1.5 
dimethylstearylammonium chlorid 
(6) Ion exchanged water 55.5 
(7) Vinylpyrolidone/dimethylaminoethyl 
10 
methacrylate copolyme 
(8) Glycerine 4 
(9) Polyethylene glycol 6000 
0.5 
______________________________________ 
(Preparation method) 
The components (1)-(5) were heated up to 70.degree. C. and mixed to prepare 
the oil phase. A mixture of the components (6)-(9) was then added to the 
oil phase using a disper for agitation to obtain an A/O type hair cream. 
The emulsified hair cosmetics of Examples 17 and 18 and Comparative 
examples 9 and 10 were evaluated using the following method. The results 
are shown in Table 6. 
The evaluation method is described below. 
[Evaluation method] 
30 cm/5 g of Japanese female hair with split ends was bundled and, after 
shampooing, approximately 5 g of the emulsified hair cosmetics of the 
examples and comparative examples was directly applied to it, followed by 
light rinsing. A hair drier with a brush was then used to brush it. The 
following items were checked immediately following and two hours following 
the completion of the brushing. 
"Application ease" (spreadability on the hair, stickiness and smoothness): 
.circleincircle.: Very good tactile sense in general. 
.largecircle.: Good tactile sense in general. 
.DELTA.: Not very good tactile sense in general. 
X: Very poor tactile sense in general. 
"Gloss" 
.circleincircle.: Glossy in general. 
.largecircle.: Glossy. 
.DELTA.: Somewhat glossy. 
x: No gloss. 
"Split ends mending effect" 
The evaluation was based on the level of detachment of split ends after 
brushing 10 times. 
.circleincircle.: Split ends are adhered and not detached. 
.largecircle.: Split ends are adhered but a small portion is detached. 
.DELTA.: Most adhered split ends are detached. 
X: All the adhered split ends are detached. 
TABLE 6 
__________________________________________________________________________ 
Split ends mending 
effect tactile sense 
Gloss 
Two hours Two hours Two hours 
Immediately following 
Immediately 
following 
Immediately 
following 
__________________________________________________________________________ 
Example 17 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
Example 18 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
.circleincircle. 
Comparative 
.DELTA. 
x .DELTA. 
.DELTA. 
.DELTA. 
x 
example 9 
Comparative 
.smallcircle. 
.DELTA. 
.smallcircle. 
.smallcircle. 
.smallcircle. 
.DELTA. 
example 10 
__________________________________________________________________________ 
The results shown in Table 6 indicate that the emulsified hair cosmetics of 
the present invention are superior in terms of the split ends mending 
effect, have a good application ease and are superior in terms of lasting 
gloss. 
Other examples of the present invention are shown below. 
______________________________________ 
EXAMPLE 19 
A/O type hair cream (styling type) 
(wt %) 
______________________________________ 
(1) Octamethylcyclotetrasiloxane 
15 
(2) Dimethyl polysiloxane 15 
(n = 1,000 in the general formula (2)) 
(3) Ion exchanged water 24.9 
(4) Ethanol 10 
(5) Perfume Appropriate amount 
(6) 2-hydroxy-4-methoxybenzophenone 
0.1 
(7) Polyether modified silicone 
30 
(50% solution of the general formula (18) 
with m = 300, n = 20, a = 15 and b = 15 in 
isoparaffin) 
(8) Betain modified dialkylamino 
5 
acrylate copolymer 
(Product name: Yukaformer AM75R205S 
from Mitsubishi Chemical Industry, Co. 
Ltd.) 
______________________________________ 
(Preparation method) 
While a mixture prepared by dissolving the component (2) in the component 
(1) was agitated with a homomixer at room temperature, a mixture of the 
components (3)-(8) was added to it to obtain an A/O type hair cream. 
______________________________________ 
EXAMPLE 20 
A/O type treatment lotion 
(wt %) 
______________________________________ 
(1) Dimethyl polysiloxane 6cs 
20 
(2) Amino modified polymer silicone 
10 
R.sup.a and R.sup.b are methyl groups, R.sup.c is 
--(CH.sub.2).sub.3 N(CH.sub.3)(CH.sub.2)N(CH.sub.3)C=O(C.sub.2 
H.sub.5), 
x = 15,000 and y = 4 in the general formula 
(3)) 
(3) Ion exchanged water 29.9 
(4) Ethanol 30 
(5) Perfume Appropriate amount 
(6) 2-hydroxy-4-methoxybenzophenone 
0.1 
(7) Polyether modified silicone 
8 
(50% solution of the general formula (18) 
with m = 400, n = 10, a = 24 and b = 24 in 
isoparaffin) 
(8) Egg yolk lecithin 0.5 
(9) Egg white 0.5 
(10) Vinylpyrolidone dimethylaminomethyl 
1 
methacrylate copolymer 
______________________________________ 
(Preparation method) 
While a mixture prepared by dissolving the component (2) in the component 
(1) was agitated with a homomixer at room temperature, a mixture of the 
components (3)-(10) was added to it to obtain an W/O type treatment 
lotion. 
______________________________________ 
EXAMPLE 21 
Hair spray (treatment type) 
(wt %) 
______________________________________ 
(1) Isoparaffin 10 
(2) Amino modified polymer silicone 
5 
R.sup.a is methyl group, R.sup.b is a hydroxyl group 
and R.sup.C is -(CH.sub.2).sub.3 N.sup.+ (CH.sub.3).sub.3 C1.sup.-, 
x = 18,000 
and y = 2 in the general formula (3)) 
(3) Amino modified polymer silicone 
5 
R.sup.a and R.sup.b are methyl groups, R.sup.C is 
-(CH.sub.2).sub.3 N(CH.sub.3).sub.2, x = 8,000 and y = 10 in 
the general formula (3)) 
(4) Ion exchanged water 13 
(5) Ethanol 23.9 
(6) Perfume Appropriate amount 
(7) Octylmethoxy cinnamate 0.1 
(8) Polyether modified silicone 
3 
(50% solution of the general formula (18) 
with m = 400, n = 10, a = 25 and b = 25 in 
isoparaffin) 
(9) Liquefied petroleum gas 
40 
______________________________________ 
(Preparation method) 
While a mixture prepared by dissolving the component (2) and the component 
(3) in the component (1) was agitated with a homomixer at room 
temperature, a mixture of the components (4)-(8) was added to it to obtain 
an A/O type hair cream. After this cream was put into an aerosol container 
and a valve was installed, the component (9) was introduced to obtain a 
hair spray. 
EXAMPLE 22 
______________________________________ 
A/O type hair cream 
(wt %) 
______________________________________ 
(1) Octamethylcyclotetrasiloxane 
15 
(2) Organic silicone resin with an 
6.0 
average component unit represented by a 
general formula R.sub.n SiO.sub.(4-n) 2 
(3) Ion exchanged water 24.9 
(4) Ethanol 15 
(5) Perfume Appropriate amount 
(6) 2-hydroxy-4-methoxybenzophenone 
0.1 
(7) Polyether modified silicone 
30 
(50% solution of the general formula (18) 
with m = 250, n = 25, a = 18 and b = 18 in 
isoparaffin) 
______________________________________ 
(Preparation method) 
While a mixture prepared by dissolving the component (2) in the component 
(1) was agitated with a homomixer at room temperature, a mixture of the 
components (3)-(7) was added to it to obtain an A/O type hair cream.