Oxyalkylenized xanthane gum thickeners in permanent hair dyeing compositions and processes

A permanent hair dyeing composition which contains an oxidation dye precursor, a coupler, an oxyalkylenized xanthane gum, and a salt of an inorganic or organic acid, and hair dyeing processes with such compositions.

BACKGROUND OF THE INVENTION 
a) Field of the Invention 
This invention relates to a hair cosmetic composition which has good 
spreadability, permits easy application to hair, and provides an excellent 
feeling of use. 
b) Description of the Related Art 
A hair cosmetic composition is generally added with one or more of various 
thickening agents with a view to improving the ease in application by 
preventing running-down and further to reducing irritation to the skin. 
Employed as such thickening agents are, for example, natural polymers such 
as xanthan gum and guar gum, semisynthetic polymers such as 
methylcellulose and ethylcellulose, and synthetic polymers such as 
polyvinyl alcohol and polyethylene oxide. 
Among these, xanthan gum is widely used because it is hardly affected by 
pH, temperature and the like and exhibits good thickening effect. 
Hair cosmetic compositions which contain xanthan gum are however 
accompanied by the problem that, when they are taken out of bottoms upon 
use, they become a lump and show poor spreadability, they cannot be easily 
applied to hair, and the feeling of use is hence significantly impaired. 
Further, xanthan gum fails to bring about sufficient thickening effect in 
systems which contain a salt and a solvent at high concentrations. 
To cope with the above-described problem, U.S. Pat. No. 3,349,077 discloses 
that xanthan gum etherified with an alkylene oxide is usable as a 
thickening agent. This etherified xanthan gum is described in the U.S. 
patent to be useful for obtaining an alcohol-base high-viscosity gel, but 
the U.S. patent has no disclosure whatsoever as to whether it would show 
sufficient thickening effect in other systems. 
Among hair cosmetic compositions, hair dye compositions, hair setting 
compositions, permanent wave compositions and the like generally contain a 
salt and a solvent at high concentrations. It has therefore been desired 
to develop a component which can exhibit sufficient thickening effects in 
these systems. 
SUMMARY OF THE INVENTION 
An object of the present invention is therefore to provide a hair cosmetic 
composition, such as a hair dye composition, hair setting composition or 
permanent wave composition, which has good spreadability, permits easy 
application, has excellent feeling of use, and shows sufficiently 
long-lasting thickening effect even if a salt and a solvent are contained 
at high concentrations. 
Under the foregoing circumstances, the present inventors have proceeded 
with extensive research. As a result, it has been found that use of an 
oxyalkylenized xanthan gum as a thickening agent in a system containing an 
oxidizing agent, a reducing agent, a film-forming polymer, an oxidation 
dye, an acid dye or the like--such as a hair dye composition, hair setting 
composition or a permanent wave composition--in which fully-controlled 
thickening effect has heretofore been unavailable due to inclusion of a 
salt and a solvent at high concentrations makes it possible to obtain a 
hair cosmetic composition having good spreadability, permitting easy 
application to hair and having an excellent feeling of use, leading to the 
completion of the present invention. 
The present invention therefore provides a hair cosmetic composition, 
comprising at least one component selected from an oxidizing agent, a 
reducing agent, a film-forming polymer, an oxidation dye, or an acid dye; 
and an oxyalkylenized xanthan gum. 
The present invention also provides a hair cosmetic composition, comprising 
at least one component selected from an oxidizing agent, a reducing agent, 
a film-forming polymer, an oxidation dye, or an acid dye; an 
oxyalkylenized xanthan gum; and at least one additional component selected 
from an inorganic acid, an organic acid or a salt thereof. 
Further, the present invention also provides a semi-permanent to temporary 
hair dye composition comprising 0.01 to 5 wt. % of an acid dye and 0.01 to 
10 wt. % of an oxyalkylenized xanthan gum, wherein the composition has a 
pH of from 2 to 5. 
The present invention also provides a hair setting composition comprising 
0.1 to 10 wt. % of a film-forming polymer and 0.1 to 10 wt. % of an 
oxyalkylenized xanthan gum, wherein the composition has a pH of from 5 to 
8. 
Still further, the present invention also provides a permanent wave 
composition comprising 1 to 10 wt. % of a reducing agent and 0.5 to 5 wt. 
% of an oxyalkylenized xanthan gum, wherein the composition has a pH of 
from 4.5 to 9.6. 
The present invention also provides a permanent hair dye composition 
comprising 0.1 to 20 wt. % of an oxidation dye and 0.1 to 5 wt. % of an 
oxyalkylenized xanthan gum, wherein the composition has a pH of from 6 to 
9.5. 
Moreover, the present invention also provides a semi-permanent to temporary 
hair dying process, which comprises applying to hair a composition 
comprising 0.01 to 5 wt. % of an acid dye and 0.01 to 10 wt. % of an 
oxyalkylenized xanthan gum, wherein the composition has a pH of from 2 to 
5. 
