Hair cosmetics

Hair cosmetic compositions comprise (A) an extract obtained by polar solvent extraction of a plant, preferable ones of which are birch, rosemary and hamamelis, and (B) a polypeptide compound including keratin, keratin derivative, silk and hydrolysate of silk. Such compositions are made into shampoo, rinse, set lotion, hair spray, etc. Hair cosmetics according to the invention can impart good hair style retentivity and good touch of feeling.

BACKGROUND OF THE INVENTION 
(i) Field of the Invention: 
This invention relates to hair cosmetic compositions and more particularly, 
to hair cosmetic compositions of the type which comprise extracts obtained 
by polar solvent extraction of plants and polypeptide compounds and which 
can impart, to hair, a suitable degree of set retentivity and good feeling 
to the touch. 
(ii) Description of the Prior Art: 
Hair style is one of the most important and charming points from the 
standpoint of beauty care and a variety of beauty treatments have been 
made. For instance, several techniques of suitably waving the hair using 
hair cosmetics are known including so-called permanent treatments by 
permanent waving techniques and transient treatments using set lotions or 
hair sprays. By the treatments, the hair is suitably set or dressed. 
However, the treatments by the permanent waving techniques may sometimes 
damage the hair considerably to such an extent that the hair cannot 
refresh. On the other hand, the treatments using set lotions of hair 
sprays are disadvantageous in that the hair is merely set transiently and 
thus the once set hair is broken simply by the action of moisture. Hence, 
both types of treatments are not satisfactory. Moreover, these techniques 
have the tendency of stiffening the hair and are not also satisfactory in 
the touch of the hair. 
Shampooes are extensively used for the purpose of washing away soiling 
attached on the hair. However, currently available shampooes also wash 
away oil necessary for the hair, so that the shampooed hair becomes dry 
and split-ends or broken hairs are undesirably involved upon brushing. To 
avoid this, hair rinses or pre-shampooes are used, of which some contain 
oils or fats, causing the hair sticky. 
SUMMARY OF THE INVENTION 
In order to obtain hair cosmetic compositions having excellent properties, 
we have made extensive studies on ingredients of the cosmetics. As a 
result, it was found that when a combination of a specific type of plant 
extract and a polypeptide is admixed with hair cosmetic compositions such 
as shampoo, rinse, set lotion, hair spray and the like, the resulting 
cosmetic compositions can impart good hair style retentivity and a 
suitable degree of feeling to the touch with ease in combing. 
According to the present invention, there is provided a hair cosmetic which 
comprises (A) an extract obtained by polar solvent extraction of a plant, 
and (B) a polypeptide compound. 
DETAILED DESCRIPTION OF THE INVENTION AND PREFFERED EMBODIMENTS 
The (A) ingredient useful in the present invention is obtained by 
extraction of plants. Examples of the plant include birch, rosemary, 
arnica, hamamelis, camomile, sage, St. John 's bread, henna, hop, lime, 
aloe, wild thyme, calendula, horsetail, mountain gentian, nettle, 
chestnut, avocado, seaweed, milfoil, coltsfoot, marigold, peach, rose, 
senna, thyme, and white lily. Of these plants, birch, rosemary, hamamelis, 
camomile, sage, aloe, henna, and St. John's bread are preferable and most 
preferably mentioned are birch and rosemary. 
Preferable sites of these preferable plants for the extraction are, for 
example, bark of birch, an entire grass part of rosemary, leaves of 
hamamelis, flower of camomile, leaves of sage, leaves of aloe, leaves of 
henna, and fruit of St. John's bread. 
The plant extract is obtained by extracting flowers, leaves, fruits, roots, 
stems and the like with solvent at a normal temperture or under heating 
conditions according to any known extraction technique. The extraction 
solvents are polar organic solvents including, for example, lower alcohols 
such as methanol, ethanol and the like, propylene glycol, 1,3-butylene 
glycol and glycerine, and water. These solvents may be used singly or in 
combination. 
The extracts of birch and rosemary which are the most preferable plants are 
commercially available. The commercially sold birch extracts include Birch 
Extract made by Novarom Co., Ltd., Boulene MCF787 by Gattefosse Co., Ltd., 
Birch Extract by Virmin Co., Ltd., Birch Extract by Nowak Co., Ltd., 
Extrapone Birch Special by Dragoco Co., Ltd., and the like. Mentioned as 
rosemary extract are rosemary Extract by Novarom Co. Ltd., Romarin MCF772 
by Gattefosse Co. Ltd., Phytelene EG009 by Virmin Co., Ltd., and Rosemary 
Extract by Nowak Co., Ltd. 
When the plant extract is in a liquid form, the ingredient (A) is used in 
an amount ranging from 0.001 to 10.0 wt %, preferably 0.01 to 1.0 wt % 
(hereinafter referred to simply as %) of the total compositon, calculated 
as a residue obtained after distillation of extraction solvent therefrom. 
The ingredient (A) or plant extract may be directly added to hair cosmetic 
compositions in the form of liquid extract, or may be added after 
concentration to a desired level or after complete removal of extraction 
solvent from the extract. 
The ingredient (B) used in the present invention are polypeptide compounds 
which are, for example, keratin and decomposition derivatives thereof, and 
silk fibers and hydrolyzate of silk. 
Keratin is derived from, for example, animal hairs, human hair, feathers, 
nails, horns, hooves, scales or the like. These materials may be used in 
the form of fine powder and are preferably used as a decomposition 
derivative thereof. Preferable keratin materials are wool, human hair, and 
feathers. 
The decomposition derivatives of keratin materials are hydrolyzates, 
oxidative decomposition products, and -SH group-modified compounds of 
reductive decomposition products. The hydrolysis, oxidation and reduction 
reactions and a subsequent modification reaction may be suitably combined. 
The hydrolysis techniques include an acid hydrolysis using hydrochloric 
acid, sulfuric acid, phosphoric acid or the like; and alkali hydrolysis 
using sodium hydroxide, sodium carbonate of the like; and an enzyme 
hydrolysis using protease. The oxidation and/or reduction reaction may be 
effected according to any known method. The disulfide bond is cleft, by 
the reduction reaction, into a thiol group (-SH). The thiol group can be 
modified by a known method to give the following groups: 
##STR1## 
Of these groups, --SCH.sub.2 COOH and 
##STR2## 
obtained by the modification are preferably. 
The chemical modification of the thiol group is conducted according to a 
method known per se as described, for example, in Textile Progress Vol. 7, 
page 1 (1975) by N. H. Leon, "Organic Sulfer Compounds" (1968) written by 
Shigeru Ooae and published by Kagaku Dojin Co., Ltd., and "Course of 
Polymer Experimentation" Vol. 12 (1957) written by Masami Oku and 
published by Kyoritsu Pub. Co. 
The decomposition products of keratin and derivatives thereof have a 
molecular weight of 100 to 100,000, preferably 350 to 30,000. 
Silk fibers which are one of the starting materials for the ingredient (B) 
may be used as a powder thereof or as a powder of a product obtained by 
washing and treating the same with acid. Preferably, silk fibers are used 
as a product obtained by hydrolysis with an acid, alkali or enzyme. The 
hydrolyzate of silk fibers may be obtained by hydrolysis with an acid such 
as hydrochloric acid, sulfuric acid, phosphoric acid or the like, and 
alkali such as sodium hydroxide, sodium carbonate or the like. Moreover, 
the acid or alkali hydrolysis may be used in combination with an enzyme 
hydrolysis. The resulting decomposition or hydrolysis product has a 
molecular weight of 100 to 100,000, preferably 350 to 30,000. 
In the practice of the invention, the ingredient (B) is used in an amount 
of 0.1 to 10 wt %, preferably 0.1 to 5.0 wt %, of the hair cosmetic 
composition. 
The mixing ratio of the ingredients (A) and (B) in the hair cosmetic 
composition of the invention is 0.1 to 10:1, preferably 1 to 8:1. 
The term "hair cosmetic or cosmetics" used herein is intended to mean all 
cosmetics applicable to the hair. For instance, there are included 
pre-shampoo treatment agents, shampooes, hair rinses, after shampoo 
agents, conditioners, hair conditioners, setting lotions, blow styling 
lotions, hair sprays, hair dyes, bleaches, first permanent waving 
solutions, second permanent waving solutions, hair liquids, hair tonics 
and the like. 
