Hiar cosmetic composition

A hair cosmetic composition comprising a polymer vesicle obtained from the polymerization of a surfactant monomer vesicle haing quaternary ammonium as a cation moiety and a polymerizable anion as a counter ion.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to a hair cosmetic composition capable of 
moisturizing hair and of protecting the hair from damage. More 
specifically, it relates to a hair cosmetic composition having an improved 
hair rinse effect and an improved protection of the surface of the hair, 
which are obtained by improving the adsorptivity of a hair cosmetic 
component. 
2. Description of the Related Art 
Conventional hair cosmetic compositions generally contain quaternary 
ammonium salts such as alkyl trimethyl ammonium chlorides and dialkyl 
dimethyl ammonium chloride as a component for providing flexibility and 
glossiness to the hair, and for preventing an electrical charge in hair, 
and fats and oil represented by higher alcohols can be generally 
formulated to strengthen the above-mentioned effects. 
Conventional hair cosmetic compositions, however, do not provide completely 
satisfactory effects, since the adsorptivity of the quaternary ammonium 
salts is poor. Therefore, because the hair is now more susceptible to 
damage due to the growing popularity of, for example, permanent waving, 
hair coloring, and drying, a problem arises in that the above-mentioned 
conventional hair cosmetic compositions do little to prevent such damage 
to the hair. 
In view of the above, various attempts have been made to improve the hair 
damage prevention effects by using, as a protective agent for the hair 
surface, various polymers such as cellulose type, keratin type, and vinyl 
type polymers in hair cosmetic compositions, but these proposed 
compositions still do not provide satisfactory protection against damage 
to the hair. This is believed to be because the polymer cannot be supplied 
as a fine particle dispersion, and thus the polymer particles cannot be 
uniformly adsorbed on the surface of the hair because the polymer acts as 
a flocculating agent or thickening agent. 
For the above-mentioned reasons, the conventional hair cosmetic 
compositions could be improved by formulating therein a moisturizing agent 
such as polysiloxane or sodium pyrrolidone carboxylate, in addition to the 
above-mentioned components, for obtaining an improved finish, but a hair 
cosmetic composition capable of satisfactorily obtaining the required 
damage prevention and moisturizing effects, especially under severe 
conditions such as the use of a hair dryer, has not been provided. 
SUMMARY OF THE INVENTION 
Accordingly, the objects of the present invention are to eliminate the 
above-mentioned disadvantages of the prior art and to provide a hair 
cosmetic composition having excellent moisturizing and damage prevention 
effects by improving the adsorptivity of the hair cosmetic components and 
thus improve the hair rinsing and hair surface protection effects. 
Other objects and advantages of the present invention will be apparent from 
the following description. 
In accordance with the present invention, there is provided a hair cosmetic 
composition comprising a polymer vesicle obtained from the polymerization 
of a surfactant monomer vesicle having quaternary ammonium as a cation 
moiety and a polymerizable anion as a counter ion. 
DESCRIPTION OF THE PREFERRED EMBODIMENTS 
As mentioned above, according to the present invention, the following 
technique has been adopted for uniformly and effectively adsorbing 
quaternary ammonium salts, which are used as a main component in 
conventional hair cosmetic compositions, and polymers, which are used as a 
protective agent in conventional hair cosmetic compositions, on the 
surface of the hair to obtain the desired characteristics. That is, 
according to the present invention, fine vesicles of quaternary ammonium 
type surfactants having a polymerizable anion introduced thereto as a 
counter ion are prepared and the counter ion is allowed to polymerize on 
the surface of the vesicle, whereby fine polymer vesicles having 
quaternary ammonium salts in the structure thereof are formed. The 
excellent hair surface protection and moisturizing effects of the polymer 
vesicles are utilized in the present invention. 
The surfactants forming the polymer vesicles according to the present 
invention include quaternary ammonium salts having the following general 
formula (I), in which two long chain type cationic portions and a 
polymerizable anion counter ion portion are contained. 
##STR1## 
wherein R.sup.1 represents a linear or branched alkyl or alkylaryl having 
8 to 32 carbon atoms, R.sup.2 represents alkyl having 2 to 3 carbon atoms, 
n is an integer of 0 to 5, R.sup.3 represents an alkyl having 1 to 4 
carbon atoms or -(OR.sub.2).sub.n H, and a counter ion A.sup.- represents 
an organic acid type anion having a polymerizable group. 