The present invention also provides a permanent hair dying process, which 
comprises applying to hair a composition comprising 0.1 to 20 wt. % of an 
oxidation dye and 0.1 to 5 wt. % of an oxyalkylenized xanthan gum, wherein 
the composition has a pH of from 6 to 9.5. 
DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS 
The oxyalkylenized xanthan gum useful in the practice of the present 
invention is available by substituting at least some of hydroxyl groups of 
xanthan gum with (poly)oxyalkylene groups and includes, for example, one 
represented by the below-described formula. Here, the term "the degree of 
substitution by (poly)oxyalkylene groups (poly)oxyalkylene substitution 
degree!" as used herein means an average number of (poly)oxyalkylene units 
--(C.sub.x H.sub.2x O).sub.y --H units in the below-described formula! 
bonded per residual group of constituent unit saccharide of xanthan gum. 
##STR1## 
wherein R represents a hydrogen atom of --(C.sub.x H.sub.2x O).sub.y --H, 
x standing for a value of from 1 to 6 and Y denoting a value of from 1 to 
20, and M.sup.+ represents a metal atom. 
Incidentally, each oxyalkylene substitution degree referred to in the 
present invention means a value determined in accordance with the method 
subscribed in ASTM D-2367-72. 
Preferred examples of the (poly)oxyalkylene group include (poly)oxyalkylene 
groups having 2-4 carbon atoms, for example, (poly)oxyethylene group, 
(poly)oxypropylene group and (poly)oxybutylene group. 
Such an oxyalkylenized xanthan gum can be prepared, for example, following 
the process disclosed in U.S. Pat. No. 3,349,077. For example, it can be 
prepared by mixing xanthan gum with an alkali and a solvent such as water, 
adding an alkylene oxide and then reacting them to each other. Usable 
examples of the alkylene oxide include ethylene oxide, propylene oxide, 
1-butene oxide and 2-butene oxide. The reaction may preferably be 
conducted at 40 to 100.degree. C., especially at 60 to 80.degree. C. for 3 
to 20 hours. 
Regarding the proportions of the alkylene oxide and xanthan gum to be 
employed in the reaction, it is preferred to determine their proportions 
so that one or more molecules of the alkylene oxide are added per molecule 
of xanthan gum. It is possible to adjust the oxyalkylene substitution 
degree and etherification degree of the resulting oxyalkylenized xanthan 
gum by modifying their proportions. Incidentally, the term "etherification 
degree" as used herein means the proportion (%) of hydroxyl groups 
ether-substituted by (poly)oxyalkylene groups out of the hydroxyl groups 
in xanthan gum. Xanthan gums having different oxyalkylene substitution 
degrees and etherification degrees can also be obtained by modifying the 
reaction time, reaction temperature and the amount of a catalyst. 
The oxyalkylene substitution degree of the oxyalkylenized xanthan gum 
obtained as described above may preferably range from 0.01 to 1.5. In 
particular, an oxyalkylene substitution degree in a range of from 0.01 to 
0.5 provides excellent water solubility and thickening property, while an 
oxyalkylene substitution degree in a range of from 1 to 1.5 leads to 
superb solubility in an organic solvent system. 
On the other hand, the etherification degree may preferably be from 0.1 to 
25%, with a range of from 0.1 to 10% being particularly preferred because 
this range provides excellent flowability. 
Further, at a high etherification degree, a system with an oxyalkylenized 
xanthan gum incorporated therein has a higher viscosity under acidic 
condition than under neutral condition when the oxyalkylenized xanthan gum 
is added in the same amount. At a high substitution degree, on the other, 
the viscosity is conversely higher under neutral conditions than under 
acidic conditions when the oxyalkylenized xanthan gum is added in the same 
amount. By using this property, it is possible to choose an appropriate 
oxyalkylenized xanthan gum depending on the application. 
The etherification degree in the present invention may preferably be 
determined as follows: 
(1) Preparation of a sample solution: 
Xanthan gum (0.1 g) is precisely weighed (Wt mg) and poured into a 
messflask (100 ml). Into the flask is added 1 N sulfuric acid (25 ml), and 
then the resultant mixture is heated in the water bath to thereby dissolve 
the xanthan gum. The solution is then cooling down and is added water 
precisely to adjust the volume of the solution to 100 ml. Thereafter, 4 ml 
of the solution is placed in a mess flask (20 ml), and is added water to 
obtain 20 ml of a sample solution. 
(2) Preparation of a standard solution: 
0.1 g of propylene glycol is weighed precisely (Ws mg), poured into a 
messflask (100 ml) and is added water to obtain a solution measured 
precisely as 100 ml. The precisely measured 3 ml of the solution is then 
placed in a messflask (100 ml) and is added water to thereby obtain a 
standard solution. 