The hair cosmetic compositions according to the invention are prepared by 
adding the essential ingredients (A) and (B) to known ingredients for 
these purpose which may vary depending on the type of hair cosmetic. The 
hair cosmetic composition may be formulated in various forms such as 
aqueous solution, ethanolic solution, emulsion, suspension, gel, solid, 
aerosol, powder and the like. 
Preparation of the hair cosmetics of the invention are described. 
(1) Shampoo 
Prepared by mixing known shampoo constituents by a usual manner along with 
one or more anionic active agents and the ingredients (A) and (B). 
Preferable anionic active agents which are used as a shampoo substrate are 
mentioned below. 
(1) Linear or branched alkylbenzenesulfonates having an alkyl group having 
from 10 to 16 carbon atoms on average. 
(2) Polyoxyalkylene alkylsulfates having a linear or branched alkyl group 
having from 8 to 20 carbon atoms on average and added with 0.5 to 8 moles, 
on average, of ethylene oxide and/or propylene oxide in one molecule 
thereof. 
(3) Alkylsulfates having an alkyl group having from 10 to 20 carbon atoms 
on average. 
(4) Olefinsulfonates having from 10 to 20 carbon atoms on average in one 
molecule thereof. 
(5) Alkanesulfonates having from 10 to 20 carbon atoms in one molecule 
thereof. 
(6) Alkylethoxycarboxylates having an alkyl group having from 10 to 20 
carbon atoms on average and added with from 0.5 to 8 moles of ethylene 
oxide on average in one molecule thereof. 
(7) Succinic acid derivatives represented by the following formula 
##STR3## 
(in which R.sub.1 represents an alkyl group or alkenyl group having from 6 
to 20 carbon atoms, X.sub.1 and Y.sub.1 independently represent an ion). 
Counter ions of these anionic active agents are, for example, alkali metal 
ions such as sodium, potassium and the like, alkaline earth metal ions 
such as calcium, magnesium and the like, ammonium ions, and alkanolamines 
having from 1 to 3 alkanol group having 2or 3 carbon atoms and including, 
for example, monoethanolamine, diethanolamine, triethanolamine, 
triisopropanolamine and the like. 
Of these anionic active agents, linear or branched alkylsulfates having 
from 10 to 16 carbon atoms on average, polyoxyethylene alkylsulfates (an 
average number of addition moles of 0.5 to 8) having an alkyl group having 
from 8 to 20 carbon atoms on average, and olefinsulfonates having from 10 
to 16 carbon atoms on average are preferably used. 
In the shampoo compositions of the invention, anionic active agents are 
generally used in an amount of from 5 to 30%, preferably 10 to 25%. 
Other ingredients may be used in the shampoo composition of the invention 
in amounts not to impede the effect of the invention, which include 
amphoteric active agents, nonionic active agents, cationic active agents, 
solubilizers such as propylene glycol, glycerine, urea and the like, 
viscosity adjusters such as ethyl alcohol, isopropyl alcohol, hydroxyethyl 
cellulose, methyl cellulose, higher alcohols and the like, perfumes, 
colorants, UV absorbers, antioxidants, preservatives, pearling agents, 
lotionizing agents, and the like. These agents may be added as desired. 
The thus obained shampoo composition not only has excellent 
hair-conditioning and washing effects, but also is less irritative than 
known shampooes when it comes in contact with eyes by mistake upon washing 
and rinsing, giving only a mild influence on the conjunctiva and the iris. 
(2) Hair rinses, hair conditioners, hair treatments 
The ingredients (A) and (B) are dissolved or dispersed in a suitable 
solvent or medium such as water, ethanol, glycerin, ethylene glycol, 
propylene glycol, 1,3-propanediol, isopropanol, polyethylene glycol or the 
like, thereby obtaining the rinse, conditions or treatment composition. 
To these compositions, may be further added any known in gredients which 
are ordinarily used in rinses, conditioners or treatments. Preferable 
ingredients which are added to the compositions are surface active agents 
such as cationic active agents, anionic active, nonionic active agents and 
amphoteric active agents. Most preferably, cationic active agents should 
be added. 
Specific examples of the surface active agents are mentioned below. 
(a) Anionic active agents 
(1) Linear or branched alkylbenzenesulfonates having an alkyl group having 
from 10 to 16 carbon atoms on average. 
(2) Alkyl or alkenyl ethoxysulfates having a linear or branched alkyl or 
alkenyl group having from 8 to 20 carbon atoms on average and having 0.5 
to 8 moles, on average, of ethylene oxide added in one molecule thereof. 
(3) Alkyl- or alkenylsulfates having an alkyl or alkenyl group having from 
10 to 20 carbon atoms on average. 
(4) Olefinsulfonates having from 10 to 20 carbon atoms on average in one 
molecule thereof. 
(5) Alkanesulfonates having from 10 to 20 carbon atoms on average in one 
molecule thereof. 
(6) Saturated or unsaturated aliphatic acid salts having from 10 to 20 
carbon atoms on average in one molecule thereof. 
(7) Alkyl or alkenyl ethoxycarboxylates having an alkyl or alkenyl group 
having from 10 to 20, preferably 12 to 16, carbon atoms on average and 
having 0.5 to 8 moles, on average, of ethylene oxide added in one molecule 
thereof. 
(8) Alpha-sulfofatty acid salts or esters represented by the following 
formula 
##STR4## 
in which Y.sub.2 represents an alkyl group having from 1 to 3 carbon atoms 
or a counter ion, M.sub.1 represents a counter ion, R.sub.2 respresents an 
alkyl or alkenyl group having from 10 to 20, preferably 12 to 16, carbon 
atoms. 
The counter ions of the anionic active agents are, for example, alkali 
metal ions such as sodium, potassium and the like, alkaline earth metal 
ions such as calcium, magnesium and the like, ammonium ions, and 
alkanolamines having from 1 to 3 alkanol groups having 2 or 3 carbon atoms 
and including, for example, monoethanolamine, diethanolamine, 
triethanolamine, triisopropanolamine and the like. 
(b) Nonionic active agents 
(1) Polyoxyethylene alkyl or alkenyl ethers having a primary or secondary 
alkyl or alkenyl group having from 8 to 20 carbon atoms on average and 
having from 3 to 12 moles of ethylene oxide added thereto. 
(2) Polyoxyethylene alkylphenyl ethers having an alkyl group having from 8 
to 12 carbon atoms on average and having from 3 to 12 moles of ethylene 
oxide added thereto. 
(3) Higher fatty acid alkanolamides represented by the following formula 
and alkylene oxide adducts thereof 
##STR5## 
in which R.sub.3 represents H or CH.sub.3, R.sub.4 represent an alkyl or 
alkenyl group having from 10 to 20 carbon atoms, n is an integer of from 1 
to 3, and m is an integer of from 0 to 3. 
(c) Amphoteric active agents 
(1) Alkylamine oxides represented by the following formula 
##STR6## 
in which R.sub.5 represents an alkyl or alkenyl group having from 10 to 20 
carbon atoms, R.sub.6 and R.sub.7 independently represent an alkyl group 
having from 1 to 3 carbon atoms and may be the same of different. 
In the above formula, it is preferred the R.sub.5 represents an alkyl or 
alkenyl group having from 12 to 16 carbon atoms and R.sub.6 and R.sub.7 
independently represent methyl group. 
(2) Compounds of the following formula 
##STR7## 
in which R.sub.8 represents an alkyl or alkenyl group having from 10 to 20 
carbon atoms, R.sub.9 and R.sub.10 independently represent an alkyl group 
having from 1 to 4 carbon atoms, p is an integer of from 1 to 3, and 
X.sub.2 represents a COO.sup.- or --SO.sup.- group. Preferably, R.sub.8 
represents an alkyl or alkenyl group having from 12 to 16 carbon atoms, 
R.sub.9 and R.sub.10 independently represent methyl group, and p is an 
integer of 3. 