The counter ion parts A.sup.- in the general formula (I) usable in the 
present invention are polymerizable organic acid type ions. Examples of 
such organic acid type ions are carboxylic acid type anions such as 
acrylic acid ion and methacrylic acid ion and sulfuric acid type anions 
such as vinyl sulfonic acid ion, styrene sulfonic acid ion, and 
2-acrylamide-2-methylpropane sulfonic acid ion. Of these anions, 
preferably carboxylic acid type ions such as acrylic and methacrylic ions, 
more preferably methacrylic ions, are used. 
The quaternary ammonium salt monomers having the formula (I) capable of 
forming the polymer vesicles can be synthesized by, for example, 
ion-exchanging the halogen ion of halogenated quaternary ammonium salt 
with an organic acid type anion having a polymerizable group by an ion 
exchange resin (see J. Am. Chem. Soc., 106, 2446-2447 (1984) and J. Am. 
Chem. Soc., 108, 2321-2327 (1986)). Alternately, a halogenated alkali 
metal salt may be removed by a desalting method from an alkali metal salt 
of an organic acid and a halogenated quaternary ammonium salt, whereby the 
desired quaternary ammonium salt monomer (I) may be synthesized. 
According to the present invention, the desired polymer vesicle is obtained 
by preparing the quaternary ammonium salt type surfactant having the 
formula (I) in the form of a vesicle, followed by the polymerization 
thereof. The preparation of the vesicle dispersion is carried out by an 
ultrasonic treatment. The temperature during the treatment is preferably 
50.degree. C. or higher and the concentration of the surfactant during the 
treatment is preferably 0.1% to 5% by weight. 
The polymerization for preparing the polymer vesicle according to the 
present invention may be carried out by either conventional 
photopolymerization methods (see J. Am. Chem. Soc., 106, 2446-2447 (1984), 
J. Am. Chem. Soc., 108, 2321-2327 (1986)), or by thermal polymerization 
methods. 
In the case of photopolymerization, as the light source for irradiating 
light, a method using a low-pressure mercury vapor lamp having a 
wavelength of 254 mm, a method using a high-pressure mercury vapor lamp 
having a wavelength of 360 mm, and a method using a high-pressure mercury 
vapor lamp in the presence of a photosensitizer may be used. Furthermore, 
both an internal irradiation and an outside irradiation method can be used 
as the irradiation method. 
In the case of thermal polymerization, a radical initator is used, and 
examples of such radical initators are water-soluble initiators such as 
persulfates, 2-carbamoylazo-isobutyronitrile, 
2,2'-azobis(N,N'-dimethyleneisobutylamidine) dihydrochloride, 
2,2'-azobis(2-amidinopropane) dihydrochloride, and 
4,4'-azobis(4-cyanopentanoic amide), and oil-soluble initiators such as 
2,2'-azobis(4-methoxy-2,4-dimethylvalenonitrile), 
2,2'-azobis(2,4-dimethylvalenonitrile), (1-phenylethyl) 
azodiphenylmethane, 2,2'-azobisisobutyronitrile, 
dimethyl-2,2'-azobisbutyrate, 2,2'-azobis(2methylbutyronitrile), and 
1,1'-azobis(1-cyclohexane carbonitrile). The polymerization temperature is 
preferably 60 to 90.degree. C., and a high polymerization conversion can 
be obtained at a polymerization time of, preferably, 5 to 6 hours. 
The polymer vesicles obtained as mentioned above preferably have a particle 
size of 10 to 1000 nm, more preferably 10 to 200 nm. The degree of the 
polymerization in the vesicles is preferably 2 to 600, more preferably 2 
to 400. 
It is considered that the hair cosmetic compositions comprising the polymer 
vesicles exhibit superior characteristics to the conventional hair 
cosmetic compositions for the following reasons. 
According to the present invention, since the counter ion portion is 
polymerized within bilayer membrane vesicles, the vesicles are formed in a 
fine and uniform bilayer membrane-polymer composite structure. 