(3) Coloring: 
Each 1 ml of the sample solution, the standard solution and water is 
precisely measured off. Then the three kind of liquids are poured into 
messflasks (25 ml) separately. Each liquid is allowed to stand for 5 or 
more minutes in the ice bath. Thereafter, to each liquid, a conc. sulfuric 
acid (8 ml) is added dropwise while stirring, and subsequently heated 
precisely for 3 minutes in a water bath. Immediately after the heating, 
the solutions are cooled down in an ice bath for 10 minutes or more, and 
then added carefully 0.6 ml of the below-described ninhydrin solution(*) 
under stirring. The resultant solutions are allowed to stand over 100 
minutes in a hot bath at constant temperature of 25.+-.0.5.degree. C. 
Then, to each of the solutions is added a conc. sulfuric acid to prepare 
25 ml solution under stirring. 
(4) Measurement: 
At 5 minutes after the addition of sulfuric acid, the absorbances (at a 
wavelenth of 590 nm) of the coloring solutions prepared based on the 
sample solution, the standard solution, and water (as a control) are 
measured. The etherification degree is calculated by the equation: 
##EQU1## 
(wherein Wt is the amont of the sample (mg), Ws is the amount of propylene 
glycol (mg), At is absorbance of the sample solution and As is absorbance 
of the standard solution.) (*) Ninhydrin solution used here is prepared by 
mixing 0.6 g of ninhydrin into 5% of sodium hydrogensulfite solution to 
obtain 20 ml solution. 
In the present invention, it is particularly preferred to use 
(poly)oxypropylenized xanthan gum which is available by reacting xanthan 
gum with propylene oxide. 
In the hair cosmetic composition according to the present invention, 
oxyalkylenized xanthan gums can be used either singly or in combination. 
It is preferred to add one or more oxyalkylenized xanthan gums in a total 
amount of from 0.01 to 10 wt. % (hereinafter indicated simply by "%") 
based on the whole composition. In particular, the addition in an amount 
of from 0.01-5%, notably 0.01 to 3% is preferred as excellent solubility 
is also brought about. 
To the hair cosmetic composition according to the present invention, at 
least one component selected from an oxidizing agent, a reducing agent, a 
film-forming polymer, an oxidation dye or an acid dye is added. The 
addition of at least one component selected from the oxidizing agent, the 
reducing agent or the oxidation dye out of the above components provides a 
permanent wave composition, a permanent hair dye composition or the like. 
On the other hand, the addition of the oxidation dye results in a 
semi-permanent to temporary hair dye composition. Further, the addition of 
the film-forming polymer leads to a hair setting composition. 
Examples of the reducing agent include thioglycolic acid; thioglycolic acid 
derivatives; cysteine, N-acylcysteine, and salts thereof; thioglyceryl 
alkyl ethers; and mercaptoalkylamides. Of these, particularly preferred 
are thioglycolic acid; glyceryl thioglycolate; L-cysteine, D-cysteine, 
N-acylcysteine, and the ammonium, quaternary ammonium, and amine (e.g., 
monoethanolamine, diethanolamine, and triethanolamine) salts of these 
cysteines; thioglyceryl alkyl ethers such as ethoxyhydroxypropanethiol, 
methoxyethoxyhydroxypropanethiol, ethoxyethoxyhydroxypropanethiol, and 
isopropoxyethoxyhydroxypropanethiol; mercaptoethyl propanamide; and 
mercaptoethylgluconamide. 
These reducing agents can be used either singly or in combination. It is 
preferred to add one or more reducing agents in a total amount of from 
0.01 to 15%, especially from 1 to 10% based on the whole composition. 
Owing to the addition of such a reducing agent, the hair cosmetic 
composition according to the present invention can be prepared into a 
first-package permanent wave composition or the like. To prepare this 
permanent wave composition, it is preferred to add the reducing agent in 
an amount of from 1 to 10% and the oxyalkylenized xanthan gum in an amount 
of from 0.5 to 5% and to adjust the pH to 4.5 to 9.6. When the hair 
cosmetic composition according to the present invention is provided as a 
permanent wave composition by the addition of the reducing agent, the set 
holding property can be improved. 
Illustrative of the oxidizing agent are potassium bromate, sodium bromate, 
sodium perborate and hydrogen peroxide. These oxidizing agent can be added 
in an amount of from 0.1 to 15%, especially from 5 to 10% based on the 
whole composition. 
By the addition of such an oxidizing agent, the hair cosmetic composition 
according to the present invention can be provided as a second-package 
permanent wave composition or a second-package permanent hair dye 
composition. 
Further, examples of the oxidation dye include oxidation dye precursors 
such as p-phenylenediamine, p-aminophenol, o-phenylenediamine, 
o-aminophenol, and derivatives thereof. On the other hand, coupling 
substances which can form various colors when combined with these 
oxidation dye precursors include, for example, m-pheylenediamine, 
m-aminophenol, polyhydric phenols and the like. 