(3) Imidazoline compounds represented by the following formula 
##STR8## 
in which R.sub.11 represents a fatty acid residue having from 10 to 20 
carbon atoms on average, R.sub.12 represents hydrogen, Na or CH.sub.2 
COOMe in which Me represents H, Na or an organic base, R.sub.13 represents 
COOMe, CH.sub.2 COOMe or 
##STR9## 
in which Me has the same meaning as defined above, and R.sub.14 represents 
a hydroxyl group, an acidic salt, or an anionic active sulfate or 
sulfonate. Preferably, R.sub.11 represents a fatty acid residue having 
from 12 to 16 carbon atoms. 
(d) Cationic active agents 
In the practive of the invention, any cationic active agents may be used 
without limitation so far as they are ordinarily used in hair rinses or 
the like. Preferable examples of the agents include quaternary ammonium 
salts represented by the following formula (1) 
##STR10## 
in which one or two of R.sub.15, R.sub.16, R.sub.17 R.sub.18 independently 
represent a long-chained alkyl group or long-chained hydroxyalkyl group 
having from 8 to 20 carbon atoms, and the others independently represent 
an alkyl or hydroxyalkyl group having from 1 to 3 carbon atoms or a benzyl 
group, and X.sub.3 represents a halogen atom or an alkyl sulfate group 
having from 1 or 2 carbon atoms. Specific examples of the quaternary 
ammonium salts are distearyldimethylammonium chloride, 
stearyltrimethylammomium methosulfate, stearyltrimethylammonium chloride, 
stearyldimethylbenzylammonium thloride, lauryldiethylbenzylammonium 
chloride, lauryltrimethlammonium bromide, distearylmethylhydroxymethyl 
chloride, cetyltrimethylammonium chloride and the like. 
Good results are obtained using these surface active agents in an amount of 
0.01 to 10%, preferably 0.5 to 5%, of the hair rinse composition. 
The hair rinse or the like composition of the invention may further 
comprise hydrocarbons such as liquid paraffin, Vaseline.RTM. Petroleum 
Jelly, solid paraffin and the like, esters such as isopropyl myristate, 
lanolin derivatives such as lanolin, refined lanolin, lanolin fatty acids 
and the like, silicone derivatives such as dimethylpolysiloxane, 
methylphenylpolysiloxane, organomodified polysiloxane and the like, 
polyethylene glycol, polypropylene glycol or polymers thereof, oils such 
as polyoxyalklene alkyl ether, polyoxyalkylene alkyl ether phosphates and 
the like, polymeric materials such as hydroxyethyl cellulose, 
hydroxypropyl cellulose, hydroxpropylmethyl cellulose, methyl cellulose, 
cationized cellulose, cationized polymers and the like, bactericides. 
preservatives, perfumes, colorants and the like. 
(3) Hair Setting Agents (setting lotions, hair sprays and the like) 
The ingredients (A) and (B) are dissolved, as usual, in polar solvents such 
as water, ethyl alcohol, propyl alcohol and the like, thereby obtaining 
hair setting agents. Any polymer compounds which are used in ordinary hair 
setting agents may also be used in the practice of the invention. Examples 
of such polymer compounds are mentioned below. 
(a) Polyvinylpyrrolidone compounds 
Specific examples of these compounds include polyvinylpyrrolidone, 
copolymers of vinylpyrrolidone and vinyl acetate, copolymers of 
vinylpyrrolidone, vinyl acetate and alkylaminoacrylates, and the like. 
These compounds are commercially available under the names of Luviskol K, 
Luviskol VA, Luviflex D410I (Yuka Badische Co., Ltd.), and PVPK, PVP/VA 
and E-735 (GAF Co., Ltd.). 
(b) Acidic vinyl ether polymer compounds 
For instance, there are mentioned lower alkyl half-esters of copolymers of 
methyl vinyl ether and maleic anhydride, which are commerically available 
under the names of Gantrez ES-225 and ES-335 (Gaf Co., Ltd.). 
(c) Acidic polyvinyl acetate polymer compounds 
Examples of these compounds include copolymers of vinyl acetate and 
crotonic acid and are commercially sold under the names of Resin 28-1310 
(National Starch Co., Ltd.), Luviset CE5055 (Yuka Badische Co., Ltd.). 
(d) Acidic acrylic polymer compounds 
For instance, copolymers of acrylic acid and/or methacrylic acid and alkyl 
acrylates and/or alkyl methacrylates, and copolymers of acrylic acid, 
alkyl acrylates and N-alkylamides are mentioned. Commercial products 
include Plasize (Gooh Chem. Co., Ltd.), Ultrahold (Ciba-Geigy A. G.), and 
the like 
(e) Amphoteric acrylic polymer compounds 
There are mentioned compounds which are obtained by copolymerizing 
dialkylaminoethyl methacrylates, dialkylaminoethyl arylates or diacetone 
acrylamides with acrylic acid, methacrylic acid, alkyl acrylates and alkyl 
methacrylates and subjecting the copolymers to amphoteric reaction with 
halogenated acetic acid. Yuka Foamer AM-TS (Mitsubishi Petrochemical Co., 
Ltd.) is typical of commerical products of these polymer compounds. 
The hair setting agents of the invention may further comprise, within 
ranges of amounts not impending the effect of the invention, arbitrary 
ingredients which may depend on the purpose. Examples of such arbitrary 
ingredients include oil substance such as higher alcohols, higher fatty 
acid acid esters, and the like, nonionic active agents serving as an 
emulsifier or solubilizer such as polyoxyethylene lauryl ether, 
polyoxyethylene sorbitan monolaurate, polyoxyethylene hardened castor oil, 
and the like, humectants such as glycerine, propylene glycol and the like, 
perfumes, colorants, and the like. 
The hair setting agents of the invention may be applied to the hair as they 
are. Alternatively, they may be applied in the form of mist by the use of 
a pump sprayer or the like or may be applied in the form of mist of foam 
after packed ina container along with a jetting agent such as flon gas, 
liquid hydrocarbons or carbon dioxide gas. 
The thus obtained hair setting agents of the invention can form a uniform, 
tough film after drying, which shows excellent hair setting ability even 
under high humidity conditions. These hair setting agents can be readily 
removed from the hair upon washing it with now widely used shampooes 
comprising anionic active agents. Thus, the hair setting agents of the 
invention satisfy both requirements of set retentivity and washability. 
(4) First permanent waving agents 
The agents can be prepared by mixing the ingredients (A) and (B) with an 
ordinary permanent waving solution comprising a reducing material as a 
substrate. 
The reducing materials which are used as a substrate of the first permanent 
waving agent may be any known materials which are ordinarily used for the 
purposes. Preferable examples include ammonium salts of thioglycollic acid 
and hydrochlorides of cysteine. 
The first permanent waving agent may be prepared by mixing the above 
ingredients together by any known technique. The waving agent may further 
comprise conventionally used ingredients such as colorants, perfumes, 
oils, opacifiers, water-soluble silicones, organic salts, urea and the 
like. These ingredients are used depending on the purpose. 
(5) Second permanent waving agents 
To ordinary second permanent waving agents comprising oxidative materials 
as a substrate are added the ingredients (A) and (B). 
The amount of an oxidative material which is used as a substrated of the 
second permanent waving agent of the invention may differ depending on 
whether or not the second agent is dissolved in solvent, or the degree of 
dilution when such an agent is used as diluted. The amount is generally in 
the range of from 1 to 30%, preferably from 3 to 20%. 
The oxidative materials which are used as a substrate of the second 
permanenet waving agent may be any materials ordinarily used for the 
purposes and include, for example, alkali metal bromates such as sodium 
bromate, potassium bromate and the like, hydrogen peroxide, sodium 
percarbonate, sodium perborate and the like. Of these, alkali metal 
bromates are perferred. 
The second permanent waving agents may further comprise, aside from the 
above essential ingredients, arbitrary ingredients used for the purposes 
in amounts not impeding the effect of the invention. Examples of such 
arbitrary ingredients include anionic active agents, amphoteric active 
agents, nonionic active agents, cationic polymer compounds, water-soluble 
silicones, urea, suitable oils, humectants, perfumes, colorants and the 
like. 