Furthermore, the polymer chains formed by polymerization provide 
hydrophobic surfaces, which are not found on vesicles of conventional 
quaternary ammonium salts and vesicles before the polymerization according 
to the present invention, and therefore, the affinity to hydrophobic 
surfaces such as hair surfaces is improved. In addition, since the fine 
shapes or configuration are retained after polymerization, the present 
vesicles can be effectively adsorbed on the surface of the hair and, as a 
result, the hair is protected by widely covering the surface with the 
bilayer membrane-polymer composite. 
On the other hand, although composite materials can be formed by mixing 
conventional cationic ammonium salts and anionic polymer substances, 
larger particles, in which the composites are only partly formed due to 
the flocculating action of the anionic polymer, exist in the thus-formed 
composites. Therefore, the adsorption to the hair becomes nonuniform, and 
the protection effect is lowered. 
When the adsorption to the surface of hair of the polymer vesicles 
according to the present invention and for a conventional mixture of 
quaternary ammonium salts and anionic polymers were compared under a 
scanning type electron microscope, the following results were obtained. 
Namely, the surface adsorbed with the polymer vesicles according to the 
present invention was uniformly covered by the fine particles and the 
design or pattern of the cuticles became unclear. Contrary to this, the 
surface adsorbed with the conventional mixture of quaternary ammonium salt 
and anionic polymer contained a portion adsorbed with the agglomerated 
large particles, and non-adsorbed portions were observed. 
In view of the above results, it can be understood that, since the polymer 
vesicles according to the present invention have an effective adsorptivity 
and uniform composite structure, the protection of the surfaces of the 
hair is greater than that of conventional hair cosmetic compositions, and 
the desired excellent moisturizing and hair damage prevention effects can 
be obtained. 
Although there are no critical limitations to the amount of the polymer 
vesicle in the hair cosmetic composition, the preferable amount is 0.1% to 
10% by weight, more preferably 0.5% to 3% by weight, based on the total 
amount of the hair cosmetic composition. 
The hair cosmetic composition of the present invention can be prepared and 
applied as the first agent in a permanent wave treatment, shampoo, hair 
liquid, hair tonic, foamy hair-care material, and the like. The hair 
cosmetic composition of the present invention can formulate optional 
conventional components in addition to the above-mentioned polymer 
vesicle, depending upon the kind of cosmetic composition desired. Examples 
of such components are oil components such as silicon derivatives, 
hydrocarbons, ester oils, higher fatty acids, high alcohols, lanolin 
derivatives; nonionic surfactants, anionic surfactants, amphoteric 
surfactants, vitamin A, B.sub.6, B.sub.12, C, D, E, H and derivatives 
thereof, protein hydrolysates, amino acids, animal and vegetable extracts, 
nonionic resins such as polyvinylpyrrolidone and derivatives thereof; 
anionic resins such as methylvinyl ether-butyl maleate copolymer; 
amphoteric resins such as acrylic acid-methacrylate copolymers; UV-ray 
absorbers such as oxybenzoin derivatives, cinnamic acid ester derivatives; 
coolness imparting agents such as l-menthol, peppermint oil; stimulation 
imparting agents such as benzyl nicotinate, Guinea pepper tincture; 
sterilizers such as gluconic acid chlorohexidine, isopropylmethylphenol; 
preservatives such as paraben; perfumes, dyes, and deterioration 
preventives. 
The present hair cosmetic composition can be readily prepared in any 
conventional manner. For example, the above-mentioned essential and 
optional components may be mixed together in an aqueous medium. 
As explained above, according to the present invention, the hair cosmetic 
composition comprising the polymer vesicles having the uniform bilayer 
membrane-polymer composite structure and exhibiting excellent moisturing 
and damage prevention effects due to the superior hair surface protection 
effect of the polymer 
obtained from their excellent adsorptivity, can be provided.

EXAMPLES 
The present invention will now be further described in more detail by 
referring to, but is by no means limited to, Examples and Comparative 
Examples, in which all percentages are % by weight unless otherwise 
specified. 
Example 1 
As a starting material, distearyl dimethyl ammonium chloride (i.e., Arquard 
2HT-75 commercially available from LACO Co.) was used after 
recrystallization from acetone. This distearyl dimethyl ammonium chloride 
actually contained 70% of a linear alkyl group having 18 carbon atoms and 
30% of a linear alkyl group having 16 carbon atoms. 