One or more of these oxidation dye precursors can preferably be added in an 
amount of from 0.1 to 20%, notably 0.1 to 10% based on the whole 
composition. Further, one or more of the coupling substances can 
preferably be added in an amount of from 0.1 to 10%, especially from 0.1 
to 5%, as needed, based on the whole composition. 
By the addition of such an oxidation dye, the hair cosmetic composition 
according to the present invention can be provided as a permanent hair dye 
composition (either as a single-pack type or as a first-package 
composition of a two-pack type). For the preparation of this permanent 
hair dye composition, it is preferred to add the oxidation dye in an 
amount of from 0.1 to 20% and the oxyalkylenized xanthan gum in an amount 
of from 0.1 to 5% and to adjust the pH to 6 to 9.5. 
The addition of the acid dye in the hair cosmetic composition according to 
the present invention makes it possible to uniformly disperse the dye in a 
large amount. Hair can therefore be evenly coated with the dye, so that 
the dyeability can also be improved. No particular limitation is imposed 
on such an acid dye insofar as it is usable in ordinary cosmetic 
composition. Illustrative examples of these acid dyes include Red No. 102 
(C.I. 16255), Yellow No. 4 (C.I. 19140), Yellow No. 5 (C.I. 15985), Red 
No. 201 (C.I. 15850), Red No. 227 (C.I. 17200), Orange No. 205 (C.I. 
15510), Brown No. 201 (C.I. 20170), Red No. 502 (C.I. 16155), Red No. 503 
(C.I. 16150), Red No. 504 (C.I. 14700), Red No. 506 (C.I. 15620), Orange 
No. 402 (C.I. 14600), Yellow No. 402 (C.I. 18950), Yellow No. 406 (C.I. 
14065), Yellow No. 407 (C.I. 18820), Red No. 213 (C.I. 45170), Red No. 214 
(C.I. 45170), Red No. 3 (C.I. 45430), Red No. 104(1) (C.I. 45410), Red No. 
105(1) (C.I. 45440), Red No. 106 (C.I. 45100), Green No. 2, Green No. 3 
(C.I. 42053), Orange N. 207 (C.I. 45425), Yellow No. 202(1) (C.I. 45350), 
Yellow No. 202(2) (C.I. 45350), Blue No. 202 (C.I. 42052), Blue No. 203 
(C.I. 42052), Blue No. 205 (C.I. 42090), Blue No. 2 (C.I. 73015), Yellow 
No. 203 (C.I. 47005), Blue No. 201 (C.I. 73060), Green No. 201 (C.I. 
61570), Blue No. 1 (C.I. 42090), Red No. 230(1) (C.I. 45380), Red No. 231 
(C.I. 45410), Red No. 232 (C.I. 45440), Green No. 204 (C.I. 59040), Green 
No. 205 (C.I. 42095), Red No. 401 (C.I. 45190), Yellow No. 403(1), (C.I. 
10316), Green No. 401 (C.I. 10020), Green No. 402 (C.I. 42085), Black No. 
401 (C.I. 20470), and Violet No. 401 (C.I. 60730). 
These acid dyes can be used either alone or in combination. It is preferred 
to add one or more of them in an amount of from 0.001 to 10%, especially 
from 0.01 to 5% based on the whole composition. 
To provide such a semi-permanent to temporary hair dye composition, it is 
preferred to add the acid dye in an amount of from 0.01 to 5% and the 
oxyalkylenized xanthan gum in an amount of 0.01 to 10% and to adjust the 
pH to 2 to 5. 
The addition of the film-forming polymer to the hair cosmetic composition 
according to the present invention provides a hair setting composition 
having excellent film characteristics. Examples of such a film-forming 
polymer include the following polymers (1) to (8): 
(1) Polyvinylpyrrolidone-base high polymers: 
Polyvinylpyrrolidones: 
Commercial products include "Luviskol K12" and "Luviskol K30" (trade names, 
products of BASF AG); and "PVP K15" and "PVP K30" (trade names, products 
of International Specialty Products, Inc.). 
Polyvinylpyrrolidone/vinyl acetate copolymers: 
Commercial products include "Luviskol VA28" and "Luviskol VA73" (trade 
names, products of BASF AG); "PVP/VA E-735" and "PVP/VA S-630)" (trade 
names, products of International Specialty Products, Inc.). 
Polvinylpyrrolidone/vinyl acetate/vinyl propionate terpolymers: 
Commercial products include "Luviskol VAP343" (trade name, product of BASF 
AG). 
Polyvinylpyrrolidone/alkyl aminoacrylate copolymers: 
Commercial products include "Luviflex" (trade name, product of BASF AG); 
and "Copolymer 845", "copolymer 937" and "Copolymer 958" (trade names, 
products of International Specialty Products, Inc.). 
Polyvinylpyrrolidone/acrylate/(meth)acrylic acid copolymers: 
Commercial products include "Luviflex VBM35" (trade name, product of BASF 
AG). 