Cationic polymer compounds mentioned above are, for example, cationic 
cellulose derivatives, cationic starch, diallyl quaternary ammonium salts, 
copolymers of diallyl quaternary ammonium salts and acrylamide, polyglycol 
and polyamide condensates, methacryloxyethyltrimethylammonium salts, and 
copolymers of metharyloxyethyltrimethylammonium salts and polyvinyl 
pyrrolidone. Of these, there are preferably used cationic cellulose a 
typical product of which is available under the name of "Polymer JR", 
diallyl quaternary ammonium salts a typical product of which is available 
under the name of "Merquat 100", and diallyl quarternary ammonium 
salt/acrylamide copolymer typical of which is a product available under 
the name of "Merquat 550". These cationic polymer compounds are generally 
used in an amount of from 0.01 to 5%, preferably 0.05 to 2%. 
The thus obtained second agent is adjusted in such a way that an aquenous 
5% solution thereof has a pH of below 9, preferably from 3.5 to 6.5. 
(6) Hair dyes 
The ingredients (A) and (B) are added to dye substrates as usual to give 
hair dyes. 
The dye substrates used in the hair dye composition of the invention are 
not critical and include any known substrates. For example, oxdiation hair 
dyes and temporary dyes are described by way of illustration only. 
(i) Oxidation hair dyes 
Dye intermediates, oxidizing agents and, if necessary, couplers or 
modifiers are mixed together. 
Examples of the dye intermediates include para or ortho compounds such as 
p-phenylenediamine, toluene-2,5-diamine, N-phenyl-p-phenylenediamine, 
4,4'-diaminodiphenylamine, p-aminophenol, p-methylaminophenol, 
o-phenylenediamine, toluene-3,4-diamine, o-aminophenol, 
p-chloro-o-phenylenediamine, p-amino-o-cresol, 
o-chloro-p-phenylenediamine, phloroglucin pyrogallol, 3,3'-iminodiphenyl, 
diphenylamine, 2,6-diaminopyridine, p-aminophenylsulfamic acid and the 
like. Couplers or nodifiers include metha compounds or phenols such as 
m-phenylenediamine, toluene-2,4-diamine, p-methoxy-m-phenylenediamine, 
m-aminophenol, alpha-naphthol, resorcin, hydroquinone, catechol and the 
like. Hydrogen peroxide is ordinarily used as the oxidizing agent. Also, 
there may be used sodium perborate, urea peroxide, sodium percarbonate, 
sodium peroxytripolyphosphate, sodium peroxypyrophosphate, sodium 
peroxyorthophoshate, sodium silicate and hydrogen peroxide adduct, sodium 
sulfate-sodium chloride-hydrogen peroxide adduct, and the like. In order 
to give an influenence on the color of the hair without taking part in the 
dye formation reaction, there may be further added direct dyes and 
particularly nitro dyes such as nitro-p-phenyenediamine, 
p-nitro-o-phenylenediamine, 2-amino-4-nitrophenol, 2-amino-5-nitrophenol, 
4-amino-2-nitrophenol and the like. If necessary, picramic acid, picric 
acid and/or 1,4-diaminoanthraqinone may be also added. 
Within ranges of amounts not impeding the effect of the invention, there 
may be also added nonionic active agents, cationic active agents, solvents 
such as propylene glycol, glycerine and the like, viscosity adjusters 
including lower alcohols such as ethyl alcohol, isopropyl alcohol and the 
like, hydroxyethyl cellulose, methyl cellulose, cationic polymer 
compounds, and higher alcohols, humectants, protein modifiers such as 
urea, perfumes, colorants, UV absorbers, antioxidants, preservatives, 
pearling agents, lotionizing agents, and the like. 
The oxidation hair agents of the invention are prepared by mixing the 
essential ingredients and the above-mentioned ingredients by a usual 
manner to give a powder preparation or a cream preparation. In 
applications, the preparation is added to water or a shampoo substrate. 
Alternatively, an oxidation dye and an oxidizing agent are separately 
provided. The essential ingreadients are added to either or both of the 
agents to give powder, cream or liquid preparation. In applications, 
separately provided systems are combined together. 
(ii) Temporary hair dyes 
Dyes and pigments are not limited to any specific ones and include, for 
example, pigments such as titanium oxide, carbon black and the like, and 
tar-base colorants such as triphenylmethane dyes, azo dyes, quinoline 
dyes, xanthene dyes, acridine dyes, azine dyes, oxazine dyes, indigoid 
dyes, stilbene dyes, thiazole dyes and the like. 
The resins are, for example, copolymers of acrylic esters or methacrylic 
esters, copolymers of monochloroacetic acid-amine salt-modified products 
of N,N'-diethylaminoethyl methacrylate and metharylic esters, copolymers 
of vinyl pyrrolidone and vinyl acetate and the like. 
The temporary hair dyes are prepared by dissolving or dispersing the 
essential ingredients, resins, dyes and pigments in a dispersion medium 
such as water, amyl alcohol, isopropanol, ethanol or acetone. As a matter 
of course, there may be further added known ingredients, which are 
ordinarily added to existing temporary hair dye compositions, including 
anionic active agents, cationic active agents, amphoteric active agents, 
nonionic active agents, polyhydric alcohols such as propylene glycol, 
glycerine, polyethylene glycol and the like, higher alcohols such as 
isostearyl alcohol, oleyl alcohol and the like, fatty acids such as 
lanolin fatty acids, fatty acids from coconut oil and the like, esters 
such as isopropyl myristate, hydrocarbons such as liquid paraffin, 
cationized polymer compounds, amines, perfumes, and the like. 
(7) Pre-shampoo treatment agents 
Pre-shampoo treatment agent is prepared by dissolving or suspending the 
ingredients (A) and (B) and, optionally, other known ingredients in a 
medium such as water. 
Known ingredients are, for example, oils and fats such as higher alcohols, 
fatty acid esters and the like, nonionic active agents serving as an 
emulsifier or solubilizing agent and including polyoxyalkylene alkyl 
ethers, and humectants such as glycerine, pyrrolidonecarboxylic acid and 
the like. These ingredients serve to control a degree of styling of the 
hair when the hair is treated with the preshampoo treatment agent of the 
invention and shampooed thereafter. That is, of liquid oil or fat 
ingredients is effective in imparting softness to the hair and humectants 
can impart moistness to the hair. In addition, use of higher alcohols 
imparts dryness to the hair.

The present invention is described by way of references and examples, which 
should not be construed as limiting the present invention thereto. 
Reference 1 
Ten kilograms of the whole of a birch tree (Betula alba) was admixed with 
20 liters of 40% 1,3-butylene glycol and immersed therein at 20.degree. to 
25.degree. C. for 10 to 15 days, followed by centrifugal separation. To 
the residue was further added 10 liters of 1,3-butylene glycol for 
re-immersion. The resulting immersion solution and the solution obtained 
by the centrifugal separation were combined and aged in a dark and cold 
place (0.degree. to 5.degree. C.) for about 40 days. As a result, there 
was obtained a brich extract in the form of a dark brown liquid containing 
5% solid matters. 
Reference 2 
Twenty liters of 50% ethanol was added to 10 kg of the whole of a birch 
tree (Betula alba) for immersion in a cold and dark place for 20 days. As 
a result, a birch extract in the form of a brown liquid containing 6.5% 
solid matters was obtained. 
Reference 3 
Ten liters of an aqueous 50% propylene glycol solution was added to 5 kg of 
leaves of rosemary (Rosemarinus Officinalis), followed by refluxing at 
50.degree. C. for 12 hours to obtain an extract. The extract was subjected 
to filtration to remove the residue therefrom to obtain a final product. 
This product was a rosemary extract in the form of a brown liquid 
containing 10% solid matters. 
Reference 4 
Ten kilograms of silk fibers obtained from the silkworm was washed with 
water, dried, cut into pieces, powdered and passed through a 200 microns 
sieve to obtain 9.5 kg of a silk powder. 