An anion exchange resin (i.e., Amberlist A-27 commercially available from 
Organo K.K.) was packed into a column and a methanol solution of 
methacrylic acid (commercially available from Junsei Chemical K.K.) was 
passed through the column to obtain a methacrylate type ion exchange 
resin. The above-mentioned distearyl dimethyl ammonium chloride in a 
methanol solution was then passed through the column to exchange the 
counter ions thereof. The solvent, i.e., methanol, was concentrated 
followed by recrystallization from acetone, and the desired polymerizable 
quaternary ammonium surfactant 2HT methacrylate having a methacrylate 
moiety introduced therein at the counter ion part was obtained in the form 
of a white crystal. 
A 5 g amount of the 2HT methacrylate obtained above and 250 g of water were 
placed in an Erlenmeyer flask, and the flask was sealed and then subjected 
to an ultrasonic treatment for 2 to 4 hours, while heating at a 
temperature of 70.degree. C. to 80.degree. C., by using a water bath type 
ultrasonic treatment apparatus (Model 521 manufactured by Bransonic Co.), 
to obtain the desired vesicle dispersion. The bilayer membrane structure 
of vesicle of this dispersion was confirmed by a transmission type 
electron miscoscope (Hitachi H-600) according to a freeze fracture type 
replica method. 
A 250 ml amount of the vesicle dispersion prepared above was placed in a 
reaction vessel, and polymerization was carried out by using a low 
pressure mercury vapor lamp (Model UVL-32LB available from Rikou Kagaku 
Sangyo Co., 32 W, wavelength 254 nm) in an internal irradiation method. 
When the disappearance of the olefin proton peak and methacrylate methyl 
proton peak was monitored by NMR, it was confirmed that the polymerization 
reaction was completed in 6 hours. The resultant polymer vesicle 
dispersion thus obtained contained vesicles having a particle size of 67 
nm, as measured by a submicron sizer (Model B-90 manufactured by 
Brookhaven Co.) and having a main distribution of a degree of 
polymerization of 4 to 30. 
Example 2 
The recrystallized distearyl dimethyl ammonium chloride used in Example 1 
and potassium methacrylate (available from Wako Pure Chemical Ind. Ltd.) 
were stirred, while heating, in methanol at a temperature of 50.degree. C. 
for 5 hours and, after the excess potassium methacrylate was filtered off, 
the methanol was concentrated and dried to solidify the resultant mixture. 
The solidified product was dissolved in methylene dichloride and, after 
the undissolved potassium chloride was filtered off, the methylene 
dichloride salt was distilled off. The resultant white solid was 
recrystallized from acetone to obtain the desired 2HT methacrylate having 
methacrylate introduced therein, at the counter ion part, in the form of 
the white solid. 
A 5 g amount of the 2HT methacrylate obtained above and 250 g of water were 
placed in an Erlenmeyer flask and the ultrasonic treatment and 
photopolymerization were carried out in the same manner as in Example 1. 
The vesicles of the resultant polymer vesicle dispersion had a particle 
size of 74 nm, as measured by the submicron sizer used in Example 1, and a 
degree of polymerization of 4 to 26. 
To evaluate the hair cosmetic compositions of the present invention 
containing the polymer vesicles obtained in Examples 1 and 2, the 
following hair cosmetic compositions according to Comparative Examples 1 
to 3 were prepared. The comparative samples were those obtained by a 
conventional technique or having a formulation such that a portion of the 
present formulation was omitted. 
COMATIVE EXAMPLE 
A 5 g amount of the distearyl dimethyl ammonium chloride used in Example 1 
and 250 g of water were placed in an Erlenmeyer flask, the mixture was 
subjected to the ultrasonic treatment as in Example 1, and a comparative 
vesicle dispersion was obtained. 
COMATIVE EXAMPLE 2 
Potassium polymethacrylate was obtained by thermally polymerizing a 5% 
aqueous solution of potassium methacrylate used in Example 2, in the 
presence of an ammonium persulfate initiator. 
The resultant aqueous potassium polymethacrylate solution was added to the 
vesicle dispersion of Comparative Example 1 in an amount such that the 
methacrylic acid unit became an equal mole to the 2HT molecule in vesicle. 