Polyvinylpyrrolidone/alkyl aminoacrylate/vinyl caprolactam: 
Commercial products include "Copolymer VC-713" (trade name, products of 
International Specialty Products, Inc.). 
(2) Acidic-vinyl-ether-base high polymers: 
Methyl vinyl ether/alkyl half ester of maleic anhydride copolymers: 
Commercial products include "Gantrez ES-225", "Gantrez ES-425" and "Gantrez 
SP-215" (trade names, products of International Specialty Products, Inc.). 
(3) Acidic-polyvinyl-acetate-base high polymers: 
Vinyl acetate/crotonic acid copolymers: 
Commercial products include "Resin 28-1310" (trade name, product of 
National Starch Company); and "Luviset CA66" (trade name; product of BASF 
AG). 
Vinyl acetate/crotonic acid/vinyl neodecanoate copolymers: 
Commercial products include "Resin 28-2930" (trade name, product of 
National Starch Company). 
Vinyl acetate/crotonic acid/vinyl propionate copolymers: 
Commercial products include "Luviset CAP" (trade name, product of BASF AG). 
(4) Acidic acrylic high polymers: 
(Meth)acrylic acid/(meth)acrylate ester copolymers: 
Commercial products include "TPlascize L53P" (trade name, product of GOO 
CHEMICAL Co., Ltd.); and "Diahold" (trade name, product of Mitsubishi 
Chemical Corporation). 
Acrylic acid/alkyl acrylate/alkylacrylamide copolymers: 
Commercial products include "Ultrahold 8" (trade name, product of BASF AG); 
"Amphomer V-42" (trade name, product of National Starch Company). 
(5) Amphoteric acrylic high polymers: 
(Meth)acrylethylbetaine/alkyl (meth)acrylate copolymers: 
Examples include copolymers of N-methacryloyloxyethyl N,N-dimethylammonium 
.alpha.-N-methylcarboxybetaine and alkyl (meth)acrylates. Commercial 
products include "Yukaformer M-75" and "Yukaformer SM" (trade names, 
product of Mitsubishi Chemical Corporation). 
Alkyl acrylate/butylaminoethyl metharylate/octylacrylamide copolymers: 
Examples include octylacrylamide/acrylate/butylaminoethyl methacrylate 
copolymer. Commercial products include "Amphomer 28-4910" (trade name, 
product of National Starch Company). 
(6) Basic acrylic high polymers: 
Acrylamide-acrylate ester tetrapolymers: 
Examples include those disclosed in Japanese Patent Application Laid-Open 
(Kokai) No. HEI 2-180911. 
(7) Cellulose derivatives: 
Cationic cellulose derivatives: 
Commercial products include "Celquat H-100" and "Celquat L-200" (trade 
names, products of National Starch Company). 
(8) Chitin and chitosan derivatives: 
Hydroxypropylchitosan 
Commercial products include "Chitofilmer" (trade name, product of Ichimaru 
Pharcos Co., Ltd. 
Salts of carboxymethyl chitin, carboxymethyl chitosan or chitosan and a 
monocarboxylic acid such as pyrrolidonecarboxylic acid, lactic acid or 
glycolic acid or dicarboxylic acid such as adipic acid or succinic acid: 
Commercial products include "Chimer PC" (pyrrolidonecarboxylate salt) and 
"Chitomer L" (oxalate salt) (trade names, product of Union Carbide 
Corporation). 
Of these film-forming polymers, particularly preferred are 
polyvinylpyrrolidone-base high polymers, acidic-vinyl-ether-base high 
polymers, acidic-polyvinyl-acetate-base high polymers, acidic acrylic high 
polymers, and amphoteric acrylic high polymers. These film-forming 
polymers can be used either alone or in combination. It is preferred to 
add the film-forming polymer in an amount of from 0.1 to 1.0%, especially 
from 0.5 to 5% based on the whole composition. 
To prepare such a hair setting composition, it is preferred to add the 
film-forming polymer in an amount of from 0.1 to 10% and the 
oxyalkylenized xanthan gum in an amount of from 0.1 to 10% and to adjust 
the pH to 5 to 8. 
Owing to the addition of the oxyalkylenized xanthan gum, the hair cosmetic 
composition according to the present invention has good spreadability, 
permits easy application and provides excellent feeling of use. Further, 
sufficient thickening effect can be obtained. Sufficient thickening effect 
can be continuously retained even in systems where conventional thickening 
agents have difficulty to achieve thickening, especially even in systems 
where a salt and a solvent are contained at high concentrations. 
Here, the salt usable for incorporation in the hair cosmetic composition 
according to the present invention can be any one of inorganic salts, 
organic salts, polymer electrolytes and the like which are employed in 
general hair cosmetic compositions. Illustrative examples include sodium 
salts, potassium salts, ammonium salts, and alkanolamine salts (e.g., 
triethanolamine salts) of inorganic acids, such as phosphoric acid, 
sulfuric acid and nitric acid, and organic acids such as citric acid, 
glycolic acid, succinic acid, tartaric acid, lactic acid, fumaric acid, 
malic acid, levulinic acid, butyric acid, valeric acid, oxalic acid, 
maleic acid and mandelic acid. 