Reference 5 
Sixty grams of silk fibers were dissolved in 600 ml of water containing 48 
g of ethylenediamine and 36 g of cupric hydroxide, followed by heating to 
60.degree. C. for 2 hours. Subsequently, the solution was adjusted in pH 
with 3H with 3N acetic acid to 6.0-7.0, and filtered, followed by placing 
the resulting filtrate in a cellulose tube C-65 and subjecting to dialysis 
in running water over one or two days and nights. The resulting dialyzate 
was filtered and made up to 2000 ml, to which was added 80 g of a strongly 
aicdic cationic exchange resin Dowex 50wx-2, followed by agitating for 20 
to 30 minutes and filtering. Thereafter, the resulting filtrate was 
admixed with an 1N sodium hydroxide solution to adjust its pH to 6.0-7.0. 
As a result, there was obtained 1900 ml of a solution containing 0.5% of 
the effective ingredient. The thus obtained silk protein had an average 
molecular weight of 2000. 
Reference 6 
Preparation of Decomposition Derivatives by oxidation of Karatin Material: 
Ten grams of wool fibers were immersed in 700 g of an aqueous 8% peracetic 
acid solution at room temperature for 1 day to carry out the oxidation 
reaction. The resulting oxidized wool fibers were filtered, washed with 
water and immersed in 700 g of a 0.1N ammoniacal solution at room 
temperature for 1 day, permitting about 90% of the wool to dissolve in the 
ammoniacal solution. About 1 g of the insoluble matters were removed by 
filtration and the aqueous ammoniacal solution of keratose to be an 
oxidized decomposition product of the wool keratin was admixed with 2N 
hydrochloric acid to adjust the pH to 4.0, whereupon alpha-keratose was 
settled as precipitate. This precipitate was filtered, washed with acetone 
and dried to obtain 5.4 g of alpha-keratose. 
Reference 7 
Keratin Materials: 
Ten grams of wool fibers were immersed in 600 ml of an aqueous solution 
with concentration of 8M urea and 0.01M tris buffer, to which was added 6 
ml of 2-mercaptoethanol, followed by adjusting the pH to 10 by means of a 
5N potassium hydroxide aqueous solution to effect the reduction reaction 
in a stream of nitrogen at room temperature. About 3 hours after 
commencement of the reaction, the wool dissolved in the reaction solution 
in an amount of about 85% thereof. While the system was adjusted with a 5N 
potassium hydroxide solution so that the pH was not below 7, 16.5 g of 
iodoacetic acid was gradually added and the pH of the system was finally 
adjusted to 8.5 to carry out the carboxymethylation reaction at room 
temperature for 2 hours. The reaction solution was filtered to remove 
insoluble matters therefrom and the resultant filtrate was charged into a 
cellulose tube wherein it was dialyzed against ion-enchanged water to 
remove low molecular weight impurities including urea. As the urea was 
dialyzed, the content in the cellulose tube became cloudy since 
water-insoluble HGT (component with high contents of glycerine and 
tyrosine was cause to precipitate. After completion of the dialysis, HGT 
was centrifugally removed and S-carboxymethyl keratin (SCMKA) was obtained 
from the neutral transparent solution of SCMKA by the isoelectric 
precipitation method. That is, 1N hydrochloric acid was added to the 
system to adjust its pH to 4.4 by which SCMKA became insoluble and 
separated as precipitate. This precipitate was filtered, washed with 
ethanol and dried to obtain 4.2 g of SCMKA. Reference 8 
Preparation of Hydrolysis Derivatives of Keratin Materials: 
Ten grams of wool fibers were immersed in 300 g of a 1% sodium 
hydrogensulfite aqueous solution, whose pH was adjusted to 6.7 by the use 
of a 5N aqueous caustic soda solution. Thereafter, 0.2 g of papain was 
added to the system to effect the hydrolysis reaction at 60.degree. C. for 
15 hours, by which about 80% of the wool dissolved. Insoluble matters were 
removed by filtration and the sulfite in the resulting filtrate was 
removed by the ultrafiltration technique using a membrane with a 
fractional molecular weight of 500. The aqueous solution of the 
hydrolysate was concentrated and freeze dried to obtain 7.7 g of the 
hydrolysate having a molecular weight of 500-2,000. 
Example 1 
Shampoo: 
Shampoo compositions of the formulations indicated in Table 1-A were 
prepared and subjected to the performance evaluation test thereof. The 
results are shown in Table 1-B. 
The performance evaluation was conducted according to the following methods 
in or throughout the examples appearing hereinafter. 
(1) Lathering or foaming test 
To an aqueous solution of 1% shampoo composition was added 0.1% of lanolin 
as an artificial dirt, followed by agitating in a cylinder for 5 minutes 
by means of a flat propeller at 40.degree. C. at 1000 r.p.m. in such a way 
that the propeller was turned in opposite directions every 10 second. 
After completion of the agitation, an amount of lathering after 30 seconds 
was measured for evaluation. 
(2) Touch of lather 
Thirty grams of human hair was wetted with water of 40.degree. C. to permit 
20 g of water to be contained. Thereafter, 1 g of each of the shampoo 
compositions was used for washing the hair therewith whereupon the touch 
of the lather was organoleptically evaluated by 20 female panelers. 
Evaluation Item 
The degree of ease in passing fingers through the hair upon washing was 
evaluated as "foam smoothness". 
Evaluation standard 
O Better foam smoothness than that of a reference 
Slightly better than a reference 
X Same in foam smoothness as a reference 
(3) Combing force 
Thirty grams of human hair was wetted with water of 40.degree. C. to permit 
20 g of water to be contained. One gram of each of the shampoo 
compositions was used to effect washing and rinsing operations two times, 
after which it was squeezed and set on a strain gauge. Subsequently, the 
hair was combed to determine a force exerted thereon (wetd combing force). 
The hair was then dried with a dryer and allowed to stand in a 
air-conditioned room of a temperature of 20.degree. C. and a relative 
humidity of 65% overnight, followed by setting on a strain gauge and 
combing to determine a force exerted thereon (dry combing force). 
(4) Hair fly 
Upon the measurement of "combing force" under dry conditions, it was 
observed whether or not there took place an electrostatic hair fly 
phenomenon. 
Evaluation 
O Occurrence of hair fly 
X No occurence of hair fly 
TABLE 1-A 
__________________________________________________________________________ 
A B C D E F G 
__________________________________________________________________________ 
Sodium polyoxyethylene (2) 
15% 15% 15% 15% 15% 15% 15% 
lauryl sulfate 
Coconut fatty acid 
3 3 3 3 3 3 3 
diethanolamide 
Rosemarry extract 
-- 0.5 0.5 -- 0.5 -- 0.5 
(Novarom Co., Ltd.) 
Oxidative decomposition 
-- -- 0.1 -- -- -- -- 
product of keratin 
(obtained in Reference 6) 
Oxidative decomposition 
-- -- -- 0.1 0.1 -- -- 
product of collagen* 
Hydrolyzed decomposition 
-- -- -- -- -- 0.1 0.1 
product of collagen** 
Perfume suitable 
suitable 
suitable 
Suitable 
Suitable 
Suitable 
Suitable 
amount 
amount 
amount 
amount 
amount 
amount 
amount 
Water balance 
balance 
balance 
balance 
balance 
balance 
balance 
(pH 7.2) 
(pH 7.2) 
(pH 7.2) 
(pH 7.2) 
(pH 7.2) 
(pH 7.2) 
(pH 7.2) 
__________________________________________________________________________ 
*, **: having average molecular weight of about 1,000. 
TABLE 1-B 
______________________________________ 
Lathering Characteristics 
Hair Finishing 
Lather Combing 
Lathering 
Smoothness 
Force (g) Hair Fly 
______________________________________ 
A 114 X 210 O 
B 105 .DELTA. 196 O 
C(product of 
138 .circleincircle. 
101 X 
invention) 
D 91 X 254 O 
E 93 .DELTA. 247 O 
F 87 X 201 O 
G 90 X 198 O 
______________________________________ 
Example 2 
Shampoo: 
Shampoo compositions of the formulation indicated in Table 2-A were 
prepared and subjected to the performance evaluation test. The results are 
shown in Table 2-B. 
The performance evaluations were effected in the same manner as in Example 
1. 