Thereafter, the ultrasonic treatment of Example 1 was carried out at a 
temperature of 50.degree. C. for 30 minutes to obtain the comparative 
mixture dispersion. 
COMATIVE EXAMPLE 3 
A 5 g amount of the 2HT methacrylate obtained in Example 1 and 250 g of 
water were placed in an Erlenmeyer flask, the ultrasonic treatment of 
Example 1 was applied to the mixture, and a comparative vesicle dispersion 
was obtained. 
The adsorptivity the water retention percentage of the vesicle dispersions 
of Examples 1 and 2 and Comparative Examples 1, 2, and 3 were evaluated 
with regard to the use of a dryer, the absence of harshness of the hair 
tips, the hair combing load, the hair luster, and the abrasion resistance, 
as follows. The results are shown in Table 1. 
Evaluation Method 
1. Adsorptivity 
A 3 g bundle of hair was thoroughly washed with a 1% aqueous sodium 
.alpha.-olefin sulfonate solution and, after rinsing with running water, 
the hair bundle was dipped in 50 ml of a 0.2% aqueous vesicle dispersion 
and allowed to stand at a temperature of 40.degree. C. for 30 minutes. 
Accordingly, the vesicles were adsorbed on the hair. The hair bundle was 
then removed from the dispersion and adhered water removed by squeezing. 
The amount of vesicle remaining in the dispersion was measured and the 
amount of vesicles adsorbed to the hair was calculated by subtracting the 
amount remaining from the original amount of vesicles. 
2. Water Retention Percentage 
After a 10 g bundle of hair having a length of 30 cm was bleached, the hair 
bundle was thoroughly washed with a 1% aqueous sodium .alpha.-olefin 
sulfonate solution, followed by rinsing with running water and drying with 
a towel. To the hair bundle, 2 ml of a 1% aqueous vesicle dispersion was 
uniformly coated, followed by rinsing with water and drying with a towel. 
A hair dryer was applied to the obtained hair bundle for 10 minutes from a 
point 10 cm away from the hair bundle and, thereafter, the weight 
(W.sub.1) of the hair bundle was measured. 
The weight (W.sub.2) of the hair bundle was also measured after vacuum 
drying at a temperature of 90.degree. C. The water retention percentage 
was determined from the following equation. 
##EQU1## 
W.sub.1 : Weight of hair bundle after drying with a dryer W.sub.2 : Weight 
of hair bundle after 90.degree. C. vacuum drying 
3. Harshness of Hair Tip 
The hair bundle was subjected to the abovementioned treatment used in the 
case of the water retention measurement, except that the bleach treatment 
was not carried out. Thereafter the hair bundle was combed 7 times. This 
treatment was repeated 6 times and the absence of harshness of the hair 
tips was organoleptically evaluated by a paired-comparison method. The 
evaluation was carried out according to the following scores. That is, in 
a paired-comparison method, an .alpha. value obtained when only distearyl 
dimethyl ammonium chloride (2HT) was formulated, was designated as a score 
"3" and an .alpha. value of untreated hair was designated as a score "1". 
From these standards, the score of each sample was determined based on the 
obtained .alpha. value. 
4. Flyaway 
The hair bundle used in the evaluation 3 was combed and the width of the 
bottom of the spread hair bundle was measured. 
5. Combing Load 
The hair bundle used in the above-mentioned evaluation of flyaway was set 
in a strain gauge and, when a comb fixed in a tensilon meter was moved at 
a rate of 4 cm/min, the load applied to the hair bundle was measured. 
6. Hair Luster 
A hair bundle composed of 50 hairs having a length of 25 cm was treated 
with a shampoo and, after towel drying, the hair bundle was dipped in 5 ml 
of a 1% aqueous vesicle dispersion at a temperature of 40.degree. C. for 5 
minutes, followed by rinsing with water and the hair bundle was dried at a 
temperature of 25.degree. C. under a relative humidity (R.H.) of 65%. 
The static abrasion coefficient of the hair bundle was determined when the 
hair bundle was rotated at 2.5 rpm, and thus the hair luster was 
evaluated. 