Illustrative of such polymer electrolytes are water-soluble sodium 
sulfonate of polyester, sodium poly(styrenesulfonate), 
poly(meth)acrylates, polymaleates and polyphosphates. 
These salts can be used either singly or in combination. One or more of 
these salts can be added preferably in an amount of from 0.1 to 20%, 
especially from 0.1 to 10%, specifically from 1 to 8% based on the whole 
composition. 
No particular limitation is imposed on the solvent usable for incorporation 
in the hair cosmetic composition according to the present invention, 
insofar as it is usable in ordinary hair cosmetic compositions. 
Illustrative examples include monohydric alcohols containing C.sub.1-6 
alkyl groups such as ethanol, 1-propanol, 2-propanol, isopropanol, 
1-butanol and 2-butanol; dihydric or polyhydric alcohols containing 
C.sub.3-8 alkyl groups such as propanediol, butanediol, pentanediol, 
hexanediol, hexantriol, heptanediol, heptanetriol, octanediol, 
octanetriol, isoprene glycol, propylene glycol, glycerin, diethylene 
glycol monoethyl ether, diethylene glycol diethyl ether, and ethylene 
glycol monoethyl ether; N-alkylpyrrolidones in liquid forms at room 
temperature, such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 
N-propyl-2-pyrrolidone, N-butyl-2-pyrrolidone, and 
N-cyclohexyl-2-pyrrolidone; lower alkylene carbonates such as ethylene 
carbonate and propylene carbonate; aromatic alcohols such as benzyl 
alcohol, cinnamyl alcohol, p-anisyl alcohol, p-methylbenzyl alcohol, 
phenoxyethanol, phenoxyisopropanol, 2-benzylethanol, and 
.beta.-phenylethyl alcohol. 
These solvents can be used either singly or in combination. One or more of 
these solvents can be added preferably in an amount of from 0.1 to 60% 
based on the whole composition. Especially, an amount of from 0.1 to 50%, 
specifically from 0.1 to 30% is preferred because sufficient spreadability 
and thickening effect can be obtained. 
To provide the hair cosmetic composition according to the present invention 
as a permanent wave composition, it is preferred to add the oxyalkylenized 
xanthan gum in an amount of from 0.5 to 5%, the salt in an amount of from 
0.5 to 5%, the solvent in an amount of from 0 to 5% and the reducing agent 
in an amount of from 1 to 10% and also to adjust the pH of from 4.5 to 
9.6. 
Further, to provide the hair cosmetic composition according to the present 
invention as a permanent hair dye composition, it is preferred to add the 
oxyalkylenized xanthan gum in an amount of from 0.1 to 5%, the salt in an 
amount of from 0.1 to 5%, the solvent in an amount of from 0 to 30% and 
the oxidation dye in an amount of 0.1 to 20% and also to adjust the pH of 
from 6 to 9.5. 
To provide the hair cosmetic composition according to the present invention 
as a semi-permanent to temporary hair dye composition, it is preferred to 
add the oxyalkylenized xanthan gum in an amount of from 0.01 to 10%, the 
salt in an amount of from 0.1 to 20%, the solvent in an amount of from 3 
to 50% and the acid dye in an amount of 0.01 to 5% and also to adjust the 
pH of from 2 to 5. 
To provide the hair cosmetic composition according to the present invention 
as a temporary hair-setting composition, it is preferred to add the 
oxyalkylenized xanthan gum in an amount of from 0.1 to 10%, the salt in an 
amount of from 0.01 to 1%, the solvent in an amount of from 0.5 to 30% and 
the film-forming polymer in an amount of 0.1 to 5% and also to adjust the 
pH to 5 to 8. 
To the hair cosmetic composition according to the present invention, 
components employed in ordinary hair cosmetic compositions can be added as 
desired in addition to the above-described components to extents not 
impairing the advantageous effects of the present invention. Illustrative 
of such additional components are surfactants such as cationic 
surfactants, anionic surfactants and nonionic surfactants; higher alcohols 
containing linear or branched, alkyl or alkenyl groups; hydrocarbons such 
as liquid paraffin and vaseline; liquid lanolin, and lanolin derivatives 
such as lanolin fatty acids; phospholipids such as lecithin; sterols such 
as cholesterol, and derivatives thereof; collagen-degraded peptide 
derivatives; perfluoropolyethers; oils and fats, such as higher 
alcohol-higher fatty acid esters, higher fatty acids, and alkyl- or 
alkenyl-containing, long-chain amide amines; animal or vegetable oils and 
fats such as mink oil and olive oil; medicinally-effective ingredients 
such as anti-dandruff agents, disinfectants and vitamins; antiseptics such 
as parabens; coloring matters such as dyes and pigments; ultraviolet light 
absorbers; plant extracts; astringents; perfume bases; and colors. 