TABLE 2-A 
______________________________________ 
H I J 
______________________________________ 
Sodium polyoxyethylene(2) 
15% 15% 15% 
lauryl sulfate 
Coconut fatty acid 
3 3 3 
diethanolamide 
Birch extract -- 0.5 0.5 
(Novarom Co., Ltd.) 
Hydrolyzate of -- -- 0.1 
silk (average molecular 
weight of 20,000) 
Perfume suitable suitable suitabe 
amount amount amount 
Water balance balance balance 
(pH 7.2) (pH 7.2) (pH 7.2) 
______________________________________ 
TABLE 2-B 
______________________________________ 
Lathering Characteristics 
Hair Finishing 
Lather Combing 
Lathering 
Smoothness 
Force (g) Hair Fly 
______________________________________ 
H 114 X 210 O 
I 107 .DELTA. 176 O 
J (product of 
142 .circleincircle. 
97 X 
invention) 
______________________________________ 
Example 3 
Hair Rinse: 
Hair rinses of the formulations indicated in Table 3-A were prepared. Five 
hundreds milliliters of a 50:1 dilution of each hair rinse was used to 
treat the hair therewith, which was subsequently rinsed with hot water two 
times and air-dried. The thus dried hair was evaluated by 20 panelers 
according to the following five-point method. 
Evaluation standard: 
Good 5, Fair 4, Moderate 3, Rather poor 2, Poor 1 
The results are shown in Table 3-B as average values. 
TABLE 3-A 
______________________________________ 
K L M N 
______________________________________ 
Distearyldimethyl- 
2% 2% 2% 2% 
ammonium chloride 
Stearyl alcohol 
1% 1% 1% 1% 
Birch extract 
-- 1% -- 1% 
(obtained in Refer- 
ence 1) 
Hydrolyzate of keratin 
-- -- 1% 1% 
(obtained in Refer- 
ence 8, average mole- 
cular weight 3000) 
Water balance balance balance 
balance 
(pH 5.0) (pH 5.0) (pH 5.0) 
(pH 5.0) 
______________________________________ 
TABLE 3-B 
______________________________________ 
Softness Smoothness 
Ease in Combing 
______________________________________ 
K 1.2 1.3 1.2 
L 2.1 2.5 3.3 
M 3.2 3.4 2.5 
N (product 
4.2 4.0 3.9 
of invention) 
______________________________________ 
Example 4 
Hair Rinse: 
Hair rinses of the formulations indicated in Table 4-A were prepared and 
evaluated in the same manner as in Example 3. The results are shown in 
Table 4-B. 
TABLE 4-A 
______________________________________ 
O P Q R 
______________________________________ 
Distearyldimethyl- 
2% 2% 2% 2% 
ammonium 
chloride 
Stearyl alcohol 
1% 1% 1% 1% 
Rosemarry extract 
-- 1% -- 1% 
(obtained in 
Reference 3) 
Hydrolyzate of silk 
-- -- 1% 1% 
(average molecular 
weight 20,000) 
Water balance balance balance 
balance 
(pH 5.0) (pH 5.0) (pH 5.0) 
(pH 5.0) 
______________________________________ 
TABLE 4-B 
______________________________________ 
Softness 
Smoothness Ease in Combing 
______________________________________ 
O 1.2 1.3 1.2 
P 2.1 2.6 3.4 
Q 3.2 3.4 2.5 
R (product 
4.5 4.1 4.4 
of invention) 
______________________________________ 
Example 5 
Hair Treatment Agent: 
Hair treatment agents of formulations (S) through (V) were prepared using 
the following fundamental composition. 
______________________________________ 
Fundamental Composition 
______________________________________ 
Liquid paraffin 5.0% 
White vaseline petroleum jelly 
2.0% 
Cetyl alcohol 2.0% 
POE(20)sorbitan monostearate 
1.0% 
Glycerine 10.0% 
Water balance 
pH 7.0 
______________________________________ 
To the above composition were added: 
(S) no material, 
(T) 1.0% of a birch extract (obtained in Reference 1), 
(U) 2.0% of a hydrolyzate of keratin (an average molecular weight of 
20,000), or 
(V) 1.0% of a birch extract (obtained in Reference 1) and 2.0% of a 
hydrolyzate of keratin (average molecular weight of 20,000). 
These hair treatments were evaluated according to the five-point method 
with respect to the following items. Average values of the respective 
evaluation tests are shown in Table 5. 
TABLE 5 
______________________________________ 
Organoleptic 
Combing Force (g) 
Evaluation Wet State Dry State 
______________________________________ 
S 2.0 420 360 
T 2.0 405 351 
U 2.3 326 265 
V (product 
4.6 116 107 
of invention) 
______________________________________ 
Example 6 
Hair Treatment Agent: 
Based on the fundamental composition of Example 5, the following 
formulations (W)-(Z) were prepared. 
(W) Nothing was added. 
(X) 1.0% of a birch extract (obtained in Reference 1) was added. 
(Y) 2.0% of a silk hydrolyzate (average molecular weight 20,000) was added. 
(Z) 1.0% of a birch extract (obtained in Reference 1) and 2.0% of a silk 
hydrolyzate were added. 
The resulting hair treatments were evaluated in the same manner as in 
Example 5 with the results shown in Table 6. 
TABLE 6 
______________________________________ 
Organoleptic 
Combing Force (g) 
Evaluation Wet State Dry State 
______________________________________ 
W 2.0 420 360 
X 2.0 405 351 
Y 2.3 326 265 
Z (product 
4.4 123 115 
of invention) 
______________________________________ 
Example 7 
Hair Setting Lotion: 
Hair setting lotions of the formulations indicated in Table 7-A were 
prepared and their set retentivity was evaluated. The results are shown in 
Table 7-B. 
TABLE 7-A 
______________________________________ 
A B C 
______________________________________ 
Ethanol 10% 10% 10% 
Birch extract -- 2.0% 2.0% 
(Vermin Co., Ltd.) 
Hydrolyzate of wool keratin 
-- -- 1.0% 
(average molecular weight 
20,000) 
Polyoxyethylene oleyl ether 
0.5% 0.5% 0.5% 
(EO 20) 
Perfum 0.1% 0.1% 0.1% 
Water balance balance balance 
______________________________________ 
##STR11## 
- in which, 
Lo=14 cm, 
Ls=a length (cm) of a curled hair immediately after suspension under 95% 
relative humidity conditions, 
Lt=a length (cm) of a curled hair 30 minutes after suspension of the hair 
under 95% R.H. conditions. 
TABLE 7-B 
______________________________________ 
Set Retentivity 
______________________________________ 
A 53% 
B 60% 
C (product of 
76% 
invention) 
______________________________________ 
Example 8 
Hair Setting Lotions: 
Hair setting lotions of the formulations indicated in Table 8-A were 
prepared to determine set retentivity in the same manner as in Example 7. 
The results are shown in Table 8-B. 
TABLE 8-A 
______________________________________ 
D E F 
______________________________________ 
Ethanol 10% 10% 10% 
Birch extract -- 2.0% 2.0% 
(Vermin Co., Ltd.) 
Silk hydrolyzate -- -- 1.0% 
(average molecular weight 
20,000) 
Polyoxyethylene oleyl ether 
0.5% 0.5% 0.5% 
(EO20) 
Perfum 0.1% 0.1% 0.1% 
Water balance balance balance 
______________________________________ 
TABLE 8-B 
______________________________________ 
Set Retentivity 
______________________________________ 
D 53% 
E 60% 
F (product of 
84% 
invention) 
______________________________________ 
Example 9 
First Permanent Waving Agent: 
Permanent waving treatments were effected using first permanent waving 
agents of the formulation indicated in Table 9-A and a second permanent 
waving agent to determine a degree of waving, wave retentivity, 
adsorptivity, and feeling to the touch. The results are shown in Table 
9-B. 
Formulation: 
TABLE 9-A 
______________________________________ 
G H I 
______________________________________ 
(1) First permanent waving agent 
Ammonium thioglycollate 
7% 7% 7% 
Birch extract -- 1% 1% 
(Novarom Co., Ltd.) 