7. Abrasion Resistance 
The hair bundle was treated in the same manner as in the evaluation of the 
hair luster. The abrasion coefficient was measured when the hair bundle 
was rotated at 50 rpm, and thus the abrasion resistance was evaluated. 
TABLE 1 
__________________________________________________________________________ 
Absence of 
harshness Hair 
Water 
of hair 
Hair 
combing Abrasion 
Adsorptivity 
retention 
tip away 
load Hair luster 
resistance 
__________________________________________________________________________ 
Evaluation 
40.degree. C., 30 min. 
Bleach 
Characteristics after 6 
Abrasion 
Item Standing 
treated 
times rinse treatment 
coefficient 
direction. 
0.2%, 50 ml 
hair of normal hair Pulley 50 rpm. 
bundle direction 
abrasion 
Conditions 
3 g hair 
Dryer Pulley 2.5 
Abrasion 
bundle drying rpm coefficient 
10 min. after 5 min. 
Example 1 
98% 12% score 5 
15 cm 
494 g 
0.10 0.27 
Example 2 
97% 11.9% 
score 5 
15 cm 
485 g 
0.11 0.30 
Comparative 
Example 1 
21% 8.2% score 3 
20 cm 
603 g 
0.22 0.73 
Comparative 
Example 2 
-- 10% score 4 
18 cm 
521 g 
0.13 0.57 
Comparative 
Example 3 
36% 10.1% 
score 3 
22 cm 
545 g 
0.16 0.78 
__________________________________________________________________________ 
As is clear from the results shown in Table 1, the absorptivity to the hair 
of the polymer vesicle dispersions of Examples 1 and 2 according to the 
present invention was much higher than that of Comparative Examples 1 and 
3; proving the superiority of absorptivity of the present polymer vesicle. 
Further, when the hair bundle was rinsed with each dispersion, followed by 
drying with a hair dryer for 10 minutes, the water retention percentages 
of the hair bundles treated with the polymer vesicles of Examples 1 and 2 
were highest. Also, the polymer vesicles of Examples 1 and 2 according to 
the present invention exhibited the greatest effects for suppressing 
harshness of the hair tips and flyaway due to damage to and a decrease in 
water content of the hair when the hair bundle was subjected to a rinse 
treatment, hair dryer drying, and repeated brushing. Actually, the load 
applied to hair treated with the polymer vesicles of Examples 1 and 2 
according to the present invention, when combing, is lowest and the damage 
of hair and harshness of the hair tips. 
Moreover, the abrasion coefficient of the surface of hair treated with each 
dispersion was lowest when treated with the polymer vesicles of EXAMPLES 1 
and 2 according to the present invention and, therefore, the hair luster 
and the abrasion resistance were excellent and the protection of the 
surface of the hair was high. 
As mentioned above, when the dispersions of Examples 1 and 2 were used, it 
was confirmed that excellent moisturizing effects and damage prevention 
effects can be clearly obtained in all of the evaluation methods. 
EXAMPLE 3 
A vesicle dispersion was prepared from 4 g of the 2HT methacrylate obtained 
by a desalting method in Example 2 and 400 g of water, by applying the 
ultrasonic treatment of Example 1. 
The resultant vesicle dispersion was placed in a reaction vessel and the 
photopolymerization was carried out for 13 hours according to an internal 
irradiation method using a high pressure mercury vapor lamp (Model 
UVL-400HA manufactured by Rikou Sangyo K.K., 400 W, wavelength 360 nm). In 
the photopolymerization, 50 mM of 2,2'-azobisisobutyronitrile was added as 
a photosensitizer. 
The resultant vesicles had a particle size of 78 nm, as measured by the 
submicron sizer used in Example 1, and a main distribution range of a 
degree of polymerization of 2 to 80. 
EXAMPLE 4 
A vesicle dispersion was prepared from 4 g of the 2HT methacrylate obtained 
by the desalting method of Example 2 and 200 g of water, which were placed 
in an Erlenmeyer flask followed by applying the ultrasonic treatment of 
Example 1. The resultant dispersion was transferred to a 4-necked glass 
separable flask and 0.6 g of 2,2'-azobis(2-amidino propane) 
dihydrochloride was added separately three times as a radical initiator. 
The thermal polymerization was then carried out at a temperature of 
60.degree. C. for 6 hours in an N.sub.2 stream, while stirring. 