The hair cosmetic composition according to the present invention can be 
prepared by a method known per se in the art. No particular limitation is 
imposed on its form, and it can be prepared into a hair setting 
composition, a temporary hair dye composition, a permanent hair dye 
composition, a permanent wave composition or the like by using various 
components, such as those described above, in combination as needed 
depending on the application purpose. 
The hair cosmetic composition according to the present invention has good 
spreadability, permits easy application to hair and gives excellent 
feeling of use. Further, even in a system containing a salt and a solvent 
at high concentrations, sufficient thickening effect remains. 
The present invention will next be described in further detail by the 
following Examples. It should however be borne in mind that the present 
invention is not limited to or by them.

PRODUCTION EXAMPLE 1 
To a closed reaction vessel equipped with a stirrer, 200 g of xanthan gum 
("Keltol", trademark; product of Kelco Company), 8 g of sodium hydroxide, 
12 g of methanol and 4 g of water were added. They were mixed under 
stirring for about 1 hour at room temperature. Propylene oxide (80 g) was 
added to the resultant mixture, followed by a reaction at 70-75.degree. C. 
for 4 hours. The reaction mixture was allowed to cool down to room 
temperature and was then neutralized with concentrated sulfuric acid. The 
resulting solid matter was dried and ground, whereby 225 g of 
oxypropylenized xanthan gum powder were obtained. The oxypropylene 
substitution degree and etherification degree of the oxypropylenized 
xanthan gum were 0.05 and 1.5 (%), respectively. 
PRODUCTION EXAMPLE 2 
To a closed reaction vessel equipped with a stirrer, 200 g of xanthan gum 
("Kelsan", trademark; product of Kelco Company), 16 g of sodium hydroxide, 
24 g of methanol and 8 g of water were added. They were mixed under 
stirring for about 1 hour at room temperature. After the mixture was 
allowed to stand overnight, 80 g of propylene oxide were added, followed 
by a reaction at 70-75.degree. C. for 4 hours. The reaction mixture was 
allowed to cool down to room temperature and was then neutralized with 
concentrated sulfuric acid. The resulting solid matter was dried and 
ground, whereby 259 g of oxypropylenized xanthan gum powder were obtained. 
The oxypropylene substitution degree and etherification degree of the 
oxypropylenized xanthan gum were 0.15 and 3.7 (%), respectively. 
PRODUCTION EXAMPLE 3 
To a closed reaction vessel equipped with a stirrer, 200 g of xanthan gum 
("Keltol", trademark; product of Kelco Company), 12 g of sodium hydroxide, 
18 g of methanol and 6 g of water were added. They were mixed under 
stirring for about 1 hour at room temperature. Propylene oxide (120 g) was 
added to the resultant mixture, followed by a reaction at 70-75.degree. C. 
for 5 hours. The reaction mixture was allowed to cool down to room 
temperature and was then neutralized with concentrated sulfuric acid. The 
resulting solid matter was dried and ground, whereby 265 g of 
oxypropylenized xanthan gum powder were obtained. The oxypropylene 
substitution degree and etherification degree of the oxypropylenized 
xanthan gum were 0.23 and 6.3 (%), respectively. 
EXAMPLE 1 
Semi-permanent hair dye compositions of the formulations shown in Table 1 
were prepared by a method known per se in the art, and their viscosities 
and flowabilities were ranked. The results are also presented in Table 1. 
(Ranking methods) 
(1) Viscosity: 
The viscosity of each semi-permanent hair dye composition was measured at 
30.degree. C. by a Brookfield type viscometer (No. 4, 30 rpm) immediately 
after its preparation and after stored at 40.degree. C. for 1 month. The 
measurement data were ranked in accordance with the following standards. 
A: The viscosity was 500 cp or higher. 
B: The viscosity was 100 cp or higher but lower than 500 cp. 
C: The viscosity was lower than 100 cp. 
(2) Flowability: 
Each hair dye composition was placed to a height of 10 cm in a glass tube 
of 5 cm in diameter and 20 cm in height. After the hair dye composition 
thoroughly shaken up and down at room temperature for 30 seconds, the hair 
dye composition was left over for 1 minute. The glass tube was then caused 
to fall down sideways over 90 degrees. Ten (10) seconds later, the surface 
smoothness of the hair dye composition was ranged in accordance with the 
following standards. 
A: The surface was smooth. 
B: The surface was not smooth. 