Silk hydrolyzate -- -- 2% 
(average molecular weight 
1,500) 
Water (ammoniacal solution 
93% 92% 90% 
for pH adjustment) 
______________________________________ 
Second permanent waving agent: 
Sodium bromate 5.0% 
Water 95.0% 
______________________________________ 
Test method: 
(1) Measurement of a degree of waving and wave retentivity 
(i) A bundle of 20 human hairs were fixed to cylinders of a wave-measuring 
plate (in which a plurality of cylinders, each having a diameter of 2 mm 
and a length of 1.5 mm, were arranged in zigzag form in two rows). The 
bundle was immersed in the first agent of each of the formulations through 
at 30.degree. C. for 10 minutes, followed by immersion in a second agent 
at 30.degree. C. for 10 minutes. Thereafter, the immersed bundle was 
sufficiently rinsed with water and removed from the plate. A degree of 
waving in still water was calculated according to the following equation. 
It should be noted that the hair used was a 20 cm long virgin hair which 
was washed with an aqueous solution of 0.5% of sodium lauryl sulfate and 
dried. 
##EQU1## 
Xo: a length of the hair fixed between points a and b of one row of the 
zigzag cylinders which are distant from each other. 
Yo: a distance between a and b. 
Zo: a distance of the hair, fixed between the point a and b, in still water 
after removal from the measuring plate. 
(ii) The hair used in (i) was slightly moved and washed while immersing in 
an aqueous solution of 0.5% sodium lauryl sulfate for 1 minute, followed 
by sufficiently rinsing and air drying for 1 day. The above procedure was 
repeated four times and, after the fifth washing, the hair was 
sufficiently rinsed. Thereafter, a distance, Zo, in still water was 
measured, from which a degree of wave was determined. A ratio of this 
degree to a degree of wave prior to washing was was calculated to give a 
wave retentivity. 
##EQU2## 
(2) Adsorptivity 
The hair used for the measurement of the degree of wave was observed 
through a scanning electron microscope in order to determine the presence 
or absence of adsorbed matters on the hair surfaces. The evaluation 
standard is shown below. 
______________________________________ 
Adsorptivity 
State of Hair Surfaces 
______________________________________ 
++ Covered with a film and being thus 
smooth. 
+ Slight amounts of adsorbed matters 
observed though the surfaces are smooth. 
- Considerable irregularities observed with 
hair cuticle being partly separated. 
______________________________________ 
(3) Evaluation of Feeling to the Touch 
A hair bundle made of Japanese virgin hairs was immersed in a first agent 
of each of formulations through at 30.degree. C. for 10 minutes and 
subsequently immersed in a second agent at 30.degree. C. for 10 minutes. 
The bundle which was sufficiently rinsed with water and air/dried was 
evaluated by 20 female panelers according to the five-point method with 
respect to the feeling of the hair bundle to the touch. The evaluation 
standard was as follows: Good=5; Fair=4; Moderate=3; Rather poor=2; 
Poor=1. The results are indicated by geometric average. 
TABLE 9-B 
______________________________________ 
Wave 
First Adsorpt- Degree of Retent- Feeling to 
Permanent 
ivity wave (5) ivity (%) 
the touch 
______________________________________ 
G - 52 73 2.4 
H + 49 70 2.1 
I ++ 56 91 3.5 
______________________________________ 
Example 10 
Second Permanent Waving Agent: 
The hair was permed using a first agent and second agents of the 
fomulations indicated below. A degree of damage of the hair during the 
perming treatment was determined by measuring weight of the hair prior to 
and after the treatment. The method of measuring the hair weight and the 
evaluation standard are described below. 
[Composition] 
______________________________________ 
First Agent: 
______________________________________ 
Thioglycollic acid 7.0% 
Polyoxyethylene hardened castor oil 
1.0% 
Perfume 0.2% 
Ammoniacal solution, water 
balance 
______________________________________ 
(pH adjusted to 9.0 by means of ammoniacal solution) 
TABLE 10 
______________________________________ 
Second Agents 
J K L 
______________________________________ 
Sodium bromate 5% 5% 5% 
Amphoteric active agent 
0.5% 0.5% 0.5% 
(Miranol CSM-SF, by Miranol 
Co., Ltd.) 
Perfume 0.1% 0.1% 0.1% 
Rosemarry extract 
-- 1.0% 1.0% 
(Vermin Co., Ltd.) 
Silk hydrolyzate -- -- 2.0% 
(average molecular weight 
1,500) 
Water balance balance balance 
______________________________________ 
[Measurement of Hair Weight] 
Ten centimeters long virgin hair was washed with an aqueous solution of 
0.5% sodium lauryl sulfate and air-dried to give a hair being tested. 
About 1 g of the hair was bundled and placed in a desiccator using a 
phosphorus pentaoxide dryer, followed by drying under reduced pressure for 
one week and measuring the dried hair to give an absolute dry weight of 
the virgin hair. The thus dried hair was immersed in the first agent or 
solution at 30.degree. C. for 10 minutes and sufficiently washed with 
water. Thereafter, the hair was further immersed in the respective second 
agents at 30.degree. C. for 10 minutes. After sufficiently rinsing with 
water, it was air-dried and dried according to the above procedure to give 
an absolute dry weight of the permed hair. 
[Evaluation Standard] 
______________________________________ 
Evaluation Content 
______________________________________ 
.circleincircle. 
The difference in absolute dry weight 
between the virgin hair and the permed 
hair is less than 1%. 
O The difference in absolute dry weight 
between the virgin hair and the permed 
hair is in the range from 1 to 5%. 
X The difference in absolute dry weight 
between the virgin hair and the permed 
hair is over 5%. 
______________________________________ 
Results 
______________________________________ 
J X 
K O 
L (product .circleincircle. 
of invention) 
______________________________________ 
Example 11 
Hair Dye: 
Two-component hair dye compositions of the formulations indicated in Table 
11 were prepared and the influence of these compositions on the hair was 
determined by measuring hair weights prior to and after the hair dyeing 
treatment. The results are shown below. 
Composition: 
TABLE 11 
______________________________________ 
First Liquid Component 
M N O 
______________________________________ 
p-Phenylenediamine 
1.0% 1.0% 1.0% 
Birch extract -- 1.0% 1.0% 
(obtained in Reference 2) 
Silk hydrolyzate 
-- -- 0.5% 
(average molecular weight 
20,000) 
Propylene glycol 
10.0% 10.0% 10.0% 
Disodium edetoate 
0.3% 0.3% 0.3% 
Sodium sulfite 0.5% 0.5% 0.5% 
Perfume 0.1% 0.1% 0.1% 
Water balance balance balance 
______________________________________ 
(pH was adjusted to 10.0 by means of an ammoniacal solution.) 
(Second liquid component) 
Evaluation Method: 
Ten centimeters long virgin hair was washed with an aqueous solution of 
0.5% sodium lauryl sulfate and air-dried to give a hair being tested. 
About 1 g of the hair was bundled and placed in a desiccator using 
phosphorus pentaoxide dryer, followed by drying under reduced pressure for 
1 week and measuring the dried hair weight to give an absolute dry weight 
of the virgin hair. 
Subsequently, the hair was dyed according to the following procedure and 
air-dried, followed by drying in the same manner as described above and 
measuring the weight of the dyed hair to give an absolute dry weight of 
the dyed hair. 
The hair weight after the hair dyeing treatment was evaluated by comparison 
with the virgin hair weight and an influence of the respective dye 
compositions on the hair was judged. 
[Evaluation Standard] 
______________________________________ 
Evaluation Content 
______________________________________ 
.circleincircle. 
The dyed hair increased in weight 
over the virgin hair. 
O The dyed hair decreased in weight by 
0-3% as compared with the virgin 
hair 
X The dyed hair decreases in weight 
over 3% as compared with the virgin 
hair. 
______________________________________ 
Dyeing Procedure: 
A mixture of the first and second liquids in equal amounts was provided as 
a dyeing solution and was dilated to have a liquor ratio of 1:5. The hair 
was immersed in the solution at room temperature for 30 minutes and dyed. 