The polymer vesicles thus obtained had a particle size of 84 nm, as 
measured by the submicron sizer used in Example 1, and a degree of 
polymerization of 2 to 150. 
Example 5 
A vesicle dispersion was prepared from 2 g of the 2HT methacrylate obtained 
by the desalting method of Example 2 and 200 g of water, which were placed 
in an Erlenmeyer flask followed by applying the ultrasonic treatment of 
Example 1. The resultant dispersion was transferred to the same reaction 
flask as used in Example 4 and 1 g of 2,2'-azobisisobutyronitrile was 
added separately two times as a radical initiator and the thermal 
polymerization was carried out at a temperature of 90.degree. C. for 5 
hours in an N.sub.2 stream. 
The resultant polymer vesicle suspension had a particle size of 67 nm, as 
measured by the submicron sizer used in Example 1, and a degree of 
polymerization of 2 to 20. 
The following Comparative Examples 4 and 5 are comparative examples of the 
above-mentioned Examples 3 to 5. 
COMATIVE EXAMPLE 4 
A 5 g amount of the same 2HT methacrylate as used in Example 2 and 250 ml 
of water were placed in an Erlenmeyer flask, followed by heating at a 
temperature of 80.degree. C., while stirring, to prepare the vesicle 
dispersion. The vesicle dispersion was photopolymerized in the same manner 
as in Example 1, and the resultant polmmer vesicle dispersion was viscous. 
The particle size, as measured by the submicron sizer, was 3000 nm and the 
degree of polymerization was 2 to 120. 
COMATIVE EXAMPLE 5 
The vesicle dispersion obtained in the same manner as in Comparative 
Example 4 was thermally polymerized as in Example 4, and the resultant 
polymer vesicle dispersion was in the form of a gel. The particle size was 
5000 nm, as measured by the submicron sizer, and the degree of 
polymerization was 2 to 700. 
When the polymer vesicles of Comparative Examples 4 and 5 and Examples 3 to 
5 were used for treating hair, and the treated hair was compared, the hair 
treated with the resides of Examples 3 to 5 exhibited a greater 
moisturizing effect and damage prevention effects. From these results, the 
optimum ranges of the particle size and degree of polymerization may be 
obtained. 
The following Examples illustrate polymer vesicles derived from materials 
other than 2HT methacrylate. 
EXAMPLE 6 
As a starting quaternary ammonium salt, didodecyl dimethyl ammonium bromide 
(commercially available from Sougo Yakko K.K.) having two linear C.sub.12 
alkyl chains was used and didodecyl dimethyl ammonium methacrylate having 
methacrylate introduced at the counter ion part was obtained by the same 
desalting method as used in Example 2. A 1 g amount of the didodecyl 
dimethyl ammonium methacrylate and 100 g of water were placed in an 
Erlenmeyer flask and a vesicle dispersion was prepared in the same manner 
as in Example 1. The photopolymerization of the vesicle dispersion was 
also carried out in the same manner as in Example 1. 
The resultant vesicle had a particle size of 21 nm, as measured by the 
submicron sizer, and a degree of polymerization of 2 to 15. 
EXAMPLE 7 
As a starting quaternary ammonium salt, ditetradecyl dimethyl ammonium 
bromide having two linear C.sub.14 alkyl chains (commercially available 
from Sougo Yakko K.K.) was used, and ditetradecyl dimethyl ammonium 
methacrylate having methacrylate introduced into the counter ion was 
obtained by the same desalting method as used in Example 2. Thereafter, a 
polymer vesicle comprising ditetradecyl dimethyl ammonium methacrylate was 
prepared in the same manner as in Example 6. 
The resultant polymer vesicles had a particle size of 34 nm, as measured by 
the submicron sizer, and a degree of polymerization of 2 to 15. 
EXAMPLE 8 
As a starting quaternary ammonium salt, dihexadecyl dimethyl ammonium 
bromide having two linear C.sub.16 alkyl groups (commercially available 
from Sougo Yakko K.K.) was used and ditetradecyl dimethyl ammonium 
methacrylate having methacrylate introduced into the counter ion part 
thereof was obtained by the same desalting method as used in Example 2. 