TABLE 1 
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Invention 
Comparative product 
Component (%) product 1 
1 2 3 4 5 6 7 8 9 
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Oxypropylenized xanthan gum (Pro. Ex. 1) 
1 -- -- -- -- -- -- -- -- -- 
Xanthan gum -- 1 -- -- -- -- -- -- -- -- 
Hydroxyethylcellulose 
-- -- 1 -- -- -- -- -- -- -- 
Hydroxypropylcellulose 
-- -- -- 1 -- -- -- -- -- -- 
Cationized cellulose 
-- -- -- -- 1 -- -- -- -- -- 
Tragacanth gum -- -- -- -- -- 1 -- -- -- -- 
Tamarind polysaccharide 
-- -- -- -- -- -- 1 -- -- -- 
Guar gum -- -- -- -- -- -- -- 1 -- -- 
Kimiloid -- -- -- -- -- -- -- -- 1 -- 
Polyvinyl alcohol -- -- -- -- -- -- -- -- -- 1 
Benzyl alcohol 3 3 3 3 3 3 3 3 3 3 
Citric acid 4 4 4 4 4 4 4 4 4 4 
Sodium hydroxide q.s.* q.s.* 
q.s.* 
q.s.* 
q.s.* 
q.s.* 
q.s.* 
q.s.* 
q.s.* 
q.s.* 
Ethanol 15 15 15 15 15 15 15 15 15 15 
Black No. 401 0.03 0.03 
0.03 0.03 
0.03 
0.03 
0.03 
0.03 
0.03 
0.03 
Violet No. 401 0.04 0.04 
0.04 0.04 
0.04 
0.04 
0.04 
0.04 
0.04 
0.04 
Orange No. 205 0.03 0.03 
0.03 0.03 
0.03 
0.03 
0.03 
0.03 
0.03 
0.03 
Purified water Balance 
Balance 
Balance 
Balance 
Balance 
Balance 
Balance 
Balance 
Balance 
Balance 
Viscosity immediately after preparation 
A A A A A A A A A C 
Viscosity one month after preparation 
A A C C C C C C C C 
Flowability A B A A A B B B A A 
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*Quantity sufficient to adjust the pH to 3. 
EXAMPLE 2 
Gel-lotion-type styling compositions of the formulations shown in Table 2 
were prepared by a method known per se, and their viscosities immediately 
after the preparation were measured in the same manner as in Example 1. 
Further, their hair-setting abilities were ranked by the below-described 
method. The results are shown in Table 2. 
(Ranking method) 
Hair-setting ability: 
A bundle of hair of 18 cm in length and 1.5 g in weight was wetted with 
water. After towel-drying, each styling composition was applied to the 
hair in an amount of 2 g. The thus-coated hair was wound around a rod of 2 
cm in diameter and was then allowed to naturally dry up. After the hair 
became dry, the curled hair was taken out of the rod. The curled hair was 
suspended for 30 minutes in a constant-temperature chamber (20.degree. C., 
98% R.H.). Uncurling of the hair was observed. The hair-setting ability 
was then ranged in accordance with the following standards. 
A: Good hair-setting ability. 
B: Average hair-setting ability. 
C: Poor hair-setting ability. 
TABLE 2 
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Invention product 
Comp. product 
Component (%) 2 3 4 5 10 11 
__________________________________________________________________________ 
Oxypropylenized xanthan gum (etherification degree: 15%) 
1 -- -- -- -- -- 
Oxypropylenized xanthan gum (etherification degree: 9%) 
-- 1 -- -- -- -- 
Oxypropylenized xanthan gum (etherification degree: 4.22%) 
-- -- 1 -- -- -- 
Oxypropylenized xanthan gum (etherification degree: 3.9%) 
-- -- -- 1 -- -- 
Xanthan gum -- -- -- -- 1 1 
Monoethanolamine 3 3 3 3 3 3 
Ethanol 50 50 50 50 50 10 
Water 46 46 46 46 46 46 
Viscosity (cp) 1100 
1000 
1080 
492 
0 65 
Hair-setting ability A A A A C B 
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EXAMPLE 3 
First-package permanent wave compositions of the formulations shown in 
Table 3 were prepared by a method known per se in the art, and their 
viscosities immediately after the preparation were measured in the same 
manner as in Example 1. The results are shown in Table 3. 
TABLE 3 
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Inventive product 
Comparative product 
Component (%) 6 7 12 13 
__________________________________________________________________________ 
Hexylene glycol 40 40 40 40 
N-acetylcysteine 8.5 8.5 8.5 8.5 
Thioglycolic acid 0.9 0.9 0.9 0.9 
Monoethanolamine 5 5 5 5 
Oxypropylenized xanthan gum (etherification degree: 9%) 
3 -- -- -- 
Oxypropylenized xanthan gum (etherification degree: 19.5%) 
-- 3 -- -- 
Xanthan gum -- -- 3 -- 
Carboxyvinyl polymer ("Carbopole 940", trade name; 
-- -- -- 3 
product of B. F. Goodrich Company 
Water Balance 
Balance 
Balance 
Balance 
pH 9.0 9.0 9.0 9.0 
Viscocity (cp) 1500 
2000 
Separated 
Separated 
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