Thereafter, the hair was washed with city water of 40.degree. C. to wash 
away the deposited dye therefrom and washed further with an aqueous 
solution of 0.5% sodium lauryl sulfate, followed by instantaneously 
immersing in an aqueous 1N acetic acid solution and washing in city water 
of 40.degree. C. 
Results: 
______________________________________ 
M X 
N O 
O (product of invention) 
.circleincircle. 
______________________________________ 
Example 12 
Hair Dye: 
Temporary hair dye compositions (hair colorants) of the mascara type having 
formulations indicated in Table 12-A were prepared. 0.5 g of each 
composition was applied to 1 g of grey hair. After drying in air, the hair 
was organoleptically evaluated by 10 expert panelers with respect to the 
gloss, smoothness and feeling. The results are shown in Table 12-B. 
Composition: 
TABLE 12-A 
______________________________________ 
P Q R 
______________________________________ 
Polymer resin* 12.0% 12.0% 12.0% 
Pigment (carbon black) 
1.0% 1.0% 1.0% 
Birch extract -- 1.0% 1.0% 
(obtained in Reference 1) 
Silk hydrolyzate 
-- -- 0.5% 
(average molecular weight 
20,000) 
Perfume 0.1% 0.1% 0.1% 
Ethanol balance balance balance 
______________________________________ 
*Polymer resin: Copolymer of monochloroacetic acidamine saltmodified 
product of N,N'--dimethylaminoethyl metharylate and methacrylic ester. 
Results: 
TABLE 12-B 
______________________________________ 
Feeling to 
Gloss Smoothness 
the Touch 
______________________________________ 
P X X X 
Q .DELTA. .DELTA. O 
R (product of 
O O O 
invention) 
______________________________________ 
Example 13 
Hair Liquid: 
[Composition] 
______________________________________ 
(a) Rosemary extract (Novarom Co., Ltd.) 
1.0% 
(b) Oxidative decomposition product of 
0.1% 
keratin (obtained in Reference 6) 
(c) Polyoxypropylene(30) butyl ether 
15.0% 
(d) Ethanol 40.0% 
(e) Water 44.0% 
______________________________________ 
[Preparation] 
The above ingredients (a) through (e) were mixed together to completely 
dissolve the components to obtain a hair liquid. 
Example 14 
Hair Tonic: [Composition] 
______________________________________ 
(a) Rosemary extract (obtained in Reference 3) 
1.0% 
(b) Hydrolyzate of keratin (obtained in 
0.1% 
Reference 8) 
(c) PCA-Al 0.5% 
(d) Ethanol 55.0% 
(e) Water 44.0% 
______________________________________ 
[Preparation] 
The above ingredients (a) through (e) were mixed and agitated until a 
uniform soultion was obtained, thereby giving a hair tonic. 
Example 15 
Hair Liquid: 
[Composition] 
______________________________________ 
(a) Birch extract (obtained in Reference 1) 
1.0% 
(b) Silk hydrolyzate (average molecular 
0.1% 
weight 20,000) 
(c) Polyoxypropylene(30) butyl ether 
15.0% 
(d) Ethanol 40.0% 
(e) Water 44.0% 
______________________________________ 
[Preparation] 
The above ingredients (a) through (e) were mixed for complete dissolution 
to obtain a hair liquid. 
Example 16 
Hair Tonic: 
[Composition] 
______________________________________ 
(a) Birch extract (Novarom Co., Ltd.) 
1.0% 
(b) Silk hydrolyzate (average molecular 
0.1% 
weight 20,000) 
(c) PCA-Al 0.5% 
(d) Ethanol 55.0% 
(e) Water 44.0% 
______________________________________ 
[Preparation] 
The above ingredients (a) through (e) were mixed and agitated until a 
uniform solution was obtained, thereby giving a hair tonic. 
Example 17 
Setting Lotion: 
Setting lotions having formulations indicated in Table 17-A were prepared 
and applied to the hair to determine the feeling of the hair to the touch 
and set retentivity. The results are shown in Table 17-B. 
TABLE 17-A 
______________________________________ 
S T U 
______________________________________ 
Birch extract -- 0.005% 0.005% 
(Dragoco Co., Ltd.) 
Oxidative decomposition 
-- -- 0.2% 
product of keratin 
(obtained in Reference 6) 
Cationic polymer 
1.0 1.0 1.0 
(Polymer JR400) 
Sodium chloride 
1.0 1.0 1.0 
Ethanol 5.0 5.0 5.0 
Water balance balance balance 
pH 7.0 7.0 7.0 
______________________________________ 
[Test Method] 
(1) Feeling of Treated Hair to the Touch 
Twenty grams of a 20 cm long hair bundle made of Japanese female hair was 
applied with 2 g of a hair cosmetic throughout the hair and then rinsed 
with running water of 40.degree. C. for 1 minute. The thus treated hair 
was organolepitcally evaluated. The organoleptic evaluation was carried 
out by paired comparison according to the following evaluation point 
using, as a reference, a hair bundle treated with a commmercial hair rinse 
comprising as its principal components a quaternary ammonium salt and a 
hydrocarbon. An average point by 20 expert panelers is indicated in Table 
appearing hereinafter. 
______________________________________ 
Evaluation Point 
Evaluation 
______________________________________ 
+2 Better in feeling than the reference 
hair bundle. 
+1 Slightly better than the reference 
hair bundle. 
0 Equal to the reference hair bundle. 
-1 Slightly poorer than the reference 
hair bundle. 
-2 Poorer than the reference hair 
bundle. 
______________________________________ 
(2) Set-retaining Effect 
A 20 cm long hair bundle having a weight of 5 g and made of Japanese female 
hair was applied with 1 g of a hair cosmetic throughout the hair and 
rinsed with running water of 40.degree. C. for 1 minute, after which an 
excess of water was removed by means of filter paper. The thus treated 
hair bundle was wound around a glass tube with a diameter of 1.5 cm so 
that a winding width was 5 cm, and fixed at opposite ends thereof. The 
bundle was allowed to stand under conditions of 65 R.H. % and 20.degree. 
C. for 24 hours and curled. After 24 hours, the wound bundle was removed 
from the tube and vertically suspended, whereupon its length was measured 
and a degree of curling was calculated according to the following 
equation. 
##EQU3## 
Ao: Length of the hair immediately after removal of the hair. Bo: Length 
of the hair 12 hours after removal of the hair. 
(3) Measurement of combing force under wetting conditions 
After completion of the evaluation of the feeling of the hair, it was fixed 
on a strain gauge, through which a nylon comb was passed 20 times while 
recording a force exerted upon the comb. An average value of the 20 
measurement was determined as a combining force. 
(4) Feeling and measurement of combing force under dry conditions 
The hair bundle after the measurement of the combing force under wet 
conditions was dried in air and then evaluated according to the evaluation 
and measurement methods described in (1) and (3) above. 
Results: 
TABLE 17-B 
______________________________________ 
Combing Force 
Feeling of Degree of under wet under dry 
the Hair Curling conditions 
conditions 
______________________________________ 
S -0.1 72% 170(g) 
194(g) 
T +0.1 76% 165 187 
U +1.4 90% 107 160 
______________________________________ 
Example 18 
Setting Lotion: 
Setting lotions of formulations indicated in Table 18-A were prepared and 
applied to the hair. The feeling of the hair and the set-retaining effect 
of the respective lotions were determined in the same manner as in Example 
17. The results are shown in Table 18-B. 
TABLE 18-A 
______________________________________ 
V W X 
______________________________________ 
Birch extract 
-- 0.005% 0.005% 
(Dragoco Co., Ltd.) 
Silk hydrolyzate 
-- -- 0.2% 
(M.W. 20,000) 
Cationic polymer 
1.0 1.0 1.0 
(Polymer JR400) 
Sodium chloride 
1.0 1.0 1.0 
Ethanol 5.0 5.0 5.0 
Water balance balance balance 
pH 7.0 7.0 7.0 
______________________________________ 
Results: 
TABLE 18-B 
______________________________________ 
Combing Force 
Feeling of Degree of under wet under dry 
the Hair Curling conditions 
conditions 
______________________________________ 
V -0.1 72% 170(g) 
194(g) 
W +0.1 76% 165 187 
X +1.3 93% 136 161 
______________________________________