Thereafter, polymer vesicles comprising dihexadecyl dimethyl ammonium 
methacrylate were prepared in the same manner as in Example 6. The polymer 
vehicles had a particle size of 46 nm, as measured by the submicron sizer, 
and a degree of polymerization of 2 to 15. 
EXAMPLE 9 
As a starting quaternary ammonium salt, dioctadecyl dimethyl ammonium 
chloride having two linear C.sub.18 alkyl chains (commercially available 
from Tokyo Kasei Kogyo K.K.) was used and dioctadecyl dimethyl ammonium 
methacrylate having methacrylate introduced into the counter ion part by 
the same desalting method as used in Example 2. Thereafter, polymer 
vesicles comprising dioctadecyl dimethyl ammonium methacrylate were 
prepared in the same manner as in Example 6. The polymer vesicles had a 
particle size of 46 nm, as measured by the submicron sizer, and a degree 
of polymerization of 2 to 15. 
EXAMPLE 10 
A methanol solution of acrylic acid was passed through a column packed with 
the same ion exchange resin as used in Example 1, to obtain acrylate type 
ion exchange resin. Then, a methanol solution of the same distearyl 
dimethyl ammonium chloride as used in Example 1 was passed through the 
column. According to the same procedure as used in Example 1, 
polymerizable quaternary ammonium surfactant 2HT acrylate having acrylate 
introduced into the counter ion part was obtained. A 5 g amount of the 2HT 
acrylate and 250 g of water were placed in an Erlenmeyer flask and the 
ultrasonic treatment and the photopolymerization was carried out in the 
same manner as in Example 1. As a result, the desired polymer vesicles 
having a particle size of 40 nm, as measured by the submicron sizer, and a 
degree of polymerization of 2 to 10 were obtained. 
Example 11 
2-Acrylamide-2'-methylpropane sulfonic acid ("AMPS" commercially available 
from Tokoyo Kassi Kogyo K.K.) was passed through a column packed with the 
same ion exchange resin to obtain an AMPS type ion exchange resin. The 
water solvent was replaced by methanol, and thereafter, a methanol 
solution of the same distearyl dimethyl ammonium chloride as used in 
Example 1 was passed through the column to obtain a polymerizable 
quaternary ammonium surfactant 2HT AMPS having AMPS introduced into the 
counter ion part. 
A 5 g amount of the 2HT AMPS obtained above and 250 g of water were placed 
in an Erlenmeyer flask and the same ultrasonic treatment and 
photopolymerization as used in Example 1 were carried out. Accordingly, 
the desired polymer vesicle dispersion having a particle size of 82 nm, as 
measured by the submicron sizer, and a degree of polymerization of 2 to 
110 was obtained. 
The hair cosmetic compositions containing the polymer vesicles obtained in 
Examples 6 to 11 exhibited excellent moisturizing and damage prevention 
effects. 
The Formulation Examples in which the polymer vesicles of Example 2 as well 
as a higher alcohol, a nonionic surfactant, and an oil, etc., were 
formulated will now be explained. 
FORMULATION EXAMPLE 1 
______________________________________ 
Ingredient % 
______________________________________ 
Polymer vesicle dispersion 
60 
Cetostearyl alcohol 
3 
Polyethyleneoxide (5 mol) 
2 
stearyl ether 
Propylene glycol 5 
Water balance 
______________________________________ 
FORMULATION EXAMPLE 2 
______________________________________ 
Ingredient % 
______________________________________ 
Polymer vesicle dispersion 
45 
Cetostearyl alcohol 
5 
Glycerol monostearate 
0.5 
Sorbitan sesquioleate 
0.5 
Glycerol 10 
Water balance 
______________________________________ 
FORMULATION EXAMPLE 3 
______________________________________ 
Ingredient % 
______________________________________ 
Polymer vesicle dispersion 
75 
Cetostearyl alcohol 
7 
Lauric monoethanol amide 
1 
Propylene glycol 5 
Vaselin 2 
Water balance 
______________________________________ 
The hair cosmetic compositions obtained in Formulation Examples 1 to 3 
according to the present invention all had excellent moisturizing and 
damage prevention effects. Note, the kinds and formulation amounts of each 
component are by no means limited to the above-mentioned Examples.